The asymmetric unit of the title compound consists of two independent molecules differing slightly in conformation and in their intermolecular interactions in the solid. 8H7NO3, consists of two molecules differing slightly in conformation and in their intermolecular interactions in the solid. The dihedral angle between the benzene and dioxolane rings is 0.20 (7)° in one molecule and 0.31 (7)° in the other. In the crystal, the two molecules are linked into dimers through pairwise O—H⋯N hydrogen bonds, with these units being formed into stacks by two different sets of aromatic π-stacking interactions. The stacks are connected by C—H⋯O hydrogen bonds. A Hirshfeld surface analysis indicates that the most significant contacts in the crystal packing are H⋯O/O⋯H (36.7%), H⋯H (32.2%) and C⋯H/H⋯C (12.7%).The asymmetric unit of the title molecule, C For the C1–C6 rings, the centroid–centroid distance is 3.6024 (11) Å with a slippage of 1.185 Å between molecules at x, y, z and −x, −y + 1, −z. These paired molecules make weak, slipped π-stacking interactions with corresponding pairs at −x + 1, −y + 1, −z + 1 with a centroid–centroid distance of 3.8479 (11) Å and a slippage of 1.947 Å. The C9–C14 ring has slipped π-stacking interactions with its counterparts in molecules at x − y + z − x + y + z + B⋯O4, C8—H8⋯O6, C15—H15A⋯O1 and C16—H16⋯O3 hydrogen bonds -2-(1H-imidazol-1-yl)ethylidene]hydroxylamine N-hydroxy-3-(1H-imidazol-1-yl)propan-1-imine isopropanol solvate  form and (Z)-3,4-methylenedioxybenzaldehyde oximium 4-toluenesulfonate A search using CCDC ConQuest of the Cambridge Structural Database  and 5(b), respectively. Fig. 6a)] and delineated into C⋯H/H⋯C [Fig. 6c)], and H⋯O/O⋯H [Fig. 6h)] interactions. For completeness, the H⋯H interactions constitute 32.2% of the surface [Fig. 6b)]. The other interactions contribute small amounts, viz., C⋯N/N⋯C (1.0%), C⋯O/O⋯C (2.4%), C⋯C (9.5%), H⋯N/N⋯H (4.1%), N⋯O/O⋯N (1.1%), N⋯N (0.0%) and O⋯O (0.4%).The Hirshfeld surface analysis was performed with 6.d]dioxole-5-carbaldehyde dissolved in 50 ml of ethanol was added to the mixture. After 5 h of stirring at 273 K, the product was allowed to precipitate and then filtered with a yield of 90%. Single crystals were recrystallized from ethanol solution.A solution of 5.0 g of sodium hydroxide dissolved in 20 ml of water was mixed with 8.0 g of hydroxylamine hydrochloride dissolved in 15 ml of water, then 8.0 g of benzo[7.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989023004139/hb8064sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023004139/hb8064Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023004139/hb8064Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023004139/hb8064Isup4.cmlSupporting information file. DOI: 2262070CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


E)-1-[(carbamothioylamino)imino]ethyl}-4-methyl-1,3-thiazol-3-ium cations are linked by O—H⋯Cl, N—H⋯Cl, N—H⋯O, N—H⋯S and C—H⋯S hydrogen bonds, forming a tri-periodic network.In the crystal, the 2-amino-5-{-1-[(carbamothioylamino)imino]ethyl}-4-methyl-1,3-thiazol-3-ium cation, one chloride anion and one water molecule of crystallization. The cation is nearly flat (r.m.s. deviation of non-H atoms is 0.0814 Å), with the largest deviation of 0.1484 (14) Å observed for one of the methyl C atoms. In the crystal, the cations are linked by O—H⋯Cl, N—H⋯Cl, N—H⋯O, N—H⋯S and C—H⋯S hydrogen bonds, forming a tri-periodic network. The most important contributions to the crystal packing are from H⋯H (35.4%), S⋯H/H⋯S (24.4%), N⋯H/H⋯N (8.7%), Cl⋯H/H⋯Cl (8.2%) and C⋯H/H⋯C (7.7%) interactions.In the hydrated title salt, C In the 1,3-thiazol-3-ium ring, as expected, the C1—N2 distance of 1.3309 (16) Å indicates double-bond character, while the C2—N2 distance of 1.3885 (14) Å has more single-bond character.The asymmetric unit of (I)N′-[(1Z)-ethylidene]ethanethiohydrazide group, the S2—C7—N4—N3, N5—C7—N4—N3, C7—N4—N3—C5 and N4—N3—C5—C6 torsion angles are 178.17 (8), −0.63 (16), 174.48 (10) and 0.16 (18)°, respectively. The title compound shows bond lengths and angles that are typical and are in agreement with those reported for the related compounds discussed in the Database survey section.In the amino-The cation is nearly flat (r.m.s. deviation of the 14 non-H atoms is 0.0814 Å), with the largest deviations observed for C6 [0.1484 (14) Å], N1 [0.1357 (10) Å], and S2 [0.1399 (6) Å].3.In the crystal of (I)Crystal Explorer 17.5 , ds Fig. 6.The two-dimensional fingerprint plots of the most abundant contacts are presented in Fig. 74.et al., 2016et al., 2012et al., 2003et al., 1996et al., 2011A search of the Cambridge Crystallographic Database , the molecular packing is determined by interionic N—H⋯Cl contacts. In the crystal of (V), the molecules of substituted urea are connected by O—H⋯O hydrogen bonds into sheets. In turn, these sheets are connected to each other via N—H⋯O hydrogen bonds with hydrogen phosphate anions, forming a tri-periodic network.In the crystal of (II), molecules are linked by O—H⋯Cl and N—H⋯Cl hydrogen bonds, forming zigzag chains along [001]. There is also a C—H⋯Cl interaction present. The crystal structure of (III) comprises a substituted thiazolium ring that is connected to a nitrate ion 5.et al., 2016v:v) solution at room temperatureThe title compound was synthesized using a reported procedure (Gomha 6.Uiso(H) = 1.5Ueq(C). The H atoms attached to the N atom and the H atoms of the water molecule were found in a difference-Fourier map. Their positional parameters were refined freely while setting Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023007090/wm5691sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023007090/wm5691Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007090/wm5691Isup3.cmlSupporting information file. DOI: 2288159CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Single-crystal X-ray crystallographic analysis of 1 confirmed the presence of the first known (arene)cuprate. Also, unlike all previously known homoleptic (anthracene)metallates of d-block elements, which contain metals coordinated only to terminal rings, the organocuprate unit in 1 contains copper bound to the 9,10-carbons of the central ring of anthracene. No other d- or f-block metal is known to afford an anthracene or other aromatic hydrocarbon complex having the architecture of organodicuprate 1.Reactions of (tricyclohexylphosphane)copper(I) chloride with two equivalents of potassium anthracene (KAn) in tetrahydrofuran (THF) at 200 K provides air-sensitive but thermally stable (at 293 K) solutions from which yellow crystalline blocks of bis[bis(tetrahydrofuran-κ Although the cuprate was originally speculated to be a copper analog of the monoatomic gold anion, Au1−, established to be present in cesium auride, CsAu , which have been proposed to exist in solid neon at 4–10 K metallates , in THF. Also, because stoichiometrically analogous naphthalene and anthracene complexes of a given d-block element may possess very similar molecular structures, particularly in the solid state ]n  ]2 (Cy = cyclohexyl)  adducts of copper(I) halides due to the ease with which coordinated or free PPh3 and mixed tertiary aryl–alkyl phosphanes undergo reductive cleavage of P—C(aryl) bonds, unlike trialkylphosphanes ]2 with four equivalents of MAn  in THF appear by NMR spectra to afford similar products in solution, owing to the facile isolation and crystallization of the potassium salt, only the latter will be described now. Thus, the addition of a colorless solution of [CuCl(PCy3)]2 in THF to a dark-blue solution of KAn (molar ratio: 2 KAn/Cu) in THF at 200 K, led to the formation of an air-sensitive but thermally stable (at 293 K) yellow–brown solution, from which yellow crystalline blocks of [K(THF)2]2[{Cu}2], 1, were isolated  halides, 2− , with X = Cl  Å] is long  to 3.98 (1) Å.To the best of our knowledge, only the long-known dimeric organoalanate complexes  is well within the range of 1.83–2.05 Å observed previously for homoleptic diorganocuprates  Å. Prior studies suggest that d10Cu–d10Cu interactions are very weak to non-existent when the Cu⋯Cu separation is greater than ∼2.50 Å in molecular entities containing CuI complexes dicuprate(2−) complex, relative to unknown monomeric monoanions, i.e. [{Cu(THF)x}]1− (x = 0–2), which would likely be strained metallacycles, vide infra. In the case of the structurally related organoaluminium complexes 2 and 3, it was proposed that the dimeric, rather than plausible monomeric structures, ‘are favored by smaller deviations from tetrahedral angles about the aluminum atoms in the dianions rather than about the aluminum atom in the hypothetical monoanions.’ However, surprisingly, the possible importance of contact ion-pairing in contributing to the stabilization of the dimers in the solid state, and possibly also in solution, was not considered ]1− (Np = naphthalene), based only on a proton NMR spectrum in THF and identification of 1,4-dihydronaphthalene as a key hydrolysis product anthracene)], 4, strongly suggests that the natures of 2 and 3 in solution merit reinvestigation. It should also be emphasized that presently we cannot rule out the possibility that monomeric forms of 1 could be present in THF or other solvents  distance of 2.057 (4) Å, which is significantly longer than the normal Al—C(Et) distance of 1.966 (4) Å present in 4 ], 5, possessing a C9—Mg—C10 angle of 71.4°. This angle is significantly sharper than the corresponding angle in 4, likely owing in part to the higher coordination number of Mg in 5. The latter also contains a rather long Mg—C distance of 2.30 (2) Å  Å metal complex to be recognized as a strained metallacycle ], 6, or 2,3:5,6-dibenzo-7-dimethylgermanorbornadiene. X-ray structure characterization of 6, Me2GeAn, revealed a sharp C9—Ge—C10 angle of 77.72 (5)°, and Ge—C distances [average 2.030 (1) Å] which are significantly longer than the Ge—C(Me) distance [average 1.943 (4) Å]  Å; Hencher & Mustoe, 19756 suffers thermal loss of anthracene at 373 K in toluene to produce in good yield an intriguing dimethylgermylene, Me2Ge, adduct [{Ge2Me4}], 7, which may arise via insertion of highly reactive Me2Ge into a strained Ge—C(bridgehead) bond of 6. However, also possible is an initial dimerization of Me2Ge to the digermene, Me4Ge2, followed by its facile [4 + 2] cycloaddition to free anthracene, which was established previously to afford 7  of ca −37 kcal mol−1 of 7 Mg solvate in crystalline 1−, the monomer of structurally characterized dimeric 3 ]z (z = 0 or −1), are presently known to form dimers (or oligomers) related to 1, 2, or 3. Calculations on the structures and relative stabilities of the monomeric forms of 1, 2, and 3, compared to the respective dimers, would be of considerable interest. Inclusion of contact ion-pairing could be of key importance in such a study, but might prove to be a nontrivial extension.Of particular relevance to our discussion is that neutral 1, which contains only Cu—C σ-bonds, all prior (arene)copper compounds have been characterized as π-complexes, including the homoleptic cationic species, [Cu(arene)2]1+ [(μ-Cl)3AlCl] (PR3)]PF6 (R = phenyl or phenoxide) were described aminomethyl)anthracene}]1+ complex, in which CuI is constrained via chelation with diphenylphosphanyl groups to lie over the central ring of nearly planar anthracene  and 2.414 (6) Å] for asymmetric π-bonding of the 1-naphthyl group, the Cu—C distances in the copper–η6-anthracene complex are in the range 2.773–3.021 Å. These are much longer than usual in (arene)copper complexes, indicative, at best, of a very weak copper–anthracene interaction (PR3)]PF6, the Cu—C distances are in the range 2.253–2.300 Å ]2 (Cy = cyclohexyl) was prepared as described previously  colorless solution of [CuCl(PCy3)]2  in THF (50 ml) and stirring continued for 12 h at 200 K. The resulting yellow–brown solution was warmed over a ca 6 h period to near 290 K (room temperature) and filtered (medium or P4 porosity frit) to remove KCl. After careful evaporation of all but about 20 ml of solvent in vacuo at 273–293 K, pentane (100 ml) was added with stirring. The resulting slurry was filtered, washed vigorously with pentane (2 × 10 ml) and dried in vacuo to afford 0.59 g  of homogeneous yellow solid [K(THF)2]2[{Cu(C14H10)}2], 1. No elemental analysis was conducted on the bulk solid 1, so its composition is based exclusively on the SCXRD study and NMR spectra. X-ray-quality yellow blocks of 1 were grown from a pentane-layered saturated solution in THF at 240 K over a 6 d period.Sublimed anthracene  and shiny pieces of potassium metal  were transferred in an argon-filled glove-box to a round-bottomed Schlenk flask, along with a glass-enclosed magnetic stirrer bar. Subsequently, THF (100 ml) was added and the mixture was stirred vigorously in the dark for 6 h at 293 K to afford a deep-blue solution of potassium anthracene (KAn), which is susceptible to photo-oxidation by visible light. This solution/slurry was cooled to 200 K with stirring and to it was transferred 1H NMR : 1.77 , 3.52 , 3.63 , 6.24 , 6.35 . 13C{1H} NMR : 24.2 , 52.4 , 66.3 , 117.7 , 117.9 , 145.2 .3}], 5 : 3.51 , 5.95 , 6.01 ; 13C{1H} NMR : 57.7 , 114.1 , 118.1 , 145.9   monomeric (anthracene)metal complex, 2[{Cu}2], contains one copper center and one anthracene ligand in contact with one [K(THF)2]1+ counter-ion. A crystallographic inversion center generates full well-resolved 1 (η6-Np)]2− metal dimer complex present in [Na(THF)2]2[{(AlMe2)}2], 3,  is greater than the corresponding sum for Na and Al (2.87 Å)  Å, K1⋯Cu1A = 3.3762 (9) Å, K1⋯K1A = 6.542 (2) Å and Cu1⋯Cu1A = 2.6171 (7) Å , than the corresponding distances in 3, i.e. Na1⋯Al1 = 4.348 (6) Å, Na1⋯Al1A = 4.455 (7) Å, Na1⋯Na1A = 7.28 (1) Å and Al1⋯Al1A = 4.95 Å. As described in Section 11 arises from the essentially linear C9—Cu—C10A angle, expected for two-coordinated d10 CuI °], resulting from the distorted tetrahedral geometry of four-coordinated AlIII, causes the Al⋯Al distance to be much longer  Å] and, as a result, its molecular structure, without the THF groups, is fairly symmetrical and deviates only slightly from Dh2 symmetry  Å  and 3.57 (1) Å, respectively], which show that the two formal 9,10-coordinated anthracene dianion units are slightly further apart in 1 than they are in 3, owing also to the different coordination numbers of copper and aluminium in these remarkable compounds, both of which are worthy of additional study.However, in er Fig. 2. Of part Å Fig. 1, with on1 and 3 are similar. Thus, for 1, the bridgehead angles C11—C10—C14 [113.3 (2)°] and C12—C9—C13 [113.1 (2)°] (Table 23 , which are both close to the value of 1.51 (5) Å observed previously for C(sp2)—C(sp3) distances 2}]1−, is structurally nearly identical, without the metal, to those observed in the dianions of 1 and 3, with an average bridgehead C—C distance of 1.485 (9) Å. The lutetium anion also has an average bridgehead C—C—C angle of 111.8 (5) Å, which is very close to the corresponding angles of 1 and 3. A key structural difference in the lutetium anion is the sharp C9—Lu—C10 angle of 67.1 (2)°, owing to the metallacyclopropane character of the complex and, likely also the large bulk of the bis(cyclopentadienyl)lutetium moiety, which may well be responsible for its stability towards dimerization or oligomerization in solution (THF) and in the solid state as a crystalline [Na(diglyme)2]1+ salt (diglyme = diethylene glycol dimethyl ether) at ca 293 K  having the shortest distances [average 3.14 (13) Å], whereas the K⋯C distances for the six C atoms closest to the long K⋯Cu contact  are longer [average 3.38 (5) Å]  to 3.24 (1) Å, but the Na—C distances of the four more crowded ring-junction C atoms are mostly longer  and C—C—C angles [average 119.9 (2)°] that are quite similar to those found in uncharged free benzene dicuprate(2−) with relatively weakly interacting cations, such as [K([2.2.2.]cryptand)]1+, tetraalkylammonium(1+), etc., would be of considerable interest. As our laboratory will be irreversibly shuttered in 2023, others are encouraged to examine these possibilities and related issues, vide infra.Interactions of the alkali metal cations with the 4-naphthalene)zirconate(2−), the first confirmed homoleptic (polyarene)metallate of a d-block metal 6]2−, our research group has been interested in discovering what other d-block elements, throughout the periodic table, would afford related and hopefully labile complexes. Thus began our exploration in a systematic fashion of the synthesis and reactivity patterns of transition-metal compounds containing metals in formal negative oxidation states 3, and particularly organic isocyanides, to determine whether the anthracenes would be displaced to produce new formal Cu complexes. Noteworthy is that although isolable Cu1− complexes remain unknown, very recently, the first unambiguous Cu0 complex was isolated, thoroughly characterized, and structurally authenticated  I, global. DOI: 10.1107/S2053229623008367/eq3012Isup2.hklStructure factors: contains datablock(s) I. DOI: 2296812CCDC reference:


N-butylamine (DBM). The aromatic compounds chosen were 2-aminopyridine (A2MP), 2-amino-4-methylpyridine (A24MP), 2-amino-6-methylpyridine (A26MP) and 4-dimethylaminopyridine (DMAP). The salts were characterised using single-crystal X-ray diffraction, thermal analysis, FTIR spectroscopy and Hirshfeld surface analysis. For all the crystal structures, N-H···O and C-H···Cl contacts were present. O-H···O contacts were found in all the crystal structures except for (3-chloro-4-hydroxyphenylacetic acid (CHPAA) is a fungal metabolite. It is a small molecule that is useful in crystal engineering studies due to the functional groups present. Six amines were selected to form salts with CHPAA. Linear derivatives included diethylamine (DEA) and di- N-butylamine (DBM), 2-aminopyridine (A2MP), 2-amino-4-methylpyridine (A24MP), 2-amino-6-methylpyridine (A26MP) and 4,4-dimethylaminopyridine (DMAP). These are depicted in Ka [Ka values of the amines are DEA (10.58), DBM (10.75), A2MP (6.84), A24MP (7.62), A26MP (7.60) DMAP (8.78). Thus, the ∆pKa values ranged from 3.78 to 7.69. Salt formation is expected when ∆pKa > 4. If <−1 ∆pKa < 4, then either salt or co-crystal can form [Multicomponent crystals are important in the pharmaceutical industry as the formation of new solid forms can improve the physicochemical properties of active pharmaceutical ingredients ,2. The ced in Ka  of CHPAAcan form . In thisPĪ, Z = 2 (d(C11···O2) of 3.4706(18) Å as well as contacts to the chlorine atom; C-H···Cl (d(C11···Cl1) = 3.821(2) Å) and N-H···Cl (d(N1···Cl1) = 3.4818(16) Å). The hydrogen bond metrics are summarised in 2− anions point directly towards each other, forming a type I halogen bond with d(Cl···Cl) = 3.517(2) Å and an angle of 174°  . Two mod(1.76 Å) ,24 and W(1.76 Å) . Subsequ(1.76 Å) ,27,28. Tivatives . The DEAchannels c within C2/c with Z = 8 .th Z = 8 a. Both Nchannels b. The voPĪ, Z = 2 (− anions (3.639(1) Å) and between 2+AMP cations (3.835(1) Å).Ī, Z = 2 a. There am below b, the ca1/cP2 and its asymmetric unit contains one anti-oriented (H13A) on the primary amine forms an additional hydrogen bond, allowing the structure to generate an extended network system described as chains oftructure a, the acd anions b are arrPĪ and its asymmetric unit contains two a-axis. The π-π stacking interactions between synthons a consist diagram b shows cPbca and its asymmetric unit contains one 2 group in DMAP. There are π–π stacking interactions between adjacent b-axis.The salt of 4-dimethylaminopyridinium-3-chloro-4-hydroxyphenylacetate, ractions a. The st−)(DBM+) displayed C-H···O interactions. The O-H···O and N-H···O hydrogen bonds gave contact distances with average values for d(H···O) = 1.79 Å, d(H···N) = 1.89 Å, d(O···O) = 2.62 Å and d(N···O) = 2.78 Å. These were followed by the C-H···O and C-H···Cl contacts which gave average values of d(H···O) = 2.55 Å, d(H··· Cl) = 3.01 Å, d(C···O) = 3.44 Å and d(C···Cl) = 3.72 Å.In summary,  and Cl···H (15.8–18.8%) contacts. There are prominent wings on the fingerprint plots for− anions in these structures. Only . Thus, salt formation with the aromatic amines resulted in increased thermal stability with the highest melting point observed for Differential scanning calorimetry (DSC) results are presented for all the salts, and thermogravimetric analysis (TGA) was completed for , A24MP (3429 cm−1) and A26MP (3461 cm−1) either disappeared or diminished in the IR spectra of the resulting salts. This can be attributed to the −NH2 group’s involvement in hydrogen bonding in the A2MP, A24MP and A26MP salts. The FTIR spectra are given in FTIR spectroscopy is often used in screening new solid forms to distinguish between co-crystal and salt formation ,33. It iPXRD analyses of all compounds obtained from the grinding and slurry experiments were performed to determine whether the salts obtained by the slow evaporation technique can also be prepared using other techniques. The calculated PXRD patterns obtained from LAZYPULVERIX  were comAll chemicals were purchased from Sigma Aldrich  and were used as received. K. Diffraction data for all compounds were collected on a Bruker APEX II diffractometer . SADABS  was usedA D2 PHASER Bruker diffractometer with Cu-Kα radiation (1.54184 Å) was used for PXRD. The voltage tube and current were at 30 kV and 10 mA max, respectively, with a scintillation counter 1-dim LYNXEYE detector. The scanning process of each sample was between 4–50° 2θ.−1.Spectra were obtained from the universal attenuated total reflectance (UTAR) infrared spectrometer Perkin Elmer spectrum two. Sample spectra were measured over the range of 4000–400 cm−1. These analyses were conducted from 303–573 K with a heating rate of 10 K min−1.DSC analyses were performed on a Perkin-Elmer 6 system with a purge of nitrogen at 20 mL minSamples of 2–5 mg were removed from the mother liquor, dried with filter paper, then crushed to a fine powder and placed in a vented pan for the DSC analysis.−)(DBM+). The Cl···Cl halogen bond was only found in (Salts of CHPAA with selected linear and aromatic amines were successfully prepared. The formation of the new solid forms was validated using DSC analysis, and in the case of the aromatic amines, the resulting salts demonstrated enhanced thermal stability compared to the starting materials. FTIR spectroscopy confirmed salt formation. The salt structures of CHPAA, except for (


The dihedral angles between the indole ring system and pendant nitrobenzodioxolane rings system and phenylsulfonyl ring are 4.81 (14) and 72.24 (19)°, respectively. In the crystal, the indole molecules are linked to each other and to the chloroform molecule by weak C—H⋯O, C—H⋯Cl, C—H⋯π, C—Br⋯π and C—Cl⋯π and aromatic π–π stacking interactions.The title indole derivative crystallizes with a partial occupancy [0.585 (4)] CHCl 24H17Br3N2O6S, crystallizes with a partial occupancy [0.585 (4)] CHCl3 solvent molecule. The dihedral angles between the indole ring system and pendant nitrobenzodioxolane rings system and phenylsulfonyl ring are 4.81 (14) and 72.24 (19)°, respectively. In the crystal, the indole molecules are linked to each other and to the chloroform molecule by weak C—H⋯O, C—H⋯Cl, C—H⋯π, C—Br⋯π and C—Cl⋯π and aromatic π–π stacking interactions. A Hirshfeld surface analysis was carried out and the intermolecular contacts with the most significant contributions are H⋯O/O⋯H (24.3%), H⋯H (18.4%), Br⋯H/H⋯Br (16.8%) and C⋯H/H⋯C (8.4%).The title indole derivative, C The C1—N1 and C4—N1 bond lengths are 1.423 (5) and 1.427 (5) Å, respectively, while in the case of N atoms in planar configurations, the reported mean value is 1.355 (14) Å vinyl moiety occurs due to an addition reaction with Br2. The Br1—C16—C15—Br2 grouping is in a trans configuration and the torsion angle has a value of 178.14 (17)°. Intramolecular C5—H5⋯O1, C15—H15⋯O2, C16—H16⋯O6 and C24—H24B⋯Br2 interactions ° with the C1–C8/N1 indole ring system Fig. 1. The C1—ns Fig. 1 are obse3.Cg2i cyclohex-3-en-1-yl}vinyl)-3-methyl-1-(phenylsulfonyl)-1H-indole tetrahydrate , H⋯H (18.4%), Br⋯H/H⋯Br (16.8%) and C⋯H/H⋯C (8.4%).The Hirshfeld surface analysis and the associated two-dimensional fingerprint plots were determined using the 6.E)-3-methyl-2-[2-vinyl]-1-(phenylsulfonyl)-1H-indole  and N-bromosuccinimide  in dry CCl4 (100 ml) containing a catalytic amount of azobisisobutyronitrile  was refluxed for 2 h. The reaction mixture was cooled to room temperature. Then, the suspended succinimide was filtered off and the filtrate was concentrated in vacuo to obtain the crude product, which upon trituration with methanol (10 ml) gave the title compound as a bright-yellow solid. Yield: 800 mg (88%) m.p. 431–433 K. The synthesized compound was crystallized by slow evaporation using chloroform as solvent.A solution of  I. DOI: 10.1107/S2056989023007120/hb8071Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023007120/hb8071Isup3.cmlSupporting information file. DOI: 2279852CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Correction: BMC Cancer 23, 540 (2023)https://doi.org/10.1186/s12885-023-10997-xFollowing publication of the original article , the autThe incorrect author name is: Ádány RózaThe correct author name is: Róza ÁdányThe author group has been updated above and the original article  has been


Intermolecular C—H⋯O and C—H⋯N hydrogen bonds connect individual molecules into layers extending parallel to (100). These layers are connected by C—H⋯π interactions. 32H29N5O2·C3H7NO, the bicyclo[3.3.1]nonane ring system adopts a half-chair/twist-boat conformation, with the phenyl rings in equatorial orientations with respect to the piperidine ring. The two oxane rings of the 2-oxabicyclo[2.2.2]octane ring system exhibit a distorted boat conformation. Intermolecular C—H⋯O and C—H⋯N hydrogen bonds connect the molecules in the crystal, generating layers extending parallel to (100). These layers are connected by C—H⋯π interactions. A Hirshfeld surface analysis was performed to quantify the contributions of the different intermolecular interactions, indicating that the most important contributions to the crystal packing are from H⋯H (52.5%), N⋯H/H⋯N (19.2%), C⋯H/H⋯C (18.8%) and O⋯H/H⋯O (8.3%) interactions.In the title compound, C The phenyl rings  are in equatorial orientations with respect to the piperidine ring (C1/C2/N3/C4/C5/C9). The two oxane rings (O9/C9/C1/C8/C7/C10 and O9/C9/C5/C6/C7/C10) of the 2-oxabicyclo[2.2.2]octane ring system (C10/O9/C9/C1/C8/C7/C6/C5) exhibit a distorted boat conformation with puckering parameters QT = 0.799 (2) Å, θ = 91.88 (14)°, φ = 247.89 (15)° for the O9/C9/C1/C8C7/C10 ring, and QT = 0.826 (2) Å, θ = 96.04 (14)°, φ = 50.59 (15)° for the O9/C9/C5/C6/C7/C10 ring.The molecular structure of the title compound is displayed in Fig. 2le Fig. 2. As showle Fig. 2 are QT 3.In the crystal, intermolecular C—H⋯O and C—H⋯N hydrogen bonds Table 1 link indCrystalExplorer17  to 1.4361 (blue) a.u. is shown in Fig. 6dnorm surface represent the aforementioned C—H⋯O and C—H⋯N interactions  points from all the contacts contributing to the Hirshfeld surface analysis in normal mode for all atoms. The most important intermolecular interactions are H⋯H contacts, contributing 52.5% to the overall crystal packing. Other interactions and their respective contributions are N⋯H/H⋯N (19.2%), C⋯H/H⋯C (18.8%), O⋯H/H⋯O (8.3%), N⋯N (0.6%), C⋯N/N⋯C (0.3%), C⋯C (0.2%) and C⋯O/O⋯C (0.1%), respectively.Fig. 7et al., 2015The Hirshfeld surface study verifies the significance of H-atom interactions in the packing formation. The contributions of H⋯H and N⋯H/H⋯N interactions imply that van der Waals interactions are important in the crystal packing   -3-azabicyclo[3.3.1]nonan-9-ol (III)    and (III) crystallize in monoclinic space groups , whereas (II) is orthorhombic . In each of the three structures, the bicyclic ring system adopts a chair/chair conformation and the phenyl rings are in equatorial orientations with respect to the piperidine ring. In (II), apart from van der Waals forces, only weak intermolecular C—H⋯O-type interactions are involved in the packing.Compounds (IV) has monoclinic symmetry  and has two molecules in the asymmetric unit. A et al., 1995via N—H⋯O hydrogen bonds.The structure of (V), which likewise is monoclinic , the bicyclic ring system adopts a twin-chair conformation. The two methyl groups attached to the bicycle are in an equatorial orientation for both rings. In the crystal, very long N—H⋯O hydrogen bonds connect the molecules into a chain perpendicular to [010].In  solution.The title compound was synthesized using a previously reported procedure (Mamedov 6.Uiso(H) = 1.2 or 1.5Ueq(C). The N-bound H atoms were located from difference-Fourier maps and refined with free atomic coordinates and Uiso = 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023001718/wm5672sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023001718/wm5672Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989023001718/wm5672Isup3.cmlSupporting information file. DOI: 2244417CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


S is established as a function of several basic geometric parameters to well characterize the noncovalent interaction energy, which exhibits a good inverse correlation with the reorganization energies of the photo-excited states or electron-pumped charged states in organic/polymeric semiconductors. In particular, the experimental 1H, 77Se, and 125Te NMR, the optical absorption and emission spectra, and single crystal structures of eight compounds fully confirm the theoretical predictions. This work provides a simple descriptor to characterize the strength of noncovalent intramolecular interactions, which is significant for molecular design and property prediction.In recent years, intramolecular noncovalent interaction has become an important means to modulate the optoelectronic performances of organic/polymeric semiconductors. However, it lacks a deep understanding and a direct quantitative relationship among the molecular geometric structure, strength of noncovalent interaction, and optoelectronic properties in organic/polymeric semiconductors. Herein, upon systematical theoretical calculations on 56 molecules with and without noncovalent interactions , we reveal the essence of the interactions and the dependence of its strength on the molecular geometry. Importantly, a descriptor  Intramolecular noncovalent interactions can block molecules in a given conformation enhancing performance of organic semiconductors. Here, the authors report a molecular descriptor to weigh them that strongly correlates with the reorganization energy of excited or charged states. Many experimental and theoretical works focus on intermolecular noncovalent interactions since they are directly responsible for the formation of molecular crystals, large clusters, folding of proteins, and binding of DNA and drugs14. However, intramolecular noncovalent interactions are less investigated, although they are also important to determine the structure of basic units for building larger aggregates17. It is noteworthy that the intramolecular interactions significantly influence the conformation of the organic/polymeric semiconductors, which is critical to determine their physicochemical properties, such as optical properties and charge transport mobilities20. Many groups have adopted the noncovalent intramolecular interactions as an important strategy for designing high-performance organic/polymeric semiconductors for different applications, including organic solar cells (OSCs)28, thin film transistors (OTFTs)32, photodetectors (OPDs)33 and light-emitting diodes (OLEDs)37, since Huang, Marks, Facchetti, and coworkers termed this intramolecular noncovalent interaction as “Noncovalent Conformational Locks (NoCLs)” owing to their conformation-locking feature in enhancing the planarity and rigidity of organic semiconductors38. For example, the noncovalent fused ring electron acceptors (NFREAs) have been developed using the NoCLs strategy, which greatly improved the power conversion efficiencies (PCEs) to reach over 15%, similar to those of the fused ring electron acceptors (FREAs), while significantly decreased the synthetic complexity28. Moreover, various NoCLs  have been used to enhance the charge transport mobilities of organic/polymeric semiconductors for OTFTs29, affording the record mobility as high as 14.9 cm2 V−1 s−1 31. Also, the OLED based on the thermally activated delayed fluorescence (TADF) obtained by the NoCLs strategy showed a high external quantum efficiency of 23.2%39. Although these investigations presented the efficacy of NoCLs in designing high-performance organic/polymeric semiconductors, they lack direct correlation between chemical structures, the strengths of NoCLs, and the optoelectronic properties of organic/polymeric semiconductors. Furthermore, the nature of intramolecular NoCLs in organic/polymeric semiconductors, whether they arise from orbital overlap or electrostatic interactions, remains controversial47.Noncovalent interactions play important roles in chemistry, biology, catalysis, and material sciences49, which dramatically increased the difficulty of experimental characterization. Moreover, due to various chemical elements or groups, there is a wide variety of noncovalent intramolecular interaction, such as cation-π, anion-π, chalcogen-π, carbonyl-π, hydrogen bonding, halogen bonding, and chalcogen-bonding in organic molecules53. Thus, the theoretical study of these interactions became very complicated and challenging.Although many efforts have been made, it is very challenging to deeply investigate the fundamentals of NoCLs. First, noncovalent interactions are very weak forces, usually one to two orders of magnitude smaller than covalent interactions1H, 77Se, and 125Te NMR, the optical absorption and emission spectra, and the single crystal structures of eight synthesized compounds fully confirmed the theoretical predictions.In this work, 56 molecules Fig.  with varM(S···O) and PhM/PhM-H(S···O) were selected as representatives to investigate the feature of X···Y NoCLs. The relaxed potential energy (E) surface (PES) scans were performed along the dihedral angle θ  analysis54 was performed to obtain the variation of energy (E(2)), and took atomic dipole moment-corrected Hirshfeld (ADCH) charge55 , and Eelec, as well as the distances between the atoms. From Fig. M(S···O) appeared at θ = 0.01o, whose E was set to zero on the PES. At equilibrium geometry, the S···O distance d(S···O) of 2.85 Å is much shorter than the sum of van der Waals radii (dv) of S and O atoms dv(S···O) of 3.32 Å; the Eelec is a small negative value due to few charges on S (qS) and O (qO) atoms  is a large negative value owing to large overlap between the n-orbital (lone pair electron of the oxygen atom) and the σ*-orbital of the S-C bond (n(O) → σ*(S-C))  are formed by the orbital interactions. Differently, the two minima on the PES of type II are very close in energy with a large energy barrier  with 0o ≤ θ ≤ 90o, and the H···O interaction is detected in PhM-H(S···O) with 90o < θ ≤ 180o. As shown in Fig. PhM(S···O) (θ = 18.92o and d(S···O) = 2.76 Å), and both the orbital interactions and the electrostatic interactions are weak at the minimal of PhM-H(S···O) (θ = 157.34o and d(H···O) = 2.31 Å). The orbital interaction in PhM(S···O) comes from n(O)→σ*(S-C) and that in PhM-H(S···O) stems from n(O)→σ*(H-C).The molecules 5 Figure  to calcuenergy (E), and toenergy (E), and tos Figure ; and the) Figure . These iier Fig. . Hence, 56 for the studied systems. For type II systems, the energy differences between two minima (PhM-H(O···Y) is more stable than PhM(O···Y), while PhM(X···O) (X = S and Se) and PhM(Te···Y)  are more stable than their corresponding PhM-H. The differences in energies between two conformations are small for the others. The potential energy surfaces of the systems were further scanned at the same level and plotted in Figure PhM(X···C) and PhM-H(X···C) , owing to a low energy barrier  of mutual transformation between them, and the others have only one conformation due to large energy barrier.The nature of NoCLs was examined at the equilibrium geometry of the studied systems. The equilibrium geometries were optimized and the frequencies were calculated at the B3LYP(D3)/6-31 + G(d) levelsee Fig. . It is oM(X···Y) ones, 9 PhM(X···Y) ones, and 11 PhM-H(X···Y) ones). It is generally believed that the NoCLs are effectively formed between two atoms if the distance between them is less than dv. According to the Δd = dv-d results given in Fig. d (>0.10 Å), being conducive to the formation of NoCL. The nature of NoCLs is either electronic interaction or orbital interaction45. From Fig. −1, which is impossible to be responsible for the NoCLs. The orbital interaction varies greatly with E(2) ranging from −5.27 to 0.00 kcal mol−1  for the systems with and without NoCLs, which is likely to be the main contributor to form NoCLs. Of 36 compounds, 15 with E(2)<−1.00 kcal mol−1 are considered to have significant NoCLs, and the strength of NoCL exhibits the order of S···F < Se···F < Te···F, S···O < Se···O < Te···O, and X···F < X···O . The orbital interaction is determined by the type, shape, and orientation of orbitals and bonds. As shown in Fig. 2), n(p)→σ*(sp2), and n(sp)→σ*(sp2) for M and PhM molecules, and n(s)→σ*(s), n(p)→σ*(s) and n(sp2)→σ*(s) for PhM-H molecules. The n(sp2)→σ*(sp2) shows the strongest interaction when p-orbital component dominates in the hybrid sp2-orbital, because the shape and orientation of the sp2-orbital are favorable for overlap, such as Te···O NoCL. While the participation of s-orbital weakens the interaction due to its very small electronic density distribution area, like H···Y NoCL. Hence, the H···Y NoCLs in PhM-H molecules are always weaker than X···Y NoCLs in M and PhM molecules. Overall, 15 of 36 molecules were predicted to have significant NoCLs, namely, X···Y  and Te···S in M and PhM, and H···S and H···Cl in PhM-H  and the length of NoCL d(S···O), the angle between S···O NoCL and S-C bond (α), and the dihedral angle between two thiophene rings (θ) which is closely related to molecular structural planarity and disorder57. It is found the E(2) as an exponential function of the distance, and the cosine function of the angle α or θ. Based on this, we proposed a simple descriptor that contains several geometrical parameters  versus S, which are calculated based on the optimized equilibrium geometries for 36 isolated systems in Fig. R2 is as high as 0.927, which indicates a very strong positive correlation between E(2) and S. Moreover, the S value varies in the order of S···O < Se···O < Te···O and S···F < Se···F < Te···F, which is in good agreement with the order of strength of NoCLs obtained above by E(2). This is mainly because from S to Te the atomic radius gradually increases while the distances of X···Y and other factors are almost unchanged, which results in the increase of Δd, corresponding to the strengthening of NoCLs in this order. In addition, as it is described above that the orbital interactions of hydrogen bond in PhM-H compounds happen between s-orbital of H atom and p- or sp2-orbital of Y atoms, and it is almost independent of the orientation of C-H bond because s-orbital is spherical. And if removing cosα from the S for PhM-H systems, the results would become better  and S were further calculated for 11 compounds of 36 with strong NoCLs at B3LYP(D3)/def2-TZVP, ωB97XD/def2-TZVP and CCSD(T)/def2-TZVP levels  and S becomes stronger at large basis set and higher theory levels. Based on the optimized geometries by B3LYP(D3)/def2-TZVP, the linear fitting coefficient is improved from R2 = 0.974 at B3LYP(D3)/def2-TZVP level to R2 = 0.991 at CCSD(T)/def2-TZVP level. Based on the optimized geometries by ωB97XD/def2-TZVP  and S with R2 = 0.992  and S of 56 compounds is still strong with R2 = 0.907  less than ca. −1.00 kcal mol−1).Considering the effect of the basis set and method on the results, the els Fig. c, d. TheP Figure , the CCS992 Fig. . In addi7 Figure . Therefoa) absorbs a phonon to form an excited state (b), the excited molecule firstly experiences a relaxation of geometrical structure to a new equilibrium point (c) by releasing reorganization energy (λES) and then decays to the ground state (d) by radiative and nonradiative processes, finally relax to the initial ground-state equilibrium point (a) by giving out reorganization energy (λGS). The reorganization energy decides the shape and width of the optical spectra. Under the framework of the linear coupling model, the sum of the two reorganization energies can be crudely considered as the Stokes shift between the absorption and emission spectra, κ = λGS + λES59. Moreover, there is a positive relationship between the nonradiative decay rate and the excited reorganization energy, in which the excitation energy is always much larger than the reorganization energy61. Consequently, small reorganization energy can effectively block the nonradiative decay process. For electron-pumped charge transfer processes, the charge transfer rates between molecule dimers can be calculated by Marcus rate equation in the high temperature and short time limits, +→M+ + M), ΔG can be approximately zero, and there is an inverse relationship between the rate constant of charge transfer and the charge reorganization energy λcharge. As a result, the molecules with small reorganization energy usually are designed to exhibit excellent charge transport property62. The λcharge can be calculated by the sum of λNS and λCS between the neutral (ground) state (NS) and the charged states (CS) in organic molecules, as shown in Fig. As it is well known that reorganization energy or relaxation energy is an important physical parameter to character the optoelectronic properties. Reorganization energy is defined as the energy dissipated from the equilibrium geometry in the initial state to the relaxed equilibrium geometry in the final state for an isolated molecule  and PhM(X···C) with X = O, S, Se, and Te were calculated as shown in Fig. S behaves good negative relationship with λopt (Stokes shift κ). The Stokes shifts of the systems with strong NoCLs are far smaller than those of the corresponding systems without NoCLs. Moreover, the larger S is, the larger the difference of Stokes shift is. For example, the Stokes shift from PhM(Se ∙ ∙∙C)  to PhM(Se ∙ ∙∙O)  is decreased by 75 nm, while that from PhM(Te ∙ ∙∙C)  to PhM(Te ∙ ∙∙O)  decreased by 118 nm. The linear correlation between Δλopt and S is very good with R2 = 0.801 for 6 pairs of compounds of type II molecules with apparent noncovalent interactions  of X = O, S, Se, and Te, and Y = O and C were synthesized ,PhM(S···O) PhM(Se···O), and PhM(Te···O). In these compounds, the d values are 2.38(9) Å for H···O, 2.68(2) Å for S···O, 2.69(1) Å for Se···O, and 2.76(0) Å for Te···O, respectively, which are much shorter than the corresponding dv, confirming the existence of strong NoCLs. Differently, both PhM/PhM-H (S···C) and PhM/PhM-H (Se···C) possess two conformations, which fully prove the theoretical predictions above. Moreover, the torsion angles between chalcogenide and phenyl rings in PhM(S···O)  and PhM(Se···O)  are much smaller than those in PhM(S···C)  and PhM(Se···C) , illustrating the “lock of planarity” function of NoCLs.To confirm the theoretical prediction, eight compounds d Figure –S18, andd Figure . The con1H-1H NOESY NMR of eight compounds was measured in d2-tetrachloroethane solution, which is always used to certify conformational preferences through spatial interactions between different 1H signals  is more stable than PhM(O···O) in d2-tetrachloroethane and the O···H NoCL is stronger than O···O one. Similarly, the cross-peak between H1 and H2 in Fig. PhM(Te···O) conformation with strong Te···O NoCLs. Both the cross-peaks between H5 and H2, and between H1 and H2 are observed in Fig. PhM(O···C) and PhM-H(O···C), and PhM(Te···C) and PhM-H(Te···C) coexist owing to freely rotatable aromatic rings without NoCLs, suggesting no effective NoCLs in these compounds. These NMR observations are consistent with the experimental results that no single conformation was observed for PhM-H(S···C) and PhM-H(Se···C) in their respective crystals as shown in Figure PhM(S···O) seems to be inconsistent with its crystal structure since it exhibits no cross-peaks neither between H6 and H2, nor between H1 and H2  calculated in Table θ of isolated PhM(S···O) is calculated to be 17.29o, which is larger than that of 4.68o/5.59o in crystal, implying a more twisted conformation in solution. Since the strengths of NoCLs decrease sharply from θ = 0o to 20o  may become very weak in solution, causing the alienation of H1 and H2. Thus, these experimental observations reinforce the reliability of theoretical predictions. In addition, The 77Se and 125Te NMR of PhM(Se···O), PhM(Se···C), PhM(Te···O), and PhM(Te···C) are further measured and the results were shown in Figure 77Se NMR of PhM(Se···O) displays one single peak of symmetric Se nucleus located at 645.70 ppm, with a downfield shift of 9.15 ppm compared to the signal of PhM(Se···C) at 636.55 ppm. Since the inductive effect of the O atom generally decays along chemical bonds and disappears after three δ bonds, this phenomenon can only be triggered by Se···O interaction. Note that this trend is in accordance with that in literature reported by Tomita64. Similarly, the downfield shift phenomenon is observed in PhM(Te···O) (851.62 ppm) in comparison to that of PhM(Te···C) (841.78 ppm) in 125Te NMR, which reveals the existence of Te···O interactions. Overall, the reflected results by 1H-1H NOESY NMR tell us that the Te···O, O···H, and S···O are significant NoCLs while the O···C, Te···C, and H···C are not effective NoCLs in these compounds, which are consistent with the theoretically predicted results.The als Fig. 63. As sh2 Figure . AccordiPhM(Te···O) with strong NoCLs as an example, the 1H-1H NOESY NMR is further measured in d2-dichloromethane (d2-DCM) and d6-dimethylsulfoxide (d6-DMSO) shown in Figure 1 and H2 appears in the three solvents. The position of the cross-peak hardly shifts with the increase of the polarity of the solvent, which implies these NoCLs are not controlled by the electrostatic interactions47.In order to reveal the nature of NoCLs, the effect of solvents on NoCLs was investigated. Taking PhM(X···C) , there display immense redshifts of the absorption peaks in PhM(X···O) , which accounts for the introduction of NoCLs for higher molecular planarity65. The resultant Stokes shift sharply decreased from PhM(X···O) to PhM(X···C) , which depicts the enhancement of rigidity brought by NoCLs. Specific Δκ values are rendered to estimate the relative ability of NoCLs in altering rigidity with 61 (63) nm for S···O interaction, 75 (66) nm for Se···O interaction, and 118 (91) nm for Te···O interaction. This implies the stronger the NoCLs, the more its ability in enhancing rigidity. Moreover, the intensity order of S···O < Se···O < Te···O of the NoCLs is perfectly reflected by the Δκ values, which are in good agreement with the theoretically calculated results above. The same experiments are carried out in tolune and THF solvents with different polarity, and the Stokes shifts and their changes exhibit extremely small changes  based on the theoretical equilibrium structures in the gas (solid) phase and the experimental S (SExp) based on the experimental crystal structures for the six compounds , which demonstrates that the SExp based on the crystal structure is also very reliable. To confirm the assumption, we arbitrarily select a series of compounds from the CCDC crystal database to calculate E(2) and the SExp based on experimental crystal structures and plot them in Fig. R2 is very high with a value of 0.972, which reveals that the S can be applied widely. Thus far, it is safe to conclude that S is a suitable descriptor for evaluating the strength of NoCLs, which would be used for further machine-learning-based molecular screening studies.To extend the application of this descriptor, twelve compounds were selected to be investigated Fig. . First, nds Fig. . Excitin1H, 77Se, and 125Te NMR, and UV-vis spectra of the eight new synthesized systems fully confirmed the theoretical predictions. This work provides an in-depth understanding and simple description of noncovalent interaction, which is important for the rational molecule design of high-performance organic/polymeric semiconductors.Herein, 56 organic semiconductors with and without noncovalent interactions  were investigated to show that the interactions are mainly derived from orbital interactions based on the theoretical calculations and experimental results. The strength of interactions followed the order of S···F < Se···F < Te···F, S···O < Se···O < Te···O, and X···F < X···O . In contrast, O···Y , X···C , and Se···Y  cannot form effective noncovalent interactions in the systems. Furthermore, it is disclosed that the strength of noncovalent interactions is closely related to the structural parameters, including the molecular planarity, the angle between two relevant orbitals, and the distance between the two related atoms. Significantly, a descriptor 66 of theory using the basis set 6-31 + G(d)  and LANL2DZ for Se and Te or def2-TZVP in Guassian16 Program67, including geometrical parameters, energy, atomic dipole moment-corrected Hirshfeld population (ADCH) charge analyses68, natural bond orbital (NBO) analysis54. NBO analysis have been carried out using Multiwfn software69. The CCSD/def2-TZVP method was used to calculate the orbital interaction. As for the solid phase, the initial structure is obtained from the X-ray crystal structure, and geometrical structures in the ground state are calculated based on QM/MM model through Gaussian16 Program. The centered molecule is treated as a high layer and calculated at B3LYP(D3)/def2-TZVP level for QM, and the surrounding molecules are treated as a low layer and computed by MM with UFF forces field. The reorganization energy is calculated using the adiabatic potential energy surface method in MOMAP72.All the geometrical and electronic structures of the investigated system in the ground state were calculated at B3LYP(D3) or ωB97XD level3)4 (5% equiv) were added under nitrogen in anhydrous toluene (20.0 mL). The mixture was stirred and refluxed at 120 °C for 12 h. Afterwards, an aqueous potassium fluoride solution  was added to the mixture. After quenching the reaction, the organic phase was extracted with dichloromethane (3 × 100 mL). The combined organic portion was collected, washed with water and brine, and dried over MgSO4. After filtration, the solution was filtered through a short silica gel column (petroleum ether), concentrated to afford the crude product, which is subjected to the recrystallization in hexane. Finally, the crystals were dried in vacuo to afford PhM(X···O)/PhM(X···C). The detailed synthesis is described in Supplementary Information, and the final products were characterized by 1H-NMR, 13C-NMR, 77Se-NMR, and 125Te-NMR. (Supplementary Section 13).Preparations of 1,4-dihexyl-2,5-diiodobenzene, 1,4-dihexyloxy-2,5-diiodobenzene, 2-tributylstannyl-derivatives are illustrated thoroughly in Supplementary Information. To a round-bottom flask (100 mL), 1,4-dihexyl-2,5-diiodobenzene  (1.0 equiv), 2-tributylstannyl-derivatives (2.5 equiv) and Pd(PPhUV-Vis absorption spectra were measured on a Gary 60 UV-Vis Spectrophotometer. Photoluminescence spectra were measured on a FLS 1000 (EDINBURGH INSTRUMENTS) with an Xenon Lamp. All liquid samples were well dissolved in chloroform. All film samples were spin-coated on glass substrates.A glass vial (5 mL) containing a chloroform or toluene solution of the compounds (2 mg) was placed inside a vial (20 mL) containing methanol. After 2–7 days, white (yellow) solid single crystals were collected.Supplementary InformationPeer Review FileDescription of Additional Supplementary FilesSupplementary Data 1Supplementary Data 2Supplementary Data 3Supplementary Data 4Supplementary Data 5Supplementary Data 6Supplementary Data 7


The PdII atom displays a slightly distorted square-planar PdP2S2 geometry with a bidentately coordinated pyridin-2-ylcarbonimidodithioate ligand and two triphenylphosphine molecules, coordinated in cis positions. The crystal structure features weak π–π [centroid–centroid distance =3.7327(15) Å] and C–H⋯π interactions and contains an almost spherically shaped void of 50.4 Å3 per unit cell.The title compound, [Pd(C DOI: 10.1107/S1600536810050518/im2253Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


Adjacent Zn atoms are bridged by the bidentate carboxylate groups into a cationic chain extending along [010]. N—H⋯N, O—H⋯N and O—H⋯O hydrogen bonds link the cationic chains, nitrate anions and uncoordinated water molecules into a supramolecular network. π–π interactions between the pyridine rings and between the pyridine and benzene rings [centroid–centroid distances = 3.615 (4) and 3.636 (4) Å] are present.In the title compound, {[Zn(C DOI: 10.1107/S1600536811021088/hg5047Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The Ru0 atom adopts a distorted trigonal–bipyramidal coordination geometry, with the C O ligand and the ketone O atom occupying the axial positions. The two triphenylphosphane ligands are cis to each other. The olefinic C=C bond is almost coplanar with the Ru0 atom and the two P atoms (maximum deviation of 0.0516 Å from the mean plane defined by the five constituent atoms). The coordinated C=C bond has a length of 1.449 (3) Å, which is significantly longer than that of a free C=C bond (1.34 Å). There are two C—H⋯π interactions involving neighbouring phenyl rings in the molecule. In the crystal, molecules are linked via two further C—H⋯π interactions.The 1-vinylpyrrolidin-2-one ligand in the title compound, [Ru(C For C=C al. 1989. For str al. 1998; Jazzar  al. 2001.6H9NO)(C18H15P)2(CO)] = 0.025wR(F2) = 0.084S = 1.157113 reflections442 parametersH-atom parameters constrainedmax = 0.66 e Å−3Δρmin = −0.80 e Å−3ΔρCrystalClear  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812014766/su2399Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The ZnII ions are bridged by the ligands, forming a helical chain along [001]. C—H⋯N and C—H⋯Cl hydrogen bonds and π–π interactions between the imidazole rings [centroid–centroid distance = 3.4244 (10) Å] assemble the chains into a three-dimensional supramolecular network.In the title complex, [Zn(C DOI: 10.1107/S1600536812012706/hy2526Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


One of the CuII ions has a square-pyramidal arrangement, which is defined by a water molecule occupying the apical position, with the equatorial ligators consisting of two N atoms from a 2,2′-bipyridine molecule, one carboxylate O atom from a terephthalate ligand and one O atom from a water molecule. The other CuII ion has a similar coordination environment, except that the apical position is occupied by a chloride ligand instead of a water molecule. An O—H⋯O and O—H⋯Cl hydrogen-bonded three-dimensional network is formed between the components.In the binuclear title compound, [Cu Cl(C10H8N2)2(H2O)3]NO3·H2O = 0.052wR(F2) = 0.172S = 1.046973 reflections412 parametersH-atom parameters constrainedmax = 0.71 e Å−3Δρmin = −0.64 e Å−3ΔρRAPID-AUTO  I, global. DOI: 10.1107/S1600536812019848/fj2542Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


Intra- and intermolecular π–π stacking is present in the crystal structure, and the centroid–centroid distances between the benzene and pyridine rings of adjacent dmphen ligands are 3.492 (3) and 3.592 (3) Å, respectively. Intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions help to stabilize the crystal structure.In the title complex, [Pb(NO DOI: 10.1107/S1600536810022312/xu2779Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


Two CdII atoms are bridged by two chloride anions, forming an inversion-related Cd2Cl2 unit; these units are further linked through thiocyanate anions, leading to a chain structure extending parallel to [010]. Weak π–π stacking interactions with centroid–centroid distances of 3.430 (4) Å and an interplanar separation of 3.390 (3) Å between the pyridine and benzene rings link the chains into a two-dimensional network parallel to (C DOI: 10.1107/S1600536811051373/wm2567Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The silver ion is surrounded by two tryptanthrin ligands, each coordinating through the N atoms, with Ag—N bond lengths of 2.247 (3) and 2.264 (3) Å, and an anionic nitrate ligand coordinating through two O atoms, with Ag—O bond lengths of 2.499 (3) and 2.591 (3) Å. The N—Ag—N plane and the O—Ag—O plane are roughly perpendicular, making a dihedral angle of 81.6 (2)°. In the crystal, C—H⋯O interactions between aromatic H atoms and keto and nitrate O atoms as well as π–π interactions [centroid-centroid distance = 3.706 (4) Å] give rise to a three-dimensional network.In the crystal structure of the title compound, [Ag(NO DOI: 10.1107/S1600536812001821/rn2096Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The benzene ring of the 4-carboxy-2-sulfonatobenzoate anion is twisted with respect to the two phen ring systems at dihedral angles of 66.38 (9) and 53.56 (9)°. In the crystal, intermolecular O—H⋯O and C—H⋯O hydrogen bonding links the molecules into chains running parallel to [100]. Intermolecular π–π stacking is also observed between parallel phen ring systems, the face-to-face distance being 3.432 (6) Å.In the title complex, [Mn(C DOI: 10.1107/S1600536810023743/xu2781Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The dihedral angle between the carboxylate group and the adjacent benzene ring is 23.00 (10)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 85.34 (4)°. An intramolecular O—H⋯O hydrogen bond occurs between coordinating water molecule and the carboxylate group. In the crystal, N—H⋯O, O—H⋯O and weak C—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular network. A weak C—H⋯π interaction also occurs in the crystal.In the title complex, [Cu(C N,N-diethylnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.025wR(F2) = 0.066S = 1.093482 reflections216 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.40 e Å−3Δρmin = −0.39 e Å−3ΔρAPEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812028814/xu5579Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The complex shows several interesting features: (i) the polyoxygenated loop of C4 effectively chelates a sodium cation in the form of a distorted octahedron and separates it from the iodide counter-ion, the shortest Na+⋯I− distance being greater than 6.5 Å; (ii) the cavity of C4 is filled by a methanol molecule; (iii) a second methanol molecule is hydrogen-bonded to the N atom of a pyridinyl substituent pendant of C4 and halogen-bonded to the I atom of a tFdIB molecule; (iv) the two I atoms of another tFdIB molecule are halogen-bonded to two iodide anions, which act as monodentate halogen-bond acceptorss; (v) one of the two tFdIB molecules is located about a centre of inversion.The title compound, [Na(C When ca62H76N2O6)]I·1.5C6F4I2·2CH4O = 0.045wR(F2) = 0.095S = 1.1333353 reflections847 parametersH-atom parameters constrainedmax = 2.33 e Å−3Δρmin = −1.52 e Å−3ΔρAPEX2  used to solve structure: SIR2002  global, I. DOI: Click here for additional data file.10.1107/S1600536813007757/bg2501Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The crystal packing is stabilized by intermolecular O—H⋯O and N—H⋯O and weak C—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distances = 3.4669 (19) and 3.764 (2) Å].In the title compound, (C DOI: 10.1107/S1600536810054371/bt5430Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


Partial hydrolysis led to the title compound, the hydrochloric acid adduct of the dichloride, having a pentacoordinated Sn atom with a trigonal–bipyramidal C2SnCl3 core. The N atom of the 2-[(diisopropylammonio)methyl]phenyl ligand forms a strong intramolecular N—H⋯Cl hydrogen bond, resulting in a zwitterionic species, [2-(iPr2HN+CH2)C6H4]SnBuCl3               −·CH2Cl2. Disorder was found in the n-butyl group, which was refined as disordered over three positions, with site occupancies of 0.22 (1), 0.51 (1) and 0.27 (2).The title compound, [Sn(C DOI: 10.1107/S1600536810050713/zl2332Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


II atom in the polymeric title compound, {[Pb(C13H11N4O)(CH3OH)2]ClO4}n, is coordinated by an N′-[1-(pyridin-2-yl-κN)ethylidene]isonicotinohydrazidate ligand via O,N,N′-donors and simultaneously bridged by a neighbouring ligand via the isonicotinoyl N atom; two additional sites are occupied by methanol O atoms. The resultant supramolecular chain is a zigzag along the c axis. The PbII atom is seven-coordinated within an N3O3 donor set and a lone pair of electrons, which defines a Ψ-pentagonal–bipyramidal coordination geometry with the pyridine N and lone pair in axial positions. The supramolecular chains are linked into the two-dimensional array via intermolecular Pb⋯N [3.020 (4) Å] interactions. Layers stack along the a axis, being connected by O—H⋯O hydrogen bonds formed between the coordinated methanol molecules and perchlorate anions.The Pb N′-[1-(2-pyridyl)ethylidene]isonicotinohydrazide ligand, see: Maurya et al. (CH4O)2]ClO4                         = 0.024                           wR(F                           2) = 0.066                           S = 1.05                           3492 reflections255 parametersH-atom parameters constrainedmax = 0.97 e Å−3                        Δρmin = −0.98 e Å−3                        Δρ                                 SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536811046769/hg5133Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The equatorial plane is formed by two trans-related N,O-bidentate pyridazine-3-carboxylate ligands and the axial positions are occupied by two water molecules. The CoII complex molecules are stacked in a column along the a-axis direction by an O—H⋯N hydrogen bond between the non-coordinating pyridazine N atom and the coordinating water molecule. These columns are further connected into a layer parallel to the ac plane by additional hydrogen bonds involving the coordinating and non-coordinating water molecules, and the non-coordinating carboxylate O atom. The crystal packing is completed by interlayer weak C—H⋯O interactions.The title compound, [Co(C For a r al. 2004.5H3N2O2)2(H2O)2]·2H2O = 0.026wR(F2) = 0.058S = 1.081369 reflections122 parameters4 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.28 e Å−3Δρmin = −0.31 e Å−3ΔρCrysAlis PRO  used to solve structure: OLEX2  I, global. DOI: 10.1107/S1600536813017340/is5284Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


One of the two quniolinium ions forms an N—H⋯Op  hydrogen bond and the other an N—H⋯Ow (w = water) hydrogen bond. The water molecules further link the components by O—H⋯Op and O—H⋯Ow hydrogen bonds. A number of C—H⋯O interactions and aromatic π–π stacking interactions [shortest centroid–centroid separation = 3.541 (7) Å] are also observed. Together, these generate a three-dimensional network.In the title compound, (C DOI: 10.1107/S1600536813027347/hb7146Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


II atom in the title compound, [Cd(C6H12NS2)2(C10H8N2)], is hexacoordinated by two dithiocarbamate ligands and the N atoms from a bidentate 2,2′-bipyridyl molecule. The coordination geometry is based on a distorted trigonal–prismatic arrangement of the N2S4 donor set. Supramolecular chains, aligned along the a-axis direction, are mediated by C—H⋯S interactions and these are connected into layers that stack along the c axis via π–π interactions [Cg(pyridyl)⋯Cg(pyridyl) = 3.6587 (13) Å].The Cd DOI: 10.1107/S1600536811006878/pk2304Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


Intermolecular π–π stacking interactions between the phen and DHB ligands [centroid–centroid distances = 3.542 (4) and 3.879 (4) Å] and between the pyridine and benzene rings of adjacent phen ligands [centroid–centroid distance = 3.751 (4) Å] stabilize the crystal structure. Intramolecular O–H⋯O hydrogen bonds are observed in the DHB ligands.In the mononuclear title complex, [Dy(C DOI: 10.1107/S1600536810048348/hy2381Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


There are two acridine molecules  and one and a half water molecules in the asymmetric unit. The half-molecule of water is located on a crystallographic twofold axis. The crystal structure is built up from two threads of molecule II sewn together with water molecules through O—H⋯O and O—H⋯N hydrogen bonds from one side and with π–π interactions [centroid–centroid distance = 3.640 (3) and 3.7431 (3) Å] between overlapping molecules II on the other side. Molecule I is attached to this thread from both sides by C—H⋯O hydrogen bonds. The threads are connected to each other by π–π interactions [centroid–centroid distances = 3.582 (3) and 3.582 (3) Å] between the inner side of molecule I and stabilized by a C—H⋯π interaction on the other side of molecule I. This thread with rows of molecule I hanging on its sides is generated by translation perpendicular to the a axis.The title compound, C Å                           b = 8.893 (5) Å                           c = 17.492 (5) Å                           V = 4107 (3) Å3                                                   Z = 16                           Kα radiationMo −1                        μ = 0.08 mmT = 197 K                           0.3 × 0.3 × 0.3 mm                                 Bruker SMART 6000 diffractometer14504 measured reflections3606 independent reflectionsI > 2σ(I)1733 reflections with R                           int = 0.068                                                            R[F                           2 > 2σ(F                           2)] = 0.058                           wR(F                           2) = 0.197                           S = 1.00                           3606 reflections272 parameters2 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.35 e Å−3                        Δρmin = −0.29 e Å−3                        Δρ                                 SMART  used to solve structure: SHELXTL  I, global. DOI: 10.1107/S1600536811038220/ez2255Isup2.hkl            Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038220/ez2255Isup3.cml            Supplementary material file. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The two imidazole rings are oriented to each other with a dihedral angle of 75.1 (2)°. Strong O—H⋯O hydrogen bonds between protonated and deprotonated carboxylate groups occur in the molecular structure. In the crystal structure extensive O—H⋯O and N—H⋯O hydrogen bonds help to stabilize the three-dimensional supramolecular framework. The propyl groups of anions are disordered over two sites with refined occupancies of 0.768 (6):0.232 (6) and 0.642 (8):0.358 (8).In the title complex, [Cd(C DOI: 10.1107/S1600536810031466/xu5001Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


One of the CuII ions is coordinated in a distorted square-planar environment and the other is coordinated in a distorted square-pyramidal environment. The long apical Cu—O bond of the square-pyramidal coordinated CuII ion is formed by a symmetry-related O atom, creating a one-dimensional polymer along [010]. In addition, short intermolecular Cl⋯Cl distances [3.444 (2) Å] and weak π–π interactions [centroid–centroid distances = 3.736 (2)–3.875 (3) Å] are observed. The crystal studied was an inversion twin with a refined twin component ratio of 0.60 (1):0.40 (1).The asymmetric unit of the title compound, [Cu DOI: 10.1107/S1600536812028462/lh5494Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


II complex, [Cu(C7H4BrO2)2(C6H6N2O)2(H2O)2], contains one half-molecule, the CuII atom being located on an inversion center. The unit cell contains two nicotinamide (NA), two 4-bromobenzoate (PBB) ligands and two coordinated water molecules. The four O atoms in the equatorial plane around the CuII ion form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxylate group and the adjacent benzene ring is 22.17 (16)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 82.80 (6)°. In the crystal, N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. A weak C—H⋯π interaction is also observed.The asymmetric unit of the title mononuclear Cu N,N-diethylnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.039                           wR(F                           2) = 0.108                           S = 1.13                           3515 reflections203 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.86 e Å−3                        Δρmin = −1.29 e Å−3                        Δρ                                 APEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536811021696/su2279Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The complex lies on an inversion center. The metal atom is surrounded by two chelating isobidentate O-propan-2-yl (4-ethoxyphenyl)dithiophosphonate ligands in a trans configuration binding through the S-donor atoms. The Ni—S bond lengths are 2.2328 (5) and 2.2369 (5) Å, an insignificant difference to be considered anisobidentate. The Ni⋯P separation is 2.8224 (5) Å and the S—P bond lengths are 2.0035 (7) and 2.0053 (7) Å. The S—Ni—S (chelating) and S—Ni—S (trans) bond angles are 88.321 (18) and 180°. The Ni—S—P bond angles are 83.26 (2) and 83.33 (2)°, indicating a very minor distortion from ideal square-planar geometry for the Ni atom. The P atom, however, is distorted quite significantly from an ideal tetrahedral geometry, as reflected by the S—P—S and O—P—C bond angles of 101.93 (3) and 100.70 (7)°, respectively. The title compound, [Ni(C DOI: Click here for additional data file.10.1107/S1600536812045114/bh2460Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The ErIII ion has a distorted dodecahedral coordination with six coordinating O atoms derived from the ferrocenecarboxylate ligands and two coordinated O atoms from one water molecule and one methanol molecule. The asymmetric unit comprises a half of the complex molecule and a methanol solvent molecule. Intramolecular O—H⋯O and C—H⋯O interactions occur. In the crystal, molecules are linked by intermolecular O—H⋯O hydrogen bonds and C—H⋯O as well as C—H⋯π interactions.In the centrosymmetric title coordination compound, [Er DOI: 10.1107/S1600536811051245/kp2371Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


Both arsine ligands are equatorial with respect to the Ru3 triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The phenyl rings of biphenyl are twisted from each other by dihedral angles of 50.5 (2), 44.5 (2) and 27.8 (2)°. The arsine-substituted phenyl rings make dihedral angles of 61.56 (18), 89.36 (18) and 83.27 (18)° with each other. The dihedral angles between the two benzene rings are 87.5 (2) and 81.95 (19)° for the two diphenylarsanyl groups. In the crystal, molecules are linked into dimers by intermolecular C—H⋯O hydrogen bonds. Weak intermolecular C—H⋯π and π–π [centroid–centroid distance = 3.601 (3) Å] interactions stabilize the crystal structure.In the title  DOI: 10.1107/S1600536811000237/ng5094Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


In the crystal, N—H⋯O and N—H⋯N hydrogen bonds link the molecules into columns in [001]. The porous crystal packing is further stabilized via π–π interactions between the pyridine rings of neighbouring molecules [centroid–centroid distance = 3.746 (3) Å] with voids of 270 Å3.In the title compound, [Ni(C DOI: 10.1107/S1600536812014109/cv5274Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The distorted tetrahedral coordination sphere is defined by chelating N atoms that define an acute angle [69.6 (3)°] and two I atoms that form a wide angle [142.80 (4)°]. The linearly coordinated HgII atom [177.0 (4)°] exists with a donor set defined by C and Cl atoms. Secondary interactions are apparent in the crystal packing with the tetrahedrally and linearly coordinated HgII atoms expanding their coordination environments by forming weak Hg⋯I [3.772 (7) Å] and Hg⋯O [2.921 (12) Å] interactions, respectively. Mercury-containing molecules stack along the a axis, are connected by π–π interactions [inter-centroid distance between pyridine and benzene rings = 3.772 (7) Å] and define channels in which the dimethyl sulfoxide molecules reside. The latter are connected by the aforementioned Hg⋯O interactions as well as C—H⋯I and C—H⋯O interactions, resulting in a three-dimensional architecture.The title dimethyl sulfoxide solvate, [Hg E)-N-(pyridin-2-ylmethylidene)arylamine-type ligands, see: Basu Baul, Kundu, Höpfl et al. I2]·C2H6OS = 0.053wR(F2) = 0.143S = 1.034848 reflections208 parametersH-atom parameters constrainedmax = 4.40 e Å−3Δρmin = −1.45 e Å−3ΔρCrysAlis PRO  used to solve structure: SHELXS97  general, I. DOI: 10.1107/S1600536813029693/hg5358Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The SnIV ion is coordinated by two N atoms [Sn—N = 2.266 (2) and 2.274 (2) Å] from the bis(2-pyridyl)selenide ligand and four chloride anions [Sn—Cl = 2.3717 (6)–2.3939 (6) Å] in a distorted octahedral geometry. The central six-membered chelate ring has a boat conformation with the Se and Sn atoms deviating by 0.692 (3) and 0.855 (3) Å, respectively, from the mean plane through the remaining four ring atoms. The pyridine rings are inclined to each other by a dihedral angle of 49.62 (8)°. The crystal packing exhibits short intermolecular Se⋯Cl contacts [3.5417 (7) and 3.5648 (7) Å], weak C—H⋯Cl hydrogen bonds and π–π stacking interactions between the pyridine rings with a centroid–centroid distance of 3.683 (3) Å.The title compound, [SnCl DOI: 10.1107/S160053681202586X/cv5309Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


In the crystal structure, the complex molecules and the uncoodinated water molecules are connected by O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds into a three-dimensional network. A π–π stacking interaction between the pyridyl ring of the ip ligand and the benzene ring of the neighboring ligand [centroid–centroid distance = 3.579 (2) Å] is also observed.In the title centrosymmetric dinuclear compound, [Mn DOI: 10.1107/S1600536810031909/hy2338Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


There are significant differences in the chemically equivalent Cd—O bond lengths [2.618 (2) Å and 2.561 (2) Å].In the title compound, [Cd(C DOI: 10.1107/S1600536811038712/lh5332Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The four O atoms in the equatorial plane around the ZnII cation form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxylate group and the adjacent benzene ring is 2.96 (11)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 79.26 (4)°. The coordinating water molecule links with the carboxylate group via an intramolecular O—H⋯O hydrogen bond. In the crystal, O—H⋯O and weak C—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular network. A π–π contact between the parallel pyridine rings of adjacent molecules may further stabilize the crystal structure [centroid–centroid distance = 3.5654 (8) Å].In the title complex, [Zn(C N,N-diethylnicotinamide, see: Bigoli et al. 2(C10H14N2O)2(H2O)2] = 0.025wR(F2) = 0.081S = 1.164409 reflections246 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.46 e Å−3Δρmin = −0.33 e Å−3ΔρAPEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812031200/xu5586Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


In the 1-benzyl-3-methylimidazolium units, the dihedral angles between imidazolium and phenyl rings are 80.47 (15) and 76.53 (14)°. The F atoms of the general-position hexafluorophosphate anion are disordered over two sets of sites in a 0.767 (17):0.233 (17) ratio. In the crystal, the hexafluorophosphate anions link the cations into three-dimensional networks via intermolecular C—H⋯F hydrogen bonds and are further consolidated by π–π stacking [centroid–centroid distances = 3.5518 (15) Å] interactions.In the title compound, K[Ag(C DOI: 10.1107/S1600536810051925/hb5767Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The two independent molecules do not differ substantially and a molecule of water completes the asymmetric unit. The synthesis of the title compound does not modify the stereochemical center, as shown by the absolute configuration found in this crystal structure. Comparison with the non-bromo starting material differs mainly by rotation features. For instance the H(methine)—C—C(methylene)—C(ipso) is 173.0 (2)° torsion angle in one molecule and 177.3 (2)° in the other, indicating a trans arrangement. This is in contrast with approximately 50° in the starting material. A short intermolecular Br⋯Br separation is observed [3.2938 (3) Å]. The molecules in the crystal are connected via a network of hydrogen bonds through an N—H⋯O hydrogen bond between the hydroxy group of the phenol of the tyrosine and the N—H of the amide of the other molecule and an O—H⋯O hydrogen bond between the hydroxy group of the carboxylic acid and the oxygen of the carbonyl of the amide.The title compound, C N-Acetyl-3,5-dibromo-l-tyrosine is a substrate of biological interest, for instance it is involved in the synthesis of isodityrosine unit, which has been found in numerous biologically active natural products that include K-13, OF4949 and vancomycin family of glycopeptide antibiotics. For the synthesis and specific optical activity of the title compound, see: Bovonsombat et al.  Åb = 22.5186 (9) Åc = 8.6486 (4) Åβ = 105.946 (1)°V = 1331.3 (1) Å3Z = 4Kα radiationMo −1μ = 6.10 mmT = 125 K0.23 × 0.17 × 0.05 mmBruker SMART CCD area-detector diffractometerSADABS; Bruker 2007Tmin = 0.334, Tmax = 0.750Absorption correction: multi-scan (18331 measured reflections7067 independent reflectionsI > 2σ(I)6449 reflections with Rint = 0.030R[F2 > 2σ(F2)] = 0.022wR(F2) = 0.048S = 0.927067 reflections361 parameters17 restraintsH atoms treated by a mixture of independent and constrained refinementmax = 0.41 e Å−3Δρmin = −0.34 e Å−3ΔρAbsolute structure: Flack 1983, 3399 FrFlack parameter: 0.005 (5)SMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812032928/bg2470Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032928/bg2470Isup3.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


Intermolecular C—H⋯Cl hydrogen bonds and π–π stacking interactions between the pyridine rings [centroid–centroid distance = 3.745 (3) Å] are present in the crystal.In the title compound, [CoCl DOI: Click here for additional data file.10.1107/S1600536812041116/hy2591Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The bridging function of the Br atoms leads to a chain structure along [100]. Interchain C—H⋯Br hydrogen bonds and π–π contacts between the thiazole rings [centroid–centroid distances = 3.810 (5) and 3.679 (5) Å] are observed.In the title coordination polymer, [CdBr DOI: 10.1107/S1600536811020861/hy2437Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


In the crystal, C—H⋯Br hydrogen bonds and π–π stacking interactions between the pyridine rings [centroid–centroid distance = 3.763 (5) Å] are present.In the title compound, [CdBr DOI: 10.1107/S1600536812033648/hy2576Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The dihedral angle between the carboxylate group and the adjacent benzene ring is 32.12 (14)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 82.02 (5)°. The coordinating water molecule links with the carboxylate group via an intramolecular O—H⋯O hydrogen bond. In the crystal, N—H⋯O, O—H⋯O and weak C—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular network.In the title complex, [Cu(C N,N-diethylnicotinamide, see: Bigoli et al. 2(C6H6N2O)2(H2O)2] = 0.021wR(F2) = 0.058S = 1.133531 reflections203 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.97 e Å−3Δρmin = −0.50 e Å−3ΔρAPEX2  used to solve structure: SHELXS97  I, global. DOI: 10.1107/S1600536812034587/xu5599Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The CuII atom is located on an inversion centre and has an overall octahedral coordination environment. Two N and two O atoms from (pyzdc)2− ligands define the equatorial plane and two water molecules are in axial positions, resulting in a typical tetragonally Jahn–Teller-distorted environment. Extensive classical O—H⋯O, O—H⋯N and N—H⋯O and non-classical C—H⋯O hydrogen bonds, as well as π–π stacking interactions between aromatic rings of the cations [centroid–centroid distance = 3.58 (9) Å], lead to the formation of a three-dimensional supramolecular structure.The title compound, (C DOI: 10.1107/S1600536811008981/wm2462Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The coordination sphere about one CoII atom comprises four O-atom donors from two bidentate chelate (Ophenolate and Ocarboxyl) and bridging dianionic ligands and two water molecules [Co—O range = 2.0249 (11)–2.1386 (14) Å], while that about the second CoII atom has four water molecules and two bridging carboxylate O-donor atoms [Co—O range = 2.0690 (14)–2.1364 (11) Å]. The coordinated water molecules as well as the water molecules of solvation give O—H⋯O water–water and water–carboxyl hydrogen-bonding interactions in the three-dimensional framework structure.In polymeric title compound, {[Co II, see: Deng et al. 2(H2O)6]·2H2O = 0.023                           wR(F                           2) = 0.061                           S = 1.07                           2560 reflections225 parametersH atoms treated by a mixture of independent and constrained refinementmax = 0.32 e Å−3                        Δρmin = −0.47 e Å−3                        Δρ                                 CrysAlis PRO  used to solve structure: SIR92 (Altomare et al., 1994SHELXL97 (Sheldrick, 2008PLATON (Spek, 2009PLATON.Data collection: 10.1107/S1600536810052694/rn2077sup1.cif            Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810052694/rn2077Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The MnII ion exhibits a centrosymmetric octahedral geometry involving two carboxylate O atoms of two different pztmb ligands and four O atoms of four coordinated water molecules. The packing shows a three-dimensional supramolecular network via O—H⋯O and O—H⋯N hydrogen bonds and π–π stacking interactions [centroid–centroid distances = 3.884 (8) and 4.034 (8) Å] between the benzene ring of one pztmb anion and the pyrazine ring of an adjacent anion.The title compound, [Mn(C DOI: 10.1107/S160053681004506X/pk2282Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The full dimer is generated by an inversion center. In the dimer, the two IrIII atoms and two bridging Cl atoms form a perfectly planar ring. The two IrIII atoms and the two terminal Cl atoms also form a rigorous plane that is orthogonal [89.48 (3)°] to the Ir2Cl2 ring. The plane of the cyclopentadienyl ligand forms a dihedral angle of 54.06 (7)° with respect to the Ir2Cl2 ring.The asymmetric unit of the title complex, [Ir For the al. 2011.2Cl4(C12H19)2] = 0.019wR(F2) = 0.040S = 1.064440 reflections141 parametersH-atom parameters constrainedmax = 1.02 e Å−3Δρmin = −1.18 e Å−3ΔρCrysAlis PRO  used to solve structure: SHELXS97  I, global. DOI: Click here for additional data file.10.1107/S1600536813005072/pk2466Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536813005072/pk2466Isup3.cmlSupplementary material file. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


II atom in the title compound, [RuCl2(C15H10)(C18H15P)2]·2C4H8O, has a distorted square-pyramidal conformation. The P and Cl atoms are at the base of the pyramid and the Ru—Cindenylidene bond is in the axial position. The two Cl ligands and the two phosphane ligands are in trans positions. The Cl—Ru—Cl and P—Ru—P angles are 157.71 (2) and 166.83 (2)°, respectively. The two independent tetrahydrofuran (THF) solvent molecules are disordered. One THF molecule was refined using a split-atom model. The second THF molecule was accounted for by using program PLATON/SQUEEZE . The molecular conformation shows three intramolecular C—H⋯Cl contacts and two C—H⋯π interactions while the crystal packing features an intermolecular C—H⋯Cl contact and two very weak intermolecular C—H⋯π contacts.The RuSpek 2009. Acta Cr DOI: 10.1107/S1600536811016692/si2353Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The Si2Cp centroid–titanium distance is 2.0763 (10) Å and the SiCp centroid–titanium distance is 2.0793 (10) Å. The angle subtended at the Ti atom by the centroids of both cyclopentadienyl rings is 131.22 (4)° and the Cl—Ti—Cl angle is 94.14 (2)°.In the title compound, [Ti(C DOI: 10.1107/S1600536811046228/fj2469Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The two heterocyclic rings of the 5-(2-pyridin-2-yl)pyrazine-2-carbonitrile ligand are almost coplanar [dihedral angle = 5.63 (8)°], and the two chelating ligands are in an anti relationship. The mononuclear units are interconnected along [010] through C—H⋯O(nitrate) and C—H⋯N(cyano) interactions, forming an infinite chain. The mononuclear units are stacked along the a axis and interconnected via intermolecular π–π stacking interactions between adjacent pyridine and pyrazine rings [centroid–centroid distances = 3.984 (2) and 3.595 (3) Å], thus forming a three-dimensional supramolecular structure.In the mononuclear title complex, [Ag(NO DOI: 10.1107/S1600536811049221/zq2135Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


A significant Jahn–Teller distortion is observed with two axial Cu—O distances significantly longer than those in the equatorial CuO2N2 plane. In the crystal, π–π stacking interactions, with centroid–centroid distances of 3.547 (3) or 3.728 (3) Å between the phenanthroline rings, form layers parallel to (011).In the title compound, [Cu(C DOI: 10.1107/S1600536811018162/sj5144Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


One of the N-bound H atoms is involved in an intramolecular N—H⋯Cl hydrogen bond, while another one interacts with the solvent methanol molecule via an N—H⋯O hydrogen bond. Intermolecular O—H⋯Cl and O—H⋯O hydrogen bonds link two further complex molecules and four solvent molecules into a centrosymmetric structural unit. The short distance of 3.624 (4) Å between the centroids of the five- and the six-membered rings of two benzimidazole fragments indicates the presence of π–π interactions.In the title complex, [CuCl(C I complexes with triphenlyphosphine ligands, see: Gennari et al. -thione ligand, see: Schneider et al. (C18H15P)2]·2CH4O = 0.086wR(F2) = 0.217S = 1.077835 reflections510 parametersH-atom parameters constrainedmax = 1.53 e Å−3Δρmin = −0.57 e Å−3ΔρSMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536814001251/cv5442Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S1600536814001251/cv5442Isup3.cdxSupporting information file. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the complex molecules are connected by O—H⋯O hydrogen bonds and π–π interactions between the benzene rings [centroid–centroid distance = 3.8924 (17) Å] into a chain along [010]. Between adjacent chains, π–π interactions occur between the pyridine rings [centroid–centroid distance = 3.898 (2) Å], giving an overall two-dimensional architecture.In the title compound, [Co(C DOI: Click here for additional data file.10.1107/S1600536813006752/hy2620Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The dipic and acr ligands are nearly planar [maximum deviation = 0.069 (3) Å in dipic and 0.091 (4) Å in acr] and the dihedral angle between their mean planes is 58.67 (7)°. The Pd—O bond lengths are nearly equal, but the Pd—N bond lengths are slightly different. There is a short C—H⋯O interaction in the molecule involving the two ligands. In the crystal, complex molecules are linked through C—H⋯O interactions, forming a three-dimensional network. There are also a number of intermolecular π–π interactions present, the shortest ring centroid–centroid distance being 3.622 (3) Å.In the title complex, [Pd(C II complex [Pt(C7H3NO4)(C13H9N)], see: Ha (C13H9N)] = 0.041wR(F2) = 0.100S = 0.993152 reflections244 parametersH-atom parameters constrainedmax = 1.21 e Å−3Δρmin = −1.14 e Å−3ΔρSMART  used to solve structure: SHELXS97  global, I. DOI: 10.1107/S1600536812011385/su2392Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


One of the Cp rings is substituted by a nitrobenzenamine group, which is essentially perpendicular to the substituted cyclopentadienyl ring, with an N—C(H2)—C—C torsion angle of 89.8 (2)°. Intramolecular N—H⋯O and N—H⋯N hydrogen bonds occur. In the crystal, weak C—H⋯O hydrogen bonds link adjacent molecules. In the title compound, [Fe(C DOI: 10.1107/S1600536812039177/zq2180Isup2.hklStructure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF reportAdditional supplementary materials:


The mononuclear units are interconnected through π–π interactions [centroid–centroid distances = 3.801 (2) and 3.979 (3) Å] and the hexafluoridophosphate anions are embedded within the interstices. C N⋯π interactions [N⋯centroid = 3.519 (2) Å] and C—H.⋯N hydrogen-bonding interactions also occur.In the mononuclear title complex, [Ag(C DOI: 10.1107/S1600536811051403/bt5734Isup2.hkl            Structure factors: contains datablock(s) I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


In the crystal, the molecules interact through intermolecular N—H⋯O hydrogen bonds between the amino and methoxy groups on the naphthalene ring systems and N—H⋯π interactions between the amino groups and the naphthalene rings. Furthermore, weak C—H⋯O hydrogen bonds and π–π stacking interactions between the benzene rings are observed. The centroid–centroid and interplanar distances between the benzene rings of the aroyl group and the naphthalene ring systems of adjacent molecules are 3.6954 (8) and 3.2375 (5) Å, respectively. The dihedral angle between the mean planes of the benzene ring and the naphthalene ring system is 83.59 (5)°. The benzene ring and the carbonyl group in the benzoyl unit are almost coplanar [C—C—C—O torsion angle = 175.91 (10)°].The title compound {systematic name: (4-aminophenyl)methanone}, C DOI: 10.1107/S1600536810041346/rz2496Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials:


The O atom, the aldehyde H atom and the benzene ring of one of the FB anions are disordered over two positions. The O atoms were freely refined [refined occupancy ratio 0.79 (2):0.21 (2)], while the aldehyde H atoms and the benzene ring atoms were refined with fixed occupancy ratios of 0.8:0.2 and 0.5:0.5, respectively. In the ordered FB anion, the carboxylate group is twisted away from the attached benzene ring (A) by 22.7 (8)°. In the disordered FB anion, the corresponding angles are 15.6 (10) and 11.4 (11)° for rings B and B′, respectively. Benzene rings A and B are oriented at a dihedral angle of 24.2 (7), A and B′ at 43.0 (8)°. The pyrazine ring makes dihedral angles of 67.5 (4), 89.6 (7) and 86.2 (7)°, respectively, with benzene rings A, B and B′. The pyrazine ligands bridge the CdII cations, forming polymeric chains running along the b-axis direction. In the crystal, O—Hwater ⋯ Ocarboxylate hydrogen bonds link adjacent chains into layers parallel to the bc plane. These layers are linked via C—Hpyrazine ⋯ Oformyl hydrogen bonds, forming a three-dimensional network. π–π interactions [centroid–centroid distances = 3.870 (11)–3.951 (5) Å] further stabilize the crystal structure. There is also a weak C—H⋯π interaction present.The polymeric title compound, [Cd(C DOI: 10.1107/S1600536813035010/su2679Isup2.hklStructure factors: contains datablock(s) I. DOI: CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal packing features π–π contacts between the pyridine rings of adjacent molecules [centroid–centroid distance = 3.773 (5) Å] and also between a pyridine ring of one molecule and the five-membered chelate ring of an adjacent molecule [centroid–centroid distance = 3.668 (4) Å].In the title complex, [HgI DOI: 10.1107/S1600536811004041/ya2136Isup2.hkl            Structure factors: contains datablocks I. DOI:  crystallographic information; 3D view; checkCIF report            Additional supplementary materials: