The asymmetric unit of the title co-crystal comprises two twisted molecules of 2,2′-thiodibenzoic acid and four molecules of triphenylphosphane oxide. The three-dimensional molecular packing is stabilized by hydroxy-O—H⋯O(oxide) hydrogen bonds and TPPO-C—H⋯O and TDBA-C—H⋯ interactions. 14H10O4S·2C18H15OP, comprises two molecules of 2,2′-thiodibenzoic acid benzoic acid] and four molecules of triphenylphosphane oxide . The two TDBA molecules are twisted about their disulfide bonds and exhibit dihedral angles of 74.40 (5) and 72.58 (5)° between the planes through the two SC6H4 residues. The carboxylic acid groups are tilted out of the planes of the rings to which they are attached forming a range of CO2/C6 dihedral angles of 19.87 (6)–60.43 (8)°. Minor conformational changes are exhibited in the TPPO molecules with the range of dihedral angles between phenyl rings being −2.1 (1) to −62.8 (1)°. In the molecular packing, each TDBA acid molecule bridges two TPPO molecules via hydroxy-O—H⋯O(oxide) hydrogen bonds to form two three-molecule aggregates. These are connected into a three-dimensional architecture by TPPO-C—H⋯O and TDBA-C—H⋯ interactions. The importance of H⋯H, O⋯H/H⋯O and C⋯H/H⋯C contacts to the calculated Hirshfeld surfaces has been demonstrated. In terms of individual molecules, O⋯H/H⋯O contacts are more important for the TDBA (ca 28%) than for the TPPO molecules (ca 13%), as expected from the chemical composition of these species. Computational chemistry indicates the four independent hydroxy-O—H⋯O(oxide) hydrogen bonds in the crystal impart about the same energy (ca 52 kJ mol−1), with DTBA-phenyl-C—H⋯O(oxide) interactions being next most stabilizing (ca 40 kJ mol−1).The asymmetric unit of the title co-crystal, 2,2′-thiodibenzoic acid–triphenylphosphane oxide (1/2), C In medicine, is dianion is found in the salt Na to 1.5018 (8) Å [P1=O1].The molecular structures of the TPPO coformers are more rigid. This is seen in the O—P—C—C torsion angles, which range from 17.7 (1) to 61.6 (1), 19.8 (1) to 61.5 (1), −2.1 (1) to −62.8 (1) and −19.2 (1) to −44.5 (1)° for the P1–P4-molecules, respectively. In the same way, the P=O bond lengths span an experimentally equivalent range, PLATON; Spek, 20093SC3OH⋯O} heterosynthon as illustrated in Fig. 4i.e. TPPO-C47—H⋯O11(carbonyl) and TPPO-C71—H⋯O5(carbonyl), operate in concert with hydroxy-O12—H⋯O3(oxide) and hydroxy-O6—H⋯O4(oxide) hydrogen bonds, respectively, to close a nine-membered {HC2PO⋯HOCO⋯} synthon. The C—H⋯O contacts are of the type TPPO-C—H⋯O and TDBA-C—H⋯O, Table 1i.e. the O5 and O11 atoms, participates in two C—H⋯O(carbonyl) interactions, leaving no formal role for the carbonyl-O7 and O9 atoms in the molecular packing. A view of the unit-cell contents is shown in Fig. 5Geometric parameters characterizing the identified –(f), the pair of TDBA-S1 and -S2 molecules, shown with the respective pairs of hydrogen bonded TPPO molecules, as well as the TPPO-P1–P4 molecules exhibit some similarities especially on the prominent close contacts as represented by the intense red regions on the corresponding dnorm surface mappings, which are mainly dominated by hydroxy-O—H⋯O(oxide) interactions.The independent 2,2′-thiodibenzoic acid (TDBA) and triphenylphosphane oxide (TPPO) molecules of (I)et al., 2008Upon close inspection on the surface mapping, minor differences are observed between the pair of TDBA molecules. Specifically, a diminutive red spot is observed near one of the terminal carboxylic groups of the S1-molecule arising from a TPPO-phenyl-C—H⋯O(carbonyl) interaction but, no such contact is apparent for the S2-molecule. As for the two pairs of TPPO molecules, the significant difference between the TPPO-P1 and -P4 molecules, linked to S1-DTBA, and the TPPO-P2 and P3 molecules, linked to the S2-TDBA, is the presence of additional red spots on the surface mapping of the phenyl rings for P1- and P2-molecules in contrast to their P3- and P4-containing counterparts. This difference may be attributed to the complementary phenyl-C—H⋯π(phenyl) interactions between centrosymmetrically-related molecules, as illustrated in Fig. 7di and de  contact distances in intervals of 0.01 Å gives the overall two-dimensional fingerprint plots for the entire asymmetric unit of (I)a), and each of the individual TDBA, Fig. 9a), and TPPO, Fig. 10a), molecules. Further, these can be delineated into specific contacts –(d) give fingerprint plots delineated into H⋯H, O⋯H/H⋯O and C⋯H/H⋯C contacts. The relative contributions of these contacts to the surfaces is given in Table 3Quantitative evaluation of the Hirshfeld surfaces by the combination of the a, is quite different for the individual components, Figs. 9a, as the former is a sum of all the individual surface contacts, which differ for the individual molecules. As expected, the same is true for the corresponding decomposed fingerprint plots. The major contribution to the overall surface of (I)i.e. 49.4%, comes from H⋯H contacts. The O⋯H/H⋯O contacts (de + di ∼ 2.34 Å) make a significant contribution at 13.7%, while the C⋯H/H⋯C interactions (de + di ∼ 2.66 Å), at 30.1%, play a more prominent role.The overall fingerprint plot for (I)3SC3OH⋯O} heterosynthon, Fig. 4a), which exhibit an almost identical claw-like fingerprint profile but arranged in the exact reverse order, i.e. Fig. 9a) cf. Fig. 10a). Among all the close interactions, H⋯H contacts, Figs. 8b, represent the dominant interactions to the individual surfaces, i.e. 41–42% for the TDBA molecules and 49–51% for the DPPO molecules, and exhibit de + di contact distances ranging from 2.24 to 2.38 Å which is very close to the sum of van der Waals radii of 2.4 Å.The formation of the 13-membered {O⋯HOCc). These feature two tips – one at relatively short de + di ∼1.6 Å that can be attributed to the hydroxy-H⋯O(oxide) hydrogen bonds for the S1- and S2-TDBA molecules, Fig. 10c), or oxide-O⋯H(hydroxy) hydrogen bonds for P1–P4-TPPO. The other tip has a relatively long de + di value of ∼2.4 Å and arises as a result of hydroxy-O⋯H(phenyl) contacts for S1- and S2-TDBA or phenyl-H⋯O(hydroxy) for P1–P4-TPPO. The O⋯H/H⋯O contacts constitute the second most dominant interactions for the TDBA molecules and third most for the TPPO molecules, Table 3The O⋯H hydrogen bonds constitute the strongest among all interactions present in the co-crystal and lead to formation of asymmetric, forceps-like profiles in the corresponding decomposed fingerprint plots, Figs. 9de + di distance range of 2.7–2.8 Å, i.e. close to the sum of van der Waals radii of 2.9 Å, despite the contacts constituting the third most dominant interaction in the TDBA molecules (ca 22%) and being the second most dominant for the TPPO molecules (ca 32%). An exception to the trend is found for the P1- and P2-TPPO molecules, which display relatively short contact distances at ca 2.6 Å owing to the formation of C—H⋯π interactions as discussed above.Similar to the H⋯H contacts, the C⋯H/H⋯C interactions contribute weakly to the molecular packing of the co-crystal as evidenced from the et al., 2018In summary the Hirshfeld surface analysis on (I)d,p) available in Crystal Explorer  of the hydroxy-O—H⋯O(oxide) hydrogen bonds is consistent across the series and lies in the range −50.7 to −53.3 kJ mol−1. The other close contacts which exerts a relatively strong influence in the energy frameworks of the co-crystal are DTBA-phenyl-C—H⋯O(oxide) interactions, with the Etot amounting of ca −40 kJ mol−1, Table 4Selected results obtained from the interaction energy calculations involving the DTBA molecules as reference molecules are tabulated in Table 4et al., 2005The only other structure of 2,2′-thiodibenzoic acid in the literature is that of the pure compound H. The observed P=O bond lengths in (I)i.e. in the range 1.4975 (8) to 1.5018 (8) Å are at the lower end of the range of such bonds.A survey of the Cambridge Structural Database : 3062 ν(C—H), 1693 ν(COO), 1236 ν(P=O), 1116 ν(P—Ar), 719 δ(P—C), 617 ν(C—S).All chemical precursors were of reagent grade and used as received without purification. Thiosalicylic acid  and triphenylphosphane  were dissolved in acetonitrile (40 ml) and the mixture subsequently added into an acetonitrile solution (25 ml) of copper(I) iodide . The reaction mixture was stirred for 1 h at room temperature before the white product was filtered, washed with cold ethanol and dried Uiso(H) set to 1.2Ueq(C). The oxygen-bound H atoms were located from difference Fourier maps and refined without constraint. Owing to poor agreement, three reflections, i.e.  global, I. DOI: 10.1107/S205698901801544X/hb7782Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901801544X/hb7782Isup3.cmlSupporting information file. DOI: 1876525CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title molecule adopts a helical structure, in which two 2,3′-bipyridyl units are twisted up and down relative to the plane of the central benzene ring. Weak intermolecular C—H⋯π interactions lead to formation of a two-dimensional supramolecular network. Hirshfeld surface analysis indicates that the molecular packing in the title compound is mainly dominated by intermolecular H⋯H and H⋯C/C⋯H interactions. 38H42N4O4, displays a helical structure induced by the combination of the C—C—C—C torsion angle [−10.8 (2)°] between two 2,3′-bipyridyl units attached to the 1,2-positions of the central benzene ring and consecutive connections between five aromatic rings through the meta- and ortho-positions. Intramolecular C—H⋯π interactions between an H atom of a pyridine ring and the centroid of a another pyridine ring contributes to the stabilization of the helical structure. In the crystal, weak C—H⋯π interactions link the title molecules into a two-dimensional supramolecular network extending parallel to the ac plane, in which the molecules with right- and left-handed helical structures are alternately arranged. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the molecular packing is dominated by van der Waals interactions between neighbouring H atoms, as well as by C—H⋯π interactions. One isopropoxyl group is disordered over two sets of sites [occupancy ratio 0.715 (5):0.285 (5)].The title molecule, C An intramolecular C—H⋯π interaction between aromatic H3 and the centroid of the N3/C17–C21 ring as well as C—H⋯N/O hydrogen bonds °, which is believed to reduce the steric hindrance between the two 2,3′-bipyridyl units. In combination with this torsion angle, the consecutive connections of five aromatic rings in the title molecule lead to a helical structure. The central benzene unit occupies A⋯Cg1i and between (methyl)H37C⋯Cg2ii  was found to be disordered over two sets of sites [occupancy ratio 0.715 (5):0.285 (5)].Crystal data, data collection and crystal structure refinement details are summarized in Table 410.1107/S2056989018013002/wm5462sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989018013002/wm5462Isup2.hklStructure factors: contains datablock(s) I. DOI: 1867774CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


It consists of octahedral [Co(NH3)6]3+ cation (Co1 site symmetry 1), tetrahedral [ReVIIO4]− anions (Re1 site symmetry 1) and octahedral [ReIVF6]2− anions ] tetroxidorhenate(VII) tetrakis[hexafluoridorhenate(IV)] hexahydrate, arose unexpectedly due to possible contamination of the K 2ReF6 starting material with KReO4. It consists of octahedral [Co(NH3)6]3+ cation (Co1 site symmetry 1), tetrahedral [ReVIIO4]− anions (Re site symmetry 1) and octahedral [ReIVF6]2− anions , [Co(NH3)6]3+ octahedral cations (mean Co—N = 1.962 Å), and the [ReO4]− tetrahedral anion (mean Re—O = 1.719 Å) are slightly distorted. A network of N—H⋯F hydrogen bonds consolidates the structure. The crystal studied was refined as a two-component twin.The title hydrated salt, tris[hexaamminecobalt(III)] tetraoxidorhenate(VII) tetrakis[hexafluoridorhenate(IV)] hexahydrate, arose unexpectedly due to possible contamination of the K VII is dominated by the tetrahedral perrhenate anion, [ReO4]−  anions  can be prepared in high yield by the reduction of a perrhenate starting material in the corresponding concentrated HX acid  with AHF2  followed by an aqueous work-up  salts as well as their X-ray single-crystal structures was recently reported , an unexpected mixed-valence rhenium(IV)–rhenium(VII) salt arose in an effort to prepare [Co(NH3)6]2[ReF6]3 by metathesis from K2[ReF6] and Co(NH3)6Cl3 in water (353 K). Yellow–orange needle-like crystals of (I) were obtained within two hours by slow evaporation in water at room temperature. The crystals of (I) are air stable over short periods, but decompose to a black material after six months of storage at ambient temperature.In the process of exploring the coordination chemistry of hexafluororhenate(IV) compounds, the title compound (I) 6]3+ cation, three distinct [ReF6]2− anions, one [ReO4]− anion, and two water molecules of crystallization: these components are held together by electrostatic forces and hydrogen bonding. Site symmetries for the metal atoms are Co1: 1 (Wyckoff position 18f), Re1: 3 (Wyckoff position 6c), Re2: 1 (Wyckoff position 18f), Re3: a), and Re4: b).The structure of (I) Fig. 1 is built3)6]3+ cation in (I) is slightly distorted; the average Co—N bond length of 1.962 Å is in agreement with the average Co—N bond lengths of 1.963 Å in [Co(NH3)6](ReO4)·2H2O 6](TcO4)3 , the shortest Co⋯Co and N⋯N separations between nearby [Co(NH3)6]3+ cations are 7.035 (1) and 4.473 (1) Å, respectively.The octahedral [Co(NH4]− anion in (I), the average Re—O bond length (1.719 Å) is in agreement with the average Re—O bond length of 1.720 Å in [Co(NH3)6](ReO4)·2H2O  the values of three Re—O bond lengths,  are slightly shorter than the fourth one [Re—O1 = 1.748 (14) Å]. In (I), all O—Re—O bond angles in the [ReO4]− anion are 109.5 (3)°. However, in [Co(NH3)6](ReO4)·2H2O, the [ReO4]− anion is slightly distorted by up to 2.7°  Å to 1.929 (6) Å. All the Re—F bond lengths in the Re3- and Re4-centred anions are of equal distances of 1.952 (6) and 1.950 (6) Å, respectively, by symmetry. Overall, the average Re—F bond length (1.834 Å) in (I) is notably shorter than the average Re—F bond length (1.951 Å) in A2[ReF6]  salts previously studied  and its component ions 6]3+) are shown in Fig. 26]2− anions and the water molecules (Table 1A perspective view of the unit-cell plots for (s Table 1.I) is the only reported hexahalogenorhenate–perrhenate structure containing both rhenium(IV) and rhenium(VII). It is noted that K2[ReF6] used for the preparation of (I) was not characterized before use and the presence of perrhenate in (I) may be due to the presence of K[ReO4] in the starting material. Efforts to isolate the technetium (Tc-99) derivative compound, [Co(NH3)6]3 [(Tc(vii)O4) (Tc(iv)F6)4] are in progress.To the best of our knowledge,  was dissolved in 2 ml of hot water (353 K), and [Co(NH3)6]Cl3  dissolved in 1 ml of  H2O was added. The solution was allowed to evaporate slowly at room temperature and yellow-orange needle-like crystals of (I) were obtained within two hours. The compound was washed with H2O (3 × 1 ml), followed by isopropanol (3 × 1 ml) and then diethyl ether (3 × 1 ml). Single crystals of (I) were grown in H2O by slow evaporation at room temperature. Yield: ca 91%. The presence of perrhenate in (I) is probably due to the presence of K[ReO4] in the starting material (i.e. K2ReF6).KCrystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019009757/hb7830sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019009757/hb7830Isup2.hklStructure factors: contains datablock(s) I. DOI: 1939234CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The anions are disordered and modelled in two orientations. The major conformations have occupancies of 57, 59, 60 and 79%The asymmetric unit of the title compound contains two diaquabis(ethylenediamine)copper(II) cations and four nitrobenzoate anions. These are connected into three-molecule aggregates  2N,N′)copper(II) bis(2-nitrobenzoate), [Cu(C2H8N2)2(H2O)2](C7H4NO4)2, two diaquabis(ethylenediamine)copper(II) cations and four nitrobenzoate anions are present in the asymmetric unit. All four anions are ‘whole-molecule’ disordered over two sets of sites. The major components have refined occupancies of 0.572 (13), 0.591 (9), 0.601 (9) and 0.794 (10). The CuII ions exhibit slightly distorted octahedral geometries. In the crystal, cations and anions are connected to each other via N—H⋯O and O—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (200). The intermolecular contacts in the crystal were further analysed using Hirshfeld surface analysis, which indicates that the most significant contacts are O⋯H/H⋯O (42.9%), followed by H⋯H (35.7%), C⋯H/H⋯C (14.2%), C⋯C (2.9%), C⋯O/O⋯C (2.2%), N⋯H/H⋯N (0.9%) and N⋯O/O⋯N (0.3%).In the title compound, diaquabis(ethylenediamine-κ Copper(II) carboxylates have been used as single precursors for the preparation of copper(II) oxide nanoparticles diaquacopper(II) cations and four 2-nitrobenzoate anions. In both cations, the CuII ion is coordinated by four N atoms of the ethylenediamine ligands which chelate the metal in the equatorial plane, and two axially coordinated water molecules forming a slightly distorted octahedral geometry. The Cu—N bond lengths range from 1.991 (6) and 2.050 (5) Å (Table 12(H2O)2]2+ cations  and 2.564 (5) Å for Cu1B] are noticeably longer than the equatorial Cu—N distances  to 1.251 (15) Å] in the nitro group are close to the values observed for related compounds reported in the literature  and (C1A–C6A) at . These interactions consolidate the three-dimensional structure copper(II) 2-nitrobenzoate  under stirring. The precipitate was filtered, dried and dissolved in a hot methanol solution containing ethylenediamine  under stirring. The mixture was filtered and single crystals were obtained after slow evaporation for one week.An aqueous solution of sodium 2-nitrobenzoate  was added to an aqueous solution of CuSOUiso(H) = 1.2Ueq(C) for all C-bound H atoms. The N-bound H atoms were located in a difference-Fourier map and refined with N—H = 0.91 Å, and with Uiso(H) = 1.5Ueq(N). The H atoms bonded to O atoms  were located in a difference map and treated as part of a rigid group with oxygen as the pivot atom. All four anions are whole-molecule disordered over two sets of sites. The major components have refined occupancies of 0.572 (13), 0.591 (9), 0.601 (9) and 794 (10). The major and minor components of disorder for each anion were constrained using the SAME command in SHELXL  I. DOI: 10.1107/S2056989019016669/lh5937Isup2.hklStructure factors: contains datablock(s) I. DOI: 1909170CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II atom in the title compound has a distorted trigonal–bipyramidal coordination environment defined by four N atoms from two bidentate 1,10-phenanthroline ligands and one oxygen atom from one-half of the monodentate N,N′-diglycinate ligand. The dinuclear complex cations and the nitrate counter-anions as well as the solvate molecules are linked by an intricate network of hydrogen bonds.The Cu 2(C12H10N2O6)(C12H8N2)4](NO3)2·C12H12N2O6·8H2O, is composed of a CuII atom with a distorted trigonal–bipyramidal coordination environment defined by four N atoms from two bidentate 1,10-phenanthroline ligands and one oxygen atom from one-half of the monodentate N,N′-diglycinate anion. The asymmetric unit is completed by one-half of the N,N′-diglycine solvent molecule, which is located on a centre of inversion, by one nitrate counter-anion and four water molecules. In the crystal, the cationic complexes are linked via intermolecular π–π stacking and through lone-pair⋯π interactions involving the N,N′-diglycinate anion and the phenanthroline ligands. The N,N′-diglycine solvent molecule is involved in classical and non-classical hydrogen-bonding interactions, as well as π–π stacking interactions. The centroid-to-centroid distances between aromatic entities are in the range 3.5402 (5)–4.3673 (4) Å. The crystal structure is stabilized by further C—H⋯O contacts as well as by O—H⋯O and N—H⋯O hydrogen bonds between water molecules, the nitrate anions, the N,N′-diglycinate ligands, N,N′-diglycine solvent molecules and phenanthroline ligands, giving rise to a supramolecular framework. A Hirshfeld surface analysis was carried out to quantify these interactions.The centrosymmetric binuclear complex cation of the title compound, [Cu In the two structures, the embedded N,N′-diglycate molecule links the cationic buildings blocks by numerous supramolecular interactions.In our synthetic approach, we employ such systems as electron-deficient bidentate aromatic ring systems such as phenanthroline or bipyridine in order to block parts of the metal cation coordination sphere. Thus, the alternative assembly process lies in the use of the offered different π-interaction possibilities, N,N′-diglycine moiety is a bis-monodentate bridging anionic ligand in its deprotonated form, as well as a solvent molecule in its neutral form in one crystal structure. The structural investigation and description of the supramolecular network is confirmed and discussed with the aid of a Hirshfeld surface analysis diglycine solvent molecule.In a continuation of this work, we have now synthesized and determined the structure of a novel copper(II) coordination compound where the 2(C12H8N2)4(C12H10N2O6)](NO3)2·(C12H12N2O6)·8H2O, comprises two bidentate phenanthroline ligands and one bridging monodentate N,N′-diglycinate ligand for each CuII atom, defining a distorted trigonal–bipyramidal coordination sphere. A crystallographic centre of inversion is located at the centroid of the bridging N,N′-diglycinate anion as well as the neutral and non-coordinating N,N′-diglycine solvent molecule. The asymmetric unit is completed by one non-coordinating nitrate counter-anion and four water molecules , 2.119 (2) and 2.111 (3) Å, and the axial positions by N1 and N3 with shorter bonds each of 1.974 (3) Å, respectively. The bond angle N1—Cu—N3 is 174.71 (11)°. The sum of the bond angles O1—Cu—N2 [136.69 (11)°], O1—Cu—N4 [103.88 (12)°] and N2—Cu—N4 [118.90 (10)°] in the equatorial plane amounts to 359.47°, indicating only slight distortions. Distances and angles within the distorted trigonal–bipyramidal coordination sphere of the CuII ion are similar to those found in the literature diglycine solvent molecule [C36—O4 = 1.205 (6) and C36—O5 = 1.316 (5) Å]. The O1—C30—O2 angle of 123.1 (4)° in the carboxylate group is slightly smaller than in the carboxylic group [O4—C36—O5 = 124.3 (4)°]. In the coordinating N,N′-diglycate ligand, the deviations of atoms defining the central benzamido entity from its least-squares plane are 0.040 (4) Å (C28), −0.084 (3) Å (O3), 0.245 (4) Å (N5) and 0.404 (4) Å (C29), while in the N,N′-diglycine solvent they are −0.018 (4) Å (C34) , 0.102 (3) Å (O6), −0.192 (4) Å (N6) and −0.257 (4) Å (C35). The angle between the amide group and the carboxylate group connected through the sp3-hybridized methylene carbon atom (N5—C29—C30) is 113.6 (3)°, and for the neutral solvent molecule it is (N6—C35—C36) 112.1 (3)°. The dihedral angle between the planar carboxylate group (O1/C30/O2) and the aromatic synthon (C25–27/C25′–C27′) of the ligand is 84.1 (3)° and thus smaller than the value found in the free solvent molecule of the aromatic synthon (C31–C33/C31′–C33‘) and the planar carboxylate group (O4/C36/O5) at 88.9 (3)°. The dihedral angle between the mean planes of the two bidentate phenanthroline ligands is 61.71 (5)°; the corresponding value between phenanthroline (N1/C1–C12/N2) and the coordinating carboxylate group (O1/C30/O2) is 79.9 (4)° and between phenanthroline (N3/C13–C24/N4) and the carboxylate group is 82.5 (3)°, respectively.The equatorial plane of the Cuvia O—H⋯O, C—H⋯O and partly via N—H⋯O hydrogen bonds with water solvent molecules, the phenanthroline ligands and the metal-coordinating N,N′-diglycinate ligands diglycine solvent molecule, as well as between phenanthroline ligands and the metal-coordinating N,N′-diglycinate ligand stack these components along the different axes  Å between Cg2⋯Cg4, 3.6686 (5) Å between Cg3⋯Cg4, and 3.5402 (5) Å between Cg5⋯Cg5, where Cg1, Cg2Cg, 3Cg, 4 and Cg5 are the centroids defined by the ring atoms N1/C1–C4/C12, C4–C7/C11–C12, N2/C7–C11, C31–C33/C31′–C33′ and C16–C19/C23–C24, respectively. These distances are in expected ranges diglycinate ligand leads to a longer Cg6⋯Cg7 separation of 4.3673 (4) Å ° and is slightly increased in comparison with the lines through C26/Cg7 and the centroids Cg6/Cg7 with a value of 16.99 (5)°. Distances shown in Fig. 4Cg7 and C15/Cg7 are 3.4440 (4) and 3.676 (6) Å and between H26/Cg7 and C26/Cg7 are 3.5049 (4) and 3.713 (5) Å with observed angles of 96.8 (3)° (C15—H15⋯Cg7) and 95.4 (3)° (C16—H26⋯Cg7), respectively. Besides the previously mentioned forces, a lone-pair⋯π interaction between the O3 atom of the carboxylate group of the metal-coordinating N,N′-diglycinate ligand and the Cg5 centroid of a phenanthroline ligand are observed and associated with a distance of 3.739 (4) Å. This value is similar to those found in the literature  analysis diglycine solvent molecule in the range −0.6806 to 1.9484 a.u. are shown in Fig. 5de ∼ 1.19 Å/di ∼ 0.85 Å and di ∼ 0.68 Å/de ∼ 1.02 Å as well as de ∼ 1.05 Å/di ∼ 0.70 Å and di ∼ 1.12 Å/de ∼ 0.78 Å, which comprise 27.9% and 42.2% of the total amount on the HS, respectively.The HS mapped over N,N′-diglycine solvent molecule involved in hydrogen bonding, the HS mapped over the electrostatic potentials were calculated using TONTO diglycine solvent molecule as the second largest contribution within the HS. This high relevance for the HS is attributed to the high proportion of hydrogen atoms in the structure of these entities. The H⋯N/N⋯H contacts contribute 3.7% to the cationic complex and 3.4% to the solvent molecule to the total HS, respectively. Short contacts of the solvent molecule with a minor contribution to the lattice of O⋯N/N⋯O (0.4%) and O⋯O (0.1%) are also observed. The contribution of the different π–π interactions used for the stacking of the cationic complex subunits and the N,N′-diglycine solvent molecule along the different axes is also significant for both entities. Therefore, the close H⋯C/C⋯H (16.7%), C⋯C (12.0%), O⋯C/C⋯O (2.1%) and N⋯C/C⋯N (1.2%) contacts of the cationic complex are assigned to C—H⋯π interactions, π–π stacking (face-to-face) and lone-pair⋯π interactions of the carbonyl group and stacking between the phenanthroline ligands diglycine solvent molecule, the close C⋯C (11.1%), H⋯C/C⋯H (9.9%), N⋯C/C⋯N (1.8%) and O⋯C/C⋯O (1.2%) contacts are assigned to π–π stacking (face-to-face), C—H⋯π interactions and stackings of the phenanthrolines and lone-pair⋯π interactions of the carbonyl group diglycinate ligand as well as the non-coordinating N,N′-diglycine solvent molecule in the HS mapped over the shape-index, which represent the face-to-face π–π stacking interactions diglycine using SciFinder diglycine, and their structures show a number of non-classical interactions  diglycine, was prepared by the method of Cleaver & Pratt (1955v/v) mixture of water and methanol (50 ml) and refluxed for 30 minutes. The mixture was allowed to cool to room temperature, and a previously prepared aqueous solution of copper acetate (1 mmol) was slowly added under continuous stirring. Pale-blue block-shaped crystals of the title compound were obtained by slow evaporation at room temperature.The starting material, ratt 1955. Cesium Uiso(H) = 1.2Ueq(C) and C—H(aromatic) = 0.94 Å and C—H(methylene) = 0.98 Å using a riding model. The water H atoms were located in a difference-Fourier map and were refined with O—H distances restrained to 0.82–0.87 Å and with Uiso(H) = 1.5Ueq(O), except O11—H11A with a fixed distance of 1.00 Å, which led to a stable and consolidated hydrogen-bonding network.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019005164/wm5501sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019005164/wm5501Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019005164/wm5501Isup3.cdxSupporting information file. DOI: 1910262CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the molecules are linked by weak C–H⋯F hydrogen bonds into the supramolecular inversion dimers. 13H6Cl3FOS, the aromatic rings are inclined to one another by 12.9 (2)°, and the thiophene ring is affected by π-conjugation. In the crystal, molecules are linked by C—H⋯F hydrogen bonds, forming an R22(8) ring motif. A Hirshfeld surface analysis was conducted to verify the contribution of the different intermolecular interactions. The shape-index surface clearly shows that the two sides of the molecules are involved in the same contacts with neighbouring molecules and the curvedness plots show flat surface patches characteristic of planar stacking.In the title chalcone–thiophene derivative, C Chalcones, considered to be the precursor of flavonoids and isoflavonoids, are abundant in edible plants. Compounds with the 1,3-diphenylprop-2-en-1-one framework are described by its generic term ‘chalcone’. They consist of open-chain flavonoids in which the two aromatic rings are joined by a three-carbon α,β-unsaturated carbonyl system. These are coloured compounds because of the presence of the –CO—CH=CH– chromophore, which depends in the presence of other auxochromes. Accumulating evidence has shown that chalcones and their derivatives could inhibit tumor initiation and progression. In view of the above, and as a part of our ongoing research on chalcone derivatives ° for the atoms O1—C5—C6—C7. The thiophene ring is affected by π conjugation. This can be explained by the longer C=S values of 1.703 (6) and 1.714 (4) Å for S1=C2 and S1=C1, respectively. The bond-angle values O1—C5—C6 [121.9 (4)°], O1—C5—C4 [118.2 (4)°] and C5—C6—C7 = 125.14 (4)° about C5 indicate that the carbon atom is in a distorted trigonal–planar configuration, which is due to steric hindrance of the oxygen atom. The molecular structure is stabilized by an intramolecular C6—-H6A⋯Cl1 hydrogen bond (Table 1S(6) motif, as shown in Fig. 1The molecular structure of the title compound, shown in Fig. 1d Table 1 that cloCg1⋯Cg1 = 3.956 (3) Å  and Cg2⋯Cg2 = 3.957 (3) Å  where Cg1 and Cg2 are the centroids of the S1/C1–C4 and C8–C13 rings, respectively.In the crystal, the molecules are linked by C—H⋯F hydrogen bonds, forming an et al., 2016E)-3-(phenyl)-1-prop-2-en-1-one as the main skeleton revealed the presence of three structures containing a similar 2,5-dichlorothiophene–chalcone moiety to the title compound but with different substituents on the terminal phenyl rings, viz. [(E)-1--3-(X)prop-2-en-1-one], where X = 4-(dimethylamino)phenyl  and shape-index (−1.0 to 1.0 a.u.), respectively. The calculated volume inside the Hirshfeld surface is 325.37 Å3 in the area of 310.17 Å3.Hirshfeld surfaces and fingerprint plots were generated for the title compound based on the crystallographic information file (CIF) using A⋯Cl1 and C10—H10A⋯F1 interactions, which play a significant role in the molecular packing of the title compound. The Hirshfeld surfaces illustrated in Fig. 4In Fig. 4The overall two-dimensional fingerprint plot for the title compound and those delineated into Cl⋯H/H⋯Cl, C⋯C, Cl⋯Cl, Cl⋯S/S⋯Cl, H⋯H, F⋯H/H⋯F, C⋯H/H⋯C contacts are illustrated in Fig. 5et al., 2013abet al., 2014et al., 2010bThe title compound was synthesized as per the procedure reported earlier (Kumar Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018010216/xu5930sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018010216/xu5930Isup2.hklStructure factors: contains datablock(s) I. DOI: 1036795CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Correction to: J Cardiovasc Magnhttps://doi.org/10.1186/s12968-019-0537-4In the original version of this article , publishGadoteriol) application (T1 native: 5 s(3 s)3 s; T1 post-contrast: 4 s(1 s)3 s(1 s)2 s; TE 1.1 ms and slice thickness 6 mm).A sampling protocol with reduced sensitivity to heart rate was applied [15] before and 15 min after contrast media  application (T1 native: 5 s(3 s)3 s; T1 post-contrast: 4 s(1 s)3 s(1 s)2 s; TE 1.1 ms and slice thickness 6 mm).A sampling protocol with reduced sensitivity to heart rate was applied [15] before and 15 min after contrast media (0.15 mmol/kg body weight The corrected information is also repeated below:


In the crystal, the only short intermolecular contacts are Cl⋯O contacts [3.173 (3) Å] that link the molecules to form a 21 helix propagating along the b-axis direction.In the title chalcone derivative, C 15H9BrCl2O, the aryl rings are inclined to each by 14.49 (17)°, and the configuration about the C=C bond is E. There is a short intramolecular C—H⋯Cl contact present resulting in the formation of an S(6) ring motif. In the crystal, the shortest intermolecular contacts are Cl⋯O contacts [3.173 (3) Å] that link the molecules to form a 21 helix propagating along the b-axis direction. The helices stack up the short crystallographic a axis, and are linked by offset π–π interactions [intercentroid distance = 3.983 (1) Å], forming layers lying parallel to the ab plane. A quantification of the intermolecular contacts in the crystal were estimated using Hirshfeld surface analysis and two-dimensional fingerprint plots.In the title chalcone derivative, C Chemically they consist of open-chain flavonoids in which the two aromatic rings are joined by a three-carbon, α-unsaturated carbonyl system and are described by the generic term ‘chalcone’. Chalcones are coloured compounds because of the presence of the –CO—CH=CH– chromophore, which depends on the presence of other auxochromes. Chalcones are finding applications as organic non-linear optical materials (NLO) because of their good SHG conversion efficiencies (Chandra Shekhara Shetty E configuration. There is a short intramolecular C—H⋯Cl contact present resulting in the formation of an S(6) ring motif °. The trans conformation of the C=C double bond in the central enone group is confirmed by the C6—C7—C8=C9 torsion angle of −179.8 (3)°. The bond angles O1—C9—C10 [120.4 (3)°], O1—C9—C8 [119.9 (3)°] and C9—C8—C7 [123.9 (4)°] about C9 indicate that this carbon atom is in a distorted trigonal–planar conformation.The molecular structure of the title compound is shown in Fig. 1if Fig. 1. The unsa axis. The shortest intermolecular contacts are Cl⋯O1i contacts .In the crystal, the molecules stack along the short crystallographic on Fig. 2. The helCrystalExplorer  shows an extensive flat surface characteristic of planar stacking – see the Supramolecular features section above.Hirshfeld surfaces and fingerprint plots were generated for the title compound using d Figs. 2 and 3 ▸,et al., 2007The overall two-dimensional fingerprint plot , including 1-(3-bromophenyl)-3-phenylprop-2-en-1-one itself ° because of the presence of the intramolecular C—H⋯Cl hydrogen bond, as shown in Fig. 1A search of the Cambridge Structural Database  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901900104X/qm2132sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901900104X/qm2132Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900104X/qm2132Isup3.cmlSupporting information file. DOI: 10.1107/S205698901900104X/qm2132sup4.pdfDetails of CSD search. DOI: 1036741CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


One showcases a novel (dppm)C(N2dppm) PCP pincer, the other contains a (dppm)C(N2) diazomethylenephosphorane moiety.In this communication, two compounds and their respective crystal structures, obtained  2(C58H51N3P4)]Cl·5.5CH3CN or Cl·5.5CH3CN , resulting from an oxygen-mediated cleavage of a triazeneylidenephosphorane ligand producing a diazomethylenephosphorane and a nitrene moiety, which in turn rearrange via a Staudinger reaction and a 1,2-hydride shift to the first title complex, involves a six-coordinate IrIII complex cation coordinated by a facial PCP pincer ligand, a benzaldimine and two chlorido ligands. The pincer system features a five- and a seven-membered ring, with the central divalent carbon of the PCP pincer ligand being connected to a phosphine and a diazophosphorane. The chlorido ligands are positioned trans to the central carbon atom and to the phosphorus donor of the seven-membered ring of the pincer system, respectively. A chloride ion serves as counter-ion for the monocationic complex. The structure of [IrI(C26H22N2P2)(C26H22P2)(C6H7N)]I(I3)·0.5I2·CH3OH·0.5CH2Cl2 or I(I3)·0.5I2·CH3OH·0.5CH2Cl2 {4, systematic name: iodido(phenylmethanimine-κN)iridium(III) iodide–triiodide–dichloromethane–iodine–methanol (2/2/1/1/2)}, accessed via treatment of the triazeneylidenephosphorane complex Cl with hydroiodic acid, consists of a dicationic six-coordinate IrIII complex, coordinated by a bidentate diazomethylenephosphorane, a benzaldimine, a chelating dppm moiety and an iodido ligand. The phosphorus atoms of the chelating dppm are trans to the central carbon atom of the diazomethylenephosphorane and the iodide ligand, respectively. Both an iodide and a triiodide moiety function as counter-ions. The acetonitrile solvent molecules in 3 are severely disordered in position and occupation. In 4, the I3− anion is positionally disordered (ratio roughly 1:1), as is the I− anion with a ratio of 9:1. The dichloromethane solvent molecule lies near a twofold rotation axis (disorder) and was refined with an occupancy of 0.5. Another disorder occurs for the solvent methanol with a 1:1 ratio.The structure of [IrCl This substitution reaction results in the formation of a labile IrI intermediate, whose coordination sphere features the PCN pincer ligand (4-Cl-C6H4N3)C(dppm) and a monodentate dppm  are created by using benzyl azide, rather than 1-azido-4-chlorobenzene, under an inert atmosphere.In this contribution, we describe the fragmentation of a triazene into diazo and nitrene parts in the coordination sphere of iridium. Recently, we reported on the synthesis of Cl (2) with hydroiodic acid. It is apparent that a rupture of the N1—N2 bond (numbering as in the structure of 4) of (BnN3)C(dppm) occurred again, resulting in the formation of a diazomethylenephosphorane (dppm)C(N2) and a benzylnitrene part. However, in this case, the diazo functionality remains unchanged, since in contrast to the formation of 3, no free phosphine functionality is available. The benzylnitrene unit again undergoes a 1,2-hydride shift and, as a benzaldimine, coordinates to the Ir metal center.In a related fragmentation reaction, compound 2) moiety contains a central divalent carbon 2)(N2), X = Cl, Br, were obtained by addition of CX4 to P((NMe2)2)(CH(N2)) C ring and one five-membered IrC(dppm) ring. A benzaldimine ligand is positioned trans to the phosphorus donor of the five-membered ring, the remaining two coordination sites being occupied by chlorido ligands cis to each other. The deviations of the angles C1—Ir1—Cl1 = 170.06 (13)° and N3—Ir1—P1 = 169.02 (11)° from a regular octahedral geometry indicate some strain in the pincer system. Both the N1—C1 bond length [1.280 (5) Å] and the N1—N2 bond length [1.445 (5) Å] are typical for a C=N double bond and an N—N single bond, respectively. The P3—N2 bond length [1.586 (4) Å] is in the range of P=N double bonds observed for iminophosphoranes  Å] and a previously reported iridium benzaldimine complex [1.260 (6) Å] involving a phosphorus donor atom trans to the benzaldimine nitrogen donor  Å, D—H⋯A 138 (4)°], while other intramolecular interactions involve atoms N1 and Cl1 and the various phenyl rings , which forms a five-membered chelate ring via one C and one P donor atom. A four-membered ring is formed by a bidentate dppm ligand and is oriented perpendicular to the plane of the five-membered ring with one phosphorus donor trans to the carbon donor of the five-membered ring. The benzaldimine ligand is located trans to the phosphorus donor of the five-membered ring, the sixth coordination site is occupied by an iodido ligand. Deviations from the octahedral symmetry around the Ir center are mainly due to the strained four-membered ring [P4—Ir1—P3 = 70.80 (5)°] with consequences for the bond angles P4—Ir1–I1 [165.12 (4)°] and C1—Ir1—P3 [170.90 (17)°]. The C1—Ir1—P1 bond angle of the five-membered ring is 84.37 (17)°. The environment around the ylidic carbon C1 is trigonal planar, with the bond angle N3—C1—P2 exhibiting the largest deviation from a regular symmetry [114.8 (5)°]. Both the N3—N2 [1.095 (9) Å] and the N3—C1 [1.305 (9) Å] bond lengths are slightly shorter, compared to the corresponding mean values of ten previously reported structures of diazo compounds 2  and [CH(dppm)2]Cl , dissolved in acetone (0.6 ml) and stirred for 3 h. The resulting white precipitate of [IrCl2H(C(dppm)2)]  were added. After stirring for 1 min, the deep-purple solution was stirred for 2 h under atmospheric conditions, resulting in the slow precipitation of a white product. Colourless to pale-yellow prismatic crystals of 3 were obtained by allowing the purple intermediate solution to stand overnight under ambient conditions.31P{1H}-NMR (CHCl3/MeOH 1:1): δ = 0.7 ; 16.9 ; 6.9 ; −43.1  ppm. 13C{1H}-NMR (CHCl3/MeOH 1:1): δ =157.9  ppm.Synthesis and crystallization of complex 4: Under an inert atmosphere, a mixture of [IrCl(cod)]2 , [CH(dppm)2]Cl   were added. After heating to 333 K for 15 min, the volatiles were removed in vacuo. The residue was dissolved in CH2Cl2 and hydroiodic acid  was added whilst stirring. The orange–brown precipitate that formed slowly was separated, washed with water and dried in vacuo. A solution of the residue in CH2Cl2/MeOH 2:1 (0.6 ml) quantitatively contained an unidentified intermediate, which transformed to the product within 1 h. Red prismatic crystals of 4 formed within a few hours, when a solution of the intermediate in CH2Cl2/MeOH (5:1) was kept at 254 K for 24 h and subsequently warmed to room temperature.31P{1H}-NMR (CH2Cl2/MeOH 2:1): δ = −15.8 ; 37.8 ; −72.1 ; −62.8  ppm. 13C{1H}-NMR (CH2Cl2/MeOH 2:1): δ = −3.0  ppm.3 are severely disordered in position and occupation. At least 5.5 molecules in the asymmetric units were refined. Occupation values were varied to give a reasonable isotropic displacement factor. All C- and N-atoms of solvent molecules were refined isotropically with bond restraints, the hydrogen atoms were omitted. The proton on N3 was freely refined.Crystal data, data collection and structure refinement details are summarized in Table 44 was found and refined with a bond restraint of 0.87 (2) Å. The I3− anion (I4–I6) is positionally disordered (ratio roughly 1:1), as is the I− anion with a ratio I2:I2A of 9:1. The dichloromethane solvent molecule lies near a twofold rotation axis (disorder) and was refined with an occupancy of 0.5. Another disorder occurs for the solvent methanol with a ratio of 1:1. The C and O atoms of methanol were refined isotropically with bond restraints of 1.40 Å. The hydrogen atoms of methanol were calculated, those of dichloromethane omitted. All other H atoms were positioned geometrically (C—H = 0.94–0.98 Å) and refined as riding with Uiso(H) = 1.2-1.5 Ueq(C).The hydrogen atom at N1 of 10.1107/S2056989019000136/su5470sup1.cifCrystal structure: contains datablock(s) global, 3, 4. DOI: 10.1107/S2056989019000136/su54703sup2.hklStructure factors: contains datablock(s) 3. DOI: 10.1107/S2056989019000136/su54704sup3.hklStructure factors: contains datablock(s) 4. DOI: 1885936, 1885935CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II complex, the axial positions are occupied by a nitrogen atom from the ligand and an oxygen atom from the sulfate anion, whereas in the CdII complex they contain two nitrogen atoms from two different ligands and the sulfate anion only serves as the charge-balancing ion. π–π stacking between pyridine rings plays a crucial role in the molecular self-assembly of the two structures.The title compounds both contain a central metal atom in a distorted octahedral geometry coordinated equatorially by four oxygen atoms from water molecules. In the Mn N,N′-bis(pyridin-4-yl)pyridine-2,6-dicarboxamide]sulfatomanganese(II) dihydrate, [Mn(SO4)(C17H13N5O2)(H2O)4]·2H2O or [Mn(H2L1)(SO4)(H2O)4]·2H2O, (I), and tetraaquabiscadmium(II) sulfate tetrahydrate, [Cd(C17H13N5O2)2(H2O)4]SO4·4H2O or [Cd(H2O)4(H2L1)2]·SO4·4H2O, (II), both contain a central metal atom in a distorted octahedral geometry coordinated equatorially by four oxygen atoms from water molecules. In (I), the axial positions are occupied by a nitrogen atom from H2L1 and an oxygen atom from the sulfate anion, whereas in (II), the axial positions contain two nitrogen atoms from two different H2L1 ligands and the sulfate anion acts as the charge-balancing ion. π–π stacking between pyridine rings and a network of hydrogen bonds involving the water molecules and the sulfate anions play a crucial role in the molecular self-assembly of the two structures.The molecular structures of tetraaqua[ This bonding feature, when combined with the flexibility and length of molecular backbone within these ligands, can lead to the construction of porous coordination compounds -1H-1,2,3-triazol-1-yl] acetic acid (SO4)(H2O)4]·2H2O, (I)2L1)2(H2O)4]SO4·4H2O, (II)N,N′-bis(pyridin-4-yl)pyridine-2,6-dicarboxamide (H2L1) as the heterocyclic nitrogen ligand.In recent years, the design of metal–organic complexes constructed from heterocyclic nitrogen-derivative ligands has witnessed an upsurge in interest due to their fascinating structures and potential applications in luminescence, catalysis, gas storage and separation (Perry 2L1) acts as a monodentate ligand. The results indicate that the rational design and selection of ligands with heterocyclic nitrogen systems is an effective synthetic strategy to construct complexes via self-assembly. The asymmetry of the [N,N′-bis(pyridin-4-yl)pyridine-2,6-dicarboxamide ligand has resulted in some novel structures PII ion exhibits an octahedral geometry, arising from coordination to five water and one sulfate oxygen atoms  and to one nitrogen (N1) atom of a pyridine group of the H2L1 ligand (Table 1II ion vary from 85.79 (7) to 177.74 (6)°. Intramolecular O4—H4⋯O8, N2—H20⋯N5 and N3—H24⋯N5 hydrogen bonds are also present (Table 3The mononuclear complex (I)d Table 1. The Mn—t Table 3.4·H2O is replaced by CdSO4·8/3H2O, complex (II)C2/c. As illustrated in Fig. 2II also shows an octahedral environment coordinating four oxygen atoms from four water molecules and two axial nitrogen atoms from two symmetry-related H2L1 ligands (Table 2II cation lie in the range 82.63 (14) to 175.09 (10)°. Intramolecular N2—H2B⋯N3 and N4—H4B⋯N3 hydrogen bonds are also present (Table 4When MnSOs Table 2. In contt Table 4.2L1) acts as a monodentate ligand. The results indicate that the rational design and selection of ligands with heterocyclic nitrogen systems is an effective synthetic strategy to construct complexes via self-assembly. The asymmetry of the [N,N′-bis(pyridin-4-yl)pyridine-2,6-dicarboxamide ligand has resulted in some novel structures. Further study is ongoing.In complexes (I)2L1 ligands play a crucial role in molecular self-assembly, with centroid-to-centroid separations of 3.5808 (13) and 3.6269 (14) Å. In addition, a number of O—H⋯N and O—H⋯O hydrogen-bonding interactions (Table 3In (I)s Table 3 connect s Table 3.via O—H⋯N and O—H⋯O hydrogen-bonding interactions (Table 42L1 ligand are important in molecular self-assembly.Complex (II)s Table 4. In (II)et al., 20162L1 skeleton. These include the methyl pyridinium compound of H2L1  was prepared using a modified literature procedure  in N,N′-dimethylformamide solution (4 mL) was gradually added to MnSO4.H2O  in a mixed solution . After standing for 5 min, the suspension was filtered and the filtrate was kept at room temperature in the dark. One week later, colourless single crystals suitable for X-ray diffraction were obtained. Complex (II)4.8/3H2O  was used instead of MnSO4.H2O.The heterocyclic nitrogen ligand (HUiso(H) = 1.2–1.5Ueq(C/N/O).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989018007351/cq2024sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989018007351/cq2024Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018007351/cq2024IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1822492, 1822490CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Two chalcones were synthesized in Claisen–Schmidt condensation reactions. In the crystals, π–π interactions and weak C—H⋯O and C—H⋯π interactions are observed. The effect of these intermolecular interactions in the solid state can be seen inthe difference between the experimental and theoretical optimized geometrical parameters. 31H23NO and C35H23NO, were synthesized via Claisen–Schmidt condensation reactions. Both structures were solved and refined using single-crystal X-ray diffraction data and optimized at the ground state using the density functional theory (DFT) method with the B3LYP/6-311++G level. In the crystals, π–π interations and weak C—H⋯O and C—H⋯π interactions are observed. The effect of these intermolecular interactions in the solid state can be seen by the difference between the experimental and theoretical optimized geometrical parameters. The structures have also been characterized by UV–Vis spectroscopy. The smallest energy gaps of 2.86 and 2.96 eV enhance the nonlinear responses of such molecular systems. Hirshfeld surface analyses and 2D  fingerprint plots were used to quantify the intermolecular interactions present in the crystal, indicating that these are the most important contribution to the crystal packing.The title chalcones, C Additionally, the UV–vis absorption and Hirshfeld surface analyses are discussed.Chalcones satisfy the criteria of three features essential for high nonlinear activity in an organic compound, which are: a strong electron donor, a highly polarizable π-conjugated bridge and a strong π-electron acceptor. A chalcone molecule with a π-conjugated system provides a large charge-transfer axis with appropriate substituent groups on the terminal aromatic rings. Polyaromatic hydrocarbons or π-conjugated materials such as anthracenyl chalcone provide the significant property for conductivity that led to tremendous advances in the field of organic electronics . The C—C distances in the central ring of the anthracene units show a little variations compared to the other rings , which are much shorter. These observations are consistent with an electronic structure for the anthracene units where a central ring displaying aromatic delocalization is flanked by two isolated diene units  Å and DFT = 1.22 Å in I; Exp = 1.213 (3) (A) and 1.218 (3) Å (B), and DFT = 1.22 Å in II] and C16=C17 . Both I and II (A and B) are twisted at the C14—C15 bond, with C1—C14—C15—C16 torsion angles of −92.6 (2) (in I), 84.8 (3) (in IIA) and 106.3 (3)° (in IIB). The corresponding torsion angles for DFT are −85.84 and 85.63°, respectively. Additionally, in compound II, rings Y and Z (A) and rings Y′ and Z′ (B) are also twisted at the C21—N1 bond, with C20—C21—N1—C24 torsion angles of Exp = 64.1 (4)° (A) and 46.2 (4)° (B), and DFT = 55.03°. The large twist angles are due to the bulkiness of the strong electron-donor anthracene ring system and substituent ring system ° and DFT = −1.38 for compound I, and Exp = −171.2 (3)° (A) and 11.4 (5)° (B), and DFT = −1.70° for compound II. The slight differences in the torsion angles between the experimental and DFT results in both compounds are due to the formation of intermolecular C—H⋯O and C—H⋯π interactions involving all the fused-ring systems, which are not taken into consideration during the optimization process  Å at atom C16] makes dihedral angles of 86.93 (19) and 21.21 (19)° with the anthracene ring [maximum deviation = 0.0117 (19) Å at C9] and ring X [maximum deviation = 0.0363 (18) Å at C29], respectively. In compound II, the enone moiety  for molecule A forms dihedral angles of 84.76 (17), 87.61 (17) and 72.35 (17)° with the anthracene ring [maximum deviation = 0.029 (3) Å at C14A], ring Y [maximum deviation = 0.008 (3) Å at C19A] and ring Z [maximum deviation = 0.043 (3) Å at C34A], respectively. The anthracene ring forms dihedral angles of 89.63 (11) and 62.11 (7)° with rings Y and Z, respectively, and the dihedral angle between rings Y and Z is 61.73 (10)°. In addition, for molecule B, the enone moiety  forms dihedral angles of 72.2 (3), 13.5 (3) and 87.2 (3)° with the anthracene ring [maximum deviation = 0.018 (4) Å at C10B], ring Y′ [maximum deviation = 0.010 (3) Å at C20B] and ring Z′ [maximum deviation = 1.441 (2) Å at N1B], respectively. The anthracene ring forms dihedral angles of 61.46 (11) and 54.80 (7)° with rings Y′ and Z′, respectively, and the dihedral angle between rings Y′ and Z′ is 48.92 (11)°.The enone moiety in I shows weak π–π interactions  involving Cg1⋯Cg5 = 3.7267 (11) Å , Cg2⋯Cg4 = 3.6669 (12) Å , Cg3⋯Cg3 = 3.6585 (11) Å  and Cg4⋯Cg4 = 3.6790 (12) Å , where Cg1, Cg2, Cg3, Cg4 and Cg5 are the centroids of rings N1/C20/C21/C26/C27, C1–C6, C1/C6–C8/C13/C14, C8–C13, C18–C20/C27-C29, respectively. The packing is further linked into an infinite three-dimensional supramolecular network.The crystal packing of ns Fig. 2a involvII  shows weak C12B—H12B⋯O1 intermolecular hydrogen bonds connecting the molecules into an infinite one-dimensional chain along the c axis. In addition, weak intermolecular C5B—H5BA⋯Cg6, C27B—H27B⋯Cg7, C28B—H28B⋯Cg8, C11A—H11A⋯Cg9 and C7B—H7B⋯Cg10 interactions are also observed in the crystal packing and further stabilize the crystal structure, where Cg6, Cg7, Cg8, Cg9 and Cg10 are the centroids of rings N1A/C24A/C29A/C30A/C35A, C1A–C6A, C1A/C6A–C8A/C13A/C14A, C18A–C23A and C24A–C29A, respectively. These weak intermolecular C—H⋯O and C—H⋯π interactions bridge the molecules into an infinite one-dimensional column along the c axis.Lists of weak hydrogen-bond intermolecular interactions are shown in Table 1II Fig. 1b shows I and II have been calculated using time-dependent DFT at the B3LYP/6-311++G level in the gas phase and give values of 396 (I) and 383 nm (II). The absorption characteristics of I and II are observed in the UV region at 393 and 388 nm, as shown in Fig. 3et al., 2017The electronic absorption spectra of I and II, respectively. Through an extrapolation of the linear trend observed in the optical spectra, the experimental energy band gaps in I and II are 2.86 and 2.96 eV, respectively. These optical band-gap values indicate the suitability of this compound for optoelectronic applications, as was also reported previously for a chalcone structure by Tejkiran et al.  energy levels of the title compounds, the corresponding electronic transfer are found to happen between the HOMO and LUMO orbitals, as shown in Fig. 4 al. 2016. In addi al. 2016 studied CrystalExplorer  show the HS mapped over dnorm, where the red spots indicate the regions of donor–acceptor interactions. The C—H⋯O contacts are only present in compound II. In addition, the presence of C—H⋯π interactions only occurs in compound II, indicated through a combination of pale-orange bright-red spots which are present on the HS mapped over shape index surface, identified with black arrows . The large flat region delineated by a blue outline refers to the π–π stacking interactions. The curved nature of the compound reveals that π–π stacking interactions are present in compound I. Meanwhile, these interactions are absent in compound II.The program ws Fig. 5b. The lII. Meanwhile, there is no spike in the fingerprint of compound I. The 7.5% O⋯H contribution shown in compound I is the average percentage interaction from the total interactions presence in I. In compound I, there are no interactions other than the π–π interactions, which makes the percentage of the O⋯H contribution is slightly higher. Hence, a discussion on the percentage difference between I. and II. is invalid. The significant C—H⋯π interactions for compound II are indicated by the wings de + di ∼ 2.6 Å.The fingerprint plot shown in Fig. 6et al., 2016I and II. There are four compounds which have an anthrancene ketone subtituent on the chalcone, including 9-anthryl styryl ketone and 9,10-anthryl bis(styryl ketone) reported by Harlow et al. (1975E)-1-(Anthracen-9-yl)-3-[4-(propan-2-yl)phenyl]prop-2-en-1-one was reported by Girisha et al. (2016E)-1-(anthracen-9-yl)-3-(2-chloro-6-fluorophenyl)prop-2-en-1-one was reported by Abdullah et al. -1,3-bis(anthracen-9-yl)prop-2-en-1-one. Other related compounds include 1-(anthracen-9-yl)-2-methylprop-2-en-1-one -1-(anthracen-9-yl)-3-[4-(piperidin-1-yl)phenyl]prop-2-en-1-one and (E)-1-(anthracen-9-yl)-3-[4-(diphenylamino)phenyl]prop-2-en-1-one -1- al. 2016, while benzaldehyde (0.5 mmol) for compounds I and II, respectively, was dissolved in methanol (20 ml). A catalytic amount of NaOH  was added to the solution dropwise under vigorous stirring. The reaction mixture was stirred for about 5–6 h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50 ml). The resultant crude products were filtered, washed successively with distilled water and recrystallized from acetone to give the corresponding chalcones (Scheme 1). Single crystals of I and II suitable for X-ray diffraction were obtained by slow evaporation from acetone solutions.A mixture of 9-acetylanthrancene (0.5 mmol) and 9-ethylcarbazole-3-carbaldehyde (0.5 mmol) and 4- and refined using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(C). A rotating group model was applied to the methyl group in I.Crystal data collection and structure refinement details are summarized in Table 210.1107/S2056989018011131/lh5878sup1.cifCrystal structure: contains datablock(s) mo_DA20_0m, mo_DA21e_0m, global. DOI: 10.1107/S2056989018011131/lh5878mo_DA20_0msup2.hklStructure factors: contains datablock(s) mo_DA20_0m. DOI: Click here for additional data file.10.1107/S2056989018011131/lh5878mo_DA20_0msup4.cmlSupporting information file. DOI: 10.1107/S2056989018011131/lh5878mo_DA21e_0msup3.hklStructure factors: contains datablock(s) mo_DA21e_0m. DOI: 10.1107/S2056989018011131/lh5878sup5.pdfSupporting information file. DOI: 1827021, 1827019CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structures of two multidentate CMPO-containing organic ligands are described. Both compounds feature N—H⋯O hydrogen bonds in the solid state. 36H34N2O4P2, (I), and diethyl [({2-[2-(diethoxyphosphinoyl)ethanamido]ethyl}carbamoyl)methyl]phosphonate, C14H30N2O8P2, (II), were synthesized via nucleophilic acyl substitution reactions between an ester and a primary amine. Hydrogen-bonding interactions are present in both crystals, but these interactions are intramolecular in the case of compound (I) and intermolecular in compound (II). Intramolecular π–π stacking interactions are also present in the crystal of compound (I) with a centroid–centroid distance of 3.9479 (12) Å and a dihedral angle of 9.56 (12)°. Intermolecular C—H⋯π interactions  give rise to supramolecular sheets that lie in the ab plane. Key geometric features for compound (I) involve a nearly planar, trans-amide group with a C—N—C—C torsion angle of 169.12 (17)°, and a torsion angle of −108.39 (15)° between the phosphine oxide phosphorus atom and the amide nitrogen atom. For compound (II), the electron density corresponding to the phosphoryl group was disordered, and was modeled as two parts with a 0.7387 (19):0.2613 (19) occupancy ratio. Compound (II) also boasts a trans-amide group that approaches planarity with a C—N—C—C torsion angle of −176.50 (16)°. The hydrogen bonds in this structure are intermolecular, with a D⋯A distance of 2.883 (2) Å and a D—H⋯A angle of 175.0 (18)° between the amide hydrogen atom and the P=O oxygen atom. These non-covalent interactions create ribbons that run along the b-axis direction.Two bis-carbamoylmethylphosphine oxide compounds, namely {[(3-{[2-(diphenylphosphinoyl)ethanamido]methyl}benzyl)carbamoyl]methyl}diphenylphosphine oxide, C Many researchers have attempted to mimic this solution stoichiometry by tethering two, three or four CMPO groups together via an organic scaffold 1H, 13C, and 31P NMR spectroscopy, and by X-ray crystallography.The carbamoylmethylphosphine oxide (CMPO) moiety has found use as the chelating portion of a ligand in the TRUEX process for the remediation of nuclear waste 4 descriptor for fourfold coordination around the phosphorus atom P1 is 0.95, indicating a nearly perfect tetrahedral geometry of the phosphine oxide group °, and is staggered with respect to the plane of the C4–C7 aromatic ring with a H1—N1—C3—C4 torsion angle of 59.1 (17)°.The structure of compound (I)x + 1, y, −z + D⋯A distance of 2.940 (2) Å and a D—H⋯A angle of 168 (2)° )° Fig. 3. The C14Pbca. Since the molecule lies on an inversion center , the asymmetric unit comprises one half of the molecule. The electron density corresponding to the atoms of the phosphoryl group was disordered and was modeled over two positions with a 0.7387 (19):0.2613 (19) occupancy ratio (see the Refinement section for more details). The complete molecular structure of the major component of compound (II)4 descriptor for fourfold coordination around the phosphorus atom of the major component, P1, is 0.93, indicating that the geometry of the phosphoryl group is slightly distorted from an ideal tetrahedron. The geometry between the amide nitrogen atom N1 and the β-phosphoryl group phosphorus atom P1 is defined by a N1—C1—C2—P1 torsion angle of −111.8 (2)°. The amide group of this compound also adopts a nearly perfect trans geometry with a C3—N1—C1—C2 torsion angle of −176.50 (16)°.Compound (II)A  with a C⋯centroid distance of 3.622 (2) Å and a C—H⋯centroid angle of 146°. These non-covalent interactions create supramolecular sheets of compound (I)ab plane ne Fig. 4.x + y + z + 1; Fig. 5D⋯A distance of 2.883 (2) Å with a D—H⋯A angle of 175.0 (18)°. This hydrogen bond forms ribbons of compound (I)b-axis direction on Fig. 6.et al., 2016via an organic scaffold. The most similar structures to compound (I)et al., 2014et al., 2006via intermolecular C—H⋯π interactions. A structure closely related to compound (II)et al., 20023)3 has been reported in this journal  1,3-Bis(aminomethyl)benzene  and the p-nitrophenyl ester of diphenylphosphonoacetate  and the solution was stirred for 3.5 h. The organic layer was separated, washed with brine (3 × 10 mL), dried over solid magnesium sulfate and concentrated under reduced pressure. The crude product was triturated multiple times with ethyl acetate to give a white solid in 91% yield. X-ray quality crystals of compound (I)1H NMR : δ 7.91 , 7.7–7.3 , 7.1–6.8 , 4.24 , 3.36 ; 13C NMR : δ 164.7 , 138.3, 132.5, 131.9, 131.2–130.5 (broad), 129.5–128.3 (broad), 126.9–126.1 (broad), 43.5, 38.6; 31P NMR : δ 30.6.Compound (II) Ethylene diamine  was dissolved in 8.3 mL of methanol. The solution was cooled to 195 K, and triethyl phosphonoacetate  was added dropwise. The reaction mixture was allowed to warm to room temperature and stirred overnight. The product precipitated from the solution, was isolated by vacuum filtration and rinsed with ethyl acetate. Some of this solid was crystalline and suitable for analysis by X-ray diffraction. The remainder of the isolated product was purified by silica gel chromatography (10:1 dichloromethane–methanol) to give compound (II)1H NMR : δ 7.75 , 4.15 , 3.34 , 2.85 , 1.33 ; 13C NMR : δ 165.4, 62.9, 35.8 , 16.5; 31P NMR : δ 24.5.Uiso(H) = 1.2Ueq(C) for methylene groups and aromatic hydrogen atoms, and Uiso(H) = 1.5Ueq(C) for methyl groups. For both compounds (I)SHELXL  were treated with SAME and EADP commands to produce bond lengths and angles that agree with known values, and to ensure physically reasonable displacement parameters.Crystal data, data collection and structure refinement details for both compounds are summarized in Table 310.1107/S205698901900820X/pk2617sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S205698901900820X/pk2617Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900820X/pk2617Isup4.cmlSupporting information file. DOI: 10.1107/S205698901900820X/pk2617IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S205698901900820X/pk2617IIsup5.cmlSupporting information file. DOI: 1921486, 1921485CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal structure of the title compound, two half-molecules are found in the asymmetric unit. The completed molecules differ only slightly in bond lengths and torsion angles. 14H14N2S2, was obtained by transmetallation of 2,2′-bis(trimethylstannyl)azobenzene with methyl lithium, and subsequent quenching with dimethyl disulfide. The asymmetric unit comprises two half-molecules, the other halves being completed by inversion symmetry at the midpoint of the azo group. The two molecules show only slight differences with respect to N=N, S—N and aromatic C=C bonds or angles. Hirshfeld surface analysis reveals that except for one weak H⋯S interaction, intermolecular interactions are dominated by van der Waals forces only.The title compound, C Azobenzenes are common motifs in dyes because of their high thermal and photochemical stability 2, (I)The molecular switch azobenzene can undergo isomerization from its thermodynamically stable Ia and Ib), the other halves being completed by application of inversion symmetry. The midpoints of the N=N bonds are located on inversion centres, resulting in a trans-configuration for the central N=N bonds  −x, 1 − y, −z; (ii) 1 − x, 1 − y, 1 − z] torsion angles of 13.2 (2) and −5.3 (2)°, respectively, in both molecules the phenyl rings are twisted slightly with respect to the azo unit. A weak distortion is also found for the N1—C1—C2—S1 torsion angles of −3.06 (16)° for Ia and −2.06 (15)° for Ib. The N=N bond lengths differ marginally , as do comparable C—C bonds. For example, the C1—C2 bond in Ia is at 1.408 (2) Å slightly shorter than Ib [1.415 (2) Å]. In comparison, this bond is longer than all other C—C distances in the ring because of repulsion of the nitrogen and the sulfur atoms attached to C1 and C2, respectively. In both molecules, the S⋯N distances  are too long to be considered as attractive interactions. Fig. 2The asymmetric unit of the title compound consists of two half-molecules  = 3.7525 (8) Å with a slippage of 1.422 Å. To further investigate the intermolecular interactions, Hirshfeld surfaces  of another molecule of Ib (S⋯H distance = 2.811 Å). The two-dimensional fingerprint plots for molecule Ib for quantification of the contributions of each type of non-covalent interaction to the Hirshfeld surface azobenzene was recently described  was purchased from Acros Organics. THF was purchased from VWR and was dried and degassed with a solvent purification system by Inert Technology.The synthesis of 2,2′- al. 2015. Dimethy2,2′-bis(Methylthio)azobenzenebis(trimethylstannyl)azobenzene  was dissolved under Schlenk conditions in THF (12.5 ml) and cooled to 195 K. Then MeLi  was added within 5 min and after 1.5 h at this temperature, dimethyl disulfide  was added in one ration. The reaction mixture was warmed to 298 K over 14 h and the solvent was removed under reduced pressure. The obtained orange solid was purified in a silica column  with a gradient of eluents from n-pentane to dichloromethane giving dark-orange crystals . Single crystals suitable for X-ray analysis were obtained by slow evaporation from a saturated n-heptane solution.In an inert reaction tube, 2,2-1H NMR : δ = 7.76 , 7.40 , 7.32 , 7.20 , 2.53  ppm.13C{1H} NMR : δ = 149.08 (C1), 141.00 (C2), 131.56 (C4), 124.81 (C3), 124.75 (C5), 118.02 (C6), 15.02 (C7) ppm.HRMS : m/z: calculated for C14H14N2S2+ 274.05929 found 274.05944.MS (EI): m/z 273.9 (5%) [M]+, 258.9 (100%) [M − CH3]+, 243.9 (5%) [M − C2H6]+, 107.9 (13%) [M − C8H10N2S]+.IR (ATR): ν = 3059 (w), 2986 (w), 2961 (w), 2918 (w), 2852 (w), 1575 (m), 1561 (w), 1457 (m), 1433 (s), 1298 (w), 1249 (w), 1217 (m), 1162 (m), 1065 (s), 1035 (m), 951 (m), 863 (w), 803 (w), 761 (s), 726 (s), 674 (s) cm−1.M.p.: 429 KRf: (n-pentane: dichloromethane 3:1): 0.55.Uiso(H) = 1.5Ueq (C-methyl) and 1.2Ueq(C) (C-phenyl).Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2056989019014592/wm5522sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019014592/wm5522Isup2.hklStructure factors: contains datablock(s) I. DOI: 1961741, 1961741CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N′,N′′′--{[methylenebis(oxy)]bis}bis(methaneylylidene))bis(isonicotinohydrazide) dihydrate, (I), and N′,N′′′--{bis}bis(methaneylylidene))bis(isonicotinohydrazide), (II), both crystallized with half a molecule in the asymmetric unit. The whole molecule of (I) is generated by twofold rotation symmetry, with the twofold rotation axis bisecting the C atom of the –O—CH2—O– bridge. The whole molecule of (II) is generated by inversion symmetry, with the central CH2—CH2 bond of the –O—(CH2)4—O– bridge being located about a center of inversion.The title compounds,  27H20Br2N6O4·2H2O, (I), and C30H28N6O4·[+ solvent], (II), both crystallize with one half-molecule in the asymmetric unit. The whole molecule of (I) is generated by twofold rotation symmetry, with the twofold rotation axis bisecting the C atom of the –O—CH2—O– bridge. This results in a folded or U-shaped conformation of the molecule. The whole molecule of (II) is generated by inversion symmetry, with the central CH2—CH2 bond of the –O—(CH2)4—O– bridge being located about a center of inversion. This results in a step-like conformation of the molecule. The central C(=O)N—N=C regions of the isonicotinohydrazide moieties in both compounds are planar and the configuration about the imine C=N bonds is E. In compound (I), the benzene and pyridine rings are inclined to each other by 37.60 (6)°. The two symmetry-related pyridine rings are inclined to each other by 74.24 (6)°, and the two symmetry-related benzene rings by 7.69 (6)°. In compound (II), the benzene and pyridine rings are inclined to each other by 25.56 (11)°. The symmetry-related pyridine rings are parallel, as are the two symmetry-related benzene rings. In the crystal of (I), a pair of water molecules link the organic molecules via Owater—H⋯O and Owater—H⋯N hydrogen bonds, forming chains along [001], and enclosing an R42(8) and two R12(5) ring motifs. The chains are linked by N—H⋯Npyridine hydrogen bonds, forming a supramolecular framework. There are also a number of C—H⋯O hydrogen bonds, and C—H⋯π and offset π–π interactions [interplanar distance = 3.294 (1) Å] present reinforcing the framework. In the crystal of (II), molecules are linked by N—H⋯Npyridine hydrogen bonds, forming a supramolecular framework. Here too there are also a number of C—H⋯O hydrogen bonds present, and a C—H⋯π interaction, reinforcing the framework. For compound (II), a region of disordered electron density was corrected for using the SQUEEZE [Spek (2015PLATON. Their formula mass and unit-cell characteristics were not taken into account during refinement.The title compounds, CSpek 2015. Acta Cr The C6—N2 and C7=N3 bond lengths differ by 0.068 (2) Å in (I)et al., 2013et al., 2013et al., 2010The bond lengths and angles in the carbohydrazide group of the title compounds can be compared with the values reported for related structures  Å] present, reinforcing the framework  is 3.766 (1) Å, α = 0.00 (6)°, β = 29°, interplanar distance = 3.294 (1) Å, offset of 1.824 Å.In the crystal of (I)s Table 3. The chak Table 3. The offpyridine hydrogen bonds, forming a supramolecular framework k Table 4. Here tok Table 4, reinfor3 with an electron count of 357 per unit cell was corrected for using the SQUEEZE routine in PLATON et al., 2007CrystalExplorer17  through white to blue . The dnorm surface was mapped over a fixed colour scale of −0.512 (red) to 1.285 (blue) for compound (I)SQUEEZED out).The Hirshfeld surfaces of compounds (I)b), O⋯H/H⋯O at 13.8% , N⋯H/H⋯N at 11.3% , Br⋯H/H⋯Br at 14.3%  and C⋯H/H⋯C contacts at 13.6% . C⋯C contacts account for 8.4%, while C⋯Br are 3.0%, C⋯N are 3.0%, and finally C⋯O contacts amount to 1.4%.The fingerprint plots are given in Figs. 98% Fig. 9c, N⋯H/H3% Fig. 9d, Br⋯H/3% Fig. 9e and C⋯6% Fig. 9f. C⋯C cb), O⋯H/H⋯O at 13.3% , N⋯H/H⋯N at 16.2% , and C⋯H/H⋯C at 33.6% . The remaining contacts are extremely weak, ca 1% each.For compound (II)% Fig. 10c, N⋯H/H% Fig. 10d, and C% Fig. 10e. The ret al., 2016i.e. (3-OR-benzylidene)isonicotinohydrazide (R = C) skeleton gave 51 hits (supporting information file S1). The majority of these compounds were with an OMe or an OEt substituent.A search of the Cambridge Structural Database isonicotinohydrazide (R = C) skeleton gave 23 hits (supporting information file S2). Again, the majority of these compounds have an OMe or an OEt substituent. However, here the most interesting and relevant compound concerns the ligand N′,N′′-bis(pyridine-4-carbohydrazide), in which a 1,2-dioxyethane bridge links two N′-benzylideneisonicotinohydrazide units. The crystal structures of two polymorphs have been described: a monoclinic P21 polymorph that crystallizes as a methanol disolvate ] bis(pyridine-4-carbohydrazide)})tetrakis(iodo)dimercury methanol disolvate , in a 250 ml round-bottom (RB) flask was added DMF (30 ml) and potassium carbonate (12.5 mmol). The mixture was stirred at room temperature and then 1,1-diiodobutane (2.5 mmol) was added dropwise and the reaction mixture was stirred for 12 h. It was then partitioned between water and ethyl acetate. The ethyl acetate layer was collected and concentrated under reduced pressure. To 1,4-bisbutane (2 mmol) and isonicotinic acid hydrazide (4 mmol) in a 250 ml RB flask was added 100 ml of methanol and two drops of glacial acetic acid. The reaction mixture was stirred at room temperature and within 5 min a white-coloured product had formed. The reaction was continued for a further 30 min. The title compound was isolated by filtration and washed with methanol, then chloroform and followed by acetone. The final product was recrystallized using DMSO and yielded colourless block-like crystals of compound (I)Compound I: To 5-bromo-2-hydroxybenzaldehyde (5 mmol), in a 250 ml RB flask, was added 50 ml of DMF and potassium carbonate (12.5 mmol). The mixture was stirred at room temperature and then 1,1-diiodomethane (2.5 mmol) was added dropwise. Then, the reaction mixture was stirred for 12 h. The product obtained was extracted in ethyl acetate medium. Methanol (100 ml) and two drops of glacial acetic acid were added to a mixture of 6,6′-[methylenebis(oxy)] bis (2 mmol) and isoniazid (4 mmol) in a 250 ml RB flask. The reaction mixture was stirred at room temperature and within 5 min a white-coloured product had formed and the reaction was continued for a further 30 min. The solid obtained was washed with methanol, then chloroform and followed by acetone. The final product was recrystallized using DMSO and yielded colourless block-like crystals of compound (II)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 53 with an electron count of 357 per unit cell was corrected for using the SQUEEZE routine in PLATON 10.1107/S2056989019005048/su5495sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989019005048/su5495Isup4.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019005048/su5495IIsup5.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989019005048/su5495Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019005048/su5495IIsup5.cmlSupporting information file. DOI: 10.1107/S2056989019005048/su5495sup6.pdfCSD search S1. DOI: 10.1107/S2056989019005048/su5495sup7.pdfCSD Search S2. DOI: 1907912, 1907913CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III atoms in the title structure have distorted octahedral coordination spheres, being C,N-chelated by two main 2-phenylpyridine ligands and N,O-chelated by one ancillary 2-[methyl]phenolato ligand.The two Ir 11H8N)2(C15H14NO3)]·2CH2Cl2, consists of two complex molecules together with four dichloromethane solvent molecules, one of which is disordered. In each complex molecule, the IrIII ion has a distorted octahedral coordination environment defined by two 2-phenylpyridine ligands, through two phenyl C and two pyridine N atoms, and by one N,O-bidentate 2-[methyl]phenolate anion. The IrIII ions lie almost in the equatorial planes with deviations of 0.0396 (17) and 0.0237 (17) Å, respectively, for the two complex molecules. In both complex molecules, the two 2-phenylpyridine ligands are nearly perpendicular to each other [dihedral angles between the least-squares-planes of 89.91 (11) and 85.13 (11)°]. In the crystal, intermolecular C—H⋯O interactions as well as intermolecular C—H⋯π interactions are present, leading to a three-dimensional network structure. One of the four dichlormethane solvent molecules shows disorder over two sets of sites [occupancy ratio 0.79 (2):0.21 (2)].The asymmetric unit of the solvated title complex, [Ir(C The equatorial plane is formed by atoms O4/C49/C38/N6. The mean deviation from the least-squares plane is 0.055 Å and the Ir2III ion is displaced by 0.0237 (17) Å from the equatorial plane towards the axial N4 atom. The deviation from a perpendicular arrangement of the two 2-phenylpyridine ligands is slightly higher than in complex 1 [the dihedral angle between the least-squares planes is 85.13 (11)°], likewise the deviation from planarity with dihedral angles of 1.69 (13)° (between rings C49–C54 and N5–C59) and 3.36 (13)° (between rings C38–C43 and N4–C48), respectively.In complex molecule 2 (Ir2), a similar bonding situation is observed, with the phenyl C atoms C38 and C49 Cg1 and H50 with Cg2 .The configurations in both complexes are stabilised by intramolecular C—H⋯O interactions between the phenolic O1 and O4 atoms as acceptors and the phenyl C1—H1 and C48—H48 groups as donors Fig. 1, as welle.g. for {(E)-2-[methyl]phenolato-κ2N,O}bisiridium(III) -2-[(phenylimino)methyl]phenolato-κ2N,O}bisiridium(III) -2-[(phenylimino)methyl]phenolato-κ2N,O}bisiridium(III) , although the title compound is very similar to a previously reported compound  into a dichloromethane (5 mL) solution of the title compound  at room temperature.The title compound was prepared according to a reported procedure (Goo sp2—H and 0.99 Å for methylene C—H with Uiso(H) = 1.2Ueq(C); C—H = 0.98 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms. One of the four dichloromethane solvent molecules shows disorder over two sets of sites [occupancy ratio 0.79 (2):0.21 (2)].Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018009970/wm5449sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018009970/wm5449Isup2.hklStructure factors: contains datablock(s) I. DOI: 1846724CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III{C(dppm)2-κ3P,C,P′}ClH(NH3C2)]Cl with ethyl diazoacetate, a well known C=C coupling reagent, leads to the formation of a C=C unit, accompanied by N2 abstraction, and reorganization of a dppm subunit and, considered as a whole, to the transformation of the PCP pincer carbodiphosphorane system to a phosphorus ylide ligand. After removal of the halogenides, the iridium center is stabilized by the carbonyl O atom through the formation of a five-membered chelate ring. A PCO pincer ligand system is thereby generated, which coordinates the iridium(III) atom threefold in a facial manner. The addition of carbon monoxide causes a replacement of the carbonyl O atom of the acetate subunit by a carbonyl ligand.The reaction of Cl with ethyl diazoacetate, a well known C=C coupling reagent, leads to the formation of a C=C unit, accompanied by N2 abstraction, reorganization of a dppm subunit and, considered as a whole, to the transformation of the PCP pincer carbodiphosphorane system to a phosphorus ylide ligand. After removal of the halogenides, the iridium center is stabilized by the carbonyl O atom through the formation of a five-membered chelate ring. A PCO pincer ligand system is thereby generated, which coordinates the iridium(III) atom threefold in a facial manner. The phosphorus electron-donor atoms and the ylide carbon atom of the resulting (CF3O3S)2 complex, also termed as [bis(diphenylphosphanyl)methane]({[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methanylidene-κ3P,C,O)hydridoiridium(III) bis(trifluoromethanesulfonate), are in plane and the hydrido ligand and the carbonyl O atom are located trans to each other, perpendicular to the meridional plane. The addition of carbon monoxide causes a replacement of the carbonyl O atom of the acetate subunit by a carbonyl ligand, thereby creating [bis(diphenylphosphanyl)methane]carbonyl({[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methanylidene-κ2P,C}hydridoiridium(III) bis(trifluoromethanesulfonate)–dichloromethane–ethyl acetate (6/2/3) or, more simply, (CF3O3S)2·0.33CH2Cl2·0.5C4H8O2. One trifluoromethanesulfonate counter-ion of 3 shows positional disorder in a 2:1 ratio. Complex 4 shows pseudo-merohedral twinning (matrix: The reaction of [Ir Addition of ethyl diazoacetate (EDA) to Cl complex 1 (Scheme 1) leads to a carbon–carbon coupling reaction via extrusion of a dppm subunit, which is stabilized by two phosphorus–iridium(III) electron donor–acceptor interactions under the formation of a four-membered chelate ring. This reaction sequence, produced by the interaction of the doubly ylidic carbon atom with an electrophile containing the extraordinarily good dinitrogen withdrawing group, may be described as Wittig-type carbon–carbon coupling reaction, which has rarely been reported in carbodiphosphorane chemistry  units, the iridium(III) center coordinates a hydrido and a chlorido ligand trans to each other. Reaction of the monocationic Cl complex 2 with two equivalents of thallium(I)trifluoromethanesulfonate (TfOTl) causes the removal of the chlorido ligand and the chloride counter-ion with concomitant coordination of the acetate carbonyl oxygen atom in a facial manner, resulting in formation of the dicationic (CF3O3S)2 complex 3.Treatment of our PCP pincer ligand system [CH(dppm)et al. (CO)3(dppm)] complex at low temperature generates the corresponding vinylidene [MnI(C=CH—CO2Me)(CO)3(dppm)]BF4 complex, which rearranges via insertion of the vinylidene ligand into the manganese–phosphorus bond upon warming to room temperature to an [MnI{(dppm)C=CH(CO2Me)}(CO)3]BF4 complex. Exposure of complex 3 to carbon monoxide gas cleaves the iridium(III) carbonyl oxygen bond under coordination of a carbonyl ligand. Up to now, we have been unable to obtain suitable single crystals of complexes 1 and 2; however, it proved possible to crystallize the (CF3O3S)2 (3) and (CF3O3S)2 (4) products, the latter as a mixed dichloromethane–ethyl acetate solvate.A similar ligand arrangement in the coordination sphere of manganese(I) was previously mentioned by Ruiz  al. 2005. Protona3 reveal an orthorhombic crystal system in space group P212121  centre is coordinated in a facial mode by the PCO pincer ligand system via a phosphine functionality, an ylidic carbon atom and a carbonyl oxygen atom of the ester group. The coordination sphere of the iridium(III) atom is completed by one bidentate dppm and one hydrido ligand. Furthermore, all phosphorus atoms and the iridium atom are positioned in a common plane and the carbonyl oxygen atom as well as the hydride anion are located perpendicularly to this plane, trans to each other. The iridium center creates with its coordination sphere a distorted octahedral geometry and the deviations are caused by the presence of the strained four-membered dppm chelate ring [P3—Ir1—P4 = 70.2 (1)°] and the tridentate PCO ligand . A C1—C4 distance of 1.335 (9) Å indicates a double bond and the sum of angles of 358.3°  permits the designation of the C1 surroundings as a planar surface. The Ir1—O1 bond length of 2.239 (4) Å is close to the value [2.262 (4) Å] in the related [Ir(CO2CH3){C(CO2CH3)CH(CO2CH3)}(PPh3)(2-Ph2PC6H4NH)] complex  complex, which is stabilized by two trifluoromethanesulfonate counter-ions  metal atom shows a distorted octahedral geometry. It coordinates a dppm unit and a PCO pincer ligand system in a meridional manner and, perpendicular to this plane, a hydrido ligand. The only difference is that the carbonyl oxygen atom of the PCO ligand system is uncoordinated and has been substituted by a carbonyl ligand. The carbonyl ligand reveals relatively long Ir1—C8 [1.965 (15) Å] and C8—O3 [1.116 (14) Å] distances, caused by the location trans to the hydrido ligand. Moreover, the substitution results in an overall lengthening of the Ir—P and the Ir—C separations  and 3.473 (10) Å 2-Synthesis of Cl (1): A mixture of 0.1 ml MeCN, 20.4 mg of [CH(dppm)2]Cl (0.0250 mmol) and 8.4 mg of [IrCl(cod)]2 (0.0125 mmol) was stirred for 1 min. The resulting solution contains predominantly the well known Cl2 ]Cl complex 1. 31P {1H} NMR : δ = 1.5 , 31.5  p.p.m.; 13C {1H} NMR : δ = −28.9  p.p.m.; 1H NMR : δ = −21.3  p.p.m.4H6O2)(dppm)-Synthesis of [Ir{CH]Cl (2): While stirring the aforementioned MeCN solution of Cl2 and Cl (1), 0.26 ml of CHCl3 and 0.24 ml of a solution of ethyl diazoacetate in CHCl3  were added successively. The Cl2 by-product is slowly transformed to 1, which in turn reacts with ethyl diazoacetate. After standing for 24 h, product 2 was generated almost quantitatively. 31P {1H} NMR : δ = 26.5 , 45.7 , −52.5 , −36.7  p.p.m.; 13C {1H} NMR : δ = 139.2  p.p.m.; 1H NMR : δ = −17.7  p.p.m.4H6O2)(dppm)-Synthesis of [Ir{C2 (3):}(dppm)H] trifluoromethanesulfonate (0.0597 mmol) were dissolved in MeOH (0.1 ml) and added to a solution of complex 2 (0.025 mmol) in chloroform/acetonitrile (5:1). After stirring for 15 min the precipitated TlCl was separated, all solvents were removed and complex 3 was obtained . Single beige–white crystals of complex 3 were grown slowly from acetone (0.5 ml), covered with 0.3 ml of hexane. 31P {1H} NMR : δ = 9.1 , 36.0 , −44.2 , −33.1  p.p.m.; 13C {1H} NMR (CDCl3): δ = 181.4  p.p.m.; 1H NMR (CDCl3): δ = −23.3  p.p.m.4H6O2)(dppm)-Synthesis of [Ir{C2 (4):}(CO)(dppm)H](CF Complex 3 was dissolved in CHCl3 (0.6 ml), the mixture was filtered and the solution was placed in an atmosphere of CO. After standing for 16 h product 4 was formed and single crystals were obtained via layering of a solution of complex 4 dissolved in CH2Cl2 with EtOAc. 31P {1H} NMR (CHCl3/CH3OH): δ = 5.3 , 57.1 , −55.6 , −44. 7  p.p.m.; 13C {1H} NMR (CDCl3/CD3OD): δ = 134.8  p.p.m.; 1H NMR (CDCl3/CD3OD): δ = −8.8  p.p.m.3 and 4 were processed without absorption corrections. In relation to the structure determination of complex 3, the hydrido ligand was detected and refined isotropically. One trifluoromethanesulfonate counter-ion shows positional disorder in a 2:1 ratio, caused by an overlying of the C9, O16 and F16 positions. These positions were also refined isotropically. The structure determination of complex 4 resulted in the detection of pseudo-merohedral twinning  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S205698901801455X/hb7757sup1.cifCrystal structure: contains datablock(s) global, 3, 4. DOI: 10.1107/S205698901801455X/hb77573sup2.hklStructure factors: contains datablock(s) 3. DOI: 10.1107/S205698901801455X/hb77574sup4.hklStructure factors: contains datablock(s) 4. DOI: 1849369, 1849368CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


E configuration with respect to the C=N double bond. The benzene rings form a dihedral angle of 58.06 (9)°. In the crystal, the molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds into chains, which are further connected into a three-dimensional network by C—H⋯π interactions.The title Schiff base compound displays an  15H13BrN2O2, displays an E configuration with respect to the C=N double bond, which forms a dihedral angle of 58.06 (9)° with the benzene ring. In the crystal, the molecules are linked into chains parallel to the b axis by N—H⋯O and C—H⋯O hydrogen bonds, giving rise to rings with an R21(6) graph-set motif. The chains are further linked into a three-dimensional network by C—H⋯π interactions. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from C⋯H (33.2%), H⋯H (27.7%), Br⋯H/H⋯Br (14.2%) and O⋯H/H⋯O (13.6%) interactions. The title compound has also been characterized by frontier molecular orbital analysis.The title Schiff base compound, C Schiff bases are of great importance in the field of coordination chemistry because they are able to form stable complexes with metal ions -4-bromo-N′-(4-methoxybenzylidene)benzohydrazide is reported.Schiff bases are nitrogen-containing compounds that were first obtained by the condensation reactions of aromatic amines and aldehydes  Å] and C7=O2 [1.222 (3) Å] bond lengths confirm their double-bond character. The C7—N1, N1—N2 and C3—Br1 bond lengths are 1.354 (3), 1.379 (3) and 1.894 (3) Å, respectively. The central O2/C7/N1/N2 fragment is approximately planar (r.m.s. deviation 0.0141 Å) and forms dihedral angles of 32.5 (2) and 27.2 (2)° with the C1–C6 and C9–C14 rings, respectively. The dihedral angle formed by the aromatic rings is 58.06 (9)°.The asymmetric unit of the title compound Fig. 1 consistsb-axis direction by N1—H1N⋯O2 and C8—H8⋯O2 hydrogen-bonding interactions  acts as an electron donor and the LUMO  acts as an electron acceptor. If the energy gap is small then the molecule is highly polarizable and has high chemical reactivity. The energy levels were computed by the DFT-B3LYP/6-311G++ method benzohydrazide benzohydrazide benzohydrazide benzohydrazide methylene)benzohydrazide methylidenebenzohydrazine  of 4-bromobenzohydrazide (0.213 mg) and a hot ethanolic solution of 4-methoxybenzaldehyde (0.136 mg). The mixture was refluxed for 8 h, then it was cooled and kept at room temperature. The powder formed was recrystallized from DMSO. Colourless block-shaped crystals suitable for X-ray analysis were obtained after a few days on slow evaporation of the solvent.Uiso(H) = 1.2Ueq or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl H atoms. Three outliers  global, I, 1. DOI: 10.1107/S2056989018013373/rz5241Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018013373/rz5241Isup3.cmlSupporting information file. DOI: 1587248CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The coordination sphere of each Sn atom is best described as a distorted trigonal bipyramid. Each stannic ion in the complex is in a C2O2N environment. The two homologous parts of the doubly deprotonated ligand are located in trans positions with respect to the C—C bond of the oxalamide group. The oxalamide group exhibits an asymmetric coordination geometry, as seen by the slight difference between the C—O and C—N bond lengths. The three-dimensional network is a multilayer of complex molecules with no strong supramolecular interactions.The binuclear complex, [Sn The stannic units are connected by the doubly deprotonated ligand which play a bridging role in a trans conformation. Each stannic unit is coordinated to the ligand via an iminolate O atom, a phenolate O atom and an imine N atom. Each Sn atom is pentacoordinated. The Sn—C bond lengths [2.158 (3)–2.168 (3) Å] are slightly shorter than the values reported for complexes containing the [Sn(tBu)2]2+ unit  and 2.0979 (18) Å, respectively, for Sn1 and Sn2] are shorter than the Sn—Oiminolate bond lengths  (Table 1phenolate distances associated with the strong coordination [1.302 (3)–1.308 (3) Å] are longer than the C—Oiminolate bonds associated with the less strong coordination [1.283 (3)–1.288 (3) Å]. The coordination sphere SnNC2O2 for each of the two Sn atoms can be characterized by the trigonality parameter τ = (β − α)/60, with α and β being the two largest angles around Sn ° for Sn1 and 130.02 (12)° for Sn2] result in compression of the bond angles with the third atom which forms the equatorial plane with the two tert-butyl groups . The sum of the angles in the basal planes are, respectively, 359.99° for Sn1 and 359.94° for Sn2. The O atoms occupy the apical positions with comparable angles of 154.61 (7)° for Sn1 and 154.73 (7)° for Sn2. The angles between the apical O atoms and the atoms in the basal plane are in the range 72.35 (7)–97.12 (11)° for Sn1 and between 72.39 (6) and 96.48 (9)° for Sn2. The ligand, which acts in a tridentate fashion, forms two rings upon coordination with the tin centres, i.e. a five-membered OCNNSn ring and a six-membered OCCCNSn ring, sharing atom N1 for Sn1 and N4 for Sn2. The angles resulting from the five-membered ring [N1—Sn1—O2 = 72.35 (7)° and N4—Sn2—O3 = 72.39 (6)°] are much smaller than the angles resulting from the six-membered ring [N1—Sn1—O1 = 82.32 (8)° and N4—Sn2—O4 = 82.39 (7)°]. The better flexibility of the six-membered ring can explain this observed difference in values. The five- and six-membered rings obtained after coordination of the ligand are not planar, as indicated by the torsion angles for the two Sn atoms in the complex: Sn1—N1—N2—C8 0.6, Sn1—O2—C8—N2 0.5, Sn1—O1—C1—C6 6.3, Sn1—N1—C7—C6 − 2, Sn2—N4—N3—C9 2.1, Sn2—O3—C9—N3 − 1.2, Sn2—O4—C16—C11 − 3.7 and Sn2—N4—C10—C11 − 0.5°. For all four tBu groups, the angles around the central C atom (Sn—C—C and C—C—C) vary in the range from 106.0 (3) to 112.3 (4)° and indicate a tetrahedral environment around the central C atom. Both tBu groups reveal an eclipsed conformation regarding the methyl groups. The C—C bond lengths are in the range 1.81 (5)–1.542 (9) Å and are comparable to the values found in the literature  was added a solution of salicylaldehyde (2 mmol) in 10 ml of the same mixture. A white precipitate appeared and the resulting mixture was stirred at room temperature for 24 h. The suspension was filtered and the solid was washed with 2 × 10 ml of water and 2 × 10 ml of ether. The solid was recrystallized from a mixture of chloroform and methanol (1:1 v/v). The white powder collected was dried under P2O5. Yield 90% (H4L). Calculated for C16H14N4O4: C 58.89, H 4.32, N 17.17%; found: C 59.02, H 4.37, N 17.24%. IR (cm−1): 3277 (ν O—H), 1664 (ν C=O), 1601 (ν C=N), 1533, 1486, 1457, 1357, 1304, 1259, 1218, 1161 (ν C—O), 776, 673. 1H NMR: δ 12.6 , 11.00 , 8.85 , 7.6–7.00 . 13C NMR: δ 158.5, 156.8, 151.98, 148.00, 132.93, 130.27, 120.37, 119.54, 117.39. To a mixture of H4L (2 mmol) and triethylamine (4 mmol) in 10 ml of ethanol was added SnCl2tBu2 (2 mmol) in ethanol (10 ml). The resulting yellow mixture was stirred under reflux for 120 min and the resulting brown solution was filtered. The filtrate was kept at 298 K and after one week yellow crystals suitable for X-ray analysis appeared and were collected by filtration. Yield 40%, m.p. 243°C. Calculated for C32H46N4Sn2O4: C 48.77, H 5.88, N 7.11%; found: C 48.64, H 5.96, N 7.09%. IR (cm−1): 1609, 1537, 1516, 1468, 1441, 1367, 1310, 1275, 1198, 1167, 1150, 870, 771, 754. 1H NMR: δ 8.85 ; 7.13–6.69 ; 1.33 . 13C NMR: δ 168.80, 163.68, 135.85, 134.72, 122.22, 116.99, 41.53, 29.96.To a solution of oxalyldihydrazine (1 mmol) in a mixture of water and methanol (1:3 Uiso(H) = 1.2Ueq(C) (1.5 for CH3 groups).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018007077/ex2008sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018007077/ex2008Isup2.hklStructure factors: contains datablock(s) I. DOI: 1842349CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: