N,N‐bisamide pincer ligand (ONO3−) is explored. Despite their differing reactivity towards nucleophilic substrates with polarised element–hydrogen bonds , both the phosphorus(III), P(ONO) (1 a), and arsenic(III), As(ONO) (1 b), compounds exhibit similar reactivity towards charged nucleophiles and electrophiles. Reactions of 1 a and 1 b with KOtBu or KNPh2 afford anionic complexes in which the nucleophilic anion associates with the pnictogen centre ([(tBuO)Pn(ONO)]− (Pn=P (2 a), As (2 b)) and [(Ph2N)Pn(ONO)]− (Pn=P (3 a), As (3 b)). Compound 2 a can subsequently be reacted with a proton source or benzylbromide to afford the phosphorus(V) compounds (tBuO)HP(ONO) (4 a) and (tBuO)BzP(ONO) (5 a), respectively, whereas analogous arsenic(V) compounds are inaccessible. Electrophilic substrates, such as HOTf and MeOTf, preferentially associate with the nitrogen atom of the ligand backbone of both 1 a and 1 b, giving rise to cationic species that can be rationalised as either ammonium salts or as amine‐stabilised phosphenium or arsenium complexes ([Pn{ON(H)O}]+ (Pn=P (6 a), As (6 b)) and [Pn{ON(Me)O}]+ (Pn=P (7 a), As (7 b)). Reaction of 1 a with an acid bearing a nucleophilic counteranion (such as HCl) gives rise to a phosphorus(V) compound HPCl(ONO) (8 a), whereas the analogous reaction with 1 b results in the addition of HCl across one of the As−O bonds to afford ClAs{(H)ONO} (8 b). Functionalisation at both the pnictogen centre and the ligand backbone is also possible by reaction of 7 a/7 b with KOtBu, which affords the neutral species (tBuO)Pn{ON(Me)O} (Pn=P (9 a), As (9 b)). The ambiphilic reactivity of these geometrically constrained complexes allows some insight into the mechanism of reactivity of 1 a towards small molecules, such as ammonia and water.The ambiphilic nature of geometrically constrained Group 15 complexes bearing the  Over the last decade significant advances have been made in the development of main‐group species that are capable of activating small molecules.More recently, geometrically constrained compounds based on phosphorus(III) have also received significant attention in this field. Studies by Arduengo,N,N‐bisamide ligand (P(ONO); 1 a).1 a exclusively reacts with nucleophilic species with protic E−H bonds, whereas non‐nucleophilic substrates, even those with polar E−H bonds, such as phenylsilane, fail to react. These observations seemed to indicate that the nucleophilic association of the substrate is necessary prior to any further reactivity taking place. This prompted us to explore the reactivity of 1 a towards both nucleophiles and electrophiles in an effort to gain a better understanding of the reaction dynamics. These results, and analogous studies on the heavier arsenic(III) analogue (1 b), are reported herein.We recently reported a phosphorus(III) compound bearing the 1 a exhibits a bent geometry in the solid state with moderate pyramidalisation at both the phosphorus and nitrogen atoms (Σangles(P)=296.1°; Σangles(N)=331.6°), in contrast with planar compound A. Theoretical calculations at the density functional theory (DFT) level revealed that the pyramidal sC isomer (or electromorph to use the term coined by Arduengo) is the most stable, but relatively close in energy to the Cv2 symmetric species (within 4 kJ mol−1). This energetic difference is within the error of the calculations, and it is worth noting that different computational analyses  actually suggest that the planar structure is lower in energy than the sC isomer . Therefore, it is highly likely that, in solution, there is a dynamic, and concerted, pyramidal inversion at the phosphorus and nitrogen atoms resulting in a wing‐like "flapping" of the ligand backbone. The calculations also revealed that, regardless of the symmetry adopted by 1 a, there is an empty, energetically accessible orbital that is largely based on the phosphorus atom, which has anti‐bonding character with respect to the P−N and P−O bonds. It is also worth noting that the P−N bond in 1 a is significantly polarised, with computed Hirshfeld charges of 0.394 and −0.171 on the phosphorus and nitrogen atoms, respectively. These observations prompted us to explore the reactivity of 1 a, and its heavier arsenic analogue (1 b), towards nucleophiles in order to establish whether they associate with the phosphorus/arsenic atom.As previously reported, 1 b can be prepared following a similar synthetic methodology to that previously reported for its lighter congener. Reaction of the protonated ligand, N,N‐bisamine, H3ONO, with AsCl3 in the presence of three molar equivalents of triethylamine, affords 1 b quantitatively, as evidenced by 1H and 13C{1H} NMR spectroscopy. The 1H NMR spectrum of 1 b in C6D6 reveals two equal intensity aromatic resonances at 8.39 and 7.51 ppm as well as two singlets at 1.71 and 1.46 ppm arising from the tert‐butyl groups. Cooling of a concentrated pentane solution afforded bright red‐orange crystals of the compound in good to high yields.The arsenic‐containing species 1 b ) of 329.1°. The sum of bond angles around the nitrogen centre, 359.9°, is significantly greater than for the lighter phosphorus‐containing analogue (331.6°). The As−O bond lengths (1.933(4) and 1.933(4) Å) are slightly elongated when compared to the expected values for single bonds (1.84–1.85 Å).1 b are closely related to the planar 10‐As‐3 compound 5‐aza‐2,8‐dioxa‐l‐arsabicyclo[3.3.0]octa‐2,4,6‐triene previously reported by Arduengo and co‐workers (As−N: 1.839(3) Å; As−O: 1.955(3) and 1.998(3) Å; Σangles(As)=320.7°).1 b and that determined crystallographically. Interestingly, attempts to optimise the sC isomer of 1 b ultimately converge to the planar (Cv2) isomer, indicating that in contrast to its phosphorus‐containing analogue, the sC geometry of 1 b is not a minimum on the potential energy hypersurface.The structure of b Figure  exhibits1 a and 1 b was explored towards a number of nucleophilic species. In a preliminary report we demonstrated that 1 a reacts with nucleophiles with polarised element–hydrogen bonds (NH3 and H2O) to give rise to five coordinate phosphorus(V) compounds. By contrast, no reaction is observed between 1 b and ammonia, whereas hydrolysis does take place but gives rise to complex reaction mixtures and does not result in any arsenic(V)‐containing compounds. Our calculations reveal that this is largely a thermodynamic phenomenon. The reaction between NH3 and 1 a is exothermic by 90 kJ mol−1, whereas the same reaction between NH3 and 1 b is thermodynamically uphill by 86 kJ mol−1. This difference in reactivity can be attributed to the increased stabilisation of the “inert pair” on descending Group 15.The reactivity of 1 a or 1 b with neutral nucleophiles, such as pyridine or PPh3. In contrast, anionic nucleophiles do react with both compounds associating with the pnictogen centre. In a typical reaction, the geometrically constrained complexes were reacted with one equivalent of KNu (Nu=OtBu or NPh2) in the presence of a cation sequestering agent  or 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane ) to aid crystallisation. These reactions yielded the anionic complexes [(tBuO)Pn(ONO)]− (Pn=P (2 a) and As (2 b)) and [(Ph2N)Pn(ONO)]− (Pn=P (3 a) and As (3 b)) as pictured in Scheme No reaction is observed for either 1 a were monitored by 31P NMR spectroscopy and show quantitative conversion to the desired products, which were observed as singlet resonances at 85.5 and 66.3 ppm for 2 a and 3 a, respectively. These resonances are shifted upfield with respect to 1 a (168.6 ppm), due to the enhanced electron density on the phosphorus centre. Similarly the 1H NMR spectra of both compounds display the requisite number of resonances for a symmetrical N,N‐bisamide ligand backbone and for the nucleophilic substituents. Reactions involving 1 b similarly give rise to products in which both of the 3,5‐di‐tert‐butyl‐2‐phenolate arms of the ligand backbone are equivalent as evidenced by 1H and 13C{1H} NMR spectroscopy.Reactions involving 2 a), 0.0365 Å (2 b) 0.0019 Å (3 a) and 0.0150 Å (3 b)) with the nucleophile orthogonal to the Pn(ONO) core. The planarity of the ligand backbone is also evident in the sum of bond angles around the nitrogen atoms . These structures are consistent with lone‐pair donation from the nucleophile into the lowest unoccupied molecular orbital (LUMO) of 1 a and 2 a. DFT calculations reveal that the most significant atomic orbital contribution to this orbital comes from the pnictogen atom p orbital that is perpendicular to the plane of the molecule . The LUMO of 1 a and 2 a are also notably pπ–pπ antibonding with respect to the Pn−N and Pn−O bonds.The structures of all four novel anionic complexes were determined by single‐crystal X‐ray diffraction Figures  and 4. TN,N‐bisamide ligand. This significant weakening of the Pn−O bonds strongly suggests that on coordination of a nucleophile, the aryloxide functionalities are susceptible to electrophilic attack. This was probed by reacting 2 a and 2 b with a pyridinium trifluoromethanesulfonate and benzyl bromide (BzBr).Upon coordination of an anionic nucleophile there is a significant elongation of the Pn−O bonds while the Pn−N bonds remain very similar to those of the parent compound  or benzyl bromide afforded the trigonal bipyramidal compounds (tBuO)HP(ONO) (4 a) and (tBuO)BzP(ONO) (5 a), respectively  to the E−H activation products that were obtained by reaction of 1 a with H2O and NH3. In fact, compound 4 a can be readily accessed by direct reaction of 1 a with HOtBu. The reactions proceeded rapidly (before the 31P NMR spectra of the reaction mixtures were recorded) at room temperature affording the compounds in quantitative yields. Consequently, we were unable to ascertain whether electrophilic association of the proton or benzyl functionalities involved the ligand backbone prior to migration of the functional group to the phosphorus centre.Reactions of [K][OTf] (Pn=P (6 a), As (6 b)) and [Pn{ON(Me)O}][OTf] (Pn=P (7 a), As (7 b)) after heating or sonicating the mixtures .31P NMR spectra of the reactions involving 1 a reveal broad resonances, with evidence of weak or non‐existent P−H coupling, at 155.5 (2JP‐H=12 Hz) and 149.4 ppm for 6 a and 7 a, respectively (cf. 168.6 ppm for 1 a), indicating that the electrophilic groups do not associate directly with the phosphorus(III) centre. The 1H NMR spectra of all four compounds are consistent with two equivalent aryloxide functionalities, which suggest functionalisation at the amide nitrogen atom. The 1H NMR resonances for the proton‐ and methyl‐group‐functionalised nitrogen atoms were observed at 14.27 and 3.72 ppm for 6 a and 7 a, respectively. Similarly, reactions involving 1 b also reveal clean conversion to the products and the 1H NMR resonances of the electrophiles associated with the nitrogen atom were observed at 11.64 and 3.41 ppm for 6 b and 7 b, respectively.In a typical reaction, one molar equivalent of EOTf  was added to a solution of either 6 a an additional molecule of HOTf. The most striking aspect of the structures is that protonation/methylation has taken place at the nitrogen centre, as evidenced by NMR spectroscopy. All four complexes adopt a distorted tetrahedral geometry around the nitrogen atom and exhibit a significant elongation of the N‐Pn bonds (N−P: 1.926(2) and 1.955(2) Å for 6 a and 7 a, respectively; N‐As: 2.028(2) and 2.127(1) Å for 6 b and 7 b, respectively) relative to 1 a (1.757(1) Å) and 1 b (1.862(3) Å). The Pn−O bonds experience a moderate contraction on protonation/methylation in the case of the phosphorus containing compounds (0.03 Å), but a much more dramatic contraction (0.13 Å) for the arsenic analogues, which is linked to a change from the planar geometry of 1 b to the bent (sC) geometry of both 6 b and 7 b. This geometric change allows for the aryloxide substituents to get closer to the arsenic centre as the pseudo‐axial arrangement of the oxygen atoms in the 10‐Pn‐3 structure of 1 b is lost on functionalisation of the ligand backbone.The structures of all four novel cationic complexes were determined by single‐crystal X‐ray diffraction Figures  and 7. T6 a: 2.790(2) and 2.898(1) Å, 6 b: 2.745(2) Å, 7 a: 2.760(2) 7 b: 2.226(1) Å) indicating a significant degree of positive charge accumulating on the pnictogen centres on functionalisation of the ligand backbone. This is corroborated by DFT calculations which show a large Hirshfeld charges on the pnictogen atoms relative to nitrogen . Thus, all four complexes can be thought of as base‐stabilised phosphenium or arsenium ions. This bonding formulation has previously been proposed for related phosphorus‐containing compounds.Interestingly, all four species exhibit close contacts between the pnictogen(III) centre and trifluoromethanesulfonate anions (1 a reacts with HOTf to afford a phosphorus(III) compound with a protonated ligand backbone (6 a), the analogous reaction with an acid that has a more nucleophilic counter‐anion, such as HCl, affords the phosphorus(V) species HPCl(ONO) (8 a). This difference in reactivity suggests that mechanistically, a sufficiently strong nucleophile is required to afford the formal phosphorus(V) oxidative addition product. Reaction of 6 a with KOtBu, affords 4 a, suggesting that nucleophilic association of the anionic −OtBu moiety with the phosphorus centre induces proton migration from the ligand backbone. Similarly, reaction of 6 a with tetradodecylammonium chloride cleanly affords 8 a and the corresponding ammonium trifluoromethane sulfonate salt. Conversely, reactions of 8 a with one equivalent of trimethylsilyl trifluoromethane sulfonate show evidence for the formation of 6 a, although full conversion was not observed at room temperature with such stoichiometric loadings.It is interesting to note that while 1 b. This is borne out in the reactivity of 1 b towards HCl. Whereas 1 a reacts with HCl to afford 8 a, the reaction of 1 b with one molar equivalent of HCl results in the addition of the acid across one of the As−O bonds resulting in the arsenic(III) compound AsCl{(H)ONO} (8 b). This was evident from the 1H NMR spectra of these reaction mixtures which reveal the presence of two inequivalent arms of N,N‐bisamide pincer ligand on protonation.In the aforementioned studies we have established the relative inaccessibility of the arsenic(V) oxidation state for 8 a and 8 b were both determined by single‐crystal X‐ray diffraction  complexes we have studied to date, the structure of 8 b clearly shows a trigonal pyramidal arsenic(III) centre in which one of the tert‐butyl‐2‐phenolate ligand arms has been protonated and is consequently no longer coordinated to the arsenic centre. The bond metric data for 8 a are similar to the other phosphorus(V) compounds reported. The P−O bond lengths to the N,N‐bisamide ligand, 1.661(4) and 1.653(4) Å, are slightly shorter than those observed for the aforementioned phosphorus(V) compounds (4 a: 1.688(1) and 1.681(1); 5 a: 1.721(1) and 1.732(1) Å). The same is also true of the P−N interatomic distance which is 1.699(5) Å in 8 a, and 1.720(1) and 1.717(1) Å in 4 a and 5 a, respectively. The P−Cl bond length is 1.918(2) Å.The structures of 8 b reveals a trigonal pyramidal geometry about the arsenic(III) centre (Σangles(As)=284.8°; Σangles(N)=355.6°) with a relatively obtuse N1‐As1‐Cl1 angle due to the steric repulsion of the chloride with the free arm of the N,N‐bisamide ligand. The As−N and As−O distances, 1.839(2) and 1.783(2) Å, respectively, are notably shorter than those observed for 1 b (As−N: 1.862(3) and As−O: 1.933(4) Å), presumably due to the relaxation of steric strain and the loss of As−N multiple bond character on bending the ligand backbone. It is worth noting that the As−N bond in 8 b is still very short and indicative of some multiple bond character.The structure of 6 a with KOtBu result in the association of the tert‐butoxide anion with the phosphorus(III) centre and migration of the ligand proton to afford the phosphorus(V) product 4 a . The facility with which the proton of the ligand backbone migrates prompted us to carry out related studies with the methylated species 7 a and 7 b. We hypothesised that methyl migration would not occur and that, consequently novel complexes in which both the nitrogen atom of the N,N‐bisamide ligand, and the heavier pnictogen centers could be functionalised.As mentioned previously, reactions of 7 a or 7 b were treated with one molar equivalent of potassium tert‐butoxide. These reactions were found to quantitively afford novel complexes bearing a symmetrical ligand environment and an additional tert‐butoxide functionality , two resonances arising from the ligand tert‐butoxide groups and a doublet due to the methyl group of the ligand backbone. Comparable spectroscopic data were recorded for the arsenic‐containing analogue, 9 b, although this sample could not be isolated as a compositionally pure compound due to its relative instability and tendency to decompose.In a typical reaction, 9 a was characterised by single‐crystal X‐ray crystallography =285.2°; Σangles(N)=345.7°). That being said, the sum of bond angles around the nitrogen atom is strongly indicative of increased planarity, which we believe to arise due to the lone‐pair–lone‐pair repulsion arising between the nitrogen and phosphorus centres. The amine and phosphine like character of these centres is evident in the long P⋅⋅⋅N interatomic distance, 2.573(2) Å, which is notably longer than that observed for 6 a and 7 a, 1.926(2) and 1.955(2) Å, respectively, and is clearly indicative of the lack of a bonding interaction between the phosphorus and nitrogen centres. The P−O bonds range from 1.627(1) to 1.665(1) Å and are consistent with bond lengths reported for other phosphites.2‐hybridised carbon atom compared to an sp3‐hybridised species Δr=(0.03 Å).Compound 1 a) and As(ONO) (1 b) towards ionic nucleophiles and electrophiles. These studies show that anionic nucleophiles readily associate with the pnictogen(III) centres in both complexes, suggesting that such an association may play an important role in the mechanism for the bond activation of NH3 and H2O by 1 a. Our studies also reveal that while phosphorus(V) compounds are readily accessible by sequential reactions involving 1 a, the corresponding arsenic(V) compounds cannot be synthesised from the heavier analogue 1 b.We have explored the reactivity of the geometrically constrained Group 15 complexes P(ONO) (−). When a more nucleophilic counter‐anion is employed (such as Cl−) these reactions result in the generation of a phosphorus(V) compound by proton migration from the ligand backbone to the phosphorus centre. As with previous studies, the analogous arsenic(V) compound was found to be inaccessible.Reactions involving charged electrophilic substrates give rise to pnictogen(III) compounds in which the electrophile associates with the nitrogen atom of the ligand backbone. Interestingly, when the electrophile in question is a proton, it will associate with the nitrogen atom of the ligand backbone only in the presence of a weakly coordinating counteranion . 1H, 13C, 31P, 19F NMR spectra were recorded at room temperature using a Bruker AVIII 500 MHz or Bruker AVIII HD NanoBay 400 MHz NMR Spectrometer. 1H and 13C{1H} spectra are reported relative to tetramethylsilane (TMS) and were referenced to the most downfield residual solvent resonance (1H NMR spectroscopy: 7.26 ppm (CDCl3), 7.16 ppm (C6D6), 5.32 pm (CD2Cl2) and 3.58 ppm ([D8]THF); 13C{1H} NMR spectroscopy: 77.16 ppm (CDCl3), 128.06 ppm (C6D6), 53.84 ppm (CD2Cl2) and 67.21 ppm ([D8]THF)). 31P NMR chemical shifts were externally referenced to an 85 % solution of H3PO4 (aq). 19F NMR chemical shifts were externally referenced to CF3COOH. Elemental analyses were performed by Elemental analysis Ltd (Devon). EI/CI mass spectra were obtained on neat samples using a Waters GCT Time of Flight Mass Spectrometer with a temperature programmed solids probe inlet, or an Agilent 7200 Accurate‐Mass Q‐TOF GCMS with a SIM Direct Inlet probe. ESI mass spectra were obtained from DMF solutions using a Waters LCT time‐of‐flight mass spectrometer with a Z‐spray source .Solvents and reagents: Hexane , pentane  and toluene  were dried using an MBraun SPS‐800 solvent system, THF  was dried over a potassium metal/benzophenone mixture and pyridine was distilled from CaH2. C6D6  was dried and stored over activated 3 Å molecular sieves. CDCl3 , CD2Cl2  and [D8]THF  were each dried over CaH2 and stored over activated 3 Å molecular sieves. H3ONO and KNPh2 were synthesised according to a previously reported synthetic procedure.3  was distilled from CaH2 prior to use. AsCl3 , KOtBu , 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo‐hexacosane , [PyH][OTf] , HOTf , MeOTf , benzyl bromide  and HCl  were used as received.Synthesis of As(ONO) (1 b): H3ONO  was dissolved in toluene (10 mL). AsCl3  was added to the stirred solution followed by NEt3 , yielding a dark orange solution and white precipitate. The mixture was stirred at room temperature for 3 h. All volatiles were removed under a dynamic vacuum and the product was extracted in pentane (3×10 mL). Removal of volatiles in vacuo yielded 1 b as a dark orange solid. Crystals suitable for single‐crystal X‐ray diffraction analysis were grown from a concentrated pentane solution at −30 °C. Yield: 880 mg (75 %); elemental analysis calcd (%) for C28H40AsNO2: C 67.59, H 8.10, N 2.82; found: C 67.15, H 8.09, N 2.93; EI MS: m/z calcd for C28H40AsNO2: 497.2275; found: 497.2272; m/z calcd for C27H37AsNO2: 482.2040; found: 482.1898. 1H NMR : δ=8.39 , 7.51 , 1.71 , 1.46 ppm . 13C{1H} NMR : δ=154.0 (Ar), 142.3 (Ar), 137.2 (Ar), 135.9 (Ar), 119.9 (Ar), 111.3 (Ar), 35.7 (C(CH3)3), 35.1 (C(CH3)3), 32.0 (C(CH3)3), 30.0 ppm (C(CH3)3).tBuO)P(ONO)] ([K(18‐crown‐6)][2 a])Synthesis of [K(18‐crown‐6)] ([K(18‐crown‐6)][2 b])Synthesis of [K(18‐crown‐6)]−: 570.29; found: 569.64; m/z calcd C28H40AsNO3 513.22; found: 513.61; 1H NMR : δ=7.54 , 6.56 , 3.38 , 1.44 , 1.33 , 1.26 ppm . 13C{1H} NMR : δ=152.6 (Ar), 135.8 (Ar), 133.5 (Ar), 130.4 (Ar), 111.6 (Ar), 107.4 (Ar), 71.2 (OC(CH3)3), 70.8 (18‐crown‐6), 35.3 (C(CH3)3), 34.9 (C(CH3)3), 32.8 (C(CH3)3), 32.8 (OC(CH3)3), 30.4 ppm 3).2N)P(ONO)] ([K(18‐crown‐6)][3 a])Synthesis of [K(18‐crown‐6)][(Ph: A preparative synthesis of [K(18‐crown‐6)][3 a] was not possible due to extremely high sensitivity of the product, which upon manipulation readily decomposes to [(Ph2N)HP(ONO)]. However, evidence for the formation of 3 a can be observed by NMR tube scale reactions. In a typical reaction, 1 a , KNPh2⋅THF0.15  and 18‐crown‐6  were added to an NMR tube equipped with a J. Young airtight tap and the mixture dissolved in [D8]THF to give a pale yellow solution. 1H NMR : δ=7.07 , 6.90–6.85 , 6.79–6.73 , 6.52–6.47 , 6.51 , 3.49 , 1.28 , 1.26 ppm ; 13C{1H} NMR : δ=151.2 , 149.4 , 135.0 (Ar), 134.8 , 129.8 , 127.6 , 125.5 , 120.0 , 112.4 (Ar), 106.7 , 70.8 , 34.9 (C(CH3)3), 24.8 (C(CH3)3), 32.5 (C(CH3)3), 30.2 ppm (C(CH3)3); 31P NMR : δ=66.3 ppm (s); 31P{1H} NMR : δ=66.3 ppm (s).2N)As(ONO)] ([K(18‐crown‐6)][3 b])Synthesis of [K]−) 513.24; found: 513.97; 1H NMR : δ=7.17 , 6.76–6.70 , 6.50 , 6.46–6.41 , 3.46 , 3.43–3.41 , 2.46–2.43 , 1.36 , 1.27 ppm ; 13C{1H} NMR : δ=152.2 (Ar), 150.5 (NPh2), 135.8 (Ar), 134.1 (Ar), 130.6 (Ar), 127.9 (NPh2), 124.5 , 119.4 , 111.8 (Ar), 107.5 (Ar), 71.0 , 68.2 , 54.5 , 35.2 (C(CH3)3), 34.8 (C(CH3)3), 32.6 (C(CH3)3), 30.3 ppm (C(CH3)3).tBuO)HP(ONO) (4 a)Synthesis of  and KOtBu  were dissolved in THF (3 mL) at room temperature. The yellow solution was stirred for 15 min after which a solution of pyridinium triflate  in THF (2 mL) was added, giving rise to a colourless solution and white precipitate. After stirring for 30 min all volatiles were removed in vacuo and the product extracted into toluene (5 mL). The solution was filtered through a cannula, concentrated to approximately 0.5 mL and then cooled to 5 °C for a week, yielding large colourless block crystals of 4 a. The product was isolated by filtration. Yield: 145 mg (83 %); elemental analysis calcd (%) for C32H50NO3P: C 72.83, H 9.55, N 2.65; found: C 72.92, H 9.62, N 2.75. EI MS: m/z calcd for C32H50NO3P: 528.3607; found: 528.3600 m/z calcd for C28H43NO3P: 472.2981; found: 472.2968; m/z calcd for C28H41NO2P: 454.2875; found: 454.2852; 1H NMR : δ=8.16 , 7.80 , 7.22 , 1.64 , 1.42 , 1.19 ppm ; 1H{31P} NMR : δ=8.16 ppm , all other resonances the same as above; 13C{1H} NMR : δ=143.0 (Ar), 141.0 , 132.7 , 129.5 , 115.4 (Ar), 106.7 , 80.0 3), 35.0 (C(CH3)3), 34.8 (C(CH3)3), 32.0 (C(CH3)3), 30.3 3), 30.2 (C(CH3)3). 31P NMR : δ=−38.7 ppm ; 31P{1H} NMR : δ=−38.7 ppm (s).tBuO)BzP(ONO) (5 a)Synthesis of  and KOtBu  were dissolved in THF (5 mL) and stirred until all solid material had dissolved. Benzyl bromide  was added, resulting in the formation of a white precipitate of KBr. The slurry was stirred for 30 min and then all volatiles were removed in vacuo. The product was extracted into hexane and filtered through a cannula. The solution was concentrated under a dynamic vacuum and cooled to −30 °C, yielding a crop of colourless crystals which were isolated by filtration. Yield: 101 mg (74 %); elemental analysis calcd (%) for C39H56NO3P: C 75.82, H 9.14, N 2.27; found: C 76.32, H 9.25, N 2.34; CI MS (NH3 carrier gas): m/z calcd C35H45NO2P⋅NH4: 562.3688; found: 562.3479; 1H NMR : δ=7.88 , 7.32–7.27 ), 7.22 , 6.96–6.90 ), 6.85–6.79 ), 3.78 ), 1.61 , 1.38 , 1.15 ppm ; 1H{31P} NMR : 3.78 ppm ) all other resonances as above; 13C{1H} NMR : δ=142.9 , 141.7 (Ar), 134.8 ), 131.8 , 130.0 ), 128.8 , 128.5 ), 126.5 ), 116.1 (Ar), 106.7 , 80.6 3), 47.2 , 35.0 (C(CH3)3), 34.7 (C(CH3)3), 32.0 (C(CH3)3), 30.4 3), 30.3 ppm (C(CH3)3); 31P NMR : δ=−20.2 ppm ; 31P{1H} NMR : δ=−20.2 ppm (s).Synthesis of [P{ON(H)O}][OTf] ([6 a]OTf): Compound 1 a (360 mg 0.794 mmol) was suspended in hexane (5 mL) and HOTf  was added, affording a colourless solution. The reaction mixture was sonicated for 15 min causing precipitation of a white solid. The solid was isolated by filtration. Yield: 325 mg (68 %); elemental analysis calcd (%) for C29H41F3NO5PS⋅HCF3O3S: C 47.81, H 5.62, N 1.86; found: C 47.78, H 5.66, N 2.02. CI MS (NH3 carrier gas): m/z calcd for C28H41NO2P⋅NH4: 472.3219; found: 472.3002; 1H NMR : δ=14.27 , 7.88 , 7.41 , 1.38 , 1.33 ppm ; 13C{1H} NMR : δ=149.9 (Ar), 147.0 , 138.2 (Ar), 128.9 (Ar), 126.3 (Ar), 116.5 (Ar), 35.6 (C(CH3)3), 35.4 (C(CH3)3), 31.4 (C(CH3)3), 29.4 ppm (C(CH3)3); 31P NMR : δ=155.5 ppm ; 31P{1H} NMR : δ=155.5 ppm ; 19F NMR : δ=−78.6 ppm.Synthesis of [As{ON(H)O}][OTf] ([6 b]OTf): Compound 1 b  was dissolved in hexane (5 mL) and HOTf  was added, resulting in a pale pink solution and the formation of a white precipitate. The mixture was stirred at room temperature for 15 min after which the solid was isolated by filtration. Yield: 64 mg (46 %); elemental analysis calcd (%) for C28H41AsF3NO5S: C 53.78, H 6.38, N 2.16; found: C 54.33, H 6.80, N 2.21. CI MS (CH4 carrier gas): m/z calcd for C28H41AsNO2: 498.2353; found: 498.2426; m/z calcd C27H37AsNO2: 482.2027; found: 482.2133; 1H NMR : δ=11.64 , 7.84 , 7.25 , 1.36 , 1.23 ppm . 13C{1H} NMR : δ=151.8 (Ar), 145.5 (Ar), 137.9 (Ar), 131.3 (Ar), 124.5 (Ar), 117.7 (Ar), 35.2 (C(CH3)3), 34.9 (C(CH3)3), 31.4 (C(CH3)3), 29.3 ppm (C(CH3)3); 19F{1H} NMR : δ=−78.3 ppm.Synthesis of [P{ON(Me)O}][OTf] ([7 a]OTf): Compound 1 a  was dissolved in toluene (5 mL) and MeOTf  was added. The solution was heated at 70 °C for 24 h resulting in the growth of colourless needle‐shaped crystals. The supernatant was removed by cannula filtration and the crystals washed with toluene (3×5 mL) and dried in vacuo. Yield: 85 mg (60 %); elemental analysis calcd (%) for C30H43F3NO5PS: C 58.33, H 7.02, N 2.27; found: C 58.50, H 7.10, N 2.35; CI MS (NH3 carrier gas): m/z calcd for C29H43NO2P⋅NH4: 486.3375; found: 486.3151; 1H NMR : δ=7.60 , 7.39 , 3.72 , 1.39 , 1.33 ppm ; 1H{31P} NMR : δ=3.72 ppm  all other resonances as above; 13C{1H} NMR : δ=149.3 (Ar), 147.0 , 139.2 (Ar), 134.0 , 126.0 (Ar), 114.8 (Ar), 47.6 , 35.6 (C(CH3)3), 35.5 (C(CH3)3), 31.5 (C(CH3)3), 29.4 ppm (C(CH3)3); 31P NMR : δ=149.4 ppm (br s); 31P{1H} NMR : δ=149.4 ppm (br s); 19F NMR : δ −78.7 ppm.Synthesis of [As{ON(Me)O}][OTf] ([7 b]OTf): Compound 1 b  was dissolved in toluene (15 mL) and MeOTf  was added to the solution, which was stirred at 80 °C for three days, resulting in the precipitation of a white/pink solid. The solid was isolated by filtration and dried in vacuo. Yield: 733 mg (78 %); elemental analysis calcd (%) for C30H43AsF3NO5S: C 54.46, H 6.55, N 2.12; found C 54.40, H 6.48, N 2.28; EI MS: m/z calcd for C29H43AsNO2⋅CF3O3S: 661.2030; found: 661.2022; m/z calcd for C29H43AsNO2: 512.2528; found: 512.2510; 1H NMR : δ=7.31 , 7.28 , 3.41 , 1.40 , 1.31 ppm ; 13C{1H} NMR : δ=149.4 (Ar), 145.6 (Ar), 139.7 (Ar), 135.0 (Ar), 124.5 (Ar), 114.8 (Ar), 46.2 (NCH3), 35.5 (C(CH3)3), 34.9 (C(CH3)3), 31.6 (C(CH3)3), 29.4 ppm (C(CH3)3); 19F NMR : δ=−77.9 ppm (br s).Synthesis of HPCl(ONO) (8 a): Compound 1 a  was dissolved in Et2O (5 mL) and HCl  was added. The colourless solution was stirred for 30 min after which all volatiles were removed in vacuo. The colourless solid was extracted into hot hexane (3 mL) and the solution filtered. Colourless crystals of 8 a grew upon standing at room temperature, which were isolated by filtration. A further crop could be isolated by concentrating the mother liquor. Yield: 139 mg (64 %); elemental analysis calcd (%) for C28H41ClNO2P: C 68.63, H 8.43, N 2.86; found: C 68.86, H 8.49, N 2.92; 1H NMR : δ=8.97 , 7.66 , 7.13 , 1.45 , 1.41 ppm ; 1H{31P} NMR : δ=8.97 ppm , all other resonances as above; 13C{1H} NMR : δ=144.2 (Ar), 139.4 , 133.9 , 126.4 , 116.6 (Ar), 106.4 , 34.6 (C(CH3)3), 34.1 (C(CH3)3), 31.1 (C(CH3)3), 29.0 ppm (C(CH3)3); 31P NMR : δ=−31.3 ppm ; 31P{1H} NMR : δ=−31.3 ppm (s).Synthesis of AsCl(HONO) (8 b): Compound 1 b  was dissolved in THF (5 mL). HCl  was added turning the solution pale yellow. The mixture was stirred at room temperature for 15 min and then concentrated in vacuo to 0.5 mL promoting the growth of colourless block crystals of the product. These were isolated by filtration. Yield: 155 mg (69 %); elemental analysis calcd (%) for C28H41AsClNO2: C 62.98, H 7.74, N 2.62; found: C 62.64, H 7.74, N 2.96; 1H NMR : δ=7.53 , 7.41 , 7.19 , 6.69 , 5.48 , 1.63 , 1.57 , 1.27 , 1.16 ppm ; 13C{1H} NMR : δ=149.7 (Ar), 147.9 (Ar), 146.1 (Ar), 143.5 (Ar), 137.4 (Ar), 137.2 (Ar), 136.7 (Ar), 124.6 (Ar), 124.0 (Ar), 123.6 (Ar), 116.5 (Ar), 108.5 (Ar), 35.6 (C(CH3)3), 35.1 (C(CH3)3), 34.8 (C(CH3)3), 34.6 (C(CH3)3), 31.7 (C(CH3)3), 31.6 (C(CH3)3), 30.0 (C(CH3)3), 29.8 ppm (C(CH3)3).tBuO)P{ON(Me)O} (9 a)Synthesis of  and KOtBu  were dissolved in THF (3 mL) at −78 °C and the reaction mixture was allowed to warm to room temperature. After one hour all volatiles were removed in vacuo. The product was extracted with hexane (3 mL) and the solution was concentrated under a dynamic vacuum and cooled to 5 °C, resulting in the formation of a colourless microcrystalline solid. Crystals suitable for X‐ray diffraction studies were grown from a concentrated hexane solution at room temperature. Yield: 72 mg (50 %); elemental analysis calcd (%) for C33H52NO3P: C 73.16, H 9.68, N 2.59; found: C 73.04, H 9.48, N 2.68. CI MS (NH3 carrier gas): m/z calcd for C29H44NO3P⋅H: 486.3137; found: 486.3140; m/z calcd for C29H43NO2P: 468.3026; found: 468.3051; 1H NMR : δ=7.40 , 7.31 , 2.89 , 1.57  1.57 , 1.25 ppm ; 13C{1H} NMR : δ=149.7 , 144.6 (Ar), 139.3 (Ar), 138.9 , 121.5 (Ar), 118.6 (Ar), 75.7 3), 42.5 , 35.5 (C(CH3)3), 34.7 (C(CH3)3), 31.8 (OC(CH3)3), 31.7 (C(CH3)3), 30.1 ppm (C(CH3)3); 31P NMR  δ=142.8 ppm (s); 31P{1H} NMR  δ=142.8 ppm (s).tBuO)As{ON(Me)O} (9 b)Synthesis of  was dissolved in THF (5 mL) and cooled to −78 °C. A solution of KOtBu  in THF (5 mL) was then added dropwise. The reaction mixture was stirred at −78 °C for 30 mins, then 30 mins at room temperature. All volatiles were removed in vacuo and the product was extracted with hexane (5 mL) and filtered via cannula. The solution was concentrated under a dynamic vacuum yielding a crude sample of 9 b as a white solid. Isolation of 9 b from other impurities has not been possible, although characterisation data confirms the presence of the expected product. EI MS: m/z calcd for C33H53AsNO3: 586.3241; found: 586.3140; m/z calcd for C29H44AsNO3 [(HO)As{ON(Me)O}]: 529.2537; found: 529.2534; m/z calcd for C29H43AsNO2 [As{ON(Me)O}]: 512.2510 ; found: 512.2500; 1H NMR : δ=7.40 , 7.32 , 2.62 , 1.59  1.54 , 1.28 ppm ; 13C{1H} NMR : δ=151.4 (Ar), 142.9 (Ar), 139.0 (Ar), 137.9 (Ar), 121.9 (Ar), 118.0 (Ar), 73.6 (OC(CH3)3), 43.0 (NCH3), 35.7 (C(CH3)3), 34.6 (C(CH3)3), 33.1 (OC(CH3)3), 31.7 (C(CH3)3), 30.1 ppm (C(CH3)3).X‐ray diffraction: Single‐crystal X‐ray diffraction data were collected using an Oxford Diffraction Supernova dual‐source diffractometer equipped with a 135 mm Atlas CCD area detector. Crystals were selected under Paratone‐N oil, mounted on micromount loops and quench‐cooled using an Oxford Cryosystems open flow N2 cooling device.λ=1.5418 Å; Oxford Diffraction Supernova). Data were processed using the CrysAlisPro package, including unit cell parameter refinement and inter‐frame scaling (which was carried out using SCALE3 ABSPACK within CrysAlisPro).F2 using the SHELXL 2013–4 package.CCDC 1489274 (1 b), 1489275 ][2 a]⋅1.5 toluene), 1489276 ([K(18‐crown‐6)][2 b]⋅THF), 1489277 ([K(18‐crown‐6)][3 a]⋅0.5 toluene⋅0.5 pentane), 1489278 ][3 b]), 1489279 (4 a), 1489280 (5 a), 1489281 ([6 a][OTf]⋅HOTf), 1489282 ([6 b][OTf]⋅0.5 hexane), 1489283 ([7 a][OTf]), 1489284 ([7 b][OTf]), 1489285 (8 a), 1489286 (8 b), and 1489287 (9 a) contain the supplementary crystallographic data. These data can be obtained free of charge by The Cambridge Crystallographic Data Centre.DFT calculations: All geometry optimisations were performed using the Amsterdam Density Functional package (ADF2014.01).As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file.


Except for van der Waals forces, there are no significant intermolecular interactions in the crystal.The molecular structure of the title titanium(IV) half-sandwich complex, [Ti(η Structural details based on the results of X-ray diffraction and of density functional theory calculations at the M06-2X level support the formulation of these complexes as non-classical monoazabutadiene complexes. However, the follow-up chemistry with various multiple bond substrates of the complexes with formulae [(η5-Cp#)Ti(η4-C21H19N)(Cl)]  shows a hidden η2-imine reactivity to five-membered titanacycles Ti(η4-C21H19N)(Cl)] with the dialkyl-substituted lithium amide LiN(Me)Cy, the formation of a titanadihydropyrrole is observed as a result of the 1,3-H-shift in the five-membered ring system in addition to the salt metathesis reaction Ti(η4-C21H19N)(C12H10N), 1, synthesized by the reaction of [(η5-Cp*)Ti(η4-C21H19N)(Cl)] with the diaryl-substituted lithium amide LiNPh2. Compound 1 maintains the η4-coordination mode of the ketimine ligand.Here we report the synthesis and crystal structure of the title compound (η1 for which the η4-coordination mode of the ketimine ligand is clearly confirmed. The N1—C17 bond length [1.383 (3) Å] is significantly elongated compared to the free ketimine   in contrast to the well-balanced C—-C distances in the C18–C23 aromatic ring system (≃ 1.39 Å). The central titanium(IV) atom is fourfold coordinated in a considerably distorted tetrahedral coordination environment, with N1—Ti1—N2 and N1—Ti1—C30 bond angles of 110.42 (9) and 84.23 (9)°, respectively. The Ti1—N1 bond length [1.963 (2) Å] is shorter than the Ti1—N2 bond length [2.009 (2) Å] and indicates weak πp–πd electron donor interactions. The Ti1—C30 bond length [2.259 (3) Å] as well as the fold angle of the central five-membered ring system (60.6°) are similar to those in other reported monoazabutadiene complexes /2 – (Ti1—N1 + Ti1—C30)/2] = 0.386 Å Ti(η4-C21H19N)(Cl)] and lithium diphenyl amide were prepared according to published procedures Ti(η4-C21H19N)(Cl)]  and lithium diphenyl amide  were dissolved in 12 ml of tetrahydrofuran. After stirring the reaction mixture for 16 h at room temperature, the solvent was evaporated in a vacuum. The residue was dissolved in 12 ml of toluene, filtered, and the precipitate of LiCl was washed with toluene (2 ×10 ml). The combined filtrates were evaporated in a vacuum and the residue was recrystallized from n-hexane to yield complex 1 as dark-red prisms in 15% crystalline yield.[ I. DOI: 10.1107/S2056989017017455/wm5424Isup2.hklStructure factors: contains datablock(s) I. DOI: 1589353CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


A and B) with similar conformations. In the crystal, they are arranged alternately, forming –A–B–A–B– chains linked by N—H⋯O(carbonyl) hydrogen bonds, which extend along the a-axis direction.The asymmetric unit of the title carbamate, contains two independent molecules . The dimethylphenyl ring, the phenyl ring and the central carbamate N—C(=O)—O group are not coplanar. In molecule A, the dimethylphenyl and phenyl rings are inclined to the carbamate group mean plane by 27.71 (13) and 71.70 (4)°, respectively, and to one another by 84.53 (13)°. The corresponding dihedral angles in molecule B are 34.33 (11), 66.32 (13) and 85.48 (12)°, respectively. In the crystal, the A and B molecules are arranged alternately linked through N—H⋯O(carbonyl) hydrogen bonds, forming –A–B–A–B– chains, which extend along [100]. Within the chains and linking neighbouring chains there are C—H⋯π interactions present, forming columns along the a-axis direction. The columns are linked by offset π–π stacking interactions, forming a three-dimensional network [shortest centroid–centroid distance = 3.606 (1) Å].The asymmetric unit of the title compound, C In molecule A, the dimethylphenyl ring (C1–C6) makes a dihedral angle of 84.53 (13)° with the phenyl ring (C10–C15), and in molecule B the dimethylphenyl ring (C16–C21) makes a dihedral angle of 85.48 (12)° with the phenyl ring (C25–C30). In molecule A, the aryl rings (C1–C6 and C10–C15) are inclined to the the mean plane of the carbamate N1—C9(=O2)—O1 unit by 27.71 (13) and 71.70 (14)°, respectively. In molecule B, rings C16–C21 and C25–C39 are inclined to the the mean plane of the carbamate N2—C24(=O24)—O13 unit by 34.33 (11) and 66.32 (13)°, respectively. The C9—N1 and C24—N2 distances are 1.336 (3) and 1.335 (3) Å, respectively, indicating partial double-bond character in the carbamate unit.The asymmetric unit of the title compound, Fig. 1A–B–A–B– chains, propagating along the a-axis direction . These interactions form columns along the a-axis direction, which are linked by offset π–π stacking interactions , forming a three-dimensional network, as illustrated in Fig. 4Cg1⋯Cg1iii = 3.738 (2) Å, interplanar distance = 3.521 (1) Å, slippage = 1.257 Å; Cg3⋯Cg3iv = 3.606 (1) Å, interplanar distance = 3.462 (1) Å, slippage = 1.007 Å; Cg1 and Cg3 are the centroids of the C1–C6 and C16–C21 rings, respectively; symmetry codes: (iii) −x + 3, −y, −z + 1; (iv) −x + 2, −y + 1, −z + 1].In the crystal, N—H⋯O(carbonyl) hydrogen bonds link the molecules to form –n Table 1. Within ns Fig. 3b, formiet al., 2016Pna21 polymorphs of phenyl phenylcarbamate itself, viz. YEHPOQ  and 85.5 (1)°, respectively, in molecules A and B of the title compound.A search of the Cambridge Structural Database  of 3,5 dimethyl aniline dissolved in 100 ml of dry THF was added a calculated 5% excess of phenylchloroforamate in 50 ml of dry THF. The addition rate was such that it took 1.5 h for complete transfer. After the addition was complete, stirring was continued overnight. Excess THF was removed under vacuum at room temperature. The crude product was extracted with ethyl acetate (3 × 100 ml), and then the organic layer was dried over anhydrous sodium sulfate. Removing the solvent under vacuum at room temperature, yielded a light-yellow product which was dried under vacuum to constant weight. Yellow block-like crystals were obtained by slow evaporation of an ethyl acetate solution at room temperature (yield 99%).Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq for the H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017006922/su5370sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017006922/su5370Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017006922/su5370Isup3.cmlSupporting information file. DOI: 1548793CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Supramolecular layers in the bc plane sustained by C—H⋯S and C—H⋯π interactions feature in the crystal.The title molecule has a approximately coplanar relationship between the methylidenehydrazinecarbodithioate (C 16H17N3S2 (systematic name: (Z)-{[(benzylsulfanyl)methanethioyl]amino}[1-(6-methylpyridin-2-yl)ethylidene]amine), the central methylidenehydrazinecarbodithioate (C2N2S2) core is almost planar (r.m.s. deviation = 0.0111 Å) and forms dihedral angles of 71.67 (3)° with the approximately orthogonally inclined thioester phenyl ring, and 7.16 (7)° with the approximately coplanar substituted pyridyl ring. The latter arrangement and the Z configuration about the imine-C=N bond allows for the formation of an intramolecular hydrazine-N—H⋯N(pyridyl) hydrogen bond that closes an S(6) loop. In the crystal, phenyl-C—H⋯S(thione), methylene-C—H⋯π(pyridyl), methylene- and phenyl-C—H⋯π(phenyl) contacts connect molecules into supramolecular layers propagating in the bc plane; the layers stack along the a axis with no directional interactions between them. The analysis of the Hirshfeld surface indicates the relative importance of an intralayer phenyl-H⋯H(pyridyl) contact upon the molecular packing.In the title dithiocarbazate ester, C Different ligands can be obtained by introducing different organic substituents, which causes variation in their biological properties, although they may differ only slightly in their molecular structures  and 7.16 (7)°, respectively, indicating nearly orthogonal and co-planar dispositions, respectively; the dihedral angle between the outer rings is 65.79 (4)°. The configuration about the imine-C9=N2 bond [1.2924 (18) Å] is Z, resulting in the hydrazine-N1—H hydrogen atom being directed towards the pyridyl-N3 atom, enabling the formation of an intermolecular amine-N1—H⋯N3(pyridyl) hydrogen bond that closes an S(6) loop, Table 1syn with the thione-S1 atom and at the same time is orientated to the opposite side of the molecule to the imine-bound methyl group.The molecular structure of (I)b-axis direction, and a number of C—H⋯π contacts, i.e. methylene-C2—H⋯π(pyridyl), phenyl-C7—H⋯π(phenyl) and methyl-C10—H⋯π(phenyl), as detailed in Table 1bc plane, Fig. 2a. Layers stack along the a axis with no directional interactions between them, Fig. 2b.The participation of the hydrazine-N1—H hydrogen and pyridyl-N3 atoms in the intramolecular N—H⋯N hydrogen bond precludes their participation in intermolecular interactions. The molecular packing features weak phenyl-C8—H⋯S2(thione) interactions, leading to chains along the et al., 2017dnorm in Fig. 3a (labelled as ‘1’). The presence of the weak intermolecular C—H⋯S contact involving the phenyl-C8 and thione-S2 atoms is evident from the diminutive red spots near these atoms in Fig. 3b (labelled as ‘3’) characterize the short surface C⋯H/H⋯C contacts and indicate the relative importance of this particular C—H⋯π contact compared with the other two C—H⋯π contacts summarized in Table 1i.e. π⋯H—C, containing π-bond acceptors, on the Hirshfeld surface mapped with the shape-index property are illustrated in Fig. 5The Hirshfeld surfaces calculated for (I)a, and those delineated  indicate the significant influence of the short interatomic phenyl-H⋯H(pyridyl) contacts in the crystal mentioned above. The intermolecular C—H⋯π interactions discussed earlier are characterized by short interatomic C⋯H/H⋯C contacts  and pyridyl  rings on the Hirshfeld surface mapped over the electrostatic potential in Fig. 4de + di ∼ 2.8 Å in Fig. 6d. The interatomic N⋯H/H⋯N contacts do not represent directional interactions as the interatomic separations are greater than sum of their van der Waals radii as evident from Fig. 6e. Similarly, the other surface contacts summarized in Table 3The overall two-dimensional fingerprint plot for (I)ts Fig. 6b indicas Table 2 and theiChemical context, there is sustained interest in this class of compound and this is reflected by the observation there are four closely related structures available for comparison, varying in the S-bound group and substitution in the 2-pyridyl ring. In common with (I)Z-configuration is noted about the imine bond allowing for the formation of an intramolecular hydrazine-N—H⋯N(pyridyl) hydrogen bond  hydrogen bonds and eight-membered {⋯HNCS}2 synthons.As mentioned in the S-Benzyldithiocarbazate (SBDTC) was prepared according to the method published by Ali & Tarafder (1977−1): 2921 ν(N—H), 1560 ν(C=N), 1055 ν(N—N), 881 ν(CSS).All chemicals were of analytical grade and were used without any further purification. fder 1977. PotassiUiso(H) set to 1.2–1.5Ueq(C). The nitrogen-bound H atom was located in a difference Fourier map, but was refined with a distance restraint of N—H = 0.88±0.01 Å, and with Uiso(H) set to 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989018001330/hb7730sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018001330/hb7730Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018001330/hb7730Isup3.cmlSupporting information file. DOI: 1818384CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The 5FC ring forms a dihedral angle of 19.97 (11)° with the ring of the picrate (PA−) anion. In the crystal, the 5FC+ cation interacts with the PA− anion through three-centre N—H⋯O hydrogen bonds, forming two conjoined rings having R21(6) and R12(6) motifs, and is extended by N—H⋯O hydrogen bonds and C—H⋯O interactions into a two-dimensional sheet structure lying parallel to (001). Also present in the crystal structure are weak C—F⋯π interactions.In the crystal structure of the title compound, 5-fluorocytosinium picrate, C New solid forms of pharmaceuticals are designed using the crystal engineering approach. These engineered solids have technological and legal importance. Among the intermolecular interactions, hydrogen bonding is the master key for molecular recognition in biological systems because of its strength and directionality  and one picrate anion (PA−)  anion, the nitro groups lie variously out of the parent benzene ring, with torsion angles C9—C8—N5—O4, C9—C10—N6—O7 and C11—C12—N7—O9 of 166.2 (2), −171.7 (2) and 147.2 (2)°, respectively.The asymmetric unit contains one 5-fluorocytosinium cation (5FC−) Fig. 1. The 5-f+ cation interact with atoms O3 and O9 of the picrate anion through three-centre N—H⋯O hydrogen bonds, forming two fused-ring motifs with graph-sets + cation acts as a three-centre donor and the O3 atom of the PA− anion acts as a three-centre acceptor. This type of interaction has also been reported in the crystal structures of 2-amino-4,6-dimethylpyrimidinium picrate  Fig. 1. One of g Table 1. A similii atom and the amino group of the 5FC+ cation are connected through an N—H⋯O hydrogen bond, forming a two-dimensional supramolecular network lying parallel to (001)  Å; C—F⋯Cg = 88.34 (12)°, where Cg is the centroid of the N1–C6 ring; symmetry code: (iv) −x, −y, −z + 1]. A similar angle [90.5 (2)°] has been reported for a C—F⋯Cg interaction in an acridinium trifluoromethane sulfonate compound  Fig. 2. Also pr1) Fig. 2 between et al., 1982et al., 2013et al., 2012et al., 2014et al., 2001et al., 2014et al., 2016et al., 2006et al., 2009et al., 1995et al., 2004et al., 2004The crystal structures of 5-fluorocytosine monohydrates (Louis A hot aqueous solution of 5-fluorocytosine (32 mg) and picric acid (57 mg) were mixed in a 1:1 molar ratio. The resulting solution was warmed to 353 K wrong symmetry description - inversion centre in central benzene ring over a water bath for half an hour and kept for slow evaporation. After a week, colourless prismatic crystals were obtained.Uiso(H) = 1.2Ueq(parent atom).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901700216X/zs2375sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901700216X/zs2375Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901700216X/zs2375Isup3.cmlSupporting information file. DOI: 1531927CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit of the crystal of the title compound contains two rivaroxaban molecules with different conformations. 19H18ClN3O5, contains two rivaroxaban molecules with different conformations; the C—C—N—C torsion angles between the oxazolidine and thiophene rings are −171.1 (7) and −106.8 (9)° in the two independent molecules. In the crystal, classical N—H⋯O hydrogen bonds and weak C—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular architecture.The asymmetric unit of the crystal of the title compound (common name rivaroxaban), C At present, the incidence of thromboic disease is extremely high; this is mainly caused by vascular endothelial injury, increased blood coagulation, increased platelet number and decreased anticoagulant activity  and −106.8 (9)°, respectively  Å for the O2A atom], whereas the oxazolidine ring of molecule B displays an envelope conformation with atom C8B as the flap. The morpholine rings of the two molecules display similar twisted boat conformations. Atoms O4 and C17 deviate from the C16/N3/C19/C18 mean plane by 0.230 (2) and 0.517 (2) Å, respectively, in molecule A and by 0.290 (2) and 0.489 (2) Å in molecule B.The molecular structure of the title compound is shown in Fig. 1y Table 1. The oxaA and B into dimers, and weak C—H⋯O hydrogen bonds link the dimers to form a three-dimensional supramolecular architecture . The O⋯H/H⋯O interactions (22.4%), which are the most significant intermolecular interactions and link the molecular dimers into infinite chains along the b axis, appear as two obvious spikes . At the top left (di < de) and bottom right (di > de) of the fingerprint plot, there are characteristic ‘wings’ that are identified resulting from the C⋯H/H⋯C interactions (18.7%) shown in Fig. 3d.The light-red spots on the Hirshfeld surface are the results of N—H⋯O, C—H⋯O and C—Cl⋯O interactions Fig. 3. The H⋯Hes Fig. 3c. At thThe crude product was supplied by the Zhejiang Huadong Pharmaceutical Co., Ltd. It was recrystallized from methanol solution, giving colourless crystals suitable for X-ray diffraction.A and H1B were found in difference-Fourier maps, but placed in calculated positions with N—H = 0.86 Å and refined as riding with Uiso(H) = 1.2Ueq(N). All other H atoms were placed in calculated positions with C—H = 0.93–0.98 Å and included in the refinement in a riding model, with Uiso(H) = 1.2 or 1.5Ueq(carrier atom).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017017819/xu5913sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017017819/xu5913Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017017819/xu5913Isup3.cmlSupporting information file. DOI: 1810879CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal of (I), supramolecular layers parallel to (10-1) are sustained by methylene-C—H⋯O(methoxy) interactions, while in (II), centrosymmetric dimers are formed via pairwise weak phenyl-C—H⋯π(phenyl) contacts.The coordination geometry in ( 4H9)2(C7H14NO2S2)2], (I), and [Sn(C6H5)3(C5H10NOS2)], (II), are described. Both structures feature asymmetrically bound dithiocarbamate ligands leading to a skew-trapezoidal bipyramidal geometry for the metal atom in (I) and a distorted tetrahedral geometry in (II). The complete molecule of (I) is generated by a crystallographic twofold axis (Sn site symmetry 2). In the crystal of (I), molecules self-assemble into a supramolecular array parallel to (10-1) via methylene-C—H⋯O(methoxy) interactions. In the crystal of (II), supramolecular dimers are formed via pairs of weak phenyl-C—H⋯π(phenyl) contacts. In each of (I) and (II), the specified assemblies connect into a three-dimensional architecture without directional interactions between them. Hirshfeld surface analyses confirm the importance of H⋯H contacts in the molecular packing of each of (I) and (II), and in the case of (I), highlight the importance of short methoxy-H⋯H(butyl) contacts between layers.The crystal and molecular structures of the two title organotin dithiocarbamate compounds, [Sn(C The coordination environment is completed by two α-carbon atoms of the n-butyl substituents. The resultant C2S4 donor set defines a skew-trapezoidal bipyramidal geometry with the tin-bound organic substituents lying over the weaker Sn—S2 bonds, which subtend an angle at the tin atom approximately 50° wider than that subtended by the S1 atoms, Table 12CN residue and have very similar conformations, as seen in the values of the C1—N1—C2—C3, N1—C2—C3—O1 and C2—C3—O1—C4 torsion angles of −94.1 (4), −67.4 (4) and −177.1 (3)°, indicating that − anti-clinal, − syn-clinal and − anti-periplanar descriptors, respectively, are in effect. For the O2-methoxyethyl group, the equivalent torsion angles are −82.0 (4), −70.3 (4) and −169.1 (3)°. The independent n-butyl substituent has an all-trans (+ anti-periplanar) conformation, as seen in the values of the Sn—C8—C9—C10 and C8—C9—C10— C11 torsion angles of 172.9 (2) and 176.3 (3)°, respectively.The tin atom in (I)b, lies on a general position and has a quite distinct coordination geometry owing to the presence of three tin-bound phenyl groups. As for (I)cf. (I)i.e. nearly 0.07 Å, Table 2cf. (I)3S2 donor set approximates a trigonal–bipyramidal geometry with the value of τ, an indicator of a five-coordinate coordination geometry, being 0.61, cf. 1.0 for an ideal trigonal bipyramid and 0.0 for an ideal square pyramid °, for S1—Sn—C11, to 119.09 (7)°, for S1—Sn—C31. The C21—Sn—C31 angle, at 115.55 (10)°, is wider by 10° than the other C—Sn—C angles, a result correlated with the close approach of the S2 atom. The 2-methoxyethyl group has a very similar conformation to the O1-methoxyethyl group in (I)The molecule in (II)b so that a supramolecular array is formed parallel to PLATON et al., 2017The Hirshfeld surface calculations for the organotin derivatives (I)A and H6B atoms lying on both the sides of twofold symmetry axis on the Hirshfeld surfaces mapped over dnorm for (I)a and b represent the dominant intermolecular C—H⋯O contacts, Table 3B and butyl-H8A atoms in Fig. 4c indicate the significant influence of intra-layer H⋯H contacts, Table 5a and b, the donors and acceptors are represented with blue and red regions around the respective atoms corresponding to positive and negative potentials, respectively.The bright-red spots near each of the methoxy-O1 and -O2, and methylene-H4dnorm for (II)c are due to polarization of charges near the respective functional groups and do not represent any significant interaction in the crystal. The weak intermolecular C—H⋯π contact and intra-layer interatomic H⋯H contacts et al., 2007de + di ∼ 2.0 Å and the distribution of points with greater density in  range ∼1.0 to 1.2 Å for (I)a, and a small peak at de + di ∼ 2.2 Å with relatively few points at de + di < 2.4 Å for (II)b. The fingerprint plot delineated into O⋯H/H⋯O contacts for (I)a, characterizes intermolecular C—H⋯O interactions as the pair of forceps-like tips at de + di ∼ 2.5 Å. A low percentage contribution due to O⋯H/H⋯O contacts is noted for (II)i.e. 29.1%, contribution from C⋯H/H⋯C contacts to the Hirshfeld surfaces of (II)de + di ∼ 2.8 Å and the distribution of points around de + di ∼ 2.9 Å in both the wings of its delineated fingerprint plot, Fig. 7bi.e. de + di > 3.0 Å, Fig. 7The overall two-dimensional fingerprint plots for (I)R′′xSn(S2CNRR′)x4–, can adopt a variety of coordination geometries, especially for x = 2 2Sn[S2CN(CH3)CH2CH2OCH3]2 . Carbon, hydrogen, nitrogen and sulfur analyses were performed on a Leco CHNS-932 Elemental Analyzer. The IR spectra were obtained on a Perkin Elmer Spectrum GX from 4000 to 400 cmSynthesis of (I) bis(2-methoxyethyl)amine  dissolved in ethanol (30 ml) was stirred for 30 min. Then, carbon disulfide  in cold ethanol was added and the resulting mixture was stirred for 2 h. A 25% ammonia solution (1–2 ml) was added to generate basic conditions. Then, di-n-butyltin(IV) dichloride  dissolved in ethanol (20–30 ml) was added dropwise into the solution and stirring was continued for 2 h. All reactions were carried out at 277 K. The precipitate that formed was dried and collected. Colourless prisms were harvested from the slow evaporation of its chloroform:ethanol (2:1 v/v) solution. Yield: 72%. M.p. 341–342 K. Elemental analysis: calculated (%): C 40.68, H 7.14, N 4.31, S 19.75. Found (%): C 41.76, H 6.07, N 4.91, S 19.25. IR (KBr cm−1): 1487 ν(C—N), 992 ν(C—S), 544 ν(Sn—C), 386 ν(Sn—S). 1H NMR (CDCl3): δ 4.13 ; 3.70 ; 3.35 ; 1.45–2.05 , 0.94 . 13C NMR (CDCl3): δ 201.52 (NCS2); 70.07 (O—CH2); 55.59 (N—CH2); 59.01 (O—CH3); 34.26 Sn—CH2; 28.55 Sn—CH2CH2; 26.41 Sn—CH2CH2CH2; 13.87 CH2CH3. 119Sn NMR (CDCl3): δ −335.5.Synthesis of (II) The synthesis of (II)v/v) solution. Yield: 78%. M.p. 366-367 K. Elemental analysis: calculated (%): C 53.71, H 4.89, N 2.72, S 12.47. Found (%): C 54.28, H 5.26, N 2.73, S 12.5. IR (KBr cm−1): 1477 ν(C—N), 997 ν(C—S), 527 ν(Sn—C), 451 ν(Sn—S). 1H NMR (CDCl3): δ 7.41–7.82 ; 4.05 ; 3.71 ; 3.51 ; 3.38 . 13C NMR (CDCl3): δ 196.97 (NCS2); 128.25–142.28 (C-aromatic); 70.09 (O—CH2); 59.06 (N—CH2); 58.10 (O—CH3); 45.81 (N—CH3);. 119Sn NMR (CDCl3): δ −183.8.Uiso(H) set to 1.2–1.5Ueq(C). For (I)−3, respectively, were located 0.88 and 1.03 Å from the S1 and Sn atoms, respectively. For (II)−3, respectively, were located 0.96 and 0.76 Å from the Sn atom.Crystal data, data collection and structure refinement details are summarized in Table 710.1107/S2056989018001901/hb7731sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018001901/hb7731Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018001901/hb7731IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1821129, 1821128CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Tumor necrosis factor-α has been proven an effective anticancer agent in preclinical studies. However, the translation of TNFα from research to clinic has been blocked by significant systemic toxicity and limited efficacy at maximal tolerated dose, which need urgently to be solved.2+ was assessed by Fura-2 in HCC cells. After changing cytosolic Ca2+ level by using agonists or inhibitors, cell apoptosis was detected by flow cytometry. We also detected the effect of ionomycin or parvalbumin on the anti-tumor activity of TNFα in a mice model. Lastly, we studied the roles of cytosolic Ca2+ in the mitochondrial-dependent intrinsic apoptosis pathway.The level of cytosolic Ca2+ influx into cytoplasm through transient receptor potential channel in HCC cells. Both cytosolic Ca2+ scavenger and Ca2+-binding protein PV effectively desensitized hepatocellular carcinoma cells to TNFα, whereas combination ionomycin or 1,4,5-inositol triphosphate significantly sensitized HCC cells to TNFα, indicating that the increased level of cytosolic Ca2+ was positively correlated with the TNFα-induced cell apoptosis in vitro. In a nude mice xenograft model, our data revealed that TNFα combined with ionomycin remarkably synergized the anti-tumor effect of TNFα. Furthermore, we found that TNFα-mediated extracellular Ca2+ influx accelerated TNFα-induced extrinsic apoptosis through activating calpain/IAP/caspase3 pathway.Here, we demonstrated that TNFα induced extracellular Ca2+ influx to enhance cell apoptosis and suggests that increasing the level of cytosolic Ca2+ might be an alternative strategy to improve the pro-apoptotic activity of TNFα in HCC cells, although suitable chemical or biological reagents need to be further tested.Our study provides the evidence supporting a novel mechanism by which TNFα induces extracellular CaThe online version of this article (10.1186/s13046-018-0714-6) contains supplementary material, which is available to authorized users. TNFα is a 23KD type II transmembrane protein, which is arranged in stable homotrimers. It is primarily produced by macrophages and a variety of other cells, including NK cells, T lymphocytes, smooth muscle cells, fibroblasts and others . Many pr2+, as a common signal transduction factor, has played many important roles in the process of cell division, growth, and death c after TNFα treatment in HCC cells. We further found that either Ca2+ scavengers or PV reduced the percentage of TNFα-induced apoptotic HCC cells  and IP3  were used to rapidly elevate [Ca2+]c as described previously [2+]c in HLF and QSG-7701 cells after TNFα treatment  treatment  only  plays critical roles in TNFα-induced extrinsic apoptotic pathway c level using fluorescent probe Fura-2/AM in SNU739 and HLF cells with treatment as indicated. BAPTA-AM: 10 μM. (b) Cell apoptosis analysis by flow cytometry 24 h after treatment as indicated before TNFα (100 ng/mL) stimulation. BAPTA-AM: 10 μM. (c) Confocal microscope analysis of [Ca2+]c level using fluorescent probe Fura-2/AM in HCC cells with treatment as indicated. EV: cells transfected with the empty vector; PV-OE: cells stably forced expressing Parvalbumin protein. (d) Apoptosis analysis by flow cytometry 24 h after treatment as indicated. (e) Western Blot analysis for Parvalbumin expression in SNU739 and HLF cells with treatment as indicated. (f) Cell apoptosis analysis by flow cytometry 24 h after treatment as indicated. CAI: 10 μM; SKF96365: 100 μM. (g) Cell apoptosis analysis by flow cytometry 24 h after treatment as indicated. siTRPM7: siRNA against TRPM7; si Ctrl: negative control siRNA. Data were shown as mean ± SD. All experiments were performed at least three times. * P < 0.05; ** P < 0.01. (ZIP 1986 kb)Additional file 4:Figure S3. Cytosolic Ca2+ sensitized HCC cells to TNFα-induced apoptosis. (a) Apoptosis analysis by flow cytometry 24 h after treatment as indicated. (b) and (c) Confocal microscope analysis of [Ca2+]c level using fluorescent probe Fura-2/AM in HLF and QSG-7701 cells with treatment as indicated. TNFα (50 ng/mL) + Iono: 50 ng/mL TNFα combined with 1 μM ionomycin, TNFα (100 ng/mL) + Iono: 100 ng/mL TNFα combined with 1 μM ionomycin, TNFα (200 ng/mL) + Iono: 200 ng/mL TNFα combined with 1 μM ionomycin. TNFα (50 ng/mL) + IP3: 50 ng/mL TNFα combined with 10 μM IP3; TNFα (100 ng/mL) + IP3: 100 ng/mL TNFα combined with 10 μM IP3; TNFα (200 ng/mL) + IP3: 200 ng/mL TNFα combined with 10 μM IP3; (d)-(f) Apoptosis analysis by flow cytometry 24 h after treatment as indicated. Data were shown as mean ± SD. All experiments were performed at least three times. * P < 0.05; ** P < 0.01. (ZIP 2448 kb)Additional file 5:Figure S4. The level of extracellular calcium influx is positively correlated with TNFα-mediated apoptosis. (a) Confocal microscope analysis of [Ca2+]c level using fluorescent probe Fura-2/AM in 10 kinds of HCC cells with treatment as indicated. (b) Apoptosis analysis by flow cytometry 24 h after treatment as indicated. All experiments were performed at least three times. (ZIP 2184 kb)Additional file 6:Figure S5. The role of TNFα-mediated Ca2+ influx in normal hepatic cells. (a) and (c) Confocal microscope analysis of [Ca2+]c level using fluorescent probe Fura-2/AM in QSG-7701 cells with treatment as indicated. TNFα: 100 ng/mL; siTRPM7: siRNA target TRPM7. (b) qRT-PCR and western blot analysis of TRPM7 mRNA and protein expression levels in QSG-7701 cells transfected with siRNA as indicated. (d) Analysis of Calpain activity after TNFα stimulation for 4 h in QSG-7701 cells with treatment as indicated. Data were shown as mean ± SD. All experiments were performed at least three times. * P < 0.05; ** P < 0.01. (JPEG 664 kb)


A new mononuclear cobalt(III) complex that has two thiolate and one thioether donor atoms is reported. I3CoIII2 complex, [Ag3{Co(L)}2]3+ [L3– = N(CH2NHCH2CH2S−)3], in which two tris(thiolate)-type mononuclear CoIII units ([Co(L)]) are bridged by three AgI ions through S atoms, with iodomethane (CH3I) gave a new CoIII mononuclear complex, [Co(LMe2)]2+ [LMe2− = N(CH2NHCH2CH2S−)(CH2NHCH2CH2SCH3)2], systematic name: {2-[(bis{[2-(methylsulfanyl)ethyl]aminomethyl}aminomethyl)amino]ethanethiolato}cobalt(III) bis(hexafluoridophosphate). This cationic complex was crystallized with PF6− anions to form the title compound, [Co(LMe2)](PF6)2. In the [Co(LMe2)]2+ cation, two of three thiolate groups in [Co(L)] are methylated while one thiolate group remains unreacted. Although a total of eight stereoisomers are possible for [Co(LMe2)]2+, only a pair of enantiomers {ΛRR- and ΔSS-[Co(LMe2)]2+} are selectively formed. In the crystal, the complex cations and the PF6− anions are connected through weak N—H⋯F, C—H⋯F and C—H⋯S hydrogen bonds into a three-dimensional structure. Two F atoms in one PF6 anion are disordered over two sets of sites with refined occupancies of 0.61 (4) and 0.39 (4) and two F atoms in the other PF6− anion are disordered over two sets of sites with occupancies of 0.5.Treatment of an S-bridged pentanuclear Ag R1S−) bound to a transition metal center readily react with alkyl halides (R2X) to form a transition metal complex with thioether groups (R1SR2). Since the resulting thioether S atoms generally turn to be asymmetric , the alkylated species are an interesting research target of coordination stereochemistry. Among a variety of alkyl halides, iodomethane (CH3I) is one of the most common alkylation reagent because of its high reactivity and simple molecular structure. For example, the reaction of a mono(thiolate)-type CoIII mononuclear complex, [Co(aet)(en)2]2+ , with iodomethane selectively produces the corresponding mono(thioether)-type complex, [Co(mtea)(en)2]3+ (mtea = NH2CH2CH2SCH3) 2], is also easily converted to the corresponding bis(thioether)-type complex, [Ni(mtea)2]2+, by treating with iodomethane. Unlike mono(thiolate)- or bis(thiolate)-type complexes, tris(thiolate)-type complexes have been found to show different reactivity toward iodomethane. That is, the reaction of a tris(thiolate)-type mononuclear rhodium(III) complex, fac(S)-[Rh(aet)3], with iodomethane afforded a unique dimethylated mono(thiolate)bis(thioether)-type complex, fac(S)-[Rh(aet)(mtea)2]2+, whereas the monomethylated bis(thiolate)mono(thioether)-type and trimethylated tris(thioether)-type species were little formed -[Rh(aet)(mtea)2]2+. However, the lack of crystallographic analytical data for fac(S)-[Rh(aet)(mtea)2]2+ prevented the further study on the stereochemistry of the dialkylated complex.It has long been recognized that thiolate groups ]2}3+ [L3– = N(CH2NHCH2CH2S−)3] ], are linearly linked by three AgI ions, reacts with iodomethane to give a mono(thiolate)bis(thioether)-type complex, [Co(LMe2)]2+ [LMe2− = N(CH2NHCH2CH2S−)(CH2NHCH2CH2SCH3)2]. It is noteworthy that the complex was crystallized as a hexafluoridophosphate salt, [Co(LMe2)](PF6)2, and its molecular structure was fully determined by single-crystal X-ray diffraction analysis. As far as we know, this is the first crystallographic characterization of a cobalt(III) complex that has two thioether and one thiolate donor groups. In addition, this is a unique example of a direct conversion of a thiolate-bridged multinuclear complex to a mononuclear thioether complex by alkylation reaction. Treatment of the thiolate-bridged pentanuclear complex {Ag3[Co(L)]2}3+ with excess iodomethane in water gave a greenish-brown suspension. After removing the insoluble solid by filtration, the purple–brown filtrate was purified by a cation–exchange column (SP-Sephadex C-25). The product was isolated as purple–brown crystals by adding a hexafluoridophosphate anion. The geometrical parameters and stereoisomerism of the title compound based on the X-ray analysis, together with the spectroscopic data, are described in this paper.In the course of our continuing study of the alkylation reaction of metal complexes with aminothiolate ligands (Okamoto LMe2)]2+, and four PF6− anions in the asymmetric unit ] moiety were methylated to form [Co(LMe2)]2+. No apparent difference was observed among the Co—S bond lengths for thiolate S atoms (Sthiolate) [2.2384 (13)–2.2478 (11) Å] and those for thioether S atoms (Sthioether) [2.2190 (13)–2.2599 (11) Å] in [Co(LMe2)]2+. However, the Co—N bonds trans to Sthiolate [2.061 (4)–2.062 (3) Å] are ca 0.05 Å longer than the Co—N bonds trans to Sthioether [2.004 (4)–2.020 (4) Å]. The difference is reasonably explained by the decrease of the trans influence due to the alkylation on S atoms. As a result of the steric repulsion between the methyl groups on the S atoms, the S—Co—S angles in [Co(LMe2)]2+ deviate considerably from 90° [86.58 (4)–95.07 (4)°].X-ray structural analysis revealed that there are two crystallographically independent yet essentially the same complex cations,  units. Considering the absolute configurations of the cobalt(III) atom (Δ and Λ) and the two asymmetric sulfur atoms (R and S), four pairs of diastereomers, ΔSS/ΛRR, ΔSR/ΛRS, ΔRS/ΛSR and ΔRR/ΛSS, are possible for [Co(LMe2)]2+. However, the asymmetric unit of this crystal contains two ΛRR isomers. As indicated by the space group C2/c, the title crystal is a racemic compound consisting of a pair of enantiomers, ΛRR and ΔSS. This result is consistent with the observation that the 13C{1H} NMR spectrum of the title compound in DMSO-d6 exhibits a total of 10 sharp singlet signals, assignable to the C1 symmetrical ΛRR and ΔSS isomers of [Co(LMe2)]2+ ]2+ in the crystal, two of three N,S-chelate rings have a gauche form with the lel (λ for Δ and δ for Λ) conformation, while one has a gauche form with the ob (λ for Λ and δ for Δ) conformation.Each Co2+ Fig. 2. For botLMe2)]2+. This complex was obtained by the unprecedented direct conversion of a thiolate-bridged AgI3CoIII2 pentanuclear complex by alkylation reaction using iodomethane. The selective formation of the ΛRR and ΔSS isomers of [Co(LMe2)]2+ observed in the crystal structure is consistent with the result of 13C{1H} NMR. The findings reported herein will provide insight into the synthesis and structures of coordination compounds containing both thiolate and thioether donor groups.In summary, we report here the first example of a crystallographically characterized mono(thiolate)bis(thioether)-type mononuclear cobalt(III) complex, [Co]2}(NO3)3·4H2O  in 100 ml of water was added CH3I . The mixture was stirred at room temperature for 1.5 days in the dark. After removing a brown powder (200 mg) by filtration, the purple–brown filtrate was poured onto an SP-Sephadex C-25 column . First, a purple band was eluted with 0.05 M aqueous NaCl. Then, a purple–brown band of [Co(LMe2)]2+ was eluted with 0.15 M aqueous NaCl. To the concentrated purple–brown eluate was added 1.0 M aqueous NH4PF6 (5 ml) and the solution was allowed to stand at room temperature for 20 d. The resulting dark purple–brown block crystals of the title compound were collected by filtration. Yield: 0.08 g (29%). Single crystals suitable for X-ray analysis were obtained by recrystallization from water by adding 1.0 M aqueous NH4PF6. Analysis: calculated for [Co(LMe2)](PF6)2: C 20.01, H 4.12, N 8.48%; found: C 20.25, H 4.06, N 8.51%. 13C{1H} NMR (DMSO-d6): δ 17.40, 18.05, 28.97, 37.20, 47.82, 49.42, 58.22, 64.39, 67.05, 67.50. One of the 13C signals overlaps with the signal from solvent. IR: 3266.8(m), 3029.6(w), 1432.8(m), 1245.8(w), 1158.0(w), 1113.7(w), 1034.6(w), 955.5(m), 839.8(s), 558.3(s).To a dark-purple solution of {Ag2) or 0.98 Å (CH3)] and refined as riding with Uiso(H) = 1.2Ueq(C) for CH2 and Uiso(H) = 1.5Ueq(C) for CH3. All H atoms bound to N atoms were refined with bond-length restraints [N—H = 0.90 (2) Å] and with Uiso(H) = 1.2Ueq(N). Two F atoms in one PF6 anion are disordered over two positions (F25A/F25B and F26A/F26B) with refined occupancies of 0.61 (4) and 0.39 (4). Two F atoms in another PF6 anion are also disordered over two positions  with site occupancies of 0.5. Reflections  I. DOI: 10.1107/S2056989017005229/is5473Isup2.hklStructure factors: contains datablock(s) I. DOI: 1542478CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The 1,3-dimethylurea molecules are also hydrogen bonded to sulfate O atoms, and project outwards from the ribbon parallel to the b axis.The packing is centred on bis(piperidinium) sulfate ribbons parallel to the  5H12N+·SO42−·2C3H8N2S, the C=S groups of the two independent 1,3-dimethylurea molecules and the sulfur atom of the anion lie on twofold axes. The packing is centred on bis(piperidinium) sulfate ribbons parallel to the c axis; the cations are hydrogen bonded to the sulfate by N—H⋯O and C—H⋯O interactions. The 1,3-dimethylurea molecules are also hydrogen bonded to sulfate O atoms, and project outwards from the ribbon parallel to the b axis.In the title compound, 2C We have published two reports on adducts of dioxane and morpholine with various methylthioureas , so that the methyl groups are cis, with Cmethyl—N—C=S torsion angles are close to zero [C11—N1—C1—S1 = 0.9 (2)° and S2—C2—N2—C21 = −2.05 (17)°]. Free 1,3-DMT crystallizes with four independent molecules, each of which has one NH group cis and one trans to C=S, but the structure is severely disordered  sulfate and 1,3-DMT Fig. 1, with thc axis in the region x, y ≃ 1/2  sulfate ribbons parallel to the /2 Fig. 2 and also2 Table 1. Each pa2 Table 1 and 3 ▸;et al., 2016trans geometry for both NH functions, but the 1:2 adduct between 1,4-dioxane and 1,3-DMT  hydrogensulfate sulfate  1,3-DMT were dissolved in 2 mL piperidine. The solution was overlayered with diethyl ether. Colourless needles formed overnight.y, Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017004820/hg5484sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989017004820/hg5484Isup2.hklStructure factors: contains datablock(s) I. DOI: 1540583CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The aryloxo magnesiate complex anion is binuclear with each Mg2O4 complex unit inversion-related and bridged through the two tridentate chelating phenolate O-donors of the ligand. The complex centres have a distorted tetrahedral stereochemistry [Mg—O range 1.8796 (17)–2.0005 (16) Å] and an Mg⋯Mg separation of 2.9430 (14) Å]. The LiO4 coodination sphere of the cation comprises four THF O-donor atoms and has a slightly distorted tetrahedral conformation [Li—O range 1.899 (5)– 1.953 (5) Å]. In the crystal, a number of stabilizing intra-anion C—H⋯O hydrogen-bonding interactions are present but no inter-species associations are found.The title ion-association metal complex, [Li(C The structure of this novel heterobimetallic complex, in an ion-association mode, is reported herein.Magnesium complexes  of the two chelating phenolate groups . The stereochemistry about each four-coordinated Mg atom is distorted tetrahedral with Mg—O(Ar) in the range 1.8796 (17)–2.0005 (16) Å – 1.953 (5) Å. Within the binuclear complex anion there are six stabilizing intra-ion methyl C—H⋯O hydrogen-bonding interactions methane  and nBuLi  was stirred in THF (20 mL) at 273 K under an N2 atmosphere for 2 h. MgEt2  was gently added to the solution. After stirring at 298 K for 6 h, the solution was filtered through celite. The filtrate was concentrated to ca 10 mL and cooled to 273 K to furnish colourless crystals, suitable for the X-ray analysis. Yield: 0.46 g (49%).A solution of tris, or 1.5Ueq(methyl C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017008337/zs2380sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017008337/zs2380Isup2.hklStructure factors: contains datablock(s) I. DOI: 1554461CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


H-pyrazol-5(4H)-one and its structural characterization by synchrotron single-crystal X-ray diffraction are reported.A synthetic approach to the new zinc complex based on aminomethylene derivative of 1-phenyl-3-methyl-4-[(quinolyl-3-yl)iminomethyl]-1 20H15N4O)2]·2.5CH3OH, I, was synthesized via the reaction of zinc acetate with the respective ligand and isolated as a methanol solvate, i.e., as 3OHI·2.5CH. The crystal structure is triclinic (space group P-1), with two complex molecules (A and B) and five methanol solvent molecules in the asymmetric unit. One of the five methanol solvent molecules is disordered over two sets of sites, with an occupancy ratio of 0.75:0.25. Molecules A and B are conformers and distinguished by the conformations of the bidentate 1-phenyl-3-methyl-4-[(quinolin-3-yl)iminomethyl]-1H-pyrazol-5-olate ligands. In both molecules, the zinc cations have distorted tetrahedral coordination spheres, binding the monoanionic ligands through the pyrazololate O and imine N atoms. The two ligands adopt slightly different conformations in terms of the orientation of the terminal phenyl and quinoline substituents with respect to the central pyrazololate moiety. The molecular geometries of A and B are supported by intramolecular C—H⋯O and C—H⋯N hydrogen bonds. In the crystal of I, molecules form dimers both by secondary intermolecular Zn⋯O [3.140 (2)–3.553 (3) Å] and π–π stacking interactions. The dimers are linked by intermolecular hydrogen bonds through the solvent methanol molecules into a three-dimensional network.The title compound, [Zn(C ComplexA and B in I are four-coordinated by two monoanionic O,N-chelating ligands, which bind to the cation through pyrazololate O and imine N atoms. The coordination sphere around each zinc cation can be described as distorted tetrahedral , with dihedral angles between the planar six-membered chelating rings  of 82.97 (7) and 84.52 (7)° for molecules A and B, respectively.The zinc cations of A and B of I adopt different conformations. The main difference pertains to the twist angles of the terminal phenyl and quinoline substituents relative to the central iminomethyl-1H-pyrazol-5-olate fragment. In molecule A  and 8.24 (11)° for the phenyl groups, and 27.47 (10) and 26.08 (6)° for the quinoline substituents. Thus, one of the two 1-phenyl-3-methyl-4-[(quinolin-3-yl)iminomethyl]-1H-pyrazol-5-olate ligands in molecule B is flattened, while one of the two pyrazololate ligands in molecule A is substantially twisted  Å, Zn1⋯O4 = 3.279 (3) Å, Zn2⋯O1 = 3.553 (3) Å and Zn2⋯O2 = 3.140 (2) Å] and π–π stacking interactions between the O2/N5/N6/N7/C21–C24 and O4/N13/N14/N15/C61–C64 imino-methyl-pyrazolonate fragments {the shortest distances are N6⋯C63 [3.083 (3) Å], C21⋯C62 [3.210 (4) Å], C24⋯C64 [3.216 (4) Å], C21⋯C61 [3.261 (3) Å], N14⋯C23 [3.293 (4) Å], C22⋯C61 [3.297 (4) Å], N6⋯C62 [3.319 (3) Å] and N14⋯C22 [3.362 (3) Å]}, as well as phenyl and pyridine rings  , where Cg3vii is the centroid of the C69vii–C74vii benzene ring; symmetry code: (vii) −x, −y, −z + 1] and π–π stacking interactions {the shortest distances are between the C75–C80 and C75viii–C80viii phenyl rings [C75⋯C79viii = 3.196 (4) Å and C80⋯C80viii = 3.279 (4) Å]; symmetry code: (viii) −x, −y + 1, −z + 1}, as well as C—H⋯O and N⋯H—O hydrogen bonds involving the solvent methanol molecules : 1664 ν(C=O), 1627 δ(NH). 1H NMR : δ 2.31 , 7.08–8.03 , 8.52 , 8.89 , 11.46 . UV–vis spectrum (nm): 232, 254, 358. PL spectrum (nm): λPL = 454, 534, λex = 450 nm. Quantum yield of PL φ = 0.002. Analysis calculated for C20H16N4O: C 73.15, H 4.91, N 17.06%; found: C 73.25, H 5.10, N 17.18%.A solution containing 1.44 g (0.01 mol) of 3-aminoquinoline in 10 ml of toluene was added to a solution of 2.02 g (0.01 mol) of 1-phenyl-3-methyl-4-formylpyrazol-5-one in 20 ml of toluene. The mixture was refluxed for 3 h with a Dean–Stark trap until water stripping was completed. Subsequently, two-thirds of the total volume was distilled off on a rotary evaporator. The precipitate which formed was filtered off and recrystallized from ethanol to give light-yellow crystals . FT–IR in KBr  in 20 ml of the same solvent  mixture and dried at 423 K, resulting in a yellow crystalline powder . FT–IR : 1608 ν(C=N). 1H NMR : δ 2.25 , 6.99–8.92 , 8.46 . UV–vis (nm): 360, 340, 304. PL (nm): λPL = 478, λex = 450 nm. Analysis calculated for C40H30N8O2Zn: C 66.72, H 4.20, N 15.56%; found: C 66.78, H 4.25, N 15.64, Zn 9.11%.A hot solution of 0.22 g of zinc acetate dihydrate (1 mmol) in 20 ml of methanol was added to hot solutions of nt Fig. 5. The reaCrystal data, data collection and structure refinement details are summarized in Table 2Scala program  using a Rayonix SX165 CCD detector. A total of 360 images were collected using an oscillation range of 1.0°  and corrected for absorption using the The data completeness of 97.8% is caused by the low (triclinic) crystal symmetry. It is very difficult to get a high data completeness for this symmetry using the φ scan mode only (‘Belok’ beamline limitation), even though we have run two different crystal orientations.I/σ statistics for high-angle reflections, we selected an exposure time so as to admit a minor fraction of intensity overloads in the low-angle part of the detector. These low-angle reflections have imprecisely measured intensities and thus were excluded from the final steps of refinement. (ii) In the present set-up of the synchrotron diffractometer, the low-temperature device eclipses a small region of the 2D detector near the high-angle limit. This small shadowed region has not been masked during integration of the diffraction frames, which erroneously resulted in zero intensity of some reflections. (iii) The quality of the single crystal chosen for the diffraction experiment was not perfect. Some systematic differences between the calculated and observed intensities are probably caused by extinction and defects present in the crystal specimen.A rather large number of reflections have been omitted from refinement due to the following reasons. (i) In order to achieve better Uiso(H) = 1.5Ueq(O)]. All other H atoms were placed in calculated positions, with C—H = 0.95–0.98 Å, and refined in a riding mode, with fixed isotropic displacement parameters [Uiso(H) = 1.5Ueq(C) for the CH3 groups and 1.2Ueq(C) for the other groups]. Disorder over two sets of sites was observed for one methanol solvent molecule (atoms O7–C83). In the last cycles of refinement, the occupancy ratio was fixed at 0.75:0.25 and each of the non-H atoms was modelled with a common displacement ellipsoid.The H atoms of the hydroxy groups were localized from difference Fourier maps and included in a riding mode, with fixed displacement parameters [10.1107/S2056989017010441/wm5401sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017010441/wm5401Isup2.hklStructure factors: contains datablock(s) I. DOI: 1562057CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-(4-chlorobenzenesulfonyl)glycinyl hydrazide with 4-nitrobenzaldehyde gives the N,N-dimethylformamide monosolvated N-acylhydrazone derivative, (E)-N-{2-[2-(4-nitrobenzylidene)- hydrazine-1-yl]-2-oxoethyl}-4-χhlorobenzenesulfonamide. Rings of Reaction of  15H13ClN4O5S·C3H7NO, contains one molecule each of the Schiff base and the solvent dimethylformamide. The hydrazone group adopts an E configuration about the C=N bond. The dihedral angle between the two aromatic rings is 86.58 (2)°. In the crystal, pairs of N—H⋯O hydrogen bonds between centrosymmetrically related molecules generates rings with an R22(10) graph-set motif. The dimers are further linked via N—H⋯O and C—H⋯O hydrogen bonds, leading to the formation of R33(11) ring motifs. C—H⋯π interactions are also observed. The intermolecular interactions in the crystal structure were quantified and analysed using Hirshfeld surface analysis, which indicates that the most significant contacts in packing are O⋯H/H⋯O (31.3%), followed by H⋯H (25.4%) and C⋯H/H⋯C (13.0%).The asymmetric unit of the title compound, C The acidity of the C—H donor group determines the strength of C—H⋯O interactions -4-chloro-N-{2-[2-(4-nitrobenzylidene)hydrazin-1-yl]-2-oxoethyl}benzenesulfonamide N,N-dimethylformamide monosolvate.Supramolecular chemistry is based upon non-covalent interactions such as hydrogen bonding, π–π stacking and van der Waals interactions  and 1.274 (6) Å, respectively, confirm their double-bond character. The C8—N2 and N2—N3 bond distances  are shorter than normal bond lengths as a result of delocalization of the π-electron density. The molecule is twisted at N1—C7 with an S1—N1—C7—C8 torsion angle of 166.5 (4)°. The other central part of the molecule is almost linear with C7—C8—N2—N3, C8—N2—N3—C9 and N2—N3—C9—C10 torsion angles of −1.6 (7), −179.7 (5) and 177.9 (4)°, respectively. The orientations of the sulfonamide group with respect to the attached phenyl ring is given by the torsion angles of C2—C1—S1—N1 = 98.1 (5)° and C6—C1—S1—N1 = −80.2 (5)°, while that of the hydrazone group with the attached phenyl ring by the torsion angles of C11—C10—C9—N3 = 1.6 (8)° and C15—C10—C9—N3 = −177.4 (5)°. The dihedral angle between the sulfonyl benzene ring and the mean plane through the SO2—NH—CH2—CO segment is 82.653 (18)°, while that between the C10–C15 phenyl ring and the mean plane through the C9—N3—N2—CO segment is 4.44 (3)°. The dihedral angle between the two aromatic rings is 86.58 (2)°. The C1–C6 and C10–C15 benzene rings are inclined to the mean plane of the central part of the hydrazone molecule  by 86.4 (3) and 4.5 (3)°, respectively.The asymmetric unit of the title compound Fig. 1 containsvia N—H⋯O and C—H⋯O hydrogen bonds, generating rings with an via N—H⋯O and C—H⋯O hydrogen bonds, leading to the formation of B) and the sulfonyl oxygen atom (O2) forming c axis, and the other involving an aromatic C—H (H14) and the nitro O4 atom, giving rise to inversion dimers with an E)-4-methyl-N-{2-[2-(4-nitrobenzylidene)hydrazin-1-yl]-2-oxoethyl}benzenesulfonamide N,N-dimethylformamide monosolvate  to analyse the close contacts in the title compound. The electrostatic potentials were calculated using TONTO  surface resolution with the 3D dnorm surfaces mapped over a fixed colour scale of −0.5849 to 1.3948. The curvedness was mapped in the colour range of −4.0 to 0.4. The electrostatic potentials were mapped on Hirshfeld surfaces using the STO-3G basis set at the Hartree–Fock level theory over a range ±0.1au.dnorm . The H⋯H interactions appear as the largest region of the fingerprint plot with a high concentration in the middle region, shown in light blue, at de = di ∼1.4 Å  with an overall contribution to the Hirshfeld surfaces of 25.4%. The C⋯H contacts, which refer to C—H⋯π interactions, contribute 13.0% of the Hirshfeld surfaces. The presence of C—H⋯π interactions is indicated by the appearance of two broad spikes having almost same de + di 3.1 Å. The C⋯C contacts contribute 4.5% of the Hirshfeld surfaces, featuring two successive triangles with a minimum (de + di) distance of ∼3.5 Å, which is greater than van der Waals separation, confirming the absence of π–π stacking interactions. This is also evident from the absence of flat regions in the Hirshfeld surface mapped over curvedness glycine (L1) obtained was crystallized from aqueous ethanol. Sulfuric acid (0.5 ml) was added to L1 (0.02 mol) dissolved in ethanol (30 ml) and the mixture was refluxed. The reaction mixture was monitored by TLC at regular intervals. After completion of the reaction, the reaction mixture was concentrated to remove the excess ethanol. The product, N-(4-chlorobenzenesulfonyl)glycine ethyl ester (L2) obtained was poured into water, neutralized with sodium bicarbonate and recrystallized from acetone. The pure L2 (0.01 mol) was then added in small portions to a stirred solution of 99% hydrazine hydrate (10 ml) in 30 ml ethanol and the mixture was refluxed for 6 h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to obtain N-(4-chlorobenzenesulfonyl)glycinyl hydrazide (L3). A mixture of L3 (0.01 mol) and 4-nitrobenzaldehyde (0.01 mol) in anhydrous methanol (30 ml) and two drops of glacial acetic acid was refluxed for 8h. After cooling, the precipitate was collected by vacuum filtration, washed with cold methanol and dried. It was recrystallized to a constant melting point from methanol (493–496 K).4-Chlorobenzenesulfonyl chloride (0.01 mol) was added to glycine (0.02 mol) dissolved in an aqueous solution of potassium carbonate . The reaction mixture was stirred at 373 K for 6 h, left overnight at room temperature, then filtered and treated with dilute hydrochloric acid. The solid −1 for the stretching bands of N—H, C=O, C=N, S=O asymmetric and S=O symmetric, respectively. 1H NMR : 3.68, 4.17 , 7.62–7.67 , 7.80–7.94 , 8.24–8.29 , 8.02 , 8.14 , 11.73, 11.75 . 13C NMR : 43.26, 44.42, 123.94, 127.85, 128.53, 129.19, 137.23, 139.77, 141.47, 144.68, 147.75, 164.52, 169.34. Plate-like yellow single crystals of the title compound suitable for X-ray analysis were grown from its DMF solution by slow evaporation of the solvent.The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3250.1, 1685.8, 1587.4, 1342.5 and 1166.9 cmUeq or 1.5Ueq(C) for methyl H atoms.. The amino H atoms were freely refined with the N—H distances restrained to 0.86 (2) Å.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901800292X/rz5227sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901800292X/rz5227Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901800292X/rz5227Isup3.cmlSupporting information file. DOI: 1433601CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The metal atom of the title compound is four coordinated. The asymmetrically appended Cl atom and a widely spread π-conjugated system of the complex molecule construct the supramolecular structures of a hydrogen-bonded chain and a π–π interacted column. 20H14ClN3O)], with an asymmetrically chloride-appended Schiff base ligand has been synthesized and structurally characterized at 100 K. In the compound, the central nickel(II) ion has a square-planar coordination geometry with N3O donors of the π-conjugated tetradentate Schiff base ligand. In the crystal, the complexes are connected into an inversion dimer via an Ni⋯Ni interaction [3.1753 (5) Å] and a pair of π–π interactions [centroid–centroid distance = 3.8416 (16) Å]. The dimers are linked via a C—H⋯Cl hydrogen bond, forming a chain along the c-axis direction. The dimer chains interact with each other through π–π interactions [centroid–centroid distance = 3.8736 (16) Å], forming a layer expanding parallel to the ac plane.The title complex, [Ni(C Up to now, a large number of salen derivatives have been prepared and used for complexation in the expectation of a wide range of features such as catalytic ability, magnetic, dielectric and luminescence properties and so on  complex using an asymmetrically chloride-appended tetradentate Schiff base ligand.Metal complexes with a tetradentate Schiff base ligand as represented by H3O type asymmetrical ligand was reported by Ghorai & Mukherjee  complex with a similar Nrjee 2014.3O donor set including one phenolate O atom, two imine N atoms and one amino N atom of the tetradentate Schiff base ligand  atom is in a square-planar coordination with an asymmetrical coordination environment formed by the Nnd Fig. 1. The Ni—et al., 1996c axis  Å] and a pair of π–π interactions between the C1–C6 and C15–C20 benzene rings [centroid–centroid distance = 3.8415 (16) Å]. Such dimerization caused by an Ni⋯Ni interaction has also been observed in symmetric Ni compounds  of Ni(CH3COO)2·4H2O  was added to the solution and stirred for 1 h. The resulting solution was allowed to stand for a few days, during which time dark-purple block-shaped crystals precipitated. They were collected by suction filtration and dried in air to give single crystals of the title compound suitable for X-ray diffraction.The tetradentate Schiff base ligand was prepared by the reaction of 2-aminobenzaldehyde  = 1.5Ueq(N). Other H atoms were treated as riding with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017004613/is5472sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017004613/is5472Isup2.hklStructure factors: contains datablock(s) I. DOI: 1539785CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular and crystal structure of the insecticide fipronil is reported. In the crystal, N—H⋯N, N—H⋯O, C—H⋯F hydrogen bonds, C—N⋯π and C—Cl⋯π interactions link adjacent molecules, forming a three-dimensional network. In addition, there are short F⋯F interactions present. 12H4Cl2F6N4OS {systematic name: 5-amino-1--4-[(trifluoromethane)sulfinyl]-1H-pyrazole-3-carbonitrile}, is a member of the phenylpyrazole group of acaricides, and one of the phenylpyrazole group of insecticides. The dihedral angle between the planes of the pyrazole and benzene rings is 89.03 (9)°. The fluorine atoms of the trifluoromethyl substituent on the benzene ring are disordered over two sets of sites, with occupancy ratios 0.620 (15):0.380 (15). In the crystal, C—N⋯π interactions [N⋯ring centroid = 3.607 (4) Å] together with N—H⋯N and C—H⋯F hydrogen bonds form a looped chain structure along [10The title compound, C It is an insecticide with extended use in the control of many agricultural vermin. Fipronil contains a trifluoromethylsulfinyl substituent that is not present in any other agrochemicals and this is thought to contribute to its remarkable potency in the field  Å; Cg1 is the centroid of the C5–C10 ring; symmetry code: (iii) −x, y, −z], together with N3—H3A⋯N4i and C9—H9⋯F2i hydrogen bonds, forming looped chains along  (red dashed lines), link adjacent chains, resulting in a two-dimensional network parallel to the (10B⋯O1ii hydrogen bonds (black dashed lines) combine with these contacts to generate a three-dimensional network structure  Å] and F3⋯F6′vi [2.855 (12) Å] interactions are also present .In the crystal, molecules are linked by C12—N4⋯0] Fig. 2. Inversine Fig. 3. Finallyre Fig. 4. Short Fet al., 2005et al., 2013II, CdII, ZnII and MnII complexes using fipronil as a ligand are known -methylidene]amino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one  = 0.88 Å, Uiso = 1.2Ueq(C) for the N—H group, d(C—H) = 0.95 Å, Uiso = 1.2Ueq(C) for aromatic C—H. Atoms F4–F6 of the CF3 substituent are disordered over two sets of sites. Their occupancies refined to 0.620 (15) and 0.380 (15).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901701310X/sj5534sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S205698901701310X/sj5534Isup2.hklStructure factors: contains datablock(s) I. DOI: 1574261CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of the title compound consists of discrete octahedral complexes that are linked by intermolecular O—H⋯S, C—H⋯Cl, C—H⋯S and C—H⋯Cl hydrogen bonding. 2(C5H4ClN)2(H2O)2], consists of one nickel(II) cation that is located on a center of inversion and one thiocyanate anion, one water molecule and one 2-chloropyridine ligand all occupying general positions. The NiII cation is octahedrally coordinated by two terminal N-bound thiocyanato ligands, two aqua ligands and two N-bound 2-chloropyridine ligands into discrete complexes. Individual complexes are linked by intermolecular O—H⋯S and O—H⋯Cl hydrogen-bonding interactions into a layered network extending parallel to the bc plane. Weak interactions of types C—H⋯S and C—H⋯Cl consolidate the crystal packing.The asymmetric unit of the title compound, [Ni(NCS) The cation is located on a center of inversion whereas all ligands are located on general positions. The NiII cation is coordinated by two terminal N-bound inorganic anionic ligands, two water molecules and two 2-chloropyridine ligands that are coordinated via the pyridine N atom in an all-trans configuration on Fig. 1. As expeb axis ·6H2O and 2-chloropyridine were purchased from Alfa Aesar. Ni(NCS)2 was synthesized by stirring 17.5 g Ba(NCS)2·3H2O (57 mmol) with 15.0 g Ni(SO4)·6H2O (57 mmol) in 500 ml water. The green residue was filtered off and the filtrate was dried using a rotary evaporator. The homogeneity was checked by X-ray powder diffraction and elemental analysis. Crystals of the title compound suitable for single crystal X-ray diffraction were obtained by the reaction of 26.2 mg Ni(NCS)2 (0.15 mmol) with 56.0 µl 2-chloropyridine (0.6 mmol) in ethanol (1.0 ml) after a few days.Ba(NCS)Uiso(H) = 1.2Ueq(C). The OH H atoms were located in a difference map, and their bond lengths constrained to 0.82 Å, with Uiso(H) = 1.5Ueq(O).Crystal data, data collection, and structure refinement details are summarized in Table 210.1107/S2056989016015218/wm5326sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016015218/wm5326Isup2.hklStructure factors: contains datablock(s) I. DOI: 1506903CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information: