Crystal and molecular structure of dithiobiuret

The crystal and molecular structure of dithiobiuret (S₂C₂N₃H₅) has been determined and refined from 1020 intensities measured by counter techniques at room temperature. The full-matrix refinement, including anisotropic temperature factors for the non-hydrogen atoms and isotropic temperature factors for the hydrogen atoms, converged to a finalR of 0·033. The structure consists of almost planar molecules in thetrans configuration with essentially only van der Waals interactions between molecules. The two independent C-S distances are 1·702(3) and 1·673(3) Å. The internal C-N distances are 1·386(4) and 1·367(4) Å, whereas the external C-N distances are 1·331(4) and 1·309(4) Å. The unit cell parameters area = 4·081(1),b = 17·684(5),c = 8·222(3) Å and = 100·56(2) °;Z = 4,D _m =D _c = 1·54 gcm^–3; the space group isP2₁/c.     

Pentacoordination in dichloro-N-2-methylthiophenyl-2′-pyridylmethyleneiminecopper(II)

Dichloro-N-2-methylthiophenyl-2-pyridylmethyleneiminecopper(II) is monoclinic:P2₁/c;a = 8·49(1),b = 10·80(1),c = 15·67(1) Å, = 92·0(3)·,Z = 4. The crystal structure has been determined at room temperature from three-dimensional X-ray photographic data and refined by differential methods with anisotropic thermal parameters to a finalR value of 8·1%. Cu(II) coordinates to two chlorine atoms (Cu-Cl = 2·255,2·443 Å) and to one sulphur (Cu-S = 2·341 Å) and to two nitrogen atoms (Cu-N = 2·011, 2·014 Å) from methylthiophenylpyridylmethyleneimine; this represents a distorted tetragonal pyramid with the organic molecule behaving as a tridentate ligand. Packing is determined by normal van der Waals contacts.     

Crystal structure of [Mn2(III)(salpa)2Cl2(H2O)2] (H2salpa = 1-(salicylaldeneamino)-3-hydroxypropane)

The manganese complex, (Mn₂(III)(salpa)₂Cl₂(H₂O)₂], has been prepared and its structure determined using x-ray crystallography. The dimer is a di-₂-alkoxo complex which is a six-coordinate manganese dimer with unsupported alkoxide bridges and a rare example of a chloride- and water-containing manganese dimer. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.315(5), b = 11.130(4), c = 11.637(5) Å, = 104.33(3)°, V = 1169.0(9) ų, and Z = 2. The structure comprises discrete binuclear clusters in which the metal atoms are bridged by two alkoxo oxygens of the salpa^2– ligands. The Mn—O and Mn—N distances are in good agreement with those found for other manganese(III) Schiff base complexes. The Mn—Cl and Mn—O3 distances are 2.585(2) and 2.371(2) Å, respectively, and the Mn ··· Mn distance is 3.001(1) Å. In the crystal, there are two types of hydrogen bonding between the H₂O molecule and the Cl atom with Cl ··· H(H₂O) distance of 2.33(6) (intramolecule: –1 + x, y, –1 + z) and 2.68(6) Å (intermolecule: –1 + x, 0.5–y, –0.5 + z).     

X-ray structure of 6-(N,N-dimethylcarbamoyl)thioquinanthrene

The crystal and molecular structures of 6-(N,N-dimethylcarbamoyl)thioquinanthrene 1 have been determined as monoclinic, with space group C2/c, a = 22.484(4) Å, b = 10.251(2) Å, c = 16.972(3) Å, = 110.18(3)°. Due to the 6-dimethylcarbamoyl substituent causing overcrowding in the environment of position 6-, the carbonyl group carbon atom (C61) deviates from planarity with the parent pyridine ring by 0.249(8) Å, and differences between respective bond lengths and bond angles in both pyridine rings by about of 4–5 are also observed. X-ray data show spatial non-equivalency of N-methyl groups. The values of the S······S,S······O distances are well below the sum of the van der Waals radii of the heteroatoms.     

Crystal structure of N-benzylmethylammonium dihydrogen-monophosphate monohydrate, [C6H5CH2NH2CH3]H2PO4·H2O

The salt N-benzylmethylammonium dihydrogenmonophosphate monohydrate is monoclinic with the following unit cell dimensions: a = 6.356(1)Å, b = 8.385(7)Å, c = 11.472(5)Å, = 104.32(1)°, space group P2₁ with Z = 2. The structure consists of infinite parallel two-dimensional [110] planes built of mutually connected ions and water molecules by strong O–H···O and N–H···O hydrogen bonding. There are no contacts other than normal van der Waals interactions between the layers.     

Molecular structures of M(tfac)3 (M=Al, Co) and Cu(H2O)(fod)2: Examples of unusual supramolecular architecture

The molecular structures of Al(tfac)₃ (1), Co(tfac)₃ (2) (H-tfac = 1,1,1-trifluoroacetylacetone) and Cu(H₂O)(fod)₂ (3) (H-fod = 1,1,1,2,2,3,3-hepta-fluoro-7,7-dimethyloctane-4,6-dione) have been determined. The metal coordination spheres in compounds 1 and 2 are essentially the same as the respective M(acac)₃ derivatives. Despite the isomorphous nature of the structures of compounds 1 and 2, the identity of the nearest intermolecular van der Waals contacts are altered by minor changes in the metal coordination sphere. The geometry about copper in compound 3 is close to that of an ideal square bipyramid with the -diketonate ligands occupying the basal plane. The water ligand in each molecule of compound 3 is hydrogen bonded to an oxygen of a -diketonate ligand on an adjacent molecule resulting in the formation of dimers, which form rods along the y-axis due to weak C–F···Cu interactions. Crystal data: (1) orthorhombic, Pca2₁, a = 14.949(3), b = 19.806(4), c = 13.624(3) Å, V = 4033(1) ų, and Z = 8, and (2) orthorhombic, Pca2₁, a = 14.930(3), b = 19.620(4), c = 13.540(3) Å, V = 3966(1) ų, and Z = 8,; (3) monoclinic, P2₁/c, a = 12.447(3), b = 10.486(2) c = 21.980(4) Å, = 102.65(3)°, V = 2799(1) ų, and Z = 4.     

Crystal structure of bis(2-butyl-4-chloro-imidazole)5-iminoethane

The title compound (C₁₈H₂₆N₆Cl₂) crystallizes in monoclinic space group P2₁/c with a = 14.867(4) Å}, b = 7.758(2) Å}, c = 9.671(3) Å}, = 108.78(1), V = 1056.0(5) Å}³, Z = 2, D_cal = 1.250 Mg/m³ at T = 293 K. The structure was solved by direct methods and refined by full-matrix least-squares procedures to final R = 0.0650 and wR = 0.1719 using 2493 reflections. The imidazole ring is planar and the n-butyl chain adopts an extended conformation. The molecules in the crystal are stabilized by N–H s N type of intermolecular hydrogen bondings in addition to van der Waals forces.     

The crystal structures of p-halo-N-(p-cyanobenzylidene)aniline and p-cyano-N-(p-halobenzylidene)aniline (halo = bromo and chloro)

p-Bromo-N-(p-cyanobenzylidene)aniline is triclinic, has space group P , at 173 K, with a = 7.3892(15), b = 12.087(2), c = 7.0283(14) Å, = 105.24(2), = 98.11(2), = 98.89(2)°, Z = 2, V = 587.4(2) ų. p-Chloro-N-(p-cyanobenzylidene)aniline is triclinic, space group P , at 173 K, with a = 7.317(2), b = 12.165(3), c = 6.990(2) Å, = 104.02(2), = 100.96(2), = 100.76(2)°, Z = 2, V = 574.7(3) ų. p-Cyano-N-(p-bromobenzylidene)aniline is orthorhombic, has space group P2₁2₁2₁, at 173 K, with a = 10.333(3), b = 4.732(3), c = 23.526(5) Å, Z = 4, V = 1150.3(8) ų. p-Cyano-N-(p-chlorobenzylidene)aniline is orthorhombic, has space group P2₁2₁2₁, at 173 K, with a = 10.161(2), b = 4.713(2), c = 23.509(5) Å, Z = 4, V = 1125.8(4) ų. In the two cyanobenzylidene compounds there are chains of molecules held together by CN······X interactions. The chains form two-dimensional sheets similar to those in the iodo analog, but with a different stacking arrangement between the sheets. In the two halobenzylidene compounds there are no CN······X contacts; rather there are short X······X and C–H······NC contacts.     

Stereochemistry of racemic hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) thiocyanate,C16H32N4Ni(SCN)2 · H2O

The diamagnetictrans-diene thiocyanate salt of the macrocyclic hexamethyl-1,4,8,11-tetraazacyclotetradecadienenickel(II) complex crystallizes in the triclinic system with unit cell dimensions:a = 7·334(4),b = 8·808(6),c = 21·04(2) Å; = 63·7(0·9), = 103·8(1·4), = 110·2(1·3) °; space groupP¯1;Z = 2. The positions of all 62 atoms of the formula unit C₁₆H₃₂N₄Ni(SCN)₂.H₂O have been determined and refined by least-squares methods toR= 0·071 for 3536 X-ray diffractometric reflections. The optical activity of the two amine groups yields a racemic isomer. The only local symmetry element of the macrocyclic complex is the twofold rotation axis with the N-H bonds oriented on the same side of the approximate ligand plane. Both the C(CH₃)₂ and the imine groups are in atrans-configuration in the ring. The space group ensures that the crystal is a racemate, containing equal numbers of both enantiomers. One of the (SCN)^– groups is at a distance Ni-S 3·28 Å, the other one is 4·65 Å. No rotational disorder of the CH₃ groups has been observed. The three C-H bonds of the CH₃ groups are in approximately antiprismatic orientations with respect to the three -bonds in the case of bonding to a C(sp³) atom. The average of the C(sp³)-C(sp²) bond lengths is 1·53 Å, and the mean value for the C(sp³)-C(sp²) bonds is 1·50 Å, with 3 = 0·03 to 0·04 Å. The distances N(sp²)-C(sp³) 1·47 Å and 1·48 Å are significantly longer than the bond lengths N(sp²)=C(sp²) of 1·28 and 1·30 Å.     

The structure of bis(trimethylammonium) undecachlorotriantimonate(III) [(CH3)3NH]2Sb3Cl11 containing a novel antimony(III) anion

The structure of [(CH₃)₃NH]₂Sb₃Cl₁₁ (space group P2₁/n; a = 10.374(2), b = 23.723(5), c = 11.884(2) Å, = 113.46(3)°; V = 2682.9(9) ų) consists of a structurally novel [Sb₃Cl^2– ₁₁] anion and two crystallographically nonequivalent trimethylammonium cations. The anion is composed of three deformed octahedra in the asymmetric part of the unit cell. The octahedra are connected with each other by edges and corners forming a characteristic polyanionic layer. Trimethylammonium cations, one ordered and one disordered, are connected to the inorganic sublattice by N—H···Cl hydrogen bonds.     

Synthesis,properties, and structure of 1,3-dimethyl-2(3H)-imidazolethione hydrogen bromide

The compound dmit·HBr (dmit=1,3-dimethyl-2(3H)-imidazolethione) has been synthesized and characterized. The crystal and molecular structure of dmit·HBr has also been determined. The compound, C₅H₉BrN₂S, crystallizes in space groupP2₁/c with four formula units in a cell of dimensionsa= 7.331(1),b=7.744(2),c=14.626(4) Å, and=99.56(2)°. The calculated and observed densities are 1.678 and 1.68(2) g cm^–3, respectively. X-ray results along with physical characterization show this compound to be a molecular adduct of dmit and hydrogen bromide which is sensitive to air, light, and moisture. Specific conductivity (10^–3 M in PhNO₂), infrared, and¹H-NMR data have also been obtained. X-ray results reveal intermolecular contracts between S and Br to be primarily van der Waals in nature. Molecular units are linked through long zigzag Br-S-Br-S chains.     

Crystal and molecular structure of chloro(2,2′,2″-terpyridine)palladium(II)chloride dihydrate,C15H15Cl2N3O2Pd

The crystal and molecular structure of chloro(2,2,2-terpyridine)palladium(II)-chloride dihydrate, C₁₅H₁₅Cl₂N₃O₂Pd, has been determined by single crystal X-ray diffraction techniques. The crystals are orthorhombic: space groupPna2₁,a = 17·217(9),b = 14·026(8),c = 6·801(5) Å,Z = 4. Least-squares refinement of 2064 non-zero manually gathered diffractometer reflexions was carried out to a conventional unweightedR of 0·069. The molecule consists of a basically planar 4-coordinate [Pd(terpy)Cl]⁺ cation and a Cl^– anion. The molecules are packed in a layer structure in which the average separation is about 3·4 Å, the closest approach being 3·13 Å between a palladium atom and one of the nitrogen atoms of a neighboring molecule. Bond distances are within acceptable limits of predicted values. Deviations from planarity in the coordinated terpyridine ligand are presumably due to its steric limitations and are similar to those found in other terpyridine complexes.This work was supported in part by the National Science Foundation under grants GP-7510 and GP-11776.     

Crystal and molecular structure of bis(2,2,6,6-tetramethylheptane-5-thiolo-3-onato)nickel(II)

The crystal structure of the nickel(II) chelate of the monothio derivative of 2,2,6,6-tetramethyl-heptane-3, 5-dione has been studied at room temperature by X-ray diffraction methods. The space group isP2₁/c and the crystal data area = 19·96(2),b = 10·25(1),c = 12·45(1) Å, = 102·17(5) °Z = 4,D _m = 1·22,D _c = 1·23 g cm^–3. Full-matrix least-squares refinement of atomic and anisotropic thermal parameters, using 2109 non-zero intensities obtained by counter methods, terminated with a conventionalR of 0·105. The nickel was found to be surrounded by acis arrangement of two oxygen and two sulphur atoms which is almost planar, but slightly distorted towards a tetrahedron. All the evidence obtained supports extensive delocalization in the chelate rings, and the entire molecule has pseudomm symmetry. Thecis, rather thantrans relationship of the ligand atoms may indicate weak S-S interaction.     

Crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)copper(III) triiodide

The crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)-copper (III) triiodide, Cu(S₂CN(C₄H₉)₂)₂ ⁺I₃ ^–, has been determined from a single-crystal X-ray diffraction study. The monoclinic unit cell, space groupP2₁/c,a = 14·026(6),b = 8·62(1),c = 25·015(9) Å, = 95·35(5) °, contains four formulaentities. Three-dimensional intensity data were obtained from Weissenberg photographs. Atomic parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·083 for 950 independent non-zero reflexions. The structure contains two symmetry-independent cations. In both cations, the copper atom is in planar coordination with four sulphur atoms, the mean Cu(III)-S bond length being 2·22(2) Å. Cu(III)-S distances are about 0·08 Å less than Cu(II)-S distances in comparable complexes.     

Intramolecular hydrogen bonding and tautomerism in N-(3-pyridil)-2-oxo-1-naphthylidenemethylamine

N-(3-pyridil)-2-oxo-1-naphthylidenemethylamine (C₁₆H₁₂N₂O) was studied by elemental analysis, IR, ¹H NMR, and UV–visible techniques and X-ray diffraction methods. The UV–visible spectrum of the compound was investigated in solutions effect polarity. The polarity of the some solvents was modifierly the additional (CF₃COOH) and [(C₂H₅)₃N]. The compound is in tautomeric equilibrium (phenol-imine O–H···N and keto-amine O···H–N forms) in polar and nonpolar solvents. The keto-amine form is observed in basic solutions of DMSO, ethanol, chloroform, benzene, cyclohexane, and in acidic solutions of chloroform and benzene, but not in acidic solutions of DMSO and ethanol. The compound crystallizes in the monoclinic, space group P2₁/a with a = 7.010(5) Å, b = 13.669(4) Å, c = 12.764(4) Å, = 101.23(4)°, V = 1199.6(10) ų, Z = 4, D _c = 1.375 g/cm³, (Mo K) = 0.088 mm^–1, R = 0.045 for 1658 reflections [I > 2(I)]. The title compound is not planar two Schiff base moieties A [C1–C11, O1] and B [N1, C12, C13, N2, C14, C15, C16] are inclined at an angle of 27.4(1)° reflecting mainly the twist about C12–N1 [C11–C12–N1–C13, 29.7(2)°]. There is a strong intramolecular hydrogen bond (O–H···N) of 2.529(2) Å.     

Crystal and molecular structure of tetrakis(N,N′-dimethylthiourea)platinum(II)chloride

The crystal and molecular structure of tetrakis(N,N-dimethylthiourea) platinum(II) chloride has been solved and refined by least-squares methods to a finalR of 0.052 from 4145 reflections measured by counter techniques. The crystals are triclinic:P¯1,a = 10.06(1),b = 10.19(2),c = 14.06(2) Å, = 89.7(1), = 101.4(1), = 90.1(1) °,Z = 2,D _m = 1.76,D _c = 1.605 g cm^–3. The structure consists of discrete Pt[SC(NHCH₃)₂] ₄ ²⁺ and Cl^– ions, linked by a network of NH^...Cl hydrogen bonds. The dimethylthiourea groups are bonded to the metal through sulfur with Pt-S bonds of 2.305(2) and 2.321(2) Å. The PtS₄ is almost square planar with 0.24 Å displacement of Pt from the best plane of the sulfur atoms. The entire cation has an approximateC ₄ symmetry. The shortest Pt^...Cl distance is 3.677(2) Å.     

Crystal and molecular structure of tetrakisthiourea cobalt (II) nitrate monohydrate,C4H16CoN8S4 2+,2NO 3 − ,H2O

The crystal structure of tetrakisthiourea cobalt(II) nitrate monohydrate has been solved and refined by full-matrix least squares, including anisotropic temperature factors, to a finalR of 0.066. The structure is made up of discrete tetrakisthiourea Co(II) molecular ions and NO ₃ ^– ions bound together by hydrogen bonds with water molecules as well as ionic and van der Waals interactions. The local configuration of the cobalt(II) and its four bonded nearest sulfur neighbors is that of a distorted tetrahedron with an average Co-S distance of 2.30 Å. Three of the Co-S bonds appear to be made with sulfur sp² orbitals and lone pairs whereas the remaining Co-S bond involves the S-C molecular orbital as the electron donor. The thiourea groups appear to be normal. Tetrakisthiourea cobalt(II) nitrate monohydrate: orthorhombic,Pbca,a = 33.704(8),b = 11.734(2),c = 10.253(2) Å,Z = 8,D _m = 1.68(2),D _e = 1.66 g cm^–3.     

Crystal and molecular structures of three trimethylamine-boron halide adducts: (CH3)3NBCl3, (CH3)3NBBr3, and (CH3)3NBI3

X-ray diffraction data from single crystals of the trimethylamine complexes of the three boron halides, BCl₃, BBr₃, and BI₃, lead to aP2₁/m monoclinic cell containing two molecules for each complex. The unit cell dimensions area = 6·68(1),b = 10·247(3),c = 6·502(6) Å, =116·2(1)° (chloro);a = 6·86(1),b = 10·612(4),c = 6·737(6) Å, = 115·8(1)° (bromo);a = 6·92(2),b = 10·86(1),c = 7·147(6) Å, = 93·9(1)° (iodo). The structures were solved by three-dimensional sharpened Patterson functions and show only the chloro and bromo compounds to be isomorphous. Refinement of 662,718 and 954 observed reflexions for the chloro, bromo and iodo complexes, respectively, using anisotropic thermal parameters yielded conventionalR factors of 0·045, 0·087 and 0·054.The molecules are shown to possess a B—N dative bond, a staggered conformation, and effective 3m (C _3v) symmetry. Average C—N bond lengths are 1·52(1) Å for all three complexes. Boronhalogen bond lengths average 1·864(4), 2·04(2) and 2·28(2) Å, while B—N bond distances are 1·609(6), 1·60(2) and 1·58(3) Å, respectively, for the chloro through iodo compounds. Bond angles are approximately tetrahedral with the C—N—C angle decreasing by several degrees in the Cl Br I series.Based in part on a dissertation submitted by Patty H. Clippard to the Rackham School of Graduate Studies of the University of Michigan, January 1969 in partial fulfillment of the requirements of the Ph.D. Degree.     

Crystal and molecular structure of tetrakis(N,N′-diallylthiourea)nickel(II) iodide

Summary The crystal structure of tetrakis(N,N-diallylthiourea)nickel(II) iodide [Ni(C₇H₁₂N₂S)₄I₂] has been determined by a three-dimensional X-ray analysis. FinalR, after anisotropic least-squares refinement, is 8·8%. The crystals are tetragonal (P4/n):a = 11·24(1),c = 15·43(1) Å,Z = 2. Ni(II) is on a 4-fold axis; the coordination around it is flattened pyramidal and involves four sulphur atoms from four diallylthiourea molecules (Ni-S = 2·221 Å). Ni(II) is out of the plane through the sulphur atoms by 0·40 Å. Two I^- ions lie on opposite sides with respect to the nickel atom along the 4-fold axis, at distances Ni...I(1) = 3·74 Å, Ni...I(2) = 6·64 Å. The orientation of the allylthiourea molecules is determined mainly by a hydrogen bond formed by one nitrogen (N(1)) with the iodine which is nearer to the nickel.The authors are indebted to Prof. C. Furlani who kindly supplied the crystals of the compound.     

Crystal structure of methyl β-D-hamameloside

The crystal structure of methyl -D-hamameloside has been determined by direct methods. The trigonal crystals have the space groupR3. Referred to hexagonal axes, there are nine molecules in the non-primitive unit cell witha =b = 18·08(2),c = 7·22(2)Å. The molecule exists in the 1C-trans-chair conformation, with the mean C-C and C-O bond lengths being 1·531 and 1·428Å respectively. The mean value for the carbon bond angle is 110·2 °. The crystal structure is composed of columns of molecules hydrogen-bonded about 3₂ axes, and with van der Waals forces holding these columns together around the 3₁ and 3-fold axes.