Crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)-gold(III) bis(1,2-dicyanoethene-1,2-dithiolato)aurate(III)

The crystal and molecular structure of bis(N,N-di-n-butyldithiocarbamato)gold(III) bis(1,2-dicyanoethene-1,2-dithiolato)aurate(III), Au[S₂CN(C₄H₉)₂]₂Au[S₂C₂(CN)₂]₂, has been determined from a single-crystal X-ray diffraction study. The monoclinic cell, space groupP2₁,/c, witha = 9·930(3),b = 12·517(3),c = 15·632(3) Å and = 110·46(3) °, contains two formula units. Three-dimensional intensity data, up to = 35 ° were collected on an automatic diffractometer. Atomic parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·04 for 1874 independent non-zero reflections. The structure consists of bis(di-n-butyldithiocarbamato)gold(III) cations and bis(l,2-dicyanoethene-l,2-dithiolato)aurate(III) anions. In both ions, the gold atom is in planar coordination with four sulphur atoms, the Au-S bond lengths being 2·333(4) and 2·337(4) Å in the cation and 2·312(4) and 2·306(5) Å in the anion.     

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).     

Crystal structure of bis(4-dimethylaminopyridinium) tribromocuprate(I) and bis(4-dimethylaminopyridinium) tetrabromocuprate(II)

The synthesis and crystal structures of two copper bromide salts of the 4-dimethylaminopyridinium (4DMAP⁺) cation are reported. The Cu(I) salt, (4DMAP)₂CuBr₃, crystallizes in the monoclinic space group C2/c, with a = 11.724(2), b = 11.055(3), c = 15.763(3) Å, = 107.64(3)°, and Z = 4. It contains isolated planar 4DMAP⁺ cations and trigonal planar CuBr₃ ^2– anions. Small distortions from idealized D _3h symmetry are observed for the anion. For the Cu(II) salt, (4DMAP)₂CuBr₄, a triclinic cell is observed with a = 8.2373(2), b = 9.2428(2), c = 14.4391(1) Å, = 93.760(1), = 94.576(1), = 105.249(1)°, and Z = 2. This compound contains discrete planar 4DMAP⁺ cations and flattened tetrahedral CuBr₄ ^2– anions. Small distortions are observed for ideal D _2d symmetry.     

Crystal structure of 1,4,8,12-tetraazacyclopentadecane copper(II) tribromocuprate(I)

The title compound is a mixed valence compound obtained as one of the products of the reaction of Cu(15-ane N₄)Br₂ with CoBr₂·6H₂O in water/acetone solvent (15-ane N₄=1,4,8,12-tetraazacyclopentadecane). The compound is tetragonal, space group P4₂/mbc witha=16.675(2)Å,c=13.185(3)Å,V=3666(1)ų, withZ=8, for p_calc=2.106 g/cc. Refinement of 674 unique observed reflection yielded final values ofR=0.088 andR _w=0.083. The compound contains chains of alternating Cu(15-ane N₄)²⁺ cations and CuBr ₃ ^2– anions. The chains run perpendicular to thec axis, and are arranged in alternate layers running parallel toa andb. The chains lie athwart the mirror planes atz=0 andz=1/2, with disorder observed for both the (15-ane N₄) rings and the CuBr ₃ ^2– anions. The Cu(II) ion is coordinated by the tetradentate macrocycle to yield an approximate square planar coordination. The CuBr ₃ ^2– anions are nearly planar with Cu–Br(ave.)=2.37Å. Long semi-coordinate Cu(II)...Br bonds of 3.0Å link the cations and anions.     

One-dimensional chain structure based on bifurcated hydrogen bonding

The structure of complex [PyH][Ni(mnt)₂], as determined by X-ray single crystal analysis, consists of pyridinium cations and [Ni(mnt)₂]^– anions. Crystallographic data for the complex: monoclinic P2₁/c, a = 16.5430(18) Å, b = 6.3847(9) Å, c = 17.430(2) Å, = 118.040(7)°, V = 1625.4(3) ų, Z = 4. The [Ni(mnt)₂]^– anion is not a planar and the CN groups bend away from the S₄ plane. The interactions between anions and cations via the formation of bifurcated N–H···NC hydrogen bonds give rise to an 1D zigzag chain of alternating cations and anions.     

Crystal structure of 3-methylrhodaninecopper(I) iodide

The crystal structure of the copper(I) complex has been determined by a three-dimensional X-ray analysis. The monoclinic unit cell, space groupP2₁/c,a = 4·195(1),b = 15·581(2),c = 13·885(2) Å and = 114·9(1) °, contains four formula-units. Intensities were collected on an automatic diffractometer. The structural parameters were refined by full-matrix least-squares methods to a conventionalR value of 0·07 for 1809 non-zero observed reflexions.In this complex, the copper atom is in tetrahedral coordination with three iodine atoms and the sulphur atom of the thiocarbonyl group of the ligand. The iodine atom is coordinated with three copper atoms. The distances are 2·683(2), 2·627(2) and 2·665(2) Å. The distances between neighbouring copper atoms are 3·008(3) and 2·960(3) Å and the corresponding angles are 68·44(6) and 68·02(6) °, suggesting weak copper-copper interactions in this complex.     

A mixed valence Cu(I)/Cu(II) chain compound: crystal structure of 1,4,8,11-tetraazacyclotetradecanecopper(II) tribromocuprate(I)

The essentially anaerobic reaction of CuBr₂ and 14ane-N₄ in water/acetone solvent (14ane-N₄ = 1,4,8,11-tetraazacyclotetradecane) yields a mixed valence Cu(I)/Cu(II) compound. The compound is orthorhombic, space group Pcnn, with a = 23.6310(1) Å, b = 23.6429(2) Å, c = 12.4537(1) Å and V = 6957.95(9) ų with Z = 16, for _calc = 2.349 g/cc. Refinement of a twinned crystal with 8,504 unique reflections yielded final values of R₁ = 0.0725 (|F| > 2) and w R₂ = 0.114 and a goodness of fit of 1.448. The compound contains chains of Cu(14ane-N₄)²⁺ cations and CuBr₃ ^2– anions, which are linked together by long semicoordinate Cu(II)···Br bonds. The chains run perpendicular to the c axis and are arranged in layers in which the chains alternately run parallel to the (1 1 0) and to the (1 –1 0) crystal directions. The Cu(II) ion is coordinated by the tetradentate macrocycle to yield an approximate square planar coordination. The CuBr₃ ^2– anions have a nearly trigonal planar with Cu–;Br(ave) = 2.38(1) Å.     

Copper(II) complexes 1-phenylpropane-1,2-dione- and benzil bis(3-piperidylthiosemicarbazone): A structural study

The crystal and molecular structure of copper(II) complexes of benzil bis(3-piperidylthiosemicarbazone), [Cu(Bnzpip)] and 1-phenylpropane-1,2-dione bis(3-piperidylthiosemicarbazone), [Cu(Pmpip)] have been determined. [Cu(Bnzpip)] is monoclinic, space group P2₁/n with a = 13.9375(10) Å, b = 11.6621(4) Å, c = 16.4710(10) Å, = 100.667(2)°, and V = 2630.9(3) ų with Z = 4, for d _calc = 1.399 g/cm³. [Cu(Pmpip)] is also monoclinic, space group P2₁/n with a = 11.292(6) Å, b = 10.219(5) Å, c = 20.292(6) Å, = 101.50(3)°, and V = 2295(2) ų with Z = 4, for d _calc = 1.525 g/cm³. Both complexes involve N₂S₂ coordination, are relatively planar except for the phenyl rings and have similar bond distances and angles to copper(II) complexes of other 3-piperidylthiosemicarbazones.     

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.     

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.     

Crystal and molecular structure of chlorotris(monomethylthiourea)silver(I)

The crystal and molecular structure of chlorotris(monomethylthiourea)silver(I) has been solved and refined by full-matrix least-squares methods to a finalR of 0·039 from 1150 reflections measured by counter techniques at ambient room temperature. The crystals are orthorhombic:Pmcn, a = 14·824(2),b = 8·524(1),c = 12·671(1) Å,Z = 4,D _m = 1·68,D _c = 1·72 gcm^–3. The structure consists of independent, distorted tetrahedral Ag(I) moieties with only weak hydrogen bonds and/or van der Waals interactions between molecules. These molecules are packed in such a way that Ag, Cl and one entire monomethylthiourea ligand all lie in a crystallographic mirror plane, and the other two ligands are related by this mirror. This arrangement, plus the alternation of the Ag-Cl bond direction, leads to a non-polar sheet of Ag, Cl and monomethylthiourea groups with other monomethylthiourea groups protruding from either side of the sheet. Only N-HCl hydrogen bonds and van der Waals interactions exist between sheets. The Ag-S distance is somewhat long at 2·649(3) Å, as is one of the Ag-S distances at 2·665(3) Å. The other two Ag-S distances are 2·520(2) Å. The geometry of the complex makes it clear that the Ag-S bond is formed by donation of an electron pair from a sulfur sp² orbital.     

Synthesis and crystal structure of two vanadium(V) hydroxylamido complexes with amino acid ligands

Two vanadium(V) hydroxylamido complexes with amino acid ligands including Alanine, [VO(NH₂O)₂(Ala)]·2H₂O, and Threonine, VO(NH₂O)₂(Thr), were synthesized and characterized by elemental analyses, IR spectrum, and single crystal X-ray diffraction. The two complexes are seven-coordinated with four nitrogen atoms and three oxygen atoms in pentagonal bipyramidal geometry. The different hydrogen bonds (N–H···O, O–H···O) observed in the two complexes result in the two-dimensional network structure. [VO(NH₂O)₂(Ala)]·2H₂O belongs to monoclinic: space group P2(1)/c, with a = 21.874(13) Å, b = 8.874(5) Å, c = 15.865(9) Å, = 100.423(8)°, V = 3029(3) ų, Z = 12, D _c = 1.678 g/cm³, (MoK) = 1.002 mm^–1, F (000) = 1584, and final R ₁ = 0.0375, wR ₂ = 0.0886 for observed reflections 1189 (IT > I> 2(I)). VO(NH₂O)₂(Thr) is rhombohedral: space group R-3, with a = 21.460(16) Å, b = 21.460(16) Å, c = 11.184(12) Å, = 120°, V = 4461(7) ų, Z = 18, D _c = 1.669 g/cm³, (MoK) = 1.012 mm^–1, F(000) = 2304, and final R ₁ = 0.0356, wR ₂ = 0.0924 for observed reflections 1306 (I > 2(I)).     

Influence of the spectator cation on the structure of anionic pyridine-2,6-dicarboxylato complexes of cobalt(II), nickel(II), and copper(II)

The structures of anionic pyridine-2,6-dicarboxylato (pdc^2–) complexes of cobalt, nickel, and copper have been studied. The stoichiometries and structures are very much dependent on whether KOH, Et₄NOH, or NaOH is used in the synthesis to deprotonate the H₂pdc ligand. Crystallographic results are: (1) K₂[Co(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.637(2)Å, b = 13.480(1)Å, c = 8.200(1)Å (2) K₂[Ni(pdc)₂] · 7H₂O, orthorhombic, Pnna, Z = 4, a = 20.648(1)Å, b = 13.375(1)Å, c = 8.2393(8)Å (3) [Co₂(H₂O)₅(pdc)₂] · 2H₂O, monoclinic, P2₁/c, Z = 4, a = 8.3880(6)Å, b = 27.384(2)Å, c = 9.6110(8)Å, = 98.271(6)° (4) [Ni(Hpdc)₂] · 3H₂O, monoclinic, P2₁/c, Z = 4, a = 13.679(1)Å, b = 10.0450(9)Å, c = 13.767(2)Å, = 115.184(7)° (5) Na₆[Co(H₂O)₆][Co(pdc)₂]₄ · 28H₂O, monoclinic, P2₁/n, Z = 2, a = 13.363(1)Å, b = 8.437(1)Å, c = 40.689(3)Å, = 91.288(5)° (6) Na[Ni(Hpdc)(pdc)] · 11.5H₂O, monoclinic, C2/m, Z = 4, a = 15.200(2)Å, b = 22.299(2)Å, c = 8.3596(7)Å, = 118.894(7)° (7) Na[Cu(Hpdc)(pdc)] · 3H₂O, monoclinic, P2₁/n, Z = 4, a = 9.516(4)Å, b = 14.917(6)Å, c = 12.247(5)Å, = 92.00(5)°. The potassium and sodium complexes have extensive K⁺—H₂O and Na⁺—H₂O networks. The fact the Et₄N⁺ ion does not appear in any of the complexes is likely due to the fact that it is incapable of forming the intricate cation—water and hydrogen-bonding networks observed in all of the other structures.     

The crystal structures of p-iodo-N-(p-cyanobenzylidene)aniline and p-cyano-N-(p-iodobenzylidene)aniline

The crystal structures of the isomers NC–C₆H₄–CH=N–C₆H₄–I (CN/I) and I–C₆H₄–CH=N–C₆H₄–CN (I/CN) have been determined. CN/I is triclinic, space group P1¯ with a = 7.504(3), b = 11.936(4), c = 7.304(2) Å, = 93.09(2), = 110.49(2), = 99.04(2)°, V = 601.1(3) ų, Z = 2, and D _x = 1.818(1) g cm^–3. In both compounds there are chains of molecules held together by CN···I interactions, with N···I distances of 3.15 and 3.26 Å, respectively. The chains form similar two-dimensional sheets, which, however, stack differently in the two compounds.     

Synthesis and structure of bis(2,6-dimethylpyrazine)(THF)copper(II) nitrate

Attempts to crystallize Cu(2,6-dmpz)(NO₃)₂ (2,6-dmpz = 2,6-dimethylpyrazine) by reaction of 2,6-dmpz with Cu(NO₃)₂·3H₂O in THF resulted in the synthesis of Cu(2,6-dmpz)₂(NO₃)₂·THF. The compound crystallized in the monoclinic space group C2/c and exists as isolated molecules with distorted square pyramidal geometry: a = 11.609(4) Å, b = 10.415(3) Å, c = 18.256(6) Å, = 108.332(4)°. The 2,6-dmpz molecules coordinate to the Cu ions through the distal (remote from the methyl) nitrogens. The molecules are arrayed in stacks parallel to the b-axis.     

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.     

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.     

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.     

Crystal and molecular structure of bis(imazapyr)diaqua copper(II)

The imidazolinone herbicide imazapyr, 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid (H₂imz) interacts with Cu(II) leading to [Cu(Himz)₂(H₂O)₂] which crystallizes in the space group Pbca, with a = 12.5370(3) Å, b = 19.8500(5) Å, c = 22.7720(9) Å, and Z = 8. The Cu(II) atom is octahedrally surrounded by four nitrogen atoms of two Himz^– anions and two water molecules. Each Himz^– acts as a chelating ligand by means of N pyridine and N lactam atoms leading to five-membered chelate rings. The Cu N distances vary from 1.948(4) to 2.299(5) Å while the Cu O are 2.114(5) and 2.256(6) Å. The imidazol N-H are involved in short intramolecular hydrogen bonds with the carboxylate groups. The structure is stabilized by an intermolecular hydrogen-bonded network involving the water molecules and the carboxylate groups.     

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.