The crystal and molecular structure of phenothiazine-10-propionitrile. The effect of crystal packing on the dihedral angle of phenothiazine heterocycles

Phenothiazine-10-propionitrile, C₁₂H₈SNC₂H₄CN, crystallizes in the centrosymmetric monoclinic space group P2₁/n, with a = 5.785(1)Å, b = 15.427(3)Å, c = 14.497(4)Å, β = 92.50(1)°, Z = 4, D_meas = 1.29(1) g cm³ and D_calc = 1.28 g cm³ at 23°. Three dimensional X-ray data were collected with a manual diffractometer using MoKα (λ 0.71069Å) radiation and by multiple film Weissenberg techniques using CuKα (λ 1.5418Å) radiation. The structure was determined by Patterson and Fourier methods and refined with 519 observed reflections by full matrix least-squares methods to an R of 0.077. The dihedral angle between the two planes of the o-phenylene rings is 135.4(3)°. In the folded heterocyclic ring the C-S-C angle is 97.8(7)° and the average C? S bond is 1.76(1)Å. A comparison of this structure to that of phenothiazine-10-propionic acid shows the two chemically similar molecules have the same dihedral angles in spite of completely different solid state packing patterns.     

Manifestations of noncovalent interactions in the solid state. Dimeric and polymeric self-assembly in imidazolium salts via face-to-face cation—cation π-stacking

Abstract

X-ray crystallographic investigation of the tertiary structure of simple 1-methylimidazolium (1-Meim) salts reveals that cation—cation face-to-face π—stacking with interplanar separations in the range typically seen for molecule—molecule and molecule—cation interactions are possible. Two salts are reported. 1-Meim-CF₃SO₃, 1, exists as a centrosymmetric dimer with an interplanar separation of only 3.16 Å. The two imidazolium rings are slipped to the extent that the interaction can be regarded as a manifestation of C—H…C—H dipole interactions. 1-Meim-NO₃ exists as a one-dimensional (1-D) polymer with interplanar separations of 3.65 Å. The cations are not as severely slipped as for 1 and the interactions can be regarded as the result of cation—cation and anion—anion complementary electrostatics. Semi-empirical calculations are used to rationalize the π-π stacking in both 1 and 2. Crystal data: 1-Meim-CF₃SO₃, 1, triclinic, P1, a=6.416(3) Å, b=7.617(4) Å, c=9.569(4) Å, α=85.36(4)°, β=86.08(3)°, γ=85.18(4)°, V=463.6(4) Å,³ Z=2, D_c =1.66 g cm^?3, μ=3.7 cm^?1, T=17°C, R=0.054 and R _w=0.076 for 1241 reflections; 1-Meim-NO₃, 2, monoclinic, P2₁/c, a=9.009(7) Å, b=9.988(6) Å, c=7.308(5) Å, β=94.93(6)°, V=655.2(8) Å,³ Z=4, D_c =1.47 g cm^?3, μ=1.2 cm^?1, T=17°C, R=0.060 and R _w=0.068 for 483 reflections.     

The crystal and molecular structure of phenothiazine-10-propionic acid

The crystal structure of phenothiazine-10-propionic acid, C₁₂H₈SNC₂H₄COOH, was determined from three-dimensional X-ray diffraction data collected with a manual diffractomer using MoKα (λ 0.71069 Å) radiation. The space group is P2₁/c with a = 7.888 (2)Å, b = 8.703 (2)Å, c = 19.700 (8)Å, β = 101.42 (1)°, Z = 4, D_meas = 1.35(2) g. cm^?3 and D_calc = 1.36 g. cm^?3 at 23°. The structure was determined by the direct method and refined with 500 observed reflections by full-matrix least squares to an R of 0.072. The molecule is folded along the S-N axis and the dihedral angle is 136.5°. The C-S-C angle is 98.5(7)° and the average C-S bond is 1.77(2)Å. The shortening of the C-S bond, the small value of the C-S-C angle and the folding of the molecule are typical of the phenothiazine class of compounds and are assumed to be due to sulfur d orbital participation in ring bonding.     

Syntheses and Crystal Structures of Copper(II) and Copper(I) dpp Complexes, [Cu(dpp)Br2] and [Cu(dpp)2][CuBr2] (dpp = 2,9‐diphenyl‐1,10‐phenanthroline)

The complexes [Cu(dpp)Br₂] ( 1 ) and [Cu(dpp)₂][CuBr₂] ( 2 ) (dpp = 2,9‐diphenyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction methods. Reaction of copper(II) bromide with the dpp ligand in dichloromethane at room temperature afforded 1 , which is a rare example of non‐square planar four‐coordinate copper(II) complexes. Complex 1 crystallizes in the monoclinic space group C2/c with a = 15.352(3), b = 13.192(3), c = 11.358(2) Å, β = 120.61(3)°, V = 1979.6(7) ų, Z = 4, D_calc = 1.865 g cm^?3. The coordination geometry about the copper center is distorted about halfway between square planar and tetrahedral. The Cu‐N distance is 2.032(2) Å and the Cu‐Br distance 2.3521(5) Å. Heating a CH₂Cl₂ or acetone solution of 1 resulted in complex 2 , which consists of a slightly distorted tetrahedral [Cu(dpp)₂]⁺ cation and a linear two‐coordinate [CuBr₂]^? anion. 2 crystallizes in the triclinic space group with a = 10.445(2), b = 11.009(2), c = 18.458(4) Å, α = 104.72(3), β = 94.71(3), γ = 103.50(3)°, V = 1973.3(7) ų, Z = 2, D_calc = 1.602 g cm^?3. The four Cu(1)‐N distances are between 2.042(3) and 2.067(3) Å, the distance of Cu(2)‐Br(1) 2.2268(8) Å, and the disordered Cu(3)‐Br(2) distances are 2.139(7) and 2.237(4) Å, respectively. Complex 2 could also be prepared by directly reacting CuBr with dpp in CH₂Cl₂.     

Complexation with diol host compounds. 13. Crystal structures and thermal analyses of inclusion compounds of 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol with cyclohexane,O-xylene,m-xylene and p-xylene

Abstract

It has been shown that host compound 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol is able to include polar guests and now we report on its ability to form clathrate compounds with apolar guests. The structures of this host with cyclohexane (1) and the ortho (2), meta (3) and para (4) xylenes have been determined and are discussed. Crystal data: (1) 2C₃₀H₂₂O₂C₆H₁₂, M _r = 913.20 g mol^?1, mono-clinic, C2/c, a = 22.851(6), b = 14.010(2), c = 17.076(6) Å, β = 108.71(3)°, V = 5178(2) ų, Z = 4, D _c = 1.17g cm^?3, N = 3326, R = 0.092. (2) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, a = 13.185(3), b = 15.466(3), c = 16.573(2) Å, α = 96.39(13)°, β = 106.96(15)°, γ = 114.94(18)°, V = 2822(2) ų, Z = 2, D _c = 1.16 g cm^?3, N = 6152, R = 0.075. (3) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, a = 13.267(5), b = 15.453(3), c = 16.654(5) Å, α = 97.12(2)°, β = 107.09(3)°, γ = 114.68(3)°, V = 2843(2) ų, Z = 2, D _c = 1.15 g cm^?3, N = 6505, R = 0.083. (4) 2C₃₀H₂₂O₂1 ½C₈H₁₀, M _r = 1976.5 g mol^?1, triclinic, P 1, α = 13.070(2), b = 15.348(3), c = 16.776(3) Å, α = 67.88<2)°, β = 74.27(1)°, γ = 65.29(1)°, V = 2817(1) ų, Z = 2, D _c = 1.15 g cm^?3, N = 6711, R = 0.050. Thermal analysis studies were also performed in order to examine their stability and the strength with which the guest species are held in the crystal lattice.     

Synthesis and Structure of N-Ethoxycarbonyl-N′-O-Methoxyphenylthiourea

N-ethoxycarbonyl-N′-o-methoxyphenylthiourea was synthesized and characterized by elemental analysis, TG-DTA analysis, IR, and ¹H NMR spectrum, and single crystal X-ray diffraction analysis. The compound crystallizes as a planar molecule in the monoclinic space group P2(1)/c, with a = 9.690(2)Å, b = 8.595(2)Å, c = 15.944(4)Å, α = 90°, β = 106.467(4)°, γ = 90°, and D_calc = 1.326 g/cm³ for Z = 4. Intramolecular H-bonds promote the stability of the title compound and change the coordination ability of the thiourea ligand. Intermolecular N─H…S H-bonds link pairs of two molecules.     

Syntheses and Characterization of Organoimido Complexes of Niobium(V); Potential CVD Precursors

New niobium imido complexes (RN)Nb(NEt₂)₃ (R = Prⁿ, Prⁱ and Bu^t), potential precursors to grow niobium containing thin films by chemical vapor deposition (CVD), were prepared by reacting the corresponding (RN)NbCl₃py₂ complexes (R = Prⁿ, Prⁱ and Bu^t; py = pyridine) with LiNEt₂ in hydrocarbon solvents. The structures of (RN)NbCl₃py₂ (R = Prⁱ and Bu^t), determined by X-ray crystallography, are mononuclear with distorted octahedral geometries, For each complex, three chloride ligands are cis to the imido ligand and occupy meridional positions. One of two py ligands is cis to and the other is trans to the imido ligand. For (PrⁱN)NbCl₃py₂, the Nb=NPrⁱ bond distance (Å) is 1.733(3) and the ∠Nb=N-Prⁱ angle (°) is 178.0(3). Crystal data: monoclinic, space group P2₁/n, a = 8.805(2), b = 14.930(4), c = 13, 407(3) Å, β = 93.37(2)°, V = 1759.5(7) ų, Z = 4, D_c = 1.565 g cm³. For (Bu^tN)NbCl₃py₂, the Nb=NBu^t bond distance (Å) is 1.734(4) and the ∠Nb=N-Bu^l angle (°) is 174.8(4). Crystal data: monoclinic, space group P2₁/c, a = 9.609(1), b = 13.591(6), c = 14.615(2) Å, β = 90.05(1)°, V = 1908.5(9) ų, Z = 4, D_c = 1.492 g cm^?3.     

Syntheses,Structures and Magnetic Properties of Three New Extended Iron‐containing Heteropolytungstates

Three new extended iron‐containing heteropolytungstates were synthesized and structurally characterized: K₆[{Fe^II(H₂O)₄}₂(H₂W₁₂O₄₂)]·15H₂O ( 1 ), Na₅[{Fe(H₂O)₃}₂{Fe(H₂O)₄}_0.5(H₂W₁₂O₄₂)]·30H₂O ( 2 ) and (H₃O)⁺₂[{Fe(H₂O)₄Fe(H₂O)₃}₂(H₂W₁₂O₄₂)]·20H₂O ( 3 ). 1 and 3 crystallize in the monoclinic system, space group P2₁/n with a = 14.9967(5), b = 10.3872(3), c = 18.8237(6)Å, β = 93.407(1)°, V = 2927.1(2)ų and D_c = 4.151 g cm^—3 for 1 , and space group P2₁/c with a = 12.1794(4), b = 22.4938(4), c = 11.6941(3) Å, β = 105.731(2)°, V = 3083.7(1) ų, and D_c = 4.043 g cm^—3 for 3 . 2 is triclinic, space group P1¯, with a = 12.121(2), b = 12.426(3), c = 13.247(3)Å, α = 68.33(3), β = 71.33(3), γ = 71.44(3)°, V = 1710.7(6)ų and D_c = 3.735 g cm^—3. In all cases, the structures are based on paradodecatungstate polyoxoanions, which are linked by iron ions into chains, layers and a three‐dimensional structure for 1 , 2 and 3 , respectively.     

The crystal and molecular structure of octafluorobiphenylene,C12F8

Octafluorobiphenylene was made by heating 1,2-diiodotetrafluorobenzene in a sealed, evacuated tube with either copper, lead or bismuth. The crystal used for the diffraction studies was grown from hexane. Crystal data: C₁₂F₈, M_r = 296.116, monoclinic, A2/a, a = 21.140(2), b = 6.430(6), c = 36.340(3) ÅA, β = 123.76(3)°, U = 4106.73 ÅA³, Z = 16, D_m = 1.884 g cm⁻³, D_x = 1.907 g cm⁻³, λ(Cuka) = 1.5418 ÅA, μ = 1.810 mm⁻¹, F(000) = 2304, measurement temperature = 293K, R = 0.059 for 2230 reflections with I > 3σ(I).     

X‐ray Investigation and Coordination Behaviour of the 1,3‐Diallylbenzimidazolium Cation in [C13H15N2]+2 [CuCl2.58Br1.42]2– and [C13H15N2]+[Cu2Cl0.67Br2.33]– Complexes

By means of alternating current electrochemical synthesis crystals of [C₁₃H₁₅N₂]⁺₂[CuCl_2.58Br_1.42]^– ( I ) and [C₁₃H₁₅N₂]⁺[Cu₂Cl_0.67Br_2.33]^– ( II ) have been obtained and structurally characterized. Compound I crystallizes in the orthorhombic system, space group Fddd, a = 7.828(1) Å, b = 26.402(2) Å, c = 28.595(3) Å, D_c = 1.4995(5) g/cm³, Z = 8, R = 0.067 for 2157 reflections. The CuX₄^2– tetrahedra are connected with the organic cations through an electrostatic interaction. Crystals of II are monoclinic, space group P2₁/c, a = 9.2293(8) Å, b = 22.1332(9) Å, c = 9.2939(9) Å, β = 118.021(4)°, D_c = 2.1251(5) g/cm³, Z = 4, R = 0.042 for 2858 reflections. A tetrahedral environment of the Cu1 atom involves four halide atoms, whereas Cu2 possesses a trigonal‐pyramidal coordination with the C=C‐bond and three halide atoms.     

Crystal structures of bis(AZIDO)bis(2-morpholin-4-ylethylamino)copper(II) and bis{2,4-dibromo-6-[(2-morpholin-4-ylethylimino)methyl] phenolato}copper(II)

Two new copper(II) complexes [Cu(MEA)₂(N₃)₂] (1) and [Cu(BMP)₂] (2), where MEA and BMP are 2-morpholin-4-ylethylamine and 2,4-dibromo-6-[(2-morpholin-4-ylethylimino)methyl]phenolate respectively, are prepared and characterized using elemental analysis, FT-IR spectroscopy, and X-ray single crystal diffraction. The crystal of 1 belongs to the triclinic system, space group P-1, with a = 6.661(2) Å, b = 8.440(3) Å, c = 8.913(3) Å, α = 102.032(3)°, β = 107.899(2)°, γ = 98.242(3)°, V = 454.6(3) ų, Z = 1, D _c = 1.490 g/cm³, R ₁ = 0.0226, and wR ₂ = 0.0564. The crystal of 2 belongs to the monoclinic system, space group P2₁/c, with α = 7.0707(7) Å, b = 15.438(1) Å, c = 14.227(1) Å, β = 96.659(2)°, V = 1542.5(3) ų, Z = 2, D _c = 1.821 g/cm³, R ₁ = 0.0437, and wR ₂ = 0.1041. In each complex, the Cu atom is in a square planar coordination. The molecules of 1 are linked through intermolecular N-H...N and N-H...O hydrogen bonds to form layers parallel to the ab plane. The molecules of 2 are linked through intermolecular C-H...Br hydrogen bonds to form a 3D network.     

Complexation with diol host compounds. Part 14. Inclusion compounds of 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl with acetonitrile,cyclohexanone, di-n-propylamine and dimethylformamide

Abstract

The structures of the inclusion compounds of 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl (H) with acetonitrile (1) (1:1), cyclohexanone (2) (1:2), di-n-propylamine (3) (1:1) and dimethylformamide (4) (1:2) are reported. Crystal data: (1) monoclinic, P2₁/c with a=10.500(3), b=15.598(3), c=18.344(3) Å, β=96.66(2)°, Z=4, D _C=1.24 g cm^?3. (2) monoclinic, P2₁/c with a=13.980(3), b=11.768(5), c=23.49(1) Å, β=98.77(3)°, Z=4, D_c =1.24 g cm^?3. (3) monoclinic, C2/c with a=29.57(1), b=13.485(4), c=18.17(1) Å, β=107.94(4)°, Z=8, D _C=1.16 g cm^?3. (4) monoclinic, C2/c with a=30.123(9), b=13.391(6), c=19.177(6) Å, β=111.23(4)°, Z=8, D _C=1.22 g cm^?3. Final R values for the four structures were 0.065, 0.120, 0.084 and 0.107 for 2937, 2830, 2071 and 3769 reflections, respectively. The host conformation is quite rigid and does not appear to be influenced by the shape and size of the guests studied. The host is held in a spiral conformation by means of an intramolecular hydrogen bond. In addition, host-guest hydrogen bonds are observed in all structures. Thermal analysis was used to evaluate the strength of binding of the guest molecules and confirmed that (1) is the most stable of the four compounds studied.     

Crystal structure of dimethylgold(III) 8-hydroxyquinolinate and 8-mercaptoquinolinate

A crystal-chemical study of dimethylgold(III) complexes with 8-hydroxyquinoline (CH₃)₂Au(OR) and 8-mercaptoquinoline (CH₃)₂Au(SR) (R = C₉H₆N) was performed. Crystal data for (CH₃)₂Au(OR): a = 8.7133(17) Å, b = 27.875(6) Å, c = 8.6688(17) Å, β = 102.76(3)°, Z = 8, ρ(calc) = 2.401 g/cm³, space group P2₁/c, R = 0.0909; for (CH₃)₂Au(SR): a = 3.5401(7) Å, b = 15.689(3) Å, c = 19.910(4) Å, β = 99.81(3)°, Z = 4, ρ(calc) = 2.361 g/cm³, space group P2₁/c, R = 0.0712. Both structures are molecular and involve neutral (CH₃)₂Au(L) molecules, L = C₉H₆NO or C₉H₆NS. In the structures, the molecules are arranged in stacks joined by van der Waals interactions. The average Au…Au intrastack distances are 3.57 Å and 4.34 Å for (CH₃)₂Au(OR) and 3.5 Å for (CH₃)₂Au(SR).     

Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster [V5O9(PhPO3)3(PhPO3H)2]2− and a comparison to the structure of the fully oxidized parent cluster [V5O7(OCH3)2(PhPO3)5]1−

The room temperature reaction of (Bu₄N)₃V₅O₁₄ with PhPO₃H₂ in methanol yields the pentanuclear V(V) cluster (Bu₄N)[V₅O₇(OCH₃)₂(PhPO₃)₅]·CH₃OH (1·CH₃OH). In contrast, the hydrothermal reaction of (Ph₄P) [VO₂Cl₂], PhPO₃H₂ and (NH₄)H₂PO₄ at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph₄P)₂[V₅O₉(PhPO₃)₃(PhPO₃H)₂] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P2₁/n,a=12.167(2) Å,b=23.348(5) Å,c=22.508(5) Å,β=98.49(2)°,V=6323.9(19) ų,Z=4,D _calc=1.558 g cm^?3; 3, triclinic, $P\bar 1$ ,a=13.478(3) Å,b=14.399(3) Å,c=23.638(5) Å,α=72.53(2)°,β=85.58(2)°,γ=69.88(4)°,V=4107.0(16) ų,Z=2, D_calc=1.479 g cm^?3.     

Synthesis and crystal structure of ((NH3CH2CH2)3N)2P6O18·6H2O

Chemical preparation and crystal structure are given for a new cyclohexaphosphate: ((NH₃CH₂CH₂)₃N)₂P₆O₁₈·6H₂O. This compound is triclinic P¯1 with the following unit-cell parameters: a = 10,281(1)Å, b = 11.083(1)Å, c = 9.307(2)Å, α = 103.83(1) °, β = 108.56(1) °, γ = 68.11(1) °, Z = 1, V = 924.2(3)ų and pcal. = 1.582 g.cm⁻³. Its atomic arrangements contain layers built by P₆O₁₈ ring anions spreading in the plans (001). Between these layers are located the organic groups which form hydrogen bonds with oxygen atoms of P₆O₁₈ rings and water molecules. Crystal structure has been solved and refined to R = 0.028 using 4540 independent reflections. The thermal behavior has been investigated and interpreted by comparison with IR absorption spectroscopy and X-ray diffraction experiments.     

The Structure of Hydrotris(imidazolyl)boratothallium(I) – the First Structurally Authenticated Tris(imidazolyl)borate Metal Complex

The title compound crystallizes in the monoclinic space group P2₁/n with a = 8.706(1), b = 9.192(1), c = 15.261(2) Å, β = 94.740(3)°, V = 1217.0(3) ų, Z = 4, D_calc = 2.278 g cm^–3. The tris(imidazolyl)borate ligand bridges between three thallium atoms. The structure consists of one‐dimensional twisted ladder‐like strands.     

Synthesis,magnetic property and DNA cleavage behavior of a new dialkoxo‐bridged diiron(III) complex

A new dialkoxo‐bridged diiron(III) complex, [Fe₂(BMA)₂(CH₃O)₂Cl₂]·2Cl·4CH₃OH ( 1 ) [BMA = N,N‐bis(2‐benzimidazolylmethyl)amine], was synthesized and characterized by UV‐visible absorption and infrared spectra and magnetic susceptibilities. The complex crystallizes in the monoclinic system, space group P2(1)/n, a = 12.9659(19) Å, b = 10.0278(16) Å, c = 17.919(2) Å, β = 93.766(8)° , V = 2324.8(6) ų, Z = 2, F(000) = 1036, D_c = 1.426 g cm^?3, µ = 0.908 mm^?1. According to X‐ray crystallographic studies, each Fe(III) ion lies in a highly distorted octahedral environment, and two Fe(III) ions are bridged by the methoxyl oxygens. Cryomagnetic analyses indicated a moderate antiferromagnetic interaction between the high‐spin Fe(III) ions, with J = ? 27.05 cm^?1. Moreover, the binding interaction of DNA with the diiron complex was investigated by spectroscopic and agarose gel electrophoretic methods, showing moderate cleavage activity on pBR322 plasmid DNA at physiological pH and temperature. Copyright © 2007 John Wiley & Sons, Ltd.     

Monomeric five-coordinate rhenium diazenido and hydrazido complexes with aromatic thiolate ligands: X-ray structures of [Re(NNC6H4-Br)2(SC6H3-2,5-Me2)(PPh3)2] and [ReO(NNMePh)(SPh)3], and of the synthetic precursor [Re(NNC6H4-4-Br)2Cl(PPh3)2]

Reaction of [ReOCl₃(PPh₃)₂] with bromophenylhydrazine in methanol yields [ReCl(N₂C₆H₄Br)₂(PPh₃)₂] (1). Complex 1 reacts with arylthiolates to give mixtures of [Re(SAr)(N₂C₆H₄Br)₂(PPh₃)₂] (2) and [Re₂(SAr)₇(NNR)₂]⁻. Complexes 1 and 2 display trigonal bipyramidal geometries with the phosphine ligands occupying the axial sites. A significant feature of the structures is the nonequivalence of the rhenium-diazenido moieties, such that for 1 the ReN(1) and N(1)N(2) distances are 1.80(2) and 1.24(3) Å, while ReN(3) and N(3)N(4) are 1.73(2) and 1.32(3) Å, and for 2 the ReN distances are 1.73(1) and 1.80(2)° with corresponding NN distances of 1.32(2) and 1.25(2) Å. Reaction of (PPh₄)[ReO(SPh)₄] (3) with unsymmetrically disubstituted hydrazines affords complexes of the type [ReO(SPh)₃(NMRR′)] (R = Me, R′ = Ph for 4). Complexes 3 and 4 display distorted square pyramidal geometries with the oxo groups apical. The significant feature of the structure of 4 is the nonlinear ReN(1)N(2) linkage, exhibiting an angle of 145.6(10)°. The angle does not appear to correlate with a significant contribution from a valence form with sp² hybridization at the α-nitrogen. Crystal data: 1: monoclinic space group, P2₁/n, a = 12.216(2) Å, b = 19.098(2) Å, c = 20.257(4) Å, β = 106.20(1)°, V = 4538.3(8) ų to give Z = 4; structure solution and refinement based on 1905 reflections converged at R = 0.070. 2: monoclinic space group P2₁/n, a = 14.393(2) Å, b = 18.842(3) Å, c = 20.717(4)Å, β = 110.26(1)°, V = 5270.5(8) ų to give Z = 4 for D = 1.53 g cm⁻¹; structure solution and refinement based on 4249 reflections to give R = 0.070. 3: monoclinic space group P2₁/n, a = 12.531(2) Å, b = 24.577(4) Å, c = 16.922(3) Å, β = 99.06(1)°, V = 5146.2(9) ų, D = 1.36 g cm⁻³ for Z = 4, 2912 reflections, R = 0.050. 4: monoclinic space group p2₁/n, a = 16.137(2) Å, b = 9.863(2) Å, c = 16.668(2) Å, β = 111.12(1)°, V = 2474.7(6) ų, D = 1.74 g cm⁻³ for Z = 4, 2940 reflections, R = 0.066.     

Aminoguanidinium cations and the square-bipyramidal hexachlorocuprate(II) anion in the (CH8N4)2[CuCl6] crystal structure

Synthesis and structure of a novel thermochromic complex (CH₈N₄)₂[CuCl₆] are reported. X-ray analysis of the compound was carried out for a single crystal 0.4×0.2×0.05 mm in size (a bright-yellow plate). The monoclinic unit cell parameters are a=7.167(1), b=15.561(3), c=7.328(1) Å, β=118.73(3)°, V=716.7(2) ų, space group P2₁, Z=2 (CH₈N₄)₂[CuCl₆] d_calc=1.99 g/cm³, μ(MoK_α)=2.65 mm^?1, R=0.0264, and R_w=0.0290 for 1411 I_hkl>2σ_I.     

Reaction of Early Transition Metal Complexes With Macrocycles III. Synthesis and Structure of 18-Crown-6·l4 (M = Ti,Sn)

Abstract

18-Crown-6 reacts with either TiCl₄ or SnCl₄ in toluene to form an addition complex in which the macrocycle functions as a bidentate ligand. The two compounds are isostructural and belong to the monoclinic space group P2₁/n. For Ti. the cell parameters are a = 10.501(6), b = 18.104(5), c = 10.955(5) Å, β = 109.76(3)°, and D_c = 1.55 g/cm³ for Z = 4; for Sn, a = 10.572(9), b = 18.139(6), c = 11.056(5) Å, β = 109.16(4)°, and D_c = 1.75 g/cm³. Least-squares refinement led to a final R = 0.037 for 1735 observed reflections for the Ti complex, and R = 0.038 for 2940 observed reflections for the Sn derivative. The M-Cl lengths range from 2.221(2)–2.285(2) Å for M = Ti, and from 2.353(2)–2.357(2) Å for M = Sn. The M—O bonds are 2.102(4) and 2.138(4) Å for M = Ti, and 2.212(4) and 2.237(4) Å for M = Sn.