The crystal and molecular structures of 2-hydroxy-1-naphthalenecarboxaldehyde and 3-hydroxy-2-naphthalenecarboxaldehyde

The crystal and molecular structures of 2-Hydroxy-1-naphthalenecarboxaldehyde (I) and 3-Hydroxy-2-naphthalenecarboxaldehyde (II) were determined. Compound (I) crystallizes in the space groupP2 ₁/n witha+5.589(2),b+9.352(2), andc+15.490(3) Å, =98.14(3)°, andZ+4. Compound (II) crystallizes inP2 ₁/n witha+16.831(11),b+5.936(3), andc+8.295(3) Å =97.24(5)°. andZ+4. The structures were solved by direct methods, and refined by fullmatrix least squares toR+0.071 andR _w+0.083 forI, andR+0.047 andR _w+0.061 forII.     

Crystal and molecular structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate complex and of two pyrimidine thiones

The crystal structures of 1-phenyl-4,6-dimethylpyrimidine-2-thionetetraaquacobalt(II) dinitrate (I)a=9.032(2),b=12.458(2),c=18.067(3)Å,=103.25(3)°,Z=4;P2₁/c,R=0.049; 1-phenyl-4,6-dimethylpyrimidine-2-thione (II)a=12.005(3),b=10.090(2),c=9.649(2)Å,=104.4(1)°,Z=4;P2₁/n,R=0.038; and 4,6-dimethylpyrimidine-2-thione (III)a=15.485(3),b=13.255(3),c=7.127(2)Å,=104.3(1)°,Z=8,C2/c,R=0.041 are reported. In (I) the coordination around the cobalt(II) is distorted octahedral involving one ligand moleculevia sulphur and nitrogen atoms and four water molecules. It is relevant that the parameters in the complexed ligand are not different from those found in the uncomplexed one (II), excepting the distances on the nitrogen atom directly involved in the coordination. Bond distances and angles in compound (III) agree with those found in (II).     

X-ray structural investigation of N-epimeric 1,8-cis- and 1,8-trans-5,12-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) diperchlorates,C12H24N4Ni(ClO4)2

The structures of 1,8-cis- and 1,8-trans-5, 12-dimethyl-1,4,8,11-tetra-azacyclotetradeca-4,11-dienenickel(II) diperchlorates (I andII, respectively) have been investigated by X-ray diffracto-metric methods. CompoundI crystallizes in a monoclinic system, space group P2₁/n, with cell dimensionsa=13.732(2),b=13.526(2),c=10.658(2) Å,=99.20(2)°; compoundII crystallizes in a monoclinic system, space group C2/c, with cell dimensionsa=15.776(2),b=9.919(1),c=12.451(1) Å,=102.27(1)°. The structures were solved by heavy atommethods and refined by a full-matrix least-squares method to giveR=0.0601 and 0.0575 forIandII, respectively. Both N-epimers show the square planar Ni(II) coordination arrangements. The ligand ofI has approximate twofold symmetry (C₂ perpendicular to the coordination plane), the moleculeII is crystallographically centrosymmetric (C_i).     

Structures of three halo(tetramethylethylenediamine)copper(I) complexes

The X-ray crystal structures of three halo(tetramethylethylenediamine)copper(I) complexes have been determined. (TMED)₂Cu⁺CuCl ₂ ^– (I) crystallizes in monoclinic space groupP2₁/n with lattice constantsa=9.332(9),b=15.126(7),c=14.49(1) Å,=96.95(7)°. (TMEDCuBr)₂ (II) crystallizes in monoclinic space groupP2₁/c with lattice constantsa=12.064(5),b=11.888(6),c=15.841(6) Å,=113.97(3)°. (TMED CuI)₂ (III) crystallizes in monoclinic space groupP2₁/c with lattice constantsa=12.401(6),b=12.159(6),c=15.412(9) Å,=109.12(4)°. Compound (I) is a molecule exhibiting two discrete environments for copper(I). The cation is a pseudotetrahedral monomer and the anion a linear monomer. Both (II) and (III) are dimers with asymmetrically bridging bromine and iodine atoms, respectively. Distortions from tetrahedral geometry are observed about the copper atoms in (II) and (III).     

2-(1-Methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2] octan-3-one: Acid-catalyzed isomerization of the Z isomer to the E isomer

Crystals of (Z)-2-(1-methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2]octan-3-one (I) were obtained from a condensation reaction of 1-methyl-1H-indole-3-carboxaldehyde with 1-aza-bicyclo[2.2.2]octan-3-one and subsequent crystallization of the product from methanol. The isomeric (E)-2-(1-methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2] octan-3-one hydrochloride (II) was obtained by treating a methanolic solution of I with a 1M solution of hydrogen chloride diethyl ether, followed by crystallization of resultant product from methanol. Crystal data: I, is monoclinic, P2₁, a = 5.7440(10), b = 11.102(2), c = 10.708(2) Å, = 91.751(10)°, and V = 682.5(2) ų with Z = 2, for D _cal= 1.296 mg/m³ and II, is monoclinic, P2₁/c, a = 8.8510(2), b = 17.4990(5), c = 20.4300(5) Å, = 101.3620(12)°, V = 3102.26(14) with Z = 8, for D _cal= 1.316 mg/m³.     

X-ray crystal structures ofcis-bis(diphenylphosphinamide)tetracarbonylmolybdenum(0) andtrans-bis(N-methyl diphenylphosphinamide)tetracarbonylmolybdenum(0)

The X-ray crystal structures ofcis-Mo(CO)₄(Ph₂PNH₂)₂,I, andtrans-Mo(CO)₄(Ph₂PNHMe)₂,II, are presented. ComplexI crystallizes in the monoclinic space groupP2₁/c(a=13.433(1),b=12.2719(8),c=17.318(2)Å;=109.79(1)°;V=2686.1(8)ų;Z=4). ComplexII crystallizes in the triclinic space groupP¯1 (a=6.9986(8),b=10.328(1),c=11.241(2)Å,=107.58(1)°,=91.76(1)°, =101.28(1)°,V=756.1(4)ų,Z=1). The molybdenum coordination geometry in each complex is a slightly distorted octahedron. The molybdenum-carbon bond lengths for the carbonyls trans to phosphorus in complexI are shorter than those the carbonyls trans to other carbonyls. The average molybdenum-phosphorus distance inI (2.525(5)Å) is similar to those in other diphenylphosphinamide complexes and longer than the molybdenum-phosphorus distance inII in 2.4585(7)Å). The distance between two nitrogen atoms incis Mo(CO)₄(Ph₂PNH₂)₂ (3.74(3)Å) is significantly larger than the sum of their van der Waals radii (3.10 Å) indicating that the two nitrogens are not hydrogen bonded.     

The structural and spectroscopic properties of 2,4,6-trinitro-diphenylamine and 2,4,6-trinitro-N-methyl-diphenylamine

The structural properties of 2,4,6-trinitro-diphenylamine (I) and 2,4,6-trinitro-N-methyl-diphenylamine (II) are determined by single crystal diffractometry and refined toR factors of 0.0282 for (I) and 0.04213 for (II). (I) crystallizes in the monoclinic space groupP2₁/n,Z=4, witha=11.436(5),b=7.674(2),c=15.083(4) Å,=106.47(2)°, and (II) inP2₁/c,Z=4, witha=12.654(5),b=7.371(1),c=15.083(4) Å,=101.76(2)°. The amino nitrogens show in both cases bond distances and angles typical of an sp² character. The presence of the proton on the amino nitrogen constrains ano-nitro group into a more planar geometry than that of the methyl derivative, uv/visible spectral data of both compounds are discussed. The methyl group on the amino nitrogen, of derivative (II) compared with that of (I) produces a relevant red shift which cannot be related to the simple differences in the geometry of the two molecules.     

Crystal and molecular structures oftrans-dichloro-(ethylene) (4-methylpyridine)platinum(II) andtrans-dichloro(ethylene) (2,4,6-trimethylpyridine)platinum(II)

The crystal and molecular structures oftrans-[PtCl₂(C₂H₄)(4-MeC₅H₄N)] (I) andtrans-[PtCl₂(C₂H₄)(2,4,6-Me₃C₅H₂N)] (II) have been determined by single-crystal x-ray methods.I crystallizes in space groupP2₁/c witha= 4.991(1), b=21.658(3), c=10.675(3) Å, =110.17(2) °,Z=4;II is orthorhombic (Pbca) witha=10.295(6),b=12.393(8),c=20.370(10) Å,Z=8.Full-matrix least-squares refinements have given finalR factors of 0.053 (1520 reflections) forI and 0.042. (1412 reflections) forII. The intensities were recorded by counter methods, and only those reflections havingI>3(I) were used in the analyses.In both complexes, platinum is four-coordinate with the two chlorine atoms, the double bond of the ethylene, and the nitrogen atom of the substituted pyridine. The two structures are discussed in terms of the arrangement of the pyridine ligand with respect to the PtCl₂(C₂H₄) moiety.     

Solid state conformational parameters in dibenzo[b,f]heteroepin drugs: Crystal structures of 3-methoxy-10-methyl-11-phenyldibenzo[b,f]thiepine and 3-allyloxy-10-ethyl-11-phenyldibenzo[b,f]oxepine

The structures of 3-methoxy-10-methyl-11-phenyldibenzo[b, f]thiepine (I) [C₂₂H₁₈OS, tetragonal,I4₁/a, witha=33.81(1),c=6.065(5)Å,Z=16] and 3-allyloxy-10-ethyl-11-phenyldibenzo[b,f]oxepine (II) [C₂₅H₂₂O₂, mono-clinic,P2₁/c,a=12.115(7),b=16.316(9),c=10.136(7)Å,=105.05(9)°,Z=4] have been determined by the symbolic addition procedure and refined by least-squares method to anR of 0.090 for 784 diffractometer-measured reflections (I) and to anR of 0.083 for 442 reflections (II). The dihedral angle between the phenyl-ring mean planes is 111.3° in (I) and 121.1° in (II), the middle seven-membered ring has the boat conformation, and the tricyclic moiety has twist and skew values of 6° and 0.42 Å in (I) and 0.3° and 0.79 Å in (II). The overall conformational characteristic for the tricyclic (6, 7, 6)-dibenzo[b,f]heteroepin derivatives have been reviewed to gain a better understanding of what requirements may be important for interaction of drugs of this class at the receptor site.     

X-ray crystallographic determination of the structure and conformation of new metabolites from microbial hydroxylation by Absidia blakesleeana ATCC 10148

The crystal structure and conformation of 10R-hydroxy-1,4,4-trimethyltricyclo[5.4.0.0^3.5]undec-7-en-9-one (II) and 10S-hydroxy-1,4,4-trimethyltricyclo[5.4.0.0^3.5]undec-7-en-9-one (III) have been determined by X-ray diffraction. In both cases the crystals were monoclinic, P2₁,a=12.907 (4),b=7.484(3),c=14.179(4) Å,=110.65 (3)°,Z=4, (II);a=16.351 (5),b=7.468 (3),c=20.917 (6) Å,=91.83 (4)°,Z=8 (III). The structure was solved by direct methods, and refined to anR _w value of 0.034 for 2483 (II) and 0.053 for 3810 (III) independent reflections, withI3.0(I). There were two crystallographically independent molecules in the case ofII and four in the case ofIII. In all independent forms of both compounds the ring substituted by a carbonyl group had the distorted³E sofa conformation; whereas the second one possessed the slightly deformed^7.10B boat conformation. The crystal structures ofII andIII are stabilized by two and four intermolecular hydrogen bonds, respectively.The nomenclature of IUPAC was applied for the names of compounds, However, for simplicity, numbering of atoms was according to Figs, 1a and 1b.     

Crystal structures of two substituted biphenyl derivatives: 5,5′-di t-butyl-2-2′-biphenyldiol and 5,5′-dimethyl-2,2′-biphenyldiol

5,5-Di t-butyl-2,2-biphenyldiol (I), C₂₀H₂₆O₂, crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 18.243(2), b = 9.947(2), c = 9.685(3) Å, and Z = 4; 5,5-dimethyl-2,2-biphenyldiol (II), C₁₄H₁₄O₂, crystallizes in the monoclinic space group P2₁/c with a = 9.959(2), b = 7.932(3), c = 15.392(2) Å, = 105.43(2)°, and Z = 4. The aromatic rings are tilted by 52.7(1) and 43.8(1)° to each other in compounds (I) and (II), respectively. Strong intra- and inter-molecular H-bonds connect the molecules in the crystals.     

Synthesis and structural characterization of bismuth complexes with sulphur-containing ligands: The crystal and molecular structures of two derivatives of BiBr3 and Bi2(SO4)3 with imidazolidine-2-thione

The paper reports the structural and spectroscopic properties of two complexes between BiBr₃, Bi₂(SO₄)₃ and imidazolidine-2-thione (etu) having formulae BiBr₃·3etu (I) and [Bi(etu)₄]₂(SO₄)₃·2H₂O (II). ComplexI is monoclinic, space groupP2₁/n,Z=4, witha=8.142(2),b=15.611(3),c=16.316(3) Å,=97.38(3)°,R=0.041.II is orthorhombic, space groupPbcn,a=10.930(1),b=16.795(1),c=27.890(1) Å,Z=4 andR=0.052. In both structures bismuth is octahedrally coordinated, inI three bromines and three sulphurs from etu molecules are present and the coordinated polyhedron is only moderately deformed, while inII four sulphurs of etu ligands and two oxygen sulphate with very different Bi-O distances [2.413(12) and 2.715(13) Å] are present.     

Energetic materials: The preparation and structural characterization of melaminium dinitramide and melaminium nitrate

Two energetic salts of the melaminium cation have been prepared and structurally characterized from room temperature X-ray single crystal diffraction data. Melaminium dinitramide (I), triclinic, P1¯, a = 6.6861(11), b = 6.9638(16), c = 10.447(2) Å , = 99.07(3), = 98.30(3), = 108.50(3)°, V = 445.6(2) ų, and Z = 2. Melaminium nitrate (II), monoclinic, P2₁/c, a = 3.5789(7), b = 20.466(4), c = 10.060(2) Å, = 94.01(2)°, V = 735.0(3) ų, and Z = 4. The crystal structures of both salts show distinct monoprotonated melaminium cations and dinitramide- or nitrate anions, respectively. Efficient packing in the solid state is achieved by extensive hydrogen bonding between two-dimensional zigzag ribbons of the melaminium cations and the respective anions resulting in high densities of the solid state structures of 1.74 (I) and 1.71 g/cm³ (II).     

Syntheses and structural characterization of two novel α-diketone bisacylhydrazones

Benzil bis(3,4,5-trimethoxybenzohydrazone) (I) and 3,3-dimethoxybenzil bis(benzohydrazone) (II) were synthesized by condensation, acid catalyzed, of the proper -diketone and the corresponding hydrazide. Compound I crystallizes in the monoclinic system, space group P2₁/n, with a = 11.464(2), b = 21.098(4), c = 13.837(2) Å, = 109.50(1)° V = 3154.8(9) ų and D _c = 1.319 g/cm³ for Z = 4. Compound II crystallizes in the triclinic system, space group P , with a = 11.106(3), b = 11.728(10), c = 10.656(5) Å, = 91.86(2), = 92.68(3), = 110.00(2)° V = 1301.1(7) ų and D _c = 1.293 g/cm³ for Z = 2.     

AgI, CdII, and HgII complexes with 2,5-bis(pyridyl)pyrazine ligands: syntheses, spectral analyses, single crystal, and powder X-ray analyses

2,5-Bis(4-pyridyl)pyrazine (4-bppz) and 2,5-bis(3-pyridyl)pyrazine (3-bppz) have been synthesized and characterized spectroscopically and crystallographically. 4-bppz [unit cell: a = 7.319(1), b = 5.746(1), c = 12.756(2) Å, = 93.16(1)° space group: P2₁/a] was characterized by X-ray single crystal diffraction methods while the structure of 3-bppz [unit cell: a = 10.9148(4), b = 4.5722(1), c = 11.4462(2) Å, = 109.571(2)° space group: P2₁/c] was determined from laboratory X-ray powder diffraction data. In these compounds, the pyrazine ring contains two symmetrically attached pyridine substituents with the nitrogen atom in the para positions for 4-bppz and in the meta positions for 3-bppz. Both compounds possess C_i symmetry with the pyridine rings twisted by 17.7° (4-bppz) and 2.6° (3-bppz) with respect to the pyrazine ring. 4-bppz was used in the formation of coordination compounds with silver(I) and cadmium(II). The silver(I) complex [Ag(OAc)(4-bppz)] _n (1) [unit cell: a = 8.472(1), b = 13.051(1), c = 19.063(2) Å, = 109.96(1)° space group: P2₁/c] is characterized by the formation of a perfectly linear chain containing the silver ions bridged by the ligand molecule, the latter using its pyridine nitrogen donor atoms for coordination. A pair of chains is interconnected by silver–silver interactions, the silver coordination sphere being completed by acetate anions. A similar one-dimensional coordination polymer, [Cd(OAc)₂(4-bppz)(MeOH)] _n (2) [unit cell: a = 8.680(1), b = 10.035(1), c = 13.445(1) Å, = 77.35(1), = 71.17(1), = 80.14(1)° space group: ], was obtained by the reaction of 4-bppz with Cd(OAc)₂. Ligand 3-bppz forms an analogous cadmium(II) complex, [Cd(OAc)₂(3-bppz)(MeOH)] _n (3) [unit cell: a = 9.306(1), b = 9.733(1), c = 11.550(1) Å, = 87.86(1), = 76.73(1), = 85.91(1)° space group: ], containing the molecules arranged in double zigzag chains. The reaction of 3-bppz with HgI₂ leads surprisingly to a binuclear complex, [Hg₂I₄(3-bppz)₂] (4) [unit cell: a = 17.555(1), b = 12.973(1), c = 16.195(1) Å, = 115.32(1)° space group: C2/c]. Two ligand molecules are bridged by two mercury(II) ions forming a cyclic structure, the tetrahedral coordination sphere of the metal being completed by iodide anions.     

Characterization of an asymmetric M(chelate)2(μ-Cl)2MCl2 dimer and isolation of corresponding DMSO adducts: X-ray crystal structures of Co(phen)2(μ-Cl)2CoCl2⋅C4H8O and M(chelate)Cl2(DMSO) x (Co, x = 1; Ni, x = 2) complexes

In aqueous solution, [M(chelate)Cl₂]x (chelate = 2,2-bipyridine, 1,10-phenanthroline) complexes can disproportionate to produce M(chelate)₂ ⁿ⁺ species that contain two chelating ligands. After extraction with organic solvent,Co(phen)₂(-Cl)₂CoCl₂(1) has been characterized by X-ray diffraction (monoclinic, C2/c, a = 10.278(2)Å, b = 22.026(5)Å, c = 12.941(3)Å, = 103.959(4)°, Z = 4, 2414 reflections [I 2 (I)], R ₁ = 0.0321, wR ₂ = 0.0864). However, addition of [M(chelate)Cl₂]x starting materials to dimethyl sulfoxide produces complexes that retain a single chelate ligand. The pentacoordinate complex Co(bpy)Cl₂DMSO (2) has been structurally characterized (triclinic, P , a = 7.824(2)Å, b = 9.570(4)Å, c = 10.025(2)Å, = 83.24(3)°, = 87.14(2)°, = 83.35(3)°, Z = 2, 2455 reflections [I 2 (I)], R ₁ = 0.0278, wR ₂ = 0.0747). In the case of nickel, two different geometric isomers are observed, depending on the chelate identity: trans-(DMSO)₂Ni(bpy)Cl₂ DMSO (3) (monoclinic, P21/c, a = 10.9149(8)Å, b = 12.1287(9)Å, c = 17.0044(13)Å, = 98.610(1)°, Z = 4,3519 reflections [I 2 (I)], R ₁ = 0.0209, wR ₂ = 0.0560) and cis-(DMSO)₂Ni(phen)Cl₂ (4) (monoclinic, P21/c, a = 8.404(2)Å, b = 14.051(4)Å, c = 16.710(4)Å, = 92.44(3)°, Z = 4, 3069 reflections [I 2 (I)], R ₁ = 0.0691, wR ₂ = 0.1782).     

Cage-annulated thiacrown ethers and thiacryptands

A series of cage-annulated sulfur-containing crown ethers and cryptands have been synthesized as possible specific metal host systems. The synthesis and structures of seven compounds are described, including a thiacryptand complex with Hg(II). The trishomocubane cage is essentially spherical except for a methylene group, which imparts no steric restrictions, and two disordered superimposed orientations occur in most structures. This superposition of four- and five-membered rings usually cannot be resolved into separate entities, resulting in distorted distances, angles, and thermal parameters for the cage. (3) I4₁ cd, a = 13.207(3) Å, b = 13.207(3) Å, c = 35.876(12) Å; (10) C2, a = 14.551(2) Å, b = 10.028(1) Å, c = 10.491(1) Å, = 107.108(2)°; (14) P2₁/n, a = 10.6277(8) Å, b = 9.8488(7) Å, c = 21.822(2) Å, = 97.945(2)°; (19) P2₁/c, a = 15.381(3) Å, b = 6.667(1) Å, c = 18.158(3) Å, = 94.838(4)°; (25) C2/c, a = 34.386(4) Å, b = 11.318(1) Å, c = 13.409(2) Å, = 110.044(2)°; (28) , a = 10.4487(8) Å, b = 11.5677(9) Å, c = 13.354(1) Å, = 71.042(1)°, = 87.344(1)°, = 65.839(1)°; (29) P2₁/c, a = 10.8138(5) Å, b = 16.4949(8) Å, c = 22.054(1) Å, = 96.087(1)°.     

The synthesis and structural characterization of silyl-substituted fluorenes

Three silyl-substituted fluorenes have been prepared by direct synthetic methods and structurally characterized by X-ray diffraction. The three silyl-substituted fluorenes studied were 9-trimethylsilylfluorene (1), 9-(tert-butyldimethyl)silylfluorene (2), and 2,7-di-tert-butyl-9-trimethylsilylfluorene (3). Complex 1 is orthorhombic, P2₁2₁2₁, a = 6.2681(14) Å, b = 14.329(3) Å, c = 15.231(4) Å, Z = 4. Complex 2 is monoclinic, P2₁/c, a = 12.1953(10) Å, b = 6.9977(6) Å, c = 19.6536(17) Å, = 93.818(2), Z = 4. Complex 3 is monoclinic, P2₁/c, a = 11.9954(9) Å, b = 9.8978(7) Å, c = 18.5464(13) Å, = 92.456(2), Z = 4. The long carbon–silicon bonds effectively remove any significant intramolecular interactions as little distortion is exhibited around the sp ³-carbon atom and the fluorenyl backbone demonstrates near planarity. The bulky silicon substituents also prevent intermolecular interactions, as only a few close contacts less than 4.0 Å exist in all three solid state structures.     

Crystallographic studies of some cyclic benzylidene acetals: Key synthons for o-glycoamino acid building blocks and solid-phase oligosaccharide synthesis

Synthesis of methyl 2-azido-2-deoxy-4,6-O-benzylidene--D-galactopyranoside (1), one of the key components in the synthesis of O-glycoamino acids, was undertaken in order to synthesize Tn and TF⁽³⁾ antigen building blocks. In pursuit of an alternative approach, benzylidenation of the crude D-galactal (2a) afforded methyl 2-deoxy-4,6-O-benzylidene--D-galactopyranoside (3c) and 3,4-O-benzylidene-D-galactal (3b) besides the expected 4,6-O-benzylidene-D-galactal (3a). Formation of compound 3c was explained based on the presence of methyl 2 deoxy--D-galactopyranoside (2b) isomer and/or trace amount of methanol in the crude mixture of deacetylated product of 2 prior to benzylidenation. On the other hand, formation of 3b in substantial quantities appears to be a thermodynamically controlled product and its formation is found to be common during prolonged Lewis-acid catalyzed benzylidenation reaction. Crystal structures of these important and useful precursors were deduced by X-ray diffraction methods to enumerate their complete molecular structure as well as to understand the effect of the cyclic acetal on the pyranose ring conformation. Compound 1 crystallizes in the orthorhombic space group P2 ₁ 2 ₁ 2 ₁ with cell dimensions a = 5.058(7), b = 12.766(7), c = 22.557(7) Å 3b crystallizes in the hexagonal space group P6 ₁ with cell dimensions a = 18.265(4), b = 18.265(3), c = 6.323(2) Å 3c crystallizes in the monoclinic space group P2 ₁ with cell dimensions a = 10.614(3), b = 4.963(2), c = 12.730(3) Å, and = 95.47(3)°.     

Structural studies of some o-substituted S-phenyl thiobenzoates. I. Crystal structure of S-phenyl o-chlorothiobenzoate and S-phenyl o-bromothiobenzoate

Structural characteristics ofS-phenylo-chlorothiobenzoate (I) andS-phenylo-bromothiobenzoate (II) have been investigated by single crystal X-ray diffraction. It was shown that the crystals are isomorphous and crystallize in the monoclinic space groupP2₁ withZ=2. The unit cell parameters are:a=10.150(3),b=7.672(2),c=7.595(2) Å,=91.28(1)° for C₁₃H₉ClOS (compoundI) anda=10.141(3),b=7.764(2),c=7.653(2) Å,=90.14(3)° for C₁₃H₉BrOS (compoundII). The structures were solved by heavy-atom methods and refined by full-matrix least-squares, from room-temperature data collected with a Philips PW 1100 diifractometer, to conventionalR factors of 0.056 forI and 0.044 forII. The structures consist of independent molecules held together by intermolecular interactions. Molecular packing is influenced by the presence ofo-substituted Cl or Br atoms. The Cl atoms in structureI as well as the Br ones in structureII are directed to the centers of the pi-electronic system of theo-substituted phenyl rings belonging to the neighboring molecules. The six ClC and BrC distances range from 3.651(10) to 3.869(9) Å and from 3.644(6) to 3.890(6) Å, respectively. The C1 (or Br) atom is additionally directed towards the two carbon atoms (C3 and C4) in anothero-substituted phenyl ring, the C1lC and BrC distances being 3.786(9) and 3.849(10) Å inI and 3.727(6) and 3.881(6) Å inII. The torsion angle C6-C7-S-C8 is-170.2(7)° inI and 168.6(4)° inII. The angles between the planar O-C7-S central fragment of the molecule, on the one hand, and theo-substituted phenyl ring, on the other, are 113.9(3)° in I and 110.9(2)° inII. The corresponding values for the angles between the O-C7-S fragment and the nonsubstituted phenyl ring are 115.8(3)° and 114.3(2)° in compoundsI andII, respectively.