Syntheses and structures of N-phenylmaleimidetriazoles and by-products

The syntheses, properties, and structures of N-phenylmaleimidetriazole derivatives are described. Intermediates and by-products are also discussed. 1b. a = 43.997(7) Å, 5.7610(9) Å, 8.245(1) Å, = 99.339(4), C₂/c; 2a. a = 13.646(4) Å, b = 7.744(2) Å, c = 10.612(3) Å, = 91.979(6), P2₁/c. 3a. a = 22.245(1) Å, b = 22.245(1) Å, 10.010(1) Å, P42/n. 3a. a = 11.727(2) Å, b = 14.075(3) Å, c = 16.080(3) Å, = 105.859(3), = 105.331(3), = 98.187(3), P-1. 3b. a = 8.561(3) Å, b = 14.755(5) Å, c = 22.771(7) Å, = 97.006(5), P2₁/c. 3c. a = 10.500(2) Å, b = 12.189(2) Å, c = 13.040(2) Å, = 109.091(3), = 106.089(3), = 101.022(3), P-1. 8a. a = 16.389(8) Å, b = 5.749(3) Å, c = 19.316(3) Å, = 97.467(9), P2₁/n. 8b. a = 5.822(2) Å, b = 10.114(3) Å, c = 16.705(4) Å, = 84.681(5), = 82.840(5), = 75.769(4), P-1. 9b. a = 11.251(1) Å, 13.335(3) Å, 13.376(3) Å, = 102.456(4), P2₁/n. 9c. a = 15.836(3) Å, b = 8.236(2) Å, c = 5.447(3) Å, = 92.551(3), P2₁/c. 10a. a = 13.177(2) Å, b = 14.597(2) Å, c = 5.5505(8) Å, = 110.979(2), Cc. 11a. a = 14.720(2) Å, b = 13.995(2) Å, c = 38.245(6) Å, = 94.430(3), P2₁/n. 12b. a = 15.067(5) Å, b = 20.378(6) Å, c = 8.669(5) Å, = 99.16(4), = 99.32(3), = 105.23(3), P-1. 13b. a = 8.2824(6) Å, b = 10.5245(7) Å, c = 15.518(1) Å, = 92.305(1), = 100.473(1), = 100.124(1), P-1. 15a. a = 15.357(3) Å, b = 7.778(2) Å, c = 22.957(2) Å, Pbca. 16b. a = 18.0384(4) Å, b = 12.474(3) Å, c = 20.078(5) Å, Pbca.     

Crystal and molecular structure of: 5-(1-oxoethyl)-1-methyl-2-(5-bromo-6-methoxy-2-naphthyl)-6-oxabicyclo[3.2.1]octan-7-one and 5-(1-oxoethyl)-1-methyl-2-(5-bromo-6-methoxy-2-naphthyl)-6-oxabicyclo[3.2.1]octane

X-ray crystallographic studies of the two title compounds have shown that the molecules crystallize in the same triclinic space group, , with very similar cell dimensions. For C₂₁H₂₁BrO₄,a=12.056(5),b=13.206(5),c=7.595(3)Å, =90.38(3), =106.07(3) and =124.42(3)° and for C₂₁H₂₃BrO₃,a=12.076(6),b=13.090(5),c=7.490(3)Å, =92.65(5), =104.90(5) and =124.55(5)°. Both compounds possess the oxabicyclo[3.2.1]octane bridged ring system and differ only at the carbon to the ring oxygen where the Csp³ in the ether is replaced by Csp²=O in the lactone. Both cyclohexane rings adopt distorted chair conformations and the lactone and ether rings approximate closely to the envelope conformation. The bromine substituent at C(4) results in distortion of the naphthalene ring. Both molecules pack with the naphthalene rings parallel to each other with interplanar spacings of 3.71 Å in the ether and 3.66Å in the lactone.     

Two acetylamino derivatives of 2,4-bis(trichloromethyl)-1,3-benzdioxin showing different types of hydrogen bonding: (a) (C13C)CH⋯O=C and (b) N-H⋯O=C

8-Acetylamino-6-methyl-2,4-bis(trichloromethyl)-1,3-benzdioxin, (I), is monoclinic,P2₁/c,a=15.174(4),b=11.977(7),c=9.911(3)Å,=99.72(2)°. 6-Acetylamino-2,4-bis(trichloromethyl)-1,3-benzdioxin, (II), is monoclinic,P2₁/_n,a=5.927(4),b=40.623(1),c =7.120(3)Å,=91.39(4)°. In compound (I) the imino hydrogen atom is locked in an intramolecular hydrogen bond to the proximate oxygen atom of the heterocyclic ring and is not available for intermolecular hydrogen bonding. Instead the weakly acidic hydrogen atom [Cl₃C-C(2)]H takes part in a hydrogen bond to the carbonyl oxygen atom in another molecule. In compound (II) a normal intermolecular hydrogen bond of the type N-HO=C occurs. The 6-acetylam-ino group is twisted about the (C_Ar-N) bond such that the angles NHO=C, C_ArH_ArO=C, NHOH_ArC_Ar, at the carbonyl oxygen group total 360° (where NH is in the related molecule). The packing in both compounds takes the form of infinite chains and in compound (II) partial overlap of the aromatic ring and the acetylamino group, with very little offset, also occurs.     

Helical chirality of pyrrolo[1,2-a][1,10]phenanthroline derivatives

The objective of the study was to confirm by X-ray analysis the phenomenon of helical chirality inferred from solution ¹H-NMR data for a series of derivatives based on the novel pyrrolo[1,2-a][1,10]phenanthroline system. The syntheses of the title compounds and their ¹H-NMR data are presented. Crystals of the representative compound ethyl, 1-(4-phenylbenzoyl)-pyrrolo[1,2-a][1,10]phenanthroline-3-carboxylate, with molecular formula C₃₁H₂₂N₂O₃, were found to crystallize in the triclinic system, space group P 1 with a = 7.8541(1), b = 11.2605(2), c = 13.4093(3) Å, = 92.244(1), = 90.292(1), = 106.475(1) and Z = 2. The X-ray analysis revealed the predicted helicity of the phenanthroline system as well as its origin, namely the proximity of the pyridine N atom and the carbonyl C atom of the phenylbenzoyl residue, with non-bonded distance N s C of only 2.465(2) Å. A secondary, but significant distortion, involving displacement of the carbonyl C atom by more than 0.5 Å from the pyrrole ring, was evident. The crystal structure is maintained by C–H s O hydrogen bonds and – interactions.     

Complexation with diol host compounds. Part 3. Molecular inclusion of 4-methylcyclohexanone and 2-methylcyclohexanone by the host,trans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene

The structures of the 12 molecular complexes oftrans-9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with 4-methylcyclohexanone (1) and with 2-methylcyclohexanone (2) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P2₂/c,a=8.838(2) Å,b=8.92(1) Å,c=20.879(8)=Å,=98.67(2)°,V=1627(2) ų,Z=2 andR=0.062 for 2201 unique MoK reflections; Compound (2):P¯1,a=8.917(3) Å,b=9.900(2) Å,c=11.250(4) Å,a=68.72(2)°,=64.39(3)°, =74.86(2)°,V=828.1(5) ų,Z=1 andR=0.098 for 2563 unique reflections. Both inclusion compounds exhibit O-HO=C hydrogen bonding interactions. The thermal properties of these compounds have been characterized by DTA and TGA thermograms.     

X-ray crystal structures of [HB(3,4,5-Me3pz)3[2Zn, [H2B(3,4,5-Me3pz)2]Zn(μ-3,4,5-Me3pz)2Zn[H2B(3,4,5-Me3pz)2], and [H2B(pz)2]2Zn (pz = pyrazolyl ring)

[HB(3,4,5-Me₃pz)₃]₂Zn (1) and [H₂B(3,4,5-Me₃pz)₂]Zn(-3,4,5-Me₃pz)₂Zn[H₂B(3,4,5-Me₃pz)₂] (2) are present in equal amounts in a crystal in the triclinic space group, P-1 with a = 11.5924(11) Å, b = 12.7799(12) Å, c = 15.7317(14) Å = 107.905(2)° = 96.796(2)°, = 105.786(2)°, and Z = 1. The structure of 1 is a trigonally distorted octahedron and is very similar to the structure of [HB(3,5-Me₂pz)₃]₂Zn showing that the introduction of the third methyl group on the pyrazolyl ring does not impact on structure. [H₂B(pz)₂]₂Zn (3) is orthorhombic, Pca2(1) with a = 10.1473(3) Å, b = 11.1117(2) Å, c = 14.1831(5) Å, = = = 90° and Z = 4. The zinc(II) centers in both 2 and 3 are similar and have pseudotetrahedral structures.     

Crystal structure of 5-fluoro-1-(2,3,6-trideoxy-α-l-glycero-hex-2-enopyranos-4-ulosyl)uracil

The present compound crystallizes in the space groupP2₁2₁2₁ withZ=4 and cell parametersa=21.687(2),b=8.155(3),c=5.883(2)Å. The structure was solved by direct methods and refined by full-matrix least-squares to a finalR value of 0.045 for 1153 observed reflections. The N-glycosidic torsion angle _CN is in the anti-range and the pyranosyl ring adopts a distorted half-chair conformation with ₂=142.7(4)°, ₂=124.4(3)° andQ=0.456(2)Å. In the crystal packing the molecules are linked together by N-HO hydrogen bonds and C-HO contacts.     

A new class of flexible energetic salts. Part 7: The structures of the guanidinium and hydroxyguanidinium salts of dinitramide

The crystal structures of two amine base salts of dinitramide, the guanidinium 1, and the hydroxyguanidinium 2, have been determined. 1 crystallizes in the triclinic space group with cell dimensions a = 8.325(2) Å, b = 9.301 (2) Å, c = 9.868(2) Å, = 84.73(3)°, = 69.25(3)°, = 67.55(3)°, while 2 crystallizes in the noncentric monoclinic space group Pc with cell dimensions a = 7.098 (2) Å, b = 3.5160 (10) Å, c = 14.358(3) Å, = 98.940(10)°. The structures of 1 and 2 contain protonated amine cations and dinitramide anions linked by hydrogen bonding. In both structures the conformations adopted by the dinitramine anions can be related to the types of hydrogen bonds it forms with the surrounding amine cations.     

Crystal structure of 751-1751-1751-1751-2751-2751-2

The title compound crystallizes in the centrosymmetric triclinic space group (No. 2) witha=10.818(1)Å,b=10.876(1)Å,c=11.072(2)Å, =98.74(1)°, =98.83(1)°, =96.61(1)°,V=125906(3)ų andZ=2. Interatomic distances include Fe–P=2.243(2)Å, Fe–CO=1.771(6)–1.781(5)Å, Fe–C(C₅H₅)=2.074(6)–2.103(5)Å and P–F=1.511(6)–1.571(4)Å.     

A comparative study on structure and conformation of three hydroxybenzylamine ligands

Structure and conformation of three tridentate ligands are determined. All these three compounds crystallize in different space groups, the details are as follows: Bis[(3,5-dimethyl,2-hydroxy)-2-hydroxy-5-methoxy]benzylcyclohexylamine (DHBC): monoclinic I2/a (a = 17.691(1) Å, b = 9.707(1) Å, c = 24.235(2) Å, = 91.028(1)°); bis[(3,5-dimethyl,2-hydroxy)-2-hydroxy-5-bromo]benzylcyclohexylamine (DHBrBC): tetragonal P4₁2₁2 (a = b = 12.1138(1) Å, c = 28.485(1) Å) and bis[(3,5-dimethyl,2-hydroxy)-2-hydroxy-5-bromo]benzylmethylamine (DHBrBM): triclinic (a = 5.228(1), b = 12.364(1) Å, c = 13.234(1) Å, = 94.04(1)°, = 95.72(1),° = 95.90(1)°). The cyclohexane rings in DHBC and DHBrBC assume chair conformation. Both the phenyl rings are planar in all the molecules and orient at angles of 75.5(1)°, 62.2(1)°, and 53.9(2)°, respectively with each other. The bond angles around N atom show the sp³ character. Inter- and intramolecular O–HN and O–HO types of hydrogen bondings stabilize the molecules in the unit cell in addition to van der Waals forces.     

Hydrogen-bonded networks formed by substituted 2,6-diarylpyrazines

The X-ray crystal structure of 2,6-bis(4-hydroxyphenyl)pyrazine and 2,6-bis(4carboxyphenyl)pyrazine are reported. The structure of the 2,6-bis(4-carboxyphenyl) pyrazine dimethylsulfoxide complex (C₁₈H₁₂N₂O₄)(C₂H₆OS) is triclinic, P-1, with a = 7.9933(8), b = 10.7165(10), c = 12.1337(12) Å, = 66.385(2), = 84.070(2), = 77.219(2). The structure comprises stacked two-dimensional sheets of the hydrogen bonded complex. The two-dimensional sheets comprise hydrogen-bonded ribbons of the (carboxyphenyl)pyrazine that are connected by bridging hydrogen bonds to the dimethylsulfoxide. The structure of 2,6-bis(4-hydroxyphenyl)pyrazine, C₁₆H₁₂N₂O₂, is monoclinic, P2₁/c, with a = 10.6107(13) Å, b = 14.6743(18) Å, c = 8.3772(10) Å and = 104.982(2). The structure reveals that two-dimensional hydrogen-bonded sheets are formed with pyrazine–phenol and phenol–phenol hydrogen bonds.     

Structural characterization and excited-state properties of luminescent <Emphasis Type="Italic">Tris</Emphasis>-(μ -3-methyl-5- trifluoromethylpyrazolato)trigold(I)

Tris-(-(3-methyl-5-trifluoromethylpyrazolato)-N:N)triangulo-trigold(I), (3,5-tfmpz)₃ Au₃, has been synthesized and exhibits a planar nine-member ring containing a central gold triangle with an average intramolecular Au–Au distance of 3.3455(8) Å. The complex crystallizes in the monoclinic space group Cc with a = 12.998(2) Å, b = 22.910 (3) Å, c = 7.217(1) Å, and = 104.781(1). The solid-state structure consists of sheets of (3,5-tfmpz)₃Au₃ units stacked in an offset fashion along the c axis such that one gold atom in each Au₃ unit (Au1) lies approximately over the midpoint of the Au1–Au3 edge of the triangle in the layer below it. The intermolecular Au–Au distances are between 3.880(1) and 4.023(1) Å, which are too long for there to be significant intertrimer bonding interaction suggesting that any supramolecular organization may be due to hydrogen-fluorine and fluorine-fluorine interactions between the molecules. The complex exhibits excitation-dependent emission at room temperature in the solid state. The structured higher energy emission (_em = 468, 517, and 556(sh) nm) is believed to be a ligand-centered ^* transition with a lower energy unstructured emission (_em = 658 nm) assigned to the classical Au–Au excited state transition.     

Synthesis and structure of tris(N-methylaminoethanoldithiocarbamato)arsenic(III)

The title compound was synthesized by the interaction of arsenic(III)chloride with freshly prepared N-methylaminoethanoldithiocarbamic acid in methanol. The compound crystallized in the triclinic system, space groupP with two molecules per unit cell, the dimensions area=6.509(10)Å,b=14.077(3)Å,c=14.195(3)Å, =64.16(2)^o, =84.67(2)^o and =84.00(2)^o. The molecule is monomeric with three short (mean 2.320(3)Å) and three long (mean 2.927(2)Å) As-S bonds. Asymmetry in the As-S bonds is due to the presence of stereochemically active lone pair on arsenic and the coordination polyhedron deviates from the usual D₃ symmetry to C₃ symmetry. Disorder exists in one of the dithiocarbamate ligands probably due to the O...O interaction arising from the water molecule. The anisobidenticity of the As-S bond distances is as a consequence of stereochemical requirement of the ligand and the lone pair of electrons on arsenic.     

Synthesis and structural characterization of the bitopic ferrocene-based tris(pyrazolyl)methane ligand Fe[C5H4CH2OCH2C(pz)3]2 (pz = pyrazolyl ring)

The structure of Fe[C₅H₄CH₂OCH₂C(pz)₃]₂ (pz = pyrazolyl ring) contains 1.5 independent molecules in the asymmetric unit. One molecule has no imposed symmetry with the iron atom located on a general position while in the other the iron atom is located on an inversion center. The two independent molecules are arranged into a three-dimensional supramolecular structure by a series of C—H s N and C—H s O weak hydrogen bonding interactions and C—H s interactions. The crystals are triclinic, space group, P , with a = 8.1202(4) Å, b = 16.7209(9) Å, c = 18.6540(10) Å = 85.8270(10), = 85.4740(10), = 81.5910(10), and Z = 3     

Synthesis and X-ray crystallography of cholest-3,5-diene-7-one-oxime

Cholest-3,5-diene-7-one-oxime (C₂₇H₄₃NO) was prepared using a usual synthetic route and its three-dimensional structure was determined by X-ray diffraction methods. The transparent platelike crystals of this compound crystallized in the monoclinic space group P2₁, with unit cell parameters a = 14.302(2) Å, b = 11.475(2) Å, c = 15.919(4) Å, = 106.04(1)°, (Cu K) = 1.5418 Å, Z = 4. The structure was solved by direct methods and refined to an R-value of 0.075 for 4640 observed reflections. Two crystallographically independent molecules were observed in the asymmetric unit cell. The ring A in both the molecules was found to exist in 1,10 half-chair conformation while ring C in chair conformation. The rings B and D in both the molecules adopted different conformations. Three intermolecular interactions of the type C–H O and C–H N were also observed.     

Crystal structures of five policyclic compounds related to the natural product forskolin

(3(Z),4,6a,9a,9b)-(±)-3a,4,6a,7,8,9,9a,9b-octahydro-4,7,7, 9b-tetramethyl-3a-[3-(methoxymethyloxy)-3-methyl-1-butenyl]-5H-naphto[1,8-de]-1,3-dioxin-6-one (I), C₂₂H₃₆O₅,M _r=378.51, monoclinic,P2₁/n,a=6.330(1),b=14.576(2),c=22.837(2)Å,=93.04(1)°,V=2104.1(2)ų,Z=4,D _c=1.19 Mg/m³, (MoK)=0.71069Å,=0.8 cm^–1,F(000)=832,T=298 K,R=0.054 for 1971 observed reflections; (7a,10a,10b,12)-(±)-7a,9, 10,10a,10b,11,12,12a-octahydro-2,2,10,10,10b,12a-hexamethyl-2H,8H-1-benzopyrano[4a,5,6,-de][1,3,2]-benzodioxin-11-one (II), C₂₀H₂₉O₄,M _r=334.5, triclinic,P-1,a=10.595(2),b=12.152(1),c=8.073(1)Å,=106.53(1),=105.65(1), =66.29(1)°,V=897.9(2)ų,Z=2,D _c=1.24 Mg/m³, (MoK)=0.71069Å,=0.8 cm^–1,F(000)=362,T=298 K,R=0.046 for 2848 observed reflections; (7a,10a,10b,12, 12a)-(±)-7a,9,10,10a,10b,11,12,12a-octahydro-2,2,10,10,10b,12a-hexamethyl-2H,8H-1-benzopyrano[4a,5,6-de][1,3,2]-benzodioxin-11, 12-diol (III), C₂₀H₃₂O₅ (two molecules in the asymmetric unit),M _r=352.2, triclinic,P-1,a=12.948(3),b=13.615(3),c=12.197(4)Å,=101.16(2),=111.88(2), =69.48(2)°,V=1863.8(9)ų,Z=2,D _C=1.26 Mg/m³,(MoK)=0.71069 Å,=0.8 cm^–1,F(000)=768,T=298 K,R=0.060 for 4570 observed reflections; 4-acetoxy-4-[[(4a,5,8a)-(±)-hexahydro-4a,6,6-trimethyl-4H-1,3-benzodioxin-4-one]-5-yl]butan-2-one (IV), C₁₇H₂₆O₆,M _r=326.4, monoclinic,P2₁/c,a=10.495(2),b=12.050(2),c=14.216(2)Å,=108.51(1)°,V=1704.8(5)ų,Z=4,D _c=1.27 Mg/m³,(MoK)=0.71069 Å,=0.9 cm^–1,F(000)=704,T=298 K,R=0.049 for2455 observed reflections; (3a,4,5,6,6a,9a,9b)-(±)-4,5-epoxy-decahydro-3, 3a-dihydroxy-2-ethoxy-4,7,7,9b-tetramethyl-naphto-[1,8-bc]-pyran-6-ol-acetate (V), C₂₀H₃₂O₇,M _r=383.5, monoclinic,C2/c,a=10.353(2),b=17.975(3),c=21.188(3)Å,=91.29(1)°,V=3942(1)ų,Z=8,D _c=1.29 Mg/m³,(MoK)=0.71069 Å,=0.8 cm^–1,F(000)=1664,T=298 K,R=0.051 for 2120 observed reflections. We report here the complete structures of four decalin derivatives (compoundsI, II, III, V) and one related compound (compoundIV) synthetized in order to find an efficient synthetic approach for the natural productforskolin.     

The molecular structures of two melampolides

The melampolide-class sesquiterpene lactone 11H,13-dihydro-14-hydroxy-(1,10)-cis-parthenolide, C₁₅H₂₂O₄, 1, crystallizes in orthorhombic space group P2₁2₁2₁ with a = 7.435(2), b = 12.678(2), c = 14.991(2) Å, V = 1413.1(8) ų and Z = 4. The aldehyde analog, C₁₅H₂₀O₄·H₂O, 2, crystallizes as the monohydrate in orthorhombic space group P2₁2₁2₁ with a = 9.061(2), b = 9.295(2), c = 17.761(4) Å, V = 1495.8(9) ų, and Z = 4. The 10-membered rings of the two molecules adopt approximate chair-boat conformations. In both compounds, the double bond at C1=C10 position of the cyclodecene ring is Z, while the C4=C5 is epoxidized with an E-configuration. The C15 methyl is and H5 is . The lactone ring is trans fused at the C6 and C7 positions to the 10-membered ring. The C13 methyl group has an orientation in both molecules.     

A comparison of the coordination preferences of Zn, Co, and Cd(II) with the heteroscorpionate ligand (2-hydroxy-3-t-butyl-methylphenyl)bis (3,5-dimethylpyrazolyl)methane

Reaction of the Zn, Cd, or Co nitrate salts with the deprotonated ligand (2-hydroxy-3-t-butyl-methylphenyl)bis(3,5-dimethylpyrazolyl)methane (L1O^–) in methanol produced the following complexes: [(L1OH)Zn(NO₃)₂] in two isomorphs, a = 40.983(8) Å, b = 9.571(2) Å, c = 15.667(8) Å, = 90, = 106.38(1), = 90, C2/c, and a = 13.027(3) Å, b = 14.781(4) Å, c = 16.107(3) Å, = 90, = 105.30(1), = 90, P2₁/n; [(L1OH)Cd(pz)(NO₃)₂] a = 14.7476(2) Å, b = 13.5411(2) Å, c = 16.7223(2) Å, = 90, = 110.3840(10), = 90, P2₁/c; and [(L1O)Co(pz)(NO₃)] a = 11.4240(2) Å, b = 13.4498(2) Å, c = 13.8056(2) Å, = 105.2080(10), = 105.8130(10), = 112.7470(10), P . The Zn adopts a pseudotetrahedral four-coordinate geometry where the potentially tridentate ligand is actually bidentate with a protonated and uncoordinated phenoxy arm. The Co complex is pseudooctahedral six-coordinate where the phenoxy arm is deprotonated and coordinated. Finally the Cd complex is seven-coordinate but the metal is not coordinated through the phenoxy group that is again protonated.     

Complexes of azobisindoles with π-organic acceptors

Complexes of azobisindoles with tetracyanoethylene and tetracyanoquinodimethane were studied by UV-Vis, FT-IR, Raman, NMR and X-ray spectroscopies. FT-IR and Raman spectra, as well as X-ray analysis, gave useful information on the participation of various sites to the association, through analysis of CN and N=N vibrational modes, while UV-Vis and NMR spectra were less helpful. The crystal structure of complexes 1-ethyl-2-phenyl-3-(1-ethyl-2-phenyl-3-azoindole)indole/TCNE,3a and 1,2-diphenyl-3-(1,2-diphenyl-3-azoindole)indole/TCNQ,5b are reported. In the two complexes, the distances between donor and acceptor planes range between 3.4 and 3.5 Å; in3a tetracyanoethylene faces the phenyl ring of the indole, while in5b the superposition of tetracyanoquinodimethane with the donor is negligible. Compound3a,P–1,a=9.504(2),b=9.513(3),c=8.941(2) Å, =97.81(4), =103.38(3), =84.14(2)°,Z=2,D _calc=2.55 g cm^–3; compound5b,P–1,a=12.648(3),b=12.205(2),c=7.263(3) Å, =103.69(2), =91.23(3), =110.61(2)°,Z=2,D _calc=2.53 g cm^–3.     

Supramolecular structure of tetrakis-μ-(4-chloro-3-nitrobenzoato)-bis(methanol)dicopper(II)

The title compound, [Cu₂(II)(4-Cl-3-NO₂–C₆H₃CO₂)₄(CH₃OH)₂] or [Cu₂(4-chloro-3-nitrobenzoate)₄(MeOH)₂] has been prepared and its structure determined using X-ray crystallography. The complex crystallizes in the triclinic space group P-1 with a = 9.6887(9)Å, b = 10.6448(9)Å, c = 11.4194(10)Å, = 108.094(2), = 110.682(2), = 105.055(2), V = 952.691(15)ų, and Z = 1. The structure consists of centrosymmetric dimers in which the Cu(II) atoms display a square pyramidal CuO₅ coordination, with four carboxylate O atoms in the basal plane [CuO 1.951(2)–1.968(2)Å] and the methanol O atoms in the apical position [CuO 2.170(2)Å]. The Cu atoms are 2.614(1)Å apart and are bridged by four benzoate groups. The discrete dimers are extended into 1D chains that result from hydrogen bonding between the coordinated methanol on one Cu(II) dimer and the nitro substituent on an adjacent Cu(II) dimer. The chains are interdigited and held by – stacking interactions forming 3D supramolecular array.