Temperature-dependent selectivity of inclusion by <Emphasis Type="Italic">trans</Emphasis>-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid

From acetophenone solution with a small amount of water, a widely used clathrate forming compound, trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid (DED), crystallizes either in the form of a clathrate with acetophenone (25°C) or in the form of hydrate (5°C). The clathrate of DED with acetophenone is triclinic, space group P-1 with the unit cell parameters: a = 8.5002(2) Å, b = 12.5247(8) Å, c = 12.8251(8) Å; α = 62.876(2)°, β = 80.454(2)°, γ = 89.789(2)°; V = 1194.4(1) ų, Z = 2; the molar ratio DED:acetophenone is 2:3. The clathrate is of channel type; the system of mutually intersecting channels propagates in [100] and [01–1] directions in the structure. The guest molecules of acetophenone are included in the channels and do not form any H-bonds with the host molecules of DED. The hydrate of DED crystallizes in monoclinic system, in space group C2/c, with the unit cell parameters: a = 31.770(6) Å, b = 8.503(2) Å, c = 12.888(3) Å; β = 104.26(3)°; V = 3374(1) ų, Z = 8; the molar ratio DED:water is 1:3. One of two carboxylic groups of the molecule of DED is deprotonated and the proton is incorporated into the hydroxonium ion H₃O⁺. The crystal structure of the hydrate of DED is of layer type with well distinguished hydrophobic and hydrophilic parts.     

Synthesis and crystal structure of three mixed-ligand silver(I) complexes constructed from 1,2-Di(4-pyridyl)ethylene and different organic carboxylate anions

The reaction of AgNO₃ with 1,2-di(4-pyridyl)ethylene (Dpe) and 2,3-pyrazinedicarboxylic acid (H₂Pzdc) or 2,2′-bipyridyl-4,4′-dicarboxylic acid (H₂Bpdc) or salicylic acid (HSa) in alcohol aqueous solution produces block-like crystals of [Ag₂(Dpe)₂]Ppzdc) · 6H₂O (I), [Ag₃(Dpe)₃](Bpdc)(NO₃) · 4H₂O (II), and [Ag₂(Dpe)₂](Sa)(NO₃) · 3H₂O (III) at room temperature. Crystal I is monoclinic: space group P2₁/m, a = 7.5370(7), b = 17.2309(16), c = 12.5131(11) Å, β = 98.3780(10)°, V = 1607.7(3) ų, Z = 2. Crystal II is triclinic: space group $P\bar 1$ , a = 8.8260(8), b = 11.1149(11), c = 13.3751(14) Å, α = 102.0140(10)°, β = 105.696(2)°, γ = 99.5940(10)°, V = 1200.4(2) ų, Z = 1. Crystal III is triclinic: space group $P\bar 1$ , a = 7.3600(6), b = 2.7549(11), c = 18.2241(16) Å, α = 106.225(2)°, β = 98.0150(10)°, γ = 99.5400(10)°, V = 1588.5(2) ų, Z = 2. All the three complexes contain sandwich-like crystal structures, in which anionic sheets built up from different anions (Pzdc^2?, Bpdc^2?, Sa^?) and lattice water molecules via rich hydrogen-bonding interactions are inserted between the cationic silver complexes layers. The lattice water molecules are situated among the framework of the crystal structure and stabilized by rich hydrogen-bonding interactions, and lattice water molecules may play a role in the orientation of the organic anions in the crystal packing.     

Acid Co(II) and Ni(II) trifluoroacetate complexes: Synthesis and crystal structure

Anhydrous and partially hydrated acid trinuclear trifluoroacetates of divalent transition metals of the composition [M₃(CF₃COO)₆(CF₃COOH)₆)](CF₃COOH) and [M₃(CF₃COO)₆(CF₃COOH)₂(H₂O)₄)](CF₃COOH)₂, respectively, where M = Co (I, III) Ni (II, IV), were synthesized and studied by X-ray diffraction. Complexes I and II were obtained by crystallization from solutions of M(CF₃COO)₂ · 4H₂O in trifluoroacetic anhydride; complexes III and IV were synthesized under the same conditions with the use of 99% trifluoroacetic acid as a solvent. Crystals I are triclinic: space group $P\bar 1$ , a = 13.199(6) Å, b = 14.649(6) Å, c = 15.818(6) Å, α = 90.04(4)°, β = 114.32(4)°, γ = 108.55(4)°, V = 2611.3(19) ų, Z = 2, R = 0.0480. Crystals II are trigonal: space group $R\bar 3$ , a = 13.307(2) Å, c = 53.13(1) Å, V = 8148(2) ų, Z = 6, R = 0.1112. Crystals III are triclinic: space group $P\bar 1$ , a = 9.001(8) Å, b = 10.379(9) Å, c = 12.119(9) Å, α = 83.67(5)°, β = 72.33(5)°, γ = 83.44(5)°, V = 1068.3(15) ų, Z = 1 Å, R = 0.1031. Crystals IV are triclinic: space group $P\bar 1$ , a = 9.121(18) Å, b = 10.379(2) Å, c = 12.109(2) Å, α = 84.59(3)°, β = 72.20(3)°, γ = 82.80(3)°, V = 1080.94(40) ų, Z = 1, R = 0.0334.     

Crystal and molecular structure of two new Schiff bases: Paeonol-ethylenediamine and paeonol-1,3-propylenediamine

Two new Schiff bases were prepared by the condensation reaction of paeonol with ethylenediamine (for compound 1) and 1,3-propylenediamine (for compound 2). The compounds were studied with single crystal X-ray diffraction method. Compound 1 is monoclinic, space group P2₁/c, a = 10.956(15) Å, b = 6.767(10) Å, c = 12.494(18) Å; β = 104.66(2)°, V = 896(2) ų, Z = 2. Compound 2 is triclinic, space group P-1, a = 6.878(2) Å, b = 12.141(4) Å, c = 12.414(4) Å; α = 101.023(6)°, β = 103.415(6)°, γ = 102.337(6)°, V = 952.8(6) ų, Z = 2. The molecular structures of 1 and 2 are similar; the molecule being centrosymmetric in 1 but asymmetric in 2.     

Bis(tetraphenylantimony) succinate,malate, and tartrate: Syntheses and structures

The reactions of pentaphenylantimony with succinic, malic, and tartaric acids (mole ratio 2: 1) in toluene afford bis(tetraphenylantimony) succinate (I), malate (II), and tartrate (III) in yields of 98, 92, and 94%, respectively. According to the X_ray diffraction analysis results, molecules I and II are centrosymmetric. In compound II, the hydroxy group in the acid residue is disordered over two positions. Crystal III includes two types of crystallographically independent molecules (a and b). The antimony atoms in compounds I, II, IIIa, and IIIb have distorted trigonal bipyramidal coordination modes. The axial angles C_axSbO_ax are 166.80(8)° (I); 174.8(2)° (II); 176.4(4)°, 177.4(3)° (IIIa); and 173.3(4)°, 172.7(4)° (IIIb). The equatorial angles C_eqSbC_eq vary in the ranges 99.3(1)°–154.5(1)° (I); 115.2(2)°–123.3(2)° (II); 115.7(4)°–123.3(4)° 115.2(5)°–125.6(5)° (IIIa); and 107.9(4)°-129.1(4)°, 113.7(4)°-124.8(5)° (IIIb). The Sb-C and Sb-O bonds are 2.138(3)-2.176(3), 2.319(2) Å (I); 2.111(6)–2.163(5), 2.243(4) Å (II); 2.072(13)–2.169(11), 2.252(7), 2.284(7) Å (IIIa); and 2.047(11)–2.190(11), 2.224(7), 2.256(7) Å (IIIb). The intramolecular distances Sb…O=C are 2.528(3) (I); 3.267(7) (II); 3.381(7), 3.436(7) (IIIa); and 3.351(7), 3.162(7) Å (IIIb). For structures I, II, and III, the CIF files are CCDC 929151, 941542, and 941543, respectively.     

Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony dicarboxylates

Tris(5-bromo-2-methoxyphenyl)antimony bis(4-nitrophenylacetate) (I), tris(5-bromo-2-methoxyphenyl)antimony bis(2-methoxybenzoate) (II), and tris(5-bromo-2-methoxyphenyl)antimony bis(phenylpropiolate) (III) have been synthesized via the reaction between tris(5-bromo-2-methoxyphenyl) antimony and 4-nitrophenylacetic acid, 2-methoxybenzoic acid, and phenylpropiolic acid, respectively, in the presence of hydrogen peroxide (molar ratio: 1: 2: 1). According to X-ray diffraction data, the antimony atom in molecules of complexes I–III has a distorted trigonal bipyramidal coordination. The OSbO axial angles and the CSbC bond angles in the equatorial plane are 173.27(15)°, 172.96(11)°, 172.99(10)°, and 115.5(2)°–123.3(2)°, 108.81(16)°–129.32(17)°, and 110.66(17)°–127.91(17)°, respectively. The Sb-O bond lengths are 2.092(4) and 2.115(4)Å in I, 2.088(3) and 2.097(2) Å in II, and 2.096(3) and 2.120(3) Å in III. The Sb-C bonds range within 2.095(6)–2.123(6) Å in I, 2.107(4)–2.117(4) Å in II, and 2.097(4)–2.116(4) Å in III. Complexes I, II, and III are observed to have intramolecular Sb…OCH₃ contacts (3.169–3.226, 3.134–3.174, and 3.147–3.196 Å, respectively) in addition to Sb…O=C interactions (3.121, 3.139Å; 2.944, 3.038 A0; 3.111, 3.120 Å).     

Structure and characterization of A 2D cobalt(II) complex [Co(L)2] n (L = 3-nitro-5-(pyridine-4-yl)benzoate)

The self-assembly of unsymmetrical tecton 3-nitro-5-(pyridin-4-yl)benzoic acid (HL)with cobalt chloride under hydrothermal conditions affords a new 2D coordination polymer [Co(L)₂] _n (1, L = 3-nitro-5-(pyridin-4-yl)benzoate), which is characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction analysis, and single crystal X-ray diffraction. Compound 1 is of the triclinic system, space group P-1 with a = 9.7857(12) Å, b = 10.3417(13) Å, c = 10.8463(13) Å, α = 85.155(2)°, β = 74.785(2)°, γ = 88.962(2)°, V = 1055.4(2) ų. The crystal structural analysis of complex 1 shows that the cobalt center is six-coordinated in an octahedral geometry by four O atoms from four different L ligands and two N atoms from two different L ligands; the Co(II) cations are bridged by μ₃-L into an interesting two-dimensional network structure. It should be pointed out that the thermal analysis results indicate that complex 1 is quite stable up to 420°C.     

Mononuclear zinc(II) complex with 2,3,5,6-tetra(2-pyridyl)pyrazine

Complex [Zn(Tppz)Cl₂] (I), where Tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, has been synthesized and characterized by elemental analyses, IR, ¹H NMR, cyclic voltammetry, and electronic spectral studies. Solid state structures of the complex have been determined by single-crystal X-ray crystallography. The structural determination shows that the mononuclear complex I is a 1D coordination polymer. Also an ORTEP drawing of complex I shows that the coordination geometry around the Zn(II) center is slightly distorted from regular square-based pyramidal. Crystal data for I: triclinic, spase group P $ \bar 1 $ , a = 10.171(2), b = 10.3550(13), c = 12.239 (2) Å, α = 64.839(9)°, β = 85.736(8)°, γ = 77.842(10)°, V = 1140.3(4) ų, Z = 2.     

Further studies on the taumerization of the hydrido (alkynyl) cluster Ru3Pt(μ-H) {μ4-ν2-C ≡ C1Bu} (CO)9(L2) to the vinylidene cluster Ru3Pt{μ4-ν2-C ≡ C(H)tBu} (CO)9(L2): X-ray structures of Ru3Pt(μ-H){μ4-ν2-C = C(H)tBu} (CO)9(L2); L2 = dppet,dppp, andS,S-dppb

The first order rate constants for the tautomerization of the hydrio(alkynyl) clusters Ru₃Pt(μ-H){μ₄-ν²-C ≡ C¹Bu}(CO)₉(L₂);1a: L₂ = dppe,1b; L₂ = dppet,1c; L₂ = dppp and1d; L₂ =S,S-dppb to the corresponding vinylidene clusters Ru₃Pt{μ₄-ν²-C = C(H)^tBu}(CO)₉(L₂)2 have been measured, and they follow the orser1d <1a <1b ～1c. The reactions involving1a and1d exhibit an inverse kinetic deuterium isotope effect. The structures of1b, 2b, 2c, and2d were determined by X-ray crystallography, and are compared with those of1a and2a which have been previously reported. Crystal data for1b, space groupPbca,a = 13.338(4) Å,b = 17.771(6) Å,c = 36.092(8) Å,Z = 8,R(R _w) = 0.059(0.058) for 2342 absorption corrected, observed data; for2b, space group P2₁/n,a = 10.566(2) Å,b = 20.234(5) Å,c = 20.270(3) Å,β = 96.11(1)°,Z = 4,R(R _w) = 0.043(0.053) for 5865 absorption corrected, observed data; for2c, space group P2₁/n,a = 14.211(5) Å,b = 19.534(2) Å,c = 15.870(2) Å,β = 100.81(2)°,Z = 4,R(R _w) = 0.055(0.031) for 6566 absorption corrected, observed data: for2d, space group P2₁2₁2₁,a = 12.309(4) Å,b = 19.047(6) Å,c = 19.206(4) Å,Z = 4,R(R _w) = 0.055(0.053) fpr 2151 absorption corrected, observed data. The fluxional behavior of1d and1e (which consists of two interconverting isomers) has been examined by variable temperature¹³C NMR spectroscopy and by³¹P EXSY.     

Heteroligand zinc(II) and copper(II) complexes with naphthylacetic acid and monoethanolamine: Syntheses and crystal structures

New heteroligand Cu(II) and Zn(II) complexes with the α-naphthylacetic acid anion (NAA) and monoethanolamine (MEA), [M(NAA)₂(MEA)₂] (M = Cu²⁺, (I), Zn²⁺ (II)), are synthesized. The crystal structures of the obtained complexes are determined by X-ray diffraction analysis (CIF files CCDC 984097 (I) and 930946 (II)). The crystals are monoclinic, for I: a = 18.8140(9) Å, b = 4.82500(14) Å, c = 16.0360(7) Å, β = 115.135(6)°, V = 1317.87(11) ų, space group P2₁/c, Z = 2; for II: a = 32.9760(14) Å, b = 5.0911(3) Å, c = 15.7994(10) Å, β = 94.418(5)°, V = 2644.6(3) ų, space group C2/c, Z = 4. In the structure of complex I, the Cu²⁺ ion arranged in the symmetry center is coordinated at the vertices of the distorted octahedron by the oxygen atoms of two NAA molecules (Cu-O(2) 2.019(4) Å) and two MEA molecules. The latter is the bidentate-chelating ligand and coordinates the metal through the O and N atoms to form the five-membered metallocycle (Cu-O(3) 2.457(5), Cu-N(1) 1.986(5) Å). In complex II, the Zn atom (on axis 2) is coordinated at the vertices of the distorted tetrahedron by the oxygen atoms of two NAA molecules (Zn-O(2) 1.976(4) Å) and the nitrogen atoms of two MEA molecules (Zn-N 2.034(6) Å). The character of the interaction of coordinated NAA and MEA ligands and methods for packing complexes I and II are considered on the basis of the structural data.     

Crystal structures of 2-ferrocenylmethylidenehydrazono-1,3-dithiane and 2-ferrocenylmethylidenehydrazono-1,3-dithiepane

Two compounds of 2-ferrocenylmethylidenehydrazono-1,3-dithiane (1) and 2-ferrocenylmethylidenehydrazono-1,3-dithiepane (2) are synthesized and their single crystal structures are determined by the X-ray diffraction method. Compound 1 belongs to the orthorhombic Pca2₁ space group with the cell parameters: a = 13.989(4) Å, b = 5.785(2) Å, c = 18.231(5) Å, V = 1475.4(7) ų; while compound 2 crystallizes in a monoclinic symmetry, P2₁/c space group with a = 15.320(2) Å, b = 5.8028(6) Å, c = 36.584(4) Å, β = 91.932(1)° and V = 3250.4(6) ų.     

Crystal structure of two complexes containing tris-(β-diketonato)magnate anion

Single crystal XRD is used to determine the structures of the complexes (H₂TMEDA)[Mg(ptac)₃]₂ (1, TMEDA = Me₂N(CH₂)₂NMe₂, ptac = ^t BuCOCHCOCF₃) and (H₂TMEDA)[Mg(hfac)₃](hfac) (2, hfac = CF₃COCHCOCF₃) at a temperature of 150 K. The crystallographic data for complex 1: a = 10.2919(3) Å, b = 10.9492(4) Å, c = 15.4159(6) Å, α = 87.117(1)°, β = 89.686(1)°, γ = 79,864(1)°, space group $P\bar 1$ Z = 1, R = 0.0573; for complex 2: a = 12.9446(2) Å, b = 23.0035(4) Å, c = 13.1473(3) Å, β = 98.779(1)°, space group P2₁/n, Z = 4, R = 0.0605. The structures are ionic; the metal atom coordinates six oxygen atoms of three β-diketonate ligands. The distances Mg-O in complex 1 are in the range 2.036(2)–2.0920(19) Å; the same distances in complex 2 are in the range 2.051(2)–2.076(2) Å. The spatial packing is determined by the system of hydrogen bonds between the (H₂TMEDA)²⁺ cations and [Mg(ptac)₃]^? (1) or hfac^? (2) anions. A thermogravimetric study of complex 1 is carried out.     

Structure and properties of tripyridine nitrosocomplexes of ruthenium: mer-[Ru(NO)Py3Cl(OH)]Cl·1.5H2O and mer-[Ru(NO)Py3Cl(H2O)]Cl2·2H2O·0.5HCl

The reaction of K₂[Ru(NO)Cl₅] with pyridine in aqueous ethanol at pH ～ 7–8 affords a nitrosoruthenium hydroxocomplex mer-[Ru(NO)Py₃Cl(OH)]Cl·1.5H₂O (I) (yield ～55%). Treatment of hydroxocomplex I with hydrochloric acid at room temperature gives the aqua complex mer-[Ru(NO)Py₃Cl(H₂O)]Cl₂·2H₂O·0.5HCl (II). The structures of the compounds are determined by X-ray crystallography: I, space group P2₁/n, a = 9.2292(4) Å, b = 11.7781(4) Å, c = 17.4915(7) Å, β = 90.9560(10)°, R = 4.84%; II, space group P-1, a = 7.3528(9) Å, b = 11.5793(11) Å, c = 13.6961(16) Å, α = 84.558(3)°, β = 87.668(4)°, γ = 74.146(4)°, R = 6.22%. Compounds I and II are characterized by powder XRD, ¹H and ¹³C NMR, and IR spectroscopy. The thermal decomposition of compound II in the inert atmosphere is examined by thermal analysis.     

Crystal structures of methyl and benzyl 5-ferrocenyl-3,5-dimethyl-2-pyrazoline-1-dithiocarboxylate

Reactions of E-4-ferrocenylpent-3-en-2-one with S-methyldithiocarbazate or S-benzyldithiocarbazate result in the formation of methyl 5-ferrocenyl-3,5-dimethyl-2-pyrazoline-1-dithiocarboxylate (1) or benzyl 5-ferrocenyl-3,5-dimethyl-2-pyrazoline-1-dithiocarboxylate (2). The single crystals of both products are obtained and their structures are identified by X-ray diffraction method with triclinic P-1 space groups. The cell parameters for compound 1 are as follows: a = 7.7029(8) Å, b = 10.1631(11) Å, c = 10.7305(12) Å, α = 101.3270(10)°, β = 90.6740(10)°, γ = 94.8390(10)°, and V = 820.40(15) ų. For compound 2, the crystallographic data are: a = 7.953(3) Å, b = 10.970(5) Å, c = 12.534(3) Å, α = 84.718(5)°, β = 81.651(3)°, γ = 76.274(4)Å, and V = 1049.1(7) ų.     

Copper(I) halide complexes with N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L2+). Synthesis and crystal structures of the complexes [L0.5CuCl2], [L0.5CuCl0.72Br1.28], and [L0.5CuBr2]

The Eschweiler-Clarke reaction of ethylenediamine with formaldehyde and formic acid yielded N,N,N′,N′-tetramethylethylenediamine, which was alkylated with allyl chloride or allyl bromide to give the corresponding N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L²⁺) dihalides. In methanolic solutions of copper(II) halide and an appropriate ligand, ac electrochemical synthesis with copper wire electrodes afforded single crystals of Cu(I) complexes with L²⁺: [L_0.5CuCl₂] (I), [L_0.5CuCl_0.72Br_1.28] (II), and [L_0.5CuBr₂] (III). The crystal structures of complexes I–III were determined by X-ray diffraction study. The isostructural crystals of I and II are monoclinic, space group P2₁/n, Z = 4. For I: a = 7.632(4) Å, b = 11.318(5) Å, c = 10.635(5) Å, β = 98.551(7)°, V = 908.4(7) ų. For II: a = 7.7415(7) Å, b = 11.4652(9) Å, c = 10.7267(10) Å, β = 98.351(4)°, V = 942.0(2) ų. The organic cation L²⁺ acts as a bridge linking a pair of separate cuprous halide fragments Cu₂X₄. Although being isostoichiometric with I and II, complex III has a different structure. The crystals of III are monoclinic, space group P2₁/c, a = 6.519(2) Å, b = 9.060(3) Å, c = 16.284(6) Å, β = 97.219(4)°, V = 954.2(6) ų, Z = 4. In structure III, the inorganic fragment forms infinite polymer chains (CuBr ₂ ^? ) _n . The organic and inorganic parts are held together only by electrostatic interactions. Structures I–III are stabilized by hydrogen bonds (C)H…X (2.6–2.9 Å).     

Copper(II) and lead(II) complexes based on 2,3,5,6-tetrakis(2-pyridyl)pyrazine as a polydentate ligand

The Cu(II) complexes [Cu(Tppz)(Dipic)] · 8H₂O (I) and [Pb₂(Tppz)Cl₄] _n (II), where Tppz, H2Dipic are 2,3,5,6-tetrakis(2-pyridyl)pyrazine, dipicolinic acid, respectively, have been synthesized and characterized by elemental analyses, IR, cyclic voltammetry, and electronic spectral studies. Solid state structures of both complexes have been determined by single crystal X-ray crystallography. An ORTEP drawing of two complexes shows that the coordination geometry around the metal center is a distorted octahedron. There are extensive conventional intermolecular O-H…O, N-H…O, and weaker C-H…O and C-H…Cl non-classical hydrogen bonds, which cause the stability of the crystal structure. Crystal data for I: monoclinic, space group: C2/c, a = 35.421(3), b = 8.422(6), c = 22.824(8) Å, β = 101.69(2)°, V = 6668(5) ų, Z = 8. Crystal data for II: triclinic, space group P \(\bar 1\) , a = 7.9534(4), b = 8.8682(5), c = 9.4245(5) Å, β = 95.086(2)°, V = 655.93(6) ų, Z = 2.     

Synthesis and study of tetraamminecobalt hydrogen hexamolybdometalates(III)

Tetraamminecobalt hydrogen hexamolybdoferrate [Co(NH₃)₄] · H[FeMo₆O₁₈(OH)₆] · 6H₂O (I) and tetraamminecobalt hydrogen hexamolybdogallate(III) [Co(NH₃)₄] · H[GaMo₆O₁₈(OH)₆] · 6H₂O (II) were synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray diffraction. Crystals of I and II are monoclinic; a = 16.21 Å, b = 5.43 Å, c = 12.32 Å, β = 119.63°, V = 1092.11 ų, ρ_calcd = 2.21 g/cm³, and Z = 1 for I; a = 16.24 Å, b = 5.59 Å, c = 12.29 Å, β = 119.79°, V = 1064.05 ų, ρ_calcd = 2.15 g/cm³, and Z = 1 for II. Compounds I and II were used as catalysts for soft oxidation of natural gas.     

Syntheses, crystal structure, and fluorescent properties of a lanthanide complex

A new complex [Dy₂(Pht)₂(HPht)₂(Phen)₂(H₂O)₄] (I), where Pht^2? = dianion of o-phthalic acid; HPht^? = mono-anion of o-phthalic acid; Phen = 1,10-phenanthroline, has been synthesized and the crystal structure was determined by X-ray crystallography. The I crystallizes in the triclinic system, space group $P\bar 1$ with lattice parameters a =10.1126(3) Å, b =10.7029(3) Å, c = 11.9360(3) Å, α = 90.2260(10)°, β = 99.5340(10)°, γ = 100.9810(10)°, V = 1249.87(6) ų, Z = 2, ρ_calcd = 1.881 mg m^?3. The photophysical property of I has been studied with excitation and emission spectra.     

New synthetic routes for the preparation of the triangular trinuclear clusters of tungsten-containing bromine atoms as terminal ligands: Structural characterization of [W3S4Br3(depe)3]PF6·0.5C7 H8 and [W3S4Br3(depe)3]Br·2CH3OH

Synthetic methods are reported for the preparation of compounds containing the trinuclear triangular cluster [W₃S₄Br₃(depe)₃[⁺. These involve reactions between WBr₅ and NaB(C₂ H₅)₃H or NaBH₄ as reducing agent in THF, and subsequent addition of methanolic solutions of NaHS and depe ligand. Both compounds, [W₃S₃Br₃(depe)₃]PF₆·0.5C₇H₈,1, and [W₃S₄Br₃(depe)₃]Br·2CH₃OH,2, are characterized by x-ray single crystal studies. Compounds1 and2 crystallize in space group \(P\bar 1\) . For1,a=10.427 (3) Å,b=15.415(4) Å,c=18.140(5) Å, α=79.36(2)°, β=73.59(2)°, γ=81.54(2)°, andV=2734.8(2) ų;R=0.050 and for 2a=10.491(3) Å,b=15.074(3) Å,c=18.246 Å, α=95.76(2)°, β=105.82(2)°, γ=98.18(2)°, andV=2718.4(3) ų;R=0.081. The two cations in1 and2 possess C₃ symmetry. The W-W distances are in the range 2.783?2.891 Å (for1) and 2.778?2.785 Å (for2) and the average W-Br distances in1 and2 are 2.616[2] Å and 2.594[4] Å, respectively. Each metal atom in the [W₃S₄Br₃(depe)₃]⁺ ions is attached to one capping sulfur atom, two bridging sulfur atoms, one bromine atom, and one chelating depe ligand. One P atom in depe ligand istrans to μ₃-S and the otherP atom istrans to a μ₂-S atom. UV-Vis and NMR spectra for these compounds are also reported.     

Thiourea-halide lattices. Part 1. Crystal structures of (n-C4H9)4N+F−·3(NH2)2CS, (n-C4H9)3(CH3) N+X−·2(NH2)2CS (X = Cl,Br), and (n-C3H7)4N+I−·(NH2)2CS

The title complexes (1, X = F;2, X = C 1; 3, X = Br and isomorphous with2; 4, X = I) have been prepared and characterized by X-ray crystallography. Crystal data, MoKα radiation:1, space groupCc,Z =4,a = 12.017(3),b = 14.263(5),c = 17.210(7) Å,β = 103.06(2)°, andR _F =0.053 for 2044 observed data;2, space groupCc,Z = 4,a = 12.817(3),b = 11.072(2),c = 16.781(5) Å,β =90.74(2)°,R _F = 0.044 for 2249 data;3,a = 12.873(4),b = 11. 119(2),c = 16.957(2) Å,β = 89.11(2)°,R _F = 0.049 for 2059 data;4, space groupP2₁/n,Z = 4,a = 8.858(2),b = 14.358(3),c = 15.379(3) Å,β = 93.88(1)°,R _F = 0.068 for 3119 data. In all four structures each thiourea molecule interacts with adjacent thiourea molecules via N-H ... S hydrogen bonds to give a ribbon-like arrangement, and also forms a pair of ‘chelating’ N-H ... X hydrogen bonds with a halide ion, resulting in an anionic framework (in1–3) or composite ribbon (in4) as a component in the crystal packing. The measured ranges of N... X distances are: 2.819(5)-2.994(7) Å for1, 3.252(3)-3.291(3)Å for 2, 3.353(6)-3.459(6)Å for3, and 3.564(5)-3.680(5) Å for 4.