THE CRYSTAL STRUCTURE OF TETRATHIOPHENE TCNQ COMPLEX

<正> C28H16N4S4 Mr=534.7 triclinic Pl, a=7.8941(15)A, b=8.8833(11)A, c=10.3229(12)A; α=109.712(10)°, β=109.125(13)°, r=97.946(13)°, V=618.21(18) A3, Z=1; μ(MoKα)=3.93 cm-1, F(000)=273.95, room temperature, final R=0.085 for 1123 independent reflections. In the title complex the planes tetra-thiophene and TCNQ are face to face mixed and packed along c axis to form one dimensional column.     

CRYSTAL STRUCTURE OF OXAZOLIDINE-2-THIONE

<正> Crystals of. oxazolidine-2-thione, G3H5SNO, are triclinic,P1, a = 5.738(3), b = 5.928(4), c = 7.763(5) A, (?) = 83.05(6)°, α= 67.68(5)°, r = 77.85(5)°, Z = 2, V = 235.8A3, Dx = 1.45 g.cm-3, P(000) = 108, Mr = 103.14, m.p. = 96.2°-97.2°C, (MoK(?)) = 0.71069A, T = 293K, μ(MoK(?)) =0.051 mm-1. The structure was solved by direct methods and. difference Fourier synthesis. The final R was 0.033 for 655 unique observed reflections. It is a new hydrolysis and rearranging product of 2-hydryoxyl ethyl glucosinolate from the seeds of Copparis masaikai Levl.. The study of its physiological activity is in progress.     

THE CRYSTAL AND MOLECULAR STRUCTURE OF N,N~'-DI-n-BUTYL-29,30-DIMBTHOXY-13,27-DICHLORO-6,20-DIAZA-3,9,17,23-TETRAOXA TRICYCLIC (23.3.1.1~(11,15))-CYCLOTRIACONTANE-1(29),11,13,15(30),25,27-HEXENE

<正> C34H52N2O6Cl2, Mr=655.70, triclinic, Pl,a=8.909(5),b=9.158(5), c=11.841(9) A,α=73.41(5)°,β=76.51(8)°,γ=80.38(6)°, V = 895.1 A3, Z=l, DC=1.223 gcm-3,λ= 0.7107 A,μ=2.299 cm-1.Full matrix least-squares refinement, final R = 0.088, Rw= 0.084 for 1039 (I>36) unique reflections. The crystal is composed of separate molecules having an approximate inversion center. The molecule is shaped like an ellipse. The distances of 0(31)-0(32), 0(41)-0(42), and N(31)-N(41) are 4.254, 4.136 and 10.930 A, respectively.     

Tetrafluoroaurate(III) der Lanthaniden M2F[AuF4]5 (M = Tb,Dy, Ho,Er)

Tetrafluoroaurates(III) of Lanthanoides M₂F[AuF₄]₅ (M = Tb, Dy, Ho, Er) Tetrafluoroaurates(III) M₂F[AuF₄]₅ with M = Tb, Dy, Ho, Er, all yellow, have been obtained. From single crystal data they crystallize triclinic, space group P1 -C¹_i (No. 2) with Tb: a = 1 194,34(7) pm, b = 798,46(6) pm, c = 902,02(7) pm, α = 89,033(7)°, β = 88,990(6)°, γ = 89,006(7)°; Dy: a = 1 191,66(9) pm, b = 796,33(8) pm, c = 899,65(9) pm, α = 88,956(8)°, β = 89,056(8)°, γ = 88,972(8)°; Ho: a = 1 189,06(10) pm, b = 795,46(6) pm, c = 896,81(7) pm, α = 88,912(8)°, β = 89,101(7)°, γ = 88,873(8)°; Er: a = 1 185,20(40), b = 793,98(14), c = 893,83(20), α = 88,751(23)°, β = 89,187(26)°, γ = 88,884(9)°     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Tetrachlorodirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of Four Linkage Isomeric Tetrachlorodirhodanoosmates(IV) By treatment of cis- or trans-[OsCl₄I₂]^2? with (SCN)₂ in dichloromethane the linkage isomers cis-[OsCl₄(NCS)₂]^2? ( 1 ), trans-[OsCl₄(NCS)(SCN)]^2? ( 2 ), cis-[OsCl₄(NCS)(SCN)]^2? ( 3 ) and trans-[OsCl₄(SCN)₂]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determinations on single crystals of cis-(Ph₄As)₂[OsCl₄(NCS)₂] (triclinic, space group P1 , a = 10.019(5), b = 11.702(5), c = 21.922(5) Å, α = 83.602(5)°, β = 85.718(5)°, γ = 73.300(5)°, Z = 2), trans-(Ph₄As)₂[OsCl₄ · (NCS)(SCN)] (monoclinic, space group P2₁/c, a = 18.025(5), b = 11.445(5), c = 23.437(5) Å, β = 94.208(5)°, Z = 4), cis-(Ph₄As)₂[OsCl₄(NCS)(SCN)] (triclinic, space group P1 , a = 10.579(5), b = 11.682(5), c = 22.557(5) Å, α = 81.073(5)°, β = 85.807(5)°, γ = 87.677(5)°, Z = 2) and trans-(Ph₄As)₂ · [OsCl₄(SCN)₂] (triclinic, space group P1 , a = 10.615(5), b = 11.691(5), c = 11.907(5) Å, α = 111.314(5)°, β = 96.718(5)°, γ = 91.446(5)°, Z = 1) reveal the complete ordering of the complex anions. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 171.2° and 174.3° ( 1 ), 162.3° ( 2 ), 172° ( 3 ) and Os? S? C angles of 108.3° ( 2 ), 105.7° ( 3 ) and 105.5° ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers are assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.59 ( 1 ), 1.67 ( 2 ), 1.60 ( 3 ) and f_d(OsS) = 1.27 ( 2 ), 1.31 ( 3 ) and 1.32 mdyn Å^?1 ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Struktur von S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantan und 9,10-Diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantan

Structure of S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane and 9,10-Diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane ( 1 ) and 9,10-diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane ( 2 ) have been prepared by the reaction of propionic acid, propionic anhydride and butyric acid, butyric anhydride, respectively, with arsenic(III)-oxide. The crystals of 1 are rhombic, a = 6.902(4), b = 11.121(5), c = 13.988(8), space group P2₁2₁2₁. The crystals of 2 are monoclinic, a = 11.757(10), b = 11.255(10), c = 18.631 (18), β = 91.78(7), space group P2₁/n. The mean bond lengths and angles in 1 are AsO = 1.790 Å, AsC = 1.959 Å, OAsO = 100.60°, CAsO = 99.65°, AsOAs = 128.77°, AsCAs = 118.73°, and in 2 they are AsO = 1.780 Å, AsC = 1.978 Å, OAsO = 101.45°, CAsO = 99.55°, AsOAs = 129.64°, AsCAs = 117.72°.     

STEREOCHEMICAL STUDIES ON CYCLOHEXANONE SEMICARBAZONE DERIVATIVES II. CRYSTAL AND MOLECULAR STRUCTURES OF 4-METHYL-CYCLOHEXANONE SEMICARBAZONE AND 4-CYCLOHEXYL-CYCLOHEXANONE SEMICARBAZONE

<正> The crystal and molecular structures of 4-methyl-cyclohexanone semicarbazone (MCSC) and 4-cyclohexyl-cyclohexanone semicarbazone (CHCSC) have been determined by X-ray diffraction methods. MCSC, monoclinic, space group C2/c with a=19. 788(5), b=8.328(2), c=14. 372(4) A , β=127. 44(1)°, final R = 0. 051, Rw = 0. 057 for 801 unique reflections. CHCSC, triclinic, space group P1 with a = 5. 874(5), b = 7. 026(3), c=17. 93(1)A, α=88. 57(4)°,β = 83.08(5)°,γ=111. 66(5)°, final R = 0. 063, Rw = 0. 057 for 2144 unique reflections. The cyclohexane ring of both compounds has a slightly distorted chair conformation. The NH CONH group in both molecules shows a configuration with the C = O bonds trans to the N-NH bond with respect to the C-NH bond. The molecules in the crystals interacted with each other forming infinite ribbons through the O....H -N hydrogen bonds.     

Crystal structure and spectroscopic properties of A[VO2(SO4)(H2O)2] · H2O (A = K, Rb, Tl, NH4) compounds

The crystal structure of dioxovanadium(V) sulfate trihydrates A[VO₂(SO₄)(H₂O)₂] · H₂O, where A is K, Rb, Tl, or NH₄, has been determined based on a combination of neutron and X-ray diffraction data. The compounds are isostructural and have a monoclinic lattice (space group P2₁, Z = 2) with unit cell parameters a = 6.24535(8), 6.26016(7), 6.25817(5), and 6.2500(1) Å; b = 9.8417(1), 9.99736(8), 9.96217(9), and 9.9742(1) Å; c = 6.52113(8), 6.69303(5), 6.70379(6), and 6.70334(9) Å; β = 106.99(1)°, 107.83(1)°, and 107.83(1)°, 107.99(1)°, respectively. The SO₄ tetrahedra and VO₄(H₂O)₂ octahedra share an oxygen vertex to form infinite isolated chains. Atoms A have CN = 10. IR and Raman spectroscopy data are reported.     

CRYSTAL AND MOLECULAR STRUCTURE OF N-CYANOMETHYL PH-THALIMIDE AND N-CYANOMETHYL SUCCIMIDE

<正> Diethylaminoacetonitrile (1) reacts with phthalimide (2) or succirnide (3) to produce N-cyanomethyl phthalimide (4) C10H6O2N2 (Mr = 186. 168) or N-cyanomethyl succirnide (5) C6H6O2N2(Mr= 138. 128),respectively. Their molecular and crystal structures were determined by IR, 1H NMR, MS and X-ray diffraction analysis, compound (4) crystallizes in monoclinic space group P21/a(P21/c) ,with cell dimensions 0=8. 225(4) ,6= 10. 956(4),c= 10. 041(5) A .β=102. 43(4)°,V=883. 1A3, μ= 0. 90cm-1, F (000) = 384, Z = 4; compound (5) crystallizes in monoclinic space group P1,with a=8. 404(2),b = 9. 710(2),c= 10. 093(2) A ,α= 104. 73(2)°,β = 108. 55(2)°, γ= 112. 03(2)°,V= 655. 2 A3,μ= 1.0cm-1 ,F(000) = 288,Z= 4. The average inner angles of the five-membered ring of (4) and (5) are about 108°. The imide and the carbon atom of the methylene radical of N-cyanomethyl and phenyl ring are all in one plane . so the bonds are delocalized and the α-hydrogen atoms of N-cyanomethyl are activated. The syntheses and crysta     

Einkristall-RöntgenStrukturanalysen von Verbindungen mit einer kovalenten Metall-Metall-Bindung. VII. Die Kristall- und Molekülstruktur von dimeren Halogenobis- (pentacarbonylrhenium)indium(III), [(Re(CO)5)2In(μ-X)]2 (X = Cl,Br, I)

Single-Crystal X-Ray Analysis of Compounds with a Covalent Metal-Metal Bond. VII. Crystal and Molecular Structure of the Halogeno-Bridged Dimers of Halogenobis(pentacarbonylrhenium)indium(III), [(Re(CO)₅)₂In(μ-X)]₂ (X = Cl, Br, I) [(Re(CO)₅)₂In(μ-X)]₂ crystallizes if X = Cl and X = Br in the monoclinic system, space group P2₁/c (No. 14), with the lattice constants X = Cl: a = 10.540(6), b = 12.961(7), c = 26.071(12) Å, β = 106.3(1) Å, Z = 4, X = Br: a = 10.548(9), b = 13.108(7), c = 26.192(15) Å, β = 106.0(2)°, Z = 4 and if X = I in the triclinic system, space group P1 (No. 2), with the lattice constants a = 10.739(2), b = 7.160(1), c = 13.647(1) Å, α = 68.65(9), β = 71.89(9), γ = 65.52(9)°, Z = 1. The central molecular fragment consists of a plane In₂X₂ ring with the mean In—X distances: X = Cl: 2.624(6) Å, X = Br: 2.764(3) Å and X = I: 2.986(2) Å and the angles In—X—In/X—In—X, X = Cl: 97.2(2)°/ 82.8(2)°, X = Br: 94.8(1)°/85.2(1)° and X = I: 96.47(5)°/83.53(5)°. Two Re(CO)₅ groups are bonded to each of these In atoms to form a distorted tetrahedral coordination. The mean In—Re bond-distances are: X = Cl: 2.797(2), X = Br: 2.796(2) and X = I:2.811 (2) Å. There is a octahedral coordination around the Re atoms.     

CRYSTAL AND MOLECULAR STRUCTURE OF TETRAKIS(THIPHENYLPHOSPHINE OXIDE)-DICHLORO-GADOLINIUM(Ⅲ)TRICHLOHO-COPPER(Ⅱ)

<正> The crystal of tetrakis(triphenylphosphine oxide)-dichloro-gadolinium trichloro-copper belongs to triclinic, space group Pl with unit cell parameters of a = 19.395(2), b = 19.708(5), c = 20.609(4)A,α= 63.32(2)° ,β=88.74(1)°,γ=81.49(1)°,V=6943.8A3,and Z=4. The final refinement converges with R=0.072 and Rw = 0.077 for 7870 observed independent reflections.     

CRYSTAL AND MOLECULAR STRUCTURE OF A DIPHENYL SULFOXIDE COMPLEX WITH CERIUM NITRATE, Ce(N0_3)_3[(C_6H_5)_2SO]_4

<正> The title complex crystallises in the triclinic, space group PT with two formula units in a unit cell of dimensions a=11.182(4), b=14.357(5), c=17.362(6) A and α= 84.08(3)°, β=72.79(3)°, r= 69.27(2)°, Dx=1.51 g.cm-3, V=2489.6(15) A3. The final index for 6319 observed reflections is 0.0274. The Ce3+ ion is coordinated by ten oxygen atoms with Ce-O distances varying from 2.469 to 2.706 A. The three nitrate groups are all bidentate ligands.     

Two-dimensional Grid-type Zinc（Ⅱ） Coordination Polymer Constructed by a New Aromatic Carboxylate Ligand

A new aromatic carboxylate ligand,namely 5-(pyrrolidin-1-yl)-1,3-benzenedicar-boxylic acid(H2pybdc),was synthesized and characterized by FT-IR and single-crystal X-ray diffraction analysis.It crystallizes in triclinic system,P1 space group with a = 10.05(5) ,b = 11.53(5),c = 12.92(6) ,α = 112.11(6)°,β = 92.79(7)°,γ = 102.98(7)°,V = 1337.113,Z = 4,Mr = 253.25,Dc = 1.258 g.cm-3,μ = 0.099 mm-1,F(000) = 536,the final R = 0.0822 and wR = 0.2575 for 1893 observed reflections(I >2σ(I)).Based on it,a two-dimensional grid-type Zn(Ⅱ) coordina-tion polymer of {[Zn(pybdc)(bpy)(H2O)].2H2O.0.5CH3OH}n(1) was solvothermally synthesized,which crystallizes in triclinic,space group P1 with a = 10.218(5) ?,b = 11.176(5) ,c =11.350(5) ,α = 95.855(5)°,β = 94.248(5)°,γ = 101.421(5)°,V = 1257.9(2) 3,Z = 2,Mr = 524.84,Dc = 1.386 g.cm-3,μ = 1.024 mm-1,F(000) = 546,the final R = 0.0635 and wR = 0.1879 for 3913 observed reflections(I >2σ(I)).     

1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe₃N)₄[(dto)₂In(dto)In(dto)₂] ( 1 ), (BzlPh₃P)₄[(dto)₂In(dto)In(dto)₂] ( 2 ), (BzlMe₃N)₃[In(dtsq)₃] ( 3 ), (Bu₄N)₃[In(dtsq)₃] ( 4 ) and (Ph₄P)[In(dtsq)₂(DMF)₂] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P2₁/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P2₁/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.     

Na4SeO5, ein neues Pentaoxoselenat(VI) – Synthese,Charakterisierung und Vergleich mit isotypem Na4MoO5

Na₄SeO₅, a Novel Pentaoxoselenate(VI) – Synthesis, Charakterisation, and Comparison with Na₄MoO₅ Na₄SeO₅ was prepared by high pressure solid state reaction at 500 °C and at a hydrostatic pressure of 2.5 Gpa from a mixture of Na₂O and Na₂SeO₄ in silver crucibles and Na₄MoO₅ by solid state reaction at 450 °C from a mixture of Na₂O and MoO₃. The crystal structures of both new compounds were solved and refined using X‐ray powder methods (Profilematching Na₄SeO₅: P1, a = 988.3(1), b = 988.4(1), c = 558.6(1) pm, α = 96.25(1)°, β = 96.24(1)°, γ = 113.41(1)°, R_p = 0.0783, R_wp = 0.1037. Profilematching Na₄MoO₅: P1, a = 999.5(1), b = 1002.0(1), c = 565.1(1) pm, α = 96.54(1)°, β = 96.29(1)°, γ = 113.35(1)°, R_p = 0.0623, R_wp = 0.0867). Both compounds contain novel XO₅^4– anions of approximately tetragonal pyramidal shape. The crystal structures are consistent with spectroscopic data (IR, Raman).     

rac‐1‐Phenyl­ethyl­ammonium carboxy­methyl­phospho­nate(1–): hydrogen‐bonded anion sheets with pendent cations

In the title compound, C₈H₁₂N⁺·C₂H₄O₅P⁻, the anions are linked by two O—H⋯O hydrogen bonds [H⋯O both 1.75 Å, O⋯O = 2.5781 (15) and 2.5834 (15) Å, and O—H⋯O = 169 and 176°] into sheets built from alternating (8) and (32) rings. Each cation is linked to an anion sheet by three N—H⋯O hydrogen bonds [H⋯O = 1.88–2.04 Å, N⋯O = 2.7603 (16)–2.9334 (17) Å and N—H⋯O = 162–166°], such that all the cations pendent from one face of the sheet are of the R configuration, while all those pendent from the opposite face are of the S configuration.     

STRUCTURE OF NEODYMIUM TRINITRATE WITH DIPHENYL SULFOXIDE LIGANDS, Nd(N0_3)_3·[(C_6H_5SO]_4

<正> Mr=2278, triclinic, Pl, a=11.154(1), b=14.310(2), c=17.295(2) A, α=84.09(1)°, β=72.97(1)°, r=69:37(1)°, V=2470.2(5)A3, Z=2; 2(MoKα)=12.9cm-1 F(000)=1154, Dx=1.53 g/cm3, room temperature. The final R=0.039, Rw=0.039 with wt=1, S=2.57 for 5710 independent reflections with | Fα|≥2.5σ(F0). The molecular configuration of the Nd-complex is similar to those of the Sm-complex and Pr-complex except for the difference in distances between central metal and the coordinated oxygen atoms.     

Synthesis,Characterization and Crystal Structures of new Palladium(II) Complexes and the first Platinum(III) Complex Containing ATT (ATT = 6‐Aza‐2‐thiothymine)

Treatment of the ligand 6‐aza‐2‐thiothymine (ATT, HL, 1 ) with palladium chloride in methanol forms the ionic complex [(HL)₄Pd]Cl₂·8MeOH ( 2 ), while its reaction with palladium iodide in same solvent produces the neutral complex trans‐[(HL)₂PdI₂]·2MeOH ( 3 ) in high yields. The reaction of 1 with Na₂[PdCl₄] in the presence of sodium acetate in a molar ratio of 2:1:2 and with platinum(II) chloride in presence of sodium acetate led to the dimer tetranuclear complexes [(L₄Pd₂)NaCl]₂·8MeOH ( 4 ) and [L₄Pt₂Cl₂]·6MeOH·H₂O ( 5 ). The latter is the first Pt^III complex of the ligand. All complexes were characterized by elemental analyses and IR spectroscopy and the crystal structures of 2 , 3 , 4 and 5 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: triclinic space group , a = 1006.6(1), b = 1006.9(1), c = 1158.1(1) pm, α = 85.20(1)°, β = 83.84(1)°, γ = 88.91(1)°, Z = 1, R₁ = 0.0278; for 3 at ?80 °C: triclinic space group , a = 490.5(1), b = 977.2(2), c = 1116.8(2) pm, α = 90.26(1)°, β = 102.33(1)°, γ = 96.08(1)°, Z = 1, R₁ = 0.0394; for 4 at ?80 °C: orthorhombic space group Ccca, a = 1791.7(2), b = 1874.1(2), c = 2044.0(1) pm, Z = 4, R₁ = 0.0341 and for 5 at ?80 °C: monoclinic space group P2₁/c, a = 1464.3(1), b = 2003.7(1), c = 1368.5(1) pm, β = 95.66(1)°, Z = 4, R₁ = 0.0429.     

Molecular structure of 2,4-dicarba-closo.heptaborane-7 by gas-phase electron diffraction

Gas phase electron diffraction patterns of 2,4-dicarba-closo-heptaborane were recorded at room temperature. Least squares analysis of the reduced intensity data show that the molecule is a pentagonal bipyramid and confirms the C_2v symmetry in the gas phase. The carbon atoms are located in the pentagonal belt and are separated by one boron atom. No significant departures from planarity of the pentagonal belt are indicated. The bond lengths in the belt are C(4)-B(3), 1.537 Å, C(4)-B(5), 1.558 Å, and B(5)-B(6), 1.659 Å. The distance from the apical B(l) atom to the B(3) is 1.852 Å, from the B(1) to the B(5) atom is 1.772 A, and from the B(1) to the C(2) atom is 1.717 Å. The bond angles in the pentagonal belt are C(2)B(3)C(4) = 100.5°, B(3)C(4)B(5) = 116.7° and C(4)B(5)B(6) = 103.0°. The angle between B(1)B(3)B(7) = 84.7°. Comparisons are made with structural data and moments of inertia determined by microwave spectroscopy.     

Synthesis,Characterization of a Novel 1,2,4‐Thiotriazine Derivative (CAMTTO), and Copper(I) and Silver(I) Complexes thereof (CAMTTO = {(4‐[(4‐Chlorobenzylidene)‐amino]‐6‐methyl‐3‐thioxo‐[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one)}

The reaction of 4‐amino‐6‐methyl‐1,2,4‐triazin‐thione‐5‐one (H₂AMTTO, 1 ) with 4‐chlorobenzaldhyde led to the corresponding iminic compound {(4‐[(4‐chloro‐benzylidene)‐amino]‐6‐methyl‐3‐thioxo[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one), CAMTTO ( 2 ). Treatment of 2 with copper(I) chloride in chloroform gave the dimeric complex [{(CAMTTO)₂CuCl}₂]·2CHCl₃ ( 3 ). Treatment of 2 with copper(I) chloride and silver(I) nitrate in the presence of the co‐ligand triphenylphophane gave the complexes [(CAMTTO)CuCl(PPh₃)₂] ( 4 ) and [(CAMTTO)Ag(PPh₃)₂]NO₃·2CHCl₃ ( 5 ). All compounds have been characterized by elemental analyses, ¹H NMR spectroscopy, IR spectroscopy, and partly by mass spectrometry and X‐ray diffraction studies. In addition 4 and 5 have been characterized by ³¹P{¹H} NMR spectroscopy. Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1370.3(1), b = 767.8(1), c = 1268.7(1) pm, β = 107.12(1)°, Z = 4, R₁ = 0.0379; for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1442.6(2), b = 878.8(1), c = 2558.7(3) pm, β = 95.31(1)°, Z = 2, R₁ = 0.0746; for 4 at ?80 °C: triclinic, space group , a = 1287.9(1), b = 1291.7(1), c = 1359.5(1) pm, α = 90.44(1)°, β = 94.81(1)°, γ = 107.54(1)°, Z = 2, R₁ = 0.0359 and for 5 at ?80 °C: triclinic, space group , a = 1060.5(1), b = 1578.2(2), c = 1689.6(2) pm, α = 87.70(1)°, β = 86.66(1)°, γ = 76.84(1)°, Z = 2, R₁ = 0.0487.