Syntheses and Characterization of New Copper Complexes with the Heterocyclic Thione,AMTTO. X‐Ray Structures of [Cu(AMTTO)Cl2], [Cu(AMTTO)2]Cl,and [Cu(AMTTO)(PPh3)2Cl] (AMTTO = 4‐Amino‐6‐methyl‐1, 2, 4‐triazine‐3‐thione‐5‐one)

The complexes [Cu(AMTTO)Cl₂] ( 2 ), [Cu(AMTTO)₂]Cl ( 3 ), and [Cu(AMTTO)(PPh₃)₂Cl] ( 4 ) have been prepared and characterized by IR spectroscopy and elemental analyses. Also single‐crystal X‐ray diffraction studies on compound 2 , 3 and 4 revealed that AMTTO acts in 2 as a bidentate ligand via nitrogen and sulfur atoms, in 3 and 4 as a monodentate via sulfur atoms. Complex 3 was already mentioned in literature, but the structure was not described in detail. The molecules in 2 form infinite chains through additional weak Cu—S interactions along [010] indicating the Jahn‐Teller distortion of the d⁹ ion Cu²⁺. The infinite chains are connected by hydrogen bonding along [100]. Crystal data for 2 at —80°C: monoclinic, space group P2₁/m, a = 666.7(1), b = 609.4(1), c = 1132.6(2) pm, b = 95.46(2)°, Z = 2, R₁ = 0.0365; for 3 at —80°C: orthorhombic, space group Pbcn, a = 1291.2(2), b = 1146.5(1), c = 1000.5(1) pm, Z = 4, R₁ = 0.0315; for 4 at —80°C: monoclinic, space group, P2₁/n, a = 879.4(1), b = 1849.3(2), c = 2293.8(3) pm, β = 92.38(1)°, Z = 4, R₁ = 0.0688.     

Synthesis,Characterization and Crystal Structure of Dimeric {[(AMTTO)2Ag]NO3}2 (AMTTO = 4‐Amino‐6‐methyl‐1, 2, 4‐triazine‐3(2H)‐thione‐5‐one)

The reaction of 4‐Amino‐6‐methyl‐1, 2, 4‐triazine‐3(2H)‐thione‐5‐one (AMTTO, 1 ) with silver nitrate in methanol led to the dimeric complex {[(AMTTO)₂Ag]NO₃}₂ ( 2 ). 2 was characterized by elemental analyses and IR spectroscopy as well as by X‐ray structure analysis. Crystal data for 2 at ?80 °C: crystal system orthorhombic, space group P2₁2₁2₁ with a = 1043.6(1), b = 1329.6(1), c = 2358.4(1) pm, Z = 8 and R₁ = 0.037. The cation possesses a highly distorted linear coordination sphere in the solid state.     

Syntheses and Crystal Structures of [(AMTTO)Pd(PPh3)Cl]Cl · MeOH and [(AMTTO)Pd(SCN)2] · MeCN

The reaction of [(AMTTO)PdCl₂] ( 1 ) (AMTTO = 4-Amino-6-methyl-1,2,4-triazine-3(2H)-thione-5-one) with triphenylphosphane and sodium thiocyanate led to the air-stable crystalline complexes [(AMTTO)Pd(PPh₃)Cl]Cl · MeOH ( 2 ) and [(AMTTO)Pd(SCN)₂] · MeCN ( 3 ) in excellent yields. 2 and 3 have been characterized by IR and ³¹P NMR spectroscopy, elemental analyses as well as X-ray diffraction studies. Crystal data for 2 at –83 °C: monoclinic, space group P2₁/n, with a = 974.4(1), b = 988.6(1), c = 2750.7(2) pm, β = 98.16(1)°, Z = 4, R₁ = 0.0241 and for 3 at –80 °C: orthorhombic, space group P2₁2₁2₁, with a = 972.0(3), b = 1168.1(4), c = 1316.6(1) pm, Z = 4, R₁ = 0.0817.     

Synthesis,Characterization, and Crystal Structure of the New Schiff‐Bases derived from 1,2,4‐Triazole and the Structure of [(PPh3)2Cu(AMTT)]NO3·EtOH (AMTT = 4‐Amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione)

The reactions of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, L1 ) with 2‐thiophen carbaldehyde, salicylaldehyde and 2‐nitrobenzaldehyde in methanol led to the corresponding Schiff‐bases ( L1a‐c ). The reaction of L1 with [(PPh₃)₂Cu]NO₃ in ethanol gave the ionic complex [(PPh₃)₂Cu(L1)]NO₃·EtOH ( 2 ) All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for L1a at 20 °C: space group P2₁/n with a = 439.6(2), b = 2074.0(9), c = 1112.8(4) pm, β = 93.51(3)°, Z = 4, R₁ = 0.0406, L1b at ?80 °C: space group P2₁/n with a = 1268.9(2), b = 739.3(1), c = 1272.5(1) pm, β = 117.97(1)°, Z = 4, R₁ = 0.0361, L1c at ?80 °C: space group P2₁/n with a = 847.8(1), b = 1502.9(2), c = 981.5(2) pm, β = 110.34(1)°, Z = 4, R₁ = 0.0376 and for 2 at ?80 °C: space group with a = 1247.8(1), b = 1270.3(1), c = 1387.5(1) pm, α = 84.32(1)°, β = 84.71(1)°, γ = 63.12(1)°, Z = 2, R₁ = 0.0539.     

Synthesis,Characterization and Crystal Structures of new Coordination Polymers of Cerium(III) and Samarium(III) Containing 2,6‐Pyridinedicarboxylic Acid

The reaction of 2,6‐pyridinedicarboxylic acid ( 1 , LH₂) with CeCl₃·7H₂O and Sm(NO₃)₃·6H₂O in the presence of triethylamine led to the coordination polymer complexes [M(L)(LH)(H₂O)₂]·4H₂O [M = Ce ( 2 ) and Sm ( 3 )]. Both complexes were characterized by elemental analyses, IR spectroscopy and the crystal structures of 2 and 3 . Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1404.6(1), b = 1122.1(1), c = 1296.1(1) pm, β = 102.09(1)°, Z = 4, R₁ = 0.0217 and for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1395.1(1), b = 1120.1(1), c = 1282.8(1) pm, β = 102.71(1)°, Z = 4, R₁ = 0.019.     

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.     

Synthesis,Characterization and Crystal Structures of 1,2,4‐Triazole based Schiff‐Bases and their Copper(I) Complexes

The reaction of of 4‐amino‐5‐ethyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AETT, L ) with furfural in methanol led to the corresponding Schiff‐Base ( L1 ). The reaction of L1 with [Cu(PPh₃)₂]Cl in methanol gave to the neutral compound [( L1 )Cu(PPh₃)₂Cl] ( 1 ). By recrystallization of 1 from CH₃CN the complex [( L1 )Cu(PPh₃)₂Cl]·CH₃CN ( 1a ) was obtained. All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for L1 at ?80 °C: space group with a = 788.4(1), b = 830.3(2), c = 928.8(2) pm, α = 84.53(1)°, β = 65.93(1)°, γ = 72.02(1)°, Z = 2, R₁ = 0.0323; for 1 at ?100 °C: space group with a = 1166.3(1), b = 1423.8(2), c = 1489.1(2) pm, α = 62.15(1)°, β = 72.04(1)°, γ = 88.82(1)°, Z = 2, R₁ = 0.0338 and for 1a at ?100 °C: space group P2₁/c with a = 1294.1(1), b = 1019.8(2), c = 3316.9(4) pm, β = 94.73(1)°, Z = 4, R₁ = 0.0435.     

A New Complex as a Dimer of a Silver Ion with AMTTO and Phosphane Ligands. The Crystal Structure of {[(AMTTO)Ag(PPh3)2]NO3}2·0.5CH3OH·0.5H2O

Reaction of 4‐amino‐6‐methyl‐1,2,4‐triazine‐3‐thione‐5‐on (AMTTO) as a bidentate ligand with silver nitrate and triphenyl phosphine as the co‐ligand make the centrosymmetric dimeric complex {[(AMTTO)Ag(PPh₃)₂]NO₃}₂·0.5CH₃OH·0.5H₂O ( 1 ). 1 was characterized by elemental analyses, IR‐ and NMR spectroscopy as well as X‐ray diffraction studies. The silver atom in 1 has distorted tetrahedral coordination. 1 crystallizes in triclinic space group . Crystal data for 1 at −80 °C: a = 1185.8(1), b = 1314.6(1), c = 1385.3(1) pm, α = 97.78(1)°, β = 111.38(1)°, γ = 92.41(1)°, Z = 2, R₁ = 0.0377.     

A Coordination Polymer from HAMTTO with Silver(I) (HAMTTO = 4‐Amino‐6‐methyl‐1,2,4‐triazine‐3‐thione‐5‐one)

The reaction of 4‐amino‐6‐methyl‐1,2,4‐triazine‐3‐thione‐5‐one, HAMTTO, with silver (I) nitrate in methanol led under deprotonation to the polymeric compound [(AMTTO)Ag]_n. The coordination polymer {[Ag(HAMTTO)]ClO₄}_n ( 1 ) is synthesized from the reaction of the latter polymeric compound with perchloric acid. Both compounds were characterized by elemental analysis and IR spectroscopy. Single‐crystal X‐ray diffraction studies on compound 1 showed that HAMTTO acts as a bidentate ligand and chelates the silver atom via its hydrazine nitrogen atom and its sulfur atom. Crystal data for 1 at ?90 °C: space group P2₁, Z = 2, a = 629.3(1), b = 748.7(1), c = 1071.7(1) pm, β = 98.28(1)°, R₁ = 0.0533.     

Syntheses and X‐Ray Crystal Structures of New Copper(I) and Silver(I) Complexes containing Thione Ligands

The reaction of [(Ph₃P)₂CuCl]₂ with 4‐amino‐6‐methyl‐1,2,4‐triazine‐thione‐5‐one (AMTTO, 1 ) in methanol and further recrystallization from methanol/acetone solution gives [(C₄H₄N₃SON(=CMe₂)Cu(PPh₃)₂Cl] ( 2 ) as a neutral complex. [(C₄H₄N₃SON(=CMe₂)Ag(PPh₃)₂]NO₃ ( 4 ) can be obtained in excellent yield by the reaction of [(AMTTO)₂Ag]NO₃ ( 3 ) with triphenylphosphane in methanol/acetone. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at –80 °C: space group P1 with a = 1233.8(1), b = 1389.7(1), c = 1417.1(1) pm, α = 89.36(1)°; β = 65.10(1)°, γ = 65.95(1)°, Z = 2, R₁ = 0.0582 and for 4 at –80 °C: space group P1, with a = 1193.3(1), b = 1308.5(1), c = 1385.3(1) pm, α = 94.69(1)°, β = 109.14(1)°, γ = 93.42(1)°, Z = 2, R₁ = 0.0716.     

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.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

Synthesis,Characterization and X‐ray Structures of AMTT‐Type Schiff bases and two CuI Complexes (AMTT= 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione)

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT) with 4‐methylbenzaldehyde and 4‐methoxybenzaldehyde in ethanol led to the iminic derivatives ‐4‐(4‐methylbenzylideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)thione ( L1 ) and 4‐(4‐methoxybenzyl‐ideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione ( L2 ). The reaction of L1 with CuCl in the presence of triphenylphosphane as co‐ligand in methanol/chloroform solution gave the Cu^I complex containing L1 , [Cu( L1 )(PPh₃)₂Cl]·0.5CH₃OH·0.25CHCl₃ ( 1 ). Treatment of L2 with the same metal salt in a molar ratio of 1:1 in methanol and further addition of a solution of PPh₃ in chloroform led to the complex [Cu( L2 )(PPh₃)₂Cl]·2.5CHCl₃ ( 2 ). The complexes and L1 were characterized by IR and NMR spectroscopy as well as by X‐ray diffraction studies. In both complexes, the Schiff base ligand is coordinated to the copper ion through its sulfur atom. The other coordination sites around the copper ion are occupied by two triphenylphosphane molecules and one chloride ion. Therefore, each Cu^I ion is in a distorted tetrahedral environment. Crystal data for L1 at ?100 °C: space group P2₁/n with a = 720.5(1), b = 1140.6(1), c = 1426.3(2) pm, β = 91.25(1)°, Z = 4, R₁ = 0.03, for 1 at ?120 °C : space group with a = 1286.3(1), b = 1740.3(1), c = 2060.2(1) pm, α = 79.085(6), β = 83.827(5), γ = 76.688(6)°, Z = 4, R₁ = 0.0649 and for 2 at ?80 °C : space group with a = 1183.7(2), b = 1370.1(2), c = 1812.1(3) pm, α = 85.69(2), β = 88.52(2), γ = 64.89(2)°, Z = 2, R₁ = 0.0488.     

Synthesis,Characterization and Crystal Structure of a Silver(I) Complex containing AMTT (AMTT = 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione)

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione with AgNO₃ in methanol led to the complex [Ag(ATT)₂]NO₃ ( 2 ). 2 was characterized by elemental analyses, IR, ¹HNMR and Raman spectroscopy as well as single‐crystal X‐ray diffraction. Crystal data for 2 at ?70 °C: space group P2₁/n with a = 1356.7(12), b = 770.4(7), c = 1475.2(12) pm, β = 111.730(15)°, Z = 4, R₁ = 0.0402.     

Synthesis,Characterization and Crystal Structure of 4‐Amino‐1,2,4‐Δ2‐triazoline‐5‐thione and its Silver(I) Complex

The reaction of 4‐amino‐1,2,4‐Δ²‐triazoline‐5‐thione (ATT, 1 ) with AgNO₃ in methanol led to the complex [Ag(ATT)₂]NO₃ ( 2 ). 2 was characterized by elemental analyses, ¹H NMR, IR, and Raman spectroscopy as well as single‐crystal X‐ray diffraction. The molecular structure of 1 was also determined by single crystal X‐ray analysis. Crystal data for 1 at ?80 C: space group C2/c with a = 2107.4(2), b = 1425.1(1), c = 688.4(1) pm, β = 104.55(1)°, Z = 16, R₁ = 0.0514, crystal data for 2 at ?80 °C: space group P2₁/c with a = 675.7(1), b = 1321.1(1), c = 1311.2(1) pm, β = 90.03(1)°, Z = 4, R₁ = 0.0437.     

Synthesis,Characterization and Crystal Structures of new 1,2,4‐Triazole based Schiff‐bases and their Copper(I) Complexes

The reaction of 4‐amino‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione (AMTT, 1 ) with 4‐methoxy benzaldehyde and 3‐methoxybenzaldehyde in methanol led to the iminic derivatives 4‐(4‐methoxybenzylideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)thione ( 2 , L1) and 4‐(3‐methoxybenzylideneamino)‐5‐methyl‐2H‐1,2,4‐triazole‐3(4H)‐thione ( 3 , L2). The reaction of the latter with [(PPh₃)₂CuCl] in methanol solution gave the first Cu^I complex of 3 , [(PPh₃)₂CuCl(L2)] ( 4 ) and in chloroform solution the complex [(PPh₃)₂CuCl(L2)]·2CHCl₃ ( 5 ). All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at ?80 °C: space group P2₁/c with a = 1351.3(3), b = 399.4(1), c = 2225.2(5) pm, β = 96.50(2)°, Z = 4, R₁ = 0.0667, for 3 at ?80 °C: space group R3c with a = b = 3020.4(2), c = 708.2(1) pm, Z = 18, R₁ = 0.0435, for 4 at ?80 °C: space group P2₁/c with a = 1427.8(1), b = 1129.0(1), c = 2622.8(2) pm, β = 97.19(1)°, Z = 4, R₁ = 0.0517 and for 5 at ?80 °C: space group with a = 1280.5(1), b = 1316.1(1), c = 1731.4(1) pm, α = 78.14(1)°, β = 86.06(1)°, γ = 64.69(1)°, Z = 2, R₁ = 0.0525.     

Syntheses,Characterization and X‐Ray Structures of the first Copper(I) and Silver(I) Complexes with ATT (ATT = 6‐Aza‐2‐thiothymine)

The reaction of copper(I) chloride with 6‐aza‐2‐thiothymine (ATT, 1 ) and triphenylphosphane in methanol/chloroform gives [(ATT)CuCl(PPh₃)] ( 2 ) as a neutral complex. [(ATT)Ag(NO₃)(PPh₃)₂]·MeOH ( 3 ) can be obtained by the reaction of 1 with silver(I) nitrate and triphenylphosphane in methanol/chloroform in excellent yields and the single crystals of 3 can be obtained from acetonitril solution. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at —80 °C: space group I2/a with a = 1859.3(1), b = 1143.2(1), c = 2208.2(1) pm, β = 104.84(1)°, Z = 8, R₁ = 0.0355 and for 3 at —80 °C: space group P2₁/c with a = 1344.1(1), b = 1553.6(1), c = 1977, 3(3) pm, β = 105.26(1)°, Z = 4, R₁ = 0.0436.     

Common Features in the Crystal Structures of the Compounds Bis(dimethylstibanyl)oxane and ‐sulfane,and the Minerals Valentinite and Stibnite (Grauspießglanz)

Bis(dimethylstibanyl)oxane ( 1 ) and ‐sulfane ( 2 ), the two simplest organoelement species with an Sb–E–Sb fragment (E = O, S), were prepared by alkaline hydrolysis of bromodimethylstibane and by oxidation of tetramethyldistibane with sulfur [18], respectively. As shown by an x‐ray structure analysis of compound 1 (m. p. < –20 °C; P2₁2₁2₁, a = 675.9(2), b = 803.1(2), c = 1666.8(4) pm at –70 ± 2 °C; Z = 4; R1 = 0.042), the molecules (O–Sb 198.8 and 209.9 pm, Sb–O–Sb 123.0°) adopt a syn‐anti conformation in the solid state and are arranged in zigzag chains along [010] via weak intermolecular O‥Sb interactions (258.5 pm, Sb–O‥Sb 117.8°, O‥Sb–O 173.5°) making use, however, of only one Me₂Sb moiety. Primary and secondary bond lengths and angles agree very well with corresponding values published for valentinite, the orthorhombic modification of antimony(III) oxide [3]. Bis(dimethylstibanyl)sulfane ( 2 ) (m. p. 29 to 31 °C) crystallizes in the uncommon space group P6₅22 (a = 927.8(3), c = 1940.9(7) pm at –100 ± 2 °C; Z = 6; R1 = 0.021). Owing to coordination numbers of (1 + 1) and (2 + 2) for both Me₂Sb groups and the sulfur atom, respectively, molecules with an approximate syn‐syn conformation (S–Sb 249.8 pm, Sb–S–Sb 92.35°) build up a three‐dimensional net of double helices which are linked together by Sb‥S contacts (316.4 pm). These parameters shed more light onto the rather complicated structure and bonding situation in stibnite (antimony(III) sulfide [4]). The molecular packing of compound 2 is compared with the structures of relevant inorganic solids, especially with that of β‐quartz [37].     

Synthesis,Characterization, and Crystal Structure of a Chromium(III)‐Complex Containing 2,6‐Pyridinedicarboxylic Acid and 1,10‐Phenanthroline

The reaction of solution 2,6‐pyridinedicarboxylic acid and 1,10‐phenanthroline ( 1 ) with CrCl₃·6H₂O led to the complex [Cr(phen)(pydc)(H₂O)][Cr(pydc)₂]·4H₂O ( 2 ) (phen is 1,10‐phenanthroline and pydcH₂ is 2,6‐pyridinedicarboxylic acid). 2 was characterized by elemental analysis, IR spectroscopy and single‐crystal structure determination. Crystal data for 2 at ?80 °C: triclinic, space group , a = 818.5(1), b = 1492.2(1), c = 1533.6(2) pm, α = 76.45(1)°, β = 84.22(1)°, γ = 77.99(1)°, Z = 2, R₁ = 0.0416.     

1, 3, 4, 4'‐Tetra(triphenylphosphanimin)‐2‐iodo‐2‐butenal‐4‐carboniumiodid, [O=C(NPPh3)C(I)=C(NPPh3)‐C(NPPh3)2]+I‐

Pale yellow single crystals of [O=C(NPPh₃)C(I)=C(NPPh₃)‐C(NPPh₃)₂]⁺I^‐·1.5 thf ( 1 ·1.5 thf) have been obtained by the reaction of INPPh₃ with thallium in thf suspension. They are characterized by IR spectroscopy and by a crystal structure determination. 1 ·1.5 thf crystallizes in the monoclinic space group P2₁/n, Z = 4, lattice dimensions at ‐83?C: a = 1101.7(1), b = 3449.0(2), c = 2000.4(1) pm, β = 104.88(1)?, R₁ = 0.0382. 1 can be understood as a cationic variation of (Z)‐2‐butenale in which all H atoms are substituted by triphenylphosphoraneimine residues and by a iodine atom, respectively.