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1.
On Reactions of Hexachlorodiberyllate with Trimethylsilyl‐N‐dimethylamide. Crystal Structures of (Ph4P)3[Be2Cl5(OSiMe3)][BeCl3(Me2NSiMe3)], (Ph4P)[BeCl3(HNMe2)], and (Ph4P)(H2NMe2)[BeCl4] Reactions of bis‐tetraphenylphosphonium hexachlorodiberyllate, (Ph4P)2[Be2Cl6], with trimethylsilyl‐N‐dimethylamide under different conditions lead to the novel chloroberyllate derivatives (Ph4P)3[Be2Cl5(OSiMe3)][BeCl3(Me2NSiMe3)] ( 1 ), (Ph4P)[BeCl3(HNMe2)] ( 2 ), and (Ph4P)(H2NMe2)[BeCl4] ( 3 ). 1 ‐ 3 were characterized by IR spectroscopy and crystal structure determinations. 1· 4CH2Cl2: Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1115.6(1), b = 2110.7(2), c = 2145.0(3) pm, α = 71.38(1)°, β = 85.66(1)°, γ = 85.24(1)°, R1 = 0.0732. The [Be2Cl5(OSiMe3)]2— ion in the structure of 1 is derived from the [Be2Cl6]2— ion by substitution of a μ‐Cl ligand by the oxygen atom of the (OSiMe3)— group. The second anion, [BeCl3(Me2NSiMe3)]—, can be described as donor acceptor complex with a short Be—N bond of 179(1) pm. 2 : Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1063.1(1), b = 1072.0(1), c = 1238.3(1) pm, α = 87.55(1)°, β = 74.86(1)°, γ = 69.73(1)°, R1 = 0.0299. The anion of 2 forms a centrosymmetric dimer [BeCl3(HNMe2)]22— via N—H···Cl bridges of the two donor acceptor complex units with Be—N separations of 175.2(2) pm. 3 : Space group Pbca, Z = 8, lattice dimensions at 193 K: a = 926.9(1), b = 2164.7(1), c = 2732.7(1) pm, R1 = 0.0495. The structure of 3 contains centrosymmetric ion quadrupoles [(Me2NH2)(BeCl4)]22— forming by N—H···Cl bridges between (Me2NH2)+ and [BeCl4]2— ions. 相似文献
2.
Phosphanimine and Phosphoraneiminato Complexes of Beryllium. Crystal Structures of [BeCl2(HNPPh3)2], [BeCl(HNPPh3)2(Py)]Cl, and [Be3Cl2(NPPh3)4] Tetraphenylphosphonium hexachlorodiberyllate, (Ph4P)2[Be2Cl6], reacts with lithium phosphoraneiminate, [LiNPPh3]6, in dichloromethane to give the three‐nuclear beryllium phosphoraneiminate [Be3Cl2(NPPh3)4] ( 3 ). As a by‐product the phosphaneimine complex [BeCl2(HNPPh3)2] ( 1 ) can be isolated, which reacts with pyridine to give the ionic complex [BeCl(HNPPh3)2(Py)]Cl ( 2 ). On the other hand, the silylated phosphanimine Me3SiNP(p‐tolyl)3 ( 5 ) does not react with BeCl2 or (Ph4P)2[Be2Cl6] forming the expected phosphoraneiminates. From CH2Cl2 solutions only the amino‐phosphonium salt [(C7H7)3PNH2]Cl ( 4 ) can be obtained. The compounds 1 ‐ 5 are characterized by single X‐ray analyses and by IR spectroscopy. 1 ·C7H8: Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 1408.9(2), b = 1750.9(2), c = 1633.2(2) pm, β = 106.50(1)°; R1 = 0.0385. 1 forms a molecular structure with short Be—N distances of 169.8(3) pm. 2 ·Py: Space group P1¯, Z = 4, lattice dimensions at 193 K: a = 969.5(1), b = 2077.1(2), c = 2266.4(2) pm, α = 72.24(1)°, β = 87.16(1)°, γ = 77.42(2)°, R1 = 0.0776. 2 forms ion pairs in which the NH atoms of the phosphaneimine ligands act as hydrogen bridges with the chloride ion. The HNPPh3 ligand realizes short Be—N bonds of 169.0(6) pm, the Be—N distance of the pyridine molecule is 182.5(6) pm. 3 ·3CH2Cl2: Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1333.2(2), b = 1370.2(2), c = 2151.8(3) pm, α = 107.14(1)°, β = 91.39(1)°, γ = 105.15(1)°, R1 = 0.0917. The structure of the three‐nuclear molecule 3 corresponds with a Be2+ ion which is tetrahedrally coordinated by the nitrogen atoms of two {ClBe(NPPh3)2}— chelates. 4 ·CH2Cl2: Space group P21/c, Z = 4, lattice dimensions at 193 K: a = 1206.6(2), b = 1798.0(2), c = 1096.2(1) pm, β = 97.65(1)°, R1 = 0.0535. 4 forms dimeric units in which the NH2 groups of the [(C7H7)3PNH2]+ cations act as hydrogen bridges with the chloride ions to give centrosymmetric eight‐membered rings. 5 : Space group P21/n, Z = 4, lattice dimensions at 193 K: a = 1074.3(2), b = 2132.2(3), c = 1075.5(2) pm, β = 110.68(1)°, R1 = 0.0664. 5 forms molecules with distances PN of 154.6(3), SiN of 168.8(3) pm, and bond angle SiNP of 134.4(2)°. 相似文献
3.
Synthesis, Vibrational Spectra, and Crystal Structures of the Nitrato Argentates (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN and (Ph4P)[Ag2(NO3)3] Tetraphenylphosphonium bromide reacts in acetonitril suspension with excess silver nitrate to give (Ph4P)[Ag(NO3)2(CH3CN)]·CH3CN ( 1 ), whereas (Ph4P)[Ag2(NO3)3] ( 2 ) is obtained in a long‐time reaction from (Ph4P)Br and excess AgNO3 in dichloromethane suspension. Both complexes were characterized by vibrational spectroscopy (IR, Raman) and by single crystal structure determinations. 1 : Space group P21/c, Z = 4, lattice dimensions at 193 K: a = 1781.5(3), b = 724.8(1), c = 2224.2(3) pm, β = 96.83(1)°, R1 = 0.0348. 1 contains isolated complex units [Ag(NO3)2(CH3CN)]?, in which the silver atom is coordinated by the chelating nitrate groups and by the nitrogen atom of the solvated CH3CN molecule with a short Ag—N distance of 220.7(4) pm. 2 : Space group I2, Z = 4, lattice dimensions at 193 K: a = 1753.4(4), b = 701.7(1), c = 2105.5(4) pm, R1 = 0.072. In the polymeric anions [Ag2(NO3)3]? each silver atom is coordinated in a chelating manner by one nitrate group and by two oxygen atoms of two bridging nitrate ions. In addition, each silver atom forms a weak π‐bonding contact with a phenyl group of the (Ph4P)+ ions with shortest Ag···C separations of 266 and 299 pm, respectively, indicating a (4+1) coordination of silver atoms. 相似文献
4.
Bis(tetraphenylphosphonium) hexachloridodiberyllate, (Ph4P)2[Be2Cl6], reacts with excess trimethylsilyl‐iso‐thiocyanate to give a mixture of colourless single crystals of (Ph4P)2[Be(NCS)4] ( 1 ) and (Ph4P)4[{Be2(NCS)4(μ‐NCS)2}{Be2(NCS)6(μ‐H2N2C2S2)}] ( 2 ), which can be separated by selection. Both complexes were characterized by X‐ray diffraction. Compound 1 can be prepared without by‐products by treatment of (Ph4P)2[BeCl4] with excess Me3SiNCS in dichloromethane solution. 1 : Space group I41/a, Z = 4, lattice dimensions at 100(2) K: a = b = 1091.2(1), c = 3937.1(3) pm, R1 = 0.0474. The [Be(NCS)4]2– ion of 1 forms tetragonally distorted tetrahedral anions with Be–N distances of 168.4(2) pm and weak intermolecular S ··· S contacts along [100] and [010]. 2 ·4CH2Cl2: Space group P , Z = 1, lattice dimensions at 100(2) K: a = 919.5(1), b = 1248.3(1), c = 2707.0(2) pm, α = 101.61(1) °, β = 95.08(1) °, γ = 94.52(1) °, R1 = 0.103. Compound 2 contains two different anionic complexes in the ratio 1:1. In {Be2(NCS)4(μ‐NCS)2}2–, the beryllium atoms are connected by (NCS)– bridging groups forming centrosymmetric eight‐membered Be2(NCS)2 rings with distances Be–N of 168(1) pm and Be–S of 235.2(9) pm. The second anion {Be2(NCS)6(μ‐H2N2C2S2)}2– consists of two {Be(NCS)3}– units, which are linked by the nitrogen atoms of the unique dimeric cyclo‐addition product of HNCS with Be–N distances of 179(1) pm. 相似文献
5.
Crystal Structures of (Ph4P)2[HfCl6]·2CH2Cl2 and (Ph4P)2[Hf2Cl10]·CH2Cl2 Colourless single crystals of (Ph4P)2[HfCl6]·2CH2Cl2 ( 1 ) and (Ph4P)2[Hf2Cl10]·CH2Cl2 ( 2 ) were obtained from hafniumtetrachloride and tetraphenylphosphonium chloride in dichloromethane solution, using the corresponding stoichiometry of the educts. Both compounds were characterized by X‐ray structure determinations. 1 : Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1018.3(1), b = 1121.0(1), c = 1240.1(1) pm, α = 70.55(1)°, β = 81.38(1)°, γ = 80.02(1)°, R1 = 0.0374. 2 : Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1124.4(1), b = 1141.9(1), c = 1281.4(1) pm, α = 63.80(1)°, β = 68.15(1)°, γ = 86.33(1)°, R1 = 0.0208. 相似文献
6.
Crystal Structures of [Ph3PMe]Cl·CH2Cl2, [Ph4P]NO3·CH2Cl2, and [Ph4P]2[SiF6]·CH2Cl2 The crystal structures of the title compounds are determined by X‐ray diffraction. In all cases, the included dichloromethane molecules as well as the phosphonium cations are involved to form hydrogen bridges with the anions. [Ph3PMe]Cl·CH2Cl2 ( 1 ): Space group , Z = 2, lattice dimensions at 100 K: a = 890.3(1), b = 988.0(1), c = 1162.5(1) pm, α = 106.57(1)°, β = 91.79(1)°, γ = 92.60(1)°, R1 = 0.0253. [Ph4P]NO3·CH2Cl2 ( 2 ): Space group P21/n, Z = 4, lattice dimensions at 193 K: a = 1057.0(1), b = 1666.0(1), c = 1358.9(1) pm, β = 100.10(1)°, R1 = 0.0359. [Ph4P]2[SiF6]·CH2Cl2 ( 3 ): Space group , Z = 2, lattice dimensions at 193 K: a = 1063.9(1), b = 1233.1(1), c = 1782.5(2) pm, α = 76.88(1)°, β = 83.46(1)°, γ = 72.29(1)°, R1 = 0.0332. 相似文献
7.
Trichloroberyllate Complexes of Dimethyl Cyanamide, Morpholine, and 4,4′‐Bipyridine The trichloroberyllate complexes (Ph4P)[BeCl3(NCNMe2)] ( 1 ), (Ph4P)[BeCl3{HN(CH2)4O}] ( 2 ), and (Ph4P)2[(BeCl3)2(4,4′‐bipy)] ( 3 ) were prepared by reactions of (Ph4P)2[Be2Cl6] with dimethyl cyanamide, trimethylsilylmorpholinate, and 4,4′‐bipyridine, respectively, in dichloromethane solutions. 1 ‐ 3 were characterized by X‐ray crystallography and by IR‐spectroscopy. 1 ·CH2Cl2: Space group P1, Z = 1, lattice dimensions at 173 K: a = 714.2(1), b = 919.5(2), c = 1233.4(2) pm, α = 94.97(1)°, β = 90.86(1)°, γ = 111.90(1)°, R1 = 0.0310. In the complex anion [BeCl3(NCNMe2)]? the dimethyl cyanamide ligand is coordinated via a linear Be–N≡C‐NMe2 arrangement, the CH2Cl2 molecules forming linear chains by hydrogen bridges ···HCH···Cl··· with the chlorine atoms of the {BeCl3?} groups. 2 : Space group , Z = 2, lattice dimensions at 173 K: a = 1050.9(1), b = 1099.7(1), c = 1308.3(2) pm, α = 87.57(1)°, β = 70.97(1)°, γ = 74.58(1)°, R1 = 0.0397. The complex anions are dimerized by centrosymmetric puckered eight‐membered [Be–N–H···Cl]2 rings. 3 ·2CH2Cl2: Space group , Z = 2, lattice dimensions at 173 K: a = 1095.4(1), b = 1559.6(2), c = 1869.8(3) pm, α = 79.12(1)°, β = 73.83(1)°, γ = 78.76(1)°, R1 = 0.0548. The complex contains dianions [Cl3Be(μ‐bipy)BeCl3]2? with Be–N distances of 177.0(6) and 178.5(6) pm. Both {BeCl3}? groups form C–H···Cl hydrogen bridges with the dichloromethane molecules. 相似文献
8.
Synthesis, Crystal Structure, and Properties of the Complexes [(H2O)Cl4Os≡N‐IrCl(C5Me5)(AsPh3)], [(Ph3Sb)Cl4Os≡N‐IrCl(C5Me5)(SbPh3)], [(Ph3Sb)2Cl3Os≡N‐IrCl(COD)] and [{(Me2PhP)2(CO)Cl2Re≡N}2ReNCl2(PMe2Ph)] The dinuclear complexes [(H2O)Cl4Os≡N‐IrCl(C5Me5)(AsPh3)]·H2O ( 1 ·H2O), [(Ph3Sb)Cl4Os≡N‐IrCl(C5Me5)(SbPh3)] ( 2 ), and [(Ph3Sb)2Cl3Os≡N‐IrCl(COD)] ( 3 ) result from the reaction of the nitrido complexes [(Ph3As)2OsNCl3] and [(Ph3Sb)2OsNCl3] with the iridium compounds [IrCl2(C5Me5)]2 and [IrCl(COD)]2 in dichloromethane. 1 crystallizes as 1 ·H2O in form of green platelets in the monoclinic space group Cm and a = 1105.53(6); b = 1486.76(9); c = 2024.88(10) pm, β = 97.191(4)°, Z = 4. The formation of 1 in air involves a ligand exchange, and the coordination of a water molecule in trans position to the Os‐N triple bond. The resulting complex fragments [(H2O)Cl4Os≡N] and [IrCl(C5Me5)(AsPh3)] are connected by an asymmetric nitrido bridge Os≡N‐Ir. The nitrido bridge is characterised by an Os‐N‐Ir bond angle of 173.7(7)°, and distances Os‐N = 168(1) pm and Ir‐N = 191(1) pm. 2 crystallizes in clumped together brown platelets with the space group and a = 1023.3(3), b = 1476.2(3), c = 1872.5(6) pm, α = 74.60(2), β = 73.84(2), γ = 76.19(2)°, Z = 2. In 2 the asymmetric nitrido bridge Os≡N‐Ir joins the two complex fragments [(Ph3Sb)Cl4Os≡N] and [IrCl(C5Me5)(SbPh3)], which are formed by a ligand exchange reaction. 3 forms dark green crystals with the triclinic space group and a = 1079.4(1), b = 1172.3(1), c = 1696.7(2) pm, α = 101.192(9),β = 92.70(1), γ = 92.61(1)°, Z = 2. The distances in the almost linear nitrido bridge (Os≡N‐Ir = 175.3(7)°) are Os‐N = 171(1) pm and Ir‐N = 183(1) pm. The reaction of [ReNCl2(PMe2Ph)3] with [Mo(CO)3(NCMe)3] unexpectedly affords the trinuclear complex [{(Me2PhP)2(OC)Cl2Re≡N}2ReNCl2(PMe2Ph)] ( 4 ) as the main product. It forms triclinic brown crystals with the composition 4 ·2THF and the space group (a = 1382.70(7), b = 1498.58(7), c = 1760.4(1) pm, α = 99.780(7), β = 99.920(7), γ = 114.064(6)°, Z = 2). In the trinuclear complex, the central fragment, [ReNCl2(PMe2Ph)] is joined in trans position to two nitrido complexes [(Me2PhP)2(CO)Cl2Re≡N], giving an almost linear Re≡N‐Re‐N≡Re arrangement. The bond angles and distances in the nitrido bridges are Re‐N‐Re = 167.8(3)°, Re‐N = 171.1(8) pm and 204.2(8) pm; and Re‐N‐Re = 168.1(4)°, Re‐N = 170.9(9) and 203.5(9) pm respectively. As expected, the Re‐N bond length to the terminal nitrido ligand on the central Re atom is much shorter at 161.2(9) pm than the triple bonds of the asymmetric bridges. 相似文献
9.
Synthesis of Phenylnitrene Complexes with N-Trimethylsilylaniline. II. Characterization and Crystal Structure of the Rhenium(V) Complexes mer-[Re(NPh)Cl3(NH2Ph)(Ph3P)] and trans-[Re(NPh)(OMe)Cl2(Ph3P)2] Reaction of [ReOCl3(Ph3P)2] with N-trimethylsilylaniline yields mer-[Re(NPh)Cl3(Ph3P)2], which reacts under air with excess of N-trimethylsilylaniline to form [Re(NPh)Cl3 · (NH2Ph)(Ph3P)]. Crystallization from CH2Cl2/MeOH affords [Re(NPh)(OMe)Cl2(Ph3P)2] as an additional product. [Re(NPh)Cl3(NH2Ph)(Ph3P)] crystallizes in the monoclinic space group P21/n with a = 1 192.3(3); b = 1 918.9(3); c = 1 266.3(3) pm; β = 101.71(1)°; Z = 4. The rhenium atom has a distorted octahedral environment with the Cl atoms in meridional positions. The phenyl nitrene ligand is coordinated with an almost linear arrangement Re? N1? C40 = 166.8(6)° and with a bond distance Re?N = 170.5(6) pm. [Re(NPh)(OMe)Cl2(Ph3P)2] · 1/2CH2Cl2 crystallizes in the triclinic space group P1 : a = 1 103.1(4); b = 1 227.9(4); c = 1 711.3(5) pm; α = 70.48(3)°; β = 72.71(3)°; γ = 80.03(3)°; Z = 2. The rhenium atom exhibits a distorted octahedral coordination with the Cl atoms and the phosphine ligands in trans positions. As a consequence of the competition of the nitrene ligand and the trans-coordinated methoxy group the Re?;N bond length is slightly lengthened to 173.2(7) pm, while the Re? O bond length of 193.4(6) pm is short. The bond angles Re? N? C70 and Re? O? C80 are 173.3(7)° and 139.1(7)°, respectively. 相似文献
10.
Tetra(N‐methylimidazole)‐beryllium‐di‐iodide, [Be(Me‐Im)4]I2 ( 1 ), was prepared from beryllium powder and iodine in N‐methylimidazole suspension to give yellow single crystal plates, which were characterized by X‐ray diffraction and IR spectroscopy. Compound 1 crystallizes tetragonally in the space group I 2d with four formula units per unit cell. Lattice dimensions at 100(2) K: a = b = 1784.9(1), c = 696.2(1) pm, R1 = 0.0238. The structure consists of homoleptic dications [Be(Me‐Im)4]2+ with short Be–N distances of 170.3(3) pm and iodide ions with weak interionic C–H ··· I contacts. Experiments to yield crystalline products from reactions of N‐methylimidazole with BeCl2 and (Ph4P)2[Be2Cl6], respectively, in dichloromethane solutions were unsuccessful. However, single crystals of [Be3(μ‐OH)3(Me‐Im)6]Cl3 ( 2 ) were obtained from these solutions in the presence of moisture air. According to X‐ray diffraction studies, two different crystal individuals ( 2a and 2b ) result, depending on the starting materials BeCl2 and (Ph4P)2[Be2Cl6], respectively [ 2a : Space group P21/n, Z = 4; 2b : Space group P , Z = 2]. As a side‐product from the reaction of N‐methylimidazole with (Ph4P)2[Be2Cl6] single crystals of (Ph4P)Cl·CH2Cl2 ( 3 ) were identified crystallographically (P21/n, Z = 4) which are isotypical with the corresponding known bromide (Ph4P)Br·CH2Cl2. 相似文献
11.
Azido Complexes of Vanadium(IV) and Vanadium(V): (Ph4P)2[VOCl2(μ‐N3)]2 and (Ph4P)2[VOCl(μ‐N3)(N3)2]2 (Ph4P)2[VOCl2(μ‐N3)]2 ( 1 ) was prepared by reaction of (Ph4P)[VO2Cl2] with trimethylsilylazide in the molar ratio 1:2 in dichloromethane solution to give dark green, moisture sensitive, non‐explosive single crystals. The reaction is accompanied by the formation of the dark blue side‐product (Ph4P)2[VOCl(μ‐N3)(N3)2]2 ( 2a ), which can be obtained as the main product by application of a large excess of Me3SiN3. Dark blue needles of 2a crystallize spontaneously from the CH2Cl2 solution within one hour at 4 °C. After standing at 4 °C under its mother liquid within 24 hours a first‐order phase transition of 2a occurs forming dark blue prismatic single crystals of 2b . According to single crystal X‐ray structure determinations, 2a and 2b crystallize in the same type of space group , however, with different lattice dimensions. The vanadium(IV) complex 1 is characterized by X‐ray structure determination and by vibrational spectroscopy (IR, Raman) as well as by EPR spectroscopy, whereas 2b is characterized by IR spectroscopy. 1 : Space group P21/n, Z = 2, a = 1009.5(1), b = 1226.6(2), c = 1943.0(2) pm, β = 98.42(1)°, R1 = 0.0672. The complex anion forms centrosymmetric units with V2N2‐four‐membered rings with a V···V distance of 335.6(1) pm and coordination number five on the vanadium(IV) atoms. 2a : Space group , Z = 1, a = 1089.0(2), b = 1097.1(2), c = 1310.1(2) pm, α = 92.99(1)°, β = 106.12(2)°, γ = 117.05(2)°, V = 1309.8(4) Å3, dcalc. = 1.440 g·cm?3, R1 = 0.0384. The complex anion forms centrosymmetric units of symmetry Ci with V2N2 four‐membered rings and VN bond lengths of 200.4(3) and 234.4(2) pm, respectively. The non‐bonding V···V distance amounts to 356.2(1) pm. 2b : Space group , Z = 1, a = 1037.3(2), b = 1157.6(2), c = 1177.2(2) pm, α = 98.48(2)°, ° = 103.82(2)°, γ = 106.33(2)°, V = 1281.8(4) Å3, dcalc. = 1.471 g·cm?3, R1 = 0.0724. The structure of the complex anion is similar to the anion of 2a with VN bond lengths of the four‐membered V2N2 ring of 203.3(4) and 235.2(4) pm, respectively, and a non‐bonding V···V distance of 357.5(1) pm. 相似文献
12.
Six polynuclear chlorobismuthates are formed in the reaction between BiCl3 and Ph4PCl by variation of the molar ratio of the educts, the solvents and the crystallisation methods: [Ph4P]3[Bi2Cl9] · 2 CH2Cl2, [Ph4P]3[Bi2Cl9] · CH3COCH3, [Ph4P]2[Bi2Cl8] · 2 CH3COCH3, [Ph4P]4[Bi4Cl16] · 3 CH3CN, [Ph4P]4[Bi6Cl22], and [Ph4P]4[Bi8Cl28]. We report the crystal structure of [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 which crystallises with triclinic symmetry in the S. G. P1 No. 2, with the lattice parameters a = 13.080(3) Å, b = 14.369(3) Å, c = 21.397(4) Å, α = 96.83(1)°, β = 95.96(1)°, γ = 95.94(2)°, V = 3943.9(1) Å3, Z = 2. The anion is formed from two face‐sharing BiCl6‐octahedra. [Ph4P]2[Bi2Cl8] · 2 CH3COCH3 crystallises with monoclinic symmetry in the S. G. P21/n, No. 14, with the lattice parameters a = 14.045(5) Å, b = 12.921(4) Å, c = 17.098(3) Å, β = 111.10(2)°, V = 2894.8(2) Å3, Z = 2. The anion is a bi‐octahedron of two square‐pyramids, joined by a common edge. The octahedral coordination is achieved with two acetone ligands. [Ph4P]4[Bi4Cl16] · 3 CH3CN crystallises in the triclinic S. G., P1, No. 2, with the lattice parameters a = 14.245(9) Å, b = 17.318(6) Å, c = 24.475(8) Å, α = 104.66(3)°, β = 95.93(3)°, γ = 106.90(4)°, V = 5486(4) Å3, Z = 2. Two Bi2Cl8 dimers in syn‐position form the cubic anion. Lattice parameters of [Ph4P]3[Bi2Cl9] · CH3COCH3 are also given. The solvated compounds are desolvated at approximately 100 °C. [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 and [Ph4P]3[Bi2Cl9] · CH3COCH3 show the same sequence of phase transitions after desolvation. All compounds melt into a liquid in which some order is observed and transform on cooling into the glassy state. 相似文献
13.
The Zintl phase K4SnTe4 reacts with tetraphenylphosphonium bromide in methanol to give the polytelluride (Ph4P)2Te4 · 2 CH3OH. The compound crystallizes in the monoclinic space group C2/c with lattice constants a = 2329.6(11) pm, b = 1472.0(6) pm, and c = 1461.9(6) pm with ß = 111.34(3)°. Significant structural units are tetratelluride(2?) anions with CH3OH molecules hydrogen bonded to both ends of the anion. 相似文献
14.
Crystal Structures of [ReCl4(PhC?CPh)]2 · 2 CH2Cl2 and PPh4[ReOCl4] Single crystals of [ReCl4(PhC?CPh)]2 · 2 CH2Cl2 were obtained by chilling dilute solutions of the solvate [ReCl4(PhC?CPh)POCl3] in CH2Cl2. PPh4[ReOCl4] was formed by the reaction of the diphenyl acetylene complex [ReCl5(PhC?CPh)] with PPh4Cl · H2O in CH2Cl2 solution. [ReCl4(PhC?CPh)]2 · 2 CH2Cl2: space group P21/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl2Re bridges with Re? Cl distances of 241.2 and 267.6 pm. The longer Re? Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re? C distances of 200 pm. PPh4[ReOCl4]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh4[RuNCl4] type; it consists of [ReOCl4]? anions and PPh4+ cations. The anions are tetragonal with C4v symmetry and bond lengths Re? O = 165.4 pm and Re? Cl = 232.6 pm; the bond angle OReCl is 106.7°. 相似文献
15.
Cluster Synthesis by Photolysis of R3PAuN3. VIII. Synthesis and Crystal Structure of [(Ph3PAu)5Mo(CO)4]PF6 · CH2Cl2 and (Ph3PAu)3Co(CO)3 Photolysis of a mixture of Ph2PAuN3 and Mo(CO)6 in THF yields [(Ph3PAu)5Mo(CO)4]+ (1), which can be crystallized from CH2Cl2/diisopropylether as orange 1 · PF6 · CH2Cl2 with the space group P21/c and a = 1681.4(5), b = 2215.6(12), c = 2761.5(9) pm, β = 91.54(3)°, Z = 4. The Au5Mo center of cluster 1 forms a capped trigonal bipyramid with the Mo atom in equatorial position and almost equal Mo? Au distances between 279.9(5) and 284.6(7) pm to all five Au atoms. The Au? Au distances range from 272.2(4) to 301.3(4) pm. The Mo(CO)4 group causes three v(C0) at 1975, 1915 and 1890cm?1. Reaction of Ph3PAuCo(CO)4 with Ph3PAuPF6 affords the known cluster cation [(Ph3PAu)4Co(CO)3]+ in high yield. It can be degraded with C1? to the neutral cluster (Ph3PAu)3Co(CO)3 (2). 2 forms air stable, yellow crystals with the space group P21/n and a = 1359.4(4), b = 2041.0(5), c = 1853.2(6)pm, β = 91.47(1)°, Z = 4. The Au3Co core of 2 has a tetrahedral structure with distances Co? Au between 250.4(1) and 254.0(2) pm and Au? Au between 279.5(1) and 285.1(1) pm. v(C0) are observed at 1963, 1905 and 1891 cm?1. Reaction of 2 with [(Ph3PAu)4Co(CO)3]+ yields the condensed cluster [(Ph3PAu)6AuCo2(CO)6]+. 相似文献
16.
The Crystal Structures of (NBu4)[(Ph3Sn)3(MoO4)2] and (NBu4)[(Ph3Sn)3(MoO4)2]·CH3CN: Organotin Molybdates with Novel 3D Networks The reaction of (NBu4)2[Mo6O19] with Ph3SnCl and NBu4OH in acetonitrile as solvent leads to the formation of (NBu4)[(Ph3Sn)3(MoO4)2] ( 5 ). 5 and (NBu4)[(Ph3Sn)3(MoO4)2]· CH3CN 6 have been characterized by single crystal structure analysis at 220 K. 5 crystallizes monoclinic with a = 1429.5(4) pm, b = 2292.2(3) pm, c = 2269.7(5) pm, β = 107.42(3)°, space group Cc, 6 crystallizes orthorhombic with a = 1820.5(1) pm, b = 1848.6(2) pm and c = 2143.9(1) pm, space group P212121. The crystal structures of 5 and 6 consist of isolated (NBu4)+ cations and anionic 3D networks of Ph3SnO2 trigonal bipyramides and MoO4 tetrahedra which are linked by common oxygen atoms. 相似文献
17.
[Be(OH2)4]Cl2 – Preparation, IR spectrum, and Crystal Structure Single crystals of [Be(OH2)4]Cl2 were prepared by the reaction of thionyl chloride at 20 °C with samples which result from evaporated, HCl containing, aqueous solutions of BeCl2. With excess of boiling thionyl chloride BeCl2 is formed. [Be(OH2)4]Cl2 is characterized by IR spectroscopy and by X‐ray crystal structure determination: Space group P21/c, Z = 4, lattice dimensions at 193 K: a = 653.53(5), b = 1298.15(14), c = 789.52(6) pm, β = 103.005(9)°, R1 = 0.027. The structure consists of slightly distorted tetrahedral [Be(OH2)2]2+ ions, which are connected with the chloride ions via nearly linear O–H···Cl hydrogen bonds to give a 3D network. 相似文献
18.
Bis(tetraphenylphosphonium)‐tris(μ‐hydroxo)hexaaquatriberylliumpentachloride, (Ph4P)2[Be3(μ‐OH)3(H2O)6]Cl5 ( 1 ), was surprisingly obtained by reaction of (Ph4P)N3 · n H2O with BeCl2 in dichloromethane suspension and subsequent crystallization from acetonitrile to give single crystals of composition 1· 5.25CH3CN. According to the crystal structure determination space group P , Z = 2, lattice dimensions at 100 K: a = 1354.8(2), b = 1708.7(2), c = 1753.2(2) pm, α = 114.28(1)°, β = 94.80(1)°, γ = 104.51(1)°, R1 = 0.0586] the [Be3(μ‐OH)3(H2O)6]3+ cations form six‐mem‐bered Be3O3 rings with boat conformation and distorted tetrahedrally coordinated beryllium atoms with the terminally coordinated H2O molecules. The structure ist characterized by a complicated three dimensional hydrogen‐bridging network including O–H ··· O, O–H ··· Cl, and O–H ··· NCCH3 contacts. DFT calculations result in nearly planar [Be3(OH)3] six‐membered ring conformations. 相似文献
19.
Azido Beryllates with Adamantan‐like Structures: Synthesis, IR Spectra, and Crystal Structures of (Ph4P)2[Be4X4(μ‐N3)6] (X = Cl, Br) The azido beryllates (Ph4P)2[Be4X4(μ‐N3)6] (X = Cl 1a , X = Br 1b ) have been prepared by the reaction of Me3SiN3 with the halogeno beryllates (Ph4P)2[Be2Cl6] and (Ph4P)2[Be2Br6], respectively, in CH2Cl2 and CH2Br2 solution, respectively. Both complexes form moisture sensitive, colourless crystals, which are nonexplosive with respect to mechanical or thermal stress. They are characterized by IR spectroscopy and by crystal structure determinations. 1a and 1b crystallize isotypically in the space group C2/c with 12 formula units per unit cell. Whereas 1a was only refined to R1 = 0.13, which is caused by disordering, 1b could be refined to R1 = 0.066. The structures contain adamantanlike dianions [Be4X4(μ‐N3)6]2— with two symmetry nonequivalent individuals which differ only slightly from one another. The Be4N6 core is formed by bridging function of the α‐nitrogen atoms of the azide groups with BeN bond lengths of 172.5 and bond lengths Nα—Nβ = 123.2 pm and Nβ—Nγ = 113.1 pm on average in the structure of 1b . 相似文献
20.
(Me2NH2)[(Ph3Sn)3(MoO4)2], a Triorganotin Molybdate with Layer Structure The reaction of [(Ph3Sn)2MoO4] with (Me2NH2)Cl in an acetonitrile/water mixture leads to the formation of (Me2NH2)[(Ph3Sn)3(MoO4)2] ( 1 ). ( 1 ) crystallizes in the space group Pca21 with a = 1967.0(4), b = 1353.1(2) and c = 2176.6(5) pm. In the crystal structure of 1 Ph3SnO2 bipyramides and MoO4 tetrahedra are linked by corner sharing to give a layer structure. Additionally the layers are connected by O···H···N hydrogen bridges between MoO4 groups and [Me2NH2]+ ions to give a 3D network structure. 相似文献