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1.
Polysulfonyl Amines. XXXVII. Preparation of Mercury Dimesylamides. Crystal and Molecular Structures of Hg[N(SO2CH3)2]2, Hg[{N(SO2CH3)2}2(DMSO)2], and Hg[{N(SO2CH3)2}2(HMPA)] Hg[N(SO2CH3)2]2 ( 1 ) and Hg2[N(SO2CH3)2]2 ( 2 a ) are formed as colourless, sparingly soluble precipitates when solutions of Hg(NO3)2 or Hg2(NO3)2 in dilute nitric acid are added to an aqueous HN(SO2CH3)2 solution. By a similar reaction, Hg2[N(SO2C6H4 ? Cl? 4)2]2 is obtained. 1 forms isolable complexes of composition Hg[N(SO2CH3)2]2 · 2 L with L = dimethyl sulfoxide (complex 3 a ), acetonitrile, dimethyl formamide, pyridine or 1,10-phenanthroline and a (1/1) complex Hg[N(SO2CH3)2]2 · HMPA ( 4 ) with hexamethyl phosphoramide. Attempted complexation of 2 a with some of these ligands induced formation of Hg0 and the corresponding HgII complexes. Crystallographic data (at -95°C) are for 1: space group 141/a, a = 990.7(2), c = 2897.7(8) pm, V = 2.844 nm3, Z = 8, Dx = 2.545Mgm?3; for 4a: space group P1 , a = 767.8(2), b = 859.2(2), c = 925.2(2)pm α = 68.44(2), β = 86.68(2), γ = 76.24(2)°, V = 0.551nm3, Z = 1, Dx = 2.113 Mgm?3; for 4: space group P21/c, a = 1041.3(3), b = 1545.4(3), c = 1542.5(3) pm, β = 100.30(2)°, V = 2.474nm3, Z = 4, Dx = 1.944Mgm3. The three compounds form molecular crystals. The molecular structures contain a linear or approximately linear, covalent NHgN moiety; the Hg? N distances and N? Hg? N angles are 206.7(4) pm and 176.3(2)° for 1, 207.2(2) pm and 180.0° for 3a, 205.7(4)/206.7(4) pm and 170.5(1)° for 4. In the complexes 3a and 4, the 0-ligands are bonded to the Hg atoms perpendicularly to the N? Hg? N axes, leading in 3a to a square-planar trans-(N2O2) coordination with Hg? 0 261.2(2) pm and N? Hg? O 92.3(1)/87.7(1)°, in 4 to a slightly distorted T-shaped (N2O) geometry with Hg? 0 246.2(4)pm and N? Hg? 0 96.7(1)/92.0(1)°. In all three structures, the primary coordination is extended to a severely distorted (N2O4) hexacoordination by the appropriate number of secondary, inter- and/or intramolecular Hg…?0 inter-actions (0 atoms from sulfonyl groups, Hg…?O distances in the range 280—300pm). The intramolecular Hg…?O interactions give rise to nearly planar four-membered [HgNSO] rings. The molecule of 1 has a two-fold axis through the bisector of the N? Hg? N angle, the molecule of 3a an inversion center at the Hg atom. The molecule of 4 has no symmetry.  相似文献   

2.
Colourless needles of mercurous dimethylglyoximato nitrate, Hg2(Dmg)2(NO3)2, grow from a diluted nitric acid solution of mercurous nitrate and dimethylglyoxime. The crystal structure (triclinic, P1¯, a = 728.50(13), b = 1066.8(2), c = 1167.9(2) pm, α = 93.78(2)°, β = 94.16(2)°, γ = 98.61(2)°, Rall = 0, 0726) contains the cations [Hg2(Dmg)2]2+ and “non‐coordinating” (NO3) anions. In the cation, two neutral dimethylglyoxime molecules coordinate bidentately with Hg—N distances in the narrow range of 236 to 239 pm to the mercurous ion, Hg22+, which exhibits a Hg—Hg bond distance of 252.23(8) pm).  相似文献   

3.
Synthesis and Structure of the Platinum(0) Compounds [(dipb)Pt]2(COD) and (dipb)3Pt2 and of the Cluster Hg6[Pt(dipb)]4 (dipb = (i-Pr)2P(CH2)4P(i-Pr)2) The reduction of (dipb)PtCl2 with Na/Hg yields (dipb)Pt as an intermediate which reacts with the amalgam to form the cluster Hg6[Pt(dipb)]4 ( 3 ) or decomposes to (dipb)3Pt2 ( 2 ) and Pt. In the presence of COD [(dipb)Pt]2(COD) ( 1 ) is obtained. 1 crystallizes monoclinicly in the space group P21/c with a = 1596.1(4), b = 996.5(2), c = 1550.4(3) pm, β = 113.65(2)°, Z = 2. In the dinuclear complex two (dipb)Pt units are bridged by a 1,2-η2-5,6-η2 bonded COD ligand. Whereby the C = C double bonds are lengthened to 145 pm. 2 forms triclinic crystals with the space group P1 and a = 1002.0(2), b = 1635.9(3), c = 868.2(2) pm, α = 94.70(2)°, β = 94.45(2)°, σ = 87.95(1)°, Z = 1. In 2 two (dipb)Pt moieties are connected by a μ-dipb ligand in a centrosymmetrical arrangement. 3 is monoclinic with the space group C2/c and a = 1273.8(3), b = 4869.2(6), c = 1660.2(3) pm, β = 95.16(2)°, Z = 4. The clusters Hg6[Pt(dipb)]4 have the symmetry C2. Central unit is a Hg6 octahedron of which four faces are occupied by Pt(dipb) groups. The bonding in the cluster is discussed on the basis of eight Pt? Hg two center bonds of 267.6 pm and two Pt? Hg? Pt three center bonds with Pt? Hg = 288.0 pm.  相似文献   

4.
(Hg2)Hg(OH)2(ClO4)2: The First Mixed Valent Mercury Perchlorate Colorless single crystals of (Hg2)Hg(OH)2(ClO4)2 (C2/c, Z = 4, a = 1847.7(5), b = 490.8(1), c = 1086.2(3) pm, β = 93.80(2)°, Rall = 0.0610) were obtained as a side product during the dehydration of Hg2(ClO4)2 · 2H2O. The crystal structure consists of infinite zig‐zag chains {1[(Hg2)1/2(OH)Hg1/2]+}2 which are separated by the ClO4 ions.  相似文献   

5.
Polycrystalline anhydrous Hg2(NO3)2 was prepared by drying Hg2(NO3)2·2H2O over concentrated sulphuric acid. Evaporation of a concentrated and slightly acidified mercury(I) nitrate solution to which the same volumetric amount of pyridine was added, led to the growth of colourless rod‐like single crystals of Hg2(NO3)2. Besides the title compound, crystals of hydrous Hg2(NO3)2·2H2O and the basic (Hg2)2(OH)(NO3)3 were formed as by‐products after a crystallization period of about 2 to 4 days at room temperature. The crystal structure was determined from two single crystal diffractometer data sets collected at —100°C and at room temperature: space group P21, Z = 4, —100°C [room temperature]: a = 6.2051(10) [6.2038(7)]Å, b = 8.3444(14) [8.3875(10)]Å, c = 11.7028(1) [11.7620(14)]Å, ß = 93.564(3) [93.415(2)]°, 3018 [3202] structure factors, 182 [182] parameters, R[2 > 2σ(2)] = 0.0266 [0.0313]. The structure is built up of two crystallographically inequivalent Hg22+ dumbbells and four NO3 groups which form molecular [O2N‐O‐Hg‐Hg‐O‐NO2] units with short Hg‐O bonds. Via long Hg‐O bonds to adjacent nitrate groups the crystal packing is achieved. The Hg‐Hg distances with an average of d(Hg‐Hg) = 2.5072Å are in the typical range for mercurous oxo compounds. The oxygen coordination around the mercury dumbbells is asymmetric with four and six oxygen atoms as ligands for the two mercury atoms of each dumbbell. The nitrate groups deviate slightly from the geometry of an equilateral triangle with an average distance of d(N‐O) = 1.255Å.  相似文献   

6.
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   

7.
Contributions on Crystal Structures and Thermal Behaviour of Anhydrous Phosphates. XXIII. Preparation, Crystal Structure, and Thermal Behaviour of the Mercury(I) Phosphates α-(Hg2)3(PO4)2, β-(Hg2)3(PO4)2, and (Hg2)2P2O7 Light-yellow single crystals of (Hg2)2P2O7 have been obtained via chemical vapour transport in a temperature gradient (500 °C → 450 °C, 23 d) using Hg2Cl2 as transport agent. Characteristic feature of the crystal structure (P2/n, Z = 2, a = 9,186(1), b = 4,902(1), c = 9,484(1) Å, β = 98,82(2)°, 1228 independent of 5004 reflections, R(F) = 0,066 for 61 variables, 7 atoms in the asymmetric unit) are Hg22+-units with d(Hg1–Hg1) = 2,508 Å and d(Hg2–Hg2) = 2,519 Å. The dumbbells Hg22+ are coordinated by oxygen, thus forming polyhedra [(Hg12)O4] and [(Hg22)O6]. These polyhedra share some oxygen atoms. In addition they are linked by the diphosphate anion P2O74– (ecliptic conformation; ∠(P,O,P) = 129°) to built up the 3-dimensional structure. Under hydrothermal conditions (T = 400 °C) orange single crystals of the mercury(I) orthophosphates α-(Hg2)3(PO4)2 and β-(Hg2)3(PO4)2 have been obtained from (Hg2)2P2O7 and H3PO4 (c = 1%). The crystal structures of both modifications have been refined from X-ray single crystal data [α-form (β-form): P21/c (P21/n), Z = 2 (2), a = 8,576(3) (7,869(3)), b = 4,956(1) (8,059(3)), c = 15,436(3) (9,217(4)) Å, β = 128,16(3) (108,76(4))°, 1218 (1602) independent reflections of 4339 (6358) reflections, R(F) = 0,039 (0,048) for 74 (74) variables, 8 (8) atoms in the asymmetric unit]. In the structure of α-(Hg2)3(PO4)2 three crystallographically independent mercury atoms, located in two independent dumbbells, are coordinated by three oxygen atoms each. Thus, [(Hg2)O6] dimers with a strongly distorted tetrahedral coordination of all mercury atoms are formed. Such dimers are present besides [(Hg2)O5]-polyhedra in the less dense crystal structure of β-(Hg2)3(PO4)2 (d(Hg–Hg) = 2,518 Å). The mercury(I) phosphates are thermally labile and disproportionate between 200 °C (β-(Hg2)3(PO4)2) and 480 °C (α-(Hg2)3(PO4)2) to elemental mercury and the corresponding mercury(II) phosphate.  相似文献   

8.
Colourless single crystals of [Hg(OH)](NO3)(H2O) were obtained by slow evaporation of an aqueous solution of Hg(NO3)2 and Bi(NO3)3. The crystal structure (orthorhombic, Pbca, Z = 8, a = 943.2(2), b = 697.6(1), c = 1349.0(2) pm, R1(all) = 0.0780) contains [Hg(OH)] = …OH–Hg–OH–Hg… zig zag chains (O–Hg–O angle: 168°, Hg–O–Hg angle: 112°, Hg–OH distance: 212 pm) to which one water molecule is attached loosely. The [Hg(OH)](H2O) chains are connected via bis‐monodentate‐bridging nitrate ions to corrugated layers that are stacked in the [001] direction. Hg2+ has an effective 2+2+2(+1) coordination.  相似文献   

9.
Red single crystals of Pt2(HSO4)2(SO4)2 were obtained by the reaction of elemental platinum with conc. sulfuric acid at 350 °C in sealed glass ampoules. The crystal structure (monoclinic, P21/c, Z = 2, a = 868.6(2), b = 826.2(1), c = 921.8(2) pm, β=116.32(1)°, Rall = 0.0348) shows dumbbell shaped Pt26+ cations which are coordinated by four SO42— and two HSO4 ions. Each of the sulfate ions is attached to another Pt26+ ion yielding layers according to equation/tex2gif-stack-1.gif[Pt2(SO4)4/2(HSO4)2/1]. The layers are connected by hydrogen bonds with the OH group of the hydrogensulfate ion as donor and the non‐bonding oxygen atom of the sulfate ion as acceptor.  相似文献   

10.
New Phosphorus-bridged Transition Metal Complexes The Crystal Structures of [Co4(CO)10(PiPr)2], [Fe3(CO)9(PtBu)(PPh)], [Cp3Fe3(CO)2(PPtBu)· (PtBu)], [(NiPPh3)2(PiPr)6], [(NiPPh3)Ni{(PtBu)3}2], and [Ni8(PtBu)6(PPh3)2] By the reaction of cyclophosphines with transition metal carbonyl-derivatives polynuclear complexes are built, in which the PR-ligands (R = organic group) are bonded in different ways to the metal. Depending on the reaction conditions the following compounds can be characterized: [Co4(CO)10 · (PiPr)2] ( 2 ), [Fe3(CO)9(PtBu)(PPh)] ( 3 ), [Cp3Fe3(CO)2(PPtBu) · (PtBu)] ( 4 ), [(NiPPh3)2(PiPr)6] ( 5 ), [(NiPPh3)Ni{(PtBu)3}2] ( 6 ) and [Ni8(PtBu)6(PPh3)2] ( 7 ). The structures of 2–7 were obtained by X-ray single crystal structure analysis ( 2 : space group Pccn (No. 56), Z = 4, a = 1001,4(2) pm, b = 1375,1(3) pm, c = 1675,5(3) pm; 3 : space group P21 (No. 4), Z = 2, a = 914,3(4) pm, b = 1268,7(4) pm, c = 1028,2(5) pm, β = 101,73(2)°; 4 : space group P1 (No. 2), Z = 2, a = 946,0(5) pm, b = 1074,4(8) pm, c = 1477,7(1,0) pm, α = 107,63(5)°, β = 94,66(5)°, γ = 111,04(5)°; 5 : space group P1 (No. 2), Z = 2, a = 1213,6(2) pm, b = 1275,0(2) pm, c = 2038,8(4) pm, α = 92,810(10)°, β = 102,75(2)°, γ = 93,380(10)°; 6 : space group P1 (No. 2), Z = 2, a = 1157,5(5) pm, b = 1371,9(6) pm, c = 1827,6(10) pm; α = 69,68(3)°, β = 80,79(3)°, γ = 69,36(3)°; 7 : space group P3 (No. 147), Z = 1, a = 1114,1(2) pm, b = 1114,1(2) pm, c = 1709,4(3) pm).  相似文献   

11.
LiLa2F3(SO4)2 and LiEr2F3(SO4)2: Fluoride‐Sulfates of the Rare‐Earth Elements with Lithium The reaction of LiF with the anhydrous sulfates M2(SO4)3 (M = La, Er) in sealed gold ampoules yields single crystals of the pseudo quaternary compounds LiLa2F3(SO4)2 and LiEr2F3(SO4)2. According to X‐ray single crystal investigations, LiLa2F3(SO4)2 crystallizes with the monoclinic (I2/a, Z = 4, a = 828.3(2), b = 694.7(1), c = 1420.9(3) pm, β = 95.30(2)°, Rall = 0.0214) and LiEr2F3(SO4)2 with the orthorhombic crystal system (Pbcn, a = 1479.1(2), b = 633.6(1), c = 813.7(1) pm, Rall = 0.0229). A common feature of both structures is a dimeric unit of metal atoms connected via three fluoride ions. This leads to relatively short metal‐metal distances (La3+–La3+: 389 pm, Er3+–Er3+: 355 pm). In LiLa2F3(SO4)2, Li+ is surrounded by four oxygen atoms of four sulfate groups and one fluoride ion in form of a trigonal bipyramid, in LiEr2F3(SO4)2 two further fluoride ligands are attached.  相似文献   

12.
Sulfates and Hydrogensulfates of Erbium: Er(HSO4)3-I, Er(HSO4)3-II, Er(SO4)(HSO4), and Er2(SO4)3 Rod shaped light pink crystals of Er(HSO4)3-I (orthorhombic, Pbca, a = 1195.0(1) pm, b = 949.30(7) pm, c = 1644.3(1) pm) grow from a solution of Er2(SO4)3 in conc. H2SO4 at 250 °C. From slightly diluted solutions (85%) which contain Na2SO4, brick shaped light pink crystals of Er(HSO4)3-II (monoclinic, P21/n, a = 520.00(5) pm, b = 1357.8(1) pm, c = 1233.4(1) pm, β = 92.13(1)°) were obtained at 250 °C and crystals of the same colour of Er(SO4)(HSO4) (monoclinic, P21/n, a = 545.62(6) pm, b = 1075.6(1) pm, c = 1053.1(1) pm, β = 104.58(1)°) at 60 °C. In both hydrogensulfates, Er3+ is surrounded by eight oxygen atoms. In Er(HSO4)3-I layers of HSO4 groups are connected only via hydrogen bridges, while Er(HSO4)3-II consists of a threedimensional polyhedra network. In the crystal structure of Er(SO4)(HSO4) Er3+ is sevenfold coordinated by oxygen atoms, which belong to four SO42–- and three HSO4-tetrahedra, respectively. The anhydrous sulfate, Er2(SO4)3, cannot be prepared from H2SO4 solutions but crystallizes from a NaCl-melt. The coordination number of Er3+ in Er2(SO4)3 (orthorhombic, Pbcn, a = 1270.9(1) pm, b = 913.01(7) pm, c = 921.67(7) pm) is six. The octahedral coordinationpolyhedra are connected via all vertices to the SO42–-tetrahedra.  相似文献   

13.
Polycationic Hg‐Pnictide Frameworks with a Novel Kind of Filling in the Structures of Hg3As2TlCl3 and Hg3Sb2TlBr3 Hg3As2TlCl3 and Hg3Sb2TlBr3 were prepared from mixtures of Hg2X2, HgX2 (X = Cl, Br), As or Sb and Tl in sealed evacuated glass ampoules in temperature gradients 330 °C → 290 °C for Hg3As2TlCl3 (red, transparent crystals) and 290 °C → 260 °C for Hg3Sb2TlBr3 (black crystals). The structures of the diamagnetic compounds were determined based on single crystal X‐ray diffraction data. Both compounds crystallize isotypically in the orthorhombic space group Pbcm with Z = 4 and the lattice constants a = 629.2(5) pm, b = 1234.1(7) pm and c = 1224.8(9) pm for Hg3As2TlCl3 and a = 661.0(4) pm, b = 1311.2(9) pm and c = 1307.1(2) pm for Hg3Sb2TlBr3. The structures can be described either as a cubic closest packing of As2/Sb2 dumb‐bells and halide anions with all octahedral interstices filled with Hg2+ and Tl+, or as a polycationic framework (Hg3Y2)2+ (Y = As, Sb) consisting of pnictide‐pnictide dumbbells each connected by six Hg atoms to a three dimensional porous arrangement. The centers of the cavities are occupied by Tl+ ions which are coordinated by six halide ions in distorted octahedral form. These TlX6 octahedra share corners in all directions in the motive of the ReO3 structure type. This new structure type shows a close relationship to the cubic family of compounds of the general formula (Hg6Y4)[MX6]X (Y = As, Sb; M = Mo, Ti, Bi, Sb; X = Cl, Br). The halide ions are connected to the Hg atoms of the polycationic network and to the Tl+ ions. Extended Hueckel calculations were used to explain the bonding character of the thallium–halide and mercury–halide bonds.  相似文献   

14.
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   

15.
Single crystals of the hitherto unknown compound Hg2(OH)(NO3)·HgO were obtained unintentionally during hydrothermal phase formation experiments in the system Ag—Hg— As—O. Hg2(OH)(NO3)·HgO (orthorhombic, Pbca, Z = 8, a = 6.4352(8), b = 11.3609(14), c = 15.958(2) Å, 1693 structure factors, 83 parameters, R1[F2 > 2σ(F2)] = 0.0431) adopts a new structure type and is composed of two types of mercury‐oxygen zig‐zag‐chains running perpendicular to each other and of intermediate nitrate groups. One type of chains runs parallel [010] and consists of (Hg—Hg—OH) units with a typical Hg—Hg distance of 2.5143(10) Å for the mercury dumbbell, whereas the other type of chains runs parallel [100] and is made up of (O—Hg—O) units with short Hg—O distances of about 2.02Å. Both types of chains are concatenated by a common O atom with a slightly longer Hg—O distance of 2.25Å. The three‐dimensional assembly is completed by nitrate groups whose O atoms show Hg—O distances > 2.80Å. Weak hydrogen bonding between the OH group and one oxygen atom belonging to the nitrate group stabilizes this arrangement. Hg2(OH)(NO3)·HgO decomposes above 200 °C to HgO.  相似文献   

16.
Preparation of Tetramethylammonium Azidosulfite and Tetramethylammonium Cyanate Sulfur Dioxide‐Adduct, [(CH3)4N]+[SO2N3], [(CH3)4N]+[SO2OCN] and Crystal Structure of [(CH3)4N]+[SO2N3] Tetramethylammonium azide forms with sulfur dioxide an azidosulfite salt. It is characterized by NMR and vibrational spectroscopy and the crystal structure analysis. [(CH3)4N]+[SO2N3] crystallizes in the monoclinic space group P21/c with a = 551.3(1) pm, b = 1095.2(1) pm, c = 1465.0(1) pm, β = 100.63(1)°, and four formula units in the unit cell. The crystal structure possesses a strong S–N interaction between the N3– anions and the SO2 molecules. The S–N distance of 200.5(2) pm is longer than a covalent single S–N bond. The structure is compared with ab initio calculated data. Furthermore an adduct of tetrametylammonium cyanate and sulfur dioxide is reported. It is characterised by NMR and vibrational spectroscopy. The structure is calculated by ab initio methods.  相似文献   

17.
Colourless single crystals of the caffeine adduct of mercurous perchlorate dihydrate, [Hg2(Caf)2](ClO4)2(H2O)2, were grown from aqueous solutions of mercurous perchlorate and caffeine by isothermal evaporation at ambient temperature. The crystal structure (monoclinic, P21/n, Z = 4, a = 1628.0(2), b = 780.4(1), c = 2229.6(3) pm, β = 99.84(1)°, R1(all data) = 0.0894) contains [trans‐Caf‐Hg‐Hg‐Caf]2+ cations with a Hg‐Hg distance of 250.88(6) pm, Hg‐N (bond) distances of 214.4(6) and 215.1(6) pm and Hg‐Hg‐N angles of 176.9(2) and 165.1(2)°, respectively. These cations are attached via weak Hg‐O contacts to dimers which are further arranged to leave large channels into which one crystal water molecule is included. The second water molecule and the two perchlorate anions are weakly attracted to one Hg atom.  相似文献   

18.
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   

19.
Chloroberyllates with Nitrogen Donor Ligands. Crystal Structures of (Ph4P)[BeCl3(py)], (Ph4P)2[(BeCl3)2(tmeda)], (Ph4P)[BeCl2{(Me3SiN)2CPh}], and (Ph4P)2[BeCl4] · 2CH2Cl2 The title compounds were obtained as colourless, moisture sensitive crystals by reactions of (Ph4P)2[Be2Cl6] with pyridine, tmeda (N, N′‐tetramethylethylendiamine), or with the silylated benzamidine PhC—[N(SiMe3)2(NSiMe3)], whereas the tetrachloro beryllate was isolated as a by‐product from a solution in dichloromethane in the presence of the silylated phosphaneimine Me3SiNP(tol)3. All compounds were characterized by crystal structure determinations and by IR spectroscopy. (Ph4P)[BeCl3(Py)] ( 1 ): Space group Pbcm, Z = 4, lattice dimensions at 193 K: a = 756.2(1), b = 1739.2(2), c = 2016.3(2) pm, R1 = 0.0626. The complex anion contains tetrahedrally coordinated beryllium atom with a Be—N distance of 176.5 pm. (Ph4P)2[(BeCl3)2(tmeda)]·2CH2Cl2 ( 2 ·2CH2Cl2). Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1072.7(1), b = 1132.6(1), c = 1248.9(1) pm, α = 95.34(1)°, β = 92.80(1)°, γ = 90.81(1)°, R1 = 0.0344. Both nitrogen atoms of the tmeda molecule coordinate with BeCl3 units forming the centrosymmetric complex anion with Be—N distances of 181.3 pm. (PPh4)[BeCl2{(Me3SiN)2CPh}] ( 3 ). Space group C2, Z = 2, lattice dimensions at 193 K: a = 1255.4(2), b = 1401.9(2), c = 1085.2(2) pm, R1 = 0.0288. In the complex anion the benzamidinato ligand {(Me3SiN)2CPh} acts as chelate with Be—N distances of 174.9 pm. (Ph4P)2[BeCl4]·2CH2Cl2 ( 4 ·2CH2Cl2). Space group P2/c, Z = 4, lattice dimensions at 193 K: a = 2295.4(1), b = 982.5(1), c = 2197.2(2) pm, β = 99.19(1)°, R1 = 0.0586. 4 ·2CH2Cl2 contains nearly ideal tetrahedral [BeCl4]2— ions, like the previously described 4 ·2, 5CH2Cl2, which crystallizes in the space group P1¯, with Be—Cl distances of 203.4 pm on average.  相似文献   

20.
Syntheses, Crystal Structures, and Thermal Behavior of Er2(SO4)3 · 8 H2O and Er2(SO4)3 · 4 H2O Evaporation of aqueous solutions of Er2(SO4)3 yields light pink single crystals of Er2(SO4)3 · 8 H2O. X-ray single crystal investigations show that the compound crystallizes monoclinically (C2/c, Z = 8, a = 1346.1(3), b = 667.21(1), c = 1816.2(6) pm, β = 101.90(3)°, Rall = 0.0169) with eightfold coordination of Er3+, according to Er(SO4)4(H2O)4. DSC- and temperature dependent X-ray powder investigations show that the decomposition of the hydrate follows a two step mechanism, firstly yielding Er2(SO4)3 · 3 H2O and finally Er2(SO4)3. Attempts to synthesize Er2(SO4)3 · 3 H2O led to another hydrate, Er2(SO4)3 · 4 H2O. There are two crystallographically different Er3+ ions in the triclinic structure (P 1, Z = 2, a = 663.5(2), b = 905.5(2), c = 1046.5(2) pm, α = 93.59(3)°, β = 107.18(2)°, γ = 99.12(3)°, Rall = 0.0248). Er(1)3+ is coordinated by five SO42– groups and three H2O molecules, Er(2)3+ is surrounded by six SO42– groups and one H2O molecule. The thermal decomposition of the tetrahydrate yields Er2(SO4)3 in a one step process. In both cases the dehydration produces the anhydrous sulfate in a modification different from the one known so far.  相似文献   

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