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1.
The Lanthanum Dodecahydro‐closo‐Dodecaborate Hydrate [La(H2O)9]2[B12H12]3·15 H2O and its Oxonium‐Chloride Derivative [La(H2O)9](H3O)Cl2[B12H12]·H2O By neutralization of an aqueous solution of the free acid (H3O)2[B12H12] with basic La2O3 and after isothermic evaporation colourless, face‐rich single crystals of a water‐rich lanthanum(III) dodecahydro‐closo‐dodecaborate hydrate [La(H2O)9]2[B12H12]3·15 H2O are isolated. The compound crystallizes in the trigonal system with the centrosymmetric space group (a = 1189.95(2), c = 7313.27(9) pm, c/a = 6.146; Z = 6; measuring temperature: 100 K). The crystal structure of [La(H2O)9]2[B12H12]3·15 H2O can be characterized by two of each other independent, one into another posed motives of lattice components. The [B12H12]2− anions (d(B–B) = 177–179 pm; d(B–H) = 105–116 pm) are arranged according to the samarium structure, while the La3+ cations are arranged according to the copper structure. The lanthanum cations are coordinated in first sphere by nine oxygen atoms from water molecules in form of a threecapped trigonal prism (d(La–O) = 251–262 pm). A coordinative influence of the [B12H12]2− anions on La3+ has not been determined. Since “zeolitic” water of hydratation is also present, obviously the classical H–Oδ–···+δH–O‐hydrogen bonds play a significant role in the stabilization of the crystal structure. During the conversion of an aqueous solution of (H3O)2[B12H12] with lanthanum trichloride an anion‐mixed salt with the composition [La(H2O)9](H3O)Cl2[B12H12]·H2O is obtained. The compound crystallizes in the hexagonal system with the non‐centrosymmetric space group (a = 808.84(3), c = 2064.51(8) pm, c/a = 2.552; Z = 2; measuring temperature: 293 K). The crystal structure can be characterized as a layer‐like structure, in which [B12H12]2− anions and H3O+ cations alternate with layers of [La(H2O)9]3+ cations (d(La–O) = 252–260 pm) and Cl− anions along [001]. The [B12H12]2− (d(B–B) = 176–179 pm; d(B–H) = 104–113 pm) and Cl− anions exhibit no coordinative influence on La3+. Hydrogen bonds are formed between the H3O+ cations and [B12H12]2− anions, also between the water molecules of [La(H2O)9]3+ and Cl− anions, which contribute to the stabilization of the crystal structure. 相似文献
2.
On the Crystal Structures of the Transition‐Metal(II) Dodecahydro‐closo‐Dodecaborate Hydrates Cu(H2O)5.5[B12H12]·2.5 H2O and Zn(H2O)6[B12H12]·6 H2O By neutralization of an aqueous solution of the free acid (H3O)2[B12H12] with basic copper(II) carbonate or zinc carbonate, blue lath‐shaped single crystals of the octahydrate Cu[B12H12]·8 H2O (≡ Cu(H2O)5.5[B12H12]·2.5 H2O) and colourless face‐rich single crystals of the dodecahydrate Zn[B12H12]·12 H2O (≡ Zn(H2O)6[B12H12]·6 H2O) could be isolated after isothermic evaporation. Copper(II) dodecahydro‐closo‐dodecaborate octahydrate crystallizes at room temperature in the monoclinic system with the non‐centrosymmetric space group Pm (Cu(H2O)5.5[B12H12]·2.5 H2O: a = 768.23(5), b = 1434.48(9), c = 777.31(5) pm, β = 90.894(6)°; Z = 2), whereas zinc dodecahydro‐closo‐dodecaborate dodecahydrate crystallizes cubic in the likewise non‐centrosymmetric space group F23 (Zn(H2O)6[B12H12]·6 H2O: a = 1637.43(9) pm; Z = 8). The crystal structure of Cu(H2O)5.5[B12H12]·2.5 H2O can be described as a monoclinic distortion variant of the CsCl‐type arrangement. As characteristic feature the formation of isolated [Cu2(H2O)11]4+ units as a condensate of two corner‐linked Jahn‐Teller distorted [Cu(H2O)6]2+ octahedra via an oxygen atom of crystal water can be considered. Since “zeolitic” water of hydratation is also present, obviously both classical H–Oδ?···+δH–O and non‐classical B–Hδ?···+δH–O hydrogen bonds play a significant role for the stabilization of the structure. A direct coordinative influence of the quasi‐icosahedral [B12H12]2? anions on the Cu2+ cations has not been determined. The zinc compound Zn(H2O)6[B12H12]·6 H2O crystallizes in a NaTl‐type related structure. Two crystallographically different [Zn(H2O)6]2+ octahedra are present, which only differ in their relative orientation within the packing of the [B12H12]2? anions. The stabilization of the crystal structure takes place mainly via H–Oδ?···+δH–O hydrogen bonds, since again the hydrogen atoms of the [B12H12]2? anions have no direct coordinative influence on the Zn2+ cations. 相似文献
3.
Dodecahydro‐ closo ‐dodecaborates of the Heavy Alkaline‐Earth Metals from Aqueous Solution: Ca(H2O)7[B12H12] · H2O, Sr(H2O)8[B12H12], and Ba(H2O)6[B12H12] The crystalline hydrates of the heavy alkaline earth metal dodecahydro‐closo‐dodecaborates (M[B12H12] · n H2O, n = 6–8; M = Ca, Sr, Ba) are easily accessible by reaction of an aqueous (H3O)2[B12H12] solution with an alkaline earth metal carbonate (MCO3). By isothermic evaporation of the respective aqueous solution we obtained colourless single crystals which are characterized by X‐ray diffraction at room temperature. The three compounds Ca(H2O)7[B12H12] · H2O (orthorhombic, P212121; a = 1161.19(7), b = 1229.63(8), c = 1232.24(8) pm; Z = 4), Sr(H2O)8[B12H12] (trigonal, R3; a = 1012.71(6), c = 1462.94(9) pm; Z = 3) and Ba(H2O)6[B12H12] (orthorhombic, Cmcm; a = 1189.26(7) pm, b = 919.23(5) pm, c = 1403.54(9) pm; Z = 4) are neither formula‐equal nor isostructural. The structure of Sr(H2O)8[B12H12] is best described as a NaCl‐type arrangement, Ba(H2O)6[B12H12] rather forms a layer‐like and Ca(H2O)7[B12H12] · H2O a channel‐like structure. In first sphere the alkaline earth metal cations Ca2+ and Sr2+ are coordinated by just seven and eight oxygen atoms from the surrounding water molecules, respectively. A direct coordinative influence of the quasi‐icosahedral [B12H12]2– cluster anions becomes noticeable only for the Ba2+ cations (CN = 12) in Ba(H2O)6[B12H12]. The dehydratation of the alkaline earth metal dodecahydro‐closo‐dodecaborate hydrates has been shown to take place in several steps. Thermal treatment leads to the anhydrous compounds Ca[B12H12], Sr[B12H12] and Ba[B12H12] at 224, 164 and 116 °C, respectively. 相似文献
4.
Synthesis, Crystal Structure, and Thermal Decomposition of Mg(H2O)6[B12H12] · 6 H2O By reaction of an aqueous solution of the free acid (H3O)2[B12H12] with MgCO3 and subsequent isothermic evaporation of the resulting solution to dryness, colourless, bead‐shaped single crystals of the dodecahydrate of magnesium dodecahydro closo‐dodecaborate Mg(H2O)6[B12H12] · 6 H2O (cubic, F4132; a = 1643.21(9) pm, Z = 8) emerge. The crystal structure is best described as a NaTl‐type arrangement in which the centers of gravity of the quasi‐icosahedral [B12H12]2— anions (d(B—B) = 178—180 pm, d(B—H) = 109 pm) occupy the positions of Tl— while the Mg2+ cations occupy the Na+ positions. A direct coordinative influence of the [B12H12]2— units at the Mg2+ cations is however not noticeable. The latter are octahedrally coordinated by six water molecules forming isolated hexaaqua complex cations [Mg(H2O)6]2+ (d(Mg—O) = 206 pm, 6×). In addition, six “zeolitic” water molecules are located in the crystal structure for the formation of a strong O—Hδ+···δ—O‐hydrogen bridge‐bonding system. The evidence of weak B—Hδ—···δ+H—O‐hydrogen bonds between water molecules and anionic [B12H12]2— clusters is also considered. Investigations on the dodecahydrate Mg[B12H12] · 12 H2O (≡ Mg(H2O)6[B12H12] · 6 H2O) by DTA/TG measurements showed that its dehydration takes place in two steps within a temperature range of 71 and 76 °C as well as at 202 °C, respectively. Thermal treatment eventually leads to the anhydrous magnesium dodecahydro closo‐dodecaborate Mg[B12H12]. 相似文献
5.
Investigations on the Crystal Structure of Lithium Dodecahydro‐closo‐dodecaborate from Aqueous Solution: Li2(H2O)7[B12H12] By neutralization of an aqueous solution of the acid (H3O)2[B12H12] with lithium hydroxide (LiOH) and subsequent isothermic evaporation of the resulting solution to dryness, it was possible to obtain the heptahydrate of lithium dodecahydro‐closo‐dodecaborate Li2[B12H12] · 7 H2O (≡ Li2(H2O)7[B12H12]). Its structure has been determined from X‐ray single crystal data at room temperature. The compound crystallizes as colourless, lath‐shaped, deliquescent crystals in the orthorhombic space group Cmcm with the lattice constants a = 1215.18(7), b = 934.31(5), c = 1444.03(9) pm and four formula units in the unit cell. The crystal structure of Li2(H2O)7[B12H12] can not be described as a simple AB2‐structure type. Instead it forms a layer‐like structure analogous to the well‐known barium compound Ba(H2O)6[B12H12]. Characteristic feature is the formation of isolated cation pairs [Li2(H2O)7]2+ in which the water molecules form two [Li(H2O)4]+ tetrahedra with eclipsed conformation, linked to a dimer via a common corner. The bridging oxygen atom (∢(Li‐ O ‐Li) = 112°) thereby formally substitutes Ba2+ in Ba(H2O)6[B12H12] according to (H2 O )Li2(H2O)6[B12H12]. A direct coordinative influence of the [B12H12]2— cluster anions to the Li+ cations is not noticeable, however. The positions of the hydrogen atoms of both the water molecules and the [B12H12]2— units have all been localized. In addition, the formation of B‐Hδ—···δ+H‐O‐hydrogen bonds between the water molecules and the hydrogen atoms from the anionic [B12H12]2— clusters is considered and their range and strength is discussed. The dehydratation of the heptahydrate has been investigated by DTA‐TG measurements and shown to take place in two steps at 56 and 151 °C, respectively. Thermal treatment leads to the anhydrous lithium dodecahydro‐closo‐dodecaborate Li2[B12H12], eventually. 相似文献
6.
Synthesis and Crystal Structure of Cadmium Dodecahydro closo‐Dodecaborate Hexahydrate, Cd(H2O)6[B12H12] Through neutralization of the aqueous free acid (H3O)2[B12H12] with cadmium carbonate (CdCO3) and after isothermic evaporation of the resulting solution, colourless lath‐shaped single crystals of Cd(H2O)6[B12H12] are obtained. Cadmium dodecahydro closo‐dodecaborate hexahydrate crystallizes at room temperature in the monoclinic system (space group: C2/m) with the lattice constants a = 1413.42(9), b = 1439.57(9), c = 749.21(5) pm and β = 97.232(4)° (Z = 4). The crystal structure of Cd(H2O)6[B12H12] can be regarded as a monoclinic distortion variant of the CsCl‐type structure. Two crystallographically different [Cd(H2O)6]2+ octahedra (d(Cd–O) = 227–230 pm) are present which only differ in their relative orientation. The intramolecular bond lengths for the quasi‐icosahedral [B12H12]2? cluster anions range in the intervals usually found for dodecahydro closo‐dodecaborates (d(B–B) = 177–179 pm, d(B–H) = 103–116 pm). The hydrogen atoms of the [B12H12]2? clusters have no direct coordinative influence on the Cd2+ cations. Due to the fact that no “zeolitic” crystal water molecules are present, a stabilization of the lattice takes place mainly via the B–Hδ?···+δH–O hydrogen bonds. 相似文献
7.
During the reaction of an aqueous solution of (H3O)2[B12H12] with Tl2CO3 anhydrous thallium(I) dodecahydro‐closo‐dodecaborate Tl2[B12H12] is obtained as colorless, spherical single crystals. It crystallizes in the cubic system with the centrosymmetric space group Fm$\bar{3}$ (a = 1074.23(8) pm, Z = 4) in an anti‐CaF2 type structure. Four quasi‐icosahedral [B12H12]2– anions (d(B–B) = 180–181 pm, d(B–H) = 111 pm) exhibit coordinative influence on each Tl+ cation and provide a twelvefold coordination in the shape of a cuboctahedron (d(Tl–H) = 296 pm). There is no observable stereochemical activity of the non‐bonding electron pairs (6s2 lone pairs) at the Tl+ cations. By neutralization of an aqueous solution of the acid (H3O)2[B12H12] with PbCO3 and after isothermic evaporation colorless, plate‐like single crystals of lead(II) dodecahydro‐closo‐dodecaborate hexahydrate Pb(H2O)3[B12H12] · 3H2O can be isolated. This compound crystallizes orthorhombically with the non‐centrosymmetric space group Pna21 (a = 1839.08(9), b = 1166.52(6), c = 717.27(4) pm, Z = 4). The crystal structure of Pb(H2O)3[B12H12] · 3H2O is characterized as a layer‐like arrangement. The Pb2+ cations are coordinated in first sphere by only three oxygen atoms from water molecules (d(Pb–O) = 247–248 pm). But a coordinative influence of the [B12H12]2– anions (d(B–B) = 173–181 pm, d(B–H) = 93–122 pm) on lead has to be stated, too, as three hydrogen atoms from three different hydroborate anions are attached to the Pb2+ cations (d(Pb–H) = 258–270 pm) completing their first‐sphere coordination number to six. These three oxygen and three hydrogen ligands are arranged as quite irregular polyhedron leaving enough space for a stereochemical lone‐pair activity (6sp) at each Pb2+ cation. Since additional intercalating water of hydration is present as well, both classical H–Oδ– ··· +δH–O‐ and unconventional B–Hδ– ··· +δH–O hydrogen bonds play a significant role in the stabilization of the entire crystal structure. 相似文献
8.
Structural Investigations on Cs2[B12H12] The crystal structure of Cs2[B12H12] has been determined from X‐ray single‐crystal data collected at room temperature. Dicesium dodecahydro‐closo‐dodecaborate crystallizes as colourless, face‐rich crystals (cubic, Fm 3; a = 1128.12(7) pm; Z = 4). Its synthesis is based on the reaction of Na[BH4] with BF3(O(C2H5)2) via the decomposition of Na[B3H8] in boiling diglyme, followed by subsequent separations, precipitations (with aqueous CsOH solution) and recrystallizations. The crystal structure is best described as anti‐CaF2‐type arrangement with the Cs+ cations in all tetrahedral interstices of the cubic closest‐packed host lattice of the icosahedral [B12H12]2–‐cluster dianions. The intramolecular bond lengths are in the range usually found in closo‐hydroborates: 178 pm for the B–B and 112 pm for the B–H distance. Twelve hydrogen atoms belonging to four [B12H12]2– icosahedra provide an almost perfect cuboctahedral coordination sphere to the Cs+ cations, and their distance of 313 pm (12 ×) attests for the salt‐like character of Cs2[B12H12] according to {(Cs+)2([B12H12]2–)}. The 11B{1H}‐NMR data in aqueous (D2O) solution are δ = –12,70 ppm (1JB–H = 125 Hz), and δ = –15,7 ppm (linewidth: δν1/2 = 295 Hz) for the solid state 11B‐MAS‐NMR. 相似文献
9.
Bis(tetramethylammonium) dodecahydrododecaborate, [(CH3)4N]2[B12H12], and bis(tetramethylammonium) dodecahydrododecaborate acetonitrile, [(CH3)4N]2[B12H12] · CH3CN, were synthesized and characterized via Infrared, 1H and 11B NMR spectroscopy. [(CH3)4N]2[B12H12] crystallizes isopunctual to the alkali metal dodecaborates. The crystal structure of [(CH3)4N]2[B12H12] · CH3CN was determined from single crystal data and refined in the orthorhombic crystal system (Pcmn, no. 62, a = 898.68(8), b = 1312.85(9) c = 1994.5(1) pm, R(|F| , 4σ) = 5.9%, wR(F2) = 18.3%). Here, the geometry of the dodecaborate anion is that of an almost ideal icosahedron, less distorted than most other dodecaborates known. By low‐temperature Guinier‐Simon diffractometry phase transitions were detected for [(CH3)4N]2[B12H12] and [(CH3)4N]2[B12H12] · CH3CN at –70 and –15 °C, respectively. 相似文献
10.
11.
Several rare‐earth cyclotriphosphate hydrates were obtained from mixtures of sodium cyclotriphosphates and the respective rare‐earth chlorides. Nd(P3O9) · 3H2O [P$\bar{6}$ , Z = 3, a = 677.90(9), c = 608.67(9) pm, R1 = 0.016, wR2 = 0.038, 312 data, 36 parameters] was obtained by a solid state reaction and is isotypic with respective rare‐earth phosphate hydrates, while all the others adopt new structure types. Nd(P3O9) · 4.5H2O [C2/c, Z = 8, a = 1644.6(3), b = 756.11(15), c = 1856.1(4) pm, β = 97.25(3)°, R1 = 0.032, wR2 = 0.081, 1763 data, 194 parameters], Nd(P3O9) · 5H2O [P21/c, Z = 4, a = 773.75(15), b = 1149.1(2), c = 1394.9(3) pm, β = 106.07(3)°, R1 = 0.042, wR2 = 0.082, 1338 data, 194 parameters], Pr(P3O9) · 5H2O [P$\bar{1}$ , Z = 2, a = 745.64(15), b = 889.07(18), c = 934.55(19) pm, α = 79.00(3), β = 80.25(3), γ = 66.48(3), R1 = 0.059, wR2 = 0.089, 1468 data, 193 parameters], Na3Nd(P3O9)2 · 6H2O [P21/n, Z = 4, a = 1059.78(18), b = 1207.25(15), c = 1645.7(4) pm, β = 99.742(17), R1 = 0.047, wR2 = 0.119, 1109 data, 351 parameters] and Na3Pr(P3O9)2 · 6H2O [P21/n, Z = 4, a = 1061.42(16), b = 1209.0(2), c = 1635.5(3) pm, β = 99.841(13), R1 = 0.035, wR2 = 0.062, 1323 data, 350 parameters] were obtained by careful crystallization at room temperature. A thorough structure discussion is given. The infrared spectrum of Nd(P3O9) · 4.5H2O is also reported. 相似文献
12.
Dursun Ali Köse Birgül Zümreoglu‐Karan Prof. Dr. Tuncer Hökelek Ertan Sahin 《无机化学与普通化学杂志》2009,635(3):563-566
The structure of [B6H9NaO14, H3BO3, 6H2O] was determined by single‐crystal X‐ray diffraction and further analyzed by FTIR spectroscopy and differential thermal/thermogravimetric analysis. The asymmetric unit contains Na–O polyhedra (distorted octahedron), [B6O8(OH)3]– fundamental building blocks, one free water molecule and one free H3BO3 molecule. In the hexaborate anion, three B3O3 rings are linked by a common oxygen atom with five trigonal and one tetrahedral boron atoms. The hexaborate group is also linked to the oxygenated environment of the sodium atom by three other six‐membered rings, each of which involve two boron atoms, three oxygen atoms, and sodium as the joint atom. 相似文献
13.
Colourless octahedral single crystals of solvent‐free Ag2[B12Cl12] (cubic, Pa3¯; a = 1238.32(7) pm, Z = 4) are obtained by the metathesis reaction of Cs2[B12Cl12] with an aqueous solution of silver nitrate (AgNO3) and recrystallization of the crude product from water. The crystal structure is best described as a distorted anti‐CaF2‐type arrangement in which the quasi‐icosahedral [B12Cl12]2— anions (d(B—B) = d(B—Cl) = 177—180 pm) are arranged in a cubic closest‐packed fashion. The tetrahedral interstices are filled with Ag+ cations which are strongly displaced from their ideal positions. Thereby each silver atom gets coordinated by six chlorine atoms from the edges of three [B12Cl12]2— anions providing a distorted octahedral coordination sphere to the Ag+ cations (d(Ag—Cl) = 283—285 pm, CN = 6). 相似文献
14.
Dirk Hinz 《无机化学与普通化学杂志》2000,626(4):1004-1011
Complex Hydroxides of Chromium: Na9[Cr(OH)6]2(OH)3 · 6 H2O and Na4[Cr(OH)6]X · H2O (X = Cl, (S2)1/2) – Synthesis, Crystal Structure, and Thermal Behaviour Green plate‐like crystals of Na9[Cr(OH)6]2(OH)3 · 6 H2O (triclinic, P1, a = 872.9(1) pm, b = 1142.0(1) pm, c = 1166.0(1) pm, α = 74.27(1)°, β = 87.54(1)°, γ = 70.69(1)°) are obtained upon slow cooling of a hot saturated solution of CrIII in conc. NaOH (50 wt%) at room temperature. In the presence of chloride or disulfide the reaction yields green prismatic crystals of Na4[Cr(OH)6]Cl · H2O (monoclinic, C2/c, a = 1138.8(2) pm, b = 1360.4(1) pm, c = 583.20(7) pm, β = 105.9(1)°) or green elongated plates of Na4[Cr(OH)6](S2)1/2 · H2O (monoclinic, P21/c, a = 580.8(1) pm, b = 1366.5(3) pm, c = 1115.0(2) pm, β = 103.71(2)°), respectively. The latter compounds crystallize in related structures. All compounds can be described as distorted cubic closest packings of the anions and the crystal water molecules with the cations occupying octahedral sites in an ordered way. The thermal decomposition of the compounds was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In all cases the final decomposition product is NaCrO2. 相似文献
15.
Andreas Fischer 《无机化学与普通化学杂志》2003,629(6):1012-1016
By slow evaporation of solutions containing UO2(ClO4)2 and an excess of HClO4, single crystals of [UO2(ClO4)2(H2O)3] ( 1 ) and [UO2(H2O)5](ClO4)2 ( 2 ) were obtained and their structures were determined. From similar solutions prepared from stoichiometric amounts of UO3 and perchloric acid, crystals of [UO2(H2O)5](ClO4)2·2H2O ( 3 ) were obtained. The trihydrate (monoclinic, P21/c, a = 545.44(1) pm, b = 1811.09(5) pm, c = 1032.46(2) pm, β = 90.016(1)°) consists of uranyl ions, which are coordinated by two monodentate perchlorate ions and three water molecules. The pentahydrate (monoclinic, P21/n, a = 529.35(2) pm, b = 1645.43(6) pm, c = 1480.18(6) pm, β = 99.847(1)°) contains uranyl ions coordinated by five water molecules. The same structural unit can be found in the heptahydrate, whose structure was re‐determined (orthorhombic, Pbcn, a = 920.9(3) pm, b = 1067.9(3) pm, c = 1445.7(3) pm). In this structure, two molecules of water of crystallization are present. 相似文献
16.
The deprotonation of the nido‐anion [B11H14]– by two equivalents of LitBu yields the anion [B11H12]3–. Three observed 11B NMR shifts of this anion in the ratio 1 : 5 : 5 are in agreement with shifts calculated by the GIAO method on the basis of the ab initio computed geometry. The deprotonation can be reversed, giving back [B11H14]– via [B11H13]2–. The thermolysis of [Li(thp)x]3[B11H12] in thp at 80 °C leads to the closo‐borate [Li(thp)3]2[B11H11] under elimination of LiH. Anhydrous air transforms [B11H12]3– into the known oxa‐nido‐dodecaborate [OB11H12]–. The rhoda‐closo‐dodecaborate [L2RhB11H11]3– is formed from [B11H12]3– and RhL3Cl (L = PPh3). 相似文献
17.
Reactions of K4[SnSe4], Na4[GeS4] or Ba2[GeSe4] with different 1,2‐diaminoethane (= en) coordinated complexes of CrCl3 ([Cr(en)2Cl2]Cl or [Cr(en)3]Cl3) in MeOH or aqueous solution yielded three novel compounds that contain complexes of Cr3+ with ortho‐chalcogenotetrelate anions [E′E4]4? (E′ = Ge, Sn; E = S; Se): the crystal structures of [K6(MeOH)9][Sn2Se6][Cr(en)2(SnSe4)]2 ( 1 ), [Na(H2O)4][Cr(en)3]2[GeS3OH]2[Cr(en)2(GeS4)] ( 2 ), and [Ba(H2O)10][{Cr(en)}2(GeSe4)2] ( 4 ) have been determined by means of single crystal X‐ray diffraction ( 1 : triclinic space group ; lattice dimensions at 203 K: a = 1175.7(2), b = 1315.3(3), c = 1326.7(3) pm, α = 61.99(3)°, β = 64.05(3)°, γ = 83.57(3)°, V = 1617.4(6)·106 pm3; R1 [I > 2σ(I)] = 0.0788; wR2 = 0.1306; 2 : monoclinic space group C2/c; lattice dimensions at 203 K: a = 2445.3(5), b = 1442.5(3), c = 1579.3(3) pm, β = 94.61(3)°, V = 5552.9(19)·106 pm3; R1 [I > 2σ(I)] = 0.0801; wR2 = 0.2046; 4 : triclinic space group ; lattice dimension at 203 K: a = 1198.4(2), b = 1236.8(3), c = 1297.5(3) pm, α = 65.69(3)°, β = 63.35(3)°, γ = 81.21(3)°, V = 1565.2(5)·106 pm3; R1 [I > 2σ(I)] = 0.0732; wR2 = 0.1855). 1 and 2 show the yet unprecedented complexation of transition metal ions by non‐bridging, single chalcogenotetrelate ligands to produce dinuclear, heterobimetallic complexes. Compound 2 contains the first structurally characterized complex with an ortho‐thiogermanate ligand. The formation of these compounds, and of a by‐product of 2 , [Cr(en)3][GeS3OH]·6H2O ( 3 : monoclinic space group C2/c; lattice dimensions at 203 K: a = 2396.8(5), b = 1463.4(3), c = 1740.1(4) pm, β = 132.99(3)°, V = 4463.8(15)·106 pm3; R1 [I > 2σ(I)] = 0.0462; wR2 = 0.1058), provides some insight in fundamental differences between the reaction behavior of [SnE4]4? anions one the one hand and [GeE4]4? anions on the other hand. The crucial role of the counterion charge becomes evident when comparing the structure motifs of the ternary anions in 1 and 2 with that observed in the Ba2+ compound 4 . 相似文献
18.
A new chemical and structural interpretation of K5Ce2(SO4)6·H2O ( I ) and a redetermination of the structure of K2Ce(SO4)3·H2O ( II ) is presented. The mixed‐valent compound I crystallizes in the space group C2/c with a = 17.7321(3), b = 7.0599(1), c = 19.4628(4) Å, β = 112.373(1)° and Z = 4. Compound I has been discussed earlier with space group Cc. In the structure of I , there are pairs of edge sharing cerium polyhedra connected by sulfate oxygen atoms in the μ3 bonding mode. These cerium dimers are linked through edge and corner sharing sulfate bridges, forming layers. The layers are joined by potassium ions which together with the water molecules are placed between the layers. No irregularity in the distribution of the CeIII and CeIV to cause the lost of a crystallographic center of symmetry was detected. We suggest that the charge exerted by the extra f1 electron for every cerium dimer is delocalized over the Ce1–O2–Ce2 moiety in a non‐bonding mode. As a result, the oxidations state of each cerium ion is a mean value between III and IV at each atomic position. Compound II crystallizes in the space group C2 with a = 20.6149(2), b = 7.0742(1), c = 17.8570(1) Å, β = 122.720(1)° and Z = 8. The hydrogen atoms have been located and the absolute structure has been established. Neither hydrogen atom positions nor anisotropic displacement parameters were given in the previous reports. In compound II , the cerium polyhedra are connected by edge and corner sharing sulfate groups forming a three‐dimensional network. This network contains Z‐shaped channels hosting the charge compensating potassium ions. 相似文献
19.
The crystal structure of RbTlI4·2H2O (cubic, , Nr. 226, Z = 24, a = 1993.5(2) pm, 327 unique reflections with Io > 2σ(Io), R1 = 0.0305, wR2 = 0.0702, GooF = 1.1199, T = 298(2) K) is characterized by an ReO3 analogous arrangement of rubidium centered [TlI4] tetrahedra. The cuboctahedral cavities of this structure are filled with crystal water molecules and additional disordered rubidium cations. 相似文献
20.
K2[CrF5·H2O] is monoclinic: a = 9.6835(3) Å, b = 7.7359(2) Å, c = 7.9564(3) Å, β = 95.94(1)°, Z = 4, space group C2/c (no 15). Its crystal structure was solved from its X‐ray powder pattern recorded on a powder diffractometer, using for the refinement the Rietveld method. It is built up from isolated octahedral [CrF5·OH2]2? anions separated by potassium cations. The dehydration of K2[CrF5·H2O] leads to anhydrous orthorhombic K2CrF5: a = 7.334(2) Å, b = 12.804(4) Å, c = 20.151(5) Å, Z = 16, space group Pbcn (no 60), isostructural with K2FeF5. 相似文献