J. X. Mi

Crystal structure of sodium gallium [monohydrogenmonophosphate-dihydrogenmonoborate-monophosphate],NaGa[BP2O7(OH)3]

BGaH3NaO10P2, monoclinic, C12/c1 (No. 15), a = 10.408(3) A, b = 8.094(2) A, c = 9.099(2) A, = 116.64(2)°, V = 685.2 A, Z = 4, Rgt(F) = 0.025, wRref(F ) = 0.068, T = 293 K. Source of material NaGa[BP2O7(OH)3] was synthesized under mild hydrothermal conditions. The reaction was carried out with mixtures of Ga metal (0.139 g) dissolved in 1ml of HCl (18%) with Na2HPO4·12H2O (1.075 g) and Na2B4O7·10H2O (0.4767 g) (molar ratio of Ga:P:B = 2:3:6) in aqueous solution. The mixture was sealed in glass tubes (after adding 1 ml H2O to achieve a degree of filling of 30%) with subsequent heating at 408 K for 60 days. The starting materials are all of analytical grade. Discussion With the increasing interest in microporous materials, synthesis of compounds like borophosphates with open framework structure have drawn much attention during the past few years and show a rich crystal chemistry [1]. Systems including a p-block metal have not been widely explored up to now besides one Al compound [2] reported only recently. The structure of the title compound is isotypic to the Fe [3] and Al analogues [2] and is characterized by isolated GaO4(OH)2 octahedra sharing common O-corners with phosphate and common O(OH)-corners with hydrogenborate groups from the ol igomeric uni ts [B2P2O7(OH)3]. The condensation of the borophosphate oligomers with Ga-coordination octahedra via common corners results in an overall three-dimensional framework which contains elliptical channels running along the [001] direction. The cross section of the channels is defined by eight-membered octahedral/tetrahedral rings (four Ga coordination octahedra, two phosphateand two borate-groups). Sodium ions are distributed within the open channels. The Ga—O bond distances are 1.925 and 1.965 A, while the Ga—OH value is increased to 1.995 A. The bond distances P—O and B—O in the oligomeric borophosphate groups correspond to respective values in the Feand Al-analogues [2,3]. Z. Kristallogr. NCS 216 (2001) 15–16 15

Crystal structure of sodium indium (monohydrogenmonophosphate- dihydrogenmonoborate-monophosphate), NaIn(BP2O7(OH)3)

B4H12In4Na4O40P8, monoclinic, C12/c1 (No. 15), a = 10.368(2) A, b = 8.520(1) A, c = 9.415(2) A, = 115.951(5)°, V = 747.8 A, Z = 1, Rgt(F) = 0.076, wRref(F) = 0.202, T = 293 K. Source of material NaIn[BP2O7(OH)3] was synthesized under mild hydrothermal conditions. The reactions were carried out with mixtures of In metal (0.230 g) dissolved in 1 ml of HCl (18%), Na2HPO4 · 12H2O (1.074 g) and Na2B4O7 · 10H2O (1.525 g) (molar ratio of In:P:B = 2:3:16) in aqueous solution. The mixtures were sealed in glass tubes (after adding 1 ml H2O to achieve a degree of filling of 30%) with subsequent heating at 408 K for 90 days. The starting materials were all of analytical purity grade. Experimental details The quality of the crystal studied was not good enough, which is reflected in the resulting high R-values. Discussion The synthesis of compounds like borophosphates with open framework structures has drawn much attention during the past few years due to their potential applications as microporous materials. The variety of crystal structures known up to now already shows a rich crystal chemistry [1]. Systems including a p-block metal have not been widely explored besides one Al [2] and one Ga [3] compound reported only recently. Two In containing phases are published in this issue [4,5]. The structure of the title compound is isotypic to the Fe [6], Al and Ga analogues [2,3] and is characterized by isolated InO4(OH)2 octahedra sharing common O-corners with hydrogen phosphate and common O(OH)-corners with hydrogenborate groups from the oligomeric units [BP2O7(OH)3]. The condensation of the borophosphate oligomers with In-coordination octahedra via common corners results in a three-dimensional framework which contains elliptical channels running along the [001] direction. The cross section of the channels is defined by eight-membered octahedral/tetrahedral rings (four In coordination octahedra, two hydrogen phosphateand two hydrogen borate-groups). Sodium ions are distributed within the open channels. The In—O bond distances 2.082 A and 2.110 A are shorter than the In—OH value (2.189 A). The bond distances P—O and B—O in the oligomeric borophosphate groups correspond to respective values in the Gaand Al-analogues [2,3] and other In compounds [4,5]. Z. Kristallogr. NCS 217 (2002) 7–8 7

Crystal structure of ammonium indium (monophosphate-hydrogenmonoborate-monophosphate), (NH4)In[BP2O8(OH)]

BH5InNO9P2, triclinic, P1 (No. 2), a = 5.2980(4) A, b = 8.4880(4) A, c = 8.3901(5) A, = 93.077(5)°, = 93.331(6)°, = 80.634(5)°, V = 371.3 A 3 , Z =2 , Rgt(F) = 0.038, wRref(F 2 ) = 0.091, T = 293 K.

Crystal structure of rubidium indium (monophosphate-hydrogenmonoborate-monophosphate), RbIn[BP2O8(OH)]

Abstract BHInO 9 P 2 Rb, triclinic, P 1 (No. 2), a = 5.3157(5) A, b = 8.3209(8) A, c = 8.4840(7) A, = 87.35(1)°, = 80.23(1)°, = 86.78(1)°, V = 369.0 A 3 , Z =2, R gt (F) = 0.042, wR ref (F 2 ) = 0.086, T = 295 K. Source of material RbIn[BP 2 O 8 (OH)] was synthesized under mild hydrothermalconditions. The reactions were carried out with mixtures of InCl 3 (1.1058 g), H 3 BO 3 (0.9277 g), RbOH (6.15 g) and 1.5ml H 3 PO 4 (85%)withmolarratioRb:In:B:P=1:3:4.1.0mlHCl(37%)wasaddedtoadjustthepHvalueas1.5.Themixturewasfilledin10 ml teflon autoclaves (filling degree 60%) and heated at 443 Kfor 10 days under autogenous pressure. The chemical composi-tionwasconfirmedbychemicalanalysis.IRspectroscopicinves-tigations show the presence of OH groups. Discussion Although systematic investigations in borophosphates have onlybeencarriedoutinrecentyears,alargenumberofnewborophos-phates has already been reported [1]. In our extensive studies ongallium and indium systems, several new compounds have beencharacterized recently [2–4].Thestructureofthetitlecompoundisisotypictothatof theK–Fe[5],NH

Crystal structure of ammonium indium di(hydrogenmonophosphate), (NH4)In[PO3(OH)]2

H6InNO8P2, monoclinic, P121/c1 (No. 14), a = 9.6004(4) A, b = 8.2820(4) A, c = 9.6693(3) A, = 116.205(4)°, V = 689.8 A 3 , Z =4 ,Rgt(F) = 0.040, wRref(F 2 ) = 0.104, T = 295 K. Source of material (NH4)In[P2O6(OH)2] was synthesized under mild hydrothermal conditions. The reactions were carried out with mixtures of InCl3, LiCl·H2O, NaBO2·4H2O and (NH4)H2PO4 with the molar ratio of 1:4:9:6 in aqueous solution. The mixture was sealed in 20 ml glass tube. The pH value of the solution was about 0.2. The filling of the solution were about 30% of the glass tubes. The glass tubes were placed in an oven with subsequent heating at 413 K for 7 days. The starting materials are all of analytical grade and used without further purification. Discussion There was only one ammonium-indium phosphate [1] and one ammonium-indium borophospahte [2] reported up to now and the title compound is another indium phosphate with ammonium cation obtained as a by-product of new borophosphate, NaIn[BP2O8(OH)] [3]. The title compound has a new structure type which is characterized by isolated InO6 octahedra sharing common O-corners with six isolated PO3(OH) tetrahedra to form a three-dimensional network structure. Every PO3(OH) tetrahedron shares common O-corners with three InO6 octahedra besides the terminal OH group. In the structure, there are eight-membered rings formed by four InO6 octahedra and four hydrogenphosphate tetrahedra. Ammonium groups are distributed within the open elliptical channels running along the a axis. In InO6 octahedron the In—O bond distances range from 2.107 A to 2.168 A. Bond lengths and angles of hydrogenphosphate PO3(OH) tetrahedra are similar to other phosphates.

Crystal structure of potassium indium (monophosphate-hydrogenmonoborate-monophosphate), KIn[BP2O8(OH)]

BHInKO9P2, triclinic, P1 (No. 2), a = 5.2638(4) A, b = 8.4791(5) A, c = 8.1469(9) A, = 91.741(7)°, = 93.061(7)°, = 79.823(5)°, V = 357.3 A, Z = 2, Rgt(F) = 0.052, wRref(F) = 0.113, T = 293 K. Source of material KIn[BP2O8(OH)] was synthesized under mild hydrothermal conditions. The reactions were carried out with mixtures of In metal (0.057 g) dissolved in 1 ml of HCl (18%), H3BO3 (0.062 g) and K2HPO4 (0.522 g) (molar ratio of In:P:B = 1:2:3) in aqueous solution. The mixtures were sealed in glass tubes (after adding 1 ml H2O to achieve a degree of filling of 30%) with subsequent heating at 418 K for 14 days. The starting materials were all of analytical purity grade. Discussion With the increasing interest in microporous materials, the syntheses of compounds like borophosphates with open framework structures have drawn much attention during the past few years and show a rich crystal chemistry [1]. Systems including a p-block metal have not been widely explored up to now besides two compounds with Al and Ga [2,3] reported only recently and two phases with In in the present issue [4,5]. The structure of the title compound is isotypic to the K-Fe [6] and ammonium-In analogues [5]. The structure is characterized by isolated InO5(OH) octahedra sharing common O-corners with phosphate and common O(OH)-corner with hydrogenborate groups from the trinuclear oligomeric units [B2P4O16(OH)2]. The condensation of the borophosphate oligomers with In-coordination octahedra via common corners results in a three-dimensional framework which contains elliptical channels running along the a axis. The cross section of the channels is defined by eight-membered octahedral/tetrahedral rings (two In coordination octahedra, four phosphateand two borate-groups). Potassium ions are distributed within the open channels. The In—O and In—OH bond distances range from 2.110 A to 2.179 A. Both the oligomeric borophosphate and the coordination octahedron of In are similar to its K-Feand NH4-In-analogues [5,6] by considering the bond distances In—O, P—O and B—O and bond angles. Z. Kristallogr. NCS 217 (2002) 3–4 3

Crystal structure of sodium tetratin(II) triphosphate, NaSn4(PO4)3

NaO 12 P 3 Sn 4 , trigonal, R3c (no. 161), a = 9.594(1) A, c = 24.186(5) A, V= 1927.8 A 3 , Z= 6, R gt (F) = 0.023, wR ref (F 2 ) = 0.056, T= 293 K.

Crystal structure of dicesium aquapentachlorochromate(III), Cs2[CrCl5(H2O)]

Cl 5 CrCs 2 H 2 O, orthorhombic, Cmcm (no. 63), a = 7.4297(6) A, b = 17.234(1) A, c = 8.0121(6) A, V = 1025.9 A 3 , Z = 4, R gt (F) = 0.041, wR ref (F 2 ) = 0.082, T = 295 K.

Crystal structure of the α-modification of caesium gallium(III) monohydrogen triphosphate, α-CsGaHP3O10

CsGaHO10P3, monoclinic, C121 (No. 5), a = 9.061(1) A, b = 8.7105(9) A, c = 6.2195(8) A, = 111.993(6)°, V = 455.2 A, Z = 2, Rgt(F) = 0.018, wRref(F) = 0.046, T = 295 K. Source of material The title compound was synthesized in aqueous solution by two steps. In the first step, the reaction was carried out with the mixture of GaCl3(1.046 metal gallium dissolved in 5 ml 37% HCl), CsCl (2.525 g) and an excess of HCl (molar ratio Ga : Cs = 1 : 1). The mixture was heated to the boiling point. While it was cooled down and evaporated in air for several days, transparent colorless crystals were obtained. After filtering from liquid, they were identified to be CsGaCl4 [1], and it was confirmed by X-ray powder diffraction. On the second step, the reaction was made with the mixture of CsGaCl4 (3.44 g), Cs(OH) · H2O (1.679 g) and 5 ml 85% H3PO4 (molar ratio 1:1:7). The starting materials were all of analytical grade. The mixture was heated (open system) to the boiling point on stove and kept heating for three days to evaporate the solvent. Three modifications of crystals of CsGaHP3O10 were obtained in the reaction product. The -modification showed in block shape; 3M-modification in thick plate and 1M-modification in thin plate. All of them were colorless and transparent. The 2O-modification reported by Anisimova (1995) as IIICsGaHP3O10 was not found in these products indicating that it should have different synthetic conditions or a different stability temperature range. Experimental details The position of the H atom was determined from a difference Fourier map.

Crystal structure of caesium gallium(III) catena-[monohydrogenmonoborate-bis(monophosphate)], CsGa[BP2O8(OH)]

BCsGaH09P2, monoclinic, P12i/cl (No. 14), a = 9.259(1) Á, è = 8.6462(9) Â, c = 9.615(1) k,ß= 103.059(6)°, V= 749.8 Â > Rgi(F) = 0.050, wRrei(F) = 0.104, T= 295 K. Correspondence author (e-mail: jtzhao@mail.sic.ac.cn) Source of material CsGa[BP208(0H)] was synthesized under mild hydrothermal conditions. The reactions were carried out with mixtures of Cs(OH) · H 2 0 ( 1.679 g), GaCl3 (0.35 g metal gallium dissolved in 2 ml 37% HCl), H3BO3 (0.618 g), LÌH2PO4 (3.118 g) and 2 ml 85% H3PO4 with molar ratio of Cs : Ga : Β : Li : Ρ = 2 : 1 : 2 : 6 : 1 2 . The mixture was filled in a teflon autoclave with about 20 ml in volume. The degree of filling was about 50%. The autoclave was placed in an oven with subsequent heating at 443 Κ for 7 days. All starting materials were of analytical grade purity. The composition was confirmed by chemical analysis (ICP) with Cs : Ga : Β : Ρ = 0.9(1):1.02(1):0.91(2):2.00(3). The Li content was below the detective limit of the analytical method. Experimental details The position of the Η atom was determined from a difference Fourier map. Discussion In our recent investigations on Ga-containing borophosphates, mild hydrothermal conditions have been proved to be efficient in preparing new compounds with different structures, such as NaGa[BP207(0H)3], KGa[BP207(0H)3] , (NH4)Ga[BP208(0H)] and RbGa[BP208(0H)] [1-4]. The title compound was also synthesized under mild hydrothermal conditions. The crystal structure of the title compound is isotypic to CsFe[BP 2 Os(OH)] [5] and contains isolated G a 0 5 ( 0 H ) octahedra sharing common O-corners with five phosphate tetrahedra and a common (OH)-corner with a hydrogenborate group to form a three dimensional framework structure. The anionic partial structure consists of open-branched vierer-single chains [ΒΡ2Οδ(ΟΗ)], which are formed by alternating hydrogenborate and phosphate tetrahedra sharing common O-corners. The [BP 20 8 (0H)] n chains run along the b axis and are connected via GaC>5(OH) octahedra sharing common corners. The caesium cations are distributed in a zigzag arrangement within the open channels with an elliptical cross-section and running along the a axis. Caesium has ten oxygen neighbours with distances ranging from 3.070 À to 3.308 Â. The Ga—O and Ga—OH bond distances in the Ga-coordinaton-octahedron range from 1.909 A to 2.117 Â. The Ρ—O bond distances range from 1.512 A to 1.572 A, and those of Β—O from 1.458 Á to 1.490 Â. Β ond lengths and angles of hydrogenborate and phosphate tetrahedra within the anionic chains are in the same ranges as observed in other borophosphates [1-4].