Crystals of triammonium cyclo-tri-μ-imido-triphosphate monohydrate, (NH4)3(PO2NH)3.H20, are composed of three ammonium cations, a trimetaphosphimate anion with a chair conformation and a water molecule per asymmetric unit. A three-dimensional network is formed by N--H...O and O--H...O hydrogen bonds

Schnick, Wolfgang

Stock, Norbert

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N. Stock

W. Schnick

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Acta Crystallographica Section C Crystal Structure Communications

Triammonium Trimetaphosphimate Monohydrate

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2645 INORGANIC COMPOUNDS Acta Cryst. (1996). C52, 2645-2647 Triammonium Trimetaphosphimate Monohydrate NORBERT STOCK AND WOLFGANG SCHNICK Laboratoriurn fi~r Anorganische Chernie der Universit~t, Universit~tsstrasse 30, D-95440 Bayreuth, Germany. E-mail: wolfgang.schnick @ uni-bayreuth, de (Received 23 April 1996," accepted 24 May 1996) Abstract Crystals of triammonium cyclo-tri-#-imido-triphosphate monohydrate, (NH4)3(PO2NH)3.H20, are composed of three ammonium cations, a trimetaphosphimate nion with a chair conformation and a water molecule per asymmetric unit. A three-dimensional etwork is formed by N- -H. . .O  and O- -H. . .O  hydrogen bonds. Comment In order to synthesize silicate-analogous framework structures built up from PN4 tetrahedra (Schnick, Horstmann & H~iser, 1996) with a defined partial substi- tution of nitrogen by oxygen, we have started a system- atic investigation of soluble P-O-N compounds (Stock & Schnick, 1996) and have now isolated the title com- pound, (I). O. n....NH.~ ,O ?o HN~p~NH 6o (i) -53 .H20 Although many salts of trimetaphosphimic acid with monovalent cations have been described from as early as 1895 (Stokes, 1895) and characterized (Herzog & Nielsen, 1958), only the crystal struc- tures of Na3(PO2NH)3.4H20, H3(PO2NH)3.2H20 and (NH4)H2(PO2NH)3.CH3OH have been reported (At- tig & Mootz, 1976; Olthof, Migchelsen & Vos, 1965). Trimetaphosphimate salts with divalent and trivalent cations have also been described (Sokol, Porai-Koshits, Berdnikov, Rozanov & Butman, 1979; Rozanov, Medvedeva, Beresnev, Sokolov & Sokol, 1981). The molecular structure of the title compound is shown in Fig. 1. In contrast to H3(PO2NH)3.2H20 and (NHn)H2(PO2NH)3.CH3OH but in analogy to Na3(PO2NH)3.4H20, the P-N ring in the title com- pound exhibits the approximate symmetry 3m, as may © 1996 International Union of Crystallography Printed in Great Britain - all rights reserved be seen from the bond lengths and valence angles. As observed in the sodium salt, one imido H atom causes a reduction of the symmetry of the anion to m. This arises from intermolecular hydrogen bonds (Attig & Mootz, 1976). Each H atom of the imido groups is involved in N- -H. . .O  hydrogen bonding [N.--O 2.884(1), 2.910(1), 2.813 (1)A], thus forming a three- dimensional network (Fig. 2). In addition, all the H atoms of the water molecule and the ammonium cations form O- -H. . .O and O- -H. . .N  hydrogen bonds [N...O 2.731 (1)-2.997 (1)A; O.. .O 2.862(1) and 2.812 (1) A] (Table 3). In analogy to (NH4)H2(PO2NH)3.CH3OH, the ammonium cations are distorted from ideal tetrahedral geometry. C• o6 o4 Fig. I. Structure of (I) showing 50ck probability displacement ellipsoids. H atoms are drawn as small circles of arbitrary size. Fig. 2. View of the crystal packing of the trimetaphosphimate rings and the water molecules illustrating the hydrogen bonds. The ammonium ions are omitted for clarity. Acta Co'stallographica Section C ISSN 0108-2701 © 1996 2646 (NH4)3(PO2NH)3 .H20 Exper imenta l  oJ O2 The starting material Na3(PO2NH)3.4H20 was obtained ac- o3 cording to the method of Nielsen & Morrow (1960). Ammo- 04 nium trimetaphosphimate was prepared by a similar method 05 to that of Stokes (1896). To a 3 x 10-4M solution of o6 07 Ag3(PO2NH)3 in water and ammonia a stoichiometric amount N I of NH4Br was added and the precipitated AgBr was removed. N2 Ag3(POeNH)3 was obtained by the addition of excess 0.1 M N3 AgNO3 to a 3 x 10-4M solution of Na3(PO2NH)3.4H20. N4 N5 Suitable crystals were grown by diffusion-controlled addition N6 of methanol to a 1 x 10 -4  M solution of trimetaphosphimate monohydrate in water. Crystal data (Nit4)3 (PO2 NH)3. H20 Mr = 306.11 Monoclinic P21 a = 6.5712 (6) ,~ b = 12.9917 (6)o,4, c = 6.9237 (3) A /3 = 102.133 (6) ° V 577.88 (6) A 3 Z=2 Dx = 1.759 Mg m -3 Om not measured Mo Ka radiation A = 0.71073,4, Cell parameters from 49 reflections 0 = 6.1-15.16 ° # = 0.549 mm-  T = 153 (2) K Platelet 0.50 x 0.45 × 0.2 mm Colourless Data collection Siemens P4 diffractometer 03 SCanS Absorption correction: none 3517 measured reflections 3106 independent reflections 3048 observed reflections [I > 2o(/)] Rint = 0.0129 Refinement Refinement on F 2 R[F 2 > 2o'(F2)] = 0.0167 wR(F 2) = 0.0447 S= 1.129 3106 reflections 163 parameters H atoms refined using a riding model starting from Fourier coordinates w = 1/[o'2(F 2) + (0.0671P) 2+ 0.9697P] where P = (F,~ + 2F,.2)/3 (A/o')m.x = -0.001 Apmax = 0.385 e ~-3  Apmi ,  = -0 .266  e ~-3  0max = 29.28  ° h= -9 - - ,8  k = - 17 ~ 17 l = -9  ---~ 9 3 standard reflections monitored every 97 reflections intensity decay: 4.22% Extinction correction: SHELXL93 (Sheldrick, 1993) Extinction coefficient: 0.169 (4) Atomic scattering factors from International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) Absolute configuration: Flack (1983) Flack parameter = -0 .07  (5) Table 1. Fractional atomic coordinates and equivalent isotropic displacement parameters (~ e ) 1 * * Ueq = ( /3)Y] iY] jUi ja t aj ai.a). X V Z Ucq PI 0.02535 (4) 0.33316 (2) 0.72015 (4) 0.00744 (6) P2 0.10742 (4) 0.19652 (2) 1.07928 (4) 0.00771 (7) P3 --0.25397 (4) 0.33577 (2) 0.99785 (4) 0.(X)800 (6) 0.16375 (13) 0.41095 (7) 0.64863 (12) 0.0119 (2) -0.10457(13)  0.26666(7) 0.56206(11) 0.0118(2) -0.0006 (2) 0.09673 (6) 1.00781 (14) 0.0131 (2) 0.30004(13) 0.18524(7) 1.24027(12) 0.0136(2) -0.34141 (14) 0.41494(7) 1.11523(13) 0.0133(2) -0.39934(13) 0.25751 (7) 0.88222(13) 0.0136(2) 0.4847 (2) 0.09424 (8) 1.60331 (15) 0.0241 (2) 0.17490 (15) 0.25983 (8) 0.89190 (14) 0.0094 (2) -0.0590 (2) 0.27646 (8) I. 15341 (14) 0.0117 (2) -0.1355 (2) 0.39647 (8) 0.83702 (14) 0.0085 (2) 0.0383 (2) 0.06228 (8) 0.6223 (2) 0.0170 (2) -0.6011 (2) 0.55749 (81 09022 (2) 0.0147 (2) 0.4845 (2) 0.35738 (8) 1.4433 (2) 0.0156 (2) Table 2. Selected geometric parameters (A, °) PI---O2 P1--O1 P I - -N I  P I - -N3 P2_ - -04  P2--O3 O2--P 1 - -O  I O2- -P1- -N I O I - -P1 - -N I  O2--P1--N3 OI - -P I - -N3  N I - -P I - -N3  O4- -P2- -O3 O4---P2--N2 O3- -P2- -N2 O4----P2--N IO3- -P2 - -N  I .5101 (8) P2--N2 .5110(9) P2--NI  .6721 ( I 0) P3~5 .6758 ( I 0) P3---O6 .5077 (9) P3--N2 .5100 (9) P3--N3 15.63 (5) N2- -P2- -N  1 10.35 (5) O5- -P3- -O6 08.05 (5) O5- -P3- -N2 108.24 (5) O6- -P3- -N2 108.31 (5) O5- -P3- -N3 105.80 (5) O6---P3--N3 114.98 (6) N2- -P3- -N3 109.66 (5) P I - -N  I - -P2 110.03 (6) P2- -N2- -P3 107.64 (5) P I - -N3- -P3  110.54 (5) .6654 (10) .6728 (10) .4983 (9) .5052 (9) .6779 ( I 0) .6830 (10) 103.34 (5) 118.64 (5) 107.17 (5) 110.17(5) 108.70 (5) 107.14 (5) 100.06 (5) 128.29 (6) 123.42 (6) 121.06 (6) Table 3. Hydrogen-bonding geometry (ft, o) D---H- • .A NI - -H I .  • .O6' N2--H2. • .02" N3--H3. • .03"' N4--H4A- -O I" N4---H4B. .03 N4--H4C. .02 N4--H4D. .07'  N5--H5A- -04'" N5--H5B. .O1" N5--H5C. .05 N5--H5D. .06"' N5--H5D- .03"' N6--H6A- -O 1" N6--H6B. -05' N~-H6C.  .04 N6--H6D. .02 TM O7--H7A- .04 O7--H7B. .O6'" D- -H  D- - -A 0.799(1) 2.813(1) 0.872(I)  2.910(1) 0.887 ( 1 ) 2.884 ( 1 ) 0.830 ( 1 ) 2.846 ( 1 ) 0.840 ( 1 ) 2.771 ( I ) 0.795(I)  2.818(I) 0.855 ( 1 ) 2.993 (2) 0.908 ( 1 ) 2.909 ( 1 ) 0.934 ( 1 ) 2.820 ( I ) 0.913(1) 2.731 (1) 0.747 ( 1 ) 2.997 ( I ) 0.747(1) 2.861 (1) 0.761 (I) 2.865(I) 0.893 ( I ) 2.849 ( 1 ) 0.865 ( I ) 2.780 ( 1 ) 0.809 ( 1 ) 2.902 ( 1 ) 0.776(1) 2.812(I) 0.855 ( I ) 2.862 ( 1 ) Symmetry  codes: (i) 1 + x ,y ,z ;  (ii) (iv) -x ,  3' - ~, 1 - z; (v) x, 3', z - 1" H- • -A D- -H-  - -A 2.021(1) 171.1(I) 2.003(I) 172.9(I) 2.003(1) 172.2(1) 2.016(1) 177.2(1) 1.985 ( 1 ) 155.4 ( I ) 2.052(I) 161.8(I) 2.157(2) 165.8(I) 2.043(1) 158.9(1) 1.903(I) 167.1 (I) 1.842 ( 1 ) 163.7 ( 1 ) 2.371 (I) 142.3 I) 2.343 (1) 127.7 I) 2.127(1) 163.8 I) 2.089 ( 1 ) 142.4 1 ) 1.936(I) 164.8 1) 2.137(I) 157.7 1) 2.038 ( I ) 175.3 1 ) 2.030(1) 164.0 I) x ,y ,  ! + z: (i i i) -x ,  ~ + y, 2 - z: (v i )x -  l , y, z; (vii) l+x ,y , l+-  The absolute structure was checked by refinement of the Flack (1983) parameter and revealed to be correct. The origin was fixed by the method of Flack & Schwarzenbach (1988). All H atoms could be unambiguously located after the anisotropic refinement of all non-H atoms. The w-scan width was 1.2 ° with an w-scan rate of 2.5 ° min -~ . The background-to-signal ratio was 0.5. Data collection: XSCANS (Siemens, 1994). Cell refinement: XSCANS. Data reduction: SHELXTL/PC (Sheldrick, 1994). Program(s) used to solve structure: SHELXTL/PC. Program(s) used to refine structure: SHELXTL/PC. Molecular graphics: SHELXTL/PC. Software used to prepare material for publica- tion: SHELXTL/PC. NORBERT STOCK AND WOLFGANG SCHNICK 2647 Financial support by the Deutsche Forschungsgemein- schaft (project SCHN 377/6-1 and Gottfried Wilhelm Leibniz program) and the Fonds der Chemischen Indus- trie is gratefully acknowledged. Lists of structure factors, anisotropic displacement parameters, H- atom coordinates and complete geometry have been deposited with the IUCr (Reference: JZ1139). Copies may be obtained through The Managing Editor, International Union of Crystallography, 5 Abbey Square, Chester CH! 2HU, England. nite metaphosphate chains and isolated MO6 octahedra. Associated with the superstructure generally found for this structure type, in which the monoclinic b axis is tripled, three crystallographically different CrO6 octahe- dra of almost ideal geometry [dave(Cr'-'-O) = 1.96 (2) ,&] were observed. Within the two independent metaphos- phate chains distinctly different bond distances from P to bridging and terminal O atoms were found [d~ve(P-- Ob) - -  1 .58(1) ,  dave(P-'--O,) = 1.49 (1) ,~]. References Attig, R. & Mootz, D. (1976). Z. Anorg. Allg. Chem. 419, 139-156. Flack, H. D. (1983). Acta C~st. A39, 876-881. Fiack, H. D. & Schwarzenbach, D. (1988). Acta Cryst. A44, 499-506. Herzog, A. H. & Nielsen, M. L. (1958). Anal. Chem. 30, 1490-1496. Nielsen, M. L. & Morrow, T. J. (1960). lnorg. Synth. 6, 99. Ohhof, R., Migchelsen, T. & Vos, A. (1965). Acta Cryst. 19, 596-603. Rozanov, I. A., Medvedeva, Y. La., Beresnev, E. N., Sokolov, Yu. A. & Sokol, V. I. (1981). Zh. Neorg. Khim. 26, 668-676. Schnick, W., Horstmann, S. & H~iser, M. (1996). Phosphorus Sulfur, 109/110, 93-96. Sheldrick, (3. M. (1993). SHELXL93. Program for the Refinement of Crystal Structures. University of (36ttingen, Germany. Sheldrick, (3. M. (1994). SHELXTL/PC. Version 5.0. Siemens Analyt- ical X-ray Instruments Inc., Madison, Wisconsin, USA. Siemens (1994). XSCANS User's Manual. Version 2.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Sokol, V. I., Porai-Koshits, M. A., Berdnikov, V. R., Rozanov, I. A. & Butman, L. A. (1979). Koord. Khim. 5, 1093-1102. Stock, N. & Schnick, W. (1996). Z. Naturforsch. Teil B. In the press. Stokes, H. N. (1895). Ber. Dtsch. Chem. Ges. 28, 437. Stokes, H. N. (1896). Am. Chem. J. 18, 629-663. Acta Cryst. (1996). C52, 2647-2650 Refinement of the Superstructure of C-Type  Chromium( I l l )  T r i s (meta -  phosphate) ,  Cr(PO3)3 MICHAEL GRUSS AND ROBERT GLAUM Institut fiir Anorganische und Analytische Chemie, Justus- Liebig-Universitiit Giessen, Heinrich-Buff-Ring 58, D-35392 Giessen, Germany. E-mail: robert.glaum@anorg.chemie.uni- giessen.de (Received 10 April 1996; accepted 29 May 1996) Abstract Single crystals of Cr(PO3)3 suitable for X-ray investi- gations were obtained under various experimental con- ditions that favour volatilization of the phosphate and its recrystallization from the gas phase. The compound belongs to the series of phosphates M(PO3)3 (M 3÷ = A1, In, Sc, Ti, V, Fe, Mo, Rh, Ru) which adopt the C-type structure, characterized by one-dimensional infi- © 1996 International Union of Crystallography Printed in Great Britain - all rights reserved Comment C-Type Cr(PO3)3 is one of the six polymorphic modifi- cations of this compound that have been reported in the literature (R6my & Boull6, 1972). Up to now only the B- type structure (described as Cr2P6Ots; Bagieu-Beucher & Guitel, 1977) and the atomic arrangement of the sub- cell of C-Cr(PO3)3 (Yakubovich, Dimitrova & Savina, 1991) have been refined using X-ray single crystal data. In the paper by Yakubovich et al. (1991), anomalously high displacement coefficients for some atoms together with unreasonable P--O distances indicate the neces- sity of a refinement of the complete structure to ob- tain reliable information on interatomic distances and bond angles. The unit cell of the substructure of C- Cr(PO3)3 given by Yakubovich et al. (1991) [la, Z - 4, a - 9.367 (6), b = 6.344(8), c = 10.544(8)A, /3 = 98.00 (6) °] is related by the transformation matrix T = ( -  1 0 - 1, 0 3 0, 1 0 0) to the cell of the superstructure reported here. Additional motivation for a detailed structure in- vestigation of C-Cr(PO3)3 was drawn from polarized single-crystal UV/visible spectra of C-Ti(PO3)3 (Glaum & Hitchman, 1996). These measurements revealed the existence of three slightly differently distorted TiO6 oc- tahedra in agreement with a structure refinement pub- lished recently (Harrison, Gier & Stucky, 1994). This observation convincingly demonstrates once more that understanding of structure-property elationships can be reached only on the basis of complete structural infor- mation. C-Cr(PO3)3 is a member of a series of isotypical tris(metaphosphates) M(PO3)3 [M = AI (van der Meer, 1976), In (Bentama, Durand & Cot, 1988), Sc (Doman- skii, Shepelev, Smolin & Litvin, 1982), Ti (Harrison, Gier & Stucky, 1994), V (Middlemiss, Hawthorne & Calvo, 1977), Mo (Watson, Borel, Chardon & Leclaire, 1994), Ru (Fukuoka, Imoto & Saito, 1995), Rh (Rittner & Glaum, 1994)] for which the structures have been re- fined from single crystal data. C-Fe(PO3)3 also belongs to this series, but has been characterized so far from powder data only (R6my & Boull6, 1972). The general aspects of the structure type have been described and discussed extensively in the references above, so apart from the specific crystallographic parameters found in this work, only a short discussion of the structure is appropriate. Acta Cr3'stallographica Section C ISSN 0108-2701 © 1996 

Acta C~st.

SHELXL93. Program for the Refinement of Crystal Structures. University of (36ttingen,

SHELXTL/PC. Version 5.0. Siemens Analytical X-ray Instruments Inc.,

XSCANS User's Manual. Version 2.1. Siemens Analytical X-ray Instruments Inc.,

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Triammonium Trimetaphosphimate Monohydrate

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