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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): i28.
Published online 2009 March 19. doi:  10.1107/S1600536809009088
PMCID: PMC2968968

A polymorph structure of copper(II) hydrogenphosphite dihydrate

Abstract

The title compound, poly[[diaqua­copper(II)]-μ3-hydrogenphosphito], [Cu(HPO3)(H2O)2]n, (I), has been prepared by hydro­thermal synthesis at 393 K. Its non-centrosymmetric polymorph structure, (II), was known previously and has been redetermined at 193 (2) K [El Bali & Massa (2002 [triangle]). Acta Cryst. E58, i29–i31]. The Cu atoms in (I) and (II) are square-pyramidal coordinated. A distorted octa­hedral geometry around the Cu atoms is considered by including the strongly elongated apical distances of 2.8716 (15) Å in (I) and 3.000 (1) Å in (II). The Cu(...)Cu separation of the dimeric unit is 3.1074 (3) Å. The secondary building units (SBU) (the Cu2O2 dimer and two HPO3 units) in (I) are inversion related and form a two-dimensional layered structure, with sheets parallel to the bc plane, whereas in the structure of (II), the chain elements are connected via screw-axis symmetry to form a three-dimensional microporous framework. In both polymorph structures, strong O—H(...)O hydrogen bonds are observed.

Related literature

For the structure of the noncentrosymmetric polymorph, see: Handlovič (1969 [triangle]) and El Bali & Massa (2002 [triangle]). For a discussion on secondary building units (SBU), see: Biradha (2007 [triangle]). For the structure of an open-framework zincophosphite built up from polyhedral 12-rings, see: Harrison et al. (2001 [triangle]).

Experimental

Crystal data

  • [Cu(HPO3)(H2O)2]
  • M r = 179.55
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-00i28-efi5.jpg
  • a = 7.12940 (10) Å
  • b = 7.33460 (10) Å
  • c = 8.8313 (2) Å
  • β = 110.4280 (10)°
  • V = 432.76 (1) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 5.32 mm−1
  • T = 296 K
  • 0.25 × 0.25 × 0.20 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008 [triangle]) T min = 0.288, T max = 0.345
  • 3641 measured reflections
  • 994 independent reflections
  • 980 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.018
  • wR(F 2) = 0.049
  • S = 1.18
  • 994 reflections
  • 85 parameters
  • 6 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009088/si2150sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009088/si2150Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Co-editor for help with the paper.

supplementary crystallographic information

Comment

Cu atoms in the asymmetric unit are pentahedrally coordinated and link three P atoms via phosphite O atoms (O1, O2, O3) with shorter distances and two water molecules (O4, O5) with longer distances (Fig. 1 and Table 1). A distorted octahedral geometry around the Cu atoms are considered when the strongly elongated apical Cu—O distances of 3.036 (14) Å (Handlovič, 1969), 3.000 (1) Å in II (El Bali & Massa, 2002), and 2.8716 (15) in I are included. The P atoms form the centers of a pseudo pyramid with the hydrogen phosphite groups, and each P links to three Cu via P—O—Cu bonds. The P—O bonds are in the range of 1.5178 (14) - 1.5337 (14) Å. The two-dimensional structure (Fig. 2) is built up from SBU (Biradha, 2007) (secondary building units, Fig.1), the corner sharing of tetra-meric units. One Cu atom links two P atom via O1 and O2. Two pentahedra Cu(H2O)2O3, and two pseudopyramids HPO3 form a dinucleus unit, noted as SBU. The Cu···Cu distance in the dimeric unit of I is 3.1074 (3) Å. The SBU and hydrogenphosphite polyhedra are connected into a one-dimensional chain by sharing the corner O3, and each chain links two other chains by sharing other atoms O3, forming a sheet along the bc-plane, containing 8-membered rings when the long Cu—O3c distance is neglected. In the structure of (CN3H6)2.Zn(HPO3)2, ZnO4 and HPO3building units form a 12-ring framework (Harrison et al., 2001). In both polymorph structures strong O—H···O hydrogen bonds are observed (Table 2).

Experimental

All reagents were of analytical grade. The title sample was prepared by Cu(NO3)2, H2O, H3(PO3) and (C2H5)3N triethylamine in the molar ratio 1:144:5:11 and heated at 393 K for 8 d. The blue single crystals were filtered, washed with distilled water and dried in air.

Refinement

The H atoms of the water molecules were located from a difference density map and were refined with distance restraints of d(H–H) = 1.40 (2) Å, d(O–H) = 0.90 (2) Å, and with isotropic displacement parameters. The H atom of the hydrogenphosphite group was freely refined.

Figures

Fig. 1.
A section of the structure of (I) showing the centrosymmetric SBU with the edge-sharing distorted CuO6 octahedra. Displacement ellipsoids are drawn at the 50% probability level. Atoms labelled a, b, c are symmetry-related. Symmetry codes: (a = - x, -1/2 ...
Fig. 2.
The layer structure of (I), viewed down the a axis.

Crystal data

[Cu(HPO3)(H2O)2]F(000) = 356
Mr = 179.55Dx = 2.756 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.1294 (1) ÅCell parameters from 3157 reflections
b = 7.3346 (1) Åθ = 3.1–27.5°
c = 8.8313 (2) ŵ = 5.32 mm1
β = 110.428 (1)°T = 296 K
V = 432.76 (1) Å3Block, blue
Z = 40.25 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer994 independent reflections
Radiation source: fine-focus sealed tube980 reflections with I > 2σ(I)
graphiteRint = 0.023
[var phi] and ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008)h = −9→9
Tmin = 0.288, Tmax = 0.345k = −9→9
3641 measured reflectionsl = −10→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.018H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.049w = 1/[σ2(Fo2) + (0.0209P)2 + 0.4287P] where P = (Fo2 + 2Fc2)/3
S = 1.18(Δ/σ)max < 0.001
994 reflectionsΔρmax = 0.44 e Å3
85 parametersΔρmin = −0.42 e Å3
6 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.134 (4)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cu10.22809 (3)0.02792 (3)0.58956 (3)0.01035 (13)
P1−0.08713 (7)0.28227 (6)0.66809 (6)0.00990 (15)
O10.1259 (2)0.21752 (19)0.69683 (17)0.0145 (3)
O20.2458 (2)−0.1406 (2)0.42031 (17)0.0144 (3)
O30.1081 (2)−0.1660 (2)0.67218 (17)0.0173 (3)
O40.3581 (2)0.22142 (19)0.50133 (17)0.0129 (3)
O50.5311 (3)0.0183 (2)0.7831 (2)0.0234 (4)
H1−0.116 (4)0.420 (4)0.582 (3)0.019 (6)*
H4A0.298 (4)0.262 (5)0.403 (3)0.056 (12)*
H4B0.482 (3)0.197 (4)0.506 (3)0.022 (7)*
H5A0.630 (4)0.073 (4)0.766 (4)0.051 (10)*
H5B0.580 (5)−0.075 (3)0.841 (4)0.043 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.01143 (18)0.01023 (17)0.01156 (17)−0.00141 (8)0.00675 (12)−0.00082 (7)
P10.0107 (3)0.0093 (2)0.0109 (2)0.00038 (17)0.00539 (19)−0.00079 (16)
O10.0100 (7)0.0186 (7)0.0154 (7)−0.0006 (5)0.0049 (6)−0.0061 (5)
O20.0115 (7)0.0159 (7)0.0179 (7)−0.0029 (5)0.0076 (6)−0.0055 (5)
O30.0229 (8)0.0169 (7)0.0156 (7)−0.0058 (6)0.0109 (6)0.0018 (6)
O40.0118 (7)0.0148 (6)0.0124 (6)−0.0009 (5)0.0046 (5)0.0008 (5)
O50.0128 (8)0.0286 (9)0.0256 (9)0.0001 (6)0.0027 (7)0.0126 (7)

Geometric parameters (Å, °)

Cu1—O31.9293 (14)P1—O2i1.5337 (14)
Cu1—O11.9607 (14)P1—H11.24 (3)
Cu1—O21.9774 (14)O2—P1i1.5337 (14)
Cu1—O41.9960 (14)O3—P1iii1.5178 (14)
Cu1—O52.2396 (17)O4—H4A0.878 (17)
Cu1—O3i2.8716 (15)O4—H4B0.890 (16)
P1—O3ii1.5178 (14)O5—H5A0.867 (18)
P1—O11.5254 (15)O5—H5B0.851 (18)
O3—Cu1—O192.95 (6)O3ii—P1—H1108.6 (12)
O3—Cu1—O288.78 (6)O1—P1—H1107.4 (13)
O1—Cu1—O2160.25 (6)O2i—P1—H1107.6 (13)
O3—Cu1—O4177.82 (6)P1—O1—Cu1131.06 (9)
O1—Cu1—O489.19 (6)P1i—O2—Cu1125.31 (8)
O2—Cu1—O489.35 (6)P1iii—O3—Cu1137.43 (9)
O3—Cu1—O597.18 (6)Cu1—O4—H4A120 (2)
O1—Cu1—O594.36 (6)Cu1—O4—H4B115.5 (18)
O2—Cu1—O5104.95 (6)H4A—O4—H4B104 (2)
O4—Cu1—O582.23 (6)Cu1—O5—H5A119 (2)
O3ii—P1—O1109.79 (8)Cu1—O5—H5B124 (2)
O3ii—P1—O2i110.37 (8)H5A—O5—H5B107 (2)
O1—P1—O2i112.85 (8)

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y+1/2, −z+3/2; (iii) −x, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H4A···O1iv0.88 (2)1.81 (2)2.658 (2)162 (4)
O4—H4B···O2v0.89 (2)1.86 (2)2.728 (2)163 (2)
O5—H5A···O2v0.87 (2)2.18 (3)2.925 (2)143 (3)
O5—H5A···O3vi0.87 (2)2.60 (3)3.380 (2)151 (3)
O5—H5B···O4vii0.85 (2)1.99 (2)2.818 (2)166 (3)

Symmetry codes: (iv) x, −y+1/2, z−1/2; (v) −x+1, −y, −z+1; (vi) −x+1, y+1/2, −z+3/2; (vii) −x+1, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2150).

References

  • Biradha, K. (2007). Curr. Sci.92, 584–585.
  • Bruker (2001). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • El Bali, B. & Massa, W. (2002). Acta Cryst. E58, i29–i31.
  • Handlovič, M. (1969). Acta Cryst. B25, 227–231.
  • Harrison, W. T. A., Phillips, M. L. F. & Nenoff, T. M. (2001). J. Chem. Soc. Dalton Trans. pp. 2459–2461.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography