A polymorph structure of copper(II) hydrogenphosphite dihydrate

Lei Yang; Suping Li; Qiufen Wang

doi:10.1107/S1600536809009088

. 2009 Mar 19;65(Pt 4):i28. doi: 10.1107/S1600536809009088

A polymorph structure of copper(II) hydrogenphosphite dihydrate

Lei Yang ^a,^*, Suping Li ^a, Qiufen Wang ^a

PMCID: PMC2968968 PMID: 21582311

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

Experimental

Crystal data

[Cu(HPO₃)(H₂O)₂]
M _r = 179.55
Monoclinic,
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 ▶) 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
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.42 e Å⁻³

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

Supplementary Material

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

e-65-00i28-sup1.cif^{(12.9KB, cif)}

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

e-65-00i28-Isup2.hkl^{(49.3KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Cu1—O3	1.9293 (14)
Cu1—O1	1.9607 (14)
Cu1—O2	1.9774 (14)
Cu1—O4	1.9960 (14)
Cu1—O5	2.2396 (17)
Cu1—O3ⁱ	2.8716 (15)

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O1—Cu1—O2	160.25 (6)
O3—Cu1—O4	177.82 (6)
O3—Cu1—O5	97.18 (6)
O2—Cu1—O5	104.95 (6)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O1ⁱⁱ	0.878 (17)	1.81 (2)	2.658 (2)	162 (4)
O4—H4B⋯O2ⁱⁱⁱ	0.890 (16)	1.864 (16)	2.728 (2)	163 (2)
O5—H5A⋯O2ⁱⁱⁱ	0.867 (18)	2.18 (3)	2.925 (2)	143 (3)
O5—H5A⋯O3^iv	0.867 (18)	2.60 (3)	3.380 (2)	151 (3)
O5—H5B⋯O4^v	0.851 (18)	1.985 (18)	2.818 (2)	166 (3)

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Symmetry codes: (ii) Inline graphic ; (iii) ; (iv) ; (v) .

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.