A polymorph structure of copper(II) hydrogenphosphite dihydrate

Yang, L.; Li, S.; Wang, Q.

doi:10.1107/S1600536809009088

inorganic compounds

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Volume 65| Part 4| April 2009| Page i28

doi:10.1107/S1600536809009088

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A polymorph structure of copper(II) hydrogenphosphite dihydrate

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

^aDepartment of Physics–Chemistry, Henan Polytechnic University, Jiao Zuo 454150, People's Republic of China
^*Correspondence e-mail: xcy78413@tom.com

(Received 7 January 2009; accepted 12 March 2009; online 19 March 2009)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.018
wR(F²) = 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

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)

O1—Cu1—O2	160.25 (6)
O3—Cu1—O4	177.82 (6)
O3—Cu1—O5	97.18 (6)
O2—Cu1—O5	104.95 (6)
Symmetry code: (i) -x, -y, -z+1.

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)
Symmetry codes: (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z+1; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

For the structure of the non-centrosymmetric 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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	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 + y, 3/2 - z; (b = - x, 1/2 + y, 3/2 - z; (c = - x, - y, 1 - z).
	Fig. 2. The layer structure of (I), viewed down the a axis.

poly[[diaquacopper(II)]-µ₃-hydrogenphosphito] top

Crystal data top

[Cu(HPO₃)(H₂O)₂]	F(000) = 356
M_r = 179.55	D_x = 2.756 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.1294 (1) Å	Cell parameters from 3157 reflections
b = 7.3346 (1) Å	θ = 3.1–27.5°
c = 8.8313 (2) Å	µ = 5.32 mm⁻¹
β = 110.428 (1)°	T = 296 K
V = 432.76 (1) Å³	Block, blue
Z = 4	0.25 × 0.25 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	994 independent reflections
Radiation source: fine-focus sealed tube	980 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008)	h = −9→9
T_min = 0.288, T_max = 0.345	k = −9→9
3641 measured reflections	l = −10→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.049	w = 1/[σ²(F_o²) + (0.0209P)² + 0.4287P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
994 reflections	Δρ_max = 0.44 e Å⁻³
85 parameters	Δρ_min = −0.42 e Å⁻³
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.134 (4)

Crystal data top

[Cu(HPO₃)(H₂O)₂]	V = 432.76 (1) Å³
M_r = 179.55	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.1294 (1) Å	µ = 5.32 mm⁻¹
b = 7.3346 (1) Å	T = 296 K
c = 8.8313 (2) Å	0.25 × 0.25 × 0.20 mm
β = 110.428 (1)°

Data collection top

Bruker APEXII CCD diffractometer	994 independent reflections
Absorption correction: multi-scan (SHELXTL; Sheldrick, 2008)	980 reflections with I > 2σ(I)
T_min = 0.288, T_max = 0.345	R_int = 0.023
3641 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	6 restraints
wR(F²) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Δρ_max = 0.44 e Å⁻³
994 reflections	Δρ_min = −0.42 e Å⁻³
85 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cu1	0.22809 (3)	0.02792 (3)	0.58956 (3)	0.01035 (13)
P1	−0.08713 (7)	0.28227 (6)	0.66809 (6)	0.00990 (15)
O1	0.1259 (2)	0.21752 (19)	0.69683 (17)	0.0145 (3)
O2	0.2458 (2)	−0.1406 (2)	0.42031 (17)	0.0144 (3)
O3	0.1081 (2)	−0.1660 (2)	0.67218 (17)	0.0173 (3)
O4	0.3581 (2)	0.22142 (19)	0.50133 (17)	0.0129 (3)
O5	0.5311 (3)	0.0183 (2)	0.7831 (2)	0.0234 (4)
H1	−0.116 (4)	0.420 (4)	0.582 (3)	0.019 (6)*
H4A	0.298 (4)	0.262 (5)	0.403 (3)	0.056 (12)*
H4B	0.482 (3)	0.197 (4)	0.506 (3)	0.022 (7)*
H5A	0.630 (4)	0.073 (4)	0.766 (4)	0.051 (10)*
H5B	0.580 (5)	−0.075 (3)	0.841 (4)	0.043 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01143 (18)	0.01023 (17)	0.01156 (17)	−0.00141 (8)	0.00675 (12)	−0.00082 (7)
P1	0.0107 (3)	0.0093 (2)	0.0109 (2)	0.00038 (17)	0.00539 (19)	−0.00079 (16)
O1	0.0100 (7)	0.0186 (7)	0.0154 (7)	−0.0006 (5)	0.0049 (6)	−0.0061 (5)
O2	0.0115 (7)	0.0159 (7)	0.0179 (7)	−0.0029 (5)	0.0076 (6)	−0.0055 (5)
O3	0.0229 (8)	0.0169 (7)	0.0156 (7)	−0.0058 (6)	0.0109 (6)	0.0018 (6)
O4	0.0118 (7)	0.0148 (6)	0.0124 (6)	−0.0009 (5)	0.0046 (5)	0.0008 (5)
O5	0.0128 (8)	0.0286 (9)	0.0256 (9)	0.0001 (6)	0.0027 (7)	0.0126 (7)

Geometric parameters (Å, º) top

Cu1—O3	1.9293 (14)	P1—O2ⁱ	1.5337 (14)
Cu1—O1	1.9607 (14)	P1—H1	1.24 (3)
Cu1—O2	1.9774 (14)	O2—P1ⁱ	1.5337 (14)
Cu1—O4	1.9960 (14)	O3—P1ⁱⁱⁱ	1.5178 (14)
Cu1—O5	2.2396 (17)	O4—H4A	0.878 (17)
Cu1—O3ⁱ	2.8716 (15)	O4—H4B	0.890 (16)
P1—O3ⁱⁱ	1.5178 (14)	O5—H5A	0.867 (18)
P1—O1	1.5254 (15)	O5—H5B	0.851 (18)

O3—Cu1—O1	92.95 (6)	O3ⁱⁱ—P1—H1	108.6 (12)
O3—Cu1—O2	88.78 (6)	O1—P1—H1	107.4 (13)
O1—Cu1—O2	160.25 (6)	O2ⁱ—P1—H1	107.6 (13)
O3—Cu1—O4	177.82 (6)	P1—O1—Cu1	131.06 (9)
O1—Cu1—O4	89.19 (6)	P1ⁱ—O2—Cu1	125.31 (8)
O2—Cu1—O4	89.35 (6)	P1ⁱⁱⁱ—O3—Cu1	137.43 (9)
O3—Cu1—O5	97.18 (6)	Cu1—O4—H4A	120 (2)
O1—Cu1—O5	94.36 (6)	Cu1—O4—H4B	115.5 (18)
O2—Cu1—O5	104.95 (6)	H4A—O4—H4B	104 (2)
O4—Cu1—O5	82.23 (6)	Cu1—O5—H5A	119 (2)
O3ⁱⁱ—P1—O1	109.79 (8)	Cu1—O5—H5B	124 (2)
O3ⁱⁱ—P1—O2ⁱ	110.37 (8)	H5A—O5—H5B	107 (2)
O1—P1—O2ⁱ	112.85 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1^iv	0.88 (2)	1.81 (2)	2.658 (2)	162 (4)
O4—H4B···O2^v	0.89 (2)	1.86 (2)	2.728 (2)	163 (2)
O5—H5A···O2^v	0.87 (2)	2.18 (3)	2.925 (2)	143 (3)
O5—H5A···O3^vi	0.87 (2)	2.60 (3)	3.380 (2)	151 (3)
O5—H5B···O4^vii	0.85 (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.

Experimental details

Crystal data
Chemical formula	[Cu(HPO₃)(H₂O)₂]
M_r	179.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.1294 (1), 7.3346 (1), 8.8313 (2)
β (°)	110.428 (1)
V (Å³)	432.76 (1)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.32
Crystal size (mm)	0.25 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SHELXTL; Sheldrick, 2008)
T_min, T_max	0.288, 0.345
No. of measured, independent and observed [I > 2σ(I)] reflections	3641, 994, 980
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.049, 1.18
No. of reflections	994
No. of parameters	85
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.42

Computer programs: APEX2 (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

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

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

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

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)

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

Acknowledgements

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

References

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