Poly[hexa­aqua­copper(II) [di-μ3-sulfato-disodiate(I)]]

Wu, W.; Xie, J.-M.; Xie, D.-P.; Xuan, Y.-W.

doi:10.1107/S1600536807067608

inorganic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page i7

doi:10.1107/S1600536807067608

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Poly[hexaaquacopper(II) [di-μ₃-sulfato-disodiate(I)]]

Wen Wu,^a,^b J.-M. Xie,^b ^* D.-P. Xie ^a and Y.-W. Xuan ^a

^aDepartment of Chemistry, Zhou Kou Normal University, 466001, People's Republic of China, and ^bDepartment of Chemistry, Jiangsu University, Zhenjiang 212003, People's Republic of China
^*Correspondence e-mail: chinawuwen@126.com

(Received 11 November 2007; accepted 18 December 2007; online 4 January 2008)

The title compound, {[Cu(H₂O)₆][Na₂(SO₄)₂]}_n, has been prepared under mild hydrothermal conditions and has been structurally characterized. It exhibits a structure in which the inorganic frameworks are three-dimensional, participating in extensive hydrogen bonding. Copper occupies a special position ( $[\overline{1}]$ ). The Na atom is coordinated by five O atoms of four sulfates [Na—O distances are between 2.825 (3) and 2.983 (3) Å]. The four O atoms of the sulfate ligand are coordinated to four Na atoms, the sulfate ligands coordinating in a chelating/bridging tetradentate mode.

Related literature

For the structure of [C₆H₁₈N₂]_0.5[Fe(SO₄)₂(H₂O)₂], see: Fu et al. (2006 )

Experimental

Crystal data

[Cu(H₂O)₆][Na₂(SO₄)₂]
M_r = 409.74
Monoclinic, P 2₁ /c
a = 6.2345 (12) Å
b = 12.333 (3) Å
c = 9.1822 (18) Å
β = 105.56 (3)°
V = 680.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.04 mm⁻¹
T = 291 (2) K
0.20 × 0.17 × 0.17 mm

Data collection

Rigaku R-AXIS IV diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.607, T_max = 0.709
2371 measured reflections
1322 independent reflections
1257 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.092
S = 1.09
1322 reflections
113 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2F⋯O4ⁱ	0.90 (3)	1.915 (15)	2.790 (3)	166 (4)
O3—H3F⋯O6ⁱⁱ	0.80 (5)	1.89 (5)	2.674 (4)	167 (5)
O1—H1F⋯O5ⁱⁱⁱ	0.90 (3)	1.82 (3)	2.719 (4)	175 (5)
O1—H1E⋯O7^iv	0.80 (5)	1.96 (5)	2.759 (4)	173 (4)
O2—H2E⋯O7	0.90 (4)	1.93 (4)	2.800 (4)	164 (5)
O3—H3E⋯O4	0.89 (3)	1.83 (3)	2.712 (3)	174 (4)
Symmetry codes: (i) x-1, y, z; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: PROCESS (Rigaku, 1996 ); cell refinement: PROCESS; data reduction: PROCESS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corporation, 1997 ); software used to prepare material for publication: TEXSAN.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067608/fi2054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807067608/fi2054Isup2.hkl

checkCIF report

Comment top

The structure of the title compound consists of an infinite three-dimensional [Na₂(SO₄)₂]_n^2n- network, the [Cu(H₂O)₆]_n²ⁿ⁺ cations reside between inorganic layers, balancing charge and donating hydrogen bonds to the layers. The asymmetric unit contains one Cu(II) cation, three water molecules, one sulfate dianion and one sodium cation. (Fig. 1). To the best of our knowledge, the title compound is the first layer structure of inorganically templated sodium sulfate. As shown in Fig. 2, sodium atoms are bridged by sulfate groups into an infinite layer structure parallel to the ab-plane. The Cu(II) cation is approximately octahedrally coordinated by the oxygen atoms of six H₂O. In each sulfate group, four oxygen atoms are coordinated to sodium, for bridged oxygen atoms, the angles of S—O—Na range from 99.08 (10) to 122.97 (13)°.

Related literature top

For the structure of [C₆H₁₈N₂]_0.5[Fe(SO₄)₂(H₂O)₂], see: Fu et al. (2006)

Experimental top

All the reagents were of AR grade and used without further purification, a mixture of potassium hydrogen phthalate (0.2040 g, 1 mmol), and NaOH (0.0040 g, 1 mmol) were dissolved in 50 ml EtOH/H₂O (V:V = 1:1) solution, and then the resultant solution was added in 10 ml double-distilled water containing Cu(NO₃)₂.3H₂O (0.2426 g, 1 mmol) and Fe₂(SO₄)₃ (0.39974 g, 1 mmol). The resulting solution was heated at 373 K for 96 h. After cooling to room temperature, blue crystals were obtained in a yield up to 56.32% based on Cu..

Computing details top

Data collection: PROCESS (Rigaku, 1996); cell refinement: PROCESS (Rigaku, 1996); data reduction: PROCESS (Rigaku, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN (Molecular Structure Corporation, 1997); software used to prepare material for publication: TEXSAN (Molecular Structure Corporation, 1997).

Figures top

	Fig. 1. ORTEP plot of 1 with 30% probability ellipsoid.
	Fig. 2. [Na₂(SO₄)₂]_n^2n- network in title compound 1.

Poly[hexaaquacopper(II) [di-µ₃-sulfato-disodiate(I)]] top

Crystal data top

[Cu(H₂O)₆][Na₂(SO₄)₂]	F(000) = 414
M_r = 409.74	D_x = 2.001 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 289 reflections
a = 6.2345 (12) Å	θ = 2–25.1°
b = 12.333 (3) Å	µ = 2.04 mm⁻¹
c = 9.1822 (18) Å	T = 291 K
β = 105.56 (3)°	Prismatic, blue
V = 680.1 (3) Å³	0.20 × 0.17 × 0.17 mm
Z = 2

Data collection top

Rigaku R-AXIS IV diffractometer	1322 independent reflections
Radiation source: fine-focus sealed tube	1257 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 0 pixels mm^-1	θ_max = 26.0°, θ_min = 2.8°
Oscillation frames scans	h = 0→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −15→15
T_min = 0.607, T_max = 0.709	l = −11→10
2371 measured reflections

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)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0419P)² + 1.2605P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
1322 reflections	Δρ_max = 0.51 e Å⁻³
113 parameters	Δρ_min = −0.42 e Å⁻³
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.053 (4)

Crystal data top

[Cu(H₂O)₆][Na₂(SO₄)₂]	V = 680.1 (3) Å³
M_r = 409.74	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.2345 (12) Å	µ = 2.04 mm⁻¹
b = 12.333 (3) Å	T = 291 K
c = 9.1822 (18) Å	0.20 × 0.17 × 0.17 mm
β = 105.56 (3)°

Data collection top

Rigaku R-AXIS IV diffractometer	1322 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1257 reflections with I > 2σ(I)
T_min = 0.607, T_max = 0.709	R_int = 0.026
2371 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	4 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.51 e Å⁻³
1322 reflections	Δρ_min = −0.42 e Å⁻³
113 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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	0.5000	0.5000	1.0000	0.0195 (2)
S1	0.76455 (13)	0.63853 (6)	0.59661 (9)	0.0249 (2)
Na1	0.8483 (3)	0.35098 (12)	0.62649 (17)	0.0382 (4)
O1	0.5346 (4)	0.3875 (2)	0.8249 (3)	0.0340 (6)
O2	0.3313 (4)	0.6137 (2)	0.8339 (3)	0.0360 (6)
H2F	0.192 (3)	0.594 (4)	0.786 (4)	0.045 (12)*
H2E	0.409 (8)	0.620 (4)	0.765 (4)	0.062 (15)*
O3	0.7863 (4)	0.5650 (2)	0.9976 (3)	0.0253 (5)
H3F	0.801 (8)	0.627 (4)	1.025 (6)	0.054 (15)*
O4	0.8777 (4)	0.56884 (18)	0.7250 (2)	0.0289 (5)
O5	0.7360 (5)	0.5768 (3)	0.4569 (3)	0.0486 (8)
O6	0.9065 (4)	0.7338 (2)	0.5942 (3)	0.0412 (7)
O7	0.5467 (4)	0.6744 (2)	0.6153 (3)	0.0357 (6)
H3E	0.825 (7)	0.563 (3)	0.911 (3)	0.036 (11)*
H1F	0.439 (7)	0.401 (4)	0.734 (3)	0.068 (16)*
H1E	0.503 (7)	0.327 (4)	0.846 (5)	0.038 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0200 (3)	0.0198 (3)	0.0185 (3)	−0.00122 (18)	0.0047 (2)	0.00199 (18)
S1	0.0269 (4)	0.0244 (4)	0.0222 (4)	0.0025 (3)	0.0046 (3)	0.0043 (3)
Na1	0.0385 (8)	0.0395 (8)	0.0391 (8)	−0.0010 (6)	0.0149 (7)	−0.0020 (6)
O1	0.0213 (14)	0.0204 (14)	0.0257 (13)	−0.0061 (11)	0.0075 (11)	0.0023 (11)
O2	0.0210 (13)	0.0221 (15)	0.0255 (13)	−0.0063 (11)	0.0076 (11)	0.0023 (11)
O3	0.0262 (11)	0.0255 (12)	0.0260 (12)	−0.0027 (9)	0.0099 (9)	−0.0009 (9)
O4	0.0315 (12)	0.0313 (13)	0.0239 (11)	0.0042 (10)	0.0075 (9)	0.0080 (9)
O5	0.0633 (19)	0.0553 (18)	0.0234 (13)	0.0095 (15)	0.0051 (12)	−0.0072 (12)
O6	0.0347 (14)	0.0320 (13)	0.0557 (17)	−0.0018 (11)	0.0100 (12)	0.0155 (12)
O7	0.0258 (12)	0.0333 (13)	0.0477 (15)	0.0045 (10)	0.0094 (11)	0.0033 (11)

Geometric parameters (Å, º) top

Cu1—O3ⁱ	1.962 (2)	Na1—O7ⁱⁱ	2.856 (3)
Cu1—O3	1.962 (2)	Na1—O6ⁱⁱⁱ	2.983 (3)
Cu1—O2ⁱ	2.130 (3)	O1—H1F	0.90 (3)
Cu1—O2	2.130 (3)	O1—H1E	0.81 (5)
Cu1—O1	2.178 (3)	O2—H2F	0.90 (3)
Cu1—O1ⁱ	2.178 (3)	O2—H2E	0.90 (4)
S1—O5	1.461 (3)	O3—H3F	0.80 (5)
S1—O6	1.475 (3)	O3—H3E	0.89 (3)
S1—O4	1.476 (2)	O6—Na1^iv	2.983 (3)
S1—O7	1.482 (3)	O7—Na1ⁱⁱ	2.856 (3)
Na1—O4	2.825 (3)

O3ⁱ—Cu1—O3	180.0	O5—S1—O7	110.99 (17)
O3ⁱ—Cu1—O2ⁱ	89.95 (10)	O6—S1—O7	109.63 (15)
O3—Cu1—O2ⁱ	90.05 (10)	O4—S1—O7	109.74 (14)
O3ⁱ—Cu1—O2	90.05 (10)	O4—Na1—O7ⁱⁱ	108.76 (8)
O3—Cu1—O2	89.95 (10)	O4—Na1—O6ⁱⁱⁱ	102.19 (8)
O2ⁱ—Cu1—O2	180.000 (1)	O7ⁱⁱ—Na1—O6ⁱⁱⁱ	138.69 (9)
O3ⁱ—Cu1—O1	91.07 (10)	Cu1—O1—H1F	113 (4)
O3—Cu1—O1	88.93 (10)	Cu1—O1—H1E	109 (3)
O2ⁱ—Cu1—O1	88.93 (10)	H1F—O1—H1E	104 (5)
O2—Cu1—O1	91.07 (10)	Cu1—O2—H2F	113 (3)
O3ⁱ—Cu1—O1ⁱ	88.93 (10)	Cu1—O2—H2E	108 (3)
O3—Cu1—O1ⁱ	91.07 (10)	H2F—O2—H2E	109 (4)
O2ⁱ—Cu1—O1ⁱ	91.07 (10)	Cu1—O3—H3F	114 (4)
O2—Cu1—O1ⁱ	88.93 (10)	Cu1—O3—H3E	118 (3)
O1—Cu1—O1ⁱ	180.000 (1)	H3F—O3—H3E	105 (4)
O5—S1—O6	109.52 (18)	S1—O4—Na1	108.78 (12)
O5—S1—O4	108.50 (16)	S1—O6—Na1^iv	122.98 (15)
O6—S1—O4	108.40 (15)	S1—O7—Na1ⁱⁱ	120.20 (14)

O5—S1—O4—Na1	−16.47 (19)	O4—S1—O6—Na1^iv	−41.0 (2)
O6—S1—O4—Na1	−135.34 (14)	O7—S1—O6—Na1^iv	78.82 (19)
O7—S1—O4—Na1	104.95 (14)	O5—S1—O7—Na1ⁱⁱ	−9.3 (2)
O7ⁱⁱ—Na1—O4—S1	−28.50 (15)	O6—S1—O7—Na1ⁱⁱ	111.83 (17)
O6ⁱⁱⁱ—Na1—O4—S1	179.25 (12)	O4—S1—O7—Na1ⁱⁱ	−129.22 (15)
O5—S1—O6—Na1^iv	−159.17 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2F···O4^v	0.90 (3)	1.92 (2)	2.790 (3)	166 (4)
O3—H3F···O6^vi	0.80 (5)	1.89 (5)	2.674 (4)	167 (5)
O1—H1F···O5ⁱⁱ	0.90 (3)	1.82 (3)	2.719 (4)	175 (5)
O1—H1E···O7^vii	0.80 (5)	1.96 (5)	2.759 (4)	173 (4)
O2—H2E···O7	0.90 (4)	1.93 (4)	2.800 (4)	164 (5)
O3—H3E···O4	0.89 (3)	1.83 (3)	2.712 (3)	174 (4)

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

Experimental details

Crystal data
Chemical formula	[Cu(H₂O)₆][Na₂(SO₄)₂]
M_r	409.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	6.2345 (12), 12.333 (3), 9.1822 (18)
β (°)	105.56 (3)
V (Å³)	680.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.04
Crystal size (mm)	0.20 × 0.17 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS IV diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.607, 0.709
No. of measured, independent and observed [I > 2σ(I)] reflections	2371, 1322, 1257
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.092, 1.09
No. of reflections	1322
No. of parameters	113
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.42

Computer programs: PROCESS (Rigaku, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2F···O4ⁱ	0.90 (3)	1.915 (15)	2.790 (3)	166 (4)
O3—H3F···O6ⁱⁱ	0.80 (5)	1.89 (5)	2.674 (4)	167 (5)
O1—H1F···O5ⁱⁱⁱ	0.90 (3)	1.82 (3)	2.719 (4)	175 (5)
O1—H1E···O7^iv	0.80 (5)	1.96 (5)	2.759 (4)	173 (4)
O2—H2E···O7	0.90 (4)	1.93 (4)	2.800 (4)	164 (5)
O3—H3E···O4	0.89 (3)	1.83 (3)	2.712 (3)	174 (4)

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

Acknowledgements

We thank the Natural Science Foundation of Henan Province and the Key Discipline Foundation of Zhoukou Normal University for financial support of this research.

References

Fu, Y., Xu, Z., Ren, J., Wu, H. & Yuan, R. (2006). Inorg. Chem. 45, 8452–8458. Web of Science CSD CrossRef PubMed CAS Google Scholar
Molecular Structure Corporation (1997). TEXSAN. Version 1.7. MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku (1996). PROCESS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar