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

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 (). 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.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](Cu-O) = 0.003 Å
• R factor = 0.036
• wR factor = 0.092
• Data-to-parameter ratio = 11.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

Alert level G
CHEMS02_ALERT_1_G  Please check that you have entered the correct
            _publ_requested_category classification of your compound;
            FI or CI or EI for inorganic; FM or CM or EM for metal-organic;
            FO or CO or EO for organic.
            From the CIF: _publ_requested_category   EM
            From the CIF: _chemical_formula_sum:H12 Cu1 Na2 O14 S2
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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

S2. Experimental

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..

S3. Refinement

H1F, H2F, H2E and H3E atoms bonded to O atoms were located in a difference map and refined with distance restraints of O—H=0.90 Å, and with U_iso(H)=1.2Ueq, other H atoms were positioned geometrically and refeined freely. The maximum peak and deepest hole are located 0.51 Å and -0.42 Å, respectively, from Cu.

Computing details

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

	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)]]

Crystal data

[Cu(H2O)6][Na2(SO4)2]	F(000) = 414
Mr = 409.74	Dx = 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) Å^3	0.20 × 0.17 × 0.17 mm
Z = 2

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 1.2605P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
1322 reflections	Δρmax = 0.51 e Å^−3
113 parameters	Δρmin = −0.42 e Å^−3
4 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.053 (4)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cu1—O3^i	1.962 (2)	Na1—O7^ii	2.856 (3)
Cu1—O3	1.962 (2)	Na1—O6^iii	2.983 (3)
Cu1—O2^i	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—O1^i	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—Na1^ii	2.856 (3)
Na1—O4	2.825 (3)
O3^i—Cu1—O3	180.0	O5—S1—O7	110.99 (17)
O3^i—Cu1—O2^i	89.95 (10)	O6—S1—O7	109.63 (15)
O3—Cu1—O2^i	90.05 (10)	O4—S1—O7	109.74 (14)
O3^i—Cu1—O2	90.05 (10)	O4—Na1—O7^ii	108.76 (8)
O3—Cu1—O2	89.95 (10)	O4—Na1—O6^iii	102.19 (8)
O2^i—Cu1—O2	180.000 (1)	O7^ii—Na1—O6^iii	138.69 (9)
O3^i—Cu1—O1	91.07 (10)	Cu1—O1—H1F	113 (4)
O3—Cu1—O1	88.93 (10)	Cu1—O1—H1E	109 (3)
O2^i—Cu1—O1	88.93 (10)	H1F—O1—H1E	104 (5)
O2—Cu1—O1	91.07 (10)	Cu1—O2—H2F	113 (3)
O3^i—Cu1—O1^i	88.93 (10)	Cu1—O2—H2E	108 (3)
O3—Cu1—O1^i	91.07 (10)	H2F—O2—H2E	109 (4)
O2^i—Cu1—O1^i	91.07 (10)	Cu1—O3—H3F	114 (4)
O2—Cu1—O1^i	88.93 (10)	Cu1—O3—H3E	118 (3)
O1—Cu1—O1^i	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—Na1^ii	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—Na1^ii	−9.3 (2)
O7^ii—Na1—O4—S1	−28.50 (15)	O6—S1—O7—Na1^ii	111.83 (17)
O6^iii—Na1—O4—S1	179.25 (12)	O4—S1—O7—Na1^ii	−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)

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···O5^ii	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.