catena-Poly[[tetra­aqua­copper(II)]-μ-tri­thionato-κ² O:O′]

Abstract

The title supra­molecular polymer, [Cu(S₃O₆)(H₂O)₄]_n, features a tetra­gonally distorted octa­hedral Cu^II centre within an O₆ donor set with the longer Cu—O bonds linking the dication and the trithio­nate dianion. Extensive O—H⋯O hydrogen-bonding inter­actions connect the supra­molecular chains into a three-dimensional network.

Related literature

For crystal structures containing the trithionate anion, see: Chun et al. (2000 ▶); Díaz de Vivar et al. (2005 ▶); Ferrari et al. (1977 ▶). For related copper(II) structures with bridging di-sulfonato ligands, see: Charbonnier et al. (1977a ▶,b ▶); Pasquale et al. (2007 ▶); Wang et al. (2005 ▶).

Experimental

Crystal data

• [Cu(S₃O₆)(H₂O)₄]

• M _r = 327.78

• Monoclinic,

• a = 7.1816 (1) Å

• b = 21.4405 (4) Å

• c = 7.7286 (1) Å

• β = 116.092 (1)°

• V = 1068.75 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 2.66 mm⁻¹

• T = 100 K

• 0.30 × 0.10 × 0.05 mm

Data collection

• Bruker SMART APEXII diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.911, T _max = 1

• 9081 measured reflections

• 2434 independent reflections

• 2291 reflections with I > 2σ(I)

• R _int = 0.020

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.108

• S = 1.03

• 2434 reflections

• 151 parameters

• 12 restraints

• H-atom parameters constrained

• Δρ_max = 1.47 e Å⁻³

• Δρ_min = −0.84 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Cu—O3	2.001 (3)
Cu—O1	2.002 (3)
Cu—O2	2.045 (3)
Cu—O4	2.047 (3)
Cu—O5	2.524 (3)
Cu—O8i	2.564 (3)

Symmetry code: (i) .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1o⋯O9	0.84	2.29	3.080 (5)	157
O1—H2o⋯O9ii	0.84	2.25	3.071 (4)	166
O2—H3o⋯O10i	0.84	2.44	3.079 (5)	133
O2—H4o⋯O6iii	0.84	2.21	3.026 (4)	165
O3—H5o⋯O6iii	0.84	2.16	2.987 (4)	169
O3—H6o⋯O10iv	0.84	2.20	3.037 (5)	174
O4—H7o⋯O9iv	0.84	2.56	3.383 (5)	166
O4—H8o⋯O8ii	0.84	2.42	3.149 (4)	146

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

The title compound, (I), was obtained from an hydrothernal synthesis (see Experimental) and characterized crystallographically. The asymmetric unit comprises a tetraaqua copper(II) cation and a trithionato dianion, Fig. 1. In the crystal structure, the ions are connected as each trithionato dianion bridges two Cu^II centres thereby forming a supramolecular chain, Fig. 2. The Cu^II centre exists in a tetragonally distorted O₆ octahedron with the Cu—O_aqua bonds [2.047 (3) - 2.047 (3) Å] being significantly shorter than the Cu—O_trithionato bonds [2.524 (3) and 2.564 (3) Å]. The Cu atom lies 0.025 (2) out of the basal plane defined by the four aqua-O atoms (RMS = 0.080 Å) in the direction of the O8ⁱ atom, and the O5–Cu–O8ⁱ axial angle is 157.74 (10) ° for i: 1 + x, y, 1 + z. Within the trithionato dianion, the S1–S2 and S2–S3 bond distances are 2.1450 (11) and 2.1184 (12) Å, respectively, and the S1–S2–S3 angle is 101.68 (5) Å. In the crystal structure, there is a considerable number of hydrogen bonding interactions. These occur within the supramolecular chain as well as between chains to form a 2-D array in the ac plane, Fig. 3. Connections between layers lead to a 3-D network, Fig. 4.

Structures containing the trithionato dianion are comparatively rare, with only three such examples (Chun et al., 2000; Díaz de Vivar et al., 2005; Ferrari et al., 1977). In the same way, structures having [Cu(OH₂)₄]²⁺ centres bridged by bi-functional sulfonato ligands are uncommon (Charbonnier et al., 1977a, b; Pasquale et al., 2007; Wang et al., 2005).

Experimental

The blue crystal used in the present study was harvested from the hydrothermal reaction of stoichiometric amounts of CuCl, SeS₂, S, and N₂H₄.H₂O. The reagents were heated to 420 K for 3 d in a 25 ml Teflon-lined stainless-steel autoclave. After the reaction, the bomb was cooled to room temperature. The solution was filtered and layered with methanol. After four weeks, blue needles of (I) were collected and dried in air.

Refinement

The O-bound H-atoms were located in a difference Fourier map and were refined with O–H and H···H restraints of 0.840±0.001 Å and 1.39±0.01 Å, respectively, and with U_iso(H) = 1.5U_eq(O).

Figures

Fig. 1.

The asymmetric unit in (I) extended to show the coordination geometry about the Cu atom, showing displacement ellipsoids at the 50% probability level. Symmetry code: (i) 1 + x, y, 1 + z.

Fig. 2.

Supramolecular chain formation in (I). Colour code: Cu, brown; S, yellow; O, red; and H, green.

Fig. 3.

Supramolecular layer formation in (I) viewed in projection down the b axis. Chains shown in Fig. 2 are linked via O–H···O (orange dashed lines) hydrogen bonds. Colour code as for Fig. 2.

Fig. 4.

Unit-cell contents for (I) highlighting the 3-D network. The O–H···O hydrogen bonds are shown as orange dashed lines. Colour code as for Fig. 2.

Crystal data

[Cu(S3O6)(H2O)4]	F(000) = 660
Mr = 327.78	Dx = 2.037 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6028 reflections
a = 7.1816 (1) Å	θ = 3.1–27.6°
b = 21.4405 (4) Å	µ = 2.66 mm−1
c = 7.7286 (1) Å	T = 100 K
β = 116.092 (1)°	Needle, blue
V = 1068.75 (3) Å3	0.30 × 0.10 × 0.05 mm
Z = 4

Data collection

Bruker SMART APEXII diffractometer	2434 independent reflections
Radiation source: sealed tube	2291 reflections with I > 2σ(I)
graphite	Rint = 0.020
φ and ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.911, Tmax = 1	k = −27→27
9081 measured reflections	l = −9→10

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0493P)2 + 7.019P] where P = (Fo2 + 2Fc2)/3
2434 reflections	(Δ/σ)max = 0.001
151 parameters	Δρmax = 1.47 e Å−3
12 restraints	Δρmin = −0.84 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cu	0.19601 (7)	0.85880 (2)	0.51918 (6)	0.01169 (14)
O1	0.2615 (5)	0.81059 (15)	0.3309 (5)	0.0268 (7)
H1O	0.1475	0.8079	0.2323	0.040*
H2O	0.3104	0.7753	0.3752	0.040*
O2	0.2609 (5)	0.93801 (15)	0.4087 (5)	0.0287 (7)
H3O	0.3791	0.9353	0.4120	0.043*
H4O	0.2480	0.9710	0.4611	0.043*
O3	0.1488 (5)	0.90825 (15)	0.7159 (5)	0.0264 (7)
H5O	0.1820	0.9459	0.7188	0.040*
H6O	0.0233	0.9046	0.6919	0.040*
O4	0.1007 (5)	0.77999 (16)	0.6068 (5)	0.0293 (7)
H7O	0.0526	0.7840	0.6876	0.044*
H8O	0.0311	0.7547	0.5190	0.044*
S1	−0.31167 (13)	0.90509 (4)	0.20735 (12)	0.01136 (19)
S2	−0.27573 (13)	0.94093 (4)	−0.03534 (11)	0.00925 (18)
S3	−0.28093 (13)	0.85804 (4)	−0.18661 (12)	0.0127 (2)
O5	−0.1785 (4)	0.85083 (12)	0.2738 (4)	0.0145 (5)
O6	−0.2390 (5)	0.95873 (13)	0.3340 (4)	0.0194 (6)
O7	−0.5286 (4)	0.89104 (14)	0.1427 (4)	0.0185 (6)
O8	−0.4614 (4)	0.82243 (13)	−0.2060 (4)	0.0168 (5)
O9	−0.0873 (4)	0.82490 (13)	−0.0809 (4)	0.0169 (5)
O10	−0.2992 (4)	0.88484 (15)	−0.3653 (4)	0.0207 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu	0.0123 (2)	0.0112 (2)	0.0125 (2)	−0.00021 (15)	0.00630 (17)	0.00000 (15)
O1	0.0282 (16)	0.0247 (15)	0.0250 (16)	0.0013 (13)	0.0094 (13)	−0.0021 (12)
O2	0.0325 (17)	0.0244 (16)	0.0334 (18)	0.0006 (13)	0.0183 (15)	0.0002 (13)
O3	0.0279 (16)	0.0248 (15)	0.0277 (16)	−0.0018 (12)	0.0133 (14)	−0.0020 (12)
O4	0.0320 (17)	0.0271 (16)	0.0283 (17)	−0.0018 (13)	0.0130 (14)	0.0019 (13)
S1	0.0125 (4)	0.0115 (4)	0.0101 (4)	0.0007 (3)	0.0050 (3)	0.0010 (3)
S2	0.0132 (4)	0.0077 (4)	0.0085 (4)	−0.0006 (3)	0.0063 (3)	0.0003 (3)
S3	0.0111 (4)	0.0163 (4)	0.0106 (4)	0.0000 (3)	0.0047 (3)	−0.0002 (3)
O5	0.0164 (13)	0.0124 (12)	0.0133 (12)	0.0027 (10)	0.0052 (10)	0.0026 (9)
O6	0.0286 (15)	0.0139 (13)	0.0148 (13)	−0.0004 (11)	0.0087 (11)	−0.0020 (10)
O7	0.0131 (13)	0.0269 (15)	0.0162 (13)	0.0011 (11)	0.0071 (11)	0.0044 (11)
O8	0.0140 (12)	0.0183 (13)	0.0173 (13)	−0.0026 (10)	0.0063 (10)	−0.0024 (10)
O9	0.0137 (12)	0.0189 (13)	0.0164 (13)	0.0031 (10)	0.0049 (10)	−0.0007 (10)
O10	0.0183 (13)	0.0321 (16)	0.0130 (13)	0.0008 (12)	0.0081 (11)	0.0034 (11)

Geometric parameters (Å, °)

Cu—O3	2.001 (3)	O3—H6O	0.8401
Cu—O1	2.002 (3)	O4—H7O	0.8401
Cu—O2	2.045 (3)	O4—H8O	0.8401
Cu—O4	2.047 (3)	S1—O7	1.443 (3)
Cu—O5	2.524 (3)	S1—O5	1.449 (3)
Cu—O8i	2.564 (3)	S1—O6	1.450 (3)
O1—H1O	0.8401	S1—S2	2.1450 (11)
O1—H2O	0.8401	S2—S3	2.1184 (12)
O2—H3O	0.8401	S3—O10	1.448 (3)
O2—H4O	0.8401	S3—O9	1.452 (3)
O3—H5O	0.8401	S3—O8	1.454 (3)
O3—Cu—O1	176.54 (14)	Cu—O4—H8O	116.6
O3—Cu—O2	91.32 (13)	H7O—O4—H8O	111.9
O1—Cu—O2	87.46 (13)	O7—S1—O5	113.51 (17)
O3—Cu—O4	89.60 (14)	O7—S1—O6	114.36 (18)
O1—Cu—O4	91.95 (14)	O5—S1—O6	114.32 (16)
O2—Cu—O4	174.05 (14)	O7—S1—S2	107.39 (12)
Cu—O1—H1O	104.4	O5—S1—S2	106.44 (12)
Cu—O1—H2O	111.0	O6—S1—S2	99.21 (12)
H1O—O1—H2O	111.9	S3—S2—S1	101.68 (5)
Cu—O2—H3O	110.1	O10—S3—O9	113.18 (17)
Cu—O2—H4O	113.9	O10—S3—O8	114.04 (17)
H3O—O2—H4O	111.5	O9—S3—O8	113.01 (17)
Cu—O3—H5O	112.9	O10—S3—S2	99.54 (13)
Cu—O3—H6O	107.9	O9—S3—S2	108.67 (12)
H5O—O3—H6O	111.2	O8—S3—S2	107.22 (12)
Cu—O4—H7O	118.0
O7—S1—S2—S3	−78.83 (14)	S1—S2—S3—O10	168.90 (12)
O5—S1—S2—S3	43.05 (12)	S1—S2—S3—O9	−72.54 (13)
O6—S1—S2—S3	161.92 (13)	S1—S2—S3—O8	49.91 (13)

Symmetry codes: (i) x+1, y, z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O9	0.84	2.29	3.080 (5)	157
O1—H2o···O9ii	0.84	2.25	3.071 (4)	166
O2—H3o···O10i	0.84	2.44	3.079 (5)	133
O2—H4o···O6iii	0.84	2.21	3.026 (4)	165
O3—H5o···O6iii	0.84	2.16	2.987 (4)	169
O3—H6o···O10iv	0.84	2.20	3.037 (5)	174
O4—H7o···O9iv	0.84	2.56	3.383 (5)	166
O4—H8o···O8ii	0.84	2.42	3.149 (4)	146

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