Hexaaqua­zinc(II) bis­(4-hydroxy­benzene­sulfonate) dihydrate

Gao, S.; Ng, S.W.

doi:10.1107/S1600536809048375

metal-organic compounds

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Volume 65| Part 12| December 2009| Page m1633

doi:10.1107/S1600536809048375

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Hexaaquazinc(II) bis(4-hydroxybenzenesulfonate) dihydrate

Shan Gao ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 14 November 2009; accepted 14 November 2009; online 21 November 2009)

The asymmetric unit of the title hydrated molecular salt, [Zn(H₂O)₆](C₆H₅O₄S)₂·2H₂O, contains two half-cations, two anions and two uncoordinated water molecules. Both cations are completed by crystallographic inversion symmetry, generating almost regular ZnO₆ octahedra. In the crystal, the cations, anions and uncoordinated water molecules are linked by O—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For the isostructural cobalt and nickel analogs of the title compound, see: Du et al. (2007 ) and Kosnic et al. (1992 ), respectively.

Experimental

Crystal data

[Zn(H₂O)₆](C₆H₅O₄S)₂·2H₂O
M_r = 555.82
Monoclinic, P 2₁ /c
a = 11.7957 (5) Å
b = 7.2590 (4) Å
c = 25.3992 (11) Å
β = 94.340 (1)°
V = 2168.57 (18) Å³
Z = 4
Mo Kα radiation
μ = 1.40 mm⁻¹
T = 293 K
0.19 × 0.19 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.777, T_max = 0.817
20669 measured reflections
4940 independent reflections
3319 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.082
S = 1.03
4940 reflections
355 parameters
18 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O2W	2.0654 (16)
Zn1—O3W	2.0692 (16)
Zn1—O1W	2.1087 (15)
Zn2—O4W	2.0763 (15)
Zn2—O6W	2.0780 (16)
Zn2—O5W	2.0849 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O1	0.84 (1)	1.93 (1)	2.763 (2)	169 (3)
O1w—H12⋯O7w	0.85 (1)	1.86 (1)	2.707 (2)	175 (2)
O2w—H21⋯O2	0.85 (1)	1.95 (1)	2.792 (2)	172 (3)
O2w—H22⋯O4ⁱ	0.85 (1)	1.92 (1)	2.745 (2)	166 (3)
O3w—H31⋯O3ⁱⁱ	0.84 (1)	1.97 (1)	2.800 (2)	168 (3)
O3w—H32⋯O7wⁱⁱ	0.84 (1)	1.95 (1)	2.790 (2)	174 (3)
O4w—H41⋯O5	0.84 (1)	1.91 (1)	2.742 (2)	174 (3)
O4w—H42⋯O1wⁱⁱⁱ	0.85 (1)	2.08 (1)	2.914 (2)	167 (3)
O5w—H51⋯O6	0.85 (1)	1.91 (1)	2.755 (2)	175 (3)
O5w—H52⋯O8^iv	0.85 (1)	1.98 (1)	2.819 (2)	168 (3)
O6w—H61⋯O8w	0.85 (1)	1.85 (1)	2.698 (2)	170 (3)
O6w—H62⋯O7^v	0.84 (1)	2.03 (1)	2.8401 (19)	163 (3)
O4—H4⋯O7ⁱ	0.85 (1)	1.93 (1)	2.777 (2)	175 (3)
O8—H8⋯O3ⁱ	0.85 (1)	1.95 (1)	2.788 (2)	172 (3)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+2, -z+1; (iii) -x+1, -y+1, -z+1; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x, -y+2, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048375/hb5229sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048375/hb5229Isup2.hkl

checkCIF report

Related literature top

For the isostructural cobalt and nickel analogs of the title compound, see: Du et al. (2007) and Kosnic et al. (1992), respectively.

Experimental top

One millimolar quantities each of zinc dichloride and p-hydroxylbenzenesulfonic acid were dissolved in water; colourless prisms of (I) were isolated after a few days.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. The molecular structure of (I) shown at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Unlabelled atoms bonded to Zn1 and Zn2 are generated by the symmetry operations (1–x, 1–y, 1–z) and (–x, 1–y, 1–z), respectively.

Hexaaquazinc(II) bis(4-hydroxybenzenesulfonate) dihydrate top

Crystal data top

[Zn(H₂O)₆](C₆H₅O₄S)₂·2H₂O	F(000) = 1152
M_r = 555.82	D_x = 1.702 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12326 reflections
a = 11.7957 (5) Å	θ = 3.2–27.5°
b = 7.2590 (4) Å	µ = 1.40 mm⁻¹
c = 25.3992 (11) Å	T = 293 K
β = 94.340 (1)°	Prism, colorless
V = 2168.57 (18) Å³	0.19 × 0.19 × 0.15 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4940 independent reflections
Radiation source: fine-focus sealed tube	3319 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scan	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −15→15
T_min = 0.777, T_max = 0.817	k = −9→9
20669 measured reflections	l = −29→32

Refinement top

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0405P)² + 0.0996P] where P = (F_o² + 2F_c²)/3
4940 reflections	(Δ/σ)_max = 0.001
355 parameters	Δρ_max = 0.33 e Å⁻³
18 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Zn(H₂O)₆](C₆H₅O₄S)₂·2H₂O	V = 2168.57 (18) Å³
M_r = 555.82	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.7957 (5) Å	µ = 1.40 mm⁻¹
b = 7.2590 (4) Å	T = 293 K
c = 25.3992 (11) Å	0.19 × 0.19 × 0.15 mm
β = 94.340 (1)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	4940 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3319 reflections with I > 2σ(I)
T_min = 0.777, T_max = 0.817	R_int = 0.040
20669 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	18 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.33 e Å⁻³
4940 reflections	Δρ_min = −0.40 e Å⁻³
355 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.5000	0.5000	0.02424 (10)
Zn2	0.0000	0.5000	0.5000	0.02415 (10)
S1	0.60479 (4)	0.93447 (8)	0.365706 (19)	0.02769 (13)
S2	0.09496 (4)	0.94376 (8)	0.36609 (2)	0.02778 (13)
O1	0.68413 (13)	0.8168 (2)	0.39683 (6)	0.0436 (4)
O2	0.48651 (12)	0.8933 (2)	0.37348 (6)	0.0367 (4)
O3	0.63007 (14)	1.1293 (2)	0.37462 (6)	0.0410 (4)
O4	0.68090 (14)	0.8205 (2)	0.14198 (5)	0.0405 (4)
O5	0.17678 (13)	0.8315 (2)	0.39749 (6)	0.0393 (4)
O6	−0.02227 (12)	0.8971 (2)	0.37348 (6)	0.0385 (4)
O7	0.11697 (13)	1.1408 (2)	0.37451 (5)	0.0359 (4)
O8	0.17676 (14)	0.8359 (2)	0.14229 (6)	0.0412 (4)
O1W	0.64682 (13)	0.6615 (2)	0.49333 (6)	0.0300 (3)
O2W	0.43907 (16)	0.5631 (3)	0.42376 (6)	0.0425 (4)
O3W	0.41407 (15)	0.7258 (2)	0.52682 (7)	0.0412 (4)
O4W	0.15569 (14)	0.5586 (3)	0.47077 (8)	0.0463 (5)
O5W	−0.08685 (14)	0.5987 (2)	0.43118 (6)	0.0361 (4)
O6W	−0.01038 (14)	0.7610 (2)	0.53290 (6)	0.0349 (4)
O7W	0.64137 (15)	0.9889 (2)	0.54413 (7)	0.0371 (4)
O8W	0.16394 (15)	0.9973 (3)	0.52453 (8)	0.0410 (4)
C1	0.62536 (16)	0.8899 (3)	0.29904 (7)	0.0243 (4)
C2	0.73038 (17)	0.8248 (3)	0.28587 (8)	0.0290 (5)
H2	0.7871	0.7971	0.3121	0.035*
C3	0.74935 (17)	0.8018 (3)	0.23319 (8)	0.0296 (5)
H3	0.8194	0.7591	0.2239	0.035*
C4	0.66492 (17)	0.8420 (3)	0.19444 (7)	0.0271 (5)
C5	0.55995 (17)	0.9073 (3)	0.20759 (8)	0.0323 (5)
H5	0.5031	0.9340	0.1813	0.039*
C6	0.54101 (17)	0.9321 (3)	0.26028 (8)	0.0299 (5)
H6	0.4714	0.9771	0.2695	0.036*
C7	0.11767 (16)	0.8998 (3)	0.29945 (8)	0.0254 (4)
C8	0.21941 (18)	0.8220 (3)	0.28634 (8)	0.0315 (5)
H8A	0.2734	0.7847	0.3128	0.038*
C9	0.23990 (18)	0.8004 (3)	0.23389 (8)	0.0329 (5)
H9	0.3080	0.7487	0.2250	0.039*
C10	0.15988 (18)	0.8550 (3)	0.19468 (8)	0.0283 (5)
C11	0.05795 (17)	0.9337 (3)	0.20744 (8)	0.0305 (5)
H11A	0.0040	0.9707	0.1810	0.037*
C12	0.03764 (17)	0.9561 (3)	0.26017 (8)	0.0283 (5)
H12A	−0.0300	1.0092	0.2691	0.034*
H4	0.7446 (14)	0.769 (4)	0.1384 (11)	0.068 (9)*
H8	0.2355 (15)	0.769 (3)	0.1402 (11)	0.060 (9)*
H11	0.659 (2)	0.694 (3)	0.4625 (5)	0.048 (8)*
H12	0.642 (2)	0.762 (2)	0.5103 (9)	0.056 (8)*
H21	0.459 (3)	0.657 (3)	0.4072 (11)	0.084 (11)*
H22	0.3924 (17)	0.494 (3)	0.4062 (9)	0.048 (8)*
H31	0.409 (2)	0.761 (4)	0.5581 (5)	0.054 (8)*
H32	0.393 (2)	0.813 (3)	0.5066 (9)	0.065 (10)*
H41	0.167 (2)	0.639 (3)	0.4480 (8)	0.058 (8)*
H42	0.2171 (14)	0.511 (3)	0.4836 (10)	0.065 (10)*
H51	−0.063 (2)	0.690 (3)	0.4144 (10)	0.073 (10)*
H52	−0.122 (2)	0.518 (3)	0.4119 (9)	0.047 (8)*
H61	0.0480 (18)	0.831 (4)	0.5340 (13)	0.102 (13)*
H62	−0.037 (2)	0.768 (4)	0.5627 (6)	0.072 (10)*
H71	0.7069 (12)	1.027 (4)	0.5550 (10)	0.053 (9)*
H72	0.603 (2)	1.004 (4)	0.5705 (8)	0.084 (12)*
H81	0.205 (2)	1.039 (4)	0.5508 (8)	0.059 (9)*
H82	0.121 (3)	1.077 (4)	0.5089 (13)	0.112 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02731 (18)	0.0253 (2)	0.02019 (17)	−0.00203 (14)	0.00222 (14)	−0.00013 (14)
Zn2	0.02819 (18)	0.0218 (2)	0.02263 (18)	−0.00079 (14)	0.00322 (14)	0.00139 (14)
S1	0.0340 (3)	0.0312 (3)	0.0185 (3)	−0.0047 (2)	0.0060 (2)	0.0007 (2)
S2	0.0349 (3)	0.0284 (3)	0.0206 (3)	−0.0069 (2)	0.0056 (2)	0.0014 (2)
O1	0.0478 (9)	0.0573 (12)	0.0259 (8)	0.0082 (8)	0.0034 (7)	0.0106 (8)
O2	0.0347 (8)	0.0444 (10)	0.0323 (8)	−0.0053 (7)	0.0119 (7)	0.0013 (7)
O3	0.0598 (10)	0.0359 (10)	0.0293 (8)	−0.0147 (8)	0.0151 (8)	−0.0076 (7)
O4	0.0484 (10)	0.0537 (12)	0.0198 (7)	0.0188 (8)	0.0061 (7)	−0.0021 (7)
O5	0.0461 (9)	0.0444 (11)	0.0272 (8)	−0.0023 (8)	0.0004 (7)	0.0092 (7)
O6	0.0368 (8)	0.0438 (11)	0.0362 (9)	−0.0103 (7)	0.0122 (7)	0.0016 (8)
O7	0.0511 (9)	0.0290 (9)	0.0292 (8)	−0.0110 (7)	0.0131 (7)	−0.0067 (7)
O8	0.0520 (11)	0.0486 (11)	0.0235 (8)	0.0167 (9)	0.0068 (8)	−0.0010 (7)
O1W	0.0377 (8)	0.0267 (9)	0.0262 (8)	−0.0057 (7)	0.0065 (7)	0.0017 (7)
O2W	0.0637 (12)	0.0380 (11)	0.0237 (9)	−0.0182 (9)	−0.0102 (8)	0.0058 (8)
O3W	0.0605 (11)	0.0352 (11)	0.0288 (9)	0.0136 (9)	0.0087 (8)	−0.0025 (8)
O4W	0.0312 (9)	0.0519 (12)	0.0574 (12)	0.0040 (9)	0.0129 (9)	0.0285 (10)
O5W	0.0480 (10)	0.0315 (10)	0.0274 (9)	−0.0078 (8)	−0.0060 (8)	0.0057 (8)
O6W	0.0509 (10)	0.0255 (9)	0.0297 (9)	−0.0042 (8)	0.0112 (8)	−0.0049 (7)
O7W	0.0358 (9)	0.0393 (10)	0.0370 (9)	−0.0047 (8)	0.0078 (8)	−0.0056 (8)
O8W	0.0379 (10)	0.0417 (11)	0.0431 (11)	−0.0049 (8)	0.0017 (9)	−0.0040 (9)
C1	0.0297 (11)	0.0248 (12)	0.0189 (9)	−0.0033 (9)	0.0048 (9)	0.0011 (8)
C2	0.0312 (11)	0.0305 (13)	0.0247 (10)	0.0054 (9)	−0.0023 (9)	−0.0004 (9)
C3	0.0303 (11)	0.0314 (13)	0.0274 (11)	0.0086 (9)	0.0053 (9)	−0.0025 (9)
C4	0.0372 (12)	0.0241 (12)	0.0202 (10)	0.0030 (9)	0.0037 (9)	−0.0026 (9)
C5	0.0308 (11)	0.0413 (15)	0.0241 (11)	0.0051 (10)	−0.0015 (9)	−0.0007 (10)
C6	0.0260 (10)	0.0362 (13)	0.0278 (11)	0.0016 (10)	0.0045 (9)	−0.0003 (9)
C7	0.0308 (11)	0.0221 (12)	0.0235 (10)	−0.0046 (9)	0.0024 (9)	−0.0016 (9)
C8	0.0347 (12)	0.0315 (13)	0.0277 (11)	0.0052 (10)	−0.0019 (10)	0.0004 (9)
C9	0.0343 (12)	0.0332 (13)	0.0316 (12)	0.0089 (10)	0.0050 (10)	−0.0027 (10)
C10	0.0381 (12)	0.0251 (12)	0.0221 (10)	0.0008 (9)	0.0057 (9)	−0.0004 (9)
C11	0.0308 (11)	0.0332 (13)	0.0267 (11)	0.0052 (10)	−0.0036 (9)	0.0004 (9)
C12	0.0273 (11)	0.0285 (12)	0.0296 (12)	0.0000 (9)	0.0046 (9)	−0.0021 (9)

Geometric parameters (Å, º) top

Zn1—O2W	2.0654 (16)	O4W—H41	0.840 (10)
Zn1—O2Wⁱ	2.0654 (16)	O4W—H42	0.847 (10)
Zn1—O3W	2.0692 (16)	O5W—H51	0.846 (10)
Zn1—O3Wⁱ	2.0692 (16)	O5W—H52	0.849 (10)
Zn1—O1Wⁱ	2.1087 (15)	O6W—H61	0.854 (10)
Zn1—O1W	2.1087 (15)	O6W—H62	0.842 (10)
Zn2—O4Wⁱⁱ	2.0763 (15)	O7W—H71	0.847 (10)
Zn2—O4W	2.0763 (15)	O7W—H72	0.846 (10)
Zn2—O6W	2.0780 (16)	O8W—H81	0.849 (10)
Zn2—O6Wⁱⁱ	2.0780 (16)	O8W—H82	0.848 (10)
Zn2—O5W	2.0849 (16)	C1—C6	1.380 (3)
Zn2—O5Wⁱⁱ	2.0849 (16)	C1—C2	1.390 (3)
S1—O2	1.4549 (14)	C2—C3	1.383 (3)
S1—O1	1.4555 (17)	C2—H2	0.9300
S1—O3	1.4598 (17)	C3—C4	1.377 (3)
S1—C1	1.7587 (19)	C3—H3	0.9300
S2—O6	1.4495 (15)	C4—C5	1.390 (3)
S2—O5	1.4542 (16)	C5—C6	1.385 (3)
S2—O7	1.4666 (16)	C5—H5	0.9300
S2—C7	1.763 (2)	C6—H6	0.9300
O4—C4	1.369 (2)	C7—C12	1.382 (3)
O4—H4	0.851 (10)	C7—C8	1.389 (3)
O8—C10	1.367 (2)	C8—C9	1.381 (3)
O8—H8	0.849 (10)	C8—H8A	0.9300
O1W—H11	0.843 (10)	C9—C10	1.378 (3)
O1W—H12	0.849 (10)	C9—H9	0.9300
O2W—H21	0.845 (10)	C10—C11	1.391 (3)
O2W—H22	0.846 (10)	C11—C12	1.388 (3)
O3W—H31	0.840 (10)	C11—H11A	0.9300
O3W—H32	0.841 (10)	C12—H12A	0.9300

O2W—Zn1—O2Wⁱ	180.0	Zn1—O3W—H31	128.5 (19)
O2W—Zn1—O3W	89.34 (7)	Zn1—O3W—H32	121.7 (19)
O2Wⁱ—Zn1—O3W	90.66 (7)	H31—O3W—H32	108 (3)
O2W—Zn1—O3Wⁱ	90.66 (7)	Zn2—O4W—H41	125.1 (18)
O2Wⁱ—Zn1—O3Wⁱ	89.34 (7)	Zn2—O4W—H42	122.1 (18)
O3W—Zn1—O3Wⁱ	180.0	H41—O4W—H42	112 (2)
O2W—Zn1—O1Wⁱ	88.23 (6)	Zn2—O5W—H51	122 (2)
O2Wⁱ—Zn1—O1Wⁱ	91.77 (6)	Zn2—O5W—H52	115.8 (18)
O3W—Zn1—O1Wⁱ	89.32 (7)	H51—O5W—H52	114 (3)
O3Wⁱ—Zn1—O1Wⁱ	90.68 (7)	Zn2—O6W—H61	119 (2)
O2W—Zn1—O1W	91.77 (6)	Zn2—O6W—H62	117 (2)
O2Wⁱ—Zn1—O1W	88.23 (6)	H61—O6W—H62	107 (3)
O3W—Zn1—O1W	90.68 (7)	H71—O7W—H72	104 (3)
O3Wⁱ—Zn1—O1W	89.32 (7)	H81—O8W—H82	114 (3)
O1Wⁱ—Zn1—O1W	180.0	C6—C1—C2	120.75 (18)
O4Wⁱⁱ—Zn2—O4W	180.0	C6—C1—S1	120.10 (15)
O4Wⁱⁱ—Zn2—O6W	87.85 (7)	C2—C1—S1	118.98 (16)
O4W—Zn2—O6W	92.15 (7)	C3—C2—C1	119.08 (19)
O4Wⁱⁱ—Zn2—O6Wⁱⁱ	92.15 (7)	C3—C2—H2	120.5
O4W—Zn2—O6Wⁱⁱ	87.85 (7)	C1—C2—H2	120.5
O6W—Zn2—O6Wⁱⁱ	180.0	C4—C3—C2	120.31 (18)
O4Wⁱⁱ—Zn2—O5W	88.76 (7)	C4—C3—H3	119.8
O4W—Zn2—O5W	91.24 (7)	C2—C3—H3	119.8
O6W—Zn2—O5W	89.07 (7)	O4—C4—C3	121.75 (18)
O6Wⁱⁱ—Zn2—O5W	90.93 (7)	O4—C4—C5	117.61 (19)
O4Wⁱⁱ—Zn2—O5Wⁱⁱ	91.24 (7)	C3—C4—C5	120.64 (18)
O4W—Zn2—O5Wⁱⁱ	88.76 (7)	C6—C5—C4	119.2 (2)
O6W—Zn2—O5Wⁱⁱ	90.93 (7)	C6—C5—H5	120.4
O6Wⁱⁱ—Zn2—O5Wⁱⁱ	89.07 (7)	C4—C5—H5	120.4
O5W—Zn2—O5Wⁱⁱ	180.0	C1—C6—C5	120.01 (19)
O2—S1—O1	112.93 (10)	C1—C6—H6	120.0
O2—S1—O3	111.38 (10)	C5—C6—H6	120.0
O1—S1—O3	111.66 (10)	C12—C7—C8	120.14 (19)
O2—S1—C1	107.25 (9)	C12—C7—S2	119.64 (15)
O1—S1—C1	106.56 (9)	C8—C7—S2	120.03 (16)
O3—S1—C1	106.63 (9)	C9—C8—C7	119.7 (2)
O6—S2—O5	113.46 (9)	C9—C8—H8A	120.2
O6—S2—O7	111.65 (9)	C7—C8—H8A	120.2
O5—S2—O7	111.33 (10)	C10—C9—C8	120.29 (19)
O6—S2—C7	107.33 (9)	C10—C9—H9	119.9
O5—S2—C7	106.41 (9)	C8—C9—H9	119.9
O7—S2—C7	106.16 (9)	O8—C10—C9	122.13 (18)
C4—O4—H4	109.9 (19)	O8—C10—C11	117.43 (19)
C10—O8—H8	107.3 (19)	C9—C10—C11	120.44 (18)
Zn1—O1W—H11	115.8 (17)	C10—C11—C12	119.2 (2)
Zn1—O1W—H12	110.2 (17)	C10—C11—H11A	120.4
H11—O1W—H12	105 (2)	C12—C11—H11A	120.4
Zn1—O2W—H21	124 (2)	C7—C12—C11	120.23 (19)
Zn1—O2W—H22	121.9 (19)	C7—C12—H12A	119.9
H21—O2W—H22	114 (3)	C11—C12—H12A	119.9

O2—S1—C1—C6	37.7 (2)	O6—S2—C7—C12	44.6 (2)
O1—S1—C1—C6	158.94 (18)	O5—S2—C7—C12	166.37 (17)
O3—S1—C1—C6	−81.67 (19)	O7—S2—C7—C12	−74.94 (19)
O2—S1—C1—C2	−146.98 (17)	O6—S2—C7—C8	−140.39 (17)
O1—S1—C1—C2	−25.8 (2)	O5—S2—C7—C8	−18.6 (2)
O3—S1—C1—C2	93.60 (18)	O7—S2—C7—C8	100.09 (18)
C6—C1—C2—C3	−0.3 (3)	C12—C7—C8—C9	−0.3 (3)
S1—C1—C2—C3	−175.53 (16)	S2—C7—C8—C9	−175.31 (17)
C1—C2—C3—C4	−0.4 (3)	C7—C8—C9—C10	−0.2 (3)
C2—C3—C4—O4	−179.9 (2)	C8—C9—C10—O8	−179.9 (2)
C2—C3—C4—C5	0.5 (3)	C8—C9—C10—C11	0.4 (3)
O4—C4—C5—C6	−179.5 (2)	O8—C10—C11—C12	−179.8 (2)
C3—C4—C5—C6	0.1 (3)	C9—C10—C11—C12	−0.1 (3)
C2—C1—C6—C5	0.9 (3)	C8—C7—C12—C11	0.6 (3)
S1—C1—C6—C5	176.08 (17)	S2—C7—C12—C11	175.62 (17)
C4—C5—C6—C1	−0.8 (3)	C10—C11—C12—C7	−0.4 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O1	0.84 (1)	1.93 (1)	2.763 (2)	169 (3)
O1w—H12···O7w	0.85 (1)	1.86 (1)	2.707 (2)	175 (2)
O2w—H21···O2	0.85 (1)	1.95 (1)	2.792 (2)	172 (3)
O2w—H22···O4ⁱⁱⁱ	0.85 (1)	1.92 (1)	2.745 (2)	166 (3)
O3w—H31···O3^iv	0.84 (1)	1.97 (1)	2.800 (2)	168 (3)
O3w—H32···O7w^iv	0.84 (1)	1.95 (1)	2.790 (2)	174 (3)
O4w—H41···O5	0.84 (1)	1.91 (1)	2.742 (2)	174 (3)
O4w—H42···O1wⁱ	0.85 (1)	2.08 (1)	2.914 (2)	167 (3)
O5w—H51···O6	0.85 (1)	1.91 (1)	2.755 (2)	175 (3)
O5w—H52···O8^v	0.85 (1)	1.98 (1)	2.819 (2)	168 (3)
O6w—H61···O8w	0.85 (1)	1.85 (1)	2.698 (2)	170 (3)
O6w—H62···O7^vi	0.84 (1)	2.03 (1)	2.8401 (19)	163 (3)
O4—H4···O7ⁱⁱⁱ	0.85 (1)	1.93 (1)	2.777 (2)	175 (3)
O8—H8···O3ⁱⁱⁱ	0.85 (1)	1.95 (1)	2.788 (2)	172 (3)

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

Experimental details

Crystal data
Chemical formula	[Zn(H₂O)₆](C₆H₅O₄S)₂·2H₂O
M_r	555.82
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.7957 (5), 7.2590 (4), 25.3992 (11)
β (°)	94.340 (1)
V (Å³)	2168.57 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.40
Crystal size (mm)	0.19 × 0.19 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.777, 0.817
No. of measured, independent and observed [I > 2σ(I)] reflections	20669, 4940, 3319
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.082, 1.03
No. of reflections	4940
No. of parameters	355
No. of restraints	18
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.40

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Selected bond lengths (Å) top

Zn1—O2W	2.0654 (16)	Zn2—O4W	2.0763 (15)
Zn1—O3W	2.0692 (16)	Zn2—O6W	2.0780 (16)
Zn1—O1W	2.1087 (15)	Zn2—O5W	2.0849 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O1	0.84 (1)	1.93 (1)	2.763 (2)	169 (3)
O1w—H12···O7w	0.85 (1)	1.86 (1)	2.707 (2)	175 (2)
O2w—H21···O2	0.85 (1)	1.95 (1)	2.792 (2)	172 (3)
O2w—H22···O4ⁱ	0.85 (1)	1.92 (1)	2.745 (2)	166 (3)
O3w—H31···O3ⁱⁱ	0.84 (1)	1.97 (1)	2.800 (2)	168 (3)
O3w—H32···O7wⁱⁱ	0.84 (1)	1.95 (1)	2.790 (2)	174 (3)
O4w—H41···O5	0.84 (1)	1.91 (1)	2.742 (2)	174 (3)
O4w—H42···O1wⁱⁱⁱ	0.85 (1)	2.08 (1)	2.914 (2)	167 (3)
O5w—H51···O6	0.85 (1)	1.91 (1)	2.755 (2)	175 (3)
O5w—H52···O8^iv	0.85 (1)	1.98 (1)	2.819 (2)	168 (3)
O6w—H61···O8w	0.85 (1)	1.85 (1)	2.698 (2)	170 (3)
O6w—H62···O7^v	0.84 (1)	2.03 (1)	2.8401 (19)	163 (3)
O4—H4···O7ⁱ	0.85 (1)	1.93 (1)	2.777 (2)	175 (3)
O8—H8···O3ⁱ	0.85 (1)	1.95 (1)	2.788 (2)	172 (3)

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

Acknowledgements

We thank the Key Project of Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Scientific Fund of Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University and the University of Malaya for supporting this study.

References

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