supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportcited insimilar papers Open access

Acta Cryst. (2009). E65, m1345    [ doi:10.1107/S1600536809040604 ]

Hexaaquazinc(II) bis(4-hydroxybenzenesulfonate) dihydrate

Z.-B. Zhu, S. Gao and S. W. Ng

Abstract top

In the crystal structure of the title compound, [Zn(H2O)6](C6H5O4S)2·2H2O, the ZnII atom lies on a center of inversion. The complex cation interacts with the anion and uncoordinated water molecules by O-H...O hydrogen bonds, generating a three-dimensional network. The anion is disordered over two equal positions along the hydroxy-sulfonate C-C axis.

Related literature top

The hexaaquanickel, hexaaquacobalt and hexaaquacopper salts are not isostructural; see: Du et al. (2007); Kosnic et al. (1992); Liu & Zeng (2007).

Experimental top

Sodium 3-carboxy-4-hydroxybenzenesulfonate (0.52 g, 2 mmol) was reacted with zinc carbonate (0.25 g, 2 mmol) in water. The mixture was sealed in a 50-ml Teflon-lined stainless-steel bomb and heat at 403 K for three days. The bomb was then allowed to cool naturally to room temperature. Colorless prismatic crystals were obtained. C&H elemental analysis. Calc. for C12H26O16S2Zn: C 25.93, H 4.71%; found: C 25.97, H 4.77%. The carboxyl group of sodium 3-carboxy-4-hydroxybenzenesulfonate was apparently cleaved under the hydrothermal conditions.

Refinement top

The aromatic ring is disordered over two positions in respect of four carbon atoms. 1,2-Related carbon-carbon distances were restrained to 1.39±0.01 Å and the 1,4-related ones to 2.78±0.01 Å. Each component ring was restrained to be nearly flat. As the disorder refined to nearly 1:1, the occupancy of the disordered atoms was set as exactly 0.5.

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The water and hydroxy H-atoms were refined with a distance restraint of N–H 0.84±0.01 Å; their temperature factors were refined.

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
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [Zn(H2O)6] 2[C6H5O4S].2H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in the aromatic ring is not shown.
Hexaaquazinc(II) bis(4-hydroxybenzenesulfonate) dihydrate top
Crystal data top
[Zn(H2O)6](C6H5O4S)2·2H2OZ = 1
Mr = 555.82F(000) = 288
Triclinic, P1Dx = 1.642 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.2763 (5) ÅCell parameters from 4800 reflections
b = 7.0509 (7) Åθ = 3.1–27.5°
c = 13.3151 (11) ŵ = 1.35 mm−1
α = 78.479 (3)°T = 293 K
β = 76.832 (2)°Prism, colorless
γ = 88.051 (3)°0.23 × 0.18 × 0.15 mm
V = 562.15 (9) Å3
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		2538 independent reflections
Radiation source: fine-focus sealed tube2283 reflections with I > 2σ(I)
graphiteRint = 0.026
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −8→7
Tmin = 0.746, Tmax = 0.823k = −9→9
5523 measured reflectionsl = −17→16
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0503P)2 + 0.0371P]
where P = (Fo2 + 2Fc2)/3
2538 reflections(Δ/σ)max = 0.001
214 parametersΔρmax = 0.35 e Å−3
26 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[Zn(H2O)6](C6H5O4S)2·2H2Oγ = 88.051 (3)°
Mr = 555.82V = 562.15 (9) Å3
Triclinic, P1Z = 1
a = 6.2763 (5) ÅMo Kα radiation
b = 7.0509 (7) ŵ = 1.35 mm−1
c = 13.3151 (11) ÅT = 293 K
α = 78.479 (3)°0.23 × 0.18 × 0.15 mm
β = 76.832 (2)°
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		2538 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2283 reflections with I > 2σ(I)
Tmin = 0.746, Tmax = 0.823Rint = 0.026
5523 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076Δρmax = 0.35 e Å−3
S = 1.04Δρmin = −0.47 e Å−3
2538 reflectionsAbsolute structure: ?
214 parametersFlack parameter: ?
26 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.50000.50000.50000.02554 (10)
S10.02762 (6)0.11701 (5)0.29910 (3)0.02660 (11)
O10.0715 (2)0.28397 (17)0.34183 (9)0.0345 (3)
O20.1531 (2)−0.04947 (19)0.33502 (10)0.0451 (3)
O3−0.2054 (2)0.07467 (19)0.31965 (10)0.0394 (3)
O40.3707 (3)0.3376 (3)−0.15810 (11)0.0584 (4)
H40.5063 (16)0.337 (4)−0.1732 (19)0.051 (7)*
O1W0.4557 (2)0.2913 (2)0.41675 (12)0.0468 (4)
H110.349 (3)0.290 (4)0.3908 (19)0.062 (7)*
H120.556 (3)0.232 (3)0.3850 (15)0.043 (6)*
O2W0.2082 (2)0.62516 (18)0.47666 (9)0.0329 (3)
H210.115 (3)0.637 (3)0.5314 (12)0.052 (7)*
H220.207 (4)0.7338 (19)0.4375 (14)0.047 (6)*
O3W0.3176 (2)0.32548 (19)0.63807 (9)0.0377 (3)
H310.292 (4)0.2107 (17)0.639 (2)0.061 (7)*
H320.313 (4)0.346 (4)0.6979 (11)0.060 (7)*
O4W0.2020 (3)0.6528 (2)0.21483 (10)0.0459 (3)
H410.142 (4)0.551 (3)0.2522 (18)0.073 (9)*
H420.159 (4)0.729 (3)0.2548 (18)0.064 (8)*
C10.1270 (3)0.1789 (2)0.16170 (12)0.0269 (3)
C40.2937 (3)0.2822 (3)−0.05256 (13)0.0371 (4)
C20.3442 (7)0.1495 (7)0.1195 (3)0.0359 (9)0.50
H20.43640.08990.16390.043*0.50
C30.4286 (7)0.2065 (7)0.0124 (3)0.0376 (11)0.50
H30.58030.1929−0.01600.045*0.50
C50.0730 (6)0.3207 (7)−0.0106 (3)0.0390 (8)0.50
H5−0.01730.3845−0.05500.047*0.50
C6−0.0097 (6)0.2634 (7)0.0973 (3)0.0349 (8)0.50
H6−0.15980.28210.12670.042*0.50
C2'0.3409 (6)0.2436 (7)0.1239 (3)0.0324 (9)0.50
H2'0.43000.25390.17150.039*0.50
C3'0.4255 (8)0.2935 (7)0.0161 (3)0.0374 (11)0.50
H3'0.57360.3353−0.01030.045*0.50
C5'0.0822 (6)0.2055 (7)−0.0137 (3)0.0416 (9)0.50
H5'−0.00430.1873−0.06110.050*0.50
C6'−0.0028 (6)0.1555 (7)0.0946 (3)0.0335 (7)0.50
H6'−0.14800.10610.12140.040*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02646 (15)0.02624 (15)0.02455 (15)0.00073 (9)−0.00629 (10)−0.00595 (9)
S10.0311 (2)0.0229 (2)0.02348 (19)−0.00025 (15)−0.00199 (16)−0.00367 (13)
O10.0408 (7)0.0331 (6)0.0298 (6)−0.0060 (5)−0.0032 (5)−0.0110 (4)
O20.0593 (9)0.0357 (7)0.0329 (6)0.0145 (6)−0.0056 (6)0.0030 (5)
O30.0338 (6)0.0404 (7)0.0410 (7)−0.0092 (5)0.0023 (5)−0.0117 (5)
O40.0538 (10)0.0940 (13)0.0232 (6)−0.0074 (9)−0.0055 (7)−0.0044 (7)
O1W0.0357 (7)0.0558 (9)0.0648 (9)0.0112 (6)−0.0203 (7)−0.0403 (7)
O2W0.0306 (6)0.0357 (7)0.0282 (6)0.0056 (5)−0.0048 (5)0.0005 (5)
O3W0.0504 (8)0.0336 (7)0.0254 (6)−0.0108 (6)−0.0037 (5)−0.0009 (5)
O4W0.0596 (9)0.0382 (8)0.0342 (7)−0.0030 (6)−0.0011 (6)−0.0044 (6)
C10.0320 (8)0.0238 (7)0.0236 (7)0.0008 (6)−0.0041 (6)−0.0044 (5)
C40.0449 (10)0.0421 (10)0.0240 (8)−0.0014 (8)−0.0075 (7)−0.0061 (7)
C20.039 (2)0.038 (2)0.0278 (18)0.007 (2)−0.0079 (15)−0.0010 (18)
C30.033 (2)0.047 (3)0.0263 (19)0.002 (2)0.0006 (15)−0.002 (2)
C50.044 (2)0.043 (2)0.0318 (19)−0.0016 (18)−0.0157 (16)−0.0018 (16)
C60.0322 (19)0.040 (2)0.0327 (18)0.0040 (17)−0.0096 (14)−0.0059 (16)
C2'0.0311 (18)0.045 (2)0.0228 (16)−0.0036 (19)−0.0072 (13)−0.0081 (18)
C3'0.034 (2)0.043 (3)0.032 (2)−0.003 (2)0.0011 (15)−0.008 (2)
C5'0.046 (2)0.055 (3)0.0289 (18)0.001 (2)−0.0176 (16)−0.0102 (18)
C6'0.0317 (18)0.039 (2)0.0320 (18)−0.0016 (16)−0.0082 (14)−0.0093 (16)
Geometric parameters (Å, °) top
Zn1—O2Wi2.0660 (11)C1—C6'1.375 (4)
Zn1—O2W2.0660 (11)C1—C21.377 (4)
Zn1—O1W2.0713 (13)C1—C2'1.380 (4)
Zn1—O1Wi2.0713 (13)C1—C61.387 (4)
Zn1—O3W2.1066 (12)C4—C31.367 (4)
Zn1—O3Wi2.1066 (12)C4—C3'1.380 (5)
S1—O21.4530 (12)C4—C5'1.395 (4)
S1—O31.4552 (13)C4—C51.409 (4)
S1—O11.4651 (12)C2—C31.384 (5)
S1—C11.7624 (15)C2—H20.9500
O4—C41.358 (2)C3—H30.9500
O4—H40.83 (1)C5—C61.392 (5)
O1W—H110.82 (1)C5—H50.9500
O1W—H120.83 (1)C6—H60.9500
O2W—H210.84 (1)C2'—C3'1.389 (5)
O2W—H220.84 (1)C2'—H2'0.9500
O3W—H310.83 (1)C3'—H3'0.9500
O3W—H320.83 (1)C5'—C6'1.395 (5)
O4W—H410.83 (1)C5'—H5'0.9500
O4W—H420.83 (1)C6'—H6'0.9500
O2Wi—Zn1—O2W180.000 (1)C6'—C1—S1120.64 (18)
O2Wi—Zn1—O1W90.22 (5)C2—C1—S1119.18 (18)
O2W—Zn1—O1W89.78 (5)C2'—C1—S1118.08 (17)
O2Wi—Zn1—O1Wi89.78 (5)C6—C1—S1120.43 (18)
O2W—Zn1—O1Wi90.22 (5)O4—C4—C3121.5 (2)
O1W—Zn1—O1Wi180.0O4—C4—C3'120.7 (2)
O2Wi—Zn1—O3W92.58 (5)O4—C4—C5'119.52 (19)
O2W—Zn1—O3W87.42 (5)C3—C4—C5'111.2 (3)
O1W—Zn1—O3W89.15 (6)C3'—C4—C5'119.8 (3)
O1Wi—Zn1—O3W90.85 (6)O4—C4—C5117.71 (19)
O2Wi—Zn1—O3Wi87.42 (5)C3—C4—C5120.6 (3)
O2W—Zn1—O3Wi92.58 (5)C3'—C4—C5112.2 (3)
O1W—Zn1—O3Wi90.85 (6)C1—C2—C3120.2 (3)
O1Wi—Zn1—O3Wi89.15 (6)C1—C2—H2119.9
O3W—Zn1—O3Wi180.0C3—C2—H2119.9
O2—S1—O3112.90 (9)C4—C3—C2120.0 (4)
O2—S1—O1110.94 (8)C4—C3—H3120.0
O3—S1—O1112.10 (7)C2—C3—H3120.0
O2—S1—C1105.84 (7)C6—C5—C4118.6 (3)
O3—S1—C1107.93 (8)C6—C5—H5120.7
O1—S1—C1106.68 (7)C4—C5—H5120.7
C4—O4—H4110.5 (17)C1—C6—C5120.0 (3)
Zn1—O1W—H11122.4 (17)C1—C6—H6120.0
Zn1—O1W—H12124.5 (16)C5—C6—H6120.0
H11—O1W—H12109 (2)C1—C2'—C3'119.9 (3)
Zn1—O2W—H21115.9 (16)C1—C2'—H2'120.1
Zn1—O2W—H22120.5 (16)C3'—C2'—H2'120.1
H21—O2W—H22103 (2)C4—C3'—C2'119.7 (4)
Zn1—O3W—H31119.8 (18)C4—C3'—H3'120.1
Zn1—O3W—H32122.9 (19)C2'—C3'—H3'120.1
H31—O3W—H32112 (2)C4—C5'—C6'120.3 (3)
H41—O4W—H42100 (3)C4—C5'—H5'119.9
C6'—C1—C2111.5 (2)C6'—C5'—H5'119.9
C6'—C1—C2'121.2 (2)C1—C6'—C5'118.9 (3)
C2—C1—C6120.3 (2)C1—C6'—H6'120.6
C2'—C1—C6112.6 (2)C5'—C6'—H6'120.6
O2—S1—C1—C6'112.2 (3)C5'—C4—C5—C676.9 (5)
O3—S1—C1—C6'−8.9 (3)C6'—C1—C6—C5−83.1 (5)
O1—S1—C1—C6'−129.6 (2)C2—C1—C6—C5−0.7 (6)
O2—S1—C1—C2−32.7 (3)C2'—C1—C6—C530.0 (5)
O3—S1—C1—C2−153.8 (3)S1—C1—C6—C5176.7 (3)
O1—S1—C1—C285.5 (3)C4—C5—C6—C13.1 (6)
O2—S1—C1—C2'−65.2 (3)C6'—C1—C2'—C3'2.6 (6)
O3—S1—C1—C2'173.7 (2)C2—C1—C2'—C3'79.8 (6)
O1—S1—C1—C2'53.1 (3)C6—C1—C2'—C3'−32.5 (5)
O2—S1—C1—C6149.9 (2)S1—C1—C2'—C3'179.9 (4)
O3—S1—C1—C628.7 (3)O4—C4—C3'—C2'177.4 (4)
O1—S1—C1—C6−91.9 (3)C3—C4—C3'—C2'−82.7 (8)
C6'—C1—C2—C335.6 (5)C5'—C4—C3'—C2'−5.3 (6)
C2'—C1—C2—C3−80.8 (6)C5—C4—C3'—C2'31.8 (5)
C6—C1—C2—C30.9 (6)C1—C2'—C3'—C41.4 (7)
S1—C1—C2—C3−176.6 (4)O4—C4—C5'—C6'−177.3 (4)
O4—C4—C3—C2−179.3 (4)C3—C4—C5'—C6'33.0 (5)
C3'—C4—C3—C284.4 (8)C3'—C4—C5'—C6'5.4 (6)
C5'—C4—C3—C2−30.3 (6)C5—C4—C5'—C6'−80.6 (5)
C5—C4—C3—C26.3 (6)C2—C1—C6'—C5'−32.4 (5)
C1—C2—C3—C4−3.7 (7)C2'—C1—C6'—C5'−2.5 (6)
O4—C4—C5—C6179.4 (4)C6—C1—C6'—C5'80.8 (5)
C3—C4—C5—C6−6.0 (6)S1—C1—C6'—C5'−179.8 (3)
C3'—C4—C5—C6−33.9 (5)C4—C5'—C6'—C1−1.5 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H11···O10.82 (1)2.00 (1)2.817 (2)175 (3)
O1w—H12···O3ii0.83 (1)1.97 (1)2.801 (2)176 (2)
O2w—H21···O1iii0.84 (1)1.99 (1)2.818 (2)168 (2)
O2w—H22···O2iv0.84 (1)1.91 (1)2.730 (2)165 (2)
O3w—H31···O3v0.83 (1)2.04 (1)2.845 (2)166 (3)
O3w—H32···O4vi0.83 (1)2.02 (1)2.827 (2)163 (3)
O4w—H41···O10.83 (1)2.02 (1)2.837 (2)166 (3)
O4w—H42···O2iv0.83 (1)2.05 (1)2.853 (2)162 (3)
O4—H4···O4wvii0.83 (1)1.79 (1)2.615 (2)176 (3)
Symmetry codes: (ii) x+1, y, z; (iii) −x, −y+1, −z+1; (iv) x, y+1, z; (v) −x, −y, −z+1; (vi) x, y, z+1; (vii) −x+1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H11···O10.82 (1)2.00 (1)2.817 (2)175 (3)
O1w—H12···O3i0.83 (1)1.97 (1)2.801 (2)176 (2)
O2w—H21···O1ii0.84 (1)1.99 (1)2.818 (2)168 (2)
O2w—H22···O2iii0.84 (1)1.91 (1)2.730 (2)165 (2)
O3w—H31···O3iv0.83 (1)2.04 (1)2.845 (2)166 (3)
O3w—H32···O4v0.83 (1)2.02 (1)2.827 (2)163 (3)
O4w—H41···O10.83 (1)2.02 (1)2.837 (2)166 (3)
O4w—H42···O2iii0.83 (1)2.05 (1)2.853 (2)162 (3)
O4—H4···O4wvi0.83 (1)1.79 (1)2.615 (2)176 (3)
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) x, y+1, z; (iv) −x, −y, −z+1; (v) x, y, z+1; (vi) −x+1, −y+1, −z.
Acknowledgements top

We thank the Natural Science Foundation of Heilongjiang Province (No. B200501), Heilongjiang University, China, and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Du, J.-M., Li, Q., Li, W., Lin, H.-M. & Guo, G.-C. (2007). Acta Cryst. E63, m2597.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Kosnic, E. J., McClymont, E. L., Hodder, R. A. & Squattrito, P. J. (1992). Inorg. Chim. Acta, 201, 143–151.

Liu, Y.-Q. & Zeng, X.-R. (2007). Acta Cryst. E63, m2414.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.