Hexaaqua­zinc(II) bis­[4-(2-hydroxy­benzyl­ideneamino)benzene­sulfonate]

In the title compound, [Zn(H₂O)₆](C₁₃H₁₀NO₄S)₂, a distorted ZnO₆ octa­hedron results from the coordination by the six water mol­ecules. Only three of the water molecules are crystallographically unique, as the Zn atom lies on an inversion center. The Zn-O bond lengths are in the range 2.054 (4)-2.073 (4) Å. A network of hydrogen bonds helps to establish the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.069
• wR factor = 0.169
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

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PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Zn1
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10

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S1. Comment

As part of our onging studies of metal coordination complexes with Shiff base ligands (Tai et al., 2005), the synthesis and structure of the title compound, (I), is reported. Six water molecules are attached to the zinc atom, resulting in a distorted ZnO₆ octahedron (Fig. 1). The C7=N1 bond length [1.280 (9) Å] implies double bond character, while C4—O9 [1.332 (9) Å] is well regarded as a single bond. The dihedral angle between the two benzene ring mean planes (C1—C6 and C8—C13) is 32.2 (3)°. A network of hydrogen bonds helps to establish the crystal packing.

Related literature

For related literature, see: Tai et al. (2005).

S2. Experimental

One mmol of zinc acetate was added to a solution of salicylaldehyde-4-aminobenzene sulfonic acid (1 mmol) in 20 ml of 95% CH₃CH₂OH. The mixture was continuously stirred for 2 h at refluxing temperature, evaporating some methanol, then, upon cooling, the solid product was collected by filtration and dried in vacuo (yield 76%). Clear blocks of (I) were obtained by evaporation from a methanol solution after a week.

S3. Refinement

The water H atoms were located in a difference map and refined as riding in their as-found relative positions with U_iso(H) = 1.2U_eq(O)". Other H atoms were placed geometrically (C—H = 0.93–0.97 Å, O—H = 0.82 Å, N—H = 0.86 Å) and refined as riding with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(O).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures

Fig. 1. The complex molecule in (I) with 50% probabiility ellipsoids (arbitrary spheres for the H atoms).

Hexaaquazinc(II) bis[4-(2-hydroxybenzylideneamino)benzenesulfonate]

Crystal data

[Zn(H2O)6](C13H10NO4S)2	F(000) = 752
Mr = 726.03	Dx = 1.546 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.3255 (10) Å	Cell parameters from 2287 reflections
b = 35.312 (3) Å	θ = 2.3–23.1°
c = 6.9832 (10) Å	µ = 0.99 mm^−1
β = 90.391 (2)°	T = 298 K
V = 1559.8 (4) Å^3	Block, colourless
Z = 2	0.35 × 0.33 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2708 independent reflections
Radiation source: fine-focus sealed tube	2170 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
phi and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −7→5
Tmin = 0.723, Tmax = 0.826	k = −42→32
6994 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.168	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 5.0428P] where P = (Fo^2 + 2Fc^2)/3
2708 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.79 e Å^−3

Special details

Experimental. 'SADABS v2.0 (Bruker, 1997)'

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
Zn1	1.0000	0.0000	0.0000	0.0366 (3)
N1	0.4209 (9)	0.23101 (16)	0.5074 (8)	0.0590 (15)
O1	0.8397 (6)	0.06182 (11)	0.5063 (6)	0.0432 (10)
O2	0.5147 (6)	0.05114 (12)	0.6744 (6)	0.0517 (11)
O3	0.5147 (6)	0.05133 (12)	0.3282 (6)	0.0508 (11)
O4	0.1459 (9)	0.28426 (15)	0.5713 (9)	0.0841 (17)
H4	0.1765	0.2635	0.5271	0.126*
O5	0.7091 (6)	0.02586 (12)	0.0024 (6)	0.0508 (11)
H5A	0.6633	0.0365	−0.0989	0.061*
H5B	0.6403	0.0352	0.0953	0.061*
O6	1.1063 (6)	0.03918 (14)	−0.1984 (7)	0.0634 (13)
H6A	1.2325	0.0438	−0.2321	0.076*
H6B	1.0273	0.0452	−0.2926	0.076*
O7	1.1046 (6)	0.03394 (15)	0.2234 (6)	0.0659 (14)
H7A	1.0205	0.0428	0.3067	0.079*
H7B	1.2285	0.0364	0.2696	0.079*
S1	0.6114 (2)	0.06635 (4)	0.5026 (2)	0.0358 (4)
C1	0.5612 (8)	0.11535 (16)	0.4999 (7)	0.0352 (12)
C2	0.7196 (10)	0.14097 (18)	0.5569 (9)	0.0504 (16)
H2	0.8529	0.1323	0.5932	0.060*
C3	0.6734 (12)	0.17949 (19)	0.5582 (10)	0.0616 (19)
H3	0.7770	0.1968	0.5946	0.074*
C4	0.4756 (11)	0.19220 (18)	0.5058 (10)	0.0534 (16)
C5	0.3215 (11)	0.16672 (18)	0.4537 (10)	0.0577 (18)
H5	0.1871	0.1755	0.4217	0.069*
C6	0.3630 (9)	0.12829 (17)	0.4482 (9)	0.0486 (15)
H6	0.2584	0.1113	0.4100	0.058*
C7	0.5591 (11)	0.25692 (19)	0.4805 (9)	0.0551 (17)
H7	0.6977	0.2500	0.4540	0.066*
C8	0.5058 (12)	0.29691 (18)	0.4902 (10)	0.0567 (17)
C9	0.3022 (13)	0.3086 (2)	0.5377 (11)	0.067 (2)
C10	0.2618 (15)	0.3473 (2)	0.5562 (11)	0.072 (2)
H10	0.1281	0.3554	0.5926	0.086*
C11	0.4158 (15)	0.3734 (2)	0.5214 (11)	0.073 (2)
H11	0.3849	0.3991	0.5311	0.087*
C12	0.6194 (16)	0.3620 (2)	0.4714 (12)	0.082 (2)
H12	0.7243	0.3798	0.4477	0.098*
C13	0.6621 (13)	0.3239 (2)	0.4578 (11)	0.067 (2)
H13	0.7978	0.3160	0.4264	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0234 (4)	0.0495 (6)	0.0370 (5)	−0.0006 (4)	−0.0002 (3)	−0.0018 (4)
N1	0.064 (4)	0.047 (3)	0.066 (4)	0.013 (3)	−0.002 (3)	−0.007 (3)
O1	0.0223 (18)	0.062 (3)	0.046 (2)	0.0040 (17)	0.0003 (16)	0.003 (2)
O2	0.037 (2)	0.066 (3)	0.052 (3)	0.003 (2)	0.0060 (19)	0.018 (2)
O3	0.032 (2)	0.064 (3)	0.057 (3)	0.0026 (19)	−0.0060 (19)	−0.011 (2)
O4	0.085 (4)	0.068 (3)	0.100 (5)	0.013 (3)	0.027 (3)	0.005 (3)
O5	0.035 (2)	0.079 (3)	0.038 (2)	0.016 (2)	0.0023 (18)	0.002 (2)
O6	0.031 (2)	0.099 (4)	0.060 (3)	−0.005 (2)	−0.003 (2)	0.030 (3)
O7	0.029 (2)	0.109 (4)	0.060 (3)	−0.002 (2)	−0.004 (2)	−0.038 (3)
S1	0.0239 (7)	0.0472 (8)	0.0362 (7)	0.0032 (6)	0.0008 (5)	−0.0001 (6)
C1	0.028 (3)	0.047 (3)	0.031 (3)	0.005 (2)	−0.001 (2)	−0.005 (2)
C2	0.039 (3)	0.060 (4)	0.053 (4)	−0.005 (3)	−0.010 (3)	0.000 (3)
C3	0.066 (5)	0.049 (4)	0.069 (5)	−0.007 (3)	−0.007 (4)	−0.012 (3)
C4	0.053 (4)	0.051 (4)	0.056 (4)	0.012 (3)	0.010 (3)	−0.002 (3)
C5	0.046 (4)	0.048 (4)	0.079 (5)	0.007 (3)	−0.007 (3)	0.000 (3)
C6	0.037 (3)	0.047 (4)	0.062 (4)	0.005 (3)	−0.014 (3)	0.001 (3)
C7	0.058 (4)	0.055 (4)	0.053 (4)	0.008 (3)	0.001 (3)	−0.005 (3)
C8	0.068 (4)	0.048 (4)	0.053 (4)	0.003 (4)	−0.002 (3)	−0.014 (3)
C9	0.081 (6)	0.061 (5)	0.058 (5)	0.006 (4)	0.006 (4)	−0.001 (4)
C10	0.104 (7)	0.052 (4)	0.059 (5)	0.019 (4)	0.005 (4)	−0.003 (3)
C11	0.108 (7)	0.047 (4)	0.062 (5)	0.019 (4)	−0.006 (4)	−0.002 (4)
C12	0.109 (8)	0.052 (5)	0.084 (6)	0.002 (5)	−0.007 (5)	0.003 (4)
C13	0.073 (5)	0.059 (5)	0.071 (5)	0.002 (4)	−0.008 (4)	−0.007 (4)

Geometric parameters (Å, º)

Zn1—O5^i	2.054 (4)	C1—C2	1.406 (8)
Zn1—O5	2.054 (4)	C2—C3	1.391 (9)
Zn1—O7^i	2.072 (4)	C2—H2	0.9300
Zn1—O7	2.072 (4)	C3—C4	1.376 (9)
Zn1—O6	2.073 (4)	C3—H3	0.9300
Zn1—O6^i	2.073 (4)	C4—C5	1.374 (9)
N1—C7	1.280 (9)	C5—C6	1.383 (9)
N1—C4	1.413 (8)	C5—H5	0.9300
O1—S1	1.453 (4)	C6—H6	0.9300
O2—S1	1.453 (4)	C7—C8	1.454 (9)
O3—S1	1.459 (4)	C7—H7	0.9300
O4—C9	1.332 (9)	C8—C13	1.394 (10)
O4—H4	0.8200	C8—C9	1.394 (10)
O5—H5A	0.8500	C9—C10	1.397 (10)
O5—H5B	0.8499	C10—C11	1.365 (11)
O6—H6A	0.8500	C10—H10	0.9300
O6—H6B	0.8500	C11—C12	1.396 (12)
O7—H7A	0.8500	C11—H11	0.9300
O7—H7B	0.8500	C12—C13	1.375 (10)
S1—C1	1.759 (6)	C12—H12	0.9300
C1—C6	1.380 (8)	C13—H13	0.9300
O5^i—Zn1—O5	180.0 (2)	C3—C2—H2	120.6
O5^i—Zn1—O7^i	91.04 (17)	C1—C2—H2	120.6
O5—Zn1—O7^i	88.96 (17)	C4—C3—C2	120.5 (6)
O5^i—Zn1—O7	88.96 (17)	C4—C3—H3	119.7
O5—Zn1—O7	91.04 (17)	C2—C3—H3	119.7
O7^i—Zn1—O7	180.0 (3)	C5—C4—C3	119.9 (6)
O5^i—Zn1—O6	89.80 (17)	C5—C4—N1	117.6 (6)
O5—Zn1—O6	90.20 (17)	C3—C4—N1	122.4 (6)
O7^i—Zn1—O6	89.2 (2)	C4—C5—C6	121.0 (6)
O7—Zn1—O6	90.8 (2)	C4—C5—H5	119.5
O5^i—Zn1—O6^i	90.20 (17)	C6—C5—H5	119.5
O5—Zn1—O6^i	89.80 (17)	C1—C6—C5	119.4 (6)
O7^i—Zn1—O6^i	90.8 (2)	C1—C6—H6	120.3
O7—Zn1—O6^i	89.2 (2)	C5—C6—H6	120.3
O6—Zn1—O6^i	180.0 (3)	N1—C7—C8	121.9 (7)
C7—N1—C4	121.6 (6)	N1—C7—H7	119.1
C9—O4—H4	109.5	C8—C7—H7	119.1
Zn1—O5—H5A	119.3	C13—C8—C9	119.6 (7)
Zn1—O5—H5B	129.9	C13—C8—C7	119.5 (7)
H5A—O5—H5B	106.9	C9—C8—C7	120.9 (7)
Zn1—O6—H6A	128.5	O4—C9—C8	122.6 (7)
Zn1—O6—H6B	119.5	O4—C9—C10	118.6 (8)
H6A—O6—H6B	106.6	C8—C9—C10	118.8 (8)
Zn1—O7—H7A	122.0	C11—C10—C9	120.9 (8)
Zn1—O7—H7B	129.4	C11—C10—H10	119.5
H7A—O7—H7B	106.4	C9—C10—H10	119.5
O1—S1—O2	111.6 (2)	C10—C11—C12	120.6 (7)
O1—S1—O3	112.7 (2)	C10—C11—H11	119.7
O2—S1—O3	112.2 (3)	C12—C11—H11	119.7
O1—S1—C1	106.7 (2)	C13—C12—C11	118.8 (8)
O2—S1—C1	107.2 (3)	C13—C12—H12	120.6
O3—S1—C1	105.9 (2)	C11—C12—H12	120.6
C6—C1—C2	120.4 (5)	C12—C13—C8	121.2 (8)
C6—C1—S1	119.5 (4)	C12—C13—H13	119.4
C2—C1—S1	120.1 (4)	C8—C13—H13	119.4
C3—C2—C1	118.8 (6)
O1—S1—C1—C6	163.8 (5)	S1—C1—C6—C5	177.4 (5)
O2—S1—C1—C6	−76.5 (5)	C4—C5—C6—C1	1.4 (10)
O3—S1—C1—C6	43.5 (5)	C4—N1—C7—C8	−177.3 (6)
O1—S1—C1—C2	−18.6 (5)	N1—C7—C8—C13	−179.4 (7)
O2—S1—C1—C2	101.1 (5)	N1—C7—C8—C9	2.8 (11)
O3—S1—C1—C2	−138.9 (5)	C13—C8—C9—O4	−179.7 (7)
C6—C1—C2—C3	−0.7 (9)	C7—C8—C9—O4	−1.9 (11)
S1—C1—C2—C3	−178.3 (5)	C13—C8—C9—C10	−1.5 (11)
C1—C2—C3—C4	0.5 (10)	C7—C8—C9—C10	176.3 (7)
C2—C3—C4—C5	0.7 (11)	O4—C9—C10—C11	−179.3 (7)
C2—C3—C4—N1	179.1 (6)	C8—C9—C10—C11	2.5 (12)
C7—N1—C4—C5	−152.7 (7)	C9—C10—C11—C12	−1.7 (12)
C7—N1—C4—C3	28.8 (10)	C10—C11—C12—C13	0.0 (12)
C3—C4—C5—C6	−1.7 (11)	C11—C12—C13—C8	0.9 (12)
N1—C4—C5—C6	179.8 (6)	C9—C8—C13—C12	−0.1 (11)
C2—C1—C6—C5	−0.2 (9)	C7—C8—C13—C12	−178.0 (7)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O3^ii	0.85	1.93	2.760 (6)	166
O7—H7A···O1	0.85	1.93	2.779 (5)	177
O6—H6B···O1^iii	0.85	1.92	2.773 (6)	176
O6—H6A···O2^iv	0.85	1.92	2.770 (6)	175
O5—H5B···O3	0.85	1.90	2.745 (6)	171
O5—H5A···O2^iii	0.85	1.91	2.742 (6)	167
O4—H4···N1	0.82	1.93	2.602 (7)	139

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