Diaqua­bis(1,10-phenanthroline-κ2N,N′)zinc(II) 2-hydr­oxy-5-sulfonatobenzoate tetra­hydrate

Zhang, K.-L.; Yang, B.; Ng, S.W.

doi:10.1107/S1600536809003055

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages m239-m240

doi:10.1107/S1600536809003055

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Diaquabis(1,10-phenanthroline-κ²N,N′)zinc(II) 2-hydroxy-5-sulfonatobenzoate tetrahydrate

Kou-Lin Zhang,^a Bo Yang ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 21 January 2009; accepted 24 January 2009; online 31 January 2009)

The water-coordinated metal centre in the title salt, [Zn(C₁₂H₈N₂)₂(H₂O)₂]C₇H₄O₆S·4H₂O, is chelated by the two bidentate N-heterocycles, leading to an overall distorted octahedral environment. The cation, dianion and solvent water molecules interact by O—H⋯O hydrogen bonds to form a layer motif. The SO₃ group is disordered over two positions with respect to the O atoms in a 0.76 (1):0.24 (1) ratio. One of the solvent water molecules is also disordered over two positions in a 0.56 (4):0.44 (4) ratio.

Related literature

For the isostructural manganese(II), nickel(II) and cobalt(II) analogues, see: Fan et al. (2005 ); Chen et al. (2005 ); Zhu & Fan (2005 ).

Experimental

Crystal data

[Zn(C₁₂H₈N₂)₂(H₂O)₂]C₇H₄O₆S·4H₂O
M_r = 750.04
Triclinic, $[P \overline 1]$
a = 10.075 (1) Å
b = 12.263 (1) Å
c = 13.927 (1) Å
α = 96.937 (2)°
β = 101.495 (2)°
γ = 98.856 (2)°
V = 1645.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 293 (2) K
0.38 × 0.30 × 0.22 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.36, T_max = 0.82
10806 measured reflections
7315 independent reflections
4849 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.095
S = 0.93
7315 reflections
513 parameters
106 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11⋯O1	0.83 (1)	1.81 (1)	2.632 (2)	170 (3)
O1W—H12⋯O6ⁱ	0.84 (1)	1.95 (1)	2.793 (4)	177 (2)
O1W—H12⋯O6′ⁱ	0.84 (1)	2.04 (2)	2.787 (7)	147 (2)
O2W—H21⋯O3W	0.85 (1)	1.87 (1)	2.714 (3)	170 (3)
O2W—H22⋯O6W	0.85 (1)	1.95 (1)	2.778 (6)	166 (3)
O2W—H22⋯O6W′	0.85 (1)	1.80 (2)	2.615 (6)	160 (3)
O3W—H31⋯O5W	0.85 (1)	1.91 (1)	2.754 (3)	173 (3)
O3W—H32⋯O5ⁱⁱ	0.85 (1)	1.95 (1)	2.805 (4)	178 (3)
O3W—H32⋯O5′ⁱⁱ	0.85 (1)	2.08 (2)	2.892 (10)	159 (3)
O4W—H41⋯O4ⁱⁱⁱ	0.86 (1)	2.17 (3)	2.962 (5)	153 (5)
O4W—H41⋯O4′ⁱⁱⁱ	0.86 (1)	1.74 (2)	2.598 (8)	173 (5)
O4W—H42⋯O5ⁱⁱ	0.86 (1)	2.22 (1)	3.065 (5)	169 (5)
O4W—H42⋯O5′ⁱⁱ	0.86 (1)	2.08 (2)	2.869 (15)	153 (4)
O5W—H51⋯O4ⁱⁱⁱ	0.84 (1)	2.07 (1)	2.900 (4)	168 (4)
O5W—H51⋯O6′ⁱⁱⁱ	0.84 (1)	2.07 (2)	2.823 (8)	148 (3)
O5W—H52⋯O2^iv	0.85 (1)	1.94 (1)	2.792 (3)	175 (3)
O6W—H61⋯O6ⁱ	0.83 (1)	2.22 (3)	2.751 (8)	122 (3)
O6W—H62⋯O4W	0.84 (1)	1.88 (2)	2.642 (7)	150 (4)
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) x-1, y, z-1; (iii) -x+1, -y+2, -z+1; (iv) x-1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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/S1600536809003055/xu2475sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003055/xu2475Isup2.hkl

checkCIF report

Related literature top

For the isostructural manganese(II), nickel(II) and cobalt(II) analogues, see: Fan et al. (2005); Chen et al. (2005); Zhu & Fan (2005).

Experimental top

1,10-Phenanthroline monohydrate (0.10 g, 0.5 mmol) was dissolved in methanol (10 ml). To this solution was added zinc nitrate hexahydrate (0.15 g, 0.5 mmol) dissolved in water (10 ml). The solution was then mixed with an aqueous solution of 5-sulfosalicylic acid (0.11 g, 0.5 mmol) and sodium hydroxide (0.04 g, 1 mmol). Crystals separated after several days. These were collected and washed with methanol; yield: 50%. CH&N elemental analysis: Calc. for C₃₁H₃₂N₄O₁₂SZn: C 49.63, H 4.27, N 7.47%. Found: C 49.71, H 4.31, N, 7.41%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. Thermal ellipsoid plot of [Zn(OH₂)₂(C₁₂H₈N₂)₂][C₇H₄O₆S].4H₂O; displacement ellipsoids are drawn at the 50% probability level, and H atoms as spheres of arbitrary radii. The disorder is not shown.

Diaquabis(1,10-phenanthroline-κ²N,N')zinc(II) 2-hydroxy-5-sulfonatobenzoate tetrahydrate top

Crystal data top

[Zn(C₁₂H₈N₂)₂(H₂O)₂]C₇H₄O₆S·4H₂O	Z = 2
M_r = 750.04	F(000) = 776
Triclinic, P1	D_x = 1.514 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.075 (1) Å	Cell parameters from 2300 reflections
b = 12.263 (1) Å	θ = 2.5–22.9°
c = 13.927 (1) Å	µ = 0.88 mm⁻¹
α = 96.937 (2)°	T = 293 K
β = 101.495 (2)°	Block, colourless
γ = 98.856 (2)°	0.38 × 0.30 × 0.22 mm
V = 1645.5 (2) Å³

Data collection top

Bruker APEXII area-detector diffractometer	7315 independent reflections
Radiation source: fine-focus sealed tube	4849 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
T_min = 0.36, T_max = 0.82	k = −14→15
10806 measured reflections	l = −18→15

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ²(F_o²) + (0.0512P)²] where P = (F_o² + 2F_c²)/3
7315 reflections	(Δ/σ)_max = 0.001
513 parameters	Δρ_max = 0.28 e Å⁻³
106 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Zn(C₁₂H₈N₂)₂(H₂O)₂]C₇H₄O₆S·4H₂O	γ = 98.856 (2)°
M_r = 750.04	V = 1645.5 (2) Å³
Triclinic, P1	Z = 2
a = 10.075 (1) Å	Mo Kα radiation
b = 12.263 (1) Å	µ = 0.88 mm⁻¹
c = 13.927 (1) Å	T = 293 K
α = 96.937 (2)°	0.38 × 0.30 × 0.22 mm
β = 101.495 (2)°

Data collection top

Bruker APEXII area-detector diffractometer	7315 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4849 reflections with I > 2σ(I)
T_min = 0.36, T_max = 0.82	R_int = 0.020
10806 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	106 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.28 e Å⁻³
7315 reflections	Δρ_min = −0.35 e Å⁻³
513 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.50705 (3)	0.73388 (2)	0.26312 (2)	0.03952 (10)
S1	1.09039 (9)	0.91846 (6)	0.82131 (5)	0.0656 (2)
N1	0.40757 (18)	0.83635 (15)	0.35340 (14)	0.0376 (4)
N2	0.5761 (2)	0.69351 (16)	0.40972 (14)	0.0417 (5)
N3	0.5781 (2)	0.59926 (17)	0.18305 (14)	0.0439 (5)
N4	0.32841 (19)	0.59452 (15)	0.22700 (14)	0.0402 (5)
O1	0.9002 (2)	0.85085 (16)	0.42946 (13)	0.0634 (5)
O2	0.9822 (2)	0.70605 (17)	0.36560 (14)	0.0701 (6)
O3	1.1172 (3)	0.59708 (19)	0.47739 (18)	0.0844 (7)
H3	1.064 (4)	0.613 (4)	0.428 (2)	0.127*
O4	0.9776 (4)	0.9750 (3)	0.7937 (2)	0.0854 (15)	0.757 (7)
O5	1.0879 (5)	0.8618 (3)	0.9044 (3)	0.0724 (11)	0.757 (7)
O6	1.2238 (5)	0.9995 (3)	0.8373 (3)	0.1028 (16)	0.757 (7)
O4'	0.9391 (7)	0.8922 (10)	0.8218 (8)	0.104 (5)	0.243 (7)
O5'	1.1646 (14)	0.8780 (11)	0.9059 (9)	0.101 (5)	0.243 (7)
O6'	1.1326 (10)	1.0279 (5)	0.8124 (7)	0.054 (3)	0.243 (7)
O1W	0.69078 (17)	0.84787 (16)	0.28148 (14)	0.0517 (4)
H11	0.757 (2)	0.841 (2)	0.3255 (15)	0.078*
H12	0.713 (3)	0.8936 (19)	0.2443 (16)	0.078*
O2W	0.42757 (19)	0.79208 (16)	0.13328 (14)	0.0555 (5)
H21	0.3404 (11)	0.779 (2)	0.114 (2)	0.083*
H22	0.459 (2)	0.8582 (13)	0.127 (2)	0.083*
O3W	0.1536 (2)	0.73101 (18)	0.05280 (15)	0.0658 (5)
H31	0.103 (3)	0.742 (3)	0.0938 (18)	0.099*
H32	0.134 (3)	0.770 (2)	0.0068 (16)	0.099*
O4W	0.2383 (3)	1.0300 (3)	0.0895 (2)	0.1163 (9)
H41	0.182 (4)	1.052 (4)	0.123 (3)	0.174*
H42	0.190 (4)	0.990 (4)	0.035 (2)	0.174*
O5W	−0.0022 (2)	0.78419 (18)	0.18724 (16)	0.0698 (6)
H51	−0.008 (4)	0.8523 (12)	0.190 (2)	0.105*
H52	−0.010 (4)	0.763 (2)	0.2422 (14)	0.105*
O6W	0.5032 (7)	1.0198 (5)	0.1338 (4)	0.0941 (15)	0.54 (6)
O6W'	0.4960 (7)	0.9808 (5)	0.0703 (5)	0.0941 (15)	0.46
H61	0.5655 (17)	1.030 (3)	0.1029 (18)	0.141*
H62	0.429 (2)	1.038 (4)	0.105 (3)	0.141*
C1	0.4359 (2)	0.82539 (18)	0.45066 (17)	0.0364 (5)
C2	0.5265 (2)	0.74973 (19)	0.48134 (17)	0.0387 (5)
C3	0.6591 (3)	0.6232 (2)	0.4370 (2)	0.0579 (7)
H3A	0.6932	0.5842	0.3887	0.069*
C4	0.6975 (3)	0.6053 (3)	0.5344 (3)	0.0764 (9)
H4	0.7556	0.5550	0.5505	0.092*
C5	0.6491 (3)	0.6622 (3)	0.6058 (2)	0.0751 (9)
H5	0.6747	0.6512	0.6713	0.090*
C6	0.5605 (3)	0.7376 (2)	0.58146 (19)	0.0545 (7)
C7	0.5041 (3)	0.8011 (3)	0.6521 (2)	0.0681 (8)
H7	0.5275	0.7939	0.7188	0.082*
C8	0.4186 (3)	0.8704 (2)	0.6232 (2)	0.0589 (8)
H8	0.3832	0.9101	0.6703	0.071*
C9	0.3807 (2)	0.88451 (19)	0.52230 (19)	0.0443 (6)
C10	0.2908 (3)	0.9557 (2)	0.4877 (2)	0.0531 (7)
H10	0.2512	0.9960	0.5317	0.064*
C11	0.2621 (3)	0.9652 (2)	0.3902 (2)	0.0542 (7)
H11A	0.2022	1.0116	0.3669	0.065*
C12	0.3231 (2)	0.90484 (19)	0.3246 (2)	0.0461 (6)
H12A	0.3035	0.9132	0.2581	0.055*
C13	0.4829 (3)	0.50289 (19)	0.15053 (16)	0.0411 (6)
C14	0.3499 (2)	0.50073 (19)	0.17326 (16)	0.0407 (5)
C15	0.2076 (3)	0.5927 (2)	0.25028 (19)	0.0496 (6)
H15	0.1927	0.6562	0.2873	0.060*
C16	0.1008 (3)	0.4998 (2)	0.2220 (2)	0.0602 (7)
H16	0.0175	0.5020	0.2407	0.072*
C17	0.1194 (3)	0.4070 (2)	0.1673 (2)	0.0624 (8)
H17	0.0484	0.3453	0.1472	0.075*
C18	0.2475 (3)	0.4041 (2)	0.14070 (18)	0.0516 (7)
C19	0.2778 (4)	0.3086 (2)	0.0854 (2)	0.0712 (9)
H19	0.2102	0.2448	0.0633	0.085*
C20	0.4028 (4)	0.3099 (2)	0.0649 (2)	0.0696 (9)
H20	0.4206	0.2463	0.0299	0.084*
C21	0.5102 (3)	0.4076 (2)	0.09595 (18)	0.0533 (7)
C22	0.6413 (3)	0.4162 (3)	0.0741 (2)	0.0641 (8)
H22A	0.6641	0.3555	0.0382	0.077*
C23	0.7349 (3)	0.5124 (3)	0.1051 (2)	0.0644 (8)
H23	0.8214	0.5180	0.0901	0.077*
C24	0.7002 (3)	0.6032 (2)	0.15969 (19)	0.0551 (7)
H24	0.7652	0.6687	0.1805	0.066*
C25	0.9671 (3)	0.7750 (2)	0.4384 (2)	0.0512 (6)
C26	1.0362 (2)	0.7593 (2)	0.54018 (19)	0.0449 (6)
C27	1.0324 (2)	0.8337 (2)	0.62312 (18)	0.0442 (6)
H27	0.9882	0.8942	0.6145	0.053*
C28	1.0928 (3)	0.8198 (2)	0.71780 (19)	0.0484 (6)
C29	1.1577 (3)	0.7286 (3)	0.7311 (2)	0.0644 (8)
H29	1.1969	0.7177	0.7947	0.077*
C30	1.1638 (3)	0.6547 (3)	0.6508 (3)	0.0714 (9)
H30	1.2075	0.5941	0.6603	0.086*
C31	1.1054 (3)	0.6693 (2)	0.5552 (2)	0.0573 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.04032 (17)	0.04133 (17)	0.03760 (16)	0.01290 (12)	0.00851 (12)	0.00213 (11)
S1	0.0877 (6)	0.0620 (5)	0.0438 (4)	0.0094 (4)	0.0046 (4)	0.0170 (4)
N1	0.0359 (11)	0.0355 (10)	0.0403 (11)	0.0103 (8)	0.0060 (9)	0.0005 (9)
N2	0.0415 (11)	0.0416 (11)	0.0453 (12)	0.0148 (9)	0.0107 (9)	0.0085 (9)
N3	0.0423 (12)	0.0524 (12)	0.0394 (11)	0.0176 (10)	0.0097 (9)	0.0041 (9)
N4	0.0406 (11)	0.0406 (11)	0.0409 (11)	0.0097 (9)	0.0107 (9)	0.0062 (9)
O1	0.0622 (12)	0.0758 (13)	0.0498 (11)	0.0292 (11)	−0.0026 (9)	0.0050 (10)
O2	0.0863 (15)	0.0732 (13)	0.0538 (12)	0.0241 (11)	0.0205 (11)	0.0014 (10)
O3	0.116 (2)	0.0723 (14)	0.0890 (18)	0.0524 (14)	0.0495 (16)	0.0187 (13)
O4	0.123 (3)	0.084 (3)	0.0535 (18)	0.055 (2)	0.0025 (17)	0.0085 (16)
O5	0.106 (3)	0.068 (2)	0.0442 (17)	0.009 (2)	0.0146 (19)	0.0256 (15)
O6	0.113 (3)	0.083 (2)	0.088 (2)	−0.029 (2)	−0.010 (2)	0.0347 (19)
O4'	0.100 (7)	0.099 (8)	0.115 (8)	−0.011 (5)	0.075 (6)	−0.024 (6)
O5'	0.139 (10)	0.096 (8)	0.065 (7)	0.025 (7)	0.007 (7)	0.026 (5)
O6'	0.066 (6)	0.046 (4)	0.064 (5)	0.021 (4)	0.025 (4)	0.025 (4)
O1W	0.0425 (10)	0.0623 (12)	0.0495 (11)	0.0061 (9)	0.0048 (8)	0.0192 (9)
O2W	0.0574 (11)	0.0635 (12)	0.0460 (11)	0.0180 (10)	0.0058 (10)	0.0111 (10)
O3W	0.0660 (13)	0.0783 (14)	0.0580 (13)	0.0261 (11)	0.0105 (10)	0.0185 (11)
O4W	0.145 (3)	0.096 (2)	0.099 (2)	0.0271 (19)	0.0184 (19)	−0.0103 (16)
O5W	0.0734 (14)	0.0677 (13)	0.0767 (15)	0.0189 (12)	0.0283 (12)	0.0169 (11)
O6W	0.115 (3)	0.091 (3)	0.078 (3)	0.013 (2)	0.024 (3)	0.023 (3)
O6W'	0.115 (3)	0.091 (3)	0.078 (3)	0.013 (2)	0.024 (3)	0.023 (3)
C1	0.0338 (12)	0.0333 (12)	0.0398 (13)	0.0011 (10)	0.0098 (10)	0.0001 (10)
C2	0.0371 (13)	0.0393 (13)	0.0390 (13)	0.0047 (10)	0.0080 (10)	0.0070 (10)
C3	0.0621 (18)	0.0594 (17)	0.0632 (19)	0.0307 (15)	0.0179 (15)	0.0210 (14)
C4	0.084 (2)	0.083 (2)	0.080 (2)	0.0452 (19)	0.0197 (19)	0.0421 (19)
C5	0.087 (2)	0.094 (2)	0.0559 (19)	0.032 (2)	0.0137 (17)	0.0404 (18)
C6	0.0597 (17)	0.0634 (17)	0.0434 (15)	0.0095 (14)	0.0134 (13)	0.0190 (13)
C7	0.084 (2)	0.084 (2)	0.0392 (16)	0.0082 (18)	0.0221 (15)	0.0144 (15)
C8	0.0627 (19)	0.0658 (18)	0.0488 (17)	0.0029 (15)	0.0277 (15)	−0.0032 (14)
C9	0.0404 (14)	0.0418 (13)	0.0487 (15)	0.0005 (11)	0.0170 (12)	−0.0036 (11)
C10	0.0445 (15)	0.0436 (14)	0.072 (2)	0.0066 (12)	0.0261 (14)	−0.0097 (13)
C11	0.0415 (15)	0.0450 (15)	0.076 (2)	0.0176 (12)	0.0113 (14)	0.0008 (14)
C12	0.0420 (14)	0.0425 (14)	0.0535 (16)	0.0158 (11)	0.0050 (12)	0.0060 (12)
C13	0.0552 (15)	0.0397 (13)	0.0308 (12)	0.0174 (12)	0.0069 (11)	0.0088 (10)
C14	0.0516 (15)	0.0383 (13)	0.0314 (12)	0.0094 (11)	0.0043 (11)	0.0095 (10)
C15	0.0439 (15)	0.0537 (16)	0.0527 (16)	0.0095 (12)	0.0134 (12)	0.0091 (12)
C16	0.0488 (17)	0.0710 (19)	0.0586 (18)	0.0008 (14)	0.0124 (14)	0.0139 (15)
C17	0.0621 (19)	0.0613 (18)	0.0537 (18)	−0.0128 (15)	0.0043 (14)	0.0145 (15)
C18	0.0693 (19)	0.0425 (14)	0.0380 (14)	0.0025 (13)	0.0045 (13)	0.0095 (11)
C19	0.106 (3)	0.0404 (16)	0.059 (2)	0.0000 (16)	0.0144 (19)	0.0007 (14)
C20	0.114 (3)	0.0418 (16)	0.0536 (18)	0.0264 (17)	0.0167 (19)	−0.0018 (13)
C21	0.083 (2)	0.0474 (15)	0.0351 (14)	0.0336 (15)	0.0106 (13)	0.0069 (12)
C22	0.092 (2)	0.073 (2)	0.0411 (16)	0.0530 (19)	0.0180 (16)	0.0075 (14)
C23	0.0593 (18)	0.101 (2)	0.0461 (17)	0.0459 (18)	0.0169 (14)	0.0138 (16)
C24	0.0457 (15)	0.0748 (19)	0.0482 (16)	0.0234 (14)	0.0118 (13)	0.0053 (14)
C25	0.0460 (15)	0.0575 (16)	0.0501 (16)	0.0075 (13)	0.0133 (13)	0.0064 (13)
C26	0.0374 (13)	0.0493 (14)	0.0539 (16)	0.0117 (11)	0.0170 (12)	0.0151 (12)
C27	0.0372 (13)	0.0491 (14)	0.0500 (15)	0.0132 (11)	0.0106 (11)	0.0139 (12)
C28	0.0452 (15)	0.0537 (15)	0.0515 (16)	0.0091 (12)	0.0146 (12)	0.0216 (13)
C29	0.0629 (19)	0.078 (2)	0.066 (2)	0.0272 (16)	0.0183 (15)	0.0413 (17)
C30	0.082 (2)	0.071 (2)	0.088 (2)	0.0460 (18)	0.0382 (19)	0.0433 (19)
C31	0.0589 (17)	0.0553 (16)	0.070 (2)	0.0202 (14)	0.0297 (15)	0.0212 (15)

Geometric parameters (Å, º) top

Zn1—O2W	2.0810 (18)	C4—C5	1.358 (4)
Zn1—O1W	2.0914 (17)	C4—H4	0.9300
Zn1—N1	2.1615 (17)	C5—C6	1.406 (4)
Zn1—N2	2.164 (2)	C5—H5	0.9300
Zn1—N3	2.1720 (18)	C6—C7	1.438 (4)
Zn1—N4	2.2130 (19)	C7—C8	1.341 (4)
S1—O6'	1.372 (5)	C7—H7	0.9300
S1—O5	1.422 (3)	C8—C9	1.420 (4)
S1—O4	1.433 (3)	C8—H8	0.9300
S1—O5'	1.448 (6)	C9—C10	1.409 (4)
S1—O6	1.503 (3)	C10—C11	1.354 (4)
S1—O4'	1.511 (6)	C10—H10	0.9300
S1—C28	1.773 (3)	C11—C12	1.400 (3)
N1—C12	1.325 (3)	C11—H11A	0.9300
N1—C1	1.355 (3)	C12—H12A	0.9300
N2—C3	1.327 (3)	C13—C21	1.410 (3)
N2—C2	1.363 (3)	C13—C14	1.434 (3)
N3—C24	1.330 (3)	C14—C18	1.407 (3)
N3—C13	1.367 (3)	C15—C16	1.398 (4)
N4—C15	1.318 (3)	C15—H15	0.9300
N4—C14	1.365 (3)	C16—C17	1.351 (4)
O1—C25	1.234 (3)	C16—H16	0.9300
O2—C25	1.288 (3)	C17—C18	1.417 (4)
O3—C31	1.351 (3)	C17—H17	0.9300
O3—H3	0.853 (11)	C18—C19	1.430 (4)
O1W—H11	0.832 (10)	C19—C20	1.344 (4)
O1W—H12	0.843 (10)	C19—H19	0.9300
O2W—H21	0.849 (10)	C20—C21	1.443 (4)
O2W—H22	0.845 (10)	C20—H20	0.9300
O3W—H31	0.849 (10)	C21—C22	1.405 (4)
O3W—H32	0.853 (10)	C22—C23	1.356 (4)
O4W—H41	0.859 (11)	C22—H22A	0.9300
O4W—H42	0.858 (11)	C23—C24	1.400 (4)
O5W—H51	0.844 (10)	C23—H23	0.9300
O5W—H52	0.851 (10)	C24—H24	0.9300
O6W—O6W'	0.937 (6)	C25—C26	1.498 (4)
O6W—H61	0.831 (11)	C26—C27	1.394 (3)
O6W—H62	0.843 (8)	C26—C31	1.408 (3)
O6W'—H61	0.857 (11)	C27—C28	1.380 (3)
O6W'—H62	1.17 (3)	C27—H27	0.9300
C1—C9	1.415 (3)	C28—C29	1.393 (4)
C1—C2	1.441 (3)	C29—C30	1.369 (4)
C2—C6	1.400 (3)	C29—H29	0.9300
C3—C4	1.388 (4)	C30—C31	1.388 (4)
C3—H3A	0.9300	C30—H30	0.9300

O2W—Zn1—O1W	89.83 (7)	C2—C6—C5	116.4 (2)
O2W—Zn1—N1	93.87 (7)	C2—C6—C7	119.3 (3)
O1W—Zn1—N1	97.42 (7)	C5—C6—C7	124.3 (3)
O2W—Zn1—N2	171.00 (7)	C8—C7—C6	121.0 (3)
O1W—Zn1—N2	90.11 (7)	C8—C7—H7	119.5
N1—Zn1—N2	77.21 (7)	C6—C7—H7	119.5
O2W—Zn1—N3	92.55 (7)	C7—C8—C9	121.5 (2)
O1W—Zn1—N3	94.26 (8)	C7—C8—H8	119.2
N1—Zn1—N3	166.67 (7)	C9—C8—H8	119.2
N2—Zn1—N3	96.43 (7)	C10—C9—C1	116.7 (2)
O2W—Zn1—N4	89.26 (7)	C10—C9—C8	124.0 (2)
O1W—Zn1—N4	170.12 (7)	C1—C9—C8	119.4 (2)
N1—Zn1—N4	92.46 (7)	C11—C10—C9	119.9 (2)
N2—Zn1—N4	92.32 (7)	C11—C10—H10	120.0
N3—Zn1—N4	75.96 (7)	C9—C10—H10	120.0
O6'—S1—O5	133.1 (4)	C10—C11—C12	119.6 (2)
O6'—S1—O4	67.2 (4)	C10—C11—H11A	120.2
O5—S1—O4	115.8 (2)	C12—C11—H11A	120.2
O6'—S1—O5'	116.8 (5)	N1—C12—C11	122.8 (2)
O5—S1—O5'	30.8 (5)	N1—C12—H12A	118.6
O4—S1—O5'	140.9 (7)	C11—C12—H12A	118.6
O6'—S1—O6	42.2 (3)	N3—C13—C21	122.9 (2)
O5—S1—O6	110.5 (2)	N3—C13—C14	117.6 (2)
O4—S1—O6	109.3 (2)	C21—C13—C14	119.5 (2)
O5'—S1—O6	82.5 (5)	N4—C14—C18	122.4 (2)
O6'—S1—O4'	112.4 (5)	N4—C14—C13	117.5 (2)
O5—S1—O4'	76.4 (5)	C18—C14—C13	120.0 (2)
O4—S1—O4'	46.8 (5)	N4—C15—C16	123.2 (2)
O5'—S1—O4'	107.2 (5)	N4—C15—H15	118.4
O6—S1—O4'	151.4 (4)	C16—C15—H15	118.4
O6'—S1—C28	114.8 (3)	C17—C16—C15	119.5 (3)
O5—S1—C28	108.38 (19)	C17—C16—H16	120.2
O4—S1—C28	108.01 (15)	C15—C16—H16	120.2
O5'—S1—C28	104.5 (6)	C16—C17—C18	119.7 (3)
O6—S1—C28	104.2 (2)	C16—C17—H17	120.2
O4'—S1—C28	99.3 (4)	C18—C17—H17	120.2
C12—N1—C1	118.06 (19)	C14—C18—C17	117.0 (2)
C12—N1—Zn1	128.06 (16)	C14—C18—C19	119.4 (3)
C1—N1—Zn1	113.88 (14)	C17—C18—C19	123.6 (3)
C3—N2—C2	117.8 (2)	C20—C19—C18	120.8 (3)
C3—N2—Zn1	128.40 (17)	C20—C19—H19	119.6
C2—N2—Zn1	113.79 (15)	C18—C19—H19	119.6
C24—N3—C13	118.0 (2)	C19—C20—C21	121.7 (3)
C24—N3—Zn1	126.88 (18)	C19—C20—H20	119.2
C13—N3—Zn1	115.07 (15)	C21—C20—H20	119.2
C15—N4—C14	118.1 (2)	C22—C21—C13	116.6 (3)
C15—N4—Zn1	128.09 (16)	C22—C21—C20	124.7 (2)
C14—N4—Zn1	113.80 (15)	C13—C21—C20	118.6 (3)
C31—O3—H3	104 (3)	C23—C22—C21	120.4 (2)
Zn1—O1W—H11	117.2 (17)	C23—C22—H22A	119.8
Zn1—O1W—H12	129.0 (17)	C21—C22—H22A	119.8
H11—O1W—H12	112.9 (17)	C22—C23—C24	119.5 (3)
Zn1—O2W—H21	116 (2)	C22—C23—H23	120.3
Zn1—O2W—H22	118 (2)	C24—C23—H23	120.3
H21—O2W—H22	109.6 (16)	N3—C24—C23	122.6 (3)
H31—O3W—H32	108.2 (16)	N3—C24—H24	118.7
H41—O4W—H42	107.2 (18)	C23—C24—H24	118.7
H51—O5W—H52	109.5 (17)	O1—C25—O2	124.6 (3)
O6W'—O6W—H61	57.6 (9)	O1—C25—C26	119.1 (2)
O6W'—O6W—H62	82 (3)	O2—C25—C26	116.2 (2)
H61—O6W—H62	113.0 (18)	C27—C26—C31	118.1 (2)
O6W—O6W'—H61	54.9 (9)	C27—C26—C25	120.4 (2)
O6W—O6W'—H62	45.5 (13)	C31—C26—C25	121.5 (2)
H61—O6W'—H62	86 (2)	C28—C27—C26	121.5 (2)
N1—C1—C9	123.0 (2)	C28—C27—H27	119.2
N1—C1—C2	117.85 (19)	C26—C27—H27	119.2
C9—C1—C2	119.2 (2)	C27—C28—C29	119.3 (3)
N2—C2—C6	123.1 (2)	C27—C28—S1	120.31 (19)
N2—C2—C1	117.3 (2)	C29—C28—S1	120.4 (2)
C6—C2—C1	119.6 (2)	C30—C29—C28	120.3 (3)
N2—C3—C4	123.0 (3)	C30—C29—H29	119.9
N2—C3—H3A	118.5	C28—C29—H29	119.9
C4—C3—H3A	118.5	C29—C30—C31	120.7 (3)
C5—C4—C3	119.0 (3)	C29—C30—H30	119.6
C5—C4—H4	120.5	C31—C30—H30	119.6
C3—C4—H4	120.5	O3—C31—C30	119.2 (3)
C4—C5—C6	120.6 (3)	O3—C31—C26	120.8 (3)
C4—C5—H5	119.7	C30—C31—C26	120.0 (3)
C6—C5—H5	119.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O1	0.83 (1)	1.81 (1)	2.632 (2)	170 (3)
O1W—H12···O6ⁱ	0.84 (1)	1.95 (1)	2.793 (4)	177 (2)
O1W—H12···O6′ⁱ	0.84 (1)	2.04 (2)	2.787 (7)	147 (2)
O2W—H21···O3W	0.85 (1)	1.87 (1)	2.714 (3)	170 (3)
O2W—H22···O6W	0.85 (1)	1.95 (1)	2.778 (6)	166 (3)
O2W—H22···O6W′	0.85 (1)	1.80 (2)	2.615 (6)	160 (3)
O3W—H31···O5W	0.85 (1)	1.91 (1)	2.754 (3)	173 (3)
O3W—H32···O5ⁱⁱ	0.85 (1)	1.95 (1)	2.805 (4)	178 (3)
O3W—H32···O5′ⁱⁱ	0.85 (1)	2.08 (2)	2.892 (10)	159 (3)
O4W—H41···O4ⁱⁱⁱ	0.86 (1)	2.17 (3)	2.962 (5)	153 (5)
O4W—H41···O4′ⁱⁱⁱ	0.86 (1)	1.74 (2)	2.598 (8)	173 (5)
O4W—H42···O5ⁱⁱ	0.86 (1)	2.22 (1)	3.065 (5)	169 (5)
O4W—H42···O5′ⁱⁱ	0.86 (1)	2.08 (2)	2.869 (15)	153 (4)
O5W—H51···O4ⁱⁱⁱ	0.84 (1)	2.07 (1)	2.900 (4)	168 (4)
O5W—H51···O6′ⁱⁱⁱ	0.84 (1)	2.07 (2)	2.823 (8)	148 (3)
O5W—H52···O2^iv	0.85 (1)	1.94 (1)	2.792 (3)	175 (3)
O6W—H61···O6ⁱ	0.83 (1)	2.22 (3)	2.751 (8)	122 (3)
O6W—H62···O4W	0.84 (1)	1.88 (2)	2.642 (7)	150 (4)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₁₂H₈N₂)₂(H₂O)₂]C₇H₄O₆S·4H₂O
M_r	750.04
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.075 (1), 12.263 (1), 13.927 (1)
α, β, γ (°)	96.937 (2), 101.495 (2), 98.856 (2)
V (Å³)	1645.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.38 × 0.30 × 0.22

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.36, 0.82
No. of measured, independent and observed [I > 2σ(I)] reflections	10806, 7315, 4849
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.095, 0.93
No. of reflections	7315
No. of parameters	513
No. of restraints	106
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.35

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O1	0.83 (1)	1.81 (1)	2.632 (2)	170 (3)
O1W—H12···O6ⁱ	0.84 (1)	1.95 (1)	2.793 (4)	177 (2)
O1W—H12···O6'ⁱ	0.84 (1)	2.04 (2)	2.787 (7)	147 (2)
O2W—H21···O3W	0.85 (1)	1.87 (1)	2.714 (3)	170 (3)
O2W—H22···O6W	0.85 (1)	1.95 (1)	2.778 (6)	166 (3)
O2W—H22···O6W'	0.85 (1)	1.80 (2)	2.615 (6)	160 (3)
O3W—H31···O5W	0.85 (1)	1.91 (1)	2.754 (3)	173 (3)
O3W—H32···O5ⁱⁱ	0.85 (1)	1.95 (1)	2.805 (4)	178 (3)
O3W—H32···O5'ⁱⁱ	0.85 (1)	2.08 (2)	2.892 (10)	159 (3)
O4W—H41···O4ⁱⁱⁱ	0.86 (1)	2.17 (3)	2.962 (5)	153 (5)
O4W—H41···O4'ⁱⁱⁱ	0.86 (1)	1.74 (2)	2.598 (8)	173 (5)
O4W—H42···O5ⁱⁱ	0.86 (1)	2.22 (1)	3.065 (5)	169 (5)
O4W—H42···O5'ⁱⁱ	0.86 (1)	2.08 (2)	2.869 (15)	153 (4)
O5W—H51···O4ⁱⁱⁱ	0.84 (1)	2.07 (1)	2.900 (4)	168 (4)
O5W—H51···O6'ⁱⁱⁱ	0.84 (1)	2.07 (2)	2.823 (8)	148 (3)
O5W—H52···O2^iv	0.85 (1)	1.94 (1)	2.792 (3)	175 (3)
O6W—H61···O6ⁱ	0.83 (1)	2.22 (3)	2.751 (8)	122 (3)
O6W—H62···O4W	0.84 (1)	1.88 (2)	2.642 (7)	150 (4)

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

Acknowledgements

The authors thank the Fujian Institute for Research on the Structure of Matter for the diffraction measurements, and the Foundation of Jiangsu Provincial Key Programme of Physical Chemistry in Yangzhou University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem., 1, 189–191. CrossRef CAS Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, J.-M., Fan, S.-R. & Zhu, L.-G. (2005). Acta Cryst. E61, m1724–m1726. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fan, S.-R., Zhu, L.-G., Xiao, H.-P. & Ng, S. W. (2005). Acta Cryst. E61, m563–m565. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
Zhu, L.-G. & Fan, S. R. (2005). Chin. J. Chem. 23, 1292–1296. Google Scholar

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