An octa­nuclear zinc(II) complex with 6,6′-dihydr­oxy-2,2′-[1,2-phenyl­enebis(nitrilo­methyl­idyne)]diphenol

Eltayeb, N.E.; Teoh, S.G.; Chantrapromma, S.; Fun, H.-K.; Adnan, R.

doi:10.1107/S1600536808017340

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m912-m913

doi:10.1107/S1600536808017340

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An octanuclear zinc(II) complex with 6,6′-dihydroxy-2,2′-[1,2-phenylenebis(nitrilomethylidyne)]diphenol

Naser Eltaher Eltayeb,^a ‡ Siang Guan Teoh,^a Suchada Chantrapromma,^b § Hoong-Kun Fun ^c ^* and Rohana Adnan ^a

^aSchool of Chemical Science, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 31 May 2008; accepted 9 June 2008; online 13 June 2008)

The asymmetric unit of the title compound, tetraaquatetrakis{μ₃-6,6′-dioxido-2,2′-[1,2-phenylenebis(nitrilomethylidyne)]diphenolato}octazinc(II) dimethyl sulfoxide tetrasolvate dihydrate, [Zn₈(C₂₀H₁₂N₂O₄)₄(H₂O)₄]·4C₂H₆OS·2H₂O, contains one quarter of a Zn^II octanuclear complex with $[\overline4]$ symmetry, one dimethyl sulfoxide molecule and one half of a water molecule which lies on a twofold rotation axis. The Zn^II atoms of the octanuclear complex have two different five-coordinate environments, viz. ZnN₂O₃ and ZnO₅. All eight Zn^II centers adopt a distorted square-pyramidal coordination; four Zn^II ions have the N₂O₂ tetradentate Schiff base ligand bound in a basal plane and the coordinated water molecule occupying the apical site, while the remaing four Zn^II ions are bound by five O atoms from three Schiff base ligands. In the crystal structure, Zn^II complex molecules, coordinated and uncoordinated water molecules and dimethyl sulfoxide molecules are linked via O—H⋯O and C—H⋯O hydrogen bonds and C—H⋯π interactions, forming a three-dimensional framework.

Related literature

For related literatures on Schiff base Zn^II coordination complexes, see: Basak et al. 2007 ; Collinson & Fenton (1996 ); Pal et al. (2005 ); Tarafder et al. (2002 ). For related structures, see: Eltayeb et al. (2007a ,b ,c ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Zn₈(C₂₀H₁₂N₂O₄)₄(H₂O)₄]·4C₂H₆OS·2H₂O
M_r = 2321.03
Tetragonal, P 4₂ /n
a = 18.1324 (3) Å
c = 13.3813 (3) Å
V = 4399.56 (14) Å³
Z = 2
Mo Kα radiation
μ = 2.32 mm⁻¹
T = 100.0 (1) K
0.57 × 0.13 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.352, T_max = 0.796
26700 measured reflections
5851 independent reflections
3700 reflections with I > 2σ(I)
R_int = 0.085

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.138
S = 1.02
5851 reflections
314 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O4ⁱ	0.84 (4)	1.72 (4)	2.535 (4)	164 (5)
O2W—H1W2⋯O5	0.85 (8)	2.28 (9)	3.032 (4)	147 (4)
O1W—H2W1⋯O5	0.83 (4)	1.95 (4)	2.772 (5)	174 (4)
C3—H3A⋯O3ⁱⁱ	0.93	2.57	3.271 (5)	132
C21—H21C⋯O4ⁱⁱⁱ	0.96	2.52	3.454 (7)	165
C21—H21B⋯Cg1^iv	0.96	2.81	3.475 (6)	127
Symmetry codes: (i) $[y, -x+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (iii) $[-y+1, x+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z. Cg1 is the centroid of the C1–C6 ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017340/ci2611sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017340/ci2611Isup2.hkl

checkCIF report

Comment top

There has been considerable interest in the synthesis of metal Schiff base complexes due to their coordination chemistry and applications (Basak et al., 2007; Eltayeb et al., 2007a,b,c; Pal et al., 2005; Tarafder et al., 2002). Zinc complexes with Schiff bases are important in biological systems and coordination chemistry (Collinson & Fenton, 1996; Tarafder et al., 2002). Previously, we have reported crystal structures of Zn^II complexes with Schiff base ligands (Eltayeb et al., 2007a,b,c). As a continuation of our research on Schiff base complexes, we report here the crystal structure of the title octanuclear Zn^II complex.

The asymmetric unit of the title compound (Fig. 1) contains one quarter of the Zn₈(C₈₀H₅₆N₈O₂₀) complex, one dimethyl sulfoxide (C₂H₆OS) and one-half of a water molecule with its O atom lying on a twofold rotation axis. The other three quarters of the octanuclear complex molecule are generated by the fourfold axis. The Zn^II atoms of the octanuclear complex has two different five-coordination environments viz. ZnN₂O₃ and ZnO₅ (Fig. 2). All eight Zn^II centers adopt a distorted square-pyramidal coordination in which four Zn^II ions (outer) (Zn1 and its three symmetry equivalents Zn1A, Zn1B and Zn1C) coordinate with the N₂O₂ tetradentate Schiff base ligand bounded in a basal plane and the coordinated water molecule occupying the apical site. The other four Zn^II ions (inner) (Zn2 and its three symmetry equivalents Zn2A, Zn2B and Zn2C) are coordinated with five O atoms from three Schiff base ligands (see Fig. 2). The Zn^II ions in each unit are connected by one µ-O (Zn1—O2—Zn2) atom (Fig. 1). The Zn—µ-O bond lengths are Zn1—O2 = 2.032 (3) and Zn2—O2 = 2.191 (3) Å. In the octanuclear cluster, the µ-O1 atoms are also in bridging positions, between the Zn^II ions (inner cavity) (Zn2—O1—Zn2B) with the Zn—µ-O distances of Zn2—O1 = 2.000 (3) Å and Zn2B—O1 = 1.981 (3) Å. The connections of the four inner Zn^II ions by bridging µ-O1 and its equivalents result in the formation of an eight membered ring (Zn2—O1—Zn2B—O1B—Zn2C—O1C—Zn2A—O1A), with the Zn···Zn contacts being 3.4878 (5) Å. The Schiff base ligand in the present complex is in an umbrella conformation with the dihedral angle between the two outer rings (C1—C6 and C15—C20) being 48.1 (2) °. In the octanuclear complex (Fig. 2), the four Schiff bases have their concave sides alternating up and down. The coordination geometry of the five-coordinate atoms Zn1 and Zn2 (and their equivalents) can be viewed as that of a slightly distorted square antiprism. Bond lengths and angles observed in the structure are in normal ranges (Allen et al., 1987) and comparable with the related structures (Eltayeb et al., 2007a,b,c).

In the crystal packing (Fig. 3), the Zn^II complex molecules, coordinated and free water molecules and dimethyl sulfoxide molecules are linked via O—H···O and C—H···O hydrogen bonds and C—H···π interactions involving the C1—C6 (centroid Cg1) ring (Table 1) forming a three-dimensional framework.

Related literature top

For related literatures on Schiff base Zn^II coordination complexes, see: Basak et al. 2007; Collinson & Fenton (1996); Pal et al. (2005); Tarafder et al. (2002). For related structures, see: Eltayeb et al. (2007a,b,c). For bond-length data, see: Allen et al. (1987). Cg1 is the centroid of the C1–C6 ring.

Experimental top

The title compound was synthesized by adding 2,3-dihydroxybenzaldehyde (0.552 g, 4 mmol) to a solution of o-phenylenediamine (0.216 g, 2 mmol) in ethanol 95% (20 ml). The mixture was refluxed with stirring for 30 min. Zinc chloride (0.544 g, 4 mmol) in ethanol (10 ml) was then added, followed by triethylamine (1.0 ml, 7.2 mmol). The mixture was stirred at room temperature for 3 h. The yellow precipitate obtained was washed with about 5 ml e thanol, dried, and then washed with copious amounts of diethylether. Orange single crystals of the title compound suitable for X-ray diffraction were formed after recrystallization in the dimethyl sulfoxide/ethanol (3:5 v/v) at room temperature after several days.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of the octanuclear complex, showing 50% probability displacement ellipsoids and the atomic numbering. H atoms of the Zn^II complex, DMSO and solvated water molecules have been omitted for clarity. Symmetry codes: (A) 1/2 - y, x, 1/2 - z; (B) y, 1/2 - x, 1/2 - z; (C) 1/2 - x, 1/2 - y, z.
	Fig. 3. The crystal packing of the title compound, viewed along the c axis, showing sheets parallel to the ab plane. Hydrogen bonds are shown as dashed lines.

tetraaquatetrakis{µ₃-6,6'-dioxido-2,2'-[1,2- phenylenebis(nitrilomethylidyne)]diphenolato}octazinc(II) dimethyl sulfoxide tetrasolvate dihydrate top

Crystal data top

[Zn₈(C₂₀H₁₂N₂O₄)₄(H₂O)₄]·4C₂H₆OS·2H₂O	D_x = 1.752 Mg m⁻³
M_r = 2321.03	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₂/n	Cell parameters from 5851 reflections
Hall symbol: -P 4bc	θ = 2.9–29.0°
a = 18.1324 (3) Å	µ = 2.32 mm⁻¹
c = 13.3813 (3) Å	T = 100 K
V = 4399.56 (14) Å³	Needle, orange
Z = 2	0.57 × 0.13 × 0.10 mm
F(000) = 2360

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5851 independent reflections
Radiation source: fine-focus sealed tube	3700 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.085
Detector resolution: 8.33 pixels mm^-1	θ_max = 29.0°, θ_min = 2.9°
ω scans	h = −24→11
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −24→24
T_min = 0.352, T_max = 0.796	l = −18→18
26700 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0592P)² + 6.834P] where P = (F_o² + 2F_c²)/3
5851 reflections	(Δ/σ)_max = 0.001
314 parameters	Δρ_max = 0.67 e Å⁻³
6 restraints	Δρ_min = −1.34 e Å⁻³

Crystal data top

[Zn₈(C₂₀H₁₂N₂O₄)₄(H₂O)₄]·4C₂H₆OS·2H₂O	Z = 2
M_r = 2321.03	Mo Kα radiation
Tetragonal, P4₂/n	µ = 2.32 mm⁻¹
a = 18.1324 (3) Å	T = 100 K
c = 13.3813 (3) Å	0.57 × 0.13 × 0.10 mm
V = 4399.56 (14) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5851 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3700 reflections with I > 2σ(I)
T_min = 0.352, T_max = 0.796	R_int = 0.085
26700 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	6 restraints
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.67 e Å⁻³
5851 reflections	Δρ_min = −1.34 e Å⁻³
314 parameters

Special details top

Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.22916 (3)	0.46426 (3)	0.07015 (4)	0.01886 (13)
Zn2	0.34013 (2)	0.35177 (2)	0.24587 (4)	0.01728 (13)
O1	0.35359 (15)	0.25401 (15)	0.1791 (2)	0.0188 (6)
O2	0.28402 (15)	0.36961 (15)	0.1029 (2)	0.0192 (6)
O3	0.14565 (15)	0.43546 (15)	0.1585 (2)	0.0189 (6)
O4	0.05238 (16)	0.38411 (16)	0.2903 (3)	0.0277 (7)
N1	0.26712 (19)	0.45884 (18)	−0.0754 (3)	0.0210 (7)
N2	0.1627 (2)	0.54198 (19)	−0.0038 (3)	0.0233 (8)
C1	0.3139 (2)	0.3234 (2)	0.0380 (3)	0.0177 (8)
C2	0.3494 (2)	0.2598 (2)	0.0780 (3)	0.0182 (8)
C3	0.3795 (2)	0.2079 (2)	0.0141 (3)	0.0222 (9)
H3A	0.4019	0.1661	0.0407	0.027*
C4	0.3768 (3)	0.2170 (2)	−0.0899 (4)	0.0282 (10)
H4A	0.3952	0.1805	−0.1320	0.034*
C5	0.3471 (2)	0.2795 (2)	−0.1285 (3)	0.0248 (9)
H5A	0.3470	0.2861	−0.1974	0.030*
C6	0.3166 (2)	0.3342 (2)	−0.0672 (3)	0.0216 (9)
C7	0.2939 (2)	0.4005 (2)	−0.1172 (3)	0.0231 (9)
H7A	0.2990	0.4016	−0.1863	0.028*
C8	0.2508 (2)	0.5228 (2)	−0.1328 (3)	0.0234 (9)
C9	0.2866 (3)	0.5429 (3)	−0.2203 (4)	0.0296 (10)
H9A	0.3238	0.5133	−0.2462	0.035*
C10	0.2663 (3)	0.6077 (3)	−0.2689 (4)	0.0349 (12)
H10A	0.2893	0.6207	−0.3285	0.042*
C11	0.2123 (3)	0.6529 (3)	−0.2295 (4)	0.0326 (11)
H11A	0.1990	0.6959	−0.2626	0.039*
C12	0.1781 (3)	0.6342 (2)	−0.1410 (4)	0.0278 (10)
H12A	0.1428	0.6655	−0.1138	0.033*
C13	0.1960 (2)	0.5688 (2)	−0.0920 (3)	0.0218 (9)
C14	0.0969 (2)	0.5594 (2)	0.0204 (4)	0.0250 (9)
H14A	0.0727	0.5940	−0.0191	0.030*
C15	0.0574 (2)	0.5294 (2)	0.1044 (3)	0.0223 (9)
C16	−0.0143 (2)	0.5597 (2)	0.1196 (4)	0.0261 (10)
H16A	−0.0298	0.5988	0.0797	0.031*
C17	−0.0604 (2)	0.5332 (2)	0.1905 (4)	0.0269 (10)
H17A	−0.1065	0.5546	0.1998	0.032*
C18	−0.0388 (2)	0.4735 (2)	0.2496 (4)	0.0250 (9)
H18A	−0.0707	0.4551	0.2978	0.030*
C19	0.0295 (2)	0.4420 (2)	0.2369 (3)	0.0209 (9)
C20	0.0805 (2)	0.4700 (2)	0.1638 (3)	0.0199 (9)
S1	0.42019 (7)	0.60730 (7)	−0.06159 (11)	0.0376 (3)
O5	0.3672 (2)	0.6353 (2)	0.0183 (3)	0.0436 (9)
C21	0.5096 (3)	0.6047 (3)	−0.0076 (5)	0.0449 (14)
H21A	0.5122	0.5650	0.0397	0.067*
H21B	0.5192	0.6506	0.0258	0.067*
H21C	0.5457	0.5972	−0.0591	0.067*
C22	0.4357 (4)	0.6846 (3)	−0.1418 (5)	0.0504 (16)
H22A	0.3913	0.6957	−0.1778	0.076*
H22B	0.4744	0.6731	−0.1881	0.076*
H22C	0.4498	0.7266	−0.1023	0.076*
O1W	0.29110 (16)	0.53937 (16)	0.1423 (3)	0.0251 (7)
H1W1	0.321 (2)	0.5050 (19)	0.154 (4)	0.038*
H2W1	0.311 (2)	0.570 (2)	0.105 (3)	0.038*
O2W	0.2500	0.7500	0.0625 (6)	0.104 (3)
H1W2	0.278 (5)	0.724 (5)	0.026 (2)	0.156*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0204 (2)	0.0191 (2)	0.0171 (3)	0.00136 (18)	0.0007 (2)	0.0010 (2)
Zn2	0.0177 (2)	0.0191 (2)	0.0150 (2)	−0.00013 (18)	0.0004 (2)	−0.0005 (2)
O1	0.0245 (14)	0.0182 (13)	0.0139 (15)	0.0013 (11)	−0.0015 (13)	0.0006 (12)
O2	0.0229 (14)	0.0219 (14)	0.0128 (14)	0.0035 (11)	0.0021 (12)	−0.0020 (12)
O3	0.0182 (13)	0.0181 (13)	0.0205 (16)	0.0015 (10)	−0.0001 (12)	0.0022 (12)
O4	0.0263 (15)	0.0267 (15)	0.0302 (19)	0.0052 (12)	0.0069 (15)	0.0101 (15)
N1	0.0245 (17)	0.0203 (16)	0.0181 (19)	0.0016 (14)	0.0011 (16)	0.0018 (15)
N2	0.0261 (18)	0.0229 (17)	0.021 (2)	0.0033 (14)	0.0014 (17)	0.0014 (16)
C1	0.0195 (19)	0.0168 (18)	0.017 (2)	−0.0004 (15)	−0.0013 (17)	−0.0030 (17)
C2	0.0204 (18)	0.0192 (18)	0.015 (2)	0.0001 (15)	0.0052 (17)	−0.0002 (18)
C3	0.025 (2)	0.021 (2)	0.020 (2)	0.0031 (16)	0.0047 (19)	0.0000 (19)
C4	0.041 (3)	0.025 (2)	0.019 (2)	0.0074 (19)	0.003 (2)	−0.0046 (19)
C5	0.035 (2)	0.026 (2)	0.013 (2)	0.0031 (18)	0.0017 (19)	−0.0014 (19)
C6	0.023 (2)	0.023 (2)	0.019 (2)	0.0008 (16)	−0.0007 (19)	−0.0020 (19)
C7	0.024 (2)	0.030 (2)	0.015 (2)	0.0005 (17)	−0.0027 (19)	0.0018 (19)
C8	0.027 (2)	0.022 (2)	0.021 (2)	0.0005 (17)	−0.004 (2)	0.0010 (19)
C9	0.036 (3)	0.029 (2)	0.023 (2)	0.0043 (19)	0.002 (2)	0.004 (2)
C10	0.045 (3)	0.030 (2)	0.030 (3)	−0.002 (2)	0.007 (2)	0.011 (2)
C11	0.040 (3)	0.028 (2)	0.029 (3)	0.002 (2)	−0.002 (2)	0.009 (2)
C12	0.029 (2)	0.025 (2)	0.030 (3)	0.0036 (17)	0.001 (2)	0.002 (2)
C13	0.022 (2)	0.024 (2)	0.019 (2)	0.0000 (16)	−0.0007 (18)	0.0058 (18)
C14	0.029 (2)	0.024 (2)	0.022 (2)	0.0078 (17)	−0.001 (2)	0.0065 (19)
C15	0.026 (2)	0.0188 (19)	0.022 (2)	0.0027 (16)	−0.0011 (19)	−0.0004 (18)
C16	0.030 (2)	0.023 (2)	0.026 (3)	0.0071 (17)	−0.003 (2)	0.001 (2)
C17	0.027 (2)	0.027 (2)	0.026 (3)	0.0071 (18)	0.000 (2)	−0.001 (2)
C18	0.025 (2)	0.027 (2)	0.023 (2)	−0.0004 (17)	0.006 (2)	0.000 (2)
C19	0.0211 (19)	0.0185 (18)	0.023 (2)	−0.0011 (15)	−0.0010 (18)	−0.0030 (18)
C20	0.0210 (19)	0.0192 (19)	0.020 (2)	0.0004 (15)	−0.0038 (18)	−0.0025 (18)
S1	0.0380 (7)	0.0359 (7)	0.0389 (8)	−0.0037 (5)	0.0043 (6)	−0.0010 (6)
O5	0.044 (2)	0.045 (2)	0.042 (2)	−0.0087 (17)	0.0120 (19)	−0.0001 (19)
C21	0.038 (3)	0.057 (4)	0.039 (3)	−0.005 (2)	0.004 (3)	0.001 (3)
C22	0.062 (4)	0.042 (3)	0.048 (4)	0.007 (3)	0.021 (3)	0.005 (3)
O1W	0.0260 (16)	0.0203 (15)	0.0290 (19)	−0.0008 (12)	−0.0009 (14)	−0.0011 (14)
O2W	0.134 (8)	0.130 (8)	0.047 (5)	0.075 (6)	0.000	0.000

Geometric parameters (Å, º) top

Zn1—O3	1.990 (3)	C8—C9	1.387 (7)
Zn1—O1W	2.012 (3)	C8—C13	1.407 (6)
Zn1—O2	2.032 (3)	C9—C10	1.393 (6)
Zn1—N1	2.069 (4)	C9—H9A	0.93
Zn1—N2	2.101 (4)	C10—C11	1.381 (7)
Zn1—H1W1	2.13 (5)	C10—H10A	0.93
Zn2—O4ⁱ	1.973 (3)	C11—C12	1.379 (7)
Zn2—O1ⁱⁱ	1.981 (3)	C11—H11A	0.93
Zn2—O1	2.000 (3)	C12—C13	1.393 (6)
Zn2—O3ⁱ	2.152 (3)	C12—H12A	0.93
Zn2—O2	2.191 (3)	C14—C15	1.439 (6)
O1—C2	1.359 (5)	C14—H14A	0.93
O1—Zn2ⁱ	1.981 (3)	C15—C20	1.403 (6)
O2—C1	1.323 (5)	C15—C16	1.426 (6)
O3—C20	1.339 (5)	C16—C17	1.353 (7)
O3—Zn2ⁱⁱ	2.152 (3)	C16—H16A	0.93
O4—C19	1.336 (5)	C17—C18	1.396 (6)
O4—Zn2ⁱⁱ	1.973 (3)	C17—H17A	0.93
N1—C7	1.291 (5)	C18—C19	1.374 (6)
N1—C8	1.423 (5)	C18—H18A	0.93
N2—C14	1.277 (5)	C19—C20	1.439 (6)
N2—C13	1.412 (6)	S1—O5	1.525 (4)
C1—C6	1.421 (6)	S1—C21	1.775 (6)
C1—C2	1.425 (5)	S1—C22	1.787 (6)
C2—C3	1.384 (6)	C21—H21A	0.96
C3—C4	1.402 (6)	C21—H21B	0.96
C3—H3A	0.93	C21—H21C	0.96
C4—C5	1.356 (6)	C22—H22A	0.96
C4—H4A	0.93	C22—H22B	0.96
C5—C6	1.402 (6)	C22—H22C	0.96
C5—H5A	0.93	O1W—H1W1	0.837 (19)
C6—C7	1.436 (6)	O1W—H2W1	0.833 (19)
C7—H7A	0.93	O2W—H1W2	0.846 (14)

O3—Zn1—O1W	108.50 (13)	N1—C7—H7A	116.9
O3—Zn1—O2	91.31 (11)	C6—C7—H7A	116.9
O1W—Zn1—O2	101.24 (12)	C9—C8—C13	120.2 (4)
O3—Zn1—N1	143.11 (13)	C9—C8—N1	124.8 (4)
O1W—Zn1—N1	107.36 (14)	C13—C8—N1	114.9 (4)
O2—Zn1—N1	90.00 (12)	C8—C9—C10	119.5 (4)
O3—Zn1—N2	91.11 (13)	C8—C9—H9A	120.3
O1W—Zn1—N2	95.28 (13)	C10—C9—H9A	120.3
O2—Zn1—N2	161.59 (13)	C11—C10—C9	120.6 (5)
N1—Zn1—N2	77.25 (14)	C11—C10—H10A	119.7
O3—Zn1—H1W1	111.9 (13)	C9—C10—H10A	119.7
O1W—Zn1—H1W1	23.1 (7)	C12—C11—C10	120.1 (4)
O2—Zn1—H1W1	78.4 (6)	C12—C11—H11A	120.0
N1—Zn1—H1W1	104.5 (13)	C10—C11—H11A	120.0
N2—Zn1—H1W1	117.4 (6)	C11—C12—C13	120.6 (4)
O4ⁱ—Zn2—O1ⁱⁱ	117.28 (13)	C11—C12—H12A	119.7
O4ⁱ—Zn2—O1	128.45 (13)	C13—C12—H12A	119.7
O1ⁱⁱ—Zn2—O1	110.27 (16)	C12—C13—C8	119.1 (4)
O4ⁱ—Zn2—O3ⁱ	78.59 (12)	C12—C13—N2	126.0 (4)
O1ⁱⁱ—Zn2—O3ⁱ	112.98 (12)	C8—C13—N2	114.9 (4)
O1—Zn2—O3ⁱ	100.78 (11)	N2—C14—C15	124.8 (4)
O4ⁱ—Zn2—O2	80.99 (12)	N2—C14—H14A	117.6
O1ⁱⁱ—Zn2—O2	92.30 (11)	C15—C14—H14A	117.6
O1—Zn2—O2	78.31 (11)	C20—C15—C16	119.2 (4)
O3ⁱ—Zn2—O2	152.81 (11)	C20—C15—C14	125.7 (4)
C2—O1—Zn2ⁱ	124.8 (2)	C16—C15—C14	114.8 (4)
C2—O1—Zn2	111.7 (2)	C17—C16—C15	121.7 (4)
Zn2ⁱ—O1—Zn2	122.36 (15)	C17—C16—H16A	119.1
C1—O2—Zn1	126.4 (3)	C15—C16—H16A	119.1
C1—O2—Zn2	106.8 (2)	C16—C17—C18	120.0 (4)
Zn1—O2—Zn2	122.72 (14)	C16—C17—H17A	120.0
C20—O3—Zn1	125.4 (3)	C18—C17—H17A	120.0
C20—O3—Zn2ⁱⁱ	111.3 (2)	C19—C18—C17	120.4 (4)
Zn1—O3—Zn2ⁱⁱ	123.20 (13)	C19—C18—H18A	119.8
C19—O4—Zn2ⁱⁱ	117.4 (3)	C17—C18—H18A	119.8
C7—N1—C8	120.9 (4)	O4—C19—C18	122.7 (4)
C7—N1—Zn1	124.9 (3)	O4—C19—C20	116.2 (4)
C8—N1—Zn1	113.6 (3)	C18—C19—C20	121.1 (4)
C14—N2—C13	121.7 (4)	O3—C20—C15	126.4 (4)
C14—N2—Zn1	125.6 (3)	O3—C20—C19	115.9 (4)
C13—N2—Zn1	112.3 (3)	C15—C20—C19	117.7 (4)
O2—C1—C6	125.2 (4)	O5—S1—C21	107.4 (3)
O2—C1—C2	116.8 (4)	O5—S1—C22	105.0 (2)
C6—C1—C2	117.9 (4)	C21—S1—C22	96.9 (3)
O1—C2—C3	122.7 (4)	S1—C21—H21A	109.5
O1—C2—C1	117.5 (3)	S1—C21—H21B	109.5
C3—C2—C1	119.8 (4)	H21A—C21—H21B	109.5
C2—C3—C4	121.3 (4)	S1—C21—H21C	109.5
C2—C3—H3A	119.4	H21A—C21—H21C	109.5
C4—C3—H3A	119.4	H21B—C21—H21C	109.5
C5—C4—C3	119.3 (4)	S1—C22—H22A	109.5
C5—C4—H4A	120.3	S1—C22—H22B	109.5
C3—C4—H4A	120.3	H22A—C22—H22B	109.5
C4—C5—C6	121.7 (4)	S1—C22—H22C	109.5
C4—C5—H5A	119.2	H22A—C22—H22C	109.5
C6—C5—H5A	119.2	H22B—C22—H22C	109.5
C5—C6—C1	119.7 (4)	Zn1—O1W—H1W1	87 (4)
C5—C6—C7	115.7 (4)	Zn1—O1W—H2W1	114 (4)
C1—C6—C7	124.5 (4)	H1W1—O1W—H2W1	109 (3)
N1—C7—C6	126.3 (4)

O4ⁱ—Zn2—O1—C2	−44.4 (3)	C6—C1—C2—C3	−5.4 (6)
O1ⁱⁱ—Zn2—O1—C2	112.0 (3)	O1—C2—C3—C4	−177.4 (4)
O3ⁱ—Zn2—O1—C2	−128.4 (2)	C1—C2—C3—C4	0.9 (6)
O2—Zn2—O1—C2	23.9 (2)	C2—C3—C4—C5	3.0 (7)
O4ⁱ—Zn2—O1—Zn2ⁱ	147.45 (15)	C3—C4—C5—C6	−2.3 (7)
O1ⁱⁱ—Zn2—O1—Zn2ⁱ	−56.06 (14)	C4—C5—C6—C1	−2.4 (7)
O3ⁱ—Zn2—O1—Zn2ⁱ	63.54 (17)	C4—C5—C6—C7	174.0 (4)
O2—Zn2—O1—Zn2ⁱ	−144.18 (17)	O2—C1—C6—C5	−177.2 (4)
O3—Zn1—O2—C1	130.5 (3)	C2—C1—C6—C5	6.2 (6)
O1W—Zn1—O2—C1	−120.3 (3)	O2—C1—C6—C7	6.7 (7)
N1—Zn1—O2—C1	−12.6 (3)	C2—C1—C6—C7	−169.9 (4)
N2—Zn1—O2—C1	33.0 (6)	C8—N1—C7—C6	176.2 (4)
O3—Zn1—O2—Zn2	−75.11 (16)	Zn1—N1—C7—C6	−13.8 (6)
O1W—Zn1—O2—Zn2	34.05 (18)	C5—C6—C7—N1	−177.3 (4)
N1—Zn1—O2—Zn2	141.76 (17)	C1—C6—C7—N1	−1.1 (7)
N2—Zn1—O2—Zn2	−172.6 (3)	C7—N1—C8—C9	−28.3 (7)
O4ⁱ—Zn2—O2—C1	107.0 (3)	Zn1—N1—C8—C9	160.6 (4)
O1ⁱⁱ—Zn2—O2—C1	−135.8 (2)	C7—N1—C8—C13	154.6 (4)
O1—Zn2—O2—C1	−25.5 (2)	Zn1—N1—C8—C13	−16.5 (5)
O3ⁱ—Zn2—O2—C1	65.3 (3)	C13—C8—C9—C10	−1.9 (7)
O4ⁱ—Zn2—O2—Zn1	−51.73 (17)	N1—C8—C9—C10	−179.0 (4)
O1ⁱⁱ—Zn2—O2—Zn1	65.53 (16)	C8—C9—C10—C11	1.6 (8)
O1—Zn2—O2—Zn1	175.75 (18)	C9—C10—C11—C12	0.2 (8)
O3ⁱ—Zn2—O2—Zn1	−93.4 (3)	C10—C11—C12—C13	−1.8 (7)
O1W—Zn1—O3—C20	87.5 (3)	C11—C12—C13—C8	1.5 (7)
O2—Zn1—O3—C20	−170.2 (3)	C11—C12—C13—N2	−177.0 (4)
N1—Zn1—O3—C20	−78.4 (4)	C9—C8—C13—C12	0.4 (7)
N2—Zn1—O3—C20	−8.4 (3)	N1—C8—C13—C12	177.7 (4)
O1W—Zn1—O3—Zn2ⁱⁱ	−95.24 (18)	C9—C8—C13—N2	179.0 (4)
O2—Zn1—O3—Zn2ⁱⁱ	7.07 (17)	N1—C8—C13—N2	−3.7 (6)
N1—Zn1—O3—Zn2ⁱⁱ	98.8 (2)	C14—N2—C13—C12	26.1 (7)
N2—Zn1—O3—Zn2ⁱⁱ	168.82 (18)	Zn1—N2—C13—C12	−159.8 (4)
O3—Zn1—N1—C7	−74.8 (4)	C14—N2—C13—C8	−152.4 (4)
O1W—Zn1—N1—C7	119.1 (3)	Zn1—N2—C13—C8	21.7 (5)
O2—Zn1—N1—C7	17.3 (4)	C13—N2—C14—C15	174.5 (4)
N2—Zn1—N1—C7	−149.3 (4)	Zn1—N2—C14—C15	1.3 (7)
O3—Zn1—N1—C8	95.8 (3)	N2—C14—C15—C20	−9.3 (8)
O1W—Zn1—N1—C8	−70.2 (3)	N2—C14—C15—C16	177.2 (4)
O2—Zn1—N1—C8	−172.0 (3)	C20—C15—C16—C17	0.7 (7)
N2—Zn1—N1—C8	21.4 (3)	C14—C15—C16—C17	174.7 (4)
O3—Zn1—N2—C14	5.9 (4)	C15—C16—C17—C18	−1.4 (7)
O1W—Zn1—N2—C14	−102.8 (4)	C16—C17—C18—C19	0.6 (7)
O2—Zn1—N2—C14	103.4 (5)	Zn2ⁱⁱ—O4—C19—C18	174.6 (3)
N1—Zn1—N2—C14	150.6 (4)	Zn2ⁱⁱ—O4—C19—C20	−5.1 (5)
O3—Zn1—N2—C13	−167.9 (3)	C17—C18—C19—O4	−178.9 (4)
O1W—Zn1—N2—C13	83.4 (3)	C17—C18—C19—C20	0.9 (7)
O2—Zn1—N2—C13	−70.4 (5)	Zn1—O3—C20—C15	4.3 (6)
N1—Zn1—N2—C13	−23.2 (3)	Zn2ⁱⁱ—O3—C20—C15	−173.3 (3)
Zn1—O2—C1—C6	3.8 (6)	Zn1—O3—C20—C19	−176.8 (3)
Zn2—O2—C1—C6	−153.8 (3)	Zn2ⁱⁱ—O3—C20—C19	5.7 (4)
Zn1—O2—C1—C2	−179.5 (3)	C16—C15—C20—O3	179.7 (4)
Zn2—O2—C1—C2	22.8 (4)	C14—C15—C20—O3	6.4 (7)
Zn2ⁱ—O1—C2—C3	−33.8 (5)	C16—C15—C20—C19	0.7 (6)
Zn2—O1—C2—C3	158.5 (3)	C14—C15—C20—C19	−172.5 (4)
Zn2ⁱ—O1—C2—C1	147.9 (3)	O4—C19—C20—O3	−0.8 (6)
Zn2—O1—C2—C1	−19.8 (4)	C18—C19—C20—O3	179.4 (4)
O2—C1—C2—O1	−4.0 (5)	O4—C19—C20—C15	178.2 (4)
C6—C1—C2—O1	173.0 (3)	C18—C19—C20—C15	−1.5 (6)
O2—C1—C2—C3	177.7 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O4ⁱ	0.84 (4)	1.72 (4)	2.535 (4)	164 (5)
O2W—H1W2···O5	0.85 (8)	2.28 (9)	3.032 (4)	147 (4)
O1W—H2W1···O5	0.83 (4)	1.95 (4)	2.772 (5)	174 (4)
C3—H3A···O3ⁱⁱⁱ	0.93	2.57	3.271 (5)	132
C21—H21C···O4^iv	0.96	2.52	3.454 (7)	165
C21—H21B···Cg1^v	0.96	2.81	3.475 (6)	127

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

Experimental details

Crystal data
Chemical formula	[Zn₈(C₂₀H₁₂N₂O₄)₄(H₂O)₄]·4C₂H₆OS·2H₂O
M_r	2321.03
Crystal system, space group	Tetragonal, P4₂/n
Temperature (K)	100
a, c (Å)	18.1324 (3), 13.3813 (3)
V (Å³)	4399.56 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.32
Crystal size (mm)	0.57 × 0.13 × 0.10

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.352, 0.796
No. of measured, independent and observed [I > 2σ(I)] reflections	26700, 5851, 3700
R_int	0.085
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.138, 1.02
No. of reflections	5851
No. of parameters	314
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.67, −1.34

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O4ⁱ	0.84 (4)	1.72 (4)	2.535 (4)	164 (5)
O2W—H1W2···O5	0.85 (8)	2.28 (9)	3.032 (4)	147 (4)
O1W—H2W1···O5	0.83 (4)	1.95 (4)	2.772 (5)	174 (4)
C3—H3A···O3ⁱⁱ	0.93	2.57	3.271 (5)	132
C21—H21C···O4ⁱⁱⁱ	0.96	2.52	3.454 (7)	165
C21—H21B···Cg1^iv	0.96	2.81	3.475 (6)	127

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

Footnotes

‡On study leave from International University of Africa, Sudan. E-mail: nasertaha90@hotmail.com.

§Additional correspondence author; e-mail: suchada.c@psu.ac.th.

Acknowledgements

The authors thank the Malaysian Government, the Ministry of Science, Technology and Innovation, Malaysia (MOSTI) and Universiti Sains Malaysia for the E-Science Fund research grant (PKIMIA/613308) and facilities. The International University of Africa (Sudan) is acknowledged for providing study leave to NEE. SC thanks Prince of Songkla University for generous support. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose Grant No. 1001/PFIZIK/811012.

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