Poly[hemi(hexa­aqua­zinc) [[μ2-1,3-bis­(1,2,4-triazol-1-yl)methane](μ2-5-sulfonato­benzene-1,3-dicarboxyl­ato)zinc] sesquihydrate]

Liu, S.-Y.; Tian, L.

doi:10.1107/S1600536811022835

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m950-m951

doi:10.1107/S1600536811022835

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Poly[hemi(hexaaquazinc) [[μ₂-1,3-bis(1,2,4-triazol-1-yl)methane](μ₂-5-sulfonatobenzene-1,3-dicarboxylato)zinc] sesquihydrate]

Shang-Yuan Liu ^a and Li Tian ^a ^*

^aCollege of Chemistry, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: lilytianli@hotmail.com

(Received 19 May 2011; accepted 13 June 2011; online 18 June 2011)

The title coordination polymer, {[Zn(H₂O)₆]_0.5[Zn(C₈H₃O₇S)(C₅H₆N₆)]·1.5H₂O}_n, synthesized under hydrothermal conditions, possesses a one-dimensional tube-like chain structure along [100], with octahedral [Zn(H₂O)₆]²⁺ groups ( $[\overline1]$ symmetry) trapped in the pores. The other Zn atom is five-coordinated in a highly distorted trigonal–biyramidal coordination that is defined by two different N atoms from two 1,3-bis(1,2,4-triazol-1-yl)methane (btrm) ligands and three carboxylate O atoms from 5-sulfonatobenzene-1,3-dicarboxylate ligands. The chains carry negative charges, whereas the free [Zn(H₂O)₆]²⁺ cations are positively charged. The [Zn(H₂O)₆]²⁺ cation is connected with the one-dimensional tubelike chain through weak classical O—H⋯O and O—H⋯N hydrogen-bonding interactions as well as through electrostatic interactions. One of the two uncoordinated water molecules exhibits half-occupancy.

Related literature

For properties of organic–inorganic hybrid materials, see: Ishikava et al. (2003 ). One of the key steps in the preparation of polymeric transition metal complexes is to select multidentate bridging ligands or mixed multidentate ligands, see: Biradha et al. (2006 ).

Experimental

Crystal data

[Zn(H₂O)₆]_0.5[Zn(C₈H₃O₇S)(C₅H₆N₆)]·1.5H₂O
M_r = 571.48
Monoclinic, P 2₁ /c
a = 10.2611 (3) Å
b = 16.9967 (4) Å
c = 11.4808 (3) Å
β = 93.812 (2)°
V = 1997.88 (9) Å³
Z = 4
Mo Kα radiation
μ = 2.00 mm⁻¹
T = 293 K
0.23 × 0.15 × 0.14 mm

Data collection

Bruker SuperNova Eos diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.657, T_max = 0.767
7740 measured reflections
3524 independent reflections
2763 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.155
S = 1.11
3524 reflections
304 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 1.67 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8A⋯O3ⁱ	0.86	1.90	2.628 (7)	141
O8—H8B⋯O11	0.86	2.40	3.126 (7)	143
O8—H8B⋯O7ⁱⁱ	0.86	2.49	2.983 (7)	117
O9—H9A⋯O6ⁱⁱⁱ	0.86	1.91	2.700 (7)	151
O9—H9B⋯O5ⁱⁱ	0.86	1.94	2.794 (7)	170
O10—H10A⋯O2	0.86	1.98	2.716 (7)	143
O10—H10B⋯O11	0.86	2.12	2.656 (7)	119
O10—H10B⋯O12	0.86	2.39	3.068 (7)	135
O11—H11A⋯O7ⁱⁱⁱ	0.86	2.37	2.887 (7)	119
O11—H11B⋯N5	0.86	2.39	3.029 (7)	131
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811022835/br2168sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022835/br2168Isup2.hkl

checkCIF report

Comment top

Organic-inorganic hybrid materials have obtained extensive attention due to not only the structural diversity but also their attractive properties, such as catalytic activity, magnetism, photochemical activity and electrical chemistry (Ishikava et al., 2003). One of the key steps for preparation of polymeric transition metal complexes is to select the multidentate bridging ligands or mixed multidentate ligands (Biradha et al., 2006). 5-Sulfoisophthalic acid as a kind of multi-carboxylic ligand is a good bridging ligand, but it has been less explored for the synthesis. On the other hand, 1,4-bis(1,2,4-triazol-1-yl)methane (abbreviated as btrm) is a flexible ligand. In this contribution, we describe the Zn(II) metal-organic frameworks constructed from the rigid multi-carboxylic ligand sip and flexible btrm ligand. A new complex {[Zn(btrp)(sip)][Zn_0.5(H₂O)]}_n was fabricated.

The title compound possesses a dinuclear structure with the asymmetric unit containing one crystallographically unique Zn²⁺ ion, one btrm ligand, one sip ligand and half of one free Zn(H₂O)₆²⁺ ion. As viewed in Fig. 1, Zn1 is five-coordinated in a highly distorted trigonal biyramid coordination sphere that is defined by two different nitrogen atoms from two btrm ligands and three carboxylic oxygen atoms. Both btrm and sip adopt two connected mode. Every sip ligand links two Zn(II) atoms to construct a one-dimensional chain, two such chains are bridged by cis-btrm ligands to produce a one-dimensional tubelike chain (Fig. 2). Noteworthily, the one-dimensional chains carry negative charges, whereas the free Zn(H₂O)₆²⁺ ion show positive electricity. Through weak classical hydrogen-bonding interactions as well as the electrostatic interactions, the Zn(H₂O)₆²⁺ ions are connected with the one-dimensional tubelike chain.

Related literature top

For properties of organic–inorganic hybrid materials, see: Ishikava et al. (2003). One of the key steps in the preparation of polymeric transition metal complexes is to select multidentate bridging ligands or mixed multidentate ligands, see: Biradha et al. (2006).

Experimental top

A mixture of [Zn(NO₃)₂]6H₂O (148 mg, 0.5 mmol), NaH₂sip (135 mg, 0.5 mmol), btrm (68 mg, 0.5 mmol), triethylamine (1.0 mmol), H₂O (12 ml) was added into a Parr Teflon-lined stainless steel vessel, and then the vessel was sealed and heated to 413 K, kept for 3 days. After that the autoclave was cooled to room temperature at a rate of 1.5 °K/h. The title compound was filtered off, washed with distilled water and dried in air (yield 65% based on Zn). Analysis, calculated for C₁₃H₁₈N₆O_11.5SZn_1.5: C 27.29, H 3.17, N 14.68; found: C 27.01, H 3.58, N 14.88%.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The coordination environments of Zn1 in the title compound.
	Fig. 2. The one-dimensional chain of the title compound.
	Fig. 3. Reaction scheme

Poly[hemi(hexaaquazinc) [[µ₂-1,3-bis(1,2,4-triazol-1-yl)methane](µ₂-5-sulfonatobenzene- 1,3-dicarboxylato)zinc] sesquihydrate] top

Crystal data top

[Zn(H₂O)₆]_0.5[Zn(C₈H₃O₇S)(C₅H₆N₆)]·1.5H₂O	F(000) = 1160
M_r = 571.48	D_x = 1.900 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4538 reflections
a = 10.2611 (3) Å	θ = 2.4–25.0°
b = 16.9967 (4) Å	µ = 2.00 mm⁻¹
c = 11.4808 (3) Å	T = 293 K
β = 93.812 (2)°	BLOCK, colourless
V = 1997.88 (9) Å³	0.23 × 0.15 × 0.14 mm
Z = 4

Data collection top

Bruker SuperNova Eos diffractometer	3524 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2763 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
Detector resolution: 16.2116 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
ω scans	h = −12→10
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −20→19
T_min = 0.657, T_max = 0.767	l = −8→13
7740 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.155	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0939P)² + 1.3769P] where P = (F_o² + 2F_c²)/3
3524 reflections	(Δ/σ)_max = 0.001
304 parameters	Δρ_max = 1.67 e Å⁻³
30 restraints	Δρ_min = −0.90 e Å⁻³

Crystal data top

[Zn(H₂O)₆]_0.5[Zn(C₈H₃O₇S)(C₅H₆N₆)]·1.5H₂O	V = 1997.88 (9) Å³
M_r = 571.48	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.2611 (3) Å	µ = 2.00 mm⁻¹
b = 16.9967 (4) Å	T = 293 K
c = 11.4808 (3) Å	0.23 × 0.15 × 0.14 mm
β = 93.812 (2)°

Data collection top

Bruker SuperNova Eos diffractometer	3524 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2763 reflections with I > 2σ(I)
T_min = 0.657, T_max = 0.767	R_int = 0.030
7740 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	30 restraints
wR(F²) = 0.155	H-atom parameters constrained
S = 1.11	Δρ_max = 1.67 e Å⁻³
3524 reflections	Δρ_min = −0.90 e Å⁻³
304 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
Zn1	−0.05241 (5)	0.44539 (3)	0.65524 (5)	0.0173 (2)
Zn2	0.5000	0.5000	1.0000	0.0242 (3)
C1	−0.1029 (5)	0.5844 (3)	0.8059 (5)	0.0223 (12)
H1	−0.1689	0.5583	0.8420	0.027*
C2	0.0432 (6)	0.6157 (3)	0.6959 (5)	0.0290 (13)
H2	0.1013	0.6129	0.6372	0.035*
C3	−0.0915 (6)	0.7063 (3)	0.9310 (4)	0.0222 (12)
H3A	−0.0726	0.7606	0.9123	0.027*
H3B	−0.1841	0.7020	0.9418	0.027*
C4	−0.0526 (5)	0.6384 (3)	1.1245 (5)	0.0226 (12)
H4	−0.1355	0.6172	1.1301	0.027*
C5	0.1439 (5)	0.6712 (3)	1.1562 (5)	0.0263 (13)
H5	0.2270	0.6761	1.1930	0.032*
C6	0.3270 (5)	0.4047 (3)	0.5589 (4)	0.0164 (11)
C7	0.3175 (5)	0.3543 (3)	0.4624 (4)	0.0177 (11)
H7	0.2362	0.3380	0.4308	0.021*
C8	0.4303 (5)	0.3289 (3)	0.4144 (4)	0.0166 (11)
C9	0.5517 (5)	0.3537 (3)	0.4584 (4)	0.0178 (11)
H9	0.6265	0.3364	0.4247	0.021*
C10	0.5614 (5)	0.4045 (3)	0.5531 (4)	0.0156 (11)
C11	0.4512 (5)	0.4286 (3)	0.6035 (4)	0.0168 (11)
H11	0.4587	0.4614	0.6685	0.020*
C12	0.2081 (5)	0.4314 (3)	0.6171 (5)	0.0191 (11)
C13	0.6940 (5)	0.4296 (3)	0.6051 (4)	0.0173 (11)
N1	−0.0406 (4)	0.5563 (2)	0.7185 (4)	0.0198 (10)
N2	−0.0580 (4)	0.6556 (2)	0.8351 (4)	0.0201 (10)
N3	0.0351 (5)	0.6768 (3)	0.7636 (4)	0.0308 (12)
N4	−0.0173 (4)	0.6839 (2)	1.0379 (4)	0.0199 (9)
N5	0.1097 (5)	0.7049 (3)	1.0573 (4)	0.0285 (11)
N6	0.0471 (4)	0.6278 (2)	1.2015 (4)	0.0210 (10)
O1	0.0957 (3)	0.4135 (2)	0.5658 (3)	0.0265 (9)
O2	0.2190 (3)	0.4662 (2)	0.7126 (3)	0.0258 (9)
O3	0.7036 (3)	0.4664 (2)	0.6994 (3)	0.0263 (9)
O4	0.7944 (3)	0.4118 (2)	0.5511 (3)	0.0245 (9)
O5	0.3252 (4)	0.1997 (2)	0.3349 (4)	0.0410 (11)
O6	0.3664 (4)	0.3024 (2)	0.1958 (4)	0.0401 (11)
O7	0.5457 (4)	0.2277 (2)	0.2870 (4)	0.0391 (11)
O8	0.3948 (5)	0.5718 (3)	1.1028 (5)	0.0574 (14)
H8A	0.3892	0.5761	1.1773	0.028*
H8B	0.3861	0.6192	1.0761	0.028*
O9	0.6329 (5)	0.5931 (3)	0.9813 (5)	0.0526 (13)
H9A	0.6046	0.6261	0.9278	0.028*
H9B	0.6511	0.6216	1.0425	0.028*
O10	0.3976 (5)	0.5446 (3)	0.8539 (5)	0.0565 (14)
H10A	0.3721	0.5071	0.8081	0.028*
H10B	0.3284	0.5688	0.8745	0.028*
O11	0.3350 (5)	0.6924 (3)	0.9006 (4)	0.0494 (12)
H11A	0.3859	0.7322	0.8968	0.028*
H11B	0.2577	0.7116	0.9057	0.028*
O12	0.133 (2)	0.5302 (11)	0.9610 (18)	0.138 (6)	0.50
S1	0.41635 (13)	0.25941 (8)	0.29848 (12)	0.0236 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0120 (3)	0.0235 (3)	0.0165 (4)	−0.0001 (2)	0.0004 (2)	−0.0058 (2)
Zn2	0.0253 (5)	0.0277 (5)	0.0200 (5)	−0.0025 (4)	0.0037 (4)	−0.0067 (4)
C1	0.021 (3)	0.020 (3)	0.026 (3)	−0.003 (2)	0.005 (2)	−0.003 (2)
C2	0.034 (3)	0.031 (3)	0.024 (3)	−0.010 (3)	0.012 (3)	0.000 (3)
C3	0.031 (3)	0.020 (3)	0.016 (3)	0.003 (2)	0.002 (2)	−0.004 (2)
C4	0.020 (3)	0.025 (3)	0.023 (3)	0.000 (2)	0.000 (2)	−0.003 (2)
C5	0.019 (3)	0.031 (3)	0.029 (3)	−0.005 (2)	0.002 (2)	−0.002 (3)
C6	0.013 (3)	0.018 (2)	0.018 (3)	0.002 (2)	0.002 (2)	0.004 (2)
C7	0.010 (3)	0.022 (3)	0.020 (3)	−0.004 (2)	−0.003 (2)	0.002 (2)
C8	0.018 (3)	0.016 (2)	0.016 (3)	−0.002 (2)	0.000 (2)	−0.001 (2)
C9	0.015 (3)	0.019 (2)	0.020 (3)	−0.002 (2)	0.004 (2)	−0.002 (2)
C10	0.012 (3)	0.021 (2)	0.013 (3)	0.000 (2)	−0.001 (2)	0.004 (2)
C11	0.016 (3)	0.019 (2)	0.014 (3)	0.000 (2)	−0.002 (2)	−0.002 (2)
C12	0.013 (3)	0.023 (3)	0.022 (3)	0.000 (2)	0.003 (2)	0.004 (2)
C13	0.015 (3)	0.022 (2)	0.015 (3)	−0.002 (2)	0.002 (2)	0.007 (2)
N1	0.018 (2)	0.023 (2)	0.019 (2)	0.0011 (18)	0.0012 (18)	−0.0030 (18)
N2	0.023 (2)	0.020 (2)	0.018 (2)	0.0012 (18)	0.0054 (19)	−0.0008 (18)
N3	0.044 (3)	0.027 (2)	0.023 (3)	−0.014 (2)	0.012 (2)	−0.004 (2)
N4	0.018 (2)	0.022 (2)	0.020 (2)	0.0000 (18)	0.0022 (18)	−0.0052 (19)
N5	0.025 (3)	0.030 (2)	0.031 (3)	−0.004 (2)	0.004 (2)	−0.001 (2)
N6	0.019 (2)	0.024 (2)	0.020 (2)	0.0025 (19)	0.0004 (18)	−0.0021 (19)
O1	0.0118 (19)	0.042 (2)	0.025 (2)	0.0029 (16)	0.0014 (16)	−0.0110 (18)
O2	0.017 (2)	0.037 (2)	0.024 (2)	0.0014 (17)	0.0025 (16)	−0.0123 (18)
O3	0.016 (2)	0.043 (2)	0.020 (2)	−0.0070 (17)	0.0008 (15)	−0.0093 (18)
O4	0.0080 (18)	0.041 (2)	0.025 (2)	0.0024 (16)	0.0027 (15)	−0.0077 (17)
O5	0.041 (3)	0.032 (2)	0.051 (3)	−0.019 (2)	0.009 (2)	−0.009 (2)
O6	0.044 (3)	0.052 (3)	0.023 (2)	−0.001 (2)	−0.0047 (19)	−0.008 (2)
O7	0.026 (2)	0.050 (2)	0.042 (3)	0.0041 (19)	0.0052 (19)	−0.022 (2)
O8	0.063 (2)	0.0562 (19)	0.054 (2)	0.0053 (17)	0.0110 (17)	−0.0018 (16)
O9	0.052 (2)	0.0526 (19)	0.053 (2)	−0.0027 (16)	−0.0012 (16)	−0.0009 (16)
O10	0.059 (2)	0.0541 (19)	0.055 (2)	0.0054 (16)	−0.0057 (17)	−0.0066 (16)
O11	0.0467 (19)	0.0461 (17)	0.057 (2)	−0.0014 (16)	0.0128 (16)	−0.0003 (16)
O12	0.138 (6)	0.138 (6)	0.138 (6)	0.000 (2)	0.009 (2)	0.000 (2)
S1	0.0189 (7)	0.0269 (7)	0.0250 (8)	−0.0024 (6)	0.0008 (6)	−0.0094 (6)

Geometric parameters (Å, º) top

Zn1—O1	1.967 (4)	C6—C11	1.402 (7)
Zn1—O4ⁱ	1.994 (4)	C6—C12	1.500 (7)
Zn1—N1	2.020 (4)	C7—C8	1.384 (7)
Zn1—N6ⁱⁱ	2.059 (4)	C7—H7	0.9300
Zn1—O3ⁱ	2.611 (4)	C8—C9	1.378 (7)
Zn2—O8ⁱⁱⁱ	2.053 (5)	C8—S1	1.778 (5)
Zn2—O8	2.053 (5)	C9—C10	1.388 (7)
Zn2—O10ⁱⁱⁱ	2.063 (5)	C9—H9	0.9300
Zn2—O10	2.063 (5)	C10—C11	1.367 (7)
Zn2—O9	2.109 (5)	C10—C13	1.510 (7)
Zn2—O9ⁱⁱⁱ	2.109 (5)	C11—H11	0.9300
C1—N1	1.315 (7)	C12—O2	1.244 (6)
C1—N2	1.331 (6)	C12—O1	1.296 (6)
C1—H1	0.9300	C13—O3	1.248 (6)
C2—N3	1.304 (7)	C13—O4	1.274 (6)
C2—N1	1.363 (7)	N2—N3	1.348 (6)
C2—H2	0.9300	N4—N5	1.355 (6)
C3—N4	1.451 (7)	O5—S1	1.459 (4)
C3—N2	1.457 (6)	O6—S1	1.452 (4)
C3—H3A	0.9700	O7—S1	1.446 (4)
C3—H3B	0.9700	O8—H8A	0.8647
C4—N6	1.319 (7)	O8—H8B	0.8647
C4—N4	1.329 (7)	O9—H9A	0.8672
C4—H4	0.9300	O9—H9B	0.8636
C5—N5	1.299 (7)	O10—H10A	0.8566
C5—N6	1.367 (7)	O10—H10B	0.8672
C5—H5	0.9300	O11—H11A	0.8576
C6—C7	1.398 (7)	O11—H11B	0.8636

O1—Zn1—O4ⁱ	102.35 (15)	C8—C9—H9	120.2
O1—Zn1—N1	114.53 (17)	C10—C9—H9	120.2
O4ⁱ—Zn1—N1	120.59 (16)	C11—C10—C9	120.0 (5)
O1—Zn1—N6ⁱⁱ	105.67 (16)	C11—C10—C13	119.8 (4)
O4ⁱ—Zn1—N6ⁱⁱ	106.46 (16)	C9—C10—C13	120.1 (4)
N1—Zn1—N6ⁱⁱ	106.17 (17)	C10—C11—C6	121.1 (5)
O1—Zn1—O3ⁱ	157.39 (13)	C10—C11—H11	119.5
O4ⁱ—Zn1—O3ⁱ	55.08 (13)	C6—C11—H11	119.5
N1—Zn1—O3ⁱ	80.70 (15)	O2—C12—O1	122.5 (5)
N6ⁱⁱ—Zn1—O3ⁱ	84.39 (15)	O2—C12—C6	120.6 (5)
O8ⁱⁱⁱ—Zn2—O10ⁱⁱⁱ	89.4 (2)	O1—C12—C6	116.9 (5)
O8—Zn2—O10ⁱⁱⁱ	90.6 (2)	O3—C13—O4	121.4 (5)
O8ⁱⁱⁱ—Zn2—O9	91.1 (2)	O3—C13—C10	120.1 (5)
O8—Zn2—O9	88.9 (2)	O4—C13—C10	118.5 (4)
O10ⁱⁱⁱ—Zn2—O9	93.5 (2)	C1—N1—C2	102.7 (4)
O10—Zn2—O9	86.5 (2)	C1—N1—Zn1	126.3 (4)
O8ⁱⁱⁱ—Zn2—O9ⁱⁱⁱ	88.9 (2)	C2—N1—Zn1	130.3 (4)
O8—Zn2—O9ⁱⁱⁱ	91.1 (2)	C1—N2—N3	109.7 (4)
O10ⁱⁱⁱ—Zn2—O9ⁱⁱⁱ	86.5 (2)	C1—N2—C3	129.3 (5)
O10—Zn2—O9ⁱⁱⁱ	93.5 (2)	N3—N2—C3	120.9 (4)
N1—C1—N2	110.2 (5)	C2—N3—N2	103.0 (4)
N1—C1—H1	124.9	C4—N4—N5	109.7 (4)
N2—C1—H1	124.9	C4—N4—C3	129.2 (5)
N3—C2—N1	114.3 (5)	N5—N4—C3	121.0 (4)
N3—C2—H2	122.9	C5—N5—N4	103.2 (4)
N1—C2—H2	122.9	C4—N6—C5	102.8 (5)
N4—C3—N2	110.3 (4)	C4—N6—Zn1ⁱⁱ	126.6 (4)
N4—C3—H3A	109.6	C5—N6—Zn1ⁱⁱ	130.4 (4)
N2—C3—H3A	109.6	C12—O1—Zn1	113.1 (3)
N4—C3—H3B	109.6	C13—O3—Zn1^iv	77.6 (3)
N2—C3—H3B	109.6	C13—O4—Zn1^iv	105.7 (3)
H3A—C3—H3B	108.1	Zn2—O8—H8A	133.7
N6—C4—N4	110.1 (5)	Zn2—O8—H8B	113.3
N6—C4—H4	125.0	H8A—O8—H8B	105.1
N4—C4—H4	125.0	Zn2—O9—H9A	111.6
N5—C5—N6	114.2 (5)	Zn2—O9—H9B	116.4
N5—C5—H5	122.9	H9A—O9—H9B	104.9
N6—C5—H5	122.9	Zn2—O10—H10A	110.1
C7—C6—C11	118.7 (5)	Zn2—O10—H10B	109.5
C7—C6—C12	121.5 (4)	H10A—O10—H10B	107.3
C11—C6—C12	119.7 (4)	H11A—O11—H11B	105.8
C8—C7—C6	119.4 (4)	O7—S1—O6	113.0 (3)
C8—C7—H7	120.3	O7—S1—O5	112.1 (3)
C6—C7—H7	120.3	O6—S1—O5	112.6 (3)
C9—C8—C7	121.2 (5)	O7—S1—C8	106.7 (2)
C9—C8—S1	120.2 (4)	O6—S1—C8	106.3 (2)
C7—C8—S1	118.6 (4)	O5—S1—C8	105.6 (2)
C8—C9—C10	119.6 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O3ⁱⁱⁱ	0.86	1.90	2.628 (7)	141
O8—H8B···O11	0.86	2.40	3.126 (7)	143
O8—H8B···O7^v	0.86	2.49	2.983 (7)	117
O9—H9A···O6^vi	0.86	1.91	2.700 (7)	151
O9—H9B···O5^v	0.86	1.94	2.794 (7)	170
O10—H10A···O2	0.86	1.98	2.716 (7)	143
O10—H10B···O11	0.86	2.12	2.656 (7)	119
O10—H10B···O12	0.86	2.39	3.068 (7)	135
O11—H11A···O7^vi	0.86	2.37	2.887 (7)	119
O11—H11B···N5	0.86	2.39	3.029 (7)	131

Symmetry codes: (iii) −x+1, −y+1, −z+2; (v) −x+1, y+1/2, −z+3/2; (vi) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Zn(H₂O)₆]_0.5[Zn(C₈H₃O₇S)(C₅H₆N₆)]·1.5H₂O
M_r	571.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.2611 (3), 16.9967 (4), 11.4808 (3)
β (°)	93.812 (2)
V (Å³)	1997.88 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.00
Crystal size (mm)	0.23 × 0.15 × 0.14

Data collection
Diffractometer	Bruker SuperNova Eos diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.657, 0.767
No. of measured, independent and observed [I > 2σ(I)] reflections	7740, 3524, 2763
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.155, 1.11
No. of reflections	3524
No. of parameters	304
No. of restraints	30
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.67, −0.90

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O3ⁱ	0.86	1.90	2.628 (7)	141
O8—H8B···O11	0.86	2.40	3.126 (7)	143
O8—H8B···O7ⁱⁱ	0.86	2.49	2.983 (7)	117
O9—H9A···O6ⁱⁱⁱ	0.86	1.91	2.700 (7)	151
O9—H9B···O5ⁱⁱ	0.86	1.94	2.794 (7)	170
O10—H10A···O2	0.86	1.98	2.716 (7)	143
O10—H10B···O11	0.86	2.12	2.656 (7)	119
O10—H10B···O12	0.86	2.39	3.068 (7)	135
O11—H11A···O7ⁱⁱⁱ	0.86	2.368	2.887 (7)	119
O11—H11B···N5	0.86	2.388	3.029 (7)	131

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, −y+1, −z+1.

Acknowledgements

LT acknowledges financial support from the Doctor's Foundation of Tianjin Normal University (No. 5RL029)

References

Biradha, K., Sarkar, M. & Rajput, L. (2006). Chem. Commun. pp. 4169–4179. Web of Science CrossRef Google Scholar
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Ishikava, N., Sugita, M., Ishikawa, T., Koshihara, S. Y. & Kaizu, Y. (2003). J. Am. Chem. Soc. 125, 8694–8695. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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