Bis(2-amino­benzothia­zol-3-ium) bis­(7-oxabicyclo­[2.2.1]heptane-2,3-dicarboxyl­ato-κ3O2,O3,O7)zincate hexa­hydrate

Zhang, F.; Lv, T.-X.; Feng, J.; Lin, Q.-Y.

doi:10.1107/S1600536812017886

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m684

doi:10.1107/S1600536812017886

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Bis(2-aminobenzothiazol-3-ium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato-κ³O²,O³,O⁷)zincate hexahydrate

Fan Zhang,^a,^b Tian-Xi Lv,^b Jie Feng ^b and Qiu-Yue Lin ^a,^b ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China, and ^bCollege of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, Zhejiang, People's Republic of China
^*Correspondence e-mail: sky51@zjnu.cn

(Received 19 April 2012; accepted 21 April 2012; online 28 April 2012)

In the title hydrated molecular salt, (C₇H₇N₂S)₂[Zn(C₈H₈O₅)₂]·6H₂O, which is isotypic with its Mn^II, Co^II and Ni^II analogues, the Zn²⁺ ion lies on a crystallographic inversion centre and a distorted ZnO₆ octahedral coordination geometry arises from the two doubly deprotonated O,O′,O′′-tridentate ligands. In the crystal, the components are linked by N—H⋯O_a, N—H⋯O_w, O_w—H⋯O_a and O_w—H⋯O_w hydrogen bonds (w = water and a = anion).

Related literature

For background to the applications of norcantharidin (systematic name: 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride), see: Zeng & Lu (2006 ). For the isotypic Mn^II, Co^II and Ni^II structures, see: Wang et al. (2010a ,b , 2012 ).

Experimental

Crystal data

(C₇H₇N₂S)₂[Zn(C₈H₈O₅)₂]·6H₂O
M_r = 844.21
Triclinic, $[P \overline 1]$
a = 6.6983 (7) Å
b = 10.1497 (11) Å
c = 13.2082 (14) Å
α = 90.172 (7)°
β = 91.097 (7)°
γ = 99.251 (7)°
V = 886.11 (16) Å³
Z = 1
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 296 K
0.12 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.914, T_max = 0.951
11657 measured reflections
3108 independent reflections
1839 reflections with I > 2σ(I)
R_int = 0.228

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.087
S = 0.91
3108 reflections
241 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	2.014 (2)
Zn1—O3	2.132 (2)
Zn1—O5	2.176 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.86	1.82	2.675 (4)	173
N2—H2A⋯O3ⁱ	0.86	2.00	2.853 (4)	172
N2—H2B⋯O2Wⁱⁱ	0.86	2.02	2.838 (4)	158
O1W—H1WA⋯O4	0.85	2.01	2.818 (3)	160
O1W—H1WB⋯O2W	0.85	1.95	2.793 (4)	170
O2W—H2WA⋯O2	0.85	1.85	2.683 (3)	167
O2W—H2WB⋯O3W	0.85	1.92	2.765 (3)	170
O3W—H3WA⋯O1Wⁱⁱ	0.85	2.21	3.024 (3)	160
O3W—H3WB⋯O1Wⁱⁱⁱ	0.85	2.00	2.793 (4)	156
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x-1, y, z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812017886/hb6746sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017886/hb6746Isup2.hkl

checkCIF report

Comment top

7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride (norcantharidin), as a traditional Chinese drug, has great anti-cancer activity. (Zeng et al., 2006). A isostructural manganese complex (Wang et al., 2010a) and a cobalt complex (Wang et al., 2010b) has been reported. The molecular structure of the title complex is shown in Fig.1. The zinc atom is six-coordinated in a distorted octahedral coordination mode, binding to two bridging O atoms of the bicycloheptane unit and four carboxylate O atoms of two symmetry-related and fully deprotonated ligands. 2-aminobenzothiazole don't involved the coordination, and N atom of thiazole ring is protonated.The crystal structure is stabilized by N—H···O hydrogen-bonding interactions between the cations and anions and O—H···O hydrogen bonds including the crystal water molecules.

Related literature top

For background to the applications of norcantharidin (systematic name: 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride), see: Zeng & Lu (2006). For the isotyic Mn^II, Co^II and Ni^II structures, see: Wang et al. (2010a,b, 2012).

Experimental top

A mixture of 0.5 mmol norcantharidin, 0.5 mmol zinc acetate, 0.5 mmol 2-aminobenzothiazole and 15 mL distilled water was sealed in a 25 mL Teflon-lined stainless vessel and heated at 443 K for 3 d, then cooled slowly to room temperature. The solution was filtered and colourless blocks were recovered.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of (I) showing displacement ellipsoids drawn at the 30% probability level. Atoms with label suffix A are generatd by (1–x, –y, –z).

Bis(2-aminobenzothiazol-3-ium) bis(7-oxabicyclo[2.2.1]heptane-2,3- dicarboxylato-κ³O²,O³,O⁷)zincate hexahydrate top

Crystal data top

(C₇H₇N₂S)₂[Zn(C₈H₈O₅)₂]·6H₂O	Z = 1
M_r = 844.21	F(000) = 440
Triclinic, P1	D_x = 1.582 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6983 (7) Å	Cell parameters from 2505 reflections
b = 10.1497 (11) Å	θ = 1.5–25.0°
c = 13.2082 (14) Å	µ = 0.89 mm⁻¹
α = 90.172 (7)°	T = 296 K
β = 91.097 (7)°	Block, colorless
γ = 99.251 (7)°	0.12 × 0.08 × 0.06 mm
V = 886.11 (16) Å³

Data collection top

Bruker APEXII CCD diffractometer	3108 independent reflections
Radiation source: fine-focus sealed tube	1839 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.228
ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.914, T_max = 0.951	k = −12→12
11657 measured reflections	l = −15→14

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 0.91	w = 1/[σ²(F_o²) + (0.0123P)²] where P = (F_o² + 2F_c²)/3
3108 reflections	(Δ/σ)_max < 0.001
241 parameters	Δρ_max = 0.48 e Å⁻³
9 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

(C₇H₇N₂S)₂[Zn(C₈H₈O₅)₂]·6H₂O	γ = 99.251 (7)°
M_r = 844.21	V = 886.11 (16) Å³
Triclinic, P1	Z = 1
a = 6.6983 (7) Å	Mo Kα radiation
b = 10.1497 (11) Å	µ = 0.89 mm⁻¹
c = 13.2082 (14) Å	T = 296 K
α = 90.172 (7)°	0.12 × 0.08 × 0.06 mm
β = 91.097 (7)°

Data collection top

Bruker APEXII CCD diffractometer	3108 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1839 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.951	R_int = 0.228
11657 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	9 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 0.91	Δρ_max = 0.48 e Å⁻³
3108 reflections	Δρ_min = −0.74 e Å⁻³
241 parameters

Special details top

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	0.5000	0.0000	0.0000	0.0324 (2)
S1	0.32760 (16)	0.26730 (12)	0.52749 (7)	0.0407 (3)
O1	0.3674 (4)	0.1456 (3)	0.06056 (17)	0.0375 (8)
O1W	0.8090 (4)	0.3956 (3)	0.37387 (17)	0.0545 (9)
H1WA	0.8277	0.3325	0.3345	0.082*
H1WB	0.7307	0.4430	0.3454	0.082*
H2WA	0.4603	0.4745	0.2298	0.082*
H2WB	0.4268	0.5366	0.3202	0.082*
H3WA	0.1928	0.5407	0.4659	0.082*
H3WB	0.0922	0.4941	0.3767	0.082*
O2	0.3636 (4)	0.3401 (3)	0.13832 (18)	0.0398 (8)
O2W	0.5164 (4)	0.5222 (3)	0.27869 (18)	0.0509 (9)
O3	0.6904 (4)	0.0121 (3)	0.13199 (17)	0.0372 (8)
O3W	0.1943 (4)	0.5453 (3)	0.40167 (19)	0.0681 (11)
O4	0.7729 (4)	0.1592 (3)	0.25795 (16)	0.0391 (8)
O5	0.7162 (3)	0.1550 (3)	−0.06915 (16)	0.0318 (8)
N1	0.2772 (4)	0.0314 (3)	0.6011 (2)	0.0314 (9)
H1A	0.2680	−0.0334	0.6434	0.038*
N2	0.3461 (4)	0.1984 (3)	0.7235 (2)	0.0407 (10)
H2A	0.3394	0.1405	0.7712	0.049*
H2B	0.3717	0.2822	0.7379	0.049*
C6	0.8584 (6)	0.3726 (4)	−0.1096 (2)	0.0353 (11)
H6A	0.8806	0.4636	−0.0841	0.042*
H6B	0.8494	0.3736	−0.1829	0.042*
C5	1.0257 (5)	0.2946 (4)	−0.0715 (3)	0.0360 (11)
H5A	1.0917	0.2585	−0.1276	0.043*
H5B	1.1265	0.3507	−0.0300	0.043*
C1	0.6712 (5)	0.2907 (4)	−0.0644 (2)	0.0318 (11)
H1B	0.5458	0.3011	−0.1008	0.038*
C4	0.9066 (5)	0.1842 (4)	−0.0096 (3)	0.0313 (11)
H4A	0.9750	0.1065	−0.0007	0.038*
C2	0.6616 (5)	0.3148 (4)	0.0498 (2)	0.0284 (10)
H2C	0.6979	0.4103	0.0652	0.034*
C3	0.8342 (5)	0.2369 (4)	0.0902 (2)	0.0281 (11)
H3A	0.9440	0.3005	0.1213	0.034*
C7	0.4500 (6)	0.2624 (4)	0.0880 (3)	0.0326 (11)
C8	0.7611 (5)	0.1281 (4)	0.1656 (3)	0.0299 (10)
C9	0.2753 (5)	0.1307 (4)	0.4436 (3)	0.0335 (11)
C10	0.2575 (5)	0.1337 (4)	0.3394 (3)	0.0407 (12)
H10A	0.2714	0.2138	0.3043	0.049*
C11	0.2178 (6)	0.0109 (5)	0.2894 (3)	0.0468 (14)
H11A	0.2094	0.0088	0.2190	0.056*
C12	0.1909 (6)	−0.1066 (5)	0.3418 (3)	0.0467 (14)
H12A	0.1586	−0.1865	0.3061	0.056*
C13	0.2104 (5)	−0.1101 (4)	0.4473 (3)	0.0386 (12)
H13A	0.1969	−0.1901	0.4826	0.046*
C14	0.2511 (5)	0.0122 (4)	0.4961 (3)	0.0293 (11)
C15	0.3173 (5)	0.1590 (4)	0.6289 (3)	0.0304 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0350 (4)	0.0305 (5)	0.0304 (4)	0.0014 (4)	−0.0001 (3)	−0.0092 (3)
S1	0.0497 (7)	0.0374 (9)	0.0338 (6)	0.0033 (6)	0.0004 (5)	−0.0002 (6)
O1	0.0345 (16)	0.038 (2)	0.0393 (16)	0.0037 (15)	0.0032 (12)	−0.0124 (15)
O1W	0.066 (2)	0.045 (2)	0.0543 (19)	0.0145 (18)	−0.0097 (15)	−0.0099 (17)
O2	0.0357 (16)	0.038 (2)	0.0468 (17)	0.0079 (15)	0.0043 (13)	−0.0186 (15)
O2W	0.056 (2)	0.041 (2)	0.0537 (18)	0.0038 (17)	−0.0062 (14)	−0.0156 (17)
O3	0.0510 (19)	0.027 (2)	0.0307 (15)	−0.0005 (16)	−0.0063 (13)	−0.0028 (14)
O3W	0.063 (2)	0.083 (3)	0.053 (2)	−0.002 (2)	0.0003 (16)	−0.014 (2)
O4	0.0530 (19)	0.037 (2)	0.0254 (15)	0.0015 (16)	−0.0020 (13)	−0.0036 (14)
O5	0.0363 (16)	0.032 (2)	0.0266 (14)	0.0046 (15)	0.0020 (12)	−0.0110 (14)
N1	0.0330 (19)	0.033 (3)	0.0284 (18)	0.0064 (18)	0.0029 (14)	0.0008 (17)
N2	0.055 (2)	0.036 (3)	0.0313 (19)	0.007 (2)	0.0034 (16)	−0.0062 (18)
C6	0.051 (3)	0.026 (3)	0.028 (2)	0.004 (2)	0.0034 (19)	−0.003 (2)
C5	0.039 (3)	0.035 (3)	0.032 (2)	0.000 (2)	0.0097 (18)	−0.002 (2)
C1	0.034 (2)	0.031 (3)	0.031 (2)	0.005 (2)	−0.0005 (18)	−0.003 (2)
C4	0.027 (2)	0.030 (3)	0.037 (2)	0.008 (2)	−0.0026 (18)	−0.005 (2)
C2	0.036 (2)	0.021 (3)	0.028 (2)	0.005 (2)	0.0018 (17)	−0.0092 (19)
C3	0.025 (2)	0.028 (3)	0.029 (2)	0.001 (2)	−0.0013 (17)	−0.011 (2)
C7	0.031 (2)	0.043 (3)	0.024 (2)	0.010 (2)	−0.0052 (17)	−0.007 (2)
C8	0.025 (2)	0.031 (3)	0.034 (2)	0.007 (2)	−0.0009 (18)	0.008 (2)
C9	0.024 (2)	0.043 (3)	0.032 (2)	0.001 (2)	0.0043 (18)	−0.004 (2)
C10	0.039 (3)	0.049 (4)	0.034 (2)	0.007 (2)	0.0040 (19)	0.007 (2)
C11	0.042 (3)	0.070 (4)	0.026 (2)	0.002 (3)	0.004 (2)	−0.008 (3)
C12	0.033 (3)	0.061 (4)	0.046 (3)	0.006 (3)	0.000 (2)	−0.024 (3)
C13	0.029 (2)	0.048 (3)	0.039 (2)	0.008 (2)	0.0051 (18)	−0.012 (2)
C14	0.023 (2)	0.042 (3)	0.023 (2)	0.005 (2)	0.0062 (16)	−0.002 (2)
C15	0.028 (2)	0.030 (3)	0.033 (2)	0.003 (2)	0.0066 (18)	−0.006 (2)

Geometric parameters (Å, º) top

Zn1—O1	2.014 (2)	C6—C1	1.521 (5)
Zn1—O1ⁱ	2.014 (2)	C6—C5	1.550 (5)
Zn1—O3ⁱ	2.132 (2)	C6—H6A	0.9700
Zn1—O3	2.132 (2)	C6—H6B	0.9700
Zn1—O5ⁱ	2.176 (3)	C5—C4	1.518 (5)
Zn1—O5	2.176 (3)	C5—H5A	0.9700
S1—C15	1.731 (4)	C5—H5B	0.9700
S1—C9	1.759 (4)	C1—C2	1.532 (4)
O1—C7	1.274 (4)	C1—H1B	0.9800
O1W—H1WA	0.8499	C4—C3	1.536 (4)
O1W—H1WB	0.8500	C4—H4A	0.9800
O2—C7	1.248 (3)	C2—C7	1.527 (5)
O2W—H2WA	0.8499	C2—C3	1.587 (5)
O2W—H2WB	0.8501	C2—H2C	0.9800
O3—C8	1.272 (4)	C3—C8	1.517 (5)
O3W—H3WA	0.8504	C3—H3A	0.9800
O3W—H3WB	0.8502	C9—C14	1.379 (5)
O4—C8	1.257 (3)	C9—C10	1.379 (4)
O5—C1	1.458 (4)	C10—C11	1.393 (5)
O5—C4	1.473 (4)	C10—H10A	0.9300
N1—C15	1.329 (4)	C11—C12	1.370 (5)
N1—C14	1.403 (4)	C11—H11A	0.9300
N1—H1A	0.8600	C12—C13	1.398 (5)
N2—C15	1.312 (4)	C12—H12A	0.9300
N2—H2A	0.8600	C13—C14	1.382 (5)
N2—H2B	0.8600	C13—H13A	0.9300

O1—Zn1—O1ⁱ	180.0	C2—C1—H1B	113.1
O1—Zn1—O3ⁱ	92.14 (9)	O5—C4—C5	101.4 (3)
O1ⁱ—Zn1—O3ⁱ	87.86 (9)	O5—C4—C3	101.8 (3)
O1—Zn1—O3	87.86 (9)	C5—C4—C3	112.1 (3)
O1ⁱ—Zn1—O3	92.14 (9)	O5—C4—H4A	113.4
O3ⁱ—Zn1—O3	180.0	C5—C4—H4A	113.4
O1—Zn1—O5ⁱ	91.98 (9)	C3—C4—H4A	113.4
O1ⁱ—Zn1—O5ⁱ	88.02 (9)	C7—C2—C1	110.4 (3)
O3ⁱ—Zn1—O5ⁱ	89.22 (10)	C7—C2—C3	115.0 (3)
O3—Zn1—O5ⁱ	90.78 (10)	C1—C2—C3	100.7 (2)
O1—Zn1—O5	88.02 (9)	C7—C2—H2C	110.1
O1ⁱ—Zn1—O5	91.98 (9)	C1—C2—H2C	110.1
O3ⁱ—Zn1—O5	90.78 (10)	C3—C2—H2C	110.1
O3—Zn1—O5	89.22 (10)	C8—C3—C4	113.7 (3)
O5ⁱ—Zn1—O5	180.0	C8—C3—C2	113.7 (3)
C15—S1—C9	90.10 (19)	C4—C3—C2	101.0 (3)
C7—O1—Zn1	128.1 (2)	C8—C3—H3A	109.4
H1WA—O1W—H1WB	110.0	C4—C3—H3A	109.4
H2WA—O2W—H2WB	109.4	C2—C3—H3A	109.4
C8—O3—Zn1	117.2 (3)	O2—C7—O1	124.0 (4)
H3WA—O3W—H3WB	109.6	O2—C7—C2	117.8 (4)
C1—O5—C4	95.2 (3)	O1—C7—C2	118.0 (3)
C1—O5—Zn1	116.69 (19)	O4—C8—O3	124.0 (4)
C4—O5—Zn1	112.0 (2)	O4—C8—C3	117.5 (3)
C15—N1—C14	113.7 (3)	O3—C8—C3	118.5 (3)
C15—N1—H1A	123.1	C14—C9—C10	121.7 (4)
C14—N1—H1A	123.1	C14—C9—S1	110.6 (3)
C15—N2—H2A	120.0	C10—C9—S1	127.7 (4)
C15—N2—H2B	120.0	C9—C10—C11	116.9 (4)
H2A—N2—H2B	120.0	C9—C10—H10A	121.6
C1—C6—C5	101.2 (3)	C11—C10—H10A	121.6
C1—C6—H6A	111.5	C12—C11—C10	121.3 (4)
C5—C6—H6A	111.5	C12—C11—H11A	119.4
C1—C6—H6B	111.5	C10—C11—H11A	119.4
C5—C6—H6B	111.5	C11—C12—C13	122.0 (4)
H6A—C6—H6B	109.4	C11—C12—H12A	119.0
C4—C5—C6	102.2 (3)	C13—C12—H12A	119.0
C4—C5—H5A	111.3	C14—C13—C12	116.1 (4)
C6—C5—H5A	111.3	C14—C13—H13A	121.9
C4—C5—H5B	111.3	C12—C13—H13A	121.9
C6—C5—H5B	111.3	C9—C14—C13	121.9 (4)
H5A—C5—H5B	109.2	C9—C14—N1	112.6 (3)
O5—C1—C6	102.7 (3)	C13—C14—N1	125.4 (4)
O5—C1—C2	102.4 (3)	N2—C15—N1	123.4 (4)
C6—C1—C2	111.6 (3)	N2—C15—S1	123.7 (3)
O5—C1—H1B	113.1	N1—C15—S1	113.0 (3)
C6—C1—H1B	113.1

O3ⁱ—Zn1—O1—C7	−122.1 (3)	C5—C4—C3—C2	72.1 (4)
O3—Zn1—O1—C7	57.9 (3)	C7—C2—C3—C8	−3.6 (4)
O5ⁱ—Zn1—O1—C7	148.6 (3)	C1—C2—C3—C8	−122.3 (3)
O5—Zn1—O1—C7	−31.4 (3)	C7—C2—C3—C4	118.6 (3)
O1—Zn1—O3—C8	−42.4 (3)	C1—C2—C3—C4	−0.1 (3)
O1ⁱ—Zn1—O3—C8	137.6 (3)	Zn1—O1—C7—O2	−169.1 (3)
O5ⁱ—Zn1—O3—C8	−134.3 (2)	Zn1—O1—C7—C2	16.1 (5)
O5—Zn1—O3—C8	45.7 (2)	C1—C2—C7—O2	−127.5 (4)
O1—Zn1—O5—C1	−10.4 (2)	C3—C2—C7—O2	119.3 (4)
O1ⁱ—Zn1—O5—C1	169.6 (2)	C1—C2—C7—O1	47.6 (5)
O3ⁱ—Zn1—O5—C1	81.7 (2)	C3—C2—C7—O1	−65.6 (4)
O3—Zn1—O5—C1	−98.3 (2)	Zn1—O3—C8—O4	138.6 (3)
O1—Zn1—O5—C4	97.84 (19)	Zn1—O3—C8—C3	−40.8 (4)
O1ⁱ—Zn1—O5—C4	−82.16 (19)	C4—C3—C8—O4	153.4 (3)
O3ⁱ—Zn1—O5—C4	−170.05 (19)	C2—C3—C8—O4	−91.7 (4)
O3—Zn1—O5—C4	9.95 (19)	C4—C3—C8—O3	−27.2 (5)
C1—C6—C5—C4	−1.3 (3)	C2—C3—C8—O3	87.7 (4)
C4—O5—C1—C6	57.0 (3)	C15—S1—C9—C14	0.6 (3)
Zn1—O5—C1—C6	174.86 (19)	C15—S1—C9—C10	−179.7 (3)
C4—O5—C1—C2	−58.8 (3)	C14—C9—C10—C11	−1.2 (5)
Zn1—O5—C1—C2	59.0 (3)	S1—C9—C10—C11	179.2 (3)
C5—C6—C1—O5	−34.6 (3)	C9—C10—C11—C12	2.2 (6)
C5—C6—C1—C2	74.5 (3)	C10—C11—C12—C13	−2.9 (6)
C1—O5—C4—C5	−57.3 (3)	C11—C12—C13—C14	2.3 (5)
Zn1—O5—C4—C5	−178.88 (18)	C10—C9—C14—C13	0.9 (6)
C1—O5—C4—C3	58.4 (3)	S1—C9—C14—C13	−179.4 (3)
Zn1—O5—C4—C3	−63.2 (3)	C10—C9—C14—N1	179.5 (3)
C6—C5—C4—O5	36.1 (3)	S1—C9—C14—N1	−0.9 (4)
C6—C5—C4—C3	−71.8 (3)	C12—C13—C14—C9	−1.4 (5)
O5—C1—C2—C7	−85.8 (3)	C12—C13—C14—N1	−179.7 (3)
C6—C1—C2—C7	165.0 (3)	C15—N1—C14—C9	0.8 (4)
O5—C1—C2—C3	36.2 (3)	C15—N1—C14—C13	179.3 (3)
C6—C1—C2—C3	−73.0 (4)	C14—N1—C15—N2	179.8 (3)
O5—C4—C3—C8	86.7 (4)	C14—N1—C15—S1	−0.3 (4)
C5—C4—C3—C8	−165.7 (3)	C9—S1—C15—N2	179.8 (3)
O5—C4—C3—C2	−35.5 (4)	C9—S1—C15—N1	−0.2 (3)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱⁱ	0.86	1.82	2.675 (4)	173
N2—H2A···O3ⁱⁱ	0.86	2.00	2.853 (4)	172
N2—H2B···O2Wⁱⁱⁱ	0.86	2.02	2.838 (4)	158
O1W—H1WA···O4	0.85	2.01	2.818 (3)	160
O1W—H1WB···O2W	0.85	1.95	2.793 (4)	170
O2W—H2WA···O2	0.85	1.85	2.683 (3)	167
O2W—H2WB···O3W	0.85	1.92	2.765 (3)	170
O3W—H3WA···O1Wⁱⁱⁱ	0.85	2.21	3.024 (3)	160
O3W—H3WB···O1W^iv	0.85	2.00	2.793 (4)	156

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

Experimental details

Crystal data
Chemical formula	(C₇H₇N₂S)₂[Zn(C₈H₈O₅)₂]·6H₂O
M_r	844.21
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.6983 (7), 10.1497 (11), 13.2082 (14)
α, β, γ (°)	90.172 (7), 91.097 (7), 99.251 (7)
V (Å³)	886.11 (16)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.12 × 0.08 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.914, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	11657, 3108, 1839
R_int	0.228
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.087, 0.91
No. of reflections	3108
No. of parameters	241
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.74

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—O1	2.014 (2)	Zn1—O5	2.176 (3)
Zn1—O3	2.132 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.86	1.82	2.675 (4)	173
N2—H2A···O3ⁱ	0.86	2.00	2.853 (4)	172
N2—H2B···O2Wⁱⁱ	0.86	2.02	2.838 (4)	158
O1W—H1WA···O4	0.85	2.01	2.818 (3)	160
O1W—H1WB···O2W	0.85	1.95	2.793 (4)	170
O2W—H2WA···O2	0.85	1.85	2.683 (3)	167
O2W—H2WB···O3W	0.85	1.92	2.765 (3)	170
O3W—H3WA···O1Wⁱⁱ	0.85	2.21	3.024 (3)	160
O3W—H3WB···O1Wⁱⁱⁱ	0.85	2.00	2.793 (4)	156

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

Acknowledgements

The authors thank the Natural Science Foundation of Zhejiang Province, China (grant No. Y407301) for financial support.

References

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