Bis(1,10-phenanthroline-κ2N,N′)(sulfato-κO)zinc(II) propane-1,2-diol monosolvate

Zhong, K.-L.

doi:10.1107/S160053681302610X

metal-organic compounds

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Volume 69| Part 10| October 2013| Page m561

doi:10.1107/S160053681302610X

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Bis(1,10-phenanthroline-κ²N,N′)(sulfato-κO)zinc(II) propane-1,2-diol monosolvate

Kai-Long Zhong ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing, 210048, People's Republic of China
^*Correspondence e-mail: zklong76@163.com

(Received 6 September 2013; accepted 21 September 2013; online 28 September 2013)

In the title compound, [Zn(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂, the Zn^II ion is in a distorted square-pyramidal coordination environment composed of four N atoms from two chelating 1,10-phenanthroline ligands and one O atom from a monodentate sulfate ligand. The Zn^II ion lies on a twofold rotation axis. The sulfate ligand and propane-1,2-diol molecules are disordered across the twofold rotation axis. The dihedral angle between the two chelating N₂C₂ groups is 83.26 (13)°. In the crystal, the complex molecule and the propane-1,2-diol molecule are connected through a pair of O—H⋯O hydrogen bonds.

CCDC reference: 962558

Related literature

For the ethane-1,2-diol solvate of the title complex, see: Zhu et al. (2006 ) and for the propane-1,3-diol solvate of the title complex, see: Cui et al. (2010 ). For related structures and background references, see: Batten & Robson (1998 ); Zhang et al. (2010 ); Zhong (2010 ); Zhong et al. (2011 ).

Experimental

Crystal data

[Zn(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂
M_r = 597.93
Monoclinic, C 2/c
a = 17.3913 (10) Å
b = 12.9247 (7) Å
c = 13.2214 (7) Å
β = 123.248 (5)°
V = 2485.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 223 K
0.35 × 0.20 × 0.15 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.968, T_max = 1.000
5735 measured reflections
2191 independent reflections
1878 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.102
S = 1.06
2191 reflections
186 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O3	0.83	2.00	2.74 (3)	149
O6—H6⋯O4	0.83	2.11	2.89 (2)	155

Data collection: CrystalClear (Rigaku, 2007 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 962558

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681302610X/lh5651sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681302610X/lh5651Isup2.hkl

checkCIF report

Comment top

The design and synthesis of metal-organic complexes or polymeric coordination networks is a rapidly developing field in coordination and supramolecular chemistry during the past decades (Batten & Robson, 1998; Zhang et al., 2010; Zhong et al., 2011). In our inverstigation, we have focused on the synthesis of complexes with N containing bidentate ligands, such as 1,10-phenanthroline (phen), 4,4'-bipyridine and 2,2'-bipyridine as auxiliary ligands, meanwhile retaining some of the solvent molcecules capable of hydrogen bonding to form higher dimensional supramolecular network. In the past few years, we have synthesized and reported Zn-complexes with bidentate-chelating sulfate ions, in which uncoordinated O atoms of the sulfate ligand and dihydric alcohol solvent molecules formed classical O—H···O hydrogen bonds vis a solvothermal reaction, e.g. [ZnSO₄(phen)₂]·C₂H₆O₂, (II), (C₂H₆O₂ is ethane-1,2-diol; Zhu et al., 2006). [ZnSO₄(phen)₂]·C₃H₈O₂, (III), (C₃H₈O₂ is propane-1,3-diol; Cui et al., 2010) and [ZnSO₄(2,2'-bipy)₂]·C₂H₆O₂ (Cui et al., 2010). The crystal structure of the title complex is reported herein.

The title compound consists of a neutral monomeric [ZnSO₄(C₁₀H₈N₂)₂] complex and a propane-1,2-diol solvent molecule. The Zn^II ion has fivefold coordination by four N atoms from two phen ligands and one O atom from an monodentate sulfate ion, in a distorted ZnN₄O square-pyramidal environment. This is different from that observed in previously reported zinc complexes (II) and (III). The Zn—N bond distances, the Zn—O bond distance, the N—Zn—N bite angle and the dihedral angle between the two chelating NCCN groups are 2.123 (3)–2.142 (2) Å, 1.959 (4) Å, 78.32 (9)° and 83.26 (13)°, respectively. The Zn^II ion is located on a twofold rotation axis (symmetry code: -x, y, - z + 1/2)(Fig.1). The sulfate ligand and propane-1,2-diol molecules are disordered across the twofold rotation axis. Depending on the symmetry unique component of disorder, either N2 or N2 (-x, y, -z+1/2) forms the apical atom of the disordered square-pyramidal coordination geometry. The [ZnSO₄(C₁₀H₈N₂)₂] and C₃H₈O₃ units are connected by a pair of intermolecular O—H···O hydrogen bonds involving the uncoordinated O atoms of the sulfate ligand.

Related literature top

For the ethane-1,2-diol solvate of the title complex, see: Zhu et al. (2006) and for the propane-1,3-diol solvate of the title complex, see: Cui et al. (2010). For related structures and background references, see: Batten & Robson (1998); Zhang et al. (2010); Zhong (2010); Zhong et al. (2011).

Experimental top

0.2 mmol phen, 0.1 mmol melamine, 0.1 mmol ZnSO₄·7H₂O, 2.0 ml propane-1,2-diol and 1.0 ml water were mixed and placed in a thick Pyrex tube, which was sealed and heated to 453 K for 72 h, whereupon colorless block-shaped crystals of (I) were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Figure 1. The molecular structure showing displacement ellipsoids drawn at the 30% probability level. The light broken lines depict O—H···O hydrogen bonds. The propane-1,2-diol molecule and the sulfate ligand are disordered over two symmetry-related positions but the disorder is not shown. Unlabeled atoms are related to the labeled atoms by the symmetry operator (-x, y, -z + 1/2).

Bis(1,10-phenanthroline-κ²N,N')(sulfato-κO)zinc(II) propane-1,2-diol monosolvate top

Crystal data top

[Zn(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂	F(000) = 1232
M_r = 597.93	D_x = 1.598 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2296 reflections
a = 17.3913 (10) Å	θ = 3.5–28.8°
b = 12.9247 (7) Å	µ = 1.13 mm⁻¹
c = 13.2214 (7) Å	T = 223 K
β = 123.248 (5)°	Block, colourless
V = 2485.4 (2) Å³	0.35 × 0.20 × 0.15 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	2191 independent reflections
Radiation source: fine-focus sealed tube	1878 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.035
Detector resolution: 28.5714 pixels mm^-1	θ_max = 25.0°, θ_min = 2.8°
ω scans	h = −20→20
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −15→14
T_min = 0.968, T_max = 1.000	l = −14→15
5735 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0486P)² + 2.9011P] where P = (F_o² + 2F_c²)/3
2191 reflections	(Δ/σ)_max < 0.001
186 parameters	Δρ_max = 0.73 e Å⁻³
4 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Zn(SO₄)(C₁₂H₈N₂)₂]·C₃H₈O₂	V = 2485.4 (2) Å³
M_r = 597.93	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.3913 (10) Å	µ = 1.13 mm⁻¹
b = 12.9247 (7) Å	T = 223 K
c = 13.2214 (7) Å	0.35 × 0.20 × 0.15 mm
β = 123.248 (5)°

Data collection top

Rigaku Mercury CCD diffractometer	2191 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	1878 reflections with I > 2σ(I)
T_min = 0.968, T_max = 1.000	R_int = 0.035
5735 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	4 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.06	Δρ_max = 0.73 e Å⁻³
2191 reflections	Δρ_min = −0.54 e Å⁻³
186 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	Occ. (<1)
Zn1	0.0000	0.30049 (4)	0.2500	0.02159 (19)
S1	0.0034 (2)	0.54103 (11)	0.2316 (3)	0.0167 (6)	0.50
O1	0.0136 (3)	0.4449 (3)	0.3022 (4)	0.0257 (5)	0.50
O2	−0.0007 (3)	0.5122 (3)	0.1220 (4)	0.0257 (5)	0.50
O3	0.0811 (6)	0.6077 (9)	0.3077 (9)	0.0257 (5)	0.50
O4	−0.0835 (7)	0.5935 (8)	0.1998 (10)	0.0257 (5)	0.50
O5	0.0562 (14)	0.7871 (13)	0.1824 (16)	0.046 (2)	0.50
H5	0.0423	0.7309	0.1988	0.069*	0.50
O6	−0.0460 (14)	0.7974 (14)	0.3059 (16)	0.046 (2)	0.50
H6	−0.0423	0.7429	0.2756	0.069*	0.50
N1	0.09382 (15)	0.27777 (19)	0.1947 (2)	0.0222 (6)
N2	0.10269 (16)	0.2072 (2)	0.3926 (2)	0.0228 (6)
C1	0.0913 (2)	0.3167 (2)	0.1003 (3)	0.0261 (7)
H1A	0.0459	0.3660	0.0520	0.031*
C2	0.1535 (2)	0.2875 (3)	0.0694 (3)	0.0284 (7)
H2A	0.1497	0.3170	0.0018	0.034*
C3	0.2194 (2)	0.2159 (3)	0.1382 (3)	0.0297 (8)
H3A	0.2607	0.1947	0.1173	0.036*
C4	0.2257 (2)	0.1735 (2)	0.2406 (3)	0.0248 (7)
C5	0.2950 (2)	0.1021 (3)	0.3207 (3)	0.0284 (7)
H5A	0.3380	0.0786	0.3038	0.034*
C6	0.3001 (2)	0.0674 (3)	0.4204 (3)	0.0293 (8)
H6A	0.3465	0.0202	0.4719	0.035*
C7	0.2354 (2)	0.1019 (2)	0.4489 (3)	0.0242 (7)
C8	0.2402 (2)	0.0709 (3)	0.5542 (3)	0.0303 (8)
H8A	0.2858	0.0244	0.6088	0.036*
C9	0.1776 (2)	0.1094 (3)	0.5760 (3)	0.0338 (8)
H9A	0.1805	0.0906	0.6466	0.041*
C10	0.1096 (2)	0.1765 (3)	0.4932 (3)	0.0297 (8)
H10A	0.0665	0.2014	0.5091	0.036*
C11	0.16579 (19)	0.1707 (2)	0.3712 (3)	0.0219 (7)
C12	0.16033 (19)	0.2076 (2)	0.2646 (3)	0.0209 (7)
C13	0.0615 (9)	0.8631 (8)	0.2607 (13)	0.082 (2)	0.50
H13A	0.0782	0.9287	0.2404	0.098*	0.50
H13B	0.1113	0.8448	0.3432	0.098*	0.50
C14	−0.0247 (9)	0.8802 (6)	0.2597 (14)	0.082 (2)	0.50
H14A	−0.0759	0.8875	0.1739	0.098*	0.50
C15	−0.0222 (8)	0.9778 (6)	0.3227 (11)	0.082 (2)	0.50
H15A	−0.0019	1.0347	0.2950	0.123*	0.50
H15B	0.0202	0.9693	0.4093	0.123*	0.50
H15C	−0.0832	0.9925	0.3046	0.123*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0229 (3)	0.0194 (3)	0.0300 (3)	0.000	0.0193 (2)	0.000
S1	0.0167 (8)	0.0184 (7)	0.0179 (19)	−0.0003 (7)	0.0114 (10)	0.0012 (7)
O1	0.0256 (9)	0.0259 (17)	0.0295 (12)	0.0019 (12)	0.0175 (9)	0.0001 (12)
O2	0.0256 (9)	0.0259 (17)	0.0295 (12)	0.0019 (12)	0.0175 (9)	0.0001 (12)
O3	0.0256 (9)	0.0259 (17)	0.0295 (12)	0.0019 (12)	0.0175 (9)	0.0001 (12)
O4	0.0256 (9)	0.0259 (17)	0.0295 (12)	0.0019 (12)	0.0175 (9)	0.0001 (12)
O5	0.077 (4)	0.033 (3)	0.070 (3)	−0.001 (3)	0.067 (3)	−0.004 (3)
O6	0.077 (4)	0.033 (3)	0.070 (3)	−0.001 (3)	0.067 (3)	−0.004 (3)
N1	0.0208 (12)	0.0242 (14)	0.0252 (14)	0.0010 (11)	0.0150 (11)	0.0031 (11)
N2	0.0233 (13)	0.0260 (15)	0.0242 (14)	−0.0001 (11)	0.0162 (11)	−0.0012 (11)
C1	0.0269 (16)	0.0261 (18)	0.0290 (18)	0.0022 (14)	0.0176 (14)	0.0056 (14)
C2	0.0328 (17)	0.034 (2)	0.0276 (18)	0.0024 (15)	0.0223 (15)	0.0040 (15)
C3	0.0285 (17)	0.036 (2)	0.0334 (19)	0.0027 (15)	0.0226 (15)	−0.0001 (15)
C4	0.0247 (15)	0.0268 (18)	0.0260 (17)	0.0018 (13)	0.0159 (14)	−0.0026 (14)
C5	0.0256 (15)	0.0322 (19)	0.0317 (19)	0.0062 (14)	0.0183 (14)	−0.0049 (15)
C6	0.0281 (16)	0.0296 (19)	0.0315 (19)	0.0078 (14)	0.0171 (15)	0.0004 (14)
C7	0.0252 (15)	0.0253 (17)	0.0220 (16)	−0.0016 (13)	0.0129 (13)	−0.0025 (13)
C8	0.0309 (17)	0.031 (2)	0.0263 (18)	0.0050 (14)	0.0140 (15)	0.0049 (14)
C9	0.0384 (18)	0.044 (2)	0.0231 (18)	0.0017 (17)	0.0198 (16)	0.0039 (16)
C10	0.0302 (16)	0.038 (2)	0.0285 (19)	0.0045 (15)	0.0208 (15)	0.0007 (15)
C11	0.0248 (15)	0.0199 (16)	0.0251 (17)	−0.0014 (13)	0.0163 (14)	−0.0029 (13)
C12	0.0198 (14)	0.0196 (16)	0.0259 (17)	−0.0012 (13)	0.0141 (13)	−0.0024 (13)
C13	0.134 (8)	0.031 (3)	0.146 (6)	−0.012 (3)	0.119 (6)	−0.008 (4)
C14	0.134 (8)	0.031 (3)	0.146 (6)	−0.012 (3)	0.119 (6)	−0.008 (4)
C15	0.134 (8)	0.031 (3)	0.146 (6)	−0.012 (3)	0.119 (6)	−0.008 (4)

Geometric parameters (Å, º) top

Zn1—O1	1.959 (4)	N2—C11	1.358 (4)
Zn1—O1ⁱ	1.959 (4)	C1—C2	1.402 (4)
Zn1—N2ⁱ	2.123 (3)	C1—H1A	0.9400
Zn1—N2	2.123 (3)	C2—C3	1.362 (5)
Zn1—N1	2.142 (2)	C2—H2A	0.9400
Zn1—N1ⁱ	2.142 (2)	C3—C4	1.408 (4)
S1—O1ⁱ	1.298 (5)	C3—H3A	0.9400
S1—O4ⁱ	1.355 (11)	C4—C12	1.408 (4)
S1—O3	1.446 (11)	C4—C5	1.424 (4)
S1—O2	1.459 (4)	C5—C6	1.348 (5)
S1—O4	1.492 (12)	C5—H5A	0.9400
S1—O1	1.505 (4)	C6—C7	1.440 (4)
S1—O3ⁱ	1.529 (12)	C6—H6A	0.9400
S1—O2ⁱ	1.998 (4)	C7—C11	1.396 (4)
O1—S1ⁱ	1.298 (4)	C7—C8	1.407 (4)
O1—O2ⁱ	1.435 (6)	C8—C9	1.362 (4)
O2—O1ⁱ	1.435 (6)	C8—H8A	0.9400
O2—S1ⁱ	1.998 (4)	C9—C10	1.389 (5)
O3—O4ⁱ	0.223 (14)	C9—H9A	0.9400
O3—S1ⁱ	1.529 (12)	C10—H10A	0.9400
O4—O3ⁱ	0.223 (14)	C11—C12	1.441 (4)
O4—S1ⁱ	1.355 (11)	C13—C14	1.508 (8)
O5—C13	1.394 (9)	C13—H13A	0.9800
O5—H5	0.8300	C13—H13B	0.9800
O6—C14	1.380 (8)	C14—C15	1.499 (9)
O6—H6	0.8300	C14—H14A	0.9900
N1—C1	1.324 (4)	C15—H15A	0.9700
N1—C12	1.357 (4)	C15—H15B	0.9700
N2—C10	1.329 (4)	C15—H15C	0.9700

O1—Zn1—N2ⁱ	137.27 (13)	C10—N2—C11	117.7 (3)
O1ⁱ—Zn1—N2ⁱ	110.38 (13)	C10—N2—Zn1	129.0 (2)
O1—Zn1—N2	110.38 (13)	C11—N2—Zn1	113.3 (2)
O1ⁱ—Zn1—N2	137.27 (13)	N1—C1—C2	122.7 (3)
N2ⁱ—Zn1—N2	110.75 (14)	N1—C1—H1A	118.6
O1—Zn1—N1	106.45 (13)	C2—C1—H1A	118.6
O1ⁱ—Zn1—N1	88.75 (13)	C3—C2—C1	119.3 (3)
N2ⁱ—Zn1—N1	92.67 (9)	C3—C2—H2A	120.3
N2—Zn1—N1	78.32 (9)	C1—C2—H2A	120.3
O1—Zn1—N1ⁱ	88.75 (13)	C2—C3—C4	120.0 (3)
O1ⁱ—Zn1—N1ⁱ	106.45 (13)	C2—C3—H3A	120.0
N2ⁱ—Zn1—N1ⁱ	78.32 (9)	C4—C3—H3A	120.0
N2—Zn1—N1ⁱ	92.67 (9)	C3—C4—C12	116.6 (3)
N1—Zn1—N1ⁱ	164.24 (14)	C3—C4—C5	123.7 (3)
O1ⁱ—S1—O4ⁱ	131.8 (5)	C12—C4—C5	119.6 (3)
O1ⁱ—S1—O3	139.5 (5)	C6—C5—C4	121.2 (3)
O4ⁱ—S1—O2	105.4 (5)	C6—C5—H5A	119.4
O3—S1—O2	111.2 (5)	C4—C5—H5A	119.4
O1ⁱ—S1—O4	109.5 (5)	C5—C6—C7	120.7 (3)
O4ⁱ—S1—O4	118.1 (7)	C5—C6—H6A	119.6
O3—S1—O4	109.9 (3)	C7—C6—H6A	119.6
O2—S1—O4	110.2 (5)	C11—C7—C8	117.8 (3)
O4ⁱ—S1—O1	105.6 (6)	C11—C7—C6	119.5 (3)
O3—S1—O1	108.2 (6)	C8—C7—C6	122.7 (3)
O2—S1—O1	109.3 (2)	C9—C8—C7	119.0 (3)
O4—S1—O1	107.9 (3)	C9—C8—H8A	120.5
O1ⁱ—S1—O3ⁱ	115.3 (5)	C7—C8—H8A	120.5
O4ⁱ—S1—O3ⁱ	112.9 (3)	C8—C9—C10	119.7 (3)
O3—S1—O3ⁱ	104.9 (7)	C8—C9—H9A	120.2
O2—S1—O3ⁱ	107.0 (5)	C10—C9—H9A	120.2
O1—S1—O3ⁱ	116.1 (3)	N2—C10—C9	123.1 (3)
O1ⁱ—S1—O2ⁱ	91.9 (2)	N2—C10—H10A	118.5
O4ⁱ—S1—O2ⁱ	90.3 (5)	C9—C10—H10A	118.5
O3—S1—O2ⁱ	86.9 (5)	N2—C11—C7	122.8 (3)
O2—S1—O2ⁱ	154.2 (3)	N2—C11—C12	117.5 (3)
O4—S1—O2ⁱ	78.4 (4)	C7—C11—C12	119.7 (3)
O3ⁱ—S1—O2ⁱ	84.5 (4)	N1—C12—C4	123.3 (3)
O1ⁱ—O1—S1ⁱ	74.3 (2)	N1—C12—C11	117.4 (2)
O1ⁱ—O1—O2ⁱ	134.1 (3)	C4—C12—C11	119.2 (3)
S1ⁱ—O1—O2ⁱ	64.3 (3)	O5—C13—C14	115.9 (14)
O1ⁱ—O1—S1	56.15 (18)	O5—C13—H13A	108.3
O2ⁱ—O1—S1	85.6 (3)	C14—C13—H13A	108.3
O1ⁱ—O1—Zn1	72.35 (12)	O5—C13—H13B	108.3
S1ⁱ—O1—Zn1	146.1 (3)	C14—C13—H13B	108.3
O2ⁱ—O1—Zn1	142.0 (3)	H13A—C13—H13B	107.4
S1—O1—Zn1	128.1 (2)	O6—C14—C15	109.9 (13)
O1ⁱ—O2—S1	53.3 (2)	O6—C14—C13	112.9 (16)
O1ⁱ—O2—S1ⁱ	48.7 (2)	C15—C14—C13	113.1 (8)
O4ⁱ—O3—S1	62 (5)	O6—C14—H14A	106.9
O4ⁱ—O3—S1ⁱ	76 (6)	C15—C14—H14A	106.9
O3ⁱ—O4—S1ⁱ	110 (5)	C13—C14—H14A	106.9
O3ⁱ—O4—S1	95 (6)	C14—C15—H15A	109.5
C13—O5—H5	109.5	C14—C15—H15B	109.5
C14—O6—H6	109.5	H15A—C15—H15B	109.5
C1—N1—C12	118.1 (2)	C14—C15—H15C	109.5
C1—N1—Zn1	129.2 (2)	H15A—C15—H15C	109.5
C12—N1—Zn1	112.58 (19)	H15B—C15—H15C	109.5

S1ⁱ—S1—O1—O1ⁱ	144.5 (10)	O2ⁱ—S1—O3—S1ⁱ	−14.0 (4)
O4ⁱ—S1—O1—O1ⁱ	−132.2 (5)	S1ⁱ—S1—O4—O3ⁱ	132 (6)
O3—S1—O1—O1ⁱ	−140.5 (5)	O1ⁱ—S1—O4—O3ⁱ	−135 (6)
O2—S1—O1—O1ⁱ	−19.2 (4)	O4ⁱ—S1—O4—O3ⁱ	53 (6)
O4—S1—O1—O1ⁱ	100.7 (6)	O3—S1—O4—O3ⁱ	54 (7)
O3ⁱ—S1—O1—O1ⁱ	101.9 (7)	O2—S1—O4—O3ⁱ	−69 (6)
O2ⁱ—S1—O1—O1ⁱ	153.1 (5)	O1—S1—O4—O3ⁱ	172 (6)
O1ⁱ—S1—O1—S1ⁱ	−144.5 (10)	O2ⁱ—S1—O4—O3ⁱ	137 (6)
O4ⁱ—S1—O1—S1ⁱ	83.3 (9)	O1ⁱ—S1—O4—S1ⁱ	92.8 (5)
O3—S1—O1—S1ⁱ	75.1 (8)	O4ⁱ—S1—O4—S1ⁱ	−79.2 (8)
O2—S1—O1—S1ⁱ	−163.7 (10)	O3—S1—O4—S1ⁱ	−77.5 (7)
O4—S1—O1—S1ⁱ	−43.8 (8)	O2—S1—O4—S1ⁱ	159.6 (5)
O3ⁱ—S1—O1—S1ⁱ	−42.6 (8)	O1—S1—O4—S1ⁱ	40.3 (5)
O2ⁱ—S1—O1—S1ⁱ	8.7 (8)	O3ⁱ—S1—O4—S1ⁱ	−132 (6)
S1ⁱ—S1—O1—O2ⁱ	−8.7 (8)	O2ⁱ—S1—O4—S1ⁱ	4.9 (4)
O1ⁱ—S1—O1—O2ⁱ	−153.1 (5)	O1—Zn1—N1—C1	−68.4 (3)
O4ⁱ—S1—O1—O2ⁱ	74.7 (4)	O1ⁱ—Zn1—N1—C1	−37.4 (3)
O3—S1—O1—O2ⁱ	66.4 (4)	N2ⁱ—Zn1—N1—C1	72.9 (3)
O2—S1—O1—O2ⁱ	−172.3 (2)	N2—Zn1—N1—C1	−176.4 (3)
O4—S1—O1—O2ⁱ	−52.5 (6)	N1ⁱ—Zn1—N1—C1	127.4 (3)
O3ⁱ—S1—O1—O2ⁱ	−51.2 (6)	O1—Zn1—N1—C12	116.5 (2)
S1ⁱ—S1—O1—Zn1	152.2 (8)	O1ⁱ—Zn1—N1—C12	147.5 (2)
O1ⁱ—S1—O1—Zn1	7.8 (2)	N2ⁱ—Zn1—N1—C12	−102.2 (2)
O4ⁱ—S1—O1—Zn1	−124.4 (4)	N2—Zn1—N1—C12	8.5 (2)
O3—S1—O1—Zn1	−132.7 (4)	N1ⁱ—Zn1—N1—C12	−47.68 (19)
O2—S1—O1—Zn1	−11.4 (5)	O1—Zn1—N2—C10	72.9 (3)
O4—S1—O1—Zn1	108.4 (6)	O1ⁱ—Zn1—N2—C10	101.2 (3)
O3ⁱ—S1—O1—Zn1	109.7 (6)	N2ⁱ—Zn1—N2—C10	−95.3 (3)
O2ⁱ—S1—O1—Zn1	160.9 (4)	N1—Zn1—N2—C10	176.3 (3)
N2ⁱ—Zn1—O1—O1ⁱ	−50.2 (4)	N1ⁱ—Zn1—N2—C10	−16.8 (3)
N2—Zn1—O1—O1ⁱ	146.2 (3)	O1—Zn1—N2—C11	−111.1 (2)
N1—Zn1—O1—O1ⁱ	62.8 (4)	O1ⁱ—Zn1—N2—C11	−82.9 (3)
N1ⁱ—Zn1—O1—O1ⁱ	−121.4 (4)	N2ⁱ—Zn1—N2—C11	80.7 (2)
O1ⁱ—Zn1—O1—S1ⁱ	11.1 (3)	N1—Zn1—N2—C11	−7.7 (2)
N2ⁱ—Zn1—O1—S1ⁱ	−39.1 (6)	N1ⁱ—Zn1—N2—C11	159.2 (2)
N2—Zn1—O1—S1ⁱ	157.3 (5)	C12—N1—C1—C2	0.8 (5)
N1—Zn1—O1—S1ⁱ	73.9 (5)	Zn1—N1—C1—C2	−174.1 (2)
N1ⁱ—Zn1—O1—S1ⁱ	−110.3 (5)	N1—C1—C2—C3	0.3 (5)
O1ⁱ—Zn1—O1—O2ⁱ	141.2 (8)	C1—C2—C3—C4	−1.3 (5)
N2ⁱ—Zn1—O1—O2ⁱ	91.0 (5)	C2—C3—C4—C12	1.2 (5)
N2—Zn1—O1—O2ⁱ	−72.6 (5)	C2—C3—C4—C5	−176.9 (3)
N1—Zn1—O1—O2ⁱ	−155.9 (5)	C3—C4—C5—C6	177.1 (3)
N1ⁱ—Zn1—O1—O2ⁱ	19.8 (5)	C12—C4—C5—C6	−1.0 (5)
O1ⁱ—Zn1—O1—S1	−6.76 (18)	C4—C5—C6—C7	−0.1 (5)
N2ⁱ—Zn1—O1—S1	−56.9 (4)	C5—C6—C7—C11	1.0 (5)
N2—Zn1—O1—S1	139.5 (3)	C5—C6—C7—C8	−177.5 (3)
N1—Zn1—O1—S1	56.1 (3)	C11—C7—C8—C9	−0.3 (5)
N1ⁱ—Zn1—O1—S1	−128.2 (3)	C6—C7—C8—C9	178.2 (3)
S1ⁱ—S1—O2—O1ⁱ	−30 (2)	C7—C8—C9—C10	1.2 (5)
O4ⁱ—S1—O2—O1ⁱ	129.5 (6)	C11—N2—C10—C9	−0.2 (5)
O3—S1—O2—O1ⁱ	135.8 (6)	Zn1—N2—C10—C9	175.6 (2)
O4—S1—O2—O1ⁱ	−102.0 (4)	C8—C9—C10—N2	−1.0 (5)
O1—S1—O2—O1ⁱ	16.4 (4)	C10—N2—C11—C7	1.2 (4)
O3ⁱ—S1—O2—O1ⁱ	−110.1 (4)	Zn1—N2—C11—C7	−175.3 (2)
O2ⁱ—S1—O2—O1ⁱ	3.7 (5)	C10—N2—C11—C12	−177.5 (3)
O1ⁱ—S1—O2—S1ⁱ	30 (2)	Zn1—N2—C11—C12	6.1 (3)
O4ⁱ—S1—O2—S1ⁱ	159 (2)	C8—C7—C11—N2	−0.9 (5)
O3—S1—O2—S1ⁱ	165 (2)	C6—C7—C11—N2	−179.5 (3)
O4—S1—O2—S1ⁱ	−72 (2)	C8—C7—C11—C12	177.7 (3)
O1—S1—O2—S1ⁱ	46 (2)	C6—C7—C11—C12	−0.9 (4)
O3ⁱ—S1—O2—S1ⁱ	−81 (2)	C1—N1—C12—C4	−0.8 (4)
O2ⁱ—S1—O2—S1ⁱ	33.3 (16)	Zn1—N1—C12—C4	174.9 (2)
S1ⁱ—S1—O3—O4ⁱ	128 (7)	C1—N1—C12—C11	176.2 (3)
O1ⁱ—S1—O3—O4ⁱ	25 (8)	Zn1—N1—C12—C11	−8.1 (3)
O2—S1—O3—O4ⁱ	−47 (7)	C3—C4—C12—N1	−0.2 (5)
O4—S1—O3—O4ⁱ	−169 (7)	C5—C4—C12—N1	178.0 (3)
O1—S1—O3—O4ⁱ	73 (7)	C3—C4—C12—C11	−177.1 (3)
O3ⁱ—S1—O3—O4ⁱ	−162 (7)	C5—C4—C12—C11	1.1 (4)
O2ⁱ—S1—O3—O4ⁱ	114 (7)	N2—C11—C12—N1	1.5 (4)
O1ⁱ—S1—O3—S1ⁱ	−103.3 (8)	C7—C11—C12—N1	−177.3 (3)
O4ⁱ—S1—O3—S1ⁱ	−128 (7)	N2—C11—C12—C4	178.6 (3)
O2—S1—O3—S1ⁱ	−175.2 (6)	C7—C11—C12—C4	−0.1 (4)
O4—S1—O3—S1ⁱ	62.4 (7)	O5—C13—C14—O6	67.9 (12)
O1—S1—O3—S1ⁱ	−55.1 (4)	O5—C13—C14—C15	−166.6 (14)
O3ⁱ—S1—O3—S1ⁱ	69.5 (5)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O3	0.83	2.00	2.74 (3)	149
O6—H6···O4	0.83	2.11	2.89 (2)	155

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O3	0.83	2.00	2.74 (3)	148.5
O6—H6···O4	0.83	2.11	2.89 (2)	155.4

Acknowledgements

This work was partially supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2013–10)

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