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Acta Cryst. (2007). E63, m2930    [ doi:10.1107/S1600536807052075 ]

Aquabis(o-phenylenediamine-[kappa]2N,N')(o-phenylenediamine-[kappa]N)zinc(II) bis(p-toluenesulfonate) trihydrate

B. Qian, W.-X. Ma, L.-D. Lu, X.-J. Yang and X. Wang

Abstract top

In the title compound, [Zn(C6H8N2)3(H2O)](C7H7SO3)2·3H2O, the Zn atom has a slightly tetragonally distorted octahedral geometry, with four shorter equatorial Zn-N and Zn-O bonds [2.153 (4)-2.189 (3) Å] and two longer axial Zn-N bonds [2.239 (4) and 2.243 (4) Å]. The crystal packing is stabilized by weak intermolecular N-H...O hydrogen bonds.

Comment top

Transition-metal complexes of the o-C6H4(NH2)2(o-phenylenediamine) ligand are of particular interest due to their oxidation-reduction propensities (Warren,1977; Milliken et al.,2003). The zinc complex of this ligand system has been synthesized using dibenzoylmethane, o-phenylenediamine and zinc(II) acetate (Ovalle-Marroquín, et al.,2002). Arenesulfonate anions are widely used industrially as surfactants and dyes (Gunderman et al.,1997). Sulfonate anions can compete with water molecules by introducing other organic ligands as auxiliiaries to the metal centers. In order to explore the structural changes in the zinc complex of the o-phenylenediamine ligand with p-toluenesulfonate, the X-ray analysis of the title compound, [Zn(C6H8N2)3(H2O)](C7H7SO3)2·3H2O(I), was undertaken.

Fig.1 shows the molecular structure of the title compound. The Zn(II) center is coordinated octahedrally by five N-atoms and one O-atom. It is interesting to note that there are two types of o-phenylenediamine ligand present, one is coordinated as bidentate and another as monodentate. This is probably due to the steric interactions within the rigid ligands. The bond length of Zn(1)—N(1),Zn(1)—N(2),Zn(1)—N(3),Zn(1)—N(4), Zn(1)—N(5),Zn(1)—O(7) are 2.239 (4) Å, 2.153 (4) Å, 2.168 (4) Å, 2.162 (4) Å, 2.243 (4) Å, 2.189 (3) Å, respectively. N(1) and N(5) occupied the axial positions.

As shown in Fig.2, all of the SO3− O-atoms, water molecules and the amino H-atoms are involved in hydrogen bonds with each other, resulting extended structures. The crystalline water molecules fill in the gaps formed by the two p-toluenesulfonate molecules and two complex cations, anchored by forming hydrogen bonds with the SO3− O-atoms.

Related literature top

For related literature, see: Gunderman et al. (1997); Milliken et al. (2003); Ovalle-Marroquín et al. (2002); Warren (1977).

Experimental top

To a stirred solution of p-toluenesulfonic acid (C7H8O3S·H2O, 0.380 g, 2.0 mmol) in water (10 ml), ZnO (0.081 g, 1.0 mmol) was added with heating in 50 °C, until all of the solid dissolved. To this solution was added o-phenylenediamine (0.618 g, 6.0 mmol) in methanol (20 ml) with heating and stirring for another 3 h. Colorless crystals of (I) suitable for X-ray diffraction were obtained after 7 days.

Refinement top

All H atoms attached to C,N and O atoms were fixed geometrically and treated as riding with C—H=0.96Å (methyl),0.93Å (aromatic C—H), 0.90Å (NH2),and 0.85Å (OH) with Uiso(H)=1.2Ueq (NH2,aromatic C—H) and Uiso(H)=1.5Ueq (OH,CH3).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Version 1.64.05; Farrugia, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. Molecular structure showing 30% probability displacement ellipsoids. Hydrogen atoms have been omitted for clarity.
[Figure 2] Fig. 2. A perspective view of the crystal packing of (I). The hydrogen-bond contacts are shown as dashed lines. Hydrogen atoms have been ommited for clarity.
Aquabis(o-phenylenediamine-κ2N,N')(o- phenylenediamine-κN)zinc(II) bis(p-toluenesulfonate) trihydrate top
Crystal data top
[Zn(C6H8N2)3(H2O)](C7H7SO3)2·3H2OZ = 2
Mr = 804.24F000 = 844
Triclinic, P1Dx = 1.442 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.498 (3) ÅCell parameters from 2226 reflections
b = 14.017 (5) Åθ = 2.2–22.2º
c = 19.455 (7) ŵ = 0.84 mm−1
α = 107.846 (4)ºT = 298 (2) K
β = 94.850 (5)ºPrism, colorless
γ = 104.759 (4)º0.23 × 0.20 × 0.13 mm
V = 1852.5 (12) Å3
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		6412 independent reflections
Radiation source: fine-focus sealed tube3908 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.032
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 1.6º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→7
Tmin = 0.831, Tmax = 0.899k = −13→16
9725 measured reflectionsl = −23→23
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.158  w = 1/[σ2(Fo2) + (0.0691P)2 + 1.0494P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
6412 reflectionsΔρmax = 0.95 e Å−3
460 parametersΔρmin = −0.65 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(C6H8N2)3(H2O)](C7H7SO3)2·3H2Oγ = 104.759 (4)º
Mr = 804.24V = 1852.5 (12) Å3
Triclinic, P1Z = 2
a = 7.498 (3) ÅMo Kα
b = 14.017 (5) ŵ = 0.84 mm−1
c = 19.455 (7) ÅT = 298 (2) K
α = 107.846 (4)º0.23 × 0.20 × 0.13 mm
β = 94.850 (5)º
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		6412 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3908 reflections with I > 2σ(I)
Tmin = 0.831, Tmax = 0.899Rint = 0.032
9725 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056460 parameters
wR(F2) = 0.158H-atom parameters constrained
S = 1.01Δρmax = 0.95 e Å−3
6412 reflectionsΔρmin = −0.65 e Å−3
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
xyzUiso*/Ueq
Zn11.03676 (8)0.79056 (4)0.26307 (3)0.0404 (2)
N11.2511 (6)0.8017 (3)0.3550 (2)0.0464 (11)
H1A1.35310.78770.33820.056*
H1B1.28620.86620.38920.056*
N20.9884 (5)0.6316 (3)0.26146 (19)0.0386 (9)
H2A0.86960.59340.24010.046*
H2B1.06630.60180.23590.046*
N31.1269 (5)0.9559 (3)0.2764 (2)0.0418 (10)
H3A1.04100.98700.29390.050*
H3B1.23680.98850.30770.050*
N41.2232 (6)0.7982 (3)0.1847 (2)0.0439 (10)
H4A1.34320.81610.20680.053*
H4B1.19620.73580.14860.053*
N50.7684 (5)0.7547 (3)0.18667 (19)0.0372 (9)
H5A0.69710.69350.18830.045*
H5B0.71470.80330.20970.045*
N60.7667 (6)0.5687 (3)0.0708 (2)0.0549 (12)
H6A0.71270.55240.10460.082*
H6B0.73630.51210.03320.082*
O10.4148 (5)0.4665 (3)0.80089 (18)0.0515 (9)
O20.7405 (5)0.4752 (3)0.80434 (19)0.0569 (10)
O30.5072 (5)0.3368 (3)0.70899 (19)0.0566 (10)
O40.5412 (6)0.0776 (3)0.3546 (2)0.0774 (13)
O50.8561 (6)0.0645 (3)0.3599 (2)0.0788 (13)
O60.6087 (5)−0.0614 (3)0.26375 (19)0.0641 (11)
O70.8509 (5)0.8151 (3)0.34339 (17)0.0519 (9)
H330.74140.77440.33840.078*
H340.83150.87280.34480.078*
O80.9193 (11)0.9066 (6)0.5003 (4)0.182 (3)
H351.00540.95230.53430.273*
H360.96940.88240.46370.273*
O90.6182 (9)0.9741 (4)0.5385 (3)0.140 (2)
H370.66030.94680.50040.210*
H380.53020.92560.54290.210*
O100.8297 (6)0.4120 (3)0.9249 (2)0.0756 (12)
H390.79740.42340.88600.113*
H400.94880.43380.93360.113*
S10.55943 (17)0.44501 (10)0.75802 (7)0.0422 (3)
S20.6815 (2)0.04591 (12)0.31382 (7)0.0536 (4)
C11.1581 (7)0.7238 (4)0.3850 (3)0.0420 (12)
C21.0222 (6)0.6357 (4)0.3364 (2)0.0373 (11)
C30.9242 (7)0.5613 (4)0.3613 (3)0.0517 (14)
H30.83490.50180.32870.062*
C40.9569 (9)0.5735 (6)0.4346 (4)0.0694 (18)
H40.88880.52230.45130.083*
C51.0880 (10)0.6599 (6)0.4829 (3)0.0714 (19)
H51.10890.66740.53230.086*
C61.1897 (9)0.7362 (5)0.4587 (3)0.0595 (15)
H61.27880.79540.49170.071*
C71.1473 (6)0.9602 (4)0.2036 (3)0.0410 (12)
C81.1933 (6)0.8772 (4)0.1559 (3)0.0401 (12)
C91.2048 (7)0.8722 (4)0.0853 (3)0.0521 (14)
H91.23550.81660.05350.063*
C101.1708 (8)0.9500 (5)0.0614 (3)0.0664 (17)
H101.17680.94640.01310.080*
C111.1282 (8)1.0324 (5)0.1087 (4)0.0663 (17)
H111.10771.08530.09260.080*
C121.1153 (7)1.0382 (4)0.1799 (3)0.0541 (14)
H121.08541.09430.21170.065*
C130.7324 (6)0.7456 (4)0.1103 (2)0.0359 (11)
C140.7316 (7)0.6549 (4)0.0545 (3)0.0423 (12)
C150.7034 (8)0.6532 (4)−0.0173 (3)0.0546 (14)
H150.70300.5936−0.05530.066*
C160.6761 (8)0.7372 (5)−0.0332 (3)0.0634 (16)
H160.65810.7342−0.08180.076*
C170.6749 (8)0.8256 (4)0.0211 (3)0.0585 (15)
H170.65570.88250.01000.070*
C180.7023 (7)0.8292 (4)0.0929 (3)0.0441 (12)
H180.70060.88910.13020.053*
C190.5793 (6)0.5248 (4)0.7027 (3)0.0391 (12)
C200.6237 (7)0.4905 (4)0.6339 (3)0.0451 (13)
H200.63940.42420.61580.054*
C210.6448 (8)0.5545 (4)0.5918 (3)0.0534 (14)
H210.67490.53040.54550.064*
C220.6224 (7)0.6542 (4)0.6169 (3)0.0510 (14)
C230.5767 (7)0.6860 (4)0.6857 (3)0.0551 (14)
H230.55910.75190.70360.066*
C240.5563 (7)0.6237 (4)0.7289 (3)0.0495 (14)
H240.52730.64790.77540.059*
C250.6477 (9)0.7232 (5)0.5713 (3)0.0736 (18)
H25A0.52890.71320.54300.110*
H25B0.73290.70560.53880.110*
H25C0.69760.79510.60260.110*
C260.7308 (7)0.1268 (4)0.2598 (3)0.0463 (13)
C270.8698 (8)0.2216 (5)0.2859 (3)0.0607 (16)
H270.93920.24350.33280.073*
C280.9073 (8)0.2843 (5)0.2432 (4)0.0667 (18)
H281.00260.34760.26190.080*
C290.8069 (8)0.2556 (4)0.1736 (3)0.0566 (15)
C300.6659 (8)0.1609 (4)0.1480 (3)0.0570 (15)
H300.59460.13990.10150.068*
C310.6290 (7)0.0970 (4)0.1903 (3)0.0532 (14)
H310.53460.03340.17160.064*
C320.8473 (10)0.3246 (5)0.1275 (4)0.086 (2)
H32A0.73220.32000.09930.129*
H32B0.92930.30180.09500.129*
H32C0.90630.39590.15880.129*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0418 (4)0.0408 (4)0.0418 (4)0.0152 (3)0.0085 (3)0.0159 (3)
N10.040 (2)0.043 (2)0.051 (3)0.012 (2)−0.002 (2)0.011 (2)
N20.036 (2)0.045 (2)0.034 (2)0.0144 (19)0.0024 (18)0.0113 (18)
N30.037 (2)0.037 (2)0.046 (2)0.0110 (18)0.0051 (19)0.0058 (19)
N40.041 (2)0.041 (2)0.049 (2)0.016 (2)0.011 (2)0.0106 (19)
N50.039 (2)0.039 (2)0.037 (2)0.0146 (18)0.0078 (18)0.0143 (18)
N60.079 (3)0.045 (3)0.046 (3)0.028 (2)0.016 (2)0.015 (2)
O10.042 (2)0.066 (2)0.050 (2)0.0176 (18)0.0210 (17)0.0211 (18)
O20.037 (2)0.083 (3)0.058 (2)0.0204 (19)0.0078 (18)0.033 (2)
O30.065 (3)0.043 (2)0.063 (2)0.0142 (18)0.023 (2)0.0183 (18)
O40.074 (3)0.108 (3)0.071 (3)0.052 (3)0.038 (2)0.033 (2)
O50.057 (3)0.114 (4)0.062 (3)0.034 (2)−0.006 (2)0.022 (2)
O60.073 (3)0.062 (3)0.056 (2)0.026 (2)0.004 (2)0.015 (2)
O70.047 (2)0.064 (2)0.052 (2)0.0278 (18)0.0117 (18)0.0197 (18)
O80.189 (6)0.212 (6)0.144 (5)0.077 (5)0.034 (5)0.044 (5)
O90.163 (6)0.109 (4)0.124 (5)0.014 (4)0.026 (4)0.030 (4)
O100.098 (3)0.075 (3)0.058 (2)0.039 (3)0.012 (2)0.018 (2)
S10.0348 (7)0.0499 (8)0.0445 (7)0.0127 (6)0.0114 (6)0.0180 (6)
S20.0449 (9)0.0709 (10)0.0451 (8)0.0280 (7)0.0071 (7)0.0111 (7)
C10.048 (3)0.050 (3)0.040 (3)0.028 (3)0.011 (2)0.020 (2)
C20.034 (3)0.044 (3)0.040 (3)0.018 (2)0.007 (2)0.019 (2)
C30.047 (3)0.056 (3)0.064 (4)0.020 (3)0.014 (3)0.033 (3)
C40.073 (5)0.094 (5)0.073 (4)0.043 (4)0.033 (4)0.053 (4)
C50.099 (5)0.098 (5)0.044 (3)0.055 (5)0.027 (4)0.038 (4)
C60.074 (4)0.063 (4)0.046 (3)0.034 (3)0.007 (3)0.014 (3)
C70.032 (3)0.042 (3)0.050 (3)0.008 (2)0.007 (2)0.018 (2)
C80.031 (3)0.040 (3)0.044 (3)0.004 (2)0.002 (2)0.013 (2)
C90.047 (3)0.056 (3)0.044 (3)0.004 (3)0.008 (3)0.014 (3)
C100.059 (4)0.085 (5)0.056 (4)0.006 (4)0.007 (3)0.039 (4)
C110.055 (4)0.072 (4)0.087 (5)0.010 (3)0.004 (3)0.056 (4)
C120.046 (3)0.046 (3)0.073 (4)0.014 (3)0.009 (3)0.024 (3)
C130.028 (3)0.041 (3)0.038 (3)0.007 (2)0.005 (2)0.016 (2)
C140.042 (3)0.042 (3)0.040 (3)0.011 (2)0.002 (2)0.012 (2)
C150.067 (4)0.057 (4)0.035 (3)0.019 (3)0.007 (3)0.009 (3)
C160.078 (4)0.077 (4)0.041 (3)0.022 (4)0.007 (3)0.028 (3)
C170.068 (4)0.059 (4)0.054 (3)0.017 (3)0.004 (3)0.030 (3)
C180.042 (3)0.045 (3)0.042 (3)0.012 (2)0.003 (2)0.013 (2)
C190.025 (3)0.046 (3)0.045 (3)0.010 (2)0.008 (2)0.013 (2)
C200.048 (3)0.050 (3)0.043 (3)0.026 (3)0.014 (2)0.014 (2)
C210.066 (4)0.068 (4)0.045 (3)0.037 (3)0.021 (3)0.027 (3)
C220.039 (3)0.056 (3)0.065 (4)0.019 (3)0.006 (3)0.027 (3)
C230.053 (4)0.043 (3)0.069 (4)0.018 (3)0.009 (3)0.016 (3)
C240.049 (3)0.046 (3)0.049 (3)0.018 (3)0.015 (3)0.006 (3)
C250.086 (5)0.080 (4)0.083 (4)0.040 (4)0.019 (4)0.053 (4)
C260.032 (3)0.053 (3)0.046 (3)0.017 (3)0.003 (2)0.003 (2)
C270.040 (3)0.062 (4)0.057 (4)0.012 (3)−0.004 (3)−0.006 (3)
C280.040 (3)0.051 (4)0.087 (5)0.004 (3)0.012 (3)0.000 (3)
C290.042 (3)0.048 (3)0.070 (4)0.008 (3)0.013 (3)0.011 (3)
C300.052 (4)0.058 (4)0.053 (3)0.010 (3)0.000 (3)0.014 (3)
C310.037 (3)0.052 (3)0.056 (3)0.007 (3)−0.001 (3)0.006 (3)
C320.081 (5)0.067 (4)0.100 (5)0.002 (4)0.019 (4)0.029 (4)
Geometric parameters (Å, °) top
Zn1—N22.154 (4)C6—H60.9300
Zn1—N42.162 (4)C7—C121.374 (7)
Zn1—N32.168 (4)C7—C81.389 (6)
Zn1—O72.188 (3)C8—C91.365 (7)
Zn1—N12.241 (4)C9—C101.380 (8)
Zn1—N52.243 (4)C9—H90.9300
N1—C11.446 (6)C10—C111.367 (8)
N1—H1A0.9000C10—H100.9300
N1—H1B0.9000C11—C121.376 (8)
N2—C21.440 (6)C11—H110.9300
N2—H2A0.9000C12—H120.9300
N2—H2B0.9000C13—C181.381 (6)
N3—C71.456 (6)C13—C141.394 (6)
N3—H3A0.9000C14—C151.385 (7)
N3—H3B0.9000C15—C161.364 (8)
N4—C81.440 (6)C15—H150.9300
N4—H4A0.9000C16—C171.363 (7)
N4—H4B0.9000C16—H160.9300
N5—C131.447 (5)C17—C181.376 (7)
N5—H5A0.9000C17—H170.9300
N5—H5B0.9000C18—H180.9300
N6—C141.419 (6)C19—C201.376 (6)
N6—H6A0.8600C19—C241.384 (6)
N6—H6B0.8599C20—C211.378 (7)
O1—S11.459 (3)C20—H200.9300
O2—S11.450 (4)C21—C221.391 (7)
O3—S11.453 (3)C21—H210.9300
O4—S21.448 (4)C22—C231.378 (7)
O5—S21.440 (4)C22—C251.489 (7)
O6—S21.450 (4)C23—C241.377 (7)
O7—H330.8500C23—H230.9300
O7—H340.8500C24—H240.9300
O8—H360.8500C25—H25A0.9600
O8—H350.8500C25—H25B0.9600
O8—H360.8500C25—H25C0.9600
O9—H370.8500C26—C271.379 (7)
O9—H380.8500C26—C311.380 (7)
O10—H390.8498C27—C281.379 (8)
O10—H400.8501C27—H270.9300
S1—C191.764 (5)C28—C291.380 (8)
S2—C261.763 (6)C28—H280.9300
C1—C61.384 (7)C29—C301.384 (7)
C1—C21.391 (6)C29—C321.503 (8)
C2—C31.357 (6)C30—C311.385 (7)
C3—C41.376 (8)C30—H300.9300
C3—H30.9300C31—H310.9300
C4—C51.362 (9)C32—H32A0.9600
C4—H40.9300C32—H32B0.9600
C5—C61.378 (8)C32—H32C0.9600
C5—H50.9300
N2—Zn1—N4102.12 (14)C12—C7—C8120.1 (5)
N2—Zn1—N3170.84 (14)C12—C7—N3123.5 (5)
N4—Zn1—N376.62 (14)C8—C7—N3116.4 (4)
N2—Zn1—O789.45 (14)C9—C8—C7120.1 (5)
N4—Zn1—O7168.41 (13)C9—C8—N4123.2 (5)
N3—Zn1—O792.07 (13)C7—C8—N4116.7 (4)
N2—Zn1—N175.34 (14)C8—C9—C10119.8 (5)
N4—Zn1—N196.55 (16)C8—C9—H9120.1
N3—Zn1—N195.71 (15)C10—C9—H9120.1
O7—Zn1—N186.97 (14)C11—C10—C9119.8 (5)
N2—Zn1—N594.31 (14)C11—C10—H10120.1
N4—Zn1—N597.55 (14)C9—C10—H10120.1
N3—Zn1—N594.84 (14)C10—C11—C12121.0 (5)
O7—Zn1—N580.68 (13)C10—C11—H11119.5
N1—Zn1—N5164.02 (14)C12—C11—H11119.5
C1—N1—Zn1104.7 (3)C7—C12—C11119.1 (5)
C1—N1—H1A110.8C7—C12—H12120.4
Zn1—N1—H1A110.8C11—C12—H12120.4
C1—N1—H1B110.8C18—C13—C14119.7 (4)
Zn1—N1—H1B110.8C18—C13—N5119.1 (4)
H1A—N1—H1B108.9C14—C13—N5121.2 (4)
C2—N2—Zn1107.4 (3)C15—C14—C13118.1 (5)
C2—N2—H2A110.2C15—C14—N6120.9 (5)
Zn1—N2—H2A110.2C13—C14—N6121.0 (4)
C2—N2—H2B110.2C16—C15—C14121.3 (5)
Zn1—N2—H2B110.2C16—C15—H15119.3
H2A—N2—H2B108.5C14—C15—H15119.3
C7—N3—Zn1105.7 (3)C17—C16—C15120.9 (5)
C7—N3—H3A110.6C17—C16—H16119.6
Zn1—N3—H3A110.6C15—C16—H16119.6
C7—N3—H3B110.6C16—C17—C18119.0 (5)
Zn1—N3—H3B110.6C16—C17—H17120.5
H3A—N3—H3B108.7C18—C17—H17120.5
C8—N4—Zn1105.7 (3)C17—C18—C13121.1 (5)
C8—N4—H4A110.6C17—C18—H18119.4
Zn1—N4—H4A110.6C13—C18—H18119.4
C8—N4—H4B110.6C20—C19—C24119.4 (5)
Zn1—N4—H4B110.6C20—C19—S1120.3 (4)
H4A—N4—H4B108.7C24—C19—S1120.3 (4)
C13—N5—Zn1131.3 (3)C19—C20—C21120.0 (5)
C13—N5—H5A104.4C19—C20—H20120.0
Zn1—N5—H5A104.4C21—C20—H20120.0
C13—N5—H5B104.4C20—C21—C22121.8 (5)
Zn1—N5—H5B104.4C20—C21—H21119.1
H5A—N5—H5B105.6C22—C21—H21119.1
C14—N6—H6A115.8C23—C22—C21116.8 (5)
C14—N6—H6B113.1C23—C22—C25121.9 (5)
H6A—N6—H6B106.2C21—C22—C25121.3 (5)
Zn1—O7—H33124.3C24—C23—C22122.4 (5)
Zn1—O7—H34104.2C24—C23—H23118.8
H33—O7—H34103.4C22—C23—H23118.8
H36—O8—H35108.1C23—C24—C19119.6 (5)
H35—O8—H36108.1C23—C24—H24120.2
H37—O9—H38106.8C19—C24—H24120.2
H39—O10—H40105.2C22—C25—H25A109.5
O2—S1—O3111.8 (2)C22—C25—H25B109.5
O2—S1—O1111.8 (2)H25A—C25—H25B109.5
O3—S1—O1112.2 (2)C22—C25—H25C109.5
O2—S1—C19107.2 (2)H25A—C25—H25C109.5
O3—S1—C19107.1 (2)H25B—C25—H25C109.5
O1—S1—C19106.3 (2)C27—C26—C31118.2 (5)
O5—S2—O4113.2 (2)C27—C26—S2121.2 (4)
O5—S2—O6112.6 (3)C31—C26—S2120.5 (4)
O4—S2—O6111.2 (3)C28—C27—C26120.8 (5)
O5—S2—C26106.2 (3)C28—C27—H27119.6
O4—S2—C26106.1 (2)C26—C27—H27119.6
O6—S2—C26107.0 (2)C27—C28—C29121.7 (5)
C6—C1—C2119.8 (5)C27—C28—H28119.2
C6—C1—N1123.4 (5)C29—C28—H28119.2
C2—C1—N1116.7 (4)C28—C29—C30117.3 (6)
C3—C2—C1120.0 (5)C28—C29—C32121.5 (5)
C3—C2—N2123.4 (5)C30—C29—C32121.2 (6)
C1—C2—N2116.6 (4)C29—C30—C31121.3 (5)
C2—C3—C4120.1 (6)C29—C30—H30119.3
C2—C3—H3119.9C31—C30—H30119.3
C4—C3—H3119.9C26—C31—C30120.7 (5)
C5—C4—C3120.6 (6)C26—C31—H31119.6
C5—C4—H4119.7C30—C31—H31119.6
C3—C4—H4119.7C29—C32—H32A109.5
C4—C5—C6120.2 (6)C29—C32—H32B109.5
C4—C5—H5119.9H32A—C32—H32B109.5
C6—C5—H5119.9C29—C32—H32C109.5
C5—C6—C1119.3 (6)H32A—C32—H32C109.5
C5—C6—H6120.3H32B—C32—H32C109.5
C1—C6—H6120.3
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.902.263.049 (6)147
N1—H1B···O9ii0.902.143.037 (7)174
N2—H2A···O1iii0.902.072.957 (6)169
N2—H2B···O2i0.902.082.971 (6)168
N3—H3A···O5iv0.902.233.114 (6)168
N3—H3B···O4v0.902.263.128 (6)162
N4—H4A···O6v0.902.203.015 (6)149
N4—H4B···O10i0.902.082.966 (6)170
N5—H5A···O1iii0.902.273.147 (6)166
N5—H5A···S1iii0.902.873.718 (5)158
N5—H5B···O6iv0.902.243.136 (6)173
N6—H6A···O1iii0.862.203.052 (6)172
N6—H6B···O10vi0.862.423.168 (6)146
O7—H33···O3iii0.852.032.842 (6)161
O7—H34···O5iv0.852.573.401 (6)166
O8—H36···O70.852.242.868 (6)130
O9—H37···O80.852.162.736 (11)125
O9—H38···O4iii0.852.122.680 (7)123
O10—H39···O20.852.002.836 (6)170
O10—H40···N6i0.852.152.960 (7)159
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x, y, z−1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3i0.902.263.049 (6)147
N1—H1B···O9ii0.902.143.037 (7)174
N2—H2A···O1iii0.902.072.957 (6)169
N2—H2B···O2i0.902.082.971 (6)168
N3—H3A···O5iv0.902.233.114 (6)168
N3—H3B···O4v0.902.263.128 (6)162
N4—H4A···O6v0.902.203.015 (6)149
N4—H4B···O10i0.902.082.966 (6)170
N5—H5A···O1iii0.902.273.147 (6)166
N5—H5A···S1iii0.902.873.718 (5)158
N5—H5B···O6iv0.902.243.136 (6)173
N6—H6A···O1iii0.862.203.052 (6)172
N6—H6B···O10vi0.862.423.168 (6)146
O7—H33···O3iii0.852.032.842 (6)161
O7—H34···O5iv0.852.573.401 (6)166
O9—H38···O4iii0.852.122.680 (7)123
O10—H40···N6i0.852.152.960 (7)159
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x, y+1, z; (v) x+1, y+1, z; (vi) x, y, z−1.
Acknowledgements top

The authors thank the National Natural Science Foundation of China (grant No. 50572039) and the Natural Science Foundation of Jiangsu Province (grant No. BK2005130).

references
References top

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