metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Tris(1,10-phenanthroline-κ2N,N′)zinc(II) bis­­(4-bromo­benzoate) 6.5-hydrate

aCollege of Material Science and Chemical Engineering, Jinhua College of Profession and Technology, Jinhua, Zhejiang 321017, People's Republic of China
*Correspondence e-mail: zbs_jy@163.com

(Received 12 March 2010; accepted 21 March 2010; online 31 March 2010)

In the title compound, [Zn(C12H8N2)3](C7H4BrO2)2·6.5H2O, the ZnII atom is coordinated by six N atoms from three 1,10-phenanthroline (phen) mol­ecules in a distorted octa­hedral geometry. The chelating phen ligands exhibit nearly perfect coplanarity (r.m.s. deviations of 0.048, 0.039 and 0.061 Å). The mean inter­planar distances of 3.51 (2) and 3.54 (4) Å between adjacent phen ligands indicate ππ stacking inter­actions, which connect the complex cations into chains along [101]. The 4-bromo­benzoate anions and the uncoordinated water mol­ecules, parts of which are not fully occupied, are linked by O—H⋯O hydrogen bonds. Two carboxyl­ate O atoms and one Br atom in the 4-bromo­benzoate anions are each disordered over two sites with occupancy factors of 0.60 and 0.40.

Related literature

For other zinc(II) complexes with 1,10-phenanthroline ligands, see: Aghabozorg et al. (2005[Aghabozorg, H., Nakhjavan, B., Zabihi, F., Ramezanipour, F. & Aghabozorg, H. R. (2005). Acta Cryst. E61, m2664-m2666.]); Chen et al. (2006[Chen, H., Xu, X.-Y., Gao, J., Yang, X.-J., Lu, L.-D. & Wang, X. (2006). Huaxue Shiji, 28, 478-480.]); Liu et al. (1998[Liu, C.-M., You, X.-Z. & Chen, W. (1998). J. Coord. Chem. 46, 233-243.]); Wei, Yuan et al. (2004[Wei, Y., Yuan, C. & Yang, P. (2004). Acta Cryst. E60, m1686-m1688.]); Wei, Zheng et al. (2002[Wei, D.-Y., Zheng, Y.-Q. & Lin, J.-L. (2002). Z. Anorg. Allg. Chem. 628, 2005-2012.]).

[Scheme 1]

Experimental

Crystal data
  • [Zn(C12H8N2)3](C7H4BrO2)2·6.5H2O

  • Mr = 1123.11

  • Triclinic, [P \overline 1]

  • a = 13.098 (3) Å

  • b = 14.240 (3) Å

  • c = 16.281 (3) Å

  • α = 108.68 (3)°

  • β = 107.13 (3)°

  • γ = 105.11 (3)°

  • V = 2528.9 (15) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 2.13 mm−1

  • T = 290 K

  • 0.28 × 0.20 × 0.19 mm

Data collection
  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.603, Tmax = 0.675

  • 19484 measured reflections

  • 8780 independent reflections

  • 5375 reflections with I > 2σ(I)

  • Rint = 0.039

Refinement
  • R[F2 > 2σ(F2)] = 0.065

  • wR(F2) = 0.250

  • S = 1.15

  • 8780 reflections

  • 667 parameters

  • 9 restraints

  • H-atom parameters constrained

  • Δρmax = 0.80 e Å−3

  • Δρmin = −0.95 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O5—H5A⋯O2 0.82 1.90 2.700 (11) 164
O5—H5B⋯O6i 0.82 2.23 2.676 (11) 114
O6—H6A⋯O3 0.82 1.97 2.763 (2) 162
O6—H6A⋯O3′ 0.82 2.03 2.767 (5) 150
O6—H6B⋯O8ii 0.82 2.20 2.788 (5) 129
O7—H7A⋯O5i 0.82 1.97 2.787 (10) 176
O7—H7B⋯O4 0.82 1.89 2.687 (11) 163
O8—H8A⋯O3 0.82 2.04 2.803 (2) 155
O8—H8A⋯O3′ 0.82 1.99 2.789 (2) 166
O8—H8B⋯O1iii 0.82 2.19 2.862 (5) 139
O8—H8B⋯O1′iii 0.82 1.96 2.685 (6) 146
O10—H10A⋯O11iv 0.82 2.24 2.806 (2) 126
O10—H10B⋯O2 0.82 2.11 2.739 (2) 134
O11—H11A⋯O5 0.82 2.27 2.826 (5) 126
O11—H11B⋯O10iv 0.82 2.33 2.806 (2) 117
O12—H12A⋯O13i 0.82 2.50 2.981 (5) 118
O12—H12B⋯O4 0.82 2.29 2.786 (2) 119
O13—H13A⋯O12v 0.82 2.19 2.796 (5) 131
O13—H13B⋯O7i 0.82 1.95 2.746 (2) 165
Symmetry codes: (i) -x+2, -y+3, -z+1; (ii) -x+1, -y+2, -z+1; (iii) x-1, y-1, z; (iv) -x+2, -y+3, -z; (v) x, y+1, z-1.

Data collection: PROCESS-AUTO (Rigaku, 1998[Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Zinc ions with 1,10-phenanthroline (phen) ligands can form tris(phen)zinc(II) (Aghabozorg et al., 2005; Chen et al., 2006; Liu et al., 1998; Wei, Yuan et al., 2004; Wei, Zheng et al., 2002). In this paper, we report the synthesis and structure of a tris(phen)zinc(II) complex.

The title compound consists of [Zn(phen)3]2+ complex cations, 4-bromobenzoate anions and uncoordinated water molecules (Fig. 1). In the cation, the ZnII atom is coordinated by six N atoms from three phen molecules to complete a distorted ZnN6 octahedral geometry. The Zn—N bond lengths are in the range of 2.126 (6)–2.199 (6)Å. The chelating phen ligands exhibit nearly perfect coplanarity. The mean interplanar distances of 3.51 (2) and 3.54 (4)Å between adjacent phen ligands indicate ππ stacking interactions (Fig. 2). The complex cations are connected to each other via ππ stacking interactions into a chain along [1 0 1]. The 4-bromobenzoate anions and the uncoordinated water molecules are linked by O—H···O hydrogen bonds (Table 1).

Related literature top

For other zinc(II) complexes with 1,10-phenanthroline ligands, see: Aghabozorg et al. (2005); Chen et al. (2006); Liu et al. (1998); Wei, Yuan et al. (2004); Wei, Zheng et al. (2002).

Experimental top

ZnSO4.7H2O (0.237 g, 0.826 mmol) was dissolved in appropriate amount of water and then 1M Na2CO3 solution was added. ZnCO3 was obtained by filtration and washed with distilled water for 5 times. The freshly prepared ZnCO3, phen.H2O (0.0496 g, 0.25 mmol) and 4-bromobenzoic acid (0.050 g, 0.25 mmol) were mixed in CH3OH/H2O (15 ml, v/v = 1:2) and stirred for 2 h. The resulting cream suspension was heated in a 23 ml Teflon-lined stainless steel autoclave at 433 K for 97 h. After the autoclave was cooled to room temperature in 43 h, the solid was filtered off. The resulting filtrate was allowed to stand at room temperature, and slow evaporation for 6 months afforded brown block single crystals.

Refinement top

C-bound H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of the water molecules were located in a difference Fourier map and refined as riding, with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O). Two carboxylate O atoms (O1 and O3) and one Br atom (Br2) are each disordered over two sites with occupancy factors of 0.60 and 0.40. Four water molecules (O10, O11, O12 and O13) are half-occupied and the two water molecules (O9 and O14) are quarter-occupied.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); 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
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms and uncoordinated water molecules are omitted for clarity.
[Figure 2] Fig. 2. The ππ stacking interactions (dashed double arrows), with the mean interplanar distances of 3.51 (2) and 3.54 (4)Å.
Tris(1,10-phenanthroline-κ2N,N')zinc(II) bis(4-bromobenzoate) 6.5-hydrate top
Crystal data top
[Zn(C12H8N2)3](C7H4BrO2)2·6.5H2OZ = 2
Mr = 1123.11F(000) = 1142
Triclinic, P1Dx = 1.475 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 13.098 (3) ÅCell parameters from 13525 reflections
b = 14.240 (3) Åθ = 3.1–25.0°
c = 16.281 (3) ŵ = 2.13 mm1
α = 108.68 (3)°T = 290 K
β = 107.13 (3)°Block, yellow
γ = 105.11 (3)°0.28 × 0.20 × 0.19 mm
V = 2528.9 (15) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer
8780 independent reflections
Radiation source: fine-focus sealed tube5375 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
ω scansθmax = 25.0°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1515
Tmin = 0.603, Tmax = 0.675k = 1616
19484 measured reflectionsl = 1917
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.250H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.1215P)2 + 3.2158P]
where P = (Fo2 + 2Fc2)/3
8780 reflections(Δ/σ)max < 0.001
667 parametersΔρmax = 0.80 e Å3
9 restraintsΔρmin = 0.95 e Å3
Crystal data top
[Zn(C12H8N2)3](C7H4BrO2)2·6.5H2Oγ = 105.11 (3)°
Mr = 1123.11V = 2528.9 (15) Å3
Triclinic, P1Z = 2
a = 13.098 (3) ÅMo Kα radiation
b = 14.240 (3) ŵ = 2.13 mm1
c = 16.281 (3) ÅT = 290 K
α = 108.68 (3)°0.28 × 0.20 × 0.19 mm
β = 107.13 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
8780 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
5375 reflections with I > 2σ(I)
Tmin = 0.603, Tmax = 0.675Rint = 0.039
19484 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0659 restraints
wR(F2) = 0.250H-atom parameters constrained
S = 1.15Δρmax = 0.80 e Å3
8780 reflectionsΔρmin = 0.95 e Å3
667 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.67519 (7)0.86835 (7)0.19869 (5)0.0560 (3)
N10.7784 (5)0.9984 (5)0.1831 (4)0.0580 (14)
N20.5521 (5)0.9405 (5)0.1550 (4)0.0587 (14)
N30.5319 (5)0.7306 (5)0.1766 (4)0.0585 (14)
N40.6269 (5)0.7512 (5)0.0531 (4)0.0600 (14)
N50.8131 (5)0.8264 (5)0.2669 (4)0.0576 (14)
N60.7160 (5)0.9524 (4)0.3480 (4)0.0538 (13)
Br10.83384 (7)1.27529 (7)0.40614 (7)0.0820 (3)
Br20.3576 (11)0.3728 (8)0.5774 (7)0.0897 (12)0.60
O11.2712 (11)1.617 (5)0.377 (3)0.087 (5)0.60
Br2'0.3469 (17)0.3886 (13)0.5953 (11)0.0897 (12)0.40
O1'1.2774 (16)1.629 (8)0.362 (6)0.087 (5)0.40
O21.1233 (5)1.6134 (5)0.2571 (5)0.0925 (18)
O30.6296 (19)0.892 (3)0.631 (3)0.087 (6)0.60
O3'0.597 (3)0.879 (5)0.636 (5)0.087 (6)0.40
O40.7686 (6)0.8797 (5)0.7350 (5)0.0960 (19)
O51.1945 (5)1.7751 (5)0.2083 (4)0.0920 (18)
H5A1.16401.71930.21180.138*
H5B1.25801.77640.20980.138*
O60.5911 (5)1.0804 (5)0.6688 (4)0.0845 (16)
H6A0.61771.03370.66200.127*
H6B0.55421.07000.61410.127*
O70.9162 (5)1.0824 (5)0.7940 (4)0.0891 (17)
H7A0.88201.12260.79030.134*
H7B0.86551.02640.78290.134*
O80.4664 (5)0.8127 (5)0.4431 (4)0.0823 (15)
H8A0.49770.82160.49830.124*
H8B0.40860.76180.39920.124*
O90.051 (3)0.206 (3)0.012 (2)0.107 (9)0.25
H9B0.07690.22580.04610.160*0.25
H9A0.07450.24300.03690.160*0.25
O100.9611 (10)1.5048 (9)0.0723 (7)0.087 (3)0.50
H10A0.89761.45620.05200.130*0.50
H10B1.01681.50630.11310.130*0.50
O111.1443 (9)1.7210 (8)0.0139 (7)0.075 (3)0.50
H11A1.18591.77200.06620.112*0.50
H11B1.08491.67860.00980.112*0.50
O120.8335 (7)0.9090 (9)0.9234 (6)0.065 (3)0.50
H12A0.81950.95750.91190.097*0.50
H12B0.80370.85620.87190.097*0.50
O131.0171 (17)1.8620 (16)0.0149 (10)0.121 (6)0.50
H13A1.00121.90480.00500.182*0.50
H13B1.04401.87170.07060.182*0.50
O140.097 (2)0.339 (3)0.031 (2)0.136 (12)0.25
H14A0.07000.36880.00430.204*0.25
H14B0.05350.33420.08160.204*0.25
C10.8918 (6)1.0293 (6)0.1990 (5)0.0642 (18)
H10.93200.98970.21850.077*
C20.9512 (7)1.1167 (7)0.1878 (6)0.076 (2)
H21.02911.13480.19910.091*
C30.8929 (7)1.1769 (7)0.1595 (6)0.075 (2)
H30.93151.23640.15220.090*
C40.7765 (6)1.1478 (6)0.1424 (5)0.0627 (18)
C50.7082 (8)1.2060 (7)0.1135 (6)0.077 (2)
H50.74131.26250.10030.093*
C60.6007 (8)1.1811 (7)0.1055 (6)0.077 (2)
H60.56151.22330.09060.092*
C70.5417 (7)1.0906 (6)0.1190 (5)0.0653 (19)
C80.4278 (7)1.0608 (7)0.1102 (6)0.075 (2)
H80.38471.10000.09470.090*
C90.3798 (7)0.9734 (7)0.1246 (6)0.078 (2)
H90.30440.95400.12060.094*
C100.4431 (6)0.9139 (6)0.1450 (5)0.0664 (19)
H100.40790.85290.15190.080*
C110.6028 (6)1.0283 (6)0.1431 (4)0.0541 (16)
C120.7218 (6)1.0589 (6)0.1556 (4)0.0538 (16)
C131.1649 (7)1.5866 (7)0.3201 (6)0.070 (2)
C141.0849 (6)1.5085 (6)0.3391 (5)0.0595 (17)
C150.9672 (7)1.4864 (6)0.3041 (6)0.071 (2)
H150.93741.51670.26480.085*
C160.8927 (7)1.4199 (6)0.3264 (6)0.070 (2)
H160.81441.40850.30520.084*
C170.9367 (7)1.3716 (6)0.3801 (5)0.0625 (18)
C181.0531 (7)1.3907 (6)0.4151 (6)0.071 (2)
H181.08181.35750.45180.085*
C191.1268 (6)1.4602 (7)0.3946 (5)0.070 (2)
H191.20571.47440.41880.084*
C210.4868 (6)0.7190 (6)0.2371 (5)0.0628 (18)
H210.52780.76750.30100.075*
C220.3804 (7)0.6374 (7)0.2098 (6)0.073 (2)
H220.35190.63180.25480.088*
C230.3192 (8)0.5664 (7)0.1168 (7)0.082 (2)
H230.24710.51280.09690.098*
C240.3663 (7)0.5747 (6)0.0502 (6)0.071 (2)
C250.3092 (8)0.5004 (7)0.0495 (7)0.088 (3)
H250.23620.44640.07270.105*
C260.3592 (9)0.5079 (7)0.1090 (6)0.087 (3)
H260.32130.45860.17270.104*
C270.4715 (7)0.5915 (6)0.0753 (5)0.070 (2)
C280.5267 (9)0.6002 (8)0.1358 (6)0.084 (2)
H280.49320.55030.19930.100*
C290.6320 (9)0.6848 (8)0.0987 (6)0.082 (3)
H290.67180.69150.13670.098*
C300.6785 (7)0.7599 (7)0.0047 (5)0.069 (2)
H300.74820.81830.01870.083*
C310.5244 (7)0.6672 (6)0.0182 (5)0.0612 (18)
C320.4730 (6)0.6576 (6)0.0832 (5)0.0611 (17)
C330.6651 (8)0.8397 (7)0.6753 (6)0.079 (2)
C340.5895 (7)0.7272 (6)0.6533 (5)0.0666 (19)
C350.4714 (7)0.6959 (7)0.6280 (6)0.078 (2)
H350.43760.74500.62340.094*
C360.4020 (7)0.5930 (7)0.6092 (6)0.078 (2)
H360.32330.57450.59500.093*
C370.4492 (7)0.5199 (6)0.6117 (5)0.070 (2)
C380.5672 (8)0.5469 (7)0.6357 (6)0.073 (2)
H380.59940.49610.63710.088*
C390.6360 (7)0.6512 (7)0.6575 (6)0.076 (2)
H390.71550.67060.67550.091*
C410.8658 (6)0.7683 (6)0.2270 (5)0.0643 (18)
H410.84960.74880.16290.077*
C420.9437 (7)0.7362 (6)0.2782 (6)0.070 (2)
H420.98000.69710.24890.084*
C430.9662 (7)0.7622 (6)0.3703 (6)0.071 (2)
H431.01580.73820.40390.086*
C440.9159 (6)0.8252 (6)0.4169 (5)0.0628 (18)
C450.9371 (7)0.8596 (7)0.5155 (6)0.076 (2)
H450.98540.83740.55250.091*
C460.8895 (7)0.9221 (7)0.5550 (6)0.075 (2)
H460.90570.94290.61930.091*
C470.8146 (6)0.9586 (6)0.5024 (5)0.0597 (17)
C480.7702 (7)1.0302 (7)0.5428 (6)0.071 (2)
H480.78601.05560.60720.085*
C490.7014 (7)1.0631 (7)0.4847 (6)0.072 (2)
H490.67271.11300.51060.087*
C500.6757 (6)1.0222 (6)0.3889 (5)0.0633 (18)
H500.62811.04430.35110.076*
C510.7871 (6)0.9222 (5)0.4041 (5)0.0561 (16)
C520.8387 (6)0.8548 (5)0.3610 (5)0.0523 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0597 (5)0.0667 (5)0.0523 (5)0.0308 (4)0.0242 (4)0.0325 (4)
N10.066 (4)0.066 (4)0.052 (3)0.035 (3)0.025 (3)0.029 (3)
N20.065 (4)0.073 (4)0.053 (3)0.034 (3)0.026 (3)0.038 (3)
N30.068 (4)0.064 (4)0.053 (3)0.032 (3)0.029 (3)0.029 (3)
N40.066 (4)0.076 (4)0.052 (3)0.039 (3)0.027 (3)0.033 (3)
N50.059 (3)0.065 (4)0.057 (3)0.026 (3)0.026 (3)0.033 (3)
N60.059 (3)0.063 (3)0.058 (3)0.030 (3)0.032 (3)0.035 (3)
Br10.0786 (6)0.0848 (6)0.0949 (6)0.0271 (5)0.0398 (5)0.0536 (5)
Br20.110 (2)0.070 (3)0.081 (3)0.0233 (16)0.0395 (18)0.032 (2)
O10.067 (4)0.106 (13)0.103 (16)0.018 (5)0.035 (5)0.075 (7)
Br2'0.110 (2)0.070 (3)0.081 (3)0.0233 (16)0.0395 (18)0.032 (2)
O1'0.067 (4)0.106 (13)0.103 (16)0.018 (5)0.035 (5)0.075 (7)
O20.079 (4)0.106 (5)0.112 (5)0.034 (3)0.039 (4)0.073 (4)
O30.093 (14)0.070 (10)0.085 (6)0.015 (14)0.020 (12)0.048 (5)
O3'0.093 (14)0.070 (10)0.085 (6)0.015 (14)0.020 (12)0.048 (5)
O40.082 (4)0.096 (5)0.093 (4)0.022 (4)0.020 (4)0.047 (4)
O50.095 (4)0.093 (4)0.109 (5)0.044 (4)0.042 (4)0.064 (4)
O60.084 (4)0.096 (4)0.087 (4)0.042 (3)0.039 (3)0.046 (3)
O70.079 (4)0.102 (5)0.104 (4)0.042 (3)0.041 (3)0.058 (4)
O80.088 (4)0.082 (4)0.076 (4)0.035 (3)0.027 (3)0.038 (3)
O90.11 (2)0.13 (3)0.10 (2)0.07 (2)0.035 (18)0.07 (2)
O100.073 (7)0.078 (7)0.063 (6)0.005 (6)0.006 (5)0.017 (6)
O110.087 (7)0.071 (7)0.060 (6)0.012 (6)0.032 (5)0.033 (5)
O120.056 (5)0.105 (8)0.055 (5)0.037 (5)0.030 (5)0.049 (6)
O130.169 (17)0.150 (16)0.066 (8)0.092 (14)0.039 (10)0.058 (11)
O140.063 (16)0.13 (3)0.13 (2)0.008 (16)0.029 (16)0.00 (2)
C10.059 (4)0.084 (5)0.065 (4)0.039 (4)0.032 (4)0.035 (4)
C20.062 (5)0.089 (6)0.081 (5)0.021 (4)0.042 (4)0.038 (5)
C30.081 (6)0.074 (5)0.089 (6)0.032 (4)0.047 (5)0.047 (5)
C40.069 (5)0.074 (5)0.059 (4)0.035 (4)0.028 (4)0.038 (4)
C50.099 (7)0.081 (6)0.082 (5)0.047 (5)0.045 (5)0.054 (5)
C60.092 (6)0.083 (6)0.081 (5)0.048 (5)0.037 (5)0.052 (5)
C70.077 (5)0.077 (5)0.060 (4)0.048 (4)0.030 (4)0.035 (4)
C80.063 (5)0.087 (6)0.086 (6)0.043 (4)0.026 (4)0.044 (5)
C90.062 (5)0.101 (7)0.094 (6)0.057 (5)0.037 (4)0.043 (5)
C100.058 (4)0.078 (5)0.075 (5)0.034 (4)0.030 (4)0.039 (4)
C110.061 (4)0.071 (4)0.045 (3)0.038 (4)0.022 (3)0.031 (3)
C120.064 (4)0.065 (4)0.044 (3)0.033 (3)0.023 (3)0.030 (3)
C130.066 (5)0.074 (5)0.080 (5)0.027 (4)0.035 (4)0.041 (5)
C140.059 (4)0.058 (4)0.064 (4)0.026 (3)0.024 (3)0.028 (4)
C150.065 (5)0.072 (5)0.079 (5)0.030 (4)0.020 (4)0.041 (4)
C160.062 (5)0.071 (5)0.089 (5)0.030 (4)0.034 (4)0.043 (5)
C170.069 (5)0.060 (4)0.058 (4)0.026 (4)0.022 (4)0.028 (4)
C180.071 (5)0.072 (5)0.076 (5)0.032 (4)0.025 (4)0.041 (4)
C190.051 (4)0.085 (5)0.072 (5)0.022 (4)0.022 (4)0.039 (4)
C210.070 (5)0.070 (5)0.069 (4)0.034 (4)0.040 (4)0.037 (4)
C220.082 (6)0.074 (5)0.078 (5)0.031 (4)0.046 (5)0.037 (5)
C230.076 (6)0.071 (5)0.104 (7)0.025 (4)0.045 (5)0.039 (5)
C240.069 (5)0.062 (5)0.075 (5)0.027 (4)0.025 (4)0.025 (4)
C250.087 (6)0.071 (6)0.080 (6)0.021 (5)0.022 (5)0.021 (5)
C260.103 (7)0.071 (6)0.052 (4)0.034 (5)0.007 (5)0.009 (4)
C270.081 (5)0.068 (5)0.048 (4)0.030 (4)0.018 (4)0.016 (4)
C280.108 (7)0.086 (6)0.056 (5)0.051 (6)0.028 (5)0.025 (5)
C290.115 (8)0.102 (7)0.059 (5)0.063 (6)0.050 (5)0.041 (5)
C300.077 (5)0.089 (6)0.057 (4)0.040 (4)0.033 (4)0.038 (4)
C310.069 (5)0.073 (5)0.062 (4)0.044 (4)0.029 (4)0.038 (4)
C320.065 (4)0.067 (5)0.060 (4)0.033 (4)0.025 (4)0.033 (4)
C330.093 (6)0.078 (6)0.070 (5)0.031 (5)0.032 (5)0.040 (5)
C340.078 (5)0.072 (5)0.061 (4)0.036 (4)0.028 (4)0.037 (4)
C350.075 (5)0.080 (6)0.086 (6)0.038 (5)0.028 (5)0.041 (5)
C360.064 (5)0.096 (6)0.083 (5)0.037 (5)0.030 (4)0.047 (5)
C370.086 (6)0.065 (5)0.060 (4)0.027 (4)0.029 (4)0.032 (4)
C380.088 (6)0.078 (6)0.071 (5)0.040 (5)0.037 (4)0.042 (4)
C390.072 (5)0.096 (6)0.082 (5)0.043 (5)0.039 (4)0.050 (5)
C410.068 (5)0.068 (5)0.065 (4)0.032 (4)0.034 (4)0.030 (4)
C420.065 (5)0.069 (5)0.099 (6)0.040 (4)0.039 (4)0.046 (5)
C430.067 (5)0.066 (5)0.089 (6)0.031 (4)0.024 (4)0.045 (5)
C440.062 (4)0.059 (4)0.073 (5)0.022 (4)0.023 (4)0.040 (4)
C450.066 (5)0.087 (6)0.073 (5)0.027 (4)0.014 (4)0.050 (5)
C460.069 (5)0.096 (6)0.054 (4)0.024 (5)0.017 (4)0.038 (4)
C470.055 (4)0.069 (5)0.054 (4)0.017 (3)0.020 (3)0.032 (4)
C480.072 (5)0.081 (5)0.061 (4)0.028 (4)0.035 (4)0.026 (4)
C490.076 (5)0.076 (5)0.068 (5)0.030 (4)0.041 (4)0.023 (4)
C500.062 (4)0.076 (5)0.064 (4)0.035 (4)0.032 (4)0.033 (4)
C510.059 (4)0.055 (4)0.057 (4)0.022 (3)0.022 (3)0.031 (3)
C520.054 (4)0.050 (4)0.058 (4)0.019 (3)0.021 (3)0.031 (3)
Geometric parameters (Å, º) top
Zn1—N12.126 (6)C9—C101.378 (10)
Zn1—N52.159 (6)C9—H90.9300
Zn1—N62.160 (5)C10—H100.9300
Zn1—N32.175 (6)C11—C121.436 (9)
Zn1—N22.195 (5)C13—C141.495 (10)
Zn1—N42.199 (6)C14—C191.376 (10)
N1—C11.352 (9)C14—C151.384 (10)
N1—C121.370 (8)C15—C161.389 (10)
N2—C101.323 (9)C15—H150.9300
N2—C111.356 (8)C16—C171.364 (10)
N3—C211.321 (8)C16—H160.9300
N3—C321.365 (9)C17—C181.377 (10)
N4—C301.328 (9)C18—C191.388 (10)
N4—C311.354 (9)C18—H180.9300
N5—C411.342 (9)C19—H190.9300
N5—C521.361 (8)C21—C221.396 (10)
N6—C501.330 (9)C21—H210.9300
N6—C511.358 (8)C22—C231.356 (12)
Br1—C171.903 (7)C22—H220.9300
Br2—C371.920 (13)C23—C241.417 (11)
O1—C131.286 (15)C23—H230.9300
Br2'—C371.878 (19)C24—C321.388 (11)
O1'—C131.297 (19)C24—C251.445 (11)
O2—C131.235 (9)C25—C261.335 (12)
O3—C331.279 (15)C25—H250.9300
O3'—C331.293 (19)C26—C271.441 (12)
O4—C331.255 (10)C26—H260.9300
O5—H5A0.8200C27—C311.378 (10)
O5—H5B0.8200C27—C281.399 (12)
O6—H6A0.8200C28—C291.377 (13)
O6—H6B0.8202C28—H280.9300
O7—H7A0.8194C29—C301.386 (11)
O7—H7B0.8200C29—H290.9300
O8—H8A0.8202C30—H300.9300
O8—H8B0.8200C31—C321.434 (10)
O9—O13i1.11 (3)C33—C341.507 (11)
O9—H9B0.8199C34—C351.382 (11)
O9—H9A0.8100C34—C391.385 (10)
O10—H10A0.8200C35—C361.386 (12)
O10—H10B0.8198C35—H350.9300
O11—H11A0.8200C36—C371.347 (11)
O11—H11B0.8201C36—H360.9300
O12—H12A0.8200C37—C381.389 (11)
O12—H12B0.8200C38—C391.386 (11)
O13—O9i1.11 (3)C38—H380.9300
O13—H13A0.8200C39—H390.9300
O13—H13B0.8201C41—C421.389 (10)
O14—H9A1.2839C41—H410.9300
O14—H14A0.8200C42—C431.341 (11)
O14—H14B0.8200C42—H420.9300
C1—C21.384 (10)C43—C441.408 (11)
C1—H10.9300C43—H430.9300
C2—C31.384 (11)C44—C521.397 (9)
C2—H20.9300C44—C451.434 (11)
C3—C41.386 (10)C45—C461.324 (12)
C3—H30.9300C45—H450.9300
C4—C121.398 (9)C46—C471.422 (10)
C4—C51.448 (10)C46—H460.9300
C5—C61.315 (11)C47—C481.383 (10)
C5—H50.9300C47—C511.412 (9)
C6—C71.438 (11)C48—C491.389 (11)
C6—H60.9300C48—H480.9300
C7—C81.389 (10)C49—C501.375 (10)
C7—C111.410 (9)C49—H490.9300
C8—C91.365 (11)C50—H500.9300
C8—H80.9300C51—C521.434 (9)
N1—Zn1—N597.8 (2)C17—C18—H18120.5
N1—Zn1—N697.9 (2)C19—C18—H18120.5
N5—Zn1—N677.1 (2)C14—C19—C18121.0 (7)
N1—Zn1—N3163.1 (2)C14—C19—H19119.5
N5—Zn1—N396.8 (2)C18—C19—H19119.5
N6—Zn1—N393.7 (2)N3—C21—C22123.2 (7)
N1—Zn1—N277.8 (2)N3—C21—H21118.4
N5—Zn1—N2168.7 (2)C22—C21—H21118.4
N6—Zn1—N293.2 (2)C23—C22—C21119.1 (7)
N3—Zn1—N289.4 (2)C23—C22—H22120.4
N1—Zn1—N493.5 (2)C21—C22—H22120.4
N5—Zn1—N495.9 (2)C22—C23—C24119.3 (8)
N6—Zn1—N4167.3 (2)C22—C23—H23120.4
N3—Zn1—N476.5 (2)C24—C23—H23120.4
N2—Zn1—N494.7 (2)C32—C24—C23118.0 (8)
C1—N1—C12117.1 (6)C32—C24—C25118.9 (8)
C1—N1—Zn1128.1 (5)C23—C24—C25123.1 (8)
C12—N1—Zn1114.8 (5)C26—C25—C24121.1 (8)
C10—N2—C11118.9 (6)C26—C25—H25119.4
C10—N2—Zn1129.4 (5)C24—C25—H25119.4
C11—N2—Zn1111.6 (4)C25—C26—C27120.7 (8)
C21—N3—C32118.3 (6)C25—C26—H26119.7
C21—N3—Zn1128.2 (5)C27—C26—H26119.7
C32—N3—Zn1112.5 (4)C31—C27—C28119.0 (8)
C30—N4—C31118.7 (6)C31—C27—C26119.2 (8)
C30—N4—Zn1128.0 (5)C28—C27—C26121.8 (8)
C31—N4—Zn1112.8 (4)C29—C28—C27118.1 (8)
C41—N5—C52117.9 (6)C29—C28—H28121.0
C41—N5—Zn1128.6 (5)C27—C28—H28121.0
C52—N5—Zn1113.1 (4)C28—C29—C30119.9 (8)
C50—N6—C51118.1 (6)C28—C29—H29120.1
C50—N6—Zn1128.7 (4)C30—C29—H29120.1
C51—N6—Zn1113.0 (4)N4—C30—C29122.1 (8)
H5A—O5—H5B105.1N4—C30—H30119.0
H6A—O6—H6B103.7C29—C30—H30119.0
H7A—O7—H7B103.8N4—C31—C27122.2 (7)
H8A—O8—H8B128.4N4—C31—C32117.4 (7)
O13i—O9—H9B85.2C27—C31—C32120.4 (7)
O13i—O9—H9A149.8N3—C32—C24122.0 (7)
H9B—O9—H9A123.1N3—C32—C31118.4 (7)
H10A—O10—H10B118.5C24—C32—C31119.5 (7)
H11A—O11—H11B116.6O4—C33—O3119.2 (16)
H12A—O12—H12B105.8O4—C33—O3'134 (3)
O9i—O13—H13A121.3O4—C33—C34118.4 (7)
O9i—O13—H13B80.3O3—C33—C34122.2 (18)
H13A—O13—H13B127.0O3'—C33—C34107 (2)
H9A—O14—H14A107.9C35—C34—C39117.5 (8)
H9A—O14—H14B107.7C35—C34—C33121.5 (7)
H14A—O14—H14B99.6C39—C34—C33121.0 (8)
N1—C1—C2123.2 (7)C34—C35—C36121.5 (8)
N1—C1—H1118.4C34—C35—H35119.2
C2—C1—H1118.4C36—C35—H35119.2
C1—C2—C3119.1 (7)C37—C36—C35119.7 (8)
C1—C2—H2120.5C37—C36—H36120.2
C3—C2—H2120.5C35—C36—H36120.2
C2—C3—C4119.4 (7)C36—C37—C38121.1 (8)
C2—C3—H3120.3C36—C37—Br2'114.4 (9)
C4—C3—H3120.3C38—C37—Br2'124.1 (8)
C3—C4—C12118.7 (6)C36—C37—Br2122.3 (7)
C3—C4—C5123.6 (7)C38—C37—Br2116.5 (7)
C12—C4—C5117.7 (7)C39—C38—C37118.5 (8)
C6—C5—C4121.7 (7)C39—C38—H38120.8
C6—C5—H5119.1C37—C38—H38120.8
C4—C5—H5119.1C34—C39—C38121.7 (8)
C5—C6—C7122.1 (7)C34—C39—H39119.2
C5—C6—H6118.9C38—C39—H39119.2
C7—C6—H6118.9N5—C41—C42122.3 (7)
C8—C7—C11117.7 (7)N5—C41—H41118.9
C8—C7—C6123.9 (7)C42—C41—H41118.9
C11—C7—C6118.3 (7)C43—C42—C41119.4 (7)
C9—C8—C7119.3 (7)C43—C42—H42120.3
C9—C8—H8120.3C41—C42—H42120.3
C7—C8—H8120.3C42—C43—C44121.0 (7)
C8—C9—C10120.0 (7)C42—C43—H43119.5
C8—C9—H9120.0C44—C43—H43119.5
C10—C9—H9120.0C52—C44—C43116.3 (7)
N2—C10—C9122.3 (7)C52—C44—C45118.5 (7)
N2—C10—H10118.8C43—C44—C45125.2 (7)
C9—C10—H10118.8C46—C45—C44121.6 (7)
N2—C11—C7121.7 (6)C46—C45—H45119.2
N2—C11—C12119.3 (6)C44—C45—H45119.2
C7—C11—C12119.1 (6)C45—C46—C47122.1 (7)
N1—C12—C4122.5 (6)C45—C46—H46118.9
N1—C12—C11116.6 (6)C47—C46—H46118.9
C4—C12—C11121.0 (6)C48—C47—C51118.3 (6)
O2—C13—O1130.0 (13)C48—C47—C46123.7 (7)
O2—C13—O1'114 (2)C51—C47—C46118.0 (7)
O2—C13—C14119.1 (7)C47—C48—C49118.4 (7)
O1—C13—C14110.9 (12)C47—C48—H48120.8
O1'—C13—C14127 (2)C49—C48—H48120.8
C19—C14—C15118.5 (7)C50—C49—C48120.2 (8)
C19—C14—C13121.1 (7)C50—C49—H49119.9
C15—C14—C13120.4 (6)C48—C49—H49119.9
C14—C15—C16121.4 (7)N6—C50—C49122.7 (7)
C14—C15—H15119.3N6—C50—H50118.7
C16—C15—H15119.3C49—C50—H50118.7
C17—C16—C15118.6 (7)N6—C51—C47122.2 (6)
C17—C16—H16120.7N6—C51—C52117.7 (6)
C15—C16—H16120.7C47—C51—C52120.1 (6)
C16—C17—C18121.5 (7)N5—C52—C44122.9 (7)
C16—C17—Br1118.9 (6)N5—C52—C51117.4 (5)
C18—C17—Br1119.6 (5)C44—C52—C51119.6 (6)
C17—C18—C19118.9 (7)
Symmetry code: (i) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O20.821.902.700 (11)164
O5—H5B···O6ii0.822.232.676 (11)114
O6—H6A···O30.821.972.763 (2)162
O6—H6A···O30.822.032.767 (5)150
O6—H6B···O8iii0.822.202.788 (5)129
O7—H7A···O5ii0.821.972.787 (10)176
O7—H7B···O40.821.892.687 (11)163
O8—H8A···O30.822.042.803 (2)155
O8—H8A···O30.821.992.789 (2)166
O8—H8B···O1iv0.822.192.862 (5)139
O8—H8B···O1iv0.821.962.685 (6)146
O10—H10A···O11v0.822.242.806 (2)126
O10—H10B···O20.822.112.739 (2)134
O11—H11A···O50.822.272.826 (5)126
O11—H11B···O10v0.822.332.806 (2)117
O12—H12A···O13ii0.822.502.981 (5)118
O12—H12B···O40.822.292.786 (2)119
O13—H13A···O12vi0.822.192.796 (5)131
O13—H13B···O7ii0.821.952.746 (2)165
Symmetry codes: (ii) x+2, y+3, z+1; (iii) x+1, y+2, z+1; (iv) x1, y1, z; (v) x+2, y+3, z; (vi) x, y+1, z1.

Experimental details

Crystal data
Chemical formula[Zn(C12H8N2)3](C7H4BrO2)2·6.5H2O
Mr1123.11
Crystal system, space groupTriclinic, P1
Temperature (K)290
a, b, c (Å)13.098 (3), 14.240 (3), 16.281 (3)
α, β, γ (°)108.68 (3), 107.13 (3), 105.11 (3)
V3)2528.9 (15)
Z2
Radiation typeMo Kα
µ (mm1)2.13
Crystal size (mm)0.28 × 0.20 × 0.19
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.603, 0.675
No. of measured, independent and
observed [I > 2σ(I)] reflections
19484, 8780, 5375
Rint0.039
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.250, 1.15
No. of reflections8780
No. of parameters667
No. of restraints9
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.80, 0.95

Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H5A···O20.821.902.700 (11)164
O5—H5B···O6i0.822.232.676 (11)114
O6—H6A···O30.821.972.763 (2)162
O6—H6A···O3'0.822.032.767 (5)150
O6—H6B···O8ii0.822.202.788 (5)129
O7—H7A···O5i0.821.972.787 (10)176
O7—H7B···O40.821.892.687 (11)163
O8—H8A···O30.822.042.803 (2)155
O8—H8A···O3'0.821.992.789 (2)166
O8—H8B···O1iii0.822.192.862 (5)139
O8—H8B···O1'iii0.821.962.685 (6)146
O10—H10A···O11iv0.822.242.806 (2)126
O10—H10B···O20.822.112.739 (2)134
O11—H11A···O50.822.272.826 (5)126
O11—H11B···O10iv0.822.332.806 (2)117
O12—H12A···O13i0.822.502.981 (5)118
O12—H12B···O40.822.292.786 (2)119
O13—H13A···O12v0.822.192.796 (5)131
O13—H13B···O7i0.821.952.746 (2)165
Symmetry codes: (i) x+2, y+3, z+1; (ii) x+1, y+2, z+1; (iii) x1, y1, z; (iv) x+2, y+3, z; (v) x, y+1, z1.
 

Acknowledgements

The authors gratefully acknowledge the financial support of the Education Office of Zhejiang Province (grant No. 20051316).

References

First citationAghabozorg, H., Nakhjavan, B., Zabihi, F., Ramezanipour, F. & Aghabozorg, H. R. (2005). Acta Cryst. E61, m2664–m2666.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationChen, H., Xu, X.-Y., Gao, J., Yang, X.-J., Lu, L.-D. & Wang, X. (2006). Huaxue Shiji, 28, 478–480.  CAS Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationLiu, C.-M., You, X.-Z. & Chen, W. (1998). J. Coord. Chem. 46, 233–243.  Web of Science CrossRef CAS Google Scholar
First citationRigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWei, Y., Yuan, C. & Yang, P. (2004). Acta Cryst. E60, m1686–m1688.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationWei, D.-Y., Zheng, Y.-Q. & Lin, J.-L. (2002). Z. Anorg. Allg. Chem. 628, 2005–2012.  CrossRef CAS Google Scholar

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