catena-Poly[[[diaqua­(1,10-phenanthroline-κ2N,N′)zinc]-μ-4,4′-bipyridine-κ2N:N′] dinitrate 4,4′-bipyridine hemisolvate monohydrate]

Xu, S.; Dai, Y.-C.; Qiu, Q.-M.; Jin, Q.-H.; Zhang, C.-L.

doi:10.1107/S1600536812036318

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1222-m1223

doi:10.1107/S1600536812036318

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catena-Poly[[[diaqua(1,10-phenanthroline-κ²N,N′)zinc]-μ-4,4′-bipyridine-κ²N:N′] dinitrate 4,4′-bipyridine hemisolvate monohydrate]

Shan Xu,^a Yong-Cheng Dai,^a Qi-Ming Qiu,^a Qiong-Hua Jin ^a ^* and Cun-Lin Zhang ^b

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China, and ^bKey Laboratory of Terahertz Optoelectronics, Ministry of Education, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: jinqh204@163.com

(Received 13 August 2012; accepted 20 August 2012; online 31 August 2012)

In the title compound, [Zn(C₁₀H₈N₂)(C₁₂H₈N₂)(H₂O)₂](NO₃)₂·0.5C₁₀H₈N₂·H₂O, the Zn^II atom is coordinated in a distorted octahedral geometry by two N atoms from two 4,4′-bipyridine (4,4′-bipy) ligands, two N atoms from a chelating 1,10-phenanthroline ligand and two O atoms from two mutually cis water molecules. The 4,4′-bipy ligands bridge the Zn^II atoms into a chain structure along [100]. The uncoordinated 4,4′-bipy molecule lies on an inversion center. O—H⋯O and O—H⋯N hydrogen bonds connect the cationic chains, the nitrate anions, the uncoordinated 4,4′-bipy molecules and the water molecules into tow-dimensional networks.

Related literature

For background to metal complexes of 1,10-phenanthroline and its derivatives in biological systems, see: Rama Krishna et al. (2000 ); Sastri et al. (2003 ). For related structures, see: Bai et al. (2009 ); Blake et al. (1998 ); Boag et al. (1999 ); Carlucci et al. (1997 ); Chen et al. (2006 ); Du & Li (2007 ); Ma et al. (2006 ); Xiong et al. (1999 ); Zhang et al. (2009 ); Zhang & Janiak (2001 ).

Experimental

Crystal data

[Zn(C₁₀H₈N₂)(C₁₂H₈N₂)(H₂O)₂](NO₃)₂·0.5C₁₀H₈N₂·H₂O
M_r = 657.94
Monoclinic, P 2₁ /c
a = 11.3910 (11) Å
b = 13.0561 (13) Å
c = 19.8509 (18) Å
β = 103.487 (1)°
V = 2870.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 298 K
0.35 × 0.31 × 0.18 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.739, T_max = 0.852
14110 measured reflections
5072 independent reflections
3309 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.132
S = 1.03
5072 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7C⋯O1ⁱ	0.85	1.89	2.737 (5)	180
O7—H7D⋯O6ⁱⁱ	0.85	1.93	2.782 (5)	180
O8—H8C⋯N5	0.85	1.89	2.724 (5)	169
O8—H8D⋯O3ⁱ	0.85	1.90	2.744 (6)	169
O9—H9C⋯O2ⁱⁱⁱ	0.85	2.24	3.091 (7)	176
O9—H9D⋯O4^iv	0.85	2.27	3.114 (8)	176
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; 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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812036318/hy2580sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036318/hy2580Isup2.hkl

checkCIF report

Comment top

1,10-Phenanthroline (phen) is a versatile ligand capable of forming highly stable complexes with transition metal ions (Bai et al., 2009; Blake et al., 1998; Chen et al., 2006; Du & Li, 2007; Ma et al., 2006; Zhang et al., 2009; Zhang & Janiak, 2001). Metal complexes of 1,10-phenanthroline and its derivatives are interesting because they play an important role in biological systems, for example, some can recognize DNA and some can induce apoptosis in human cancer cells (Rama Krishna et al., 2000; Sastri et al., 2003). 4,4'-Bipyridine (4,4'-bipy) can act as a Lewis base. It can also be cocrystallized with hydrogen donors such as alcohols or transition metal complexes to form macromolecular arrays as bidentate ligands (Blake et al., 1998; Boag et al., 1999; Carlucci et al., 1997; Du & Li, 2007; Xiong et al., 1999). Here we report the structure of the title compound, a new zinc(II) complex with phen and 4,4'-bipy ligands.

In the title complex (Fig. 1), the Zn^II atom adopts a six-coordinated distorted octahedral geometry, where the donor atoms are two N atoms from a chelating phen ligand, two N atoms from two 4,4'-bipy ligands and two O atoms from two water molecules. The 4,4'-bipy ligands bridge the Zn^II atoms into a chain structure along [100] (Fig. 2). Two nitrate anions, half of a 4,4'-bipy molecule and a water molecule in the asymmetric unit are involved in the formation of O—H···O and O—H···N hydrogen bonds (Table 1). Compared with the similar comlpexes reported in literature (Bai et al., 2009; Blake et al., 1998; Du & Li, 2007), the Zn—N distances are longer, the Zn—O distances are shorter, and the N—Zn—N bite angles are smaller. The O—Zn—O bite angle is smaller than those in the reported zinc complexes (Bai et al., 2009).

Related literature top

For background to metal complexes of 1,10-phenanthroline and its derivatives in biological systems, see: Rama Krishna et al. (2000); Sastri et al. (2003). For related structures, see: Bai et al. (2009); Blake et al. (1998); Boag et al. (1999); Carlucci et al. (1997); Chen et al. (2006); Du & Li (2007); Ma et al. (2006); Xiong et al. (1999); Zhang et al. (2009); Zhang & Janiak (2001).

Experimental top

Zn(NO₃)₂ (0.2 mmol) was dissolved in 5 ml water and a hot methanolic solution (5 ml) of 4,4'-bipyridine (0.2 mmol) was added to the solution. After the mixture was stirred for 10 min, 1,10-phenanthroline (0.4 mmol) was added. The resulting solution was refluxed for 30 min and then allowed to cool to ambient temperature. The filtrate was evaporated slowly at room temperature for several weeks to yield yellow crystalline products.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 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) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) 1+x, y, z; (ii) 1-x, 2-y, -z.]
	Fig. 2. A view of the chain structure and hydrogen bonding interactions (dashed lines).

catena-Poly[[[diaqua(1,10-phenanthroline-κ²N,N')zinc]- µ-4,4'-bipyridine-κ²N:N'] dinitrate 4,4'-bipyridine hemisolvate monohydrate] top

Crystal data top

[Zn(C₁₀H₈N₂)(C₁₂H₈N₂)(H₂O)₂](NO₃)₂·0.5C₁₀H₈N₂·H₂O	F(000) = 1356
M_r = 657.94	D_x = 1.522 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3365 reflections
a = 11.3910 (11) Å	θ = 2.4–22.8°
b = 13.0561 (13) Å	µ = 0.92 mm⁻¹
c = 19.8509 (18) Å	T = 298 K
β = 103.487 (1)°	Block, yellow
V = 2870.9 (5) Å³	0.35 × 0.31 × 0.18 mm
Z = 4

Data collection top

Bruker APEX CCD diffractometer	5072 independent reflections
Radiation source: fine-focus sealed tube	3309 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
T_min = 0.739, T_max = 0.852	k = −15→10
14110 measured reflections	l = −22→23

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0523P)² + 3.4384P] where P = (F_o² + 2F_c²)/3
5072 reflections	(Δ/σ)_max = 0.001
397 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Zn(C₁₀H₈N₂)(C₁₂H₈N₂)(H₂O)₂](NO₃)₂·0.5C₁₀H₈N₂·H₂O	V = 2870.9 (5) Å³
M_r = 657.94	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.3910 (11) Å	µ = 0.92 mm⁻¹
b = 13.0561 (13) Å	T = 298 K
c = 19.8509 (18) Å	0.35 × 0.31 × 0.18 mm
β = 103.487 (1)°

Data collection top

Bruker APEX CCD diffractometer	5072 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3309 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.852	R_int = 0.045
14110 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.03	Δρ_max = 0.81 e Å⁻³
5072 reflections	Δρ_min = −0.42 e Å⁻³
397 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	0.79800 (4)	0.79895 (4)	0.38707 (2)	0.03238 (17)
N1	0.8386 (3)	0.7200 (3)	0.48637 (17)	0.0397 (9)
N2	0.7735 (3)	0.6396 (3)	0.35719 (18)	0.0373 (8)
N3	−0.0104 (3)	0.7983 (3)	0.38878 (17)	0.0363 (8)
N4	0.6095 (3)	0.8140 (3)	0.38381 (17)	0.0337 (8)
N5	0.6004 (4)	0.9079 (4)	0.1717 (2)	0.0576 (11)
N6	1.0006 (4)	0.0462 (4)	0.3071 (3)	0.0659 (13)
N7	0.3949 (6)	0.6227 (5)	0.1489 (3)	0.0878 (16)
O1	0.9895 (4)	0.0465 (3)	0.3673 (2)	0.0837 (13)
O2	1.0852 (4)	0.0946 (4)	0.2944 (3)	0.1126 (17)
O3	0.9290 (5)	0.0019 (4)	0.2633 (2)	0.120 (2)
O4	0.4873 (5)	0.6379 (5)	0.1878 (3)	0.147 (3)
O5	0.2995 (7)	0.6575 (6)	0.1641 (4)	0.183 (3)
O6	0.3835 (4)	0.5724 (3)	0.0954 (2)	0.0823 (13)
O7	0.8234 (2)	0.9520 (2)	0.42605 (15)	0.0448 (8)
H7C	0.8747	0.9816	0.4078	0.054*
H7D	0.7603	0.9890	0.4194	0.054*
O8	0.7743 (2)	0.8506 (2)	0.28439 (14)	0.0476 (8)
H8C	0.7144	0.8618	0.2507	0.057*
H8D	0.8287	0.8944	0.2826	0.057*
O9	0.3302 (5)	0.0820 (4)	0.4013 (2)	0.1229 (18)
H9C	0.2611	0.0847	0.3736	0.148*
H9D	0.3830	0.0968	0.3789	0.148*
C1	0.8733 (4)	0.7593 (4)	0.5490 (2)	0.0553 (13)
H1	0.8777	0.8301	0.5541	0.066*
C2	0.9036 (5)	0.6974 (6)	0.6082 (3)	0.0771 (18)
H2	0.9285	0.7271	0.6518	0.093*
C3	0.8967 (5)	0.5944 (6)	0.6017 (3)	0.0782 (18)
H3	0.9166	0.5530	0.6409	0.094*
C4	0.8602 (4)	0.5505 (5)	0.5369 (3)	0.0611 (14)
C5	0.8325 (4)	0.6162 (4)	0.4794 (2)	0.0423 (11)
C6	0.7960 (4)	0.5739 (4)	0.4114 (2)	0.0424 (11)
C7	0.7839 (4)	0.4668 (4)	0.4024 (3)	0.0593 (14)
C8	0.7443 (6)	0.4308 (5)	0.3349 (3)	0.0785 (18)
H8	0.7346	0.3608	0.3266	0.094*
C9	0.7204 (6)	0.4973 (5)	0.2817 (3)	0.0773 (17)
H9	0.6925	0.4737	0.2366	0.093*
C10	0.7374 (4)	0.6014 (4)	0.2944 (3)	0.0510 (12)
H10	0.7226	0.6461	0.2569	0.061*
C11	0.8484 (5)	0.4422 (5)	0.5253 (4)	0.0796 (18)
H11	0.8674	0.3981	0.5630	0.096*
C12	0.8109 (6)	0.4029 (5)	0.4618 (4)	0.0801 (18)
H12	0.8023	0.3323	0.4564	0.096*
C13	0.0304 (4)	0.7574 (4)	0.3374 (2)	0.0434 (11)
H13	−0.0247	0.7248	0.3019	0.052*
C14	0.1494 (4)	0.7604 (4)	0.3336 (2)	0.0442 (11)
H14	0.1729	0.7300	0.2965	0.053*
C15	0.2337 (3)	0.8084 (3)	0.3850 (2)	0.0315 (9)
C16	0.1911 (3)	0.8501 (4)	0.4388 (2)	0.0426 (11)
H16	0.2441	0.8832	0.4750	0.051*
C17	0.0713 (4)	0.8429 (4)	0.4390 (2)	0.0428 (11)
H17	0.0457	0.8708	0.4762	0.051*
C18	0.5701 (3)	0.8456 (3)	0.4383 (2)	0.0366 (10)
H18	0.6270	0.8680	0.4770	0.044*
C19	0.4508 (3)	0.8473 (3)	0.4409 (2)	0.0350 (10)
H19	0.4284	0.8705	0.4804	0.042*
C20	0.3639 (3)	0.8139 (3)	0.3839 (2)	0.0308 (9)
C21	0.4049 (3)	0.7837 (3)	0.3263 (2)	0.0360 (10)
H21	0.3501	0.7623	0.2864	0.043*
C22	0.5252 (3)	0.7853 (3)	0.3281 (2)	0.0358 (10)
H22	0.5499	0.7655	0.2886	0.043*
C23	0.5748 (6)	1.0034 (5)	0.1576 (3)	0.087 (2)
H23	0.5841	1.0487	0.1946	0.105*
C24	0.5350 (6)	1.0426 (4)	0.0921 (3)	0.082 (2)
H24	0.5182	1.1122	0.0860	0.098*
C25	0.5200 (4)	0.9801 (3)	0.0361 (2)	0.0395 (10)
C26	0.5451 (6)	0.8796 (4)	0.0508 (3)	0.0810 (19)
H26	0.5353	0.8320	0.0151	0.097*
C27	0.5849 (6)	0.8484 (5)	0.1182 (3)	0.086 (2)
H27	0.6020	0.7792	0.1261	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0222 (2)	0.0411 (3)	0.0338 (3)	0.0005 (2)	0.00634 (18)	0.0014 (2)
N1	0.0302 (18)	0.053 (3)	0.035 (2)	0.0011 (17)	0.0064 (15)	0.0012 (18)
N2	0.0286 (18)	0.039 (2)	0.044 (2)	0.0014 (16)	0.0082 (15)	−0.0020 (19)
N3	0.0218 (16)	0.050 (2)	0.0361 (19)	0.0012 (16)	0.0058 (15)	0.0011 (18)
N4	0.0244 (17)	0.042 (2)	0.0363 (19)	0.0003 (15)	0.0103 (15)	0.0024 (16)
N5	0.059 (3)	0.061 (3)	0.046 (3)	0.001 (2)	−0.001 (2)	0.009 (2)
N6	0.067 (3)	0.067 (3)	0.068 (3)	−0.014 (3)	0.024 (3)	0.014 (3)
N7	0.095 (5)	0.088 (4)	0.081 (4)	−0.027 (4)	0.022 (4)	−0.007 (4)
O1	0.085 (3)	0.093 (3)	0.078 (3)	−0.041 (2)	0.027 (2)	0.001 (2)
O2	0.106 (4)	0.127 (4)	0.118 (4)	−0.047 (3)	0.052 (3)	0.014 (3)
O3	0.137 (4)	0.156 (5)	0.063 (3)	−0.090 (4)	0.015 (3)	−0.010 (3)
O4	0.119 (4)	0.205 (7)	0.092 (4)	−0.058 (4)	−0.026 (3)	−0.014 (4)
O5	0.163 (7)	0.150 (6)	0.252 (9)	−0.036 (5)	0.081 (6)	−0.076 (6)
O6	0.100 (3)	0.084 (3)	0.068 (3)	−0.027 (2)	0.031 (2)	−0.027 (2)
O7	0.0361 (16)	0.0462 (19)	0.0530 (19)	−0.0017 (14)	0.0124 (14)	−0.0019 (16)
O8	0.0310 (16)	0.071 (2)	0.0373 (17)	−0.0045 (15)	0.0010 (13)	0.0162 (16)
O9	0.142 (5)	0.132 (5)	0.089 (4)	0.002 (4)	0.014 (3)	−0.008 (3)
C1	0.053 (3)	0.070 (4)	0.041 (3)	−0.004 (3)	0.007 (2)	−0.005 (3)
C2	0.084 (4)	0.112 (6)	0.030 (3)	0.008 (4)	0.002 (3)	0.005 (3)
C3	0.088 (5)	0.093 (5)	0.051 (4)	0.012 (4)	0.010 (3)	0.030 (4)
C4	0.056 (3)	0.073 (4)	0.054 (3)	0.011 (3)	0.012 (3)	0.023 (3)
C5	0.032 (2)	0.048 (3)	0.047 (3)	0.006 (2)	0.010 (2)	0.011 (2)
C6	0.029 (2)	0.046 (3)	0.052 (3)	0.005 (2)	0.009 (2)	0.000 (2)
C7	0.056 (3)	0.044 (3)	0.079 (4)	0.003 (2)	0.018 (3)	0.008 (3)
C8	0.103 (5)	0.042 (4)	0.086 (5)	−0.008 (3)	0.014 (4)	−0.015 (3)
C9	0.106 (5)	0.054 (4)	0.067 (4)	−0.010 (3)	0.010 (3)	−0.013 (3)
C10	0.053 (3)	0.049 (3)	0.049 (3)	−0.002 (2)	0.007 (2)	−0.004 (3)
C11	0.085 (4)	0.067 (4)	0.087 (5)	0.022 (3)	0.019 (4)	0.044 (4)
C12	0.099 (5)	0.049 (4)	0.091 (5)	0.008 (3)	0.020 (4)	0.023 (4)
C13	0.028 (2)	0.061 (3)	0.039 (2)	−0.005 (2)	0.0034 (19)	−0.009 (2)
C14	0.029 (2)	0.065 (3)	0.041 (3)	−0.002 (2)	0.0120 (19)	−0.010 (2)
C15	0.0221 (19)	0.035 (2)	0.037 (2)	0.0014 (18)	0.0067 (17)	0.004 (2)
C16	0.024 (2)	0.059 (3)	0.043 (3)	0.000 (2)	0.0042 (19)	−0.012 (2)
C17	0.030 (2)	0.063 (3)	0.037 (2)	0.003 (2)	0.0095 (19)	−0.009 (2)
C18	0.027 (2)	0.047 (3)	0.034 (2)	−0.0030 (19)	0.0032 (18)	−0.002 (2)
C19	0.030 (2)	0.041 (3)	0.036 (2)	0.0031 (19)	0.0113 (18)	−0.002 (2)
C20	0.024 (2)	0.034 (2)	0.033 (2)	0.0018 (17)	0.0050 (17)	0.0063 (19)
C21	0.030 (2)	0.045 (3)	0.031 (2)	0.0014 (19)	0.0024 (17)	0.004 (2)
C22	0.028 (2)	0.046 (3)	0.034 (2)	0.0023 (19)	0.0073 (18)	−0.004 (2)
C23	0.149 (6)	0.063 (4)	0.038 (3)	0.002 (4)	−0.002 (3)	−0.007 (3)
C24	0.156 (6)	0.038 (3)	0.040 (3)	0.006 (3)	0.000 (3)	−0.002 (3)
C25	0.040 (2)	0.037 (3)	0.037 (2)	0.0005 (19)	−0.0012 (19)	−0.006 (2)
C26	0.142 (6)	0.040 (3)	0.047 (3)	0.010 (3)	−0.006 (3)	−0.009 (3)
C27	0.132 (6)	0.048 (4)	0.063 (4)	0.013 (4)	−0.007 (4)	0.015 (3)

Geometric parameters (Å, º) top

Zn1—O8	2.104 (3)	C6—C7	1.412 (7)
Zn1—O7	2.138 (3)	C7—C8	1.393 (7)
Zn1—N4	2.142 (3)	C7—C12	1.418 (7)
Zn1—N2	2.163 (4)	C8—C9	1.344 (8)
Zn1—N3ⁱ	2.175 (3)	C8—H8	0.9300
Zn1—N1	2.176 (3)	C9—C10	1.387 (7)
N1—C1	1.317 (5)	C9—H9	0.9300
N1—C5	1.362 (6)	C10—H10	0.9300
N2—C10	1.316 (5)	C11—C12	1.335 (8)
N2—C6	1.354 (5)	C11—H11	0.9300
N3—C13	1.328 (5)	C12—H12	0.9300
N3—C17	1.329 (5)	C13—C14	1.375 (5)
N4—C18	1.329 (5)	C13—H13	0.9300
N4—C22	1.338 (5)	C14—C15	1.378 (6)
N5—C27	1.295 (7)	C14—H14	0.9300
N5—C23	1.296 (7)	C15—C16	1.383 (5)
N6—O3	1.194 (6)	C15—C20	1.490 (5)
N6—O2	1.227 (5)	C16—C17	1.369 (5)
N6—O1	1.230 (5)	C16—H16	0.9300
N7—O4	1.167 (6)	C17—H17	0.9300
N7—O6	1.229 (6)	C18—C19	1.373 (5)
N7—O5	1.278 (8)	C18—H18	0.9300
O7—H7C	0.8500	C19—C20	1.389 (5)
O7—H7D	0.8500	C19—H19	0.9300
O8—H8C	0.8500	C20—C21	1.388 (5)
O8—H8D	0.8500	C21—C22	1.363 (5)
O9—H9C	0.8500	C21—H21	0.9300
O9—H9D	0.8500	C22—H22	0.9300
C1—C2	1.401 (7)	C23—C24	1.373 (7)
C1—H1	0.9300	C23—H23	0.9300
C2—C3	1.352 (8)	C24—C25	1.357 (6)
C2—H2	0.9300	C24—H24	0.9300
C3—C4	1.381 (8)	C25—C26	1.361 (7)
C3—H3	0.9300	C25—C25ⁱⁱ	1.492 (8)
C4—C5	1.403 (6)	C26—C27	1.370 (7)
C4—C11	1.434 (8)	C26—H26	0.9300
C5—C6	1.427 (6)	C27—H27	0.9300

O8—Zn1—O7	91.55 (12)	C6—C7—C12	118.8 (5)
O8—Zn1—N4	92.31 (11)	C9—C8—C7	119.8 (5)
O7—Zn1—N4	88.58 (12)	C9—C8—H8	120.1
O8—Zn1—N2	93.64 (13)	C7—C8—H8	120.1
O7—Zn1—N2	174.80 (12)	C8—C9—C10	119.8 (5)
N4—Zn1—N2	90.88 (12)	C8—C9—H9	120.1
O8—Zn1—N3ⁱ	85.28 (11)	C10—C9—H9	120.1
O7—Zn1—N3ⁱ	86.98 (12)	N2—C10—C9	122.9 (5)
N4—Zn1—N3ⁱ	174.89 (13)	N2—C10—H10	118.5
N2—Zn1—N3ⁱ	93.77 (13)	C9—C10—H10	118.5
O8—Zn1—N1	168.97 (13)	C12—C11—C4	121.9 (5)
O7—Zn1—N1	97.62 (13)	C12—C11—H11	119.0
N4—Zn1—N1	94.05 (12)	C4—C11—H11	119.0
N2—Zn1—N1	77.27 (14)	C11—C12—C7	121.2 (6)
N3ⁱ—Zn1—N1	89.06 (12)	C11—C12—H12	119.4
C1—N1—C5	118.6 (4)	C7—C12—H12	119.4
C1—N1—Zn1	128.6 (3)	N3—C13—C14	123.8 (4)
C5—N1—Zn1	112.6 (3)	N3—C13—H13	118.1
C10—N2—C6	118.2 (4)	C14—C13—H13	118.1
C10—N2—Zn1	128.1 (3)	C13—C14—C15	119.9 (4)
C6—N2—Zn1	113.7 (3)	C13—C14—H14	120.0
C13—N3—C17	116.3 (3)	C15—C14—H14	120.0
C13—N3—Zn1ⁱⁱⁱ	121.3 (3)	C14—C15—C16	116.1 (4)
C17—N3—Zn1ⁱⁱⁱ	122.3 (3)	C14—C15—C20	122.4 (4)
C18—N4—C22	116.5 (3)	C16—C15—C20	121.5 (4)
C18—N4—Zn1	122.0 (3)	C17—C16—C15	120.3 (4)
C22—N4—Zn1	121.4 (3)	C17—C16—H16	119.9
C27—N5—C23	114.8 (5)	C15—C16—H16	119.9
O3—N6—O2	122.4 (5)	N3—C17—C16	123.5 (4)
O3—N6—O1	120.1 (5)	N3—C17—H17	118.2
O2—N6—O1	117.5 (5)	C16—C17—H17	118.2
O4—N7—O6	124.0 (7)	N4—C18—C19	124.2 (4)
O4—N7—O5	118.0 (7)	N4—C18—H18	117.9
O6—N7—O5	118.0 (7)	C19—C18—H18	117.9
Zn1—O7—H7C	108.6	C18—C19—C20	119.1 (4)
Zn1—O7—H7D	115.9	C18—C19—H19	120.4
H7C—O7—H7D	108.4	C20—C19—H19	120.4
Zn1—O8—H8C	135.8	C21—C20—C19	116.6 (3)
Zn1—O8—H8D	109.0	C21—C20—C15	121.7 (3)
H8C—O8—H8D	108.1	C19—C20—C15	121.7 (3)
H9C—O9—H9D	108.3	C22—C21—C20	120.3 (4)
N1—C1—C2	121.9 (5)	C22—C21—H21	119.9
N1—C1—H1	119.1	C20—C21—H21	119.9
C2—C1—H1	119.1	N4—C22—C21	123.3 (4)
C3—C2—C1	119.8 (5)	N4—C22—H22	118.3
C3—C2—H2	120.1	C21—C22—H22	118.3
C1—C2—H2	120.1	N5—C23—C24	124.8 (5)
C2—C3—C4	120.0 (5)	N5—C23—H23	117.6
C2—C3—H3	120.0	C24—C23—H23	117.6
C4—C3—H3	120.0	C25—C24—C23	120.2 (5)
C3—C4—C5	117.7 (6)	C25—C24—H24	119.9
C3—C4—C11	123.7 (6)	C23—C24—H24	119.9
C5—C4—C11	118.5 (5)	C24—C25—C26	115.1 (4)
N1—C5—C4	122.0 (5)	C24—C25—C25ⁱⁱ	121.9 (5)
N1—C5—C6	118.5 (4)	C26—C25—C25ⁱⁱ	122.9 (5)
C4—C5—C6	119.5 (5)	C25—C26—C27	120.1 (5)
N2—C6—C7	122.1 (4)	C25—C26—H26	120.0
N2—C6—C5	117.8 (4)	C27—C26—H26	120.0
C7—C6—C5	120.1 (5)	N5—C27—C26	125.0 (6)
C8—C7—C6	117.2 (5)	N5—C27—H27	117.5
C8—C7—C12	124.0 (6)	C26—C27—H27	117.5

O8—Zn1—N1—C1	143.1 (6)	N2—C6—C7—C8	−1.6 (7)
O7—Zn1—N1—C1	−2.8 (4)	C5—C6—C7—C8	178.1 (4)
N4—Zn1—N1—C1	−91.9 (4)	N2—C6—C7—C12	179.0 (4)
N2—Zn1—N1—C1	178.1 (4)	C5—C6—C7—C12	−1.3 (7)
N3ⁱ—Zn1—N1—C1	84.0 (4)	C6—C7—C8—C9	0.4 (8)
O8—Zn1—N1—C5	−32.9 (8)	C12—C7—C8—C9	179.7 (6)
O7—Zn1—N1—C5	−178.8 (3)	C7—C8—C9—C10	1.2 (10)
N4—Zn1—N1—C5	92.1 (3)	C6—N2—C10—C9	0.7 (7)
N2—Zn1—N1—C5	2.1 (3)	Zn1—N2—C10—C9	−177.4 (4)
N3ⁱ—Zn1—N1—C5	−92.0 (3)	C8—C9—C10—N2	−1.9 (9)
O8—Zn1—N2—C10	−9.1 (4)	C3—C4—C11—C12	178.9 (6)
N4—Zn1—N2—C10	83.2 (4)	C5—C4—C11—C12	−0.7 (9)
N3ⁱ—Zn1—N2—C10	−94.6 (4)	C4—C11—C12—C7	1.7 (10)
N1—Zn1—N2—C10	177.2 (4)	C8—C7—C12—C11	−180.0 (6)
O8—Zn1—N2—C6	172.7 (3)	C6—C7—C12—C11	−0.7 (9)
N4—Zn1—N2—C6	−94.9 (3)	C17—N3—C13—C14	−0.9 (7)
N3ⁱ—Zn1—N2—C6	87.2 (3)	Zn1ⁱⁱⁱ—N3—C13—C14	175.9 (4)
N1—Zn1—N2—C6	−1.0 (3)	N3—C13—C14—C15	−0.4 (7)
O8—Zn1—N4—C18	−142.9 (3)	C13—C14—C15—C16	1.0 (7)
O7—Zn1—N4—C18	−51.4 (3)	C13—C14—C15—C20	179.8 (4)
N2—Zn1—N4—C18	123.4 (3)	C14—C15—C16—C17	−0.3 (7)
N1—Zn1—N4—C18	46.1 (3)	C20—C15—C16—C17	−179.2 (4)
O8—Zn1—N4—C22	41.6 (3)	C13—N3—C17—C16	1.6 (7)
O7—Zn1—N4—C22	133.1 (3)	Zn1ⁱⁱⁱ—N3—C17—C16	−175.1 (4)
N2—Zn1—N4—C22	−52.0 (3)	C15—C16—C17—N3	−1.0 (7)
N1—Zn1—N4—C22	−129.3 (3)	C22—N4—C18—C19	2.1 (6)
C5—N1—C1—C2	−0.1 (7)	Zn1—N4—C18—C19	−173.6 (3)
Zn1—N1—C1—C2	−175.8 (4)	N4—C18—C19—C20	0.3 (7)
N1—C1—C2—C3	−0.5 (8)	C18—C19—C20—C21	−2.1 (6)
C1—C2—C3—C4	0.2 (9)	C18—C19—C20—C15	176.6 (4)
C2—C3—C4—C5	0.7 (8)	C14—C15—C20—C21	9.3 (6)
C2—C3—C4—C11	−179.0 (6)	C16—C15—C20—C21	−171.9 (4)
C1—N1—C5—C4	1.0 (6)	C14—C15—C20—C19	−169.3 (4)
Zn1—N1—C5—C4	177.4 (3)	C16—C15—C20—C19	9.5 (6)
C1—N1—C5—C6	−179.4 (4)	C19—C20—C21—C22	1.6 (6)
Zn1—N1—C5—C6	−3.0 (5)	C15—C20—C21—C22	−177.1 (4)
C3—C4—C5—N1	−1.3 (7)	C18—N4—C22—C21	−2.6 (6)
C11—C4—C5—N1	178.4 (4)	Zn1—N4—C22—C21	173.1 (3)
C3—C4—C5—C6	179.1 (4)	C20—C21—C22—N4	0.8 (6)
C11—C4—C5—C6	−1.2 (7)	C27—N5—C23—C24	−0.5 (10)
C10—N2—C6—C7	1.1 (6)	N5—C23—C24—C25	−0.2 (11)
Zn1—N2—C6—C7	179.4 (3)	C23—C24—C25—C26	1.1 (9)
C10—N2—C6—C5	−178.6 (4)	C23—C24—C25—C25ⁱⁱ	−178.4 (6)
Zn1—N2—C6—C5	−0.3 (4)	C24—C25—C26—C27	−1.3 (9)
N1—C5—C6—N2	2.3 (6)	C25ⁱⁱ—C25—C26—C27	178.1 (6)
C4—C5—C6—N2	−178.1 (4)	C23—N5—C27—C26	0.2 (10)
N1—C5—C6—C7	−177.4 (4)	C25—C26—C27—N5	0.8 (11)
C4—C5—C6—C7	2.2 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7C···O1^iv	0.85	1.89	2.737 (5)	180
O7—H7D···O6^v	0.85	1.93	2.782 (5)	180
O8—H8C···N5	0.85	1.89	2.724 (5)	169
O8—H8D···O3^iv	0.85	1.90	2.744 (6)	169
O9—H9C···O2ⁱⁱⁱ	0.85	2.24	3.091 (7)	176
O9—H9D···O4^vi	0.85	2.27	3.114 (8)	176

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

Experimental details

Crystal data
Chemical formula	[Zn(C₁₀H₈N₂)(C₁₂H₈N₂)(H₂O)₂](NO₃)₂·0.5C₁₀H₈N₂·H₂O
M_r	657.94
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.3910 (11), 13.0561 (13), 19.8509 (18)
β (°)	103.487 (1)
V (Å³)	2870.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.35 × 0.31 × 0.18

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.739, 0.852
No. of measured, independent and observed [I > 2σ(I)] reflections	14110, 5072, 3309
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.132, 1.03
No. of reflections	5072
No. of parameters	397
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.42

Computer programs: SMART (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7C···O1ⁱ	0.85	1.89	2.737 (5)	180
O7—H7D···O6ⁱⁱ	0.85	1.93	2.782 (5)	180
O8—H8C···N5	0.85	1.89	2.724 (5)	169
O8—H8D···O3ⁱ	0.85	1.90	2.744 (6)	169
O9—H9C···O2ⁱⁱⁱ	0.85	2.24	3.091 (7)	176
O9—H9D···O4^iv	0.85	2.27	3.114 (8)	176

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 21171119), the National Keystone Basic Research Program (973 Program) under grant Nos. 2007CB310408 and 2006CB302901, and the Committee of Education of the Beijing Foundation of China (grant No. KM201210028020).

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