Tris(1,10-phenanthroline-5,6-dione-κ2N,N′)zinc bis­(perchlorate) acetonitrile monosolvate

Zhao, J.; Zhang, H.; Zhang, Z.; Zhao, H.; Zhu, G.

doi:10.1107/S1600536811037081

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Pages m1422-m1423

https://doi.org/10.1107/S1600536811037081

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Tris(1,10-phenanthroline-5,6-dione-κ²N,N′)zinc bis(perchlorate) acetonitrile monosolvate

Jing Zhao,^a Heng Zhang,^b Zhaozhi Zhang,^c Haiyan Zhao ^d and Guoyi Zhu ^a ^*

^aChangchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China, ^bInstrumental Analysis Center, Hebei Normal University, Shijiazhuang 050016, People's Republic of China, ^cDepartment of Applied Chemistry, Hengshui University, Hengshui 053000, People's Republic of China, and ^dCollege of Science, Hebei University of Science and Technology, Shijiazhuang 050018, People's Republic of China
^*Correspondence e-mail: zhuguoyi@ciac.jl.cn

(Received 4 September 2011; accepted 13 September 2011; online 30 September 2011)

In the title compound, [Zn(C₁₂H₆N₂O₂)₃](ClO₄)₂·CH₃CN, the Zn^II atom is coordinated by six N atoms from three chelating 1,10-phenanthroline-5,6-dione ligands in a distorted octahedral environment. In the crystal, intermolecular C—H⋯O hydrogen bonds and O⋯π and N⋯π interactions [O⋯centroid distances = 2.907 (5) and 2.843 (7) Å; N⋯centroid distance = 2.861 (10) Å] link the complex cations, perchlorate anions and acetonitrile solvent molecules into a three-dimensional network.

Related literature

For the coordination chemistry of 1,10-phenanthroline-5,6-dione, see: Brechin et al. (2008 ); Khalaji et al. (2007 ); Ma et al. (2010 ); Rezvani et al. (2010 ). For the biological and electrochemical properties of transition metal complexes with 1,10-phenanthroline-5,6-dione, see: Boghaei & Asl (2007 ); Goss & Abruna (1985 ); Kou et al. (2009 ).

Experimental

Crystal data

[Zn(C₁₂H₆N₂O₂)₃](ClO₄)₂·C₂H₃N
M_r = 935.91
Orthorhombic, P 2₁ 2₁ 2₁
a = 13.446 (6) Å
b = 14.125 (6) Å
c = 20.483 (8) Å
V = 3890 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 296 K
0.30 × 0.12 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.785, T_max = 0.905
23200 measured reflections
9569 independent reflections
5533 reflections with I > 2σ(I)
R_int = 0.079

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.220
S = 0.97
9569 reflections
562 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.16 e Å⁻³
Δρ_min = −0.39 e Å⁻³
Absolute structure: Flack (1983 ), 4095 Friedel pairs
Flack parameter: 0.12 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H14⋯O13ⁱ	0.93	2.51	3.238 (9)	135
C2—H15⋯O3ⁱⁱ	0.93	2.58	3.030 (13)	110
C10—H12⋯O7ⁱⁱⁱ	0.93	2.59	3.513 (14)	170
C25—H17⋯O4ⁱⁱ	0.93	2.51	3.136 (15)	125
C24—H26⋯O2^iv	0.93	2.36	3.036 (10)	129
C34—H7⋯O9^v	0.93	2.47	3.302 (12)	150
C38—H38A⋯O3^vi	0.96	2.51	2.995 (16)	112
C38—H38B⋯O13^vii	0.96	2.51	3.436 (19)	163
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+2, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) x, y-1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811037081/hy2471sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037081/hy2471Isup2.hkl

checkCIF report

Comment top

The coordination chemistry of the chelating ligand 1,10-phenanthroline-5,6-dione has been examined in several studies (Khalaji et al., 2007; Ma et al., 2010; Rezvani et al., 2010). Carrying an O-quinone and N-pyridine moiety to form stable complexes with a wide variety of metal ions, this ligand is considered to have many interesting biological and electrochemical properties (Boghaei & Asl, 2007; Goss & Abruna, 1985; Kou et al., 2009). As far as we know, 1,10-phenanthroline-5,6-dione usually binds to metals through its imine N atoms, in some cases both the N and O donors are used simultaneously (Brechin et al., 2008). In this paper, we report the crystal structure of the title compound in the hope of exploring some spectroscopic properties of d¹⁰ metal complexes.

The title compound consists of a [Zn(C₁₂H₆N₂O₂)₃]²⁺ complex cations, two perchlorate anions and an acetonitrile solvent molecule. As shown in Fig. 1, three bidentate 1,10-phenanthroline-5,6-dione ligands are coordinated to the Zn^II atom solely via two N atoms. The coordination geometry around the Zn^II atom is distorted octahedral, with bite angles of 76.88 (18)–77.9 (2)° for the three bidentate ligands. The cis bond angles at the Zn^II atom fall in the range of 76.85 (18)–100.0 (2)° and the trans bond angles are 164.96 (17), 170.57 (18) and 173.9 (2)°, suggesting a significant deviation from a perfect octahedral coordination. The Zn—N bond lengths range from 2.117 (5) to 2.202 (5) Å, with an average of 2.158 (5) Å. There is no strong hydrogen bond in the crystal, as shown in Fig. 2. Weak intermolecular C—H···O hydrogen bonds (Table 1) and O···π and N···π interactions [O···centroid distances = 2.907 (5) and 2.843 (7) Å, N···centroid distance = 2.861 (10) Å] link the complex molecules, perchlorate anions and acetonitrile solvent molecules into a three-dimensional network.

Related literature top

For the coordination chemistry of 1,10-phenanthroline-5,6-dione, see: Brechin et al. (2008); Khalaji et al. (2007); Ma et al. (2010); Rezvani et al. (2010). For the biological and electrochemical properties of transition metal complexes with 1,10-phenanthroline-5,6-dione, see: Boghaei & Asl (2007); Goss & Abruna (1985); Kou et al. (2009).

Experimental top

The title compound was prepared by adding a solution of Zn(ClO₄)₂.2H₂O (28.2 mg, 0.1 mmol) in 3 ml acetonitrile to a solution containing 1,10-phenanthroline-5,6-dione (63.1 mg, 0.3 mmol) in 12 ml acetonitrile. The mixture was stirred at room temperature for 5 h and then filtered. Yellow crystals suitable for X-ray diffraction were obtained by slow evaporation of the solvent after two days. They were collected by filtration, washed with diethyl ether and dried in air.

Structure description top

For the coordination chemistry of 1,10-phenanthroline-5,6-dione, see: Brechin et al. (2008); Khalaji et al. (2007); Ma et al. (2010); Rezvani et al. (2010). For the biological and electrochemical properties of transition metal complexes with 1,10-phenanthroline-5,6-dione, see: Boghaei & Asl (2007); Goss & Abruna (1985); Kou et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The packing diagram viewed along the a axis.

Tris(1,10-phenanthroline-5,6-dione-κ²N,N')zinc bis(perchlorate) acetonitrile monosolvate top

Crystal data top

[Zn(C₁₂H₆N₂O₂)₃](ClO₄)₂·C₂H₃N	F(000) = 1896
M_r = 935.91	D_x = 1.598 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5261 reflections
a = 13.446 (6) Å	θ = 2.3–22.5°
b = 14.125 (6) Å	µ = 0.85 mm⁻¹
c = 20.483 (8) Å	T = 296 K
V = 3890 (3) Å³	Prism, yellow
Z = 4	0.30 × 0.12 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	9569 independent reflections
Radiation source: fine-focus sealed tube	5533 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.079
φ and ω scans	θ_max = 28.6°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→17
T_min = 0.785, T_max = 0.905	k = −18→18
23200 measured reflections	l = −27→24

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.075	w = 1/[σ²(F_o²) + (0.1231P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.220	(Δ/σ)_max = 0.001
S = 0.97	Δρ_max = 1.16 e Å⁻³
9569 reflections	Δρ_min = −0.39 e Å⁻³
562 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0031 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 4095 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.12 (2)

Crystal data top

[Zn(C₁₂H₆N₂O₂)₃](ClO₄)₂·C₂H₃N	V = 3890 (3) Å³
M_r = 935.91	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 13.446 (6) Å	µ = 0.85 mm⁻¹
b = 14.125 (6) Å	T = 296 K
c = 20.483 (8) Å	0.30 × 0.12 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	9569 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5533 reflections with I > 2σ(I)
T_min = 0.785, T_max = 0.905	R_int = 0.079
23200 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	H-atom parameters constrained
wR(F²) = 0.220	Δρ_max = 1.16 e Å⁻³
S = 0.97	Δρ_min = −0.39 e Å⁻³
9569 reflections	Absolute structure: Flack (1983), 4095 Friedel pairs
562 parameters	Absolute structure parameter: 0.12 (2)
1 restraint

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.30685 (6)	0.98904 (5)	0.06979 (3)	0.0455 (2)
Cl1	0.67594 (16)	0.99782 (14)	0.20658 (10)	0.0753 (6)
Cl2	0.34979 (14)	0.98420 (14)	0.80652 (8)	0.0625 (5)
C1	0.0895 (6)	0.9679 (5)	0.1240 (3)	0.064 (2)
H14	0.1171	0.9259	0.1540	0.077*
C2	−0.0107 (6)	0.9882 (7)	0.1292 (4)	0.072 (2)
H15	−0.0495	0.9619	0.1621	0.086*
C3	−0.0496 (7)	1.0470 (6)	0.0851 (3)	0.068 (2)
H34	−0.1173	1.0604	0.0864	0.082*
C4	0.0077 (6)	1.0874 (5)	0.0385 (3)	0.0545 (16)
C5	0.1094 (5)	1.0680 (4)	0.0373 (3)	0.0454 (15)
C6	−0.0314 (6)	1.1548 (6)	−0.0103 (3)	0.0589 (18)
C7	0.0375 (6)	1.2115 (5)	−0.0490 (4)	0.0607 (19)
C8	0.1777 (5)	1.1146 (4)	−0.0073 (3)	0.0434 (14)
C9	0.1438 (6)	1.1861 (4)	−0.0494 (3)	0.0500 (16)
C10	0.2105 (7)	1.2283 (5)	−0.0905 (3)	0.061 (2)
H12	0.1899	1.2756	−0.1191	0.073*
C11	0.3100 (7)	1.1998 (5)	−0.0890 (3)	0.0560 (16)
H9	0.3567	1.2267	−0.1169	0.067*
C12	0.3362 (6)	1.1323 (5)	−0.0463 (3)	0.0537 (17)
H23	0.4026	1.1138	−0.0453	0.064*
C13	0.2120 (8)	0.8282 (5)	−0.0163 (3)	0.073 (3)
H32	0.1532	0.8421	0.0056	0.088*
C14	0.2102 (9)	0.7601 (5)	−0.0669 (4)	0.082 (3)
H21	0.1518	0.7281	−0.0773	0.098*
C15	0.2969 (11)	0.7423 (5)	−0.1005 (4)	0.092 (4)
H25	0.2984	0.6983	−0.1343	0.111*
C16	0.3771 (8)	0.7886 (5)	−0.0837 (3)	0.069 (2)
C17	0.3754 (7)	0.8544 (4)	−0.0322 (3)	0.055 (2)
C18	0.4704 (11)	0.7718 (7)	−0.1200 (5)	0.098 (4)
C19	0.5643 (12)	0.8214 (10)	−0.0980 (5)	0.121 (5)
C20	0.4652 (6)	0.9057 (5)	−0.0147 (3)	0.0535 (17)
C21	0.5537 (8)	0.8898 (6)	−0.0445 (4)	0.078 (2)
C22	0.6343 (8)	0.9412 (9)	−0.0293 (5)	0.104 (3)
H33	0.6935	0.9344	−0.0523	0.124*
C23	0.6262 (7)	1.0052 (8)	0.0220 (5)	0.094 (3)
H36	0.6809	1.0397	0.0363	0.113*
C24	0.5360 (6)	1.0154 (6)	0.0506 (4)	0.0677 (19)
H26	0.5304	1.0583	0.0849	0.081*
C25	0.3351 (6)	0.8160 (5)	0.1594 (3)	0.0554 (18)
H17	0.3106	0.7802	0.1249	0.067*
C26	0.3698 (7)	0.7699 (5)	0.2160 (4)	0.067 (2)
H27	0.3689	0.7042	0.2182	0.080*
C27	0.4033 (6)	0.8194 (5)	0.2656 (3)	0.0543 (17)
H20	0.4261	0.7888	0.3029	0.065*
C28	0.4046 (5)	0.9162 (5)	0.2621 (3)	0.0463 (15)
C29	0.3698 (5)	0.9579 (4)	0.2062 (3)	0.0421 (14)
C30	0.4395 (6)	0.9750 (5)	0.3177 (3)	0.0555 (17)
C31	0.4307 (6)	1.0827 (6)	0.3127 (3)	0.0597 (19)
C32	0.3645 (5)	1.0629 (4)	0.1986 (3)	0.0410 (13)
C33	0.3887 (5)	1.1216 (5)	0.2506 (3)	0.0484 (15)
C34	0.3719 (7)	1.2171 (5)	0.2433 (3)	0.062 (2)
H7	0.3864	1.2586	0.2772	0.075*
C35	0.3347 (6)	1.2500 (5)	0.1872 (3)	0.061 (2)
H24	0.3202	1.3140	0.1823	0.073*
C36	0.3182 (6)	1.1875 (4)	0.1369 (3)	0.0540 (17)
H8	0.2952	1.2108	0.0972	0.065*
C37	0.5814 (10)	0.1897 (9)	0.8669 (5)	0.113 (4)
C38	0.5824 (12)	0.1612 (15)	0.8005 (6)	0.193 (9)
H38A	0.6089	0.2114	0.7741	0.289*
H38B	0.5159	0.1470	0.7866	0.289*
H38C	0.6233	0.1058	0.7958	0.289*
N1	0.1489 (4)	1.0048 (4)	0.0788 (2)	0.0461 (11)
N2	0.2743 (4)	1.0902 (3)	−0.0054 (2)	0.0449 (12)
N3	0.2912 (6)	0.8710 (4)	0.0003 (2)	0.0595 (17)
N4	0.4580 (5)	0.9700 (4)	0.0335 (2)	0.0522 (14)
N5	0.3368 (5)	0.9083 (3)	0.1546 (2)	0.0467 (14)
N6	0.3339 (4)	1.0955 (3)	0.1430 (2)	0.0436 (13)
N7	0.5798 (8)	0.2050 (7)	0.9193 (4)	0.105 (3)
O1	−0.1211 (5)	1.1624 (5)	−0.0184 (3)	0.0876 (18)
O2	0.0074 (5)	1.2760 (4)	−0.0809 (3)	0.0803 (17)
O3	0.4753 (8)	0.7195 (6)	−0.1651 (4)	0.140 (4)
O4	0.6416 (9)	0.7953 (10)	−0.1217 (5)	0.203 (6)
O5	0.4748 (5)	0.9415 (4)	0.3661 (2)	0.0744 (16)
O6	0.4577 (5)	1.1315 (4)	0.3557 (2)	0.0781 (17)
O7	0.652 (2)	1.0724 (6)	0.1856 (7)	0.351 (17)
O8	0.7584 (9)	0.966 (2)	0.1956 (13)	0.42 (2)
O9	0.6192 (12)	0.9199 (6)	0.1767 (7)	0.200 (6)
O10	0.6744 (18)	0.9940 (10)	0.2718 (6)	0.312 (12)
O11	0.3492 (6)	0.9109 (5)	0.7595 (3)	0.105 (2)
O12	0.2624 (5)	0.9759 (4)	0.8471 (3)	0.0815 (16)
O13	0.3483 (6)	1.0713 (4)	0.7743 (3)	0.094 (2)
O14	0.4366 (5)	0.9798 (5)	0.8447 (3)	0.096 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0575 (4)	0.0389 (3)	0.0400 (3)	0.0035 (3)	−0.0038 (3)	0.0016 (3)
Cl1	0.0823 (14)	0.0599 (11)	0.0837 (11)	0.0149 (10)	0.0214 (10)	0.0215 (9)
Cl2	0.0698 (11)	0.0661 (11)	0.0515 (7)	−0.0053 (10)	−0.0100 (8)	0.0028 (8)
C1	0.071 (5)	0.074 (5)	0.049 (3)	−0.011 (4)	0.004 (4)	0.020 (3)
C2	0.068 (5)	0.085 (5)	0.062 (4)	0.000 (5)	0.015 (4)	0.010 (4)
C3	0.061 (5)	0.089 (5)	0.054 (4)	0.008 (4)	0.007 (4)	−0.004 (3)
C4	0.059 (4)	0.060 (4)	0.045 (3)	0.001 (3)	−0.005 (3)	−0.004 (3)
C5	0.061 (4)	0.041 (3)	0.034 (3)	−0.005 (3)	−0.005 (3)	−0.001 (2)
C6	0.056 (5)	0.071 (5)	0.049 (3)	0.018 (4)	0.003 (3)	0.000 (3)
C7	0.070 (5)	0.045 (4)	0.067 (4)	0.002 (4)	−0.013 (4)	−0.004 (3)
C8	0.057 (4)	0.036 (3)	0.038 (3)	0.002 (3)	−0.003 (3)	−0.003 (2)
C9	0.065 (5)	0.039 (3)	0.045 (3)	0.003 (3)	−0.010 (3)	−0.002 (2)
C10	0.098 (7)	0.046 (3)	0.039 (3)	0.000 (4)	0.002 (4)	0.012 (2)
C11	0.066 (5)	0.050 (4)	0.052 (3)	−0.008 (4)	−0.001 (4)	0.010 (2)
C12	0.061 (5)	0.058 (4)	0.043 (3)	−0.002 (3)	−0.007 (3)	−0.001 (3)
C13	0.111 (8)	0.056 (4)	0.052 (4)	−0.019 (5)	0.003 (5)	−0.002 (3)
C14	0.119 (9)	0.057 (4)	0.069 (5)	−0.015 (5)	−0.032 (6)	−0.001 (4)
C15	0.171 (12)	0.045 (4)	0.061 (4)	−0.022 (6)	−0.003 (7)	−0.006 (3)
C16	0.108 (7)	0.046 (4)	0.054 (4)	0.014 (4)	−0.013 (4)	−0.005 (3)
C17	0.094 (6)	0.035 (3)	0.037 (3)	0.016 (3)	−0.007 (4)	0.000 (2)
C18	0.145 (11)	0.069 (6)	0.081 (6)	0.035 (7)	0.003 (7)	−0.002 (5)
C19	0.141 (12)	0.154 (11)	0.068 (5)	0.079 (10)	0.003 (7)	−0.022 (6)
C20	0.071 (5)	0.044 (3)	0.045 (3)	0.022 (3)	−0.002 (3)	0.006 (3)
C21	0.087 (6)	0.072 (5)	0.075 (5)	0.039 (5)	−0.003 (5)	−0.006 (4)
C22	0.067 (6)	0.148 (10)	0.097 (7)	0.048 (6)	0.002 (6)	0.020 (7)
C23	0.063 (5)	0.112 (8)	0.108 (7)	0.002 (6)	0.001 (5)	0.008 (7)
C24	0.071 (5)	0.060 (4)	0.072 (4)	0.001 (4)	−0.017 (4)	−0.005 (3)
C25	0.068 (5)	0.044 (4)	0.054 (3)	0.004 (3)	0.001 (3)	0.008 (3)
C26	0.093 (6)	0.045 (4)	0.062 (4)	0.019 (4)	0.014 (4)	0.018 (3)
C27	0.062 (5)	0.059 (4)	0.042 (3)	0.010 (3)	0.001 (3)	0.012 (3)
C28	0.050 (4)	0.053 (4)	0.036 (3)	0.005 (3)	0.006 (3)	0.004 (2)
C29	0.048 (4)	0.040 (3)	0.039 (3)	0.001 (2)	0.006 (3)	0.004 (2)
C30	0.059 (4)	0.067 (5)	0.041 (3)	0.000 (4)	0.003 (3)	0.010 (3)
C31	0.060 (5)	0.077 (5)	0.041 (3)	−0.015 (4)	−0.002 (3)	−0.001 (3)
C32	0.046 (4)	0.035 (3)	0.042 (3)	0.002 (2)	0.005 (3)	−0.002 (2)
C33	0.051 (4)	0.050 (4)	0.045 (3)	−0.004 (3)	0.003 (3)	−0.010 (3)
C34	0.087 (6)	0.049 (4)	0.051 (4)	−0.012 (4)	0.008 (4)	−0.012 (3)
C35	0.077 (6)	0.040 (3)	0.066 (4)	0.001 (3)	0.008 (4)	−0.005 (3)
C36	0.075 (5)	0.041 (3)	0.046 (3)	0.003 (3)	0.004 (4)	0.003 (2)
C37	0.123 (10)	0.134 (10)	0.083 (6)	−0.054 (8)	0.016 (7)	−0.012 (6)
C38	0.132 (12)	0.35 (3)	0.098 (8)	−0.110 (16)	0.031 (9)	−0.062 (12)
N1	0.047 (3)	0.045 (3)	0.046 (2)	−0.005 (2)	−0.006 (2)	0.011 (2)
N2	0.058 (4)	0.044 (3)	0.034 (2)	0.003 (2)	0.002 (2)	0.0067 (19)
N3	0.096 (5)	0.040 (3)	0.042 (3)	−0.011 (3)	−0.012 (3)	−0.001 (2)
N4	0.067 (4)	0.047 (3)	0.043 (2)	0.001 (3)	−0.001 (3)	−0.006 (2)
N5	0.067 (4)	0.032 (2)	0.041 (2)	0.006 (2)	−0.001 (3)	0.0039 (18)
N6	0.056 (4)	0.035 (2)	0.039 (2)	0.002 (2)	0.007 (2)	0.0011 (18)
N7	0.114 (7)	0.123 (7)	0.079 (5)	−0.009 (6)	0.007 (6)	−0.028 (5)
O1	0.072 (4)	0.116 (5)	0.075 (3)	0.020 (4)	0.001 (3)	0.012 (3)
O2	0.081 (4)	0.061 (3)	0.098 (4)	0.017 (3)	−0.024 (4)	0.011 (3)
O3	0.208 (11)	0.110 (6)	0.102 (5)	0.059 (6)	0.006 (6)	−0.050 (4)
O4	0.146 (9)	0.318 (15)	0.146 (8)	0.132 (10)	−0.013 (7)	−0.111 (9)
O5	0.084 (4)	0.091 (4)	0.049 (2)	−0.005 (3)	−0.012 (3)	0.017 (2)
O6	0.094 (5)	0.091 (4)	0.049 (2)	−0.007 (4)	−0.013 (3)	−0.011 (3)
O7	0.70 (5)	0.064 (6)	0.291 (15)	0.024 (12)	−0.32 (2)	−0.017 (7)
O8	0.087 (8)	0.65 (5)	0.54 (4)	0.020 (16)	0.048 (14)	−0.36 (4)
O9	0.290 (17)	0.062 (5)	0.249 (12)	−0.044 (7)	0.061 (12)	−0.011 (6)
O10	0.59 (4)	0.191 (12)	0.152 (9)	0.00 (2)	0.128 (16)	0.040 (9)
O11	0.101 (5)	0.098 (5)	0.115 (5)	−0.006 (4)	−0.002 (5)	−0.047 (4)
O12	0.098 (4)	0.085 (4)	0.061 (3)	−0.004 (3)	0.003 (3)	0.006 (3)
O13	0.128 (6)	0.084 (4)	0.070 (3)	0.009 (4)	−0.007 (4)	0.031 (3)
O14	0.081 (4)	0.119 (5)	0.088 (4)	−0.012 (4)	−0.030 (3)	0.034 (4)

Geometric parameters (Å, º) top

Zn1—N5	2.117 (5)	C16—C18	1.478 (15)
Zn1—N1	2.143 (5)	C17—N3	1.334 (10)
Zn1—N2	2.146 (5)	C17—C20	1.453 (11)
Zn1—N6	2.154 (5)	C18—O3	1.184 (11)
Zn1—N4	2.181 (6)	C18—C19	1.514 (19)
Zn1—N3	2.202 (5)	C19—O4	1.204 (15)
Cl1—O7	1.180 (10)	C19—C21	1.468 (13)
Cl1—O8	1.219 (14)	C20—N4	1.345 (8)
Cl1—O10	1.338 (12)	C20—C21	1.357 (12)
Cl1—O9	1.472 (12)	C21—C22	1.341 (16)
Cl2—O13	1.396 (6)	C22—C23	1.391 (15)
Cl2—O14	1.407 (6)	C22—H33	0.9300
Cl2—O11	1.415 (6)	C23—C24	1.355 (12)
Cl2—O12	1.444 (6)	C23—H36	0.9300
C1—N1	1.330 (8)	C24—N4	1.277 (9)
C1—C2	1.382 (12)	C24—H26	0.9300
C1—H14	0.9300	C25—N5	1.307 (8)
C2—C3	1.334 (11)	C25—C26	1.409 (9)
C2—H15	0.9300	C25—H17	0.9300
C3—C4	1.353 (10)	C26—C27	1.312 (11)
C3—H34	0.9300	C26—H27	0.9300
C4—C5	1.395 (10)	C27—C28	1.369 (9)
C4—C6	1.476 (10)	C27—H20	0.9300
C5—N1	1.342 (7)	C28—C29	1.370 (8)
C5—C8	1.453 (9)	C28—C30	1.485 (9)
C6—O1	1.221 (10)	C29—N5	1.343 (8)
C6—C7	1.460 (11)	C29—C32	1.492 (8)
C7—O2	1.191 (8)	C30—O5	1.197 (8)
C7—C9	1.473 (11)	C30—C31	1.529 (11)
C8—N2	1.345 (9)	C31—O6	1.176 (8)
C8—C9	1.404 (8)	C31—C33	1.495 (10)
C9—C10	1.366 (10)	C32—N6	1.296 (7)
C10—C11	1.398 (13)	C32—C33	1.389 (8)
C10—H12	0.9300	C33—C34	1.376 (10)
C11—C12	1.342 (9)	C34—C35	1.336 (10)
C11—H9	0.9300	C34—H7	0.9300
C12—N2	1.321 (8)	C35—C36	1.375 (9)
C12—H23	0.9300	C35—H24	0.9300
C13—N3	1.271 (11)	C36—N6	1.323 (8)
C13—C14	1.414 (11)	C36—H8	0.9300
C13—H32	0.9300	C37—N7	1.096 (12)
C14—C15	1.377 (16)	C37—C38	1.419 (15)
C14—H21	0.9300	C38—H38A	0.9600
C15—C16	1.307 (14)	C38—H38B	0.9600
C15—H25	0.9300	C38—H38C	0.9600
C16—C17	1.406 (9)

N5—Zn1—N1	100.0 (2)	C16—C18—C19	118.9 (8)
N5—Zn1—N2	170.57 (18)	O4—C19—C21	125.8 (15)
N1—Zn1—N2	77.9 (2)	O4—C19—C18	117.3 (12)
N5—Zn1—N6	76.85 (18)	C21—C19—C18	116.5 (11)
N1—Zn1—N6	92.0 (2)	N4—C20—C21	120.3 (8)
N2—Zn1—N6	93.96 (18)	N4—C20—C17	117.3 (6)
N5—Zn1—N4	92.1 (2)	C21—C20—C17	122.4 (7)
N1—Zn1—N4	164.96 (17)	C22—C21—C20	121.0 (9)
N2—Zn1—N4	91.6 (2)	C22—C21—C19	116.8 (11)
N6—Zn1—N4	99.5 (2)	C20—C21—C19	122.0 (11)
N5—Zn1—N3	98.09 (19)	C21—C22—C23	117.6 (10)
N1—Zn1—N3	92.3 (2)	C21—C22—H33	121.2
N2—Zn1—N3	91.20 (19)	C23—C22—H33	121.2
N6—Zn1—N3	173.9 (2)	C24—C23—C22	117.8 (10)
N4—Zn1—N3	77.0 (2)	C24—C23—H36	121.1
O7—Cl1—O8	120 (2)	C22—C23—H36	121.1
O7—Cl1—O10	113.3 (10)	N4—C24—C23	124.3 (8)
O8—Cl1—O10	100.6 (16)	N4—C24—H26	117.9
O7—Cl1—O9	112.2 (9)	C23—C24—H26	117.9
O8—Cl1—O9	96.8 (12)	N5—C25—C26	121.1 (7)
O10—Cl1—O9	112.1 (10)	N5—C25—H17	119.4
O13—Cl2—O14	108.3 (5)	C26—C25—H17	119.4
O13—Cl2—O11	108.8 (4)	C27—C26—C25	120.3 (7)
O14—Cl2—O11	110.6 (5)	C27—C26—H27	119.8
O13—Cl2—O12	109.4 (4)	C25—C26—H27	119.8
O14—Cl2—O12	110.6 (3)	C26—C27—C28	119.7 (6)
O11—Cl2—O12	109.1 (4)	C26—C27—H20	120.1
N1—C1—C2	123.9 (7)	C28—C27—H20	120.1
N1—C1—H14	118.1	C27—C28—C29	118.0 (6)
C2—C1—H14	118.1	C27—C28—C30	121.5 (6)
C3—C2—C1	117.4 (7)	C29—C28—C30	120.5 (6)
C3—C2—H15	121.3	N5—C29—C28	123.0 (5)
C1—C2—H15	121.3	N5—C29—C32	114.9 (5)
C2—C3—C4	121.1 (8)	C28—C29—C32	122.1 (6)
C2—C3—H34	119.4	O5—C30—C28	122.6 (7)
C4—C3—H34	119.4	O5—C30—C31	118.7 (7)
C3—C4—C5	119.2 (7)	C28—C30—C31	118.7 (6)
C3—C4—C6	123.1 (7)	O6—C31—C33	122.5 (7)
C5—C4—C6	117.6 (6)	O6—C31—C30	120.6 (7)
N1—C5—C4	120.5 (6)	C33—C31—C30	116.9 (6)
N1—C5—C8	116.7 (6)	N6—C32—C33	122.5 (5)
C4—C5—C8	122.8 (6)	N6—C32—C29	117.4 (5)
O1—C6—C7	120.3 (7)	C33—C32—C29	120.1 (6)
O1—C6—C4	120.1 (8)	C34—C33—C32	117.6 (6)
C7—C6—C4	119.7 (7)	C34—C33—C31	121.0 (6)
O2—C7—C6	120.1 (8)	C32—C33—C31	121.4 (6)
O2—C7—C9	120.8 (8)	C35—C34—C33	119.8 (6)
C6—C7—C9	119.1 (6)	C35—C34—H7	120.1
N2—C8—C9	121.1 (6)	C33—C34—H7	120.1
N2—C8—C5	118.4 (5)	C34—C35—C36	118.7 (6)
C9—C8—C5	120.5 (6)	C34—C35—H24	120.6
C10—C9—C8	118.6 (7)	C36—C35—H24	120.6
C10—C9—C7	122.3 (6)	N6—C36—C35	122.3 (6)
C8—C9—C7	119.1 (6)	N6—C36—H8	118.8
C9—C10—C11	119.3 (6)	C35—C36—H8	118.8
C9—C10—H12	120.3	N7—C37—C38	174.8 (16)
C11—C10—H12	120.3	C37—C38—H38A	109.5
C12—C11—C10	118.1 (7)	C37—C38—H38B	109.5
C12—C11—H9	121.0	H38A—C38—H38B	109.5
C10—C11—H9	121.0	C37—C38—H38C	109.5
N2—C12—C11	124.6 (7)	H38A—C38—H38C	109.5
N2—C12—H23	117.7	H38B—C38—H38C	109.5
C11—C12—H23	117.7	C1—N1—C5	117.7 (6)
N3—C13—C14	122.3 (10)	C1—N1—Zn1	127.9 (5)
N3—C13—H32	118.9	C5—N1—Zn1	114.0 (4)
C14—C13—H32	118.9	C12—N2—C8	118.4 (5)
C15—C14—C13	118.4 (9)	C12—N2—Zn1	128.7 (5)
C15—C14—H21	120.8	C8—N2—Zn1	112.8 (4)
C13—C14—H21	120.8	C13—N3—C17	119.6 (6)
C16—C15—C14	118.4 (8)	C13—N3—Zn1	127.8 (6)
C16—C15—H25	120.8	C17—N3—Zn1	112.0 (5)
C14—C15—H25	120.8	C24—N4—C20	118.8 (7)
C15—C16—C17	121.0 (10)	C24—N4—Zn1	127.6 (5)
C15—C16—C18	119.1 (9)	C20—N4—Zn1	113.5 (5)
C17—C16—C18	119.9 (9)	C25—N5—C29	117.9 (5)
N3—C17—C16	120.3 (8)	C25—N5—Zn1	126.5 (4)
N3—C17—C20	119.6 (6)	C29—N5—Zn1	115.3 (4)
C16—C17—C20	120.1 (8)	C32—N6—C36	118.9 (5)
O3—C18—C16	122.7 (13)	C32—N6—Zn1	114.7 (4)
O3—C18—C19	118.4 (12)	C36—N6—Zn1	126.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H14···O13ⁱ	0.93	2.51	3.238 (9)	135
C2—H15···O3ⁱⁱ	0.93	2.58	3.030 (13)	110
C10—H12···O7ⁱⁱⁱ	0.93	2.59	3.513 (14)	170
C25—H17···O4ⁱⁱ	0.93	2.51	3.136 (15)	125
C24—H26···O2^iv	0.93	2.36	3.036 (10)	129
C34—H7···O9^v	0.93	2.47	3.302 (12)	150
C38—H38A···O3^vi	0.96	2.51	2.995 (16)	112
C38—H38B···O13^vii	0.96	2.51	3.436 (19)	163

Symmetry codes: (i) −x+1/2, −y+2, z−1/2; (ii) x−1/2, −y+3/2, −z; (iii) x−1/2, −y+5/2, −z; (iv) x+1/2, −y+5/2, −z; (v) −x+1, y+1/2, −z+1/2; (vi) −x+1, y−1/2, −z+1/2; (vii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Zn(C₁₂H₆N₂O₂)₃](ClO₄)₂·C₂H₃N
M_r	935.91
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	13.446 (6), 14.125 (6), 20.483 (8)
V (Å³)	3890 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.30 × 0.12 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.785, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	23200, 9569, 5533
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.220, 0.97
No. of reflections	9569
No. of parameters	562
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.16, −0.39
Absolute structure	Flack (1983), 4095 Friedel pairs
Absolute structure parameter	0.12 (2)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H14···O13ⁱ	0.93	2.51	3.238 (9)	135
C2—H15···O3ⁱⁱ	0.93	2.58	3.030 (13)	110
C10—H12···O7ⁱⁱⁱ	0.93	2.59	3.513 (14)	170
C25—H17···O4ⁱⁱ	0.93	2.51	3.136 (15)	125
C24—H26···O2^iv	0.93	2.36	3.036 (10)	129
C34—H7···O9^v	0.93	2.47	3.302 (12)	150
C38—H38A···O3^vi	0.96	2.51	2.995 (16)	112
C38—H38B···O13^vii	0.96	2.51	3.436 (19)	163

Acknowledgements

This work was supported by the Youth Foundation of Hebei Normal University (No. L2006Q20).

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