[μ-1,3-Bis(3,5-dimethyl-1H-pyrazol-1-yl-κN2)propan-2-olato-κ2O:O]bis­[(ethanol-κO)zinc(II)] bis­(perchlorate)

Tian, D.-M.; Shi, C.-Y.

doi:10.1107/S160053681004479X

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1520

https://doi.org/10.1107/S160053681004479X

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[μ-1,3-Bis(3,5-dimethyl-1H-pyrazol-1-yl-κN²)propan-2-olato-κ²O:O]bis[(ethanol-κO)zinc(II)] bis(perchlorate)

Da-Min Tian ^a ^* and Chong-Yu Shi ^b

^aDepartment of Chemistry and Chemical Engineering, Henan University of Urban Construction, Pingdingshan, Henan 467044, People's Republic of China, and ^bZhongzhou University, Zhongzhou 450044, People's Republic of China
^*Correspondence e-mail: tiandamin2009@163.com

(Received 22 October 2010; accepted 2 November 2010; online 6 November 2010)

In the centrosymmetric dinuclear title complex, [Zn₂(C₁₃H₁₉N₄O)₂(C₂H₅OH)₂](ClO₄)₂, the Zn^II atom is in a distorted trigonal-bipyramidal coordination geometry. The equatorial plane is constructed by one N atom and one O atom from two 1,3-bis(3,5-dimethylpyrazol-1-yl)propan-2-olate (bppo) ligands and one O atom from an ethanol molecule. One N atom and one O atom from the two bppo ligands occupy the axial positions. Intermolecular O—H⋯O hydrogen bonds between the ethanol molecules and perchlorate anions, and O⋯π interactions between the perchlorate anions and pyrazole rings [O⋯centroid distances = 3.494 (3) and 3.413 (3) Å], lead to a chain structure along [010].

Related literature

For related structures, see: Montoya et al. (2007 ).

Experimental

Crystal data

[Zn₂(C₁₃H₁₉N₄O)₂(C₂H₆O)₂](ClO₄)₂
M_r = 916.42
Triclinic, $[P \overline 1]$
a = 8.8570 (18) Å
b = 11.148 (2) Å
c = 11.300 (2) Å
α = 111.13 (3)°
β = 100.40 (3)°
γ = 100.11 (3)°
V = 987.8 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.42 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.20 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.765, T_max = 0.765
7788 measured reflections
3482 independent reflections
3172 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.083
S = 1.07
3482 reflections
249 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—N1	2.076 (2)
Zn1—N3ⁱ	2.042 (2)
Zn1—O6	1.9908 (16)
Zn1—O6ⁱ	2.0428 (16)
Zn1—O7	2.1292 (18)
Symmetry code: (i) -x+1, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O3	0.85	2.03	2.860 (3)	165

Data collection: SMART (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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681004479X/hy2370sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681004479X/hy2370Isup2.hkl

checkCIF report

Comment top

Pyrazole-derived ligands have been extensively studied in recent years. These ligands are known as anionic or neutral groups to coordinate to metal centers through N atoms in monodentate and exobidentate modes. It is essential to study the syntheses and crystal structures of the complexes formed by pyrazole systematically, and to inquire into the factors that influence the formation and structure of such complexes. Such studies may lead to the design and synthesis of functional materials, and also provide a theoretical foundation for supramolecular chemistry and crystal engineering (Montoya et al., 2007). As part of our studies on the synthesis and characterization of these compounds, we report here the synthesis and crystal structure of the title compound.

In the title compound (Fig. 1), the Zn^II atom is five-coordinated by two O atoms and two N atoms from two 1,3-bis(3,5-dimethyl-pyrazol-1-yl)propan-2-olate (bppo) ligands and one O atom from an ethanol molecule in a distorted trigonal–bipyramidal geometry (Table 1). The equatorial plane is constructed by N3ⁱ and O6 from the two bppo ligands and O7 from the ethanol molecule. The N1 and O6ⁱ atoms occupy the axial positions [symmetry code: (i) 1 - x, -y, -z]. Two hydroxyl O atoms bridge the Zn atoms, forming a dinuclear complex. Intermolecular O—H···O hydrogen bonds between the ethanol molecules and perchlorate anions (Table 2) and O···π interactions between the perchlorate anions and pyrazole rings, O2···Cg1ⁱⁱ and O3···Cg2, [Cg1 and Cg2 are the centroids of C2/C3/C4/N3/N4 ring and C6/C7/C8/N1/N2 ring; symmetry code: (ii) x, -1 + y, z; O—centroid distances = 3.494 (3) and 3.413 (3) Å, respectively], lead to a chain structure along [010] (Fig. 2).

Related literature top

For related structures, see: Montoya et al. (2007).

Experimental top

1,3-Bis(3,5-dimethyl-pyrazol-1-yl)propan-2-ol and ZnCl₂.6H₂O were available commercially and were used without further purification. 1,3-Bis(3,5-dimethyl-pyrazol-1-yl)propan-2-ol (124 mg, 0.5 mmol) were dissolved in anhydrous alcohol (15 ml). To this solution was added ZuCl₂.6H₂O (122 mg, 0.5 mmol) in anhydrous alcohol (10 ml). After keeping the resulting solution in air to evaporate about half of the solvent, blue prismatic crystals of the title compound were formed. The crystals were isolated, washed with alcohol three times and dried in a vacuum desiccator using silica gel (yield: 75%). Analysis, calculated for C₃₀H₅₀Cl₂N₈O₁₂Zn₂: C 39.32, H 5.50, N, 12.23%; found: C 39.42, H 5.28, N 12.35%.

Structure description top

For related structures, see: Montoya et al. (2007).

Computing details top

Data collection: SMART (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) and DIAMOND (Brandenburg, 1999); 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 50% probability level. H atoms have been omitted for clarity. [Symmetry code: (A) 1 - x, -y, -z.]
	Fig. 2. The chain structure in the title compound. Dashed lines denote O···π interactions.

[µ-1,3-Bis(3,5-dimethyl-1H-pyrazol-1-yl-κN²)propan- 2-olato-κ²O:O]bis[(ethanol-κO)zinc(II)] bis(perchlorate) top

Crystal data top

[Zn₂(C₁₃H₁₉N₄O)₂(C₂H₆O)₂](ClO₄)₂	Z = 1
M_r = 916.42	F(000) = 476
Triclinic, P1	D_x = 1.541 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8570 (18) Å	Cell parameters from 2230 reflections
b = 11.148 (2) Å	θ = 2.3–25.7°
c = 11.300 (2) Å	µ = 1.42 mm⁻¹
α = 111.13 (3)°	T = 293 K
β = 100.40 (3)°	Block, colourless
γ = 100.11 (3)°	0.22 × 0.20 × 0.20 mm
V = 987.8 (5) Å³

Data collection top

Bruker APEX CCD diffractometer	3482 independent reflections
Radiation source: fine-focus sealed tube	3172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
φ and ω scans	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.765, T_max = 0.765	k = −13→13
7788 measured reflections	l = −13→13

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0486P)² + 0.4173P] where P = (F_o² + 2F_c²)/3
3482 reflections	(Δ/σ)_max < 0.001
249 parameters	Δρ_max = 0.50 e Å⁻³
2 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Zn₂(C₁₃H₁₉N₄O)₂(C₂H₆O)₂](ClO₄)₂	γ = 100.11 (3)°
M_r = 916.42	V = 987.8 (5) Å³
Triclinic, P1	Z = 1
a = 8.8570 (18) Å	Mo Kα radiation
b = 11.148 (2) Å	µ = 1.42 mm⁻¹
c = 11.300 (2) Å	T = 293 K
α = 111.13 (3)°	0.22 × 0.20 × 0.20 mm
β = 100.40 (3)°

Data collection top

Bruker APEX CCD diffractometer	3482 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3172 reflections with I > 2σ(I)
T_min = 0.765, T_max = 0.765	R_int = 0.017
7788 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	2 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.07	Δρ_max = 0.50 e Å⁻³
3482 reflections	Δρ_min = −0.22 e Å⁻³
249 parameters

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

	x	y	z	U_iso*/U_eq
Zn1	0.44360 (3)	−0.13668 (2)	0.00434 (2)	0.03250 (11)
N1	0.3373 (2)	−0.18995 (19)	0.13387 (19)	0.0385 (4)
N2	0.3198 (2)	−0.09350 (19)	0.24246 (19)	0.0364 (4)
O6	0.40890 (17)	0.04471 (14)	0.07488 (15)	0.0331 (3)
O7	0.6260 (2)	−0.21497 (19)	0.07459 (19)	0.0528 (5)
H7A	0.6208	−0.2359	0.1393	0.079*
C5	0.2447 (4)	−0.4353 (3)	0.0179 (3)	0.0597 (7)
H5A	0.2756	−0.4202	−0.0538	0.089*
H5B	0.1397	−0.4941	−0.0135	0.089*
H5C	0.3182	−0.4748	0.0544	0.089*
C6	0.2460 (3)	−0.3054 (2)	0.1218 (2)	0.0413 (5)
C7	0.1694 (3)	−0.2813 (3)	0.2213 (3)	0.0453 (6)
H7	0.0970	−0.3442	0.2334	0.054*
C8	0.2202 (3)	−0.1478 (3)	0.2983 (2)	0.0413 (5)
C9	0.1855 (4)	−0.0683 (3)	0.4239 (3)	0.0606 (8)
H9A	0.2773	−0.0431	0.4961	0.091*
H9B	0.0971	−0.1210	0.4368	0.091*
H9C	0.1599	0.0104	0.4193	0.091*
C10	0.4166 (3)	0.0433 (2)	0.2899 (2)	0.0381 (5)
H10A	0.5279	0.0435	0.3030	0.046*
H10B	0.4016	0.0957	0.3743	0.046*
C11	0.3753 (3)	0.1084 (2)	0.1951 (2)	0.0331 (5)
H11	0.2605	0.0997	0.1770	0.040*
C13	0.7924 (3)	−0.1751 (4)	0.0899 (3)	0.0641 (8)
H13A	0.8108	−0.1760	0.0076	0.077*
H13B	0.8423	−0.2383	0.1110	0.077*
C14	0.8653 (5)	−0.0412 (4)	0.1945 (6)	0.1128 (18)
H14A	0.8059	0.0190	0.1808	0.169*
H14B	0.9729	−0.0113	0.1926	0.169*
H14C	0.8647	−0.0439	0.2783	0.169*
C12	0.4601 (3)	0.2576 (2)	0.2567 (2)	0.0367 (5)
H12A	0.4222	0.2976	0.1977	0.044*
H12B	0.4328	0.2998	0.3385	0.044*
N3	0.7009 (2)	0.25422 (18)	0.17989 (19)	0.0366 (4)
N4	0.6328 (2)	0.28347 (18)	0.28297 (18)	0.0359 (4)
C1	0.7043 (4)	0.3867 (3)	0.5278 (3)	0.0630 (8)
H1A	0.6439	0.4506	0.5295	0.094*
H1B	0.8007	0.4283	0.5977	0.094*
H1C	0.6428	0.3136	0.5389	0.094*
C2	0.7442 (3)	0.3366 (2)	0.3990 (2)	0.0437 (6)
C3	0.8885 (3)	0.3381 (3)	0.3704 (3)	0.0501 (6)
H3	0.9877	0.3674	0.4306	0.060*
C15	0.9736 (3)	0.2689 (3)	0.1524 (3)	0.0614 (8)
H15A	0.9241	0.1944	0.0696	0.092*
H15B	1.0653	0.2525	0.1974	0.092*
H15C	1.0055	0.3479	0.1373	0.092*
C4	0.8579 (3)	0.2875 (2)	0.2346 (3)	0.0433 (6)
O1	0.7169 (4)	−0.2927 (3)	0.4897 (3)	0.1003 (9)
O2	0.5741 (4)	−0.4532 (3)	0.2842 (4)	0.1233 (12)
O3	0.6271 (4)	−0.2330 (3)	0.3209 (3)	0.0955 (9)
O4	0.8318 (4)	−0.3383 (4)	0.3177 (3)	0.1242 (12)
Cl1	0.68858 (8)	−0.33052 (6)	0.35237 (7)	0.05214 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03703 (16)	0.02905 (16)	0.03013 (16)	0.00679 (10)	0.01162 (11)	0.01013 (11)
N1	0.0468 (11)	0.0325 (10)	0.0367 (11)	0.0091 (8)	0.0174 (9)	0.0121 (8)
N2	0.0422 (10)	0.0341 (10)	0.0325 (10)	0.0070 (8)	0.0130 (8)	0.0131 (8)
O6	0.0396 (8)	0.0292 (8)	0.0296 (8)	0.0076 (6)	0.0132 (6)	0.0099 (6)
O7	0.0477 (10)	0.0682 (12)	0.0590 (12)	0.0215 (9)	0.0158 (9)	0.0403 (10)
C5	0.078 (2)	0.0344 (14)	0.0638 (19)	0.0087 (13)	0.0274 (16)	0.0154 (13)
C6	0.0462 (13)	0.0354 (13)	0.0418 (14)	0.0060 (10)	0.0114 (11)	0.0175 (11)
C7	0.0459 (13)	0.0442 (14)	0.0467 (15)	0.0021 (11)	0.0137 (11)	0.0231 (12)
C8	0.0449 (13)	0.0474 (14)	0.0365 (13)	0.0088 (10)	0.0155 (10)	0.0218 (11)
C9	0.0747 (19)	0.0637 (18)	0.0458 (16)	0.0113 (15)	0.0313 (15)	0.0207 (14)
C10	0.0417 (12)	0.0356 (12)	0.0318 (12)	0.0043 (9)	0.0096 (10)	0.0104 (10)
C11	0.0325 (11)	0.0335 (11)	0.0330 (12)	0.0086 (9)	0.0139 (9)	0.0105 (9)
C13	0.0497 (16)	0.099 (3)	0.066 (2)	0.0353 (16)	0.0243 (15)	0.0470 (19)
C14	0.068 (2)	0.086 (3)	0.177 (5)	0.002 (2)	−0.007 (3)	0.072 (3)
C12	0.0416 (12)	0.0318 (12)	0.0366 (13)	0.0108 (9)	0.0159 (10)	0.0107 (10)
N3	0.0364 (10)	0.0339 (10)	0.0340 (10)	0.0066 (8)	0.0112 (8)	0.0079 (8)
N4	0.0401 (10)	0.0319 (10)	0.0304 (10)	0.0054 (8)	0.0095 (8)	0.0082 (8)
C1	0.080 (2)	0.0609 (18)	0.0336 (15)	0.0046 (15)	0.0084 (14)	0.0131 (13)
C2	0.0550 (15)	0.0314 (12)	0.0344 (13)	0.0021 (10)	0.0037 (11)	0.0098 (10)
C3	0.0450 (14)	0.0431 (14)	0.0467 (16)	0.0014 (11)	−0.0047 (12)	0.0134 (12)
C15	0.0406 (14)	0.0656 (19)	0.075 (2)	0.0121 (13)	0.0207 (14)	0.0229 (16)
C4	0.0392 (12)	0.0352 (13)	0.0489 (15)	0.0062 (10)	0.0078 (11)	0.0133 (11)
O1	0.135 (2)	0.135 (3)	0.0666 (17)	0.065 (2)	0.0451 (17)	0.0586 (18)
O2	0.125 (2)	0.0526 (16)	0.163 (3)	−0.0057 (15)	0.031 (2)	0.0271 (18)
O3	0.140 (2)	0.0671 (16)	0.0824 (18)	0.0311 (16)	0.0106 (17)	0.0403 (14)
O4	0.088 (2)	0.178 (3)	0.116 (3)	0.040 (2)	0.0609 (19)	0.051 (2)
Cl1	0.0664 (4)	0.0457 (4)	0.0509 (4)	0.0129 (3)	0.0249 (3)	0.0234 (3)

Geometric parameters (Å, º) top

Zn1—N1	2.076 (2)	C11—H11	0.9800
Zn1—N3ⁱ	2.042 (2)	C13—C14	1.468 (6)
Zn1—O6	1.9908 (16)	C13—H13A	0.9700
Zn1—O6ⁱ	2.0428 (16)	C13—H13B	0.9700
Zn1—O7	2.1292 (18)	C14—H14A	0.9600
Zn1—Zn1ⁱ	3.0784 (9)	C14—H14B	0.9600
N1—C6	1.340 (3)	C14—H14C	0.9600
N1—N2	1.364 (3)	C12—N4	1.460 (3)
N2—C8	1.353 (3)	C12—H12A	0.9700
N2—C10	1.461 (3)	C12—H12B	0.9700
O6—C11	1.401 (3)	N3—C4	1.341 (3)
O6—Zn1ⁱ	2.0428 (16)	N3—N4	1.370 (3)
O7—C13	1.422 (3)	N3—Zn1ⁱ	2.042 (2)
O7—H7A	0.8500	N4—C2	1.346 (3)
C5—C6	1.496 (4)	C1—C2	1.491 (4)
C5—H5A	0.9600	C1—H1A	0.9600
C5—H5B	0.9600	C1—H1B	0.9600
C5—H5C	0.9600	C1—H1C	0.9600
C6—C7	1.385 (4)	C2—C3	1.372 (4)
C7—C8	1.366 (4)	C3—C4	1.385 (4)
C7—H7	0.9300	C3—H3	0.9300
C8—C9	1.497 (4)	C15—C4	1.495 (4)
C9—H9A	0.9600	C15—H15A	0.9600
C9—H9B	0.9600	C15—H15B	0.9600
C9—H9C	0.9600	C15—H15C	0.9600
C10—C11	1.522 (3)	O1—Cl1	1.414 (3)
C10—H10A	0.9700	O2—Cl1	1.401 (3)
C10—H10B	0.9700	O3—Cl1	1.422 (3)
C11—C12	1.534 (3)	O4—Cl1	1.402 (3)

O6—Zn1—N3ⁱ	112.71 (8)	C10—C11—C12	111.32 (19)
O6—Zn1—O6ⁱ	80.52 (7)	O6—C11—H11	107.6
N3ⁱ—Zn1—O6ⁱ	89.87 (7)	C10—C11—H11	107.6
O6—Zn1—N1	91.69 (7)	C12—C11—H11	107.6
N3ⁱ—Zn1—N1	106.21 (8)	O7—C13—C14	111.5 (3)
O6ⁱ—Zn1—N1	163.86 (7)	O7—C13—H13A	109.3
O6—Zn1—O7	130.72 (8)	C14—C13—H13A	109.3
N3ⁱ—Zn1—O7	115.77 (8)	O7—C13—H13B	109.3
O6ⁱ—Zn1—O7	91.14 (7)	C14—C13—H13B	109.3
N1—Zn1—O7	83.23 (8)	H13A—C13—H13B	108.0
O6—Zn1—Zn1ⁱ	40.88 (4)	C13—C14—H14A	109.5
N3ⁱ—Zn1—Zn1ⁱ	104.37 (6)	C13—C14—H14B	109.5
O6ⁱ—Zn1—Zn1ⁱ	39.63 (4)	H14A—C14—H14B	109.5
N1—Zn1—Zn1ⁱ	131.04 (6)	C13—C14—H14C	109.5
O7—Zn1—Zn1ⁱ	115.79 (6)	H14A—C14—H14C	109.5
C6—N1—N2	106.23 (19)	H14B—C14—H14C	109.5
C6—N1—Zn1	132.19 (16)	N4—C12—C11	112.81 (18)
N2—N1—Zn1	119.85 (14)	N4—C12—H12A	109.0
C8—N2—N1	110.49 (19)	C11—C12—H12A	109.0
C8—N2—C10	129.5 (2)	N4—C12—H12B	109.0
N1—N2—C10	119.68 (18)	C11—C12—H12B	109.0
C11—O6—Zn1	126.98 (13)	H12A—C12—H12B	107.8
C11—O6—Zn1ⁱ	124.67 (13)	C4—N3—N4	105.54 (19)
Zn1—O6—Zn1ⁱ	99.48 (7)	C4—N3—Zn1ⁱ	134.36 (17)
C13—O7—Zn1	128.78 (17)	N4—N3—Zn1ⁱ	117.88 (14)
C13—O7—H7A	103.2	C2—N4—N3	111.10 (19)
Zn1—O7—H7A	118.4	C2—N4—C12	129.4 (2)
C6—C5—H5A	109.5	N3—N4—C12	119.52 (18)
C6—C5—H5B	109.5	C2—C1—H1A	109.5
H5A—C5—H5B	109.5	C2—C1—H1B	109.5
C6—C5—H5C	109.5	H1A—C1—H1B	109.5
H5A—C5—H5C	109.5	C2—C1—H1C	109.5
H5B—C5—H5C	109.5	H1A—C1—H1C	109.5
N1—C6—C7	109.4 (2)	H1B—C1—H1C	109.5
N1—C6—C5	121.1 (2)	N4—C2—C3	106.6 (2)
C7—C6—C5	129.4 (2)	N4—C2—C1	122.5 (2)
C8—C7—C6	107.2 (2)	C3—C2—C1	130.8 (2)
C8—C7—H7	126.4	C2—C3—C4	106.8 (2)
C6—C7—H7	126.4	C2—C3—H3	126.6
N2—C8—C7	106.7 (2)	C4—C3—H3	126.6
N2—C8—C9	123.0 (2)	C4—C15—H15A	109.5
C7—C8—C9	130.2 (2)	C4—C15—H15B	109.5
C8—C9—H9A	109.5	H15A—C15—H15B	109.5
C8—C9—H9B	109.5	C4—C15—H15C	109.5
H9A—C9—H9B	109.5	H15A—C15—H15C	109.5
C8—C9—H9C	109.5	H15B—C15—H15C	109.5
H9A—C9—H9C	109.5	N3—C4—C3	109.9 (2)
H9B—C9—H9C	109.5	N3—C4—C15	121.5 (2)
N2—C10—C11	112.67 (19)	C3—C4—C15	128.6 (2)
N2—C10—H10A	109.1	O2—Cl1—O4	110.6 (2)
C11—C10—H10A	109.1	O2—Cl1—O1	110.3 (2)
N2—C10—H10B	109.1	O4—Cl1—O1	109.0 (2)
C11—C10—H10B	109.1	O2—Cl1—O3	107.9 (2)
H10A—C10—H10B	107.8	O4—Cl1—O3	110.9 (2)
O6—C11—C10	111.91 (18)	O1—Cl1—O3	108.07 (18)
O6—C11—C12	110.58 (18)

O6—Zn1—N1—C6	144.8 (2)	C10—N2—C8—C7	−174.6 (2)
N3ⁱ—Zn1—N1—C6	30.5 (2)	N1—N2—C8—C9	176.0 (2)
O6ⁱ—Zn1—N1—C6	−154.6 (2)	C10—N2—C8—C9	3.1 (4)
O7—Zn1—N1—C6	−84.4 (2)	C6—C7—C8—N2	2.3 (3)
Zn1ⁱ—Zn1—N1—C6	157.08 (19)	C6—C7—C8—C9	−175.3 (3)
O6—Zn1—N1—N2	−18.00 (17)	C8—N2—C10—C11	−120.3 (3)
N3ⁱ—Zn1—N1—N2	−132.25 (17)	N1—N2—C10—C11	67.4 (3)
O6ⁱ—Zn1—N1—N2	42.6 (3)	Zn1—O6—C11—C10	17.7 (2)
O7—Zn1—N1—N2	112.83 (18)	Zn1ⁱ—O6—C11—C10	−122.81 (16)
Zn1ⁱ—Zn1—N1—N2	−5.7 (2)	Zn1—O6—C11—C12	142.41 (15)
C6—N1—N2—C8	0.5 (3)	Zn1ⁱ—O6—C11—C12	1.9 (2)
Zn1—N1—N2—C8	167.30 (16)	N2—C10—C11—O6	−64.4 (2)
C6—N1—N2—C10	174.2 (2)	N2—C10—C11—C12	171.27 (17)
Zn1—N1—N2—C10	−19.0 (3)	Zn1—O7—C13—C14	67.8 (4)
N3ⁱ—Zn1—O6—C11	126.18 (16)	O6—C11—C12—N4	−60.2 (2)
O6ⁱ—Zn1—O6—C11	−147.97 (19)	C10—C11—C12—N4	64.9 (2)
N1—Zn1—O6—C11	17.82 (17)	C4—N3—N4—C2	1.5 (2)
O7—Zn1—O6—C11	−64.70 (18)	Zn1ⁱ—N3—N4—C2	166.94 (15)
Zn1ⁱ—Zn1—O6—C11	−147.97 (19)	C4—N3—N4—C12	−179.55 (19)
N3ⁱ—Zn1—O6—Zn1ⁱ	−85.85 (8)	Zn1ⁱ—N3—N4—C12	−14.1 (2)
O6ⁱ—Zn1—O6—Zn1ⁱ	0.0	C11—C12—N4—C2	−111.0 (3)
N1—Zn1—O6—Zn1ⁱ	165.79 (8)	C11—C12—N4—N3	70.2 (3)
O7—Zn1—O6—Zn1ⁱ	83.27 (10)	N3—N4—C2—C3	−1.9 (3)
O6—Zn1—O7—C13	−62.0 (3)	C12—N4—C2—C3	179.3 (2)
N3ⁱ—Zn1—O7—C13	106.8 (2)	N3—N4—C2—C1	175.6 (2)
O6ⁱ—Zn1—O7—C13	16.4 (2)	C12—N4—C2—C1	−3.3 (4)
N1—Zn1—O7—C13	−148.4 (2)	N4—C2—C3—C4	1.5 (3)
Zn1ⁱ—Zn1—O7—C13	−15.8 (2)	C1—C2—C3—C4	−175.6 (3)
N2—N1—C6—C7	1.0 (3)	N4—N3—C4—C3	−0.5 (3)
Zn1—N1—C6—C7	−163.53 (18)	Zn1ⁱ—N3—C4—C3	−162.39 (18)
N2—N1—C6—C5	−175.6 (2)	N4—N3—C4—C15	179.5 (2)
Zn1—N1—C6—C5	20.0 (4)	Zn1ⁱ—N3—C4—C15	17.6 (4)
N1—C6—C7—C8	−2.0 (3)	C2—C3—C4—N3	−0.7 (3)
C5—C6—C7—C8	174.1 (3)	C2—C3—C4—C15	179.4 (3)
N1—N2—C8—C7	−1.8 (3)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O3	0.85	2.03	2.860 (3)	165

Experimental details

Crystal data
Chemical formula	[Zn₂(C₁₃H₁₉N₄O)₂(C₂H₆O)₂](ClO₄)₂
M_r	916.42
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.8570 (18), 11.148 (2), 11.300 (2)
α, β, γ (°)	111.13 (3), 100.40 (3), 100.11 (3)
V (Å³)	987.8 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.42
Crystal size (mm)	0.22 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.765, 0.765
No. of measured, independent and observed [I > 2σ(I)] reflections	7788, 3482, 3172
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.083, 1.07
No. of reflections	3482
No. of parameters	249
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.22

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

Selected bond lengths (Å) top

Zn1—N1	2.076 (2)	Zn1—O6ⁱ	2.0428 (16)
Zn1—N3ⁱ	2.042 (2)	Zn1—O7	2.1292 (18)
Zn1—O6	1.9908 (16)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O3	0.85	2.03	2.860 (3)	165

Acknowledgements

We are grateful for support from Henan University of Urban Construction.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Montoya, V., Pons, J., Garcia-Antón, J., Solans, X., Font-Bardia, M. & Ros, J. (2007). Inorg. Chim. Acta, 360, 625–637. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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