Diacetatobis[1,3-bis­(benzimidazol-2-yl)benzene]zinc(II) dihydrate

Meng, F.-Y.; Teng, L.; Chen, X.M.; Zhao, B.L.; Jiao, P.

doi:10.1107/S160053680706878X

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page m319

doi:10.1107/S160053680706878X

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Diacetatobis[1,3-bis(benzimidazol-2-yl)benzene]zinc(II) dihydrate

Fa-Yan Meng,^a ^* Lei Teng,^a Xue Mei Chen,^a Bi Lin Zhao ^a and Ping Jiao ^a

^aSchool of Chemistry and Materials Engineering, Huangshi Institute of Technology, Huangshi 435003, People's Republic of China
^*Correspondence e-mail: mfy1114@yahoo.com.cn

(Received 19 November 2007; accepted 30 December 2007; online 9 January 2008)

In the title complex, [Zn(CH₃COO)₂(C₂₀H₁₄N₄)₂]·2H₂O, the Zn^II atom, which lies on a crystallographic twofold axis, is coordinated by two O atoms of two acetate ligands and two N atoms from two 1,3-bis(benzimidazol-2-yl)benzene ligands in a distorted tetrahedral geometry. The complex molecules and solvent water molecules are connected via O—H⋯N, O—H⋯O and N—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For related literature, see: Meng et al. (2007 ); Chawla et al. (1997 ); Shivakumaraiah et al. (2003 ).

Experimental

Crystal data

[Zn(C₂H₃O₂)₂(C₂₀H₁₄N₄)₂]·2H₂O
M_r = 840.19
Orthorhombic, P b c n
a = 14.1429 (3) Å
b = 16.7005 (4) Å
c = 16.5588 (3) Å
V = 3911.08 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 153 (2) K
0.42 × 0.29 × 0.26 mm

Data collection

Rigaku R-AXIS SPIDER diffractometer
Absorption correction: multi-scan (Higashi, 1995 ) T_min = 0.760, T_max = 0.841
36097 measured reflections
4483 independent reflections
4032 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.080
S = 1.06
4483 reflections
285 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O3	0.871 (9)	1.817 (9)	2.6848 (14)	174.0 (17)
N3—H3N⋯O1ⁱ	0.858 (9)	2.158 (10)	3.0079 (14)	170.6 (17)
O3—H3AO⋯N4ⁱⁱ	0.839 (9)	1.968 (10)	2.8046 (16)	175 (2)
O3—H3BO⋯O2ⁱⁱⁱ	0.839 (9)	1.991 (10)	2.8295 (15)	179 (2)
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2000 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680706878X/bg2142sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680706878X/bg2142Isup2.hkl

checkCIF report

Comment top

Benzimidazolyl derivatives and their transition metal complexes have been extensively investigated (Shivakumaraiah et al., 2003). In previous works zinc terephthalate and zinc succinate adducts of 1,3-bis(benzimidazol-2-ylmethyl)benzene have been reported (Meng et al., 2007; Meng et al., 2007). The present work reports the crystal structure of [Zn(ac)₂(L)₂]^.2H₂O, (I), where L is 1,3-bis(benzimidazol-2-ylmethyl)benzene and ac is the acetate ion, which assumes a similar geometry to previously reported complexes in the literature (Meng et al., 2007). (shown in scheme I). The crystal structure of (I) consists of the mononuclear zinc(II) complex and solvato water molecules (Fig. 1). The Zn atom is four-coordinate with two N atoms and two O atoms from the 1,3-bis(benzimidazol-2- ylmethyl)benzene and the acetate ligands, respectively. (Zn—O: 2.0145 (9) Å, Zn—N: 2.0477 (10) Å, coordination angle range: 101.39 (4)- 127.50 (5) °.). The complex and solvent water molecules are connected via O—H···N, O—H···O and N—H···O hydrogen bonds to form a three-dimensional network (Table 1).

Related literature top

For related literature, see: Meng et al. (2007); Chawla et al. (1997); Shivakumaraiah et al. (2003).

Experimental top

The N-heterocycle was prepared according to reported procedure (Chawla & Gill,1997). Zinc nitrate hexahydrate (0.074 g, 0.25 mmol), 1,3-bis(benzimidazolyl-2-ylmethyl)benzene (0.15 g, 0.5 mmol), acetic acid (2 ml) and water (15 ml) were placed in a 23 ml Teflon-lined stainless steel Parr bomb. The bomb was heated at 433 K for 5 days and cooled to room temperature at 5 K h^-1.Colorless block crystals were obtained in 15% yield.

Computing details top

Data collection: RAPID-AUTO (Rigaku 2004); cell refinement: RAPID-AUTO (Rigaku 2004); data reduction: RAPID-AUTO (Rigaku 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).

Figures top

Fig. 1. Molecular unit of (I) showing the coordination geometry of zinc. Displacement ellipsoids drawn at a 50% probability level. The independent part of the molecule drawn with heavy bonds; the (overlapping) symmetry related one, with light bonds. Only H atoms invovled in H-bonding (in dashed lines) have been included.[Symmery code (i): 1 - x, y, 1/2 - z].

Diacetatobis[1,3-bis(benzimidazol-2-yl)benzene]zinc(II) dihydrate top

Crystal data top

[Zn(C₂H₃O₂)₂(C₂₀H₁₄N₄)₂]·2H₂O	F(000) = 1744
M_r = 840.19	D_x = 1.427 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 29371 reflections
a = 14.1429 (3) Å	θ = 3.1–27.5°
b = 16.7005 (4) Å	µ = 0.69 mm⁻¹
c = 16.5588 (3) Å	T = 153 K
V = 3911.08 (13) Å³	Block, colourless
Z = 4	0.42 × 0.29 × 0.26 mm

Data collection top

Rigaku R-axis SPIDER diffractometer	4483 independent reflections
Radiation source: Rotating Anode	4032 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (Higashi, 1995)	h = −18→18
T_min = 0.761, T_max = 0.841	k = −21→21
36097 measured reflections	l = −21→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0456P)² + 1.3144P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4483 reflections	Δρ_max = 0.35 e Å⁻³
285 parameters	Δρ_min = −0.35 e Å⁻³
4 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (3)

Crystal data top

[Zn(C₂H₃O₂)₂(C₂₀H₁₄N₄)₂]·2H₂O	V = 3911.08 (13) Å³
M_r = 840.19	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 14.1429 (3) Å	µ = 0.69 mm⁻¹
b = 16.7005 (4) Å	T = 153 K
c = 16.5588 (3) Å	0.42 × 0.29 × 0.26 mm

Data collection top

Rigaku R-axis SPIDER diffractometer	4483 independent reflections
Absorption correction: multi-scan (Higashi, 1995)	4032 reflections with I > 2σ(I)
T_min = 0.761, T_max = 0.841	R_int = 0.022
36097 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	4 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.35 e Å⁻³
4483 reflections	Δρ_min = −0.35 e Å⁻³
285 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
Zn	0.5000	0.200846 (12)	0.2500	0.02036 (8)
O1	0.43810 (7)	0.14750 (5)	0.15455 (5)	0.0247 (2)
O2	0.38164 (9)	0.08183 (6)	0.25947 (6)	0.0346 (2)
N1	0.59696 (7)	0.27314 (6)	0.19415 (6)	0.0199 (2)
N2	0.65402 (8)	0.38807 (6)	0.14616 (6)	0.0229 (2)
N3	0.58881 (8)	0.23678 (7)	0.50153 (7)	0.0239 (2)
N4	0.62077 (8)	0.34087 (7)	0.58182 (7)	0.0270 (2)
C1	0.62241 (8)	0.26200 (7)	0.11345 (7)	0.0200 (2)
C2	0.62085 (9)	0.19356 (8)	0.06492 (8)	0.0243 (3)
H2	0.5999	0.1434	0.0853	0.029*
C3	0.65122 (10)	0.20211 (8)	−0.01423 (8)	0.0287 (3)
H3	0.6509	0.1567	−0.0488	0.034*
C4	0.68243 (10)	0.27583 (9)	−0.04472 (8)	0.0309 (3)
H4	0.7013	0.2794	−0.0997	0.037*
C5	0.68638 (10)	0.34315 (8)	0.00321 (8)	0.0277 (3)
H5	0.7083	0.3930	−0.0172	0.033*
C6	0.65670 (9)	0.33473 (7)	0.08296 (7)	0.0220 (2)
C7	0.61950 (8)	0.34911 (7)	0.21111 (7)	0.0203 (2)
C8	0.61087 (8)	0.38614 (7)	0.29088 (7)	0.0214 (2)
C9	0.59900 (9)	0.46915 (8)	0.30015 (8)	0.0252 (3)
H9	0.5977	0.5031	0.2541	0.030*
C10	0.58919 (10)	0.50126 (8)	0.37704 (9)	0.0284 (3)
H10	0.5807	0.5573	0.3833	0.034*
C11	0.59159 (9)	0.45248 (8)	0.44476 (8)	0.0264 (3)
H11	0.5852	0.4752	0.4971	0.032*
C12	0.60338 (9)	0.36969 (7)	0.43607 (8)	0.0223 (2)
C13	0.60420 (9)	0.31727 (8)	0.50712 (8)	0.0229 (2)
C14	0.61670 (10)	0.27139 (8)	0.62767 (8)	0.0272 (3)
C15	0.63182 (12)	0.26000 (10)	0.71047 (9)	0.0375 (3)
H15	0.6462	0.3038	0.7450	0.045*
C16	0.62511 (14)	0.18299 (11)	0.74009 (9)	0.0405 (4)
H16	0.6352	0.1738	0.7960	0.049*
C17	0.60381 (11)	0.11817 (9)	0.69005 (9)	0.0359 (3)
H17	0.5993	0.0661	0.7128	0.043*
C18	0.58912 (10)	0.12804 (8)	0.60805 (9)	0.0305 (3)
H18	0.5750	0.0840	0.5738	0.037*
C19	0.59617 (9)	0.20575 (8)	0.57840 (8)	0.0248 (3)
C20	0.61400 (9)	0.33772 (7)	0.35896 (8)	0.0219 (3)
H20	0.6236	0.2817	0.3528	0.026*
C21	0.39227 (9)	0.08843 (7)	0.18557 (8)	0.0236 (3)
C22	0.35683 (12)	0.02507 (9)	0.12828 (9)	0.0359 (3)
H22A	0.4009	−0.0202	0.1280	0.043*
H22B	0.3522	0.0475	0.0738	0.043*
H22C	0.2943	0.0067	0.1458	0.043*
H2N	0.6812 (12)	0.4349 (7)	0.1461 (11)	0.043 (5)*
H3N	0.5746 (13)	0.2099 (9)	0.4590 (8)	0.038 (5)*
O3	0.73576 (9)	0.53271 (6)	0.13461 (7)	0.0396 (3)
H3AO	0.7035 (13)	0.5725 (9)	0.1205 (12)	0.055 (6)*
H3BO	0.7795 (12)	0.5466 (12)	0.1658 (11)	0.057 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.02511 (12)	0.01605 (12)	0.01992 (12)	0.000	0.00432 (7)	0.000
O1	0.0304 (5)	0.0176 (4)	0.0262 (5)	−0.0038 (3)	0.0034 (4)	0.0008 (3)
O2	0.0477 (6)	0.0271 (5)	0.0291 (5)	−0.0057 (5)	0.0114 (4)	0.0010 (4)
N1	0.0221 (5)	0.0175 (5)	0.0201 (5)	−0.0003 (4)	0.0027 (4)	−0.0001 (4)
N2	0.0252 (5)	0.0195 (5)	0.0239 (5)	−0.0036 (4)	−0.0017 (4)	0.0035 (4)
N3	0.0279 (6)	0.0229 (5)	0.0208 (5)	−0.0006 (4)	−0.0004 (4)	−0.0012 (4)
N4	0.0323 (6)	0.0267 (6)	0.0219 (5)	−0.0011 (4)	−0.0026 (4)	−0.0012 (4)
C1	0.0184 (5)	0.0218 (6)	0.0196 (6)	0.0018 (4)	0.0014 (4)	0.0022 (5)
C2	0.0241 (6)	0.0228 (6)	0.0260 (6)	0.0022 (5)	0.0035 (5)	−0.0003 (5)
C3	0.0284 (7)	0.0333 (7)	0.0243 (6)	0.0048 (5)	0.0026 (5)	−0.0045 (5)
C4	0.0289 (7)	0.0421 (8)	0.0216 (6)	0.0030 (6)	0.0033 (5)	0.0035 (6)
C5	0.0276 (6)	0.0318 (7)	0.0237 (6)	−0.0022 (5)	0.0004 (5)	0.0090 (5)
C6	0.0205 (6)	0.0229 (6)	0.0226 (6)	−0.0001 (5)	−0.0016 (5)	0.0030 (5)
C7	0.0200 (5)	0.0182 (5)	0.0227 (6)	0.0001 (4)	−0.0008 (5)	0.0020 (5)
C8	0.0205 (6)	0.0202 (6)	0.0236 (6)	−0.0015 (4)	−0.0018 (5)	−0.0015 (5)
C9	0.0278 (6)	0.0191 (6)	0.0287 (6)	−0.0012 (5)	−0.0045 (5)	0.0013 (5)
C10	0.0335 (7)	0.0187 (6)	0.0332 (7)	0.0014 (5)	−0.0055 (6)	−0.0043 (5)
C11	0.0288 (6)	0.0240 (6)	0.0263 (6)	0.0019 (5)	−0.0022 (5)	−0.0063 (5)
C12	0.0211 (6)	0.0219 (6)	0.0239 (6)	−0.0001 (4)	−0.0022 (5)	−0.0009 (5)
C13	0.0219 (6)	0.0233 (6)	0.0233 (6)	0.0009 (5)	−0.0011 (5)	−0.0023 (5)
C14	0.0276 (7)	0.0285 (7)	0.0255 (6)	−0.0005 (5)	−0.0012 (5)	0.0005 (5)
C15	0.0499 (9)	0.0384 (8)	0.0241 (7)	−0.0034 (7)	−0.0054 (6)	−0.0009 (6)
C16	0.0507 (10)	0.0463 (9)	0.0246 (7)	0.0003 (8)	−0.0030 (6)	0.0074 (6)
C17	0.0404 (8)	0.0334 (7)	0.0338 (7)	0.0027 (6)	0.0038 (6)	0.0093 (6)
C18	0.0341 (7)	0.0260 (6)	0.0313 (7)	0.0015 (5)	0.0036 (6)	0.0016 (6)
C19	0.0224 (6)	0.0287 (6)	0.0234 (6)	0.0013 (5)	0.0013 (5)	0.0016 (5)
C20	0.0229 (6)	0.0182 (6)	0.0246 (6)	−0.0002 (4)	−0.0018 (5)	−0.0016 (5)
C21	0.0241 (6)	0.0177 (6)	0.0290 (6)	0.0003 (4)	0.0019 (5)	0.0022 (5)
C22	0.0432 (9)	0.0275 (7)	0.0370 (8)	−0.0092 (6)	−0.0095 (6)	0.0003 (6)
O3	0.0458 (7)	0.0217 (5)	0.0511 (7)	−0.0099 (5)	−0.0215 (5)	0.0115 (5)

Geometric parameters (Å, º) top

Zn—O1	2.0145 (9)	C8—C20	1.3880 (17)
Zn—O1ⁱ	2.0145 (9)	C8—C9	1.4047 (17)
Zn—N1	2.0477 (10)	C9—C10	1.3886 (19)
Zn—N1ⁱ	2.0477 (10)	C9—H9	0.9500
O1—C21	1.2873 (15)	C10—C11	1.386 (2)
O2—C21	1.2378 (16)	C10—H10	0.9500
N1—C7	1.3380 (16)	C11—C12	1.4001 (17)
N1—C1	1.3964 (15)	C11—H11	0.9500
N2—C7	1.3485 (16)	C12—C20	1.3923 (17)
N2—C6	1.3748 (16)	C12—C13	1.4664 (18)
N2—H2N	0.871 (9)	C14—C19	1.3970 (19)
N3—C13	1.3649 (16)	C14—C15	1.4006 (19)
N3—C19	1.3782 (17)	C15—C16	1.380 (2)
N3—H3N	0.858 (9)	C15—H15	0.9500
N4—C13	1.3193 (17)	C16—C17	1.396 (2)
N4—C14	1.3878 (17)	C16—H16	0.9500
C1—C2	1.3974 (17)	C17—C18	1.384 (2)
C1—C6	1.4020 (17)	C17—H17	0.9500
C2—C3	1.3867 (19)	C18—C19	1.3912 (19)
C2—H2	0.9500	C18—H18	0.9500
C3—C4	1.402 (2)	C20—H20	0.9500
C3—H3	0.9500	C21—C22	1.5069 (18)
C4—C5	1.377 (2)	C22—H22A	0.9800
C4—H4	0.9500	C22—H22B	0.9800
C5—C6	1.3928 (18)	C22—H22C	0.9800
C5—H5	0.9500	O3—H3AO	0.839 (9)
C7—C8	1.4636 (17)	O3—H3BO	0.839 (9)

O1—Zn—O1ⁱ	127.50 (5)	C11—C10—C9	120.81 (12)
O1—Zn—N1	101.39 (4)	C11—C10—H10	119.6
O1ⁱ—Zn—N1	108.91 (4)	C9—C10—H10	119.6
O1—Zn—N1ⁱ	108.91 (4)	C10—C11—C12	120.01 (12)
O1ⁱ—Zn—N1ⁱ	101.39 (4)	C10—C11—H11	120.0
N1—Zn—N1ⁱ	107.74 (6)	C12—C11—H11	120.0
C21—O1—Zn	104.16 (8)	C20—C12—C11	119.07 (12)
C7—N1—C1	105.41 (10)	C20—C12—C13	120.39 (11)
C7—N1—Zn	128.60 (8)	C11—C12—C13	120.54 (12)
C1—N1—Zn	121.75 (8)	N4—C13—N3	112.71 (12)
C7—N2—C6	107.73 (10)	N4—C13—C12	125.12 (12)
C7—N2—H2N	126.4 (12)	N3—C13—C12	122.16 (11)
C6—N2—H2N	124.6 (12)	N4—C14—C19	110.20 (12)
C13—N3—C19	107.19 (11)	N4—C14—C15	130.00 (13)
C13—N3—H3N	127.4 (12)	C19—C14—C15	119.79 (13)
C19—N3—H3N	125.3 (12)	C16—C15—C14	117.66 (14)
C13—N4—C14	104.82 (11)	C16—C15—H15	121.2
N1—C1—C2	130.94 (11)	C14—C15—H15	121.2
N1—C1—C6	108.57 (11)	C15—C16—C17	121.78 (14)
C2—C1—C6	120.46 (11)	C15—C16—H16	119.1
C3—C2—C1	117.04 (12)	C17—C16—H16	119.1
C3—C2—H2	121.5	C18—C17—C16	121.50 (14)
C1—C2—H2	121.5	C18—C17—H17	119.3
C2—C3—C4	121.89 (13)	C16—C17—H17	119.3
C2—C3—H3	119.1	C17—C18—C19	116.54 (14)
C4—C3—H3	119.1	C17—C18—H18	121.7
C5—C4—C3	121.48 (12)	C19—C18—H18	121.7
C5—C4—H4	119.3	N3—C19—C18	132.16 (13)
C3—C4—H4	119.3	N3—C19—C14	105.07 (11)
C4—C5—C6	116.86 (12)	C18—C19—C14	122.74 (13)
C4—C5—H5	121.6	C8—C20—C12	121.19 (11)
C6—C5—H5	121.6	C8—C20—H20	119.4
N2—C6—C5	131.66 (12)	C12—C20—H20	119.4
N2—C6—C1	106.12 (11)	O2—C21—O1	121.59 (12)
C5—C6—C1	122.22 (12)	O2—C21—C22	121.30 (12)
N1—C7—N2	112.11 (11)	O1—C21—C22	117.02 (12)
N1—C7—C8	124.76 (11)	C21—C22—H22A	109.5
N2—C7—C8	123.11 (11)	C21—C22—H22B	109.5
C20—C8—C9	119.35 (11)	H22A—C22—H22B	109.5
C20—C8—C7	118.95 (11)	C21—C22—H22C	109.5
C9—C8—C7	121.70 (12)	H22A—C22—H22C	109.5
C10—C9—C8	119.55 (12)	H22B—C22—H22C	109.5
C10—C9—H9	120.2	H3AO—O3—H3BO	110.7 (19)
C8—C9—H9	120.2

O1ⁱ—Zn—O1—C21	40.82 (7)	C20—C8—C9—C10	−0.95 (19)
N1—Zn—O1—C21	165.66 (8)	C7—C8—C9—C10	178.68 (12)
N1ⁱ—Zn—O1—C21	−80.92 (8)	C8—C9—C10—C11	0.4 (2)
O1—Zn—N1—C7	137.44 (10)	C9—C10—C11—C12	−0.4 (2)
O1ⁱ—Zn—N1—C7	−86.05 (11)	C10—C11—C12—C20	0.97 (19)
N1ⁱ—Zn—N1—C7	23.14 (9)	C10—C11—C12—C13	−178.81 (12)
O1—Zn—N1—C1	−15.92 (10)	C14—N4—C13—N3	0.51 (15)
O1ⁱ—Zn—N1—C1	120.59 (9)	C14—N4—C13—C12	−178.52 (12)
N1ⁱ—Zn—N1—C1	−130.22 (10)	C19—N3—C13—N4	−0.16 (15)
C7—N1—C1—C2	175.43 (13)	C19—N3—C13—C12	178.90 (11)
Zn—N1—C1—C2	−25.88 (18)	C20—C12—C13—N4	160.33 (13)
C7—N1—C1—C6	−2.48 (13)	C11—C12—C13—N4	−19.9 (2)
Zn—N1—C1—C6	156.20 (8)	C20—C12—C13—N3	−18.61 (18)
N1—C1—C2—C3	−179.94 (13)	C11—C12—C13—N3	161.17 (12)
C6—C1—C2—C3	−2.24 (19)	C13—N4—C14—C19	−0.68 (15)
C1—C2—C3—C4	0.1 (2)	C13—N4—C14—C15	177.69 (15)
C2—C3—C4—C5	1.5 (2)	N4—C14—C15—C16	−178.56 (15)
C3—C4—C5—C6	−0.9 (2)	C19—C14—C15—C16	−0.3 (2)
C7—N2—C6—C5	−179.54 (13)	C14—C15—C16—C17	−0.2 (3)
C7—N2—C6—C1	−0.20 (13)	C15—C16—C17—C18	0.5 (3)
C4—C5—C6—N2	177.96 (13)	C16—C17—C18—C19	−0.3 (2)
C4—C5—C6—C1	−1.29 (19)	C13—N3—C19—C18	−178.53 (14)
N1—C1—C6—N2	1.67 (13)	C13—N3—C19—C14	−0.26 (14)
C2—C1—C6—N2	−176.50 (11)	C17—C18—C19—N3	177.85 (14)
N1—C1—C6—C5	−178.92 (12)	C17—C18—C19—C14	−0.2 (2)
C2—C1—C6—C5	2.91 (19)	N4—C14—C19—N3	0.59 (15)
C1—N1—C7—N2	2.43 (14)	C15—C14—C19—N3	−177.97 (13)
Zn—N1—C7—N2	−154.27 (9)	N4—C14—C19—C18	179.06 (13)
C1—N1—C7—C8	−175.89 (11)	C15—C14—C19—C18	0.5 (2)
Zn—N1—C7—C8	27.41 (17)	C9—C8—C20—C12	1.52 (18)
C6—N2—C7—N1	−1.44 (14)	C7—C8—C20—C12	−178.12 (11)
C6—N2—C7—C8	176.92 (11)	C11—C12—C20—C8	−1.53 (19)
N1—C7—C8—C20	25.18 (18)	C13—C12—C20—C8	178.26 (12)
N2—C7—C8—C20	−152.96 (12)	Zn—O1—C21—O2	10.67 (15)
N1—C7—C8—C9	−154.45 (12)	Zn—O1—C21—C22	−165.93 (10)
N2—C7—C8—C9	27.41 (18)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3	0.87 (1)	1.82 (1)	2.6848 (14)	174 (2)
N3—H3N···O1ⁱ	0.86 (1)	2.16 (1)	3.0079 (14)	171 (2)
O3—H3AO···N4ⁱⁱ	0.84 (1)	1.97 (1)	2.8046 (16)	175 (2)
O3—H3BO···O2ⁱⁱⁱ	0.84 (1)	1.99 (1)	2.8295 (15)	179 (2)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₂H₃O₂)₂(C₂₀H₁₄N₄)₂]·2H₂O
M_r	840.19
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	153
a, b, c (Å)	14.1429 (3), 16.7005 (4), 16.5588 (3)
V (Å³)	3911.08 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.42 × 0.29 × 0.26

Data collection
Diffractometer	Rigaku R-axis SPIDER diffractometer
Absorption correction	Multi-scan (Higashi, 1995)
T_min, T_max	0.761, 0.841
No. of measured, independent and observed [I > 2σ(I)] reflections	36097, 4483, 4032
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.080, 1.06
No. of reflections	4483
No. of parameters	285
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.35

Computer programs: RAPID-AUTO (Rigaku 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3	0.871 (9)	1.817 (9)	2.6848 (14)	174.0 (17)
N3—H3N···O1ⁱ	0.858 (9)	2.158 (10)	3.0079 (14)	170.6 (17)
O3—H3AO···N4ⁱⁱ	0.839 (9)	1.968 (10)	2.8046 (16)	175 (2)
O3—H3BO···O2ⁱⁱⁱ	0.839 (9)	1.991 (10)	2.8295 (15)	179 (2)

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

Acknowledgements

We thank the Huangshi Institute of Technology (Grant No. 07yjz07A) for supporting this study.

References

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