A neutral cubane with a ZnII4O4 core: tetra­benzoato­tetra­kis(μ3-hydroxydi-2-pyridylmethano­lato)tetra­zinc(II)–acetone–methanol (1/2/1)

Shin, D.H.; Han, S.-H.; Kim, P.-G.; Kim, C.; Kim, Y.

doi:10.1107/S1600536809017772

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages m658-m659

doi:10.1107/S1600536809017772

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A neutral cubane with a Zn^II₄O₄ core: tetrabenzoatotetrakis(μ₃-hydroxydi-2-pyridylmethanolato)tetrazinc(II)–acetone–methanol (1/2/1)

Dong Hoon Shin,^a Sim-Hee Han,^b Pan-Gi Kim,^c Cheal Kim ^a ^* and Youngmee Kim ^d ^*

^aDepartment of Fine Chemistry, and Eco-Product and Materials Education Center, Seoul National University of Technology, Seoul 139-743, Republic of Korea, ^bDivision of Forest Genetic Resources, Korea Forest Research Institute, Suwon, Gyeonggi-Do 441-350, Republic of Korea, ^cDepartment of Forest & Environment Resources, Kyungpook National University, Sangju 742-711, Republic of Korea, and ^dDepartment of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Republic of Korea
^*Correspondence e-mail: chealkim@sunt.ac.kr, ymeekim@ewha.ac.kr

(Received 28 April 2009; accepted 12 May 2009; online 20 May 2009)

In the title compound, [Zn₄(C₁₁H₉N₂O₂)₄(C₇H₅O₂)₄]·2(CH₃)₂CO·CH₃OH, the tetranuclear molecule lies on a fourfold inversion axis. Zn^II ions and μ₃-O atoms in the cubane core occupy alternating vertices, forming two interpenetrating tetrahedra. Each Zn^II ion is further coordinated by two N atoms from two different (py)₂C(OH)O ligands (py is pyridyl) and one O atom from a monodentate benzoate ligand, forming a distorted octahedral environment. The (py)₂C(OH)O ligand acts in an η¹:η³:η¹:μ₃ manner, forming two five-membered ZnNCCO chelating rings with two different Zn^II atoms sharing a common C—O bond, and an alkoxide-type bond to a third Zn^II ion. There are four symmetry-related intramolecular O—H⋯O hydrogen bonds between the two types of ligands. In the asymmetric unit, there is a half-occupancy acetone solvent molecule and a half-occupancy methanol solvent molecule that lies on a twofold rotation axis.

Related literature

For background to transition metal ions as the major cationic contributors to the inorganic composition of natural water and biological fluids, see: Daniele et al. (2008 ); For related crystal structures, see: Lee et al. (2008 ); Park et al. (2008 ); Yu et al. (2008 ); Stoumpos et al. (2008 ); Papaefstathiou & Perlepes (2002 ); Papatriantafyllopoulou et al. (2007 ).

Experimental

Crystal data

[Zn₄(C₁₁H₉N₂O₂)₄(C₇H₅O₂)₄]·2C₃H₆O·CH₄O
M_r = 6795.70
Tetragonal, $[I \overline 42d ]$
a = 14.3201 (4) Å
c = 37.730 (2) Å
V = 7737.1 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.30 mm⁻¹
T = 170 K
0.10 × 0.08 × 0.05 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.883, T_max = 0.937
22787 measured reflections
4628 independent reflections
4279 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.110
S = 1.09
4628 reflections
245 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 1.37 e Å⁻³
Δρ_min = −0.42 e Å⁻³
Absolute structure: Flack (1983 ), 2045 Friedel pairs
Flack parameter: 0.002 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O4	0.86	1.81	2.664 (3)	172

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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: 10.1107/S1600536809017772/lh2815sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017772/lh2815Isup2.hkl

checkCIF report

Comment top

Transition metal ions have, recently, received attention as the major cationic contributors to the inorganic composition of natural water and biological fluids (Daniele, et al., 2008). While the main interest is focused on the interaction of transition metal ions with biologically active molecules such as amino acids, proteins, sugars and nucleotides, the study on the interaction of the transition metal ions with fulvic acids and humic acids, mainly found in soil, is in incipient stages. As models to examine the interaction, therefore, we have previously used copper(II) benzoate as a building block and reported the structures of copper(II) benzoates with quinoxaline, 6-methylquinoline, and 3-methylquinoline (Lee, et al., 2008; Yu, et al., 2008; Park, et al., 2008). In this work, we have employed zinc(II) benzoate as a building block and di-2-pyridyl ketone as a ligand. We report herein the structure of the product of zinc(II) benzoate with di-2-pyridyl ketone.

The crystal structure contains tetranuclear [Zn₄(O₂CPh)₄{(py)₂C(OH)O}₄] molecules (Fig. 1), similar to the corresponding Mn₄ cubane compound (Stoumpos, et al., 2008). The tetramolecular molecule lies on a fourfold inversion center and hence the asymmetric unit contains a quarter of a molecule. Zn^II ions and µ₃-O atoms in the cubane [Zn^II₄(µ₃-OR)₄]⁴⁺ core occupy alternate vertices. Thus, the molecule consists of two interpenetrating tetrahedra: one contains four µ₃-O atoms originating from the (py)₂C(OH)O ligands, and the other contains four Zn^II atoms. Each Zn^II center is coordinated by two N atoms from two different (py)₂C(OH)O ligands and one O atom from a monodentate PhCO₂^- ligand to form a distorted octahedral geometry. The (py)₂C(OH)O ligands acts as η¹:η³:η¹:µ₃ to form two five-membered ZnNCCO chelating rings with two different Zn^II ions sharing a common C—O edge and an alkoxide-type bond to a third Zn^II ion. This ligation mode is common for the hydrated di-2-pyridyl ketone, (py)₂C(OH)O^- (Papaefstathiou & Perlepes, 2002; Papatriantafyllopoulou, et al., 2007). There are intramolecular hydrogen bonds interactions between the protonated O atom of the (py)₂C(OH)O ligand and the uncoordinated O atom of the monodentate PhCO₂ group.

Related literature top

For background to transition metal ions as the major cationic contributors to the inorganic composition of natural water and biological fluids, see: Daniele et al. (2008); For related crystal structures, see: Lee et al. (2008); Park et al. (2008); Yu et al. (2008); Stoumpos et al. (2008); Papaefstathiou & Perlepes (2002); Papatriantafyllopoulou et al., (2007).

Experimental top

38.0 mg (0.125 mmol) of Zn(NO₃)₂^.6H₂O and 35.5 mg (0.25 mmol) of C₆H₅COONH₄ were dissolved in 4 ml water and carefully layered by 4 ml solution of a mixture of acetone, methanol and ethanol (2/2/2) of di-2-pyridyl ketone ligand (46.1 mg, 0.25 mmol). Crystals of the title compound suitable for X-ray analysis were obtained in a few weeks.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. Partially labeled molecular structure of the title complex. Displacement ellipsoids areshown at the 30% probability level. The green dotted lines represent hydrogen bonds. Solvent molecules are not shown.

Tetrabenzoatotetrakis(µ₃-hydroxydi-2-pyridylmethanolato)tetrazinc(II)– acetone–methanol (1/2/1) top

Crystal data top

[Zn₄(C₁₁H₉N₂O₂)₄(C₇H₅O₂)₄]·2C₃H₆O·CH₄O	D_x = 1.458 Mg m⁻³
M_r = 6795.70	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42d	Cell parameters from 8208 reflections
Hall symbol: I -4 2bw	θ = 2.8–27.0°
a = 14.3201 (4) Å	µ = 1.30 mm⁻¹
c = 37.730 (2) Å	T = 170 K
V = 7737.1 (5) Å³	Polyhedron, colorless
Z = 1	0.10 × 0.08 × 0.05 mm
F(000) = 3496

Data collection top

Bruker SMART CCD diffractometer	4628 independent reflections
Radiation source: fine-focus sealed tube	4279 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 28.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −18→18
T_min = 0.883, T_max = 0.937	k = −9→18
22787 measured reflections	l = −48→48

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0787P)² + 0.4409P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
4628 reflections	Δρ_max = 1.37 e Å⁻³
245 parameters	Δρ_min = −0.42 e Å⁻³
5 restraints	Absolute structure: Flack (1983), 2045 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.002 (13)

Crystal data top

[Zn₄(C₁₁H₉N₂O₂)₄(C₇H₅O₂)₄]·2C₃H₆O·CH₄O	Z = 1
M_r = 6795.70	Mo Kα radiation
Tetragonal, I42d	µ = 1.30 mm⁻¹
a = 14.3201 (4) Å	T = 170 K
c = 37.730 (2) Å	0.10 × 0.08 × 0.05 mm
V = 7737.1 (5) Å³

Data collection top

Bruker SMART CCD diffractometer	4628 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	4279 reflections with I > 2σ(I)
T_min = 0.883, T_max = 0.937	R_int = 0.029
22787 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.110	Δρ_max = 1.37 e Å⁻³
S = 1.09	Δρ_min = −0.42 e Å⁻³
4628 reflections	Absolute structure: Flack (1983), 2045 Friedel pairs
245 parameters	Absolute structure parameter: 0.002 (13)
5 restraints

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	Occ. (<1)
Zn1	0.61621 (2)	0.51226 (2)	0.470190 (8)	0.01677 (10)
O1	0.50301 (15)	0.59983 (13)	0.47540 (5)	0.0177 (4)
O2	0.53176 (14)	0.75354 (15)	0.45808 (6)	0.0237 (5)
H2O	0.5908	0.7429	0.4575	0.036*
O3	0.73924 (15)	0.58089 (15)	0.47172 (6)	0.0257 (4)
O4	0.71640 (16)	0.73233 (17)	0.46138 (9)	0.0390 (6)
N1	0.58789 (18)	0.55925 (18)	0.41603 (6)	0.0197 (5)
N2	0.67260 (17)	0.38313 (19)	0.45377 (6)	0.0204 (5)
C1	0.6300 (2)	0.5287 (2)	0.38641 (8)	0.0262 (6)
H1	0.6712	0.4768	0.3881	0.031*
C2	0.6162 (3)	0.5691 (3)	0.35381 (9)	0.0366 (8)
H2	0.6465	0.5455	0.3333	0.044*
C3	0.5566 (3)	0.6455 (3)	0.35178 (10)	0.0404 (10)
H3	0.5448	0.6748	0.3296	0.049*
C4	0.5141 (3)	0.6789 (3)	0.38253 (8)	0.0331 (8)
H4	0.4741	0.7318	0.3818	0.040*
C5	0.5320 (2)	0.6328 (2)	0.41431 (8)	0.0210 (6)
C6	0.4901 (2)	0.6676 (2)	0.44992 (7)	0.0187 (5)
C7	0.6154 (2)	0.3128 (2)	0.44535 (7)	0.0192 (5)
C8	0.6484 (2)	0.2278 (2)	0.43286 (9)	0.0256 (6)
H8	0.6064	0.1783	0.4277	0.031*
C9	0.7445 (3)	0.2165 (2)	0.42796 (10)	0.0325 (8)
H9	0.7685	0.1604	0.4181	0.039*
C10	0.8032 (2)	0.2871 (3)	0.43751 (10)	0.0330 (8)
H10	0.8689	0.2797	0.4353	0.040*
C11	0.7658 (2)	0.3707 (2)	0.45060 (9)	0.0280 (7)
H11	0.8069	0.4197	0.4574	0.034*
C12	0.7640 (2)	0.6651 (2)	0.47105 (9)	0.0227 (6)
C13	0.8626 (2)	0.6836 (2)	0.48381 (8)	0.0237 (6)
C14	0.9023 (2)	0.7726 (2)	0.48046 (11)	0.0341 (8)
H14	0.8676	0.8218	0.4699	0.041*
C15	0.9924 (3)	0.7888 (3)	0.49264 (12)	0.0461 (10)
H15	1.0196	0.8489	0.4900	0.055*
C16	1.0423 (3)	0.7181 (3)	0.50846 (13)	0.0474 (11)
H16	1.1039	0.7295	0.5168	0.057*
C17	1.0032 (3)	0.6313 (3)	0.51216 (11)	0.0398 (8)
H17	1.0374	0.5829	0.5234	0.048*
C18	0.9141 (2)	0.6138 (3)	0.49960 (9)	0.0306 (7)
H18	0.8882	0.5530	0.5019	0.037*
O1S	0.9292 (16)	1.1086 (15)	0.3972 (6)	0.218 (6)*	0.50
C1S	0.9466 (13)	1.0280 (17)	0.3923 (6)	0.218 (6)*	0.50
C2S	0.965 (2)	0.972 (2)	0.4275 (8)	0.218 (6)*	0.50
H2S1	1.0259	0.9886	0.4372	0.328*	0.50
H2S2	0.9634	0.9045	0.4224	0.328*	0.50
H2S3	0.9160	0.9865	0.4448	0.328*	0.50
C3S	0.9503 (19)	0.975 (2)	0.3559 (7)	0.218 (6)*	0.50
H3S1	0.8956	0.9340	0.3537	0.328*	0.50
H3S2	1.0073	0.9370	0.3547	0.328*	0.50
H3S3	0.9504	1.0201	0.3364	0.328*	0.50
O2S	0.7500	1.0096 (11)	0.3750	0.110 (5)*	0.50
H2S	0.7197	1.0292	0.3574	0.164*	0.25
C21S	0.7500	0.9049 (11)	0.3750	0.139 (10)*	0.50
H21A	0.7999	0.8821	0.3595	0.208*	0.25
H21B	0.6896	0.8821	0.3664	0.208*	0.25
H21C	0.7605	0.8821	0.3992	0.208*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01658 (17)	0.01739 (17)	0.01634 (15)	0.00064 (12)	0.00086 (12)	0.00068 (12)
O1	0.0189 (9)	0.0175 (9)	0.0167 (9)	0.0029 (8)	0.0001 (8)	0.0034 (7)
O2	0.0206 (10)	0.0193 (10)	0.0311 (11)	−0.0009 (9)	0.0009 (8)	−0.0005 (9)
O3	0.0216 (11)	0.0258 (11)	0.0296 (11)	−0.0035 (9)	0.0013 (9)	−0.0002 (10)
O4	0.0214 (11)	0.0262 (13)	0.0693 (19)	−0.0015 (9)	−0.0062 (11)	0.0019 (12)
N1	0.0201 (12)	0.0213 (12)	0.0176 (11)	0.0003 (9)	0.0009 (9)	0.0007 (9)
N2	0.0182 (12)	0.0232 (12)	0.0199 (11)	0.0025 (11)	0.0015 (9)	0.0025 (10)
C1	0.0244 (15)	0.0299 (16)	0.0244 (14)	0.0035 (13)	0.0059 (12)	0.0000 (12)
C2	0.044 (2)	0.044 (2)	0.0218 (15)	0.0112 (18)	0.0101 (15)	0.0016 (14)
C3	0.050 (2)	0.048 (2)	0.0227 (16)	0.0158 (19)	0.0113 (16)	0.0114 (15)
C4	0.0378 (19)	0.0376 (18)	0.0238 (15)	0.0120 (16)	0.0058 (14)	0.0085 (13)
C5	0.0206 (14)	0.0214 (14)	0.0211 (14)	0.0008 (12)	0.0015 (10)	0.0043 (11)
C6	0.0199 (14)	0.0168 (13)	0.0194 (12)	0.0026 (12)	0.0006 (11)	0.0040 (10)
C7	0.0206 (14)	0.0207 (13)	0.0163 (12)	0.0010 (12)	0.0005 (11)	0.0006 (10)
C8	0.0267 (15)	0.0255 (16)	0.0245 (15)	0.0056 (13)	−0.0002 (12)	−0.0017 (12)
C9	0.0317 (18)	0.0298 (17)	0.0361 (18)	0.0124 (15)	0.0060 (15)	−0.0024 (14)
C10	0.0231 (16)	0.0371 (19)	0.0388 (19)	0.0086 (14)	0.0068 (14)	0.0018 (15)
C11	0.0214 (15)	0.0312 (17)	0.0315 (17)	−0.0005 (13)	0.0033 (12)	0.0037 (14)
C12	0.0192 (14)	0.0267 (15)	0.0221 (14)	−0.0017 (11)	0.0049 (12)	−0.0030 (13)
C13	0.0204 (15)	0.0263 (16)	0.0246 (14)	−0.0009 (12)	0.0040 (12)	−0.0069 (12)
C14	0.0275 (18)	0.0260 (17)	0.049 (2)	−0.0028 (14)	0.0040 (14)	−0.0056 (14)
C15	0.0283 (18)	0.0291 (18)	0.081 (3)	−0.0061 (16)	−0.001 (2)	−0.0103 (19)
C16	0.0218 (17)	0.048 (2)	0.072 (3)	−0.0035 (16)	−0.0083 (18)	−0.020 (2)
C17	0.0292 (17)	0.038 (2)	0.052 (2)	0.0050 (16)	−0.0075 (17)	−0.0062 (17)
C18	0.0270 (16)	0.0290 (16)	0.0357 (17)	−0.0039 (14)	−0.0012 (13)	−0.0028 (14)

Geometric parameters (Å, º) top

Zn1—O3	2.018 (2)	C9—C10	1.365 (5)
Zn1—O1	2.059 (2)	C9—H9	0.9500
Zn1—O1ⁱ	2.0776 (19)	C10—C11	1.401 (5)
Zn1—N2	2.111 (3)	C10—H10	0.9500
Zn1—N1	2.189 (2)	C11—H11	0.9500
Zn1—O1ⁱⁱ	2.351 (2)	C12—C13	1.515 (4)
O1—C6	1.378 (3)	C13—C18	1.378 (5)
O1—Zn1ⁱⁱⁱ	2.0777 (19)	C13—C14	1.401 (5)
O1—Zn1ⁱⁱ	2.352 (2)	C14—C15	1.389 (5)
O2—C6	1.402 (4)	C14—H14	0.9500
O2—H2O	0.8587	C15—C16	1.376 (6)
O3—C12	1.257 (4)	C15—H15	0.9500
O4—C12	1.235 (4)	C16—C17	1.371 (6)
N1—C5	1.325 (4)	C16—H16	0.9500
N1—C1	1.343 (4)	C17—C18	1.384 (5)
N2—C7	1.336 (4)	C17—H17	0.9500
N2—C11	1.352 (4)	C18—H18	0.9500
C1—C2	1.374 (5)	O1S—C1S	1.195 (10)
C1—H1	0.9500	C1S—C2S	1.57 (2)
C2—C3	1.391 (5)	C1S—C3S	1.57 (2)
C2—H2	0.9500	C2S—H2S1	0.9800
C3—C4	1.394 (5)	C2S—H2S2	0.9800
C3—H3	0.9500	C2S—H2S3	0.9800
C4—C5	1.392 (4)	C3S—H3S1	0.9800
C4—H4	0.9500	C3S—H3S2	0.9800
C5—C6	1.553 (4)	C3S—H3S3	0.9800
C6—C7ⁱⁱ	1.546 (4)	O2S—C21S	1.499 (2)
C7—C8	1.388 (4)	O2S—H2S	0.8400
C7—C6ⁱⁱ	1.546 (4)	C21S—H21A	0.9800
C8—C9	1.398 (5)	C21S—H21B	0.9800
C8—H8	0.9500	C21S—H21C	0.9800

O3—Zn1—O1	112.83 (9)	C7—C8—H8	120.6
O3—Zn1—O1ⁱ	96.98 (9)	C9—C8—H8	120.6
O1—Zn1—O1ⁱ	83.16 (8)	C10—C9—C8	119.1 (3)
O3—Zn1—N2	95.80 (9)	C10—C9—H9	120.5
O1—Zn1—N2	149.64 (9)	C8—C9—H9	120.5
O1ⁱ—Zn1—N2	103.94 (9)	C9—C10—C11	119.4 (3)
O3—Zn1—N1	92.22 (9)	C9—C10—H10	120.3
O1—Zn1—N1	75.88 (9)	C11—C10—H10	120.3
O1ⁱ—Zn1—N1	159.01 (9)	N2—C11—C10	121.4 (3)
N2—Zn1—N1	93.79 (10)	N2—C11—H11	119.3
O3—Zn1—O1ⁱⁱ	164.53 (8)	C10—C11—H11	119.3
O1—Zn1—O1ⁱⁱ	80.57 (8)	O4—C12—O3	126.7 (3)
O1ⁱ—Zn1—O1ⁱⁱ	76.33 (8)	O4—C12—C13	118.1 (3)
N2—Zn1—O1ⁱⁱ	72.80 (8)	O3—C12—C13	115.2 (3)
N1—Zn1—O1ⁱⁱ	98.82 (8)	C18—C13—C14	118.8 (3)
C6—O1—Zn1	117.87 (17)	C18—C13—C12	120.6 (3)
C6—O1—Zn1ⁱⁱⁱ	126.55 (17)	C14—C13—C12	120.6 (3)
Zn1—O1—Zn1ⁱⁱⁱ	104.24 (9)	C15—C14—C13	119.9 (4)
C6—O1—Zn1ⁱⁱ	108.97 (17)	C15—C14—H14	120.0
Zn1—O1—Zn1ⁱⁱ	98.51 (8)	C13—C14—H14	120.1
Zn1ⁱⁱⁱ—O1—Zn1ⁱⁱ	94.78 (7)	C16—C15—C14	120.2 (4)
C6—O2—H2O	104.9	C16—C15—H15	119.9
C12—O3—Zn1	135.5 (2)	C14—C15—H15	119.9
C5—N1—C1	119.3 (3)	C17—C16—C15	119.9 (4)
C5—N1—Zn1	113.71 (19)	C17—C16—H16	120.0
C1—N1—Zn1	126.4 (2)	C15—C16—H16	120.0
C7—N2—C11	119.1 (3)	C16—C17—C18	120.5 (4)
C7—N2—Zn1	119.66 (19)	C16—C17—H17	119.8
C11—N2—Zn1	121.3 (2)	C18—C17—H17	119.8
N1—C1—C2	122.9 (3)	C13—C18—C17	120.6 (4)
N1—C1—H1	118.6	C13—C18—H18	119.7
C2—C1—H1	118.5	C17—C18—H18	119.7
C1—C2—C3	118.0 (3)	O1S—C1S—C2S	114 (2)
C1—C2—H2	121.0	O1S—C1S—C3S	128 (2)
C3—C2—H2	121.0	C2S—C1S—C3S	119 (2)
C2—C3—C4	119.4 (3)	C1S—C2S—H2S1	109.5
C2—C3—H3	120.3	C1S—C2S—H2S2	109.4
C4—C3—H3	120.3	H2S1—C2S—H2S2	109.5
C5—C4—C3	118.3 (3)	C1S—C2S—H2S3	109.5
C5—C4—H4	120.9	H2S1—C2S—H2S3	109.5
C3—C4—H4	120.9	H2S2—C2S—H2S3	109.5
N1—C5—C4	122.0 (3)	C1S—C3S—H3S1	109.5
N1—C5—C6	116.5 (2)	C1S—C3S—H3S2	109.4
C4—C5—C6	121.4 (3)	H3S1—C3S—H3S2	109.5
O1—C6—O2	114.1 (2)	C1S—C3S—H3S3	109.5
O1—C6—C7ⁱⁱ	109.6 (2)	H3S1—C3S—H3S3	109.5
O2—C6—C7ⁱⁱ	106.3 (2)	H3S2—C3S—H3S3	109.5
O1—C6—C5	109.0 (2)	C21S—O2S—H2S	109.5
O2—C6—C5	107.9 (2)	O2S—C21S—H21A	109.00
C7ⁱⁱ—C6—C5	109.8 (2)	O2S—C21S—H21B	109.00
N2—C7—C8	122.1 (3)	H21A—C21S—H21B	110.00
N2—C7—C6ⁱⁱ	115.9 (2)	O2S—C21S—H21C	109.00
C8—C7—C6ⁱⁱ	122.0 (3)	H21A—C21S—H21C	109.00
C7—C8—C9	118.8 (3)	H21B—C21S—H21C	109.00

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O4	0.86	1.81	2.664 (3)	172

Experimental details

Crystal data
Chemical formula	[Zn₄(C₁₁H₉N₂O₂)₄(C₇H₅O₂)₄]·2C₃H₆O·CH₄O
M_r	6795.70
Crystal system, space group	Tetragonal, I42d
Temperature (K)	170
a, c (Å)	14.3201 (4), 37.730 (2)
V (Å³)	7737.1 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.30
Crystal size (mm)	0.10 × 0.08 × 0.05

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.883, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	22787, 4628, 4279
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.110, 1.09
No. of reflections	4628
No. of parameters	245
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.37, −0.42
Absolute structure	Flack (1983), 2045 Friedel pairs
Absolute structure parameter	0.002 (13)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
O2—H2O···O4	0.86	1.81	2.664 (3)	172

Acknowledgements

Financial support from the Korea Ministry of the Environment `ET-Human resource development Project' and the Cooperative Research Program for Agricultural Science & Technology Development (20070301–036-019–02) is gratefully acknowledged.

References

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