Tetra-μ-benzoato-bis­{[4-(pyrrolidin-1-yl)pyridine]zinc(II)}

Yu, S.M.; Koo, K.; Kim, P.-G.; Kim, C.; Kim, Y.

doi:10.1107/S1600536809052714

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Pages m61-m62

doi:10.1107/S1600536809052714

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Tetra-μ-benzoato-bis{[4-(pyrrolidin-1-yl)pyridine]zinc(II)}

Seung Man Yu,^a Kyosang Koo,^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, ^bKorea Division of Forest Disaster Management, Korea Forest Research Institute, Seoul 130-712, 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 23 November 2009; accepted 8 December 2009; online 12 December 2009)

The central part of the title centrosymmetric dinuclear complex, [Zn₂(C₇H₅O₂)₄(C₉H₁₂N₂)₂], has a paddle-wheel conformation with four benzoate ligands bridging two symmetry-related Zn^II ions. The distorted square-pyramidal coordination environment around the Zn^II ion is completed by an N atom from a 4-(pyrrolidin-1-yl)pyridine ligand. The Zn⋯Zn separation of 2.9826 (12) Å does not represent a formal direct metal–metal bond. The Zn^II ion is displaced by 0.381 (1) Å from the mean plane of the four basal O atoms. Two of the C atoms of the pyrrolidine ring are disordered over two sites with refined occupancies of 0.53 (2) and 0.47 (2).

Related literature

For crystal structures containing the [Zn₂(O₂CPh)₄] unit, see: Necefoglu et al. (2002 ); Zeleňák et al. (2004 ); Karmakar et al. (2006 ); Ohmura et al. (2005 ). For the crystal structures of copper(II) and zinc(II) benzoates with quinoxaline, 6-methylquinoline, 3-methylquinoline, di-2-pyridyl ketone and trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene, see: Lee et al. (2008 ); Yu et al. (2008 , 2009 ); Park et al. (2008 ); Shin et al. (2009 ); Song et al. (2009 ). For transition metal ions as the major cation contributors to the inorganic composition of natural water and biological fluids, see: Daniele et al. (2008 ); Parkin (2004 ); Tshuva & Lippard (2004 ).

Experimental

Crystal data

[Zn₂(C₇H₅O₂)₄(C₉H₁₂N₂)₂]
M_r = 911.59
Monoclinic, P 2₁ /n
a = 11.0021 (11) Å
b = 11.4303 (11) Å
c = 16.9508 (16) Å
β = 93.869 (2)°
V = 2126.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.19 mm⁻¹
T = 293 K
0.08 × 0.08 × 0.01 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.909, T_max = 0.988
11271 measured reflections
4159 independent reflections
2284 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.179
S = 0.90
4159 reflections
270 parameters
7 restraints
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.71 e Å⁻³

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/S1600536809052714/lh2962sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052714/lh2962Isup2.hkl

checkCIF report

Comment top

Recently, great attention has been paid to transition metal ions as the major cation contributors to the inorganic composition of natural water and biological fluids (Daniele, et al., 2008; Parkin, 2004; Tshuva & Lippard, 2004). Some biologically active molecules that have potential interactions with transition metal ions are amino acids, proteins, sugars, nucleotides, fulvic acids and humic acids. In particular, the study on the interaction of transition metal ions with fulvic acids and humic acids, mainly found in soil, is being extensively investigated. As models to examine these interactions we have previously used copper(II) and zinc(II) benzoates as building blocks and reported the structures of copper(II) and zinc(II) benzoates with quinoxaline, 6-methylquinoline, 3-methylquinoline, di-2-pyridylketone, andtrans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (Lee, et al., 2008; Yu, et al., 2008; Park, et al., 2008; Shin, et al., 2009; Yu, et al., 2009; Song, et al., 2009). The related paddle-wheel type structures for Zn complexes have been previouly reported (Necefoglu, et al., 2002; Zeleňák, et al.,2004; Kamakar, et al., 2006; Ohmura, et al., 2005). In this work, we have employed zinc(II) benzoate as a building block and 4-(pyrrolidin-1-yl)pyridine as a ligand. We report herein the structure of the title complex.

The molecular structure of the title complex is shown in Fig. 1. The asymmetric unit contains half of the complex with the formula unit being generated by an inversion center. The central part of the complex had a paddle-wheel type conformation four benzoate ligands bridging two symmetry related Zn^II ions. The distorted square-pyramidal coordination environment around the unique Zn^II ion is completed by an N atom from a 4-(pyrrolidin-1-yl)pyridine ligand. The Zn^II ion is displaced by 0.381 (1) Å from the mean plane of the four basal oxygen atoms.

Related literature top

For crystal structures containing the [Zn₂(O₂CPh)₄] unit, see: Necefoglu et al. (2002); Zeleňák et al. (2004); Karmakar et al. (2006); Ohmura et al. (2005). For the crystal structures of copper(II) and zinc(II) benzoates with quinoxaline, 6-methylquinoline, 3-methylquinoline, di-2-pyridyl ketone and trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene, see: Lee et al. (2008); Yu et al. (2008,2009); Park et al. (2008); Shin et al. (2009); Yu et al. (2009); Song et al. (2009). For transition metal ions as the major cation contributors to the inorganic composition of natural water and biological fluids, see: Daniele et al. (2008); Parkin (2004); Tshuva & Lippard (2004).

Experimental top

30.4 mg (0.1 mmol) of Zn(NO₃)₂^.6H₂O and 28.0 mg (0.2 mmol) of C₆H₅COONH₄ were dissolved in 4 ml H₂O and carefully layered by 4 ml me thanol solution of 4-(pyrrolidin-1-yl)pyridine (30.3 mg, 0.2 mmol). Suitable crystals of the title compound 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. The molecular structure of the title complex showing the atom-labeling scheme. Displacement ellipsoids are shown at the 30% probability level. H atoms have been omitted for clarity. The disordered part of pyrrol group is shown by green bonds [Symmetry code: (i) -x, -y + 1, -z].

Tetra-µ-benzoato-bis{[4-(pyrrolidin-1-yl)pyridine]zinc(II)} top

Crystal data top

[Zn₂(C₇H₅O₂)₄(C₉H₁₂N₂)₂]	F(000) = 944
M_r = 911.59	D_x = 1.423 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1481 reflections
a = 11.0021 (11) Å	θ = 2.3–19.2°
b = 11.4303 (11) Å	µ = 1.19 mm⁻¹
c = 16.9508 (16) Å	T = 293 K
β = 93.869 (2)°	Plate, colorless
V = 2126.8 (4) Å³	0.08 × 0.08 × 0.01 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	4159 independent reflections
Radiation source: fine-focus sealed tube	2284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −13→13
T_min = 0.909, T_max = 0.988	k = −13→14
11271 measured reflections	l = −17→20

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.1079P)²] where P = (F_o² + 2F_c²)/3
4159 reflections	(Δ/σ)_max < 0.001
270 parameters	Δρ_max = 0.94 e Å⁻³
7 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

[Zn₂(C₇H₅O₂)₄(C₉H₁₂N₂)₂]	V = 2126.8 (4) Å³
M_r = 911.59	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.0021 (11) Å	µ = 1.19 mm⁻¹
b = 11.4303 (11) Å	T = 293 K
c = 16.9508 (16) Å	0.08 × 0.08 × 0.01 mm
β = 93.869 (2)°

Data collection top

Bruker SMART CCD diffractometer	4159 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2284 reflections with I > 2σ(I)
T_min = 0.909, T_max = 0.988	R_int = 0.068
11271 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	7 restraints
wR(F²) = 0.179	H-atom parameters constrained
S = 0.90	Δρ_max = 0.94 e Å⁻³
4159 reflections	Δρ_min = −0.71 e Å⁻³
270 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	Occ. (<1)
Zn1	0.11885 (5)	0.44449 (5)	0.02560 (4)	0.0380 (2)
O11	0.1576 (4)	0.5331 (3)	−0.0760 (2)	0.0524 (11)
O12	0.0192 (4)	0.3879 (4)	0.1160 (2)	0.0574 (11)
O21	0.1591 (3)	0.5941 (3)	0.0872 (2)	0.0528 (10)
O22	0.0201 (4)	0.3274 (3)	−0.0446 (2)	0.0562 (11)
N31	0.2720 (4)	0.3488 (4)	0.0436 (2)	0.0389 (10)
N32	0.5772 (4)	0.1339 (4)	0.0637 (3)	0.0494 (12)
C11	0.0949 (5)	0.5977 (5)	−0.1189 (3)	0.0409 (13)
C12	0.1545 (5)	0.6638 (4)	−0.1822 (3)	0.0428 (14)
C13	0.2792 (6)	0.6570 (5)	−0.1882 (3)	0.0556 (16)
H13	0.3250	0.6061	−0.1554	0.067*
C14	0.3364 (7)	0.7242 (6)	−0.2419 (4)	0.072 (2)
H14	0.4207	0.7224	−0.2436	0.086*
C15	0.2653 (9)	0.7955 (7)	−0.2942 (5)	0.089 (3)
H15	0.3025	0.8385	−0.3325	0.107*
C16	0.1429 (8)	0.8024 (6)	−0.2898 (4)	0.074 (2)
H16	0.0974	0.8523	−0.3236	0.089*
C17	0.0854 (6)	0.7365 (5)	−0.2356 (3)	0.0542 (15)
H17	0.0011	0.7397	−0.2342	0.065*
C21	0.0822 (6)	0.6758 (5)	0.0839 (3)	0.0444 (14)
C22	0.1148 (5)	0.7854 (4)	0.1296 (3)	0.0384 (13)
C23	0.0408 (6)	0.8808 (5)	0.1229 (4)	0.0638 (18)
H23	−0.0297	0.8774	0.0894	0.077*
C24	0.0676 (7)	0.9824 (6)	0.1645 (5)	0.084 (3)
H24	0.0174	1.0476	0.1580	0.101*
C25	0.1670 (8)	0.9853 (6)	0.2142 (5)	0.082 (2)
H25	0.1835	1.0527	0.2438	0.098*
C26	0.2463 (7)	0.8915 (6)	0.2234 (4)	0.0710 (19)
H26	0.3159	0.8950	0.2576	0.085*
C27	0.2173 (6)	0.7926 (5)	0.1794 (4)	0.0579 (17)
H27	0.2695	0.7286	0.1838	0.069*
C31	0.3724 (5)	0.3727 (5)	0.0069 (3)	0.0455 (14)
H31	0.3719	0.4391	−0.0249	0.055*
C32	0.4768 (5)	0.3064 (5)	0.0126 (4)	0.0531 (16)
H32	0.5441	0.3287	−0.0142	0.064*
C33	0.4810 (5)	0.2046 (5)	0.0591 (3)	0.0422 (13)
C34	0.3747 (5)	0.1802 (5)	0.0984 (4)	0.0517 (16)
H34	0.3719	0.1152	0.1312	0.062*
C35	0.2759 (5)	0.2528 (5)	0.0879 (3)	0.0478 (15)
H35	0.2066	0.2335	0.1136	0.057*
C36	0.6859 (5)	0.1549 (5)	0.0198 (4)	0.0573 (17)
H36A	0.7297	0.2235	0.0398	0.069*	0.47 (2)
H36B	0.6639	0.1656	−0.0361	0.069*	0.47 (2)
C37	0.7631 (14)	0.0439 (11)	0.0341 (9)	0.054 (4)*	0.47 (2)
H37A	0.7416	−0.0159	−0.0050	0.065*	0.47 (2)
H37B	0.8495	0.0607	0.0340	0.065*	0.47 (2)
C38	0.7273 (7)	0.008 (2)	0.1161 (9)	0.067 (6)*	0.47 (2)
H38A	0.7685	0.0566	0.1567	0.080*	0.47 (2)
H38B	0.7467	−0.0731	0.1268	0.080*	0.47 (2)
C39	0.5882 (5)	0.0289 (5)	0.1122 (4)	0.0607 (18)
H39A	0.5441	−0.0362	0.0872	0.073*	0.47 (2)
H39B	0.5595	0.0420	0.1643	0.073*	0.47 (2)
H36C	0.7113	0.2360	0.0238	0.069*	0.53 (2)
H36D	0.6710	0.1345	−0.0355	0.069*	0.53 (2)
C37A	0.7824 (9)	0.0733 (12)	0.0611 (11)	0.073 (5)*	0.53 (2)
H37C	0.8362	0.0425	0.0231	0.088*	0.53 (2)
H37D	0.8310	0.1156	0.1016	0.088*	0.53 (2)
C38A	0.7126 (9)	−0.0257 (12)	0.0979 (11)	0.063 (5)*	0.53 (2)
H38C	0.7539	−0.0514	0.1473	0.076*	0.53 (2)
H38D	0.7034	−0.0919	0.0622	0.076*	0.53 (2)
H39C	0.5231	−0.0254	0.0971	0.073*	0.53 (2)
H39D	0.5839	0.0486	0.1676	0.073*	0.53 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0382 (4)	0.0339 (3)	0.0421 (4)	0.0065 (3)	0.0043 (3)	0.0011 (3)
O11	0.061 (3)	0.051 (2)	0.047 (2)	0.011 (2)	0.011 (2)	0.017 (2)
O12	0.055 (3)	0.064 (3)	0.056 (3)	0.007 (2)	0.016 (2)	0.016 (2)
O21	0.052 (3)	0.040 (2)	0.064 (3)	0.007 (2)	−0.011 (2)	−0.010 (2)
O22	0.054 (3)	0.050 (2)	0.063 (3)	−0.002 (2)	−0.010 (2)	−0.014 (2)
N31	0.038 (3)	0.038 (2)	0.041 (3)	0.005 (2)	0.002 (2)	0.005 (2)
N32	0.043 (3)	0.052 (3)	0.053 (3)	0.016 (2)	0.006 (2)	0.010 (2)
C11	0.055 (4)	0.034 (3)	0.035 (3)	−0.005 (3)	0.012 (3)	−0.003 (2)
C12	0.053 (4)	0.037 (3)	0.039 (3)	−0.004 (3)	0.012 (3)	−0.004 (3)
C13	0.063 (4)	0.061 (4)	0.044 (3)	−0.008 (3)	0.013 (3)	−0.005 (3)
C14	0.073 (5)	0.076 (5)	0.068 (5)	−0.023 (4)	0.027 (4)	−0.015 (4)
C15	0.135 (8)	0.071 (5)	0.066 (5)	−0.035 (5)	0.046 (6)	0.000 (4)
C16	0.109 (7)	0.066 (5)	0.046 (4)	−0.005 (4)	0.004 (4)	0.018 (3)
C17	0.063 (4)	0.051 (4)	0.048 (4)	−0.004 (3)	−0.001 (3)	0.008 (3)
C21	0.062 (4)	0.035 (3)	0.037 (3)	−0.002 (3)	0.017 (3)	0.004 (2)
C22	0.037 (3)	0.041 (3)	0.037 (3)	−0.007 (2)	0.005 (3)	−0.005 (2)
C23	0.047 (4)	0.049 (4)	0.096 (5)	0.006 (3)	0.003 (4)	−0.018 (4)
C24	0.062 (5)	0.060 (5)	0.128 (7)	0.012 (4)	−0.026 (5)	−0.038 (5)
C25	0.103 (7)	0.052 (4)	0.093 (6)	−0.013 (4)	0.022 (5)	−0.028 (4)
C26	0.083 (5)	0.068 (5)	0.059 (4)	−0.015 (4)	−0.016 (4)	−0.013 (4)
C27	0.080 (5)	0.038 (3)	0.054 (4)	0.000 (3)	0.000 (4)	0.002 (3)
C31	0.040 (3)	0.046 (3)	0.050 (3)	0.003 (3)	0.001 (3)	0.015 (3)
C32	0.048 (4)	0.055 (4)	0.058 (4)	0.004 (3)	0.016 (3)	0.012 (3)
C33	0.042 (3)	0.041 (3)	0.044 (3)	0.009 (3)	0.001 (3)	−0.001 (3)
C34	0.053 (4)	0.043 (3)	0.061 (4)	0.011 (3)	0.012 (3)	0.017 (3)
C35	0.043 (3)	0.043 (3)	0.059 (4)	0.005 (3)	0.016 (3)	0.011 (3)
C36	0.047 (4)	0.064 (4)	0.062 (4)	0.015 (3)	0.013 (3)	0.006 (3)
C39	0.061 (4)	0.050 (4)	0.072 (4)	0.017 (3)	0.006 (4)	0.009 (3)
C36A	0.047 (4)	0.064 (4)	0.062 (4)	0.015 (3)	0.013 (3)	0.006 (3)
C39A	0.061 (4)	0.050 (4)	0.072 (4)	0.017 (3)	0.006 (4)	0.009 (3)

Geometric parameters (Å, º) top

Zn1—N31	2.014 (4)	C23—H23	0.9300
Zn1—O21	2.036 (4)	C24—C25	1.335 (11)
Zn1—O12	2.048 (4)	C24—H24	0.9300
Zn1—O22	2.053 (4)	C25—C26	1.384 (11)
Zn1—O11	2.068 (4)	C25—H25	0.9300
Zn1—Zn1ⁱ	2.9826 (12)	C26—C27	1.380 (8)
O11—C11	1.216 (6)	C26—H26	0.9300
O12—C11ⁱ	1.270 (6)	C27—H27	0.9300
O21—C21	1.260 (6)	C31—C32	1.374 (7)
O22—C21ⁱ	1.268 (7)	C31—H31	0.9300
N31—C35	1.329 (6)	C32—C33	1.404 (7)
N31—C31	1.333 (6)	C32—H32	0.9300
N32—C33	1.330 (6)	C33—C34	1.412 (7)
N32—C39	1.454 (7)	C34—C35	1.370 (7)
N32—C36	1.470 (7)	C34—H34	0.9300
C11—O12ⁱ	1.270 (6)	C35—H35	0.9300
C11—C12	1.500 (7)	C36—C37	1.536 (7)
C12—C13	1.384 (8)	C36—H36A	0.9700
C12—C17	1.413 (8)	C36—H36B	0.9700
C13—C14	1.375 (8)	C37—C38	1.525 (10)
C13—H13	0.9300	C37—H37A	0.9700
C14—C15	1.403 (11)	C37—H37B	0.9700
C14—H14	0.9300	C38—C39	1.545 (7)
C15—C16	1.356 (10)	C38—H38A	0.9700
C15—H15	0.9300	C38—H38B	0.9700
C16—C17	1.374 (8)	C39—H39A	0.9700
C16—H16	0.9300	C39—H39B	0.9700
C17—H17	0.9300	C37A—C38A	1.524 (10)
C21—O22ⁱ	1.268 (7)	C37A—H37C	0.9700
C21—C22	1.504 (7)	C37A—H37D	0.9700
C22—C23	1.361 (8)	C38A—H38C	0.9700
C22—C27	1.364 (8)	C38A—H38D	0.9700
C23—C24	1.380 (9)

N31—Zn1—O21	103.14 (17)	C25—C24—H24	120.6
N31—Zn1—O12	101.53 (16)	C23—C24—H24	120.6
O21—Zn1—O12	89.46 (17)	C24—C25—C26	122.3 (7)
N31—Zn1—O22	97.95 (17)	C24—C25—H25	118.9
O21—Zn1—O22	158.90 (16)	C26—C25—H25	118.9
O12—Zn1—O22	86.50 (17)	C27—C26—C25	117.0 (7)
N31—Zn1—O11	100.06 (16)	C27—C26—H26	121.5
O21—Zn1—O11	88.04 (16)	C25—C26—H26	121.5
O12—Zn1—O11	158.27 (16)	C22—C27—C26	122.3 (6)
O22—Zn1—O11	88.11 (16)	C22—C27—H27	118.8
N31—Zn1—Zn1ⁱ	169.40 (13)	C26—C27—H27	118.8
O21—Zn1—Zn1ⁱ	87.02 (11)	N31—C31—C32	124.7 (5)
O12—Zn1—Zn1ⁱ	81.31 (12)	N31—C31—H31	117.7
O22—Zn1—Zn1ⁱ	71.90 (12)	C32—C31—H31	117.7
O11—Zn1—Zn1ⁱ	77.01 (12)	C31—C32—C33	119.5 (5)
C11—O11—Zn1	130.8 (4)	C31—C32—H32	120.2
C11ⁱ—O12—Zn1	124.6 (4)	C33—C32—H32	120.2
C21—O21—Zn1	118.5 (4)	N32—C33—C32	122.2 (5)
C21ⁱ—O22—Zn1	137.7 (4)	N32—C33—C34	122.2 (5)
C35—N31—C31	115.9 (4)	C32—C33—C34	115.6 (5)
C35—N31—Zn1	122.0 (3)	C35—C34—C33	119.6 (5)
C31—N31—Zn1	122.0 (4)	C35—C34—H34	120.2
C33—N32—C39	124.8 (4)	C33—C34—H34	120.2
C33—N32—C36	122.8 (5)	N31—C35—C34	124.7 (5)
C39—N32—C36	112.4 (4)	N31—C35—H35	117.6
O11—C11—O12ⁱ	125.3 (5)	C34—C35—H35	117.6
O11—C11—C12	118.4 (5)	N32—C36—C37	104.2 (6)
O12ⁱ—C11—C12	116.3 (5)	N32—C36—H36A	110.9
C13—C12—C17	118.6 (5)	C37—C36—H36A	110.9
C13—C12—C11	120.5 (6)	N32—C36—H36B	110.9
C17—C12—C11	120.8 (5)	C37—C36—H36B	110.9
C14—C13—C12	121.2 (7)	H36A—C36—H36B	108.9
C14—C13—H13	119.4	C38—C37—C36	100.9 (9)
C12—C13—H13	119.4	C38—C37—H37A	111.6
C13—C14—C15	118.8 (7)	C36—C37—H37A	111.6
C13—C14—H14	120.6	C38—C37—H37B	111.6
C15—C14—H14	120.6	C36—C37—H37B	111.6
C16—C15—C14	120.8 (6)	H37A—C37—H37B	109.4
C16—C15—H15	119.6	C37—C38—C39	103.7 (8)
C14—C15—H15	119.6	C37—C38—H38A	111.0
C15—C16—C17	120.6 (7)	C39—C38—H38A	111.0
C15—C16—H16	119.7	C37—C38—H38B	111.0
C17—C16—H16	119.7	C39—C38—H38B	111.0
C16—C17—C12	119.9 (6)	H38A—C38—H38B	109.0
C16—C17—H17	120.0	N32—C39—C38	101.2 (8)
C12—C17—H17	120.0	N32—C39—H39A	111.5
O21—C21—O22ⁱ	124.9 (5)	C38—C39—H39A	111.5
O21—C21—C22	117.3 (6)	N32—C39—H39B	111.5
O22ⁱ—C21—C22	117.9 (5)	C38—C39—H39B	111.5
C23—C22—C27	118.0 (5)	H39A—C39—H39B	109.3
C23—C22—C21	120.2 (5)	C38A—C37A—H37C	110.4
C27—C22—C21	121.8 (5)	C38A—C37A—H37D	110.4
C22—C23—C24	121.6 (7)	H37C—C37A—H37D	108.6
C22—C23—H23	119.2	C37A—C38A—H38C	111.0
C24—C23—H23	119.2	C37A—C38A—H38D	111.0
C25—C24—C23	118.8 (7)	H38C—C38A—H38D	109.0

N31—Zn1—O11—C11	173.5 (5)	C14—C15—C16—C17	−2.3 (11)
O21—Zn1—O11—C11	−83.5 (5)	C15—C16—C17—C12	2.2 (10)
O12—Zn1—O11—C11	0.1 (8)	C13—C12—C17—C16	−2.8 (9)
O22—Zn1—O11—C11	75.8 (5)	C11—C12—C17—C16	175.6 (5)
Zn1ⁱ—Zn1—O11—C11	3.9 (5)	Zn1—O21—C21—O22ⁱ	0.0 (7)
N31—Zn1—O12—C11ⁱ	−162.7 (4)	Zn1—O21—C21—C22	−179.7 (3)
O21—Zn1—O12—C11ⁱ	94.0 (5)	O21—C21—C22—C23	174.1 (5)
O22—Zn1—O12—C11ⁱ	−65.2 (5)	O22ⁱ—C21—C22—C23	−5.6 (7)
O11—Zn1—O12—C11ⁱ	10.7 (8)	O21—C21—C22—C27	−6.7 (7)
Zn1ⁱ—Zn1—O12—C11ⁱ	7.0 (4)	O22ⁱ—C21—C22—C27	173.6 (5)
N31—Zn1—O21—C21	176.1 (4)	C27—C22—C23—C24	0.3 (9)
O12—Zn1—O21—C21	−82.2 (4)	C21—C22—C23—C24	179.5 (6)
O22—Zn1—O21—C21	−3.3 (7)	C22—C23—C24—C25	−2.0 (12)
O11—Zn1—O21—C21	76.2 (4)	C23—C24—C25—C26	2.4 (13)
Zn1ⁱ—Zn1—O21—C21	−0.8 (4)	C24—C25—C26—C27	−1.0 (12)
N31—Zn1—O22—C21ⁱ	−175.1 (5)	C23—C22—C27—C26	1.1 (9)
O21—Zn1—O22—C21ⁱ	4.4 (8)	C21—C22—C27—C26	−178.1 (5)
O12—Zn1—O22—C21ⁱ	83.8 (5)	C25—C26—C27—C22	−0.8 (10)
O11—Zn1—O22—C21ⁱ	−75.2 (5)	C35—N31—C31—C32	−0.5 (9)
Zn1ⁱ—Zn1—O22—C21ⁱ	1.8 (5)	Zn1—N31—C31—C32	−175.5 (5)
O21—Zn1—N31—C35	110.2 (4)	N31—C31—C32—C33	0.8 (10)
O12—Zn1—N31—C35	18.1 (5)	C39—N32—C33—C32	178.5 (6)
O22—Zn1—N31—C35	−70.0 (4)	C36—N32—C33—C32	−1.1 (9)
O11—Zn1—N31—C35	−159.4 (4)	C39—N32—C33—C34	−3.7 (9)
Zn1ⁱ—Zn1—N31—C35	−86.5 (8)	C36—N32—C33—C34	176.7 (6)
O21—Zn1—N31—C31	−75.2 (5)	C31—C32—C33—N32	176.6 (6)
O12—Zn1—N31—C31	−167.3 (4)	C31—C32—C33—C34	−1.3 (9)
O22—Zn1—N31—C31	104.7 (4)	N32—C33—C34—C35	−176.4 (6)
O11—Zn1—N31—C31	15.2 (5)	C32—C33—C34—C35	1.6 (9)
Zn1ⁱ—Zn1—N31—C31	88.1 (8)	C31—N31—C35—C34	0.8 (9)
Zn1—O11—C11—O12ⁱ	−10.9 (9)	Zn1—N31—C35—C34	175.8 (5)
Zn1—O11—C11—C12	171.0 (3)	C33—C34—C35—N31	−1.4 (10)
O11—C11—C12—C13	−4.1 (8)	C33—N32—C36—C37	−172.3 (9)
O12ⁱ—C11—C12—C13	177.6 (5)	C39—N32—C36—C37	8.1 (10)
O11—C11—C12—C17	177.5 (5)	N32—C36—C37—C38	−30.5 (16)
O12ⁱ—C11—C12—C17	−0.7 (7)	C36—C37—C38—C39	42 (2)
C17—C12—C13—C14	3.6 (9)	C33—N32—C39—C38	−162.0 (9)
C11—C12—C13—C14	−174.8 (5)	C36—N32—C39—C38	17.6 (10)
C12—C13—C14—C15	−3.6 (9)	C37—C38—C39—N32	−36.8 (17)
C13—C14—C15—C16	3.0 (11)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₇H₅O₂)₄(C₉H₁₂N₂)₂]
M_r	911.59
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.0021 (11), 11.4303 (11), 16.9508 (16)
β (°)	93.869 (2)
V (Å³)	2126.8 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.08 × 0.08 × 0.01

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.909, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	11271, 4159, 2284
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.179, 0.90
No. of reflections	4159
No. of parameters	270
No. of restraints	7
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.71

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

Financial support from Korea Ministry Environment `ET-Human resource development Project' and the Korean Science & Engineering Foundation (2009–0074066) is gratefully acknowledged.

References

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