Tetra­kis(μ-4-methyl­benzoato-κO:O′)bis­{[4-(dimethyl­amino)pyridine-κN1]zinc(II)}

Bai, L.-S.; Liu, X.-H.; Xiao, Z.-P.

doi:10.1107/S1600536809027603

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m948-m949

doi:10.1107/S1600536809027603

Open

access

Tetrakis(μ-4-methylbenzoato-κO:O′)bis{[4-(dimethylamino)pyridine-κN¹]zinc(II)}

Lin-Shan Bai,^a Xin-Hua Liu ^a and Zhu-Ping Xiao ^a,^b ^*

^aKey Laboratory of Anhui Educational Department, Anhui University of Technology, Maanshan 243002, People's Republic of China, and ^bState Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: xiaozhuping2005@163.com

(Received 4 July 2009; accepted 14 July 2009; online 18 July 2009)

In the centrosymmetric title binuclear complex, [Zn₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂], the Zn atoms [Zn⋯Zn = 3.0287 (6) Å] are bridged by four 4-methylbenzoate ligands. The four nearest O atoms around each Zn^II atom form a distorted square-planar arrangement with the distorted square-pyramidal coordination completed by the pyridine N atom of the 4-(dimethylamino)pyridine ligand. In the crystal structure, weak intermolecular C—H⋯O interactions link the molecules into infinite chains. The chains are further linked by weak C—H⋯π interactions, forming a three-dimensional network.

Related literature

For potential applications of organometallic complexes, see: Sommerfeldt et al. (2008 ); Huang et al. (2007 ); Neville et al. (2008 ). Zinc derivatives are used in photodynamic therapy because of their unique photosensitizing properties, see: Tabata et al. (2000 ); Shi et al. (2008 ); Xiao et al. (2008 ); Yang et al. (2008 ). For comparative bond lengths, see: Halcrow et al. (2000 ); For related structures, see: Yang et al. (2004 ); You et al. (2003 , 2004 ); Wang et al. (2009 ).

Experimental

Crystal data

[Zn₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂]
M_r = 915.66
Monoclinic, P 2₁ /n
a = 8.9311 (18) Å
b = 9.967 (2) Å
c = 24.756 (5) Å
β = 90.64 (3)°
V = 2203.5 (8) Å³
Z = 2
Mo Kα radiation
μ = 1.15 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: ψ scan (SADABS; Sheldrick, 1996 ) T_min = 0.758, T_max = 0.792
12095 measured reflections
4326 independent reflections
3432 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.085
S = 1.03
4326 reflections
275 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

O1—Zn1ⁱ	2.0564 (16)
O2—Zn1	2.0626 (15)
O3—Zn1	2.0438 (15)
O4—Zn1ⁱ	2.0320 (16)
N1—Zn1	2.0160 (16)

O3—Zn1—O1ⁱ	86.16 (7)
O3—Zn1—O2	88.75 (6)
O4ⁱ—Zn1—O1ⁱ	89.51 (7)
O4ⁱ—Zn1—O2	86.67 (7)
O4ⁱ—Zn1—O3	157.18 (6)
N1—Zn1—O1ⁱ	99.01 (7)
N1—Zn1—O2	103.64 (7)
N1—Zn1—O3	100.83 (7)
N1—Zn1—O4ⁱ	101.98 (7)
Symmetry code: (i) -x+2, -y+2, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21C⋯O3ⁱⁱ	0.96	2.54	3.484 (3)	168
C23—H23B⋯Cg1ⁱⁱⁱ	0.96	2.99	3.925 (4)	165
Symmetry codes: (ii) x+1, y, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ . Cg1 is the centroid of atoms C3–C8.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); 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 global, I. DOI: 10.1107/S1600536809027603/hk2733sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027603/hk2733Isup2.hkl

checkCIF report

Comment top

Numerous organometallic complexes have been designed for a number of potential applications, such as in synthetic chemistry (Sommerfeldt et al., 2008), as luminescence materials (Huang et al., 2007) and as magnetic materials (Neville et al., 2008). Zinc derivatives are particularly interesting owing to their unique photosensitizing properties for photodynamic therapy (Tabata et al., 2000; Shi et al., 2008; Xiao et al., 2008; Yang et al., 2008;), magnetic circularly polarized luminescence (MCPL) and magnetic circular dichroism (MCD) spectra. We have reported the structures of a few zinc(II) complexes (Yang et al., 2004; You et al., 2003, 2004). As an extension of our work on the structural characterizations of zinc compounds, we report herein the crystal structure of the title compound.

The title compound is a binuclear compound (Fig. 1), consisting of four 4-methylbenzoato and two 4-(N,N-diamino)pyridine ligands. It has a centre of symmetry. The 4-(N,N-diamino)pyridine ligands are coordinated to Zn atoms through pyridine N atoms only. The 4-methylbenzoato groups act as bridging ligands. The Zn···ZnA distance is 3.0287 (6) Å and the N1-Zn1···Zn1A angle is 169.82 (5) [symmetry code: (A) 2 - x, 2 - y, -z]. The four O atoms of the bridging 4-methylbenzoato ligands around each Zn atom form a distorted square plane (Table 1). A distorted square-pyramidal arrangement around each Zn atom is completed by the pyridine N atom of 4-(N,N-diamino)pyridine ligand (Table 1). The dihedral angle between plane through Zn1, O1, O2, C2, Zn1A, O1A, O2A, C2A and the plane through Zn1, O3, O4, C1, Zn1A, O3A, O4A, C1A is 87.931 (24) °. The Zn-O bonds are in the range of 2.0320 (16)-2.0626 (15) Å, and are in accordance with the corresponding values in a similar compound (Wang et al., 2009). The Zn1-N1 [2.0160 (16) Å] bond is significantly shorter than the corresponding reported values (Halcrow et al., 2000).

In the crystal structure, weak intermolecular C-H···O interactions (Table 2) link the molecules into infinite chains (Fig. 2), in which they are further linked by weak C—H···π interactions (Table 2) to form a three-dimensional network (Fig. 3).

Related literature top

For potential applications of organometallic complexes, see: Sommerfeldt et al. (2008); Huang et al. (2007); Neville et al. (2008). Zinc derivatives are used in photodynamic therapy because of their unique photosensitizing properties, see: Tabata et al. (2000); Shi et al. (2008); Xiao et al. (2008); Yang et al. (2008). For Comparative bond lengths, see: Halcrow et al. (2000); For related structures, see: Yang et al. (2004); You et al. (2003, 2004); Wang et al. (2009). Cg1 is the centroid of atoms C3–C8.

Experimental top

For the preparation of the title compound, zinc oxide (0.5 mmol) and 4-methylbenzoic acid (1 mmol) were dissolved in aqueous ammonia (10 ml, 30%,) and then, 4-(N,N-dimethylamino)pyridine (0.5 mmol) was added. The resulting solution was stirred at room temperature and then filtered. Crystals suitable for X-ray analysis were obtained after 13 to 15 d by volatilization of the solvents.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code: (A) 2 - x, 2 - y, -z]. H atoms have been omitted for clarity.
	Fig. 2. The chain formed through C—H···O intermolecular hydrogen bonds. Hydrogen bonds are shown as dashed lines.
	Fig. 3. A partial packing diagram, with C—H···π contacts shown as dashed lines.

Tetrakis(µ-4-methylbenzoato-κO:O')bis{[4- (dimethylamino)pyridine-κN¹]zinc(II)} top

Crystal data top

[Zn₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂]	F(000) = 952
M_r = 915.66	D_x = 1.380 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3875 reflections
a = 8.9311 (18) Å	θ = 1.8–29.5°
b = 9.967 (2) Å	µ = 1.15 mm⁻¹
c = 24.756 (5) Å	T = 294 K
β = 90.64 (3)°	Block, colorless
V = 2203.5 (8) Å³	0.30 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	4326 independent reflections
Radiation source: fine-focus sealed tube	3432 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.7°
Absorption correction: ψ scan (SADABS; Sheldrick, 1996)	h = −11→10
T_min = 0.758, T_max = 0.792	k = −11→12
12095 measured reflections	l = −30→28

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0468P)² + 0.3207P] where P = (F_o² + 2F_c²)/3
4326 reflections	(Δ/σ)_max = 0.001
275 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Zn₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂]	V = 2203.5 (8) Å³
M_r = 915.66	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9311 (18) Å	µ = 1.15 mm⁻¹
b = 9.967 (2) Å	T = 294 K
c = 24.756 (5) Å	0.30 × 0.20 × 0.20 mm
β = 90.64 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4326 independent reflections
Absorption correction: ψ scan (SADABS; Sheldrick, 1996)	3432 reflections with I > 2σ(I)
T_min = 0.758, T_max = 0.792	R_int = 0.020
12095 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
4326 reflections	Δρ_min = −0.28 e Å⁻³
275 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
Zn1	1.13033 (2)	0.90381 (2)	0.006145 (10)	0.05090 (10)
O1	0.83151 (18)	0.93234 (15)	−0.05487 (7)	0.0678 (4)
O2	1.01833 (16)	0.78450 (16)	−0.04910 (6)	0.0653 (4)
O3	0.98300 (16)	0.84236 (16)	0.06369 (6)	0.0635 (4)
O4	0.79517 (17)	0.98974 (15)	0.05820 (6)	0.0662 (4)
N1	1.31222 (17)	0.79423 (16)	0.02637 (7)	0.0513 (4)
N2	1.67263 (18)	0.53691 (18)	0.05771 (7)	0.0564 (4)
C1	0.8638 (2)	0.8943 (2)	0.08022 (9)	0.0531 (5)
C2	0.8981 (2)	0.8279 (2)	−0.06917 (9)	0.0535 (5)
C3	0.8268 (2)	0.7505 (2)	−0.11421 (8)	0.0508 (5)
C4	0.8823 (3)	0.6275 (2)	−0.13030 (9)	0.0609 (6)
H4	0.9639	0.5903	−0.1121	0.073*
C5	0.8182 (3)	0.5598 (3)	−0.17289 (10)	0.0756 (7)
H5	0.8576	0.4774	−0.1832	0.091*
C6	0.6971 (4)	0.6111 (3)	−0.20062 (12)	0.0881 (8)
C7	0.6411 (3)	0.7325 (3)	−0.18418 (12)	0.0934 (9)
H7	0.5589	0.7689	−0.2023	0.112*
C8	0.7040 (3)	0.8013 (3)	−0.14147 (10)	0.0724 (6)
H8	0.6632	0.8828	−0.1309	0.087*
C9	0.8005 (2)	0.8393 (2)	0.13138 (8)	0.0540 (5)
C10	0.6700 (3)	0.8879 (3)	0.15302 (11)	0.0788 (7)
H10	0.6151	0.9527	0.1344	0.095*
C11	0.6197 (3)	0.8414 (3)	0.20207 (12)	0.0911 (9)
H11	0.5312	0.8757	0.2159	0.109*
C12	0.6974 (3)	0.7456 (3)	0.23093 (10)	0.0764 (7)
C13	0.8222 (3)	0.6931 (3)	0.20795 (10)	0.0796 (7)
H13	0.8736	0.6245	0.2256	0.096*
C14	0.8740 (3)	0.7392 (3)	0.15917 (9)	0.0699 (6)
H14	0.9603	0.7019	0.1448	0.084*
C15	1.4414 (2)	0.8023 (2)	−0.00023 (9)	0.0560 (5)
H15	1.4486	0.8667	−0.0273	0.067*
C16	1.5632 (2)	0.7230 (2)	0.00943 (9)	0.0558 (5)
H16	1.6499	0.7354	−0.0104	0.067*
C17	1.5585 (2)	0.62332 (19)	0.04898 (8)	0.0483 (5)
C18	1.4256 (2)	0.6191 (2)	0.07871 (9)	0.0612 (6)
H18	1.4165	0.5590	0.1072	0.073*
C19	1.3102 (2)	0.7026 (2)	0.06594 (9)	0.0626 (6)
H19	1.2234	0.6955	0.0862	0.075*
C20	1.6662 (3)	0.4385 (3)	0.10068 (11)	0.0752 (7)
H20A	1.6706	0.4833	0.1350	0.113*
H20B	1.7495	0.3781	0.0978	0.113*
H20C	1.5743	0.3889	0.0977	0.113*
C21	1.8086 (2)	0.5430 (2)	0.02665 (10)	0.0648 (6)
H21A	1.7837	0.5548	−0.0109	0.097*
H21B	1.8637	0.4611	0.0313	0.097*
H21C	1.8685	0.6172	0.0389	0.097*
C22	0.6270 (6)	0.5356 (5)	−0.24752 (17)	0.166 (2)
H22A	0.6512	0.5800	−0.2807	0.249*
H22B	0.5203	0.5335	−0.2434	0.249*
H22C	0.6651	0.4456	−0.2482	0.249*
C23	0.6490 (4)	0.7010 (4)	0.28691 (11)	0.1126 (12)
H23A	0.6595	0.6054	0.2900	0.169*
H23B	0.5463	0.7254	0.2923	0.169*
H23C	0.7108	0.7440	0.3138	0.169*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.04359 (14)	0.04260 (15)	0.06657 (18)	0.00739 (9)	0.00287 (10)	−0.00171 (11)
O1	0.0702 (10)	0.0516 (9)	0.0817 (11)	0.0032 (7)	−0.0006 (8)	−0.0136 (8)
O2	0.0597 (9)	0.0620 (10)	0.0741 (10)	0.0013 (7)	−0.0071 (8)	−0.0082 (8)
O3	0.0556 (9)	0.0614 (9)	0.0738 (10)	0.0026 (7)	0.0160 (7)	0.0037 (8)
O4	0.0654 (9)	0.0570 (9)	0.0766 (10)	0.0070 (7)	0.0126 (8)	0.0074 (8)
N1	0.0447 (9)	0.0450 (9)	0.0641 (10)	0.0063 (7)	0.0043 (8)	0.0011 (8)
N2	0.0457 (9)	0.0522 (10)	0.0712 (11)	0.0056 (8)	−0.0056 (8)	0.0082 (9)
C1	0.0511 (11)	0.0467 (12)	0.0616 (13)	−0.0043 (9)	0.0032 (10)	−0.0070 (10)
C2	0.0528 (12)	0.0482 (12)	0.0598 (12)	−0.0067 (9)	0.0100 (10)	−0.0005 (10)
C3	0.0499 (11)	0.0485 (11)	0.0540 (11)	−0.0045 (9)	0.0080 (9)	0.0017 (9)
C4	0.0607 (13)	0.0546 (13)	0.0676 (14)	0.0030 (10)	0.0008 (11)	−0.0032 (11)
C5	0.0865 (18)	0.0614 (15)	0.0790 (17)	0.0038 (13)	0.0002 (14)	−0.0168 (13)
C6	0.098 (2)	0.085 (2)	0.0801 (18)	−0.0004 (16)	−0.0184 (16)	−0.0201 (15)
C7	0.092 (2)	0.094 (2)	0.094 (2)	0.0121 (16)	−0.0355 (16)	−0.0111 (17)
C8	0.0743 (15)	0.0655 (15)	0.0772 (16)	0.0103 (12)	−0.0059 (13)	−0.0044 (13)
C9	0.0538 (11)	0.0495 (12)	0.0587 (12)	−0.0059 (9)	0.0051 (10)	−0.0104 (10)
C10	0.0797 (17)	0.0779 (18)	0.0793 (17)	0.0133 (13)	0.0220 (14)	0.0023 (14)
C11	0.0867 (19)	0.099 (2)	0.088 (2)	0.0087 (17)	0.0367 (16)	−0.0091 (18)
C12	0.0894 (19)	0.0836 (18)	0.0564 (14)	−0.0188 (15)	0.0126 (13)	−0.0142 (14)
C13	0.0849 (18)	0.0905 (19)	0.0635 (15)	−0.0005 (15)	0.0011 (13)	0.0089 (14)
C14	0.0683 (14)	0.0770 (16)	0.0646 (14)	0.0052 (12)	0.0088 (11)	0.0022 (13)
C15	0.0511 (11)	0.0451 (11)	0.0720 (14)	0.0026 (9)	0.0079 (10)	0.0118 (10)
C16	0.0430 (10)	0.0507 (12)	0.0738 (14)	0.0031 (9)	0.0099 (9)	0.0090 (11)
C17	0.0431 (10)	0.0436 (11)	0.0582 (12)	−0.0005 (8)	−0.0043 (9)	−0.0020 (9)
C18	0.0523 (12)	0.0662 (14)	0.0651 (14)	0.0066 (10)	0.0034 (10)	0.0185 (11)
C19	0.0475 (11)	0.0728 (15)	0.0679 (14)	0.0083 (10)	0.0120 (10)	0.0096 (12)
C20	0.0672 (15)	0.0716 (16)	0.0866 (17)	0.0099 (12)	−0.0103 (13)	0.0199 (14)
C21	0.0490 (12)	0.0591 (13)	0.0863 (16)	0.0112 (10)	0.0010 (11)	−0.0007 (12)
C22	0.186 (5)	0.159 (4)	0.150 (4)	0.019 (3)	−0.084 (3)	−0.075 (3)
C23	0.145 (3)	0.133 (3)	0.0599 (16)	−0.024 (2)	0.0253 (18)	−0.0083 (18)

Geometric parameters (Å, º) top

Zn1—Zn1ⁱ	3.0287 (6)	C12—C13	1.362 (4)
Zn1—O1ⁱ	2.0564 (16)	C12—C23	1.523 (4)
Zn1—O4ⁱ	2.0320 (16)	C13—C14	1.377 (3)
O1—Zn1ⁱ	2.0564 (16)	C13—H13	0.9300
O2—Zn1	2.0626 (15)	C14—H14	0.9300
O3—Zn1	2.0438 (15)	C15—N1	1.337 (3)
O4—Zn1ⁱ	2.0320 (16)	C15—C16	1.365 (3)
N1—Zn1	2.0160 (16)	C15—H15	0.9300
C1—O4	1.253 (2)	C16—C17	1.396 (3)
C1—O3	1.256 (2)	C16—H16	0.9300
C1—C9	1.497 (3)	C17—N2	1.350 (2)
C2—O1	1.252 (3)	C17—C18	1.404 (3)
C2—O2	1.255 (3)	C18—C19	1.359 (3)
C2—C3	1.492 (3)	C18—H18	0.9300
C3—C8	1.378 (3)	C19—N1	1.340 (3)
C3—C4	1.383 (3)	C19—H19	0.9300
C4—C5	1.372 (3)	C20—N2	1.449 (3)
C4—H4	0.9300	C20—H20A	0.9600
C5—C6	1.373 (4)	C20—H20B	0.9600
C5—H5	0.9300	C20—H20C	0.9600
C6—C7	1.373 (4)	C21—N2	1.446 (3)
C6—C22	1.513 (4)	C21—H21A	0.9600
C7—C8	1.375 (4)	C21—H21B	0.9600
C7—H7	0.9300	C21—H21C	0.9600
C8—H8	0.9300	C22—H22A	0.9600
C9—C14	1.375 (3)	C22—H22B	0.9600
C9—C10	1.376 (3)	C22—H22C	0.9600
C10—C11	1.379 (4)	C23—H23A	0.9600
C10—H10	0.9300	C23—H23B	0.9600
C11—C12	1.376 (4)	C23—H23C	0.9600
C11—H11	0.9300

O1ⁱ—Zn1—Zn1ⁱ	71.24 (5)	C9—C10—H10	119.7
O1ⁱ—Zn1—O2	157.33 (6)	C11—C10—H10	119.7
O2—Zn1—Zn1ⁱ	86.09 (5)	C12—C11—C10	121.5 (3)
O3—Zn1—Zn1ⁱ	76.09 (5)	C12—C11—H11	119.2
O3—Zn1—O1ⁱ	86.16 (7)	C10—C11—H11	119.2
O3—Zn1—O2	88.75 (6)	C13—C12—C11	117.4 (2)
O4ⁱ—Zn1—Zn1ⁱ	81.30 (5)	C13—C12—C23	120.6 (3)
O4ⁱ—Zn1—O1ⁱ	89.51 (7)	C11—C12—C23	121.9 (3)
O4ⁱ—Zn1—O2	86.67 (7)	C12—C13—C14	121.5 (3)
O4ⁱ—Zn1—O3	157.18 (6)	C12—C13—H13	119.2
N1—Zn1—Zn1ⁱ	169.82 (5)	C14—C13—H13	119.2
N1—Zn1—O1ⁱ	99.01 (7)	C9—C14—C13	121.2 (2)
N1—Zn1—O2	103.64 (7)	C9—C14—H14	119.4
N1—Zn1—O3	100.83 (7)	C13—C14—H14	119.4
N1—Zn1—O4ⁱ	101.98 (7)	N1—C15—C16	124.71 (19)
C2—O1—Zn1ⁱ	138.60 (15)	N1—C15—H15	117.6
C2—O2—Zn1	118.06 (14)	C16—C15—H15	117.6
C1—O3—Zn1	131.15 (15)	C15—C16—C17	120.32 (19)
C1—O4—Zn1ⁱ	125.07 (14)	C15—C16—H16	119.8
C15—N1—C19	114.85 (17)	C17—C16—H16	119.8
C15—N1—Zn1	122.82 (14)	N2—C17—C16	122.49 (18)
C19—N1—Zn1	122.25 (13)	N2—C17—C18	122.56 (19)
C17—N2—C21	121.69 (18)	C16—C17—C18	114.95 (18)
C17—N2—C20	120.89 (18)	C19—C18—C17	120.2 (2)
C21—N2—C20	117.35 (18)	C19—C18—H18	119.9
O4—C1—O3	125.7 (2)	C17—C18—H18	119.9
O4—C1—C9	117.31 (19)	N1—C19—C18	124.83 (19)
O3—C1—C9	117.00 (19)	N1—C19—H19	117.6
O1—C2—O2	125.5 (2)	C18—C19—H19	117.6
O1—C2—C3	116.2 (2)	N2—C20—H20A	109.5
O2—C2—C3	118.28 (19)	N2—C20—H20B	109.5
C8—C3—C4	118.0 (2)	H20A—C20—H20B	109.5
C8—C3—C2	120.5 (2)	N2—C20—H20C	109.5
C4—C3—C2	121.5 (2)	H20A—C20—H20C	109.5
C5—C4—C3	120.7 (2)	H20B—C20—H20C	109.5
C5—C4—H4	119.7	N2—C21—H21A	109.5
C3—C4—H4	119.7	N2—C21—H21B	109.5
C4—C5—C6	121.4 (2)	H21A—C21—H21B	109.5
C4—C5—H5	119.3	N2—C21—H21C	109.5
C6—C5—H5	119.3	H21A—C21—H21C	109.5
C7—C6—C5	117.9 (3)	H21B—C21—H21C	109.5
C7—C6—C22	121.1 (3)	C6—C22—H22A	109.5
C5—C6—C22	121.0 (3)	C6—C22—H22B	109.5
C6—C7—C8	121.4 (3)	H22A—C22—H22B	109.5
C6—C7—H7	119.3	C6—C22—H22C	109.5
C8—C7—H7	119.3	H22A—C22—H22C	109.5
C7—C8—C3	120.7 (2)	H22B—C22—H22C	109.5
C7—C8—H8	119.7	C12—C23—H23A	109.5
C3—C8—H8	119.7	C12—C23—H23B	109.5
C14—C9—C10	117.6 (2)	H23A—C23—H23B	109.5
C14—C9—C1	120.44 (19)	C12—C23—H23C	109.5
C10—C9—C1	122.0 (2)	H23A—C23—H23C	109.5
C9—C10—C11	120.7 (3)	H23B—C23—H23C	109.5

O1—C2—C3—C8	6.7 (3)	C16—C15—N1—Zn1	−174.77 (17)
O2—C2—C3—C8	−172.9 (2)	C18—C19—N1—C15	−1.8 (3)
O1—C2—C3—C4	−174.11 (19)	C18—C19—N1—Zn1	174.94 (19)
O2—C2—C3—C4	6.3 (3)	C16—C17—N2—C21	0.5 (3)
C8—C3—C4—C5	1.3 (3)	C18—C17—N2—C21	−180.0 (2)
C2—C3—C4—C5	−177.9 (2)	C16—C17—N2—C20	177.3 (2)
C3—C4—C5—C6	−0.4 (4)	C18—C17—N2—C20	−3.2 (3)
C4—C5—C6—C7	−0.4 (5)	O2—C2—O1—Zn1ⁱ	9.7 (4)
C4—C5—C6—C22	−179.9 (3)	C3—C2—O1—Zn1ⁱ	−169.87 (15)
C5—C6—C7—C8	0.2 (5)	O1—C2—O2—Zn1	−7.3 (3)
C22—C6—C7—C8	179.8 (4)	C3—C2—O2—Zn1	172.26 (13)
C6—C7—C8—C3	0.7 (5)	O4—C1—O3—Zn1	11.8 (3)
C4—C3—C8—C7	−1.5 (4)	C9—C1—O3—Zn1	−166.70 (13)
C2—C3—C8—C7	177.8 (2)	O3—C1—O4—Zn1ⁱ	−5.9 (3)
O4—C1—C9—C14	−176.7 (2)	C9—C1—O4—Zn1ⁱ	172.51 (13)
O3—C1—C9—C14	1.9 (3)	C15—N1—Zn1—O4ⁱ	0.20 (17)
O4—C1—C9—C10	1.8 (3)	C19—N1—Zn1—O4ⁱ	−176.33 (16)
O3—C1—C9—C10	−179.6 (2)	C15—N1—Zn1—O3	−179.00 (16)
C14—C9—C10—C11	2.9 (4)	C19—N1—Zn1—O3	4.47 (18)
C1—C9—C10—C11	−175.6 (2)	C15—N1—Zn1—O1ⁱ	−91.22 (17)
C9—C10—C11—C12	0.0 (5)	C19—N1—Zn1—O1ⁱ	92.25 (17)
C10—C11—C12—C13	−3.3 (5)	C15—N1—Zn1—O2	89.65 (17)
C10—C11—C12—C23	175.5 (3)	C19—N1—Zn1—O2	−86.88 (17)
C11—C12—C13—C14	3.7 (4)	C15—N1—Zn1—Zn1ⁱ	−107.6 (3)
C23—C12—C13—C14	−175.1 (3)	C19—N1—Zn1—Zn1ⁱ	75.8 (3)
C10—C9—C14—C13	−2.6 (4)	C1—O3—Zn1—N1	161.67 (19)
C1—C9—C14—C13	176.0 (2)	C1—O3—Zn1—O4ⁱ	−16.3 (3)
C12—C13—C14—C9	−0.8 (4)	C1—O3—Zn1—O1ⁱ	63.22 (19)
N1—C15—C16—C17	0.9 (3)	C1—O3—Zn1—O2	−94.7 (2)
C15—C16—C17—N2	175.8 (2)	C1—O3—Zn1—Zn1ⁱ	−8.39 (18)
C15—C16—C17—C18	−3.8 (3)	C2—O2—Zn1—N1	−179.95 (14)
N2—C17—C18—C19	−175.6 (2)	C2—O2—Zn1—O4ⁱ	−78.43 (16)
C16—C17—C18—C19	3.9 (3)	C2—O2—Zn1—O3	79.21 (15)
C17—C18—C19—N1	−1.2 (4)	C2—O2—Zn1—O1ⁱ	2.3 (3)
C16—C15—N1—C19	2.0 (3)	C2—O2—Zn1—Zn1ⁱ	3.07 (15)

Symmetry code: (i) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21C···O3ⁱⁱ	0.96	2.54	3.484 (3)	168
C23—H23B···Cg1ⁱⁱⁱ	0.96	2.99	3.925 (4)	165

Symmetry codes: (ii) x+1, y, z; (iii) x−1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂]
M_r	915.66
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	8.9311 (18), 9.967 (2), 24.756 (5)
β (°)	90.64 (3)
V (Å³)	2203.5 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	ψ scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.758, 0.792
No. of measured, independent and observed [I > 2σ(I)] reflections	12095, 4326, 3432
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.085, 1.03
No. of reflections	4326
No. of parameters	275
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.28

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

O1—Zn1ⁱ	2.0564 (16)	O4—Zn1ⁱ	2.0320 (16)
O2—Zn1	2.0626 (15)	N1—Zn1	2.0160 (16)
O3—Zn1	2.0438 (15)

O3—Zn1—O1ⁱ	86.16 (7)	N1—Zn1—O1ⁱ	99.01 (7)
O3—Zn1—O2	88.75 (6)	N1—Zn1—O2	103.64 (7)
O4ⁱ—Zn1—O1ⁱ	89.51 (7)	N1—Zn1—O3	100.83 (7)
O4ⁱ—Zn1—O2	86.67 (7)	N1—Zn1—O4ⁱ	101.98 (7)
O4ⁱ—Zn1—O3	157.18 (6)

Symmetry code: (i) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21C···O3ⁱⁱ	0.96	2.54	3.484 (3)	168.2
C23—H23B···Cg1ⁱⁱⁱ	0.96	2.99	3.925 (4)	165.00

Symmetry codes: (ii) x+1, y, z; (iii) x−1/2, −y+3/2, z+1/2.

References

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Halcrow, M. A., Kilner, C. A. & Thornton-Pett, M. (2000). Acta Cryst. C56, 1425–1426. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Huang, Y.-L., Huang, M.-Y., Chan, T.-H., Chang, B. C. & Lii, K. L. (2007). Chem. Mater. 19, 3232–3237. Web of Science CSD CrossRef CAS Google Scholar
Neville, S. M., Halder, G. J., Chapman, K. W., Duriska, M. B., Southon, P. D., Cashion, J. D., Letard, J. F., Moubaraki, B., Murray, K. S. & Kepert, C. J. (2008). J. Am. Chem. Soc. 130, 2869–2876. Web of Science CSD CrossRef PubMed 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
Shi, L., Fang, R.-Q., Xue, J.-Y., Xiao, Z.-P., Tan, S.-H. & Zhu, H.-L. (2008). Aust. J. Chem. 61, 288–296. Web of Science CSD CrossRef CAS Google Scholar
Sommerfeldt, H. M., Meermann, C., Tornroos, K. W. & Anwander, R. (2008). Inorg. Chem. 47, 4696–4705. Web of Science CSD CrossRef PubMed CAS Google Scholar
Tabata, K., Fukushima, K. & Okura, I. (2000). J. Porphyrins Phthaolcyanines, 4, 278–284. CrossRef CAS Google Scholar
Wang, P., Ma, J.-P., Li, X.-Y., Huang, R.-Q. & Dong, Y.-B. (2009). Acta Cryst. C65, m78–m81. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xiao, Z.-P., Fang, F.-Q., Li, H.-Q., Xue, J.-Y., Zheng, Y. & Zhu, H.-L. (2008). Eur. J. Med. Chem. 43, 1828–1836. Web of Science CSD CrossRef PubMed CAS Google Scholar
Yang, F.-J., Fang, X., Yu, H.-Y. & Wang, J.-D. (2008). Acta Cryst. C64, m375–m377. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Yang, H.-L., You, Z.-L. & Zhu, H.-L. (2004). Acta Cryst. E60, m1213–m1214. Web of Science CSD CrossRef IUCr Journals Google Scholar
You, Z.-L., Lin, Y.-S., Liu, W.-S., Tan, M.-Y. & Zhu, H.-L. (2003). Acta Cryst. E59, m1025–m1027. Web of Science CSD CrossRef IUCr Journals Google Scholar
You, Z.-L., Zhu, H.-L. & Liu, W.-S. (2004). Acta Cryst. E60, m560–m562. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m948-m949

doi:10.1107/S1600536809027603

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)