Crystal structure of [2-({4-[2,6-bis(pyri­din-2-yl)pyri­din-4-yl]phenyl}(methyl)amino)­ethanol-κ3N,N′,N′′]bis­(thio­cyan­ato-κN)zinc N,N-di­methyl­formamide monosolvate

Wang, S.-C.; Pan, R.-C.; Song, W.-Y.; Li, S.-L.

doi:10.1107/S1600536814019527

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages m347-m348

doi:10.1107/S1600536814019527

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Crystal structure of [2-({4-[2,6-bis(pyridin-2-yl)pyridin-4-yl]phenyl}(methyl)amino)ethanol-κ³N,N′,N′′]bis(thiocyanato-κN)zinc N,N-dimethylformamide monosolvate

Shi-Chao Wang,^a Rou-Chen Pan,^a Wan-Ying Song ^a and Sheng-Li Li ^a ^*

^aDepartment of Chemistry, Anhui University, Hefei 230039, People's Republic of China, Key Laboratory of Functional Inorganic Materials Chemistry, Hefei 230039, People's Republic of China
^*Correspondence e-mail: lsl1968@ahu.edu.cn

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 25 August 2014; accepted 28 August 2014; online 6 September 2014)

In the title compound, [Zn(NCS)₂(C₂₄H₂₂N₄O)]·C₃H₇NO, the Zn^II cation is N,N′,N′′-chelated by one 2-({4-[2,6-bis(pyridin-2-yl)pyridin-4-yl]phenyl}(methyl)amino)ethanol ligand and coordinated by two thiocyanate anions in a distorted N₅ trigonal–bipyramidal geometry. In the molecule, the three pyridine rings are approximately coplanar [maximum deviation = 0.026 (5) Å], and the mean plane of the three pyridine rings is twisted to the benzene ring with a small dihedral angle of 5.9 (2)°. In the crystal, complex molecules are linked by weak C—H⋯O hydrogen bonds into supramolecular chains propagated along [110]; π–π stacking is observed between adjacent chains [centroid–centroid distance = 3.678 (4) Å]. The dimethylformamide solvent molecules are linked with the complex chains via weak C—H⋯O hydrogen bonds.

Keywords: crystal structure; zinc complex; thiocyanate ligand; hydrogen bonding; π–π stacking.

CCDC reference: 1020385

1. Related literature

For the crystal structures of related Zn^II thiocyanate complexes, see: Nie et al. (2014 ); Kharat et al. (2012 ); Eryazici et al. (2008 ).

2. Experimental

2.1. Crystal data

[Zn(NCS)₂(C₂₄H₂₂N₄O)]·C₃H₇NO
M_r = 637.08
Triclinic, $[P \overline 1]$
a = 9.565 (5) Å
b = 12.969 (5) Å
c = 13.652 (5) Å
α = 115.656 (5)°
β = 94.646 (5)°
γ = 91.621 (5)°
V = 1517.7 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.99 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.20 mm

2.2. Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.757, T_max = 0.827
10881 measured reflections
5293 independent reflections
3729 reflections with I > 2σ(I)
R_int = 0.029

2.3. Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.174
S = 0.99
5293 reflections
373 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—N2	2.051 (4)
Zn1—N3	2.163 (4)
Zn1—N4	2.224 (4)
Zn1—N5	1.953 (5)
Zn1—N6	1.969 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O2ⁱ	0.93	2.54	3.457 (8)	170
C14—H14⋯O2ⁱ	0.93	2.54	3.470 (7)	177
C16—H16⋯O2ⁱ	0.93	2.43	3.356 (9)	178
C24—H24⋯O1ⁱⁱ	0.93	2.58	3.488 (13)	164
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) x+1, y+1, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1020385

Crystal structure: contains datablocks I, Global. DOI: 10.1107/S1600536814019527/xu5817sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814019527/xu5817Isup2.hkl

checkCIF report

Comment top

Zinc complexes with terpyridine derivatives are currently attracting attention for their interesting molecular topologies and crystal packing motifs, as well as the fact that they may be designed with specific applications in bioinorganic chemistry and material (Nie et al., 2014; Kharat et al., 2012). In turn, countless Zn terpyridine complexes have been surveyed and their crystals were demonstrated. However, the crystal of Zn(SCN)₂ terpyridine complexes are rarely mentioned (Eryazici et al., 2008). In this paper, we report the crystal structure of the terpyridine- Zinc complex. The molecular structure with the numbering scheme is shown in Fig. 1, the Zn^II is coordinated by three N atoms from terpyridine ligand and two thiocyanate anions in a highly distorted square-pyramidal trigonal bipyramidal geometry. Bond distances and angles around the Zn^II center are in the range 1.954 (5)–2.224 (4) Å and 74.93 (14)–124.48 (17)°, respectively. The dihedral angle between pyridine ring and phenyl ring is 6.24°, which can ascribe to the existence of the dimethylformamide molecule that restricts the rotation of single bonds and increase molecule planarity by C— H···O interactions. The one-dimensional chains are assembled by C24—H24···O1 (2.583 Å) hydrogen bond between adjacent complex molecules (Fig.2). In addition, two-dimensional networks formed by multiply C—H···S hydrogen bonds. The distances of C6—H6··· S2, C21—H21···S2 and C17—H17···S2 are nearly the same, which are 2.970 Å, 2.952 Å and 2.964 Å, respectively (Fig.3).

Related literature top

For the crystal structures of related Zn^II thiocyanate complexes, see: Nie et al. (2014); Kharat et al. (2012); Eryazici et al. (2008).

Experimental top

To a solution of Zn(SCN)₂ (0.18 g, 1 mmol) in freshly distilled ethanol (50 ml), was added N-methyl-N-(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)phenyl)amino)ethanol (0.38 g, 1 mmol). The mixture was refluxed for 4 h. Then resulted orange suspension was filtered, washed with ethanol and dried in vacuo. Subsequent diffusion of diethyl ether into the concentrated dimethylformamide solution gave complex as air-stable orange crystals.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted.
	Fig. 2. The one-dimensional chain structure of the title compound, Hydrogen atoms are omitted for clarity.
	Fig. 3. The two-dimensional networks of the title compound, Hydrogen atoms are omitted for clarity.

[2-({4-[2,6-Bis(pyridin-2-yl)pyridin-4-yl]phenyl}(methyl)amino)ethanol-κ³N,N',N'']bis(thiocyanato-κN)zinc N,N-dimethylformamide monosolvate top

Crystal data top

[Zn(NCS)₂(C₂₄H₂₂N₄O)]·C₃H₇NO	Z = 2
M_r = 637.08	F(000) = 660
Triclinic, P1	D_x = 1.394 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 9.565 (5) Å	Cell parameters from 2689 reflections
b = 12.969 (5) Å	θ = 2.6–21.8°
c = 13.652 (5) Å	µ = 0.99 mm⁻¹
α = 115.656 (5)°	T = 298 K
β = 94.646 (5)°	Block, orange
γ = 91.621 (5)°	0.30 × 0.20 × 0.20 mm
V = 1517.7 (11) Å³

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	5293 independent reflections
Radiation source: fine-focus sealed tube	3729 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
phi and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→11
T_min = 0.757, T_max = 0.827	k = −15→15
10881 measured reflections	l = −14→16

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.174	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0928P)² + 1.3834P] where P = (F_o² + 2F_c²)/3
5293 reflections	(Δ/σ)_max = 0.006
373 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

[Zn(NCS)₂(C₂₄H₂₂N₄O)]·C₃H₇NO	γ = 91.621 (5)°
M_r = 637.08	V = 1517.7 (11) Å³
Triclinic, P1	Z = 2
a = 9.565 (5) Å	Mo Kα radiation
b = 12.969 (5) Å	µ = 0.99 mm⁻¹
c = 13.652 (5) Å	T = 298 K
α = 115.656 (5)°	0.30 × 0.20 × 0.20 mm
β = 94.646 (5)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	5293 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	3729 reflections with I > 2σ(I)
T_min = 0.757, T_max = 0.827	R_int = 0.029
10881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.174	H-atom parameters constrained
S = 0.99	Δρ_max = 0.87 e Å⁻³
5293 reflections	Δρ_min = −0.72 e Å⁻³
373 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	0.69718 (6)	1.21976 (4)	0.76963 (4)	0.0543 (2)
S2	0.5329 (2)	1.42626 (13)	0.57934 (12)	0.0919 (6)
S1	1.18423 (19)	1.2588 (2)	0.87203 (16)	0.1314 (9)
C11	0.4729 (5)	0.8990 (4)	0.6857 (3)	0.0493 (10)
H11	0.4628	0.8285	0.6244	0.059*
C7	0.3121 (5)	0.8217 (4)	0.7783 (4)	0.0508 (11)
N4	0.7085 (4)	1.0716 (3)	0.6082 (3)	0.0570 (10)
C10	0.4020 (4)	0.9141 (4)	0.7772 (3)	0.0473 (10)
N2	0.5729 (4)	1.0896 (3)	0.7721 (3)	0.0462 (8)
C21	0.6321 (5)	0.8772 (4)	0.4976 (4)	0.0616 (13)
H21	0.5795	0.8117	0.4886	0.074*
C20	0.6351 (5)	0.9760 (4)	0.5926 (3)	0.0474 (10)
C15	0.5317 (5)	1.2277 (4)	0.9491 (4)	0.0509 (11)
C14	0.4221 (5)	1.0233 (4)	0.8652 (4)	0.0514 (11)
H14	0.3781	1.0387	0.9280	0.062*
C25	0.5934 (6)	1.3671 (4)	0.6558 (4)	0.0601 (12)
N3	0.6160 (4)	1.2966 (3)	0.9271 (3)	0.0552 (9)
C13	0.5056 (4)	1.1074 (4)	0.8597 (3)	0.0464 (10)
C12	0.5556 (4)	0.9861 (4)	0.6862 (3)	0.0458 (10)
C5	0.2196 (6)	0.6233 (4)	0.6932 (4)	0.0746 (16)
H5	0.2168	0.5511	0.6346	0.089*
C4	0.1361 (5)	0.6400 (4)	0.7783 (4)	0.0641 (13)
C8	0.2290 (5)	0.8372 (4)	0.8625 (4)	0.0595 (12)
H8	0.2308	0.9098	0.9205	0.071*
N1	0.0541 (6)	0.5523 (4)	0.7781 (4)	0.0904 (16)
C9	0.1450 (5)	0.7506 (4)	0.8635 (4)	0.0636 (13)
H9	0.0928	0.7657	0.9222	0.076*
C16	0.4713 (5)	1.2637 (4)	1.0458 (4)	0.0632 (13)
H16	0.4126	1.2139	1.0592	0.076*
C22	0.7081 (6)	0.8762 (5)	0.4153 (4)	0.0701 (14)
H22	0.7072	0.8101	0.3500	0.084*
C6	0.3040 (6)	0.7096 (4)	0.6943 (4)	0.0671 (14)
H6	0.3589	0.6938	0.6370	0.081*
C17	0.5010 (6)	1.3769 (5)	1.1227 (4)	0.0736 (15)
H17	0.4627	1.4041	1.1891	0.088*
C26	1.0166 (7)	1.2465 (5)	0.8394 (4)	0.0734 (15)
C23	0.7846 (6)	0.9739 (5)	0.4315 (5)	0.0787 (16)
H23	0.8370	0.9751	0.3775	0.094*
C18	0.5873 (6)	1.4481 (5)	1.0997 (5)	0.0775 (16)
H18	0.6069	1.5244	1.1499	0.093*
C24	0.7831 (6)	1.0690 (5)	0.5274 (5)	0.0733 (15)
H24	0.8356	1.1351	0.5379	0.088*
N6	0.6325 (5)	1.3253 (4)	0.7093 (4)	0.0690 (11)
C19	0.6443 (6)	1.4058 (4)	1.0021 (4)	0.0687 (14)
H19	0.7042	1.4538	0.9874	0.082*
O2	0.7459 (6)	0.9090 (5)	0.9008 (4)	0.1267 (19)
O1	−0.0642 (12)	0.3133 (8)	0.5213 (8)	0.253 (5)
H1C	−0.1604	0.2942	0.4900	0.379*
C3	−0.0373 (8)	0.5720 (6)	0.8653 (6)	0.111 (3)
H3A	0.0188	0.6023	0.9346	0.166*
H3B	−0.0860	0.5009	0.8525	0.166*
H3C	−0.1045	0.6258	0.8657	0.166*
N7	0.8572 (6)	0.8651 (5)	0.7513 (5)	0.0909 (16)
N5	0.8987 (5)	1.2422 (4)	0.8163 (4)	0.0756 (13)
C29	0.8300 (9)	0.9318 (8)	0.8483 (7)	0.114 (2)
H29	0.8783	1.0037	0.8819	0.137*
C2	0.0517 (11)	0.4346 (7)	0.6910 (7)	0.129 (3)
H2A	0.1441	0.4184	0.6657	0.155*
H2B	0.0240	0.3797	0.7177	0.155*
C28	0.7953 (10)	0.7508 (8)	0.6975 (8)	0.141 (3)
H28A	0.8676	0.6985	0.6717	0.212*
H28B	0.7307	0.7431	0.6368	0.212*
H28C	0.7459	0.7337	0.7478	0.212*
C1	−0.0503 (12)	0.4279 (10)	0.6026 (10)	0.182 (5)
H1A	−0.1403	0.4510	0.6300	0.219*
H1B	−0.0184	0.4786	0.5724	0.219*
C27	0.9575 (8)	0.8978 (9)	0.6971 (8)	0.144 (4)
H27A	0.9899	0.9767	0.7405	0.216*
H27B	0.9148	0.8882	0.6273	0.216*
H27C	1.0356	0.8506	0.6868	0.216*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0543 (4)	0.0515 (3)	0.0586 (4)	−0.0060 (2)	−0.0007 (2)	0.0270 (3)
S2	0.1544 (17)	0.0717 (9)	0.0591 (9)	0.0319 (10)	0.0163 (9)	0.0352 (8)
S1	0.0642 (11)	0.216 (3)	0.0843 (12)	0.0322 (13)	0.0012 (9)	0.0380 (14)
C11	0.058 (3)	0.044 (2)	0.040 (2)	0.001 (2)	0.006 (2)	0.0134 (19)
C7	0.048 (3)	0.052 (3)	0.052 (3)	−0.001 (2)	0.007 (2)	0.022 (2)
N4	0.059 (2)	0.058 (2)	0.056 (2)	−0.0086 (19)	0.0118 (19)	0.0269 (19)
C10	0.046 (2)	0.049 (2)	0.048 (3)	0.0038 (19)	0.0056 (19)	0.022 (2)
N2	0.048 (2)	0.048 (2)	0.0406 (19)	0.0012 (16)	0.0037 (16)	0.0170 (17)
C21	0.068 (3)	0.065 (3)	0.049 (3)	−0.006 (2)	0.013 (2)	0.021 (2)
C20	0.049 (2)	0.052 (3)	0.041 (2)	0.002 (2)	0.0045 (19)	0.020 (2)
C15	0.052 (3)	0.051 (3)	0.044 (3)	0.003 (2)	−0.002 (2)	0.018 (2)
C14	0.052 (3)	0.059 (3)	0.042 (2)	0.006 (2)	0.012 (2)	0.020 (2)
C25	0.078 (3)	0.049 (3)	0.048 (3)	0.006 (2)	0.013 (2)	0.015 (2)
N3	0.062 (2)	0.049 (2)	0.050 (2)	0.0015 (18)	−0.0014 (18)	0.0191 (18)
C13	0.045 (2)	0.049 (2)	0.043 (2)	0.0040 (19)	0.0044 (19)	0.018 (2)
C12	0.048 (2)	0.047 (2)	0.045 (2)	0.0013 (19)	0.0058 (19)	0.023 (2)
C5	0.096 (4)	0.055 (3)	0.066 (3)	−0.014 (3)	0.030 (3)	0.017 (3)
C4	0.071 (3)	0.064 (3)	0.060 (3)	−0.009 (3)	0.014 (3)	0.029 (3)
C8	0.068 (3)	0.053 (3)	0.052 (3)	−0.005 (2)	0.015 (2)	0.018 (2)
N1	0.115 (4)	0.072 (3)	0.072 (3)	−0.035 (3)	0.029 (3)	0.019 (3)
C9	0.071 (3)	0.067 (3)	0.055 (3)	−0.002 (3)	0.024 (2)	0.026 (3)
C16	0.066 (3)	0.065 (3)	0.051 (3)	0.007 (2)	0.008 (2)	0.016 (2)
C22	0.084 (4)	0.069 (3)	0.053 (3)	−0.005 (3)	0.019 (3)	0.021 (3)
C6	0.077 (4)	0.062 (3)	0.060 (3)	−0.008 (3)	0.026 (3)	0.022 (3)
C17	0.088 (4)	0.065 (3)	0.051 (3)	0.006 (3)	0.009 (3)	0.009 (3)
C26	0.074 (4)	0.091 (4)	0.049 (3)	0.013 (3)	0.009 (3)	0.024 (3)
C23	0.090 (4)	0.090 (4)	0.065 (4)	−0.001 (3)	0.029 (3)	0.038 (3)
C18	0.088 (4)	0.057 (3)	0.062 (3)	0.002 (3)	−0.003 (3)	0.004 (3)
C24	0.079 (4)	0.075 (4)	0.070 (4)	−0.013 (3)	0.014 (3)	0.035 (3)
N6	0.086 (3)	0.059 (3)	0.066 (3)	0.002 (2)	0.001 (2)	0.032 (2)
C19	0.081 (4)	0.050 (3)	0.065 (3)	−0.003 (3)	−0.001 (3)	0.017 (3)
O2	0.142 (5)	0.142 (5)	0.098 (4)	−0.003 (4)	0.047 (3)	0.050 (3)
O1	0.304 (13)	0.181 (8)	0.201 (9)	−0.063 (8)	0.005 (8)	0.024 (7)
C3	0.141 (6)	0.099 (5)	0.088 (5)	−0.033 (4)	0.046 (4)	0.035 (4)
N7	0.090 (4)	0.110 (4)	0.090 (4)	0.039 (3)	0.033 (3)	0.054 (4)
N5	0.054 (3)	0.090 (3)	0.081 (3)	−0.010 (2)	−0.005 (2)	0.038 (3)
C29	0.125 (7)	0.135 (7)	0.095 (6)	0.028 (5)	0.032 (5)	0.058 (5)
C2	0.177 (9)	0.112 (6)	0.097 (6)	−0.048 (6)	0.042 (6)	0.042 (5)
C28	0.159 (9)	0.111 (7)	0.146 (8)	0.044 (6)	0.004 (6)	0.051 (6)
C1	0.167 (10)	0.183 (11)	0.143 (9)	−0.081 (9)	0.005 (8)	0.029 (9)
C27	0.090 (5)	0.252 (12)	0.157 (8)	0.045 (6)	0.039 (5)	0.145 (8)

Geometric parameters (Å, º) top

Zn1—N2	2.051 (4)	N1—C3	1.472 (7)
Zn1—N3	2.163 (4)	C9—H9	0.9300
Zn1—N4	2.224 (4)	C16—C17	1.389 (7)
Zn1—N5	1.953 (5)	C16—H16	0.9300
Zn1—N6	1.969 (4)	C22—C23	1.367 (8)
S2—C25	1.623 (6)	C22—H22	0.9300
S1—C26	1.613 (7)	C6—H6	0.9300
C11—C12	1.359 (6)	C17—C18	1.372 (8)
C11—C10	1.410 (6)	C17—H17	0.9300
C11—H11	0.9300	C26—N5	1.139 (7)
C7—C8	1.395 (6)	C23—C24	1.357 (8)
C7—C6	1.404 (7)	C23—H23	0.9300
C7—C10	1.462 (6)	C18—C19	1.369 (8)
N4—C20	1.331 (6)	C18—H18	0.9300
N4—C24	1.351 (6)	C24—H24	0.9300
C10—C14	1.401 (6)	C19—H19	0.9300
N2—C13	1.339 (5)	O2—C29	1.229 (8)
N2—C12	1.341 (5)	O1—C1	1.412 (12)
C21—C20	1.370 (6)	O1—H1C	0.9600
C21—C22	1.382 (7)	C3—H3A	0.9600
C21—H21	0.9300	C3—H3B	0.9600
C20—C12	1.499 (6)	C3—H3C	0.9600
C15—N3	1.330 (6)	N7—C29	1.283 (9)
C15—C16	1.378 (6)	N7—C27	1.418 (8)
C15—C13	1.505 (6)	N7—C28	1.423 (10)
C14—C13	1.366 (6)	C29—H29	0.9300
C14—H14	0.9300	C2—C1	1.459 (13)
C25—N6	1.130 (6)	C2—H2A	0.9700
N3—C19	1.343 (6)	C2—H2B	0.9700
C5—C6	1.355 (7)	C28—H28A	0.9600
C5—C4	1.405 (7)	C28—H28B	0.9600
C5—H5	0.9300	C28—H28C	0.9600
C4—N1	1.362 (6)	C1—H1A	0.9700
C4—C9	1.397 (7)	C1—H1B	0.9700
C8—C9	1.368 (6)	C27—H27A	0.9600
C8—H8	0.9300	C27—H27B	0.9600
N1—C2	1.471 (9)	C27—H27C	0.9600

N5—Zn1—N6	113.0 (2)	C15—C16—H16	121.1
N5—Zn1—N2	122.32 (17)	C17—C16—H16	121.1
N6—Zn1—N2	124.49 (17)	C23—C22—C21	118.9 (5)
N5—Zn1—N3	99.89 (17)	C23—C22—H22	120.6
N6—Zn1—N3	100.04 (16)	C21—C22—H22	120.6
N2—Zn1—N3	75.96 (14)	C5—C6—C7	122.8 (5)
N5—Zn1—N4	96.67 (17)	C5—C6—H6	118.6
N6—Zn1—N4	95.28 (16)	C7—C6—H6	118.6
N2—Zn1—N4	74.93 (14)	C18—C17—C16	119.4 (5)
N3—Zn1—N4	150.86 (15)	C18—C17—H17	120.3
C12—C11—C10	120.8 (4)	C16—C17—H17	120.3
C12—C11—H11	119.6	N5—C26—S1	177.1 (6)
C10—C11—H11	119.6	C24—C23—C22	119.2 (5)
C8—C7—C6	114.9 (4)	C24—C23—H23	120.4
C8—C7—C10	123.1 (4)	C22—C23—H23	120.4
C6—C7—C10	122.0 (4)	C19—C18—C17	119.3 (5)
C20—N4—C24	118.1 (4)	C19—C18—H18	120.3
C20—N4—Zn1	115.1 (3)	C17—C18—H18	120.3
C24—N4—Zn1	126.8 (3)	N4—C24—C23	122.6 (5)
C14—C10—C11	115.6 (4)	N4—C24—H24	118.7
C14—C10—C7	122.6 (4)	C23—C24—H24	118.7
C11—C10—C7	121.7 (4)	C25—N6—Zn1	166.5 (4)
C13—N2—C12	118.7 (4)	N3—C19—C18	121.7 (5)
C13—N2—Zn1	120.2 (3)	N3—C19—H19	119.1
C12—N2—Zn1	121.1 (3)	C18—C19—H19	119.1
C20—C21—C22	119.1 (5)	C1—O1—H1C	109.1
C20—C21—H21	120.4	N1—C3—H3A	109.5
C22—C21—H21	120.4	N1—C3—H3B	109.5
N4—C20—C21	122.1 (4)	H3A—C3—H3B	109.5
N4—C20—C12	114.6 (4)	N1—C3—H3C	109.5
C21—C20—C12	123.2 (4)	H3A—C3—H3C	109.5
N3—C15—C16	122.7 (4)	H3B—C3—H3C	109.5
N3—C15—C13	115.0 (4)	C29—N7—C27	122.1 (8)
C16—C15—C13	122.3 (4)	C29—N7—C28	120.4 (7)
C13—C14—C10	120.5 (4)	C27—N7—C28	117.3 (8)
C13—C14—H14	119.7	C26—N5—Zn1	174.8 (5)
C10—C14—H14	119.7	O2—C29—N7	125.8 (9)
N6—C25—S2	178.5 (5)	O2—C29—H29	117.1
C15—N3—C19	118.9 (4)	N7—C29—H29	117.1
C15—N3—Zn1	115.7 (3)	C1—C2—N1	106.5 (9)
C19—N3—Zn1	125.4 (4)	C1—C2—H2A	110.4
N2—C13—C14	122.3 (4)	N1—C2—H2A	110.4
N2—C13—C15	113.2 (4)	C1—C2—H2B	110.4
C14—C13—C15	124.5 (4)	N1—C2—H2B	110.4
N2—C12—C11	122.0 (4)	H2A—C2—H2B	108.6
N2—C12—C20	114.2 (4)	N7—C28—H28A	109.5
C11—C12—C20	123.7 (4)	N7—C28—H28B	109.5
C6—C5—C4	121.8 (5)	H28A—C28—H28B	109.5
C6—C5—H5	119.1	N7—C28—H28C	109.5
C4—C5—H5	119.1	H28A—C28—H28C	109.5
N1—C4—C9	122.4 (5)	H28B—C28—H28C	109.5
N1—C4—C5	121.6 (5)	O1—C1—C2	108.1 (11)
C9—C4—C5	116.1 (4)	O1—C1—H1A	110.1
C9—C8—C7	123.0 (4)	C2—C1—H1A	110.1
C9—C8—H8	118.5	O1—C1—H1B	110.1
C7—C8—H8	118.5	C2—C1—H1B	110.1
C4—N1—C2	121.9 (5)	H1A—C1—H1B	108.4
C4—N1—C3	121.0 (5)	N7—C27—H27A	109.5
C2—N1—C3	117.1 (5)	N7—C27—H27B	109.5
C8—C9—C4	121.4 (4)	H27A—C27—H27B	109.5
C8—C9—H9	119.3	N7—C27—H27C	109.5
C4—C9—H9	119.3	H27A—C27—H27C	109.5
C15—C16—C17	117.9 (5)	H27B—C27—H27C	109.5

N5—Zn1—N4—C20	121.1 (3)	C13—N2—C12—C11	−0.5 (6)
N6—Zn1—N4—C20	−124.9 (3)	Zn1—N2—C12—C11	−179.5 (3)
N2—Zn1—N4—C20	−0.6 (3)	C13—N2—C12—C20	179.7 (4)
N3—Zn1—N4—C20	−3.3 (5)	Zn1—N2—C12—C20	0.7 (5)
N5—Zn1—N4—C24	−57.5 (5)	C10—C11—C12—N2	−0.5 (7)
N6—Zn1—N4—C24	56.4 (5)	C10—C11—C12—C20	179.4 (4)
N2—Zn1—N4—C24	−179.3 (5)	N4—C20—C12—N2	−1.2 (6)
N3—Zn1—N4—C24	178.1 (4)	C21—C20—C12—N2	179.6 (4)
C12—C11—C10—C14	0.7 (6)	N4—C20—C12—C11	179.0 (4)
C12—C11—C10—C7	179.8 (4)	C21—C20—C12—C11	−0.2 (7)
C8—C7—C10—C14	6.0 (7)	C6—C5—C4—N1	−178.4 (6)
C6—C7—C10—C14	−173.5 (5)	C6—C5—C4—C9	0.2 (9)
C8—C7—C10—C11	−173.0 (4)	C6—C7—C8—C9	−0.4 (8)
C6—C7—C10—C11	7.5 (7)	C10—C7—C8—C9	−179.9 (5)
N5—Zn1—N2—C13	92.5 (4)	C9—C4—N1—C2	−176.4 (7)
N6—Zn1—N2—C13	−93.1 (3)	C5—C4—N1—C2	2.1 (10)
N3—Zn1—N2—C13	−0.4 (3)	C9—C4—N1—C3	4.1 (9)
N4—Zn1—N2—C13	−179.1 (3)	C5—C4—N1—C3	−177.4 (6)
N5—Zn1—N2—C12	−88.5 (4)	C7—C8—C9—C4	−0.8 (8)
N6—Zn1—N2—C12	85.9 (4)	N1—C4—C9—C8	179.5 (6)
N3—Zn1—N2—C12	178.6 (3)	C5—C4—C9—C8	0.9 (8)
N4—Zn1—N2—C12	−0.1 (3)	N3—C15—C16—C17	0.0 (7)
C24—N4—C20—C21	−0.9 (7)	C13—C15—C16—C17	−179.4 (4)
Zn1—N4—C20—C21	−179.7 (4)	C20—C21—C22—C23	0.3 (8)
C24—N4—C20—C12	179.9 (4)	C4—C5—C6—C7	−1.5 (10)
Zn1—N4—C20—C12	1.1 (5)	C8—C7—C6—C5	1.5 (8)
C22—C21—C20—N4	0.4 (7)	C10—C7—C6—C5	−179.0 (5)
C22—C21—C20—C12	179.5 (4)	C15—C16—C17—C18	0.4 (8)
C11—C10—C14—C13	0.0 (6)	C21—C22—C23—C24	−0.4 (9)
C7—C10—C14—C13	−179.1 (4)	C16—C17—C18—C19	−1.0 (9)
C16—C15—N3—C19	0.2 (7)	C20—N4—C24—C23	0.8 (8)
C13—C15—N3—C19	179.6 (4)	Zn1—N4—C24—C23	179.4 (4)
C16—C15—N3—Zn1	−179.9 (4)	C22—C23—C24—N4	−0.2 (9)
C13—C15—N3—Zn1	−0.5 (5)	S2—C25—N6—Zn1	87 (18)
N5—Zn1—N3—C15	−120.5 (3)	N5—Zn1—N6—C25	107 (2)
N6—Zn1—N3—C15	123.8 (3)	N2—Zn1—N6—C25	−67 (2)
N2—Zn1—N3—C15	0.5 (3)	N3—Zn1—N6—C25	−147 (2)
N4—Zn1—N3—C15	3.2 (5)	N4—Zn1—N6—C25	8 (2)
N5—Zn1—N3—C19	59.3 (4)	C15—N3—C19—C18	−0.8 (8)
N6—Zn1—N3—C19	−56.3 (4)	Zn1—N3—C19—C18	179.3 (4)
N2—Zn1—N3—C19	−179.6 (4)	C17—C18—C19—N3	1.2 (9)
N4—Zn1—N3—C19	−177.0 (4)	S1—C26—N5—Zn1	148 (8)
C12—N2—C13—C14	1.2 (6)	N6—Zn1—N5—C26	−133 (5)
Zn1—N2—C13—C14	−179.8 (3)	N2—Zn1—N5—C26	42 (5)
C12—N2—C13—C15	−178.7 (4)	N3—Zn1—N5—C26	122 (5)
Zn1—N2—C13—C15	0.3 (5)	N4—Zn1—N5—C26	−34 (5)
C10—C14—C13—N2	−1.0 (7)	C27—N7—C29—O2	−179.2 (7)
C10—C14—C13—C15	179.0 (4)	C28—N7—C29—O2	−4.5 (12)
N3—C15—C13—N2	0.2 (5)	C4—N1—C2—C1	−85.3 (9)
C16—C15—C13—N2	179.6 (4)	C3—N1—C2—C1	94.2 (8)
N3—C15—C13—C14	−179.7 (4)	N1—C2—C1—O1	−175.1 (7)
C16—C15—C13—C14	−0.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.93	2.54	3.457 (8)	170
C14—H14···O2ⁱ	0.93	2.54	3.470 (7)	177
C16—H16···O2ⁱ	0.93	2.43	3.356 (9)	178
C24—H24···O1ⁱⁱ	0.93	2.58	3.488 (13)	164

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

Selected bond lengths (Å) top

Zn1—N2	2.051 (4)	Zn1—N5	1.953 (5)
Zn1—N3	2.163 (4)	Zn1—N6	1.969 (4)
Zn1—N4	2.224 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O2ⁱ	0.93	2.54	3.457 (8)	170
C14—H14···O2ⁱ	0.93	2.54	3.470 (7)	177
C16—H16···O2ⁱ	0.93	2.43	3.356 (9)	178
C24—H24···O1ⁱⁱ	0.93	2.58	3.488 (13)	164

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

Acknowledgements

This work was supported by Anhui Provincial Natural Science Foundation (grant No. 1308085MB24) and the Educational Commission of Anhui Province of China (grant No. KJ2012A025).

References

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