catena-Poly[[bis­(dicyanamido-κN1)cobalt(II)]bis­{μ-1,2-bis­[(1,2,4-triazol-1-yl)meth­yl]benzene-κ2N4:N4′}]

Zhang, J.; Shen, X.

doi:10.1107/S1600536814012331

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 7| July 2014| Page m244

https://doi.org/10.1107/S1600536814012331

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catena-Poly[[bis(dicyanamido-κN¹)cobalt(II)]bis{μ-1,2-bis[(1,2,4-triazol-1-yl)methyl]benzene-κ²N⁴:N^4′}]

Jixia Zhang ^a and Xiaoping Shen ^a ^*

^aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: xiaopingshen@163.com

(Received 22 May 2014; accepted 27 May 2014; online 4 June 2014)

In the title complex, [Co(C₂N₃)₂(C₁₂H₁₂N₆)₂]_n the Co^II atom lies on a centre of symmetry and displays a slightly distorted octahedral coordination geometry. The 1,2-bis[(1,2,4-triazol-1-yl)methyl]benzene ligands link adjacent metal atoms into polymeric chains parallel to the c axis, forming centrosymmetric 26-membered metallamacrocycles. The conformation of the metallamacrocycles is stabilized by pairs of C—H⋯N hydrogen bonds. The dihedral angles formed by the planes of the triazole rings with those of the benzene ring are 79.4 (2) and 79.1 (2)°. In the crystal, the chains interact through C—H⋯N hydrogen bonds, forming a three-dimensional network.

CCDC reference: 1005518

Related literature

For background to transition metal complexes of 1,2,4-triazole derivatives, see: Haasnoot (2000 ); Cui et al. (2012 ); Han et al. (2012 ); Wang et al. (2012 ).

Experimental

Crystal data

[Co(C₂N₃)₂(C₁₂H₁₂N₆)₂]
M_r = 671.58
Triclinic, $[P \overline 1]$
a = 8.517 (2) Å
b = 9.092 (2) Å
c = 9.622 (3) Å
α = 93.984 (7)°
β = 95.015 (7)°
γ = 97.587 (7)°
V = 733.2 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.18 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.831, T_max = 0.893
7244 measured reflections
2658 independent reflections
2118 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.111
S = 1.05
2658 reflections
214 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯N9ⁱ	0.93	2.54	3.308 (4)	140
C11—H11A⋯N5ⁱⁱ	0.93	2.56	3.217 (5)	128
C12—H12A⋯N9ⁱⁱⁱ	0.93	2.48	3.286 (4)	145
Symmetry codes: (i) x-1, y-1, z; (ii) -x+2, -y, -z+1; (iii) -x+2, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2000 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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

CCDC reference: 1005518

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S1600536814012331/rz5127sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012331/rz5127Isup2.hkl

checkCIF report

Comment top

A large number of mononuclear, oligonuclear and polynuclear transition metal complexes of 1,2,4-triazole derivatives have been synthesized and characterized due to their magnetic properties and novel topologies (Haasnoot, 2000; Cui et al., Han et al., and Wang et al., 2012). As a contribution to this field, we report herein the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. Each cobalt(II) atom lies on a centre of symmetry and displays a slightly distorted octahedral coordination geometry, provided by four nitrogen atoms from four symmetry-related obtz ligands forming the equatorial plane and by two nitrogen atoms from two dca anions at the apices (obtz = 1,2-bis(1,2,4-triazol-1-ylmethyl)benzene, dca = dicyanamide). Two centrosymmetrically-related obtz ligands link adjacent cobalt(II) atoms to form 22-membered metallamacrocycles, which are connected into one-dimensional chains running parallel to the c axis (Fig. 2). The Co···Co separations within the chain are equal to the c-axis translation (9.622 (3) Å). The obtz ligands exhibit a gauche conformation. The triazole rings form a dihedral angle of 80.5 (2)° and are inclined by 79.4 (2) and 79.1 (2)° with respect to the benzene ring. The conformation of the metallamacrocycles is enforced by pairs of C—H···N hydrogen bonds (Table 1). In the crystal, chains interact through C—H···N hydrogen bonds (Table 1) to form a three-dimensional network.

Related literature top

For background to transition metal complexes of 1,2,4-triazole derivatives, see: Haasnoot (2000); Cui et al. (2012); Han et al. (2012); Wang et al. (2012).

Experimental top

A 20 ml H₂O/MeOH solution (1:1 v/v) of Co(NO₃)₂^.6H₂O (0.5 mmol) was added to one leg of an "H-shaped" tube, and a 20 ml H₂O/MeOH (1:1 v/v) solution of obtz (1.0 mmol) and Na[N(CN)₂] (1.0 mmol) was added to the other leg of the tube. After two weeks, well shaped single crystals were obtained. Yield: 61%. Found: C, 50.03; H, 3.54; N, 37.49. Calcd. for C₂₈H₂₄CoN₁₈ (I): C, 50.08; H, 3.60; N, 37.55%.

Structure description top

For background to transition metal complexes of 1,2,4-triazole derivatives, see: Haasnoot (2000); Cui et al. (2012); Han et al. (2012); Wang et al. (2012).

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 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 asymmetric unit of the title compound with displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (i) -x + 2, -y, -z; (ii) -x + 2, -y, -z + 1; (iii) x, y, z - 1]. Hydrogen atoms are omitted for clarity.
	Fig. 2. The polymeric one-dimensional chain in the title compound. Hydrogen atoms are omitted for clarity.

catena-Poly[[bis(dicyanamido-κN¹)cobalt(II)]bis{µ-1,2-bis[(1,2,4-triazol-1-yl)methyl]benzene-κ²N⁴:N^4'}] top

Crystal data top

[Co(C₂N₃)₂(C₁₂H₁₂N₆)₂]	Z = 1
M_r = 671.58	F(000) = 345
Triclinic, P1	D_x = 1.521 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 8.517 (2) Å	Cell parameters from 2443 reflections
b = 9.092 (2) Å	θ = 3.1–25.4°
c = 9.622 (3) Å	µ = 0.64 mm⁻¹
α = 93.984 (7)°	T = 293 K
β = 95.015 (7)°	Block, orange
γ = 97.587 (7)°	0.30 × 0.20 × 0.18 mm
V = 733.2 (3) Å³

Data collection top

Rigaku Mercury CCD diffractometer	2658 independent reflections
Radiation source: fine-focus sealed tube	2118 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.3°, θ_min = 3.1°
ω scans	h = −9→10
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −10→10
T_min = 0.831, T_max = 0.893	l = −11→9
7244 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0447P)² + 0.3399P] where P = (F_o² + 2F_c²)/3
2658 reflections	(Δ/σ)_max < 0.001
214 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Co(C₂N₃)₂(C₁₂H₁₂N₆)₂]	γ = 97.587 (7)°
M_r = 671.58	V = 733.2 (3) Å³
Triclinic, P1	Z = 1
a = 8.517 (2) Å	Mo Kα radiation
b = 9.092 (2) Å	µ = 0.64 mm⁻¹
c = 9.622 (3) Å	T = 293 K
α = 93.984 (7)°	0.30 × 0.20 × 0.18 mm
β = 95.015 (7)°

Data collection top

Rigaku Mercury CCD diffractometer	2658 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	2118 reflections with I > 2σ(I)
T_min = 0.831, T_max = 0.893	R_int = 0.041
7244 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
2658 reflections	Δρ_min = −0.29 e Å⁻³
214 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
Co1	1.0000	0.0000	0.0000	0.0318 (2)
N1	0.6352 (3)	0.1812 (3)	0.2157 (2)	0.0372 (6)
N2	0.5728 (4)	0.0354 (3)	0.2084 (3)	0.0596 (8)
N3	0.7995 (3)	0.0625 (3)	0.1044 (2)	0.0344 (6)
N4	0.7413 (3)	0.1313 (3)	0.6393 (2)	0.0399 (6)
N5	0.8430 (4)	0.0608 (3)	0.5692 (3)	0.0589 (8)
N6	0.8898 (3)	0.0428 (3)	0.8003 (2)	0.0358 (6)
N7	1.1984 (3)	0.4878 (3)	0.0020 (3)	0.0530 (8)
N8	1.1042 (3)	0.2262 (3)	0.0262 (3)	0.0433 (7)
N9	1.4468 (3)	0.6425 (3)	0.0931 (3)	0.0545 (8)
C1	0.6521 (4)	0.3991 (3)	0.3874 (3)	0.0397 (7)
C2	0.6915 (4)	0.3559 (4)	0.5211 (3)	0.0408 (8)
C3	0.7892 (4)	0.4559 (4)	0.6162 (4)	0.0562 (9)
H3A	0.8178	0.4273	0.7048	0.067*
C4	0.8452 (5)	0.5969 (4)	0.5828 (4)	0.0673 (11)
H4A	0.9114	0.6621	0.6483	0.081*
C5	0.8034 (5)	0.6410 (4)	0.4529 (4)	0.0695 (11)
H5A	0.8385	0.7370	0.4308	0.083*
C6	0.7093 (5)	0.5422 (4)	0.3556 (4)	0.0562 (9)
H6A	0.6834	0.5715	0.2668	0.067*
C7	0.5494 (4)	0.2970 (4)	0.2755 (3)	0.0463 (8)
H7A	0.4564	0.2499	0.3151	0.056*
H7B	0.5130	0.3552	0.2015	0.056*
C8	0.6221 (4)	0.2075 (4)	0.5666 (3)	0.0469 (8)
H8A	0.5403	0.2229	0.6281	0.056*
H8B	0.5722	0.1446	0.4849	0.056*
C9	0.6753 (4)	−0.0309 (4)	0.1403 (4)	0.0540 (9)
H9A	0.6631	−0.1333	0.1188	0.065*
C10	0.7693 (3)	0.1939 (3)	0.1547 (3)	0.0348 (7)
H10A	0.8339	0.2835	0.1482	0.042*
C11	0.9294 (4)	0.0098 (4)	0.6696 (3)	0.0539 (9)
H11A	1.0116	−0.0449	0.6525	0.065*
C12	0.7701 (4)	0.1187 (3)	0.7761 (3)	0.0401 (7)
H12A	0.7136	0.1580	0.8448	0.048*
C13	1.1548 (3)	0.3483 (3)	0.0180 (3)	0.0356 (7)
C14	1.3340 (4)	0.5617 (3)	0.0535 (3)	0.0396 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0361 (3)	0.0240 (3)	0.0352 (3)	0.0040 (2)	0.0037 (2)	0.0028 (2)
N1	0.0416 (15)	0.0357 (15)	0.0358 (14)	0.0106 (12)	0.0040 (12)	0.0037 (11)
N2	0.0564 (19)	0.0465 (18)	0.077 (2)	−0.0006 (15)	0.0282 (16)	−0.0005 (16)
N3	0.0371 (14)	0.0302 (14)	0.0366 (13)	0.0042 (11)	0.0064 (11)	0.0045 (11)
N4	0.0457 (15)	0.0430 (15)	0.0340 (14)	0.0121 (12)	0.0061 (12)	0.0100 (12)
N5	0.078 (2)	0.066 (2)	0.0397 (16)	0.0324 (17)	0.0117 (15)	0.0035 (15)
N6	0.0418 (15)	0.0306 (14)	0.0362 (14)	0.0077 (11)	0.0069 (11)	0.0018 (11)
N7	0.0491 (17)	0.0319 (16)	0.074 (2)	−0.0018 (13)	−0.0094 (15)	0.0137 (14)
N8	0.0464 (16)	0.0276 (15)	0.0554 (17)	0.0016 (12)	0.0081 (13)	0.0027 (12)
N9	0.0522 (18)	0.0388 (17)	0.070 (2)	0.0013 (15)	0.0032 (16)	−0.0001 (15)
C1	0.0480 (19)	0.0432 (19)	0.0336 (16)	0.0219 (15)	0.0086 (14)	0.0063 (14)
C2	0.0428 (18)	0.0438 (19)	0.0388 (17)	0.0132 (15)	0.0090 (14)	0.0051 (15)
C3	0.067 (2)	0.057 (2)	0.043 (2)	0.0051 (19)	0.0021 (18)	0.0044 (18)
C4	0.080 (3)	0.056 (2)	0.061 (3)	0.001 (2)	−0.001 (2)	−0.004 (2)
C5	0.091 (3)	0.045 (2)	0.072 (3)	0.002 (2)	0.011 (2)	0.012 (2)
C6	0.077 (3)	0.053 (2)	0.046 (2)	0.022 (2)	0.0127 (19)	0.0172 (18)
C7	0.051 (2)	0.056 (2)	0.0377 (17)	0.0278 (17)	0.0034 (15)	0.0071 (16)
C8	0.0436 (19)	0.055 (2)	0.0440 (19)	0.0090 (16)	0.0008 (15)	0.0165 (16)
C9	0.054 (2)	0.0355 (19)	0.073 (2)	−0.0015 (16)	0.0240 (19)	−0.0050 (17)
C10	0.0358 (17)	0.0304 (16)	0.0385 (16)	0.0042 (13)	0.0046 (14)	0.0050 (13)
C11	0.072 (2)	0.055 (2)	0.0413 (19)	0.0341 (19)	0.0077 (17)	0.0024 (17)
C12	0.0437 (19)	0.0464 (19)	0.0329 (16)	0.0124 (15)	0.0099 (14)	0.0031 (14)
C13	0.0378 (17)	0.0336 (18)	0.0356 (17)	0.0055 (14)	0.0047 (13)	0.0023 (14)
C14	0.049 (2)	0.0287 (17)	0.0442 (18)	0.0092 (16)	0.0119 (16)	0.0059 (14)

Geometric parameters (Å, º) top

Co1—N8ⁱ	2.118 (3)	N9—C14	1.148 (4)
Co1—N8	2.118 (3)	C1—C6	1.392 (5)
Co1—N6ⁱⁱ	2.147 (2)	C1—C2	1.397 (4)
Co1—N6ⁱⁱⁱ	2.147 (2)	C1—C7	1.506 (4)
Co1—N3	2.174 (2)	C2—C3	1.381 (4)
Co1—N3ⁱ	2.174 (2)	C2—C8	1.510 (4)
N1—C10	1.325 (4)	C3—C4	1.377 (5)
N1—N2	1.356 (4)	C3—H3A	0.9300
N1—C7	1.472 (4)	C4—C5	1.370 (5)
N2—C9	1.319 (4)	C4—H4A	0.9300
N3—C10	1.322 (4)	C5—C6	1.374 (5)
N3—C9	1.352 (4)	C5—H5A	0.9300
N4—C12	1.333 (4)	C6—H6A	0.9300
N4—N5	1.344 (4)	C7—H7A	0.9700
N4—C8	1.459 (4)	C7—H7B	0.9700
N5—C11	1.311 (4)	C8—H8A	0.9700
N6—C12	1.318 (4)	C8—H8B	0.9700
N6—C11	1.354 (4)	C9—H9A	0.9300
N6—Co1^iv	2.147 (2)	C10—H10A	0.9300
N7—C14	1.296 (4)	C11—H11A	0.9300
N7—C13	1.297 (4)	C12—H12A	0.9300
N8—C13	1.147 (4)

N8ⁱ—Co1—N8	180.00 (6)	C4—C3—H3A	119.3
N8ⁱ—Co1—N6ⁱⁱ	88.36 (9)	C2—C3—H3A	119.3
N8—Co1—N6ⁱⁱ	91.64 (9)	C5—C4—C3	120.0 (4)
N8ⁱ—Co1—N6ⁱⁱⁱ	91.64 (9)	C5—C4—H4A	120.0
N8—Co1—N6ⁱⁱⁱ	88.36 (9)	C3—C4—H4A	120.0
N6ⁱⁱ—Co1—N6ⁱⁱⁱ	180.00 (13)	C4—C5—C6	119.5 (4)
N8ⁱ—Co1—N3	91.36 (9)	C4—C5—H5A	120.3
N8—Co1—N3	88.64 (9)	C6—C5—H5A	120.3
N6ⁱⁱ—Co1—N3	88.73 (9)	C5—C6—C1	121.3 (3)
N6ⁱⁱⁱ—Co1—N3	91.27 (9)	C5—C6—H6A	119.3
N8ⁱ—Co1—N3ⁱ	88.64 (9)	C1—C6—H6A	119.3
N8—Co1—N3ⁱ	91.36 (9)	N1—C7—C1	112.1 (2)
N6ⁱⁱ—Co1—N3ⁱ	91.27 (9)	N1—C7—H7A	109.2
N6ⁱⁱⁱ—Co1—N3ⁱ	88.73 (9)	C1—C7—H7A	109.2
N3—Co1—N3ⁱ	180.00 (12)	N1—C7—H7B	109.2
C10—N1—N2	109.0 (2)	C1—C7—H7B	109.2
C10—N1—C7	130.1 (3)	H7A—C7—H7B	107.9
N2—N1—C7	120.8 (3)	N4—C8—C2	112.7 (3)
C9—N2—N1	103.0 (3)	N4—C8—H8A	109.0
C10—N3—C9	102.4 (3)	C2—C8—H8A	109.0
C10—N3—Co1	131.0 (2)	N4—C8—H8B	109.0
C9—N3—Co1	126.5 (2)	C2—C8—H8B	109.0
C12—N4—N5	109.6 (2)	H8A—C8—H8B	107.8
C12—N4—C8	129.0 (3)	N2—C9—N3	114.4 (3)
N5—N4—C8	121.4 (2)	N2—C9—H9A	122.8
C11—N5—N4	102.8 (3)	N3—C9—H9A	122.8
C12—N6—C11	102.3 (3)	N3—C10—N1	111.2 (3)
C12—N6—Co1^iv	127.4 (2)	N3—C10—H10A	124.4
C11—N6—Co1^iv	130.2 (2)	N1—C10—H10A	124.4
C14—N7—C13	124.1 (3)	N5—C11—N6	114.8 (3)
C13—N8—Co1	169.2 (3)	N5—C11—H11A	122.6
C6—C1—C2	119.0 (3)	N6—C11—H11A	122.6
C6—C1—C7	118.3 (3)	N6—C12—N4	110.5 (3)
C2—C1—C7	122.7 (3)	N6—C12—H12A	124.7
C3—C2—C1	118.7 (3)	N4—C12—H12A	124.7
C3—C2—C8	119.4 (3)	N8—C13—N7	174.2 (3)
C1—C2—C8	121.8 (3)	N9—C14—N7	171.4 (3)
C4—C3—C2	121.5 (3)

C10—N1—N2—C9	−0.8 (4)	C2—C1—C6—C5	0.0 (5)
C7—N1—N2—C9	175.3 (3)	C7—C1—C6—C5	179.9 (3)
N8ⁱ—Co1—N3—C10	−178.4 (3)	C10—N1—C7—C1	−56.9 (4)
N8—Co1—N3—C10	1.6 (3)	N2—N1—C7—C1	128.0 (3)
N6ⁱⁱ—Co1—N3—C10	93.2 (3)	C6—C1—C7—N1	105.8 (3)
N6ⁱⁱⁱ—Co1—N3—C10	−86.8 (3)	C2—C1—C7—N1	−74.3 (4)
N8ⁱ—Co1—N3—C9	5.4 (3)	C12—N4—C8—C2	102.7 (4)
N8—Co1—N3—C9	−174.6 (3)	N5—N4—C8—C2	−77.0 (4)
N6ⁱⁱ—Co1—N3—C9	−83.0 (3)	C3—C2—C8—N4	−49.1 (4)
N6ⁱⁱⁱ—Co1—N3—C9	97.0 (3)	C1—C2—C8—N4	134.9 (3)
C12—N4—N5—C11	−0.4 (4)	N1—N2—C9—N3	0.4 (4)
C8—N4—N5—C11	179.3 (3)	C10—N3—C9—N2	0.1 (4)
N6ⁱⁱ—Co1—N8—C13	162.9 (13)	Co1—N3—C9—N2	177.2 (2)
N6ⁱⁱⁱ—Co1—N8—C13	−17.1 (13)	C9—N3—C10—N1	−0.6 (3)
N3—Co1—N8—C13	−108.5 (13)	Co1—N3—C10—N1	−177.47 (18)
N3ⁱ—Co1—N8—C13	71.5 (13)	N2—N1—C10—N3	0.9 (3)
C6—C1—C2—C3	−1.5 (5)	C7—N1—C10—N3	−174.6 (3)
C7—C1—C2—C3	178.6 (3)	N4—N5—C11—N6	0.1 (4)
C6—C1—C2—C8	174.6 (3)	C12—N6—C11—N5	0.3 (4)
C7—C1—C2—C8	−5.3 (5)	Co1^iv—N6—C11—N5	−175.5 (2)
C1—C2—C3—C4	1.3 (5)	C11—N6—C12—N4	−0.6 (3)
C8—C2—C3—C4	−174.9 (3)	Co1^iv—N6—C12—N4	175.45 (18)
C2—C3—C4—C5	0.4 (6)	N5—N4—C12—N6	0.7 (4)
C3—C4—C5—C6	−1.9 (6)	C8—N4—C12—N6	−179.0 (3)
C4—C5—C6—C1	1.7 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N9^v	0.93	2.54	3.308 (4)	140
C11—H11A···N5ⁱⁱ	0.93	2.56	3.217 (5)	128
C12—H12A···N9^vi	0.93	2.48	3.286 (4)	145

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N9ⁱ	0.93	2.54	3.308 (4)	140
C11—H11A···N5ⁱⁱ	0.93	2.56	3.217 (5)	128
C12—H12A···N9ⁱⁱⁱ	0.93	2.48	3.286 (4)	145

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

Acknowledgements

The authors thank the National Natural Science Foundation of China (No. 51072071) for financial support.

References

Cui, G. H., He, C. H., Jiao, C. H., Geng, J. C. & Blatov, V. A. (2012). CrystEngComm, 14, 4210–4216. Web of Science CSD CrossRef CAS Google Scholar
Haasnoot, J. G. (2000). Coord. Chem. Rev. 200–202, 131–185. Web of Science CrossRef CAS Google Scholar
Han, M. L., Wang, J. G., Ma, L. F., Guo, H. & Wang, L. Y. (2012). CrystEngComm, 14, 2691–2701. Web of Science CSD CrossRef CAS Google Scholar
Jacobson, R. (1998). Private communication to Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, N., Ma, J. G., Shi, W. & Cheng, P. (2012). CrystEngComm, 14, 5634–5638. Web of Science CSD CrossRef CAS Google Scholar

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