Poly[(μ3-5-tert-butyl­benzene-1,3-di­carboxyl­ato)di­pyridine­cobalt(II)]

Noh, K.; Kim, J.

doi:10.1107/S1600536813026640

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Pages m579-m580

doi:10.1107/S1600536813026640

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Poly[(μ₃-5-tert-butylbenzene-1,3-dicarboxylato)dipyridinecobalt(II)]

Kyungkyou Noh ^a and Jaheon Kim ^a ^*

^aDepartment of Chemistry, Soongsil University, 369 Sangdo-Ro, Dongjak-Gu, Seoul 156-743, Republic of Korea
^*Correspondence e-mail: jaheon@ssu.ac.kr

(Received 24 September 2013; accepted 26 September 2013; online 2 October 2013)

In the title compound, [Co(C₁₂H₁₂O₄)(C₅H₅N)₂]_n, the Co^II cation is coordinated by four O atoms from three 5-tert-butylbenzene-1,3-dicarboxylate anions and two N atoms from pyridine molecules in a distorted octahedral geometry. One carboxylate group of the anionic ligand chelates a Co^II cation while another carboxylate group bridges two Co^II cations, resulting in a polymeric layer parallel to (101). Weak C—H⋯O hydrogen bonds occur between adjacent polymeric layers. In the crystal, one of pyridine molecules is equally disordered over two positions.

CCDC reference: 963433

Related literature

For metal-organic frameworks composed of cobalt cations and 5-tert-butylbenzene-1,3-dicarboxylate ligands without additional bridging ligands, see: Chen et al. (2011 ); Du et al. (2009 ); Ma et al. (2009 ); Qin & Ju (2010 ). For a copper(II) complex with 5-tert-butylbenzene-1,3-dicarboxylate ligand, see: Li & Zhou (2010 ).

Experimental

Crystal data

[Co(C₁₂H₁₂O₄)(C₅H₅N)₂]
M_r = 437.34
Monoclinic, P 2₁ /n
a = 9.7357 (3) Å
b = 15.6699 (6) Å
c = 13.0764 (5) Å
β = 94.791 (1)°
V = 1987.93 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 173 K
0.50 × 0.40 × 0.30 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.663, T_max = 0.775
12370 measured reflections
4580 independent reflections
3843 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.135
S = 1.11
4580 reflections
314 parameters
66 restraints
H-atom parameters constrained
Δρ_max = 1.25 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.014 (2)
Co1—O2ⁱ	2.0608 (19)
Co1—O3ⁱⁱ	2.324 (2)
Co1—O4ⁱⁱ	2.103 (2)
Co1—N1	2.182 (3)
Co1—N2	2.195 (9)
Co1—N2A	2.117 (11)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O4ⁱⁱⁱ	0.95	2.55	3.287 (5)	134
Symmetry code: (iii) -x+1, -y, -z+2.

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: CrystalMaker (CrystalMaker Software, 2013 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 963433

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813026640/xu5741sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026640/xu5741Isup2.hkl

checkCIF report

1. Comment top

The bent ligand, 5-tert-1,3-benzenedicarboxylic acid (H₂BDC_^tBu) can form interesting metal-organic polyhedra (MOPs) through solvothermal reactions with copper ions which frequently give paddle-wheel type clusters (Li & Zhou, 2010). In contrast, the reactions between cobalt ion and H₂BDC_^tBu provide various types of metal-organic frameworks (MOFs) including even a molecular cyclic compound: for examples such as rings, chains, layers, and three-dimensional networks, see Chen et al., 2011; Du et al., 2009; Ma et al., 2009; Qin & Ju, 2010. The combination of a diverse coordination property of cobalt ion, and a bulky tert-butyl groups in the anionic ligand can give a possibility of making interesting MOFs. For example, a reaction between cobalt ions and the ligands in polar solvent, the hydrophobic tertiary butyl groups assembled together, making polar carboxylate groups be exposed to pores to give hydrophilic environment (Ma et al., 2009). In searching for new Co-BDC_^tBu frameworks, we obtained a two-dimensional layered structure of which inter-layer space is filled with hydrophobic and coordinated pyridine molecules and tert-butyl groups of the anionic ligands.

2. Experimental top

Cobalt(II) nitrate tetrahydrate (40 mg) and 5-tert-butylbenzene-1,3-dicarboxylic acid (31 mg) were dissolved in a mixed solvent (N,N-dimethylformamide, 8.0 ml; ethanol, 0.4 ml; pyridine, 0.4 ml). This reaction mixture was transferred to a Teflon-lined vessel (23 ml), and heated at 378 K and for 2 days. Large violet block crystals were obtained and used for single crystal X-ray diffraction analyses.

3. Refinement top

In the asymmetric unit, one of two pyridine molecules is disordered over two positions with a site occupancy factor of 0.5, respectively. The site occupancy factors were converged to 0.50787 and 0.49213 for each disordered portion with isotropic thermal parameters, and thus the factors were fixed to 0.5 respectively at the final stage of refinement; the thermal parameters did not converge when the site occupancy factors were refined together. Due to the disorder, the geometry of disordered pyridine was restrained by FLAT and SAME SHELX instructions. In addition, the anisotropic thermal parameters of N2, N2A, C30, and C30A atoms were treated isotropically using an ISOR instruction. However, the C19A thermal parameters were equaled to those of C19 using an EADP instruction. Hydrogen atoms of the aromatic and methyl groups were placed at calculated positions with C—H = 0.95 Å and 0.98 Å, respectively and allowed to ride with U_iso(H) = 1.2 U_eq(C).

Related literature top

For metal-organic frameworks composed of cobalt cations and 5-tert-butylbenzene-1,3-dicarboxylate ligands without additional bridging ligands, see: Chen et al. (2011); Du et al. (2009); Ma et al. (2009); Qin & Ju (2010). For a copper(II) complex with 5-tert-1,3-benzenedicarboxylate ligand, see: Li & Zhou (2010).

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: CrystalMaker (CrystalMaker Software, 2013); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. (a) An asymmetric unit of the title compound is shown with the atomic numbering scheme. Displacement ellipsoids are drawn at 50% probability level. Hydrogen atoms are omitted for simplicity. (b) The full coordination environment of the cobalt cluster is shown with ball-and-stick models. The atoms in the asymmetric unit are highlited with empty balls.
	Fig. 2. A two-dimensional layer approximately parallel to the (101) plane is represented.
	Fig. 3. (a) The layer in Figure 2 is drawn with the lattice lines along the b axis. (b) A packing view is shown with three layers represented with different colors.

Poly[(µ₃-5-tert-butylbenzene-1,3-dicarboxylato)dipyridinecobalt(II)] top

Crystal data top

[Co(C₁₂H₁₂O₄)(C₅H₅N)₂]	F(000) = 908
M_r = 437.34	D_x = 1.461 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6406 reflections
a = 9.7357 (3) Å	θ = 2.5–28.2°
b = 15.6699 (6) Å	µ = 0.90 mm⁻¹
c = 13.0764 (5) Å	T = 173 K
β = 94.791 (1)°	Block, violet
V = 1987.93 (12) Å³	0.50 × 0.40 × 0.30 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	4580 independent reflections
Radiation source: fine-focus sealed tube	3843 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
phi and ω scans	θ_max = 27.9°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
T_min = 0.663, T_max = 0.775	k = −17→20
12370 measured reflections	l = −17→13

Refinement top

Refinement on F²	66 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.049	w = 1/[σ²(F_o²) + (0.059P)² + 3.5707P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.135	(Δ/σ)_max = 0.001
S = 1.11	Δρ_max = 1.25 e Å⁻³
4580 reflections	Δρ_min = −0.64 e Å⁻³
314 parameters

Crystal data top

[Co(C₁₂H₁₂O₄)(C₅H₅N)₂]	V = 1987.93 (12) Å³
M_r = 437.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.7357 (3) Å	µ = 0.90 mm⁻¹
b = 15.6699 (6) Å	T = 173 K
c = 13.0764 (5) Å	0.50 × 0.40 × 0.30 mm
β = 94.791 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	4580 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3843 reflections with I > 2σ(I)
T_min = 0.663, T_max = 0.775	R_int = 0.021
12370 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	66 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.11	Δρ_max = 1.25 e Å⁻³
4580 reflections	Δρ_min = −0.64 e Å⁻³
314 parameters

Special details top

Geometry. 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 > 2sigma(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)
Co1	0.44382 (4)	0.12814 (2)	0.54417 (3)	0.02396 (13)
O1	0.4499 (3)	0.01260 (13)	0.61177 (17)	0.0394 (5)
O2	0.4464 (2)	−0.12667 (11)	0.58392 (15)	0.0263 (4)
O3	0.1852 (2)	−0.30891 (12)	0.83448 (16)	0.0342 (5)
O4	0.1101 (2)	−0.24206 (13)	0.96689 (15)	0.0305 (4)
C1	0.3528 (3)	−0.07399 (16)	0.73420 (19)	0.0207 (5)
C2	0.3038 (3)	−0.15329 (16)	0.76379 (19)	0.0210 (5)
H2	0.3153	−0.2024	0.7228	0.025*
C3	0.2379 (3)	−0.15960 (17)	0.8543 (2)	0.0234 (5)
C4	0.2262 (3)	−0.08775 (18)	0.9164 (2)	0.0261 (5)
H4	0.1828	−0.0932	0.9785	0.031*
C5	0.2770 (3)	−0.00814 (17)	0.8893 (2)	0.0244 (5)
C6	0.3373 (3)	−0.00254 (16)	0.7962 (2)	0.0236 (5)
H6	0.3687	0.0514	0.7744	0.028*
C7	0.4206 (3)	−0.06185 (16)	0.63520 (19)	0.0203 (5)
C8	0.1748 (3)	−0.24228 (17)	0.8864 (2)	0.0257 (5)
C9	0.2610 (3)	0.07170 (19)	0.9557 (2)	0.0326 (6)
C10	0.3841 (5)	0.1310 (3)	0.9510 (4)	0.0771 (17)
H10A	0.3773	0.1777	1.0001	0.116*
H10B	0.3850	0.1544	0.8816	0.116*
H10C	0.4694	0.0990	0.9683	0.116*
C11	0.1368 (5)	0.1215 (3)	0.9076 (5)	0.0868 (19)
H11A	0.0537	0.0863	0.9085	0.130*
H11B	0.1520	0.1362	0.8365	0.130*
H11C	0.1252	0.1739	0.9469	0.130*
C12	0.2442 (10)	0.0500 (3)	1.0652 (3)	0.127 (3)
H12A	0.3234	0.0162	1.0930	0.190*
H12B	0.1595	0.0168	1.0693	0.190*
H12C	0.2386	0.1026	1.1051	0.190*
N1	0.6310 (3)	0.16214 (15)	0.63878 (19)	0.0302 (5)
C13	0.6260 (4)	0.1716 (3)	0.7395 (3)	0.0621 (12)
H13	0.5418	0.1585	0.7678	0.074*
C14	0.7352 (5)	0.1993 (4)	0.8058 (3)	0.0688 (13)
H14	0.7255	0.2045	0.8772	0.083*
C15	0.8549 (4)	0.2186 (3)	0.7673 (3)	0.0533 (10)
H15	0.9311	0.2387	0.8108	0.064*
C16	0.8649 (5)	0.2088 (4)	0.6645 (4)	0.0734 (15)
H16	0.9488	0.2211	0.6353	0.088*
C17	0.7502 (4)	0.1806 (3)	0.6033 (3)	0.0550 (10)
H17	0.7583	0.1743	0.5318	0.066*
N2	0.2472 (9)	0.1037 (5)	0.4542 (7)	0.0300 (18)	0.5
C18	0.2420 (11)	0.0415 (5)	0.3860 (6)	0.055 (3)	0.5
H18	0.3222	0.0071	0.3851	0.066*	0.5
C19	0.1310 (12)	0.0203 (7)	0.3143 (8)	0.091 (3)	0.5
H19	0.1370	−0.0260	0.2679	0.109*	0.5
C20	0.0168 (10)	0.0680 (5)	0.3141 (7)	0.067 (2)	0.5
H20	−0.0607	0.0562	0.2671	0.080*	0.5
C21	0.0130 (8)	0.1349 (5)	0.3834 (7)	0.082 (4)	0.5
H21	−0.0664	0.1699	0.3855	0.098*	0.5
C22	0.1299 (8)	0.1485 (5)	0.4496 (7)	0.068 (3)	0.5
H22	0.1262	0.1945	0.4967	0.082*	0.5
N2A	0.2579 (10)	0.0868 (5)	0.4638 (8)	0.038 (2)	0.5
C18A	0.2377 (10)	0.0736 (5)	0.3620 (8)	0.074 (4)	0.5
H18A	0.3156	0.0820	0.3239	0.089*	0.5
C19A	0.1159 (12)	0.0489 (5)	0.3055 (10)	0.091 (3)	0.5
H19A	0.1105	0.0410	0.2332	0.109*	0.5
C20A	0.0078 (12)	0.0374 (6)	0.3605 (8)	0.079 (3)	0.5
H20A	−0.0778	0.0206	0.3263	0.094*	0.5
C21A	0.0159 (9)	0.0488 (6)	0.4613 (7)	0.109 (6)	0.5
H21A	−0.0621	0.0404	0.4991	0.131*	0.5
C22A	0.1429 (8)	0.0734 (5)	0.5102 (7)	0.072 (3)	0.5
H22A	0.1477	0.0811	0.5824	0.086*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0331 (2)	0.01763 (19)	0.0226 (2)	−0.00231 (14)	0.01078 (14)	−0.00066 (13)
O1	0.0653 (16)	0.0189 (10)	0.0373 (12)	−0.0033 (10)	0.0248 (11)	0.0037 (8)
O2	0.0347 (10)	0.0209 (9)	0.0248 (9)	−0.0011 (8)	0.0112 (8)	−0.0027 (7)
O3	0.0502 (13)	0.0207 (10)	0.0335 (11)	−0.0038 (9)	0.0152 (9)	0.0009 (8)
O4	0.0393 (11)	0.0279 (10)	0.0258 (10)	−0.0057 (8)	0.0123 (8)	0.0022 (8)
C1	0.0210 (11)	0.0217 (12)	0.0195 (11)	0.0009 (9)	0.0027 (9)	0.0011 (9)
C2	0.0230 (12)	0.0188 (11)	0.0213 (12)	0.0006 (9)	0.0034 (10)	−0.0010 (9)
C3	0.0245 (12)	0.0228 (12)	0.0234 (13)	−0.0011 (10)	0.0039 (10)	0.0021 (10)
C4	0.0285 (13)	0.0279 (14)	0.0226 (13)	0.0004 (11)	0.0070 (10)	0.0005 (10)
C5	0.0267 (13)	0.0238 (13)	0.0229 (12)	0.0016 (10)	0.0031 (10)	−0.0027 (10)
C6	0.0271 (13)	0.0197 (12)	0.0242 (13)	−0.0006 (10)	0.0035 (10)	0.0008 (10)
C7	0.0199 (11)	0.0198 (12)	0.0213 (12)	0.0009 (9)	0.0035 (9)	0.0011 (9)
C8	0.0302 (14)	0.0231 (13)	0.0243 (13)	−0.0022 (10)	0.0046 (11)	0.0044 (10)
C9	0.0412 (17)	0.0268 (14)	0.0315 (15)	−0.0020 (12)	0.0128 (12)	−0.0084 (11)
C10	0.079 (3)	0.058 (3)	0.100 (4)	−0.031 (2)	0.045 (3)	−0.053 (3)
C11	0.067 (3)	0.070 (3)	0.121 (5)	0.031 (2)	−0.005 (3)	−0.051 (3)
C12	0.307 (11)	0.044 (3)	0.036 (2)	−0.032 (4)	0.056 (4)	−0.018 (2)
N1	0.0379 (13)	0.0244 (11)	0.0284 (12)	−0.0031 (10)	0.0042 (10)	0.0017 (9)
C13	0.052 (2)	0.102 (4)	0.0326 (19)	−0.022 (2)	0.0082 (16)	−0.013 (2)
C14	0.069 (3)	0.100 (4)	0.036 (2)	−0.016 (3)	−0.0039 (19)	−0.017 (2)
C15	0.056 (2)	0.048 (2)	0.052 (2)	−0.0120 (17)	−0.0178 (18)	0.0064 (17)
C16	0.048 (2)	0.112 (4)	0.059 (3)	−0.029 (3)	−0.005 (2)	0.024 (3)
C17	0.043 (2)	0.086 (3)	0.0362 (19)	−0.014 (2)	0.0033 (15)	0.0108 (19)
N2	0.023 (3)	0.025 (3)	0.042 (3)	0.007 (2)	0.006 (2)	0.002 (3)
C18	0.052 (5)	0.043 (4)	0.066 (7)	−0.020 (4)	−0.020 (5)	0.018 (4)
C19	0.054 (4)	0.151 (10)	0.065 (4)	−0.018 (5)	−0.006 (3)	0.000 (5)
C20	0.056 (4)	0.067 (4)	0.075 (4)	0.009 (3)	−0.015 (4)	−0.004 (4)
C21	0.040 (4)	0.076 (6)	0.123 (9)	0.027 (4)	−0.037 (5)	−0.056 (6)
C22	0.057 (5)	0.061 (5)	0.084 (7)	0.016 (4)	−0.008 (5)	−0.033 (5)
N2A	0.032 (4)	0.030 (4)	0.054 (4)	0.009 (3)	0.011 (3)	0.005 (3)
C18A	0.032 (4)	0.144 (13)	0.046 (5)	−0.005 (7)	0.003 (4)	−0.023 (8)
C19A	0.054 (4)	0.151 (10)	0.065 (4)	−0.018 (5)	−0.006 (3)	0.000 (5)
C20A	0.083 (5)	0.081 (5)	0.073 (5)	0.009 (4)	0.015 (4)	0.013 (4)
C21A	0.051 (5)	0.203 (16)	0.078 (7)	−0.065 (8)	0.030 (5)	−0.050 (9)
C22A	0.053 (5)	0.103 (8)	0.061 (5)	−0.022 (5)	0.016 (4)	−0.012 (5)

Geometric parameters (Å, º) top

Co1—O1	2.014 (2)	C12—H12B	0.9800
Co1—O2ⁱ	2.0608 (19)	C12—H12C	0.9800
Co1—O3ⁱⁱ	2.324 (2)	N1—C17	1.317 (4)
Co1—O4ⁱⁱ	2.103 (2)	N1—C13	1.330 (4)
Co1—N1	2.182 (3)	C13—C14	1.384 (5)
Co1—N2	2.195 (9)	C13—H13	0.9500
Co1—N2A	2.117 (11)	C14—C15	1.342 (6)
O1—C7	1.245 (3)	C14—H14	0.9500
O2—C7	1.254 (3)	C15—C16	1.365 (6)
O2—Co1ⁱ	2.0608 (19)	C15—H15	0.9500
O3—C8	1.254 (3)	C16—C17	1.391 (5)
O3—Co1ⁱⁱⁱ	2.324 (2)	C16—H16	0.9500
O4—C8	1.271 (3)	C17—H17	0.9500
O4—Co1ⁱⁱⁱ	2.102 (2)	N2—C22	1.337 (10)
C1—C6	1.398 (4)	N2—C18	1.320 (10)
C1—C2	1.397 (3)	C18—C19	1.410 (11)
C1—C7	1.513 (3)	C18—H18	0.9500
C2—C3	1.396 (4)	C19—C20	1.340 (12)
C2—H2	0.9500	C19—H19	0.9500
C3—C4	1.398 (4)	C20—C21	1.388 (10)
C3—C8	1.508 (4)	C20—H20	0.9500
C4—C5	1.398 (4)	C21—C22	1.388 (10)
C4—H4	0.9500	C21—H21	0.9500
C5—C6	1.399 (4)	C22—H22	0.9500
C5—C9	1.538 (4)	N2A—C22A	1.333 (11)
C6—H6	0.9500	N2A—C18A	1.346 (11)
C9—C12	1.494 (5)	C18A—C19A	1.398 (11)
C9—C10	1.522 (5)	C18A—H18A	0.9500
C9—C11	1.529 (6)	C19A—C20A	1.336 (12)
C10—H10A	0.9800	C19A—H19A	0.9500
C10—H10B	0.9800	C20A—C21A	1.325 (11)
C10—H10C	0.9800	C20A—H20A	0.9500
C11—H11A	0.9800	C21A—C22A	1.398 (10)
C11—H11B	0.9800	C21A—H21A	0.9500
C11—H11C	0.9800	C22A—H22A	0.9500
C12—H12A	0.9800

O1—Co1—O2ⁱ	110.40 (8)	H11A—C11—H11C	109.5
O1—Co1—O4ⁱⁱ	153.91 (8)	H11B—C11—H11C	109.5
O2ⁱ—Co1—O4ⁱⁱ	95.64 (7)	C9—C12—H12A	109.5
O1—Co1—N2A	86.3 (2)	C9—C12—H12B	109.5
O2ⁱ—Co1—N2A	94.2 (3)	H12A—C12—H12B	109.5
O4ⁱⁱ—Co1—N2A	93.6 (2)	C9—C12—H12C	109.5
O1—Co1—N1	88.74 (10)	H12A—C12—H12C	109.5
O2ⁱ—Co1—N1	89.90 (9)	H12B—C12—H12C	109.5
O4ⁱⁱ—Co1—N1	89.70 (9)	C17—N1—C13	115.5 (3)
N2A—Co1—N1	174.4 (2)	C17—N1—Co1	124.9 (2)
O1—Co1—N2	94.1 (2)	C13—N1—Co1	119.4 (2)
O2ⁱ—Co1—N2	92.9 (2)	N1—C13—C14	124.4 (4)
O4ⁱⁱ—Co1—N2	86.0 (2)	N1—C13—H13	117.8
N1—Co1—N2	175.1 (2)	C14—C13—H13	117.8
O1—Co1—O3ⁱⁱ	94.57 (8)	C15—C14—C13	118.8 (4)
O2ⁱ—Co1—O3ⁱⁱ	154.98 (7)	C15—C14—H14	120.6
O4ⁱⁱ—Co1—O3ⁱⁱ	59.36 (7)	C13—C14—H14	120.6
N2A—Co1—O3ⁱⁱ	88.9 (3)	C14—C15—C16	118.7 (4)
N1—Co1—O3ⁱⁱ	89.01 (9)	C14—C15—H15	120.7
N2—Co1—O3ⁱⁱ	86.7 (2)	C16—C15—H15	120.7
C7—O1—Co1	162.0 (2)	C15—C16—C17	118.8 (4)
C7—O2—Co1ⁱ	125.77 (16)	C15—C16—H16	120.6
C8—O3—Co1ⁱⁱⁱ	84.88 (16)	C17—C16—H16	120.6
C8—O4—Co1ⁱⁱⁱ	94.51 (17)	N1—C17—C16	123.8 (4)
C6—C1—C2	119.7 (2)	N1—C17—H17	118.1
C6—C1—C7	118.1 (2)	C16—C17—H17	118.1
C2—C1—C7	122.1 (2)	C22—N2—C18	111.9 (8)
C3—C2—C1	119.3 (2)	C22—N2—Co1	129.5 (6)
C3—C2—H2	120.3	C18—N2—Co1	118.3 (7)
C1—C2—H2	120.3	N2—C18—C19	127.5 (10)
C2—C3—C4	120.0 (2)	N2—C18—H18	116.3
C2—C3—C8	121.6 (2)	C19—C18—H18	116.3
C4—C3—C8	118.4 (2)	C20—C19—C18	117.4 (11)
C5—C4—C3	121.6 (2)	C20—C19—H19	121.3
C5—C4—H4	119.2	C18—C19—H19	121.3
C3—C4—H4	119.2	C19—C20—C21	119.1 (9)
C4—C5—C6	117.4 (2)	C19—C20—H20	120.4
C4—C5—C9	121.9 (2)	C21—C20—H20	120.4
C6—C5—C9	120.7 (2)	C20—C21—C22	117.3 (7)
C1—C6—C5	121.9 (2)	C20—C21—H21	121.4
C1—C6—H6	119.1	C22—C21—H21	121.4
C5—C6—H6	119.1	N2—C22—C21	126.9 (8)
O1—C7—O2	124.5 (2)	N2—C22—H22	116.6
O1—C7—C1	117.0 (2)	C21—C22—H22	116.6
O2—C7—C1	118.5 (2)	C22A—N2A—C18A	111.5 (9)
O3—C8—O4	121.2 (2)	C22A—N2A—Co1	122.6 (8)
O3—C8—C3	120.7 (2)	C18A—N2A—Co1	125.9 (7)
O4—C8—C3	118.0 (2)	N2A—C18A—C19A	127.8 (9)
C12—C9—C10	109.1 (4)	N2A—C18A—H18A	116.1
C12—C9—C11	111.4 (5)	C19A—C18A—H18A	116.1
C10—C9—C11	105.7 (4)	C20A—C19A—C18A	115.1 (11)
C12—C9—C5	112.3 (3)	C20A—C19A—H19A	122.5
C10—C9—C5	110.9 (3)	C18A—C19A—H19A	122.5
C11—C9—C5	107.3 (3)	C19A—C20A—C21A	122.3 (11)
C9—C10—H10A	109.5	C19A—C20A—H20A	118.9
C9—C10—H10B	109.5	C21A—C20A—H20A	118.9
H10A—C10—H10B	109.5	C20A—C21A—C22A	117.9 (9)
C9—C10—H10C	109.5	C20A—C21A—C21A^iv	115.4 (7)
H10A—C10—H10C	109.5	C20A—C21A—H21A	121.0
H10B—C10—H10C	109.5	C22A—C21A—H21A	121.0
C9—C11—H11A	109.5	N2A—C22A—C21A	125.4 (9)
C9—C11—H11B	109.5	N2A—C22A—H22A	117.3
H11A—C11—H11B	109.5	C21A—C22A—H22A	117.3
C9—C11—H11C	109.5

C6—C1—C2—C3	1.1 (4)	C6—C5—C9—C12	−159.0 (5)
C7—C1—C2—C3	−177.7 (2)	C4—C5—C9—C10	146.6 (4)
C1—C2—C3—C4	−2.6 (4)	C6—C5—C9—C10	−36.7 (4)
C1—C2—C3—C8	175.9 (2)	C4—C5—C9—C11	−98.4 (4)
C2—C3—C4—C5	1.3 (4)	C6—C5—C9—C11	78.3 (4)
C8—C3—C4—C5	−177.3 (3)	C17—N1—C13—C14	0.4 (7)
C3—C4—C5—C6	1.4 (4)	Co1—N1—C13—C14	−174.9 (4)
C3—C4—C5—C9	178.2 (3)	N1—C13—C14—C15	0.3 (9)
C2—C1—C6—C5	1.7 (4)	C13—C14—C15—C16	−1.0 (8)
C7—C1—C6—C5	−179.4 (2)	C14—C15—C16—C17	1.0 (8)
C4—C5—C6—C1	−2.9 (4)	C13—N1—C17—C16	−0.4 (7)
C9—C5—C6—C1	−179.8 (3)	Co1—N1—C17—C16	174.5 (4)
Co1—O1—C7—O2	79.6 (7)	C15—C16—C17—N1	−0.3 (8)
Co1—O1—C7—C1	−102.2 (6)	C22—N2—C18—C19	−0.02 (6)
Co1ⁱ—O2—C7—O1	5.1 (4)	Co1—N2—C18—C19	−173.7 (5)
Co1ⁱ—O2—C7—C1	−172.99 (16)	N2—C18—C19—C20	0.03 (7)
C6—C1—C7—O1	−4.8 (4)	C18—C19—C20—C21	−0.09 (15)
C2—C1—C7—O1	174.1 (3)	C19—C20—C21—C22	0.14 (19)
C6—C1—C7—O2	173.5 (2)	C18—N2—C22—C21	0.08 (16)
C2—C1—C7—O2	−7.7 (4)	Co1—N2—C22—C21	172.8 (6)
Co1ⁱⁱⁱ—O3—C8—O4	0.3 (3)	C20—C21—C22—N2	−0.1 (2)
Co1ⁱⁱⁱ—O3—C8—C3	−179.1 (2)	C22A—N2A—C18A—C19A	0.04 (6)
Co1ⁱⁱⁱ—O4—C8—O3	−0.3 (3)	Co1—N2A—C18A—C19A	−177.9 (5)
Co1ⁱⁱⁱ—O4—C8—C3	179.0 (2)	N2A—C18A—C19A—C20A	−0.02 (7)
C2—C3—C8—O3	3.1 (4)	C18A—C19A—C20A—C21A	0.09 (15)
C4—C3—C8—O3	−178.4 (3)	C19A—C20A—C21A—C22A	−0.2 (2)
C2—C3—C8—O4	−176.3 (3)	C18A—N2A—C22A—C21A	−0.12 (15)
C4—C3—C8—O4	2.2 (4)	Co1—N2A—C22A—C21A	177.9 (5)
C4—C5—C9—C12	24.3 (5)	C20A—C21A—C22A—N2A	0.2 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O4^v	0.95	2.55	3.287 (5)	134

Symmetry code: (v) −x+1, −y, −z+2.

Selected bond lengths (Å) top

Co1—O1	2.014 (2)	Co1—N1	2.182 (3)
Co1—O2ⁱ	2.0608 (19)	Co1—N2	2.195 (9)
Co1—O3ⁱⁱ	2.324 (2)	Co1—N2A	2.117 (11)
Co1—O4ⁱⁱ	2.103 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O4ⁱⁱⁱ	0.95	2.55	3.287 (5)	134

Symmetry code: (iii) −x+1, −y, −z+2.

Acknowledgements

This research was supported by the Ministry of Knowledge Economy (MKE) and the Korea Institute for Advancement in Technology (KIAT) through the Workforce Development Program in Strategic Technology.

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, L.-J., Su, J.-B., Huang, R.-B., Lin, S., Yang, M.-X. & Huang, H. (2011). Dalton Trans. 40, 9731–9736. Web of Science CSD CrossRef CAS PubMed Google Scholar
CrystalMaker Software (2013). CrystalMaker. CrystalMaker Software Ltd, Yarnton, England. Google Scholar
Du, Z.-X., Wang, L.-Y. & Hou, H.-W. (2009). Z. Anorg. Allg. Chem. 635, 1659–1663. Web of Science CSD CrossRef CAS Google Scholar
Li, J.-R. & Zhou, H.-C. (2010). Nat. Chem. 2, 893–898. Web of Science CSD CrossRef PubMed Google Scholar
Ma, L.-F., Wang, L.-Y., Lu, D.-H., Batten, S. R. & Wang, J.-G. (2009). Cryst. Growth Des. 9, 1741–1749. Web of Science CSD CrossRef CAS Google Scholar
Qin, J.-H. & Ju, F.-Y. (2010). Chin. J. Struct. Chem. 29, 1108–1114. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar