Poly[dinitrato[μ3-2,4,6-tris­(4-pyrid­yl)-1,3,5-triazine]cobalt(II)]

Wang, Y.-P.; Zhang, N.; He, X.; Shao, M.; Li, M.-X.

doi:10.1107/S1600536811017661

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m751

doi:10.1107/S1600536811017661

Open

access

Poly[dinitrato[μ₃-2,4,6-tris(4-pyridyl)-1,3,5-triazine]cobalt(II)]

Ya-Ping Wang,^a Ning Zhang,^a Xiang He,^a Min Shao ^b and Ming-Xing Li ^a ^*

^aDepartment of Chemistry, College of Science, Shanghai University, Shanghai 200444, People's Republic of China, and ^bLaboratory for Microstructures, Shanghai University, Shanghai 200444, People's Republic of China
^*Correspondence e-mail: mx_li@mail.shu.edu.cn

(Received 19 April 2011; accepted 10 May 2011; online 14 May 2011)

The solvothermal reaction of Co(NO₃)₂ and 2,4,6-tris(4-pyridyl)-1,3,5-triazine in dimethylformamide/ethanol mixed solvent afforded the title coordination polymer, [Co(NO₃)₂(C₁₈H₁₂N₆)]_n, in which the Co^II atom is seven-coordinated by pyridyl groups of three different ligands and two chelating nitrate anions. The complex displays a nano-sized porous metal–organic framework that belongs to a (10,3) topological network.

Related literature

For metal–organic frameworks, see: Yaghi et al. (2003 ). For 2,4,6-tris(4-pyridyl)-1,3,5-triazine (tpt) coordination polymers, see: Fujita et al. (2005 ); Li et al. (2008 ). For a related nickel–tpt–nitrato coordination polymer, see: Abrahams et al. (1999 ).

Experimental

Crystal data

[Co(NO₃)₂(C₁₈H₁₂N₆)]
M_r = 495.29
Orthorhombic, P b c n
a = 26.193 (3) Å
b = 9.8005 (11) Å
c = 16.2950 (18) Å
V = 4183.0 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.844, T_max = 0.918
20432 measured reflections
3710 independent reflections
2756 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.108
S = 1.03
3710 reflections
298 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.231 (2)
Co1—O2	2.214 (2)
Co1—O4	2.357 (4)
Co1—O5	2.194 (3)
Co1—N3	2.128 (3)
Co1—N4ⁱ	2.191 (2)
Co1—N5ⁱⁱ	2.178 (2)
Symmetry codes: (i) $[-x+1, y-1, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 I, global. DOI: 10.1107/S1600536811017661/tk2740sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811017661/tk2740Isup2.hkl

checkCIF report

Comment top

The construction of metal-organic frameworks (MOF's) has become a very active research field in recent years, due to their intriguing structural motifs and potential applications in functional materials (Yaghi et al., 2003). 2,4,6-Tris(4-pyridyl)-1,3,5-triazine (tpt) is an excellent multipyridyl ligand due to its regular trigonal structure, good rigidity and varied coordination modes. This essentially planar ligand has afforded a number of unusual and highly symmetrical coordination polymers (Fujita, et al., 2005), which often display porous metal-organic frameworks enclosing nano-sized cages, cavities, chambers, and channels (Li, et al., 2008). By solvothermal reaction of Co(NO₃)₂ with tpt, we have prepared a porous metal-organic framework [Co(tpt)(NO₃)₂]_n (I). Herein, we report its synthesis and crystal structure.

As shown in Fig. 1, the cobalt center in (I) is seven-coordinated by three pyridyl groups from different tpt ligands and two chelating nitrates, resulting in a pentagonal-bipyramidal geometry, Table 1. Pyridyl N4ⁱ and N5ⁱⁱ occupy the axial positions defining a N4ⁱ-Co1-N5ⁱⁱ bond angle of 170.62 (10) °; see Table 1 for symmetry operations. Pyridyl N3 and four nitrate oxygen donors essentially lie in an equatorial plane. One nitrate anion chelates to Co1 with similar bond lengths while the other nitrate coordinates with disparate Co—O bond distances, Table 1. Seven-coordinate Co(II) complexes are rarely observed but the long Co1-O4 distance is emphasized. Previously, a coordination polymer [Ni(tpt)(NO₃)₂]_n was reported (Abrahams, et al., 1999), where Ni^II is six-coordinated by three oxygen atoms from monodentate and bidentate nitrates as well as three pyridyl nitrogens.

Tpt acts as an exo-tridentate ligand to connect three Co^II atoms through three pyridyl N-donors. This results in a 3D metal-organic framework as shown in Fig. 2. The coordination polymer shows two types of rings. One is a four-metal macrocycle containing four tpt ligands. The other one is a two-metal cycle containing two tpt ligands. From the viewpoint of network topology, the tpt ligand can be represented by a 3-connector, while Co^II atom is a 3-connecting node. So the polymeric network can be simplified to a (10,3) topological network. Interestingly, the packing diagram shows a nano-sized porous metal-organic framework. The approximate dimensions of the pores are 1.3 nm × 1.3 nm.

Related literature top

For metal–organic frameworks, see: Yaghi et al. (2003). For 2,4,6-tris(4-pyridyl)-1,3,5-triazine (tpt) coordination polymers, see: Fujita et al. (2005); Li et al. (2008). For a related nickel–tpt–nitrato coordination polymer, see: Abrahams et al. (1999).

Experimental top

A mixture of Co(NO₃)₂.6H₂O (29.1 mg, 0.1 mmol), tpt (31.2 mg, 0.1 mmol) and 7 ml DMF/ethanol (1:6) was sealed in a 10 ml Teflon-lined stainless steel reactor, which was heated at 433 K for 72 h. The reaction mixture was cooled to room temperature at a rate of 10 K h^-1. Pink blocks were collected by filtration, washed with ethanol and dried in air. Yield: 33.4%. Anal. calcd for C₁₈H₁₂CoN₈O₆ (%): C, 43.65; H, 2.44; N, 22.62. Found: C, 43.24; H, 2.37; N, 22.51. IR (KBr pellet, cm^-1): 3064w, 1618m, 1578m, 1524 s, 1471 s, 1383 s, 1301 s, 1058m, 1027m, 806 s, 654m, 514m.

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 crystallographic asymmetric unit in (I) showing atom labelling and displacement ellipsoids at the 50% probability level.
	Fig. 2. View of porous metal-organic framework in (I).

Poly[dinitrato[µ₃-2,4,6-tris(4-pyridyl)-1,3,5-triazine]cobalt(II)] top

Crystal data top

[Co(NO₃)₂(C₁₈H₁₂N₆)]	F(000) = 2008
M_r = 495.29	D_x = 1.573 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 4158 reflections
a = 26.193 (3) Å	θ = 2.5–24.6°
b = 9.8005 (11) Å	µ = 0.88 mm⁻¹
c = 16.2950 (18) Å	T = 298 K
V = 4183.0 (8) Å³	Block, pink
Z = 8	0.20 × 0.20 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3710 independent reflections
Radiation source: fine-focus sealed tube	2756 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −31→26
T_min = 0.844, T_max = 0.918	k = −11→10
20432 measured reflections	l = −19→19

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0467P)² + 3.8374P] where P = (F_o² + 2F_c²)/3
3710 reflections	(Δ/σ)_max = 0.001
298 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Co(NO₃)₂(C₁₈H₁₂N₆)]	V = 4183.0 (8) Å³
M_r = 495.29	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 26.193 (3) Å	µ = 0.88 mm⁻¹
b = 9.8005 (11) Å	T = 298 K
c = 16.2950 (18) Å	0.20 × 0.20 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3710 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	2756 reflections with I > 2σ(I)
T_min = 0.844, T_max = 0.918	R_int = 0.049
20432 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.03	Δρ_max = 0.45 e Å⁻³
3710 reflections	Δρ_min = −0.33 e Å⁻³
298 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	0.380905 (14)	−0.17895 (4)	0.06119 (2)	0.03151 (15)
C1	0.41284 (12)	0.0886 (4)	0.1400 (2)	0.0534 (10)
H1	0.4429	0.0692	0.1121	0.064*
C2	0.41134 (12)	0.2035 (4)	0.1879 (2)	0.0543 (10)
H2	0.4402	0.2581	0.1932	0.065*
C3	0.36691 (11)	0.2379 (3)	0.22819 (18)	0.0329 (7)
C4	0.32551 (12)	0.1533 (4)	0.2173 (2)	0.0453 (9)
H4	0.2944	0.1735	0.2421	0.054*
C5	0.33059 (12)	0.0391 (4)	0.1696 (2)	0.0493 (9)
H5	0.3023	−0.0172	0.1634	0.059*
C6	0.36517 (10)	0.3595 (3)	0.28256 (18)	0.0306 (7)
C7	0.40612 (10)	0.5367 (3)	0.34072 (18)	0.0315 (7)
C8	0.45454 (11)	0.6099 (3)	0.35741 (19)	0.0358 (7)
C9	0.49982 (12)	0.5414 (4)	0.3548 (3)	0.0610 (11)
H9	0.5005	0.4493	0.3409	0.073*
C10	0.54451 (12)	0.6091 (4)	0.3727 (3)	0.0626 (12)
H10	0.5748	0.5598	0.3712	0.075*
C11	0.50274 (14)	0.8051 (4)	0.3941 (3)	0.0669 (12)
H11	0.5031	0.8974	0.4072	0.080*
C12	0.45627 (12)	0.7447 (4)	0.3782 (3)	0.0645 (12)
H12	0.4263	0.7954	0.3816	0.077*
C13	0.32363 (10)	0.4965 (3)	0.36998 (18)	0.0316 (7)
C14	0.27651 (11)	0.5375 (3)	0.41360 (19)	0.0327 (7)
C15	0.27784 (12)	0.6350 (4)	0.4739 (2)	0.0511 (10)
H15	0.3086	0.6758	0.4881	0.061*
C16	0.23372 (12)	0.6722 (4)	0.5132 (2)	0.0536 (10)
H16	0.2356	0.7391	0.5535	0.064*
C17	0.18746 (12)	0.5219 (4)	0.4389 (2)	0.0499 (9)
H17	0.1563	0.4813	0.4265	0.060*
C18	0.22980 (11)	0.4795 (4)	0.3962 (2)	0.0480 (9)
H18	0.2270	0.4125	0.3561	0.058*
N1	0.43623 (10)	−0.1599 (3)	−0.07207 (18)	0.0479 (8)
N2	0.32636 (13)	−0.3756 (5)	0.1387 (3)	0.0779 (12)
N3	0.37372 (9)	0.0033 (3)	0.13120 (16)	0.0383 (6)
N4	0.54694 (9)	0.7393 (3)	0.39189 (17)	0.0392 (6)
N5	0.18823 (9)	0.6176 (3)	0.49676 (16)	0.0360 (6)
N6	0.36465 (9)	0.5756 (3)	0.38169 (16)	0.0375 (6)
N7	0.40796 (9)	0.4331 (3)	0.28751 (15)	0.0329 (6)
N8	0.32213 (9)	0.3851 (3)	0.32351 (15)	0.0322 (6)
O1	0.42965 (8)	−0.0587 (2)	−0.02471 (14)	0.0457 (6)
O2	0.41055 (9)	−0.2649 (3)	−0.05510 (15)	0.0544 (6)
O3	0.46583 (11)	−0.1558 (3)	−0.12993 (18)	0.0806 (10)
O4	0.33747 (13)	−0.2722 (4)	0.1748 (3)	0.0995 (12)
O5	0.34510 (11)	−0.3810 (4)	0.0677 (3)	0.0866 (10)
O6	0.29912 (12)	−0.4647 (4)	0.1665 (2)	0.1130 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0236 (2)	0.0317 (2)	0.0393 (3)	0.00198 (17)	−0.00248 (17)	−0.00143 (19)
C1	0.0303 (18)	0.055 (2)	0.075 (3)	−0.0103 (16)	0.0153 (17)	−0.027 (2)
C2	0.0327 (18)	0.053 (2)	0.077 (3)	−0.0157 (16)	0.0185 (17)	−0.032 (2)
C3	0.0247 (15)	0.0353 (17)	0.0385 (17)	−0.0025 (13)	0.0011 (13)	−0.0060 (14)
C4	0.0280 (17)	0.049 (2)	0.059 (2)	−0.0034 (15)	0.0099 (15)	−0.0156 (17)
C5	0.0275 (17)	0.051 (2)	0.070 (2)	−0.0092 (15)	0.0074 (16)	−0.0219 (19)
C6	0.0236 (15)	0.0348 (17)	0.0335 (16)	0.0012 (13)	−0.0003 (12)	−0.0003 (13)
C7	0.0242 (15)	0.0329 (17)	0.0375 (17)	−0.0003 (13)	0.0002 (13)	−0.0039 (14)
C8	0.0261 (16)	0.0394 (19)	0.0418 (18)	−0.0040 (13)	0.0052 (13)	−0.0082 (15)
C9	0.0279 (18)	0.047 (2)	0.108 (3)	0.0008 (16)	−0.003 (2)	−0.032 (2)
C10	0.0259 (18)	0.054 (2)	0.108 (3)	0.0025 (16)	−0.0035 (19)	−0.037 (2)
C11	0.037 (2)	0.035 (2)	0.128 (4)	−0.0017 (16)	−0.020 (2)	−0.013 (2)
C12	0.0267 (18)	0.045 (2)	0.122 (4)	0.0059 (16)	−0.014 (2)	−0.020 (2)
C13	0.0213 (14)	0.0378 (18)	0.0357 (16)	0.0022 (13)	0.0011 (12)	−0.0008 (14)
C14	0.0262 (16)	0.0313 (17)	0.0405 (17)	0.0001 (13)	0.0032 (13)	0.0001 (14)
C15	0.0251 (17)	0.054 (2)	0.074 (3)	−0.0056 (15)	0.0085 (17)	−0.024 (2)
C16	0.0354 (19)	0.055 (2)	0.070 (3)	−0.0054 (17)	0.0116 (17)	−0.028 (2)
C17	0.0266 (17)	0.058 (2)	0.065 (2)	−0.0078 (16)	0.0038 (16)	−0.020 (2)
C18	0.0298 (17)	0.056 (2)	0.058 (2)	−0.0054 (16)	0.0062 (15)	−0.0229 (19)
N1	0.0316 (15)	0.067 (2)	0.0448 (17)	−0.0062 (14)	0.0026 (13)	−0.0058 (16)
N2	0.038 (2)	0.074 (3)	0.121 (4)	0.004 (2)	−0.014 (2)	0.045 (3)
N3	0.0272 (13)	0.0413 (16)	0.0464 (16)	−0.0018 (11)	0.0000 (12)	−0.0108 (13)
N4	0.0268 (14)	0.0416 (17)	0.0493 (16)	−0.0040 (12)	−0.0020 (12)	−0.0044 (13)
N5	0.0254 (13)	0.0362 (15)	0.0464 (16)	−0.0004 (11)	0.0068 (11)	−0.0010 (13)
N6	0.0239 (13)	0.0404 (16)	0.0482 (16)	−0.0015 (11)	0.0043 (12)	−0.0095 (13)
N7	0.0247 (13)	0.0352 (15)	0.0390 (14)	−0.0035 (11)	0.0019 (11)	−0.0045 (12)
N8	0.0251 (13)	0.0356 (15)	0.0358 (14)	−0.0025 (11)	0.0037 (11)	−0.0046 (12)
O1	0.0426 (13)	0.0465 (15)	0.0481 (14)	0.0017 (11)	0.0020 (11)	−0.0023 (12)
O2	0.0508 (15)	0.0579 (16)	0.0546 (15)	−0.0161 (13)	0.0068 (12)	−0.0125 (13)
O3	0.0626 (18)	0.113 (3)	0.0658 (18)	−0.0285 (17)	0.0321 (15)	−0.0233 (18)
O4	0.076 (2)	0.065 (2)	0.157 (4)	0.0020 (19)	−0.011 (2)	0.005 (2)
O5	0.0478 (18)	0.097 (3)	0.115 (3)	−0.0097 (17)	−0.0112 (18)	0.039 (2)
O6	0.072 (2)	0.114 (3)	0.153 (3)	−0.039 (2)	−0.014 (2)	0.087 (3)

Geometric parameters (Å, º) top

Co1—O1	2.231 (2)	C10—N4	1.315 (4)
Co1—O2	2.214 (2)	C10—H10	0.9300
Co1—O4	2.357 (4)	C11—N4	1.326 (4)
Co1—O5	2.194 (3)	C11—C12	1.378 (5)
Co1—N3	2.128 (3)	C11—H11	0.9300
Co1—N4ⁱ	2.191 (2)	C12—H12	0.9300
Co1—N5ⁱⁱ	2.178 (2)	C13—N8	1.329 (4)
C1—N3	1.330 (4)	C13—N6	1.339 (4)
C1—C2	1.370 (5)	C13—C14	1.480 (4)
C1—H1	0.9300	C14—C15	1.371 (4)
C2—C3	1.378 (4)	C14—C18	1.378 (4)
C2—H2	0.9300	C15—C16	1.371 (4)
C3—C4	1.377 (4)	C15—H15	0.9300
C3—C6	1.485 (4)	C16—N5	1.333 (4)
C4—C5	1.370 (5)	C16—H16	0.9300
C4—H4	0.9300	C17—N5	1.330 (4)
C5—N3	1.338 (4)	C17—C18	1.373 (4)
C5—H5	0.9300	C17—H17	0.9300
C6—N8	1.334 (4)	C18—H18	0.9300
C6—N7	1.335 (4)	N1—O3	1.221 (4)
C7—N6	1.331 (4)	N1—O2	1.260 (4)
C7—N7	1.336 (4)	N1—O1	1.268 (4)
C7—C8	1.482 (4)	N2—O4	1.207 (5)
C8—C9	1.364 (4)	N2—O6	1.215 (5)
C8—C12	1.365 (5)	N2—O5	1.258 (5)
C9—C10	1.377 (5)	N4—Co1ⁱⁱⁱ	2.191 (2)
C9—H9	0.9300	N5—Co1^iv	2.178 (2)

N3—Co1—N5ⁱⁱ	87.31 (10)	N4—C10—H10	118.0
N3—Co1—N4ⁱ	101.33 (10)	C9—C10—H10	118.0
N5ⁱⁱ—Co1—N4ⁱ	170.62 (10)	N4—C11—C12	123.9 (3)
N3—Co1—O5	133.94 (13)	N4—C11—H11	118.1
N5ⁱⁱ—Co1—O5	85.25 (10)	C12—C11—H11	118.1
N4ⁱ—Co1—O5	91.23 (10)	C8—C12—C11	119.4 (3)
N3—Co1—O2	144.01 (10)	C8—C12—H12	120.3
N5ⁱⁱ—Co1—O2	89.09 (10)	C11—C12—H12	120.3
N4ⁱ—Co1—O2	81.77 (10)	N8—C13—N6	125.5 (3)
O5—Co1—O2	81.26 (13)	N8—C13—C14	118.2 (2)
N3—Co1—O1	86.76 (9)	N6—C13—C14	116.3 (3)
N5ⁱⁱ—Co1—O1	91.58 (9)	C15—C14—C18	117.2 (3)
N4ⁱ—Co1—O1	85.33 (9)	C15—C14—C13	120.8 (3)
O5—Co1—O1	138.75 (13)	C18—C14—C13	122.0 (3)
O2—Co1—O1	57.55 (9)	C14—C15—C16	119.9 (3)
N3—Co1—O4	82.06 (12)	C14—C15—H15	120.0
N5ⁱⁱ—Co1—O4	94.84 (11)	C16—C15—H15	120.0
N4ⁱ—Co1—O4	90.02 (11)	N5—C16—C15	123.6 (3)
O5—Co1—O4	53.52 (14)	N5—C16—H16	118.2
O2—Co1—O4	133.93 (12)	C15—C16—H16	118.2
O1—Co1—O4	166.82 (12)	N5—C17—C18	124.0 (3)
N3—C1—C2	123.8 (3)	N5—C17—H17	118.0
N3—C1—H1	118.1	C18—C17—H17	118.0
C2—C1—H1	118.1	C17—C18—C14	119.2 (3)
C1—C2—C3	119.8 (3)	C17—C18—H18	120.4
C1—C2—H2	120.1	C14—C18—H18	120.4
C3—C2—H2	120.1	O3—N1—O2	122.3 (3)
C4—C3—C2	117.1 (3)	O3—N1—O1	122.0 (3)
C4—C3—C6	122.4 (3)	O2—N1—O1	115.6 (3)
C2—C3—C6	120.4 (3)	O4—N2—O6	124.3 (6)
C5—C4—C3	119.3 (3)	O4—N2—O5	112.9 (4)
C5—C4—H4	120.4	O6—N2—O5	122.8 (5)
C3—C4—H4	120.4	C1—N3—C5	115.8 (3)
N3—C5—C4	124.1 (3)	C1—N3—Co1	121.2 (2)
N3—C5—H5	117.9	C5—N3—Co1	123.0 (2)
C4—C5—H5	117.9	C10—N4—C11	115.9 (3)
N8—C6—N7	125.3 (3)	C10—N4—Co1ⁱⁱⁱ	118.7 (2)
N8—C6—C3	118.4 (3)	C11—N4—Co1ⁱⁱⁱ	124.5 (2)
N7—C6—C3	116.3 (2)	C17—N5—C16	116.0 (3)
N6—C7—N7	124.9 (3)	C17—N5—Co1^iv	121.6 (2)
N6—C7—C8	117.9 (3)	C16—N5—Co1^iv	122.4 (2)
N7—C7—C8	117.1 (2)	C7—N6—C13	114.7 (3)
C9—C8—C12	117.1 (3)	C6—N7—C7	114.8 (2)
C9—C8—C7	120.0 (3)	C13—N8—C6	114.5 (2)
C12—C8—C7	122.8 (3)	N1—O1—Co1	92.67 (18)
C8—C9—C10	119.7 (3)	N1—O2—Co1	93.69 (19)
C8—C9—H9	120.2	N2—O4—Co1	93.4 (3)
C10—C9—H9	120.2	N2—O5—Co1	100.0 (3)
N4—C10—C9	124.0 (3)

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

Experimental details

Crystal data
Chemical formula	[Co(NO₃)₂(C₁₈H₁₂N₆)]
M_r	495.29
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	298
a, b, c (Å)	26.193 (3), 9.8005 (11), 16.2950 (18)
V (Å³)	4183.0 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.20 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.844, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	20432, 3710, 2756
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.108, 1.03
No. of reflections	3710
No. of parameters	298
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.33

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

Selected bond lengths (Å) top

Co1—O1	2.231 (2)	Co1—N3	2.128 (3)
Co1—O2	2.214 (2)	Co1—N4ⁱ	2.191 (2)
Co1—O4	2.357 (4)	Co1—N5ⁱⁱ	2.178 (2)
Co1—O5	2.194 (3)

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

Acknowledgements

The project was supported by the Leading Academic Discipline Project of Shanghai Municipal Education Commission (J50102), and the Natural Science Foundation of Shanghai (10ZR1411100).

References

Abrahams, B. F., Batten, S. R., Grannas, M. J., Hamit, H., Hoskins, B. F. & Robson, R. (1999). Angew. Chem. Int. Ed. 38, 1475–1477. Web of Science CrossRef CAS Google Scholar
Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fujita, M., Tominaga, M., Hori, A. & Therrien, B. (2005). Acc. Chem. Res. 38, 371–380. Web of Science CrossRef Google Scholar
Li, M. X., Miao, Z. X., Shao, M., Liang, S. W. & Zhu, S. R. (2008). Inorg. Chem. 47, 4481–4489. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2007). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yaghi, O. M., O'Keeffe, M., Ockwig, N. W., Chae, H. K., Eddaoudi, M. & Kim, J. (2003). Nature (London), 423, 705–714. Web of Science CrossRef PubMed CAS Google Scholar