Bis{2-[bis­(3,5-dimethyl-1H-pyrazol-1-yl-κN2)meth­yl]pyridine-κN}cobalt(II) dinitrate

Xiao, C.-H.; Song, X.-Y.; Sun, Z.; Cao, P.; Pang, T.

doi:10.1107/S1600536812021435

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m857

doi:10.1107/S1600536812021435

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Bis{2-[bis(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]pyridine-κN}cobalt(II) dinitrate

Chao-Hu Xiao,^a Xue-Yan Song,^a ^* Zan Sun,^a Ping Cao ^a and Ting Pang ^a

^aKey Laboratory of Polymer Materials of Gansu Province, Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: nkbenbenyi@hotmail.com

(Received 22 April 2012; accepted 11 May 2012; online 31 May 2012)

The central Co^II ion in the title complex, [Co(C₁₆H₁₉N₅)₂](NO₃)₂, is located on a twofold rotation axis and has a slightly distorted octahedral coordination sphere. It is bonded to six N atoms from two 2-[bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl]pyridine ligands. In the crystal, molecules are linked by weak C—H⋯O interactions.

Related literature

For potential applications of similar rigid ligands in electrochemistry, see: Morin et al. (2011 ), in catalysis, see: Zhang et al. (2009 ), and for their fluxional behaviour, see: Otten et al. (2009 ); Arroyo et al. (2000 ). For N-heterocyclic rigid scorpion-type ligands, see: Reger et al. (2005 ); Liu et al. (2011 ).

Experimental

Crystal data

[Co(C₁₆H₁₉N₅)₂](NO₃)₂
M_r = 745.67
Monoclinic, I 2/a
a = 17.700 (14) Å
b = 10.965 (9) Å
c = 18.37 (2) Å
β = 90.431 (6)°
V = 3565 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 296 K
0.40 × 0.36 × 0.32 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.805, T_max = 0.841
8860 measured reflections
3297 independent reflections
2334 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.131
S = 1.10
3297 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3ⁱ	0.93	2.45	3.345 (6)	162
C5—H5A⋯O2ⁱⁱ	0.96	2.56	3.405 (7)	147
C10—H10B⋯O3ⁱⁱⁱ	0.96	2.56	3.498 (7)	167
C10—H10C⋯O3ⁱⁱ	0.96	2.29	3.197 (7)	156
C12—H12⋯O1^iv	0.93	2.39	3.193 (6)	145
C13—H13⋯O1^v	0.93	2.57	3.286 (7)	134
C14—H14⋯O3ⁱⁱ	0.93	2.47	3.322 (6)	152
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) -x+1, -y+1, -z+1; (v) x-1, y-1, z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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/S1600536812021435/su2416sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021435/su2416Isup2.hkl

checkCIF report

Comment top

Rigid ligands have captivated attention not only because of their various coordination possibilities and high structural stability, but also because of their potential applications in electrochemistry (Morin et al., 2011), catalysis (Zhang et al., 2009), and fluxional behaviour (Otten et al., 2009; Arroyo et al., 2000). In addition, N-heterocyclic rigid scorpion-type ligands have attracted increased attention due to their nitrogen coordination sites (Reger et al., 2005; Liu et al., 2011). Herein, we report on the synthesis and crystal structure the title complex, [C_O(bpz*mpy)₂](NO₃)₂, synthesized by the reaction of 2-(bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl)pyridine (bpz*mpy), with Co(NO₃).6H₂O.

The molecular structure of the title complex is shown in Fig. 1. The Co atom is situated on a twofold rotation axis and is coordinated by 6 N- atoms from two (bpz*mpy) ligands. The Co—N bond lengths range from 2.131 (2) to 2.149 (3) Å, hence the central cobalt ion has a slightly distorted octahedral coordination sphere.

In the crystal, molecules are linked by weak C—H···O interactions (Table 1 and Fig. 2).

Related literature top

For potential applications of similar rigid ligands in electrochemistry, see: Morin et al. (2011), in catalysis, see: Zhang et al. (2009), and for their fluxional behaviour, see: Otten et al. (2009); Arroyo et al. (2000). For N-heterocyclic rigid scorpion-type ligands, see: Reger et al. (2005); Liu et al. (2011).

Experimental top

To a solution of 2-(bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl)pyridine (0.2 mmol, 56.3 mg) in 10 ml of methanol, Co(NO₃).6H₂O (0.1 mmol, 29.1 mg) was added. The solution was stirred at r.t. for 30 min. Yellow and block-like crystals were obtained by evaporation after one week [Yield: 46 wt%].

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 compound. Displacement ellipsoids are drawn at the 30% probability level [only one of the nitrate anions is shown; H atoms have been omitted for clarity].
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Weak C-H···O and C-H···N interaction are shown as dashed lines.

Bis{2-[bis(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]pyridine- κN}cobalt(II) dinitrate top

Crystal data top

[Co(C₁₆H₁₉N₅)₂](NO₃)₂	F(000) = 1556
M_r = 745.67	D_x = 1.389 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 3198 reflections
a = 17.700 (14) Å	θ = 3.1–25.0°
b = 10.965 (9) Å	µ = 0.54 mm⁻¹
c = 18.37 (2) Å	T = 296 K
β = 90.431 (6)°	Block, yellow
V = 3565 (6) Å³	0.40 × 0.36 × 0.32 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3297 independent reflections
Radiation source: fine-focus sealed tube	2334 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −21→20
T_min = 0.805, T_max = 0.841	k = −13→13
8860 measured reflections	l = −22→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.048P)² + 5.1694P] where P = (F_o² + 2F_c²)/3
3297 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Co(C₁₆H₁₉N₅)₂](NO₃)₂	V = 3565 (6) Å³
M_r = 745.67	Z = 4
Monoclinic, I2/a	Mo Kα radiation
a = 17.700 (14) Å	µ = 0.54 mm⁻¹
b = 10.965 (9) Å	T = 296 K
c = 18.37 (2) Å	0.40 × 0.36 × 0.32 mm
β = 90.431 (6)°

Data collection top

Bruker APEXII CCD diffractometer	3297 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2334 reflections with I > 2σ(I)
T_min = 0.805, T_max = 0.841	R_int = 0.033
8860 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.10	Δρ_max = 0.46 e Å⁻³
3297 reflections	Δρ_min = −0.40 e Å⁻³
235 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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	0.25000	0.48144 (5)	0.50000	0.0385 (2)
N1	0.30500 (13)	0.4768 (2)	0.39615 (13)	0.0435 (8)
N2	0.25949 (14)	0.4837 (2)	0.33569 (13)	0.0437 (8)
N3	0.17509 (14)	0.6129 (2)	0.45372 (14)	0.0471 (9)
N4	0.15529 (14)	0.5976 (2)	0.38206 (14)	0.0440 (9)
N5	0.17558 (14)	0.3508 (2)	0.45023 (13)	0.0408 (8)
C1	0.37561 (18)	0.4765 (3)	0.37070 (18)	0.0493 (11)
C2	0.3744 (2)	0.4835 (3)	0.2951 (2)	0.0619 (14)
C3	0.3009 (2)	0.4882 (3)	0.27378 (18)	0.0570 (11)
C4	0.4428 (2)	0.4700 (4)	0.4198 (2)	0.0730 (15)
C5	0.2655 (3)	0.4970 (5)	0.1993 (2)	0.098 (2)
C6	0.14640 (19)	0.7205 (3)	0.4735 (2)	0.0584 (14)
C7	0.1088 (2)	0.7730 (3)	0.4140 (3)	0.0724 (16)
C8	0.11550 (19)	0.6944 (3)	0.3566 (2)	0.0604 (14)
C9	0.1552 (3)	0.7711 (4)	0.5482 (2)	0.0830 (17)
C10	0.0875 (3)	0.7046 (4)	0.2799 (3)	0.096 (2)
C11	0.1499 (2)	0.2504 (3)	0.48366 (18)	0.0521 (11)
C12	0.0989 (2)	0.1722 (3)	0.4522 (2)	0.0626 (14)
C13	0.0733 (2)	0.1950 (3)	0.3826 (2)	0.0647 (14)
C14	0.09957 (19)	0.2970 (3)	0.34717 (18)	0.0532 (11)
C15	0.14991 (16)	0.3725 (3)	0.38241 (15)	0.0378 (9)
C16	0.17815 (17)	0.4864 (3)	0.34485 (16)	0.0411 (9)
O1	0.9501 (3)	0.9744 (3)	0.40558 (19)	0.1213 (19)
O2	0.8920 (2)	0.8352 (4)	0.3465 (2)	0.137 (2)
O3	0.9660 (2)	0.9549 (3)	0.29408 (17)	0.1124 (15)
N6	0.93398 (18)	0.9236 (3)	0.34876 (17)	0.0573 (11)
H2	0.41620	0.48470	0.26470	0.0740*
H4A	0.42860	0.49340	0.46820	0.1090*
H4B	0.48120	0.52430	0.40250	0.1090*
H4C	0.46200	0.38810	0.42050	0.1090*
H5A	0.23610	0.42510	0.18980	0.1460*
H5B	0.30440	0.50400	0.16340	0.1460*
H5C	0.23340	0.56750	0.19700	0.1460*
H7	0.08390	0.84760	0.41360	0.0870*
H9A	0.16930	0.70690	0.58120	0.1250*
H9B	0.10830	0.80640	0.56340	0.1250*
H9C	0.19380	0.83260	0.54830	0.1250*
H10A	0.12970	0.71300	0.24770	0.1430*
H10B	0.05530	0.77470	0.27540	0.1430*
H10C	0.05950	0.63260	0.26730	0.1430*
H11	0.16760	0.23320	0.53030	0.0630*
H12	0.08180	0.10440	0.47760	0.0750*
H13	0.03900	0.14280	0.36000	0.0770*
H14	0.08350	0.31460	0.30000	0.0640*
H16	0.15530	0.48820	0.29610	0.0490*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0381 (3)	0.0442 (3)	0.0330 (3)	0.0000	−0.0040 (2)	0.0000
N1	0.0362 (14)	0.0570 (16)	0.0372 (14)	−0.0025 (11)	−0.0030 (11)	0.0051 (12)
N2	0.0422 (14)	0.0556 (16)	0.0332 (14)	−0.0038 (12)	−0.0014 (11)	0.0093 (12)
N3	0.0456 (15)	0.0466 (16)	0.0491 (17)	0.0057 (12)	−0.0076 (12)	−0.0009 (12)
N4	0.0404 (14)	0.0433 (15)	0.0480 (16)	−0.0011 (11)	−0.0096 (12)	0.0079 (12)
N5	0.0487 (15)	0.0442 (15)	0.0296 (13)	−0.0063 (11)	−0.0017 (11)	0.0055 (11)
C1	0.0429 (18)	0.0565 (19)	0.0487 (19)	0.0004 (15)	0.0063 (15)	0.0060 (16)
C2	0.054 (2)	0.080 (3)	0.052 (2)	0.0016 (18)	0.0191 (17)	0.0083 (18)
C3	0.065 (2)	0.068 (2)	0.0382 (18)	−0.0038 (18)	0.0082 (16)	0.0114 (16)
C4	0.0379 (19)	0.102 (3)	0.079 (3)	0.0016 (19)	−0.0014 (18)	0.005 (2)
C5	0.097 (3)	0.159 (5)	0.037 (2)	0.004 (3)	0.005 (2)	0.020 (3)
C6	0.051 (2)	0.047 (2)	0.077 (3)	0.0039 (16)	−0.0050 (18)	−0.0030 (18)
C7	0.054 (2)	0.042 (2)	0.121 (4)	0.0073 (16)	−0.016 (2)	0.010 (2)
C8	0.050 (2)	0.047 (2)	0.084 (3)	−0.0003 (16)	−0.0178 (19)	0.0205 (19)
C9	0.092 (3)	0.063 (3)	0.094 (3)	0.020 (2)	−0.003 (3)	−0.023 (2)
C10	0.108 (4)	0.077 (3)	0.101 (4)	0.005 (3)	−0.052 (3)	0.031 (3)
C11	0.071 (2)	0.0503 (19)	0.0351 (18)	−0.0071 (17)	0.0008 (16)	0.0088 (15)
C12	0.081 (3)	0.052 (2)	0.055 (2)	−0.0218 (19)	0.0063 (19)	0.0017 (17)
C13	0.076 (3)	0.061 (2)	0.057 (2)	−0.0229 (19)	−0.004 (2)	−0.0063 (18)
C14	0.057 (2)	0.060 (2)	0.0425 (19)	−0.0131 (17)	−0.0052 (16)	−0.0012 (16)
C15	0.0388 (16)	0.0419 (16)	0.0326 (16)	−0.0018 (12)	−0.0008 (13)	0.0026 (13)
C16	0.0446 (17)	0.0462 (17)	0.0324 (15)	−0.0060 (13)	−0.0084 (13)	0.0086 (13)
O1	0.212 (5)	0.093 (2)	0.059 (2)	−0.021 (3)	0.018 (2)	−0.0085 (18)
O2	0.152 (4)	0.151 (4)	0.107 (3)	−0.085 (3)	0.006 (3)	0.013 (3)
O3	0.151 (3)	0.129 (3)	0.0576 (19)	−0.058 (3)	0.021 (2)	0.0059 (19)
N6	0.069 (2)	0.0579 (18)	0.0448 (19)	0.0007 (16)	−0.0044 (15)	0.0120 (15)

Geometric parameters (Å, º) top

Co1—N1	2.149 (3)	C8—C10	1.494 (7)
Co1—N3	2.131 (3)	C11—C12	1.370 (5)
Co1—N5	2.146 (3)	C12—C13	1.376 (5)
Co1—N1ⁱ	2.149 (3)	C13—C14	1.377 (5)
Co1—N3ⁱ	2.131 (3)	C14—C15	1.375 (5)
Co1—N5ⁱ	2.146 (3)	C15—C16	1.514 (5)
O1—N6	1.215 (5)	C2—H2	0.9300
O2—N6	1.222 (5)	C4—H4A	0.9600
O3—N6	1.207 (5)	C4—H4B	0.9600
N1—N2	1.369 (4)	C4—H4C	0.9600
N1—C1	1.338 (4)	C5—H5C	0.9600
N2—C3	1.359 (4)	C5—H5A	0.9600
N2—C16	1.451 (4)	C5—H5B	0.9600
N3—N4	1.370 (4)	C7—H7	0.9300
N3—C6	1.336 (4)	C9—H9A	0.9600
N4—C16	1.457 (4)	C9—H9B	0.9600
N4—C8	1.355 (4)	C9—H9C	0.9600
N5—C11	1.342 (4)	C10—H10A	0.9600
N5—C15	1.344 (4)	C10—H10B	0.9600
C1—C2	1.391 (5)	C10—H10C	0.9600
C1—C4	1.489 (5)	C11—H11	0.9300
C2—C3	1.357 (5)	C12—H12	0.9300
C3—C5	1.504 (5)	C13—H13	0.9300
C6—C7	1.399 (6)	C14—H14	0.9300
C6—C9	1.487 (5)	C16—H16	0.9800
C7—C8	1.368 (6)

N1—Co1—N3	86.93 (9)	C11—C12—C13	119.3 (3)
N1—Co1—N5	83.49 (9)	C12—C13—C14	118.5 (3)
N1—Co1—N1ⁱ	177.29 (9)	C13—C14—C15	119.1 (3)
N1—Co1—N3ⁱ	94.91 (9)	C14—C15—C16	119.8 (3)
N1—Co1—N5ⁱ	94.69 (9)	N5—C15—C16	117.3 (3)
N3—Co1—N5	84.46 (9)	N5—C15—C14	122.9 (3)
N1ⁱ—Co1—N3	94.91 (9)	N2—C16—N4	110.5 (2)
N3—Co1—N3ⁱ	94.88 (9)	N2—C16—C15	111.6 (2)
N3—Co1—N5ⁱ	178.29 (9)	N4—C16—C15	112.5 (2)
N1ⁱ—Co1—N5	94.69 (9)	C1—C2—H2	126.00
N3ⁱ—Co1—N5	178.29 (9)	C3—C2—H2	126.00
N5—Co1—N5ⁱ	96.25 (9)	C1—C4—H4C	110.00
N1ⁱ—Co1—N3ⁱ	86.93 (9)	H4A—C4—H4C	109.00
N1ⁱ—Co1—N5ⁱ	83.49 (9)	H4B—C4—H4C	109.00
N3ⁱ—Co1—N5ⁱ	84.46 (9)	H4A—C4—H4B	109.00
Co1—N1—N2	116.82 (17)	C1—C4—H4A	110.00
Co1—N1—C1	137.8 (2)	C1—C4—H4B	110.00
N2—N1—C1	105.2 (2)	H5A—C5—H5B	109.00
N1—N2—C3	111.3 (2)	H5A—C5—H5C	109.00
N1—N2—C16	119.0 (2)	H5B—C5—H5C	109.00
C3—N2—C16	129.7 (3)	C3—C5—H5A	110.00
Co1—N3—N4	117.03 (17)	C3—C5—H5B	110.00
Co1—N3—C6	136.5 (2)	C3—C5—H5C	110.00
N4—N3—C6	105.9 (2)	C6—C7—H7	126.00
N3—N4—C8	111.4 (2)	C8—C7—H7	126.00
N3—N4—C16	118.9 (2)	C6—C9—H9A	109.00
C8—N4—C16	129.7 (3)	H9A—C9—H9C	109.00
Co1—N5—C11	124.2 (2)	H9B—C9—H9C	109.00
Co1—N5—C15	118.61 (19)	C6—C9—H9C	109.00
C11—N5—C15	117.1 (3)	H9A—C9—H9B	109.00
O1—N6—O2	122.1 (4)	C6—C9—H9B	110.00
O1—N6—O3	118.4 (4)	C8—C10—H10A	110.00
O2—N6—O3	119.1 (3)	C8—C10—H10B	109.00
C2—C1—C4	127.9 (3)	H10B—C10—H10C	109.00
N1—C1—C4	122.2 (3)	H10A—C10—H10C	109.00
N1—C1—C2	110.0 (3)	C8—C10—H10C	109.00
C1—C2—C3	107.3 (3)	H10A—C10—H10B	110.00
C2—C3—C5	131.1 (4)	N5—C11—H11	118.00
N2—C3—C5	122.7 (3)	C12—C11—H11	119.00
N2—C3—C2	106.2 (3)	C11—C12—H12	120.00
N3—C6—C7	109.3 (3)	C13—C12—H12	120.00
N3—C6—C9	122.9 (3)	C12—C13—H13	121.00
C7—C6—C9	127.8 (3)	C14—C13—H13	121.00
C6—C7—C8	107.4 (3)	C15—C14—H14	120.00
C7—C8—C10	130.5 (3)	C13—C14—H14	120.00
N4—C8—C7	106.0 (3)	N2—C16—H16	107.00
N4—C8—C10	123.5 (3)	N4—C16—H16	107.00
N5—C11—C12	123.0 (3)	C15—C16—H16	107.00

N3—Co1—N1—N2	−38.51 (18)	C6—N3—N4—C8	0.7 (3)
N3—Co1—N1—C1	136.0 (3)	N4—N3—C6—C7	−0.3 (3)
N5—Co1—N1—N2	46.26 (18)	Co1—N3—C6—C9	−9.4 (5)
N5—Co1—N1—C1	−139.3 (3)	C6—N3—N4—C16	−179.3 (3)
N3ⁱ—Co1—N1—N2	−133.15 (18)	Co1—N3—N4—C8	−172.3 (2)
N3ⁱ—Co1—N1—C1	41.3 (3)	Co1—N3—C6—C7	170.7 (2)
N5ⁱ—Co1—N1—N2	142.02 (18)	Co1—N3—N4—C16	7.7 (3)
N5ⁱ—Co1—N1—C1	−43.5 (3)	N4—N3—C6—C9	179.7 (3)
N1—Co1—N3—N4	36.26 (19)	C8—N4—C16—C15	−122.9 (3)
N1—Co1—N3—C6	−133.9 (3)	N3—N4—C8—C10	178.8 (3)
N5—Co1—N3—N4	−47.50 (19)	N3—N4—C16—N2	−68.3 (3)
N5—Co1—N3—C6	142.3 (3)	N3—N4—C8—C7	−0.9 (4)
N1ⁱ—Co1—N3—N4	−141.75 (19)	C16—N4—C8—C7	179.2 (3)
N1ⁱ—Co1—N3—C6	48.1 (3)	N3—N4—C16—C15	57.1 (3)
N3ⁱ—Co1—N3—N4	130.92 (19)	C8—N4—C16—N2	111.6 (3)
N3ⁱ—Co1—N3—C6	−39.3 (3)	C16—N4—C8—C10	−1.1 (5)
N1—Co1—N5—C11	137.7 (3)	C11—N5—C15—C16	179.4 (3)
N1—Co1—N5—C15	−45.4 (2)	Co1—N5—C15—C16	2.3 (3)
N3—Co1—N5—C11	−134.8 (3)	C15—N5—C11—C12	−0.9 (5)
N3—Co1—N5—C15	42.1 (2)	C11—N5—C15—C14	−0.1 (4)
N1ⁱ—Co1—N5—C11	−40.3 (3)	Co1—N5—C15—C14	−177.2 (2)
N1ⁱ—Co1—N5—C15	136.6 (2)	Co1—N5—C11—C12	176.0 (3)
N5ⁱ—Co1—N5—C11	43.7 (3)	C4—C1—C2—C3	−179.7 (4)
N5ⁱ—Co1—N5—C15	−139.5 (2)	N1—C1—C2—C3	0.0 (4)
Co1—N1—N2—C3	175.87 (19)	C1—C2—C3—N2	−0.2 (4)
Co1—N1—N2—C16	−3.6 (3)	C1—C2—C3—C5	179.7 (4)
C1—N1—N2—C3	−0.3 (3)	N3—C6—C7—C8	−0.3 (4)
C1—N1—N2—C16	−179.7 (3)	C9—C6—C7—C8	179.8 (4)
N2—N1—C1—C4	179.9 (3)	C6—C7—C8—C10	−179.0 (4)
Co1—N1—C1—C2	−174.7 (2)	C6—C7—C8—N4	0.7 (4)
N2—N1—C1—C2	0.2 (3)	N5—C11—C12—C13	1.3 (5)
Co1—N1—C1—C4	5.0 (5)	C11—C12—C13—C14	−0.6 (5)
C3—N2—C16—C15	120.1 (3)	C12—C13—C14—C15	−0.3 (5)
N1—N2—C16—C15	−60.6 (3)	C13—C14—C15—C16	−178.8 (3)
N1—N2—C3—C2	0.3 (3)	C13—C14—C15—N5	0.7 (5)
C16—N2—C3—C5	−0.2 (5)	N5—C15—C16—N2	61.6 (3)
N1—N2—C3—C5	−179.6 (3)	C14—C15—C16—N2	−119.0 (3)
C3—N2—C16—N4	−113.9 (3)	C14—C15—C16—N4	116.2 (3)
C16—N2—C3—C2	179.6 (3)	N5—C15—C16—N4	−63.3 (3)
N1—N2—C16—N4	65.4 (3)

Symmetry code: (i) −x+1/2, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ⁱⁱ	0.93	2.45	3.345 (6)	162
C5—H5A···O2ⁱⁱⁱ	0.96	2.56	3.405 (7)	147
C10—H10B···O3^iv	0.96	2.56	3.498 (7)	167
C10—H10C···O3ⁱⁱⁱ	0.96	2.29	3.197 (7)	156
C12—H12···O1^v	0.93	2.39	3.193 (6)	145
C13—H13···O1^vi	0.93	2.57	3.286 (7)	134
C14—H14···O3ⁱⁱⁱ	0.93	2.47	3.322 (6)	152

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₆H₁₉N₅)₂](NO₃)₂
M_r	745.67
Crystal system, space group	Monoclinic, I2/a
Temperature (K)	296
a, b, c (Å)	17.700 (14), 10.965 (9), 18.37 (2)
β (°)	90.431 (6)
V (Å³)	3565 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.54
Crystal size (mm)	0.40 × 0.36 × 0.32

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.805, 0.841
No. of measured, independent and observed [I > 2σ(I)] reflections	8860, 3297, 2334
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.131, 1.10
No. of reflections	3297
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.40

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ⁱ	0.93	2.45	3.345 (6)	162
C5—H5A···O2ⁱⁱ	0.96	2.56	3.405 (7)	147
C10—H10B···O3ⁱⁱⁱ	0.96	2.56	3.498 (7)	167
C10—H10C···O3ⁱⁱ	0.96	2.29	3.197 (7)	156
C12—H12···O1^iv	0.93	2.39	3.193 (6)	145
C13—H13···O1^v	0.93	2.57	3.286 (7)	134
C14—H14···O3ⁱⁱ	0.93	2.47	3.322 (6)	152

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

Acknowledgements

This work was supported by the Natural Science Foundation of Gansu (No. 0710RJZA113).

References

Arroyo, N., Torre, F. G., Jalón, F. A., Manzano, B. R., Moreno-Lara, B. & Rodríguez, A. M. (2000). J. Organomet. Chem. 603, 174–184. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, J.-C., Guo, G.-Z., Xiao, C.-H., Song, X.-Y. & Li, M. (2011). Acta Cryst. E67, m1691. Web of Science CSD CrossRef IUCr Journals Google Scholar
Morin, T. J., Wanniarachchi, S., Gwengo, C., Makura, V., Tatlock, H. M., Lindeman, S. V., Bennett, B., Long, G. J., Grandjean, F. & Gardinier, J. R. (2011). J. Chem. Soc. Dalton Trans. 40, 8024–8034. CrossRef CAS Google Scholar
Otten, E., Batinas, A. A., Meetsma, A. & Hessen, B. (2009). J. Am. Chem. Soc. 131, 5298–5312. Web of Science CrossRef PubMed CAS Google Scholar
Reger, D. L., Gardinier, J. R., Christian Grattan, T. & Smith, M. D. (2005). J. Organomet. Chem. 690, 1901–1912. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, J., Li, A. F. & Andy Hor, T. S. (2009). Dalton Trans. pp. 9327–9333. Web of Science CSD CrossRef Google Scholar

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