Dicyanido[tris­(2-pyridyl­meth­yl)amine]­cobalt(III) hexa­fluorido­phosphate

Yu, F.; Li, B.

doi:10.1107/S1600536811012001

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m566

doi:10.1107/S1600536811012001

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Dicyanido[tris(2-pyridylmethyl)amine]cobalt(III) hexafluoridophosphate

Fan Yu ^a ^* and Bao Li ^b

^aSchool of Chemistry and Environmental Engineering, Jianghan University, Wuhan, Hubei 430056, People's Republic of China, and ^bDepartment of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, People's Republic of China
^*Correspondence e-mail: yufan0714@163.com

(Received 3 March 2011; accepted 31 March 2011; online 13 April 2011)

In the title complex, [Co(CN)₂(C₁₈H₁₈N₄)]PF₆, the Co^III atom together with one of the pyridyl rings and two cyanide anions are located on a mirror plane, while the P atom is located on an inversion centre. The Co^III atom exhibits an octahedral geometry, coordinated by four N atoms from the tris(2-pyridylmethyl)amine ligand with an average Co—N distance of 1.953 (2) Å, and two cyanide C atoms with an average Co—C distance of 1.895 (2) Å. The crystal packing is stabilized by intermolecular C—H⋯N and C—H⋯F interactions.

Related literature

For related structures, see: Guo et al. (2007 ), Liu et al. (2010 ).

Experimental

Crystal data

[Co(CN)₂(C₁₈H₁₈N₄)]PF₆
M_r = 546.30
Orthorhombic, P b c m
a = 10.703 (2) Å
b = 13.472 (3) Å
c = 15.151 (3) Å
V = 2184.7 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.722, T_max = 0.792
26914 measured reflections
2173 independent reflections
2053 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.070
S = 1.08
2173 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯N4ⁱ	0.93	2.60	3.339 (3)	137
C6—H6A⋯F3ⁱ	0.96	2.29	3.234 (2)	169
C7—H7A⋯F2ⁱⁱ	0.93	2.44	3.128 (3)	131
C9—H9A⋯N5ⁱⁱⁱ	0.93	2.57	3.410 (2)	151
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+2, -y, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); 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 (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012001/vm2083sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012001/vm2083Isup2.hkl

checkCIF report

Comment top

Transitional metal-cyanide systems have been extensively investigated due to their versatile structure and physical properties, especially in the field of molecular-based magnets. A large number of cyanide-bridged heterobimetallic or homometallic coordination complexes that exhibit excellent magnetic properties has been constructed by using the hexacyanoferrate(III) and hexacyanocobaltate(III) anions as templates (Liu et al., 2010). In constrast, complexes constructed by using the octacyanotungsten(IV) anion are rare. In an attempt to synthesize new complexes, we decided to use octacyanotungsten(IV) anions as template and new compounds containing cyanides have been obtained. The octacyanotungsten(IV) anion was not coordinated to Co atom via cyanide bridges, but acts as source of in situ cyanide generation.

In the title compound, the cobalt(III) centers are coordinated by two cyanides and tris(2-pyridylmethyl)amine (Fig. 1). Each cobalt(III) ion is coordinated by four N atoms with average Co—N distance of 1.957 (2) Å and two C atoms with average Co—C distance of 1.895 (2) Å in a rigid octahedral geometry, in accordance with those observed in other [Co(N)₄(CN)₂]^- units (Guo et al., 2007). The dihedral angle of two types of pyridyl rings is about 80.17°, indicating the nearly perpendicular occupation of these pyridyl rings. The crystal packing is stabilized by C—H···N and C—H···F hydrogen bonding interactons (Table 1, Fig. 2).

Related literature top

For related structures, see: Guo et al. (2007), Liu et al. (2010).

Experimental top

0.01 mmol K₄W(CN)₈ in 5 ml H₂O was added in a tube, and 3 ml H₂O was layered on as a buffer. A solution containing 0.1 mmol CoCl₂.6H₂O, 0.11 mmol tris(2-pyridylmethyl)amine and 0.11 mmol KPF₆ in 5 mL acetone and 1 ml H₂O was stirred for 30 min and layered on top of the previous solution. After half a year, yellow crystals were obtained.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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. Molecular structure of the title compound showing atomic numbering and 30% probability displacement ellipsoids.Symmetry codes: (i) x,y,-z + 1/2; (ii) x,-y + 1/2,-z.
	Fig. 2. The packing of title compound, viewed down the b axis. Symmetry codes: (i) x,y,-z + 1/2; (ii) x,-y + 1/2,-z.

Dicyanido[tris(2-pyridylmethyl)amine]cobalt(III) hexafluoridophosphate top

Crystal data top

[Co(CN)₂(C₁₈H₁₈N₄)]PF₆	F(000) = 1104
M_r = 546.30	D_x = 1.658 Mg m⁻³ D_m = 1.658 Mg m⁻³ D_m measured by not measured
Orthorhombic, Pbcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2c 2b	Cell parameters from 27644 reflections
a = 10.703 (2) Å	θ = 6.1–54.9°
b = 13.472 (3) Å	µ = 0.93 mm⁻¹
c = 15.151 (3) Å	T = 293 K
V = 2184.7 (8) Å³	Block, yellow
Z = 4	0.40 × 0.30 × 0.25 mm

Data collection top

Bruker SMART APEX diffractometer	2173 independent reflections
Radiation source: fine-focus sealed tube	2053 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 0 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −16→14
T_min = 0.722, T_max = 0.792	l = −18→18
26914 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.043P)² + 0.5717P] where P = (F_o² + 2F_c²)/3
2173 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³
1.234 constraints

Crystal data top

[Co(CN)₂(C₁₈H₁₈N₄)]PF₆	V = 2184.7 (8) Å³
M_r = 546.30	Z = 4
Orthorhombic, Pbcm	Mo Kα radiation
a = 10.703 (2) Å	µ = 0.93 mm⁻¹
b = 13.472 (3) Å	T = 293 K
c = 15.151 (3) Å	0.40 × 0.30 × 0.25 mm

Data collection top

Bruker SMART APEX diffractometer	2173 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2053 reflections with I > 2σ(I)
T_min = 0.722, T_max = 0.792	R_int = 0.028
26914 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.070	H-atom parameters constrained
S = 1.08	Δρ_max = 0.27 e Å⁻³
2173 reflections	Δρ_min = −0.24 e Å⁻³
176 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.82856 (2)	0.057628 (17)	0.2500	0.02656 (10)
N1	0.64937 (15)	0.02901 (13)	0.2500	0.0308 (3)
N2	0.82831 (10)	0.04135 (9)	0.37718 (8)	0.0326 (3)
N3	0.85307 (16)	−0.08775 (13)	0.2500	0.0328 (4)
N4	0.8016 (2)	0.28241 (14)	0.2500	0.0499 (5)
N5	1.10402 (19)	0.11315 (17)	0.2500	0.0508 (5)
C1	0.5562 (2)	0.09626 (16)	0.2500	0.0412 (5)
H1A	0.5761	0.1634	0.2500	0.049*
C2	0.4321 (2)	0.0686 (2)	0.2500	0.0501 (6)
H2A	0.3694	0.1163	0.2500	0.060*
C3	0.4029 (2)	−0.0304 (2)	0.2500	0.0503 (6)
H3A	0.3199	−0.0507	0.2500	0.060*
C4	0.4976 (2)	−0.09968 (17)	0.2500	0.0470 (5)
H4A	0.4792	−0.1671	0.2500	0.056*
P1	0.43435 (6)	0.2500	0.0000	0.04841 (17)
C6	0.7279 (2)	−0.13885 (15)	0.2500	0.0408 (5)
H6A	0.7219	−0.1806	0.3012	0.049*
F2	0.54077 (17)	0.23947 (14)	0.07289 (13)	0.1109 (6)
F1	0.43287 (15)	0.13526 (10)	−0.01878 (13)	0.0969 (5)
C13	0.80941 (18)	0.19751 (15)	0.2500	0.0333 (4)
C8	0.76782 (18)	0.07851 (15)	0.52469 (11)	0.0524 (4)
H8A	0.7322	0.1225	0.5647	0.063*
F3	0.32765 (16)	0.23608 (13)	0.07209 (10)	0.0978 (5)
C10	0.86385 (17)	−0.07628 (14)	0.49189 (11)	0.0447 (4)
H10A	0.8939	−0.1378	0.5098	0.054*
C7	0.77754 (15)	0.10373 (12)	0.43633 (10)	0.0417 (3)
H7A	0.7483	0.1652	0.4175	0.050*
C12	0.92406 (15)	−0.11166 (11)	0.33220 (10)	0.0400 (3)
H12A	1.0122	−0.0977	0.3241	0.048*
H12B	0.9146	−0.1813	0.3469	0.048*
C9	0.81121 (17)	−0.01197 (16)	0.55256 (11)	0.0510 (4)
H9A	0.8053	−0.0299	0.6117	0.061*
C14	1.0012 (2)	0.08893 (15)	0.2500	0.0340 (4)
C11	0.87139 (14)	−0.04806 (10)	0.40424 (10)	0.0357 (3)
C5	0.6211 (2)	−0.06763 (14)	0.2500	0.0336 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02638 (16)	0.02409 (15)	0.02921 (15)	0.00029 (9)	0.000	0.000
N1	0.0296 (8)	0.0301 (8)	0.0326 (8)	−0.0016 (6)	0.000	0.000
N2	0.0312 (6)	0.0339 (6)	0.0328 (6)	−0.0008 (4)	−0.0014 (4)	−0.0005 (5)
N3	0.0355 (9)	0.0281 (8)	0.0348 (8)	0.0041 (7)	0.000	0.000
N4	0.0456 (11)	0.0296 (9)	0.0746 (14)	−0.0006 (8)	0.000	0.000
N5	0.0318 (10)	0.0664 (13)	0.0541 (11)	−0.0040 (9)	0.000	0.000
C1	0.0311 (10)	0.0343 (10)	0.0583 (13)	0.0002 (8)	0.000	0.000
C2	0.0318 (12)	0.0533 (14)	0.0654 (16)	0.0017 (9)	0.000	0.000
C3	0.0301 (11)	0.0612 (14)	0.0595 (14)	−0.0113 (10)	0.000	0.000
C4	0.0449 (13)	0.0394 (11)	0.0566 (13)	−0.0155 (10)	0.000	0.000
P1	0.0461 (3)	0.0473 (3)	0.0519 (3)	0.000	0.000	−0.0053 (3)
C6	0.0452 (12)	0.0269 (9)	0.0505 (12)	−0.0053 (8)	0.000	0.000
F2	0.0979 (12)	0.1154 (13)	0.1194 (13)	0.0305 (10)	−0.0483 (10)	0.0004 (10)
F1	0.0994 (11)	0.0502 (7)	0.1411 (14)	−0.0045 (7)	0.0406 (10)	−0.0180 (8)
C13	0.0278 (9)	0.0317 (10)	0.0403 (10)	−0.0021 (7)	0.000	0.000
C8	0.0529 (10)	0.0681 (11)	0.0362 (8)	0.0019 (9)	0.0042 (7)	−0.0091 (8)
F3	0.0994 (12)	0.1130 (13)	0.0809 (10)	−0.0082 (9)	0.0396 (8)	−0.0240 (9)
C10	0.0443 (8)	0.0509 (9)	0.0389 (8)	−0.0040 (7)	−0.0058 (7)	0.0106 (7)
C7	0.0447 (9)	0.0440 (8)	0.0363 (7)	0.0040 (6)	0.0014 (6)	−0.0046 (6)
C12	0.0448 (8)	0.0345 (7)	0.0409 (8)	0.0085 (6)	−0.0051 (6)	0.0058 (6)
C9	0.0497 (9)	0.0721 (12)	0.0314 (7)	−0.0062 (8)	0.0000 (7)	0.0057 (8)
C14	0.0330 (11)	0.0348 (9)	0.0341 (9)	0.0025 (8)	0.000	0.000
C11	0.0330 (7)	0.0379 (7)	0.0361 (7)	−0.0021 (6)	−0.0041 (6)	0.0044 (6)
C5	0.0383 (11)	0.0328 (10)	0.0296 (9)	−0.0057 (8)	0.000	0.000

Geometric parameters (Å, º) top

Co1—C14	1.895 (2)	C4—C5	1.390 (3)
Co1—C13	1.896 (2)	C4—H4A	0.9300
Co1—N2ⁱ	1.9393 (13)	P1—F1ⁱⁱ	1.5719 (14)
Co1—N2	1.9393 (13)	P1—F1	1.5719 (14)
Co1—N1	1.9563 (17)	P1—F3ⁱⁱ	1.5913 (15)
Co1—N3	1.9760 (18)	P1—F3	1.5913 (15)
N1—C5	1.337 (3)	P1—F2	1.5928 (16)
N1—C1	1.347 (3)	P1—F2ⁱⁱ	1.5928 (16)
N2—C7	1.343 (2)	C6—C5	1.492 (3)
N2—C11	1.3534 (19)	C6—H6A	0.9600
N3—C12	1.4940 (17)	C8—C9	1.371 (3)
N3—C12ⁱ	1.4940 (17)	C8—C7	1.385 (2)
N3—C6	1.507 (3)	C8—H8A	0.9300
N4—C13	1.147 (3)	C10—C9	1.383 (3)
N5—C14	1.148 (3)	C10—C11	1.384 (2)
C1—C2	1.379 (3)	C10—H10A	0.9300
C1—H1A	0.9300	C7—H7A	0.9300
C2—C3	1.370 (4)	C12—C11	1.498 (2)
C2—H2A	0.9300	C12—H12A	0.9700
C3—C4	1.378 (4)	C12—H12B	0.9700
C3—H3A	0.9300	C9—H9A	0.9300

C14—Co1—C13	83.35 (8)	F1ⁱⁱ—P1—F3	89.11 (10)
C14—Co1—N2ⁱ	91.52 (3)	F1—P1—F3	90.06 (9)
C13—Co1—N2ⁱ	96.45 (4)	F3ⁱⁱ—P1—F3	88.28 (14)
C14—Co1—N2	91.52 (3)	F1ⁱⁱ—P1—F2	88.24 (9)
C13—Co1—N2	96.45 (4)	F1—P1—F2	92.58 (10)
N2ⁱ—Co1—N2	167.01 (7)	F3ⁱⁱ—P1—F2	178.30 (9)
C14—Co1—N1	178.51 (8)	F3—P1—F2	91.54 (11)
C13—Co1—N1	95.16 (8)	F1ⁱⁱ—P1—F2ⁱⁱ	92.58 (10)
N2ⁱ—Co1—N1	88.64 (3)	F1—P1—F2ⁱⁱ	88.24 (9)
N2—Co1—N1	88.64 (3)	F3ⁱⁱ—P1—F2ⁱⁱ	91.54 (11)
C14—Co1—N3	95.23 (8)	F3—P1—F2ⁱⁱ	178.30 (9)
C13—Co1—N3	178.58 (8)	F2—P1—F2ⁱⁱ	88.69 (16)
N2ⁱ—Co1—N3	83.58 (4)	C5—C6—N3	112.79 (17)
N2—Co1—N3	83.58 (4)	C5—C6—H6A	109.0
N1—Co1—N3	86.26 (7)	N3—C6—H6A	109.0
C5—N1—C1	119.17 (18)	N4—C13—Co1	177.95 (19)
C5—N1—Co1	114.45 (14)	C9—C8—C7	119.36 (16)
C1—N1—Co1	126.38 (15)	C9—C8—H8A	120.3
C7—N2—C11	119.50 (13)	C7—C8—H8A	120.3
C7—N2—Co1	126.35 (11)	C9—C10—C11	119.30 (16)
C11—N2—Co1	113.65 (10)	C9—C10—H10A	120.3
C12—N3—C12ⁱ	112.94 (16)	C11—C10—H10A	120.3
C12—N3—C6	110.72 (10)	N2—C7—C8	121.45 (16)
C12ⁱ—N3—C6	110.72 (10)	N2—C7—H7A	119.3
C12—N3—Co1	106.33 (9)	C8—C7—H7A	119.3
C12ⁱ—N3—Co1	106.33 (9)	N3—C12—C11	107.02 (12)
C6—N3—Co1	109.56 (12)	N3—C12—H12A	110.3
N1—C1—C2	122.0 (2)	C11—C12—H12A	110.3
N1—C1—H1A	119.0	N3—C12—H12B	110.3
C2—C1—H1A	119.0	C11—C12—H12B	110.3
C3—C2—C1	118.9 (2)	H12A—C12—H12B	108.6
C3—C2—H2A	120.6	C8—C9—C10	119.36 (15)
C1—C2—H2A	120.6	C8—C9—H9A	120.3
C2—C3—C4	119.4 (2)	C10—C9—H9A	120.3
C2—C3—H3A	120.3	N5—C14—Co1	176.3 (2)
C4—C3—H3A	120.3	N2—C11—C10	121.03 (15)
C3—C4—C5	119.3 (2)	N2—C11—C12	114.62 (13)
C3—C4—H4A	120.4	C10—C11—C12	124.34 (14)
C5—C4—H4A	120.4	N1—C5—C4	121.2 (2)
F1ⁱⁱ—P1—F1	178.85 (13)	N1—C5—C6	116.95 (18)
F1ⁱⁱ—P1—F3ⁱⁱ	90.06 (9)	C4—C5—C6	121.88 (19)
F1—P1—F3ⁱⁱ	89.11 (10)

C14—Co1—N1—C5	180.0	C2—C3—C4—C5	0.0
C13—Co1—N1—C5	180.0	C12—N3—C6—C5	116.97 (11)
N2ⁱ—Co1—N1—C5	83.65 (4)	C12ⁱ—N3—C6—C5	−116.97 (11)
N2—Co1—N1—C5	−83.65 (4)	Co1—N3—C6—C5	0.0
N3—Co1—N1—C5	0.0	C14—Co1—C13—N4	0.0
C14—Co1—N1—C1	0.0	N2ⁱ—Co1—C13—N4	−90.79 (3)
C13—Co1—N1—C1	0.0	N2—Co1—C13—N4	90.79 (3)
N2ⁱ—Co1—N1—C1	−96.35 (4)	N1—Co1—C13—N4	180.0
N2—Co1—N1—C1	96.35 (4)	N3—Co1—C13—N4	0.0
N3—Co1—N1—C1	180.0	C11—N2—C7—C8	−0.2 (2)
C14—Co1—N2—C7	107.30 (14)	Co1—N2—C7—C8	171.16 (13)
C13—Co1—N2—C7	23.82 (14)	C9—C8—C7—N2	0.2 (3)
N2ⁱ—Co1—N2—C7	−149.2 (2)	C12ⁱ—N3—C12—C11	156.60 (11)
N1—Co1—N2—C7	−71.22 (14)	C6—N3—C12—C11	−78.58 (16)
N3—Co1—N2—C7	−157.61 (14)	Co1—N3—C12—C11	40.35 (14)
C14—Co1—N2—C11	−80.90 (11)	C7—C8—C9—C10	0.0 (3)
C13—Co1—N2—C11	−164.38 (11)	C11—C10—C9—C8	−0.1 (3)
N2ⁱ—Co1—N2—C11	22.6 (4)	C13—Co1—C14—N5	0.0
N1—Co1—N2—C11	100.58 (11)	N2ⁱ—Co1—C14—N5	96.31 (4)
N3—Co1—N2—C11	14.19 (11)	N2—Co1—C14—N5	−96.31 (4)
C14—Co1—N3—C12	60.30 (10)	N1—Co1—C14—N5	0.0
C13—Co1—N3—C12	60.30 (10)	N3—Co1—C14—N5	180.0
N2ⁱ—Co1—N3—C12	151.25 (11)	C7—N2—C11—C10	0.1 (2)
N2—Co1—N3—C12	−30.65 (10)	Co1—N2—C11—C10	−172.35 (12)
N1—Co1—N3—C12	−119.70 (10)	C7—N2—C11—C12	179.11 (14)
C14—Co1—N3—C12ⁱ	−60.30 (10)	Co1—N2—C11—C12	6.70 (16)
C13—Co1—N3—C12ⁱ	−60.30 (10)	C9—C10—C11—N2	0.1 (2)
N2ⁱ—Co1—N3—C12ⁱ	30.65 (10)	C9—C10—C11—C12	−178.84 (16)
N2—Co1—N3—C12ⁱ	−151.25 (11)	N3—C12—C11—N2	−31.69 (18)
N1—Co1—N3—C12ⁱ	119.70 (10)	N3—C12—C11—C10	147.32 (16)
C14—Co1—N3—C6	180.0	C1—N1—C5—C4	0.0
C13—Co1—N3—C6	180.0	Co1—N1—C5—C4	180.0
N2ⁱ—Co1—N3—C6	−89.05 (3)	C1—N1—C5—C6	180.0
N2—Co1—N3—C6	89.05 (3)	Co1—N1—C5—C6	0.0
N1—Co1—N3—C6	0.0	C3—C4—C5—N1	0.0
C5—N1—C1—C2	0.0	C3—C4—C5—C6	180.0
Co1—N1—C1—C2	180.0	N3—C6—C5—N1	0.0
N1—C1—C2—C3	0.0	N3—C6—C5—C4	180.0
C1—C2—C3—C4	0.0

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N4ⁱⁱⁱ	0.93	2.60	3.339 (3)	137
C6—H6A···F3ⁱⁱⁱ	0.96	2.29	3.234 (2)	169
C7—H7A···F2ⁱ	0.93	2.44	3.128 (3)	131
C9—H9A···N5^iv	0.93	2.57	3.410 (2)	151

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

Experimental details

Crystal data
Chemical formula	[Co(CN)₂(C₁₈H₁₈N₄)]PF₆
M_r	546.30
Crystal system, space group	Orthorhombic, Pbcm
Temperature (K)	293
a, b, c (Å)	10.703 (2), 13.472 (3), 15.151 (3)
V (Å³)	2184.7 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.40 × 0.30 × 0.25

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.722, 0.792
No. of measured, independent and observed [I > 2σ(I)] reflections	26914, 2173, 2053
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.070, 1.08
No. of reflections	2173
No. of parameters	176
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.24

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), 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
C3—H3A···N4ⁱ	0.93	2.60	3.339 (3)	137
C6—H6A···F3ⁱ	0.96	2.29	3.234 (2)	169
C7—H7A···F2ⁱⁱ	0.93	2.44	3.128 (3)	131
C9—H9A···N5ⁱⁱⁱ	0.93	2.57	3.410 (2)	151

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

Acknowledgements

Jianghan University and Huazhong University of Science and Technology are thanked for their generous financial support and for a start-up grant.

References

Bruker (1997). SMART. Bruker AXS Inc., Madison,Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Liu, T., Zhang, Y. J., Kanegawa, S. & Sato, O. (2010). J. Am. Chem. Soc. 132, 8250–8251. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar