Bis(2-amino­benzonitrile)tetra­aqua­cobalt(II) dichloride

Ru, Z.-L.; Wang, G.-X.

doi:10.1107/S1600536809050272

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1688

doi:10.1107/S1600536809050272

Open

access

Bis(2-aminobenzonitrile)tetraaquacobalt(II) dichloride

Zong-Ling Ru ^a and Guo-Xi Wang ^a ^*

^aDepartment of Chemical & Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: aywgx@yahoo.com.cn

(Received 7 November 2009; accepted 23 November 2009; online 28 November 2009)

In the crystal structure of the title compound, [Co(C₇H₆N₂)₂(H₂O)₄]Cl₂, the Co^II cation lies on an inversion center and is coordinated by two 2-aminobenzonitrile ligands and four water molecules in a distorted octahedral geometry. The Cl⁻ counter-anion links with the complex cations via O—H⋯Cl and N—H⋯Cl hydrogen bonding. Intermolecular O—H⋯N hydrogen bonding links the complex cations, forming supramolecular chains running along the b axis.

Related literature

For the chemistry of nitrile derivatives, see: Jin et al. (1994 ); Brewis et al. (2003 ). For a related structure, see: Fu & Zhao (2007 ).

Experimental

Crystal data

[Co(C₇H₆N₂)₂(H₂O)₄]Cl₂
M_r = 438.17
Monoclinic, P 2₁ /n
a = 12.492 (3) Å
b = 6.5864 (13) Å
c = 12.608 (3) Å
β = 109.24 (3)°
V = 979.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 298 K
0.35 × 0.30 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.732, T_max = 0.871
9255 measured reflections
2227 independent reflections
1872 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.072
S = 1.13
2227 reflections
115 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1W	2.0899 (14)
Co1—O2W	2.0550 (13)
Co1—N1	2.1566 (15)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯Cl1ⁱ	0.84	2.33	3.1600 (16)	170
O1W—H1WB⋯Cl1ⁱⁱ	0.86	2.27	3.1099 (15)	167
O2W—H2WA⋯N2ⁱⁱⁱ	0.91	1.99	2.868 (2)	162
O2W—H2WB⋯Cl1^iv	0.88	2.27	3.1438 (17)	178
N2—H2B⋯Cl1^v	0.92	2.53	3.4433 (18)	172
Symmetry codes: (i) x-1, y-1, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) $[-x+{\script{1\over 2}}, y-{\script{3\over 2}}, -z+{\script{1\over 2}}]$ ; (v) -x+1, -y+2, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809050272/xu2671sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050272/xu2671Isup2.hkl

checkCIF report

Comment top

Nitrile derivatives have found wide range of applications in industry and coordination chemistry as ligands. For example, phthalonitriles have been used as starting materials for phthalocyanines (Jin et al., 1994), which are important components for dyes, pigments, gas sensors, optical limiters and liquid crystals, and which are also used in medicine, as singlet oxygen photosensitisers for photodynamic therapy (Brewis et al., 2003). Recently, we have reported a few benzonitrile compounds (Fu & Zhao, 2007). As an extension of our work on the structural characterization, we report here the crystal structure of the title compound tetra-aqua-bis(2-aminobenzonitrile)-cobalt(II) dichloride.

The crystal data show that in the title compound, the Co(II) lies on an inversion center. The distorted octahedral Co(II) environment contains two N atoms from two planar trans-related 2-aminobenzonitrile ligands in the axial positions and four aqua O atoms in the equatorial plane. In the crystal, O—H···Cl, N—H···Cl and O—H···N hydrogen bonds generate an infinite two-dimensional network (Fig.1).

Related literature top

For the chemistry of nitrile derivatives, see: Jin et al. (1994); Brewis et al. (2003). For a related structure, see: Fu & Zhao (2007).

Experimental top

A mixture of 2-aminobenzonitrile (0.1 mmol) and CoCl₂ (0.1 mmol) and water (1 ml) sealed in a glass tube were maintained at 343 K. Crystals suitable for X-ray analysis were obtained after 5 d.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Bis(2-aminobenzonitrile)tetraaquacobalt(II) dichloride top

Crystal data top

[Co(C₇H₆N₂)₂(H₂O)₄]Cl₂	F(000) = 450
M_r = 438.17	D_x = 1.486 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1872 reflections
a = 12.492 (3) Å	θ = 3.4–27.5°
b = 6.5864 (13) Å	µ = 1.17 mm⁻¹
c = 12.608 (3) Å	T = 298 K
β = 109.24 (3)°	Block, red
V = 979.4 (3) Å³	0.35 × 0.30 × 0.15 mm
Z = 2

Data collection top

Rigaku Mercury2 diffractometer	2227 independent reflections
Radiation source: fine-focus sealed tube	1872 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
ω scan	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.732, T_max = 0.871	l = −16→16
9255 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0216P)² + 0.2674P] where P = (F_o² + 2F_c²)/3
2227 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.30 e Å⁻³
4 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Co(C₇H₆N₂)₂(H₂O)₄]Cl₂	V = 979.4 (3) Å³
M_r = 438.17	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.492 (3) Å	µ = 1.17 mm⁻¹
b = 6.5864 (13) Å	T = 298 K
c = 12.608 (3) Å	0.35 × 0.30 × 0.15 mm
β = 109.24 (3)°

Data collection top

Rigaku Mercury2 diffractometer	2227 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1872 reflections with I > 2σ(I)
T_min = 0.732, T_max = 0.871	R_int = 0.038
9255 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	4 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.13	Δρ_max = 0.30 e Å⁻³
2227 reflections	Δρ_min = −0.35 e Å⁻³
115 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	0.0000	0.0000	0.5000	0.02435 (11)
Cl1	0.62659 (4)	0.99536 (7)	0.26701 (4)	0.04265 (15)
O1W	−0.10877 (11)	0.0642 (2)	0.33800 (10)	0.0348 (3)
H1WA	−0.1770	0.0308	0.3213	0.052*
H1WB	−0.1014	0.1829	0.3137	0.052*
N2	0.26587 (14)	0.6024 (3)	0.55539 (14)	0.0406 (4)
H2A	0.2560	0.4991	0.5944	0.061*
H2B	0.2997	0.7116	0.5990	0.061*
O2W	0.03539 (12)	−0.2770 (2)	0.44423 (12)	0.0469 (4)
H2WA	0.1036	−0.3409	0.4710	0.070*
H2WB	−0.0087	−0.3427	0.3854	0.070*
C7	0.33808 (16)	0.3068 (3)	0.33515 (15)	0.0366 (4)
H7	0.3225	0.1808	0.3001	0.044*
C2	0.28925 (14)	0.3621 (3)	0.41754 (14)	0.0281 (4)
C3	0.31432 (14)	0.5491 (3)	0.47396 (15)	0.0292 (4)
N1	0.14159 (13)	0.1374 (2)	0.46523 (13)	0.0365 (4)
C5	0.43102 (16)	0.6305 (4)	0.35985 (18)	0.0451 (5)
H5	0.4774	0.7220	0.3393	0.054*
C4	0.38513 (16)	0.6849 (3)	0.44191 (17)	0.0389 (5)
H4	0.4012	0.8116	0.4760	0.047*
C1	0.20887 (15)	0.2307 (3)	0.44319 (15)	0.0297 (4)
C6	0.40921 (17)	0.4417 (4)	0.30739 (17)	0.0436 (5)
H6	0.4424	0.4067	0.2539	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02442 (18)	0.02295 (18)	0.02613 (18)	−0.00363 (13)	0.00896 (14)	−0.00016 (13)
Cl1	0.0385 (3)	0.0368 (3)	0.0443 (3)	−0.0048 (2)	0.0024 (2)	−0.0060 (2)
O1W	0.0330 (7)	0.0356 (7)	0.0326 (7)	−0.0032 (6)	0.0067 (6)	0.0048 (6)
N2	0.0416 (9)	0.0438 (10)	0.0384 (9)	−0.0046 (8)	0.0157 (8)	−0.0119 (8)
O2W	0.0411 (8)	0.0367 (8)	0.0517 (9)	0.0072 (6)	0.0001 (7)	−0.0150 (7)
C7	0.0305 (10)	0.0490 (12)	0.0309 (10)	0.0002 (9)	0.0110 (8)	−0.0040 (9)
C2	0.0214 (8)	0.0363 (10)	0.0270 (9)	−0.0044 (8)	0.0084 (7)	0.0020 (8)
C3	0.0222 (9)	0.0344 (10)	0.0284 (9)	0.0000 (7)	0.0049 (7)	0.0017 (7)
N1	0.0336 (8)	0.0413 (9)	0.0365 (9)	−0.0094 (8)	0.0139 (7)	0.0002 (7)
C5	0.0287 (10)	0.0601 (14)	0.0461 (12)	−0.0085 (10)	0.0117 (9)	0.0209 (11)
C4	0.0295 (10)	0.0354 (10)	0.0467 (12)	−0.0068 (8)	0.0058 (9)	0.0047 (9)
C1	0.0286 (9)	0.0333 (10)	0.0270 (9)	−0.0031 (8)	0.0089 (8)	−0.0022 (7)
C6	0.0325 (10)	0.0703 (15)	0.0325 (11)	0.0001 (10)	0.0167 (9)	0.0073 (10)

Geometric parameters (Å, º) top

Co1—O1W	2.0899 (14)	C7—C6	1.381 (3)
Co1—O1Wⁱ	2.0899 (14)	C7—C2	1.415 (2)
Co1—O2W	2.0550 (13)	C7—H7	0.9300
Co1—O2Wⁱ	2.0550 (13)	C2—C3	1.405 (3)
Co1—N1	2.1566 (15)	C2—C1	1.441 (2)
Co1—N1ⁱ	2.1566 (15)	C3—C4	1.408 (3)
O1W—H1WA	0.8377	N1—C1	1.147 (2)
O1W—H1WB	0.8551	C5—C4	1.385 (3)
N2—C3	1.398 (2)	C5—C6	1.392 (3)
N2—H2A	0.8715	C5—H5	0.9300
N2—H2B	0.9196	C4—H4	0.9300
O2W—H2WA	0.9097	C6—H6	0.9300
O2W—H2WB	0.8784

O2W—Co1—O2Wⁱ	180.00 (8)	Co1—O2W—H2WB	125.5
O2W—Co1—O1W	89.38 (5)	H2WA—O2W—H2WB	109.6
O2Wⁱ—Co1—O1W	90.62 (5)	C6—C7—C2	119.31 (19)
O2W—Co1—O1Wⁱ	90.62 (5)	C6—C7—H7	120.3
O2Wⁱ—Co1—O1Wⁱ	89.38 (5)	C2—C7—H7	120.3
O1W—Co1—O1Wⁱ	180.00 (5)	C3—C2—C7	121.28 (16)
O2W—Co1—N1	91.13 (6)	C3—C2—C1	117.92 (15)
O2Wⁱ—Co1—N1	88.87 (6)	C7—C2—C1	120.75 (17)
O1W—Co1—N1	91.66 (6)	N2—C3—C2	120.91 (16)
O1Wⁱ—Co1—N1	88.34 (6)	N2—C3—C4	121.11 (17)
O2W—Co1—N1ⁱ	88.87 (6)	C2—C3—C4	117.90 (17)
O2Wⁱ—Co1—N1ⁱ	91.13 (6)	C1—N1—Co1	171.82 (16)
O1W—Co1—N1ⁱ	88.34 (6)	C4—C5—C6	121.43 (18)
O1Wⁱ—Co1—N1ⁱ	91.66 (6)	C4—C5—H5	119.3
N1—Co1—N1ⁱ	180.0	C6—C5—H5	119.3
Co1—O1W—H1WA	118.2	C5—C4—C3	120.27 (19)
Co1—O1W—H1WB	115.0	C5—C4—H4	119.9
H1WA—O1W—H1WB	111.8	C3—C4—H4	119.9
C3—N2—H2A	113.3	N1—C1—C2	175.48 (19)
C3—N2—H2B	114.3	C7—C6—C5	119.73 (18)
H2A—N2—H2B	113.3	C7—C6—H6	120.1
Co1—O2W—H2WA	124.4	C5—C6—H6	120.1

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Cl1ⁱⁱ	0.84	2.33	3.1600 (16)	170
O1W—H1WB···Cl1ⁱⁱⁱ	0.86	2.27	3.1099 (15)	167
O2W—H2WA···N2^iv	0.91	1.99	2.868 (2)	162
O2W—H2WB···Cl1^v	0.88	2.27	3.1438 (17)	178
N2—H2B···Cl1^vi	0.92	2.53	3.4433 (18)	172

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

Experimental details

Crystal data
Chemical formula	[Co(C₇H₆N₂)₂(H₂O)₄]Cl₂
M_r	438.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	12.492 (3), 6.5864 (13), 12.608 (3)
β (°)	109.24 (3)
V (Å³)	979.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.17
Crystal size (mm)	0.35 × 0.30 × 0.15

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.732, 0.871
No. of measured, independent and observed [I > 2σ(I)] reflections	9255, 2227, 1872
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.072, 1.13
No. of reflections	2227
No. of parameters	115
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.35

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O1W	2.0899 (14)	Co1—N1	2.1566 (15)
Co1—O2W	2.0550 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Cl1ⁱ	0.84	2.33	3.1600 (16)	170.3
O1W—H1WB···Cl1ⁱⁱ	0.86	2.27	3.1099 (15)	166.7
O2W—H2WA···N2ⁱⁱⁱ	0.91	1.99	2.868 (2)	161.8
O2W—H2WB···Cl1^iv	0.88	2.27	3.1438 (17)	178.2
N2—H2B···Cl1^v	0.92	2.53	3.4433 (18)	172.2

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

Acknowledgements

This work was supported by a start-up grant from Anyang Institute of Technology, China.

References

Brewis, M., Helliwell, M. & McKeown, N. B. (2003). Tetrahedron, 59, 3863–3872. Web of Science CSD CrossRef CAS Google Scholar
Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jin, Z., Nolan, K., McArthur, C. R., Lever, A. B. P. & Leznoff, C. C. (1994). J. Organomet. Chem. 468, 205–212. CrossRef CAS Web of Science Google Scholar
Rigaku (2005). 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