{2,2′-[o-Phenyl­enebis(nitrilo­methyl­idyne)]diphenolato}dipyridinecobalt(III) perchlorate

Salehi, M.; Meghdadi, S.; Amirnasr, M.; Mereiter, K.

doi:10.1107/S1600536809027330

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m942-m943

doi:10.1107/S1600536809027330

Open

access

{2,2′-[o-Phenylenebis(nitrilomethylidyne)]diphenolato}dipyridinecobalt(III) perchlorate

Mehdi Salehi,^a Soraia Meghdadi,^a Mehdi Amirnasr ^a ^* and Kurt Mereiter ^b

^aDepartment of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran, and ^bFaculty of Chemistry, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: amirnasr@cc.iut.ac.ir

(Received 25 June 2009; accepted 11 July 2009; online 18 July 2009)

The title compound, [Co(C₂₀H₁₄N₂O₂)(C₅H₅N)₂]ClO₄ or [Co(salophen)(py)₂]ClO₄, where salophen is o-phenylenebis(nitrilomethylidyne)]diphenolate and py is pyridine, contains a six-coordinate mononuclear cobalt(III) atom. The two phenolic O atoms and the two imine N atoms are located in cis positions. There are two pyridine molecules attached to the metal atom, filling the axial sites with a mutually perpendicular disposition of the pyridine planes [86.11 (5)°]. The Co complexes are stacked in layers parallel to (100). Coherence of the structure is provided by a variety of C—H⋯O interactions between the complexes and the perchlorate counter anion.

Related literature

For general background to transition metal Schiff-base complexes with a tetradentate N₂O₂ ligand configuration, see: Schenk et al. (2007 ); Yamada (1999 ). For related Co complexes, see: Amirnasr et al. (2001 ); Khandar et al. (2007 ). For oxygenation and oxidation reactions of related Co complexes, see: Nishinaga & Tomita (1980 ); Park et al. (1998 ); Speiser & Stahl (1995 ). For the antimicrobial activity of related Co complexes, see: Kumar et al. (2009 ); Miodragović et al. (2006 ); Mishra et al. (2008 ).

Experimental

Crystal data

[Co(C₂₀H₁₄N₂O₂)(C₅H₅N)₂]ClO₄
M_r = 630.91
Monoclinic, C 2/c
a = 33.4032 (16) Å
b = 10.6586 (5) Å
c = 16.3498 (8) Å
β = 112.179 (1)°
V = 5390.3 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 200 K
0.44 × 0.18 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.86, T_max = 0.95
24638 measured reflections
7804 independent reflections
6268 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.086
S = 1.03
7804 reflections
379 parameters
H-atom parameters constrained
Δρ_max = 0.38 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
C5—H5⋯O4ⁱ	0.95	2.40	3.293 (3)	157
C11—H11⋯O6ⁱⁱ	0.95	2.49	3.261 (3)	138
C12—H12⋯O3	0.95	2.59	3.501 (2)	161
C14—H14⋯O3ⁱⁱⁱ	0.95	2.51	3.002 (2)	112
C29—H29⋯O1^iv	0.95	2.47	3.111 (2)	124
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iv) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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/S1600536809027330/dn2470sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027330/dn2470Isup2.hkl

checkCIF report

Comment top

Transition metal Schiff-base complexes with the tetradentate ligand configuration N₂O₂ have been extensively studied (Yamada et al., 1999; Schenk et al., 2007). Some of these complexes have interesting applications, e.g., their ability to reversibly bind oxygen, and their use in catalysis for oxygenation and oxidation reactions of organic compounds (Nishinaga et al., 1980; Park et al., 1998; Speiser et al., 1995). Among these metal complexes, cobalt(III) Schiff base complexes with two amines in axial positions have especially attracted interest due to their ability as antimicrobial agents (Kumar et al., 2009; Miodragović et al., 2006; Mishra et al., 2008). The synthesis and reactivity of these complexes have also been playing an important part in the development of coordination chemistry. In this context, we herein report the synthesis and structure of the title compound, [Co(salophen)(py)₂]ClO₄, (I), and make a brief comparison with reported structures.

As illustrated in Fig. 1, compound (I) is the perchlorate salt of a mononuclear cobalt(III) complex cation. Bond distances and angles are given in the supplementary materials. The Schiff base ligand acts as a tetradentate ligand. The coordination polyhedron about Co is approximately octahedral, with a point group symmetry close to Cs. The three trans angles at the Co(III) centre are close to 180° and all other angles are close to 90°, ranging from 84.41 (5)° to 95.86 (5)°. The Co–O and Co–N distances of the coordinated salophen in the equatorial plane, Co(1)–O(1) = 1.8833 (10) Å, Co(1)–O(2) = 1.8806 (10) Å, Co(1)–N(1) = 1.8947 (12) Å, Co(1)–N(2) = 1.8953 (12) Å, are comparable with the Co–O and Co–N distances found in the related complexes [Co^III(salophen)(morpholine)₂]ClO₄and [Co^III(salophen)(pyrrolidine)₂]ClO₄, [Co–O_av = 1.8815 (2) Å, Co–N_av = 1.8925 (2) Å, Amirnasr et al., 2001], and [Co^III(salophen)(4-picoline)₂]ClO₄.CH₂Cl₂ [Co–O_av = 1.888 (3) Å, Co–N_av = 1.906 (4) Å, Khandar et al., 2007]. The salophen ligands in the title compound and in [Co^III(salophen)(4-picoline)₂]ClO₄.CH₂Cl₂ [Khandar et al., 2007] share a similar strong distortion, each having one phenolate moiety distinctly bent off from the least-squares plane of the remaining salophen ligand atoms, as is schematically shown by the chemical diagram of (I) and by the fact that in (I) the angle between the two least squares planes of phenolate O(1)—C(1)—C(2)—C(3)—C(4)—C(5)—C(6) and the rest of the salophen ligand is 25.27 (6)°. The two complexes differ however in the mutual orientations of the pyridine/picoline ligands – nearly perpendicular in (I) (interplanar angle 86.11 (5)°), but almost parallel in the picoline compound.

In the crystal structure of (I), the Co complexes are stacked in layers parallel to (100) with four layers per unit cell and Co at x = 0.107, 0.393, 0.607, and 0.823 (Fig. 2). Coherence of the structure is provided by a variety of C—H···O interactions (Table 1; contains only interactions with C—H···O angles > 110°) and by π-π stacking between symmetry equivalent pairs of pyridine rings N(4) through C(30) (centroid–centroid distance 3.652 (1) Å, ring–ring dihedral angle 10.5°, ring slippage 0.51 Å, shortest interatomic distances C30–C30(-x,y,1/2 - z) = 3.428 (3) Å and N4–C29(-x,y,1/2 - z) = 3.534 (2) Å).

Related literature top

For general background to transition metal Schiff-base complexes with a tetradentate N₂O₂ ligand configuration, see: Schenk et al. (2007); Yamada et al., (1999). For related Co complexes, see: Amirnasr et al. (2001); Khandar et al. (2007). For oxygenation and oxidation reactions of related Co complexes, see: Nishinaga & Tomita (1980); Park et al. (1998); Speiser et al. (1995). For the antimicrobial activity of related Co complexes, see: Kumar et al. (2009); Miodragović et al. (2006); Mishra et al. (2008).

Experimental top

To a stirring solution of Co(CH₃COO)₂.4H₂O (0.125 g, 0.5 mmol) in methanol (25 ml) was added an equimolar of salophen (0.158 g, 0.5 mmol). The red solution turned brown immediately upon the formation of [Co^II(salophen)] complex. To this solution was added 4 mmol of pyridine, and air was bubbled through the reaction mixture for about 3 h. To the resulting brown solution was then added 0.5 mmol (0.0615 g) of NaClO₄and stirred for 5 minutes. Brown crystals of the complex suitable for X-ray crystallography were obtained after three days by slow evaporation of the methanol. The crystals were filtered off and washed with a small amount of cold methanol and dried under vacuum. Yield: 80%.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 ORTEP drawing of (I), with the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of (I), viewed along the b axis.

{2,2'-[o- Phenylenebis(nitrilomethylidyne)]diphenolato}dipyridinecobalt(III) perchlorate top

Crystal data top

[Co(C₂₀H₁₄N₂O₂)(C₅H₅N)₂]ClO₄	F(000) = 2592
M_r = 630.91	D_x = 1.555 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9429 reflections
a = 33.4032 (16) Å	θ = 2.3–30.1°
b = 10.6586 (5) Å	µ = 0.79 mm⁻¹
c = 16.3498 (8) Å	T = 200 K
β = 112.179 (1)°	Prism, brown
V = 5390.3 (4) Å³	0.44 × 0.18 × 0.07 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	7804 independent reflections
Radiation source: fine-focus sealed tube	6268 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 30.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −46→31
T_min = 0.86, T_max = 0.95	k = −14→14
24638 measured reflections	l = −22→22

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0413P)² + 3.8856P] where P = (F_o² + 2F_c²)/3
7804 reflections	(Δ/σ)_max = 0.001
379 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Co(C₂₀H₁₄N₂O₂)(C₅H₅N)₂]ClO₄	V = 5390.3 (4) Å³
M_r = 630.91	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 33.4032 (16) Å	µ = 0.79 mm⁻¹
b = 10.6586 (5) Å	T = 200 K
c = 16.3498 (8) Å	0.44 × 0.18 × 0.07 mm
β = 112.179 (1)°

Data collection top

Bruker APEXII CCD diffractometer	7804 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	6268 reflections with I > 2σ(I)
T_min = 0.86, T_max = 0.95	R_int = 0.024
24638 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.03	Δρ_max = 0.38 e Å⁻³
7804 reflections	Δρ_min = −0.40 e Å⁻³
379 parameters

Special details top

Experimental. Thin prisms from methanol. Bruker Kappa APEXII CCD diffractometer, full-sphere data collection. The temperature of 200 K was selected because crystals cracked at 100 K.

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	0.107115 (6)	0.532208 (17)	0.407335 (12)	0.02150 (6)
O1	0.05857 (3)	0.63179 (9)	0.39475 (7)	0.0278 (2)
O2	0.08497 (3)	0.42434 (10)	0.47107 (7)	0.0271 (2)
N1	0.12843 (4)	0.64456 (11)	0.34353 (8)	0.0235 (2)
N2	0.15559 (4)	0.43132 (11)	0.41820 (8)	0.0226 (2)
N3	0.14061 (4)	0.62115 (11)	0.51660 (8)	0.0253 (2)
N4	0.07267 (4)	0.44507 (11)	0.29606 (8)	0.0244 (2)
C1	0.05714 (5)	0.75357 (13)	0.38370 (10)	0.0264 (3)
C2	0.02490 (5)	0.82090 (15)	0.40153 (12)	0.0369 (4)
H2	0.0047	0.7764	0.4189	0.044*
C3	0.02208 (6)	0.94902 (16)	0.39429 (14)	0.0433 (4)
H3	0.0003	0.9918	0.4073	0.052*
C4	0.05072 (6)	1.01725 (16)	0.36813 (14)	0.0437 (4)
H4	0.0489	1.1061	0.3644	0.052*
C5	0.08176 (6)	0.95457 (15)	0.34766 (12)	0.0369 (3)
H5	0.1010	1.0010	0.3287	0.044*
C6	0.08562 (5)	0.82224 (13)	0.35431 (10)	0.0276 (3)
C7	0.11850 (5)	0.76275 (13)	0.33164 (9)	0.0265 (3)
H7	0.1341	0.8133	0.3061	0.032*
C8	0.16154 (4)	0.58912 (13)	0.32072 (9)	0.0243 (2)
C9	0.17806 (5)	0.63868 (15)	0.26110 (10)	0.0294 (3)
H9	0.1667	0.7144	0.2305	0.035*
C10	0.21117 (5)	0.57614 (16)	0.24715 (10)	0.0318 (3)
H10	0.2222	0.6081	0.2056	0.038*
C11	0.22845 (5)	0.46652 (15)	0.29348 (11)	0.0316 (3)
H11	0.2520	0.4264	0.2849	0.038*
C12	0.21183 (5)	0.41546 (15)	0.35168 (10)	0.0289 (3)
H12	0.2236	0.3403	0.3827	0.035*
C13	0.17757 (4)	0.47570 (13)	0.36432 (9)	0.0234 (2)
C14	0.16751 (5)	0.33115 (13)	0.46680 (9)	0.0251 (3)
H14	0.1938	0.2922	0.4708	0.030*
C15	0.14396 (5)	0.27522 (13)	0.51476 (9)	0.0263 (3)
C16	0.16013 (6)	0.16128 (15)	0.55987 (10)	0.0339 (3)
H16	0.1865	0.1283	0.5599	0.041*
C17	0.13848 (6)	0.09751 (16)	0.60357 (11)	0.0399 (4)
H17	0.1496	0.0208	0.6329	0.048*
C18	0.09986 (6)	0.14678 (16)	0.60434 (11)	0.0375 (3)
H18	0.0848	0.1031	0.6346	0.045*
C19	0.08332 (5)	0.25753 (15)	0.56190 (10)	0.0320 (3)
H19	0.0574	0.2902	0.5647	0.038*
C20	0.10420 (5)	0.32399 (13)	0.51409 (9)	0.0252 (3)
C21	0.12183 (5)	0.64920 (15)	0.57425 (10)	0.0321 (3)
H21	0.0938	0.6176	0.5640	0.039*
C22	0.14240 (6)	0.72265 (17)	0.64774 (11)	0.0385 (4)
H22	0.1286	0.7408	0.6876	0.046*
C23	0.18298 (6)	0.76947 (16)	0.66309 (11)	0.0373 (3)
H23	0.1972	0.8217	0.7127	0.045*
C24	0.20263 (5)	0.73919 (16)	0.60521 (11)	0.0352 (3)
H24	0.2308	0.7693	0.6147	0.042*
C25	0.18075 (5)	0.66448 (15)	0.53339 (10)	0.0299 (3)
H25	0.1946	0.6427	0.4942	0.036*
C26	0.07423 (5)	0.31985 (14)	0.28919 (10)	0.0301 (3)
H26	0.0932	0.2735	0.3381	0.036*
C27	0.04929 (6)	0.25592 (16)	0.21358 (11)	0.0377 (4)
H27	0.0513	0.1672	0.2106	0.045*
C28	0.02138 (5)	0.32254 (17)	0.14223 (11)	0.0373 (3)
H28	0.0036	0.2805	0.0899	0.045*
C29	0.01988 (5)	0.45122 (17)	0.14867 (11)	0.0357 (3)
H29	0.0013	0.4994	0.1004	0.043*
C30	0.04581 (5)	0.50935 (15)	0.22635 (10)	0.0309 (3)
H30	0.0445	0.5981	0.2305	0.037*
Cl1	0.203707 (13)	0.02747 (4)	0.38080 (2)	0.03354 (9)
O3	0.24141 (5)	0.10462 (14)	0.41527 (11)	0.0619 (4)
O4	0.16645 (5)	0.10872 (14)	0.34374 (11)	0.0570 (4)
O5	0.19906 (7)	−0.04830 (17)	0.44767 (11)	0.0740 (5)
O6	0.20593 (6)	−0.04926 (15)	0.31171 (11)	0.0634 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01951 (9)	0.02155 (9)	0.02323 (10)	−0.00096 (7)	0.00782 (7)	0.00160 (7)
O1	0.0234 (5)	0.0236 (4)	0.0379 (6)	0.0002 (4)	0.0133 (4)	0.0029 (4)
O2	0.0244 (5)	0.0270 (5)	0.0314 (5)	−0.0001 (4)	0.0122 (4)	0.0058 (4)
N1	0.0224 (5)	0.0250 (5)	0.0231 (5)	−0.0015 (4)	0.0086 (4)	0.0012 (4)
N2	0.0202 (5)	0.0240 (5)	0.0222 (5)	−0.0011 (4)	0.0066 (4)	−0.0006 (4)
N3	0.0261 (5)	0.0261 (5)	0.0240 (5)	−0.0002 (4)	0.0097 (4)	0.0004 (4)
N4	0.0198 (5)	0.0269 (5)	0.0251 (5)	−0.0012 (4)	0.0069 (4)	0.0010 (4)
C1	0.0236 (6)	0.0248 (6)	0.0294 (7)	0.0008 (5)	0.0085 (5)	0.0021 (5)
C2	0.0328 (8)	0.0305 (7)	0.0540 (10)	0.0039 (6)	0.0240 (7)	0.0056 (7)
C3	0.0427 (9)	0.0335 (8)	0.0627 (12)	0.0093 (7)	0.0300 (9)	0.0058 (8)
C4	0.0489 (10)	0.0247 (7)	0.0651 (12)	0.0060 (7)	0.0299 (9)	0.0058 (7)
C5	0.0384 (8)	0.0264 (6)	0.0504 (10)	0.0007 (6)	0.0219 (7)	0.0059 (7)
C6	0.0273 (7)	0.0244 (6)	0.0310 (7)	0.0007 (5)	0.0110 (5)	0.0036 (5)
C7	0.0272 (7)	0.0257 (6)	0.0267 (7)	−0.0022 (5)	0.0104 (5)	0.0034 (5)
C8	0.0217 (6)	0.0273 (6)	0.0236 (6)	−0.0029 (5)	0.0082 (5)	−0.0019 (5)
C9	0.0285 (7)	0.0333 (7)	0.0276 (7)	−0.0027 (5)	0.0121 (6)	0.0018 (6)
C10	0.0290 (7)	0.0414 (8)	0.0280 (7)	−0.0057 (6)	0.0142 (6)	−0.0028 (6)
C11	0.0261 (7)	0.0383 (8)	0.0328 (8)	−0.0014 (6)	0.0140 (6)	−0.0063 (6)
C12	0.0252 (6)	0.0312 (7)	0.0303 (7)	0.0006 (5)	0.0108 (5)	−0.0026 (6)
C13	0.0203 (6)	0.0269 (6)	0.0222 (6)	−0.0030 (5)	0.0070 (5)	−0.0035 (5)
C14	0.0227 (6)	0.0260 (6)	0.0228 (6)	0.0014 (5)	0.0042 (5)	−0.0005 (5)
C15	0.0281 (6)	0.0265 (6)	0.0213 (6)	−0.0001 (5)	0.0061 (5)	0.0012 (5)
C16	0.0394 (8)	0.0308 (7)	0.0278 (7)	0.0051 (6)	0.0083 (6)	0.0039 (6)
C17	0.0529 (10)	0.0299 (7)	0.0326 (8)	0.0018 (7)	0.0113 (7)	0.0095 (6)
C18	0.0451 (9)	0.0355 (8)	0.0298 (8)	−0.0089 (7)	0.0115 (7)	0.0069 (6)
C19	0.0314 (7)	0.0354 (7)	0.0281 (7)	−0.0051 (6)	0.0099 (6)	0.0052 (6)
C20	0.0264 (6)	0.0253 (6)	0.0212 (6)	−0.0042 (5)	0.0059 (5)	0.0011 (5)
C21	0.0325 (7)	0.0372 (8)	0.0300 (7)	0.0013 (6)	0.0158 (6)	0.0001 (6)
C22	0.0444 (9)	0.0448 (9)	0.0294 (8)	0.0056 (7)	0.0175 (7)	−0.0039 (6)
C23	0.0449 (9)	0.0350 (8)	0.0270 (7)	0.0012 (7)	0.0077 (6)	−0.0062 (6)
C24	0.0339 (8)	0.0372 (8)	0.0311 (7)	−0.0070 (6)	0.0084 (6)	−0.0053 (6)
C25	0.0283 (7)	0.0342 (7)	0.0275 (7)	−0.0040 (6)	0.0109 (6)	−0.0039 (6)
C26	0.0300 (7)	0.0273 (6)	0.0284 (7)	−0.0033 (6)	0.0059 (6)	0.0014 (5)
C27	0.0413 (9)	0.0313 (7)	0.0353 (8)	−0.0063 (6)	0.0086 (7)	−0.0048 (6)
C28	0.0306 (8)	0.0468 (8)	0.0287 (7)	−0.0050 (7)	0.0045 (6)	−0.0070 (6)
C29	0.0260 (7)	0.0476 (8)	0.0278 (7)	0.0061 (6)	0.0037 (6)	0.0016 (6)
C30	0.0271 (7)	0.0321 (7)	0.0302 (7)	0.0055 (6)	0.0069 (5)	0.0022 (5)
Cl1	0.0386 (2)	0.03535 (19)	0.02889 (18)	−0.00695 (15)	0.01530 (15)	−0.00310 (14)
O3	0.0448 (7)	0.0543 (8)	0.0685 (10)	−0.0165 (6)	0.0010 (7)	−0.0043 (7)
O4	0.0409 (7)	0.0565 (8)	0.0734 (10)	0.0025 (6)	0.0215 (7)	0.0056 (7)
O5	0.1066 (14)	0.0717 (11)	0.0531 (9)	−0.0091 (9)	0.0409 (10)	0.0203 (8)
O6	0.0824 (11)	0.0645 (9)	0.0529 (9)	−0.0057 (8)	0.0366 (8)	−0.0224 (7)

Geometric parameters (Å, º) top

Co1—O2	1.8806 (10)	C12—C13	1.394 (2)
Co1—O1	1.8833 (10)	C12—H12	0.9500
Co1—N1	1.8947 (12)	C14—C15	1.433 (2)
Co1—N2	1.8953 (12)	C14—H14	0.9500
Co1—N3	1.9577 (12)	C15—C16	1.418 (2)
Co1—N4	1.9789 (12)	C15—C20	1.422 (2)
O1—C1	1.3089 (17)	C16—C17	1.373 (2)
O2—C20	1.3078 (17)	C16—H16	0.9500
N1—C7	1.2985 (18)	C17—C18	1.397 (3)
N1—C8	1.4222 (18)	C17—H17	0.9500
N2—C14	1.3004 (18)	C18—C19	1.375 (2)
N2—C13	1.4238 (18)	C18—H18	0.9500
N3—C25	1.3448 (19)	C19—C20	1.418 (2)
N3—C21	1.3484 (19)	C19—H19	0.9500
N4—C26	1.3420 (19)	C21—C22	1.380 (2)
N4—C30	1.3421 (19)	C21—H21	0.9500
C1—C2	1.413 (2)	C22—C23	1.376 (3)
C1—C6	1.420 (2)	C22—H22	0.9500
C2—C3	1.371 (2)	C23—C24	1.378 (2)
C2—H2	0.9500	C23—H23	0.9500
C3—C4	1.391 (3)	C24—C25	1.378 (2)
C3—H3	0.9500	C24—H24	0.9500
C4—C5	1.377 (2)	C25—H25	0.9500
C4—H4	0.9500	C26—C27	1.382 (2)
C5—C6	1.417 (2)	C26—H26	0.9500
C5—H5	0.9500	C27—C28	1.383 (2)
C6—C7	1.433 (2)	C27—H27	0.9500
C7—H7	0.9500	C28—C29	1.378 (3)
C8—C9	1.393 (2)	C28—H28	0.9500
C8—C13	1.403 (2)	C29—C30	1.384 (2)
C9—C10	1.382 (2)	C29—H29	0.9500
C9—H9	0.9500	C30—H30	0.9500
C10—C11	1.394 (2)	Cl1—O5	1.4142 (15)
C10—H10	0.9500	Cl1—O6	1.4190 (14)
C11—C12	1.382 (2)	Cl1—O3	1.4296 (14)
C11—H11	0.9500	Cl1—O4	1.4479 (15)

O2—Co1—O1	84.41 (4)	C11—C12—H12	120.4
O2—Co1—N1	178.39 (5)	C13—C12—H12	120.4
O1—Co1—N1	94.06 (5)	C12—C13—C8	119.92 (13)
O2—Co1—N2	95.85 (5)	C12—C13—N2	125.63 (13)
O1—Co1—N2	179.15 (5)	C8—C13—N2	114.44 (12)
N1—Co1—N2	85.69 (5)	N2—C14—C15	124.82 (13)
O2—Co1—N3	89.96 (5)	N2—C14—H14	117.6
O1—Co1—N3	89.93 (5)	C15—C14—H14	117.6
N1—Co1—N3	89.55 (5)	C16—C15—C20	119.23 (14)
N2—Co1—N3	90.89 (5)	C16—C15—C14	117.44 (14)
O2—Co1—N4	90.50 (5)	C20—C15—C14	123.19 (13)
O1—Co1—N4	89.22 (5)	C17—C16—C15	121.51 (16)
N1—Co1—N4	89.96 (5)	C17—C16—H16	119.2
N2—Co1—N4	89.97 (5)	C15—C16—H16	119.2
N3—Co1—N4	178.98 (5)	C16—C17—C18	119.21 (15)
C1—O1—Co1	123.99 (9)	C16—C17—H17	120.4
C20—O2—Co1	125.60 (9)	C18—C17—H17	120.4
C7—N1—C8	122.95 (12)	C19—C18—C17	120.97 (15)
C7—N1—Co1	124.59 (10)	C19—C18—H18	119.5
C8—N1—Co1	111.89 (9)	C17—C18—H18	119.5
C14—N2—C13	122.71 (12)	C18—C19—C20	121.28 (16)
C14—N2—Co1	125.23 (10)	C18—C19—H19	119.4
C13—N2—Co1	112.04 (9)	C20—C19—H19	119.4
C25—N3—C21	118.18 (13)	O2—C20—C19	117.45 (13)
C25—N3—Co1	122.34 (10)	O2—C20—C15	124.79 (13)
C21—N3—Co1	119.26 (10)	C19—C20—C15	117.74 (13)
C26—N4—C30	118.12 (13)	N3—C21—C22	121.62 (15)
C26—N4—Co1	121.08 (10)	N3—C21—H21	119.2
C30—N4—Co1	120.76 (10)	C22—C21—H21	119.2
O1—C1—C2	117.78 (13)	C23—C22—C21	119.79 (16)
O1—C1—C6	124.30 (13)	C23—C22—H22	120.1
C2—C1—C6	117.91 (13)	C21—C22—H22	120.1
C3—C2—C1	121.39 (15)	C22—C23—C24	118.79 (15)
C3—C2—H2	119.3	C22—C23—H23	120.6
C1—C2—H2	119.3	C24—C23—H23	120.6
C2—C3—C4	120.97 (16)	C25—C24—C23	118.93 (16)
C2—C3—H3	119.5	C25—C24—H24	120.5
C4—C3—H3	119.5	C23—C24—H24	120.5
C5—C4—C3	119.30 (15)	N3—C25—C24	122.65 (15)
C5—C4—H4	120.3	N3—C25—H25	118.7
C3—C4—H4	120.3	C24—C25—H25	118.7
C4—C5—C6	121.29 (15)	N4—C26—C27	122.41 (14)
C4—C5—H5	119.4	N4—C26—H26	118.8
C6—C5—H5	119.4	C27—C26—H26	118.8
C5—C6—C1	119.08 (14)	C26—C27—C28	119.22 (16)
C5—C6—C7	118.49 (14)	C26—C27—H27	120.4
C1—C6—C7	122.43 (13)	C28—C27—H27	120.4
N1—C7—C6	124.61 (13)	C29—C28—C27	118.61 (15)
N1—C7—H7	117.7	C29—C28—H28	120.7
C6—C7—H7	117.7	C27—C28—H28	120.7
C9—C8—C13	120.43 (13)	C28—C29—C30	119.17 (15)
C9—C8—N1	125.36 (13)	C28—C29—H29	120.4
C13—C8—N1	114.21 (12)	C30—C29—H29	120.4
C10—C9—C8	119.06 (14)	N4—C30—C29	122.47 (15)
C10—C9—H9	120.5	N4—C30—H30	118.8
C8—C9—H9	120.5	C29—C30—H30	118.8
C9—C10—C11	120.52 (14)	O5—Cl1—O6	109.89 (11)
C9—C10—H10	119.7	O5—Cl1—O3	111.16 (11)
C11—C10—H10	119.7	O6—Cl1—O3	110.03 (11)
C12—C11—C10	120.86 (14)	O5—Cl1—O4	109.71 (11)
C12—C11—H11	119.6	O6—Cl1—O4	107.85 (10)
C10—C11—H11	119.6	O3—Cl1—O4	108.12 (9)
C11—C12—C13	119.11 (14)

O2—Co1—O1—C1	153.07 (12)	C5—C6—C7—N1	172.43 (15)
N1—Co1—O1—C1	−26.44 (12)	C1—C6—C7—N1	−7.1 (2)
N3—Co1—O1—C1	63.11 (12)	C7—N1—C8—C9	−20.5 (2)
N4—Co1—O1—C1	−116.34 (12)	Co1—N1—C8—C9	167.85 (12)
O1—Co1—O2—C20	−173.59 (12)	C7—N1—C8—C13	159.31 (13)
N2—Co1—O2—C20	7.22 (12)	Co1—N1—C8—C13	−12.36 (14)
N3—Co1—O2—C20	−83.66 (12)	C13—C8—C9—C10	−1.6 (2)
N4—Co1—O2—C20	97.24 (12)	N1—C8—C9—C10	178.21 (13)
O1—Co1—N1—C7	21.49 (12)	C8—C9—C10—C11	−1.4 (2)
N2—Co1—N1—C7	−159.33 (12)	C9—C10—C11—C12	2.5 (2)
N3—Co1—N1—C7	−68.41 (12)	C10—C11—C12—C13	−0.6 (2)
N4—Co1—N1—C7	110.70 (12)	C11—C12—C13—C8	−2.4 (2)
O1—Co1—N1—C8	−167.01 (9)	C11—C12—C13—N2	176.48 (13)
N2—Co1—N1—C8	12.17 (9)	C9—C8—C13—C12	3.5 (2)
N3—Co1—N1—C8	103.10 (9)	N1—C8—C13—C12	−176.31 (12)
N4—Co1—N1—C8	−77.80 (9)	C9—C8—C13—N2	−175.50 (12)
O2—Co1—N2—C14	−7.55 (12)	N1—C8—C13—N2	4.70 (17)
N1—Co1—N2—C14	171.98 (12)	C14—N2—C13—C12	4.6 (2)
N3—Co1—N2—C14	82.50 (12)	Co1—N2—C13—C12	−173.76 (11)
N4—Co1—N2—C14	−98.05 (12)	C14—N2—C13—C8	−176.42 (12)
O2—Co1—N2—C13	170.81 (9)	Co1—N2—C13—C8	5.17 (14)
N1—Co1—N2—C13	−9.66 (9)	C13—N2—C14—C15	−173.08 (13)
N3—Co1—N2—C13	−99.15 (9)	Co1—N2—C14—C15	5.1 (2)
N4—Co1—N2—C13	80.30 (9)	N2—C14—C15—C16	175.93 (13)
O2—Co1—N3—C25	142.20 (12)	N2—C14—C15—C20	0.2 (2)
O1—Co1—N3—C25	−133.39 (12)	C20—C15—C16—C17	−0.6 (2)
N1—Co1—N3—C25	−39.34 (12)	C14—C15—C16—C17	−176.47 (15)
N2—Co1—N3—C25	46.35 (12)	C15—C16—C17—C18	−0.7 (3)
O2—Co1—N3—C21	−43.24 (12)	C16—C17—C18—C19	0.2 (3)
O1—Co1—N3—C21	41.17 (12)	C17—C18—C19—C20	1.6 (2)
N1—Co1—N3—C21	135.23 (12)	Co1—O2—C20—C19	177.06 (10)
N2—Co1—N3—C21	−139.09 (12)	Co1—O2—C20—C15	−4.4 (2)
O2—Co1—N4—C26	−51.73 (12)	C18—C19—C20—O2	175.84 (14)
O1—Co1—N4—C26	−136.13 (12)	C18—C19—C20—C15	−2.8 (2)
N1—Co1—N4—C26	129.81 (12)	C16—C15—C20—O2	−176.25 (14)
N2—Co1—N4—C26	44.12 (12)	C14—C15—C20—O2	−0.6 (2)
O2—Co1—N4—C30	125.70 (12)	C16—C15—C20—C19	2.3 (2)
O1—Co1—N4—C30	41.29 (12)	C14—C15—C20—C19	177.89 (13)
N1—Co1—N4—C30	−52.76 (12)	C25—N3—C21—C22	1.5 (2)
N2—Co1—N4—C30	−138.45 (12)	Co1—N3—C21—C22	−173.33 (12)
Co1—O1—C1—C2	−161.34 (12)	N3—C21—C22—C23	0.3 (3)
Co1—O1—C1—C6	19.2 (2)	C21—C22—C23—C24	−1.5 (3)
O1—C1—C2—C3	177.90 (17)	C22—C23—C24—C25	0.8 (3)
C6—C1—C2—C3	−2.6 (3)	C21—N3—C25—C24	−2.1 (2)
C1—C2—C3—C4	0.7 (3)	Co1—N3—C25—C24	172.49 (12)
C2—C3—C4—C5	1.2 (3)	C23—C24—C25—N3	1.0 (3)
C3—C4—C5—C6	−1.2 (3)	C30—N4—C26—C27	−0.1 (2)
C4—C5—C6—C1	−0.7 (3)	Co1—N4—C26—C27	177.38 (13)
C4—C5—C6—C7	179.73 (17)	N4—C26—C27—C28	−0.5 (3)
O1—C1—C6—C5	−177.95 (15)	C26—C27—C28—C29	0.9 (3)
C2—C1—C6—C5	2.6 (2)	C27—C28—C29—C30	−0.8 (3)
O1—C1—C6—C7	1.6 (2)	C26—N4—C30—C29	0.2 (2)
C2—C1—C6—C7	−177.91 (15)	Co1—N4—C30—C29	−177.29 (12)
C8—N1—C7—C6	−179.53 (13)	C28—C29—C30—N4	0.3 (3)
Co1—N1—C7—C6	−8.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4ⁱ	0.95	2.40	3.293 (3)	157
C11—H11···O6ⁱⁱ	0.95	2.49	3.261 (3)	138
C12—H12···O3	0.95	2.59	3.501 (2)	161
C14—H14···O3ⁱⁱⁱ	0.95	2.51	3.002 (2)	112
C29—H29···O1^iv	0.95	2.47	3.111 (2)	124

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

Experimental details

Crystal data
Chemical formula	[Co(C₂₀H₁₄N₂O₂)(C₅H₅N)₂]ClO₄
M_r	630.91
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	33.4032 (16), 10.6586 (5), 16.3498 (8)
β (°)	112.179 (1)
V (Å³)	5390.3 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.44 × 0.18 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.86, 0.95
No. of measured, independent and observed [I > 2σ(I)] reflections	24638, 7804, 6268
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.086, 1.03
No. of reflections	7804
No. of parameters	379
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.40

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), 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
C5—H5···O4ⁱ	0.95	2.40	3.293 (3)	157.00
C11—H11···O6ⁱⁱ	0.95	2.49	3.261 (3)	138
C12—H12···O3	0.95	2.59	3.501 (2)	161
C14—H14···O3ⁱⁱⁱ	0.95	2.51	3.002 (2)	112
C29—H29···O1^iv	0.95	2.47	3.111 (2)	124

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

Acknowledgements

Partial support of this work by the Isfahan University of Technology Research Council is gratefully acknowledged.

References

Amirnasr, M., Schenk, K. J., Gorji, A. & Vafazadeh, R. (2001). Polyhedron, 20, 695–702. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Khandar, A. A., Shaabani, B., Belaj, F. & Bakhtiari, A. (2007). Inorg. Chim. Acta, 360, 3255–3264. Web of Science CSD CrossRef CAS Google Scholar
Kumar, R. S., Arunachalam, S., Periasamy, V. S., Preethy, C. P., Riyasdeen, A. & Akbarsha, M. A. (2009). J. Inorg. Biochem. 103, 117–127. Web of Science CrossRef PubMed CAS Google Scholar
Miodragović, D. U., Bogdanović, G. A., Miodragović, Z. M., Radulović, M. D., Novaković, S. B., Kaluderović, G. N. & Kozlowski, H. (2006). J. Inorg. Biochem. 100, 1568–1574. Web of Science PubMed Google Scholar
Mishra, A., Kaushik, N. K., Verma, A. K. & Gupta, R. (2008). Eur. J. Med. Chem. 43, 2189–2196. Web of Science CrossRef PubMed CAS Google Scholar
Nishinaga, A. & Tomita, H. (1980). J. Mol. Catal. 7, 179–199. CrossRef CAS Google Scholar
Park, S., Mathur, V. K. & Planalp, R. P. (1998). Polyhedron, 17, 325–330. Web of Science CrossRef CAS Google Scholar
Schenk, K. J., Meghdadi, S., Amirnasr, M., Habibi, M. H., Amiri, A., Salehi, M. & Kashi, A. (2007). Polyhedron, 26, 5448–5457. 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
Speiser, B. & Stahl, H. (1995). Angew. Chem. Int. Ed. 34, 1086–1089. CrossRef CAS Google Scholar
Yamada, S. (1999). Coord. Chem. Rev. 190–192, 537–555. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m942-m943

doi:10.1107/S1600536809027330

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

{2,2′-[o-Phenyl­enebis(nitrilo­methyl­­idyne)]diphenolato}di­pyridinecobalt(III) perchlorate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

{2,2′-[o-Phenylenebis(nitrilomethylidyne)]diphenolato}dipyridinecobalt(III) perchlorate