Crystal structure of bis­(4-nitro­aniline-κN1)(5,10,15,20-tetra­phenyl­por­phy­rin­ato-κ4N)cobalt(III) chloride di­chloro­methane monosolvate

Belghith, Y.; Mansour, A.; Nasri, H.

doi:10.1107/S1600536814016274

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Pages m312-m313

doi:10.1107/S1600536814016274

Open

access

Crystal structure of bis(4-nitroaniline-κN¹)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)cobalt(III) chloride dichloromethane monosolvate

Yassine Belghith,^a ^* Anissa Mansour ^b and Habib Nasri ^a

^aLaboratoire de Physico-chimie des Matériaux, Faculté des Sciences de Monastir, Avenue de l'environnement, 5019 Monastir, University of Monastir, Tunisia, and ^bUniversity of Dammam, PO Box 1982, Dammam, Kingdom of Saudi Arabia
^*Correspondence e-mail: yassinbelghith@gmail.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 10 July 2014; accepted 13 July 2014; online 1 August 2014)

The reaction of [Co^III(TPP)Cl] (TPP is the dianion of 5,10,15,20-tetraphenylporphyrin) with an excess of 4-nitroaniline in dichloromethane leads to the title compound, [Co^III(C₄₄H₂₈N₄)(C₆H₆N₂O₂)₂]Cl·CH₂Cl₂. The Co^III ion lies on an inversion centre and is octahedrally coordinated by two N atoms of the NH₂ groups of the two 4-nitroaniline trans-axial ligands and four pyrrole N atoms of the porphyrin. The asymmetric unit contains one half of the [Co^III(TPP)(4-nitroaniline)₂]⁺ ion complex, one chloride counter-ion (lying on a twofold rotation axis) and one half dichloromethane solvent molecule, where the C atom lies on a twofold rotation axis. The average equatorial Co—N(pyrrole) distance (Co—Np) is 1.982 (2) Å and the axial Co—N(4-nitroaniline) bond length is 2.006 (2) Å. The crystal packing is stabilized by an N—H⋯Cl hydrogen bond between the N atom of the amino group of the 4-nitroaniline axial ligand and the chloride counter-ion. The supramolecular architecture is further stabilized by weak C—H⋯π interactions.

Keywords: crystal structure; cobalt(III) complex; 5,10,15,20-tetraphenylporphyrin ligand.

CCDC reference: 1013796

1. Related literature

For the synthesis of the title compound, see: Madure & Scheidt (1976 ). For related structures, see: Dhifet et al. (2010 ); Konarev et al. (2003 ); Jentzen et al. (1995 ); Mansour et al. (2013 ); Zhang et al. (2005 ); Feng (2012 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

2. Experimental

2.1. Crystal data

[Co(C₄₄H₂₈N₄)(C₆H₆N₂O₂)₂]Cl·CH₂Cl₂
M_r = 1068.30
Monoclinic, P 2/c
a = 13.3527 (9) Å
b = 12.4492 (10) Å
c = 14.8935 (14) Å
β = 95.604 (4)°
V = 2463.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 150 K
0.40 × 0.24 × 0.11 mm

2.2. Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.819, T_max = 0.939
20514 measured reflections
4853 independent reflections
4083 reflections with I > 2σ(I)
R_int = 0.038

2.3. Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.097
S = 1.04
4853 reflections
338 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.96 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg7 and Cg8 are the centroids of the C11/C12–C16 and C17/C18–C22 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯Cl2	0.88 (4)	2.32 (3)	3.174 (2)	164 (3)
C13—H13⋯Cg8ⁱ	0.95	3.00	3.723 (3)	134
C20—H20⋯Cg7ⁱⁱ	0.95	2.94	3.788 (2)	150
Symmetry codes: (i) x, y-1, z; (ii) -x-1, -y, -z+1.

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1013796

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814016274/xu5802sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814016274/xu5802Isup2.hkl

checkCIF report

Comment top

In continuation of our research on the crystal structures of porphyrin complexes (Dhifet et al., 2010) we herein report the crystal structure of the title compound. The coordination geometry around the Co^III is octahedral where the N-donor atoms from the four pyrrole moieties of the meso-tetraphenylporphyrin (TPP) occupy equatorial positions along the porphyrin core. The nitrogen atoms of the amino groups of the two 4-nitroaniline trans axial ligands occupy the axial positions (Fig. 1).

The average equatorial cobalt–pyrrole N atom distance [Co—Np = 1.982 (2) Å] is (i) longer than the one of the [Co^II(TPP)] complex (Konarev et al., 2003) [Co—Np = 1.923 (4) Å which presents a very ruffled porphyrin core (Jentzen et al., 1995), (ii) very close the Co—Np bond length [1.9885 (5) Å] of the dimer {[Co^II(TPP)(µ-4,4'-bipy)].2bipy}_n (Mansour et al., 2013) which exhibits a practically planar porphyrin core. Thus, our synthetic derivative should display a planar conformation of the porphyrin core which is confirmed by the very small desplacements of the atoms of the porphyrin core with respect to the CoN₄C₂₀ mean plane [between -0.052 (1) Å and 0.041 (1) Å].

The distance between the cobalt cation and the nitrogen of the amino group of the 4-nitroaniline is 2.006 (2) Å. It is noteworthy that in the Cambridge Structural Database (CSD, Version 5.35; Allen, 2002) there are only one reported structure of a N-bonded 4-nitroaniline complex [PdCl₂(p-NO₂C₆H₄NH₂)₂] (Feng, 2012) and one reported structure of a N-bonded 4-nitroanilinato coordination compound [Os^IV(Br-salch)(p-NO₂C₆H₄NH)₂] (Zhang et al., 2005) (Br-salch = (3,5-dibromosalicylidene)-1,2-cyclohexane-diamine].

The crystal packing of the title compound is stabilized by N—H···Cl intermolecular hydrogen bonding between the nitrogen N5 of amino group of the 4-nitroaniline and the Cl2 counterion and by weak C—H···π intermolecular interactions involving Cg pyrrole and phenyl rings (Table 1 and Fig. 2).

Related literature top

For the synthesis of the title compound, see: Madure & Scheidt (1976). For related structures, see: Dhifet et al. (2010); Konarev et al. (2003); Jentzen et al. (1995); Mansour et al. (2013); Zhang et al. (2005); Feng (2012). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

To a solution of [Co^III(TPP)Cl] (100 mg, 0.141 mmol) (Madure & Scheidt, 1976) in dichloromethane (10 mL) was added an excess of 4-nitroaniline (80 mg, 0.579 mmol). The reaction mixture was stirred at room temperature and at the end of the reaction, the color of the solution changed from red-orange to dark–red. Crystals of the title complex were obtained by diffusion of hexanes through the dichloromethane solution.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. An ORTEP view of the molecular structure of the title molecule with the atom-numbering. Displacement ellipsoids are drawn at 50%. The H atoms have been omitted for clarity.
	Fig. 2. The crystal structure of the title compound plotted in projection along [100]. H atoms have been omitted.

Bis(4-nitroaniline-κN¹)(5,10,15,20-tetraphenylporphyrinato-κ⁴N)cobalt(III) chloride dichloromethane monosolvate top

Crystal data top

[Co(C₄₄H₂₈N₄)(C₆H₆N₂O₂)₂]Cl·CH₂Cl₂	F(000) = 1100
M_r = 1068.30	D_x = 1.440 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yC	Cell parameters from 22812 reflections
a = 13.3527 (9) Å	θ = 3.0–26.0°
b = 12.4492 (10) Å	µ = 0.57 mm⁻¹
c = 14.8935 (14) Å	T = 150 K
β = 95.604 (4)°	Prism, black
V = 2463.9 (3) Å³	0.40 × 0.24 × 0.11 mm
Z = 2

Data collection top

Bruker APEXII diffractometer	4853 independent reflections
Radiation source: fine-focus sealed tube	4083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
CCD rotation images, thin slices scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −15→16
T_min = 0.819, T_max = 0.939	k = −15→13
20514 measured reflections	l = −18→18

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.037P)² + 2.4863P] where P = (F_o² + 2F_c²)/3
4853 reflections	(Δ/σ)_max = 0.001
338 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.96 e Å⁻³

Crystal data top

[Co(C₄₄H₂₈N₄)(C₆H₆N₂O₂)₂]Cl·CH₂Cl₂	V = 2463.9 (3) Å³
M_r = 1068.30	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 13.3527 (9) Å	µ = 0.57 mm⁻¹
b = 12.4492 (10) Å	T = 150 K
c = 14.8935 (14) Å	0.40 × 0.24 × 0.11 mm
β = 95.604 (4)°

Data collection top

Bruker APEXII diffractometer	4853 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	4083 reflections with I > 2σ(I)
T_min = 0.819, T_max = 0.939	R_int = 0.038
20514 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.63 e Å⁻³
4853 reflections	Δρ_min = −0.96 e Å⁻³
338 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2sigma(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	Occ. (<1)
Co1	0.0000	0.0000	0.5000	0.01228 (11)
N1	0.02932 (12)	−0.15405 (13)	0.48224 (11)	0.0141 (4)
N2	−0.14475 (12)	−0.03522 (14)	0.50284 (11)	0.0151 (4)
N3	0.01549 (13)	−0.01847 (15)	0.63444 (12)	0.0163 (4)
H3A	−0.034 (2)	−0.061 (3)	0.640 (2)	0.050*
H3B	0.007 (2)	0.046 (3)	0.656 (2)	0.050*
N4	0.37671 (17)	−0.1997 (2)	0.79687 (15)	0.0439 (6)
O1	0.44300 (15)	−0.1385 (2)	0.82761 (14)	0.0564 (6)
O2	0.38324 (17)	−0.2986 (2)	0.79970 (15)	0.0616 (7)
C1	−0.03818 (15)	−0.23849 (16)	0.47479 (13)	0.0161 (4)
C2	−0.14203 (15)	−0.23050 (17)	0.47355 (14)	0.0170 (4)
C3	−0.19067 (15)	−0.13424 (17)	0.48748 (14)	0.0164 (4)
C4	−0.29731 (16)	−0.12384 (18)	0.48996 (15)	0.0218 (5)
H4	−0.3456	−0.1796	0.4797	0.026*
C5	−0.31655 (16)	−0.02085 (18)	0.50949 (15)	0.0215 (5)
H5	−0.3805	0.0090	0.5176	0.026*
C6	−0.22209 (15)	0.03581 (17)	0.51590 (14)	0.0160 (4)
C7	−0.21196 (15)	0.14533 (17)	0.53055 (14)	0.0168 (4)
C8	−0.12188 (15)	0.19990 (17)	0.52819 (14)	0.0163 (4)
C9	−0.11209 (16)	0.31445 (17)	0.53702 (15)	0.0206 (5)
H9	−0.1649	0.3642	0.5434	0.025*
C10	−0.01374 (16)	0.33815 (17)	0.53458 (15)	0.0200 (5)
H10	0.0156	0.4077	0.5384	0.024*
C11	−0.20377 (15)	−0.32921 (17)	0.45060 (15)	0.0188 (4)
C12	−0.25842 (16)	−0.38074 (18)	0.51311 (16)	0.0236 (5)
H12	−0.2578	−0.3531	0.5726	0.028*
C13	−0.31392 (17)	−0.47253 (19)	0.48862 (19)	0.0305 (6)
H13	−0.3504	−0.5076	0.5318	0.037*
C14	−0.31641 (18)	−0.51302 (19)	0.40228 (19)	0.0321 (6)
H14	−0.3542	−0.5759	0.3861	0.038*
C15	−0.26382 (18)	−0.46183 (19)	0.33937 (18)	0.0313 (6)
H15	−0.2661	−0.4890	0.2796	0.038*
C16	−0.20733 (17)	−0.37009 (18)	0.36355 (16)	0.0253 (5)
H16	−0.1710	−0.3353	0.3201	0.030*
C17	−0.30262 (15)	0.20696 (16)	0.55320 (14)	0.0172 (4)
C18	−0.38252 (15)	0.22896 (18)	0.48905 (15)	0.0203 (5)
H18	−0.3799	0.2061	0.4285	0.024*
C19	−0.46643 (16)	0.28433 (18)	0.51305 (16)	0.0232 (5)
H19	−0.5203	0.3001	0.4685	0.028*
C20	−0.47187 (16)	0.31632 (19)	0.60080 (17)	0.0267 (5)
H20	−0.5298	0.3531	0.6171	0.032*
C21	−0.39250 (18)	0.2947 (2)	0.66542 (17)	0.0313 (6)
H21	−0.3961	0.3163	0.7262	0.038*
C22	−0.30775 (17)	0.24141 (19)	0.64141 (16)	0.0262 (5)
H22	−0.2528	0.2284	0.6856	0.031*
C23	0.10649 (15)	−0.06513 (17)	0.67693 (13)	0.0179 (4)
C24	0.11492 (17)	−0.17626 (19)	0.68680 (15)	0.0232 (5)
H24	0.0600	−0.2215	0.6668	0.028*
C25	0.20399 (19)	−0.2201 (2)	0.72605 (16)	0.0311 (6)
H25	0.2110	−0.2957	0.7331	0.037*
C26	0.28217 (18)	−0.1523 (2)	0.75473 (15)	0.0307 (6)
C27	0.27532 (17)	−0.0420 (2)	0.74682 (16)	0.0304 (6)
H27	0.3302	0.0028	0.7679	0.036*
C28	0.18596 (17)	0.00184 (19)	0.70711 (15)	0.0237 (5)
H28	0.1793	0.0775	0.7006	0.028*
Cl2	0.0000	0.19408 (6)	0.7500	0.02607 (19)
Cl1	−0.07442 (8)	0.55949 (7)	0.67168 (6)	0.0712 (3)
C29	0.0000	0.4862 (4)	0.7500	0.0670 (15)
H29A	−0.0441	0.4391	0.7825	0.080*	0.50
H29B	0.0441	0.4391	0.7175	0.080*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01021 (19)	0.0130 (2)	0.0136 (2)	0.00020 (14)	0.00090 (14)	−0.00036 (15)
N1	0.0125 (8)	0.0149 (9)	0.0149 (9)	−0.0002 (7)	0.0015 (6)	0.0006 (7)
N2	0.0136 (8)	0.0149 (9)	0.0170 (9)	0.0001 (7)	0.0018 (7)	−0.0012 (7)
N3	0.0151 (9)	0.0171 (10)	0.0164 (9)	−0.0001 (7)	0.0007 (7)	0.0000 (7)
N4	0.0283 (13)	0.078 (2)	0.0256 (12)	0.0227 (13)	0.0045 (10)	0.0145 (12)
O1	0.0248 (10)	0.106 (2)	0.0370 (12)	0.0146 (12)	−0.0023 (9)	0.0107 (12)
O2	0.0546 (14)	0.0739 (18)	0.0554 (14)	0.0394 (12)	0.0005 (11)	0.0199 (12)
C1	0.0178 (10)	0.0154 (10)	0.0151 (10)	−0.0008 (8)	0.0015 (8)	0.0008 (8)
C2	0.0158 (10)	0.0172 (11)	0.0177 (11)	−0.0016 (8)	0.0011 (8)	0.0009 (8)
C3	0.0161 (10)	0.0174 (11)	0.0157 (10)	−0.0028 (8)	0.0018 (8)	0.0005 (8)
C4	0.0148 (10)	0.0199 (12)	0.0306 (13)	−0.0030 (9)	0.0020 (9)	−0.0009 (9)
C5	0.0123 (10)	0.0228 (12)	0.0298 (12)	−0.0004 (8)	0.0043 (9)	−0.0022 (9)
C6	0.0127 (10)	0.0194 (11)	0.0160 (10)	0.0007 (8)	0.0021 (8)	−0.0006 (8)
C7	0.0144 (10)	0.0195 (11)	0.0163 (10)	0.0031 (8)	−0.0002 (8)	−0.0012 (8)
C8	0.0159 (10)	0.0173 (11)	0.0154 (10)	0.0020 (8)	0.0005 (8)	−0.0005 (8)
C9	0.0177 (10)	0.0179 (11)	0.0257 (12)	0.0038 (9)	0.0000 (9)	−0.0002 (9)
C10	0.0212 (11)	0.0136 (11)	0.0250 (12)	−0.0002 (8)	0.0002 (9)	0.0009 (9)
C11	0.0122 (10)	0.0149 (11)	0.0289 (12)	0.0021 (8)	0.0003 (8)	0.0015 (9)
C12	0.0198 (11)	0.0193 (12)	0.0317 (13)	0.0011 (9)	0.0025 (9)	0.0035 (9)
C13	0.0183 (11)	0.0211 (12)	0.0517 (17)	−0.0021 (9)	0.0024 (11)	0.0121 (11)
C14	0.0210 (12)	0.0164 (12)	0.0570 (18)	−0.0022 (9)	−0.0058 (11)	0.0011 (11)
C15	0.0285 (13)	0.0226 (13)	0.0416 (15)	0.0005 (10)	−0.0034 (11)	−0.0092 (11)
C16	0.0227 (11)	0.0231 (12)	0.0300 (13)	−0.0020 (9)	0.0017 (9)	−0.0003 (10)
C17	0.0134 (10)	0.0139 (10)	0.0245 (11)	−0.0003 (8)	0.0031 (8)	−0.0007 (8)
C18	0.0157 (10)	0.0212 (11)	0.0241 (12)	−0.0018 (9)	0.0018 (8)	−0.0025 (9)
C19	0.0140 (10)	0.0232 (12)	0.0319 (13)	−0.0010 (9)	0.0000 (9)	0.0026 (10)
C20	0.0172 (11)	0.0263 (13)	0.0377 (14)	0.0061 (9)	0.0089 (10)	−0.0027 (10)
C21	0.0320 (13)	0.0371 (15)	0.0256 (13)	0.0085 (11)	0.0073 (10)	−0.0076 (11)
C22	0.0220 (11)	0.0306 (13)	0.0253 (12)	0.0069 (10)	−0.0012 (9)	−0.0026 (10)
C23	0.0188 (10)	0.0233 (12)	0.0116 (10)	0.0043 (9)	0.0020 (8)	0.0021 (8)
C24	0.0265 (12)	0.0240 (12)	0.0190 (11)	0.0021 (9)	0.0020 (9)	0.0023 (9)
C25	0.0378 (14)	0.0310 (14)	0.0251 (13)	0.0130 (11)	0.0061 (10)	0.0081 (10)
C26	0.0245 (12)	0.0509 (17)	0.0165 (12)	0.0146 (11)	0.0011 (9)	0.0084 (11)
C27	0.0204 (12)	0.0479 (16)	0.0222 (12)	−0.0027 (11)	−0.0011 (9)	0.0022 (11)
C28	0.0233 (11)	0.0276 (12)	0.0197 (11)	−0.0018 (9)	−0.0009 (9)	0.0004 (9)
Cl2	0.0409 (5)	0.0192 (4)	0.0185 (4)	0.000	0.0051 (3)	0.000
Cl1	0.1153 (8)	0.0558 (5)	0.0398 (5)	0.0400 (5)	−0.0065 (5)	−0.0044 (4)
C29	0.059 (3)	0.045 (3)	0.089 (4)	0.000	−0.033 (3)	0.000

Geometric parameters (Å, º) top

Co1—N1ⁱ	1.9802 (17)	C11—C12	1.394 (3)
Co1—N1	1.9802 (17)	C12—C13	1.391 (3)
Co1—N2ⁱ	1.9863 (16)	C12—H12	0.9500
Co1—N2	1.9863 (16)	C13—C14	1.379 (4)
Co1—N3ⁱ	2.0060 (17)	C13—H13	0.9500
Co1—N3	2.0060 (17)	C14—C15	1.380 (4)
N1—C1	1.382 (3)	C14—H14	0.9500
N1—C8ⁱ	1.384 (3)	C15—C16	1.396 (3)
N2—C3	1.386 (3)	C15—H15	0.9500
N2—C6	1.388 (3)	C16—H16	0.9500
N3—C23	1.437 (3)	C17—C22	1.390 (3)
N3—H3A	0.86 (3)	C17—C18	1.388 (3)
N3—H3B	0.87 (3)	C18—C19	1.392 (3)
N4—O1	1.223 (3)	C18—H18	0.9500
N4—O2	1.234 (4)	C19—C20	1.375 (3)
N4—C26	1.477 (3)	C19—H19	0.9500
C1—C2	1.389 (3)	C20—C21	1.387 (3)
C1—C10ⁱ	1.435 (3)	C20—H20	0.9500
C2—C3	1.388 (3)	C21—C22	1.388 (3)
C2—C11	1.500 (3)	C21—H21	0.9500
C3—C4	1.434 (3)	C22—H22	0.9500
C4—C5	1.345 (3)	C23—C28	1.389 (3)
C4—H4	0.9500	C23—C24	1.395 (3)
C5—C6	1.440 (3)	C24—C25	1.385 (3)
C5—H5	0.9500	C24—H24	0.9500
C6—C7	1.385 (3)	C25—C26	1.378 (4)
C7—C8	1.385 (3)	C25—H25	0.9500
C7—C17	1.499 (3)	C26—C27	1.380 (4)
C8—N1ⁱ	1.384 (3)	C27—C28	1.391 (3)
C8—C9	1.437 (3)	C27—H27	0.9500
C9—C10	1.350 (3)	C28—H28	0.9500
C9—H9	0.9500	Cl1—C29	1.719 (3)
C10—C1ⁱ	1.435 (3)	C29—Cl1ⁱⁱ	1.719 (3)
C10—H10	0.9500	C29—H29A	0.9900
C11—C16	1.389 (3)	C29—H29B	0.9900

N1ⁱ—Co1—N1	180.0	C16—C11—C12	118.8 (2)
N1ⁱ—Co1—N2ⁱ	89.69 (7)	C16—C11—C2	118.72 (19)
N1—Co1—N2ⁱ	90.31 (7)	C12—C11—C2	122.5 (2)
N1ⁱ—Co1—N2	90.31 (7)	C13—C12—C11	120.2 (2)
N1—Co1—N2	89.69 (7)	C13—C12—H12	119.9
N2ⁱ—Co1—N2	180.0	C11—C12—H12	119.9
N1ⁱ—Co1—N3ⁱ	91.14 (7)	C14—C13—C12	120.6 (2)
N1—Co1—N3ⁱ	88.86 (7)	C14—C13—H13	119.7
N2ⁱ—Co1—N3ⁱ	87.66 (7)	C12—C13—H13	119.7
N2—Co1—N3ⁱ	92.34 (7)	C13—C14—C15	119.8 (2)
N1ⁱ—Co1—N3	88.86 (7)	C13—C14—H14	120.1
N1—Co1—N3	91.14 (7)	C15—C14—H14	120.1
N2ⁱ—Co1—N3	92.34 (7)	C14—C15—C16	120.0 (2)
N2—Co1—N3	87.66 (7)	C14—C15—H15	120.0
N3ⁱ—Co1—N3	180.000 (15)	C16—C15—H15	120.0
C1—N1—C8ⁱ	105.06 (16)	C11—C16—C15	120.6 (2)
C1—N1—Co1	127.70 (13)	C11—C16—H16	119.7
C8ⁱ—N1—Co1	127.22 (14)	C15—C16—H16	119.7
C3—N2—C6	105.46 (16)	C22—C17—C18	118.96 (19)
C3—N2—Co1	127.49 (13)	C22—C17—C7	119.08 (19)
C6—N2—Co1	126.97 (14)	C18—C17—C7	121.95 (19)
C23—N3—Co1	119.10 (13)	C17—C18—C19	120.3 (2)
C23—N3—H3A	110 (2)	C17—C18—H18	119.8
Co1—N3—H3A	100 (2)	C19—C18—H18	119.8
C23—N3—H3B	111 (2)	C20—C19—C18	120.4 (2)
Co1—N3—H3B	105 (2)	C20—C19—H19	119.8
H3A—N3—H3B	113 (3)	C18—C19—H19	119.8
O1—N4—O2	124.2 (2)	C19—C20—C21	119.7 (2)
O1—N4—C26	117.9 (3)	C19—C20—H20	120.1
O2—N4—C26	117.9 (3)	C21—C20—H20	120.1
N1—C1—C2	126.09 (19)	C22—C21—C20	120.1 (2)
N1—C1—C10ⁱ	110.37 (17)	C22—C21—H21	120.0
C2—C1—C10ⁱ	123.51 (19)	C20—C21—H21	120.0
C3—C2—C1	122.76 (19)	C17—C22—C21	120.5 (2)
C3—C2—C11	119.10 (17)	C17—C22—H22	119.8
C1—C2—C11	118.04 (18)	C21—C22—H22	119.8
C2—C3—N2	125.91 (18)	C28—C23—C24	120.7 (2)
C2—C3—C4	124.20 (19)	C28—C23—N3	119.1 (2)
N2—C3—C4	109.87 (18)	C24—C23—N3	120.2 (2)
C5—C4—C3	107.63 (19)	C25—C24—C23	119.5 (2)
C5—C4—H4	126.2	C25—C24—H24	120.2
C3—C4—H4	126.2	C23—C24—H24	120.2
C4—C5—C6	107.25 (18)	C26—C25—C24	118.8 (2)
C4—C5—H5	126.4	C26—C25—H25	120.6
C6—C5—H5	126.4	C24—C25—H25	120.6
C7—C6—N2	125.92 (18)	C25—C26—C27	122.8 (2)
C7—C6—C5	124.32 (19)	C25—C26—N4	118.5 (2)
N2—C6—C5	109.74 (18)	C27—C26—N4	118.7 (2)
C6—C7—C8	123.40 (19)	C26—C27—C28	118.3 (2)
C6—C7—C17	118.07 (18)	C26—C27—H27	120.9
C8—C7—C17	118.49 (19)	C28—C27—H27	120.9
C7—C8—N1ⁱ	126.01 (19)	C23—C28—C27	119.9 (2)
C7—C8—C9	123.79 (19)	C23—C28—H28	120.0
N1ⁱ—C8—C9	110.20 (18)	C27—C28—H28	120.0
C10—C9—C8	107.13 (19)	Cl1ⁱⁱ—C29—Cl1	115.8 (3)
C10—C9—H9	126.4	Cl1ⁱⁱ—C29—H29A	108.3
C8—C9—H9	126.4	Cl1—C29—H29A	108.3
C9—C10—C1ⁱ	107.11 (19)	Cl1ⁱⁱ—C29—H29B	108.3
C9—C10—H10	126.4	Cl1—C29—H29B	108.3
C1ⁱ—C10—H10	126.4	H29A—C29—H29B	107.4

N1ⁱ—Co1—N1—C1	32 (100)	C5—C6—C7—C8	−173.8 (2)
N2ⁱ—Co1—N1—C1	−178.83 (17)	N2—C6—C7—C17	−173.47 (19)
N2—Co1—N1—C1	1.17 (17)	C5—C6—C7—C17	8.3 (3)
N3ⁱ—Co1—N1—C1	−91.18 (17)	C6—C7—C8—N1ⁱ	−4.9 (3)
N3—Co1—N1—C1	88.82 (17)	C17—C7—C8—N1ⁱ	172.92 (19)
N1ⁱ—Co1—N1—C8ⁱ	−150 (100)	C6—C7—C8—C9	175.5 (2)
N2ⁱ—Co1—N1—C8ⁱ	−1.01 (17)	C17—C7—C8—C9	−6.7 (3)
N2—Co1—N1—C8ⁱ	178.99 (17)	C7—C8—C9—C10	178.0 (2)
N3ⁱ—Co1—N1—C8ⁱ	86.64 (17)	N1ⁱ—C8—C9—C10	−1.7 (2)
N3—Co1—N1—C8ⁱ	−93.36 (17)	C8—C9—C10—C1ⁱ	−0.6 (2)
N1ⁱ—Co1—N2—C3	174.74 (17)	C3—C2—C11—C16	108.9 (2)
N1—Co1—N2—C3	−5.26 (17)	C1—C2—C11—C16	−67.5 (3)
N2ⁱ—Co1—N2—C3	−10 (11)	C3—C2—C11—C12	−70.5 (3)
N3ⁱ—Co1—N2—C3	83.59 (17)	C1—C2—C11—C12	113.2 (2)
N3—Co1—N2—C3	−96.41 (17)	C16—C11—C12—C13	1.1 (3)
N1ⁱ—Co1—N2—C6	−1.48 (17)	C2—C11—C12—C13	−179.5 (2)
N1—Co1—N2—C6	178.52 (17)	C11—C12—C13—C14	−0.6 (3)
N2ⁱ—Co1—N2—C6	173 (11)	C12—C13—C14—C15	−0.3 (4)
N3ⁱ—Co1—N2—C6	−92.63 (17)	C13—C14—C15—C16	0.8 (4)
N3—Co1—N2—C6	87.37 (17)	C12—C11—C16—C15	−0.7 (3)
N1ⁱ—Co1—N3—C23	−125.89 (16)	C2—C11—C16—C15	180.0 (2)
N1—Co1—N3—C23	54.11 (16)	C14—C15—C16—C11	−0.3 (4)
N2ⁱ—Co1—N3—C23	−36.25 (16)	C6—C7—C17—C22	105.9 (2)
N2—Co1—N3—C23	143.75 (16)	C8—C7—C17—C22	−72.1 (3)
N3ⁱ—Co1—N3—C23	88 (33)	C6—C7—C17—C18	−72.9 (3)
C8ⁱ—N1—C1—C2	−174.5 (2)	C8—C7—C17—C18	109.1 (2)
Co1—N1—C1—C2	3.7 (3)	C22—C17—C18—C19	−0.2 (3)
C8ⁱ—N1—C1—C10ⁱ	3.7 (2)	C7—C17—C18—C19	178.6 (2)
Co1—N1—C1—C10ⁱ	−178.12 (14)	C17—C18—C19—C20	−1.1 (3)
N1—C1—C2—C3	−5.6 (3)	C18—C19—C20—C21	1.0 (4)
C10ⁱ—C1—C2—C3	176.5 (2)	C19—C20—C21—C22	0.3 (4)
N1—C1—C2—C11	170.66 (19)	C18—C17—C22—C21	1.6 (3)
C10ⁱ—C1—C2—C11	−7.3 (3)	C7—C17—C22—C21	−177.3 (2)
C1—C2—C3—N2	0.9 (3)	C20—C21—C22—C17	−1.6 (4)
C11—C2—C3—N2	−175.24 (19)	Co1—N3—C23—C28	91.4 (2)
C1—C2—C3—C4	−177.6 (2)	Co1—N3—C23—C24	−88.0 (2)
C11—C2—C3—C4	6.2 (3)	C28—C23—C24—C25	−0.8 (3)
C6—N2—C3—C2	−178.0 (2)	N3—C23—C24—C25	178.53 (19)
Co1—N2—C3—C2	5.2 (3)	C23—C24—C25—C26	0.2 (3)
C6—N2—C3—C4	0.7 (2)	C24—C25—C26—C27	0.6 (4)
Co1—N2—C3—C4	−176.13 (14)	C24—C25—C26—N4	179.7 (2)
C2—C3—C4—C5	176.8 (2)	O1—N4—C26—C25	−175.1 (2)
N2—C3—C4—C5	−2.0 (3)	O2—N4—C26—C25	4.1 (3)
C3—C4—C5—C6	2.3 (3)	O1—N4—C26—C27	4.0 (3)
C3—N2—C6—C7	−177.7 (2)	O2—N4—C26—C27	−176.8 (2)
Co1—N2—C6—C7	−0.8 (3)	C25—C26—C27—C28	−0.9 (4)
C3—N2—C6—C5	0.7 (2)	N4—C26—C27—C28	−179.9 (2)
Co1—N2—C6—C5	177.58 (14)	C24—C23—C28—C27	0.6 (3)
C4—C5—C6—C7	176.5 (2)	N3—C23—C28—C27	−178.75 (19)
C4—C5—C6—N2	−1.9 (3)	C26—C27—C28—C23	0.2 (3)
N2—C6—C7—C8	4.4 (3)

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

Hydrogen-bond geometry (Å, º) top

Cg7 and Cg8 are the centroids of the C11/C12–C16 and C17/C18–C22 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···Cl2	0.88 (4)	2.32 (3)	3.174 (2)	164 (3)
C13—H13···Cg8ⁱⁱⁱ	0.95	3.00	3.723 (3)	134
C20—H20···Cg7^iv	0.95	2.94	3.788 (2)	150

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

Hydrogen-bond geometry (Å, º) top

Cg7 and Cg8 are the centroids of the C11/C12–C16 and C17/C18–C22 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···Cl2	0.88 (4)	2.32 (3)	3.174 (2)	164 (3)
C13—H13···Cg8ⁱ	0.95	3.00	3.723 (3)	134
C20—H20···Cg7ⁱⁱ	0.95	2.94	3.788 (2)	150

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

Acknowledgements

The authors gratefully acknowledge financial support from the Ministry of Higher Education and Scientific Research of Tunisia.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Dhifet, M., Belkhiria, M. S., Daran, J.-C., Schulz, C. E. & Nasri, H. (2010). Inorg. Chim. Acta, 363, 3208–3213. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Feng, T.-J. (2012). Acta Cryst. E68, m1351. CSD CrossRef IUCr Journals Google Scholar
Jentzen, W., Simpson, M. C., Hobbs, J. D., Song, X., Ema, T., Nelson, N. Y., Medforth, C. J., Smith, K. M., Veyrat, M., Mazzanti, M., Ramasseul, R., Marchon, J.-C., Takeuchi, T., Goddard, W. A. & Shelnutt, J. A. (1995). J. Am. Chem. Soc. 117, 11085–11097. CrossRef CAS Web of Science Google Scholar
Konarev, D., Khasanov, S. S., Saito, G., Lybovskaya, R. N., Yoshida, Y. & Otsuka, A. (2003). Chem. Eur. J. 9, 3837–3848. Web of Science CSD CrossRef PubMed CAS Google Scholar
Madure, P. & Scheidt, W. R. (1976). Inorg. Chem. 15, 3182–3184. Google Scholar
Mansour, A., Belghith, Y., Belkhiria, M. S., Bujacz, A., Guérineau, V. & Nasri, H. (2013). J. Porphyrins Phthalocyanines, 17, 1094–1103. 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., Liang, J.-L., Sun, X.-R., Zhou, H.-B., Zhu, N.-Y., Zhou, Z.-Y., Chan, P. W. H. & Che, C.-M. (2005). Inorg. Chem. 44, 3942–3954. Web of Science CSD CrossRef PubMed 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 70| Part 9| September 2014| Pages m312-m313

doi:10.1107/S1600536814016274

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\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)