(2,3,7,8,12,13,17,18-Octa­ethyl­porphyrinato-κ4N)cobalt(II)–2-nitro­benzaldehyde (1/2)

Mansour, A.; Daran, J.-C.; Nasri, H.

doi:10.1107/S1600536812036112

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page m1214

doi:10.1107/S1600536812036112

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(2,3,7,8,12,13,17,18-Octaethylporphyrinato-κ⁴N)cobalt(II)–2-nitrobenzaldehyde (1/2)

Anissa Mansour,^a ^* Jean-Claude Daran ^b and Habib Nasri ^a

^aDépartement de Chimie, Faculté des Sciences de Monastir, Université de Monastir, Avenue de l'Environnement, 5019 Monastir, Tunisia, and ^bLaboratoire de Chimie de Coordination, CNRS UPR 8241 205 route de Norbonne, 31077 Toulouse, Cedex 04, France
^*Correspondence e-mail: anissamansour@gmail.com

(Received 14 July 2012; accepted 16 August 2012; online 25 August 2012)

The asymmetric unit of the title compound, [Co(C₃₆H₄₄N₄)]·2C₇H₅NO₃, is composed of one half of the complex, arranged about an inversion center, and a complete 2-nitrobenzaldehyde (NBA) molecule. The structure consists of columns that contain interleaved molecules of NBA and [Co^II(OEP)] (OEP is 2,3,7,8,12,13,17,18-octaethylporphyrin), which are stacked along the a axis. The Co^II atom is involved in a π interaction with the ring of the NBA molecule with a centroid–metal distance of 3.508 (6) Å. There is an intramolecular C—H⋯O hydrogen bond in the NBA molecule.

Related literature

For the synthesis, see: Scheidt & Tyrk (1994 ). For related structures, see: Olmstead et al. (2003 ); Smirnov et al. (1998 ); Ben Moussa et al. (2011 ); Dhifet et al. (2010 ); Ellison et al. (2000 ).

Experimental

Crystal data

[Co(C₃₆H₄₄N₄)]·2C₇H₅NO₃
M_r = 893.92
Monoclinic, P 2₁ /c
a = 10.1952 (11) Å
b = 21.2230 (17) Å
c = 10.1601 (10) Å
β = 100.771 (9)°
V = 2159.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 180 K
0.52 × 0.26 × 0.14 mm

Data collection

Agilent Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.797, T_max = 0.939
11654 measured reflections
3782 independent reflections
2969 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.197
S = 1.13
3782 reflections
272 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.99 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C106—H106⋯O32	1.19 (7)	1.82 (7)	2.701 (7)	126 (5)

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812036112/gw2124sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036112/gw2124Isup2.hkl

checkCIF report

Comment top

In continuation of our research on the crystal structures of porphyrin complexes (Ben Moussa et al., 2011; Dhifet et al., 2010) we herein report the synthesis and crystal structure of the title compound. The x unit contains one half molecule of [Co^II(OEP)] and a whole molecule of nitrobenzaldehyde.

For our derivative, the average equatorial cobalt-pyrrole nitrogen atoms distance Co—N_p [1.972 (4) Å] is typical for a Co(II) octaethylporphyrin where the porphyrin core is nearly planar (Figure 1) (Scheidt & Tyrk, 1994) and similar to the value of 1.969 (2) Å found in the [Co^II(OEP)].TNFM (TNFM = (2, 4, 7-trinitrofluoreylidene)malontrile) (Smirnov et al., 1998) and 1.986 (14) Å in the [Co(F₂₈TPP)].2tol complex (Tol = toluene and F₂₈TPP = tetrakis(pentafluorophenyl)porphyrin) (Olmstead et al., 2003).

It is known that OEP metalloporphyrins can be dimerized as is the case of the [Fe^III(OEP)(NO)]⁺ complex (Ellison et al., 2000). For this species the distance between two adjacent porphyrinato mean plans is 3.41 Å which indicated a strong π-π interaction. This complex forms a tight cofacial π-π dimer in the solid state.The most interesting feature of (I), is the rather strong π-interaction between the cobalt metal of the [Co^II(OEP)] and the centroid of the phenyl rings of the nitrobenzaldehyde molecule (Figure 1) where the Co···Cg intermolecular distance is 3.508 Å (Cg is the centroid of the phenyl ring of the NBA molecule) and the angle between this distance and the perpendicular from the cobalt to the plane of the phenyl is 23.39 ° (Table 2). The cobalt atom is nearly perpendicular to the C101 atom (Figure 2). This structure present a striking resemblance with the one of the [Co^II(F₂₈TPP)].2tol complex (Olmstead et al., 2003) where the cobalt atom is centered roughly at the midpoint at the two adjacent carbons bonds in the toluene rings and the Co—C distances are 3.05 and 3.13 Å. It is noteworthy that the structure of (I) consists of columns that contain interleaved molecules of NBA and [Co^II(OEP)] which are stacked a long the crystallographic a axis (Figure 3).

A unique C—H···O (nitrobenzaldehyde) intramoleculair hydrogen bond of 1.82 (7) Å is found in the structure (Table 1).

Related literature top

For the synthesis, see: Scheidt & Tyrk (1994). For related structures, see: Olmstead et al. (2003); Smirnov et al. (1998); Ben Moussa et al. (2011); Dhifet et al. (2010); Ellison et al. (2000).

Experimental top

[Co^II(OEP)] (Scheidt & Tyrk, 1994) (100 mg, 0.17 mmol) and nitrobenzaldehyde (190 mg, 1.26 mmol) in 25 ml of chlorobenzene were stirred over night at room temperature. The color changes from red-pink to dark red and crystals of complex (I) were prepared by slow diffusion of hexanes into the chlorobenzene solution.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective drawings from the X-ray crystal structure determination of (I) that highlights π-interraction between the [Co^II(OEP)] complex and the 2-nitrobenzaldehyde molecule. H atoms have been omitted for clarity.
	Fig. 2. An ORTEP drawing of the structure of [Co^II(OEP)].NBA, with the atom-numbering scheme. Dislacement ellipsoids are drawing at 35% and H atoms have been omitted for clarity.Symmetry code: ('): -x, -y, -z.
	Fig. 3. Drawing showing the packing in lattice of [Co^II(OEP)].NBA, viewed down the b axis.

(2,3,7,8,12,13,17,18-Octaethylporphyrinato- κ⁴N)cobalt(II)–2-nitrobenzaldehyde (1/2) top

Crystal data top

[Co(C₃₆H₄₄N₄)]·2C₇H₅NO₃	F(000) = 942
M_r = 893.92	D_x = 1.375 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4505 reflections
a = 10.1952 (11) Å	θ = 3.1–28.3°
b = 21.2230 (17) Å	µ = 0.46 mm⁻¹
c = 10.1601 (10) Å	T = 180 K
β = 100.771 (9)°	Prism, purple
V = 2159.6 (4) Å³	0.52 × 0.26 × 0.14 mm
Z = 2

Data collection top

Agilent Xcalibur Sapphire1 long-nozzle diffractometer	3782 independent reflections
Radiation source: fine-focus sealed tube	2969 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 8.2632 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −25→22
T_min = 0.797, T_max = 0.939	l = −12→11
11654 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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.197	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0484P)² + 9.9571P] where P = (F_o² + 2F_c²)/3
3782 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.99 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Co(C₃₆H₄₄N₄)]·2C₇H₅NO₃	V = 2159.6 (4) Å³
M_r = 893.92	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.1952 (11) Å	µ = 0.46 mm⁻¹
b = 21.2230 (17) Å	T = 180 K
c = 10.1601 (10) Å	0.52 × 0.26 × 0.14 mm
β = 100.771 (9)°

Data collection top

Agilent Xcalibur Sapphire1 long-nozzle diffractometer	3782 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	2969 reflections with I > 2σ(I)
T_min = 0.797, T_max = 0.939	R_int = 0.038
11654 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	0 restraints
wR(F²) = 0.197	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	Δρ_max = 0.99 e Å⁻³
3782 reflections	Δρ_min = −0.45 e Å⁻³
272 parameters

Special details top

Experimental. Absorption correction: empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. CrysAlisPro (Agilent Technologies,2012)

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 > 2σ(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
Co	0.5000	0.0000	1.0000	0.0223 (3)
N1	0.3667 (4)	0.06811 (18)	0.9652 (4)	0.0219 (8)
N2	0.6428 (4)	0.06272 (18)	1.0557 (4)	0.0241 (9)
C1	0.5113 (5)	0.1592 (2)	1.0282 (4)	0.0284 (11)
H1	0.5142	0.2029	1.0362	0.034*
C2	0.8358 (5)	−0.0066 (2)	1.1098 (4)	0.0278 (11)
H2	0.9279	−0.0084	1.1384	0.033*
C11	0.2321 (5)	0.0628 (2)	0.9185 (4)	0.0249 (10)
C12	0.1692 (5)	0.1241 (2)	0.9020 (5)	0.0294 (11)
C13	0.2667 (5)	0.1669 (2)	0.9403 (5)	0.0298 (11)
C14	0.3887 (5)	0.1319 (2)	0.9805 (4)	0.0235 (10)
C21	0.6293 (5)	0.1270 (2)	1.0647 (4)	0.0237 (10)
C22	0.7556 (5)	0.1565 (2)	1.1157 (5)	0.0289 (11)
C23	0.8479 (5)	0.1099 (2)	1.1354 (5)	0.0294 (11)
C24	0.7768 (4)	0.0520 (2)	1.0987 (4)	0.0220 (10)
C121	0.0251 (5)	0.1352 (3)	0.8455 (5)	0.0366 (13)
H12A	−0.0004	0.1764	0.8734	0.044*
H12B	−0.0282	0.1039	0.8813	0.044*
C122	−0.0048 (6)	0.1315 (3)	0.6913 (5)	0.0425 (14)
H12C	0.0467	0.1628	0.6554	0.064*
H12D	−0.0981	0.1390	0.6591	0.064*
H12E	0.0185	0.0905	0.6633	0.064*
C131	0.2557 (5)	0.2373 (2)	0.9361 (5)	0.0356 (12)
H13A	0.3161	0.2549	1.0124	0.043*
H13B	0.1655	0.2494	0.9432	0.043*
C132	0.2888 (7)	0.2648 (3)	0.8080 (7)	0.0515 (16)
H13C	0.3767	0.2516	0.7987	0.077*
H13D	0.2857	0.3099	0.8118	0.077*
H13E	0.2250	0.2501	0.7325	0.077*
C221	0.7747 (5)	0.2255 (2)	1.1470 (5)	0.0346 (12)
H22A	0.7175	0.2497	1.0780	0.041*
H22B	0.8665	0.2369	1.1451	0.041*
C222	0.7430 (6)	0.2430 (3)	1.2831 (6)	0.0454 (15)
H22C	0.6508	0.2341	1.2838	0.068*
H22D	0.7597	0.2871	1.2994	0.068*
H22E	0.7984	0.2189	1.3517	0.068*
C231	0.9941 (5)	0.1149 (3)	1.1924 (5)	0.0351 (12)
H23A	1.0250	0.1567	1.1744	0.042*
H23B	1.0422	0.0847	1.1478	0.042*
C232	1.0261 (3)	0.10290 (19)	1.3431 (2)	0.0475 (15)
H23C	0.9777	0.1323	1.3878	0.071*
H23D	1.1201	0.1082	1.3752	0.071*
H23E	1.0005	0.0607	1.3612	0.071*
N3	0.4262 (3)	0.10463 (13)	0.6484 (2)	0.0731 (19)
O1	0.7932 (3)	0.01832 (13)	0.7585 (2)	0.0880 (18)
O31	0.3191 (3)	0.12778 (13)	0.6159 (2)	0.109 (2)
O32	0.5322 (3)	0.13821 (13)	0.6534 (2)	0.112 (2)
C100	0.4442 (2)	0.03814 (12)	0.6568 (2)	0.0412 (14)
C101	0.5620 (3)	0.00702 (11)	0.7012 (2)	0.0372 (12)
C102	0.5715 (3)	−0.05699 (11)	0.7001 (2)	0.0581 (19)
H102	0.6525	−0.0767	0.7326	0.070*
C103	0.4612 (7)	−0.0916 (3)	0.6509 (6)	0.0528 (16)
H103	0.4679	−0.1352	0.6466	0.063*
C104	0.3390 (6)	−0.0629 (3)	0.6070 (5)	0.0442 (15)
H104	0.2643	−0.0877	0.5766	0.053*
C105	0.3263 (7)	0.0006 (4)	0.6076 (6)	0.0558 (17)
H105	0.2441	0.0197	0.5772	0.067*
C106	0.6934 (6)	0.0416 (4)	0.7524 (6)	0.0517 (17)
H106	0.683 (7)	0.097 (3)	0.732 (6)	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.0218 (5)	0.0259 (5)	0.0186 (4)	−0.0027 (4)	0.0019 (3)	−0.0006 (4)
N1	0.020 (2)	0.029 (2)	0.0165 (18)	−0.0002 (16)	0.0020 (15)	−0.0001 (15)
N2	0.031 (2)	0.030 (2)	0.0122 (18)	−0.0023 (17)	0.0055 (16)	0.0010 (15)
C1	0.036 (3)	0.026 (2)	0.022 (2)	−0.004 (2)	0.002 (2)	0.0014 (19)
C2	0.024 (2)	0.040 (3)	0.019 (2)	−0.004 (2)	0.0026 (18)	0.000 (2)
C11	0.031 (3)	0.030 (3)	0.014 (2)	0.002 (2)	0.0063 (19)	0.0008 (18)
C12	0.031 (3)	0.036 (3)	0.023 (2)	0.008 (2)	0.009 (2)	0.002 (2)
C13	0.033 (3)	0.037 (3)	0.019 (2)	0.005 (2)	0.005 (2)	0.000 (2)
C14	0.022 (3)	0.030 (3)	0.019 (2)	0.0018 (19)	0.0042 (18)	−0.0004 (19)
C21	0.025 (3)	0.029 (3)	0.016 (2)	−0.004 (2)	0.0028 (19)	−0.0007 (18)
C22	0.031 (3)	0.035 (3)	0.021 (2)	−0.012 (2)	0.005 (2)	−0.001 (2)
C23	0.032 (3)	0.039 (3)	0.018 (2)	−0.012 (2)	0.007 (2)	−0.002 (2)
C24	0.018 (2)	0.032 (3)	0.015 (2)	−0.0056 (19)	0.0013 (18)	−0.0001 (18)
C121	0.031 (3)	0.044 (3)	0.035 (3)	0.012 (2)	0.006 (2)	−0.002 (2)
C122	0.039 (3)	0.053 (4)	0.032 (3)	0.007 (3)	−0.003 (2)	0.001 (3)
C131	0.031 (3)	0.036 (3)	0.039 (3)	0.010 (2)	0.005 (2)	−0.003 (2)
C132	0.057 (4)	0.038 (3)	0.061 (4)	0.005 (3)	0.013 (3)	0.011 (3)
C221	0.033 (3)	0.035 (3)	0.035 (3)	−0.017 (2)	0.003 (2)	−0.001 (2)
C222	0.050 (4)	0.042 (3)	0.044 (3)	−0.012 (3)	0.007 (3)	−0.012 (3)
C231	0.026 (3)	0.050 (3)	0.028 (3)	−0.017 (2)	0.002 (2)	−0.003 (2)
C232	0.031 (3)	0.078 (4)	0.029 (3)	−0.008 (3)	−0.005 (2)	−0.001 (3)
N3	0.088 (5)	0.068 (4)	0.067 (4)	0.020 (4)	0.023 (4)	0.003 (3)
O1	0.058 (4)	0.108 (5)	0.094 (4)	−0.016 (3)	0.005 (3)	−0.016 (4)
O31	0.099 (5)	0.085 (4)	0.138 (6)	0.051 (4)	0.005 (4)	0.016 (4)
O32	0.109 (6)	0.104 (5)	0.126 (6)	−0.037 (4)	0.033 (5)	−0.041 (4)
C100	0.052 (4)	0.050 (4)	0.025 (3)	0.008 (3)	0.017 (3)	0.008 (2)
C101	0.047 (3)	0.044 (3)	0.025 (3)	0.008 (3)	0.017 (2)	0.008 (2)
C102	0.088 (6)	0.049 (4)	0.045 (4)	−0.003 (4)	0.033 (4)	0.003 (3)
C103	0.052 (4)	0.069 (4)	0.043 (3)	−0.005 (3)	0.023 (3)	0.005 (3)
C104	0.043 (4)	0.062 (4)	0.029 (3)	−0.023 (3)	0.010 (3)	0.000 (3)
C105	0.060 (4)	0.080 (5)	0.031 (3)	0.001 (4)	0.017 (3)	0.005 (3)
C106	0.028 (3)	0.085 (5)	0.041 (3)	0.006 (3)	0.005 (3)	0.015 (3)

Geometric parameters (Å, º) top

Co—N1	1.970 (4)	C131—H13B	0.9700
Co—N1ⁱ	1.970 (4)	C132—H13C	0.9600
Co—N2	1.976 (4)	C132—H13D	0.9600
Co—N2ⁱ	1.976 (4)	C132—H13E	0.9600
N1—C11	1.370 (6)	C221—C222	1.524 (8)
N1—C14	1.376 (6)	C221—H22A	0.9700
N2—C24	1.373 (6)	C221—H22B	0.9700
N2—C21	1.376 (6)	C222—H22C	0.9600
C1—C21	1.373 (7)	C222—H22D	0.9600
C1—C14	1.381 (7)	C222—H22E	0.9600
C1—H1	0.9300	C231—C232	1.526 (5)
C2—C24	1.376 (7)	C231—H23A	0.9700
C2—C11ⁱ	1.383 (7)	C231—H23B	0.9700
C2—H2	0.9300	C232—H23C	0.9600
C11—C2ⁱ	1.383 (7)	C232—H23D	0.9600
C11—C12	1.445 (7)	C232—H23E	0.9600
C12—C13	1.350 (7)	N3—O31	1.1858
C12—C121	1.492 (7)	N3—O32	1.2882
C13—C14	1.441 (7)	N3—C100	1.4235
C13—C131	1.499 (7)	O1—C106	1.123 (7)
C21—C22	1.438 (7)	C100—C101	1.3708
C22—C23	1.353 (7)	C100—C105	1.451 (7)
C22—C221	1.503 (7)	C101—C102	1.3620
C23—C24	1.442 (7)	C101—C106	1.531 (7)
C23—C231	1.499 (7)	C102—C103	1.357 (7)
C121—C122	1.542 (7)	C102—H102	0.9300
C121—H12A	0.9700	C103—C104	1.383 (9)
C121—H12B	0.9700	C103—H103	0.9300
C122—H12C	0.9600	C104—C105	1.354 (9)
C122—H12D	0.9600	C104—H104	0.9300
C122—H12E	0.9600	C105—H105	0.9300
C131—C132	1.520 (8)	C106—H106	1.19 (7)
C131—H13A	0.9700

N1—Co—N1ⁱ	180.000 (1)	C13—C131—H13B	109.1
N1—Co—N2	90.21 (16)	C132—C131—H13B	109.1
N1ⁱ—Co—N2	89.79 (16)	H13A—C131—H13B	107.9
N1—Co—N2ⁱ	89.79 (16)	C131—C132—H13C	109.5
N1ⁱ—Co—N2ⁱ	90.21 (16)	C131—C132—H13D	109.5
N2—Co—N2ⁱ	180.00 (16)	H13C—C132—H13D	109.5
C11—N1—C14	104.5 (4)	C131—C132—H13E	109.5
C11—N1—Co	127.9 (3)	H13C—C132—H13E	109.5
C14—N1—Co	127.5 (3)	H13D—C132—H13E	109.5
C24—N2—C21	104.4 (4)	C22—C221—C222	112.9 (4)
C24—N2—Co	127.9 (3)	C22—C221—H22A	109.0
C21—N2—Co	127.6 (3)	C222—C221—H22A	109.0
C21—C1—C14	125.2 (5)	C22—C221—H22B	109.0
C21—C1—H1	117.4	C222—C221—H22B	109.0
C14—C1—H1	117.4	H22A—C221—H22B	107.8
C24—C2—C11ⁱ	124.6 (4)	C221—C222—H22C	109.5
C24—C2—H2	117.7	C221—C222—H22D	109.5
C11ⁱ—C2—H2	117.7	H22C—C222—H22D	109.5
N1—C11—C2ⁱ	124.9 (4)	C221—C222—H22E	109.5
N1—C11—C12	111.2 (4)	H22C—C222—H22E	109.5
C2ⁱ—C11—C12	123.9 (5)	H22D—C222—H22E	109.5
C13—C12—C11	106.6 (5)	C23—C231—C232	112.7 (4)
C13—C12—C121	128.6 (5)	C23—C231—H23A	109.0
C11—C12—C121	124.8 (5)	C232—C231—H23A	109.0
C12—C13—C14	106.5 (4)	C23—C231—H23B	109.0
C12—C13—C131	128.1 (5)	C232—C231—H23B	109.0
C14—C13—C131	125.3 (5)	H23A—C231—H23B	107.8
N1—C14—C1	124.8 (4)	C231—C232—H23C	109.5
N1—C14—C13	111.2 (4)	C231—C232—H23D	109.5
C1—C14—C13	124.0 (4)	H23C—C232—H23D	109.5
C1—C21—N2	124.6 (4)	C231—C232—H23E	109.5
C1—C21—C22	124.1 (4)	H23C—C232—H23E	109.5
N2—C21—C22	111.2 (4)	H23D—C232—H23E	109.5
C23—C22—C21	106.6 (4)	O31—N3—O32	120.2
C23—C22—C221	128.4 (5)	O31—N3—C100	122.0
C21—C22—C221	124.9 (5)	O32—N3—C100	116.6
C22—C23—C24	106.4 (4)	C101—C100—N3	126.4
C22—C23—C231	128.3 (5)	C101—C100—C105	117.9 (3)
C24—C23—C231	125.2 (5)	N3—C100—C105	115.7 (3)
N2—C24—C2	124.8 (4)	C102—C101—C100	122.5
N2—C24—C23	111.3 (4)	C102—C101—C106	115.0 (3)
C2—C24—C23	123.9 (4)	C100—C101—C106	122.5 (3)
C12—C121—C122	112.1 (4)	C103—C102—C101	119.2 (3)
C12—C121—H12A	109.2	C103—C102—H102	120.4
C122—C121—H12A	109.2	C101—C102—H102	120.4
C12—C121—H12B	109.2	C102—C103—C104	121.0 (6)
C122—C121—H12B	109.2	C102—C103—H103	119.5
H12A—C121—H12B	107.9	C104—C103—H103	119.5
C121—C122—H12C	109.5	C105—C104—C103	121.2 (6)
C121—C122—H12D	109.5	C105—C104—H104	119.4
H12C—C122—H12D	109.5	C103—C104—H104	119.4
C121—C122—H12E	109.5	C104—C105—C100	118.3 (6)
H12C—C122—H12E	109.5	C104—C105—H105	120.9
H12D—C122—H12E	109.5	C100—C105—H105	120.9
C13—C131—C132	112.3 (4)	O1—C106—C101	122.3 (7)
C13—C131—H13A	109.1	O1—C106—H106	120 (3)
C132—C131—H13A	109.1	C101—C106—H106	112 (3)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C106—H106···O32	1.19 (7)	1.82 (7)	2.701 (7)	126 (5)

Experimental details

Crystal data
Chemical formula	[Co(C₃₆H₄₄N₄)]·2C₇H₅NO₃
M_r	893.92
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	180
a, b, c (Å)	10.1952 (11), 21.2230 (17), 10.1601 (10)
β (°)	100.771 (9)
V (Å³)	2159.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.52 × 0.26 × 0.14

Data collection
Diffractometer	Agilent Xcalibur Sapphire1 long-nozzle diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.797, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	11654, 3782, 2969
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.197, 1.13
No. of reflections	3782
No. of parameters	272
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.99, −0.45

Computer programs: CrysAlis PRO (Agilent, 2012), SIR2004 (Burla et al., 2005), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C106—H106···O32	1.19 (7)	1.82 (7)	2.701 (7)	126 (5)

Interaction between the Co atom and the phenyl ring of the nitrobenzaldehyde. top

Cg1 is the centroid of the C100-C101-C102-C103-C104-C105 phenyl ring. Symmetry codes: (i) 1/2-X, -1/2+Y, 1-Z ; (ii) -1/2+X, 1/2-Y, Z

	Cg···Co (Å)	Co-Perp (Å)	Beta (°)
Co···Cg1ⁱ	3.508	-3.219	23.39
Co···Cg1ⁱⁱ	3.508	-3.219	23.39

Acknowledgements

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

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