Tetra­kis(μ-2-phenyl­acetato-κ2O:O′)bis­{[4-(di­methyl­amino)­pyridine-κN1]cobalt(II)}

Benslimane, M.; Redjel, Y.K.; Dénès, G.; Merazig, H.

doi:10.1107/S1600536813023258

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Pages m517-m518

doi:10.1107/S1600536813023258

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Tetrakis(μ-2-phenylacetato-κ²O:O′)bis{[4-(dimethylamino)pyridine-κN¹]cobalt(II)}

Meriem Benslimane,^a ^* Yasmine Kheira Redjel,^a Georges Dénès ^b and Hocine Merazig ^a

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, Faculté des Sciences Exactes, Département de Chimie, Université de Constantine 1, 25000 Constantine, Algeria, and ^bDepartment of Chemistry and Biochemistry, Concordia University, Montréal, Canada
^*Correspondence e-mail: b_meriem80@yahoo.fr

(Received 5 August 2013; accepted 19 August 2013; online 23 August 2013)

The title compound, [Co₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂], crystallizes as a centrosymmetric dimer containing two Co^II atoms bridged by four bidentate phenylacetate ligands in syn–syn bridging modes. Each Co^II atom is five-coordinated by four O atoms from four different carboxylate ligands and the ring N atom of a 4-(dimethylamino)pyridine unit, generating a distorted square-pyramidal geometry in which the four O atoms form the basal plane and the N atom occupies the axial position. In the crystal, C—H⋯O interactions link the dinuclear complex molecules into a three-dimensional network.

Related literature

For properties of the 4-(dimethylamino)pyridine ligand as a homogeneous catalyst, see: Satgé et al. (2004 ). For transition metal complexes of 4-(dimethylamino)pyridine which exhibit luminescence properties, see: Araki et al. (2005 ). For biological and magnetic properties of carboxylic acid complexes of cobalt(II), see: Cotton et al. (1999 ). For related centrosymmetric dinuclear cobalt(II) complexes bridged by carboxylates, see: Cui et al. (1999 ); Catterick & Thornton (1977 ).

Experimental

Crystal data

[Co₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂]
M_r = 902.74
Triclinic, $[P \overline 1]$
a = 8.107 (5) Å
b = 11.043 (5) Å
c = 12.573 (5) Å
α = 99.766 (5)°
β = 101.878 (5)°
γ = 105.335 (5)°
V = 1031.9 (9) Å³
Z = 1
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 150 K
0.15 × 0.10 × 0.01 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.902, T_max = 0.991
9238 measured reflections
3645 independent reflections
3352 reflections with I > 2σ(I))
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.060
S = 1.05
3645 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.25 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
C6—H6A⋯O2ⁱ	0.96	2.53	3.337 (3)	142
C23—H23⋯O3ⁱⁱ	0.93	2.58	3.469 (3)	159
Symmetry codes: (i) x, y, z+1; (ii) -x+2, -y, -z.

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813023258/lr2113sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813023258/lr2113Isup2.hkl

checkCIF report

Comment top

The N-heteroaromatic ligand 4-(dimethylamino)pyridine (DMAP) finds use as a homogeneous catalyst in cellulose acylation in the synthesis of biodegradable plastics (Satgé et al., 2004). DMAP is also known to form transition metal complexes which exhibit luminescence properties (Araki et al., 2005). Our interest in cobalt(II) carboxylates with DMAP evolves from their catalytic activity. Moreover, carboxylic acid complexes of cobalt(II) have properties of special interest in the fields of biology and magnetism (Cotton et al., 1999). The coordination chemistry of centrosymmetric dinuclear Co²⁺ complexes bridged by carboxylates has been investigated (Cui et al., 1999, Catterick et al., 1977). In order to explore further the coordination behaviour of the Co²⁺ ion, the title complex, incorporating phenylacetate and DMAP as co-ligand has been prepared and its crystal structure is reported here.

The title molecule is a centrosymmetric dimer with four bidentate phenylacetate groups as bridging ligands between two Co^II centres, to each of which a DMAP group is also coordinated, as shown in Fig. 1. The coordination geometry about each Co atom is distorted square pyramidal, with four O atoms from four different carboxylate ligands forming the basal plane and a pyridine N atom occupying the axial position, where the most distorted angle is 101.39 (5)° for O2ⁱ—Co—N2 [symmetry code: (i) -x + 1,-y,-z]. The interatomic distances of Co—O [2.0224 (12)–2.0628 (16) Å], Co—N2 [2.0460 (16) Å] and Co···Co [2.8019 (12) Å] agree well with the related values recorded for the structures of the analogous pivalate (Cui et al., 1999) and benzoate (Catterick et al., 1977). The Co(II) atom is 0.2286 (2) Å from the mean plane formed by the four equatorial O atoms. On the other hand, the coordinated N2 atom also lies in the same direction, at a distance of 2.2643 (13) Å from the plane. The dihedral angles between the mean planes through the C10—C15 and C18—C23 benzene rings and the DMPA plane are 7.46 (9)° and 72.08 (9)°, respectively. The dihedral angle between the planes trough Co1/O3/O4/C16/Co1ⁱ/O3ⁱ/O4ⁱ/C16ⁱ and Co1/O1/O2/C8/Co1ⁱ/O1ⁱ/O2ⁱ/C8ⁱ [symmetry code:(i) 1 - x, -y, -z] is 87.22 (4)°, which is close to the ideal value of 90°. Nonclassical C—H···O hydrogen bonds (Table 1) occur in the structure, which link adjacent complex molecule into a three-dimensional network , Fig. 2 and Fig. 3.

Related literature top

For properties of the 4-(dimethylamino)pyridine ligand as a homogeneous catalyst, see: Satgé et al. (2004). For transition metal complexes of 4-(dimethylamino)pyridine which exhibit luminescence properties, see: Araki et al. (2005). For biological and magnetic properties of carboxylic acid complexes of cobalt(II), see: Cotton et al. (1999). For related centrosymmetric dinuclear cobalt(II) complexes bridged by carboxylates, see: Cui et al. (1999); Catterick & Thornton (1977).

Experimental top

CoCl_2.2H₂O (0.116 g,1 mmol) was dissolved in methanol (10 ml). To this solution, phenyacetic acid (C₆H₅CH₂COOH; 0.136 g, 1 mmol) was added and the mixture was stirred for ca 10 min to obtain a bleu solution. 4-(Dimethylamino)pyridine (0.122 g, 1 mmol) was added and the mixture was stirred for an additional 2 h. Single crystals suitable for X-ray diffraction were obtained from a methanol solution of the title complex by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SIR92 (Altomare et al., 1993); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Symmetry code, (i):1 - x, -y, -z.
	Fig. 2. The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines. Symmetry code, (ii): x, y, 1 + z.
	Fig. 3. The crystal packing of the title compound, viewed along the a axis. Hydrogen bonds are shown as dashed lines.Symmetry code, (iii):2 - x, -y, -z.

Tetrakis(µ-2-phenylacetato-κ²O:O')bis{[4-(dimethylamino)pyridine-κN¹]cobalt(II)} top

Crystal data top

[Co₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂]	Z = 1
M_r = 902.74	F(000) = 470
Triclinic, P1	D_x = 1.453 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.107 (5) Å	Cell parameters from 4872 reflections
b = 11.043 (5) Å	θ = 2.3–25°
c = 12.573 (5) Å	µ = 0.86 mm⁻¹
α = 99.766 (5)°	T = 150 K
β = 101.878 (5)°	Box, blue
γ = 105.335 (5)°	0.15 × 0.1 × 0.01 mm
V = 1031.9 (9) Å³

Data collection top

Bruker APEXII CCD diffractometer	3645 independent reflections
Radiation source: fine-focus sealed tube	3352 reflections with I > 2σ(I))
Graphite monochromator	R_int = 0.019
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −9→9
T_min = 0.902, T_max = 0.991	k = −13→13
9238 measured reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0206P)² + 0.6871P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.060	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.25 e Å⁻³
3645 reflections	Δρ_min = −0.24 e Å⁻³
271 parameters

Crystal data top

[Co₂(C₈H₇O₂)₄(C₇H₁₀N₂)₂]	γ = 105.335 (5)°
M_r = 902.74	V = 1031.9 (9) Å³
Triclinic, P1	Z = 1
a = 8.107 (5) Å	Mo Kα radiation
b = 11.043 (5) Å	µ = 0.86 mm⁻¹
c = 12.573 (5) Å	T = 150 K
α = 99.766 (5)°	0.15 × 0.1 × 0.01 mm
β = 101.878 (5)°

Data collection top

Bruker APEXII CCD diffractometer	3645 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	3352 reflections with I > 2σ(I))
T_min = 0.902, T_max = 0.991	R_int = 0.019
9238 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.05	Δρ_max = 0.25 e Å⁻³
3645 reflections	Δρ_min = −0.24 e Å⁻³
271 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	0.56888 (3)	0.01135 (2)	0.114253 (18)	0.01603 (8)
O1	0.70384 (17)	0.18802 (11)	0.09742 (10)	0.0256 (3)
O3	0.75242 (16)	−0.06983 (12)	0.07678 (10)	0.0241 (3)
O2	0.59969 (17)	0.17191 (12)	−0.08452 (10)	0.0248 (3)
O4	0.64516 (17)	−0.08060 (13)	−0.10383 (10)	0.0277 (3)
N1	0.7414 (2)	0.15583 (15)	0.63408 (12)	0.0259 (3)
N2	0.64381 (19)	0.06270 (13)	0.28539 (11)	0.0178 (3)
C10	0.7997 (2)	0.46694 (16)	0.12315 (14)	0.0192 (4)
C3	0.7158 (2)	−0.00546 (16)	0.34964 (14)	0.0197 (4)
H3	0.7415	−0.0764	0.3139	0.024*
C11	0.7164 (3)	0.55861 (17)	0.10444 (16)	0.0256 (4)
H11	0.6661	0.5599	0.0313	0.031*
C1	0.7158 (2)	0.12779 (17)	0.52207 (14)	0.0195 (4)
C18	0.8183 (2)	−0.25048 (16)	−0.17600 (14)	0.0181 (4)
C13	0.7818 (3)	0.64805 (18)	0.30092 (16)	0.0302 (4)
H13	0.7766	0.7085	0.3603	0.036*
C17	0.8651 (2)	−0.18185 (17)	−0.05447 (14)	0.0205 (4)
H17A	0.9855	−0.1236	−0.0338	0.025*
H17B	0.8624	−0.2454	−0.0097	0.025*
C23	0.9124 (2)	−0.20046 (17)	−0.24739 (15)	0.0222 (4)
H23	1.0052	−0.1233	−0.2202	0.027*
C2	0.7540 (2)	0.02208 (17)	0.46401 (14)	0.0216 (4)
H2	0.8051	−0.0289	0.5033	0.026*
C19	0.6790 (2)	−0.36483 (17)	−0.21909 (15)	0.0245 (4)
H19	0.6135	−0.399	−0.1724	0.029*
C9	0.8102 (3)	0.37074 (16)	0.02588 (15)	0.0236 (4)
H9A	0.9324	0.3717	0.0358	0.028*
H9B	0.7754	0.3982	−0.0424	0.028*
C14	0.8655 (3)	0.55707 (19)	0.32101 (16)	0.0311 (4)
H14	0.9163	0.5563	0.3942	0.037*
C4	0.6139 (2)	0.16674 (17)	0.34079 (14)	0.0228 (4)
H4	0.568	0.2179	0.299	0.027*
C15	0.8741 (2)	0.46726 (18)	0.23306 (15)	0.0267 (4)
H15	0.9303	0.4063	0.2476	0.032*
C5	0.6466 (2)	0.20198 (17)	0.45452 (15)	0.0246 (4)
H5	0.6231	0.2753	0.4876	0.029*
C22	0.8696 (3)	−0.26441 (19)	−0.35918 (15)	0.0274 (4)
H22	0.934	−0.23	−0.4062	0.033*
C16	0.7435 (2)	−0.10501 (16)	−0.02568 (14)	0.0180 (4)
C20	0.6361 (3)	−0.42857 (18)	−0.33028 (16)	0.0291 (4)
H20	0.5425	−0.5053	−0.3579	0.035*
C12	0.7061 (3)	0.64871 (18)	0.19226 (17)	0.0322 (5)
H12	0.6487	0.7091	0.178	0.039*
C8	0.6943 (2)	0.23260 (16)	0.01192 (14)	0.0186 (4)
C7	0.8177 (3)	0.0810 (2)	0.70317 (16)	0.0328 (5)
H7A	0.8256	0.1152	0.7802	0.049*
H7B	0.9341	0.0858	0.6946	0.049*
H7C	0.7438	−0.0076	0.6804	0.049*
C21	0.7319 (3)	−0.37875 (19)	−0.40079 (15)	0.0292 (4)
H21	0.7037	−0.4219	−0.4756	0.035*
C6	0.6940 (3)	0.2633 (2)	0.68950 (16)	0.0353 (5)
H6A	0.721	0.2693	0.7686	0.053*
H6B	0.5694	0.2493	0.6611	0.053*
H6C	0.7601	0.3421	0.6754	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02007 (13)	0.01633 (13)	0.01213 (12)	0.00678 (9)	0.00475 (9)	0.00211 (9)
O1	0.0329 (7)	0.0188 (6)	0.0213 (7)	0.0030 (5)	0.0044 (6)	0.0066 (5)
O3	0.0262 (7)	0.0258 (7)	0.0218 (7)	0.0115 (5)	0.0093 (5)	0.0010 (5)
O2	0.0293 (7)	0.0213 (6)	0.0190 (6)	0.0020 (5)	0.0056 (6)	0.0022 (5)
O4	0.0278 (7)	0.0354 (8)	0.0261 (7)	0.0202 (6)	0.0074 (6)	0.0073 (6)
N1	0.0366 (9)	0.0275 (8)	0.0140 (7)	0.0111 (7)	0.0067 (7)	0.0044 (6)
N2	0.0212 (7)	0.0178 (7)	0.0146 (7)	0.0072 (6)	0.0048 (6)	0.0029 (6)
C10	0.0187 (9)	0.0152 (8)	0.0212 (9)	0.0001 (7)	0.0075 (7)	0.0034 (7)
C3	0.0234 (9)	0.0163 (8)	0.0209 (9)	0.0086 (7)	0.0065 (7)	0.0030 (7)
C11	0.0319 (10)	0.0201 (9)	0.0238 (9)	0.0060 (8)	0.0054 (8)	0.0080 (8)
C1	0.0196 (9)	0.0213 (9)	0.0160 (8)	0.0035 (7)	0.0054 (7)	0.0040 (7)
C18	0.0181 (8)	0.0187 (9)	0.0209 (9)	0.0111 (7)	0.0059 (7)	0.0041 (7)
C13	0.0418 (12)	0.0204 (9)	0.0283 (10)	0.0084 (9)	0.0156 (9)	0.0003 (8)
C17	0.0190 (9)	0.0212 (9)	0.0213 (9)	0.0081 (7)	0.0052 (7)	0.0023 (7)
C23	0.0182 (9)	0.0231 (9)	0.0252 (9)	0.0068 (7)	0.0047 (7)	0.0066 (8)
C2	0.0265 (10)	0.0217 (9)	0.0196 (9)	0.0109 (8)	0.0055 (7)	0.0085 (7)
C19	0.0248 (10)	0.0238 (9)	0.0256 (10)	0.0062 (8)	0.0090 (8)	0.0068 (8)
C9	0.0301 (10)	0.0185 (9)	0.0221 (9)	0.0041 (8)	0.0114 (8)	0.0047 (7)
C14	0.0390 (12)	0.0316 (11)	0.0200 (9)	0.0107 (9)	0.0046 (9)	0.0034 (8)
C4	0.0330 (10)	0.0216 (9)	0.0180 (9)	0.0151 (8)	0.0061 (8)	0.0057 (7)
C15	0.0289 (10)	0.0255 (10)	0.0270 (10)	0.0132 (8)	0.0043 (8)	0.0059 (8)
C5	0.0346 (11)	0.0213 (9)	0.0199 (9)	0.0144 (8)	0.0069 (8)	0.0016 (7)
C22	0.0283 (10)	0.0366 (11)	0.0224 (10)	0.0131 (9)	0.0097 (8)	0.0117 (8)
C16	0.0165 (8)	0.0139 (8)	0.0234 (9)	0.0029 (7)	0.0081 (7)	0.0030 (7)
C20	0.0277 (10)	0.0222 (9)	0.0285 (10)	0.0035 (8)	0.0000 (8)	−0.0017 (8)
C12	0.0420 (12)	0.0205 (10)	0.0393 (12)	0.0154 (9)	0.0124 (10)	0.0098 (9)
C8	0.0189 (9)	0.0179 (9)	0.0208 (9)	0.0070 (7)	0.0089 (7)	0.0026 (7)
C7	0.0410 (12)	0.0410 (12)	0.0191 (10)	0.0146 (10)	0.0071 (9)	0.0124 (9)
C21	0.0347 (11)	0.0350 (11)	0.0169 (9)	0.0160 (9)	0.0022 (8)	0.0006 (8)
C6	0.0547 (14)	0.0327 (11)	0.0196 (10)	0.0140 (10)	0.0148 (9)	0.0022 (8)

Geometric parameters (Å, º) top

Co1—O3	2.0224 (15)	C13—H13	0.93
Co1—O1	2.0382 (14)	C17—C16	1.519 (2)
Co1—O2ⁱ	2.0429 (15)	C17—H17A	0.97
Co1—N2	2.0460 (16)	C17—H17B	0.97
Co1—O4ⁱ	2.0628 (16)	C23—C22	1.388 (3)
Co1—Co1ⁱ	2.8020 (12)	C23—H23	0.93
O1—C8	1.253 (2)	C2—H2	0.93
O3—C16	1.262 (2)	C19—C20	1.381 (3)
O2—C8	1.256 (2)	C19—H19	0.93
O2—Co1ⁱ	2.0429 (15)	C9—C8	1.524 (2)
O4—C16	1.247 (2)	C9—H9A	0.97
O4—Co1ⁱ	2.0628 (16)	C9—H9B	0.97
N1—C1	1.349 (2)	C14—C15	1.381 (3)
N1—C6	1.453 (2)	C14—H14	0.93
N1—C7	1.454 (2)	C4—C5	1.366 (2)
N2—C3	1.343 (2)	C4—H4	0.93
N2—C4	1.345 (2)	C15—H15	0.93
C10—C11	1.383 (3)	C5—H5	0.93
C10—C15	1.388 (3)	C22—C21	1.380 (3)
C10—C9	1.510 (2)	C22—H22	0.93
C3—C2	1.369 (2)	C20—C21	1.384 (3)
C3—H3	0.93	C20—H20	0.93
C11—C12	1.387 (3)	C12—H12	0.93
C11—H11	0.93	C7—H7A	0.96
C1—C2	1.410 (2)	C7—H7B	0.96
C1—C5	1.411 (2)	C7—H7C	0.96
C18—C23	1.386 (2)	C21—H21	0.93
C18—C19	1.388 (3)	C6—H6A	0.96
C18—C17	1.506 (2)	C6—H6B	0.96
C13—C12	1.380 (3)	C6—H6C	0.96
C13—C14	1.382 (3)

O3—Co1—O1	93.27 (6)	C3—C2—H2	120.1
O3—Co1—O2ⁱ	87.33 (6)	C1—C2—H2	120.1
O1—Co1—O2ⁱ	163.77 (5)	C20—C19—C18	120.91 (17)
O3—Co1—N2	102.92 (6)	C20—C19—H19	119.5
O1—Co1—N2	94.29 (5)	C18—C19—H19	119.5
O2ⁱ—Co1—N2	101.39 (5)	C10—C9—C8	114.21 (14)
O3—Co1—O4ⁱ	163.73 (5)	C10—C9—H9A	108.7
O1—Co1—O4ⁱ	85.64 (6)	C8—C9—H9A	108.7
O2ⁱ—Co1—O4ⁱ	89.27 (7)	C10—C9—H9B	108.7
N2—Co1—O4ⁱ	93.35 (5)	C8—C9—H9B	108.7
O3—Co1—Co1ⁱ	89.34 (4)	H9A—C9—H9B	107.6
O1—Co1—Co1ⁱ	79.04 (4)	C15—C14—C13	120.40 (18)
O2ⁱ—Co1—Co1ⁱ	84.75 (4)	C15—C14—H14	119.8
N2—Co1—Co1ⁱ	166.44 (4)	C13—C14—H14	119.8
O4ⁱ—Co1—Co1ⁱ	74.50 (4)	N2—C4—C5	124.16 (16)
C8—O1—Co1	129.17 (11)	N2—C4—H4	117.9
C16—O3—Co1	116.62 (11)	C5—C4—H4	117.9
C8—O2—Co1ⁱ	121.65 (11)	C14—C15—C10	120.78 (17)
C16—O4—Co1ⁱ	133.30 (12)	C14—C15—H15	119.6
C1—N1—C6	120.56 (16)	C10—C15—H15	119.6
C1—N1—C7	121.55 (16)	C4—C5—C1	120.39 (16)
C6—N1—C7	117.89 (15)	C4—C5—H5	119.8
C3—N2—C4	115.61 (15)	C1—C5—H5	119.8
C3—N2—Co1	124.00 (11)	C21—C22—C23	120.28 (18)
C4—N2—Co1	120.31 (11)	C21—C22—H22	119.9
C11—C10—C15	118.12 (17)	C23—C22—H22	119.9
C11—C10—C9	120.35 (16)	O4—C16—O3	125.35 (16)
C15—C10—C9	121.52 (16)	O4—C16—C17	118.12 (15)
N2—C3—C2	124.67 (16)	O3—C16—C17	116.52 (15)
N2—C3—H3	117.7	C19—C20—C21	120.23 (18)
C2—C3—H3	117.7	C19—C20—H20	119.9
C10—C11—C12	121.52 (18)	C21—C20—H20	119.9
C10—C11—H11	119.2	C13—C12—C11	119.52 (18)
C12—C11—H11	119.2	C13—C12—H12	120.2
N1—C1—C2	122.71 (16)	C11—C12—H12	120.2
N1—C1—C5	122.05 (16)	O1—C8—O2	125.30 (16)
C2—C1—C5	115.23 (16)	O1—C8—C9	117.19 (15)
C23—C18—C19	118.53 (16)	O2—C8—C9	117.50 (15)
C23—C18—C17	120.81 (16)	N1—C7—H7A	109.5
C19—C18—C17	120.66 (16)	N1—C7—H7B	109.5
C12—C13—C14	119.66 (18)	H7A—C7—H7B	109.5
C12—C13—H13	120.2	N1—C7—H7C	109.5
C14—C13—H13	120.2	H7A—C7—H7C	109.5
C18—C17—C16	114.52 (14)	H7B—C7—H7C	109.5
C18—C17—H17A	108.6	C22—C21—C20	119.40 (17)
C16—C17—H17A	108.6	C22—C21—H21	120.3
C18—C17—H17B	108.6	C20—C21—H21	120.3
C16—C17—H17B	108.6	N1—C6—H6A	109.5
H17A—C17—H17B	107.6	N1—C6—H6B	109.5
C18—C23—C22	120.65 (17)	H6A—C6—H6B	109.5
C18—C23—H23	119.7	N1—C6—H6C	109.5
C22—C23—H23	119.7	H6A—C6—H6C	109.5
C3—C2—C1	119.85 (16)	H6B—C6—H6C	109.5

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2ⁱⁱ	0.96	2.53	3.337 (3)	142
C23—H23···O3ⁱⁱⁱ	0.93	2.58	3.469 (3)	159

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O2ⁱ	0.9600	2.5300	3.337 (3)	142.00
C23—H23···O3ⁱⁱ	0.9300	2.5800	3.469 (3)	159.00

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

Acknowledgements

This work was supported by the University of Constantine 1.

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