(5,10,15,20-Tetra­phenyl­porphyrinato-κ4N)zinc–18-crown-6 (1/1)

Denden, Z.; Bel Haj Hassen, L.; Belkhiria, M.S.; Daran, J.-C.; Nasri, H.

doi:10.1107/S1600536813018126

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages m444-m445

doi:10.1107/S1600536813018126

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(5,10,15,20-Tetraphenylporphyrinato-κ⁴N)zinc–18-crown-6 (1/1)

Zouhour Denden,^a Leila Bel Haj Hassen,^a Mohamed Salah Belkhiria,^a Jean-Claude Daran ^b and Habib Nasri ^a ^*

^aLaboratoire de Physico-chimie des Matériaux, Université de Monastir, Faculté des Sciences 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: hnasri1@gmail.com

(Received 25 June 2013; accepted 1 July 2013; online 10 July 2013)

In the title compound, [Zn(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆, the Zn^II ion lies on an inversion center and the asymmetric unit contains one half of a Zn(TPP) complex (TPP = 5,10,15,20-tetraphenylporphyrin dianion) and one half of a centrosymmetric 18-crown-6 molecule. The Zn(TPP) complex exhibits a nearly planar conformation of the porphyrin core [maximum deviation = 0.106 (2) Å] with an average Zn—N distance of 2.047 (2) Å. The title compound is considered as a one-dimensional polymer along [010], in which the Zn(TPP) moiety is linked to the closest O atoms of two symmetry-related 18-crown-6 molecules with a Zn—O distance of 2.582 (1) Å, completing a distorted octahedral coordination environment of the metal ion. The chains are mainly sustained by weak C—H⋯π interactions. An ethylene group of the 18-crown-6 molecule is disordered over three sites with occupancies of 0.50, 0.25 and 0.25.

Related literature

For related structures, see: Cheng & Scheidt (1995 ); Diskin-Posner et al. (1999 ); Ezzayani et al. (2013 ); Kojima et al. (2009 ); Kumar et al. (1997 ); Mansour et al. (2010 ); Ricard et al. (2001 ); Suijkerbuijk et al. (2007 ); Toumi et al. (2013 ). For the SIMU/ISOR restraints used in the refinement, see: McArdle (1995 ). For a description of the Cambridge Strcutural Database, see: Allen (2002 ). For the synthesis, see: Oberda et al. (2011 ).

Experimental

Crystal data

[Zn(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆
M_r = 942.39
Triclinic, $[P \overline 1]$
a = 10.2170 (3) Å
b = 11.1190 (4) Å
c = 11.8243 (3) Å
α = 104.384 (3)°
β = 105.912 (3)°
γ = 108.096 (3)°
V = 1143.23 (8) Å³
Z = 1
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 180 K
0.48 × 0.45 × 0.33 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.918, T_max = 1.000
22963 measured reflections
4503 independent reflections
3774 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.108
S = 1.07
4503 reflections
310 parameters
30 restraints
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg3 are the centroids of the N1/C1–C4, N2/C6–C9 and C11–C16 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯Cg1ⁱ	0.93	2.98	3.824 (2)	152
C20—H20⋯Cg3ⁱⁱ	0.93	2.84	3.746 (2)	164
C24—H24A⋯Cg2	0.97	2.73	3.686 (3)	167
Symmetry codes: (i) -x+2, -y, -z+2; (ii) -x+3, -y, -z+2.

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; 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

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813018126/hy2633sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018126/hy2633Isup2.hkl

checkCIF report

Comment top

In continuation of our research on the crystal structures of metalloporphyrins resulting from the interactions of porphyrin complexes type [M^II(TPP)] (TPP is a dianion of 5,10,15,20-tetraphenylporphyrin and M is a metal) with 18-crown-6 (18-C-6), we recently reported the molecular structures of three metalloporphyrines involving 18-C-6. The first one is (tetraphenylporphyrinato)cobalt(II)-18-C-6 with the formula [Co^II(TPP)].(18-C-6) (Mansour et al., 2010) and the second structure concerns the coordination complex diaqua(tetraphenylporphyrinato)magnesium(II)-18-C-6 with the formula [Mg(TPP)(H₂O)₂].(18-C-6) (Ezzayani et al., 2013). The third metalloporphyrin-18-C-6 derivative is the [Cd(TPP)(H₂O)].(18-C-6) species (Toumi et al., 2013). By the other hand a search of Cambridge Structural Database (CSD, version 5.34; Allen, 2002) reveals only two zinc–porphyrin structures involving 18-C-6 molecules, with the same formula [Zn(TPP)(H₂O)].(18-C-6) [CSD refcodes: ZOLXUT (Cheng & Scheidt, 1995), and XIYGAN (Diskin-Posner et al., 1999)]. The average equatorial Zn—N distance equal to 2.071 (1) Å lies in the range [2.035 (2)–2.081 (5) Å] of related porphyrin species, i.e. [Zn(TPP)(H₂O)₂] (Suijkerbuijk et al., 2007) and [Zn(TPP)(4-pyridinamine)] (Kojima et al., 2009). In order to gain more insight into the interactions of 18-C-6 with zinc–porphyrin complexes, we report herein the synthesis and crystal structure of the title compound, [Zn(TPP)].(18-C-6).

In the title compound, two symmetry-related 18-C-6 molecules are weakly bonded to the Zn^II ion via the O1 atom with a distance of 2.582 (1) Å (Fig. 1). It is noteworthy that the Zn—O bond length values for metalloporphyrin type [Zn(porph)(OR)] (R = an alkyl or aryl group) are within the large range [2.147 (5)–2.708 (2) Å] [CSD refcodes: BOQPIG (Ricard et al., 2001), and GETGER (Kumar et al., 1997)]. Consequently, we can consider that for the title compound, the 18-C-6 molecule is weakly coordinated to the central metal. We noticed the striking resemblance of the title compound and the related compound [Co^II(TPP)].(18-C-6): (i) the two structures are isomorphs and they have the space group P1 and the cell parameters are very close; (ii) the Co—O(18-C-6) distance [2.533 (2) Å] is quite close to the value of the title compound. The porphyrin core presents a nearly planar conformation with maximum and minimum deviations from the C₂₀N₄ least-squares plane of 0.106 (2) and 0.000 (2) Å for C10 and C3 atoms, respectively, while the Zn^II ion is at 0.05 (1) Å from the plane.

The crystal structure of the title compound resembles to one-dimensional coordination polymer, where each [Zn(TPP)] moiety is linked to two symmetry-related 18-C-6 molecules through the O1 and O1ⁱ atoms (symmetry code: (i) 2-x, -y, 1-z) (Fig. 2). These chains are mainly sustained by weak C—H···π interactions (Table 1).

Related literature top

For related structures, see: Cheng & Scheidt (1995); Diskin-Posner et al. (1999); Ezzayani et al. (2013); Kojima et al. (2009); Kumar et al. (1997); Mansour et al. (2010); Ricard et al. (2001); Suijkerbuijk et al. (2007); Toumi et al. (2013). For the SIMU/ISOR restraints used in the refinement, see: McArdle (1995). For a description of the Cambridge Strcutural Database, see: Allen (2002). For the synthesis, see: Oberda et al. (2011).

Experimental top

The reaction of the Zn(TPP) complex (15 mg, 0.022 mmol) (Oberda et al., 2011) with an excess of 18-C-6 (80 mg, 0.302 mmol) in 15 ml of chlorobenzene at room temperature yielded after two hours a red-purple solution. Crystals of the title compound were obtained by diffusion of hexane into the chlorobenzene solution.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell refinement: CrysAlis RED (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); 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. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 40% probability level. H atoms have been omitted for clarity. [Symmtry codes: (i) -x+2, -y, -z+1; (ii) -x+2, -y-1, -z+1.]
	Fig. 2. A drawing showing the one-dimensional structure of the title compound. H atoms have been omitted for clarity. [Symmetry code: (i) 2-x, -y, 1-z.]

(5,10,15,20-Tetraphenylporphyrinato-κ⁴N)zinc–18-crown-6 (1/1) top

Crystal data top

[Zn(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆	Z = 1
M_r = 942.39	F(000) = 494
Triclinic, P1	D_x = 1.369 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.2170 (3) Å	Cell parameters from 13909 reflections
b = 11.1190 (4) Å	θ = 3.3–29.1°
c = 11.8243 (3) Å	µ = 0.60 mm⁻¹
α = 104.384 (3)°	T = 180 K
β = 105.912 (3)°	Block, violet
γ = 108.096 (3)°	0.48 × 0.45 × 0.33 mm
V = 1143.23 (8) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer	4503 independent reflections
Radiation source: fine-focus sealed tube	3774 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 16.1978 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −13→13
T_min = 0.918, T_max = 1.000	l = −14→14
22963 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0591P)² + 0.5621P] where P = (F_o² + 2F_c²)/3
4503 reflections	(Δ/σ)_max < 0.001
310 parameters	Δρ_max = 0.95 e Å⁻³
30 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Zn(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆	γ = 108.096 (3)°
M_r = 942.39	V = 1143.23 (8) Å³
Triclinic, P1	Z = 1
a = 10.2170 (3) Å	Mo Kα radiation
b = 11.1190 (4) Å	µ = 0.60 mm⁻¹
c = 11.8243 (3) Å	T = 180 K
α = 104.384 (3)°	0.48 × 0.45 × 0.33 mm
β = 105.912 (3)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	4503 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	3774 reflections with I > 2σ(I)
T_min = 0.918, T_max = 1.000	R_int = 0.023
22963 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	30 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.07	Δρ_max = 0.95 e Å⁻³
4503 reflections	Δρ_min = −0.67 e Å⁻³
310 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 > 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	Occ. (<1)
Zn	1.0000	0.0000	0.5000	0.03274 (14)
N1	1.11054 (18)	−0.01373 (18)	0.66650 (15)	0.0230 (4)
N2	0.79951 (17)	−0.10495 (17)	0.50470 (15)	0.0213 (3)
C1	1.2617 (2)	0.0346 (2)	0.72913 (18)	0.0219 (4)
C2	1.2919 (2)	−0.0065 (2)	0.83665 (19)	0.0248 (4)
H2	1.3854	0.0140	0.8949	0.030*
C3	1.1598 (2)	−0.0801 (2)	0.83723 (18)	0.0243 (4)
H3	1.1450	−0.1199	0.8958	0.029*
C4	1.0454 (2)	−0.0857 (2)	0.72994 (18)	0.0215 (4)
C5	0.8921 (2)	−0.1589 (2)	0.69362 (18)	0.0214 (4)
C6	0.7795 (2)	−0.1682 (2)	0.58835 (18)	0.0217 (4)
C7	0.6231 (2)	−0.2468 (2)	0.5519 (2)	0.0274 (5)
H7	0.5805	−0.2996	0.5927	0.033*
C8	0.5497 (2)	−0.2298 (2)	0.4477 (2)	0.0270 (4)
H8	0.4471	−0.2677	0.4038	0.032*
C9	0.6606 (2)	−0.1415 (2)	0.41709 (18)	0.0215 (4)
C10	1.3700 (2)	0.1076 (2)	0.69132 (18)	0.0221 (4)
C11	0.8443 (2)	−0.2378 (2)	0.77232 (18)	0.0218 (4)
C12	0.8211 (3)	−0.3733 (2)	0.7389 (2)	0.0355 (5)
H12	0.8369	−0.4151	0.6684	0.043*
C13	0.7744 (3)	−0.4473 (2)	0.8098 (2)	0.0382 (6)
H13	0.7593	−0.5383	0.7867	0.046*
C14	0.7504 (2)	−0.3870 (2)	0.9138 (2)	0.0318 (5)
H14	0.7190	−0.4368	0.9611	0.038*
C15	0.7733 (3)	−0.2519 (2)	0.9478 (2)	0.0338 (5)
H15	0.7569	−0.2105	1.0181	0.041*
C16	0.8207 (2)	−0.1776 (2)	0.8774 (2)	0.0288 (5)
H16	0.8366	−0.0864	0.9013	0.035*
C17	1.5297 (2)	0.1524 (2)	0.77206 (18)	0.0228 (4)
C18	1.6208 (2)	0.1016 (2)	0.7256 (2)	0.0303 (5)
H18	1.5813	0.0383	0.6437	0.036*
C19	1.7692 (3)	0.1441 (3)	0.7995 (2)	0.0373 (5)
H19	1.8287	0.1094	0.7672	0.045*
C20	1.8297 (2)	0.2382 (3)	0.9214 (2)	0.0366 (6)
H20	1.9298	0.2674	0.9706	0.044*
C21	1.7406 (2)	0.2884 (2)	0.9696 (2)	0.0337 (5)
H21	1.7805	0.3507	1.0519	0.040*
C22	1.59147 (13)	0.24577 (12)	0.89529 (11)	0.0270 (4)
H22	1.5321	0.2801	0.9283	0.032*
O1	0.99283 (13)	−0.23197 (12)	0.38069 (11)	0.0414 (4)
C23	0.88485 (13)	−0.30609 (12)	0.25589 (11)	0.0415 (6)
H23A	0.9247	−0.3582	0.2072	0.050*
H23B	0.8669	−0.2424	0.2171	0.050*
C24	0.7397 (3)	−0.4009 (3)	0.2491 (2)	0.0423 (6)
H24A	0.7125	−0.3563	0.3149	0.051*
H24B	0.6622	−0.4252	0.1681	0.051*
O2	0.7523 (2)	−0.51824 (18)	0.26441 (18)	0.0450 (4)
C25	0.6304 (3)	−0.6046 (3)	0.2816 (3)	0.0473 (6)
H25A	0.5470	−0.6566	0.2012	0.057*
H25B	0.5991	−0.5509	0.3380	0.057*
C26	0.6787 (3)	−0.6981 (3)	0.3367 (3)	0.0510 (7)
H26A	0.5923	−0.7734	0.3282	0.061*
H26B	0.7329	−0.7344	0.2921	0.061*
O3	0.7692 (2)	−0.6263 (2)	0.4630 (2)	0.0602 (5)
C27A	0.9180 (7)	−0.6327 (7)	0.5200 (6)	0.0541 (7)	0.50
H27A	0.9569	−0.6576	0.4558	0.065*	0.50
H27B	0.9902	−0.5461	0.5848	0.065*	0.50
C28A	0.8820 (7)	−0.7408 (7)	0.5755 (6)	0.0492 (8)	0.50
H28A	0.8521	−0.7103	0.6447	0.059*	0.50
H28B	0.7999	−0.8229	0.5118	0.059*	0.50
C27B	0.8033 (15)	−0.7226 (13)	0.5251 (14)	0.0541 (7)	0.25
H27C	0.7839	−0.7096	0.6022	0.065*	0.25
H27D	0.7453	−0.8165	0.4685	0.065*	0.25
C28B	0.9557 (13)	−0.6854 (13)	0.5508 (13)	0.0492 (8)	0.25
H28C	1.0109	−0.5895	0.6021	0.059*	0.25
H28D	0.9724	−0.7018	0.4725	0.059*	0.25
C27C	0.8191 (15)	−0.7395 (13)	0.4715 (13)	0.0541 (7)	0.25
H27E	0.7387	−0.8215	0.4604	0.065*	0.25
H27F	0.8663	−0.7600	0.4127	0.065*	0.25
C28C	0.9287 (15)	−0.6667 (14)	0.6059 (12)	0.0492 (8)	0.25
H28E	0.8790	−0.6567	0.6645	0.059*	0.25
H28F	0.9991	−0.5779	0.6184	0.059*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.01801 (19)	0.0560 (3)	0.0266 (2)	0.00947 (17)	0.00743 (14)	0.02734 (18)
N1	0.0178 (8)	0.0310 (9)	0.0204 (8)	0.0074 (7)	0.0065 (7)	0.0138 (7)
N2	0.0182 (8)	0.0277 (9)	0.0180 (8)	0.0078 (7)	0.0058 (6)	0.0116 (7)
C1	0.0206 (9)	0.0250 (10)	0.0183 (9)	0.0085 (8)	0.0049 (8)	0.0089 (8)
C2	0.0232 (10)	0.0294 (11)	0.0200 (10)	0.0106 (9)	0.0040 (8)	0.0110 (8)
C3	0.0257 (10)	0.0285 (11)	0.0191 (9)	0.0102 (9)	0.0066 (8)	0.0125 (8)
C4	0.0234 (10)	0.0252 (10)	0.0176 (9)	0.0098 (8)	0.0080 (8)	0.0103 (8)
C5	0.0249 (10)	0.0227 (10)	0.0185 (9)	0.0091 (8)	0.0105 (8)	0.0091 (8)
C6	0.0217 (10)	0.0245 (10)	0.0198 (9)	0.0076 (8)	0.0101 (8)	0.0096 (8)
C7	0.0226 (10)	0.0338 (12)	0.0268 (11)	0.0072 (9)	0.0112 (9)	0.0158 (9)
C8	0.0188 (10)	0.0318 (11)	0.0272 (11)	0.0057 (9)	0.0078 (8)	0.0127 (9)
C9	0.0184 (9)	0.0255 (10)	0.0198 (9)	0.0077 (8)	0.0070 (8)	0.0091 (8)
C10	0.0199 (9)	0.0244 (10)	0.0201 (9)	0.0088 (8)	0.0054 (8)	0.0082 (8)
C11	0.0181 (9)	0.0258 (10)	0.0194 (9)	0.0054 (8)	0.0055 (8)	0.0113 (8)
C12	0.0522 (15)	0.0290 (12)	0.0245 (11)	0.0139 (11)	0.0175 (10)	0.0089 (9)
C13	0.0504 (15)	0.0233 (11)	0.0313 (12)	0.0065 (11)	0.0106 (11)	0.0109 (10)
C14	0.0276 (11)	0.0368 (13)	0.0288 (11)	0.0050 (10)	0.0084 (9)	0.0213 (10)
C15	0.0431 (13)	0.0442 (14)	0.0296 (11)	0.0230 (11)	0.0229 (10)	0.0214 (10)
C16	0.0379 (12)	0.0288 (11)	0.0281 (11)	0.0163 (10)	0.0170 (9)	0.0152 (9)
C17	0.0202 (10)	0.0256 (10)	0.0225 (10)	0.0072 (8)	0.0060 (8)	0.0137 (8)
C18	0.0275 (11)	0.0339 (12)	0.0295 (11)	0.0125 (10)	0.0107 (9)	0.0116 (9)
C19	0.0259 (11)	0.0465 (14)	0.0495 (14)	0.0193 (11)	0.0167 (11)	0.0254 (12)
C20	0.0182 (10)	0.0450 (14)	0.0424 (13)	0.0069 (10)	0.0018 (9)	0.0274 (11)
C21	0.0298 (12)	0.0333 (12)	0.0255 (11)	0.0041 (10)	0.0001 (9)	0.0134 (9)
C22	0.0256 (10)	0.0277 (11)	0.0254 (10)	0.0092 (9)	0.0071 (8)	0.0110 (9)
O1	0.0372 (9)	0.0465 (10)	0.0370 (9)	0.0164 (8)	0.0067 (7)	0.0185 (8)
C23	0.0559 (16)	0.0368 (13)	0.0301 (12)	0.0170 (12)	0.0140 (11)	0.0145 (10)
C24	0.0449 (14)	0.0412 (14)	0.0350 (13)	0.0208 (12)	0.0062 (11)	0.0106 (11)
O2	0.0465 (10)	0.0412 (10)	0.0627 (12)	0.0218 (9)	0.0329 (9)	0.0252 (9)
C25	0.0296 (12)	0.0583 (17)	0.0482 (15)	0.0101 (12)	0.0137 (11)	0.0212 (13)
C26	0.0595 (18)	0.0364 (14)	0.0672 (19)	0.0201 (13)	0.0383 (16)	0.0188 (13)
O3	0.0635 (8)	0.0611 (8)	0.0590 (8)	0.0356 (6)	0.0160 (6)	0.0219 (6)
C27A	0.0561 (9)	0.0546 (9)	0.0546 (9)	0.0271 (7)	0.0179 (7)	0.0225 (7)
C28A	0.0508 (10)	0.0514 (10)	0.0503 (10)	0.0242 (8)	0.0202 (7)	0.0213 (8)
C27B	0.0561 (9)	0.0546 (9)	0.0546 (9)	0.0271 (7)	0.0179 (7)	0.0225 (7)
C28B	0.0508 (10)	0.0514 (10)	0.0503 (10)	0.0242 (8)	0.0202 (7)	0.0213 (8)
C27C	0.0561 (9)	0.0546 (9)	0.0546 (9)	0.0271 (7)	0.0179 (7)	0.0225 (7)
C28C	0.0508 (10)	0.0514 (10)	0.0503 (10)	0.0242 (8)	0.0202 (7)	0.0213 (8)

Geometric parameters (Å, º) top

Zn—N2	2.0421 (16)	C21—C22	1.389 (2)
Zn—N1	2.0524 (16)	C21—H21	0.9300
N1—C1	1.372 (2)	C22—H22	0.9300
N1—C4	1.374 (2)	O1—C28Aⁱⁱ	1.397 (6)
N2—C9	1.371 (2)	O1—C23	1.4185
N2—C6	1.372 (2)	O1—C28Bⁱⁱ	1.487 (13)
C1—C10	1.405 (3)	O1—C28Cⁱⁱ	1.587 (12)
C1—C2	1.443 (3)	C23—C24	1.496 (3)
C2—C3	1.347 (3)	C23—H23A	0.9700
C2—H2	0.9300	C23—H23B	0.9700
C3—C4	1.443 (3)	C24—O2	1.400 (3)
C3—H3	0.9300	C24—H24A	0.9700
C4—C5	1.402 (3)	C24—H24B	0.9700
C5—C6	1.400 (3)	O2—C25	1.417 (3)
C5—C11	1.504 (3)	C25—C26	1.492 (4)
C6—C7	1.439 (3)	C25—H25A	0.9700
C7—C8	1.346 (3)	C25—H25B	0.9700
C7—H7	0.9300	C26—O3	1.384 (4)
C8—C9	1.445 (3)	C26—H26A	0.9700
C8—H8	0.9300	C26—H26B	0.9700
C9—C10ⁱ	1.406 (3)	O3—C27C	1.513 (12)
C10—C9ⁱ	1.406 (3)	O3—C27B	1.513 (13)
C10—C17	1.493 (3)	O3—C27A	1.517 (6)
C11—C16	1.379 (3)	C27A—C28A	1.504 (9)
C11—C12	1.384 (3)	C27A—H27A	0.9700
C12—C13	1.388 (3)	C27A—H27B	0.9700
C12—H12	0.9300	C28A—O1ⁱⁱ	1.397 (6)
C13—C14	1.370 (3)	C28A—H28A	0.9700
C13—H13	0.9300	C28A—H28B	0.9700
C14—C15	1.380 (3)	C27B—C28B	1.403 (18)
C14—H14	0.9300	C27B—H27C	0.9700
C15—C16	1.386 (3)	C27B—H27D	0.9700
C15—H15	0.9300	C28B—O1ⁱⁱ	1.487 (12)
C16—H16	0.9300	C28B—H28C	0.9700
C17—C22	1.392 (2)	C28B—H28D	0.9700
C17—C18	1.393 (3)	C27C—C28C	1.502 (18)
C18—C19	1.382 (3)	C27C—H27E	0.9700
C18—H18	0.9300	C27C—H27F	0.9700
C19—C20	1.383 (4)	C28C—O1ⁱⁱ	1.587 (12)
C19—H19	0.9300	C28C—H28E	0.9700
C20—C21	1.381 (4)	C28C—H28F	0.9700
C20—H20	0.9300

N2—Zn—N2ⁱ	180.0	C20—C21—H21	120.0
N2—Zn—N1ⁱ	89.28 (6)	C22—C21—H21	120.0
N2ⁱ—Zn—N1ⁱ	90.72 (6)	C21—C22—C17	120.83 (16)
N2—Zn—N1	90.72 (6)	C21—C22—H22	119.6
N2ⁱ—Zn—N1	89.28 (6)	C17—C22—H22	119.6
N1ⁱ—Zn—N1	180.0	C28Aⁱⁱ—O1—C23	121.4 (3)
C1—N1—C4	106.75 (16)	C23—O1—C28Bⁱⁱ	115.6 (5)
C1—N1—Zn	127.32 (13)	C23—O1—C28Cⁱⁱ	99.7 (5)
C4—N1—Zn	125.65 (13)	O1—C23—C24	113.75 (11)
C9—N2—C6	106.67 (16)	O1—C23—H23A	108.8
C9—N2—Zn	127.28 (13)	C24—C23—H23A	108.8
C6—N2—Zn	125.51 (13)	O1—C23—H23B	108.8
N1—C1—C10	125.32 (18)	C24—C23—H23B	108.8
N1—C1—C2	109.25 (17)	H23A—C23—H23B	107.7
C10—C1—C2	125.37 (18)	O2—C24—C23	109.77 (19)
C3—C2—C1	107.45 (17)	O2—C24—H24A	109.7
C3—C2—H2	126.3	C23—C24—H24A	109.7
C1—C2—H2	126.3	O2—C24—H24B	109.7
C2—C3—C4	107.10 (17)	C23—C24—H24B	109.7
C2—C3—H3	126.5	H24A—C24—H24B	108.2
C4—C3—H3	126.5	C24—O2—C25	114.6 (2)
N1—C4—C5	125.70 (17)	O2—C25—C26	108.3 (2)
N1—C4—C3	109.43 (17)	O2—C25—H25A	110.0
C5—C4—C3	124.81 (18)	C26—C25—H25A	110.0
C6—C5—C4	125.74 (18)	O2—C25—H25B	110.0
C6—C5—C11	116.99 (17)	C26—C25—H25B	110.0
C4—C5—C11	117.24 (17)	H25A—C25—H25B	108.4
N2—C6—C5	126.10 (18)	O3—C26—C25	108.8 (2)
N2—C6—C7	109.46 (17)	O3—C26—H26A	109.9
C5—C6—C7	124.44 (18)	C25—C26—H26A	109.9
C8—C7—C6	107.41 (18)	O3—C26—H26B	109.9
C8—C7—H7	126.3	C25—C26—H26B	109.9
C6—C7—H7	126.3	H26A—C26—H26B	108.3
C7—C8—C9	107.03 (18)	C26—O3—C27C	91.8 (5)
C7—C8—H8	126.5	C26—O3—C27B	109.8 (6)
C9—C8—H8	126.5	C26—O3—C27A	121.5 (3)
N2—C9—C10ⁱ	125.72 (18)	C28A—C27A—O3	103.6 (5)
N2—C9—C8	109.42 (17)	C28A—C27A—H27A	111.0
C10ⁱ—C9—C8	124.69 (18)	O3—C27A—H27A	111.0
C1—C10—C9ⁱ	124.99 (18)	C28A—C27A—H27B	111.0
C1—C10—C17	117.65 (17)	O3—C27A—H27B	111.0
C9ⁱ—C10—C17	117.36 (18)	H27A—C27A—H27B	109.0
C16—C11—C12	118.84 (19)	O1ⁱⁱ—C28A—C27A	109.5 (5)
C16—C11—C5	120.98 (18)	O1ⁱⁱ—C28A—H28A	109.8
C12—C11—C5	120.17 (18)	C27A—C28A—H28A	109.8
C11—C12—C13	120.5 (2)	O1ⁱⁱ—C28A—H28B	109.8
C11—C12—H12	119.8	C27A—C28A—H28B	109.8
C13—C12—H12	119.8	H28A—C28A—H28B	108.2
C14—C13—C12	120.3 (2)	C28B—C27B—O3	102.5 (10)
C14—C13—H13	119.8	C28B—C27B—H27C	111.3
C12—C13—H13	119.8	O3—C27B—H27C	111.3
C13—C14—C15	119.6 (2)	C28B—C27B—H27D	111.3
C13—C14—H14	120.2	O3—C27B—H27D	111.3
C15—C14—H14	120.2	H27C—C27B—H27D	109.2
C14—C15—C16	120.2 (2)	C27B—C28B—O1ⁱⁱ	108.4 (10)
C14—C15—H15	119.9	C27B—C28B—H28C	110.0
C16—C15—H15	119.9	O1ⁱⁱ—C28B—H28C	110.0
C11—C16—C15	120.6 (2)	C27B—C28B—H28D	110.0
C11—C16—H16	119.7	O1ⁱⁱ—C28B—H28D	110.0
C15—C16—H16	119.7	H28C—C28B—H28D	108.4
C22—C17—C18	118.35 (17)	C28C—C27C—O3	96.2 (9)
C22—C17—C10	121.02 (17)	C28C—C27C—H27E	112.5
C18—C17—C10	120.63 (18)	O3—C27C—H27E	112.5
C19—C18—C17	120.8 (2)	C28C—C27C—H27F	112.5
C19—C18—H18	119.6	O3—C27C—H27F	112.5
C17—C18—H18	119.6	H27E—C27C—H27F	110.0
C18—C19—C20	120.3 (2)	C27C—C28C—O1ⁱⁱ	100.7 (9)
C18—C19—H19	119.9	C27C—C28C—H28E	111.6
C20—C19—H19	119.9	O1ⁱⁱ—C28C—H28E	111.6
C21—C20—C19	119.7 (2)	C27C—C28C—H28F	111.6
C21—C20—H20	120.1	O1ⁱⁱ—C28C—H28F	111.6
C19—C20—H20	120.1	H28E—C28C—H28F	109.4
C20—C21—C22	120.0 (2)

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

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the N1/C1–C4, N2/C6–C9 and C11–C16 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···Cg1ⁱⁱⁱ	0.93	2.98	3.824 (2)	152
C20—H20···Cg3^iv	0.93	2.84	3.746 (2)	164
C24—H24A···Cg2	0.97	2.73	3.686 (3)	167

Symmetry codes: (iii) −x+2, −y, −z+2; (iv) −x+3, −y, −z+2.

Experimental details

Crystal data
Chemical formula	[Zn(C₄₄H₂₈N₄)]·C₁₂H₂₄O₆
M_r	942.39
Crystal system, space group	Triclinic, P1
Temperature (K)	180
a, b, c (Å)	10.2170 (3), 11.1190 (4), 11.8243 (3)
α, β, γ (°)	104.384 (3), 105.912 (3), 108.096 (3)
V (Å³)	1143.23 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.48 × 0.45 × 0.33

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.918, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22963, 4503, 3774
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.108, 1.07
No. of reflections	4503
No. of parameters	310
No. of restraints	30
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.67

Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the N1/C1–C4, N2/C6–C9 and C11–C16 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···Cg1ⁱ	0.93	2.98	3.824 (2)	152
C20—H20···Cg3ⁱⁱ	0.93	2.84	3.746 (2)	164
C24—H24A···Cg2	0.97	2.73	3.686 (3)	167

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

Acknowledgements

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

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Volume 69| Part 8| August 2013| Pages m444-m445

doi:10.1107/S1600536813018126

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