Diaqua­(5,10,15,20-tetra­phenyl­porphyrinato-κ4N)magnesium–18-crown-6 (1/1)

Ezzayani, K.; Nasri, S.; Belkhiria, M.S.; Daran, J.-C.; Nasri, H.

doi:10.1107/S1600536813001219

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Pages m114-m115

doi:10.1107/S1600536813001219

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Diaqua(5,10,15,20-tetraphenylporphyrinato-κ⁴N)magnesium–18-crown-6 (1/1)

Khaireddine Ezzayani,^a Soumaya Nasri,^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 Narbonne, 31077 Toulouse, Cedex 04, France
^*Correspondence e-mail: hnasri1@gmail.com

(Received 6 January 2013; accepted 12 January 2013; online 19 January 2013)

In the title compound, [Mg(C₄₄H₂₈N₄)(H₂O)₂]·C₁₂H₂₄O₆, the Mg^II cation lies on an inversion center and is octahedrally coordinated by the four N atoms of the deprotonated tetraphenylporphyrin (TPP) ligand and by two water molecules. The asymmetric unit contains one half of the [Mg(TPP)(H₂O)₂] complex and one half of an 18-crown-6 molecule. The average equatorial magnesium–pyrrole N atom distance (Mg—N_p) is 2.071 (1) Å and the axial Mg—O(H₂O) bond length is 2.213 (1) Å. The crystal packing is stabilized by two O—H⋯O hydrogen bonds between coordinating water molecules and adjacent 18-crown-6 molecules, and exhibits a one-dimensional supramolecular structure along the a axis. The supramolecular architecture is futher stabilized by weak C—H⋯π interactions. The 18-crown-6 molecule is disordered over two sets of sites with an occupancy ratio of 0.8:0.2.

Related literature

For general background to magnesium porphyrin species and their applications, see: Ghosh et al. (2010 ). For related structures, see: Belghith et al. (2012 ); McArdle (1995 ); McKee et al. (1984 ); Choon et al. (1986 ); McKee & Rodley (1988 ); Gryz et al. (2007 ); Imaz et al. (2005 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

[Mg(C₄₄H₂₈N₄)(H₂O)₂]·C₁₂H₂₄O₆
M_r = 937.36
Triclinic, $[P \overline 1]$
a = 8.1440 (3) Å
b = 12.3080 (4) Å
c = 12.4170 (4) Å
α = 86.894 (3)°
β = 75.163 (3)°
γ = 79.529 (3)°
V = 1183.06 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 180 K
0.56 × 0.51 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur (Sapphire1) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.946, T_max = 0.981
23613 measured reflections
4650 independent reflections
4013 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.118
S = 1.04
4650 reflections
400 parameters
119 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 and Cg4 are the centroids of the N2/C6–C9 and C17–C22 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2A	0.97 (2)	2.08 (2)	2.984 (2)	153 (2)
O1—H2O1⋯O2Aⁱ	0.97 (2)	2.22 (2)	3.105 (2)	150 (2)
O1—H1O1⋯O2B	0.97 (2)	2.33 (2)	3.297 (10)	170 (2)
O1—H2O1⋯O2Bⁱ	0.97 (2)	2.19 (2)	2.962 (8)	135 (1)
C15—H15⋯Cg4ⁱⁱ	0.93	2.96	3.730 (2)	141
C27A—H27A⋯Cg2ⁱⁱⁱ	0.97	2.86	3.671 (5)	142
C26B—H26D⋯Cg2	0.97	2.89	3.678 (11)	139
C27B—H27D⋯Cg2ⁱⁱⁱ	0.97	2.94	3.715 (17)	139
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x, y-1, z; (iii) x+1, y, z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813001219/xu5669sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813001219/xu5669Isup2.hkl

checkCIF report

Comment top

In continuation of our research on the crystal structures of porphyrin complexes (Belghith et al., 2012) we herein report the synthesis and crystal structure of the bis-aqua-Mg tetraphenylporhyrin derivative [Mg(TPP)(H₂O)₂].(18-C-6). In this complex, the coordination geometry of the Mg²⁺ ion is octahedral with four Mg—N(pyrrole) bonds in the equatorial porphyrin plane and two Mg—O bonds with the two symmetry related water axial ligands. The average equatorial distance (Mg–Np) equal to 2.071 (1) Å lies in the range [2.065 (4) - 2.092 (7) Å] of the related porphyrin species [Mg(TPP)(4-pic)₂] (4-pic = 4-picoline: C₆H₇N) (McKee et al., 1984) and [Mg(TPP)(H₂O)] (Choon et al., 1986).

The axial Mg—O(H₂O) bond length [2.213 (1) Å] is quite longer than in the related derivative [Mg(TPP)(H₂O)] (2.053 (5) Å) (McKee & Rodley, 1988) but is within the range [2.063 (2) - 2.75 (2) Å] found for several magnesium-aqua non-porphyrin complexes (CSD refcodes DEZNIG; Gryz et al., 2007 and FIVYEP; Imaz et al., 2005) (CDS, version 5.32 Allen, 2002).

The crystal structure of our derivative resembles to one-dimensional coordination polymer where each one of two [Mg(TPP)] moieties is linked to an ether crown 18-C-6 molecule via H bonds between the oxygen atom O2A of this species and the O1 atom of the water axial ligand of the [Mg(TPP)(H₂O)₂] derivative (Fig. 2).

These linear chains are parallel to the a axis and are mainly sustained by weak C—H···Cg interactions, where Cg is the centroid of the pyrrole or phenyl rings (Table 1).

Related literature top

For general background to magnesium porphyrin species and their applications, see: Ghosh et al. (2010). For related structures, see: Belghith et al. (2012); McArdle (1995); McKee et al. (1984); Choon et al. (1986); McKee & Rodley (1988); Gryz et al. (2007); Imaz et al. (2005). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

To a solution of [Mg(TPP)] (15 mg, 0.024 mmol) in chlorobenzene (15 ml) was added an excess of (18-crown-6) (100 mg, 0.378 mmol). The reaction mixture was stirred at room temperature and at the end of the reaction, the color of the solution gradually changes from purple to blue – purple. The resulting material was crystallized by diffusion of hexanes through the chlorobenzene solution which yielded [Mg(TPP)(H₂O)₂].(18-C-6). The two water molecules coordinated to the magnesium come from the hygroscopic 18-crown-6 reagent used in excess.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP diagram of the structure of [Mg(TPP)(H₂O)₂].(18-C-6) showing the atom-numbering scheme. Displacement ellipsoids are drawn at 45%. [Symmtry code: (i) -x, -y, -z + 1].
	Fig. 2. Drawing showing the packing in the lattice of [Mg(TPP)(H₂O)₂].(18-C-6) viewed down the b axis. H atoms have been omitted for clarity.

Diaqua(5,10,15,20-tetraphenylporphyrinato-κ⁴N)magnesium– 1,4,7,10,13,16-hexaoxacyclooctadecane (1/1) top

Crystal data top

[Mg(C₄₄H₂₈N₄)(H₂O)₂]·C₁₂H₂₄O₆	Z = 1
M_r = 937.36	F(000) = 496
Triclinic, P1	D_x = 1.316 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1440 (3) Å	Cell parameters from 14229 reflections
b = 12.3080 (4) Å	θ = 2.9–28.4°
c = 12.4170 (4) Å	µ = 0.10 mm⁻¹
α = 86.894 (3)°	T = 180 K
β = 75.163 (3)°	Prism, purple
γ = 79.529 (3)°	0.56 × 0.51 × 0.19 mm
V = 1183.06 (7) Å³

Data collection top

Oxford Diffraction Xcalibur (Sapphire1) diffractometer	4650 independent reflections
Radiation source: fine-focus sealed tube	4013 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 8.2632 pixels mm^-1	θ_max = 26.0°, θ_min = 2.9°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −15→15
T_min = 0.946, T_max = 0.981	l = −15→15
23613 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0568P)² + 0.6503P] where P = (F_o² + 2F_c²)/3
4650 reflections	(Δ/σ)_max < 0.001
400 parameters	Δρ_max = 0.46 e Å⁻³
119 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Mg(C₄₄H₂₈N₄)(H₂O)₂]·C₁₂H₂₄O₆	γ = 79.529 (3)°
M_r = 937.36	V = 1183.06 (7) Å³
Triclinic, P1	Z = 1
a = 8.1440 (3) Å	Mo Kα radiation
b = 12.3080 (4) Å	µ = 0.10 mm⁻¹
c = 12.4170 (4) Å	T = 180 K
α = 86.894 (3)°	0.56 × 0.51 × 0.19 mm
β = 75.163 (3)°

Data collection top

Oxford Diffraction Xcalibur (Sapphire1) diffractometer	4650 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	4013 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.981	R_int = 0.031
23613 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	119 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.46 e Å⁻³
4650 reflections	Δρ_min = −0.28 e Å⁻³
400 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 > 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	Occ. (<1)
Mg1	0.0000	0.0000	0.5000	0.01893 (17)
O1	0.27384 (14)	−0.00267 (10)	0.49625 (10)	0.0273 (3)
H1O1	0.323 (3)	−0.0256 (18)	0.5592 (13)	0.050*
H2O1	0.360 (2)	−0.0260 (18)	0.4278 (12)	0.050*
N1	−0.05837 (16)	−0.03608 (10)	0.66901 (10)	0.0189 (3)
N2	−0.06769 (16)	0.16696 (10)	0.53555 (10)	0.0185 (3)
C1	−0.04664 (19)	−0.13929 (12)	0.71606 (12)	0.0197 (3)
C2	−0.1086 (2)	−0.12941 (13)	0.83554 (13)	0.0253 (3)
H2	−0.1120	−0.1871	0.8872	0.030*
C3	−0.1607 (2)	−0.02077 (13)	0.85834 (13)	0.0256 (3)
H3	−0.2093	0.0103	0.9284	0.031*
C4	−0.12687 (19)	0.03831 (12)	0.75337 (12)	0.0203 (3)
C5	−0.15851 (19)	0.15423 (12)	0.74036 (12)	0.0202 (3)
C6	−0.12549 (19)	0.21291 (12)	0.63867 (12)	0.0198 (3)
C7	−0.1471 (2)	0.33201 (13)	0.62737 (13)	0.0239 (3)
H7	−0.1822	0.3827	0.6851	0.029*
C8	−0.1069 (2)	0.35562 (12)	0.51726 (13)	0.0234 (3)
H8	−0.1091	0.4256	0.4848	0.028*
C9	−0.05984 (19)	0.25119 (12)	0.45940 (12)	0.0193 (3)
C10	0.01238 (19)	−0.23950 (12)	0.65711 (12)	0.0198 (3)
C11	0.0337 (2)	−0.34328 (12)	0.72424 (12)	0.0215 (3)
C12	0.1988 (2)	−0.40022 (13)	0.71999 (14)	0.0277 (4)
H12	0.2936	−0.3734	0.6755	0.033*
C13	0.2240 (3)	−0.49656 (14)	0.78129 (15)	0.0346 (4)
H13	0.3353	−0.5339	0.7777	0.042*
C14	0.0846 (3)	−0.53712 (14)	0.84755 (15)	0.0355 (4)
H14	0.1015	−0.6014	0.8892	0.043*
C15	−0.0798 (3)	−0.48205 (15)	0.85186 (15)	0.0373 (4)
H15	−0.1743	−0.5097	0.8958	0.045*
C16	−0.1050 (2)	−0.38552 (14)	0.79099 (14)	0.0311 (4)
H16	−0.2166	−0.3485	0.7950	0.037*
C17	−0.2409 (2)	0.22080 (12)	0.84322 (12)	0.0214 (3)
C18	−0.1582 (2)	0.22428 (13)	0.92774 (13)	0.0262 (3)
H18	−0.0482	0.1834	0.9210	0.031*
C19	−0.2371 (2)	0.28757 (14)	1.02156 (13)	0.0295 (4)
H19	−0.1797	0.2894	1.0771	0.035*
C20	−0.4005 (2)	0.34789 (14)	1.03309 (13)	0.0296 (4)
H20	−0.4535	0.3906	1.0961	0.036*
C21	−0.4850 (2)	0.34448 (14)	0.95063 (14)	0.0319 (4)
H21	−0.5958	0.3844	0.9585	0.038*
C22	−0.4054 (2)	0.28192 (14)	0.85624 (14)	0.0275 (4)
H22	−0.4631	0.2808	0.8007	0.033*
C23A	0.5253 (4)	−0.1823 (3)	0.7059 (2)	0.0620 (12)	0.80
H23A	0.6378	−0.1605	0.6826	0.074*	0.80
H23B	0.5341	−0.2468	0.7539	0.074*	0.80
O4A	0.4741 (2)	−0.20837 (18)	0.61214 (18)	0.0495 (5)	0.80
C24A	0.3972 (4)	−0.0906 (3)	0.7682 (2)	0.0682 (10)	0.80
H24A	0.2828	−0.1097	0.7866	0.082*	0.80
H24B	0.4258	−0.0775	0.8370	0.082*	0.80
O2A	0.4010 (3)	0.0049 (2)	0.70026 (15)	0.0583 (5)	0.80
C25A	0.3047 (6)	0.1004 (4)	0.7585 (5)	0.0708 (16)	0.80
H25A	0.3639	0.1206	0.8110	0.085*	0.80
H25B	0.1925	0.0859	0.8001	0.085*	0.80
C26A	0.2830 (3)	0.1925 (3)	0.6784 (3)	0.0665 (10)	0.80
H26A	0.2331	0.1705	0.6218	0.080*	0.80
H26B	0.2067	0.2563	0.7168	0.080*	0.80
C27A	0.4410 (6)	0.3090 (3)	0.5543 (3)	0.0657 (11)	0.80
H27A	0.5529	0.3318	0.5349	0.079*	0.80
H27B	0.3573	0.3703	0.5919	0.079*	0.80
C28A	0.3963 (4)	0.2866 (3)	0.4501 (2)	0.0658 (9)	0.80
H28A	0.2878	0.2595	0.4680	0.079*	0.80
H28B	0.3831	0.3543	0.4071	0.079*	0.80
O3A	0.4463 (2)	0.2189 (2)	0.62918 (17)	0.0605 (6)	0.80
C23B	0.485 (2)	−0.1672 (8)	0.7359 (12)	0.0502 (12)	0.20
H23C	0.3729	−0.1875	0.7676	0.060*	0.20
H23D	0.5497	−0.1783	0.7925	0.060*	0.20
C24B	0.3936 (16)	0.0228 (9)	0.7901 (8)	0.0497 (11)	0.20
H24C	0.4858	0.0447	0.8157	0.060*	0.20
H24D	0.3206	−0.0108	0.8523	0.060*	0.20
C25B	0.290 (2)	0.1223 (19)	0.750 (2)	0.0485 (11)	0.20
H25C	0.2036	0.1007	0.7179	0.058*	0.20
H25D	0.2324	0.1728	0.8103	0.058*	0.20
C26B	0.3267 (13)	0.2581 (8)	0.6048 (9)	0.0466 (11)	0.20
H26C	0.2533	0.3143	0.6558	0.056*	0.20
H26D	0.2538	0.2265	0.5689	0.056*	0.20
C27B	0.453 (2)	0.3115 (11)	0.5178 (11)	0.0464 (12)	0.20
H27C	0.3923	0.3764	0.4874	0.056*	0.20
H27D	0.5364	0.3346	0.5508	0.056*	0.20
C28B	0.5792 (17)	−0.2380 (10)	0.6372 (11)	0.0500 (13)	0.20
H28C	0.6817	−0.2096	0.5971	0.060*	0.20
H28D	0.6139	−0.3131	0.6611	0.060*	0.20
O2B	0.4649 (11)	−0.0550 (7)	0.7021 (7)	0.0507 (11)	0.20
O3B	0.4086 (12)	0.1731 (7)	0.6670 (7)	0.0473 (10)	0.20
O4B	0.5366 (12)	0.2356 (7)	0.4328 (7)	0.0463 (12)	0.20

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mg1	0.0259 (4)	0.0142 (3)	0.0152 (3)	−0.0009 (3)	−0.0041 (3)	−0.0010 (3)
O1	0.0240 (6)	0.0324 (6)	0.0247 (6)	−0.0030 (5)	−0.0060 (5)	−0.0011 (5)
N1	0.0217 (6)	0.0157 (6)	0.0181 (6)	0.0000 (5)	−0.0050 (5)	−0.0011 (5)
N2	0.0218 (6)	0.0166 (6)	0.0162 (6)	−0.0011 (5)	−0.0047 (5)	−0.0009 (5)
C1	0.0203 (7)	0.0195 (7)	0.0189 (7)	−0.0011 (6)	−0.0060 (6)	0.0010 (6)
C2	0.0327 (9)	0.0228 (8)	0.0183 (8)	−0.0021 (6)	−0.0050 (6)	0.0026 (6)
C3	0.0340 (9)	0.0235 (8)	0.0163 (7)	−0.0016 (7)	−0.0030 (6)	−0.0012 (6)
C4	0.0222 (7)	0.0205 (7)	0.0171 (7)	−0.0005 (6)	−0.0045 (6)	−0.0022 (6)
C5	0.0221 (7)	0.0193 (7)	0.0185 (7)	−0.0002 (6)	−0.0057 (6)	−0.0034 (6)
C6	0.0212 (7)	0.0184 (7)	0.0195 (7)	−0.0007 (6)	−0.0061 (6)	−0.0030 (6)
C7	0.0309 (8)	0.0180 (7)	0.0224 (8)	−0.0007 (6)	−0.0075 (6)	−0.0043 (6)
C8	0.0315 (8)	0.0154 (7)	0.0237 (8)	−0.0029 (6)	−0.0084 (6)	−0.0010 (6)
C9	0.0202 (7)	0.0169 (7)	0.0206 (7)	−0.0015 (5)	−0.0061 (6)	−0.0003 (6)
C10	0.0201 (7)	0.0182 (7)	0.0208 (7)	−0.0020 (6)	−0.0058 (6)	0.0015 (6)
C11	0.0315 (8)	0.0163 (7)	0.0170 (7)	−0.0025 (6)	−0.0074 (6)	−0.0017 (6)
C12	0.0316 (9)	0.0249 (8)	0.0265 (8)	−0.0020 (7)	−0.0092 (7)	0.0017 (7)
C13	0.0434 (10)	0.0252 (9)	0.0355 (10)	0.0053 (7)	−0.0183 (8)	0.0001 (7)
C14	0.0617 (12)	0.0185 (8)	0.0255 (9)	−0.0017 (8)	−0.0139 (8)	0.0036 (7)
C15	0.0500 (11)	0.0271 (9)	0.0297 (9)	−0.0097 (8)	−0.0001 (8)	0.0056 (7)
C16	0.0330 (9)	0.0263 (8)	0.0300 (9)	−0.0026 (7)	−0.0030 (7)	0.0038 (7)
C17	0.0282 (8)	0.0164 (7)	0.0178 (7)	−0.0024 (6)	−0.0034 (6)	−0.0006 (6)
C18	0.0286 (8)	0.0265 (8)	0.0220 (8)	0.0001 (6)	−0.0067 (6)	−0.0022 (6)
C19	0.0400 (10)	0.0301 (9)	0.0192 (8)	−0.0059 (7)	−0.0085 (7)	−0.0024 (6)
C20	0.0414 (10)	0.0233 (8)	0.0187 (8)	−0.0019 (7)	0.0007 (7)	−0.0047 (6)
C21	0.0314 (9)	0.0286 (9)	0.0290 (9)	0.0063 (7)	−0.0027 (7)	−0.0054 (7)
C22	0.0308 (9)	0.0269 (8)	0.0235 (8)	0.0010 (7)	−0.0083 (7)	−0.0039 (6)
C23A	0.042 (2)	0.091 (3)	0.054 (3)	−0.0160 (18)	−0.0204 (18)	0.040 (2)
O4A	0.0354 (10)	0.0570 (13)	0.0543 (13)	−0.0082 (9)	−0.0101 (9)	0.0096 (10)
C24A	0.060 (2)	0.115 (3)	0.0319 (14)	−0.032 (2)	−0.0086 (13)	0.0206 (17)
O2A	0.0538 (13)	0.0805 (16)	0.0346 (10)	−0.0104 (11)	−0.0002 (9)	−0.0045 (10)
C25A	0.047 (2)	0.106 (5)	0.053 (3)	−0.029 (3)	0.0190 (19)	−0.045 (3)
C26A	0.0301 (15)	0.077 (2)	0.089 (3)	−0.0051 (14)	−0.0012 (15)	−0.050 (2)
C27A	0.056 (2)	0.068 (2)	0.078 (3)	−0.0151 (16)	−0.020 (2)	−0.008 (2)
C28A	0.0435 (17)	0.076 (2)	0.076 (2)	−0.0041 (15)	−0.0145 (16)	−0.0034 (18)
O3A	0.0388 (11)	0.0919 (18)	0.0554 (13)	−0.0145 (11)	−0.0143 (10)	−0.0184 (13)
C23B	0.0502 (13)	0.0501 (13)	0.0497 (13)	−0.0081 (7)	−0.0120 (7)	0.0002 (7)
C24B	0.0495 (12)	0.0499 (12)	0.0491 (12)	−0.0080 (7)	−0.0117 (7)	0.0003 (7)
C25B	0.0482 (12)	0.0488 (12)	0.0483 (12)	−0.0084 (7)	−0.0120 (7)	−0.0004 (7)
C26B	0.0461 (12)	0.0469 (12)	0.0472 (12)	−0.0086 (7)	−0.0120 (7)	−0.0007 (7)
C27B	0.0459 (13)	0.0468 (13)	0.0471 (13)	−0.0086 (7)	−0.0125 (7)	0.0001 (7)
C28B	0.0501 (14)	0.0499 (14)	0.0498 (14)	−0.0082 (8)	−0.0125 (8)	−0.0002 (8)
O2B	0.0504 (12)	0.0504 (12)	0.0499 (12)	−0.0074 (7)	−0.0112 (7)	0.0010 (7)
O3B	0.0470 (12)	0.0478 (12)	0.0474 (12)	−0.0088 (7)	−0.0117 (7)	−0.0008 (7)
O4B	0.0457 (14)	0.0465 (14)	0.0471 (14)	−0.0084 (8)	−0.0127 (8)	0.0009 (8)

Geometric parameters (Å, º) top

Mg1—N2	2.0697 (12)	C21—C22	1.383 (2)
Mg1—N2ⁱ	2.0697 (12)	C21—H21	0.9300
Mg1—N1	2.0717 (12)	C22—H22	0.9300
Mg1—N1ⁱ	2.0717 (12)	C23A—O4A	1.404 (3)
Mg1—O1	2.2130 (11)	C23A—C24A	1.488 (4)
Mg1—O1ⁱ	2.2130 (11)	C23A—H23A	0.9700
O1—H1O1	0.972 (10)	C23A—H23B	0.9700
O1—H2O1	0.972 (10)	O4A—C28Aⁱⁱ	1.389 (4)
N1—C4	1.3659 (19)	C24A—O2A	1.410 (3)
N1—C1	1.3669 (18)	C24A—H24A	0.9700
N2—C6	1.3615 (19)	C24A—H24B	0.9700
N2—C9	1.3638 (19)	O2A—C25A	1.410 (5)
C1—C10	1.411 (2)	C25A—C26A	1.484 (3)
C1—C2	1.444 (2)	C25A—H25A	0.9700
C2—C3	1.350 (2)	C25A—H25B	0.9700
C2—H2	0.9300	C26A—O3A	1.402 (3)
C3—C4	1.446 (2)	C26A—H26A	0.9700
C3—H3	0.9300	C26A—H26B	0.9700
C4—C5	1.411 (2)	C27A—O3A	1.409 (3)
C5—C6	1.409 (2)	C27A—C28A	1.483 (3)
C5—C17	1.493 (2)	C27A—H27A	0.9700
C6—C7	1.448 (2)	C27A—H27B	0.9700
C7—C8	1.350 (2)	C28A—O4Aⁱⁱ	1.389 (4)
C7—H7	0.9300	C28A—H28A	0.9700
C8—C9	1.447 (2)	C28A—H28B	0.9700
C8—H8	0.9300	C23B—O2B	1.413 (6)
C9—C10ⁱ	1.407 (2)	C23B—C28B	1.497 (6)
C10—C9ⁱ	1.407 (2)	C23B—H23C	0.9700
C10—C11	1.495 (2)	C23B—H23D	0.9700
C11—C16	1.386 (2)	C24B—O2B	1.427 (6)
C11—C12	1.388 (2)	C24B—C25B	1.497 (6)
C12—C13	1.386 (2)	C24B—H24C	0.9700
C12—H12	0.9300	C24B—H24D	0.9700
C13—C14	1.378 (3)	C25B—O3B	1.420 (6)
C13—H13	0.9300	C25B—H25C	0.9700
C14—C15	1.375 (3)	C25B—H25D	0.9700
C14—H14	0.9300	C26B—O3B	1.435 (6)
C15—C16	1.385 (2)	C26B—C27B	1.500 (6)
C15—H15	0.9300	C26B—H26C	0.9700
C16—H16	0.9300	C26B—H26D	0.9700
C17—C22	1.387 (2)	C27B—O4B	1.400 (6)
C17—C18	1.391 (2)	C27B—H27C	0.9700
C18—C19	1.382 (2)	C27B—H27D	0.9700
C18—H18	0.9300	C28B—O4Bⁱⁱ	1.433 (15)
C19—C20	1.377 (2)	C28B—H28C	0.9700
C19—H19	0.9300	C28B—H28D	0.9700
C20—C21	1.378 (3)	O4B—C28Bⁱⁱ	1.433 (15)
C20—H20	0.9300

N2—Mg1—N2ⁱ	180.0	C20—C21—C22	120.24 (16)
N2—Mg1—N1	89.79 (5)	C20—C21—H21	119.9
N2ⁱ—Mg1—N1	90.21 (5)	C22—C21—H21	119.9
N2—Mg1—N1ⁱ	90.21 (5)	C21—C22—C17	120.94 (15)
N2ⁱ—Mg1—N1ⁱ	89.79 (5)	C21—C22—H22	119.5
N1—Mg1—N1ⁱ	180.0	C17—C22—H22	119.5
N2—Mg1—O1	92.86 (5)	O4A—C23A—C24A	109.8 (3)
N2ⁱ—Mg1—O1	87.14 (5)	O4A—C23A—H23A	109.7
N1—Mg1—O1	91.48 (4)	C24A—C23A—H23A	109.7
N1ⁱ—Mg1—O1	88.52 (4)	O4A—C23A—H23B	109.7
N2—Mg1—O1ⁱ	87.14 (5)	C24A—C23A—H23B	109.7
N2ⁱ—Mg1—O1ⁱ	92.86 (5)	H23A—C23A—H23B	108.2
N1—Mg1—O1ⁱ	88.52 (4)	C28Aⁱⁱ—O4A—C23A	108.6 (2)
N1ⁱ—Mg1—O1ⁱ	91.48 (4)	O2A—C24A—C23A	108.2 (2)
O1—Mg1—O1ⁱ	180.0	O2A—C24A—H24A	110.1
Mg1—O1—H1O1	123.5 (14)	C23A—C24A—H24A	110.1
Mg1—O1—H2O1	117.8 (14)	O2A—C24A—H24B	110.1
H1O1—O1—H2O1	108.9 (19)	C23A—C24A—H24B	110.1
C4—N1—C1	107.47 (12)	H24A—C24A—H24B	108.4
C4—N1—Mg1	126.28 (10)	C24A—O2A—C25A	112.3 (3)
C1—N1—Mg1	126.10 (10)	O2A—C25A—C26A	109.6 (4)
C6—N2—C9	107.51 (12)	O2A—C25A—H25A	109.8
C6—N2—Mg1	126.51 (10)	C26A—C25A—H25A	109.8
C9—N2—Mg1	125.97 (10)	O2A—C25A—H25B	109.8
N1—C1—C10	125.43 (13)	C26A—C25A—H25B	109.8
N1—C1—C2	109.09 (13)	H25A—C25A—H25B	108.2
C10—C1—C2	125.46 (14)	O3A—C26A—C25A	107.9 (3)
C3—C2—C1	107.21 (13)	O3A—C26A—H26A	110.1
C3—C2—H2	126.4	C25A—C26A—H26A	110.1
C1—C2—H2	126.4	O3A—C26A—H26B	110.1
C2—C3—C4	107.15 (14)	C25A—C26A—H26B	110.1
C2—C3—H3	126.4	H26A—C26A—H26B	108.4
C4—C3—H3	126.4	O3A—C27A—C28A	114.9 (3)
N1—C4—C5	125.54 (13)	O3A—C27A—H27A	108.5
N1—C4—C3	109.05 (13)	C28A—C27A—H27A	108.5
C5—C4—C3	125.41 (14)	O3A—C27A—H27B	108.5
C6—C5—C4	126.02 (14)	C28A—C27A—H27B	108.5
C6—C5—C17	116.87 (13)	H27A—C27A—H27B	107.5
C4—C5—C17	117.07 (13)	O4Aⁱⁱ—C28A—C27A	109.7 (3)
N2—C6—C5	125.61 (13)	O4Aⁱⁱ—C28A—H28A	109.7
N2—C6—C7	109.11 (13)	C27A—C28A—H28A	109.7
C5—C6—C7	125.28 (14)	O4Aⁱⁱ—C28A—H28B	109.7
C8—C7—C6	107.17 (14)	C27A—C28A—H28B	109.7
C8—C7—H7	126.4	H28A—C28A—H28B	108.2
C6—C7—H7	126.4	C26A—O3A—C27A	113.0 (3)
C7—C8—C9	106.88 (13)	O2B—C23B—C28B	109.3 (10)
C7—C8—H8	126.6	O2B—C23B—H23C	109.8
C9—C8—H8	126.6	C28B—C23B—H23C	109.8
N2—C9—C10ⁱ	125.84 (13)	O2B—C23B—H23D	109.8
N2—C9—C8	109.24 (13)	C28B—C23B—H23D	109.8
C10ⁱ—C9—C8	124.92 (14)	H23C—C23B—H23D	108.3
C9ⁱ—C10—C1	126.30 (14)	O2B—C24B—C25B	109.7 (16)
C9ⁱ—C10—C11	116.47 (13)	O2B—C24B—H24C	109.7
C1—C10—C11	117.18 (13)	C25B—C24B—H24C	109.7
C16—C11—C12	118.25 (14)	O2B—C24B—H24D	109.7
C16—C11—C10	122.71 (14)	C25B—C24B—H24D	109.7
C12—C11—C10	119.04 (14)	H24C—C24B—H24D	108.2
C13—C12—C11	120.79 (16)	O3B—C25B—C24B	106.3 (10)
C13—C12—H12	119.6	O3B—C25B—H25C	110.5
C11—C12—H12	119.6	C24B—C25B—H25C	110.5
C14—C13—C12	120.16 (17)	O3B—C25B—H25D	110.5
C14—C13—H13	119.9	C24B—C25B—H25D	110.5
C12—C13—H13	119.9	H25C—C25B—H25D	108.7
C15—C14—C13	119.68 (16)	O3B—C26B—C27B	113.2 (12)
C15—C14—H14	120.2	O3B—C26B—H26C	108.9
C13—C14—H14	120.2	C27B—C26B—H26C	108.9
C14—C15—C16	120.15 (17)	O3B—C26B—H26D	108.9
C14—C15—H15	119.9	C27B—C26B—H26D	108.9
C16—C15—H15	119.9	H26C—C26B—H26D	107.8
C15—C16—C11	120.96 (17)	O4B—C27B—C26B	109.0 (10)
C15—C16—H16	119.5	O4B—C27B—H27C	109.9
C11—C16—H16	119.5	C26B—C27B—H27C	109.9
C22—C17—C18	118.08 (14)	O4B—C27B—H27D	109.9
C22—C17—C5	119.67 (14)	C26B—C27B—H27D	109.9
C18—C17—C5	122.25 (14)	H27C—C27B—H27D	108.3
C19—C18—C17	120.96 (15)	O4Bⁱⁱ—C28B—C23B	107.2 (13)
C19—C18—H18	119.5	O4Bⁱⁱ—C28B—H28C	110.3
C17—C18—H18	119.5	C23B—C28B—H28C	110.3
C20—C19—C18	120.19 (16)	O4Bⁱⁱ—C28B—H28D	110.3
C20—C19—H19	119.9	C23B—C28B—H28D	110.3
C18—C19—H19	119.9	H28C—C28B—H28D	108.5
C19—C20—C21	119.59 (15)	C23B—O2B—C24B	115.3 (10)
C19—C20—H20	120.2	C25B—O3B—C26B	113.4 (10)
C21—C20—H20	120.2	C27B—O4B—C28Bⁱⁱ	106.0 (12)

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

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg4 are the centroids of the N2/C6–C9 and C17–C22 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2A	0.97 (2)	2.08 (2)	2.984 (2)	153 (2)
O1—H2O1···O2Aⁱⁱ	0.97 (2)	2.22 (2)	3.105 (2)	150 (2)
O1—H1O1···O2B	0.97 (2)	2.33 (2)	3.297 (10)	170 (2)
O1—H2O1···O2Bⁱⁱ	0.97 (2)	2.19 (2)	2.962 (8)	135 (1)
C15—H15···Cg4ⁱⁱⁱ	0.93	2.96	3.730 (2)	141
C27A—H27A···Cg2^iv	0.97	2.86	3.671 (5)	142
C26B—H26D···Cg2	0.97	2.89	3.678 (11)	139
C27B—H27D···Cg2^iv	0.97	2.94	3.715 (17)	139

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

Experimental details

Crystal data
Chemical formula	[Mg(C₄₄H₂₈N₄)(H₂O)₂]·C₁₂H₂₄O₆
M_r	937.36
Crystal system, space group	Triclinic, P1
Temperature (K)	180
a, b, c (Å)	8.1440 (3), 12.3080 (4), 12.4170 (4)
α, β, γ (°)	86.894 (3), 75.163 (3), 79.529 (3)
V (Å³)	1183.06 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.56 × 0.51 × 0.19

Data collection
Diffractometer	Oxford Diffraction Xcalibur (Sapphire1) diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2009)
T_min, T_max	0.946, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	23613, 4650, 4013
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.118, 1.04
No. of reflections	4650
No. of parameters	400
No. of restraints	119
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.28

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

Cg2 and Cg4 are the centroids of the N2/C6–C9 and C17–C22 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2A	0.97 (2)	2.083 (19)	2.984 (2)	153.2 (18)
O1—H2O1···O2Aⁱ	0.972 (16)	2.222 (16)	3.105 (2)	150.4 (16)
O1—H1O1···O2B	0.97 (2)	2.334 (23)	3.297 (10)	170 (2)
O1—H2O1···O2Bⁱ	0.97 (2)	2.190 (19)	2.962 (8)	135 (1)
C15—H15···Cg4ⁱⁱ	0.9300	2.96	3.730 (2)	141
C27A—H27A···Cg2ⁱⁱⁱ	0.9700	2.86	3.671 (5)	142
C26B—H26D···Cg2	0.9700	2.89	3.678 (11)	139
C27B—H27D···Cg2ⁱⁱⁱ	0.9700	2.94	3.715 (17)	139

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

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 2| February 2013| Pages m114-m115

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