Crystal structure of di­aqua­[5,10,15,20-tetra­kis­(4-bromo­phen­yl)porphyrinato-κ4N]magnesium

Amiri, N.; Nasri, S.; Roisnel, T.; Simonneaux, G.; Nasri, H.

doi:10.1107/S2056989015003722

metal-organic compounds

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Crystal structure of diaqua[5,10,15,20-tetrakis(4-bromophenyl)porphyrinato-κ⁴N]magnesium

Nesrine Amiri,^a ^* Soumaya Nasri,^a Thierry Roisnel,^b Gérard Simonneaux ^c and Habib Nasri ^a

^aDépartement de Chimie, Faculté des Sciences de Monastir, Université de Monastir, Avenue de l'environnement, 5019 Monastir, Tunisia, ^bCentre de Diffractométrie X, Institut des Sciences Chimiques de Rennes, UMR 6226, CNRS–Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France, and ^cInstitute of Sciences Chimiques of Rennes, Ingénierie Chimique et Molécules pour le vivant, UMR 6226 CNRS, Campus de Beaulieu, 35042 Rennes Cedex, France
^*Correspondence e-mail: nesamiri@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 11 February 2015; accepted 23 February 2015; online 28 February 2015)

The title compound, [Mg(C₄₄H₂₄Br₄N₄)(H₂O)₂] or [Mg(TBrPP)(H₂O)₂], where TBrPP is the 5,10,15,20-tetrakis(4-bromophenyl)porphyrinato ligand, was obtained unintentionally as a by-product of the reaction of the [Mg(TBrPP)] complex with an excess of dimethylglyoxime in dichloromethane. The entire molecule exhibits point group symmetry 4/m. In the asymmetric unit, except for two C atoms of the phenyl ring, all other atoms lie on special positions. The Mg^II atom is situated at a site with symmetry 4/m, while the N and the C atoms of the porphyrin macrocycle, as well as two C atoms of the phenyl ring and the Br atom lie in the mirror plane containing the porphyrin core. The H atoms of the axially bonded water molecule are incompatible with the fourfold rotation axis and are disordered over two sites. In the crystal, molecules are packed in rows along [001]. Weak intermolecular C—H⋯π and C—H⋯Br interactions, as well as O—H⋯Br hydrogen bonds, stabilize the crystal packing.

Keywords: crystal structure; magnesium porphyrin complex; O—H⋯Br hydrogen bonds; C—H⋯Br interactions; C—H⋯π interactions.

CCDC reference: 1050856

1. Related literature

For general background to magnesium porphyrin species and their applications, see: Ghosh et al. (2010 ). For the synthesis of the [Mg^II(TPP)(H₂O)] complex (TPP is the 5,10,15,20-tetraphenylporphyrinate ligand), see: Timkovich & Tulinsky (1969 ). In the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2014 ), there are six magnesium porphyrin structures with aqua ligands deposited. Four from these structures are monoaqua species, derived from [Mg(TOMePP)(H₂O)] (TOMePP is the 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinate ligand; Yang & Jacobson, 1991 ) and one is a diaqua derivative, [Mg(TPP)(H₂O)₂]·(18-C-6) where 18-C-6 is 18-crown-6 ether (Ezzayani et al., 2013 ). For the related porphyrin species [Mg(TPP)(4-pic)₂] (4-pic = 4-picoline) and [Mg(TPP)(H₂O)], see: McKee et al. (1984 ) and Ong et al. (1986 ), respectively. The H atom position of the aqua axial ligand was calculated with the program CALC-OH (Nardelli, 1999 ).

2. Experimental

2.1. Crystal data

[Mg(C₄₄H₂₄Br₄N₄)(H₂O)₂]
M_r = 988.65
Tetragonal, I 4/m
a = 14.8313 (10) Å
c = 9.3966 (8) Å
V = 2066.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 3.95 mm⁻¹
T = 150 K
0.37 × 0.27 × 0.14 mm

2.2. Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.409, T_max = 0.575
4471 measured reflections
1248 independent reflections
940 reflections with I > 2σ(I)
R_int = 0.034

2.3. Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.073
S = 1.06
1248 reflections
81 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/C1–C4 pyrrole ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯Cg1ⁱ	0.95	2.74	3.615 (3)	153
O1—H1O1⋯Br1ⁱⁱ	1.10 (5)	2.69 (5)	3.741 (3)	159 (4)
C2—H2⋯Br1ⁱⁱⁱ	0.95	2.97	3.914 (3)	175 (1)
Symmetry codes: (i) y, -x, -z; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) y, -x, z.

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1050856

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015003722/wm5127sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015003722/wm5127Isup2.hkl

checkCIF report

Synthesis and crystallization top

To a solution of [Mg(TBrPP)] (15 mg, 0.015 mmol) in dichloromethane (10 ml) was added an excess of dimethylglyoxime (50 mg, 0.431 mmol). The reaction mixture was stirred at room temperature and at the end of the reaction, the color of the solution gradually changed from purple to blue–purple. Black coloured crystals of the title complex were obtained by diffusion of n-hexane through the dichloromethane solution. The two water molecules coordinating to the magnesium atom most probably originated from the undistilled dichloromethane solvent.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). The H atom position of the axially bonded aqua ligand was calculated with the CALC-OH program (Nardelli, 1999). The molecular symmetry of the water molecule is not compatible with the fourfold axis, hence the occupancy of this H atom was fixed to 0.5.

Related literature top

For general background to magnesium porphyrin species and their applications, see: Ghosh et al. (2010). For the synthesis of the [Mg^II(TPP)(H₂O)] complex (TPP is the 5,10,15,20-tetraphenylporphyrinate ligand), see: Timkovich & Tulinsky (1969). In the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2014), there are six magnesium porphyrin structures with aqua ligands deposited. Four from these structures are monoaqua species, derived from [Mg(TOMePP)(H₂O)] (TOMePP is the 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinate ligand; Yang & Jacobson, 1991) and one is a diaqua derivative, [Mg(TPP)(H₂O)₂]·(18-C-6) where 18-C-6 is 18-crown-6 ether (Ezzayani et al., 2013). For the related porphyrin species [Mg(TPP)(4-pic)₂] (4-pic = 4-picoline) and [Mg(TPP)(H₂O)], see: McKee et al. (1984) and Ong et al. (1986), respectively. The H atom position of the aqua axial ligand was calculated with the program CALC-OH (Nardelli, 1999).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. A view of the molecular structure of [Mg(C₄₄H₂₄N₄Br₄)(H₂O)₂] showing the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 2. A portion of the crystal packing of the title complex, viewed down [001], showing C—H···π interactions (dotted light-blue lines) and C—H···Br and O—H···Br hydrogen bonds (dashed pink lines).

Diaqua[5,10,15,20-tetrakis(4–bromophenyl)porphyrinato-κ⁴N]magnesium top

Crystal data top

[Mg(C₄₄H₂₄Br₄N₄)(H₂O)₂]	D_x = 1.589 Mg m⁻³
M_r = 988.65	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4/m	Cell parameters from 1411 reflections
Hall symbol: -I 4	θ = 2.6–26.9°
a = 14.8313 (10) Å	µ = 3.95 mm⁻¹
c = 9.3966 (8) Å	T = 150 K
V = 2066.9 (2) Å³	Prism, black
Z = 2	0.37 × 0.27 × 0.14 mm
F(000) = 976

Data collection top

Bruker APEXII diffractometer	940 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
CCD rotation images, thin slices scans	θ_max = 27.5°, θ_min = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −14→19
T_min = 0.409, T_max = 0.575	k = −18→18
4471 measured reflections	l = −5→12
1248 independent 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0364P)² + 0.9155P] where P = (F_o² + 2F_c²)/3
1248 reflections	(Δ/σ)_max = 0.009
81 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Mg(C₄₄H₂₄Br₄N₄)(H₂O)₂]	Z = 2
M_r = 988.65	Mo Kα radiation
Tetragonal, I4/m	µ = 3.95 mm⁻¹
a = 14.8313 (10) Å	T = 150 K
c = 9.3966 (8) Å	0.37 × 0.27 × 0.14 mm
V = 2066.9 (2) Å³

Data collection top

Bruker APEXII diffractometer	1248 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	940 reflections with I > 2σ(I)
T_min = 0.409, T_max = 0.575	R_int = 0.034
4471 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.50 e Å⁻³
1248 reflections	Δρ_min = −0.34 e Å⁻³
81 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)
Mg	0.5	0.5	0.5	0.0248 (5)
O1	0.5	0.5	0.2636 (4)	0.0376 (9)
H1O1	0.473 (4)	0.560 (3)	0.210 (6)	0.045*	0.5
N1	0.46158 (17)	0.36592 (17)	0.5	0.0192 (6)
C1	0.3751 (2)	0.3337 (2)	0.5	0.0183 (7)
C2	0.3771 (2)	0.2366 (2)	0.5	0.0195 (7)
H2	0.3262	0.1977	0.5	0.023*
C3	0.4643 (2)	0.2109 (2)	0.5	0.0219 (7)
H3	0.4865	0.1508	0.5	0.026*
C4	0.5177 (2)	0.2931 (2)	0.5	0.0196 (7)
C5	0.2966 (2)	0.3872 (2)	0.5	0.0179 (7)
C11	0.2081 (2)	0.33768 (19)	0.5	0.0192 (7)
C12	0.16663 (16)	0.31403 (16)	0.6263 (3)	0.0307 (6)
H12	0.1942	0.3299	0.714	0.037*
C13	0.08517 (16)	0.26732 (17)	0.6273 (3)	0.0324 (6)
H13	0.0572	0.2512	0.7146	0.039*
C14	0.0463 (2)	0.2451 (2)	0.5	0.0229 (7)
Br1	−0.06342 (2)	0.17805 (2)	0.5	0.03531 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mg	0.0142 (7)	0.0142 (7)	0.0461 (16)	0	0	0
O1	0.0376 (13)	0.0376 (13)	0.038 (2)	0	0	0
N1	0.0124 (13)	0.0162 (14)	0.0290 (16)	−0.0007 (10)	0	0
C1	0.0169 (16)	0.0150 (16)	0.0231 (18)	−0.0024 (12)	0	0
C2	0.0199 (16)	0.0152 (15)	0.0233 (18)	−0.0031 (12)	0	0
C3	0.0246 (17)	0.0137 (15)	0.0274 (19)	0.0007 (13)	0	0
C4	0.0186 (16)	0.0167 (16)	0.0234 (18)	−0.0014 (13)	0	0
C5	0.0164 (16)	0.0165 (16)	0.0209 (18)	−0.0009 (13)	0	0
C11	0.0166 (16)	0.0114 (15)	0.0296 (19)	0.0002 (12)	0	0
C12	0.0260 (13)	0.0389 (15)	0.0272 (14)	−0.0117 (11)	0.0002 (11)	−0.0054 (12)
C13	0.0295 (14)	0.0356 (15)	0.0321 (15)	−0.0096 (11)	0.0095 (12)	−0.0013 (12)
C14	0.0158 (16)	0.0129 (16)	0.040 (2)	−0.0010 (12)	0	0
Br1	0.01523 (19)	0.0223 (2)	0.0684 (3)	−0.00419 (14)	0	0

Geometric parameters (Å, º) top

Mg—N1ⁱ	2.069 (2)	C3—C4	1.454 (4)
Mg—N1	2.069 (2)	C3—H3	0.95
Mg—N1ⁱⁱ	2.069 (2)	C4—C5ⁱⁱⁱ	1.412 (4)
Mg—N1ⁱⁱⁱ	2.069 (2)	C5—C4ⁱ	1.412 (4)
Mg—O1ⁱⁱ	2.221 (4)	C5—C11	1.504 (4)
Mg—O1	2.221 (4)	C11—C12	1.382 (3)
O1—H1O1	1.10 (5)	C11—C12^iv	1.382 (3)
N1—C4	1.363 (4)	C12—C13	1.393 (3)
N1—C1	1.368 (4)	C12—H12	0.95
C1—C5	1.409 (4)	C13—C14	1.369 (3)
C1—C2	1.440 (4)	C13—H13	0.95
C2—C3	1.348 (4)	C14—C13^iv	1.369 (3)
C2—H2	0.95	C14—Br1	1.906 (3)

N1ⁱ—Mg—N1	89.998 (2)	N1—C4—C3	109.4 (3)
N1—Mg—N1ⁱⁱ	180.00 (14)	C5ⁱⁱⁱ—C4—C3	125.1 (3)
O1ⁱⁱ—Mg—O1	180	C1—C5—C4ⁱ	126.4 (3)
Mg—O1—H1O1	117 (3)	C1—C5—C11	116.5 (3)
C4—N1—C1	107.1 (2)	C4ⁱ—C5—C11	117.1 (3)
C4—N1—Mg	126.4 (2)	C12—C11—C12^iv	118.3 (3)
C1—N1—Mg	126.5 (2)	C12—C11—C5	120.85 (15)
N1—C1—C5	125.3 (3)	C12^iv—C11—C5	120.85 (15)
N1—C1—C2	109.3 (3)	C11—C12—C13	121.3 (2)
C5—C1—C2	125.5 (3)	C11—C12—H12	119.4
C3—C2—C1	107.6 (3)	C13—C12—H12	119.4
C3—C2—H2	126.2	C14—C13—C12	118.7 (2)
C1—C2—H2	126.2	C14—C13—H13	120.7
C2—C3—C4	106.6 (3)	C12—C13—H13	120.7
C2—C3—H3	126.7	C13—C14—C13^iv	121.9 (3)
C4—C3—H3	126.7	C13—C14—Br1	119.04 (15)
N1—C4—C5ⁱⁱⁱ	125.5 (3)	C13^iv—C14—Br1	119.05 (15)

N1ⁱ—Mg—N1—C4	180	C1—N1—C4—C3	0
N1ⁱⁱⁱ—Mg—N1—C4	0	Mg—N1—C4—C3	180
O1ⁱⁱ—Mg—N1—C4	−90	C2—C3—C4—N1	0
O1—Mg—N1—C4	90	C2—C3—C4—C5ⁱⁱⁱ	180
N1ⁱ—Mg—N1—C1	0	N1—C1—C5—C4ⁱ	0
N1ⁱⁱⁱ—Mg—N1—C1	180	C2—C1—C5—C4ⁱ	180
O1ⁱⁱ—Mg—N1—C1	90	N1—C1—C5—C11	180
O1—Mg—N1—C1	−90	C2—C1—C5—C11	0
C4—N1—C1—C5	180	C1—C5—C11—C12	89.7 (3)
Mg—N1—C1—C5	0	C4ⁱ—C5—C11—C12	−90.3 (3)
C4—N1—C1—C2	0	C1—C5—C11—C12^iv	−89.7 (3)
Mg—N1—C1—C2	180	C4ⁱ—C5—C11—C12^iv	90.3 (3)
N1—C1—C2—C3	0	C12^iv—C11—C12—C13	0.2 (5)
C5—C1—C2—C3	180	C5—C11—C12—C13	−179.3 (2)
C1—C2—C3—C4	0	C11—C12—C13—C14	−0.1 (4)
C1—N1—C4—C5ⁱⁱⁱ	180	C12—C13—C14—C13^iv	0.1 (5)
Mg—N1—C4—C5ⁱⁱⁱ	0	C12—C13—C14—Br1	178.2 (2)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/C1–C4 pyrrole ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cg1^v	0.95	2.74	3.615 (3)	153
O1—H1O1···Br1^vi	1.10 (5)	2.69 (5)	3.741 (3)	159 (4)
C2—H2···Br1^vii	0.95	2.97	3.914 (3)	175 (1)

Symmetry codes: (v) y, −x, −z; (vi) x+1/2, y+1/2, z−1/2; (vii) y, −x, z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/C1–C4 pyrrole ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cg1ⁱ	0.95	2.74	3.615 (3)	153
O1—H1O1···Br1ⁱⁱ	1.10 (5)	2.69 (5)	3.741 (3)	159 (4)
C2—H2···Br1ⁱⁱⁱ	0.95	2.966	3.914 (3)	175.2 (2)

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

Acknowledgements

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

References

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