Crystal structure of di-aqua-[5,10,15,20-tetra-kis-(4-bromo-phen-yl)porphyrinato-κ(4) N]magnesium.

The title compound, [Mg(C44H24Br4N4)(H2O)2] or [Mg(TBrPP)(H2O)2], where TBrPP is the 5,10,15,20-tetra-kis-(4-bromo-phen-yl)porphyrinato ligand, was obtained unintentionally as a by-product of the reaction of the [Mg(TBrPP)] complex with an excess of di-methyl-glyoxime in di-chloro-methane. The entire mol-ecule 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 mol-ecule are incompatible with the fourfold rotation axis and are disordered over two sites. In the crystal, mol-ecules are packed in rows along [001]. Weak inter-molecular C-H⋯π and C-H⋯Br inter-actions, as well as O-H⋯Br hydrogen bonds, stabilize the crystal packing.

Related literature

For general background to magnesium porphyrin species and their applications, see: Ghosh et al. (2010 ▸). For the synthesis of the [MgII(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 ▸).

Experimental

Crystal data

[Mg(C44H24Br4N4)(H2O)2]

M = 988.65

Tetragonal,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.073

S = 1.06

1248 reflections

81 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.34 e Å−3

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 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015003722/wm5127sup1.cif

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

Click here for additional data file.

44 24 4 4 2 2 . DOI: 10.1107/S2056989015003722/wm5127fig1.tif

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.

Click here for additional data file.

. DOI: 10.1107/S2056989015003722/wm5127fig2.tif

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).

CCDC reference: 1050856

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Mg(C44H24Br4N4)(H2O)2]	Dx = 1.589 Mg m−3
Mr = 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

Bruker APEXII diffractometer	940 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
CCD rotation images, thin slices scans	θmax = 27.5°, θmin = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −14→19
Tmin = 0.409, Tmax = 0.575	k = −18→18
4471 measured reflections	l = −5→12
1248 independent reflections

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(Fo2) + (0.0364P)2 + 0.9155P] where P = (Fo2 + 2Fc2)/3
1248 reflections	(Δ/σ)max = 0.009
81 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)

	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

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—C12iv	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—C13iv	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—C12iv	118.3 (3)
C1—N1—Mg	126.5 (2)	C12—C11—C5	120.85 (15)
N1—C1—C5	125.3 (3)	C12iv—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—C13iv	121.9 (3)
C4—C3—H3	126.7	C13—C14—Br1	119.04 (15)
N1—C4—C5iii	125.5 (3)	C13iv—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—C12iv	−89.7 (3)
Mg—N1—C1—C2	180	C4i—C5—C11—C12iv	90.3 (3)
N1—C1—C2—C3	0	C12iv—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—C13iv	0.1 (5)
Mg—N1—C4—C5iii	0	C12—C13—C14—Br1	178.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···Cg1v	0.95	2.74	3.615 (3)	153
O1—H1O1···Br1vi	1.10 (5)	2.69 (5)	3.741 (3)	159 (4)
C2—H2···Br1vii	0.95	2.97	3.914 (3)	175 (1)

Table 1

Hydrogen-bond geometry (, )

Cg1 is the centroid of the N1/C1C4 pyrrole ring.

DHA	DH	HA	D A	DHA
C13H13Cg1i	0.95	2.74	3.615(3)	153
O1H1O1Br1ii	1.10(5)	2.69(5)	3.741(3)	159(4)
C2H2Br1iii	0.95	2.97	3.914(3)	175(1)

Symmetry codes: (i) ; (ii) ; (iii) .