metal-organic compounds
Aqua(4-cyanopyridine-κN4)(5,10,15,20-tetraphenylporphyrinato-κ4N)magnesium
aLaboratoire de Physico-chimie des Matériaux, Université de Monastir, Faculté des Sciences de Monastir, Avenue de l'Environnement, 5019 Monastir, Tunisia, bFaculdade de Medicina, Veterinària, Universidade Tecnica de Lisboa, Avenida da Universidade Tecnica, 1300-477 Lisboa, Portugal, and cREQUIMTE/CQFB Departamento de Quimica, Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal
*Correspondence e-mail: hnasri1@gmail.com
In the title complex, [Mg(C44H28N4)(C6H4N2)(H2O)], the Mg2+ cation is octahedrally coordinated and lies on an inversion center with the axially located 4-cyanopyridine and aqua ligands exhibiting 50% substitutional disorder. The cyano-bound 4-cyanopyridine molecule also is disordered across the inversion centre. The four N atoms of the pyrrole rings of the dianionic 5,10,15,20-tetraphenylporphyrin ligand occupy the equatorial sites of the octahedron [Mg—N = 2.0552 (10) and 2.0678 (11) Å] and the axial Mg—(N,O) bond length is 2.3798 (12) Å. The crystal packing is stabilized by weak intermolecular C—H⋯π interactions.
Related literature
For general background to magnesium porphyrin species and their applications, see: Ghosh et al. (2010). For the synthesis of the [Mg(TPP)(H2O)] (TPP is tetraphenylporphyrin) complex, see: Timkovich & Tulinsky (1969). For related structures, see: Choon et al. (1986); Imaz et al. (2005); Hibbs et al. (2003); Etkin et al. (1998); Yang et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; 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
https://doi.org/10.1107/S1600536812049434/zs2246sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049434/zs2246Isup2.hkl
To a solution of [Mg(TPP)(H2O)] (Timkovich & Tulinsky, 1969) (15 mg, 0.022 mmol) in chlorobenzene (10 ml) was added an excess of 4-cyanopyridine (50 mg, 0.480 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. Crystals of the title complex were obtained by diffusion of n-hexane through the chlorobenzene solution.
The H atoms of the statistically disordered aqua ligand were not consideredted. and all H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were not located
The majority of the reported metalloporphyrin structures involve metals from the first-row transition series. However, the structures of magnesium
are also of interest because of their relationship to chlorophyll. but the Cambridge Structural Database (CSD; Allen, 2002) contains only 24 structures of these. In order to gain more insight into the geometry of the latter species, we report herein the of the title complex, [Mg(TPP)(4-CNpy)(H2O)] (where TPP is the 5,10,15,20-tetraphenylporphyrin dianion and 4-CNpy is 4-cyanopyridine).In the title complex the Mg cation is octahedrally coordinated and lies on an inversion center with the axially-located 4-cyanopyridine and aqua ligands having occupancy factors of 0.5. The atoms of these disordered ligands are divided in two parts: in part 1, the fragment containing the atoms N3, C23, C24, C25A and C26A and in part 2, the atoms O1, N4, C25B and C26B, related by the symmetry code (i) -x, -y+1, -z+1. The 4-cyanopyridine ligand also has inversion symmetry with 50% occupancy [symmetry code (ii): -x+1, -y, -z+1] (Fig. 1). The average equatorial Mg—N(pyrrole) bond distance [2.062 (1) Å] is normal for Mg–porphyrin complexes. The Mg—O(H2O) bond length [2.3798 (12)Å] is longer than that found in the related complex [Mg(TPP)(H2O)] (2.012 (6) Å) (Choon et al., 1986) but is shorter than the one reported for the non-porphyrin complex catena-[diaquatetrakis(µ4-oxalato)-tris(µ2-oxalato)- dimagnesium-dipotassium-diuranium(IV) nonahydrate clathrate] [2.747 (5) Å] (Imaz et al., 2005).
The axial Mg—N(4-CNpy) bond length [2.3798 (12) Å] is longer than that found in the [Mg(TPP)][TCNQF4] complex [2.266 (2) Å] (where TCNQF4 is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) (Hibbs et al., 2003), but is within the range of 2.152 (2)–2.57 (1) Å found for several magnesium-nitrile non-porphyrin complexes in the CSD [refcodes FEGQAJ (Etkin et al., 1998) and SISWUN (Yang et al., 2008) (Allen, 2002).
The π intermolecular interactions involving Cg pyrrole and phenyl rings (Table 1 and Fig. 2).
resembles a one-dimensional coordination polymer where two [Mg(TPP)] moieties are linked by statistically 50% disordered 4-cyanopyridine and H2O ligands. The crystal packing of the title compound is stabilized by weak C—H···For general background to magnesium porphyrin species and their applications, see: Ghosh et al. (2010). For the synthesis of the [Mg(TPP)(H2O)] complex, see: Timkovich & Tulinsky (1969). For related structures, see: Choon et al. (1986); Imaz et al. (2005); Hibbs et al. (2003); Etkin et al. (1998); Yang et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).[Mg(C44H28N4)(C6H4N2)(H2O)] | Z = 1 |
Mr = 757.13 | F(000) = 394.0 |
Triclinic, P1 | Dx = 1.293 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9080 (3) Å | Cell parameters from 6453 reflections |
b = 10.7550 (4) Å | θ = 2.7–27.9° |
c = 11.9530 (6) Å | µ = 0.09 mm−1 |
α = 63.446 (1)° | T = 296 K |
β = 89.364 (2)° | Block, purple |
γ = 73.408 (1)° | 0.48 × 0.40 × 0.24 mm |
V = 972.60 (7) Å3 |
Bruker APEXII CCD diffractometer | 3792 independent reflections |
Radiation source: fine-focus sealed tube | 3307 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
φ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −8→10 |
Tmin = 0.955, Tmax = 0.978 | k = −13→13 |
11765 measured reflections | l = −14→14 |
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) = 0.103 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0446P)2 + 0.2998P] where P = (Fo2 + 2Fc2)/3 |
3792 reflections | (Δ/σ)max = 0.001 |
268 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
[Mg(C44H28N4)(C6H4N2)(H2O)] | γ = 73.408 (1)° |
Mr = 757.13 | V = 972.60 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.9080 (3) Å | Mo Kα radiation |
b = 10.7550 (4) Å | µ = 0.09 mm−1 |
c = 11.9530 (6) Å | T = 296 K |
α = 63.446 (1)° | 0.48 × 0.40 × 0.24 mm |
β = 89.364 (2)° |
Bruker APEXII CCD diffractometer | 3792 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 3307 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.978 | Rint = 0.023 |
11765 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.22 e Å−3 |
3792 reflections | Δρmin = −0.54 e Å−3 |
268 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mg | 0.0000 | 0.5000 | 0.5000 | 0.0558 (3) | |
N1 | 0.12116 (13) | 0.31528 (11) | 0.66326 (11) | 0.0307 (3) | |
N2 | −0.15077 (13) | 0.39306 (11) | 0.48540 (10) | 0.0289 (2) | |
C1 | 0.25095 (15) | 0.29941 (14) | 0.73443 (12) | 0.0291 (3) | |
C2 | 0.30581 (17) | 0.15246 (14) | 0.83701 (13) | 0.0327 (3) | |
H2 | 0.3920 | 0.1139 | 0.8989 | 0.039* | |
C3 | 0.20800 (17) | 0.08127 (14) | 0.82614 (13) | 0.0320 (3) | |
H3 | 0.2143 | −0.0154 | 0.8793 | 0.038* | |
C4 | 0.09273 (15) | 0.18314 (13) | 0.71703 (12) | 0.0286 (3) | |
C5 | −0.02834 (15) | 0.15157 (13) | 0.66983 (12) | 0.0279 (3) | |
C6 | −0.14087 (15) | 0.25020 (13) | 0.56257 (12) | 0.0284 (3) | |
C7 | −0.26537 (16) | 0.21639 (15) | 0.51694 (14) | 0.0336 (3) | |
H7 | −0.2849 | 0.1269 | 0.5526 | 0.040* | |
C8 | −0.34809 (16) | 0.33799 (15) | 0.41330 (14) | 0.0342 (3) | |
H8 | −0.4355 | 0.3485 | 0.3642 | 0.041* | |
C9 | −0.27529 (15) | 0.44944 (14) | 0.39274 (13) | 0.0292 (3) | |
C10 | 0.32299 (15) | 0.40857 (14) | 0.70979 (13) | 0.0294 (3) | |
C11 | 0.45965 (16) | 0.37258 (14) | 0.80258 (13) | 0.0312 (3) | |
C12 | 0.61223 (18) | 0.34910 (18) | 0.77378 (16) | 0.0457 (4) | |
H12 | 0.6319 | 0.3527 | 0.6960 | 0.055* | |
C13 | 0.7370 (2) | 0.32017 (19) | 0.85992 (19) | 0.0557 (5) | |
H13 | 0.8394 | 0.3047 | 0.8393 | 0.067* | |
C14 | 0.7102 (2) | 0.31430 (17) | 0.97470 (17) | 0.0544 (5) | |
H14 | 0.7938 | 0.2953 | 1.0321 | 0.065* | |
C15 | 0.5591 (3) | 0.3367 (2) | 1.00457 (16) | 0.0604 (5) | |
H15 | 0.5402 | 0.3322 | 1.0828 | 0.073* | |
C16 | 0.4342 (2) | 0.36610 (19) | 0.91893 (15) | 0.0484 (4) | |
H16 | 0.3321 | 0.3816 | 0.9401 | 0.058* | |
C17 | −0.03842 (15) | −0.00131 (14) | 0.73710 (12) | 0.0286 (3) | |
C18 | −0.1134 (2) | −0.04637 (17) | 0.84312 (16) | 0.0474 (4) | |
H18 | −0.1529 | 0.0167 | 0.8777 | 0.057* | |
C19 | −0.1303 (2) | −0.18509 (18) | 0.89874 (17) | 0.0546 (5) | |
H19 | −0.1808 | −0.2143 | 0.9703 | 0.065* | |
C20 | −0.07258 (19) | −0.27960 (16) | 0.84860 (15) | 0.0423 (4) | |
H20 | −0.0866 | −0.3714 | 0.8846 | 0.051* | |
C21 | 0.00540 (19) | −0.23746 (15) | 0.74544 (14) | 0.0402 (3) | |
H21 | 0.0466 | −0.3015 | 0.7122 | 0.048* | |
C22 | 0.02310 (18) | −0.09931 (15) | 0.69032 (13) | 0.0355 (3) | |
H22 | 0.0773 | −0.0721 | 0.6207 | 0.043* | |
N3 | 0.17377 (15) | 0.40333 (15) | 0.38534 (13) | 0.0541 (3) | 0.50 |
C23 | 0.2697 (3) | 0.2742 (3) | 0.4230 (3) | 0.0370 (6) | 0.50 |
C24 | 0.38443 (16) | 0.13429 (15) | 0.45960 (14) | 0.0406 (3) | 0.50 |
C25A | 0.43163 (19) | 0.04190 (18) | 0.58443 (17) | 0.0465 (4) | 0.50 |
H25A | 0.3859 | 0.0692 | 0.6437 | 0.056* | 0.50 |
C26A | 0.45348 (19) | 0.09187 (17) | 0.37545 (16) | 0.0436 (4) | 0.50 |
H26A | 0.4230 | 0.1538 | 0.2894 | 0.052* | 0.50 |
O1 | 0.17377 (15) | 0.40333 (15) | 0.38534 (13) | 0.0541 (3) | 0.50 |
C25B | 0.43163 (19) | 0.04190 (18) | 0.58443 (17) | 0.0465 (4) | 0.50 |
H25B | 0.3859 | 0.0692 | 0.6437 | 0.056* | 0.50 |
C26B | 0.45348 (19) | 0.09187 (17) | 0.37545 (16) | 0.0436 (4) | 0.50 |
H26B | 0.4230 | 0.1538 | 0.2894 | 0.052* | 0.50 |
N4 | 0.38443 (16) | 0.13429 (15) | 0.45960 (14) | 0.0406 (3) | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mg | 0.0624 (5) | 0.0257 (4) | 0.0585 (5) | −0.0250 (3) | −0.0308 (4) | 0.0055 (3) |
N1 | 0.0329 (6) | 0.0214 (5) | 0.0355 (6) | −0.0107 (5) | −0.0004 (5) | −0.0098 (5) |
N2 | 0.0306 (6) | 0.0205 (5) | 0.0339 (6) | −0.0090 (4) | 0.0014 (5) | −0.0103 (5) |
C1 | 0.0312 (7) | 0.0237 (6) | 0.0315 (7) | −0.0080 (5) | 0.0023 (5) | −0.0125 (5) |
C2 | 0.0379 (7) | 0.0262 (7) | 0.0306 (7) | −0.0092 (6) | −0.0013 (6) | −0.0106 (6) |
C3 | 0.0408 (8) | 0.0219 (6) | 0.0301 (7) | −0.0105 (6) | 0.0026 (6) | −0.0090 (5) |
C4 | 0.0326 (7) | 0.0216 (6) | 0.0318 (7) | −0.0093 (5) | 0.0063 (5) | −0.0121 (5) |
C5 | 0.0312 (7) | 0.0224 (6) | 0.0317 (7) | −0.0103 (5) | 0.0074 (5) | −0.0127 (5) |
C6 | 0.0299 (7) | 0.0228 (6) | 0.0352 (7) | −0.0112 (5) | 0.0076 (5) | −0.0141 (6) |
C7 | 0.0333 (7) | 0.0256 (7) | 0.0430 (8) | −0.0143 (6) | 0.0042 (6) | −0.0137 (6) |
C8 | 0.0314 (7) | 0.0289 (7) | 0.0430 (8) | −0.0134 (6) | 0.0013 (6) | −0.0147 (6) |
C9 | 0.0285 (7) | 0.0250 (6) | 0.0357 (7) | −0.0094 (5) | 0.0038 (5) | −0.0149 (6) |
C10 | 0.0294 (7) | 0.0251 (6) | 0.0336 (7) | −0.0084 (5) | 0.0027 (5) | −0.0137 (6) |
C11 | 0.0364 (7) | 0.0207 (6) | 0.0353 (7) | −0.0104 (5) | −0.0002 (6) | −0.0111 (6) |
C12 | 0.0351 (8) | 0.0512 (9) | 0.0553 (10) | −0.0066 (7) | 0.0015 (7) | −0.0325 (8) |
C13 | 0.0335 (8) | 0.0517 (10) | 0.0795 (13) | −0.0031 (7) | −0.0095 (8) | −0.0341 (10) |
C14 | 0.0607 (11) | 0.0328 (8) | 0.0578 (11) | −0.0146 (8) | −0.0252 (9) | −0.0103 (8) |
C15 | 0.0873 (15) | 0.0642 (12) | 0.0346 (9) | −0.0411 (11) | −0.0020 (9) | −0.0162 (8) |
C16 | 0.0549 (10) | 0.0589 (10) | 0.0407 (9) | −0.0323 (8) | 0.0104 (7) | −0.0224 (8) |
C17 | 0.0307 (7) | 0.0229 (6) | 0.0311 (7) | −0.0108 (5) | 0.0024 (5) | −0.0101 (5) |
C18 | 0.0646 (11) | 0.0353 (8) | 0.0525 (10) | −0.0237 (8) | 0.0282 (8) | −0.0246 (8) |
C19 | 0.0731 (12) | 0.0412 (9) | 0.0552 (10) | −0.0326 (9) | 0.0328 (9) | −0.0190 (8) |
C20 | 0.0516 (9) | 0.0259 (7) | 0.0459 (9) | −0.0199 (7) | 0.0004 (7) | −0.0090 (6) |
C21 | 0.0512 (9) | 0.0269 (7) | 0.0447 (8) | −0.0114 (6) | 0.0011 (7) | −0.0188 (7) |
C22 | 0.0448 (8) | 0.0293 (7) | 0.0337 (7) | −0.0133 (6) | 0.0081 (6) | −0.0148 (6) |
N3 | 0.0445 (7) | 0.0621 (9) | 0.0702 (9) | −0.0178 (6) | 0.0123 (6) | −0.0423 (8) |
C23 | 0.0330 (14) | 0.0408 (16) | 0.0484 (17) | −0.0179 (13) | 0.0103 (12) | −0.0266 (14) |
C24 | 0.0332 (7) | 0.0348 (7) | 0.0597 (9) | −0.0124 (6) | 0.0090 (6) | −0.0258 (7) |
C25A | 0.0426 (9) | 0.0494 (9) | 0.0586 (10) | −0.0149 (7) | 0.0168 (8) | −0.0342 (9) |
C26A | 0.0428 (9) | 0.0408 (8) | 0.0469 (9) | −0.0141 (7) | 0.0085 (7) | −0.0196 (7) |
O1 | 0.0445 (7) | 0.0621 (9) | 0.0702 (9) | −0.0178 (6) | 0.0123 (6) | −0.0423 (8) |
C25B | 0.0426 (9) | 0.0494 (9) | 0.0586 (10) | −0.0149 (7) | 0.0168 (8) | −0.0342 (9) |
C26B | 0.0428 (9) | 0.0408 (8) | 0.0469 (9) | −0.0141 (7) | 0.0085 (7) | −0.0196 (7) |
N4 | 0.0332 (7) | 0.0348 (7) | 0.0597 (9) | −0.0124 (6) | 0.0090 (6) | −0.0258 (7) |
Mg—N2i | 2.0552 (10) | C12—C13 | 1.391 (2) |
Mg—N2 | 2.0552 (10) | C12—H12 | 0.9300 |
Mg—N1i | 2.0678 (11) | C13—C14 | 1.366 (3) |
Mg—N1 | 2.0678 (11) | C13—H13 | 0.9300 |
Mg—N3 | 2.3798 (12) | C14—C15 | 1.371 (3) |
Mg—O1i | 2.3798 (12) | C14—H14 | 0.9300 |
Mg—N3i | 2.3798 (12) | C15—C16 | 1.386 (2) |
N1—C1 | 1.3670 (17) | C15—H15 | 0.9300 |
N1—C4 | 1.3720 (16) | C16—H16 | 0.9300 |
N2—C9 | 1.3666 (17) | C17—C18 | 1.380 (2) |
N2—C6 | 1.3700 (16) | C17—C22 | 1.3835 (18) |
C1—C10 | 1.4121 (18) | C18—C19 | 1.389 (2) |
C1—C2 | 1.4421 (18) | C18—H18 | 0.9300 |
C2—C3 | 1.3545 (19) | C19—C20 | 1.377 (2) |
C2—H2 | 0.9300 | C19—H19 | 0.9300 |
C3—C4 | 1.4371 (19) | C20—C21 | 1.367 (2) |
C3—H3 | 0.9300 | C20—H20 | 0.9300 |
C4—C5 | 1.4109 (18) | C21—C22 | 1.3866 (19) |
C5—C6 | 1.4068 (19) | C21—H21 | 0.9300 |
C5—C17 | 1.5029 (17) | C22—H22 | 0.9300 |
C6—C7 | 1.4425 (18) | N3—C23 | 1.278 (3) |
C7—C8 | 1.345 (2) | C23—C24 | 1.429 (3) |
C7—H7 | 0.9300 | C24—C26A | 1.355 (2) |
C8—C9 | 1.4473 (18) | C24—C25A | 1.357 (2) |
C8—H8 | 0.9300 | C25A—C26Aii | 1.379 (2) |
C9—C10i | 1.4079 (19) | C25A—H25A | 0.9300 |
C10—C11 | 1.4962 (18) | C26A—C25Aii | 1.379 (2) |
C11—C12 | 1.379 (2) | C26A—H26A | 0.9300 |
C11—C16 | 1.381 (2) | ||
N2i—Mg—N2 | 180.0 | N2—C9—C8 | 109.27 (11) |
N2i—Mg—N1i | 89.69 (4) | C10i—C9—C8 | 124.75 (12) |
N2—Mg—N1i | 90.31 (4) | C9i—C10—C1 | 125.94 (12) |
N2i—Mg—N1 | 90.31 (4) | C9i—C10—C11 | 116.57 (11) |
N2—Mg—N1 | 89.69 (4) | C1—C10—C11 | 117.46 (12) |
N1i—Mg—N1 | 180.00 (6) | C12—C11—C16 | 118.37 (14) |
N2i—Mg—N3 | 90.58 (4) | C12—C11—C10 | 121.54 (13) |
N2—Mg—N3 | 89.42 (4) | C16—C11—C10 | 120.07 (13) |
N1i—Mg—N3 | 92.22 (5) | C11—C12—C13 | 120.64 (16) |
N1—Mg—N3 | 87.78 (5) | C11—C12—H12 | 119.7 |
N2i—Mg—O1i | 89.42 (4) | C13—C12—H12 | 119.7 |
N2—Mg—O1i | 90.58 (4) | C14—C13—C12 | 120.42 (17) |
N1i—Mg—O1i | 87.78 (5) | C14—C13—H13 | 119.8 |
N1—Mg—O1i | 92.22 (5) | C12—C13—H13 | 119.8 |
N3—Mg—O1i | 180.0 | C13—C14—C15 | 119.42 (15) |
N2i—Mg—N3i | 89.42 (4) | C13—C14—H14 | 120.3 |
N2—Mg—N3i | 90.58 (4) | C15—C14—H14 | 120.3 |
N1i—Mg—N3i | 87.78 (5) | C14—C15—C16 | 120.40 (17) |
N1—Mg—N3i | 92.22 (5) | C14—C15—H15 | 119.8 |
N3—Mg—N3i | 180.0 | C16—C15—H15 | 119.8 |
O1i—Mg—N3i | 0.00 (5) | C11—C16—C15 | 120.74 (16) |
C1—N1—C4 | 106.86 (11) | C11—C16—H16 | 119.6 |
C1—N1—Mg | 126.20 (9) | C15—C16—H16 | 119.6 |
C4—N1—Mg | 126.85 (9) | C18—C17—C22 | 118.23 (12) |
C9—N2—C6 | 107.11 (10) | C18—C17—C5 | 121.67 (12) |
C9—N2—Mg | 126.19 (9) | C22—C17—C5 | 120.06 (12) |
C6—N2—Mg | 126.63 (9) | C17—C18—C19 | 120.57 (14) |
N1—C1—C10 | 125.41 (12) | C17—C18—H18 | 119.7 |
N1—C1—C2 | 109.50 (11) | C19—C18—H18 | 119.7 |
C10—C1—C2 | 125.07 (12) | C20—C19—C18 | 120.41 (15) |
C3—C2—C1 | 106.99 (12) | C20—C19—H19 | 119.8 |
C3—C2—H2 | 126.5 | C18—C19—H19 | 119.8 |
C1—C2—H2 | 126.5 | C21—C20—C19 | 119.51 (13) |
C2—C3—C4 | 107.15 (12) | C21—C20—H20 | 120.2 |
C2—C3—H3 | 126.4 | C19—C20—H20 | 120.2 |
C4—C3—H3 | 126.4 | C20—C21—C22 | 120.09 (13) |
N1—C4—C5 | 125.00 (12) | C20—C21—H21 | 120.0 |
N1—C4—C3 | 109.50 (11) | C22—C21—H21 | 120.0 |
C5—C4—C3 | 125.48 (12) | C17—C22—C21 | 121.14 (13) |
C6—C5—C4 | 125.88 (12) | C17—C22—H22 | 119.4 |
C6—C5—C17 | 115.96 (11) | C21—C22—H22 | 119.4 |
C4—C5—C17 | 118.15 (11) | C23—N3—Mg | 129.10 (16) |
N2—C6—C5 | 125.82 (11) | N3—C23—C24 | 176.0 (3) |
N2—C6—C7 | 109.15 (11) | C26A—C24—C25A | 118.27 (14) |
C5—C6—C7 | 125.04 (12) | C26A—C24—C23 | 123.09 (18) |
C8—C7—C6 | 107.45 (12) | C25A—C24—C23 | 118.58 (17) |
C8—C7—H7 | 126.3 | C24—C25A—C26Aii | 120.85 (15) |
C6—C7—H7 | 126.3 | C24—C25A—H25A | 119.6 |
C7—C8—C9 | 107.02 (12) | C26Aii—C25A—H25A | 119.6 |
C7—C8—H8 | 126.5 | C24—C26A—C25Aii | 120.88 (15) |
C9—C8—H8 | 126.5 | C24—C26A—H26A | 119.6 |
N2—C9—C10i | 125.94 (12) | C25Aii—C26A—H26A | 119.6 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Cg12 and Cg14 are the centroids of the N2/C6–C9 C17–C22 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···Cg12iii | 0.93 | 2.97 | 3.8860 (19) | 168 |
C14—H14···Cg14iv | 0.93 | 2.70 | 3.584 (2) | 159 |
C21—H21···Cg12v | 0.93 | 2.85 | 3.6240 (18) | 141 |
Symmetry codes: (iii) x+1, y, z; (iv) −x+1, −y, −z+2; (v) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mg(C44H28N4)(C6H4N2)(H2O)] |
Mr | 757.13 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 8.9080 (3), 10.7550 (4), 11.9530 (6) |
α, β, γ (°) | 63.446 (1), 89.364 (2), 73.408 (1) |
V (Å3) | 972.60 (7) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.48 × 0.40 × 0.24 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.955, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11765, 3792, 3307 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.103, 1.07 |
No. of reflections | 3792 |
No. of parameters | 268 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.54 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012).
Cg12 and Cg14 are the centroids of the N2/C6–C9 C17–C22 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···Cg12i | 0.93 | 2.97 | 3.8860 (19) | 168 |
C14—H14···Cg14ii | 0.93 | 2.70 | 3.584 (2) | 159 |
C21—H21···Cg12iii | 0.93 | 2.85 | 3.6240 (18) | 141 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y, −z+2; (iii) −x, −y, −z+1. |
Acknowledgements
We are grateful to the Fundacão para a Ciência e Tecnologia (FCT, Portugal) for support through projects SFRH/ BPD/24889/2005 and PTDC/BIA-PRO/103980/2008 and for funding the purchase of the single-crystal diffractometer. We thank Paula Branda from the Universidade de Aveiro for the crystal mounting and data collection.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The majority of the reported metalloporphyrin structures involve metals from the first-row transition series. However, the structures of magnesium porphyrins are also of interest because of their relationship to chlorophyll. but the Cambridge Structural Database (CSD; Allen, 2002) contains only 24 structures of these. In order to gain more insight into the geometry of the latter species, we report herein the crystal structure of the title complex, [Mg(TPP)(4-CNpy)(H2O)] (where TPP is the 5,10,15,20-tetraphenylporphyrin dianion and 4-CNpy is 4-cyanopyridine).
In the title complex the Mg cation is octahedrally coordinated and lies on an inversion center with the axially-located 4-cyanopyridine and aqua ligands having occupancy factors of 0.5. The atoms of these disordered ligands are divided in two parts: in part 1, the fragment containing the atoms N3, C23, C24, C25A and C26A and in part 2, the atoms O1, N4, C25B and C26B, related by the symmetry code (i) -x, -y+1, -z+1. The 4-cyanopyridine ligand also has inversion symmetry with 50% occupancy [symmetry code (ii): -x+1, -y, -z+1] (Fig. 1). The average equatorial Mg—N(pyrrole) bond distance [2.062 (1) Å] is normal for Mg–porphyrin complexes. The Mg—O(H2O) bond length [2.3798 (12)Å] is longer than that found in the related complex [Mg(TPP)(H2O)] (2.012 (6) Å) (Choon et al., 1986) but is shorter than the one reported for the non-porphyrin complex catena-[diaquatetrakis(µ4-oxalato)-tris(µ2-oxalato)- dimagnesium-dipotassium-diuranium(IV) nonahydrate clathrate] [2.747 (5) Å] (Imaz et al., 2005).
The axial Mg—N(4-CNpy) bond length [2.3798 (12) Å] is longer than that found in the [Mg(TPP)][TCNQF4] complex [2.266 (2) Å] (where TCNQF4 is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) (Hibbs et al., 2003), but is within the range of 2.152 (2)–2.57 (1) Å found for several magnesium-nitrile non-porphyrin complexes in the CSD [refcodes FEGQAJ (Etkin et al., 1998) and SISWUN (Yang et al., 2008) (Allen, 2002).
The crystal structure resembles a one-dimensional coordination polymer where two [Mg(TPP)] moieties are linked by statistically 50% disordered 4-cyanopyridine and H2O ligands. The crystal packing of the title compound is stabilized by weak C—H···π intermolecular interactions involving Cg pyrrole and phenyl rings (Table 1 and Fig. 2).