Aqua-(4-cyano-pyridine-κN (4))(5,10,15,20-tetra-phenyl-porphyrinato-κ(4) N)magnesium.

In the title complex, [Mg(C44H28N4)(C6H4N2)(H2O)], the Mg(2+) cation is octa-hedrally coordinated and lies on an inversion center with the axially located 4-cyano-pyridine and aqua ligands exhibiting 50% substitutional disorder. The cyano-bound 4-cyano-pyridine mol-ecule also is disordered across the inversion centre. The four N atoms of the pyrrole rings of the dianionic 5,10,15,20-tetra-phenyl-porphyrin ligand occupy the equatorial sites of the octa-hedron [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 inter-molecular C-H⋯π inter-actions.

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

[Mg(C44H28N4)(C6H4N2)(H2O)]

M = 757.13

Triclinic,

a = 8.9080 (3) Å

b = 10.7550 (4) Å

c = 11.9530 (6) Å

α = 63.446 (1)°

β = 89.364 (2)°

γ = 73.408 (1)°

V = 972.60 (7) Å3

Z = 1

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.48 × 0.40 × 0.24 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.955, T max = 0.978

11765 measured reflections

3792 independent reflections

3307 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.103

S = 1.07

3792 reflections

268 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.54 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: 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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812049434/zs2246sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049434/zs2246Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[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

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

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

Table 1

Hydrogen-bond geometry (Å, °)

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) ; (ii) ; (iii) .