5,10,15,20-Tetra-kis(3,5-difluoro-phen-yl)porphyrin.

The crystal structure of the title compound, C(44)H(22)F(8)N(4), shows an unusual non-planar geometry of the porphyrin ring although the mol-ecule is free of steric crowding around the periphery of the macrocycle. The mol-ecular packing exhibits weak inter-molecular hydrogen bonding (C-H⋯F) and C-H⋯π inter-actions. The molecular symmetry is .

Related literature

For the stereochemistry of porphyrins and metalloporphyrins, see: Senge (2000 ▶); Scheidt & Lee (1987 ▶). For a related structure, see: Silvers & Tulinsky (1967 ▶). For the preparation of the title compound, see: Tamiaki et al. (2000 ▶). For C—H⋯π and C—H⋯F inter­actions, see: Steiner (2002 ▶); Thalladi et al. (1998 ▶).

Experimental

Crystal data

C44H22F8N4

M = 758.66

Tetragonal,

a = 15.426 (5) Å

c = 13.991 (5) Å

V = 3329.3 (19) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 233 (2) K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.965, T max = 0.986

20353 measured reflections

1145 independent reflections

1049 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.098

S = 1.07

1145 reflections

127 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-32 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062782/si2056sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062782/si2056Isup2.hkl

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

C44H22F8N4	Dx = 1.514 Mg m−3
Mr = 758.66	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42d	Cell parameters from 5676 reflections
Hall symbol: I -4 2bw	θ = 2.7–27.4°
a = 15.426 (5) Å	µ = 0.12 mm−1
c = 13.991 (5) Å	T = 233 K
V = 3329.3 (19) Å3	Plate, purple
Z = 4	0.30 × 0.20 × 0.20 mm
F(000) = 1544

Bruker APEXII CCD area-detector diffractometer	1145 independent reflections
Radiation source: fine-focus sealed tube	1049 reflections with I > 2σ(I)
graphite	Rint = 0.041
ω and φ scan	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −20→20
Tmin = 0.965, Tmax = 0.986	k = −19→18
20353 measured reflections	l = −18→15

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0579P)2 + 1.6388P] where P = (Fo2 + 2Fc2)/3
1145 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.15 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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)
C1	0.62343 (12)	−0.15392 (12)	0.26244 (14)	0.0234 (4)
C2	0.71372 (13)	−0.17616 (13)	0.25131 (18)	0.0289 (4)
H2	0.7375	−0.2314	0.2561	0.035*
C3	0.75734 (13)	−0.10209 (12)	0.23267 (16)	0.0285 (4)
H3	0.8164	−0.0970	0.2205	0.034*
C4	0.69521 (12)	−0.03261 (13)	0.23514 (15)	0.0233 (4)
C5	0.71381 (12)	0.05575 (12)	0.22542 (14)	0.0225 (4)
C6	0.80391 (13)	0.08176 (12)	0.19734 (15)	0.0240 (4)
C7	0.87363 (13)	0.07798 (15)	0.25940 (16)	0.0310 (5)
H7	0.8665	0.0583	0.3217	0.037*
C8	0.95385 (14)	0.10405 (16)	0.22687 (18)	0.0353 (5)
C9	0.96818 (14)	0.13294 (16)	0.1348 (2)	0.0385 (6)
H9	1.0230	0.1496	0.1141	0.046*
C10	0.89782 (17)	0.13583 (16)	0.07556 (17)	0.0380 (5)
C11	0.81595 (13)	0.11143 (15)	0.10383 (16)	0.0299 (5)
H11	0.7695	0.1146	0.0616	0.036*
N1	0.61430 (10)	−0.06642 (10)	0.25215 (12)	0.0230 (4)
H1	0.5666	−0.0377	0.2557	0.028*	0.50
F1	1.02219 (8)	0.10061 (13)	0.28671 (12)	0.0550 (5)
F2	0.90872 (12)	0.16429 (14)	−0.01500 (13)	0.0632 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0216 (9)	0.0199 (8)	0.0288 (10)	0.0015 (7)	−0.0003 (8)	0.0020 (7)
C2	0.0221 (9)	0.0225 (9)	0.0420 (11)	0.0048 (7)	0.0006 (9)	0.0041 (9)
C3	0.0190 (9)	0.0260 (9)	0.0404 (11)	0.0033 (7)	0.0033 (8)	0.0040 (9)
C4	0.0180 (8)	0.0239 (9)	0.0280 (9)	0.0000 (7)	0.0029 (8)	0.0009 (7)
C5	0.0193 (8)	0.0209 (9)	0.0273 (9)	0.0001 (7)	0.0017 (7)	0.0001 (7)
C6	0.0211 (9)	0.0183 (8)	0.0325 (9)	0.0001 (7)	0.0040 (8)	−0.0020 (8)
C7	0.0237 (10)	0.0389 (11)	0.0302 (10)	−0.0006 (8)	0.0031 (8)	−0.0023 (9)
C8	0.0207 (9)	0.0393 (12)	0.0458 (12)	−0.0035 (9)	−0.0008 (9)	−0.0085 (11)
C9	0.0239 (10)	0.0382 (12)	0.0533 (14)	−0.0089 (9)	0.0134 (10)	−0.0070 (11)
C10	0.0377 (12)	0.0366 (12)	0.0396 (12)	−0.0041 (10)	0.0124 (10)	0.0048 (10)
C11	0.0252 (9)	0.0305 (10)	0.0340 (10)	−0.0003 (9)	0.0014 (8)	0.0046 (9)
N1	0.0169 (7)	0.0201 (8)	0.0319 (9)	−0.0001 (6)	0.0009 (7)	0.0015 (6)
F1	0.0214 (7)	0.0862 (13)	0.0575 (9)	−0.0066 (7)	−0.0062 (6)	−0.0118 (10)
F2	0.0548 (10)	0.0853 (13)	0.0495 (9)	−0.0146 (9)	0.0159 (8)	0.0246 (9)

C1—N1	1.365 (2)	C6—C11	1.398 (3)
C1—C5i	1.404 (3)	C7—C8	1.378 (3)
C1—C2	1.443 (3)	C7—H7	0.9300
C2—C3	1.351 (3)	C8—F1	1.347 (3)
C2—H2	0.9300	C8—C9	1.381 (4)
C3—C4	1.438 (3)	C9—C10	1.366 (4)
C3—H3	0.9300	C9—H9	0.9300
C4—N1	1.373 (3)	C10—F2	1.351 (3)
C4—C5	1.400 (3)	C10—C11	1.376 (3)
C5—C1ii	1.404 (3)	C11—H11	0.9300
C5—C6	1.499 (3)	N1—H1	0.8600
C6—C7	1.383 (3)
N1—C1—C5i	125.93 (17)	C8—C7—C6	118.6 (2)
N1—C1—C2	108.87 (16)	C8—C7—H7	120.7
C5i—C1—C2	125.04 (17)	C6—C7—H7	120.7
C3—C2—C1	107.48 (17)	F1—C8—C7	119.1 (2)
C3—C2—H2	126.3	F1—C8—C9	117.9 (2)
C1—C2—H2	126.3	C7—C8—C9	123.1 (2)
C2—C3—C4	107.07 (17)	C10—C9—C8	116.69 (19)
C2—C3—H3	126.5	C10—C9—H9	121.7
C4—C3—H3	126.5	C8—C9—H9	121.7
N1—C4—C5	124.97 (17)	F2—C10—C9	118.7 (2)
N1—C4—C3	109.07 (16)	F2—C10—C11	118.2 (2)
C5—C4—C3	125.93 (18)	C9—C10—C11	123.1 (2)
C4—C5—C1ii	125.26 (18)	C10—C11—C6	118.7 (2)
C4—C5—C6	118.44 (16)	C10—C11—H11	120.6
C1ii—C5—C6	116.28 (17)	C6—C11—H11	120.6
C7—C6—C11	119.85 (18)	C1—N1—C4	107.47 (16)
C7—C6—C5	123.03 (19)	C1—N1—H1	126.3
C11—C6—C5	117.12 (18)	C4—N1—H1	126.3
N1—C1—C2—C3	−1.2 (3)	C6—C7—C8—F1	−179.98 (19)
C5i—C1—C2—C3	174.4 (2)	C6—C7—C8—C9	−0.7 (4)
C1—C2—C3—C4	1.9 (3)	F1—C8—C9—C10	−180.0 (2)
C2—C3—C4—N1	−2.0 (3)	C7—C8—C9—C10	0.7 (4)
C2—C3—C4—C5	175.8 (2)	C8—C9—C10—F2	179.5 (2)
N1—C4—C5—C1ii	4.3 (3)	C8—C9—C10—C11	−0.2 (4)
C3—C4—C5—C1ii	−173.2 (2)	F2—C10—C11—C6	179.9 (2)
N1—C4—C5—C6	−174.02 (18)	C9—C10—C11—C6	−0.4 (4)
C3—C4—C5—C6	8.5 (3)	C7—C6—C11—C10	0.4 (3)
C4—C5—C6—C7	−74.1 (3)	C5—C6—C11—C10	−180.0 (2)
C1ii—C5—C6—C7	107.5 (2)	C5i—C1—N1—C4	−175.62 (19)
C4—C5—C6—C11	106.3 (2)	C2—C1—N1—C4	−0.1 (2)
C1ii—C5—C6—C11	−72.1 (2)	C5—C4—N1—C1	−176.6 (2)
C11—C6—C7—C8	0.1 (3)	C3—C4—N1—C1	1.3 (2)
C5—C6—C7—C8	−179.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···C1iii	0.93	2.87	3.634 (2)	140
C3—H3···F1iv	0.93	2.66	3.484 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯C1i	0.93	2.87	3.634 (2)	140
C3—H3⋯F1ii	0.93	2.66	3.484 (2)	148

Symmetry codes: (i) ; (ii) .