5,10,15,20-Tetra-kis(4-acetyl-oxyphen-yl)porphyrin including an unknown solvate.

Mol-ecules of the title compound, C52H38N4O8, are located on an inversion center so that the asymmetric cell contains one half of the mol-ecule. The macrocycle exhibits a ruffled conformation with a maximum deviation of 0.16 Å for the 24 macrocycle atoms: the dihedral angle between adjacent five-membered rings is 5.13 (19)°. The benzene rings are rotated by 70.25 (19)° with respect to their adjacent protonated five-membered rings, and by 65.56 (19)° with respect to the unprotonated rings. The porphyrin conformation is supported by bifurcated N-H⋯(N,N) hydrogen bonds. The structure contained poorly resolved solvent mol-ecules in voids of volume 217 Å(3) per unit cell. The latter were treated using the SQUEEZE routine in PLATON [Spek (2009 ▶). Acta Cryst. D65, 148-155]. As the solvent could not be identified exactly, it was not included in the calculation of the overall formula weight, density and absorption coefficient.

Related literature

For general background on porphyrin and porphyrin precursors synthesized in our group, see Paixão, Matos Beja et al. (2002 ▶); Paixão, Ramos Silva et al. (2002 ▶); Paixão et al. (2003 ▶); Ramos Silva et al. (2002a ▶,b ▶); Sobral et al. (2001a ▶,b ▶). For the applications of porphyrins, see: Zhang et al. (2010 ▶); Eichhorn (2000 ▶).

Experimental

Crystal data

C52H38N4O8

M = 846.86

Triclinic,

a = 6.6203 (2) Å

b = 14.1043 (3) Å

c = 14.4936 (3) Å

α = 113.862 (1)°

β = 97.771 (2)°

γ = 98.060 (2)°

V = 1197.58 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.08 mm−1

T = 293 K

0.30 × 0.12 × 0.04 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.790, T max = 0.999

24062 measured reflections

4566 independent reflections

2956 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.080

wR(F 2) = 0.248

S = 1.14

4566 reflections

291 parameters

H-atom parameters constrained

Δρmax = 0.98 e Å−3

Δρmin = −0.51 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812047332/hb6985sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047332/hb6985Isup2.hkl

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

C52H38N4O8	Z = 1
Mr = 846.86	F(000) = 442
Triclinic, P1	Dx = 1.174 Mg m−3
a = 6.6203 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.1043 (3) Å	Cell parameters from 4592 reflections
c = 14.4936 (3) Å	θ = 2.9–21.4°
α = 113.862 (1)°	µ = 0.08 mm−1
β = 97.771 (2)°	T = 293 K
γ = 98.060 (2)°	Plate, violet
V = 1197.58 (5) Å3	0.30 × 0.12 × 0.04 mm

Bruker APEX CCD area-detector diffractometer	4566 independent reflections
Radiation source: fine-focus sealed tube	2956 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 25.8°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −8→8
Tmin = 0.790, Tmax = 0.999	k = −17→17
24062 measured reflections	l = −17→17

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)] = 0.080	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.248	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.1221P)2 + 0.5589P] where P = (Fo2 + 2Fc2)/3
4566 reflections	(Δ/σ)max = 0.040
291 parameters	Δρmax = 0.98 e Å−3
0 restraints	Δρmin = −0.51 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
N1	0.7700 (3)	0.90482 (18)	0.36681 (17)	0.0397 (6)
H1	0.8553	0.9529	0.4212	0.048*
N2	1.1829 (3)	1.03171 (17)	0.41002 (17)	0.0400 (6)
O1	0.8965 (4)	0.7835 (2)	−0.19208 (16)	0.0709 (7)
O2	1.2299 (4)	0.8442 (2)	−0.1891 (2)	0.0810 (8)
O3	−0.1992 (4)	0.5305 (2)	0.3829 (3)	0.0907 (9)
O4	−0.1461 (12)	0.4164 (5)	0.2427 (5)	0.270 (4)
C1	0.5249 (4)	0.8381 (2)	0.4526 (2)	0.0404 (7)
C2	0.5916 (4)	0.8419 (2)	0.3666 (2)	0.0399 (7)
C3	0.4952 (4)	0.7749 (2)	0.2613 (2)	0.0477 (8)
H3	0.3713	0.7240	0.2377	0.057*
C4	0.6157 (5)	0.7981 (3)	0.2015 (2)	0.0511 (8)
H4	0.5881	0.7664	0.1297	0.061*
C5	0.7918 (4)	0.8795 (2)	0.2676 (2)	0.0418 (7)
C6	0.9617 (4)	0.9196 (2)	0.2367 (2)	0.0414 (7)
C7	1.1447 (4)	0.9906 (2)	0.3043 (2)	0.0419 (7)
C8	1.3182 (5)	1.0335 (2)	0.2720 (2)	0.0513 (8)
H8	1.3306	1.0176	0.2044	0.062*
C9	1.4573 (5)	1.1004 (3)	0.3576 (2)	0.0511 (8)
H9	1.5846	1.1402	0.3606	0.061*
C10	1.3752 (4)	1.1001 (2)	0.4445 (2)	0.0410 (7)
C11	0.9478 (5)	0.8834 (2)	0.1239 (2)	0.0453 (7)
C12	1.0830 (5)	0.8245 (3)	0.0745 (2)	0.0601 (9)
H12	1.1829	0.8067	0.1125	0.072*
C13	1.0738 (6)	0.7915 (3)	−0.0297 (3)	0.0672 (10)
H13	1.1658	0.7517	−0.0620	0.081*
C14	0.9254 (5)	0.8187 (3)	−0.0849 (2)	0.0558 (9)
C15	0.7864 (5)	0.8749 (3)	−0.0391 (2)	0.0579 (9)
H15	0.6848	0.8913	−0.0777	0.070*
C16	0.7987 (5)	0.9072 (3)	0.0653 (2)	0.0529 (8)
H16	0.7046	0.9458	0.0969	0.063*
C17	1.0572 (6)	0.7993 (3)	−0.2359 (3)	0.0599 (9)
C18	0.9824 (6)	0.7539 (3)	−0.3500 (3)	0.0720 (11)
H18A	0.9996	0.8098	−0.3718	0.108*
H18B	0.8375	0.7197	−0.3682	0.108*
H18C	1.0620	0.7030	−0.3834	0.108*
C19	0.3332 (4)	0.7556 (2)	0.4305 (2)	0.0411 (7)
C20	0.1366 (5)	0.7666 (3)	0.3969 (3)	0.0550 (8)
H20	0.1215	0.8276	0.3888	0.066*
C21	−0.0373 (5)	0.6893 (3)	0.3751 (3)	0.0620 (9)
H21	−0.1685	0.6967	0.3505	0.074*
C22	−0.0155 (5)	0.6014 (3)	0.3900 (3)	0.0575 (9)
C23	0.1759 (5)	0.5883 (3)	0.4238 (3)	0.0658 (10)
H23	0.1896	0.5280	0.4334	0.079*
C24	0.3492 (5)	0.6658 (3)	0.4436 (3)	0.0575 (9)
H24	0.4804	0.6570	0.4664	0.069*
C25	−0.2590 (11)	0.4459 (5)	0.3054 (5)	0.119 (2)
C26	−0.4600 (7)	0.3784 (4)	0.2982 (4)	0.1021 (16)
H26A	−0.4679	0.3064	0.2502	0.153*
H26B	−0.5742	0.4039	0.2748	0.153*
H26C	−0.4677	0.3812	0.3649	0.153*

	U11	U22	U33	U12	U13	U23
N1	0.0341 (12)	0.0479 (12)	0.0322 (12)	−0.0020 (10)	0.0051 (9)	0.0165 (10)
N2	0.0370 (13)	0.0456 (12)	0.0342 (12)	−0.0015 (10)	0.0070 (10)	0.0176 (10)
O1	0.0544 (14)	0.1086 (19)	0.0343 (11)	−0.0056 (13)	0.0089 (10)	0.0232 (12)
O2	0.0619 (16)	0.0996 (19)	0.0612 (15)	−0.0139 (15)	0.0127 (13)	0.0248 (14)
O3	0.0685 (18)	0.0697 (16)	0.109 (2)	−0.0121 (14)	0.0007 (16)	0.0276 (16)
O4	0.299 (7)	0.196 (5)	0.175 (5)	−0.122 (5)	0.121 (5)	−0.023 (4)
C1	0.0297 (14)	0.0450 (14)	0.0472 (16)	0.0001 (12)	0.0055 (12)	0.0239 (12)
C2	0.0334 (14)	0.0447 (14)	0.0406 (15)	0.0011 (12)	0.0046 (11)	0.0207 (12)
C3	0.0365 (15)	0.0565 (17)	0.0412 (16)	−0.0064 (13)	0.0007 (12)	0.0199 (14)
C4	0.0438 (17)	0.0618 (18)	0.0358 (15)	−0.0013 (14)	−0.0014 (13)	0.0166 (14)
C5	0.0394 (15)	0.0483 (15)	0.0353 (14)	0.0039 (13)	0.0025 (12)	0.0191 (12)
C6	0.0424 (15)	0.0488 (15)	0.0327 (14)	0.0037 (13)	0.0065 (12)	0.0196 (12)
C7	0.0421 (16)	0.0486 (15)	0.0362 (14)	0.0010 (13)	0.0090 (12)	0.0221 (12)
C8	0.0513 (18)	0.0622 (18)	0.0382 (15)	−0.0011 (15)	0.0123 (13)	0.0229 (14)
C9	0.0425 (16)	0.0617 (18)	0.0452 (16)	−0.0079 (14)	0.0144 (13)	0.0236 (14)
C10	0.0362 (15)	0.0457 (14)	0.0408 (15)	0.0016 (12)	0.0069 (12)	0.0210 (12)
C11	0.0430 (16)	0.0534 (16)	0.0367 (15)	0.0012 (13)	0.0084 (12)	0.0198 (13)
C12	0.0515 (19)	0.085 (2)	0.0425 (17)	0.0186 (17)	0.0065 (14)	0.0258 (16)
C13	0.060 (2)	0.089 (3)	0.0459 (19)	0.0179 (19)	0.0127 (16)	0.0211 (18)
C14	0.0491 (18)	0.075 (2)	0.0317 (15)	−0.0069 (16)	0.0033 (13)	0.0195 (15)
C15	0.0530 (19)	0.079 (2)	0.0444 (17)	0.0081 (17)	0.0056 (14)	0.0324 (16)
C16	0.0493 (18)	0.0665 (19)	0.0443 (17)	0.0124 (15)	0.0132 (14)	0.0243 (15)
C17	0.060 (2)	0.067 (2)	0.0448 (18)	0.0034 (17)	0.0142 (16)	0.0192 (16)
C18	0.079 (3)	0.086 (3)	0.0442 (19)	0.010 (2)	0.0208 (18)	0.0222 (18)
C19	0.0344 (15)	0.0481 (15)	0.0400 (15)	−0.0001 (12)	0.0073 (11)	0.0214 (12)
C20	0.0360 (16)	0.0550 (17)	0.078 (2)	0.0039 (14)	0.0074 (15)	0.0366 (16)
C21	0.0350 (17)	0.067 (2)	0.085 (2)	0.0023 (15)	0.0050 (16)	0.0390 (18)
C22	0.0392 (17)	0.0559 (18)	0.068 (2)	−0.0092 (15)	0.0073 (15)	0.0252 (16)
C23	0.053 (2)	0.0539 (18)	0.092 (3)	−0.0018 (16)	0.0063 (18)	0.0406 (18)
C24	0.0377 (17)	0.0606 (19)	0.078 (2)	0.0025 (14)	0.0046 (15)	0.0387 (17)
C25	0.136 (5)	0.106 (4)	0.081 (3)	−0.023 (4)	0.005 (3)	0.027 (3)
C26	0.071 (3)	0.084 (3)	0.126 (4)	−0.032 (2)	0.001 (3)	0.042 (3)

N1—C5	1.368 (4)	C11—C16	1.380 (4)
N1—C2	1.374 (3)	C11—C12	1.380 (5)
N1—H1	0.8600	C12—C13	1.378 (5)
N2—C7	1.372 (3)	C12—H12	0.9300
N2—C10	1.376 (3)	C13—C14	1.376 (5)
O1—C17	1.348 (4)	C13—H13	0.9300
O1—C14	1.402 (4)	C14—C15	1.364 (5)
O2—C17	1.187 (4)	C15—C16	1.379 (4)
O3—C25	1.226 (6)	C15—H15	0.9300
O3—C22	1.425 (4)	C16—H16	0.9300
O4—C25	1.235 (8)	C17—C18	1.490 (5)
C1—C2	1.395 (4)	C18—H18A	0.9600
C1—C10i	1.394 (4)	C18—H18B	0.9600
C1—C19	1.497 (4)	C18—H18C	0.9600
C2—C3	1.425 (4)	C19—C24	1.370 (4)
C3—C4	1.356 (4)	C19—C20	1.379 (4)
C3—H3	0.9300	C20—C21	1.373 (4)
C4—C5	1.424 (4)	C20—H20	0.9300
C4—H4	0.9300	C21—C22	1.365 (5)
C5—C6	1.396 (4)	C21—H21	0.9300
C6—C7	1.406 (4)	C22—C23	1.360 (5)
C6—C11	1.488 (4)	C23—C24	1.378 (4)
C7—C8	1.445 (4)	C23—H23	0.9300
C8—C9	1.333 (4)	C24—H24	0.9300
C8—H8	0.9300	C25—C26	1.489 (7)
C9—C10	1.439 (4)	C26—H26A	0.9600
C9—H9	0.9300	C26—H26B	0.9600
C10—C1i	1.394 (4)	C26—H26C	0.9600
C5—N1—C2	109.8 (2)	C15—C14—C13	121.4 (3)
C5—N1—H1	125.1	C15—C14—O1	115.9 (3)
C2—N1—H1	125.1	C13—C14—O1	122.5 (3)
C7—N2—C10	105.8 (2)	C14—C15—C16	119.0 (3)
C17—O1—C14	121.0 (3)	C14—C15—H15	120.5
C25—O3—C22	118.6 (5)	C16—C15—H15	120.5
C2—C1—C10i	126.2 (3)	C11—C16—C15	121.4 (3)
C2—C1—C19	116.0 (2)	C11—C16—H16	119.3
C10i—C1—C19	117.6 (3)	C15—C16—H16	119.3
N1—C2—C1	126.8 (2)	O2—C17—O1	124.2 (3)
N1—C2—C3	106.9 (2)	O2—C17—C18	126.3 (3)
C1—C2—C3	126.2 (3)	O1—C17—C18	109.5 (3)
C4—C3—C2	108.1 (2)	C17—C18—H18A	109.5
C4—C3—H3	126.0	C17—C18—H18B	109.5
C2—C3—H3	126.0	H18A—C18—H18B	109.5
C3—C4—C5	108.2 (3)	C17—C18—H18C	109.5
C3—C4—H4	125.9	H18A—C18—H18C	109.5
C5—C4—H4	125.9	H18B—C18—H18C	109.5
N1—C5—C6	126.7 (2)	C24—C19—C20	117.8 (3)
N1—C5—C4	107.0 (3)	C24—C19—C1	120.2 (3)
C6—C5—C4	126.2 (3)	C20—C19—C1	121.9 (3)
C5—C6—C7	124.7 (3)	C21—C20—C19	121.2 (3)
C5—C6—C11	117.3 (2)	C21—C20—H20	119.4
C7—C6—C11	118.0 (3)	C19—C20—H20	119.4
N2—C7—C6	125.5 (3)	C22—C21—C20	119.3 (3)
N2—C7—C8	110.0 (2)	C22—C21—H21	120.4
C6—C7—C8	124.5 (3)	C20—C21—H21	120.4
C9—C8—C7	106.8 (3)	C21—C22—C23	121.0 (3)
C9—C8—H8	126.6	C21—C22—O3	118.3 (3)
C7—C8—H8	126.6	C23—C22—O3	120.1 (3)
C8—C9—C10	107.8 (3)	C22—C23—C24	119.0 (3)
C8—C9—H9	126.1	C22—C23—H23	120.5
C10—C9—H9	126.1	C24—C23—H23	120.5
N2—C10—C1i	125.9 (3)	C23—C24—C19	121.6 (3)
N2—C10—C9	109.6 (2)	C23—C24—H24	119.2
C1i—C10—C9	124.6 (3)	C19—C24—H24	119.2
C16—C11—C12	117.9 (3)	O3—C25—O4	120.1 (6)
C16—C11—C6	121.1 (3)	O3—C25—C26	116.5 (6)
C12—C11—C6	121.0 (3)	O4—C25—C26	123.1 (5)
C13—C12—C11	121.7 (3)	C25—C26—H26A	109.5
C13—C12—H12	119.1	C25—C26—H26B	109.5
C11—C12—H12	119.1	H26A—C26—H26B	109.5
C14—C13—C12	118.5 (3)	C25—C26—H26C	109.5
C14—C13—H13	120.7	H26A—C26—H26C	109.5
C12—C13—H13	120.7	H26B—C26—H26C	109.5
C5—N1—C2—C1	174.5 (3)	C7—C6—C11—C12	63.6 (4)
C5—N1—C2—C3	−1.0 (3)	C16—C11—C12—C13	1.1 (5)
C10i—C1—C2—N1	1.9 (5)	C6—C11—C12—C13	−179.2 (3)
C19—C1—C2—N1	−175.0 (3)	C11—C12—C13—C14	0.1 (6)
C10i—C1—C2—C3	176.6 (3)	C12—C13—C14—C15	−1.5 (5)
C19—C1—C2—C3	−0.3 (4)	C12—C13—C14—O1	−176.2 (3)
N1—C2—C3—C4	0.2 (3)	C17—O1—C14—C15	131.0 (4)
C1—C2—C3—C4	−175.3 (3)	C17—O1—C14—C13	−54.0 (5)
C2—C3—C4—C5	0.6 (4)	C13—C14—C15—C16	1.5 (5)
C2—N1—C5—C6	−174.2 (3)	O1—C14—C15—C16	176.6 (3)
C2—N1—C5—C4	1.4 (3)	C12—C11—C16—C15	−1.1 (5)
C3—C4—C5—N1	−1.2 (4)	C6—C11—C16—C15	179.3 (3)
C3—C4—C5—C6	174.4 (3)	C14—C15—C16—C11	−0.2 (5)
N1—C5—C6—C7	2.8 (5)	C14—O1—C17—O2	−1.2 (6)
C4—C5—C6—C7	−171.9 (3)	C14—O1—C17—C18	179.9 (3)
N1—C5—C6—C11	−177.8 (3)	C2—C1—C19—C24	105.4 (3)
C4—C5—C6—C11	7.5 (5)	C10i—C1—C19—C24	−71.8 (4)
C10—N2—C7—C6	−177.7 (3)	C2—C1—C19—C20	−74.7 (4)
C10—N2—C7—C8	0.6 (3)	C10i—C1—C19—C20	108.2 (3)
C5—C6—C7—N2	−0.6 (5)	C24—C19—C20—C21	−1.3 (5)
C11—C6—C7—N2	179.9 (3)	C1—C19—C20—C21	178.7 (3)
C5—C6—C7—C8	−178.7 (3)	C19—C20—C21—C22	1.9 (6)
C11—C6—C7—C8	1.9 (5)	C20—C21—C22—C23	−1.4 (6)
N2—C7—C8—C9	−0.7 (4)	C20—C21—C22—O3	170.2 (3)
C6—C7—C8—C9	177.6 (3)	C25—O3—C22—C21	104.7 (5)
C7—C8—C9—C10	0.5 (4)	C25—O3—C22—C23	−83.6 (6)
C7—N2—C10—C1i	178.3 (3)	C21—C22—C23—C24	0.3 (6)
C7—N2—C10—C9	−0.3 (3)	O3—C22—C23—C24	−171.1 (3)
C8—C9—C10—N2	−0.1 (4)	C22—C23—C24—C19	0.3 (6)
C8—C9—C10—C1i	−178.7 (3)	C20—C19—C24—C23	0.2 (5)
C5—C6—C11—C16	63.8 (4)	C1—C19—C24—C23	−179.9 (3)
C7—C6—C11—C16	−116.7 (3)	C22—O3—C25—O4	10.6 (10)
C5—C6—C11—C12	−115.8 (3)	C22—O3—C25—C26	−175.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2	0.86	2.35	2.885 (3)	121
N1—H1···N2i	0.86	2.42	2.944 (3)	120

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2	0.86	2.35	2.885 (3)	121
N1—H1⋯N2i	0.86	2.42	2.944 (3)	120

Symmetry code: (i) .