5,15-Bis(4-pentyl-oxyphen-yl)porphyrin.

In the title compound, C42H42N4O2, the complete molecule is generated by a crystallographic inversion centre. The porphyrin system exhibits a near planar macrocycle conformation with an average deviation from the least-squares plane of the 24 macrocycle atoms of 0.037 (5) Å. The phenyl ipso C atoms are positioned above and below the porphyrin plane by 0.35 (1) Å and the macrocycle shows evidence of in-plane rectangular elongation with N⋯N separations of 3.032 (5) and 2.803 (5) Å. Two intramolecular N-H⋯N hydrogen bonds occur.

Related literature

For the conformation of porphyrins, see: Scheidt & Lee (1987 ▶); Senge et al. (1997 ▶); Senge (2006 ▶). For the synthesis of such compounds, see: Wiehe et al. (2005 ▶).

Experimental

Crystal data

C42H42N4O2

M = 634.80

Triclinic,

a = 9.5222 (6) Å

b = 9.5799 (6) Å

c = 10.2195 (6) Å

α = 67.777 (1)°

β = 88.063 (1)°

γ = 72.464 (1)°

V = 819.49 (9) Å3

Z = 1

Mo Kα radiation

μ = 0.08 mm−1

T = 90 K

0.30 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.97, T max = 0.99

9093 measured reflections

3606 independent reflections

2489 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.109

S = 1.04

3606 reflections

219 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: XP in SHELXTL.

Crystal structure: contains datablock(s) I, 2R. DOI: 10.1107/S160053681301550X/zl2552sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681301550X/zl2552Isup2.hkl

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

C42H42N4O2	Z = 1
Mr = 634.80	F(000) = 338
Triclinic, P1	Dx = 1.286 Mg m−3Dm = n/d Mg m−3Dm measured by not measured
Hall symbol: -P 1	Melting point: n/d K
a = 9.5222 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5799 (6) Å	Cell parameters from 1771 reflections
c = 10.2195 (6) Å	θ = 4.5–60.7°
α = 67.777 (1)°	µ = 0.08 mm−1
β = 88.063 (1)°	T = 90 K
γ = 72.464 (1)°	Parallelpiped, red
V = 819.49 (9) Å3	0.30 × 0.10 × 0.08 mm

Bruker SMART APEXII diffractometer	3606 independent reflections
Radiation source: fine-focus sealed tube	2489 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 8.3 pixels mm-1	θmax = 27.1°, θmin = 2.2°
ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −12→12
Tmin = 0.97, Tmax = 0.99	l = −13→13
9093 measured 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0433P)2 + 0.1316P] where P = (Fo2 + 2Fc2)/3
3606 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.23 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
N21	0.64309 (14)	−0.19503 (16)	0.46008 (14)	0.0171 (3)
H21	0.5815	−0.1069	0.4627	0.047 (6)*
N24	0.36841 (13)	−0.12143 (15)	0.61217 (14)	0.0160 (3)
C1	0.62390 (16)	−0.34160 (19)	0.52069 (17)	0.0179 (4)
C2	0.74472 (17)	−0.4492 (2)	0.48647 (18)	0.0190 (4)
H2A	0.7600	−0.5592	0.5123	0.023*
C3	0.83431 (17)	−0.36651 (19)	0.41037 (17)	0.0185 (4)
H3A	0.9229	−0.4090	0.3740	0.022*
C4	0.77200 (16)	−0.20511 (19)	0.39479 (17)	0.0169 (4)
C5	0.83034 (16)	−0.07952 (19)	0.33369 (17)	0.0169 (4)
C16	0.24129 (16)	−0.07563 (19)	0.67302 (16)	0.0164 (3)
C17	0.18961 (17)	−0.2107 (2)	0.74985 (18)	0.0195 (4)
H17A	0.1041	−0.2097	0.8006	0.023*
C18	0.28721 (17)	−0.3376 (2)	0.73457 (18)	0.0198 (4)
H18A	0.2843	−0.4437	0.7732	0.024*
C19	0.39727 (16)	−0.28065 (19)	0.64781 (17)	0.0172 (4)
C20	0.51314 (16)	−0.37959 (19)	0.60556 (17)	0.0185 (4)
H20A	0.5167	−0.4877	0.6396	0.022*
C51	0.98127 (17)	−0.11283 (19)	0.28262 (17)	0.0177 (4)
C52	1.01657 (17)	−0.1671 (2)	0.17315 (18)	0.0206 (4)
H52A	0.9421	−0.1859	0.1286	0.025*
C53	1.15769 (17)	−0.1945 (2)	0.12745 (18)	0.0207 (4)
H53A	1.1792	−0.2316	0.0527	0.025*
C54	1.26742 (16)	−0.16720 (19)	0.19238 (18)	0.0188 (4)
C55	1.23542 (17)	−0.11454 (19)	0.30202 (17)	0.0192 (4)
H55A	1.3103	−0.0965	0.3467	0.023*
C56	1.09475 (17)	−0.08822 (19)	0.34664 (18)	0.0192 (4)
H56A	1.0744	−0.0526	0.4224	0.023*
O1	1.41004 (11)	−0.18754 (14)	0.15628 (12)	0.0226 (3)
C57	1.45008 (17)	−0.2298 (2)	0.03660 (18)	0.0227 (4)
H57A	1.3832	−0.1524	−0.0488	0.027*
H57B	1.4430	−0.3366	0.0554	0.027*
C58	1.60744 (17)	−0.2284 (2)	0.01421 (18)	0.0211 (4)
H58A	1.6702	−0.2943	0.1048	0.025*
H58B	1.6106	−0.1185	−0.0147	0.025*
C59	1.66924 (17)	−0.2919 (2)	−0.09922 (19)	0.0249 (4)
H59A	1.6492	−0.3934	−0.0788	0.030*
H59B	1.6167	−0.2157	−0.1927	0.030*
C510	1.83383 (17)	−0.3191 (2)	−0.10777 (18)	0.0217 (4)
H51A	1.8868	−0.3995	−0.0159	0.026*
H51B	1.8546	−0.2190	−0.1236	0.026*
C511	1.89275 (18)	−0.3744 (2)	−0.22522 (19)	0.0277 (4)
H51C	2.0009	−0.4029	−0.2182	0.042*
H51D	1.8518	−0.2889	−0.3175	0.042*
H51E	1.8637	−0.4673	−0.2159	0.042*

	U11	U22	U33	U12	U13	U23
N21	0.0139 (7)	0.0134 (7)	0.0229 (8)	−0.0023 (5)	0.0014 (5)	−0.0075 (6)
N24	0.0136 (6)	0.0145 (7)	0.0195 (7)	−0.0030 (5)	−0.0003 (5)	−0.0071 (6)
C1	0.0159 (8)	0.0165 (8)	0.0220 (9)	−0.0040 (6)	−0.0007 (6)	−0.0088 (7)
C2	0.0184 (8)	0.0141 (8)	0.0241 (9)	−0.0023 (6)	0.0006 (7)	−0.0090 (7)
C3	0.0148 (8)	0.0197 (9)	0.0206 (9)	−0.0017 (6)	0.0021 (6)	−0.0103 (7)
C4	0.0119 (7)	0.0192 (9)	0.0184 (9)	−0.0012 (6)	0.0004 (6)	−0.0087 (7)
C5	0.0151 (8)	0.0190 (9)	0.0171 (8)	−0.0047 (6)	0.0008 (6)	−0.0078 (7)
C16	0.0156 (8)	0.0186 (9)	0.0146 (8)	−0.0046 (6)	0.0001 (6)	−0.0065 (7)
C17	0.0179 (8)	0.0206 (9)	0.0199 (9)	−0.0071 (7)	0.0040 (6)	−0.0071 (7)
C18	0.0193 (8)	0.0156 (9)	0.0237 (9)	−0.0066 (7)	0.0022 (7)	−0.0059 (7)
C19	0.0153 (8)	0.0159 (8)	0.0201 (9)	−0.0046 (6)	−0.0004 (6)	−0.0066 (7)
C20	0.0180 (8)	0.0136 (8)	0.0236 (9)	−0.0054 (6)	−0.0001 (6)	−0.0063 (7)
C51	0.0171 (8)	0.0144 (8)	0.0191 (9)	−0.0031 (6)	0.0028 (6)	−0.0052 (7)
C52	0.0183 (8)	0.0214 (9)	0.0221 (9)	−0.0066 (7)	0.0012 (7)	−0.0080 (8)
C53	0.0232 (9)	0.0212 (9)	0.0189 (9)	−0.0060 (7)	0.0045 (7)	−0.0100 (7)
C54	0.0146 (8)	0.0146 (8)	0.0222 (9)	−0.0026 (6)	0.0047 (6)	−0.0036 (7)
C55	0.0193 (8)	0.0165 (9)	0.0204 (9)	−0.0057 (7)	−0.0015 (7)	−0.0053 (7)
C56	0.0197 (8)	0.0182 (9)	0.0184 (9)	−0.0034 (7)	0.0021 (6)	−0.0078 (7)
O1	0.0168 (6)	0.0286 (7)	0.0251 (7)	−0.0071 (5)	0.0065 (5)	−0.0135 (6)
C57	0.0202 (8)	0.0268 (10)	0.0229 (9)	−0.0062 (7)	0.0069 (7)	−0.0127 (8)
C58	0.0180 (8)	0.0183 (9)	0.0233 (9)	−0.0047 (7)	0.0060 (7)	−0.0050 (7)
C59	0.0204 (9)	0.0312 (11)	0.0260 (10)	−0.0096 (8)	0.0071 (7)	−0.0135 (8)
C510	0.0185 (8)	0.0216 (9)	0.0237 (9)	−0.0046 (7)	0.0049 (7)	−0.0088 (8)
C511	0.0209 (9)	0.0360 (11)	0.0324 (11)	−0.0105 (8)	0.0071 (8)	−0.0190 (9)

N21—C1	1.370 (2)	C52—H52A	0.9500
N21—C4	1.3722 (19)	C53—C54	1.394 (2)
N21—H21	0.8800	C53—H53A	0.9500
N24—C19	1.367 (2)	C54—O1	1.3710 (18)
N24—C16	1.3711 (19)	C54—C55	1.384 (2)
C1—C20	1.388 (2)	C55—C56	1.381 (2)
C1—C2	1.428 (2)	C55—H55A	0.9500
C2—C3	1.362 (2)	C56—H56A	0.9500
C2—H2A	0.9500	O1—C57	1.4335 (19)
C3—C4	1.427 (2)	C57—C58	1.511 (2)
C3—H3A	0.9500	C57—H57A	0.9900
C4—C5	1.399 (2)	C57—H57B	0.9900
C5—C16i	1.412 (2)	C58—C59	1.527 (2)
C5—C51	1.496 (2)	C58—H58A	0.9900
C16—C5i	1.412 (2)	C58—H58B	0.9900
C16—C17	1.457 (2)	C59—C510	1.515 (2)
C17—C18	1.348 (2)	C59—H59A	0.9900
C17—H17A	0.9500	C59—H59B	0.9900
C18—C19	1.448 (2)	C510—C511	1.514 (2)
C18—H18A	0.9500	C510—H51A	0.9900
C19—C20	1.396 (2)	C510—H51B	0.9900
C20—H20A	0.9500	C511—H51C	0.9800
C51—C52	1.394 (2)	C511—H51D	0.9800
C51—C56	1.403 (2)	C511—H51E	0.9800
C52—C53	1.389 (2)
C1—N21—C4	110.37 (13)	C54—C53—H53A	120.3
C1—N21—H21	124.8	O1—C54—C55	114.91 (14)
C4—N21—H21	124.8	O1—C54—C53	125.17 (15)
C19—N24—C16	105.16 (13)	C55—C54—C53	119.92 (14)
N21—C1—C20	126.59 (15)	C56—C55—C54	120.09 (15)
N21—C1—C2	106.65 (13)	C56—C55—H55A	120.0
C20—C1—C2	126.68 (15)	C54—C55—H55A	120.0
C3—C2—C1	108.13 (15)	C55—C56—C51	121.49 (16)
C3—C2—H2A	125.9	C55—C56—H56A	119.3
C1—C2—H2A	125.9	C51—C56—H56A	119.3
C2—C3—C4	108.17 (14)	C54—O1—C57	118.76 (12)
C2—C3—H3A	125.9	O1—C57—C58	106.88 (13)
C4—C3—H3A	125.9	O1—C57—H57A	110.3
N21—C4—C5	124.67 (14)	C58—C57—H57A	110.3
N21—C4—C3	106.62 (14)	O1—C57—H57B	110.3
C5—C4—C3	128.61 (14)	C58—C57—H57B	110.3
C4—C5—C16i	123.29 (14)	H57A—C57—H57B	108.6
C4—C5—C51	118.72 (14)	C57—C58—C59	111.63 (14)
C16i—C5—C51	117.82 (14)	C57—C58—H58A	109.3
N24—C16—C5i	125.69 (15)	C59—C58—H58A	109.3
N24—C16—C17	110.71 (14)	C57—C58—H58B	109.3
C5i—C16—C17	123.59 (14)	C59—C58—H58B	109.3
C18—C17—C16	106.36 (14)	H58A—C58—H58B	108.0
C18—C17—H17A	126.8	C510—C59—C58	113.42 (14)
C16—C17—H17A	126.8	C510—C59—H59A	108.9
C17—C18—C19	106.69 (15)	C58—C59—H59A	108.9
C17—C18—H18A	126.7	C510—C59—H59B	108.9
C19—C18—H18A	126.7	C58—C59—H59B	108.9
N24—C19—C20	126.46 (14)	H59A—C59—H59B	107.7
N24—C19—C18	111.07 (13)	C59—C510—C511	113.04 (14)
C20—C19—C18	122.44 (15)	C59—C510—H51A	109.0
C1—C20—C19	128.88 (15)	C511—C510—H51A	109.0
C1—C20—H20A	115.6	C59—C510—H51B	109.0
C19—C20—H20A	115.6	C511—C510—H51B	109.0
C52—C51—C56	117.34 (14)	H51A—C510—H51B	107.8
C52—C51—C5	123.54 (14)	C510—C511—H51C	109.5
C56—C51—C5	119.12 (15)	C510—C511—H51D	109.5
C53—C52—C51	121.78 (15)	H51C—C511—H51D	109.5
C53—C52—H52A	119.1	C510—C511—H51E	109.5
C51—C52—H52A	119.1	H51C—C511—H51E	109.5
C52—C53—C54	119.38 (16)	H51D—C511—H51E	109.5
C52—C53—H53A	120.3
C4—N21—C1—C20	174.18 (15)	C2—C1—C20—C19	176.51 (16)
C4—N21—C1—C2	−2.51 (18)	N24—C19—C20—C1	0.4 (3)
N21—C1—C2—C3	1.54 (18)	C18—C19—C20—C1	178.43 (16)
C20—C1—C2—C3	−175.14 (16)	C4—C5—C51—C52	63.4 (2)
C1—C2—C3—C4	−0.05 (19)	C16i—C5—C51—C52	−121.15 (18)
C1—N21—C4—C5	−174.17 (15)	C4—C5—C51—C56	−116.84 (18)
C1—N21—C4—C3	2.48 (18)	C16i—C5—C51—C56	58.6 (2)
C2—C3—C4—N21	−1.45 (18)	C56—C51—C52—C53	−0.7 (2)
C2—C3—C4—C5	175.01 (16)	C5—C51—C52—C53	179.07 (15)
N21—C4—C5—C16i	−2.8 (3)	C51—C52—C53—C54	0.0 (2)
C3—C4—C5—C16i	−178.73 (16)	C52—C53—C54—O1	−179.13 (15)
N21—C4—C5—C51	172.32 (14)	C52—C53—C54—C55	0.5 (2)
C3—C4—C5—C51	−3.6 (3)	O1—C54—C55—C56	179.34 (14)
C19—N24—C16—C5i	179.15 (15)	C53—C54—C55—C56	−0.4 (2)
C19—N24—C16—C17	0.37 (17)	C54—C55—C56—C51	−0.4 (2)
N24—C16—C17—C18	0.14 (18)	C52—C51—C56—C55	0.9 (2)
C5i—C16—C17—C18	−178.68 (15)	C5—C51—C56—C55	−178.90 (15)
C16—C17—C18—C19	−0.56 (18)	C55—C54—O1—C57	−175.16 (14)
C16—N24—C19—C20	177.47 (16)	C53—C54—O1—C57	4.5 (2)
C16—N24—C19—C18	−0.72 (17)	C54—O1—C57—C58	174.70 (13)
C17—C18—C19—N24	0.84 (19)	O1—C57—C58—C59	172.84 (13)
C17—C18—C19—C20	−177.45 (15)	C57—C58—C59—C510	−170.19 (15)
N21—C1—C20—C19	0.5 (3)	C58—C59—C510—C511	−177.21 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···N24	0.88	2.50	3.033 (2)	119
N21—H21···N24i	0.88	2.22	2.804 (2)	123

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21⋯N24	0.88	2.50	3.033 (2)	119
N21—H21⋯N24i	0.88	2.22	2.804 (2)	123

Symmetry code: (i) .