meso-(4-Nitro­phenyl)­dipyrro­methane

Patra, G.K.; Diskin-Posner, Y.; Goldberg, I.

doi:10.1107/S160053680200613X

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meso-(4-Nitrophenyl)dipyrromethane

G. K. Patra, Y. Diskin-Posner and I. Goldberg

The title compound, meso-(4-nitrophenyl)di-2-pyrrolylmethane, C₁₅H₁₃N₃O₂, was synthesized by an acid-catalysed single-pot reaction of pyrrole and p-nitrobenzaldehyde. The molecular structure has been characterized precisely by low-temperature single-crystal analysis. The crystal structure exhibits weak N—H

O intermolecular hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680200613X/cf6166sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680200613X/cf6166Isup2.hkl Contains datablock I

CCDC reference: 185786

checkCIF report

Key indicators

Single-crystal X-ray study
T = 110 K
Mean (C-C) = 0.002 Å
R factor = 0.044
wR factor = 0.114
Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_420  Alert C D-H Without Acceptor       N(3)   -   H(3)              ?


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

Dipyrromethane derivatives are useful building blocks in the synthesis of porphyrin model systems, with direct approaches to trans-substituted porphyrins by condensation of dipyrromethanes with aldehydes (Lee & Lindsey, 1994). Acidolysis of the dipyrromethane is negligible under the conditions of the porphyrin-forming reaction. Most of the dipyrromethanes are indefinitely stable in the purified form when stored at 273 K in the absence of light. Only a few crystal structures of dipyrromethane derivatives have been reported (Lin et al., 1996; Bennis & Gallagher, 1998; Gallagher & Moriarty, 1999). Herein we describe the synthesis and the structure of the title compound, (I), at ca 110 K. In the crystal, molecules related by a screw axis form weak N—H8···O20(2 - x, y - 1/2, 1/2 - z) hydrogen bonds, with N—H = 0.92 (2) Å, N···O = 3.051 (2) Å, H···O = 2.18 (2) Å, and N—H···O = 158.5 (15)°.

Experimental top

A solution of p-nitrobenzaldehyde (0.906 g, 6 mmol) in pyrrole (16.8 ml, 240 mmol) was degassed by bubbling with argon for 10 min. Then trifluoroacetic acid (0.05 ml, 0.06 mmol) was added to the reaction mixture and it was stirred for 30 min at room temperature. The reaction mixture was diluted with 200 ml of CH₂Cl₂, washed successively with 0.1 N aq. NaOH and water, and dried with anhydrous Na₂SO₄. The solvent was removed under pressure, and then the unreacted pyrrole was removed by vacuum distillation. The black–green semi-solid thus obtained was treated with n-hexane to give a solid compound. This solid was dissolved in methanol (a small amount remained undissolved) and decolorized by charcoal powder. Slow evaporation of the methanol solution afforded yellow crystals of (I), which were suitable for X-ray analysis. Yield 0.721 g (45%). ¹H NMR (200 MHz, CDCl₃, TMS): δ 8.17 (d, J = 6 Hz, 2H), 7.90 (bs, 4H, 2H), 7.35 (d, J = 6 Hz, 2H), 6.76 (q, 2H), 5.89 (m, 2H), 5.58 (s, 1H, meso-H).

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski, 1985); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labeling scheme. Ellipsoids are drawn at the 50% probability level.
	Fig. 2. Perspective view of the crystal structure of (I), viewed approximately down the a axis.

Meso-(4-nitrophenyl)dipyrromethane top

Crystal data top

C₁₅H₁₃N₃O₂	F(000) = 560
M_r = 267.28	D_x = 1.371 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.1940 (2) Å	Cell parameters from 2204 reflections
b = 11.4380 (3) Å	θ = 2.6–27.9°
c = 11.3180 (3) Å	µ = 0.09 mm⁻¹
β = 101.1840 (11)°	T = 110 K
V = 1294.61 (5) Å³	Prism, yellow
Z = 4	0.25 × 0.20 × 0.20 mm

Data collection top

Nonius KappaCCD diffractometer	2204 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 27.9°, θ_min = 2.6°
Detector resolution: 56 microns pixels mm^-1	h = −13→13
ϕ scans	k = −13→15
5274 measured reflections	l = −14→14
3061 independent reflections

Refinement top

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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F²) = 0.114	All H-atom parameters refined
S = 1.00	w = 1/[σ²(F_o²) + (0.0491P)² + 0.4783P] where P = (F_o² + 2F_c²)/3
3061 reflections	(Δ/σ)_max < 0.001
233 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₅H₁₃N₃O₂	V = 1294.61 (5) Å³
M_r = 267.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.1940 (2) Å	µ = 0.09 mm⁻¹
b = 11.4380 (3) Å	T = 110 K
c = 11.3180 (3) Å	0.25 × 0.20 × 0.20 mm
β = 101.1840 (11)°

Data collection top

Nonius KappaCCD diffractometer	2204 reflections with I > 2σ(I)
5274 measured reflections	R_int = 0.030
3061 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.114	All H-atom parameters refined
S = 1.00	Δρ_max = 0.23 e Å⁻³
3061 reflections	Δρ_min = −0.32 e Å⁻³
233 parameters

Special details top

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.

All H-atoms were refined as free parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.71718 (15)	0.24320 (13)	0.46676 (13)	0.0170 (3)
H1	0.6903 (16)	0.2895 (15)	0.5327 (15)	0.019 (4)*
C2	0.73658 (15)	0.11850 (13)	0.51152 (13)	0.0180 (3)
N3	0.64868 (13)	0.06777 (12)	0.57390 (12)	0.0219 (3)
H3	0.576 (2)	0.1025 (17)	0.5957 (17)	0.032 (5)*
C4	0.68709 (18)	−0.04556 (15)	0.60190 (16)	0.0264 (4)
H4	0.6387 (19)	−0.0936 (17)	0.6465 (18)	0.037 (5)*
C5	0.79928 (17)	−0.06728 (14)	0.55633 (16)	0.0256 (4)
H5	0.8481 (19)	−0.1380 (18)	0.5644 (18)	0.033 (5)*
C6	0.83019 (16)	0.03651 (14)	0.49864 (15)	0.0223 (4)
H6	0.9047 (19)	0.0500 (16)	0.4568 (17)	0.029 (5)*
C7	0.60386 (15)	0.25283 (13)	0.35952 (13)	0.0187 (3)
N8	0.58732 (14)	0.17396 (12)	0.26644 (12)	0.0216 (3)
H8	0.640 (2)	0.1097 (19)	0.2610 (19)	0.044 (6)*
C9	0.47908 (16)	0.20564 (16)	0.17972 (15)	0.0248 (4)
H9	0.4528 (19)	0.1562 (18)	0.1103 (19)	0.035 (5)*
C10	0.42647 (17)	0.30507 (16)	0.21796 (15)	0.0247 (4)
H10	0.355 (2)	0.3456 (16)	0.1776 (17)	0.028 (5)*
C11	0.50562 (16)	0.33531 (15)	0.33154 (15)	0.0216 (3)
H11	0.4942 (18)	0.4020 (16)	0.3787 (16)	0.025 (5)*
C12	0.84894 (15)	0.29540 (13)	0.44531 (13)	0.0169 (3)
C13	0.95693 (15)	0.30651 (13)	0.54247 (14)	0.0186 (3)
H13	0.9480 (16)	0.2790 (15)	0.6227 (16)	0.020 (4)*
C14	1.07547 (16)	0.35851 (13)	0.52783 (14)	0.0191 (3)
H14	1.1474 (18)	0.3695 (15)	0.5959 (16)	0.022 (4)*
C15	1.08470 (15)	0.39904 (13)	0.41442 (14)	0.0174 (3)
C16	0.98115 (16)	0.38888 (14)	0.31622 (14)	0.0204 (3)
H16	0.9890 (18)	0.4192 (15)	0.2382 (18)	0.026 (5)*
C17	0.86333 (16)	0.33571 (14)	0.33279 (14)	0.0207 (3)
H17	0.7869 (19)	0.3308 (16)	0.2644 (17)	0.028 (5)*
N18	1.20583 (13)	0.46113 (11)	0.39800 (12)	0.0212 (3)
O19	1.29820 (11)	0.47170 (10)	0.48469 (11)	0.0265 (3)
O20	1.20881 (12)	0.50178 (12)	0.29768 (11)	0.0337 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0155 (7)	0.0185 (7)	0.0170 (7)	0.0006 (6)	0.0034 (6)	−0.0017 (6)
C2	0.0159 (7)	0.0205 (7)	0.0173 (7)	−0.0018 (6)	0.0028 (6)	0.0000 (6)
N3	0.0184 (7)	0.0241 (7)	0.0244 (7)	−0.0009 (6)	0.0075 (6)	0.0010 (6)
C4	0.0271 (9)	0.0238 (8)	0.0275 (9)	−0.0073 (7)	0.0031 (7)	0.0034 (7)
C5	0.0278 (9)	0.0178 (8)	0.0293 (9)	0.0012 (7)	0.0006 (7)	−0.0013 (7)
C6	0.0196 (8)	0.0241 (8)	0.0233 (8)	0.0007 (6)	0.0042 (6)	−0.0007 (7)
C7	0.0169 (8)	0.0204 (7)	0.0195 (8)	−0.0016 (6)	0.0053 (6)	−0.0004 (6)
N8	0.0198 (7)	0.0220 (7)	0.0234 (7)	0.0000 (5)	0.0052 (5)	−0.0028 (6)
C9	0.0209 (8)	0.0335 (9)	0.0197 (8)	−0.0076 (7)	0.0037 (6)	−0.0012 (7)
C10	0.0162 (8)	0.0335 (9)	0.0235 (8)	0.0014 (7)	0.0020 (6)	0.0081 (7)
C11	0.0208 (8)	0.0227 (8)	0.0223 (8)	0.0013 (6)	0.0066 (6)	0.0002 (7)
C12	0.0169 (8)	0.0144 (7)	0.0196 (7)	0.0015 (6)	0.0041 (6)	−0.0006 (6)
C13	0.0204 (8)	0.0185 (7)	0.0163 (7)	0.0007 (6)	0.0023 (6)	0.0017 (6)
C14	0.0181 (8)	0.0177 (7)	0.0202 (7)	0.0019 (6)	0.0007 (6)	−0.0009 (6)
C15	0.0152 (7)	0.0144 (7)	0.0234 (8)	−0.0001 (5)	0.0054 (6)	−0.0006 (6)
C16	0.0222 (8)	0.0223 (8)	0.0178 (7)	−0.0011 (6)	0.0062 (6)	0.0011 (7)
C17	0.0193 (8)	0.0237 (8)	0.0178 (7)	−0.0020 (6)	0.0004 (6)	−0.0006 (6)
N18	0.0182 (7)	0.0181 (7)	0.0283 (7)	0.0003 (5)	0.0073 (6)	−0.0017 (6)
O19	0.0170 (6)	0.0269 (6)	0.0341 (7)	−0.0020 (5)	0.0009 (5)	−0.0022 (5)
O20	0.0312 (7)	0.0416 (7)	0.0299 (7)	−0.0089 (6)	0.0101 (5)	0.0091 (6)

Geometric parameters (Å, º) top

C1—C7	1.509 (2)	C9—H9	0.96 (2)
C1—C2	1.514 (2)	C10—C11	1.422 (2)
C1—C12	1.532 (2)	C10—H10	0.910 (19)
C1—H1	0.996 (17)	C11—H11	0.951 (19)
C2—C6	1.366 (2)	C12—C17	1.389 (2)
C2—N3	1.372 (2)	C12—C13	1.403 (2)
N3—C4	1.373 (2)	C13—C14	1.385 (2)
N3—H3	0.92 (2)	C13—H13	0.981 (18)
C4—C5	1.365 (3)	C14—C15	1.385 (2)
C4—H4	0.95 (2)	C14—H14	0.963 (18)
C5—C6	1.419 (2)	C15—C16	1.381 (2)
C5—H5	0.94 (2)	C15—N18	1.4673 (19)
C6—H6	0.982 (19)	C16—C17	1.391 (2)
C7—C11	1.368 (2)	C16—H16	0.97 (2)
C7—N8	1.372 (2)	C17—H17	0.988 (19)
N8—C9	1.375 (2)	N18—O19	1.2269 (17)
N8—H8	0.92 (2)	N18—O20	1.2327 (17)
C9—C10	1.363 (3)

C7—C1—C2	111.59 (12)	N8—C9—H9	119.0 (12)
C7—C1—C12	113.72 (12)	C9—C10—C11	107.51 (15)
C2—C1—C12	111.02 (12)	C9—C10—H10	126.3 (12)
C7—C1—H1	106.6 (9)	C11—C10—H10	126.1 (12)
C2—C1—H1	106.7 (10)	C7—C11—C10	107.66 (15)
C12—C1—H1	106.8 (9)	C7—C11—H11	126.0 (11)
C6—C2—N3	107.70 (14)	C10—C11—H11	126.3 (11)
C6—C2—C1	131.29 (14)	C17—C12—C13	118.84 (14)
N3—C2—C1	120.97 (13)	C17—C12—C1	121.78 (13)
C2—N3—C4	109.41 (14)	C13—C12—C1	119.35 (13)
C2—N3—H3	126.7 (12)	C14—C13—C12	121.02 (14)
C4—N3—H3	123.9 (12)	C14—C13—H13	119.2 (10)
C5—C4—N3	107.87 (15)	C12—C13—H13	119.8 (10)
C5—C4—H4	131.1 (12)	C15—C14—C13	118.18 (14)
N3—C4—H4	121.1 (12)	C15—C14—H14	121.3 (11)
C4—C5—C6	107.37 (15)	C13—C14—H14	120.4 (11)
C4—C5—H5	125.7 (12)	C16—C15—C14	122.61 (14)
C6—C5—H5	126.9 (12)	C16—C15—N18	117.99 (13)
C2—C6—C5	107.64 (15)	C14—C15—N18	119.31 (14)
C2—C6—H6	124.4 (11)	C15—C16—C17	118.25 (14)
C5—C6—H6	127.9 (11)	C15—C16—H16	121.3 (11)
C11—C7—N8	107.47 (14)	C17—C16—H16	120.4 (11)
C11—C7—C1	130.44 (14)	C12—C17—C16	121.09 (14)
N8—C7—C1	122.05 (14)	C12—C17—H17	119.5 (11)
C9—N8—C7	109.68 (14)	C16—C17—H17	119.3 (11)
C9—N8—H8	124.1 (14)	O19—N18—O20	123.18 (14)
C7—N8—H8	126.3 (14)	O19—N18—C15	118.72 (13)
C10—C9—N8	107.69 (15)	O20—N18—C15	118.10 (13)
C10—C9—H9	133.2 (12)

C7—C1—C2—C6	103.51 (19)	C1—C7—C11—C10	178.16 (15)
C12—C1—C2—C6	−24.5 (2)	C9—C10—C11—C7	−0.35 (19)
C7—C1—C2—N3	−74.05 (18)	C7—C1—C12—C17	−6.5 (2)
C12—C1—C2—N3	157.96 (13)	C2—C1—C12—C17	120.33 (16)
C6—C2—N3—C4	0.73 (18)	C7—C1—C12—C13	171.38 (13)
C1—C2—N3—C4	178.81 (13)	C2—C1—C12—C13	−61.80 (17)
C2—N3—C4—C5	−0.46 (19)	C17—C12—C13—C14	1.1 (2)
N3—C4—C5—C6	0.02 (19)	C1—C12—C13—C14	−176.80 (13)
N3—C2—C6—C5	−0.70 (18)	C12—C13—C14—C15	−0.2 (2)
C1—C2—C6—C5	−178.51 (15)	C13—C14—C15—C16	−0.4 (2)
C4—C5—C6—C2	0.43 (19)	C13—C14—C15—N18	176.13 (13)
C2—C1—C7—C11	138.64 (17)	C14—C15—C16—C17	0.0 (2)
C12—C1—C7—C11	−94.8 (2)	N18—C15—C16—C17	−176.57 (13)
C2—C1—C7—N8	−43.78 (19)	C13—C12—C17—C16	−1.5 (2)
C12—C1—C7—N8	82.75 (17)	C1—C12—C17—C16	176.34 (14)
C11—C7—N8—C9	−0.15 (18)	C15—C16—C17—C12	1.0 (2)
C1—C7—N8—C9	−178.23 (14)	C16—C15—N18—O19	179.40 (14)
C7—N8—C9—C10	−0.07 (18)	C14—C15—N18—O19	2.7 (2)
N8—C9—C10—C11	0.26 (19)	C16—C15—N18—O20	0.5 (2)
N8—C7—C11—C10	0.31 (18)	C14—C15—N18—O20	−176.22 (14)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃N₃O₂
M_r	267.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	110
a, b, c (Å)	10.1940 (2), 11.4380 (3), 11.3180 (3)
β (°)	101.1840 (11)
V (Å³)	1294.61 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5274, 3061, 2204
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.114, 1.00
No. of reflections	3061
No. of parameters	233
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.32

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski, 1985), DENZO, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.

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