Dibenzyl 3,3'-diethyl-4,4'-dimethyl-2,2'-methylenebis(pyrrole-5-carboxylate).

In the title compound, C(31)H(34)N(2)O(4), the two pyrrole rings are bent around the central methyl-ene C atom, making a dihedral angle of 64.83 (7)°. In the crystal, mol-ecules are linked into dimers via N-H⋯O=C hydrogen bonds. These dimers are packed through π⋯π inter-actions between neighboring pyrrole rings with a separation between the mean planes of symmetry-related pyrrole rings of 3.61 (2) Å and a centroid-centroid distance of 4.33 Å. Parallel phenyl groups in neighboring dimers also exhibit efficient π⋯π inter-actions, characterized by an inter-plane separation of 3.378 (8) Å and a centroid-centroid distance of 3.97 Å.

Related literature

For the preparation of the title compound, see: Twyman & Sanders (1999 ▶). For related structures, see: Bonnett et al. (1972 ▶); Senge (2005 ▶); Vega et al. (2003 ▶). For the use of dipyrrylmethanes in organic synthesis, see: Chen et al. (2000 ▶) and references cited therein; Jasat & Dolphin (1997 ▶); Shanmugathasan et al. (2000 ▶).

Experimental

Crystal data

C31H34N2O4

M = 498.60

Monoclinic,

a = 14.2002 (9) Å

b = 7.9220 (5) Å

c = 25.0939 (16) Å

β = 104.373 (3)°

V = 2734.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 162 K

0.35 × 0.32 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.972, T max = 0.993

37570 measured reflections

6304 independent reflections

4371 reflections with I > 2σ(I)

R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.136

S = 1.05

6304 reflections

346 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, globle. DOI: 10.1107/S1600536810004459/bh2271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004459/bh2271Isup2.hkl

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

C31H34N2O4	F(000) = 1064
Mr = 498.60	Dx = 1.211 Mg m−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 9928 reflections
a = 14.2002 (9) Å	θ = 2.6–24.4°
b = 7.9220 (5) Å	µ = 0.08 mm−1
c = 25.0939 (16) Å	T = 162 K
β = 104.373 (3)°	Plate, colourless
V = 2734.6 (3) Å3	0.35 × 0.32 × 0.08 mm
Z = 4

Bruker SMART APEX CCD diffractometer	6304 independent reflections
Radiation source: fine-focus sealed tube	4371 reflections with I > 2σ(I)
graphite	Rint = 0.059
φ and ω scans	θmax = 27.6°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −18→18
Tmin = 0.972, Tmax = 0.993	k = −10→10
37570 measured reflections	l = −31→32

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0505P)2 + 0.953P] where P = (Fo2 + 2Fc2)/3
6304 reflections	(Δ/σ)max = 0.001
346 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.26 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
O1	0.84641 (10)	0.85654 (17)	0.91775 (6)	0.0528 (4)
O2	0.75643 (10)	0.65074 (17)	0.86750 (7)	0.0603 (4)
O3	0.76635 (7)	0.24675 (15)	0.68188 (4)	0.0342 (3)
O4	0.87580 (7)	0.18152 (15)	0.63406 (4)	0.0334 (3)
N1	0.90073 (10)	0.43117 (18)	0.88502 (5)	0.0310 (3)
H1	0.8449 (15)	0.396 (3)	0.8648 (8)	0.047 (6)*
N2	0.90338 (9)	0.17664 (17)	0.77990 (5)	0.0285 (3)
H2	0.8449 (14)	0.204 (2)	0.7845 (7)	0.045 (5)*
C1	0.91713 (12)	0.5906 (2)	0.90767 (7)	0.0339 (4)
C2	1.01355 (12)	0.5990 (2)	0.93634 (6)	0.0348 (4)
C3	1.05588 (12)	0.4413 (2)	0.93042 (6)	0.0327 (4)
C4	0.98377 (11)	0.3399 (2)	0.89853 (6)	0.0295 (3)
C5	0.98552 (12)	0.1610 (2)	0.87970 (6)	0.0319 (4)
H5A	0.9283	0.1010	0.8863	0.038*
H5B	1.0445	0.1051	0.9021	0.038*
C6	0.98473 (11)	0.1445 (2)	0.82008 (6)	0.0294 (3)
C7	1.05896 (11)	0.1041 (2)	0.79533 (7)	0.0315 (4)
C8	1.01998 (11)	0.1126 (2)	0.73787 (7)	0.0310 (4)
C9	0.92347 (11)	0.1592 (2)	0.72921 (6)	0.0287 (3)
C10	1.06422 (14)	0.7464 (2)	0.96891 (8)	0.0461 (5)
H10A	1.0161	0.8318	0.9723	0.069*
H10B	1.1105	0.7954	0.9501	0.069*
H10C	1.0991	0.7081	1.0056	0.069*
C11	1.07570 (12)	0.0804 (3)	0.69528 (7)	0.0426 (4)
H11A	1.0525	0.1566	0.6640	0.064*
H11B	1.0659	−0.0369	0.6827	0.064*
H11C	1.1451	0.1004	0.7113	0.064*
C12	1.16037 (12)	0.3931 (3)	0.95415 (7)	0.0422 (4)
H12A	1.1652	0.2685	0.9563	0.051*
H12B	1.1815	0.4379	0.9921	0.051*
C13	1.22892 (14)	0.4582 (3)	0.92102 (9)	0.0538 (5)
H13A	1.2952	0.4199	0.9380	0.081*
H13B	1.2273	0.5818	0.9203	0.081*
H13C	1.2085	0.4148	0.8833	0.081*
C14	1.16166 (11)	0.0618 (2)	0.82435 (7)	0.0399 (4)
H14A	1.1742	0.1008	0.8630	0.048*
H14B	1.2061	0.1243	0.8067	0.048*
C15	1.18485 (14)	−0.1252 (3)	0.82408 (9)	0.0533 (5)
H15A	1.2535	−0.1434	0.8425	0.080*
H15B	1.1721	−0.1653	0.7860	0.080*
H15C	1.1440	−0.1875	0.8435	0.080*
C16	0.84033 (13)	0.7142 (2)	0.89944 (8)	0.0416 (4)
C17	0.67700 (17)	0.7704 (3)	0.85195 (13)	0.0862 (9)
H17A	0.6956	0.8644	0.8306	0.103*
H17B	0.6614	0.8179	0.8852	0.103*
C18	0.59147 (15)	0.6804 (3)	0.81813 (9)	0.0532 (5)
C19	0.58054 (18)	0.6486 (3)	0.76239 (10)	0.0682 (7)
H19A	0.6301	0.6828	0.7453	0.082*
C20	0.4995 (2)	0.5688 (3)	0.73183 (10)	0.0717 (7)
H20A	0.4937	0.5482	0.6939	0.086*
C21	0.4286 (2)	0.5196 (3)	0.75463 (12)	0.0751 (8)
H21A	0.3728	0.4646	0.7328	0.090*
C22	0.43577 (19)	0.5477 (3)	0.80892 (13)	0.0766 (8)
H22A	0.3850	0.5135	0.8250	0.092*
C23	0.51800 (19)	0.6269 (3)	0.84062 (10)	0.0637 (6)
H23A	0.5234	0.6445	0.8787	0.076*
C24	0.84815 (11)	0.1997 (2)	0.68106 (6)	0.0276 (3)
C25	0.80269 (12)	0.2219 (2)	0.58423 (6)	0.0359 (4)
H25A	0.7837	0.3421	0.5844	0.043*
H25B	0.7441	0.1514	0.5814	0.043*
C26	0.84675 (12)	0.1871 (2)	0.53687 (6)	0.0324 (4)
C27	0.81372 (12)	0.0548 (2)	0.50133 (7)	0.0405 (4)
H27A	0.7629	−0.0156	0.5069	0.049*
C28	0.85450 (14)	0.0244 (3)	0.45761 (7)	0.0478 (5)
H28A	0.8312	−0.0662	0.4331	0.057*
C29	0.92838 (15)	0.1244 (3)	0.44945 (7)	0.0490 (5)
H29A	0.9560	0.1032	0.4193	0.059*
C30	0.96260 (15)	0.2558 (3)	0.48502 (8)	0.0496 (5)
H30A	1.0142	0.3247	0.4796	0.060*
C31	0.92170 (14)	0.2872 (2)	0.52860 (7)	0.0414 (4)
H31A	0.9452	0.3780	0.5530	0.050*

	U11	U22	U33	U12	U13	U23
O1	0.0556 (8)	0.0344 (8)	0.0696 (9)	−0.0040 (6)	0.0177 (7)	−0.0095 (7)
O2	0.0426 (8)	0.0386 (8)	0.0881 (11)	0.0093 (6)	−0.0059 (7)	−0.0128 (7)
O3	0.0246 (6)	0.0458 (7)	0.0335 (6)	0.0038 (5)	0.0095 (5)	0.0045 (5)
O4	0.0264 (6)	0.0474 (7)	0.0267 (5)	0.0018 (5)	0.0072 (5)	−0.0004 (5)
N1	0.0286 (7)	0.0331 (8)	0.0300 (7)	−0.0034 (6)	0.0047 (6)	−0.0023 (6)
N2	0.0198 (6)	0.0365 (8)	0.0293 (7)	0.0011 (6)	0.0067 (5)	−0.0012 (6)
C1	0.0390 (9)	0.0325 (9)	0.0308 (8)	−0.0042 (7)	0.0098 (7)	−0.0021 (7)
C2	0.0396 (9)	0.0388 (10)	0.0255 (8)	−0.0079 (8)	0.0073 (7)	0.0008 (7)
C3	0.0335 (9)	0.0401 (10)	0.0227 (7)	−0.0062 (7)	0.0035 (6)	0.0036 (7)
C4	0.0287 (8)	0.0353 (9)	0.0241 (7)	−0.0025 (7)	0.0061 (6)	0.0021 (7)
C5	0.0295 (8)	0.0349 (9)	0.0297 (8)	0.0011 (7)	0.0042 (7)	0.0040 (7)
C6	0.0240 (7)	0.0305 (9)	0.0317 (8)	−0.0014 (6)	0.0035 (6)	−0.0017 (7)
C7	0.0229 (8)	0.0337 (9)	0.0365 (9)	−0.0017 (7)	0.0046 (6)	−0.0067 (7)
C8	0.0220 (7)	0.0355 (9)	0.0355 (8)	−0.0026 (7)	0.0073 (6)	−0.0065 (7)
C9	0.0238 (7)	0.0340 (9)	0.0288 (8)	−0.0018 (6)	0.0074 (6)	−0.0033 (7)
C10	0.0522 (11)	0.0449 (11)	0.0387 (10)	−0.0128 (9)	0.0062 (8)	−0.0066 (9)
C11	0.0289 (9)	0.0586 (12)	0.0426 (10)	0.0007 (8)	0.0137 (7)	−0.0106 (9)
C12	0.0365 (10)	0.0486 (11)	0.0344 (9)	−0.0041 (8)	−0.0044 (7)	0.0032 (8)
C13	0.0353 (10)	0.0589 (13)	0.0647 (13)	−0.0043 (9)	0.0075 (9)	0.0014 (11)
C14	0.0229 (8)	0.0482 (11)	0.0455 (10)	0.0012 (7)	0.0026 (7)	−0.0091 (9)
C15	0.0381 (10)	0.0506 (12)	0.0624 (13)	0.0104 (9)	−0.0042 (9)	−0.0059 (10)
C16	0.0437 (10)	0.0353 (10)	0.0461 (10)	−0.0035 (8)	0.0115 (8)	−0.0010 (8)
C17	0.0564 (14)	0.0475 (14)	0.133 (2)	0.0215 (11)	−0.0170 (15)	−0.0224 (15)
C18	0.0521 (12)	0.0439 (12)	0.0589 (13)	0.0229 (10)	0.0051 (10)	−0.0037 (10)
C19	0.0650 (15)	0.0705 (16)	0.0724 (16)	0.0287 (13)	0.0233 (13)	0.0057 (13)
C20	0.0748 (17)	0.0749 (17)	0.0536 (13)	0.0352 (14)	−0.0066 (13)	−0.0125 (13)
C21	0.0650 (16)	0.0567 (15)	0.089 (2)	0.0198 (13)	−0.0085 (14)	−0.0120 (14)
C22	0.0667 (16)	0.0588 (16)	0.108 (2)	0.0098 (13)	0.0284 (16)	0.0136 (16)
C23	0.0788 (17)	0.0564 (14)	0.0533 (13)	0.0223 (13)	0.0112 (12)	0.0034 (11)
C24	0.0241 (7)	0.0294 (8)	0.0307 (8)	−0.0033 (6)	0.0096 (6)	−0.0001 (7)
C25	0.0302 (8)	0.0458 (10)	0.0304 (8)	0.0040 (7)	0.0053 (7)	0.0059 (8)
C26	0.0316 (8)	0.0368 (9)	0.0276 (8)	0.0038 (7)	0.0051 (7)	0.0050 (7)
C27	0.0331 (9)	0.0471 (11)	0.0364 (9)	−0.0033 (8)	−0.0005 (7)	−0.0010 (8)
C28	0.0486 (11)	0.0553 (12)	0.0332 (9)	0.0020 (10)	−0.0018 (8)	−0.0113 (9)
C29	0.0591 (12)	0.0605 (13)	0.0285 (9)	0.0076 (10)	0.0133 (8)	−0.0004 (9)
C30	0.0582 (12)	0.0535 (13)	0.0430 (10)	−0.0070 (10)	0.0236 (9)	0.0045 (10)
C31	0.0520 (11)	0.0392 (10)	0.0353 (9)	−0.0073 (8)	0.0154 (8)	−0.0030 (8)

O1—C16	1.213 (2)	C13—H13A	0.9800
O2—C16	1.356 (2)	C13—H13B	0.9800
O2—C17	1.451 (2)	C13—H13C	0.9800
O3—C24	1.2249 (18)	C14—C15	1.518 (3)
O4—C24	1.3400 (18)	C14—H14A	0.9900
O4—C25	1.4490 (18)	C14—H14B	0.9900
N1—C4	1.352 (2)	C15—H15A	0.9800
N1—C1	1.381 (2)	C15—H15B	0.9800
N1—H1	0.87 (2)	C15—H15C	0.9800
N2—C6	1.356 (2)	C17—C18	1.481 (3)
N2—C9	1.3778 (19)	C17—H17A	0.9900
N2—H2	0.893 (19)	C17—H17B	0.9900
C1—C2	1.381 (2)	C18—C23	1.371 (3)
C1—C16	1.442 (3)	C18—C19	1.391 (3)
C2—C3	1.410 (3)	C19—C20	1.368 (4)
C2—C10	1.502 (2)	C19—H19A	0.9500
C3—C4	1.388 (2)	C20—C21	1.334 (4)
C3—C12	1.504 (2)	C20—H20A	0.9500
C4—C5	1.496 (2)	C21—C22	1.359 (4)
C5—C6	1.499 (2)	C21—H21A	0.9500
C5—H5A	0.9900	C22—C23	1.389 (4)
C5—H5B	0.9900	C22—H22A	0.9500
C6—C7	1.387 (2)	C23—H23A	0.9500
C7—C8	1.412 (2)	C25—C26	1.500 (2)
C7—C14	1.497 (2)	C25—H25A	0.9900
C8—C9	1.383 (2)	C25—H25B	0.9900
C8—C11	1.501 (2)	C26—C27	1.381 (2)
C9—C24	1.437 (2)	C26—C31	1.384 (2)
C10—H10A	0.9800	C27—C28	1.383 (3)
C10—H10B	0.9800	C27—H27A	0.9500
C10—H10C	0.9800	C28—C29	1.370 (3)
C11—H11A	0.9800	C28—H28A	0.9500
C11—H11B	0.9800	C29—C30	1.379 (3)
C11—H11C	0.9800	C29—H29A	0.9500
C12—C13	1.519 (3)	C30—C31	1.382 (2)
C12—H12A	0.9900	C30—H30A	0.9500
C12—H12B	0.9900	C31—H31A	0.9500
C16—O2—C17	115.28 (16)	C15—C14—H14A	108.8
C24—O4—C25	115.60 (12)	C7—C14—H14B	108.8
C4—N1—C1	109.76 (14)	C15—C14—H14B	108.8
C4—N1—H1	125.8 (13)	H14A—C14—H14B	107.7
C1—N1—H1	124.5 (13)	C14—C15—H15A	109.5
C6—N2—C9	109.53 (13)	C14—C15—H15B	109.5
C6—N2—H2	126.6 (12)	H15A—C15—H15B	109.5
C9—N2—H2	123.8 (12)	C14—C15—H15C	109.5
N1—C1—C2	107.62 (15)	H15A—C15—H15C	109.5
N1—C1—C16	121.18 (15)	H15B—C15—H15C	109.5
C2—C1—C16	131.20 (16)	O1—C16—O2	122.53 (17)
C1—C2—C3	107.20 (15)	O1—C16—C1	126.65 (18)
C1—C2—C10	126.87 (17)	O2—C16—C1	110.82 (16)
C3—C2—C10	125.92 (16)	O2—C17—C18	108.16 (17)
C4—C3—C2	107.49 (14)	O2—C17—H17A	110.1
C4—C3—C12	126.53 (16)	C18—C17—H17A	110.1
C2—C3—C12	125.98 (15)	O2—C17—H17B	110.1
N1—C4—C3	107.93 (15)	C18—C17—H17B	110.1
N1—C4—C5	120.59 (14)	H17A—C17—H17B	108.4
C3—C4—C5	131.48 (15)	C23—C18—C19	116.8 (2)
C4—C5—C6	113.68 (13)	C23—C18—C17	120.8 (2)
C4—C5—H5A	108.8	C19—C18—C17	122.3 (2)
C6—C5—H5A	108.8	C20—C19—C18	121.0 (2)
C4—C5—H5B	108.8	C20—C19—H19A	119.5
C6—C5—H5B	108.8	C18—C19—H19A	119.5
H5A—C5—H5B	107.7	C21—C20—C19	120.9 (2)
N2—C6—C7	108.19 (14)	C21—C20—H20A	119.6
N2—C6—C5	121.31 (13)	C19—C20—H20A	119.6
C7—C6—C5	130.45 (14)	C20—C21—C22	120.4 (3)
C6—C7—C8	107.30 (13)	C20—C21—H21A	119.8
C6—C7—C14	126.19 (15)	C22—C21—H21A	119.8
C8—C7—C14	126.51 (14)	C21—C22—C23	119.4 (3)
C9—C8—C7	107.16 (13)	C21—C22—H22A	120.3
C9—C8—C11	127.60 (15)	C23—C22—H22A	120.3
C7—C8—C11	125.22 (14)	C18—C23—C22	121.4 (2)
N2—C9—C8	107.80 (13)	C18—C23—H23A	119.3
N2—C9—C24	118.19 (13)	C22—C23—H23A	119.3
C8—C9—C24	133.88 (14)	O3—C24—O4	122.27 (14)
C2—C10—H10A	109.5	O3—C24—C9	124.37 (14)
C2—C10—H10B	109.5	O4—C24—C9	113.36 (13)
H10A—C10—H10B	109.5	O4—C25—C26	107.03 (13)
C2—C10—H10C	109.5	O4—C25—H25A	110.3
H10A—C10—H10C	109.5	C26—C25—H25A	110.3
H10B—C10—H10C	109.5	O4—C25—H25B	110.3
C8—C11—H11A	109.5	C26—C25—H25B	110.3
C8—C11—H11B	109.5	H25A—C25—H25B	108.6
H11A—C11—H11B	109.5	C27—C26—C31	119.28 (16)
C8—C11—H11C	109.5	C27—C26—C25	120.65 (16)
H11A—C11—H11C	109.5	C31—C26—C25	120.07 (16)
H11B—C11—H11C	109.5	C26—C27—C28	120.15 (17)
C3—C12—C13	113.60 (15)	C26—C27—H27A	119.9
C3—C12—H12A	108.8	C28—C27—H27A	119.9
C13—C12—H12A	108.8	C29—C28—C27	120.34 (18)
C3—C12—H12B	108.8	C29—C28—H28A	119.8
C13—C12—H12B	108.8	C27—C28—H28A	119.8
H12A—C12—H12B	107.7	C28—C29—C30	119.98 (17)
C12—C13—H13A	109.5	C28—C29—H29A	120.0
C12—C13—H13B	109.5	C30—C29—H29A	120.0
H13A—C13—H13B	109.5	C29—C30—C31	119.88 (18)
C12—C13—H13C	109.5	C29—C30—H30A	120.1
H13A—C13—H13C	109.5	C31—C30—H30A	120.1
H13B—C13—H13C	109.5	C30—C31—C26	120.35 (17)
C7—C14—C15	113.73 (15)	C30—C31—H31A	119.8
C7—C14—H14A	108.8	C26—C31—H31A	119.8

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3i	0.87 (2)	2.09 (2)	2.9334 (18)	163.4 (18)
N2—H2···O3i	0.89 (2)	2.00 (2)	2.8610 (17)	162.8 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3i	0.87 (2)	2.09 (2)	2.9334 (18)	163.4 (18)
N2—H2⋯O3i	0.89 (2)	2.00 (2)	2.8610 (17)	162.8 (17)

Symmetry code: (i) .