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

Kim, H.-J.

doi:10.1107/S1600536810004459

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o566

doi:10.1107/S1600536810004459

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

Hee-Joon Kim ^a ^*

^aDepartment of Applied Chemistry, Kumoh National Institute of Technology, 1 Yangho-dong, Gumi 730-701, Republic of Korea
^*Correspondence e-mail: hjk@kumoh.ac.kr

(Received 21 January 2010; accepted 4 February 2010; online 10 February 2010)

In the title compound, C₃₁H₃₄N₂O₄, the two pyrrole rings are bent around the central methylene C atom, making a dihedral angle of 64.83 (7)°. In the crystal, molecules are linked into dimers via N—H⋯O=C hydrogen bonds. These dimers are packed through π⋯π interactions 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 interactions, characterized by an interplane 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_r = 498.60
Monoclinic, P 2/n
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[F² > 2σ(F²)] = 0.049
wR(F²) = 0.136
S = 1.05
6304 reflections
346 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

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) $[-x+{\script{3\over 2}}, y, -z+{\script{3\over 2}}]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

Dipyrrylmethanes have been widely used as versatile precursors in the synthesis of porphyrins (Shanmugathasan et al., 2000), related polypyrrolic macrocycles (Jasat et al., 1997) and pigments (Chen et al., 2000). For the synthesis of novel porphyrins, the title compound was prepared and its crystal structure determined. Related structure of dipyrrylmethanes derivatives were previously reported (Bonnett et al., 1972; Senge et al., 2005; Vega et al., 2003).

The molecular structure of the title compound is shown in Figure 1. The two pyrrole rings are bent with the dihedral angle of 64.83 (7)° around the attached methylene carbon atom C5. As shown in Figure 2, the molecules are linked by paired N—H···O=C hydrogen bonds into dimers in the crystal lattice. The structural parameters for the intermolecular hydrogen bonds resulting in the formation of dimers are given in Table 1. These dimeric units are packed through π···π interactions between neighboring pyrrole rings as well as neighboring phenyl rings as shown in Figure 3. The interplane and a centroid-to-centroid separations between the parallel pyrrole groups are 3.61 (2) and 4.33 Å, respectively. The parallel phenyl groups in neighboring dimers in the crystal also exhibit efficient π···π interactions: interplane separation of 3.378 (8) Å, and centroid-to-centroid distance of 3.973 Å.

Related literature top

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

Experimental top

The title compound was prepared according to the reported procedure (Twyman et al., 1999). Crystals suitable for X-ray crystallographic work were grown by slow vapor diffusion of n-hexane into a toluene solution.

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound showing 30 % probability displacement ellipsoids. Hydrogen atoms except for the N—H groups are omitted for clarity.
	Fig. 2. Hydrogen bonded dimer in the crystal of the title compound.
	Fig. 3. Packing diagram for the hydrogen bonded dimers of the title compound in the crystal lattice.

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

Crystal data top

C₃₁H₃₄N₂O₄	F(000) = 1064
M_r = 498.60	D_x = 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

Data collection top

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

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)] = 0.049	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(F_o²) + (0.0505P)² + 0.953P] where P = (F_o² + 2F_c²)/3
6304 reflections	(Δ/σ)_max = 0.001
346 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³
0 constraints

Crystal data top

C₃₁H₃₄N₂O₄	V = 2734.6 (3) Å³
M_r = 498.60	Z = 4
Monoclinic, P2/n	Mo Kα radiation
a = 14.2002 (9) Å	µ = 0.08 mm⁻¹
b = 7.9220 (5) Å	T = 162 K
c = 25.0939 (16) Å	0.35 × 0.32 × 0.08 mm
β = 104.373 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	6304 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	4371 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.993	R_int = 0.059
37570 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.29 e Å⁻³
6304 reflections	Δρ_min = −0.26 e Å⁻³
346 parameters

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) −x+3/2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₃₁H₃₄N₂O₄
M_r	498.60
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	162
a, b, c (Å)	14.2002 (9), 7.9220 (5), 25.0939 (16)
β (°)	104.373 (3)
V (Å³)	2734.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.32 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.972, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	37570, 6304, 4371
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.136, 1.05
No. of reflections	6304
No. of parameters	346
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.26

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) −x+3/2, y, −z+3/2.

Acknowledgements

This work was supported by Kumoh National Institute of Technology.

References

Bonnett, R., Hursthouse, M. B. & Neidle, S. (1972). J. Chem. Soc. Perkin Trans. 2, pp. 1335–1340. CSD CrossRef Google Scholar
Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, WI, USA. Google Scholar
Chen, J., Burghart, A., Derecskei-Kovacs, A. & Burgess, K. (2000). J. Org. Chem. 65, 2900–2906. Web of Science CrossRef PubMed CAS Google Scholar
Jasat, A. & Dolphin, D. (1997). Chem. Rev. 97, 2267–2340. CrossRef PubMed CAS Web of Science Google Scholar
Senge, M. O. (2005). Acta Cryst. E61, o506–o508. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shanmugathasan, S., Edwards, C. & Boyle, R. W. (2000). Tetrahedron, 56, 1025–1046. Web of Science CrossRef CAS Google Scholar
Twyman, L. J. & Sanders, J. K. M. (1999). Tetrahedron Lett. 40, 6681–6684. Web of Science CrossRef CAS Google Scholar
Vega, I. E. D., Camiolo, S., Gale, P. A., Hursthouse, M. B. & Light, M. E. (2003). Chem. Commun. pp. 1686–1687. Web of Science CSD CrossRef Google Scholar