N-(3-Oxo-2-phenyl-2,3-dihydro-1H-pyrrolo[1,2-c]imidazol-1-yl)-N′-phenyl-N-(2,4,6-trimethyl­phen­yl)urea ethyl acetate solvate

Imhof, W.

doi:10.1107/S1600536807060928

N-(3-Oxo-2-phenyl-2,3-dihydro-1H-pyrrolo[1,2-c]imidazol-1-yl)-N′-phenyl-N-(2,4,6-trimethylphenyl)urea ethyl acetate solvate

The title compound, C₂₈H₂₆N₄O₂·C₄H₈O₂, was prepared from (2,4,6-trimethylphenyl)(1H-pyrrol-2-ylmethylene)amine and phenyl isocyanate in the presence of catalytic amounts of [Pd(PPh₃)₄]. Recrystallization of the crude product from a pentane–ethyl acetate mixture (10:1) yielded the title compound as the ethyl acetate solvate. The pyrrolo[1,2-c]imidazole core is essentially planar. In addition, a new stereogenic center at the ring C atom of the biheterocyclic group attached to the urea N atom has been formed during the reaction sequence. The crystal structure is influenced by various N—H

O and C—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807060928/hg2325sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807060928/hg2325Isup2.hkl Contains datablock I

CCDC reference: 673089

checkCIF report

Key indicators

Single-crystal X-ray study
T = 203 K
Mean (C-C) = 0.003 Å
R factor = 0.042
wR factor = 0.115
Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT480_ALERT_4_C Long H...A H-Bond Reported H24    ..  O1      ..       2.64 Ang.

Author Response: The corresponding C---H...O interactions are quite long, nevertheless well inside the range discussed by Desiraju and Steiner in their book concerning the weak hydrogen bond (Desiraju & Steiner, 1999).

PLAT480_ALERT_4_C Long H...A H-Bond Reported H18    ..  O3      ..       2.67 Ang.

PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  O4      ..       2.62 Ang.

PLAT480_ALERT_4_C Long H...A H-Bond Reported H27    ..  O4      ..       2.65 Ang.


Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               4780
           From the CIF: _diffrn_reflns_limit_ max hkl   19.   13.   18.
           From the CIF: _diffrn_reflns_limit_ min hkl  -19.  -12.  -18.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   19.   13.   20.
           Calculated minimum hkl  -19.  -13.  -20.
PLAT793_ALERT_1_G Check the Absolute Configuration of C5     .....          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Derivatives of the title compound have only been described once and have been synthesized due to their molluscicidal activity (Mishriky et al., 1998). To the best of our knowledge this report represents the first structural investigation of a 3-Oxo-2-phenyl-2,3-dihydro-1H- pyrrolo[1,2-c]imidazole derivative.

The title compound (Scheme 1) is produced by the reaction of one equivalent of the imine with two equivalents of phenylisocyanate. Corresponding to the observations of Mishriky et al. this reaction most probably proceeds in two steps. First, one isocyanate moiety inserts into the N—H bond of the pyrrole ring forming 2-(2',4',6'-trimethyl-phenyl)iminomethyl-pyrrole-1-carboxylic acid phenylamide. This class of heterocyclic compounds has already been described as intermediates in the synthesis of 1H-pyrrolo[1,2-c]imidazoles (Mishriky et al., 1998) and have in one case also been structurally characterized (Imhof, 2007). The bicyclic ring system of the title compound is then produced via the nucleophilic attack of the amide nitrogen towards the imine carbon atom with the concomitant transfer of the amide hydrogen atom towards the former imine nitrogen. Subsequent insertion of the second isocyanate moiety into the newly formed amide N—H function at the former imine nitrogen atom leads to the formation of the title compound.

The molecular structure of the title compound is shown in Figure 1. As it is expected the 1,2-dihydro-pyrrolo[1,2-c]imidazol-3-one core (C1, C2, C3, C4, C5, C6, N1, N2, O1) is essentially planar. During the reaction a new stereogenic center at C5 is produced. Nevertheless, due to the non-chirality of all substrates and solvents of course the racemate is formed. The observed space group is P2₁/c, therefore exhibiting both enantiomeric forms of the title compound. Figure 1 represents the R-enantiomer. Bond lengths and angles in the heterocyclic compound show expected values (cf. Supplementary Material).

The title compound crystallizes as ethyl acetate solvate. The crystal structure is determined by N—H···O and C—H···O hydrogen bonds between two neighboring molecules of the title compound with O1 acting as the acceptor of a bifurcated hydrogen bond, therefore prducing infinite chains (Figure 2). In addition, weaker C—H···O hydrogen bonds of the title compound towards the solvent molecules with the carbonyl oxygen atom of ethyl acetate also act as the acceptor of a bifurcated hydrogen bond to produce four membered cyclic systems consisting of two molecules of the title compound and two molecules of ethyl acetate (Figure 3). The center of this cyclic arrangement is also a crystallographic center of inversion. The cyclic aggregates are further connected by another C—H···O interaction of the ester oxygen atom towards an aromatic C—H group of a mesityl substituent ending up in the formation of infinte chains of the cyclic arrangements shown in Figure 3. The lengths of these C—H···O hydrogen bonds are in the typical range compared to other structural investigations (Desiraju & Steiner, 1999).

Related literature top

For related literature, see: Mishriky et al. (1998); Imhof (2007); Desiraju & Steiner (1999).

Experimental top

215 mg (1.01 mmol) Mesityl-(1H-pyrrol-2-ylmethylene)-amine and 180 mg (1.515 mmol) phenylisocyanate were refluxed in 20 ml of THF together with 46 mg (0.04 mmol) [Pd(PPh₃)₄] and 3 mg glacial acetic acid for 2 hrs. Evaporation of the solvent yielded an orange oil. Column chromatography on silica yielded 40 mg (12%) of 2-mesityliminomethyl-pyrrole-1-carboxylic acid phenylamidethe using a mixture of pentane and ethyl acetate (8:1) as the eluent. With a ratio of 4:1 the title compound was obtained (108 mg, 24%). Colorless crystals of the title compound were produced from a pentane solution at 253 K.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: XP (Siemens, 1990).

Figures top

	Fig. 1. The molecular structure of the title compoud showing the labelling scheme. Displacement ellipsoids are presented at the 40% probalitiy level.
	Fig. 2. Infinite chains of the title compound along the c axis.
	Fig. 3. Infinite chains of cyclic hydrogen bonded aggregates.

2-(3-Oxo-2-phenyl-2,3-dihydro-1H-pyrrolo[1,2-c]imidazol-1-yl)- N-phenyl-2-(2,4,6-trimethylphenyl)acetamide ethyl acetate solvate top

Crystal data top

C₂₈H₂₆N₄O₂·C₄H₈O₂	F(000) = 1144
M_r = 538.63	D_x = 1.271 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8455 reflections
a = 16.2289 (11) Å	θ = 2.3–25.0°
b = 11.0873 (7) Å	µ = 0.09 mm⁻¹
c = 16.8630 (8) Å	T = 203 K
β = 111.907 (4)°	Quader, light yellow
V = 2815.1 (3) Å³	0.4 × 0.3 × 0.3 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3265 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.0°, θ_min = 2.3°
ω–scan, phi–scan	h = −19→19
8455 measured reflections	k = −12→13
4780 independent reflections	l = −18→18

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 0.83	w = 1/[σ²(F_o²) + (0.0883P)²] where P = (F_o² + 2F_c²)/3
4780 reflections	(Δ/σ)_max = 0.025
366 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₈H₂₆N₄O₂·C₄H₈O₂	V = 2815.1 (3) Å³
M_r = 538.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.2289 (11) Å	µ = 0.09 mm⁻¹
b = 11.0873 (7) Å	T = 203 K
c = 16.8630 (8) Å	0.4 × 0.3 × 0.3 mm
β = 111.907 (4)°

Data collection top

Nonius KappaCCD diffractometer	3265 reflections with I > 2σ(I)
8455 measured reflections	R_int = 0.026
4780 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 0.83	Δρ_max = 0.17 e Å⁻³
4780 reflections	Δρ_min = −0.20 e Å⁻³
366 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.

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

	x	y	z	U_iso*/U_eq
O1	0.26955 (9)	0.30094 (11)	0.32304 (7)	0.0502 (3)
N1	0.14653 (10)	0.29652 (13)	0.19593 (9)	0.0392 (4)
C1	0.07187 (14)	0.25677 (17)	0.20841 (13)	0.0521 (5)
H1	0.0688	0.2283	0.2591	0.078*
O2	0.23868 (8)	0.13806 (10)	0.11232 (7)	0.0432 (3)
N2	0.27078 (10)	0.37447 (12)	0.19455 (8)	0.0355 (3)
C2	0.00374 (14)	0.26760 (18)	0.13176 (14)	0.0553 (5)
H2	−0.0551	0.2471	0.1207	0.083*
N3	0.23943 (9)	0.31621 (12)	0.04532 (8)	0.0324 (3)
C3	0.03661 (12)	0.31543 (17)	0.07091 (12)	0.0461 (5)
H3	0.0040	0.3320	0.0137	0.069*
N4	0.26166 (9)	0.13536 (12)	−0.01321 (8)	0.0356 (3)
H4	0.2563	0.1775	−0.0577	0.053*
C4	0.12517 (12)	0.33192 (15)	0.11321 (10)	0.0368 (4)
C5	0.20816 (11)	0.38032 (15)	0.10422 (10)	0.0335 (4)
H5	0.1985	0.4651	0.0868	0.050*
C6	0.23449 (13)	0.32051 (15)	0.24712 (11)	0.0392 (4)
C7	0.24625 (11)	0.19124 (15)	0.05201 (10)	0.0336 (4)
C8	0.35420 (12)	0.43446 (15)	0.22519 (10)	0.0367 (4)
C9	0.42748 (13)	0.38264 (17)	0.28751 (10)	0.0447 (5)
H9	0.4230	0.3067	0.3090	0.067*
C10	0.50732 (13)	0.4440 (2)	0.31774 (12)	0.0531 (5)
H10	0.5561	0.4095	0.3603	0.080*
C11	0.51548 (14)	0.5558 (2)	0.28541 (13)	0.0571 (5)
H11	0.5695	0.5965	0.3057	0.086*
C12	0.44309 (15)	0.60616 (19)	0.22320 (14)	0.0614 (6)
H12	0.4483	0.6813	0.2010	0.092*
C13	0.36229 (13)	0.54674 (17)	0.19292 (12)	0.0508 (5)
H13	0.3135	0.5822	0.1509	0.076*
C14	0.26130 (11)	0.38359 (14)	−0.01744 (9)	0.0321 (4)
C15	0.34965 (11)	0.38869 (14)	−0.01265 (10)	0.0346 (4)
C16	0.36662 (12)	0.45074 (15)	−0.07668 (10)	0.0378 (4)
H16	0.4246	0.4529	−0.0749	0.057*
C17	0.30080 (12)	0.50961 (15)	−0.14316 (10)	0.0382 (4)
C18	0.21474 (12)	0.50428 (15)	−0.14451 (10)	0.0389 (4)
H18	0.1699	0.5446	−0.1877	0.058*
C19	0.19304 (11)	0.44124 (15)	−0.08405 (10)	0.0345 (4)
C20	0.42454 (12)	0.32755 (17)	0.05762 (11)	0.0440 (4)
H20A	0.4187	0.2417	0.0503	0.066*
H20B	0.4224	0.3491	0.1120	0.066*
H20C	0.4802	0.3529	0.0555	0.066*
C21	0.32114 (14)	0.57668 (18)	−0.21132 (11)	0.0511 (5)
H21A	0.3843	0.5802	−0.1962	0.077*
H21B	0.2977	0.6571	−0.2163	0.077*
H21C	0.2944	0.5355	−0.2649	0.077*
C22	0.09814 (12)	0.43324 (18)	−0.09162 (11)	0.0445 (4)
H22A	0.0898	0.4823	−0.0483	0.067*
H22B	0.0839	0.3509	−0.0844	0.067*
H22C	0.0600	0.4614	−0.1470	0.067*
C23	0.28586 (11)	0.01230 (15)	−0.01252 (10)	0.0356 (4)
C24	0.34908 (12)	−0.01721 (16)	−0.04676 (10)	0.0424 (4)
H24	0.3751	0.0432	−0.0679	0.064*
C25	0.37323 (15)	−0.13587 (18)	−0.04937 (12)	0.0558 (5)
H25	0.4149	−0.1552	−0.0731	0.084*
C26	0.33646 (15)	−0.22613 (18)	−0.01726 (13)	0.0597 (6)
H26	0.3539	−0.3059	−0.0181	0.090*
C27	0.27349 (15)	−0.19684 (17)	0.01613 (12)	0.0537 (5)
H27	0.2477	−0.2576	0.0372	0.081*
C28	0.24790 (13)	−0.07770 (15)	0.01877 (11)	0.0438 (4)
H28	0.2054	−0.0589	0.0415	0.066*
O3	0.08918 (9)	0.79550 (12)	0.18966 (8)	0.0534 (4)
O4	0.14584 (10)	0.66986 (14)	0.11965 (9)	0.0656 (4)
C29	0.15269 (16)	0.6166 (2)	0.25872 (13)	0.0648 (6)
H29A	0.1092	0.5538	0.2481	0.097*
H29B	0.1533	0.6643	0.3064	0.097*
H29C	0.2103	0.5815	0.2714	0.097*
C30	0.13003 (12)	0.69448 (18)	0.18177 (12)	0.0477 (5)
C31	0.06762 (15)	0.88484 (19)	0.12199 (13)	0.0580 (5)
H31A	0.0655	0.8472	0.0693	0.087*
H31B	0.1128	0.9472	0.1372	0.087*
C32	−0.01968 (17)	0.9382 (2)	0.10986 (19)	0.0841 (8)
H32A	−0.0651	0.8781	0.0877	0.126*
H32B	−0.0315	1.0042	0.0703	0.126*
H32C	−0.0192	0.9671	0.1637	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0721 (10)	0.0464 (8)	0.0334 (7)	−0.0057 (7)	0.0210 (6)	0.0013 (5)
N1	0.0473 (10)	0.0367 (8)	0.0400 (8)	−0.0032 (7)	0.0236 (7)	−0.0015 (6)
C1	0.0641 (14)	0.0455 (11)	0.0614 (13)	−0.0056 (10)	0.0403 (12)	−0.0001 (9)
O2	0.0604 (9)	0.0351 (7)	0.0410 (6)	0.0059 (6)	0.0270 (6)	0.0056 (5)
N2	0.0429 (9)	0.0327 (8)	0.0302 (7)	−0.0008 (7)	0.0131 (6)	−0.0002 (6)
C2	0.0476 (13)	0.0550 (13)	0.0712 (14)	−0.0049 (10)	0.0313 (11)	0.0003 (10)
N3	0.0393 (8)	0.0284 (8)	0.0324 (7)	0.0038 (6)	0.0168 (6)	0.0010 (5)
C3	0.0416 (12)	0.0457 (11)	0.0528 (11)	0.0004 (9)	0.0198 (9)	−0.0018 (8)
N4	0.0451 (9)	0.0308 (8)	0.0343 (7)	0.0044 (6)	0.0187 (6)	0.0030 (6)
C4	0.0437 (11)	0.0316 (9)	0.0398 (9)	0.0018 (8)	0.0209 (8)	−0.0022 (7)
C5	0.0371 (10)	0.0311 (9)	0.0328 (8)	0.0028 (7)	0.0138 (7)	−0.0003 (6)
C6	0.0541 (12)	0.0301 (10)	0.0371 (10)	0.0000 (8)	0.0212 (9)	−0.0022 (7)
C7	0.0341 (10)	0.0337 (10)	0.0330 (9)	0.0028 (7)	0.0124 (7)	0.0009 (7)
C8	0.0430 (11)	0.0335 (10)	0.0348 (8)	0.0009 (8)	0.0156 (8)	−0.0046 (7)
C9	0.0499 (12)	0.0443 (11)	0.0388 (9)	0.0088 (9)	0.0153 (9)	−0.0005 (8)
C10	0.0422 (12)	0.0663 (14)	0.0436 (10)	0.0079 (11)	0.0076 (9)	−0.0084 (9)
C11	0.0431 (13)	0.0571 (14)	0.0667 (13)	−0.0074 (10)	0.0153 (10)	−0.0182 (11)
C12	0.0512 (14)	0.0457 (12)	0.0831 (15)	−0.0077 (10)	0.0201 (12)	0.0027 (11)
C13	0.0446 (12)	0.0411 (11)	0.0599 (12)	−0.0011 (9)	0.0119 (9)	0.0071 (9)
C14	0.0389 (10)	0.0266 (9)	0.0333 (8)	0.0009 (7)	0.0162 (7)	−0.0013 (7)
C15	0.0389 (10)	0.0305 (9)	0.0339 (8)	0.0004 (8)	0.0131 (7)	−0.0025 (7)
C16	0.0389 (10)	0.0358 (10)	0.0427 (9)	−0.0036 (8)	0.0197 (8)	−0.0055 (7)
C17	0.0464 (11)	0.0336 (10)	0.0364 (9)	−0.0026 (8)	0.0174 (8)	−0.0016 (7)
C18	0.0461 (11)	0.0347 (10)	0.0336 (9)	0.0035 (8)	0.0123 (8)	0.0030 (7)
C19	0.0392 (10)	0.0297 (9)	0.0341 (9)	0.0018 (8)	0.0132 (8)	−0.0015 (7)
C20	0.0385 (11)	0.0454 (11)	0.0473 (10)	0.0040 (9)	0.0151 (8)	0.0043 (8)
C21	0.0590 (13)	0.0518 (12)	0.0468 (10)	−0.0017 (10)	0.0247 (9)	0.0076 (9)
C22	0.0408 (11)	0.0492 (11)	0.0418 (9)	0.0063 (9)	0.0136 (8)	0.0072 (8)
C23	0.0385 (10)	0.0322 (10)	0.0331 (8)	0.0029 (8)	0.0100 (7)	−0.0023 (7)
C24	0.0442 (11)	0.0433 (11)	0.0400 (9)	0.0074 (9)	0.0160 (8)	−0.0004 (8)
C25	0.0647 (14)	0.0527 (13)	0.0493 (11)	0.0187 (11)	0.0203 (10)	−0.0055 (9)
C26	0.0779 (16)	0.0367 (12)	0.0545 (12)	0.0147 (11)	0.0131 (11)	−0.0064 (9)
C27	0.0682 (14)	0.0328 (11)	0.0529 (11)	−0.0049 (10)	0.0142 (10)	−0.0003 (9)
C28	0.0479 (12)	0.0360 (10)	0.0472 (10)	−0.0012 (9)	0.0174 (9)	−0.0005 (8)
O3	0.0595 (9)	0.0494 (8)	0.0511 (8)	0.0117 (7)	0.0205 (7)	−0.0004 (6)
O4	0.0703 (11)	0.0714 (10)	0.0585 (9)	0.0184 (8)	0.0280 (8)	−0.0045 (7)
C29	0.0708 (16)	0.0627 (14)	0.0616 (13)	0.0168 (12)	0.0254 (11)	0.0055 (10)
C30	0.0391 (11)	0.0529 (12)	0.0479 (11)	0.0006 (10)	0.0125 (9)	−0.0074 (9)
C31	0.0669 (15)	0.0512 (13)	0.0535 (11)	0.0068 (10)	0.0197 (10)	0.0030 (9)
C32	0.0685 (17)	0.0624 (16)	0.118 (2)	0.0154 (13)	0.0304 (15)	0.0237 (15)

Geometric parameters (Å, º) top

O1—C6	1.2109 (19)	C17—C18	1.390 (2)
N1—C4	1.364 (2)	C17—C21	1.505 (2)
N1—C1	1.377 (2)	C18—C19	1.386 (2)
N1—C6	1.391 (2)	C18—H18	0.9300
C1—C2	1.357 (3)	C19—C22	1.500 (2)
C1—H1	0.9300	C20—H20A	0.9600
O2—C7	1.2207 (19)	C20—H20B	0.9600
N2—C6	1.371 (2)	C20—H20C	0.9600
N2—C8	1.421 (2)	C21—H21A	0.9600
N2—C5	1.484 (2)	C21—H21B	0.9600
C2—C3	1.424 (3)	C21—H21C	0.9600
C2—H2	0.9300	C22—H22A	0.9600
N3—C7	1.391 (2)	C22—H22B	0.9600
N3—C14	1.4436 (19)	C22—H22C	0.9600
N3—C5	1.4579 (19)	C23—C28	1.377 (2)
C3—C4	1.357 (3)	C23—C24	1.391 (2)
C3—H3	0.9300	C24—C25	1.378 (3)
N4—C7	1.364 (2)	C24—H24	0.9300
N4—C23	1.419 (2)	C25—C26	1.375 (3)
N4—H4	0.8600	C25—H25	0.9300
C4—C5	1.509 (2)	C26—C27	1.377 (3)
C5—H5	0.9800	C26—H26	0.9300
C8—C9	1.384 (2)	C27—C28	1.390 (3)
C8—C13	1.384 (3)	C27—H27	0.9300
C9—C10	1.381 (3)	C28—H28	0.9300
C9—H9	0.9300	O3—C30	1.333 (2)
C10—C11	1.381 (3)	O3—C31	1.452 (2)
C10—H10	0.9300	O4—C30	1.199 (2)
C11—C12	1.368 (3)	C29—C30	1.486 (3)
C11—H11	0.9300	C29—H29A	0.9600
C12—C13	1.384 (3)	C29—H29B	0.9600
C12—H12	0.9300	C29—H29C	0.9600
C13—H13	0.9300	C31—C32	1.478 (3)
C14—C19	1.403 (2)	C31—H31A	0.9700
C14—C15	1.407 (2)	C31—H31B	0.9700
C15—C16	1.392 (2)	C32—H32A	0.9600
C15—C20	1.505 (2)	C32—H32B	0.9600
C16—C17	1.389 (2)	C32—H32C	0.9600
C16—H16	0.9300

C4—N1—C1	110.25 (15)	C18—C17—C21	120.92 (16)
C4—N1—C6	112.97 (14)	C19—C18—C17	122.64 (16)
C1—N1—C6	136.39 (15)	C19—C18—H18	118.7
C2—C1—N1	106.06 (16)	C17—C18—H18	118.7
C2—C1—H1	127.0	C18—C19—C14	118.51 (16)
N1—C1—H1	127.0	C18—C19—C22	120.14 (15)
C6—N2—C8	123.34 (13)	C14—C19—C22	121.34 (15)
C6—N2—C5	112.82 (14)	C15—C20—H20A	109.5
C8—N2—C5	123.18 (12)	C15—C20—H20B	109.5
C1—C2—C3	109.16 (18)	H20A—C20—H20B	109.5
C1—C2—H2	125.4	C15—C20—H20C	109.5
C3—C2—H2	125.4	H20A—C20—H20C	109.5
C7—N3—C14	122.75 (12)	H20B—C20—H20C	109.5
C7—N3—C5	117.88 (12)	C17—C21—H21A	109.5
C14—N3—C5	119.36 (12)	C17—C21—H21B	109.5
C4—C3—C2	106.22 (17)	H21A—C21—H21B	109.5
C4—C3—H3	126.9	C17—C21—H21C	109.5
C2—C3—H3	126.9	H21A—C21—H21C	109.5
C7—N4—C23	124.30 (13)	H21B—C21—H21C	109.5
C7—N4—H4	117.9	C19—C22—H22A	109.5
C23—N4—H4	117.9	C19—C22—H22B	109.5
C3—C4—N1	108.30 (15)	H22A—C22—H22B	109.5
C3—C4—C5	143.58 (16)	C19—C22—H22C	109.5
N1—C4—C5	108.02 (14)	H22A—C22—H22C	109.5
N3—C5—N2	113.50 (13)	H22B—C22—H22C	109.5
N3—C5—C4	116.47 (13)	C28—C23—C24	119.55 (16)
N2—C5—C4	100.16 (12)	C28—C23—N4	122.56 (15)
N3—C5—H5	108.8	C24—C23—N4	117.88 (15)
N2—C5—H5	108.8	C25—C24—C23	120.02 (18)
C4—C5—H5	108.8	C25—C24—H24	120.0
O1—C6—N2	128.03 (18)	C23—C24—H24	120.0
O1—C6—N1	126.19 (16)	C26—C25—C24	120.78 (19)
N2—C6—N1	105.73 (14)	C26—C25—H25	119.6
O2—C7—N4	123.91 (15)	C24—C25—H25	119.6
O2—C7—N3	121.27 (13)	C25—C26—C27	119.12 (18)
N4—C7—N3	114.82 (13)	C25—C26—H26	120.4
C9—C8—C13	119.40 (17)	C27—C26—H26	120.4
C9—C8—N2	120.92 (16)	C26—C27—C28	120.88 (19)
C13—C8—N2	119.68 (15)	C26—C27—H27	119.6
C8—C9—C10	119.86 (18)	C28—C27—H27	119.6
C8—C9—H9	120.1	C23—C28—C27	119.64 (17)
C10—C9—H9	120.1	C23—C28—H28	120.2
C11—C10—C9	120.75 (19)	C27—C28—H28	120.2
C11—C10—H10	119.6	C30—O3—C31	118.53 (14)
C9—C10—H10	119.6	C30—C29—H29A	109.5
C12—C11—C10	119.18 (19)	C30—C29—H29B	109.5
C12—C11—H11	120.4	H29A—C29—H29B	109.5
C10—C11—H11	120.4	C30—C29—H29C	109.5
C11—C12—C13	120.9 (2)	H29A—C29—H29C	109.5
C11—C12—H12	119.6	H29B—C29—H29C	109.5
C13—C12—H12	119.6	O4—C30—O3	123.69 (18)
C12—C13—C8	119.93 (18)	O4—C30—C29	124.52 (19)
C12—C13—H13	120.0	O3—C30—C29	111.79 (16)
C8—C13—H13	120.0	O3—C31—C32	108.63 (18)
C19—C14—C15	120.72 (14)	O3—C31—H31A	110.0
C19—C14—N3	119.08 (14)	C32—C31—H31A	110.0
C15—C14—N3	120.18 (14)	O3—C31—H31B	110.0
C16—C15—C14	117.89 (15)	C32—C31—H31B	110.0
C16—C15—C20	119.87 (16)	H31A—C31—H31B	108.3
C14—C15—C20	122.22 (14)	C31—C32—H32A	109.5
C17—C16—C15	122.90 (16)	C31—C32—H32B	109.5
C17—C16—H16	118.6	H32A—C32—H32B	109.5
C15—C16—H16	118.6	C31—C32—H32C	109.5
C16—C17—C18	117.31 (15)	H32A—C32—H32C	109.5
C16—C17—C21	121.77 (17)	H32B—C32—H32C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O1ⁱ	0.86	2.11	2.899 (2)	151
C24—H24···O1ⁱ	0.93	2.64	3.181 (2)	118
C18—H18···O3ⁱⁱ	0.93	2.67	3.556 (2)	160
C3—H3···O4ⁱⁱⁱ	0.93	2.62	3.467 (2)	151
C27—H27···O4^iv	0.93	2.65	3.496 (2)	151

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z; (iv) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₂₈H₂₆N₄O₂·C₄H₈O₂
M_r	538.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	203
a, b, c (Å)	16.2289 (11), 11.0873 (7), 16.8630 (8)
β (°)	111.907 (4)
V (Å³)	2815.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.4 × 0.3 × 0.3

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8455, 4780, 3265
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.115, 0.83
No. of reflections	4780
No. of parameters	366
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.20

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1990).