Methyl 3-(4-bromo­phen­yl)-2-(1H-indol-3-ylmeth­yl)-5-[1-(4-methoxy­phen­yl)-4-oxo-2-phenyl­azetidin-2-yl]-4-nitro­pyrrolidine-2-carboxyl­ate

Nirmala, S.; Kamala, E.T.S.; Sudha, L.; Arumugam, N.; Raghunathan, R.

doi:10.1107/S1600536808014190

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages o1095-o1096

doi:10.1107/S1600536808014190

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Methyl 3-(4-bromophenyl)-2-(1H-indol-3-ylmethyl)-5-[1-(4-methoxyphenyl)-4-oxo-2-phenylazetidin-2-yl]-4-nitropyrrolidine-2-carboxylate

S. Nirmala,^a E. Theboral Sugi Kamala,^a L. Sudha,^b ^* N. Arumugam ^c and R. Raghunathan ^c

^aDepartment of Physics, Easwari Engineering College, Ramapuram, Chennai 600 089, India, ^bDepartment of Physics, SRM University, Ramapuram Campus, Chennai 600 089, India, and ^cDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: sudharose18@gmail.com

(Received 10 April 2008; accepted 12 May 2008; online 17 May 2008)

In the title compound, C₃₇H₃₃BrN₄O₆, the pyrrolidine ring adopts an envelope conformation. The β-lactam ring is planar and makes dihedral angles of 70.16 (13) and 28.32 (13)° with the phenyl and 4-methoxyphenyl rings, respectively. The molecular packing is stabilized by intramolecular C—H⋯O interactions and the crystal packing is determined by intermolecular N—H⋯O hydrogen bonds, and C—H⋯O and C—H⋯π interactions.

Related literature

For related literature, see: Kamala et al. (2008 ); Lukacs & Ohno (1990 ); Sundari Bhaskaran et al. (2006 ); Suzuki et al. (1994 ); Yang et al. (1987 ); Amal Raj et al. (2003 ); Cremer & Pople (1975 ); Nardelli (1995 ); Ülkü et al. (1997 ).

Experimental

Crystal data

C₃₇H₃₃BrN₄O₆
M_r = 709.58
Monoclinic, C c
a = 11.3988 (4) Å
b = 34.8587 (13) Å
c = 8.7039 (3) Å
β = 100.982 (2)°
V = 3395.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 293 (2) K
0.30 × 0.22 × 0.22 mm

Data collection

Bruker Kappa APEX2 diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.703, T_max = 0.769
37282 measured reflections
8532 independent reflections
6397 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.120
S = 1.04
8532 reflections
433 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 4142 Friedel pairs
Flack parameter: 0.008 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O4	0.98	2.27	2.717 (3)	107
C4—H4⋯O4ⁱ	0.93	2.57	3.186 (3)	124
C31—H31⋯O4ⁱⁱ	0.93	2.55	3.399 (3)	152
N1—H1A⋯O5ⁱⁱⁱ	0.86	2.02	2.820 (3)	155
C18—H18⋯Cg^iv	0.93	2.80	3.641 (4)	151
Symmetry codes: (i) x, y, z-1; (ii) $[x, -y+2, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x, y, z+1. Cg is the centroid of the indole benzene ring.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014190/rk2086sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014190/rk2086Isup2.hkl

checkCIF report

Comment top

β–Lactams with a substituent at the N atom, which is easily removable under mild conditions have found wide applicability in the synthesis of bicyclic β–lactam antibiotics (Lukacs & Ohno, 1990). Substituted pyrrolidines have gained much importance because they are the structural elements of many alkaloids. It has been found that they exhibit antifungal activity against various pathogens (Amal Raj et al., 2003). Optically active pyrrolidine derivatives have been used as intermediates in controlled asymmetric synthesis (Suzuki et al., 1994). Since the title compound, (I), also contains an indole unit it may also exhibit some biological activity. In view of these, the structure of title compound is determined to establish the conformation of the molecule (Fig. 1).

The bond lengths and angles in I are agree with those observed in a similar structure (Sundari Bhaskaran et al., 2006; Kamala et al., 2008). The β–lactam ring is planar with its internal angles in the range 84.4 (2) to 95.5 (2)°. The C–C–C bond angle in the β–lactam ring is comparable to the values in related reported structures (Ulku et al., 1997). The bond N4?C16, is shorter than the bond lengths, N4—C14 and N4—C17 and is close to the length of a double bond, a feature observed in β–propiolactam (Yang et al., 1987) and where C and N are sp² hybridized.

The methoxy group is coplanar with the C17/C18/C19/C20/C21/C22 benzene ring: dihedral angle C21–C20–O6–C23 = 161.0 (4)°. The methoxyphenyl and the phenyl rings bridged by the β–lactam ring are oriented at an angle of 42.32 (11)° with respect to each other, whereas the β–lactam ring makes a dihedral angles of 28.32 (13)° and 70.16 (13)° with them respectively. The indole moiety is planar and makes a dihedral angle of 38.01 (11)°, 62.8 (7)° and 73.8 (9)° with the β–lactam, bromophenyl and phenyl rings respectively. The nitro–group is orthogonal to indole moiety [89.2 (2)°] and makes a dihedral angle of 66.6 (3)° with the β–lactam ring.

The pyrrolidine ring N2/C10/C11/C12/C13 adopts an envelope conformation, with asymmetry parameters (Nardelli, 1995), ΔC_S(C13) = 0.038 (2) and puckering parameters (Cremer & Pople, 1975) q₂ = 0.377 (2)Å and ϕ = 150.8 (3)°. Atom C13 deviates from the mean plane defined by N2/C10/C11/C12 on 0.573 (8) Å.

In the crystal structure of I (Fig.2), adjacent molecules are linked by N—H···O and C—H···O hydrogen bonds into chains. In addition, the packing is stabilized by C—H···Cg interactions involving C3/C4/C5/C6/C7/C8 rings with centroid Cg.

Related literature top

For related literature, see: Kamala et al. (2008); Lukacs & Ohno (1990); Sundari Bhaskaran et al. (2006); Suzuki et al. (1994); Yang et al. (1987).

For related literature, see: Amal Raj, Raghunathan, Sridevi Kumari & Raman (2003); Cremer & Pople (1975); Nardelli (1995); Ülkü et al. (1997).

Experimental top

The β–lactam aldehyde (1 mol) was treated with tryptophanmethylester hydrochloride (1 mol) in the presence of Et₃N (2.5 mol) and anhydrous MgSO₄ (2 g) in dry dichloromethane (10 ml) at room temperature for 12 h to give the imine. The imine was washed with water and dried over Na₂SO₄. The solvent was evaporated under vacuum. The imine (1 mol) was then strirred with silver(I) acetate and p–bromo nitrostyrene (1 mol) in the presence of Et₃N (1.2 mol) and molecular sieves in dry toluene (30 ml) at room temperature for 12 h. The reaction mixture was filtered through a plug celite. The solvent was evaporated under reduced pressure and the residue was subjected to column chromatography on silica gel (100–200 mesh), with hexane–ethyl acetate (7:3) as eluent to give the product. The compound was recrystallized from ethyl acetate.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of I. The displacement ellipsoids are drawn at 30% probability level. H atoms are presented as a small spheres of arbitrary radius. The intramolecular H–bond are drawn by dashed line.
	Fig. 2. The packing of the molecules viewed down the a axis. Dashed lines indicate hydrogen bonds. H atoms not involed in hydrogen bonds have been ommited for clarity. Symmetry codes: (i) x, y, z - 1; (ii) x, -y + 2, z - 1/2; (iii) x + 1/2, -y + 3/2, z - 1/2; (iv) x, y, z + 1.

Methyl 3-(4-bromophenyl)-2-(1H-indol-3-ylmethyl)-5-[1-(4-methoxyphenyl)- 4-oxo-2-phenylazetidin-2-yl]-4-nitropyrrolidine-2-carboxylate top

Crystal data top

C₃₇H₃₃BrN₄O₆	F(000) = 1464
M_r = 709.58	D_x = 1.388 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 13968 reflections
a = 11.3988 (4) Å	θ = 2.3–23.4°
b = 34.8587 (13) Å	µ = 1.26 mm⁻¹
c = 8.7039 (3) Å	T = 293 K
β = 100.982 (2)°	Prism, colourless
V = 3395.1 (2) Å³	0.30 × 0.22 × 0.22 mm
Z = 4

Data collection top

Bruker Kappa APEX2 diffractometer	8532 independent reflections
Radiation source: fine–focus sealed tube	6397 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and ϕ scans	θ_max = 28.7°, θ_min = 1.2°
Absorption correction: multi-scan (Blessing, 1995)	h = −15→15
T_min = 0.703, T_max = 0.769	k = −46→46
37282 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²) + (0.0682P)² + 0.1826P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
8532 reflections	Δρ_max = 0.43 e Å⁻³
433 parameters	Δρ_min = −0.37 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 4142 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.008 (6)

Crystal data top

C₃₇H₃₃BrN₄O₆	V = 3395.1 (2) Å³
M_r = 709.58	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 11.3988 (4) Å	µ = 1.26 mm⁻¹
b = 34.8587 (13) Å	T = 293 K
c = 8.7039 (3) Å	0.30 × 0.22 × 0.22 mm
β = 100.982 (2)°

Data collection top

Bruker Kappa APEX2 diffractometer	8532 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	6397 reflections with I > 2σ(I)
T_min = 0.703, T_max = 0.769	R_int = 0.028
37282 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.120	Δρ_max = 0.43 e Å⁻³
S = 1.04	Δρ_min = −0.37 e Å⁻³
8532 reflections	Absolute structure: Flack (1983), 4142 Friedel pairs
433 parameters	Absolute structure parameter: 0.008 (6)
2 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
C1	1.0310 (3)	0.82854 (8)	0.0512 (3)	0.0541 (6)
H1	0.9961	0.8156	0.1244	0.065*
C2	0.9937 (2)	0.86265 (6)	−0.0140 (3)	0.0406 (5)
C3	1.07094 (19)	0.87204 (7)	−0.1184 (3)	0.0388 (5)
C4	1.0793 (2)	0.90284 (8)	−0.2186 (3)	0.0490 (6)
H4	1.0255	0.9231	−0.2262	0.059*
C5	1.1678 (3)	0.90276 (10)	−0.3055 (4)	0.0609 (7)
H5	1.1734	0.9231	−0.3728	0.073*
C6	1.2498 (3)	0.87257 (11)	−0.2947 (4)	0.0628 (8)
H6	1.3096	0.8734	−0.3539	0.075*
C7	1.2437 (2)	0.84207 (9)	−0.1991 (4)	0.0594 (7)
H7	1.2978	0.8219	−0.1932	0.071*
C8	1.1543 (2)	0.84186 (7)	−0.1104 (3)	0.0446 (5)
C9	0.8907 (2)	0.88613 (7)	0.0180 (3)	0.0405 (5)
H9A	0.8213	0.8697	0.0119	0.049*
H9B	0.8715	0.9057	−0.0622	0.049*
C10	0.91742 (18)	0.90557 (6)	0.1798 (2)	0.0352 (5)
C11	0.81174 (18)	0.93273 (6)	0.2125 (3)	0.0349 (4)
H11	0.8474	0.9573	0.2510	0.042*
C12	0.7686 (2)	0.91299 (6)	0.3488 (3)	0.0386 (5)
H12	0.6811	0.9128	0.3319	0.046*
C13	0.8177 (2)	0.87176 (6)	0.3464 (3)	0.0385 (5)
H13	0.7664	0.8584	0.2596	0.046*
C14	0.8218 (2)	0.84705 (7)	0.4896 (3)	0.0435 (5)
H14	0.8738	0.8578	0.5822	0.052*
C15	0.6981 (3)	0.83327 (8)	0.5252 (3)	0.0538 (6)
H15	0.6945	0.8369	0.6359	0.065*
C16	0.7435 (3)	0.79315 (9)	0.4961 (4)	0.0637 (8)
C17	0.9507 (3)	0.78706 (8)	0.4405 (3)	0.0561 (7)
C18	1.0634 (3)	0.80218 (9)	0.4846 (4)	0.0689 (9)
H18	1.0722	0.8259	0.5342	0.083*
C19	1.1637 (4)	0.78329 (10)	0.4579 (5)	0.0771 (10)
H19	1.2383	0.7949	0.4852	0.093*
C20	1.1543 (4)	0.74769 (10)	0.3916 (5)	0.0737 (9)
C21	1.0396 (5)	0.73262 (11)	0.3432 (6)	0.0990 (15)
H21	1.0312	0.7087	0.2950	0.119*
C22	0.9395 (4)	0.75174 (10)	0.3643 (6)	0.0893 (13)
H22	0.8642	0.7413	0.3281	0.107*
C23	1.3582 (4)	0.74477 (16)	0.3661 (7)	0.1051 (14)
H23A	1.4164	0.7267	0.3445	0.158*
H23B	1.3853	0.7559	0.4674	0.158*
H23C	1.3475	0.7646	0.2881	0.158*
C24	0.5431 (3)	0.82771 (10)	0.2772 (4)	0.0665 (8)
H24	0.5881	0.8082	0.2445	0.080*
C25	0.4380 (3)	0.83898 (13)	0.1818 (4)	0.0798 (10)
H25	0.4118	0.8263	0.0876	0.096*
C26	0.3718 (3)	0.86851 (12)	0.2234 (5)	0.0801 (10)
H26	0.3024	0.8766	0.1571	0.096*
C27	0.4099 (3)	0.88592 (13)	0.3652 (5)	0.0802 (10)
H27	0.3645	0.9057	0.3958	0.096*
C28	0.5143 (3)	0.87489 (11)	0.4641 (4)	0.0685 (8)
H28	0.5386	0.8874	0.5591	0.082*
C29	0.5832 (3)	0.84510 (8)	0.4218 (3)	0.0544 (6)
C30	0.71391 (19)	0.94108 (6)	0.0732 (3)	0.0363 (4)
C31	0.7291 (2)	0.97173 (7)	−0.0228 (3)	0.0465 (6)
H31	0.7989	0.9862	−0.0002	0.056*
C32	0.6435 (2)	0.98119 (8)	−0.1500 (4)	0.0544 (7)
H32	0.6561	1.0016	−0.2139	0.065*
C33	0.5397 (2)	0.96064 (8)	−0.1828 (3)	0.0508 (6)
C34	0.5213 (2)	0.93019 (9)	−0.0920 (4)	0.0586 (7)
H34	0.4507	0.9161	−0.1153	0.070*
C35	0.6090 (2)	0.92037 (8)	0.0358 (3)	0.0498 (6)
H35	0.5969	0.8995	0.0973	0.060*
C36	1.0328 (2)	0.92886 (7)	0.1965 (3)	0.0419 (5)
C37	1.1292 (3)	0.97884 (10)	0.0855 (6)	0.0814 (11)
H37A	1.1137	0.9966	−0.0002	0.122*
H37B	1.1957	0.9628	0.0749	0.122*
H37C	1.1476	0.9927	0.1823	0.122*
N1	1.1279 (2)	0.81582 (6)	−0.0061 (3)	0.0549 (5)
H1A	1.1659	0.7948	0.0197	0.066*
N2	0.93345 (17)	0.87641 (5)	0.3021 (2)	0.0397 (4)
H2	0.9983	0.8644	0.3403	0.048*
N3	0.8208 (2)	0.93141 (6)	0.5030 (3)	0.0462 (5)
N4	0.8479 (2)	0.80657 (6)	0.4657 (3)	0.0533 (5)
O1	1.11802 (17)	0.92443 (7)	0.2958 (3)	0.0690 (6)
O2	1.02387 (15)	0.95506 (5)	0.0846 (2)	0.0551 (4)
O3	0.7714 (2)	0.92499 (8)	0.6116 (3)	0.0771 (7)
O4	0.91172 (19)	0.95038 (6)	0.5130 (2)	0.0617 (5)
O5	0.7038 (3)	0.76121 (7)	0.4957 (4)	0.0892 (8)
O6	1.2477 (3)	0.72571 (8)	0.3636 (4)	0.0996 (10)
Br1	0.42238 (4)	0.974927 (13)	−0.35828 (4)	0.08931 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0691 (16)	0.0355 (13)	0.0601 (16)	0.0073 (11)	0.0179 (13)	0.0020 (11)
C2	0.0465 (11)	0.0341 (12)	0.0418 (12)	0.0011 (9)	0.0097 (9)	−0.0032 (10)
C3	0.0393 (10)	0.0357 (12)	0.0389 (12)	0.0034 (9)	0.0016 (9)	−0.0057 (9)
C4	0.0522 (12)	0.0504 (15)	0.0435 (14)	0.0073 (11)	0.0067 (11)	0.0041 (11)
C5	0.0677 (17)	0.0685 (18)	0.0483 (15)	−0.0068 (14)	0.0159 (13)	0.0043 (14)
C6	0.0496 (14)	0.089 (2)	0.0536 (16)	−0.0031 (14)	0.0189 (12)	−0.0149 (16)
C7	0.0468 (13)	0.0708 (19)	0.0589 (17)	0.0136 (12)	0.0055 (12)	−0.0192 (15)
C8	0.0451 (12)	0.0426 (13)	0.0427 (13)	0.0089 (9)	0.0000 (10)	−0.0086 (11)
C9	0.0417 (11)	0.0359 (12)	0.0437 (12)	0.0013 (9)	0.0078 (9)	0.0000 (9)
C10	0.0327 (8)	0.0302 (10)	0.0436 (13)	0.0009 (8)	0.0094 (9)	0.0040 (9)
C11	0.0365 (10)	0.0263 (10)	0.0431 (12)	−0.0011 (8)	0.0103 (8)	0.0000 (9)
C12	0.0389 (10)	0.0354 (11)	0.0419 (12)	−0.0018 (8)	0.0085 (9)	0.0004 (9)
C13	0.0467 (11)	0.0272 (10)	0.0407 (11)	−0.0055 (9)	0.0060 (9)	−0.0010 (9)
C14	0.0566 (13)	0.0337 (12)	0.0378 (11)	−0.0081 (10)	0.0027 (10)	0.0031 (9)
C15	0.0735 (17)	0.0474 (15)	0.0435 (14)	−0.0171 (12)	0.0186 (12)	0.0037 (11)
C16	0.090 (2)	0.0456 (16)	0.0543 (16)	−0.0199 (14)	0.0108 (15)	0.0120 (13)
C17	0.0870 (19)	0.0333 (13)	0.0462 (14)	−0.0035 (12)	0.0080 (13)	0.0045 (11)
C18	0.0743 (19)	0.0456 (16)	0.073 (2)	0.0130 (14)	−0.0217 (15)	−0.0056 (14)
C19	0.079 (2)	0.0572 (19)	0.082 (2)	0.0090 (16)	−0.0163 (17)	0.0014 (17)
C20	0.104 (3)	0.0501 (17)	0.0684 (19)	0.0108 (17)	0.0196 (18)	0.0024 (15)
C21	0.138 (4)	0.0461 (18)	0.128 (4)	−0.017 (2)	0.064 (3)	−0.032 (2)
C22	0.107 (3)	0.0497 (18)	0.122 (3)	−0.0272 (19)	0.050 (3)	−0.026 (2)
C23	0.089 (3)	0.113 (4)	0.105 (3)	0.030 (3)	−0.003 (2)	0.004 (3)
C24	0.0708 (18)	0.0644 (19)	0.0642 (19)	−0.0175 (15)	0.0123 (15)	−0.0084 (15)
C25	0.071 (2)	0.097 (3)	0.065 (2)	−0.0285 (19)	−0.0031 (17)	−0.0118 (18)
C26	0.0577 (17)	0.100 (3)	0.081 (2)	−0.0084 (18)	0.0086 (16)	0.001 (2)
C27	0.0580 (18)	0.105 (3)	0.081 (2)	−0.0011 (17)	0.0217 (17)	−0.003 (2)
C28	0.0642 (18)	0.089 (2)	0.0569 (17)	−0.0115 (16)	0.0242 (14)	−0.0088 (16)
C29	0.0562 (14)	0.0562 (16)	0.0527 (15)	−0.0229 (12)	0.0150 (12)	0.0019 (12)
C30	0.0364 (10)	0.0284 (10)	0.0459 (12)	0.0033 (8)	0.0127 (9)	0.0020 (9)
C31	0.0422 (11)	0.0388 (13)	0.0579 (15)	−0.0039 (9)	0.0082 (11)	0.0151 (11)
C32	0.0532 (14)	0.0470 (15)	0.0642 (17)	0.0012 (11)	0.0142 (13)	0.0201 (13)
C33	0.0498 (13)	0.0488 (14)	0.0513 (14)	0.0102 (11)	0.0038 (11)	0.0088 (12)
C34	0.0437 (12)	0.0555 (17)	0.0703 (18)	−0.0125 (11)	−0.0051 (12)	0.0120 (14)
C35	0.0457 (12)	0.0443 (14)	0.0563 (15)	−0.0075 (10)	0.0017 (11)	0.0168 (12)
C36	0.0369 (10)	0.0364 (12)	0.0532 (13)	0.0003 (8)	0.0110 (10)	−0.0011 (10)
C37	0.068 (2)	0.071 (2)	0.109 (3)	−0.0308 (16)	0.026 (2)	0.015 (2)
N1	0.0716 (14)	0.0342 (11)	0.0589 (14)	0.0197 (10)	0.0124 (11)	0.0003 (10)
N2	0.0430 (9)	0.0298 (10)	0.0463 (11)	0.0066 (7)	0.0086 (8)	0.0070 (8)
N3	0.0578 (12)	0.0345 (11)	0.0452 (11)	0.0106 (9)	0.0070 (9)	−0.0021 (9)
N4	0.0763 (15)	0.0329 (11)	0.0496 (12)	−0.0102 (10)	0.0087 (10)	0.0055 (9)
O1	0.0425 (9)	0.0822 (15)	0.0772 (14)	−0.0107 (9)	−0.0016 (9)	0.0147 (12)
O2	0.0468 (9)	0.0451 (10)	0.0736 (13)	−0.0128 (7)	0.0120 (8)	0.0133 (9)
O3	0.0954 (17)	0.0919 (17)	0.0507 (12)	−0.0014 (13)	0.0306 (12)	−0.0115 (11)
O4	0.0706 (12)	0.0474 (11)	0.0580 (11)	−0.0057 (9)	−0.0105 (9)	−0.0032 (9)
O5	0.115 (2)	0.0477 (12)	0.1045 (19)	−0.0364 (13)	0.0203 (16)	0.0114 (12)
O6	0.128 (3)	0.0694 (16)	0.109 (2)	0.0224 (17)	0.042 (2)	−0.0027 (15)
Br1	0.0742 (2)	0.0972 (3)	0.0835 (2)	0.00646 (19)	−0.01798 (16)	0.0311 (2)

Geometric parameters (Å, º) top

C1—C2	1.351 (4)	C19—C20	1.364 (5)
C1—N1	1.370 (4)	C19—H19	0.9300
C1—H1	0.9300	C20—O6	1.371 (5)
C2—C3	1.419 (3)	C20—C21	1.397 (7)
C2—C9	1.500 (3)	C21—C22	1.364 (6)
C3—C4	1.398 (4)	C21—H21	0.9300
C3—C8	1.410 (3)	C22—H22	0.9300
C4—C5	1.371 (4)	C23—O6	1.420 (6)
C4—H4	0.9300	C23—H23A	0.9600
C5—C6	1.399 (5)	C23—H23B	0.9600
C5—H5	0.9300	C23—H23C	0.9600
C6—C7	1.359 (5)	C24—C25	1.379 (5)
C6—H6	0.9300	C24—C29	1.393 (4)
C7—C8	1.391 (4)	C24—H24	0.9300
C7—H7	0.9300	C25—C26	1.366 (6)
C8—N1	1.357 (4)	C25—H25	0.9300
C9—C10	1.540 (3)	C26—C27	1.369 (6)
C9—H9A	0.9700	C26—H26	0.9300
C9—H9B	0.9700	C27—C28	1.384 (5)
C10—N2	1.458 (3)	C27—H27	0.9300
C10—C36	1.529 (3)	C28—C29	1.393 (5)
C10—C11	1.600 (3)	C28—H28	0.9300
C11—C30	1.511 (3)	C30—C35	1.381 (3)
C11—C12	1.532 (3)	C30—C31	1.388 (3)
C11—H11	0.9800	C31—C32	1.369 (4)
C12—N3	1.505 (3)	C31—H31	0.9300
C12—C13	1.544 (3)	C32—C33	1.366 (4)
C12—H12	0.9800	C32—H32	0.9300
C13—N2	1.453 (3)	C33—C34	1.363 (4)
C13—C14	1.508 (3)	C33—Br1	1.895 (3)
C13—H13	0.9800	C34—C35	1.390 (4)
C14—N4	1.465 (3)	C34—H34	0.9300
C14—C15	1.576 (4)	C35—H35	0.9300
C14—H14	0.9800	C36—O1	1.180 (3)
C15—C29	1.498 (4)	C36—O2	1.325 (3)
C15—C16	1.529 (5)	C37—O2	1.458 (3)
C15—H15	0.9800	C37—H37A	0.9600
C16—O5	1.202 (4)	C37—H37B	0.9600
C16—N4	1.350 (4)	C37—H37C	0.9600
C17—C18	1.374 (5)	N1—H1A	0.8600
C17—C22	1.393 (5)	N2—H2	0.8600
C17—N4	1.408 (4)	N3—O3	1.210 (3)
C18—C19	1.377 (5)	N3—O4	1.218 (3)
C18—H18	0.9300

C2—C1—N1	110.1 (2)	C20—C19—H19	119.8
C2—C1—H1	125.0	C18—C19—H19	119.8
N1—C1—H1	125.0	C19—C20—O6	125.6 (4)
C1—C2—C3	106.7 (2)	C19—C20—C21	117.6 (4)
C1—C2—C9	126.7 (2)	O6—C20—C21	116.8 (3)
C3—C2—C9	126.6 (2)	C22—C21—C20	122.3 (3)
C4—C3—C8	118.6 (2)	C22—C21—H21	118.8
C4—C3—C2	134.5 (2)	C20—C21—H21	118.8
C8—C3—C2	106.9 (2)	C21—C22—C17	119.5 (4)
C5—C4—C3	119.2 (3)	C21—C22—H22	120.3
C5—C4—H4	120.4	C17—C22—H22	120.3
C3—C4—H4	120.4	O6—C23—H23A	109.5
C4—C5—C6	121.1 (3)	O6—C23—H23B	109.5
C4—C5—H5	119.5	H23A—C23—H23B	109.5
C6—C5—H5	119.5	O6—C23—H23C	109.5
C7—C6—C5	121.2 (2)	H23A—C23—H23C	109.5
C7—C6—H6	119.4	H23B—C23—H23C	109.5
C5—C6—H6	119.4	C25—C24—C29	121.2 (3)
C6—C7—C8	118.2 (3)	C25—C24—H24	119.4
C6—C7—H7	120.9	C29—C24—H24	119.4
C8—C7—H7	120.9	C26—C25—C24	121.1 (3)
N1—C8—C7	130.8 (2)	C26—C25—H25	119.5
N1—C8—C3	107.4 (2)	C24—C25—H25	119.5
C7—C8—C3	121.8 (3)	C25—C26—C27	118.4 (4)
C2—C9—C10	112.56 (19)	C25—C26—H26	120.8
C2—C9—H9A	109.1	C27—C26—H26	120.8
C10—C9—H9A	109.1	C26—C27—C28	121.7 (4)
C2—C9—H9B	109.1	C26—C27—H27	119.2
C10—C9—H9B	109.1	C28—C27—H27	119.2
H9A—C9—H9B	107.8	C27—C28—C29	120.3 (3)
N2—C10—C36	108.35 (18)	C27—C28—H28	119.9
N2—C10—C9	109.65 (18)	C29—C28—H28	119.9
C36—C10—C9	109.74 (18)	C24—C29—C28	117.3 (3)
N2—C10—C11	106.06 (16)	C24—C29—C15	121.5 (3)
C36—C10—C11	109.40 (17)	C28—C29—C15	121.2 (3)
C9—C10—C11	113.48 (17)	C35—C30—C31	117.5 (2)
C30—C11—C12	114.28 (18)	C35—C30—C11	124.2 (2)
C30—C11—C10	115.92 (18)	C31—C30—C11	118.3 (2)
C12—C11—C10	103.63 (16)	C32—C31—C30	121.4 (2)
C30—C11—H11	107.5	C32—C31—H31	119.3
C12—C11—H11	107.5	C30—C31—H31	119.3
C10—C11—H11	107.5	C33—C32—C31	119.9 (2)
N3—C12—C11	111.63 (18)	C33—C32—H32	120.0
N3—C12—C13	109.04 (19)	C31—C32—H32	120.0
C11—C12—C13	103.74 (18)	C34—C33—C32	120.7 (3)
N3—C12—H12	110.7	C34—C33—Br1	120.6 (2)
C11—C12—H12	110.7	C32—C33—Br1	118.8 (2)
C13—C12—H12	110.7	C33—C34—C35	119.3 (2)
N2—C13—C14	113.3 (2)	C33—C34—H34	120.4
N2—C13—C12	104.45 (17)	C35—C34—H34	120.4
C14—C13—C12	118.4 (2)	C30—C35—C34	121.3 (2)
N2—C13—H13	106.7	C30—C35—H35	119.4
C14—C13—H13	106.7	C34—C35—H35	119.4
C12—C13—H13	106.7	O1—C36—O2	124.4 (2)
N4—C14—C13	114.1 (2)	O1—C36—C10	125.0 (2)
N4—C14—C15	87.00 (18)	O2—C36—C10	110.6 (2)
C13—C14—C15	116.6 (2)	O2—C37—H37A	109.5
N4—C14—H14	112.3	O2—C37—H37B	109.5
C13—C14—H14	112.3	H37A—C37—H37B	109.5
C15—C14—H14	112.3	O2—C37—H37C	109.5
C29—C15—C16	115.9 (2)	H37A—C37—H37C	109.5
C29—C15—C14	120.7 (2)	H37B—C37—H37C	109.5
C16—C15—C14	84.4 (2)	C8—N1—C1	108.9 (2)
C29—C15—H15	111.1	C8—N1—H1A	125.5
C16—C15—H15	111.1	C1—N1—H1A	125.5
C14—C15—H15	111.1	C13—N2—C10	106.14 (17)
O5—C16—N4	131.8 (4)	C13—N2—H2	126.9
O5—C16—C15	135.1 (3)	C10—N2—H2	126.9
N4—C16—C15	93.1 (2)	O3—N3—O4	124.1 (2)
C18—C17—C22	118.0 (3)	O3—N3—C12	117.0 (2)
C18—C17—N4	122.2 (3)	O4—N3—C12	118.8 (2)
C22—C17—N4	119.8 (3)	C16—N4—C17	130.8 (2)
C17—C18—C19	122.1 (3)	C16—N4—C14	95.5 (2)
C17—C18—H18	119.0	C17—N4—C14	133.2 (2)
C19—C18—H18	119.0	C36—O2—C37	116.1 (3)
C20—C19—C18	120.4 (4)	C20—O6—C23	116.9 (3)

N1—C1—C2—C3	0.1 (3)	C24—C25—C26—C27	−2.3 (6)
N1—C1—C2—C9	−179.8 (2)	C25—C26—C27—C28	1.5 (6)
C1—C2—C3—C4	−179.9 (3)	C26—C27—C28—C29	−0.8 (5)
C9—C2—C3—C4	0.0 (4)	C25—C24—C29—C28	−1.5 (4)
C1—C2—C3—C8	0.0 (3)	C25—C24—C29—C15	−179.3 (3)
C9—C2—C3—C8	179.9 (2)	C27—C28—C29—C24	0.7 (4)
C8—C3—C4—C5	0.0 (4)	C27—C28—C29—C15	178.5 (3)
C2—C3—C4—C5	179.9 (3)	C16—C15—C29—C24	−21.8 (3)
C3—C4—C5—C6	−0.4 (4)	C14—C15—C29—C24	77.4 (3)
C4—C5—C6—C7	0.8 (5)	C16—C15—C29—C28	160.5 (3)
C5—C6—C7—C8	−0.8 (4)	C14—C15—C29—C28	−100.3 (3)
C6—C7—C8—N1	−179.4 (3)	C12—C11—C30—C35	−26.5 (3)
C6—C7—C8—C3	0.4 (4)	C10—C11—C30—C35	93.9 (3)
C4—C3—C8—N1	179.9 (2)	C12—C11—C30—C31	152.7 (2)
C2—C3—C8—N1	−0.1 (3)	C10—C11—C30—C31	−86.9 (3)
C4—C3—C8—C7	0.0 (4)	C35—C30—C31—C32	0.0 (4)
C2—C3—C8—C7	−179.9 (2)	C11—C30—C31—C32	−179.3 (2)
C1—C2—C9—C10	72.9 (3)	C30—C31—C32—C33	1.1 (4)
C3—C2—C9—C10	−107.0 (3)	C31—C32—C33—C34	−1.4 (5)
C2—C9—C10—N2	−65.0 (2)	C31—C32—C33—Br1	179.2 (2)
C2—C9—C10—C36	53.9 (2)	C32—C33—C34—C35	0.6 (5)
C2—C9—C10—C11	176.64 (18)	Br1—C33—C34—C35	179.9 (2)
N2—C10—C11—C30	−131.23 (19)	C31—C30—C35—C34	−0.8 (4)
C36—C10—C11—C30	112.1 (2)	C11—C30—C35—C34	178.4 (3)
C9—C10—C11—C30	−10.8 (2)	C33—C34—C35—C30	0.6 (5)
N2—C10—C11—C12	−5.2 (2)	N2—C10—C36—O1	−2.4 (3)
C36—C10—C11—C12	−121.86 (19)	C9—C10—C36—O1	−122.1 (3)
C9—C10—C11—C12	115.22 (19)	C11—C10—C36—O1	112.8 (3)
C30—C11—C12—N3	−133.95 (19)	N2—C10—C36—O2	178.07 (18)
C10—C11—C12—N3	98.99 (19)	C9—C10—C36—O2	58.4 (2)
C30—C11—C12—C13	108.8 (2)	C11—C10—C36—O2	−66.7 (2)
C10—C11—C12—C13	−18.3 (2)	C7—C8—N1—C1	179.9 (3)
N3—C12—C13—N2	−82.7 (2)	C3—C8—N1—C1	0.1 (3)
C11—C12—C13—N2	36.4 (2)	C2—C1—N1—C8	−0.1 (3)
N3—C12—C13—C14	44.5 (3)	C14—C13—N2—C10	−171.01 (19)
C11—C12—C13—C14	163.6 (2)	C12—C13—N2—C10	−40.8 (2)
N2—C13—C14—N4	−68.2 (3)	C36—C10—N2—C13	145.89 (18)
C12—C13—C14—N4	169.0 (2)	C9—C10—N2—C13	−94.4 (2)
N2—C13—C14—C15	−167.4 (2)	C11—C10—N2—C13	28.5 (2)
C12—C13—C14—C15	69.8 (3)	C11—C12—N3—O3	161.8 (2)
N4—C14—C15—C29	−116.5 (3)	C13—C12—N3—O3	−84.1 (3)
C13—C14—C15—C29	−1.0 (4)	C11—C12—N3—O4	−21.0 (3)
N4—C14—C15—C16	0.30 (19)	C13—C12—N3—O4	93.0 (2)
C13—C14—C15—C16	115.8 (2)	O5—C16—N4—C17	−8.2 (6)
C29—C15—C16—O5	−57.5 (5)	C15—C16—N4—C17	173.2 (3)
C14—C15—C16—O5	−178.9 (4)	O5—C16—N4—C14	179.0 (4)
C29—C15—C16—N4	121.1 (2)	C15—C16—N4—C14	0.4 (2)
C14—C15—C16—N4	−0.3 (2)	C18—C17—N4—C16	−147.7 (3)
C22—C17—C18—C19	−1.0 (5)	C22—C17—N4—C16	34.2 (5)
N4—C17—C18—C19	−179.1 (3)	C18—C17—N4—C14	22.5 (5)
C17—C18—C19—C20	−2.8 (6)	C22—C17—N4—C14	−155.6 (3)
C18—C19—C20—O6	−178.0 (4)	C13—C14—N4—C16	−118.3 (2)
C18—C19—C20—C21	4.1 (6)	C15—C14—N4—C16	−0.3 (2)
C19—C20—C21—C22	−1.8 (7)	C13—C14—N4—C17	69.2 (4)
O6—C20—C21—C22	−179.9 (4)	C15—C14—N4—C17	−172.9 (3)
C20—C21—C22—C17	−1.9 (7)	O1—C36—O2—C37	1.6 (4)
C18—C17—C22—C21	3.2 (6)	C10—C36—O2—C37	−178.9 (3)
N4—C17—C22—C21	−178.6 (4)	C19—C20—O6—C23	−17.0 (6)
C29—C24—C25—C26	2.4 (5)	C21—C20—O6—C23	161.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O4	0.98	2.27	2.717 (3)	107
C4—H4···O4ⁱ	0.93	2.57	3.186 (3)	124
C31—H31···O4ⁱⁱ	0.93	2.55	3.399 (3)	152
N1—H1A···O5ⁱⁱⁱ	0.86	2.02	2.820 (3)	155
C18—H18···Cg^iv	0.93	2.80	3.641 (4)	151

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

Experimental details

Crystal data
Chemical formula	C₃₇H₃₃BrN₄O₆
M_r	709.58
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	11.3988 (4), 34.8587 (13), 8.7039 (3)
β (°)	100.982 (2)
V (Å³)	3395.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.26
Crystal size (mm)	0.30 × 0.22 × 0.22

Data collection
Diffractometer	Bruker Kappa APEX2 diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.703, 0.769
No. of measured, independent and observed [I > 2σ(I)] reflections	37282, 8532, 6397
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.675

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.120, 1.04
No. of reflections	8532
No. of parameters	433
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.37
Absolute structure	Flack (1983), 4142 Friedel pairs
Absolute structure parameter	0.008 (6)

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O4	0.98	2.27	2.717 (3)	106.5
C4—H4···O4ⁱ	0.93	2.57	3.186 (3)	123.9
C31—H31···O4ⁱⁱ	0.93	2.55	3.399 (3)	151.9
N1—H1A···O5ⁱⁱⁱ	0.86	2.02	2.820 (3)	154.9
C18—H18···Cg^iv	0.93	2.80	3.641 (4)	151.0

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

Acknowledgements

SN thanks Professor M. N. Ponnuswamy, Department of Crystallography and Biophysics, University of Madras, India, for his guidance and valuable suggestions. SN thanks SRM management, India, for their support.

References

Amal Raj, A., Raghunathan, R., Sridevi Kumari, M. R. & Raman, N. (2003). Bioorg. Med. Chem. 11, 407–409. Web of Science PubMed Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages o1095-o1096

doi:10.1107/S1600536808014190

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Methyl 3-(4-bromo­phen­yl)-2-(1H-indol-3-ylmeth­yl)-5-[1-(4-meth­oxy­phen­yl)-4-oxo-2-phenyl­azetidin-2-yl]-4-nitro­pyrrolidine-2-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Methyl 3-(4-bromophenyl)-2-(1H-indol-3-ylmethyl)-5-[1-(4-methoxyphenyl)-4-oxo-2-phenylazetidin-2-yl]-4-nitropyrrolidine-2-carboxylate