Diethyl 4-acetyl-5-(2-nitro-phen-yl)pyrrolidine-2,2-dicarboxyl-ate.

The title compound, C(18)H(22)N(2)O(7), was synthesized by the 1,3-dipolar cyclo-addition reaction of but-3-en-2-one, diethyl 2-amino-malonate and 2-nitro-benzaldehyde. In the mol-ecule, the pyrrolidine ring possesses an envelope conformation. Inter-molecular N-H⋯O and C-H⋯O hydrogen bonds are present in the crystal structure.

Related literature

For the biological activity of pyrrolidine derivatives, see: Coldham & Hufton (2005 ▶); Grigg (1995 ▶); Kravchenko et al. (2005 ▶); Nair & Suja (2007 ▶); Pandey et al. (2006 ▶); Sardina & Rapoport (1996 ▶); Witherup et al. (1995 ▶). For a related structure, see: He (2009 ▶).

Experimental

Crystal data

C18H22N2O7

M = 378.38

Monoclinic,

a = 10.687 (5) Å

b = 7.760 (5) Å

c = 12.030 (5) Å

β = 97.455 (5)°

V = 989.2 (9) Å3

Z = 2

Cu Kα radiation

μ = 0.83 mm−1

T = 291 K

0.38 × 0.36 × 0.30 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.743, T max = 0.789

19238 measured reflections

2105 independent reflections

1915 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.081

wR(F 2) = 0.166

S = 1.04

2105 reflections

249 parameters

42 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.42 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045691/xu5078sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045691/xu5078Isup2.hkl

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

C18H22N2O7	F(000) = 400
Mr = 378.38	Dx = 1.270 Mg m−3
Monoclinic, P21	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2yb	Cell parameters from 11509 reflections
a = 10.687 (5) Å	θ = 4.2–72.3°
b = 7.760 (5) Å	µ = 0.83 mm−1
c = 12.030 (5) Å	T = 291 K
β = 97.455 (5)°	Block, colorless
V = 989.2 (9) Å3	0.38 × 0.36 × 0.30 mm
Z = 2

Oxford Diffraction Gemini S Ultra diffractometer	2105 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1915 reflections with I > 2σ(I)
mirror	Rint = 0.023
ω scans	θmax = 72.6°, θmin = 4.2°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −13→13
Tmin = 0.743, Tmax = 0.789	k = −8→9
19238 measured reflections	l = −14→14

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)] = 0.081	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.166	w = 1/[σ2(Fo2) + (0.025P)2 + 1.3702P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2105 reflections	Δρmax = 0.33 e Å−3
249 parameters	Δρmin = −0.42 e Å−3
42 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.017 (3)

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.

	x	y	z	Uiso*/Ueq
O3	0.0038 (5)	0.2421 (8)	0.5230 (4)	0.0881 (16)
N2	0.2698 (5)	0.3189 (8)	0.6658 (4)	0.0681 (15)
O5	0.1828 (5)	0.4223 (10)	0.8609 (6)	0.117 (2)
C3	0.2453 (6)	0.4941 (9)	0.4653 (6)	0.0641 (16)
H3	0.1941	0.5184	0.5202	0.077*
O1	0.4209 (6)	0.0223 (8)	0.4138 (5)	0.0957 (18)
C2	0.3126 (5)	0.3415 (9)	0.4718 (5)	0.0566 (14)
O6	0.4399 (5)	0.1838 (10)	0.8411 (4)	0.108 (2)
O4	0.0249 (5)	0.2457 (11)	0.8118 (5)	0.112 (2)
O2	0.5571 (5)	0.1618 (10)	0.3371 (5)	0.120 (2)
C8	0.1956 (6)	0.0846 (9)	0.5533 (5)	0.0631 (16)
H8	0.2247	−0.0192	0.5180	0.076*
N1	0.4602 (6)	0.1556 (10)	0.3797 (5)	0.0784 (17)
C7	0.3030 (5)	0.2205 (9)	0.5697 (4)	0.0589 (15)
H7	0.3841	0.1624	0.5905	0.071*
C1	0.3875 (5)	0.3157 (10)	0.3870 (5)	0.0605 (15)
C16	0.1311 (7)	0.2862 (12)	0.8096 (6)	0.079 (2)
C4	0.2514 (6)	0.6116 (10)	0.3802 (6)	0.0776 (19)
H4	0.2028	0.7113	0.3771	0.093*
C12	0.0663 (7)	0.1228 (11)	0.3583 (5)	0.085 (2)
H12A	−0.0097	0.1760	0.3228	0.128*
H12B	0.0620	0.0007	0.3455	0.128*
H12C	0.1375	0.1694	0.3274	0.128*
C11	0.0803 (6)	0.1578 (9)	0.4820 (5)	0.0649 (16)
O7	0.2881 (6)	0.0324 (11)	0.9076 (6)	0.130 (2)
C10	0.2269 (6)	0.1943 (11)	0.7453 (5)	0.0721 (19)
C6	0.3975 (6)	0.4353 (11)	0.3036 (6)	0.0732 (19)
H6	0.4511	0.4149	0.2500	0.088*
C13	0.3357 (7)	0.1387 (14)	0.8371 (6)	0.092 (2)
C9	0.1723 (8)	0.0442 (10)	0.6740 (5)	0.080 (2)
H9A	0.0826	0.0330	0.6782	0.096*
H9B	0.2137	−0.0625	0.6995	0.096*
C5	0.3294 (7)	0.5809 (11)	0.3001 (6)	0.084 (2)
H5	0.3350	0.6611	0.2435	0.101*
C17	0.1066 (10)	0.5318 (17)	0.9259 (8)	0.128 (3)
H17A	0.0174	0.5231	0.8985	0.154*
H17B	0.1325	0.6515	0.9246	0.154*
C14	0.3850 (10)	−0.0385 (18)	1.0007 (8)	0.137 (3)
H14A	0.3874	−0.1634	0.9994	0.165*
H14B	0.4687	0.0064	0.9954	0.165*
C15	0.3341 (11)	0.0277 (19)	1.1036 (8)	0.153 (3)
H15A	0.3856	−0.0141	1.1694	0.229*
H15B	0.2490	−0.0121	1.1036	0.229*
H15C	0.3352	0.1514	1.1034	0.229*
C18	0.1366 (11)	0.455 (2)	1.0415 (9)	0.158 (3)
H18A	0.0896	0.5141	1.0925	0.237*
H18B	0.2253	0.4664	1.0663	0.237*
H18C	0.1141	0.3350	1.0391	0.237*
H10	0.342 (4)	0.377 (8)	0.693 (5)	0.07 (2)*

	U11	U22	U33	U12	U13	U23
O3	0.066 (2)	0.101 (4)	0.099 (4)	−0.003 (3)	0.016 (3)	−0.005 (3)
N2	0.073 (3)	0.076 (4)	0.056 (3)	−0.017 (3)	0.011 (2)	−0.010 (3)
O5	0.081 (3)	0.119 (5)	0.154 (4)	−0.015 (4)	0.020 (3)	−0.040 (5)
C3	0.059 (3)	0.062 (4)	0.073 (4)	−0.001 (3)	0.015 (3)	−0.002 (3)
O1	0.105 (4)	0.091 (4)	0.092 (4)	0.024 (4)	0.015 (3)	0.000 (4)
C2	0.048 (3)	0.065 (4)	0.057 (3)	−0.007 (3)	0.004 (2)	−0.003 (3)
O6	0.075 (3)	0.172 (7)	0.075 (3)	0.018 (4)	0.004 (2)	−0.009 (4)
O4	0.080 (3)	0.162 (7)	0.097 (4)	−0.018 (4)	0.025 (3)	0.000 (4)
O2	0.090 (3)	0.153 (6)	0.126 (4)	0.051 (4)	0.051 (3)	0.031 (5)
C8	0.072 (4)	0.058 (4)	0.059 (3)	−0.007 (3)	0.003 (3)	0.000 (3)
N1	0.076 (4)	0.093 (5)	0.067 (3)	0.020 (4)	0.011 (3)	−0.001 (4)
C7	0.058 (3)	0.066 (4)	0.051 (3)	−0.007 (3)	0.003 (2)	0.000 (3)
C1	0.053 (3)	0.070 (4)	0.058 (3)	0.005 (3)	0.007 (2)	0.000 (3)
C16	0.068 (4)	0.106 (7)	0.067 (4)	0.001 (5)	0.018 (3)	0.010 (4)
C4	0.076 (4)	0.066 (5)	0.091 (5)	0.002 (4)	0.014 (4)	0.005 (4)
C12	0.090 (5)	0.086 (6)	0.073 (4)	−0.010 (5)	−0.018 (3)	−0.001 (4)
C11	0.062 (3)	0.062 (4)	0.070 (4)	−0.014 (3)	0.006 (3)	−0.002 (3)
O7	0.124 (3)	0.135 (4)	0.131 (3)	−0.003 (3)	0.011 (2)	0.020 (3)
C10	0.071 (4)	0.092 (5)	0.053 (3)	−0.014 (4)	0.005 (3)	0.002 (4)
C6	0.072 (4)	0.084 (5)	0.065 (4)	0.002 (4)	0.019 (3)	0.001 (4)
C13	0.070 (4)	0.127 (7)	0.078 (4)	0.001 (4)	0.010 (3)	−0.023 (3)
C9	0.104 (5)	0.076 (5)	0.060 (4)	−0.021 (4)	0.008 (4)	0.006 (4)
C5	0.090 (5)	0.077 (5)	0.086 (5)	−0.005 (5)	0.018 (4)	0.015 (5)
C17	0.126 (4)	0.131 (4)	0.132 (3)	0.013 (3)	0.031 (3)	−0.018 (3)
C14	0.139 (4)	0.140 (4)	0.130 (3)	0.006 (3)	0.007 (2)	0.017 (3)
C15	0.165 (4)	0.155 (5)	0.134 (3)	0.009 (3)	0.004 (3)	−0.002 (3)
C18	0.168 (5)	0.165 (5)	0.142 (3)	0.009 (3)	0.026 (3)	−0.001 (3)

O3—C11	1.202 (8)	C12—C11	1.501 (9)
N2—C7	1.467 (8)	C12—H12A	0.9600
N2—C10	1.474 (9)	C12—H12B	0.9600
N2—H10	0.92 (5)	C12—H12C	0.9600
O5—C16	1.308 (10)	O7—C13	1.330 (11)
O5—C17	1.470 (11)	O7—C14	1.525 (11)
C3—C4	1.378 (9)	C10—C9	1.518 (10)
C3—C2	1.383 (9)	C10—C13	1.557 (10)
C3—H3	0.9300	C6—C5	1.342 (11)
O1—N1	1.208 (9)	C6—H6	0.9300
C2—C1	1.390 (8)	C9—H9A	0.9700
C2—C7	1.521 (8)	C9—H9B	0.9700
O6—C13	1.162 (9)	C5—H5	0.9300
O4—C16	1.181 (8)	C17—C18	1.509 (9)
O2—N1	1.214 (7)	C17—H17A	0.9700
C8—C11	1.517 (8)	C17—H17B	0.9700
C8—C9	1.537 (8)	C14—C15	1.506 (9)
C8—C7	1.552 (8)	C14—H14A	0.9700
C8—H8	0.9800	C14—H14B	0.9700
N1—C1	1.474 (9)	C15—H15A	0.9600
C7—H7	0.9800	C15—H15B	0.9600
C1—C6	1.382 (9)	C15—H15C	0.9600
C16—C10	1.536 (10)	C18—H18A	0.9600
C4—C5	1.375 (9)	C18—H18B	0.9600
C4—H4	0.9300	C18—H18C	0.9600
C7—N2—C10	107.3 (6)	N2—C10—C16	107.8 (6)
C7—N2—H10	105 (4)	C9—C10—C16	114.1 (6)
C10—N2—H10	114 (4)	N2—C10—C13	112.0 (6)
C16—O5—C17	119.2 (7)	C9—C10—C13	112.7 (7)
C4—C3—C2	122.3 (6)	C16—C10—C13	104.9 (5)
C4—C3—H3	118.9	C5—C6—C1	119.7 (6)
C2—C3—H3	118.9	C5—C6—H6	120.1
C3—C2—C1	115.3 (6)	C1—C6—H6	120.1
C3—C2—C7	119.1 (5)	O6—C13—O7	127.1 (9)
C1—C2—C7	125.6 (6)	O6—C13—C10	124.7 (9)
C11—C8—C9	113.0 (5)	O7—C13—C10	108.2 (7)
C11—C8—C7	110.5 (5)	C10—C9—C8	106.3 (6)
C9—C8—C7	103.1 (5)	C10—C9—H9A	110.5
C11—C8—H8	110.0	C8—C9—H9A	110.5
C9—C8—H8	110.0	C10—C9—H9B	110.5
C7—C8—H8	110.0	C8—C9—H9B	110.5
O1—N1—O2	122.1 (8)	H9A—C9—H9B	108.7
O1—N1—C1	119.4 (6)	C6—C5—C4	120.0 (7)
O2—N1—C1	118.5 (8)	C6—C5—H5	120.0
N2—C7—C2	109.7 (6)	C4—C5—H5	120.0
N2—C7—C8	101.8 (5)	O5—C17—C18	101.2 (9)
C2—C7—C8	116.4 (4)	O5—C17—H17A	111.5
N2—C7—H7	109.6	C18—C17—H17A	111.5
C2—C7—H7	109.6	O5—C17—H17B	111.5
C8—C7—H7	109.6	C18—C17—H17B	111.5
C6—C1—C2	122.8 (7)	H17A—C17—H17B	109.3
C6—C1—N1	115.6 (6)	C15—C14—O7	101.4 (8)
C2—C1—N1	121.6 (6)	C15—C14—H14A	111.5
O4—C16—O5	123.5 (8)	O7—C14—H14A	111.5
O4—C16—C10	126.3 (8)	C15—C14—H14B	111.5
O5—C16—C10	110.1 (6)	O7—C14—H14B	111.5
C5—C4—C3	119.8 (7)	H14A—C14—H14B	109.3
C5—C4—H4	120.1	C14—C15—H15A	109.5
C3—C4—H4	120.1	C14—C15—H15B	109.5
C11—C12—H12A	109.5	H15A—C15—H15B	109.5
C11—C12—H12B	109.5	C14—C15—H15C	109.5
H12A—C12—H12B	109.5	H15A—C15—H15C	109.5
C11—C12—H12C	109.5	H15B—C15—H15C	109.5
H12A—C12—H12C	109.5	C17—C18—H18A	109.5
H12B—C12—H12C	109.5	C17—C18—H18B	109.5
O3—C11—C12	121.3 (7)	H18A—C18—H18B	109.5
O3—C11—C8	121.1 (6)	C17—C18—H18C	109.5
C12—C11—C8	117.6 (6)	H18A—C18—H18C	109.5
C13—O7—C14	114.4 (7)	H18B—C18—H18C	109.5
N2—C10—C9	105.4 (5)
C4—C3—C2—C1	0.5 (9)	C7—N2—C10—C16	−150.7 (5)
C4—C3—C2—C7	178.7 (6)	C7—N2—C10—C13	94.5 (7)
C10—N2—C7—C2	164.3 (5)	O4—C16—C10—N2	120.5 (8)
C10—N2—C7—C8	40.5 (6)	O5—C16—C10—N2	−57.8 (8)
C3—C2—C7—N2	−25.6 (7)	O4—C16—C10—C9	3.7 (11)
C1—C2—C7—N2	152.3 (6)	O5—C16—C10—C9	−174.5 (7)
C3—C2—C7—C8	89.2 (7)	O4—C16—C10—C13	−120.0 (9)
C1—C2—C7—C8	−92.9 (7)	O5—C16—C10—C13	61.8 (9)
C11—C8—C7—N2	84.9 (6)	C2—C1—C6—C5	−2.4 (10)
C9—C8—C7—N2	−36.2 (6)	N1—C1—C6—C5	176.5 (7)
C11—C8—C7—C2	−34.3 (8)	C14—O7—C13—O6	−1.7 (14)
C9—C8—C7—C2	−155.3 (6)	C14—O7—C13—C10	178.0 (8)
C3—C2—C1—C6	1.7 (9)	N2—C10—C13—O6	−2.8 (12)
C7—C2—C1—C6	−176.3 (6)	C9—C10—C13—O6	115.9 (10)
C3—C2—C1—N1	−177.2 (6)	C16—C10—C13—O6	−119.5 (10)
C7—C2—C1—N1	4.8 (9)	N2—C10—C13—O7	177.5 (7)
O1—N1—C1—C6	−148.9 (7)	C9—C10—C13—O7	−63.8 (8)
O2—N1—C1—C6	29.6 (9)	C16—C10—C13—O7	60.8 (9)
O1—N1—C1—C2	30.0 (10)	N2—C10—C9—C8	4.1 (8)
O2—N1—C1—C2	−151.4 (6)	C16—C10—C9—C8	122.2 (6)
C17—O5—C16—O4	0.4 (13)	C13—C10—C9—C8	−118.4 (6)
C17—O5—C16—C10	178.7 (7)	C11—C8—C9—C10	−99.6 (7)
C2—C3—C4—C5	−2.0 (11)	C7—C8—C9—C10	19.7 (7)
C9—C8—C11—O3	30.1 (9)	C1—C6—C5—C4	0.8 (11)
C7—C8—C11—O3	−84.8 (8)	C3—C4—C5—C6	1.3 (11)
C9—C8—C11—C12	−150.7 (6)	C16—O5—C17—C18	93.1 (11)
C7—C8—C11—C12	94.4 (7)	C13—O7—C14—C15	119.5 (10)
C7—N2—C10—C9	−28.4 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H10···O2i	0.92 (5)	2.51 (6)	3.244 (9)	138 (5)
C18—H18A···O4ii	0.96	2.53	3.460 (15)	162 (6)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H10⋯O2i	0.92 (5)	2.51 (6)	3.244 (9)	138 (5)
C18—H18A⋯O4ii	0.96	2.53	3.460 (15)	162 (6)

Symmetry codes: (i) ; (ii) .