2,2-Diethyl 3,4-dimethyl 5-(4-cyano-phen-yl)pyrrolidine-2,2,3,4-tetra-carboxyl-ate.

The title compound, C(21)H(24)N(2)O(8), was synthesized by a 1,3-dipolar cyclo-addition reaction of dimethyl fumarate, diethyl 2-amino-malonate and 4-cyano-benzaldehyde. Both methyl ester groups display a trans configuration and the pyrrolidine ring possesses an envelope conformation, with the C atom in the 3-position as the flap. In the crystal, N-H⋯N hydrogen bonds and weak C-H⋯O inter-actions occur.

Related literature

For the biological activity of pyrrolidine derivatives, see: Coldham & Hufton (2005 ▶); Pandey et al. (2006 ▶); Schreiber et al. (2000 ▶). For a related structure, see: He et al. (2010 ▶).

Experimental

Crystal data

C21H24N2O8

M = 432.42

Orthorhombic,

a = 8.4720 (2) Å

b = 10.3043 (2) Å

c = 25.8774 (5) Å

V = 2259.05 (8) Å3

Z = 4

Cu Kα radiation

μ = 0.83 mm−1

T = 291 K

0.38 × 0.30 × 0.30 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 ▶) T min = 0.744, T max = 0.789

26556 measured reflections

2565 independent reflections

2050 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.141

S = 1.03

2565 reflections

288 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.40 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 datablock(s) global, I. DOI: 10.1107/S1600536812029625/xu5557sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029625/xu5557Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812029625/xu5557Isup3.cml

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

C21H24N2O8	Dx = 1.271 Mg m−3
Mr = 432.42	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 10771 reflections
a = 8.4720 (2) Å	θ = 1.7–72.3°
b = 10.3043 (2) Å	µ = 0.83 mm−1
c = 25.8774 (5) Å	T = 291 K
V = 2259.05 (8) Å3	Block, colorless
Z = 4	0.38 × 0.30 × 0.30 mm
F(000) = 912

Oxford Diffraction Gemini S Ultra diffractometer	2565 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2050 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.027
Detector resolution: 15.9149 pixels mm-1	θmax = 72.6°, θmin = 3.4°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −12→10
Tmin = 0.744, Tmax = 0.789	l = −31→31
26556 measured reflections

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.141	w = 1/[σ2(Fo2) + (0.0724P)2 + 0.5988P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2565 reflections	Δρmax = 0.40 e Å−3
288 parameters	Δρmin = −0.22 e Å−3
2 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: 0.0015 (4)

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
O2	1.0668 (3)	0.9425 (2)	0.20700 (8)	0.0707 (7)
O5	1.0369 (4)	0.7873 (2)	0.40309 (11)	0.0880 (9)
O8	0.8498 (4)	1.0544 (3)	0.46182 (9)	0.0865 (9)
N2	0.8356 (4)	0.9769 (3)	0.35733 (10)	0.0622 (7)
O1	1.1491 (5)	1.1320 (3)	0.23785 (10)	0.0928 (10)
C9	1.0464 (4)	0.9727 (3)	0.29624 (11)	0.0548 (7)
H9	1.1073	0.8930	0.3016	0.066*
O6	1.1628 (4)	0.9441 (3)	0.44645 (10)	0.0898 (9)
O4	1.3158 (4)	1.1691 (3)	0.37339 (11)	0.0874 (8)
O7	0.9598 (5)	1.2258 (3)	0.42249 (12)	0.1046 (12)
C5	0.7612 (4)	1.0072 (3)	0.26561 (11)	0.0542 (7)
C2	0.5727 (4)	1.1296 (3)	0.19214 (13)	0.0632 (9)
C8	0.8696 (4)	0.9382 (3)	0.30325 (11)	0.0530 (7)
H8	0.8559	0.8442	0.2997	0.064*
C12	1.0926 (4)	1.0266 (3)	0.24488 (12)	0.0597 (8)
C6	0.7360 (4)	1.1396 (3)	0.26702 (13)	0.0620 (8)
H6	0.7825	1.1885	0.2931	0.074*
C10	1.0857 (4)	1.0649 (3)	0.34090 (12)	0.0592 (8)
H10	1.0539	1.1535	0.3320	0.071*
C4	0.6885 (5)	0.9354 (4)	0.22681 (13)	0.0668 (9)
H4	0.7047	0.8462	0.2251	0.080*
C11	0.9802 (4)	1.0124 (3)	0.38427 (12)	0.0602 (8)
C7	0.6433 (4)	1.2009 (3)	0.23057 (14)	0.0658 (9)
H7	0.6287	1.2903	0.2320	0.079*
C19	0.9328 (5)	1.1127 (3)	0.42459 (13)	0.0716 (10)
C16	1.0612 (5)	0.8987 (3)	0.41186 (13)	0.0683 (10)
C3	0.5921 (5)	0.9951 (4)	0.19062 (15)	0.0754 (11)
H3	0.5409	0.9460	0.1656	0.091*
C14	1.2688 (5)	1.0600 (4)	0.35092 (14)	0.0719 (10)
C13	1.0929 (7)	0.9876 (5)	0.15484 (13)	0.0955 (15)
H13A	1.2035	1.0033	0.1497	0.115*
H13B	1.0352	1.0665	0.1493	0.115*
H13C	1.0575	0.9228	0.1308	0.115*
C20	0.7915 (8)	1.1323 (5)	0.50465 (15)	0.1021 (16)
H20A	0.8668	1.2001	0.5128	0.122*
H20B	0.6923	1.1729	0.4952	0.122*
C17	1.2540 (8)	0.8528 (5)	0.47718 (19)	0.1127 (19)
H17A	1.1848	0.7871	0.4916	0.135*
H17B	1.3318	0.8100	0.4556	0.135*
C15	1.4850 (5)	1.1640 (7)	0.3860 (2)	0.1114 (17)
H15A	1.5435	1.1382	0.3559	0.167*
H15B	1.5020	1.1022	0.4132	0.167*
H15C	1.5198	1.2481	0.3971	0.167*
C21	0.7690 (9)	1.0492 (6)	0.54894 (18)	0.121 (2)
H21A	0.8670	1.0078	0.5575	0.145*
H21B	0.6912	0.9845	0.5410	0.145*
H21C	0.7337	1.1003	0.5778	0.145*
C18	1.3299 (11)	0.9207 (8)	0.5172 (3)	0.189 (4)
H18A	1.2602	0.9860	0.5306	0.227*
H18B	1.4238	0.9610	0.5040	0.227*
H18C	1.3575	0.8613	0.5443	0.227*
O3	1.3504 (4)	0.9759 (4)	0.33931 (18)	0.1249 (14)
N1	0.4052 (5)	1.2386 (4)	0.12122 (16)	0.0982 (12)
C1	0.4786 (5)	1.1909 (4)	0.15304 (15)	0.0752 (10)
H1	0.780 (5)	0.924 (4)	0.3757 (16)	0.113*

	U11	U22	U33	U12	U13	U23
O2	0.1013 (19)	0.0581 (13)	0.0527 (11)	−0.0096 (14)	0.0014 (12)	−0.0020 (11)
O5	0.126 (2)	0.0517 (14)	0.0863 (18)	0.0007 (16)	−0.0135 (18)	0.0065 (12)
O8	0.134 (3)	0.0700 (15)	0.0558 (12)	−0.0049 (18)	0.0108 (16)	−0.0103 (12)
N2	0.0743 (17)	0.0655 (17)	0.0469 (13)	−0.0087 (16)	−0.0029 (13)	0.0032 (12)
O1	0.148 (3)	0.0629 (16)	0.0677 (15)	−0.0344 (19)	0.0105 (18)	0.0011 (13)
C9	0.0710 (19)	0.0417 (15)	0.0516 (15)	0.0009 (15)	−0.0052 (15)	0.0015 (13)
O6	0.121 (2)	0.0700 (15)	0.0782 (16)	−0.0008 (18)	−0.0441 (17)	0.0122 (13)
O4	0.0833 (17)	0.094 (2)	0.0853 (17)	−0.0168 (17)	−0.0061 (16)	−0.0093 (16)
O7	0.170 (4)	0.0548 (16)	0.089 (2)	−0.0019 (19)	0.017 (2)	−0.0071 (13)
C5	0.0664 (18)	0.0482 (16)	0.0479 (15)	−0.0017 (15)	−0.0027 (14)	−0.0003 (13)
C2	0.0652 (19)	0.064 (2)	0.0606 (18)	0.0040 (18)	−0.0029 (16)	0.0074 (16)
C8	0.0706 (19)	0.0414 (14)	0.0472 (14)	−0.0014 (15)	−0.0051 (13)	0.0015 (13)
C12	0.074 (2)	0.0487 (16)	0.0569 (17)	0.0013 (16)	−0.0020 (16)	0.0020 (14)
C6	0.077 (2)	0.0460 (17)	0.0625 (18)	−0.0003 (17)	−0.0093 (17)	−0.0035 (15)
C10	0.078 (2)	0.0439 (15)	0.0556 (16)	−0.0060 (16)	−0.0124 (15)	0.0046 (14)
C4	0.085 (2)	0.0502 (17)	0.0648 (18)	0.0030 (18)	−0.0177 (19)	−0.0071 (16)
C11	0.088 (2)	0.0463 (16)	0.0465 (14)	−0.0032 (17)	−0.0107 (16)	0.0025 (13)
C7	0.069 (2)	0.0536 (18)	0.075 (2)	0.0036 (17)	−0.0033 (19)	0.0058 (17)
C19	0.106 (3)	0.0555 (19)	0.0537 (18)	0.001 (2)	−0.013 (2)	0.0007 (15)
C16	0.096 (3)	0.0555 (19)	0.0534 (17)	−0.0025 (19)	−0.0080 (19)	0.0078 (15)
C3	0.090 (3)	0.069 (2)	0.068 (2)	0.001 (2)	−0.024 (2)	−0.0083 (18)
C14	0.087 (3)	0.065 (2)	0.065 (2)	−0.011 (2)	−0.0043 (19)	−0.0079 (19)
C13	0.143 (4)	0.092 (3)	0.0511 (18)	−0.016 (3)	0.009 (2)	−0.0015 (19)
C20	0.147 (5)	0.094 (3)	0.064 (2)	0.014 (3)	0.006 (3)	−0.020 (2)
C17	0.140 (5)	0.094 (3)	0.104 (3)	0.014 (4)	−0.046 (4)	0.027 (3)
C15	0.064 (2)	0.148 (5)	0.122 (4)	−0.008 (3)	−0.014 (3)	−0.017 (4)
C21	0.158 (5)	0.123 (4)	0.081 (3)	−0.002 (4)	0.032 (3)	−0.016 (3)
C18	0.220 (9)	0.184 (7)	0.164 (6)	0.007 (7)	−0.125 (7)	0.040 (6)
O3	0.095 (2)	0.101 (2)	0.179 (4)	0.024 (2)	−0.037 (3)	−0.040 (3)
N1	0.092 (2)	0.103 (3)	0.099 (3)	0.012 (2)	−0.028 (2)	0.020 (2)
C1	0.070 (2)	0.080 (2)	0.075 (2)	0.004 (2)	−0.008 (2)	0.008 (2)

O2—C12	1.327 (4)	C10—C14	1.573 (6)
O2—C13	1.445 (4)	C10—H10	0.9800
O5—C16	1.188 (4)	C4—C3	1.386 (5)
O8—C19	1.335 (5)	C4—H4	0.9300
O8—C20	1.455 (5)	C11—C19	1.523 (5)
N2—C11	1.456 (5)	C11—C16	1.534 (5)
N2—C8	1.484 (4)	C7—H7	0.9300
N2—H1	0.86 (2)	C3—H3	0.9300
O1—C12	1.201 (4)	C14—O3	1.149 (5)
C9—C12	1.493 (4)	C13—H13A	0.9600
C9—C10	1.532 (4)	C13—H13B	0.9600
C9—C8	1.550 (5)	C13—H13C	0.9600
C9—H9	0.9800	C20—C21	1.443 (7)
O6—C16	1.327 (5)	C20—H20A	0.9700
O6—C17	1.454 (5)	C20—H20B	0.9700
O4—C14	1.327 (5)	C17—C18	1.405 (8)
O4—C15	1.471 (5)	C17—H17A	0.9700
O7—C19	1.189 (5)	C17—H17B	0.9700
C5—C6	1.381 (4)	C15—H15A	0.9600
C5—C4	1.391 (5)	C15—H15B	0.9600
C5—C8	1.516 (4)	C15—H15C	0.9600
C2—C7	1.374 (5)	C21—H21A	0.9600
C2—C3	1.396 (5)	C21—H21B	0.9600
C2—C1	1.435 (5)	C21—H21C	0.9600
C8—H8	0.9800	C18—H18A	0.9600
C6—C7	1.380 (5)	C18—H18B	0.9600
C6—H6	0.9300	C18—H18C	0.9600
C10—C11	1.534 (5)	N1—C1	1.143 (5)
C12—O2—C13	117.1 (3)	O7—C19—O8	125.1 (4)
C19—O8—C20	118.7 (3)	O7—C19—C11	125.7 (4)
C11—N2—C8	110.8 (3)	O8—C19—C11	109.1 (3)
C11—N2—H1	111 (3)	O5—C16—O6	125.6 (4)
C8—N2—H1	117 (3)	O5—C16—C11	124.8 (4)
C12—C9—C10	112.6 (3)	O6—C16—C11	109.6 (3)
C12—C9—C8	116.3 (3)	C4—C3—C2	119.4 (4)
C10—C9—C8	105.3 (3)	C4—C3—H3	120.3
C12—C9—H9	107.4	C2—C3—H3	120.3
C10—C9—H9	107.4	O3—C14—O4	124.9 (4)
C8—C9—H9	107.4	O3—C14—C10	125.1 (4)
C16—O6—C17	119.1 (3)	O4—C14—C10	110.0 (4)
C14—O4—C15	111.1 (4)	O2—C13—H13A	109.5
C6—C5—C4	118.4 (3)	O2—C13—H13B	109.5
C6—C5—C8	122.7 (3)	H13A—C13—H13B	109.5
C4—C5—C8	118.8 (3)	O2—C13—H13C	109.5
C7—C2—C3	120.0 (3)	H13A—C13—H13C	109.5
C7—C2—C1	121.1 (3)	H13B—C13—H13C	109.5
C3—C2—C1	118.9 (4)	C21—C20—O8	108.8 (4)
N2—C8—C5	111.2 (3)	C21—C20—H20A	109.9
N2—C8—C9	103.7 (3)	O8—C20—H20A	109.9
C5—C8—C9	113.7 (3)	C21—C20—H20B	109.9
N2—C8—H8	109.4	O8—C20—H20B	109.9
C5—C8—H8	109.4	H20A—C20—H20B	108.3
C9—C8—H8	109.4	C18—C17—O6	108.9 (5)
O1—C12—O2	123.0 (3)	C18—C17—H17A	109.9
O1—C12—C9	125.2 (3)	O6—C17—H17A	109.9
O2—C12—C9	111.8 (3)	C18—C17—H17B	109.9
C7—C6—C5	121.5 (3)	O6—C17—H17B	109.9
C7—C6—H6	119.3	H17A—C17—H17B	108.3
C5—C6—H6	119.3	O4—C15—H15A	109.5
C9—C10—C11	101.9 (3)	O4—C15—H15B	109.5
C9—C10—C14	108.6 (3)	H15A—C15—H15B	109.5
C11—C10—C14	116.3 (3)	O4—C15—H15C	109.5
C9—C10—H10	109.9	H15A—C15—H15C	109.5
C11—C10—H10	109.9	H15B—C15—H15C	109.5
C14—C10—H10	109.9	C20—C21—H21A	109.5
C3—C4—C5	120.8 (3)	C20—C21—H21B	109.5
C3—C4—H4	119.6	H21A—C21—H21B	109.5
C5—C4—H4	119.6	C20—C21—H21C	109.5
N2—C11—C19	106.1 (3)	H21A—C21—H21C	109.5
N2—C11—C10	103.2 (2)	H21B—C21—H21C	109.5
C19—C11—C10	114.6 (3)	C17—C18—H18A	109.5
N2—C11—C16	114.0 (3)	C17—C18—H18B	109.5
C19—C11—C16	108.5 (3)	H18A—C18—H18B	109.5
C10—C11—C16	110.4 (3)	C17—C18—H18C	109.5
C2—C7—C6	119.8 (3)	H18A—C18—H18C	109.5
C2—C7—H7	120.1	H18B—C18—H18C	109.5
C6—C7—H7	120.1	N1—C1—C2	178.8 (5)
C11—N2—C8—C5	−130.9 (3)	C3—C2—C7—C6	1.3 (6)
C11—N2—C8—C9	−8.3 (3)	C1—C2—C7—C6	−178.6 (4)
C6—C5—C8—N2	48.9 (4)	C5—C6—C7—C2	0.6 (6)
C4—C5—C8—N2	−133.6 (3)	C20—O8—C19—O7	−2.4 (7)
C6—C5—C8—C9	−67.7 (4)	C20—O8—C19—C11	−179.8 (4)
C4—C5—C8—C9	109.8 (4)	N2—C11—C19—O7	−106.8 (5)
C12—C9—C8—N2	−142.0 (3)	C10—C11—C19—O7	6.4 (6)
C10—C9—C8—N2	−16.5 (3)	C16—C11—C19—O7	130.3 (5)
C12—C9—C8—C5	−21.1 (4)	N2—C11—C19—O8	70.6 (4)
C10—C9—C8—C5	104.4 (3)	C10—C11—C19—O8	−176.2 (3)
C13—O2—C12—O1	−6.8 (6)	C16—C11—C19—O8	−52.3 (4)
C13—O2—C12—C9	174.4 (4)	C17—O6—C16—O5	−0.3 (7)
C10—C9—C12—O1	−2.6 (6)	C17—O6—C16—C11	−179.8 (4)
C8—C9—C12—O1	119.0 (4)	N2—C11—C16—O5	18.0 (6)
C10—C9—C12—O2	176.1 (3)	C19—C11—C16—O5	136.0 (4)
C8—C9—C12—O2	−62.2 (4)	C10—C11—C16—O5	−97.7 (5)
C4—C5—C6—C7	−1.1 (6)	N2—C11—C16—O6	−162.5 (3)
C8—C5—C6—C7	176.5 (3)	C19—C11—C16—O6	−44.5 (4)
C12—C9—C10—C11	161.4 (3)	C10—C11—C16—O6	81.8 (4)
C8—C9—C10—C11	33.7 (3)	C5—C4—C3—C2	2.3 (6)
C12—C9—C10—C14	−75.3 (4)	C7—C2—C3—C4	−2.7 (6)
C8—C9—C10—C14	157.0 (3)	C1—C2—C3—C4	177.1 (4)
C6—C5—C4—C3	−0.5 (6)	C15—O4—C14—O3	−5.2 (7)
C8—C5—C4—C3	−178.1 (4)	C15—O4—C14—C10	176.6 (4)
C8—N2—C11—C19	150.5 (3)	C9—C10—C14—O3	−22.5 (6)
C8—N2—C11—C10	29.7 (3)	C11—C10—C14—O3	91.7 (5)
C8—N2—C11—C16	−90.1 (3)	C9—C10—C14—O4	155.7 (3)
C9—C10—C11—N2	−38.3 (3)	C11—C10—C14—O4	−90.1 (4)
C14—C10—C11—N2	−156.2 (3)	C19—O8—C20—C21	−155.3 (5)
C9—C10—C11—C19	−153.2 (3)	C16—O6—C17—C18	−169.0 (6)
C14—C10—C11—C19	88.9 (4)	C7—C2—C1—N1	126 (23)
C9—C10—C11—C16	83.9 (3)	C3—C2—C1—N1	−54 (23)
C14—C10—C11—C16	−34.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···N1i	0.86 (4)	2.47 (4)	3.240 (5)	148 (4)
C8—H8···O1ii	0.98	2.39	3.333 (4)	161 (1)
C13—H13C···O7ii	0.96	2.46	3.388 (6)	163
C18—H18C···O5iii	0.96	2.55	3.453 (9)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯N1i	0.86 (4)	2.47 (4)	3.240 (5)	148 (4)
C8—H8⋯O1ii	0.98	2.39	3.333 (4)	161 (1)
C13—H13C⋯O7ii	0.96	2.46	3.388 (6)	163
C18—H18C⋯O5iii	0.96	2.55	3.453 (9)	157

Symmetry codes: (i) ; (ii) ; (iii) .