Crystal structure of ethyl 2-(4-chlorophenyl)-3-cyclopentyl-4-oxo-1-propyl-imidazolidine-5-carboxylate.

The title compound, C20H27ClN2O3, was obtained via an original synthesis method. The central heterocyclic ring adopts a shallow envelope conformation, with the N atom bearing the cyclo-pentane ring as the flap [deviation from the other atoms = 0.442 (2) Å]. The cyclo-pentane ring adopts a twisted conformation about one of the CN-C bonds: the exocyclic C-N bond adopts an equatorial orientation. The dihedral angles between the central ring (all atoms) and the pendant five- and six-membered rings are 10.3 (2) and 87.76 (14)°, respectively. In the crystal, C-H⋯O inter-actions link the mol-ecules into [011] chains. A weak C-H⋯Cl inter-action links the chains into (100) sheets. A mechanism for the cyclization reaction is proposed.

Related literature

For background to the biological properties of imidazolidin-4-one rings, see: Chambel et al. (2006 ▸); Vale et al. (2008a ▸,b ▸,c ▸); Gomes et al. (2004 ▸); Araujo et al. (2005 ▸); Qin et al. (2009 ▸). For imidazolidin-4-one rings in Diels–Alder reactions, see: Lin et al. (2013 ▸). For the synthesis and mechanistic studies, see: Gomes et al. (2006 ▸); Zhang et al. (2008 ▸).

Experimental

Crystal data

C20H27ClN2O3

M = 378.89

Triclinic,

a = 9.083 (7) Å

b = 11.201 (6) Å

c = 11.846 (6) Å

α = 117.75 (4)°

β = 90.49 (5)°

γ = 104.08 (6)°

V = 1024.1 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.21 mm−1

T = 298 K

0.4 × 0.3 × 0.2 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

6270 measured reflections

4439 independent reflections

2533 reflections with I > 2σ(I)

R int = 0.024

2 standard reflections every 120 reflections intensity decay: 4%

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.180

S = 0.99

4439 reflections

295 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.19 e Å−3

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▸; Macíček & Yordanov, 1992 ▸); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015015364/hb7486sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015015364/hb7486Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015015364/hb7486Isup3.cml

Click here for additional data file.

20 27 2 3 . DOI: 10.1107/S2056989015015364/hb7486fig1.tif

Synthesis protocol of C20H27ClN2O3.

Click here for additional data file.

. DOI: 10.1107/S2056989015015364/hb7486fig2.tif

Perspective view of the title compound showing 50% displacement ellipsoids.

Click here for additional data file.

20 27 2 3 . DOI: 10.1107/S2056989015015364/hb7486fig3.tif

Unit cell projection of C20H27ClN2O3 showing two mol­ecules per cell.

CCDC reference: 1419261

Additional supporting information: crystallographic information; 3D view; checkCIF report

C20H27ClN2O3	Z = 2
Mr = 378.89	F(000) = 404
Triclinic, P1	Dx = 1.229 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.083 (7) Å	Cell parameters from 25 reflections
b = 11.201 (6) Å	θ = 10–15°
c = 11.846 (6) Å	µ = 0.21 mm−1
α = 117.75 (4)°	T = 298 K
β = 90.49 (5)°	Prism, colorless
γ = 104.08 (6)°	0.4 × 0.3 × 0.2 mm
V = 1024.1 (11) Å3

Enraf–Nonius CAD-4 diffractometer	Rint = 0.024
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 2.1°
Graphite monochromator	h = −11→3
ω/2θ scans	k = −14→14
6270 measured reflections	l = −15→15
4439 independent reflections	2 standard reflections every 120 reflections
2533 reflections with I > 2σ(I)	intensity decay: 4%

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.180	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.1064P)2 + 0.0609P] where P = (Fo2 + 2Fc2)/3
4439 reflections	(Δ/σ)max = 0.043
295 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.19 e Å−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
Cl1	1.01028 (10)	0.71959 (8)	0.06769 (7)	0.0791 (3)
O1	0.5260 (2)	0.67479 (19)	0.72389 (18)	0.0698 (6)
O2	0.5879 (2)	0.87245 (18)	0.91481 (16)	0.0650 (5)
O3	0.4728 (3)	0.9785 (2)	0.69803 (19)	0.0759 (6)
N1	0.7774 (2)	0.82492 (19)	0.64046 (17)	0.0461 (5)
N2	0.5635 (2)	0.8158 (2)	0.53131 (18)	0.0502 (5)
C1	0.8327 (3)	0.6004 (3)	0.1915 (2)	0.0570 (7)
C2	0.7634 (3)	0.7335 (2)	0.4011 (2)	0.0441 (5)
C3	0.4957 (4)	0.7979 (4)	0.9770 (3)	0.0732 (9)
C4	0.9202 (4)	0.8525 (3)	0.3002 (2)	0.0606 (7)
C5	0.6794 (3)	0.7399 (2)	0.5138 (2)	0.0442 (5)
C6	0.9138 (3)	0.7244 (3)	0.1961 (2)	0.0538 (6)
C7	0.6788 (3)	0.8889 (2)	0.7346 (2)	0.0503 (6)
C8	0.5893 (3)	0.7974 (3)	0.7891 (2)	0.0502 (6)
C9	0.5592 (3)	0.9044 (2)	0.6558 (2)	0.0527 (6)
C10	0.7574 (3)	0.6052 (2)	0.2946 (2)	0.0507 (6)
C11	0.4526 (4)	0.7868 (3)	0.4255 (3)	0.0635 (7)
C12	0.8435 (3)	0.8565 (3)	0.4024 (2)	0.0559 (7)
C13	1.0021 (4)	0.7211 (4)	0.5907 (3)	0.0706 (8)
C14	0.8731 (3)	0.7538 (3)	0.6745 (2)	0.0555 (6)
C15	0.9604 (4)	0.8461 (4)	0.8118 (3)	0.0717 (8)
C16	1.1058 (4)	0.8014 (6)	0.8072 (4)	0.1159 (15)
H16A	1.1940	0.8836	0.8458	0.139*
H16B	1.1023	0.7511	0.8556	0.139*
C17	1.1201 (4)	0.7121 (5)	0.6750 (4)	0.1030 (12)
H17A	1.1022	0.6159	0.6581	0.124*
H17B	1.2224	0.7432	0.6574	0.124*
C18	0.5848 (5)	0.7287 (5)	1.0162 (4)	0.1136 (14)
H18A	0.5229	0.6808	1.0561	0.170*
H18B	0.6730	0.7974	1.0764	0.170*
H18C	0.6176	0.6619	0.9419	0.170*
C19	0.3480 (4)	0.6381 (3)	0.3616 (3)	0.0785 (9)
H19A	0.4093	0.5724	0.3275	0.094*
H19B	0.2937	0.6217	0.4255	0.094*
C20	0.2353 (5)	0.6120 (6)	0.2556 (4)	0.1300 (17)
H20A	0.1705	0.5173	0.2180	0.195*
H20B	0.2886	0.6256	0.1911	0.195*
H20C	0.1737	0.6762	0.2892	0.195*
H1	0.626 (2)	0.645 (2)	0.4965 (19)	0.032 (5)*
H2	0.697 (3)	0.519 (2)	0.297 (2)	0.041 (6)*
H3	0.734 (3)	0.979 (3)	0.802 (3)	0.067 (8)*
H4	0.392 (4)	0.738 (4)	0.923 (3)	0.096 (11)*
H5	0.826 (3)	0.513 (3)	0.115 (3)	0.073 (8)*
H6	0.972 (3)	0.937 (3)	0.310 (3)	0.073 (9)*
H7	0.806 (3)	0.668 (3)	0.667 (2)	0.051 (6)*
H8	0.497 (4)	0.796 (3)	0.365 (3)	0.082 (10)*
H9	0.952 (4)	0.624 (3)	0.516 (3)	0.091 (10)*
H10	0.842 (3)	0.951 (3)	0.476 (3)	0.075 (8)*
H11	0.908 (4)	0.827 (3)	0.868 (3)	0.090 (10)*
H12	0.470 (4)	0.875 (4)	1.053 (4)	0.098 (11)*
H13	0.375 (4)	0.834 (4)	0.460 (3)	0.107 (12)*
H14	1.051 (4)	0.812 (4)	0.585 (3)	0.100 (11)*
H15	0.982 (4)	0.953 (4)	0.834 (3)	0.091 (10)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0968 (6)	0.0929 (6)	0.0563 (4)	0.0280 (5)	0.0331 (4)	0.0418 (4)
O1	0.0915 (14)	0.0523 (11)	0.0569 (11)	0.0042 (10)	0.0224 (10)	0.0269 (9)
O2	0.0894 (14)	0.0616 (11)	0.0461 (9)	0.0212 (10)	0.0243 (9)	0.0274 (8)
O3	0.0993 (16)	0.0773 (13)	0.0715 (13)	0.0525 (12)	0.0327 (11)	0.0386 (11)
N1	0.0511 (11)	0.0486 (11)	0.0392 (9)	0.0109 (9)	0.0068 (8)	0.0231 (8)
N2	0.0523 (12)	0.0537 (11)	0.0478 (11)	0.0174 (9)	0.0079 (9)	0.0259 (9)
C1	0.0669 (17)	0.0512 (14)	0.0442 (13)	0.0164 (13)	0.0117 (12)	0.0160 (12)
C2	0.0476 (13)	0.0434 (12)	0.0386 (11)	0.0092 (10)	0.0040 (10)	0.0195 (10)
C3	0.098 (3)	0.077 (2)	0.0580 (17)	0.034 (2)	0.0333 (18)	0.0390 (16)
C4	0.082 (2)	0.0509 (15)	0.0496 (14)	0.0093 (14)	0.0154 (13)	0.0292 (13)
C5	0.0466 (13)	0.0408 (12)	0.0431 (12)	0.0079 (10)	0.0092 (10)	0.0206 (10)
C6	0.0582 (15)	0.0662 (16)	0.0408 (12)	0.0165 (12)	0.0115 (11)	0.0291 (12)
C7	0.0661 (16)	0.0399 (12)	0.0402 (12)	0.0088 (11)	0.0116 (11)	0.0185 (10)
C8	0.0585 (15)	0.0484 (14)	0.0449 (12)	0.0150 (12)	0.0134 (11)	0.0232 (11)
C9	0.0648 (16)	0.0467 (13)	0.0522 (14)	0.0180 (12)	0.0199 (12)	0.0268 (11)
C10	0.0552 (15)	0.0440 (13)	0.0485 (13)	0.0104 (11)	0.0102 (11)	0.0205 (11)
C11	0.0627 (18)	0.0772 (19)	0.0590 (17)	0.0239 (16)	0.0066 (14)	0.0375 (16)
C12	0.0757 (18)	0.0411 (13)	0.0445 (13)	0.0083 (12)	0.0145 (12)	0.0192 (11)
C13	0.074 (2)	0.081 (2)	0.0568 (17)	0.0360 (18)	0.0077 (15)	0.0262 (17)
C14	0.0581 (16)	0.0553 (15)	0.0593 (15)	0.0118 (13)	0.0038 (13)	0.0346 (13)
C15	0.073 (2)	0.100 (3)	0.0519 (16)	0.0268 (18)	0.0068 (14)	0.0434 (17)
C16	0.080 (3)	0.208 (5)	0.073 (2)	0.058 (3)	0.0089 (19)	0.070 (3)
C17	0.087 (3)	0.151 (3)	0.083 (2)	0.061 (3)	0.008 (2)	0.053 (2)
C18	0.129 (3)	0.156 (4)	0.120 (3)	0.067 (3)	0.041 (3)	0.104 (3)
C19	0.072 (2)	0.084 (2)	0.0719 (19)	0.0244 (17)	0.0029 (16)	0.0309 (17)
C20	0.087 (3)	0.165 (4)	0.110 (3)	0.025 (3)	−0.030 (2)	0.050 (3)

Cl1—C6	1.747 (3)	C11—C19	1.515 (5)
O1—C8	1.197 (3)	C11—H8	0.86 (3)
O2—C8	1.328 (3)	C11—H13	0.96 (4)
O2—C3	1.478 (3)	C12—H10	1.01 (3)
O3—C9	1.222 (3)	C13—C17	1.511 (5)
N1—C7	1.464 (3)	C13—C14	1.543 (4)
N1—C5	1.478 (3)	C13—H9	1.01 (3)
N1—C14	1.478 (3)	C13—H14	1.03 (4)
N2—C9	1.348 (3)	C14—C15	1.535 (4)
N2—C11	1.460 (4)	C14—H7	0.97 (2)
N2—C5	1.466 (3)	C15—C16	1.515 (5)
C1—C6	1.380 (4)	C15—H11	0.90 (3)
C1—C10	1.391 (3)	C15—H15	1.07 (3)
C1—H5	0.96 (3)	C16—C17	1.441 (5)
C2—C12	1.385 (3)	C16—H16A	0.9700
C2—C10	1.390 (3)	C16—H16B	0.9700
C2—C5	1.525 (3)	C17—H17A	0.9700
C3—C18	1.452 (5)	C17—H17B	0.9701
C3—H4	1.01 (4)	C18—H18A	0.9600
C3—H12	0.99 (4)	C18—H18B	0.9600
C4—C6	1.376 (4)	C18—H18C	0.9600
C4—C12	1.390 (4)	C19—C20	1.483 (5)
C4—H6	0.90 (3)	C19—H19A	0.9700
C5—H1	0.97 (2)	C19—H19B	0.9700
C7—C9	1.518 (4)	C20—H20A	0.9600
C7—C8	1.533 (3)	C20—H20B	0.9599
C7—H3	0.95 (3)	C20—H20C	0.9600
C10—H2	1.00 (2)
C8—O2—C3	116.5 (2)	C2—C12—C4	120.8 (2)
C7—N1—C5	106.60 (19)	C2—C12—H10	119.8 (16)
C7—N1—C14	116.08 (19)	C4—C12—H10	119.3 (16)
C5—N1—C14	115.95 (19)	C17—C13—C14	103.6 (3)
C9—N2—C11	123.2 (2)	C17—C13—H9	109.5 (18)
C9—N2—C5	113.4 (2)	C14—C13—H9	103.7 (19)
C11—N2—C5	123.1 (2)	C17—C13—H14	105 (2)
C6—C1—C10	119.3 (2)	C14—C13—H14	105.6 (19)
C6—C1—H5	118.8 (17)	H9—C13—H14	127 (3)
C10—C1—H5	121.8 (17)	N1—C14—C15	112.0 (2)
C12—C2—C10	119.2 (2)	N1—C14—C13	113.7 (2)
C12—C2—C5	120.1 (2)	C15—C14—C13	103.3 (2)
C10—C2—C5	120.7 (2)	N1—C14—H7	107.9 (14)
C18—C3—O2	110.8 (3)	C15—C14—H7	109.7 (14)
C18—C3—H4	117 (2)	C13—C14—H7	110.2 (14)
O2—C3—H4	111 (2)	C16—C15—C14	104.7 (3)
C18—C3—H12	111 (2)	C16—C15—H11	107 (2)
O2—C3—H12	103 (2)	C14—C15—H11	111 (2)
H4—C3—H12	103 (3)	C16—C15—H15	113.1 (18)
C6—C4—C12	119.1 (2)	C14—C15—H15	107.8 (18)
C6—C4—H6	125.9 (19)	H11—C15—H15	113 (3)
C12—C4—H6	115.0 (19)	C17—C16—C15	109.3 (3)
N2—C5—N1	101.47 (18)	C17—C16—H16A	109.8
N2—C5—C2	110.85 (19)	C15—C16—H16A	109.8
N1—C5—C2	113.85 (19)	C17—C16—H16B	109.8
N2—C5—H1	107.4 (12)	C15—C16—H16B	109.8
N1—C5—H1	113.1 (12)	H16A—C16—H16B	108.3
C2—C5—H1	109.7 (12)	C16—C17—C13	107.5 (3)
C4—C6—C1	121.2 (2)	C16—C17—H17A	110.2
C4—C6—Cl1	119.1 (2)	C13—C17—H17A	110.2
C1—C6—Cl1	119.7 (2)	C16—C17—H17B	110.2
N1—C7—C9	103.22 (19)	C13—C17—H17B	110.2
N1—C7—C8	115.3 (2)	H17A—C17—H17B	108.5
C9—C7—C8	105.8 (2)	C3—C18—H18A	109.5
N1—C7—H3	111.6 (16)	C3—C18—H18B	109.5
C9—C7—H3	109.3 (16)	H18A—C18—H18B	109.5
C8—C7—H3	111.0 (16)	C3—C18—H18C	109.5
O1—C8—O2	125.5 (2)	H18A—C18—H18C	109.5
O1—C8—C7	123.1 (2)	H18B—C18—H18C	109.5
O2—C8—C7	111.4 (2)	C20—C19—C11	111.8 (3)
O3—C9—N2	127.3 (3)	C20—C19—H19A	109.3
O3—C9—C7	126.4 (2)	C11—C19—H19A	109.3
N2—C9—C7	106.2 (2)	C20—C19—H19B	109.3
C2—C10—C1	120.4 (2)	C11—C19—H19B	109.3
C2—C10—H2	116.7 (12)	H19A—C19—H19B	107.9
C1—C10—H2	122.9 (12)	C19—C20—H20A	109.5
N2—C11—C19	112.9 (3)	C19—C20—H20B	109.5
N2—C11—H8	112 (2)	H20A—C20—H20B	109.5
C19—C11—H8	106 (2)	C19—C20—H20C	109.5
N2—C11—H13	109 (2)	H20A—C20—H20C	109.5
C19—C11—H13	97 (2)	H20B—C20—H20C	109.5
H8—C11—H13	119 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H2···O1i	1.00 (2)	2.50 (3)	3.454 (4)	160 (2)
C3—H12···O3ii	0.99 (4)	2.59 (4)	3.439 (5)	143 (3)
C16—H16B···Cl1iii	0.97	2.80	3.662 (6)	148

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C10H2O1i	1.00(2)	2.50(3)	3.454(4)	160(2)
C3H12O3ii	0.99(4)	2.59(4)	3.439(5)	143(3)
C16H16BCl1iii	0.97	2.80	3.662(6)	148

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