The structure of the title compound, C11H14Cl3NO, is stabilized by intra- and intermolecular hydrogen bonds. The cyclopentene ring adopts an envelope conformation while the pyrrolidinyl moiety adopts a twist conformation.
Supporting information
CCDC reference: 214838
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.004 Å
- R factor = 0.040
- wR factor = 0.124
- Data-to-parameter ratio = 17.9
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
A solution of freshly distilled trichloroacetyl chloride (17.8 mmol, 3.23 g) in dry ether was added dropwise over a period of 1 h to a cooled mixture (in an ice–salt bath) of triethylamine (17.8 mmol, 1.80 g) and 1-(1-pyrrolidinyl)cyclopentene (17.8 mmol, 2.69 g) in 50 ml anhydrous ether while stirring under a nitrogen atmosphere. The reaction mixture was stirred overnight then ammonium chloride was removed by filtration and the solvent was evaporated under reduced procedure. The residue was dissolved in hexane, dried over MgSO4, filtered and then the solvent was evaporated. The crude product was recrystallized from hexane to give 2.74 g (55%) 2-trichloroacetyl-1-(1-pyrrolidinyl)cyclopentene as a pure yellow solid. M.p. 363 K; IR (KBr): 1624 (C═O), 1520 (C═C) cm−1; 1H NMR: δ 2.90–3.00 (t, 4H, NCH2), 2.50–2.65 (t, 4H, NCH2CH2), 1.90–2.00 (m, 4H, CH2CH2CH2), 1.75–1.85 (m, 2H, CH2CH2CH2).
H atoms were placed geometrically 0.97 Å from their parent atoms and their displacement parameters were refined isotropically.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 1990).
Crystal data top
C11H14Cl3NO | Dx = 1.462 Mg m−3 |
Mr = 282.58 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 25 reflections |
a = 11.4236 (10) Å | θ = 10.2–18.2° |
b = 10.2623 (9) Å | µ = 0.69 mm−1 |
c = 21.899 (3) Å | T = 295 K |
V = 2567.3 (5) Å3 | Prism, light yellow |
Z = 8 | 0.48 × 0.48 × 0.12 mm |
F(000) = 1168 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.029 |
ω/2θ scans | θmax = 26.3°, θmin = 2.6° |
Absorption correction: empirical (using intensity measurements) ψ scan (North et al., 1968) | h = 0→14 |
Tmin = 0.732, Tmax = 0.922 | k = −12→12 |
5032 measured reflections | l = −27→0 |
2597 independent reflections | 3 standard reflections every 120 min |
1823 reflections with I > 2σ(I) | intensity decay: 3% |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.0651P)2 + 0.494P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.124 | (Δ/σ)max = 0.001 |
S = 1.08 | Δρmax = 0.32 e Å−3 |
2597 reflections | Δρmin = −0.28 e Å−3 |
145 parameters | |
Crystal data top
C11H14Cl3NO | V = 2567.3 (5) Å3 |
Mr = 282.58 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.4236 (10) Å | µ = 0.69 mm−1 |
b = 10.2623 (9) Å | T = 295 K |
c = 21.899 (3) Å | 0.48 × 0.48 × 0.12 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1823 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ scan (North et al., 1968) | Rint = 0.029 |
Tmin = 0.732, Tmax = 0.922 | 3 standard reflections every 120 min |
5032 measured reflections | intensity decay: 3% |
2597 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.32 e Å−3 |
2597 reflections | Δρmin = −0.28 e Å−3 |
145 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.9731 (2) | 0.2548 (2) | −0.67784 (10) | 0.0501 (6) | |
C2 | 0.98078 (19) | 0.2878 (2) | −0.60772 (9) | 0.0431 (5) | |
C3 | 1.0816 (2) | 0.3516 (2) | −0.58535 (10) | 0.0465 (5) | |
C4 | 1.1721 (2) | 0.4275 (3) | −0.62241 (12) | 0.0667 (7) | |
H4A | 1.1381 | 0.4625 | −0.6595 | 0.08* | |
H4B | 1.2386 | 0.3731 | −0.6329 | 0.08* | |
C5 | 1.2078 (3) | 0.5368 (3) | −0.57850 (14) | 0.0760 (8) | |
H5A | 1.2882 | 0.5631 | −0.5857 | 0.091* | |
H5B | 1.1573 | 0.6121 | −0.5835 | 0.091* | |
C6 | 1.1942 (2) | 0.4793 (2) | −0.51507 (12) | 0.0579 (6) | |
H6A | 1.2681 | 0.4451 | −0.5003 | 0.07* | |
H6B | 1.1658 | 0.5442 | −0.4865 | 0.07* | |
C7 | 1.10581 (18) | 0.3716 (2) | −0.52342 (11) | 0.0448 (5) | |
C8 | 1.1101 (2) | 0.3374 (3) | −0.41216 (11) | 0.0614 (7) | |
H8A | 1.0792 | 0.4211 | −0.3995 | 0.074* | |
H8B | 1.1949 | 0.3397 | −0.4096 | 0.074* | |
C9 | 1.0613 (4) | 0.2298 (4) | −0.37376 (13) | 0.0919 (10) | |
H9A | 1.1142 | 0.2091 | −0.3405 | 0.11* | |
H9B | 0.9862 | 0.2547 | −0.3567 | 0.11* | |
C10 | 1.0481 (4) | 0.1171 (3) | −0.41488 (12) | 0.0835 (10) | |
H10A | 0.9861 | 0.06 | −0.4008 | 0.1* | |
H10B | 1.1204 | 0.0677 | −0.4172 | 0.1* | |
C11 | 1.0178 (2) | 0.1750 (2) | −0.47640 (11) | 0.0583 (6) | |
H11A | 1.0501 | 0.1229 | −0.5093 | 0.07* | |
H11B | 0.9336 | 0.1811 | −0.4816 | 0.07* | |
Cl1 | 0.86432 (7) | 0.13690 (8) | −0.69227 (3) | 0.0681 (2) | |
Cl2 | 1.10738 (7) | 0.19236 (8) | −0.70669 (3) | 0.0729 (3) | |
Cl3 | 0.93559 (8) | 0.39891 (7) | −0.71824 (3) | 0.0804 (3) | |
N1 | 1.07128 (16) | 0.30468 (19) | −0.47504 (8) | 0.0464 (4) | |
O1 | 0.89261 (14) | 0.26091 (18) | −0.57823 (7) | 0.0565 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0637 (14) | 0.0508 (12) | 0.0358 (11) | 0.0122 (12) | 0.0004 (10) | 0.0018 (9) |
C2 | 0.0514 (12) | 0.0421 (11) | 0.0357 (10) | 0.0048 (10) | 0.0032 (9) | −0.0003 (9) |
C3 | 0.0478 (12) | 0.0438 (11) | 0.0481 (12) | 0.0016 (10) | 0.0052 (9) | 0.0019 (10) |
C4 | 0.0617 (16) | 0.0762 (18) | 0.0622 (16) | −0.0130 (14) | 0.0138 (13) | 0.0049 (13) |
C5 | 0.0642 (17) | 0.0676 (18) | 0.096 (2) | −0.0189 (15) | 0.0049 (15) | 0.0087 (16) |
C6 | 0.0462 (12) | 0.0525 (14) | 0.0751 (17) | −0.0040 (11) | −0.0019 (11) | −0.0090 (12) |
C7 | 0.0393 (11) | 0.0441 (12) | 0.0510 (12) | 0.0054 (9) | −0.0002 (9) | −0.0073 (10) |
C8 | 0.0660 (16) | 0.0733 (17) | 0.0450 (13) | 0.0065 (13) | −0.0107 (11) | −0.0185 (12) |
C9 | 0.124 (3) | 0.109 (3) | 0.0433 (15) | −0.004 (2) | −0.0101 (17) | 0.0026 (16) |
C10 | 0.128 (3) | 0.0701 (19) | 0.0522 (16) | 0.0028 (19) | −0.0050 (17) | 0.0112 (14) |
C11 | 0.0770 (17) | 0.0523 (14) | 0.0456 (12) | −0.0077 (13) | 0.0011 (11) | −0.0012 (10) |
Cl1 | 0.0849 (5) | 0.0712 (4) | 0.0483 (4) | −0.0035 (4) | −0.0106 (3) | −0.0133 (3) |
Cl2 | 0.0799 (5) | 0.0866 (5) | 0.0523 (4) | 0.0188 (4) | 0.0131 (3) | −0.0133 (3) |
Cl3 | 0.1183 (7) | 0.0656 (4) | 0.0574 (4) | 0.0201 (4) | −0.0095 (4) | 0.0172 (3) |
N1 | 0.0499 (10) | 0.0484 (10) | 0.0410 (9) | −0.0006 (9) | −0.0037 (8) | −0.0088 (8) |
O1 | 0.0538 (9) | 0.0763 (12) | 0.0393 (8) | −0.0105 (9) | 0.0023 (7) | −0.0092 (8) |
Geometric parameters (Å, º) top
C1—C2 | 1.575 (3) | C6—H6B | 0.97 |
C1—Cl1 | 1.763 (3) | C7—N1 | 1.322 (3) |
C1—Cl3 | 1.776 (2) | C8—N1 | 1.485 (3) |
C1—Cl2 | 1.778 (2) | C8—C9 | 1.496 (4) |
C2—O1 | 1.228 (3) | C8—H8A | 0.97 |
C2—C3 | 1.412 (3) | C8—H8B | 0.97 |
C3—C7 | 1.399 (3) | C9—C10 | 1.474 (4) |
C3—C4 | 1.528 (3) | C9—H9A | 0.97 |
C4—C5 | 1.532 (4) | C9—H9B | 0.97 |
C4—H4A | 0.97 | C10—C11 | 1.513 (4) |
C4—H4B | 0.97 | C10—H10A | 0.97 |
C5—C6 | 1.517 (4) | C10—H10B | 0.97 |
C5—H5A | 0.97 | C11—N1 | 1.465 (3) |
C5—H5B | 0.97 | C11—H11A | 0.97 |
C6—C7 | 1.509 (3) | C11—H11B | 0.97 |
C6—H6A | 0.97 | | |
| | | |
C2—C1—Cl1 | 111.19 (16) | N1—C7—C3 | 129.9 (2) |
C2—C1—Cl3 | 108.69 (16) | N1—C7—C6 | 118.9 (2) |
Cl1—C1—Cl3 | 108.19 (13) | C3—C7—C6 | 110.9 (2) |
C2—C1—Cl2 | 112.06 (16) | N1—C8—C9 | 104.1 (2) |
Cl1—C1—Cl2 | 107.27 (13) | N1—C8—H8A | 110.9 |
Cl3—C1—Cl2 | 109.35 (13) | C9—C8—H8A | 110.9 |
O1—C2—C3 | 126.2 (2) | N1—C8—H8B | 110.9 |
O1—C2—C1 | 114.77 (19) | C9—C8—H8B | 110.9 |
C3—C2—C1 | 118.9 (2) | H8A—C8—H8B | 109 |
C7—C3—C2 | 124.4 (2) | C10—C9—C8 | 105.9 (2) |
C7—C3—C4 | 107.8 (2) | C10—C9—H9A | 110.6 |
C2—C3—C4 | 127.2 (2) | C8—C9—H9A | 110.6 |
C3—C4—C5 | 102.7 (2) | C10—C9—H9B | 110.6 |
C3—C4—H4A | 111.2 | C8—C9—H9B | 110.6 |
C5—C4—H4A | 111.2 | H9A—C9—H9B | 108.7 |
C3—C4—H4B | 111.2 | C9—C10—C11 | 105.0 (2) |
C5—C4—H4B | 111.2 | C9—C10—H10A | 110.7 |
H4A—C4—H4B | 109.1 | C11—C10—H10A | 110.7 |
C6—C5—C4 | 105.2 (2) | C9—C10—H10B | 110.7 |
C6—C5—H5A | 110.7 | C11—C10—H10B | 110.7 |
C4—C5—H5A | 110.7 | H10A—C10—H10B | 108.8 |
C6—C5—H5B | 110.7 | N1—C11—C10 | 104.1 (2) |
C4—C5—H5B | 110.7 | N1—C11—H11A | 110.9 |
H5A—C5—H5B | 108.8 | C10—C11—H11A | 110.9 |
C7—C6—C5 | 104.0 (2) | N1—C11—H11B | 110.9 |
C7—C6—H6A | 110.9 | C10—C11—H11B | 110.9 |
C5—C6—H6A | 110.9 | H11A—C11—H11B | 109 |
C7—C6—H6B | 110.9 | C7—N1—C11 | 125.44 (19) |
C5—C6—H6B | 110.9 | C7—N1—C8 | 122.4 (2) |
H6A—C6—H6B | 109 | C11—N1—C8 | 110.40 (19) |
| | | |
Cl1—C1—C2—O1 | −21.2 (2) | C2—C3—C7—C6 | −160.4 (2) |
Cl3—C1—C2—O1 | 97.8 (2) | C4—C3—C7—C6 | 11.4 (3) |
Cl2—C1—C2—O1 | −141.23 (18) | C5—C6—C7—N1 | −177.4 (2) |
Cl1—C1—C2—C3 | 162.98 (17) | C5—C6—C7—C3 | 8.2 (3) |
Cl3—C1—C2—C3 | −78.0 (2) | N1—C8—C9—C10 | 25.6 (3) |
Cl2—C1—C2—C3 | 42.9 (3) | C8—C9—C10—C11 | −33.3 (4) |
O1—C2—C3—C7 | 13.1 (4) | C9—C10—C11—N1 | 27.4 (3) |
C1—C2—C3—C7 | −171.5 (2) | C3—C7—N1—C11 | 13.8 (4) |
O1—C2—C3—C4 | −157.1 (2) | C6—C7—N1—C11 | −159.4 (2) |
C1—C2—C3—C4 | 18.2 (3) | C3—C7—N1—C8 | 177.4 (2) |
C7—C3—C4—C5 | −26.0 (3) | C6—C7—N1—C8 | 4.2 (3) |
C2—C3—C4—C5 | 145.6 (2) | C10—C11—N1—C7 | 153.6 (2) |
C3—C4—C5—C6 | 30.5 (3) | C10—C11—N1—C8 | −11.7 (3) |
C4—C5—C6—C7 | −24.2 (3) | C9—C8—N1—C7 | −174.1 (2) |
C2—C3—C7—N1 | 26.0 (4) | C9—C8—N1—C11 | −8.3 (3) |
C4—C3—C7—N1 | −162.2 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···Cl3 | 0.97 | 2.73 | 3.434 (3) | 130 |
C6—H6B···O1i | 0.97 | 2.54 | 3.502 (3) | 171 |
C8—H8B···O1ii | 0.97 | 2.50 | 3.388 (4) | 152 |
C11—H11B···O1 | 0.97 | 2.32 | 2.792 (3) | 109 |
Symmetry codes: (i) −x+2, −y+1, −z−1; (ii) x+1/2, −y+1/2, −z−1. |
Experimental details
Crystal data |
Chemical formula | C11H14Cl3NO |
Mr | 282.58 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 295 |
a, b, c (Å) | 11.4236 (10), 10.2623 (9), 21.899 (3) |
V (Å3) | 2567.3 (5) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.48 × 0.48 × 0.12 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) ψ scan (North et al., 1968) |
Tmin, Tmax | 0.732, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5032, 2597, 1823 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.623 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.124, 1.08 |
No. of reflections | 2597 |
No. of parameters | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.28 |
Selected geometric parameters (Å, º) topC1—C2 | 1.575 (3) | C5—C6 | 1.517 (4) |
C1—Cl1 | 1.763 (3) | C6—C7 | 1.509 (3) |
C1—Cl3 | 1.776 (2) | C7—N1 | 1.322 (3) |
C1—Cl2 | 1.778 (2) | C8—N1 | 1.485 (3) |
C2—O1 | 1.228 (3) | C8—C9 | 1.496 (4) |
C2—C3 | 1.412 (3) | C9—C10 | 1.474 (4) |
C3—C7 | 1.399 (3) | C10—C11 | 1.513 (4) |
C3—C4 | 1.528 (3) | C11—N1 | 1.465 (3) |
C4—C5 | 1.532 (4) | | |
| | | |
C2—C1—Cl1 | 111.19 (16) | N1—C7—C3 | 129.9 (2) |
C2—C1—Cl3 | 108.69 (16) | N1—C7—C6 | 118.9 (2) |
C2—C1—Cl2 | 112.06 (16) | C3—C7—C6 | 110.9 (2) |
O1—C2—C3 | 126.2 (2) | N1—C8—C9 | 104.1 (2) |
O1—C2—C1 | 114.77 (19) | C10—C9—C8 | 105.9 (2) |
C7—C3—C2 | 124.4 (2) | C9—C10—C11 | 105.0 (2) |
C2—C3—C4 | 127.2 (2) | N1—C11—C10 | 104.1 (2) |
C3—C4—C5 | 102.7 (2) | C7—N1—C11 | 125.44 (19) |
C6—C5—C4 | 105.2 (2) | C7—N1—C8 | 122.4 (2) |
C7—C6—C5 | 104.0 (2) | C11—N1—C8 | 110.40 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···Cl3 | 0.97 | 2.73 | 3.434 (3) | 130 |
C6—H6B···O1i | 0.97 | 2.54 | 3.502 (3) | 171 |
C8—H8B···O1ii | 0.97 | 2.50 | 3.388 (4) | 152 |
C11—H11B···O1 | 0.97 | 2.32 | 2.792 (3) | 109 |
Symmetry codes: (i) −x+2, −y+1, −z−1; (ii) x+1/2, −y+1/2, −z−1. |
Besides the well known methods for the acylation of enamines (Cook, 1969), we have recently investigated the synthesis of α- and α'-diacetylated enamino ketones under the presence of zinc, which is an unusual catalyst for the acylation reactions (Şenöz & Tuno¯glu, 2003). The crystal structures of 2,6-bis(trichloroacetyl)-1-(1-morpholinyl)cyclohexene and 2,6-bis(trichloroacetyl)cyclohexanone have been reported elsewhere (Özbey et al., 2000, 2003). Zinc catalyses ketene formations over [2 + 2]-cycloaddition reactions (Şenöz & Yıldırır, 1996; Brady, 1981), however, we have obtained diacetylated product, 2,6-bis((trichloroacetyl)-1-(1-pyrrolidinyl)cyclopentene by the corresponding cyclic enaminoketone, 1-(1-pyrrolidinyl)cyclopentene, with zinc catalyst. The same enamine yielded monoacetylated product, 2-trichloroacetyl-1-(1-pyrrolidinyl)cyclopentene by the effect of triethylamine used to prevent salt formation without using zinc, as in the literature.
Here we report the crystal structure of 2-trichloroacetyl-1-(1-pyrrolidinyl)cyclopentene, (I), obtained by the reaction of 1-(1-pyrrolidinyl)cyclopentene with trichloroacetyl chloride. The X-ray crystal analysis shows that the cyclopentene ring adopts a half-chair conformation, twisted at C5. Atom C5 is displaced from the C3/C4/C6/C7 mean plane by −0.430 (3) Å. The puckering parameters (Cremer & Pople, 1975) of this ring are Q = 0.299 (3) Å and θ = 232.1 (5)°. The pyrrolidinyl moiety deviates from the half-chair conformation by the ring-puckering parameters of Q = 0.309 (4) Å and θ = 273.0 (5)°. The ketone group at C3 and the pyrolidinyl ring at C7 are slightly twisted in opposite directions, with torsion angles C1—C2—C3—C7 and C3—C7—N1—C8 of −171.5 (2) and 177.4 (2)°, respectively. The hydrogen-bond interaction between atoms O1 and C11 can be caused the planarity of this part of the molecule.
The molecule stabilizes with inter- and intramolecular hydrogen bonds. Details of the hydrogen-bonding geometry are given in Table 2.