Trimethyl 5-(2-chloro-4-fluoro­phen­yl)-2-phenyl­pyrrolidine-2,3,4-tricarboxyl­ate

He, L.; Chen, L.-M.

doi:10.1107/S1600536809044274

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2927

https://doi.org/10.1107/S1600536809044274

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Trimethyl 5-(2-chloro-4-fluorophenyl)-2-phenylpyrrolidine-2,3,4-tricarboxylate

Long He ^a ^* and Lian-Mei Chen ^a

^aCollege of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, People's Republic of China
^*Correspondence e-mail: helongcwnu@yahoo.com.cn

(Received 24 October 2009; accepted 24 October 2009; online 31 October 2009)

The title compound, C₂₂H₂₁ClFNO₆, was synthesized by the 1,3-dipolar cycloaddition reaction of dimethyl maleate, methyl 2-amino-2-phenylacetate and 2-chloro-4-fluorobenzaldehyde. The pyrrolidine ring possesses an envelope conformation and the two benzene rings are oriented at a dihedral angle of 68.28 (7)°. Weak intermolecular C—H⋯O hydrogen bonding is present in the crystal structure. One methyl group is disordered over two positions with a site-occupancy ratio of 0.651 (12):0.349 (12).

Related literature

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

Experimental

Crystal data

C₂₂H₂₁ClFNO₆
M_r = 449.85
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.474 (3) Å
b = 15.057 (8) Å
c = 15.182 (5) Å
V = 2165.7 (15) Å³
Z = 4
Cu Kα radiation
μ = 1.98 mm⁻¹
T = 298 K
0.38 × 0.36 × 0.03 mm

Data collection

Oxford Diffraction Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.520, T_max = 0.943
32943 measured reflections
3442 independent reflections
3332 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.060
S = 1.05
3442 reflections
290 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1456 Friedel pairs
Flack parameter: −0.001 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O5ⁱ	0.93	2.56	3.380 (3)	147
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809044274/xu2655sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044274/xu2655Isup2.hkl

checkCIF report

Comment top

Substituted pyrrolidine compound is an important class of heterocyclic compounds with wide spread applications to the synthesis of biologically active compounds and natural products (Coldham et al., 2005; Nair et al., 2007; Pandey et al., 2006; Sardina et al., 1996; Witherup et al. 1995).

The molecular structure of (I) is shown in Fig. 1. Bond lengths and angles in (I) are normal. The pyrrolidine ring possesses an envelope conformation. The dihedral angle between the C1—C6 and C11—C16 benzene planes is 68.28 (7)°.

Related literature top

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

Experimental top

2-Chloro-4-fluorobenzaldehyde (0.063 g, 0.4 mmol), anhydrous sodium sulfate (200 mg) and dimethyl maleate (0.029 g, 0.2 mmol) were added to a solution of methyl 2-amino-2-phenylacetate(0.049 g, 0.3 mmol) in chloroform (2 ml). To the stirred mixture, acetic acid (0.012 g, 0.2 mmol) was added. After the mixture had been stirred at 323k for 10 h, the reaction was quenched with a saturated solution of sodium bicarbonate (5 ml). The mixture was extracted with diethyl ether, evaporated and separated by flash chromatograghy. A colourless powder was obtained. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution.

Structure description top

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

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms).

Trimethyl 5-(2-chloro-4-fluorophenyl)-2-phenylpyrrolidine-2,3,4-tricarboxylate top

Crystal data top

C₂₂H₂₁ClFNO₆	F(000) = 936
M_r = 449.85	D_x = 1.380 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2ac 2ab	Cell parameters from 23516 reflections
a = 9.474 (3) Å	θ = 2.9–62.8°
b = 15.057 (8) Å	µ = 1.98 mm⁻¹
c = 15.182 (5) Å	T = 298 K
V = 2165.7 (15) Å³	Platelet, colourless
Z = 4	0.38 × 0.36 × 0.03 mm

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	3442 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	3332 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 15.9149 pixels mm^-1	θ_max = 62.6°, θ_min = 4.1°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −17→17
T_min = 0.520, T_max = 0.943	l = −17→17
32943 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.024	w = 1/[σ²(F_o²) + (0.0318P)² + 0.3155P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.060	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.12 e Å⁻³
3442 reflections	Δρ_min = −0.16 e Å⁻³
290 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0055 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1456 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.001 (11)

Crystal data top

C₂₂H₂₁ClFNO₆	V = 2165.7 (15) Å³
M_r = 449.85	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 9.474 (3) Å	µ = 1.98 mm⁻¹
b = 15.057 (8) Å	T = 298 K
c = 15.182 (5) Å	0.38 × 0.36 × 0.03 mm

Data collection top

Oxford Diffraction Gemini S Ultra diffractometer	3442 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	3332 reflections with I > 2σ(I)
T_min = 0.520, T_max = 0.943	R_int = 0.025
32943 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.060	Δρ_max = 0.12 e Å⁻³
S = 1.05	Δρ_min = −0.16 e Å⁻³
3442 reflections	Absolute structure: Flack (1983), 1456 Friedel pairs
290 parameters	Absolute structure parameter: −0.001 (11)
1 restraint

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.

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	Occ. (<1)
Cl1	0.87819 (6)	0.40571 (3)	0.69190 (3)	0.06039 (14)
F1	1.10815 (14)	0.42498 (8)	0.39470 (7)	0.0789 (4)
O1	0.64936 (15)	0.70388 (7)	0.55124 (8)	0.0578 (3)
O2	0.59938 (18)	0.55992 (8)	0.53671 (8)	0.0715 (4)
O3	0.50206 (14)	0.80786 (9)	0.73253 (11)	0.0735 (4)
O4	0.41937 (11)	0.67622 (8)	0.68953 (9)	0.0568 (3)
O5	0.79799 (13)	0.86655 (7)	0.67762 (8)	0.0553 (3)
O6	0.74501 (13)	0.87248 (7)	0.82137 (7)	0.0509 (3)
N1	0.89048 (14)	0.69866 (8)	0.69034 (9)	0.0390 (3)
H1	0.870 (2)	0.7278 (11)	0.6438 (12)	0.047*
C1	1.0498 (2)	0.46980 (13)	0.46390 (11)	0.0546 (4)
C2	1.00115 (19)	0.42137 (12)	0.53368 (11)	0.0500 (4)
H2	1.0094	0.3598	0.5350	0.060*
C3	0.93922 (17)	0.46752 (10)	0.60228 (10)	0.0417 (4)
C4	0.92532 (15)	0.55915 (10)	0.60251 (10)	0.0386 (3)
C5	0.98023 (19)	0.60471 (12)	0.53049 (11)	0.0509 (4)
H5	0.9745	0.6664	0.5293	0.061*
C6	1.0431 (2)	0.56086 (13)	0.46054 (12)	0.0588 (5)
H6	1.0796	0.5921	0.4128	0.071*
C7	0.85178 (16)	0.60535 (9)	0.67778 (9)	0.0379 (3)
H7	0.8783	0.5738	0.7318	0.045*
C8	0.68738 (15)	0.60534 (10)	0.67347 (10)	0.0393 (3)
H8	0.6491	0.5473	0.6902	0.047*
C9	0.65018 (15)	0.67691 (10)	0.74326 (10)	0.0390 (3)
H9	0.6296	0.6450	0.7980	0.047*
C10	0.79423 (16)	0.72962 (10)	0.75935 (10)	0.0372 (3)
C11	0.85468 (17)	0.70603 (9)	0.85036 (10)	0.0386 (3)
C12	0.99477 (17)	0.68067 (11)	0.86012 (11)	0.0468 (4)
H12	1.0537	0.6788	0.8111	0.056*
C13	1.0475 (2)	0.65805 (12)	0.94231 (13)	0.0589 (5)
H13	1.1410	0.6401	0.9477	0.071*
C14	0.9633 (2)	0.66181 (12)	1.01602 (12)	0.0604 (5)
H14	0.9992	0.6464	1.0710	0.073*
C15	0.8256 (2)	0.68856 (12)	1.00731 (12)	0.0565 (5)
H15	0.7685	0.6928	1.0569	0.068*
C16	0.77124 (19)	0.70915 (11)	0.92558 (11)	0.0478 (4)
H16	0.6769	0.7254	0.9207	0.057*
C17	0.77865 (16)	0.83067 (10)	0.74725 (11)	0.0409 (3)
C18	0.7123 (2)	0.96590 (11)	0.81177 (15)	0.0666 (5)
H18A	0.7012	0.9922	0.8690	0.100*
H18B	0.6263	0.9724	0.7790	0.100*
H18C	0.7878	0.9950	0.7810	0.100*
C19	0.51912 (18)	0.73007 (12)	0.72121 (11)	0.0462 (4)
C20	0.2893 (2)	0.71857 (16)	0.66086 (19)	0.0810 (7)
H20A	0.2229	0.6739	0.6429	0.121*
H20B	0.3088	0.7573	0.6121	0.121*
H20C	0.2502	0.7524	0.7086	0.121*
C21	0.64215 (18)	0.63050 (10)	0.58152 (10)	0.0442 (4)
C22A	0.5863 (10)	0.5705 (4)	0.4390 (3)	0.0813 (19)	0.651 (12)
H22A	0.6715	0.5505	0.4112	0.122*	0.651 (12)
H22B	0.5708	0.6319	0.4251	0.122*	0.651 (12)
H22C	0.5081	0.5358	0.4181	0.122*	0.651 (12)
C22B	0.5167 (16)	0.5848 (8)	0.4569 (7)	0.0813 (19)	0.349 (12)
H22D	0.4260	0.6070	0.4744	0.122*	0.349 (12)
H22E	0.5046	0.5335	0.4201	0.122*	0.349 (12)
H22F	0.5664	0.6300	0.4248	0.122*	0.349 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0909 (3)	0.0400 (2)	0.0503 (2)	0.0019 (2)	0.0084 (2)	0.00626 (17)
F1	0.0926 (9)	0.0837 (8)	0.0604 (6)	0.0170 (7)	0.0228 (6)	−0.0173 (6)
O1	0.0762 (9)	0.0468 (7)	0.0505 (7)	−0.0035 (6)	−0.0099 (6)	0.0073 (5)
O2	0.1081 (12)	0.0502 (7)	0.0562 (7)	−0.0174 (7)	−0.0325 (7)	0.0010 (6)
O3	0.0495 (7)	0.0544 (8)	0.1167 (13)	0.0096 (6)	−0.0117 (7)	−0.0141 (8)
O4	0.0371 (6)	0.0568 (7)	0.0766 (8)	−0.0006 (5)	−0.0088 (6)	−0.0026 (7)
O5	0.0692 (8)	0.0449 (6)	0.0519 (7)	0.0018 (5)	0.0049 (6)	0.0112 (5)
O6	0.0651 (8)	0.0368 (5)	0.0507 (6)	0.0065 (5)	−0.0016 (6)	−0.0044 (5)
N1	0.0423 (7)	0.0352 (6)	0.0393 (6)	−0.0019 (5)	0.0035 (6)	−0.0011 (5)
C1	0.0541 (10)	0.0627 (11)	0.0468 (10)	0.0104 (9)	0.0073 (8)	−0.0100 (8)
C2	0.0556 (10)	0.0442 (9)	0.0502 (9)	0.0081 (8)	−0.0030 (8)	−0.0062 (7)
C3	0.0452 (9)	0.0401 (8)	0.0399 (8)	0.0012 (7)	−0.0021 (7)	0.0014 (6)
C4	0.0372 (8)	0.0399 (8)	0.0387 (8)	0.0003 (6)	−0.0026 (6)	0.0005 (6)
C5	0.0582 (10)	0.0446 (9)	0.0499 (9)	0.0028 (8)	0.0104 (8)	0.0041 (7)
C6	0.0666 (12)	0.0620 (12)	0.0478 (10)	0.0016 (10)	0.0155 (9)	0.0046 (8)
C7	0.0412 (8)	0.0349 (7)	0.0376 (7)	−0.0011 (6)	0.0000 (6)	0.0004 (6)
C8	0.0409 (8)	0.0351 (7)	0.0419 (8)	−0.0020 (6)	−0.0008 (6)	0.0021 (6)
C9	0.0374 (8)	0.0407 (8)	0.0389 (8)	−0.0026 (7)	0.0007 (7)	0.0022 (6)
C10	0.0365 (8)	0.0372 (8)	0.0380 (8)	0.0002 (6)	0.0017 (6)	0.0001 (6)
C11	0.0420 (8)	0.0329 (7)	0.0410 (8)	−0.0010 (6)	−0.0030 (7)	0.0002 (6)
C12	0.0405 (9)	0.0459 (9)	0.0541 (10)	−0.0006 (7)	−0.0036 (7)	−0.0052 (7)
C13	0.0521 (11)	0.0548 (10)	0.0697 (12)	0.0039 (9)	−0.0210 (10)	0.0005 (9)
C14	0.0737 (14)	0.0547 (11)	0.0529 (11)	−0.0088 (10)	−0.0200 (10)	0.0087 (9)
C15	0.0655 (12)	0.0618 (10)	0.0421 (9)	−0.0092 (9)	−0.0007 (8)	0.0058 (8)
C16	0.0450 (9)	0.0541 (9)	0.0443 (9)	0.0005 (7)	0.0005 (7)	0.0030 (7)
C17	0.0386 (8)	0.0377 (8)	0.0465 (9)	−0.0006 (6)	−0.0021 (7)	0.0002 (7)
C18	0.0837 (13)	0.0395 (9)	0.0766 (13)	0.0132 (9)	−0.0060 (12)	−0.0070 (9)
C19	0.0404 (9)	0.0466 (10)	0.0517 (9)	0.0001 (7)	0.0018 (7)	−0.0010 (7)
C20	0.0436 (11)	0.0816 (15)	0.1177 (19)	0.0075 (10)	−0.0185 (12)	−0.0039 (14)
C21	0.0432 (9)	0.0443 (9)	0.0450 (8)	−0.0014 (7)	−0.0051 (7)	−0.0002 (7)
C22A	0.126 (6)	0.070 (2)	0.0474 (18)	−0.010 (3)	−0.027 (2)	−0.0089 (17)
C22B	0.126 (6)	0.070 (2)	0.0474 (18)	−0.010 (3)	−0.027 (2)	−0.0089 (17)

Geometric parameters (Å, º) top

Cl1—C3	1.7469 (16)	C8—H8	0.9800
F1—C1	1.366 (2)	C9—C19	1.515 (2)
O1—C21	1.1987 (19)	C9—C10	1.597 (2)
O2—C21	1.325 (2)	C9—H9	0.9800
O2—C22B	1.490 (7)	C10—C11	1.537 (2)
O2—C22A	1.497 (4)	C10—C17	1.540 (2)
O3—C19	1.195 (2)	C11—C12	1.389 (2)
O4—C19	1.335 (2)	C11—C16	1.390 (2)
O4—C20	1.454 (2)	C12—C13	1.387 (3)
O5—C17	1.201 (2)	C12—H12	0.9300
O6—C17	1.3283 (19)	C13—C14	1.375 (3)
O6—C18	1.448 (2)	C13—H13	0.9300
N1—C7	1.4645 (18)	C14—C15	1.371 (3)
N1—C10	1.465 (2)	C14—H14	0.9300
N1—H1	0.855 (18)	C15—C16	1.379 (2)
C1—C2	1.366 (3)	C15—H15	0.9300
C1—C6	1.373 (3)	C16—H16	0.9300
C2—C3	1.383 (2)	C18—H18A	0.9600
C2—H2	0.9300	C18—H18B	0.9600
C3—C4	1.386 (2)	C18—H18C	0.9600
C4—C5	1.392 (2)	C20—H20A	0.9600
C4—C7	1.508 (2)	C20—H20B	0.9600
C5—C6	1.385 (2)	C20—H20C	0.9600
C5—H5	0.9300	C22A—H22A	0.9600
C6—H6	0.9300	C22A—H22B	0.9600
C7—C8	1.559 (2)	C22A—H22C	0.9600
C7—H7	0.9800	C22B—H22D	0.9600
C8—C21	1.509 (2)	C22B—H22E	0.9600
C8—C9	1.552 (2)	C22B—H22F	0.9600

C21—O2—C22B	112.1 (5)	C12—C11—C10	121.02 (14)
C21—O2—C22A	116.7 (3)	C16—C11—C10	121.26 (14)
C22B—O2—C22A	28.9 (4)	C13—C12—C11	120.50 (17)
C19—O4—C20	116.19 (15)	C13—C12—H12	119.7
C17—O6—C18	115.25 (14)	C11—C12—H12	119.7
C7—N1—C10	104.04 (11)	C14—C13—C12	120.89 (17)
C7—N1—H1	109.1 (12)	C14—C13—H13	119.6
C10—N1—H1	106.6 (12)	C12—C13—H13	119.6
F1—C1—C2	117.99 (17)	C15—C14—C13	119.02 (17)
F1—C1—C6	118.91 (17)	C15—C14—H14	120.5
C2—C1—C6	123.10 (16)	C13—C14—H14	120.5
C1—C2—C3	117.32 (16)	C14—C15—C16	120.55 (18)
C1—C2—H2	121.3	C14—C15—H15	119.7
C3—C2—H2	121.3	C16—C15—H15	119.7
C2—C3—C4	122.85 (15)	C15—C16—C11	121.28 (17)
C2—C3—Cl1	117.35 (12)	C15—C16—H16	119.4
C4—C3—Cl1	119.79 (12)	C11—C16—H16	119.4
C3—C4—C5	116.95 (14)	O5—C17—O6	124.68 (14)
C3—C4—C7	120.33 (13)	O5—C17—C10	122.33 (14)
C5—C4—C7	122.72 (14)	O6—C17—C10	112.97 (13)
C6—C5—C4	121.88 (16)	O6—C18—H18A	109.5
C6—C5—H5	119.1	O6—C18—H18B	109.5
C4—C5—H5	119.1	H18A—C18—H18B	109.5
C1—C6—C5	117.86 (17)	O6—C18—H18C	109.5
C1—C6—H6	121.1	H18A—C18—H18C	109.5
C5—C6—H6	121.1	H18B—C18—H18C	109.5
N1—C7—C4	115.18 (12)	O3—C19—O4	123.47 (16)
N1—C7—C8	104.82 (12)	O3—C19—C9	126.67 (16)
C4—C7—C8	115.45 (12)	O4—C19—C9	109.81 (14)
N1—C7—H7	107.0	O4—C20—H20A	109.5
C4—C7—H7	107.0	O4—C20—H20B	109.5
C8—C7—H7	107.0	H20A—C20—H20B	109.5
C21—C8—C9	113.13 (12)	O4—C20—H20C	109.5
C21—C8—C7	108.82 (12)	H20A—C20—H20C	109.5
C9—C8—C7	101.43 (11)	H20B—C20—H20C	109.5
C21—C8—H8	111.0	O1—C21—O2	124.03 (15)
C9—C8—H8	111.0	O1—C21—C8	124.77 (14)
C7—C8—H8	111.0	O2—C21—C8	111.13 (13)
C19—C9—C8	113.72 (13)	O2—C22A—H22A	109.5
C19—C9—C10	118.14 (13)	O2—C22A—H22B	109.5
C8—C9—C10	104.80 (12)	H22A—C22A—H22B	109.5
C19—C9—H9	106.5	O2—C22A—H22C	109.5
C8—C9—H9	106.5	H22A—C22A—H22C	109.5
C10—C9—H9	106.5	H22B—C22A—H22C	109.5
N1—C10—C11	109.71 (12)	O2—C22B—H22D	109.5
N1—C10—C17	106.78 (12)	O2—C22B—H22E	109.5
C11—C10—C17	111.80 (12)	H22D—C22B—H22E	109.5
N1—C10—C9	105.33 (12)	O2—C22B—H22F	109.5
C11—C10—C9	109.94 (12)	H22D—C22B—H22F	109.5
C17—C10—C9	113.00 (12)	H22E—C22B—H22F	109.5
C12—C11—C16	117.72 (15)

F1—C1—C2—C3	−178.45 (16)	N1—C10—C11—C12	14.85 (19)
C6—C1—C2—C3	1.8 (3)	C17—C10—C11—C12	−103.41 (16)
C1—C2—C3—C4	0.0 (3)	C9—C10—C11—C12	130.23 (15)
C1—C2—C3—Cl1	−179.53 (14)	N1—C10—C11—C16	−165.02 (14)
C2—C3—C4—C5	−1.5 (2)	C17—C10—C11—C16	76.71 (18)
Cl1—C3—C4—C5	177.95 (12)	C9—C10—C11—C16	−49.64 (18)
C2—C3—C4—C7	177.68 (14)	C16—C11—C12—C13	1.0 (2)
Cl1—C3—C4—C7	−2.8 (2)	C10—C11—C12—C13	−178.87 (15)
C3—C4—C5—C6	1.5 (3)	C11—C12—C13—C14	−1.2 (3)
C7—C4—C5—C6	−177.73 (16)	C12—C13—C14—C15	−0.1 (3)
F1—C1—C6—C5	178.39 (17)	C13—C14—C15—C16	1.7 (3)
C2—C1—C6—C5	−1.9 (3)	C14—C15—C16—C11	−1.9 (3)
C4—C5—C6—C1	0.2 (3)	C12—C11—C16—C15	0.6 (2)
C10—N1—C7—C4	173.79 (12)	C10—C11—C16—C15	−179.57 (15)
C10—N1—C7—C8	45.80 (14)	C18—O6—C17—O5	8.4 (2)
C3—C4—C7—N1	156.57 (14)	C18—O6—C17—C10	−172.84 (15)
C5—C4—C7—N1	−24.3 (2)	N1—C10—C17—O5	24.6 (2)
C3—C4—C7—C8	−80.97 (18)	C11—C10—C17—O5	144.60 (15)
C5—C4—C7—C8	98.19 (18)	C9—C10—C17—O5	−90.74 (18)
N1—C7—C8—C21	81.72 (14)	N1—C10—C17—O6	−154.16 (13)
C4—C7—C8—C21	−46.10 (17)	C11—C10—C17—O6	−34.15 (18)
N1—C7—C8—C9	−37.78 (14)	C9—C10—C17—O6	90.51 (15)
C4—C7—C8—C9	−165.60 (12)	C20—O4—C19—O3	5.6 (3)
C21—C8—C9—C19	30.15 (18)	C20—O4—C19—C9	−176.82 (16)
C7—C8—C9—C19	146.52 (13)	C8—C9—C19—O3	−140.85 (18)
C21—C8—C9—C10	−100.31 (14)	C10—C9—C19—O3	−17.4 (3)
C7—C8—C9—C10	16.07 (14)	C8—C9—C19—O4	41.67 (18)
C7—N1—C10—C11	84.15 (14)	C10—C9—C19—O4	165.13 (13)
C7—N1—C10—C17	−154.52 (12)	C22B—O2—C21—O1	−19.4 (7)
C7—N1—C10—C9	−34.13 (14)	C22A—O2—C21—O1	12.0 (5)
C19—C9—C10—N1	−117.73 (14)	C22B—O2—C21—C8	163.6 (7)
C8—C9—C10—N1	10.09 (15)	C22A—O2—C21—C8	−165.1 (5)
C19—C9—C10—C11	124.14 (14)	C9—C8—C21—O1	38.7 (2)
C8—C9—C10—C11	−108.04 (13)	C7—C8—C21—O1	−73.2 (2)
C19—C9—C10—C17	−1.53 (19)	C9—C8—C21—O2	−144.27 (15)
C8—C9—C10—C17	126.29 (13)	C7—C8—C21—O2	103.82 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O5ⁱ	0.93	2.56	3.380 (3)	147

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₁ClFNO₆
M_r	449.85
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	9.474 (3), 15.057 (8), 15.182 (5)
V (Å³)	2165.7 (15)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.98
Crystal size (mm)	0.38 × 0.36 × 0.03

Data collection
Diffractometer	Oxford Diffraction Gemini S Ultra
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.520, 0.943
No. of measured, independent and observed [I > 2σ(I)] reflections	32943, 3442, 3332
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.576

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.060, 1.05
No. of reflections	3442
No. of parameters	290
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.16
Absolute structure	Flack (1983), 1456 Friedel pairs
Absolute structure parameter	−0.001 (11)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O5ⁱ	0.93	2.56	3.380 (3)	147.2

Symmetry code: (i) x+1/2, −y+3/2, −z+1.

Acknowledgements

The diffraction measurements were made at Sichuan University. We acknowledge financial support from China West Normal University.

References

Coldham, I. & Hufton, R. (2005). Chem. Rev. 105, 2765–2810. Web of Science CrossRef PubMed CAS Google Scholar
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Nair, V. & Suja, T. D. (2007). Tetrahedron, 63, 12247–12275. Web of Science CrossRef CAS Google Scholar
Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
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Witherup, K. M., Ransom, R. W., Graham, A. C., Bernard, A. M., Salvatore, M. J., Lumma, W. C., Anderson, P. S., Pitzenberger, S. M. & Varga, S. L. (1995). J. Am. Chem. Soc. 117, 6682–6685. CrossRef CAS Web of Science Google Scholar
Yu, Z.-F., Li, J., Sun, J.-W. & Yu, L. (2007). Acta Cryst. E63, o17–o18. Web of Science CSD CrossRef IUCr Journals Google Scholar

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

Tri­methyl 5-(2-chloro-4-fluoro­phen­yl)-2-phenyl­pyrrolidine-2,3,4-tri­carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Trimethyl 5-(2-chloro-4-fluorophenyl)-2-phenylpyrrolidine-2,3,4-tricarboxylate