A redetermination of 1-(2-fluoro­phen­yl)pyrrolidine-2,5-dione

The crystal structure of the title compound, C₁₀H₈FNO₂, has been redetermined with greater precision and with a detailed investigation of the inter­molecular inter­actions [previous report; space group: Pca2₁; cell: a = 11.064 (2), b = 10.271 (2), c = 8.053 (2) Å; R factor: 0,061; temperature (K): 295; Taira, Takayama & Terada (1988). J. Chem. Soc. Perkin Trans. 2, pp. 1439–1445]. The mol­ecule is non-planar with the benzene and pyrrolidine rings tilted by 63.18 (12)° with respect to one another. In the crystal structure, inter­molecular C—H...O and C—H...F hydrogen bonds together with C—H...π inter­actions link the mol­ecules into a three-dimensional network. The C—H...O and C—H...F hydrogen bonds generate edge-fused R₂²(8)R₂²(11)R₄³(17) and R₆⁴(25) hydrogen-bonded rings.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.095
• Data-to-parameter ratio = 7.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT115_ALERT_5_B ADDSYM Detects Noncrystallographic Inversion ...         85 PerFi

Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.69 mm
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.39
PLAT432_ALERT_2_C Short Inter X...Y Contact  O1     ..  C10     ..       3.01 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4     ..  O2      ..       2.68 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9B    ..  F1      ..       2.60 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9A    ..  O1      ..       2.63 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.97
           From the CIF: _reflns_number_total                946
           Count of symmetry unique reflns          964
           Completeness (_total/calc)             98.13%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The crystal structures of several pyrrolidine-2,5-dione (succinimide) derivatives have been reported with respect to their biological properties, e.g. antiepileptic (Allen & Kennard, 1993; Argay & Seres, 1973), anticonvulsive (Argay & Seres, 1973; Kwiatkowski et al., 1990; Kwiatkowski & Karolak-Wojciechowska, 1992; Karolak-Wojciechowska et al., 1996), fungicidal (Taira et al., 1988; Haberle et al., 1989;Zhang et al., 2007), antiantrogenic (Zhang et al., 2007; Rankin et al., 1989), and other pharmacological activities (Kwiatkowski & Karolak-Wojciechowska, 1990; Malamas et al., 1994; Toupet et al., 1996; Argay et al., 1999; Zhang et al., 2007). In each of these compounds, the ring nitrogen is substituted either by a methyl group or differently substituted phenyl and pyridine rings or a morpholinomethyl group. Against this background, we present here the crystal structure of the title compound, (I), with better precision and incorporating a detailed investigation of the intermolecular interactions.

The title compound, (I), is not planar, with a dihedral angle of 63.18 (12)° between the benzene and pyrrolidine rings [This angle is 63.5° in the previous determination (Taira et al., 1988)]. The crystal packing is stabilized by C—H···O and C—H···F intermolecular hydrogen bonds and also by C—H···π interactions (Table 2). The intermolecular hydrogen bonds generate edge-fused R₂²(8)R₂²(11)R₄³(17) (Fig. 2) and R₆⁴(25) (Fig. 3) (Etter, 1990; Bernstein et al., 1995) hydrogen bonded rings in a three- dimensional network (Fig. 5). In addition, C—H···π interactions form chains of molecules along the [001] direction (Table 2, Fig.4).

Related literature

For ring motif details, see: Bernstein et al. (1995); Etter (1990). For background, see: Taira, et al. (1988); Rankin et al. (1989); Allen & Kennard (1993); Malamas et al. (1994); Toupet et al. (1996); Zhang et al. (2007). For related structures, see: Argay & Seres (1973); Kwiatkowski et al. (1990); Kwiatkowski & Karolak-Wojciechowska (1990, 1992); Karolak-Wojciechowska et al. (1996); Argay et al. (1999). For details of the preparation, see: Haberle et al. (1989).

S2. Experimental

Compound (I) was prepared as described by Haberle et al. (1989), using succinic acid anhydride and 2-fluoroaniline as starting materials. Well shaped crystals of (I) were obtained by slow evaporation of an ethanol solution [m.p.:422–423 K].

S3. Refinement

The H atoms were included in calculated positions and refined using a riding model approximation. Constrained C—H bond lengths and isotropic U parameters: 0.93 Å and U_iso(H) = 1.2U_eq(C) for Csp²—H; 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene C—H; The absolute structure could not be determined, and 745 Friedel pairs were averaged before the last refinement.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); 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: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the formation of an R2^2(8)R2^2(11)R4^3(17) motifs. H atoms not involved in hydrogen bonds have been omitted for clarity. [Symmetry codes: (i) x, 1 - y, z; (ii) 1 - x, 1 - y, z + 1/2; (iii) x + 1/2, 1 - y, z; (iv) 1 - x, 1 - y, z - 1/2].
	Fig. 3. Part of the crystal structure of (I), showing the formation of an R6^4(25) motif. H atoms not involved in hydrogen bonds have been omitted for clarity. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) x, y + 1, z; (iii) x + 1/2, -y, z; (iv) 3/2 - x, y, z + 1/2; (v) x + 1/2, 1 - y, z].
	Fig. 4. Part of the crystal structure of (I), showing the C—H···π interactions along the c axis. H atoms not involved in hydrogen bonds have been omitted for clarity.
	Fig. 5. A packing diagram for (I), with hydrogen bonds drawn as dashed lines. H atoms not involved in hydrogen bonds have been omitted for clarity.

1-(2-fluorophenyl)pyrrolidine-2,5-dione

Crystal data

C10H8FNO2	F(000) = 400
Mr = 193.17	Dx = 1.402 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 3862 reflections
a = 11.0620 (13) Å	θ = 2.7–27.2°
b = 10.2689 (13) Å	µ = 0.11 mm^−1
c = 8.0586 (8) Å	T = 296 K
V = 915.41 (18) Å^3	Prism, colorless
Z = 4	0.69 × 0.56 × 0.43 mm

Data collection

STOE IPDS 2 diffractometer	946 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	826 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.023
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.7°
w–scan rotation method	h = −13→13
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −10→12
Tmin = 0.940, Tmax = 0.967	l = −9→8
3862 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0609P)^2 + 0.0455P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
946 reflections	Δρmax = 0.23 e Å^−3
128 parameters	Δρmin = −0.12 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (6)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.38002 (19)	0.3133 (2)	0.4596 (3)	0.0474 (6)
C2	0.4685 (2)	0.3725 (2)	0.5537 (4)	0.0595 (7)
C3	0.4684 (3)	0.5036 (3)	0.5824 (4)	0.0741 (9)
H3	0.5292	0.5423	0.6449	0.089*
C4	0.3764 (3)	0.5768 (3)	0.5169 (5)	0.0771 (9)
H4	0.3747	0.6661	0.5357	0.093*
C5	0.2876 (3)	0.5205 (3)	0.4247 (5)	0.0732 (9)
H5	0.2258	0.5715	0.3814	0.088*
C6	0.2887 (2)	0.3884 (3)	0.3953 (4)	0.0614 (7)
H6	0.2278	0.3503	0.3321	0.074*
C7	0.2954 (2)	0.0911 (2)	0.4864 (4)	0.0549 (6)
C8	0.3285 (3)	−0.0423 (3)	0.4281 (4)	0.0656 (7)
H8A	0.2674	−0.0760	0.3532	0.079*
H8B	0.3364	−0.1014	0.5213	0.079*
C9	0.4468 (3)	−0.0271 (3)	0.3403 (5)	0.0679 (8)
H9A	0.5096	−0.0756	0.3972	0.081*
H9B	0.4409	−0.0588	0.2272	0.081*
C10	0.4745 (2)	0.1146 (2)	0.3419 (4)	0.0545 (6)
N1	0.38437 (15)	0.17631 (17)	0.4328 (3)	0.0474 (5)
O1	0.20830 (18)	0.1239 (2)	0.5658 (3)	0.0823 (7)
O2	0.55827 (15)	0.1717 (2)	0.2795 (3)	0.0732 (6)
F1	0.55669 (16)	0.29716 (17)	0.6176 (3)	0.0897 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0537 (11)	0.0447 (11)	0.0437 (15)	−0.0033 (9)	0.0037 (11)	−0.0015 (9)
C2	0.0654 (13)	0.0553 (13)	0.0577 (18)	−0.0068 (11)	−0.0085 (13)	0.0018 (14)
C3	0.094 (2)	0.0570 (14)	0.072 (2)	−0.0178 (14)	−0.0115 (16)	−0.0071 (15)
C4	0.112 (2)	0.0448 (13)	0.075 (2)	0.0022 (14)	0.0022 (18)	−0.0083 (14)
C5	0.0858 (19)	0.0602 (15)	0.074 (2)	0.0203 (13)	0.0016 (18)	−0.0027 (16)
C6	0.0556 (13)	0.0668 (15)	0.062 (2)	0.0064 (11)	−0.0023 (12)	−0.0096 (14)
C7	0.0585 (13)	0.0551 (13)	0.0510 (15)	−0.0114 (11)	−0.0018 (13)	0.0013 (11)
C8	0.0771 (15)	0.0497 (12)	0.0701 (19)	−0.0079 (12)	−0.0116 (16)	0.0015 (14)
C9	0.0761 (16)	0.0555 (15)	0.072 (2)	0.0138 (12)	−0.0120 (15)	−0.0074 (15)
C10	0.0517 (11)	0.0587 (14)	0.0531 (16)	0.0089 (11)	−0.0025 (12)	0.0013 (13)
N1	0.0479 (9)	0.0472 (10)	0.0472 (13)	−0.0046 (7)	0.0011 (9)	−0.0030 (9)
O1	0.0748 (12)	0.0819 (13)	0.0903 (17)	−0.0166 (10)	0.0332 (12)	−0.0054 (13)
O2	0.0589 (9)	0.0771 (12)	0.0836 (17)	0.0052 (8)	0.0204 (10)	0.0022 (11)
F1	0.0911 (12)	0.0716 (10)	0.1065 (18)	−0.0084 (8)	−0.0444 (11)	0.0065 (10)

Geometric parameters (Å, º)

C1—C6	1.373 (4)	C7—O1	1.205 (3)
C1—C2	1.380 (3)	C7—N1	1.386 (3)
C1—N1	1.424 (3)	C7—C8	1.494 (4)
C2—F1	1.347 (3)	C8—C9	1.496 (5)
C2—C3	1.366 (4)	C8—H8A	0.9700
C3—C4	1.370 (5)	C8—H8B	0.9700
C3—H3	0.9300	C9—C10	1.487 (4)
C4—C5	1.361 (4)	C9—H9A	0.9700
C4—H4	0.9300	C9—H9B	0.9700
C5—C6	1.376 (4)	C10—O2	1.206 (3)
C5—H5	0.9300	C10—N1	1.390 (3)
C6—H6	0.9300
C6—C1—C2	118.8 (2)	N1—C7—C8	107.9 (2)
C6—C1—N1	121.5 (2)	C7—C8—C9	105.5 (2)
C2—C1—N1	119.6 (2)	C7—C8—H8A	110.6
F1—C2—C3	120.2 (2)	C9—C8—H8A	110.6
F1—C2—C1	118.1 (2)	C7—C8—H8B	110.6
C3—C2—C1	121.7 (2)	C9—C8—H8B	110.6
C2—C3—C4	118.5 (3)	H8A—C8—H8B	108.8
C2—C3—H3	120.8	C10—C9—C8	106.1 (2)
C4—C3—H3	120.8	C10—C9—H9A	110.5
C5—C4—C3	120.9 (3)	C8—C9—H9A	110.5
C5—C4—H4	119.6	C10—C9—H9B	110.5
C3—C4—H4	119.6	C8—C9—H9B	110.5
C4—C5—C6	120.4 (3)	H9A—C9—H9B	108.7
C4—C5—H5	119.8	O2—C10—N1	123.3 (2)
C6—C5—H5	119.8	O2—C10—C9	129.1 (2)
C1—C6—C5	119.6 (3)	N1—C10—C9	107.6 (2)
C1—C6—H6	120.2	C7—N1—C10	112.69 (19)
C5—C6—H6	120.2	C7—N1—C1	123.52 (19)
O1—C7—N1	123.8 (3)	C10—N1—C1	123.70 (19)
O1—C7—C8	128.3 (3)
C6—C1—C2—F1	179.2 (3)	C8—C9—C10—O2	−176.7 (3)
N1—C1—C2—F1	−0.1 (4)	C8—C9—C10—N1	3.7 (3)
C6—C1—C2—C3	−0.9 (4)	O1—C7—N1—C10	−179.3 (3)
N1—C1—C2—C3	179.8 (3)	C8—C7—N1—C10	0.6 (3)
F1—C2—C3—C4	−179.3 (3)	O1—C7—N1—C1	−2.8 (4)
C1—C2—C3—C4	0.8 (5)	C8—C7—N1—C1	177.2 (2)
C2—C3—C4—C5	−0.3 (5)	O2—C10—N1—C7	177.6 (3)
C3—C4—C5—C6	−0.1 (5)	C9—C10—N1—C7	−2.8 (3)
C2—C1—C6—C5	0.4 (4)	O2—C10—N1—C1	1.1 (4)
N1—C1—C6—C5	179.7 (3)	C9—C10—N1—C1	−179.3 (2)
C4—C5—C6—C1	0.0 (5)	C6—C1—N1—C7	−61.5 (3)
O1—C7—C8—C9	−178.3 (3)	C2—C1—N1—C7	117.8 (3)
N1—C7—C8—C9	1.7 (3)	C6—C1—N1—C10	114.6 (3)
C7—C8—C9—C10	−3.3 (3)	C2—C1—N1—C10	−66.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2^i	0.97	2.58	3.483 (3)	155
C8—H8B···O2^ii	0.97	2.49	3.370 (4)	151
C4—H4···O2^iii	0.93	2.68	3.417 (4)	137
C9—H9B···F1^iv	0.97	2.60	3.304 (4)	129
C9—H9A···O1^v	0.97	2.63	3.558 (4)	160
C3—H3···Cg1^iii	0.93	2.97	3.724 (3)	140

Symmetry codes: (i) x−1/2, −y, z; (ii) −x+1, −y, z+1/2; (iii) −x+1, −y+1, z+1/2; (iv) −x+1, −y, z−1/2; (v) x+1/2, −y, z.