4-Chloro-3-fluoro-2-methyl-aniline-pyrrolidine-2,5-dione (1/1).

Chlorination of 3-fluoro-2-methyl-aniline with N-chloro-succinimide gave one major regioisomer whose structure was determined by X-ray crystallography. The product was found to have cocrystallized with succinimide, giving the title compound, C(7)H(7)ClFN·C(4)H(5)NO(2). The crystal structure is stabilized by N-H⋯O hydrogen-bonding and π-π stacking inter-actions with a centroid-centroid distance of 3.4501 (8) Å.

Related literature

For related literature, see: Lazar et al. (2004 ▶); Marterer et al. (2003 ▶); Nickson & Roche-Dolson (1985 ▶); Shapiro et al. (2006 ▶); Tukada & Mazaki (1997 ▶); Zanka & Kubota (1999 ▶); Görbitz (1999 ▶).

Experimental

Crystal data

C7H7ClFN·C4H5NO2

M = 258.68

Triclinic,

a = 7.3853 (2) Å

b = 7.4390 (2) Å

c = 11.5571 (4) Å

α = 73.1036 (13)°

β = 85.9336 (12)°

γ = 71.3703 (14)°

V = 575.53 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.34 mm−1

T = 120 K

0.75 × 0.44 × 0.41 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.47, T max = 0.87

16689 measured reflections

2904 independent reflections

2610 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.087

S = 0.88

2904 reflections

154 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.37 e Å−3

Data collection: COLLECT (Nonius, 2001 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: CRYSTALS.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018795/lh2642sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018795/lh2642Isup2.hkl

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

C7H7ClFN·C4H5NO2	Z = 2
Mr = 258.68	F000 = 268
Triclinic, P1	Dx = 1.493 Mg m−3
a = 7.3853 (2) Å	Mo Kα radiation λ = 0.71073 Å
b = 7.4390 (2) Å	Cell parameters from 2870 reflections
c = 11.5571 (4) Å	θ = 5–29º
α = 73.1036 (13)º	µ = 0.34 mm−1
β = 85.9336 (12)º	T = 120 K
γ = 71.3703 (14)º	Plate, colourless
V = 575.53 (3) Å3	0.75 × 0.44 × 0.41 mm

Nonius KappaCCD diffractometer	2610 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.033
T = 120 K	θmax = 28.7º
ω scans	θmin = 5.4º
Absorption correction: multi-scan(DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.47, Tmax = 0.87	k = −10→9
16689 measured reflections	l = −15→15
2904 independent reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032	Method = Modified Sheldrick w = 1/[σ2(F2) + (0.05P)2 + 0.35P], where P = [max(Fo2,0) + 2Fc2]/3
wR(F2) = 0.087	(Δ/σ)max = 0.001
S = 0.88	Δρmax = 0.38 e Å−3
2904 reflections	Δρmin = −0.37 e Å−3
154 parameters	Extinction correction: None
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
C11	0.94307 (16)	0.30918 (17)	0.66142 (11)	0.0207
N12	0.99166 (15)	0.16670 (15)	0.59934 (9)	0.0223
C13	1.10284 (16)	−0.01507 (17)	0.66627 (11)	0.0205
C14	1.14595 (16)	−0.00013 (17)	0.78815 (10)	0.0204
C15	1.04097 (16)	0.21516 (17)	0.78494 (11)	0.0211
O16	1.15499 (13)	−0.16202 (13)	0.62979 (8)	0.0275
O17	0.83954 (13)	0.47656 (13)	0.62086 (8)	0.0280
H141	1.2797	−0.0325	0.7987	0.0245*
H142	1.0987	−0.0916	0.8511	0.0240*
H151	1.1221	0.2859	0.7939	0.0258*
H152	0.9471	0.2271	0.8474	0.0263*
H1	0.9510	0.1824	0.5287	0.0265*
C1	0.34402 (16)	0.96277 (18)	0.14329 (10)	0.0201
C2	0.28607 (16)	1.11710 (17)	0.19551 (11)	0.0207
C3	0.34232 (16)	1.08204 (17)	0.31427 (11)	0.0217
C4	0.45586 (16)	0.89539 (17)	0.37673 (10)	0.0210
C5	0.51642 (16)	0.74038 (17)	0.32214 (10)	0.0188
C6	0.45694 (16)	0.77380 (17)	0.20237 (10)	0.0194
C7	0.51289 (19)	0.60873 (19)	0.14308 (12)	0.0269
N8	0.63360 (16)	0.55949 (16)	0.38422 (10)	0.0277
Cl9	0.14163 (4)	1.34735 (4)	0.11329 (3)	0.0293
F10	0.28435 (11)	0.99849 (12)	0.02806 (6)	0.0291
H31	0.3012	1.1851	0.3475	0.0277*
H41	0.4953	0.8705	0.4581	0.0257*
H71	0.6503	0.5518	0.1414	0.0420*
H72	0.4641	0.5027	0.1863	0.0416*
H73	0.4639	0.6536	0.0618	0.0429*
H9	0.6698	0.4664	0.3519	0.0324*
H11	0.6736	0.5392	0.4585	0.0317*

	U11	U22	U33	U12	U13	U23
C11	0.0199 (5)	0.0202 (5)	0.0235 (6)	−0.0059 (4)	0.0007 (4)	−0.0088 (4)
N12	0.0264 (5)	0.0201 (5)	0.0187 (5)	−0.0024 (4)	−0.0048 (4)	−0.0072 (4)
C13	0.0196 (5)	0.0201 (5)	0.0209 (5)	−0.0039 (4)	−0.0013 (4)	−0.0064 (4)
C14	0.0196 (5)	0.0216 (5)	0.0195 (5)	−0.0049 (4)	−0.0029 (4)	−0.0061 (4)
C15	0.0198 (5)	0.0232 (5)	0.0221 (6)	−0.0066 (4)	−0.0014 (4)	−0.0090 (4)
O16	0.0325 (5)	0.0212 (4)	0.0259 (5)	0.0005 (4)	−0.0056 (4)	−0.0108 (4)
O17	0.0302 (5)	0.0206 (4)	0.0305 (5)	−0.0012 (3)	−0.0058 (4)	−0.0090 (4)
C1	0.0196 (5)	0.0262 (6)	0.0156 (5)	−0.0089 (4)	−0.0015 (4)	−0.0051 (4)
C2	0.0180 (5)	0.0187 (5)	0.0228 (6)	−0.0049 (4)	−0.0023 (4)	−0.0023 (4)
C3	0.0217 (5)	0.0206 (5)	0.0237 (6)	−0.0051 (4)	0.0005 (4)	−0.0094 (4)
C4	0.0213 (5)	0.0228 (5)	0.0184 (5)	−0.0043 (4)	−0.0026 (4)	−0.0074 (4)
C5	0.0165 (5)	0.0190 (5)	0.0196 (5)	−0.0041 (4)	0.0003 (4)	−0.0050 (4)
C6	0.0181 (5)	0.0218 (5)	0.0205 (5)	−0.0081 (4)	0.0020 (4)	−0.0077 (4)
C7	0.0290 (6)	0.0277 (6)	0.0276 (6)	−0.0077 (5)	0.0010 (5)	−0.0144 (5)
N8	0.0317 (6)	0.0207 (5)	0.0241 (5)	0.0027 (4)	−0.0051 (4)	−0.0071 (4)
Cl9	0.02920 (17)	0.02088 (16)	0.03136 (17)	−0.00375 (11)	−0.00674 (12)	−0.00040 (11)
F10	0.0341 (4)	0.0346 (4)	0.0175 (3)	−0.0092 (3)	−0.0072 (3)	−0.0055 (3)

C11—N12	1.3890 (14)	C2—C3	1.3885 (17)
C11—C15	1.5141 (16)	C2—Cl9	1.7335 (12)
C11—O17	1.2075 (14)	C3—C4	1.3826 (16)
N12—C13	1.3689 (15)	C3—H31	0.913
N12—H1	0.852	C4—C5	1.4075 (16)
C13—C14	1.5082 (16)	C4—H41	0.952
C13—O16	1.2235 (14)	C5—C6	1.4096 (16)
C14—C15	1.5309 (16)	C5—N8	1.3629 (14)
C14—H141	0.947	C6—C7	1.5076 (16)
C14—H142	0.970	C7—H71	0.968
C15—H151	0.943	C7—H72	0.963
C15—H152	0.968	C7—H73	0.955
C1—C2	1.3848 (17)	N8—H9	0.842
C1—C6	1.3826 (16)	N8—H11	0.882
C1—F10	1.3569 (13)
N12—C11—C15	107.80 (9)	C1—C2—C3	118.84 (11)
N12—C11—O17	124.27 (11)	C1—C2—Cl9	119.74 (9)
C15—C11—O17	127.93 (11)	C3—C2—Cl9	121.41 (9)
C11—N12—C13	113.60 (10)	C2—C3—C4	119.37 (11)
C11—N12—H1	125.7	C2—C3—H31	117.6
C13—N12—H1	120.5	C4—C3—H31	123.1
N12—C13—C14	108.74 (9)	C3—C4—C5	121.32 (11)
N12—C13—O16	123.80 (11)	C3—C4—H41	119.8
C14—C13—O16	127.46 (11)	C5—C4—H41	118.9
C13—C14—C15	104.82 (9)	C4—C5—C6	119.65 (11)
C13—C14—H141	109.5	C4—C5—N8	120.21 (11)
C15—C14—H141	111.9	C6—C5—N8	120.13 (10)
C13—C14—H142	109.2	C5—C6—C1	117.02 (10)
C15—C14—H142	111.7	C5—C6—C7	120.92 (11)
H141—C14—H142	109.5	C1—C6—C7	122.05 (11)
C14—C15—C11	104.97 (9)	C6—C7—H71	111.7
C14—C15—H151	114.0	C6—C7—H72	111.2
C11—C15—H151	109.0	H71—C7—H72	106.7
C14—C15—H152	112.8	C6—C7—H73	111.5
C11—C15—H152	109.9	H71—C7—H73	108.1
H151—C15—H152	106.2	H72—C7—H73	107.4
C2—C1—C6	123.78 (11)	C5—N8—H9	120.4
C2—C1—F10	118.07 (10)	C5—N8—H11	120.3
C6—C1—F10	118.14 (10)	H9—N8—H11	119.3

D—H···A	D—H	H···A	D···A	D—H···A
N12—H1···O16i	0.85	2.11	2.945 (2)	168
N8—H9···O16i	0.84	2.18	2.915 (2)	147
N8—H11···O17	0.88	2.17	3.030 (2)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N12—H1⋯O16i	0.85	2.11	2.945 (2)	168
N8—H9⋯O16i	0.84	2.18	2.915 (2)	147
N8—H11⋯O17	0.88	2.17	3.030 (2)	166

Symmetry code: (i) .