1-(3-Chloro-4-methyl­phenyl)-3-pyrroline-2,5-dione

The structure of the title compound, C₁₁H₈ClNO₂, (I), comprises a twisted mol­ecule with the dihedral angle between the two rings being 49.9 (2)°. Several C—H...X short contacts exist to both O atoms, but not to the Cl atom. The resultant structure packs in a noncentrosymmetric space group (Pna2₁) and the bulk material exhibits a second harmonic signal of I/I_urea = 0.09.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.052
• wR factor = 0.131
• Data-to-parameter ratio = 15.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.47
         From the CIF: _reflns_number_total               2076
         Count of symmetry unique reflns         1285
         Completeness (_total/calc)            161.56%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       791
         Fraction of Friedel pairs measured     0.616
         Are heavy atom types Z>Si present          yes
          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.

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S1. Comment

NO COMMENT

S2. Experimental

The title compound, (I), was prepared by Spa Contract Synthesis. Crystals of (I) were grown from an acetone solution.

S3. Refinement

All H atoms were included in the refinement at calculated positions as riding models with C—H set to 0.95 (Ar—H) and 0.98 Å (CH₃). The number of Friedel pairs is 560.

Computing details

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular configuration and atom numbering scheme for (I), showing 50% probability ellipsoids.

1-(3-Chloro-4-methylphenyl)pyrroline-2,5-dione

Crystal data

C11H8ClNO2	Dx = 1.499 Mg m^−3
Mr = 221.63	Melting point: 413-413.5 K K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
a = 10.473 (2) Å	Cell parameters from 4247 reflections
b = 24.303 (5) Å	θ = 2.9–39.4°
c = 3.8594 (8) Å	µ = 0.36 mm^−1
V = 982.3 (3) Å^3	T = 150 K
Z = 4	Needle, yellow
F(000) = 456	0.55 × 0.05 × 0.05 mm

Data collection

Enraf Nonius KappaCCD area-detector diffractometer	2076 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	1583 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.091
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ and ω scans	h = 0→13
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = 0→31
Tmin = 0.825, Tmax = 0.982	l = −4→4
6579 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)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0742P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
2076 reflections	Δρmax = 0.49 e Å^−3
137 parameters	Δρmin = −0.37 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.28 (11)

Special details

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

Geometry. Mean plane data ex SHELXL97 ###########################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

0.9742 (0.0184) x + 9.8588 (0.0416) y + 3.5093 (0.0032) z = 6.8087 (0.0172)

* 0.0050 (0.0021) N1 * -0.0016 (0.0021) C2 * -0.0025 (0.0024) C3 * 0.0054 (0.0024) C4 * -0.0062 (0.0021) C5

Rms deviation of fitted atoms = 0.0045

2.9354 (0.0144) x + 8.5212 (0.0291) y - 3.4487 (0.0025) z = 2.0297 (0.0144)

Angle to previous plane (with approximate e.s.d.) = 49.89 (0.09)

* 0.0015 (0.0022) C6 * 0.0015 (0.0023) C7 * -0.0036 (0.0023) C8 * 0.0027 (0.0023) C9 * 0.0002 (0.0026) C10 * -0.0023 (0.0024) C11

Rms deviation of fitted atoms = 0.0022

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.6048 (3)	0.34814 (10)	0.7957 (7)	0.0263 (7)
C2	0.6172 (3)	0.29531 (13)	0.9388 (9)	0.0265 (7)
O2	0.5295 (2)	0.26786 (9)	1.0459 (7)	0.0329 (6)
C3	0.7553 (3)	0.28254 (13)	0.9360 (10)	0.0300 (8)
H3	0.7927	0.2493	1.0174	0.038*
C4	0.8180 (3)	0.32409 (15)	0.8042 (9)	0.0358 (9)
H4	0.9080	0.3260	0.7769	0.045*
C5	0.7259 (3)	0.36778 (15)	0.7037 (10)	0.0334 (8)
O5	0.7472 (2)	0.41149 (10)	0.5664 (8)	0.0452 (7)
C6	0.4875 (3)	0.37742 (12)	0.7585 (9)	0.0234 (7)
C7	0.3849 (3)	0.35109 (12)	0.6061 (8)	0.0242 (7)
H7	0.3931	0.3145	0.5218	0.030*
C8	0.2704 (3)	0.37884 (12)	0.5787 (8)	0.0241 (7)
Cl8	0.14304 (7)	0.34360 (3)	0.3922 (3)	0.0320 (2)
C9	0.2546 (3)	0.43270 (13)	0.6965 (8)	0.0262 (7)
C10	0.3599 (3)	0.45747 (13)	0.8481 (9)	0.0257 (7)
H10	0.3522	0.4941	0.9320	0.032*
C11	0.4767 (3)	0.43050 (11)	0.8816 (10)	0.0275 (7)
H11	0.5474	0.4483	0.9871	0.034*
C12	0.1308 (3)	0.46269 (16)	0.6597 (10)	0.0355 (9)
H121	0.1087	0.4657	0.4137	0.044*
H122	0.1390	0.4996	0.7594	0.044*
H123	0.0635	0.4425	0.7819	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0243 (15)	0.0187 (14)	0.0359 (19)	0.0001 (10)	0.0013 (11)	0.0037 (11)
C2	0.0348 (19)	0.0190 (16)	0.0258 (18)	0.0012 (14)	0.0020 (14)	−0.0002 (14)
O2	0.0312 (13)	0.0221 (12)	0.0455 (13)	−0.0001 (11)	0.0054 (10)	0.0060 (10)
C3	0.0289 (17)	0.0222 (16)	0.039 (2)	0.0068 (14)	−0.0007 (15)	0.0023 (14)
C4	0.0275 (19)	0.032 (2)	0.048 (3)	0.0034 (15)	0.0025 (15)	0.0066 (16)
C5	0.033 (2)	0.0281 (19)	0.0394 (19)	−0.0001 (16)	0.0007 (16)	0.0051 (15)
O5	0.0360 (15)	0.0275 (14)	0.0722 (19)	−0.0013 (11)	0.0068 (14)	0.0197 (13)
C6	0.0239 (17)	0.0203 (15)	0.0262 (16)	0.0023 (14)	0.0019 (13)	0.0037 (11)
C7	0.0286 (18)	0.0196 (17)	0.0243 (18)	0.0000 (13)	0.0019 (13)	0.0002 (13)
C8	0.0267 (17)	0.0224 (16)	0.0233 (16)	−0.0044 (14)	0.0001 (13)	0.0003 (12)
Cl8	0.0281 (4)	0.0350 (4)	0.0330 (4)	−0.0040 (3)	−0.0014 (4)	−0.0035 (4)
C9	0.0299 (19)	0.0240 (17)	0.0248 (17)	0.0024 (14)	0.0049 (14)	0.0037 (14)
C10	0.0317 (18)	0.0184 (14)	0.0269 (19)	0.0018 (13)	0.0062 (13)	0.0015 (13)
C11	0.0324 (17)	0.0215 (15)	0.0286 (16)	−0.0042 (13)	0.0000 (16)	0.0009 (15)
C12	0.040 (2)	0.029 (2)	0.037 (2)	0.0099 (16)	−0.0013 (15)	0.0003 (14)

Geometric parameters (Å, º)

N1—C5	1.401 (4)	C7—C8	1.380 (4)
N1—C2	1.404 (4)	C7—H7	0.95
N1—C6	1.427 (4)	C8—C9	1.396 (4)
C2—O2	1.208 (4)	C8—Cl8	1.741 (3)
C2—C3	1.480 (4)	C9—C10	1.386 (5)
C3—C4	1.307 (5)	C9—C12	1.494 (4)
C3—H3	0.95	C10—C11	1.393 (4)
C4—C5	1.486 (5)	C10—H10	0.95
C4—H4	0.95	C11—H11	0.95
C5—O5	1.208 (4)	C12—H121	0.98
C6—C11	1.380 (4)	C12—H122	0.98
C6—C7	1.382 (5)	C12—H123	0.98
C5—N1—C2	109.1 (3)	C6—C7—H7	120.6
C5—N1—C6	125.7 (3)	C7—C8—C9	122.4 (3)
C2—N1—C6	125.1 (3)	C7—C8—Cl8	117.2 (2)
O2—C2—N1	124.7 (3)	C9—C8—Cl8	120.4 (2)
O2—C2—C3	129.0 (3)	C10—C9—C8	116.8 (3)
N1—C2—C3	106.2 (3)	C10—C9—C12	121.2 (3)
C4—C3—C2	109.4 (3)	C8—C9—C12	121.9 (3)
C4—C3—H3	125.3	C9—C10—C11	122.2 (3)
C2—C3—H3	125.3	C9—C10—H10	118.9
C3—C4—C5	109.2 (3)	C11—C10—H10	118.9
C3—C4—H4	125.4	C6—C11—C10	118.7 (3)
C5—C4—H4	125.4	C6—C11—H11	120.6
O5—C5—N1	125.3 (3)	C10—C11—H11	120.6
O5—C5—C4	128.6 (3)	C9—C12—H121	109.5
N1—C5—C4	106.1 (3)	C9—C12—H122	109.5
C11—C6—C7	121.0 (3)	H121—C12—H122	109.5
C11—C6—N1	120.2 (3)	C9—C12—H123	109.5
C7—C6—N1	118.8 (3)	H121—C12—H123	109.5
C8—C7—C6	118.8 (3)	H122—C12—H123	109.5
C8—C7—H7	120.6
C5—N1—C2—O2	179.2 (3)	C5—N1—C6—C7	131.6 (3)
C6—N1—C2—O2	0.6 (5)	C2—N1—C6—C7	−50.0 (5)
C5—N1—C2—C3	0.6 (4)	C11—C6—C7—C8	0.0 (5)
C6—N1—C2—C3	−178.0 (3)	N1—C6—C7—C8	178.2 (3)
O2—C2—C3—C4	−178.4 (4)	C6—C7—C8—C9	0.6 (5)
N1—C2—C3—C4	0.1 (4)	C6—C7—C8—Cl8	−178.9 (2)
C2—C3—C4—C5	−0.8 (4)	C7—C8—C9—C10	−0.7 (5)
C2—N1—C5—O5	178.1 (4)	Cl8—C8—C9—C10	178.7 (3)
C6—N1—C5—O5	−3.3 (6)	C7—C8—C9—C12	178.9 (3)
C2—N1—C5—C4	−1.0 (4)	Cl8—C8—C9—C12	−1.7 (4)
C6—N1—C5—C4	177.6 (3)	C8—C9—C10—C11	0.3 (5)
C3—C4—C5—O5	−178.0 (4)	C12—C9—C10—C11	−179.3 (3)
C3—C4—C5—N1	1.1 (4)	C7—C6—C11—C10	−0.3 (5)
C5—N1—C6—C11	−50.1 (5)	N1—C6—C11—C10	−178.6 (3)
C2—N1—C6—C11	128.3 (3)	C9—C10—C11—C6	0.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2^i	0.95	2.52	3.150 (4)	124
C7—H7···O2^ii	0.95	2.59	3.325 (4)	135
C10—H10···O5^iii	0.95	2.57	3.480 (4)	160

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