3-Benzoyl­methyl-2-chloro-N-methyl­maleimide

In the title compound, C₁₃H₁₀ClNO₃, the dihedral angle between the two rings is 68.9 (3)°. The crystal structure is stabilized by weak inter­molecular C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.049
• wR factor = 0.150
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ...    1214.40 Ang-3
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

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

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

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S1. Comment

We have investigated the photo-induced reaction of 3,4-dichloromaleimide (3,4-dichloro-pyrrole-2,5-dione) and 2-trimethylsiloxyphenylethene, and obtained the title compound, (I), as one of the products. An X-ray crystallographic analysis was undertaken to establish its structure and configuration.

In the structure of (I) (Fig. 1), bond lengths and angles are in good agreement with the expected values (Allen et al., 1987). Both the maleimide ring and the phenyl ring are planar to within ±0.02 Å. The carbonyl group linked to the phenyl ring is nearly in the plane of the phenyl ring, with atom C7 deviating by 0.019 (3) Å. Similarly, atom Cll is in the plane of the maleimide ring, with a deviation of 0.045 (3) Å. On the other hand, the methylene group lies approximately on the cross line of the two ring planes. The calculated deviations for this atom from the phenyl and maleimide rings are 0.058 (2) and 0.100 (2) Å, respectively. Finally, the dihedral angle between the phenyl and maleimide rings is 68.9 (3)°.

In the packing of the title compound, the molecules are linked into layers (Fig. 2) by C3—H3A···O3 and C8—H8B···O1 intermolecular contacts (Table 2). No significant π–π interactions are observed in the crystal structure.

S2. Experimental

The title compound was one of the products of a photo-induced reaction between 3,4-dichloromaleimide (3,4-dichloro-pyrrole-2,5-dione) and an excess amount of 2-trimethylsiloxyphenylethene in benzene [Please give brief details of quantities, volume of solvent, wavelength of radiation, time etc.]. The title compound was isolated using column chromatography (yield 35%). Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a petroleum ether–ethyl acetate (4:1) solution.

S3. Refinement

H atoms were positioned geometrically and treated as riding on their parent C atoms, with C—H distances constrained to 0.93 (aromatic CH), 0.97 (methylene CH₂) or 0.96 Å (methyl CH₃), and with U_iso(H) = 1.2U_eq(C) for aromatic CH and methylene CH₂, or 1.5U_eq(C) for the methyl group.

Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The packing structure of (I), viewed along [100].

3-Benzoylmethyl-2-chloro-N-methylmaleimide

Crystal data

C13H10ClNO3	F(000) = 544
Mr = 263.67	Dx = 1.442 Mg m^−3
Monoclinic, P21/n	Melting point: 448.2 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.474 (2) Å	Cell parameters from 25 reflections
b = 24.185 (3) Å	θ = 1.7–25.0°
c = 9.283 (2) Å	µ = 0.31 mm^−1
β = 98.78 (3)°	T = 298 K
V = 1214.4 (5) Å^3	Block, colourless
Z = 4	0.40 × 0.40 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	1321 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.066
Graphite monochromator	θmax = 25.0°, θmin = 1.7°
ω/2θ scans	h = 0→6
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995)	k = 0→28
Tmin = 0.885, Tmax = 0.965	l = −11→10
2298 measured reflections	3 standard reflections every 200 reflections
2085 independent reflections	intensity decay: none

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)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.150	w = 1/[σ^2(Fo^2) + (0.0337P)^2 + P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
2085 reflections	Δρmax = 0.32 e Å^−3
163 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (3)

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
N	−0.1184 (4)	0.11267 (11)	0.4283 (3)	0.0471 (6)
O1	−0.2122 (4)	0.27081 (9)	0.2373 (3)	0.0677 (7)
O2	−0.2164 (4)	0.19502 (9)	0.5287 (2)	0.0599 (6)
O3	0.0564 (5)	0.04984 (10)	0.2877 (3)	0.0679 (7)
C1	0.2725 (7)	0.42659 (15)	0.4167 (4)	0.0636 (10)
H1A	0.4201	0.4410	0.4652	0.076*
C2	0.0843 (8)	0.46136 (15)	0.3606 (4)	0.0674 (11)
H2A	0.1065	0.4994	0.3698	0.081*
C3	−0.1370 (7)	0.44084 (15)	0.2909 (4)	0.0649 (10)
H3A	−0.2649	0.4648	0.2552	0.078*
C4	−0.1677 (6)	0.38457 (14)	0.2744 (3)	0.0530 (8)
H4A	−0.3166	0.3706	0.2265	0.064*
C5	0.0209 (5)	0.34839 (12)	0.3283 (3)	0.0422 (7)
C6	0.2421 (6)	0.36993 (13)	0.4009 (4)	0.0512 (8)
H6A	0.3696	0.3462	0.4389	0.061*
C7	−0.0222 (5)	0.28831 (13)	0.3063 (3)	0.0424 (7)
C8	0.1775 (6)	0.24851 (13)	0.3731 (4)	0.0482 (8)
H8A	0.3191	0.2519	0.3224	0.058*
H8B	0.2304	0.2586	0.4743	0.058*
C9	0.0931 (5)	0.19025 (12)	0.3660 (3)	0.0411 (7)
C10	−0.0976 (5)	0.16902 (13)	0.4524 (3)	0.0443 (7)
C11	0.0328 (6)	0.09613 (13)	0.3307 (3)	0.0455 (7)
C12	0.1621 (5)	0.14741 (12)	0.2931 (3)	0.0436 (7)
C13	−0.2828 (7)	0.07543 (15)	0.4933 (4)	0.0643 (10)
H13A	−0.2630	0.0384	0.4597	0.097*
H13B	−0.4511	0.0869	0.4651	0.097*
H13C	−0.2418	0.0766	0.5975	0.097*
Cl	0.36553 (16)	0.14479 (4)	0.17204 (9)	0.0645 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N	0.0496 (15)	0.0452 (16)	0.0495 (15)	−0.0031 (12)	0.0172 (12)	0.0047 (11)
O1	0.0555 (15)	0.0588 (15)	0.0793 (16)	−0.0098 (12)	−0.0202 (13)	0.0021 (12)
O2	0.0616 (14)	0.0650 (16)	0.0573 (14)	0.0040 (12)	0.0224 (12)	−0.0097 (11)
O3	0.0755 (17)	0.0481 (16)	0.0850 (17)	−0.0023 (12)	0.0283 (14)	−0.0060 (12)
C1	0.069 (2)	0.059 (2)	0.066 (2)	−0.0207 (19)	0.0246 (19)	−0.0201 (18)
C2	0.094 (3)	0.044 (2)	0.077 (3)	−0.004 (2)	0.052 (2)	−0.0083 (18)
C3	0.071 (2)	0.054 (2)	0.074 (2)	0.0184 (18)	0.029 (2)	0.0080 (18)
C4	0.0515 (19)	0.055 (2)	0.0566 (19)	0.0056 (15)	0.0205 (15)	0.0031 (16)
C5	0.0448 (17)	0.0464 (18)	0.0379 (15)	0.0001 (13)	0.0142 (13)	0.0011 (13)
C6	0.0486 (18)	0.054 (2)	0.0523 (18)	−0.0066 (15)	0.0108 (15)	−0.0038 (15)
C7	0.0411 (17)	0.0490 (18)	0.0370 (15)	−0.0045 (14)	0.0053 (13)	0.0030 (13)
C8	0.0441 (16)	0.0469 (18)	0.0531 (18)	−0.0034 (13)	0.0060 (14)	0.0025 (14)
C9	0.0399 (16)	0.0419 (17)	0.0411 (16)	0.0008 (13)	0.0046 (12)	0.0034 (13)
C10	0.0449 (17)	0.0474 (18)	0.0400 (16)	0.0016 (14)	0.0046 (14)	0.0010 (14)
C11	0.0484 (17)	0.0417 (18)	0.0457 (17)	0.0026 (14)	0.0052 (14)	0.0014 (14)
C12	0.0414 (16)	0.0509 (18)	0.0400 (16)	0.0022 (13)	0.0111 (13)	0.0057 (14)
C13	0.064 (2)	0.065 (2)	0.069 (2)	−0.0120 (18)	0.0271 (19)	0.0113 (18)
Cl	0.0606 (6)	0.0790 (7)	0.0604 (5)	−0.0022 (4)	0.0299 (4)	0.0015 (4)

Geometric parameters (Å, º)

N—C11	1.377 (4)	C5—C6	1.394 (4)
N—C10	1.383 (4)	C5—C7	1.481 (4)
N—C13	1.466 (4)	C6—H6A	0.9300
O1—C7	1.211 (3)	C7—C8	1.516 (4)
O2—C10	1.208 (4)	C8—C9	1.481 (4)
O3—C11	1.202 (3)	C8—H8A	0.9700
C1—C2	1.369 (5)	C8—H8B	0.9700
C1—C6	1.385 (4)	C9—C12	1.324 (4)
C1—H1A	0.9300	C9—C10	1.501 (4)
C2—C3	1.376 (5)	C11—C12	1.495 (4)
C2—H2A	0.9300	C12—Cl	1.700 (3)
C3—C4	1.377 (5)	C13—H13A	0.9600
C3—H3A	0.9300	C13—H13B	0.9600
C4—C5	1.387 (4)	C13—H13C	0.9600
C4—H4A	0.9300
C11—N—C10	110.6 (3)	C9—C8—C7	112.6 (3)
C11—N—C13	124.1 (3)	C9—C8—H8A	109.1
C10—N—C13	125.4 (3)	C7—C8—H8A	109.1
C2—C1—C6	119.8 (3)	C9—C8—H8B	109.1
C2—C1—H1A	120.0	C7—C8—H8B	109.1
C6—C1—H1A	120.0	H8A—C8—H8B	107.8
C1—C2—C3	120.9 (3)	C12—C9—C8	131.1 (3)
C1—C2—H2A	119.8	C12—C9—C10	106.3 (3)
C3—C2—H2A	119.8	C8—C9—C10	122.6 (3)
C4—C3—C2	119.8 (4)	O2—C10—N	124.7 (3)
C4—C3—H3A	120.1	O2—C10—C9	127.8 (3)
C2—C3—H3A	120.1	N—C10—C9	107.1 (3)
C3—C4—C5	120.7 (3)	O3—C11—N	126.5 (3)
C3—C4—H4A	119.7	O3—C11—C12	128.0 (3)
C5—C4—H4A	119.7	N—C11—C12	105.5 (3)
C6—C5—C4	118.6 (3)	C9—C12—C11	110.4 (3)
C6—C5—C7	123.1 (3)	C9—C12—Cl	129.2 (3)
C4—C5—C7	118.3 (3)	C11—C12—Cl	120.4 (2)
C1—C6—C5	120.3 (3)	N—C13—H13A	109.5
C1—C6—H6A	119.9	N—C13—H13B	109.5
C5—C6—H6A	119.9	H13A—C13—H13B	109.5
O1—C7—C5	121.7 (3)	N—C13—H13C	109.5
O1—C7—C8	119.8 (3)	H13A—C13—H13C	109.5
C5—C7—C8	118.5 (3)	H13B—C13—H13C	109.5
C6—C1—C2—C3	1.1 (6)	C11—N—C10—C9	−2.3 (3)
C1—C2—C3—C4	−1.3 (6)	C13—N—C10—C9	179.4 (3)
C2—C3—C4—C5	0.3 (5)	C12—C9—C10—O2	−176.2 (3)
C3—C4—C5—C6	0.7 (5)	C8—C9—C10—O2	5.2 (5)
C3—C4—C5—C7	−179.5 (3)	C12—C9—C10—N	3.0 (3)
C2—C1—C6—C5	−0.1 (5)	C8—C9—C10—N	−175.5 (3)
C4—C5—C6—C1	−0.8 (5)	C10—N—C11—O3	180.0 (3)
C7—C5—C6—C1	179.4 (3)	C13—N—C11—O3	−1.7 (6)
C6—C5—C7—O1	−176.7 (3)	C10—N—C11—C12	0.8 (3)
C4—C5—C7—O1	3.5 (5)	C13—N—C11—C12	179.1 (3)
C6—C5—C7—C8	3.5 (4)	C8—C9—C12—C11	175.8 (3)
C4—C5—C7—C8	−176.3 (3)	C10—C9—C12—C11	−2.6 (3)
O1—C7—C8—C9	−10.1 (4)	C8—C9—C12—Cl	−3.7 (5)
C5—C7—C8—C9	169.7 (3)	C10—C9—C12—Cl	177.9 (2)
C7—C8—C9—C12	113.5 (4)	O3—C11—C12—C9	−177.9 (3)
C7—C8—C9—C10	−68.3 (4)	N—C11—C12—C9	1.3 (4)
C11—N—C10—O2	177.0 (3)	O3—C11—C12—Cl	1.6 (5)
C13—N—C10—O2	−1.3 (5)	N—C11—C12—Cl	−179.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···O3	0.95	2.55	2.925 (5)	102
C3—H3A···O3^i	0.93	2.59	3.499 (5)	163
C8—H8B···O1^ii	0.97	2.51	3.375 (5)	147

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