Crystal structure of 1,7,8,9-tetra-chloro-4-(3,5-di-chloro-benz-yl)-10,10-dimeth-oxy-4-aza-tri-cyclo-[5.2.1.0(2,6)]dec-8-ene-3,5-dione.

In the title compound, C17H11Cl6NO4, the configuration of the cyclo-alkene skeleton is endo,cis. The benzene ring is twisted by 58.94 (8)° from the attached pyrrolidine ring. Two carbonyl groups play a key role in the crystal packing. A short inter-molecular C⋯O distance of 3.017 (3) Å reveals that one carbonyl group is involved in dipole-dipole inter-actions, which link two adjacent enanti-omers into an inversion dimer. Another carbonyl group provides an acceptor for the weak inter-molecular C-H⋯O hydrogen bonds which link these dimers into layers parallel to (011).

Related literature

For related crystal structures, see: Shan et al. (2012 ▸); Kossakowski et al. (2009 ▸). For the biological activity of related compounds, see: Kossakowski et al. (2006 ▸, 2008 ▸); Struga et al. (2007 ▸).

Experimental

Crystal data

C17H11Cl6NO4

M = 505.97

Triclinic,

a = 8.9905 (18) Å

b = 11.351 (2) Å

c = 11.482 (2) Å

α = 119.52 (3)°

β = 94.51 (3)°

γ = 90.23 (3)°

V = 1015.2 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.87 mm−1

T = 296 K

0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

10037 measured reflections

4611 independent reflections

3865 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.111

S = 1.05

4611 reflections

254 parameters

H-atom parameters constrained

Δρmax = 0.70 e Å−3

Δρmin = −0.64 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989014025961/cv5477sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025961/cv5477Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014025961/cv5477Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989014025961/cv5477fig1.tif

View of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989014025961/cv5477fig2.tif

A portion of the crystal packing viewed approximately along [01-1]. The dipole-dipole and inter­molecular C—H⋯O inter­actions are shown by dashed lines. H atoms not involved in C—H⋯O inter­actions are omitted for clarity.

CCDC reference: 1036270

Additional supporting information: crystallographic information; 3D view; checkCIF report

C17H11Cl6NO4	Z = 2
Mr = 505.97	F(000) = 508
Triclinic, P1	Dx = 1.655 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9905 (18) Å	Cell parameters from 4035 reflections
b = 11.351 (2) Å	θ = 3.0–27.3°
c = 11.482 (2) Å	µ = 0.87 mm−1
α = 119.52 (3)°	T = 296 K
β = 94.51 (3)°	Column, colourless
γ = 90.23 (3)°	0.25 × 0.20 × 0.15 mm
V = 1015.2 (4) Å3

Bruker APEXII CCD diffractometer	3865 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 27.5°, θmin = 3.0°
φ and ω scans	h = −10→11
10037 measured reflections	k = −14→14
4611 independent reflections	l = −14→14

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043	H-atom parameters constrained
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.0412P)2 + 0.6429P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
4611 reflections	Δρmax = 0.70 e Å−3
254 parameters	Δρmin = −0.64 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.041 (3)

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.

	x	y	z	Uiso*/Ueq
Cl1	0.86211 (7)	0.64648 (6)	0.01529 (7)	0.04952 (18)
Cl2	0.42071 (6)	1.01968 (7)	0.22921 (7)	0.04994 (18)
Cl3	0.68066 (8)	1.06565 (7)	0.47167 (6)	0.05378 (19)
Cl4	0.95541 (7)	0.84784 (7)	0.33571 (7)	0.05465 (19)
Cl5	1.13965 (11)	1.59013 (7)	0.35138 (9)	0.0729 (3)
Cl6	1.36383 (11)	1.31140 (9)	0.58471 (9)	0.0808 (3)
O1	1.08016 (17)	0.94674 (16)	0.09979 (18)	0.0439 (4)
O2	0.72222 (19)	1.24926 (16)	0.29413 (19)	0.0498 (4)
O3	0.54476 (19)	0.70159 (18)	0.11801 (19)	0.0484 (4)
O4	0.53317 (18)	0.77943 (16)	−0.03513 (15)	0.0412 (4)
N4	0.92584 (19)	1.11941 (17)	0.21831 (17)	0.0314 (4)
C1	0.7734 (2)	0.8000 (2)	0.1025 (2)	0.0314 (4)
C2	0.8098 (2)	0.9081 (2)	0.0613 (2)	0.0298 (4)
H2A	0.8017	0.8681	−0.0367	0.036*
C3	0.9573 (2)	0.9867 (2)	0.1245 (2)	0.0314 (4)
C5	0.7731 (2)	1.1424 (2)	0.2225 (2)	0.0330 (4)
C6	0.6890 (2)	1.0109 (2)	0.1241 (2)	0.0299 (4)
H6A	0.6270	1.0203	0.0553	0.036*
C7	0.5955 (2)	0.9495 (2)	0.1918 (2)	0.0323 (4)
C8	0.6949 (2)	0.9539 (2)	0.3068 (2)	0.0335 (4)
C9	0.8003 (2)	0.8677 (2)	0.2542 (2)	0.0343 (5)
C10	0.5982 (2)	0.7951 (2)	0.0854 (2)	0.0340 (5)
C11	1.0373 (2)	1.2261 (2)	0.2981 (2)	0.0333 (4)
C12	1.0362 (3)	1.3406 (2)	0.2843 (2)	0.0409 (5)
H12A	0.9684	1.3467	0.2222	0.049*
C13	1.1394 (3)	1.4455 (2)	0.3660 (3)	0.0449 (6)
C14	1.2412 (3)	1.4386 (2)	0.4583 (3)	0.0472 (6)
H14A	1.3094	1.5104	0.5128	0.057*
C15	1.2391 (3)	1.3220 (2)	0.4674 (2)	0.0438 (5)
C16	1.1374 (2)	1.2143 (2)	0.3883 (2)	0.0371 (5)
H16A	1.1369	1.1365	0.3960	0.044*
C17	0.3854 (3)	0.6908 (4)	0.1208 (4)	0.0770 (10)
H17A	0.3617	0.6226	0.1436	0.115*
H17B	0.3366	0.6663	0.0339	0.115*
H17C	0.3516	0.7763	0.1866	0.115*
C18	0.5309 (4)	0.6462 (3)	−0.1513 (3)	0.0659 (9)
H18A	0.4837	0.6481	−0.2282	0.099*
H18B	0.4761	0.5833	−0.1356	0.099*
H18C	0.6314	0.6183	−0.1673	0.099*

	U11	U22	U33	U12	U13	U23
Cl1	0.0530 (4)	0.0289 (3)	0.0557 (4)	0.0074 (2)	−0.0005 (3)	0.0132 (3)
Cl2	0.0286 (3)	0.0601 (4)	0.0557 (4)	0.0069 (2)	0.0054 (3)	0.0243 (3)
Cl3	0.0559 (4)	0.0620 (4)	0.0311 (3)	0.0005 (3)	0.0030 (3)	0.0138 (3)
Cl4	0.0498 (4)	0.0656 (4)	0.0509 (4)	0.0087 (3)	−0.0132 (3)	0.0330 (3)
Cl5	0.1059 (7)	0.0302 (3)	0.0815 (5)	−0.0056 (3)	0.0087 (5)	0.0269 (3)
Cl6	0.0848 (6)	0.0607 (5)	0.0737 (5)	−0.0117 (4)	−0.0449 (4)	0.0228 (4)
O1	0.0299 (8)	0.0397 (9)	0.0530 (10)	0.0028 (6)	0.0050 (7)	0.0157 (8)
O2	0.0422 (9)	0.0303 (8)	0.0605 (11)	0.0061 (7)	0.0023 (8)	0.0103 (8)
O3	0.0439 (9)	0.0454 (10)	0.0604 (11)	−0.0151 (7)	−0.0078 (8)	0.0314 (9)
O4	0.0420 (9)	0.0352 (8)	0.0356 (8)	−0.0046 (6)	−0.0142 (7)	0.0117 (7)
N4	0.0293 (9)	0.0271 (8)	0.0332 (9)	−0.0022 (6)	−0.0018 (7)	0.0121 (7)
C1	0.0332 (10)	0.0242 (9)	0.0327 (10)	−0.0013 (7)	−0.0050 (8)	0.0120 (8)
C2	0.0312 (10)	0.0291 (10)	0.0269 (9)	0.0003 (8)	−0.0012 (8)	0.0127 (8)
C3	0.0327 (11)	0.0302 (10)	0.0304 (10)	−0.0008 (8)	0.0009 (8)	0.0147 (8)
C5	0.0340 (11)	0.0291 (10)	0.0357 (10)	0.0007 (8)	−0.0008 (9)	0.0163 (9)
C6	0.0289 (10)	0.0287 (10)	0.0308 (10)	−0.0007 (7)	−0.0033 (8)	0.0147 (8)
C7	0.0259 (10)	0.0343 (11)	0.0328 (10)	−0.0009 (8)	−0.0019 (8)	0.0143 (9)
C8	0.0329 (11)	0.0382 (11)	0.0295 (10)	−0.0052 (8)	−0.0013 (8)	0.0175 (9)
C9	0.0345 (11)	0.0368 (11)	0.0354 (11)	−0.0046 (8)	−0.0063 (9)	0.0222 (9)
C10	0.0326 (11)	0.0315 (10)	0.0352 (10)	−0.0053 (8)	−0.0068 (9)	0.0159 (9)
C11	0.0337 (11)	0.0279 (10)	0.0329 (10)	−0.0038 (8)	0.0024 (8)	0.0109 (8)
C12	0.0456 (13)	0.0327 (11)	0.0433 (12)	0.0004 (9)	0.0026 (10)	0.0183 (10)
C13	0.0556 (15)	0.0258 (10)	0.0477 (13)	−0.0016 (9)	0.0114 (12)	0.0128 (10)
C14	0.0459 (14)	0.0309 (11)	0.0450 (13)	−0.0068 (9)	0.0004 (11)	0.0041 (10)
C15	0.0429 (13)	0.0364 (12)	0.0381 (11)	−0.0010 (9)	−0.0052 (10)	0.0089 (10)
C16	0.0394 (12)	0.0309 (11)	0.0360 (11)	−0.0017 (8)	−0.0003 (9)	0.0134 (9)
C17	0.0500 (17)	0.078 (2)	0.113 (3)	−0.0235 (16)	0.0000 (18)	0.056 (2)
C18	0.076 (2)	0.0465 (16)	0.0449 (15)	0.0048 (14)	−0.0211 (14)	0.0028 (13)

Cl1—C1	1.758 (2)	C5—C6	1.507 (3)
Cl2—C7	1.752 (2)	C6—C7	1.558 (3)
Cl3—C8	1.698 (2)	C6—H6A	0.9800
Cl4—C9	1.696 (2)	C7—C8	1.514 (3)
Cl5—C13	1.730 (2)	C7—C10	1.568 (3)
Cl6—C15	1.735 (3)	C8—C9	1.318 (3)
O1—C3	1.197 (3)	C11—C16	1.375 (3)
O2—C5	1.199 (3)	C11—C12	1.385 (3)
O3—C10	1.383 (3)	C12—C13	1.383 (3)
O3—C17	1.442 (3)	C12—H12A	0.9300
O4—C10	1.385 (3)	C13—C14	1.377 (4)
O4—C18	1.440 (3)	C14—C15	1.379 (4)
N4—C5	1.399 (3)	C14—H14A	0.9300
N4—C3	1.400 (3)	C15—C16	1.386 (3)
N4—C11	1.436 (3)	C16—H16A	0.9300
C1—C9	1.515 (3)	C17—H17A	0.9600
C1—C2	1.558 (3)	C17—H17B	0.9600
C1—C10	1.569 (3)	C17—H17C	0.9600
C2—C3	1.511 (3)	C18—H18A	0.9600
C2—C6	1.538 (3)	C18—H18B	0.9600
C2—H2A	0.9800	C18—H18C	0.9600
C10—O3—C17	117.0 (2)	C8—C9—Cl4	127.64 (18)
C10—O4—C18	117.17 (19)	C1—C9—Cl4	123.58 (17)
C5—N4—C3	113.59 (17)	O3—C10—O4	113.93 (18)
C5—N4—C11	121.92 (17)	O3—C10—C7	118.24 (19)
C3—N4—C11	124.39 (18)	O4—C10—C7	106.81 (17)
C9—C1—C2	107.61 (16)	O3—C10—C1	108.32 (17)
C9—C1—C10	100.14 (17)	O4—C10—C1	116.35 (18)
C2—C1—C10	100.16 (16)	C7—C10—C1	91.53 (15)
C9—C1—Cl1	114.51 (15)	C16—C11—C12	122.2 (2)
C2—C1—Cl1	114.82 (15)	C16—C11—N4	119.76 (19)
C10—C1—Cl1	117.67 (14)	C12—C11—N4	118.0 (2)
C3—C2—C6	105.59 (16)	C13—C12—C11	117.7 (2)
C3—C2—C1	114.53 (17)	C13—C12—H12A	121.2
C6—C2—C1	102.43 (16)	C11—C12—H12A	121.2
C3—C2—H2A	111.3	C14—C13—C12	122.2 (2)
C6—C2—H2A	111.3	C14—C13—Cl5	119.21 (19)
C1—C2—H2A	111.3	C12—C13—Cl5	118.6 (2)
O1—C3—N4	124.78 (19)	C13—C14—C15	118.0 (2)
O1—C3—C2	127.70 (19)	C13—C14—H14A	121.0
N4—C3—C2	107.52 (17)	C15—C14—H14A	121.0
O2—C5—N4	124.4 (2)	C14—C15—C16	122.0 (2)
O2—C5—C6	127.7 (2)	C14—C15—Cl6	119.06 (19)
N4—C5—C6	107.93 (17)	C16—C15—Cl6	118.9 (2)
C5—C6—C2	105.31 (16)	C11—C16—C15	117.9 (2)
C5—C6—C7	113.74 (17)	C11—C16—H16A	121.0
C2—C6—C7	103.90 (16)	C15—C16—H16A	121.0
C5—C6—H6A	111.2	O3—C17—H17A	109.5
C2—C6—H6A	111.2	O3—C17—H17B	109.5
C7—C6—H6A	111.2	H17A—C17—H17B	109.5
C8—C7—C6	107.50 (16)	O3—C17—H17C	109.5
C8—C7—C10	100.17 (17)	H17A—C17—H17C	109.5
C6—C7—C10	99.80 (16)	H17B—C17—H17C	109.5
C8—C7—Cl2	116.77 (15)	O4—C18—H18A	109.5
C6—C7—Cl2	112.98 (15)	O4—C18—H18B	109.5
C10—C7—Cl2	117.57 (15)	H18A—C18—H18B	109.5
C9—C8—C7	107.49 (18)	O4—C18—H18C	109.5
C9—C8—Cl3	127.66 (18)	H18A—C18—H18C	109.5
C7—C8—Cl3	124.45 (16)	H18B—C18—H18C	109.5
C8—C9—C1	108.25 (19)
C9—C1—C2—C3	48.4 (2)	Cl1—C1—C9—C8	−160.38 (16)
C10—C1—C2—C3	152.57 (17)	C2—C1—C9—Cl4	−101.47 (19)
Cl1—C1—C2—C3	−80.38 (19)	C10—C1—C9—Cl4	154.36 (16)
C9—C1—C2—C6	−65.4 (2)	Cl1—C1—C9—Cl4	27.5 (2)
C10—C1—C2—C6	38.79 (18)	C17—O3—C10—O4	−54.4 (3)
Cl1—C1—C2—C6	165.84 (13)	C17—O3—C10—C7	72.3 (3)
C5—N4—C3—O1	176.3 (2)	C17—O3—C10—C1	174.4 (2)
C11—N4—C3—O1	−0.1 (3)	C18—O4—C10—O3	−51.2 (3)
C5—N4—C3—C2	−2.6 (2)	C18—O4—C10—C7	176.3 (2)
C11—N4—C3—C2	−178.97 (18)	C18—O4—C10—C1	75.9 (3)
C6—C2—C3—O1	−176.5 (2)	C8—C7—C10—O3	60.5 (2)
C1—C2—C3—O1	71.6 (3)	C6—C7—C10—O3	170.41 (18)
C6—C2—C3—N4	2.3 (2)	Cl2—C7—C10—O3	−67.1 (2)
C1—C2—C3—N4	−109.57 (19)	C8—C7—C10—O4	−169.50 (16)
C3—N4—C5—O2	−178.8 (2)	C6—C7—C10—O4	−59.55 (19)
C11—N4—C5—O2	−2.4 (3)	Cl2—C7—C10—O4	62.9 (2)
C3—N4—C5—C6	1.8 (2)	C8—C7—C10—C1	−51.33 (17)
C11—N4—C5—C6	178.21 (18)	C6—C7—C10—C1	58.61 (17)
O2—C5—C6—C2	−179.5 (2)	Cl2—C7—C10—C1	−178.91 (15)
N4—C5—C6—C2	−0.1 (2)	C9—C1—C10—O3	−70.1 (2)
O2—C5—C6—C7	−66.4 (3)	C2—C1—C10—O3	179.76 (16)
N4—C5—C6—C7	112.96 (19)	Cl1—C1—C10—O3	54.6 (2)
C3—C2—C6—C5	−1.3 (2)	C9—C1—C10—O4	160.04 (18)
C1—C2—C6—C5	118.88 (17)	C2—C1—C10—O4	49.9 (2)
C3—C2—C6—C7	−121.17 (17)	Cl1—C1—C10—O4	−75.2 (2)
C1—C2—C6—C7	−0.97 (19)	C9—C1—C10—C7	50.40 (18)
C5—C6—C7—C8	−47.1 (2)	C2—C1—C10—C7	−59.74 (17)
C2—C6—C7—C8	66.9 (2)	Cl1—C1—C10—C7	175.13 (15)
C5—C6—C7—C10	−151.10 (17)	C5—N4—C11—C16	121.4 (2)
C2—C6—C7—C10	−37.14 (18)	C3—N4—C11—C16	−62.5 (3)
C5—C6—C7—Cl2	83.22 (19)	C5—N4—C11—C12	−56.3 (3)
C2—C6—C7—Cl2	−162.83 (13)	C3—N4—C11—C12	119.8 (2)
C6—C7—C8—C9	−68.0 (2)	C16—C11—C12—C13	−0.6 (3)
C10—C7—C8—C9	35.8 (2)	N4—C11—C12—C13	177.0 (2)
Cl2—C7—C8—C9	163.88 (16)	C11—C12—C13—C14	0.2 (4)
C6—C7—C8—Cl3	105.23 (19)	C11—C12—C13—Cl5	−179.64 (17)
C10—C7—C8—Cl3	−151.01 (16)	C12—C13—C14—C15	0.4 (4)
Cl2—C7—C8—Cl3	−22.9 (2)	Cl5—C13—C14—C15	−179.70 (19)
C7—C8—C9—C1	−1.3 (2)	C13—C14—C15—C16	−0.8 (4)
Cl3—C8—C9—C1	−174.27 (16)	C13—C14—C15—Cl6	−178.90 (19)
C7—C8—C9—Cl4	170.36 (16)	C12—C11—C16—C15	0.3 (3)
Cl3—C8—C9—Cl4	−2.6 (3)	N4—C11—C16—C15	−177.3 (2)
C2—C1—C9—C8	70.7 (2)	C14—C15—C16—C11	0.4 (4)
C10—C1—C9—C8	−33.5 (2)	Cl6—C15—C16—C11	178.55 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14A···O2i	0.93	2.57	3.265 (4)	132
C18—H18A···O2ii	0.96	2.45	3.260 (4)	141

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C14H14AO2i	0.93	2.57	3.265(4)	132
C18H18AO2ii	0.96	2.45	3.260(4)	141

Symmetry codes: (i) ; (ii) .