Crystal structure of 1,7,8,9-tetra-chloro-4-(2-fluoro-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, C17H12Cl4FNO4, the configuration of the cyclo-alkene skeleton is endo,cis. The benzene ring is twisted by 71.01 (11)° from the attached pyrrolidine ring. In the crystal, one of the methine groups of the fused-ring system forms a weak C-H⋯O hydrogen bond. The other methine groups participates in a C-H⋯F inter-action to the same adjacent mol-ecule. Together, these generate [010] chains.

Related literature

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

Experimental

Crystal data

C17H12Cl4FNO4

M = 455.08

Orthorhombic,

a = 9.965 (2) Å

b = 10.982 (2) Å

c = 16.926 (3) Å

V = 1852.1 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.67 mm−1

T = 296 K

0.20 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer

17912 measured reflections

4238 independent reflections

3231 reflections with I > 2σ(I)

R int = 0.069

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.101

S = 1.00

4238 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack (1983 ▸), 1826 Friedel pairs

Absolute structure parameter: −0.02 (7)

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/S2056989014026279/hb7331sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014026279/hb7331Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014026279/hb7331Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989014026279/hb7331fig1.tif

View of the mol­ecule of (I) showing displacement ellipsoids drawn at the 30% probability level.

Click here for additional data file.

X X x y z x y z . DOI: 10.1107/S2056989014026279/hb7331fig2.tif

The C—H⋯X(X=O/F) inter­actions, dashed lines. Non-essential H atoms are omitted for clarity. Symmetry code: (i) 1 − x,  + y,  − z. (ii) 1 − x, y − ,  − z.

CCDC reference: 1036764

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

C17H12Cl4FNO4	F(000) = 920
Mr = 455.08	Dx = 1.632 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4520 reflections
a = 9.965 (2) Å	θ = 3.0–27.5°
b = 10.982 (2) Å	µ = 0.67 mm−1
c = 16.926 (3) Å	T = 296 K
V = 1852.1 (6) Å3	Prismatic, colorless
Z = 4	0.20 × 0.15 × 0.10 mm

Bruker APEXII CCD diffractometer	3231 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.069
Graphite monochromator	θmax = 27.5°, θmin = 3.0°
φ and ω scans	h = −12→12
17912 measured reflections	k = −14→14
4238 independent reflections	l = −21→21

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)] = 0.046	H-atom parameters constrained
wR(F2) = 0.101	w = 1/[σ2(Fo2) + (0.050P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
4238 reflections	Δρmax = 0.28 e Å−3
244 parameters	Δρmin = −0.27 e Å−3
0 restraints	Absolute structure: Flack (1983), 1826 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (7)

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	0.09057 (8)	0.72603 (7)	0.11428 (5)	0.0470 (2)
Cl2	0.31474 (10)	0.49911 (9)	0.37871 (5)	0.0614 (3)
Cl3	0.28576 (9)	0.30235 (7)	0.23337 (6)	0.0541 (2)
Cl4	0.16447 (10)	0.44681 (8)	0.07087 (5)	0.0549 (3)
F1	0.5234 (2)	0.33581 (19)	0.09916 (14)	0.0675 (6)
O1	0.4175 (2)	0.6801 (2)	0.03909 (14)	0.0582 (7)
O2	0.5994 (2)	0.4890 (2)	0.25327 (14)	0.0578 (6)
O3	0.1973 (2)	0.74679 (18)	0.30831 (13)	0.0420 (5)
O4	0.0408 (2)	0.59723 (19)	0.27636 (13)	0.0416 (5)
N4	0.5329 (2)	0.5781 (2)	0.13621 (15)	0.0354 (6)
C1	0.2012 (3)	0.6451 (2)	0.17531 (17)	0.0305 (6)
C2	0.3479 (3)	0.6939 (3)	0.17719 (17)	0.0328 (6)
H2A	0.3501	0.7825	0.1839	0.039*
C3	0.4315 (3)	0.6544 (3)	0.1073 (2)	0.0380 (7)
C5	0.5247 (3)	0.5554 (3)	0.21679 (19)	0.0394 (7)
C6	0.4076 (3)	0.6283 (3)	0.24928 (18)	0.0354 (7)
H6A	0.4383	0.6870	0.2889	0.042*
C7	0.2890 (3)	0.5511 (3)	0.28159 (17)	0.0365 (7)
C8	0.2570 (3)	0.4540 (3)	0.22159 (18)	0.0347 (7)
C9	0.2065 (3)	0.5094 (3)	0.15910 (17)	0.0335 (6)
C10	0.1705 (3)	0.6410 (3)	0.26658 (18)	0.0344 (7)
C11	0.6311 (3)	0.5241 (3)	0.08502 (18)	0.0357 (7)
C12	0.6251 (3)	0.4016 (3)	0.06730 (19)	0.0400 (7)
C13	0.7166 (4)	0.3465 (3)	0.0191 (2)	0.0529 (9)
H13A	0.7117	0.2634	0.0090	0.063*
C14	0.8162 (4)	0.4165 (3)	−0.0142 (2)	0.0517 (9)
H14A	0.8782	0.3810	−0.0481	0.062*
C15	0.8242 (3)	0.5388 (3)	0.0026 (2)	0.0511 (9)
H15A	0.8925	0.5855	−0.0195	0.061*
C16	0.7320 (3)	0.5925 (3)	0.0517 (2)	0.0458 (8)
H16A	0.7378	0.6753	0.0626	0.055*
C17	0.1104 (3)	0.8490 (3)	0.2942 (2)	0.0523 (9)
H17A	0.1389	0.9166	0.3260	0.078*
H17B	0.0199	0.8275	0.3078	0.078*
H17C	0.1144	0.8712	0.2394	0.078*
C18	−0.0074 (4)	0.5857 (4)	0.3562 (2)	0.0682 (12)
H18A	−0.0975	0.5547	0.3556	0.102*
H18B	−0.0063	0.6640	0.3814	0.102*
H18C	0.0493	0.5306	0.3848	0.102*

	U11	U22	U33	U12	U13	U23
Cl1	0.0449 (4)	0.0488 (4)	0.0472 (5)	0.0125 (4)	−0.0076 (4)	0.0056 (4)
Cl2	0.0770 (6)	0.0779 (6)	0.0295 (4)	0.0107 (5)	−0.0045 (4)	0.0089 (4)
Cl3	0.0587 (5)	0.0322 (4)	0.0714 (6)	0.0060 (4)	0.0034 (5)	0.0080 (4)
Cl4	0.0725 (6)	0.0539 (5)	0.0382 (5)	0.0019 (4)	−0.0065 (4)	−0.0174 (4)
F1	0.0668 (13)	0.0489 (11)	0.0869 (17)	−0.0211 (11)	0.0124 (13)	−0.0032 (11)
O1	0.0571 (15)	0.0707 (17)	0.0467 (15)	0.0238 (14)	0.0139 (13)	0.0245 (13)
O2	0.0512 (13)	0.0732 (16)	0.0489 (14)	0.0201 (14)	−0.0076 (12)	0.0059 (13)
O3	0.0397 (12)	0.0425 (12)	0.0438 (12)	0.0047 (10)	0.0007 (10)	−0.0187 (10)
O4	0.0354 (12)	0.0516 (13)	0.0380 (13)	−0.0048 (10)	0.0104 (9)	−0.0076 (10)
N4	0.0318 (13)	0.0332 (13)	0.0410 (16)	0.0069 (11)	0.0050 (11)	0.0015 (12)
C1	0.0289 (15)	0.0310 (14)	0.0315 (15)	0.0016 (12)	−0.0015 (13)	−0.0001 (12)
C2	0.0293 (14)	0.0277 (14)	0.0413 (17)	0.0005 (12)	0.0025 (13)	−0.0005 (13)
C3	0.0356 (16)	0.0309 (15)	0.048 (2)	0.0011 (13)	0.0073 (15)	0.0087 (14)
C5	0.0314 (16)	0.0379 (16)	0.049 (2)	0.0036 (14)	−0.0049 (15)	−0.0054 (15)
C6	0.0324 (15)	0.0363 (15)	0.0374 (17)	0.0006 (13)	−0.0038 (14)	−0.0072 (14)
C7	0.0409 (16)	0.0403 (15)	0.0282 (16)	0.0041 (14)	−0.0019 (14)	0.0023 (13)
C8	0.0369 (16)	0.0315 (14)	0.0356 (16)	0.0003 (13)	0.0015 (14)	0.0023 (13)
C9	0.0369 (15)	0.0328 (14)	0.0308 (15)	0.0001 (14)	0.0031 (12)	−0.0060 (13)
C10	0.0360 (16)	0.0357 (15)	0.0316 (16)	0.0008 (13)	−0.0004 (13)	−0.0054 (12)
C11	0.0343 (15)	0.0340 (15)	0.0389 (16)	0.0052 (13)	0.0005 (13)	0.0005 (13)
C12	0.0393 (18)	0.0385 (17)	0.0422 (19)	−0.0049 (14)	0.0008 (14)	0.0015 (14)
C13	0.062 (2)	0.0429 (18)	0.054 (2)	0.0043 (18)	−0.0030 (19)	−0.0170 (17)
C14	0.052 (2)	0.063 (2)	0.0401 (19)	0.0176 (18)	0.0028 (17)	−0.0024 (17)
C15	0.0406 (19)	0.055 (2)	0.057 (2)	0.0036 (17)	0.0133 (18)	0.0102 (18)
C16	0.0453 (19)	0.0336 (16)	0.058 (2)	−0.0006 (15)	0.0057 (17)	0.0055 (16)
C17	0.047 (2)	0.0437 (18)	0.066 (2)	0.0124 (16)	−0.0026 (18)	−0.0189 (17)
C18	0.064 (3)	0.086 (3)	0.054 (2)	−0.009 (2)	0.030 (2)	−0.004 (2)

Cl1—C1	1.753 (3)	C6—C7	1.554 (4)
Cl2—C7	1.759 (3)	C6—H6A	0.9800
Cl3—C8	1.702 (3)	C7—C8	1.506 (4)
Cl4—C9	1.696 (3)	C7—C10	1.560 (4)
F1—C12	1.356 (4)	C8—C9	1.320 (4)
O1—C3	1.197 (4)	C11—C16	1.376 (4)
O2—C5	1.211 (4)	C11—C12	1.380 (4)
O3—C10	1.385 (3)	C12—C13	1.365 (5)
O3—C17	1.438 (4)	C13—C14	1.376 (5)
O4—C10	1.389 (3)	C13—H13A	0.9300
O4—C18	1.440 (4)	C14—C15	1.375 (5)
N4—C5	1.389 (4)	C14—H14A	0.9300
N4—C3	1.401 (4)	C15—C16	1.372 (5)
N4—C11	1.435 (4)	C15—H15A	0.9300
C1—C9	1.516 (4)	C16—H16A	0.9300
C1—C2	1.557 (4)	C17—H17A	0.9600
C1—C10	1.576 (4)	C17—H17B	0.9600
C2—C3	1.511 (4)	C17—H17C	0.9600
C2—C6	1.537 (4)	C18—H18A	0.9600
C2—H2A	0.9800	C18—H18B	0.9600
C5—C6	1.518 (4)	C18—H18C	0.9600
C10—O3—C17	117.0 (2)	C8—C9—Cl4	127.8 (2)
C10—O4—C18	116.9 (3)	C1—C9—Cl4	123.3 (2)
C5—N4—C3	114.1 (3)	O3—C10—O4	114.1 (2)
C5—N4—C11	124.0 (2)	O3—C10—C7	107.6 (2)
C3—N4—C11	121.9 (3)	O4—C10—C7	117.7 (2)
C9—C1—C2	108.0 (2)	O3—C10—C1	116.0 (2)
C9—C1—C10	99.0 (2)	O4—C10—C1	107.9 (2)
C2—C1—C10	99.9 (2)	C7—C10—C1	91.8 (2)
C9—C1—Cl1	114.4 (2)	C16—C11—C12	118.4 (3)
C2—C1—Cl1	115.35 (19)	C16—C11—N4	121.3 (3)
C10—C1—Cl1	118.0 (2)	C12—C11—N4	120.3 (3)
C3—C2—C6	105.9 (2)	F1—C12—C13	120.0 (3)
C3—C2—C1	113.7 (2)	F1—C12—C11	117.7 (3)
C6—C2—C1	102.6 (2)	C13—C12—C11	122.2 (3)
C3—C2—H2A	111.4	C12—C13—C14	118.6 (3)
C6—C2—H2A	111.4	C12—C13—H13A	120.7
C1—C2—H2A	111.4	C14—C13—H13A	120.7
O1—C3—N4	124.2 (3)	C15—C14—C13	120.2 (3)
O1—C3—C2	128.5 (3)	C15—C14—H14A	119.9
N4—C3—C2	107.2 (3)	C13—C14—H14A	119.9
O2—C5—N4	124.9 (3)	C16—C15—C14	120.3 (3)
O2—C5—C6	127.2 (3)	C16—C15—H15A	119.8
N4—C5—C6	107.8 (2)	C14—C15—H15A	119.8
C5—C6—C2	104.9 (2)	C15—C16—C11	120.2 (3)
C5—C6—C7	115.1 (2)	C15—C16—H16A	119.9
C2—C6—C7	104.0 (2)	C11—C16—H16A	119.9
C5—C6—H6A	110.8	O3—C17—H17A	109.5
C2—C6—H6A	110.8	O3—C17—H17B	109.5
C7—C6—H6A	110.8	H17A—C17—H17B	109.5
C8—C7—C6	108.0 (2)	O3—C17—H17C	109.5
C8—C7—C10	100.3 (2)	H17A—C17—H17C	109.5
C6—C7—C10	99.9 (2)	H17B—C17—H17C	109.5
C8—C7—Cl2	115.6 (2)	O4—C18—H18A	109.5
C6—C7—Cl2	113.3 (2)	O4—C18—H18B	109.5
C10—C7—Cl2	117.9 (2)	H18A—C18—H18B	109.5
C9—C8—C7	107.1 (2)	O4—C18—H18C	109.5
C9—C8—Cl3	127.5 (2)	H18A—C18—H18C	109.5
C7—C8—Cl3	125.3 (2)	H18B—C18—H18C	109.5
C8—C9—C1	108.7 (3)
C9—C1—C2—C3	49.3 (3)	Cl1—C1—C9—C8	−160.5 (2)
C10—C1—C2—C3	152.2 (2)	C2—C1—C9—Cl4	−106.0 (3)
Cl1—C1—C2—C3	−80.2 (3)	C10—C1—C9—Cl4	150.4 (2)
C9—C1—C2—C6	−64.6 (3)	Cl1—C1—C9—Cl4	24.0 (3)
C10—C1—C2—C6	38.3 (2)	C17—O3—C10—O4	−55.9 (4)
Cl1—C1—C2—C6	165.98 (19)	C17—O3—C10—C7	171.5 (3)
C5—N4—C3—O1	−176.4 (3)	C17—O3—C10—C1	70.5 (3)
C11—N4—C3—O1	0.4 (5)	C18—O4—C10—O3	−49.8 (4)
C5—N4—C3—C2	3.3 (3)	C18—O4—C10—C7	77.8 (4)
C11—N4—C3—C2	−179.9 (3)	C18—O4—C10—C1	179.7 (3)
C6—C2—C3—O1	177.2 (3)	C8—C7—C10—O3	−170.1 (2)
C1—C2—C3—O1	65.3 (4)	C6—C7—C10—O3	−59.5 (3)
C6—C2—C3—N4	−2.4 (3)	Cl2—C7—C10—O3	63.6 (3)
C1—C2—C3—N4	−114.3 (3)	C8—C7—C10—O4	59.3 (3)
C3—N4—C5—O2	177.5 (3)	C6—C7—C10—O4	169.9 (2)
C11—N4—C5—O2	0.8 (5)	Cl2—C7—C10—O4	−67.0 (3)
C3—N4—C5—C6	−2.7 (3)	C8—C7—C10—C1	−52.0 (2)
C11—N4—C5—C6	−179.4 (3)	C6—C7—C10—C1	58.5 (2)
O2—C5—C6—C2	−179.2 (3)	Cl2—C7—C10—C1	−178.3 (2)
N4—C5—C6—C2	0.9 (3)	C9—C1—C10—O3	161.4 (2)
O2—C5—C6—C7	−65.6 (4)	C2—C1—C10—O3	51.1 (3)
N4—C5—C6—C7	114.5 (3)	Cl1—C1—C10—O3	−74.7 (3)
C3—C2—C6—C5	0.9 (3)	C9—C1—C10—O4	−69.1 (3)
C1—C2—C6—C5	120.4 (2)	C2—C1—C10—O4	−179.4 (2)
C3—C2—C6—C7	−120.4 (3)	Cl1—C1—C10—O4	54.8 (3)
C1—C2—C6—C7	−0.9 (3)	C9—C1—C10—C7	50.8 (2)
C5—C6—C7—C8	−47.1 (3)	C2—C1—C10—C7	−59.4 (2)
C2—C6—C7—C8	67.1 (3)	Cl1—C1—C10—C7	174.7 (2)
C5—C6—C7—C10	−151.4 (2)	C5—N4—C11—C16	−110.9 (4)
C2—C6—C7—C10	−37.3 (3)	C3—N4—C11—C16	72.6 (4)
C5—C6—C7—Cl2	82.2 (3)	C5—N4—C11—C12	69.9 (4)
C2—C6—C7—Cl2	−163.61 (19)	C3—N4—C11—C12	−106.6 (3)
C6—C7—C8—C9	−68.4 (3)	C16—C11—C12—F1	−178.6 (3)
C10—C7—C8—C9	35.7 (3)	N4—C11—C12—F1	0.6 (5)
Cl2—C7—C8—C9	163.6 (2)	C16—C11—C12—C13	1.0 (5)
C6—C7—C8—Cl3	110.2 (3)	N4—C11—C12—C13	−179.8 (3)
C10—C7—C8—Cl3	−145.7 (2)	F1—C12—C13—C14	178.1 (3)
Cl2—C7—C8—Cl3	−17.8 (3)	C11—C12—C13—C14	−1.5 (5)
C7—C8—C9—C1	−0.7 (3)	C12—C13—C14—C15	1.4 (6)
Cl3—C8—C9—C1	−179.2 (2)	C13—C14—C15—C16	−0.9 (6)
C7—C8—C9—Cl4	174.6 (2)	C14—C15—C16—C11	0.3 (5)
Cl3—C8—C9—Cl4	−4.0 (4)	C12—C11—C16—C15	−0.4 (5)
C2—C1—C9—C8	69.5 (3)	N4—C11—C16—C15	−179.6 (3)
C10—C1—C9—C8	−34.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O2i	0.98	2.55	3.487 (4)	159
C6—H6A···F1i	0.98	2.53	3.500 (4)	170

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C2H2AO2i	0.98	2.55	3.487(4)	159
C6H6AF1i	0.98	2.53	3.500(4)	170

Symmetry code: (i) .