endo-6,syn-7-Di­chloro-exo-6-phenyl­sulfonylbi­cyclo­[3.1.1]­heptane

The reaction between 1-(phenyl­sulfonyl)­tri­cyclo­[4.1.0.0^2,7]­heptane, (1), and nitryl chloride in (CH₃)₂O gives rise to formation of a mixture of chlorination products instead of the expected nitro compounds. This mixture consists of the title compound, C₁₃H₁₄Cl₂O₂S, (2), and exo-6,syn-7-di­chloro-endo-6-phenyl­sulfonyl­bi­cyclo­[3.1.1]­heptane, (3), in the ratio 88:12. The structure of the major product, (2), was established by X-ray analysis. In (2), the phenyl­sulfonyl group has an axial orientation, and both Cl atoms are in equatorial positions.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.033
• wR factor = 0.091
• Data-to-parameter ratio = 14.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

---

Computing details

Data collection: P3 (Siemens, 1989); cell refinement: P3; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

endo-6,syn-7-Dichloro-exo-6-phenylsulfonylbicyclo[3.1.1]heptane

Crystal data

C13H14Cl2O2S	F(000) = 632
Mr = 305.20	Dx = 1.472 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.162 (4) Å	Cell parameters from 24 reflections
b = 16.710 (11) Å	θ = 10–11°
c = 13.403 (7) Å	µ = 0.61 mm^−1
β = 93.58 (4)°	T = 173 K
V = 1377.3 (14) Å^3	Squared prism, colorless
Z = 4	0.50 × 0.30 × 0.30 mm

Data collection

Siemens P3 diffractometer	Rint = 0.044
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 2.0°
Graphite monochromator	h = 0→7
θ/2θ scans	k = 0→19
2602 measured reflections	l = −15→15
2372 independent reflections	2 standard reflections every 98 reflections
1699 reflections with I > 2σ(I)	intensity decay: 3.2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: difference Fourier map
wR(F^2) = 0.091	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0625P)^2] where P = (Fo^2 + 2Fc^2)/3
2372 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Experimental. Data for compound (2)

¹H-NMR(CDCl₃): δ (p.p.m)=1.49–1.82 m (2H, H4A,H4B), 2.08–3.43 m (4H, H3A,H3B and H5A,H5B), 3.30–3.40 m (2H, H2, H6), 5.51 m (1H, H7, J=5.7 Hz), 7.52–7.78 m (3H) and 7.90–8.02 m (2H, H_arom.).

¹³C-NMR (CDCl₃): δ (p.p.m) = 12.0 (C4), 25.4 (C3 and C5), 48.8 (C2 and C6), 54.2 (C7), 87.4 (C1), 128.6, 130.2, 134.8, 136.7 (C8—C13).

Data for compound (3) ¹³C-NMR (CDCl₃): δ (p.p.m) = 12.9 (C4), 22.8 (C3 and C5), 54.3 (C2 and C6), 56.0 (C7), 84.1 (C1), 128.6, 129.1, 133.8, 136.7 (C8—C13).

¹H and ¹³C NMR spectra were recorded on a Bruker AC-300 spectrometer, 300 MHz. Column chromatography was conducted with Al₂O₃ (II activity grade), eluent: light petroleum ether / (CH₃)₂O (2:1).

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
S1	0.21181 (8)	0.62945 (3)	0.22954 (3)	0.03760 (15)
Cl1	0.14223 (9)	0.48753 (3)	0.11317 (4)	0.05414 (18)
Cl2	0.71061 (12)	0.44518 (5)	0.41168 (6)	0.0864 (3)
O1	−0.0184 (2)	0.62872 (9)	0.23553 (12)	0.0527 (4)
O2	0.3414 (3)	0.66498 (9)	0.30968 (11)	0.0571 (4)
C1	0.2991 (3)	0.52588 (11)	0.21868 (14)	0.0358 (4)
C2	0.2919 (3)	0.48122 (12)	0.32036 (15)	0.0446 (5)
H2	0.1879	0.5033	0.3677	0.054*
C3	0.2772 (4)	0.39123 (13)	0.3021 (2)	0.0585 (6)
H3A	0.1285	0.3778	0.2750	0.070*
H3B	0.3027	0.3629	0.3667	0.070*
C4	0.4424 (4)	0.36123 (14)	0.2290 (2)	0.0651 (7)
H4A	0.5373	0.3210	0.2639	0.078*
H4B	0.3615	0.3337	0.1727	0.078*
C5	0.5873 (4)	0.42551 (13)	0.1857 (2)	0.0580 (6)
H5A	0.7415	0.4115	0.2021	0.070*
H5B	0.5632	0.4256	0.1120	0.070*
C6	0.5451 (3)	0.50958 (12)	0.22478 (15)	0.0429 (5)
H6	0.6377	0.5530	0.1987	0.052*
C7	0.5281 (4)	0.50812 (14)	0.33851 (17)	0.0529 (6)
H7	0.5337	0.5639	0.3656	0.064*
C8	0.2730 (3)	0.67785 (11)	0.11791 (14)	0.0393 (4)
C9	0.1114 (4)	0.68692 (13)	0.04310 (17)	0.0525 (5)
H9	−0.0271	0.6631	0.0492	0.063*
C10	0.1521 (5)	0.73076 (16)	−0.04068 (19)	0.0713 (8)
H10	0.0414	0.7375	−0.0925	0.086*
C11	0.3512 (6)	0.76439 (16)	−0.0490 (2)	0.0775 (9)
H11	0.3776	0.7954	−0.1065	0.093*
C12	0.5147 (5)	0.75418 (14)	0.0243 (2)	0.0735 (9)
H12	0.6537	0.7770	0.0164	0.088*
C13	0.4780 (4)	0.71071 (13)	0.11006 (18)	0.0532 (5)
H13	0.5895	0.7037	0.1615	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0389 (3)	0.0353 (3)	0.0386 (3)	0.00035 (19)	0.0020 (2)	−0.00411 (19)
Cl1	0.0588 (4)	0.0481 (3)	0.0537 (3)	−0.0065 (2)	−0.0110 (2)	−0.0122 (2)
Cl2	0.0721 (5)	0.1030 (6)	0.0811 (5)	0.0265 (4)	−0.0185 (4)	0.0218 (4)
O1	0.0393 (8)	0.0572 (9)	0.0630 (9)	0.0037 (6)	0.0147 (7)	−0.0013 (7)
O2	0.0744 (10)	0.0453 (8)	0.0496 (9)	−0.0015 (7)	−0.0126 (7)	−0.0118 (7)
C1	0.0352 (10)	0.0335 (10)	0.0387 (10)	−0.0034 (8)	0.0011 (8)	−0.0019 (8)
C2	0.0436 (11)	0.0485 (12)	0.0426 (11)	0.0033 (9)	0.0098 (9)	0.0087 (9)
C3	0.0578 (14)	0.0449 (12)	0.0740 (15)	−0.0002 (10)	0.0151 (12)	0.0162 (11)
C4	0.0651 (16)	0.0413 (13)	0.0907 (19)	0.0066 (10)	0.0183 (14)	0.0030 (12)
C5	0.0521 (13)	0.0496 (13)	0.0740 (16)	0.0079 (10)	0.0168 (12)	0.0003 (11)
C6	0.0358 (11)	0.0420 (11)	0.0516 (12)	−0.0022 (8)	0.0076 (9)	0.0044 (9)
C7	0.0468 (13)	0.0562 (13)	0.0543 (13)	0.0065 (10)	−0.0091 (10)	0.0070 (10)
C8	0.0409 (11)	0.0315 (10)	0.0458 (11)	0.0049 (8)	0.0068 (8)	0.0001 (8)
C9	0.0528 (12)	0.0499 (13)	0.0544 (12)	0.0130 (10)	0.0011 (10)	0.0051 (10)
C10	0.094 (2)	0.0665 (16)	0.0539 (14)	0.0278 (15)	0.0095 (13)	0.0163 (12)
C11	0.116 (3)	0.0534 (15)	0.0676 (17)	0.0306 (16)	0.0440 (18)	0.0206 (13)
C12	0.0779 (19)	0.0437 (13)	0.105 (2)	0.0025 (12)	0.0519 (18)	0.0054 (14)
C13	0.0461 (12)	0.0409 (11)	0.0740 (15)	0.0019 (9)	0.0135 (10)	0.0012 (10)

Geometric parameters (Å, º)

S1—O1	1.4260 (17)	C5—C6	1.527 (3)
S1—O2	1.4269 (16)	C5—H5A	0.9900
S1—C8	1.762 (2)	C5—H5B	0.9900
S1—C1	1.821 (2)	C6—C7	1.535 (3)
Cl1—C1	1.781 (2)	C6—H6	1.0000
Cl2—C7	1.787 (2)	C7—H7	1.0000
C1—C6	1.538 (3)	C8—C9	1.377 (3)
C1—C2	1.557 (3)	C8—C13	1.387 (3)
C2—C3	1.525 (3)	C9—C10	1.377 (3)
C2—C7	1.528 (3)	C9—H9	0.9500
C2—H2	1.0000	C10—C11	1.360 (4)
C3—C4	1.541 (4)	C10—H10	0.9500
C3—H3A	0.9900	C11—C12	1.374 (5)
C3—H3B	0.9900	C11—H11	0.9500
C4—C5	1.534 (3)	C12—C13	1.390 (3)
C4—H4A	0.9900	C12—H12	0.9500
C4—H4B	0.9900	C13—H13	0.9500
O1—S1—O2	118.22 (10)	C6—C5—H5B	108.9
O1—S1—C8	108.55 (10)	C4—C5—H5B	108.9
O2—S1—C8	107.99 (10)	H5A—C5—H5B	107.7
O1—S1—C1	107.23 (9)	C5—C6—C7	110.47 (18)
O2—S1—C1	107.55 (10)	C5—C6—C1	109.46 (17)
C8—S1—C1	106.76 (9)	C7—C6—C1	85.82 (15)
C6—C1—C2	87.15 (15)	C5—C6—H6	115.8
C6—C1—Cl1	117.56 (14)	C7—C6—H6	115.8
C2—C1—Cl1	118.61 (14)	C1—C6—H6	115.8
C6—C1—S1	117.34 (13)	C2—C7—C6	88.29 (17)
C2—C1—S1	111.16 (13)	C2—C7—Cl2	118.34 (16)
Cl1—C1—S1	104.90 (10)	C6—C7—Cl2	118.33 (17)
C3—C2—C7	111.22 (18)	C2—C7—H7	110.1
C3—C2—C1	109.69 (18)	C6—C7—H7	110.1
C7—C2—C1	85.39 (15)	Cl2—C7—H7	110.1
C3—C2—H2	115.6	C9—C8—C13	121.5 (2)
C7—C2—H2	115.6	C9—C8—S1	119.05 (16)
C1—C2—H2	115.6	C13—C8—S1	119.35 (17)
C2—C3—C4	112.82 (19)	C8—C9—C10	119.5 (2)
C2—C3—H3A	109.0	C8—C9—H9	120.3
C4—C3—H3A	109.0	C10—C9—H9	120.3
C2—C3—H3B	109.0	C11—C10—C9	119.9 (3)
C4—C3—H3B	109.0	C11—C10—H10	120.1
H3A—C3—H3B	107.8	C9—C10—H10	120.1
C5—C4—C3	115.85 (19)	C10—C11—C12	120.9 (2)
C5—C4—H4A	108.3	C10—C11—H11	119.5
C3—C4—H4A	108.3	C12—C11—H11	119.5
C5—C4—H4B	108.3	C11—C12—C13	120.5 (3)
C3—C4—H4B	108.3	C11—C12—H12	119.8
H4A—C4—H4B	107.4	C13—C12—H12	119.8
C6—C5—C4	113.52 (19)	C8—C13—C12	117.7 (2)
C6—C5—H5A	108.9	C8—C13—H13	121.1
C4—C5—H5A	108.9	C12—C13—H13	121.1
O1—S1—C1—C6	−172.22 (14)	Cl1—C1—C6—C7	−147.90 (15)
O2—S1—C1—C6	−44.10 (17)	S1—C1—C6—C7	85.49 (16)
C8—S1—C1—C6	71.59 (17)	C3—C2—C7—C6	82.25 (19)
O1—S1—C1—C2	−74.16 (16)	C1—C2—C7—C6	−27.10 (15)
O2—S1—C1—C2	53.95 (16)	C3—C2—C7—Cl2	−39.3 (2)
C8—S1—C1—C2	169.65 (13)	C1—C2—C7—Cl2	−148.65 (17)
O1—S1—C1—Cl1	55.20 (12)	C5—C6—C7—C2	−81.78 (19)
O2—S1—C1—Cl1	−176.68 (10)	C1—C6—C7—C2	27.45 (15)
C8—S1—C1—Cl1	−60.99 (12)	C5—C6—C7—Cl2	39.8 (2)
C6—C1—C2—C3	−83.84 (18)	C1—C6—C7—Cl2	149.01 (16)
Cl1—C1—C2—C3	36.2 (2)	O1—S1—C8—C9	−17.73 (19)
S1—C1—C2—C3	157.88 (15)	O2—S1—C8—C9	−147.04 (16)
C6—C1—C2—C7	27.06 (15)	C1—S1—C8—C9	97.57 (17)
Cl1—C1—C2—C7	147.10 (15)	O1—S1—C8—C13	157.86 (16)
S1—C1—C2—C7	−91.22 (15)	O2—S1—C8—C13	28.56 (19)
C7—C2—C3—C4	−45.3 (3)	C1—S1—C8—C13	−86.84 (17)
C1—C2—C3—C4	47.4 (3)	C13—C8—C9—C10	−1.2 (3)
C2—C3—C4—C5	−1.3 (3)	S1—C8—C9—C10	174.29 (17)
C3—C4—C5—C6	1.1 (3)	C8—C9—C10—C11	0.3 (4)
C4—C5—C6—C7	45.3 (3)	C9—C10—C11—C12	1.1 (4)
C4—C5—C6—C1	−47.5 (3)	C10—C11—C12—C13	−1.6 (4)
C2—C1—C6—C5	83.33 (18)	C9—C8—C13—C12	0.8 (3)
Cl1—C1—C6—C5	−37.7 (2)	S1—C8—C13—C12	−174.72 (17)
S1—C1—C6—C5	−164.27 (15)	C11—C12—C13—C8	0.6 (3)
C2—C1—C6—C7	−26.92 (15)