2-Iodo­benzene­sulfonyl chloride

Robertson, S.D.; Slawin, A.M.Z.; Woollins, J.D.

doi:10.1107/S1600536806002558

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 2| February 2006| Pages o744-o745

https://doi.org/10.1107/S1600536806002558

2-Iodobenzenesulfonyl chloride

Stuart D. Robertson,^a Alexandra M. Z. Slawin ^a and J. Derek Woollins ^a ^*

^aDepartment of Chemistry, University of St Andrews, St Andrews KY16 9ST, Scotland
^*Correspondence e-mail: jdw3@st-and.ac.uk

(Received 13 January 2006; accepted 20 January 2006; online 25 January 2006)

In the molecule of 2-iodobenzenesulfonyl chloride, C₆H₄IO₂S⁺·Cl⁻, the ortho substitution by large atoms causes angular distortions at the ring C atoms rather than significant displacement of the substituents out of the ring plane.

Comment

The title compound, (I) (Fig. 1), was prepared as an intermediate in the synthesis of dibenzo[ce][1,2]dithiine and its related oxides (Aucott et al., 2004 ; Aucott et al., 2004a ,b ; Aucott, Kilian et al., 2005 ; Aucott, Milton et al., 2005 ) as part of a study of conformationally restricted molecules.

Compound (I) crystallizes in the monoclinic space group P2₁/n. The aromatic ring is essentially planar, with atom S1 0.14 (1) Å and I1 −0.08 (1) Å from this plane. The SO₂Cl group is oriented with O2 close to the aromatic plane [0.16 (1) Å] and O1 and Cl1 lying 1.13 (1) and −1.165 (1) Å above and below this plane, respectively. The ortho substitution of two heavy atoms results in enlargement of angles at carbon of the aromatic ring; C2—C1—I1 = 125.00 (18)° and S1—C2—C1 = 123.23 (19)°.

Figure 1
The structure of (I)

, with displacement ellipsoids drawn at the 50% probability level.

Experimental

2-Iodobenzenesulfonyl chloride was prepared as previously described (Chau & Kice, 1977 ) and was crystallized from chloroform/hexane (1:1 v/v) to give well formed colourless blocks.

Crystal data

C₆H₄IO₂S⁺·Cl⁻
M_r = 302.50
Monoclinic, P 2₁ /n
a = 8.338 (3) Å
b = 12.741 (3) Å
c = 8.517 (2) Å
β = 109.797 (7)°
V = 851.3 (4) Å³
Z = 4
D_x = 2.360 Mg m⁻³
Mo Kα radiation
Cell parameters from 3111 reflections
θ = 2.5–25.4°
μ = 4.26 mm⁻¹
T = 93 (2) K
Block, colourless
0.10 × 0.10 × 0.08 mm

Data collection

Rigaku MM007/Mercury CCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Bruker, 2001 )T_min = 0.600, T_max = 0.710
4840 measured reflections
1496 independent reflections
1457 reflections with I > 2σ(I)
R_int = 0.013
θ_max = 25.4°
h = −10 → 9
k = −15 → 12
l = −8 → 10

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.016
wR(F²) = 0.033
S = 1.13
1496 reflections
101 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0044P)² + 1.4521P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.46 e Å⁻³

All H atoms were included in calculated positions (C—H = 0.95 Å) and were refined as riding atoms, with U_iso(H) = 1.2U_eq(C).

Data collection: CrystalClear (Rigaku/MSC, 2004 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806002558/jh6039sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806002558/jh6039Isup2.hkl

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

2-iodobenzenesulfonyl chloride top

Crystal data top

C₆H₄IO₂S⁺·Cl⁻	F(000) = 568
M_r = 302.50	D_x = 2.360 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 52 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.338 (3) Å	Cell parameters from 3111 reflections
b = 12.741 (3) Å	θ = 2.5–25.4°
c = 8.517 (2) Å	µ = 4.27 mm⁻¹
β = 109.797 (7)°	T = 93 K
V = 851.3 (4) Å³	Block, colourless
Z = 4	0.10 × 0.10 × 0.08 mm

Data collection top

CCD diffractometer	1496 independent reflections
Radiation source: rotating anode	1457 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.013
Detector resolution: 0.83 pixels mm^-1	θ_max = 25.4°, θ_min = 3.0°
dtprofit.ref scans	h = −10→9
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −15→12
T_min = 0.600, T_max = 0.710	l = −8→10
4840 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.033	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0044P)² + 1.4521P] where P = (F_o² + 2F_c²)/3
1496 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
I1	0.42383 (2)	0.287007 (12)	0.57459 (2)	0.01844 (6)
Cl1	0.02906 (7)	0.14086 (5)	0.52384 (8)	0.02264 (14)
S1	0.19229 (7)	0.11930 (5)	0.76112 (7)	0.01317 (13)
O1	0.2205 (2)	0.22062 (13)	0.8354 (2)	0.0182 (4)
O2	0.1205 (2)	0.03818 (14)	0.8311 (2)	0.0202 (4)
C1	0.4827 (3)	0.13418 (19)	0.6674 (3)	0.0139 (5)
C2	0.3799 (3)	0.07205 (19)	0.7313 (3)	0.0136 (5)
C3	0.4261 (3)	−0.0310 (2)	0.7824 (3)	0.0166 (5)
H3A	0.3538	−0.0732	0.8218	0.020*
C4	0.5777 (3)	−0.0718 (2)	0.7755 (3)	0.0193 (5)
H4A	0.6104	−0.1416	0.8113	0.023*
C5	0.6816 (3)	−0.0095 (2)	0.7156 (3)	0.0195 (5)
H5A	0.7863	−0.0369	0.7120	0.023*
C6	0.6340 (3)	0.0915 (2)	0.6613 (3)	0.0172 (5)
H6A	0.7056	0.1324	0.6192	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02291 (10)	0.01213 (9)	0.02630 (10)	−0.00095 (6)	0.01621 (7)	0.00174 (6)
Cl1	0.0135 (3)	0.0286 (3)	0.0237 (3)	0.0021 (3)	0.0034 (2)	0.0029 (3)
S1	0.0122 (3)	0.0123 (3)	0.0173 (3)	−0.0002 (2)	0.0079 (2)	−0.0014 (2)
O1	0.0191 (9)	0.0130 (9)	0.0281 (10)	−0.0027 (7)	0.0153 (8)	−0.0062 (7)
O2	0.0192 (9)	0.0195 (9)	0.0272 (10)	−0.0004 (8)	0.0147 (8)	−0.0002 (8)
C1	0.0145 (12)	0.0118 (12)	0.0161 (11)	−0.0011 (9)	0.0061 (9)	−0.0020 (10)
C2	0.0110 (12)	0.0159 (12)	0.0143 (11)	−0.0007 (9)	0.0046 (9)	−0.0035 (10)
C3	0.0178 (12)	0.0168 (13)	0.0151 (12)	−0.0021 (10)	0.0054 (10)	−0.0007 (10)
C4	0.0213 (13)	0.0153 (13)	0.0186 (12)	0.0057 (10)	0.0031 (10)	−0.0006 (10)
C5	0.0128 (12)	0.0230 (14)	0.0213 (13)	0.0035 (10)	0.0041 (10)	−0.0062 (11)
C6	0.0134 (12)	0.0217 (14)	0.0188 (12)	−0.0033 (10)	0.0086 (10)	−0.0064 (10)

Geometric parameters (Å, º) top

I1—C1	2.096 (2)	C3—C4	1.386 (4)
Cl1—S1	2.0368 (10)	C3—H3A	0.9500
S1—O1	1.4217 (18)	C4—C5	1.392 (4)
S1—O2	1.4222 (18)	C4—H4A	0.9500
S1—C2	1.773 (2)	C5—C6	1.379 (4)
C1—C6	1.390 (3)	C5—H5A	0.9500
C1—C2	1.405 (3)	C6—H6A	0.9500
C2—C3	1.396 (3)

O1—S1—O2	120.22 (11)	C4—C3—C2	119.9 (2)
O1—S1—C2	110.53 (11)	C4—C3—H3A	120.0
O2—S1—C2	109.27 (11)	C2—C3—H3A	120.0
O1—S1—Cl1	105.86 (8)	C3—C4—C5	119.4 (2)
O2—S1—Cl1	106.21 (8)	C3—C4—H4A	120.3
C2—S1—Cl1	103.26 (8)	C5—C4—H4A	120.3
C6—C1—C2	118.3 (2)	C6—C5—C4	120.7 (2)
C6—C1—I1	116.68 (18)	C6—C5—H5A	119.7
C2—C1—I1	125.00 (18)	C4—C5—H5A	119.7
C3—C2—C1	120.7 (2)	C5—C6—C1	120.9 (2)
C3—C2—S1	116.03 (18)	C5—C6—H6A	119.5
C1—C2—S1	123.23 (19)	C1—C6—H6A	119.5

C6—C1—C2—C3	−2.0 (3)	Cl1—S1—C2—C1	68.7 (2)
I1—C1—C2—C3	176.66 (17)	C1—C2—C3—C4	2.2 (4)
C6—C1—C2—S1	175.12 (18)	S1—C2—C3—C4	−175.14 (19)
I1—C1—C2—S1	−6.2 (3)	C2—C3—C4—C5	−0.8 (4)
O1—S1—C2—C3	133.11 (19)	C3—C4—C5—C6	−0.8 (4)
O2—S1—C2—C3	−1.3 (2)	C4—C5—C6—C1	1.0 (4)
Cl1—S1—C2—C3	−114.05 (18)	C2—C1—C6—C5	0.4 (4)
O1—S1—C2—C1	−44.1 (2)	I1—C1—C6—C5	−178.36 (18)
O2—S1—C2—C1	−178.58 (19)

References

Aucott, S. M., Kilian, P., Milton, H. L., Robertson, S. D., Slawin, A. M. Z. & Woollins, J. D. (2005). Inorg. Chem. 44, 2710–2718. Web of Science CSD CrossRef PubMed CAS Google Scholar
Aucott, S. M., Milton, H. L., Robertson, S. D., Slawin, A. M. Z., Walker, G. D. & Woollins, J. D. (2004). Chem. Eur. J. 10, 1666–1676. Web of Science CSD CrossRef PubMed CAS Google Scholar
Aucott, S. M., Milton, H. L., Robertson, S. D., Slawin, A. M. Z. & Woollins, J. D. (2004a). Heteroatom Chem., 15, 531–542. Web of Science CSD CrossRef Google Scholar
Aucott, S. M., Milton, H. L., Robertson, S. D., Slawin, A. M. Z. & Woollins, J. D. (2004b). Dalton Trans. pp. 3347–3352. Web of Science CSD CrossRef Google Scholar
Aucott, S. M., Milton, H. L., Robertson, S. D., Slawin, A. M. Z. & Woollins, J. D. (2005). Heteroatom Chem., 16, 346–350. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2001). SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chau, M. M. & Kice, J. L. (1977). J. Org. Chem. 42, 3265–3270. CrossRef CAS Web of Science Google Scholar
Rigaku/MSC (2004). CrystalClear. Version 1.3.6. Rigaku/MSC, 9009 New Trails Drive, The Woodlands, TX77381-5209, USA. Google Scholar
Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997b). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA. Aucott, Kilian. Google Scholar

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