Crystal structure of 2-[(di-chloro-methane)sulfon-yl]pyridine.

The asymmetric unit of the title compound, C6H5Cl2NO2S, contains two mol-ecules with similar conformations (r.m.s. overlay fit for the non-H atoms = 0.067 Å). Atoms attached to the pendent Csp (3)-S bond are arranged in a staggered conformation with one of the Cl atoms anti to the C atom in the aromatic ring [C-S-C-Cl torsion angles = 178.41 (11) and -176.70 (13)°]. In the crystal, mol-ecules are linked by C-H⋯N and C-H⋯O hydrogen bonds, generating a three-dimensional network, and weak aromatic π-π stacking is also observed [centroid-centroid separation = 3.8902 (17) Å].

Related literature

For the biological activity of sulfone derivatives, see: Chen et al. (2012 ▶); Drews (2000 ▶); Raja et al. (2009 ▶). For the uses of halomethyl sulfone derivatives in organic synthesis, see: Li & Hu (2005 ▶); Prakash et al. (2013 ▶); Zhao et al. (2010 ▶). For the synthesis of the starting material, see: Kamiyama et al. (1988 ▶).

Experimental

Crystal data

C6H5Cl2NO2S

M = 226.07

Monoclinic,

a = 9.9647 (10) Å

b = 12.2131 (11) Å

c = 15.7158 (15) Å

β = 108.483 (1)°

V = 1814.0 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.90 mm−1

T = 293 K

0.21 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.615, T max = 0.746

10817 measured reflections

3570 independent reflections

2907 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.102

S = 1.03

3570 reflections

218 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.37 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814025148/hb7316sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814025148/hb7316Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814025148/hb7316Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814025148/hb7316fig1.tif

Mol­ecular structure of the title compound. The displacement ellipsoids are drawn at the 50% probability level.

CCDC reference: 1034519

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

C6H5Cl2NO2S	F(000) = 912
Mr = 226.07	Dx = 1.656 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.9647 (10) Å	Cell parameters from 4116 reflections
b = 12.2131 (11) Å	θ = 4.3–54.4°
c = 15.7158 (15) Å	µ = 0.90 mm−1
β = 108.483 (1)°	T = 293 K
V = 1814.0 (3) Å3	Prism, colorless
Z = 8	0.21 × 0.16 × 0.12 mm

Bruker SMART CCD diffractometer	2907 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.034
Absorption correction: multi-scan (SADABS; Bruker, 2007)	θmax = 26.0°, θmin = 2.2°
Tmin = 0.615, Tmax = 0.746	h = −12→12
10817 measured reflections	k = −15→13
3570 independent reflections	l = −19→14

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.048P)2 + 0.7592P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.37 e Å−3
3570 reflections	Δρmin = −0.37 e Å−3
218 parameters	Extinction correction: SHELXL2013 (Sheldrick, 2013), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0286 (15)

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.

	x	y	z	Uiso*/Ueq
S1	0.22031 (6)	0.33604 (5)	0.12351 (4)	0.04809 (18)
S2	0.34445 (7)	0.72345 (5)	0.63426 (4)	0.05073 (19)
Cl1	0.13628 (8)	0.50108 (5)	0.23115 (5)	0.0676 (2)
Cl2	0.16196 (8)	0.27131 (5)	0.28379 (5)	0.0647 (2)
Cl3	0.19229 (9)	0.60561 (8)	0.73732 (6)	0.0850 (3)
Cl4	0.32582 (10)	0.81316 (7)	0.79958 (5)	0.0874 (3)
N1	0.4188 (2)	0.47686 (16)	0.13024 (13)	0.0499 (5)
N2	0.4604 (2)	0.53408 (16)	0.62759 (13)	0.0517 (5)
O1	0.0757 (2)	0.32158 (16)	0.07175 (13)	0.0733 (6)
O2	0.3169 (2)	0.24747 (14)	0.13497 (12)	0.0672 (5)
O3	0.2167 (2)	0.77708 (15)	0.58491 (13)	0.0734 (6)
O4	0.4775 (2)	0.77492 (15)	0.64783 (14)	0.0699 (5)
C1	0.2303 (2)	0.37906 (17)	0.23599 (15)	0.0447 (5)
H1	0.3296	0.3910	0.2713	0.054*
C2	0.2870 (2)	0.45238 (18)	0.08275 (14)	0.0429 (5)
C3	0.2047 (3)	0.5082 (2)	0.00872 (16)	0.0529 (6)
H3	0.1126	0.4864	−0.0220	0.064*
C4	0.2646 (3)	0.5977 (2)	−0.01787 (17)	0.0592 (6)
H4	0.2135	0.6385	−0.0675	0.071*
C5	0.4002 (3)	0.6258 (2)	0.02950 (19)	0.0607 (7)
H5	0.4425	0.6861	0.0123	0.073*
C6	0.4741 (3)	0.5646 (2)	0.10274 (18)	0.0578 (6)
H6	0.5663	0.5851	0.1345	0.069*
C7	0.3368 (3)	0.6905 (2)	0.74546 (16)	0.0523 (6)
H7	0.4239	0.6524	0.7792	0.063*
C8	0.3445 (2)	0.59091 (18)	0.58779 (15)	0.0454 (5)
C9	0.2333 (3)	0.5566 (2)	0.51689 (17)	0.0596 (6)
H9	0.1550	0.6010	0.4916	0.072*
C10	0.2428 (3)	0.4520 (2)	0.48428 (19)	0.0691 (8)
H10	0.1695	0.4238	0.4367	0.083*
C11	0.3620 (3)	0.3912 (2)	0.52340 (19)	0.0648 (7)
H11	0.3718	0.3217	0.5019	0.078*
C12	0.4667 (3)	0.4344 (2)	0.59470 (19)	0.0612 (7)
H12	0.5463	0.3918	0.6215	0.073*

	U11	U22	U33	U12	U13	U23
S1	0.0590 (4)	0.0370 (3)	0.0447 (3)	−0.0097 (2)	0.0115 (3)	−0.0018 (2)
S2	0.0659 (4)	0.0382 (3)	0.0499 (3)	0.0138 (3)	0.0209 (3)	0.0044 (2)
Cl1	0.0791 (5)	0.0434 (3)	0.0909 (5)	0.0082 (3)	0.0420 (4)	0.0000 (3)
Cl2	0.0849 (5)	0.0483 (4)	0.0719 (4)	−0.0087 (3)	0.0407 (4)	0.0051 (3)
Cl3	0.0800 (5)	0.1064 (7)	0.0806 (5)	−0.0173 (5)	0.0426 (4)	−0.0035 (5)
Cl4	0.1221 (7)	0.0714 (5)	0.0727 (5)	0.0256 (5)	0.0367 (5)	−0.0173 (4)
N1	0.0482 (11)	0.0488 (11)	0.0503 (11)	−0.0034 (9)	0.0123 (9)	0.0050 (9)
N2	0.0576 (12)	0.0422 (10)	0.0543 (11)	0.0135 (9)	0.0164 (9)	0.0040 (9)
O1	0.0736 (13)	0.0696 (12)	0.0613 (11)	−0.0329 (10)	−0.0005 (10)	0.0030 (9)
O2	0.1029 (15)	0.0415 (9)	0.0640 (11)	0.0094 (9)	0.0362 (11)	0.0002 (8)
O3	0.0935 (14)	0.0607 (11)	0.0617 (11)	0.0395 (10)	0.0183 (10)	0.0112 (9)
O4	0.0863 (14)	0.0513 (10)	0.0810 (13)	−0.0130 (9)	0.0390 (11)	−0.0032 (9)
C1	0.0474 (12)	0.0372 (11)	0.0512 (13)	−0.0037 (9)	0.0182 (10)	−0.0011 (9)
C2	0.0505 (13)	0.0383 (11)	0.0400 (11)	−0.0032 (9)	0.0145 (10)	−0.0009 (9)
C3	0.0541 (14)	0.0567 (14)	0.0444 (12)	0.0023 (11)	0.0104 (11)	0.0039 (11)
C4	0.0749 (18)	0.0531 (14)	0.0522 (14)	0.0128 (13)	0.0240 (13)	0.0148 (11)
C5	0.0749 (18)	0.0466 (13)	0.0696 (17)	−0.0037 (12)	0.0357 (15)	0.0081 (12)
C6	0.0539 (14)	0.0545 (14)	0.0655 (16)	−0.0086 (12)	0.0198 (12)	0.0043 (12)
C7	0.0574 (14)	0.0522 (13)	0.0493 (13)	0.0141 (11)	0.0195 (11)	0.0013 (11)
C8	0.0556 (13)	0.0390 (11)	0.0437 (12)	0.0071 (10)	0.0187 (10)	0.0023 (9)
C9	0.0640 (16)	0.0594 (15)	0.0512 (14)	0.0108 (12)	0.0124 (12)	0.0016 (12)
C10	0.083 (2)	0.0644 (17)	0.0554 (15)	−0.0077 (15)	0.0154 (14)	−0.0098 (13)
C11	0.093 (2)	0.0406 (13)	0.0681 (17)	0.0037 (13)	0.0359 (16)	−0.0039 (12)
C12	0.0751 (18)	0.0419 (13)	0.0687 (17)	0.0158 (12)	0.0259 (14)	0.0032 (12)

S1—O2	1.4212 (19)	C2—C3	1.373 (3)
S1—O1	1.4235 (19)	C3—C4	1.372 (4)
S1—C2	1.772 (2)	C3—H3	0.9300
S1—C1	1.816 (2)	C4—C5	1.364 (4)
S2—O4	1.421 (2)	C4—H4	0.9300
S2—O3	1.4231 (19)	C5—C6	1.374 (4)
S2—C8	1.776 (2)	C5—H5	0.9300
S2—C7	1.818 (2)	C6—H6	0.9300
Cl1—C1	1.749 (2)	C7—H7	0.9800
Cl2—C1	1.756 (2)	C8—C9	1.364 (3)
Cl3—C7	1.746 (3)	C9—C10	1.390 (4)
Cl4—C7	1.743 (2)	C9—H9	0.9300
N1—C2	1.323 (3)	C10—C11	1.370 (4)
N1—C6	1.338 (3)	C10—H10	0.9300
N2—C8	1.323 (3)	C11—C12	1.371 (4)
N2—C12	1.332 (3)	C11—H11	0.9300
C1—H1	0.9800	C12—H12	0.9300
O2—S1—O1	120.03 (13)	C3—C4—H4	120.5
O2—S1—C2	109.84 (11)	C4—C5—C6	119.7 (2)
O1—S1—C2	108.69 (11)	C4—C5—H5	120.2
O2—S1—C1	105.72 (10)	C6—C5—H5	120.2
O1—S1—C1	108.98 (12)	N1—C6—C5	122.7 (2)
C2—S1—C1	102.05 (10)	N1—C6—H6	118.6
O4—S2—O3	120.59 (13)	C5—C6—H6	118.6
O4—S2—C8	110.07 (11)	Cl4—C7—Cl3	111.61 (13)
O3—S2—C8	108.19 (12)	Cl4—C7—S2	107.87 (13)
O4—S2—C7	105.97 (12)	Cl3—C7—S2	110.24 (13)
O3—S2—C7	108.84 (12)	Cl4—C7—H7	109.0
C8—S2—C7	101.49 (11)	Cl3—C7—H7	109.0
C2—N1—C6	115.8 (2)	S2—C7—H7	109.0
C8—N2—C12	116.0 (2)	N2—C8—C9	125.9 (2)
Cl1—C1—Cl2	112.46 (13)	N2—C8—S2	113.44 (17)
Cl1—C1—S1	109.92 (12)	C9—C8—S2	120.67 (18)
Cl2—C1—S1	106.89 (11)	C8—C9—C10	116.8 (2)
Cl1—C1—H1	109.2	C8—C9—H9	121.6
Cl2—C1—H1	109.2	C10—C9—H9	121.6
S1—C1—H1	109.2	C11—C10—C9	118.9 (3)
N1—C2—C3	125.8 (2)	C11—C10—H10	120.6
N1—C2—S1	113.34 (16)	C9—C10—H10	120.6
C3—C2—S1	120.84 (18)	C10—C11—C12	119.0 (2)
C4—C3—C2	116.9 (2)	C10—C11—H11	120.5
C4—C3—H3	121.5	C12—C11—H11	120.5
C2—C3—H3	121.5	N2—C12—C11	123.4 (2)
C5—C4—C3	119.1 (2)	N2—C12—H12	118.3
C5—C4—H4	120.5	C11—C12—H12	118.3
O2—S1—C1—Cl1	170.96 (12)	O4—S2—C7—Cl4	68.31 (15)
O1—S1—C1—Cl1	−58.75 (15)	O3—S2—C7—Cl4	−62.76 (16)
C2—S1—C1—Cl1	56.09 (14)	C8—S2—C7—Cl4	−176.70 (13)
O2—S1—C1—Cl2	−66.71 (14)	O4—S2—C7—Cl3	−169.59 (13)
O1—S1—C1—Cl2	63.58 (14)	O3—S2—C7—Cl3	59.34 (16)
C2—S1—C1—Cl2	178.41 (11)	C8—S2—C7—Cl3	−54.61 (15)
C6—N1—C2—C3	0.5 (4)	C12—N2—C8—C9	−0.3 (4)
C6—N1—C2—S1	−179.51 (18)	C12—N2—C8—S2	−179.28 (19)
O2—S1—C2—N1	−50.8 (2)	O4—S2—C8—N2	45.1 (2)
O1—S1—C2—N1	176.04 (17)	O3—S2—C8—N2	178.72 (18)
C1—S1—C2—N1	61.00 (19)	C7—S2—C8—N2	−66.86 (19)
O2—S1—C2—C3	129.1 (2)	O4—S2—C8—C9	−134.0 (2)
O1—S1—C2—C3	−4.0 (2)	O3—S2—C8—C9	−0.3 (2)
C1—S1—C2—C3	−119.0 (2)	C7—S2—C8—C9	114.1 (2)
N1—C2—C3—C4	−0.4 (4)	N2—C8—C9—C10	0.6 (4)
S1—C2—C3—C4	179.66 (18)	S2—C8—C9—C10	179.4 (2)
C2—C3—C4—C5	0.2 (4)	C8—C9—C10—C11	−1.1 (4)
C3—C4—C5—C6	−0.1 (4)	C9—C10—C11—C12	1.5 (4)
C2—N1—C6—C5	−0.5 (4)	C8—N2—C12—C11	0.7 (4)
C4—C5—C6—N1	0.3 (4)	C10—C11—C12—N2	−1.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N2i	0.98	2.37	3.321 (3)	163
C5—H5···O3ii	0.93	2.64	3.220 (3)	121
C6—H6···O3ii	0.93	2.54	3.177 (3)	126
C7—H7···N1i	0.98	2.36	3.303 (3)	162
C11—H11···O1iii	0.93	2.64	3.292 (3)	128

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C1H1N2i	0.98	2.37	3.321(3)	163
C5H5O3ii	0.93	2.64	3.220(3)	121
C6H6O3ii	0.93	2.54	3.177(3)	126
C7H7N1i	0.98	2.36	3.303(3)	162
C11H11O1iii	0.93	2.64	3.292(3)	128

Symmetry codes: (i) ; (ii) ; (iii) .