Crystal structure of p-toluene­sulfonyl­methyl isocyanide

Abstract

The mol­ecule of the commercially available title compound, C₉H₉NO₂S, has crystallographically imposed mirror symmetry, the mirror plane passing through the isocyanide group and the para-C atoms, the methyl C atom and the S atom of the methyl 4-tolyl sulfone moiety. In the crystal, C—H⋯O hydrogen-bond inter­actions link the mol­ecules into chains running parallel to the b axis.

Related literature  

The title compound is an isocyanide derivative of methyl 4-tolyl sulfone (Ye, 2007 ▸), an important reaction inter­mediate obtained during the synthesis of mesotrione, a well known herbicide (Smith et al., 2008 ▸).

Experimental  

Crystal data  

• C₉H₉NO₂S

• M _r = 195.23

• Orthorhombic,

• a = 22.342 (5) Å

• b = 8.881 (2) Å

• c = 4.8462 (12) Å

• V = 961.6 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.30 mm⁻¹

• T = 273 K

• 0.49 × 0.32 × 0.15 mm

Data collection  

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000 ▸) T _min = 0.864, T _max = 0.961

• 5160 measured reflections

• 955 independent reflections

• 733 reflections with I > 2σ(I)

• R _int = 0.044

Refinement  

• R[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 0.119

• S = 1.11

• 955 reflections

• 77 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.39 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2000 ▸); cell refinement: SAINT (Bruker, 2000 ▸); 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, PARST (Nardelli, 1995 ▸) and PLATON (Spek, 2009 ▸).

Supplementary Material

CCDC reference: 1063415

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C6H6AO1i	0.97	2.47	3.2519(18)	138
C6H6AO1ii	0.97	2.54	3.296(4)	135
C6H6BO1iii	0.97	2.54	3.296(4)	135
C6H6BO1iv	0.97	2.47	3.2519(18)	138

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

supplementary crystallographic information

S1. Comment

The title compound is an isocyanide derivative of the previously reported compound methyl 4-tolyl sulfone (Ye, 2007), an important reaction intermediate obtained during the synthesis of mesotrione, a well known herbicide (Smith et al., 2008). The compound was crystallized as part of our ongoing research project involving the study of the crystal structures and enzyme inhibition abilities of commercially available molecular libraries. The molecule has crystallographically imposed mirror symmetry, atoms C1, C4–C7, N1, S1 lying on the mirror plane (Fig. 1). The least-square mean line through C6, N1 and C7 forms an angle of 79.4 (3)° with the normal to the plane of the benzene ring. The crystal structure is stabilized by C6—H6A···O1, and C6—H6B···O1 intermolecular hydrogen interactions that link the molecules to form chains running parallel to the b axis (Fig. 2).

S2. Experimental

The title compound is a commercially available Sigma-Aldrich product. Colourless single crystals suitable for X-ray analysis were obtained from slow evaporation of a methanol solution at room temperature.

S3. Refinement

Aromatic and methylene H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.93-0.97 Å, and with U_iso(H)= 1.2U_eq(C). The methyl H5A atom lying on a mirror plane was located in a difference Fourier map and refined isotropically, with the C5–H5A bond length constrained to be 1.1 (1) Å.

Figures

Fig. 1.

The molecular structure of title compound with displacement ellipsoids drawn at the 30% probability level.

Fig. 2.

Crystal packing of the title compound, showing the formation of chains parallel to the b axis via C—H···O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding are omitted.

Crystal data

C9H9NO2S	F(000) = 408
Mr = 195.23	Dx = 1.349 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 830 reflections
a = 22.342 (5) Å	θ = 2.9–22.3°
b = 8.881 (2) Å	µ = 0.30 mm−1
c = 4.8462 (12) Å	T = 273 K
V = 961.6 (4) Å3	Plate, colourless
Z = 4	0.49 × 0.32 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	955 independent reflections
Radiation source: fine-focus sealed tube	733 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω scan	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −27→25
Tmin = 0.864, Tmax = 0.961	k = −10→10
5160 measured reflections	l = −5→5

Refinement

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ2(Fo2) + (0.0557P)2 + 0.1844P] where P = (Fo2 + 2Fc2)/3
955 reflections	(Δ/σ)max < 0.001
77 parameters	Δρmax = 0.39 e Å−3
1 restraint	Δρmin = −0.19 e Å−3

Special details

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	Occ. (<1)
S1	0.28836 (4)	0.2500	0.85946 (16)	0.0354 (3)
O1	0.28301 (8)	0.11111 (18)	1.0084 (3)	0.0462 (5)
N1	0.17475 (16)	0.2500	0.7198 (6)	0.0483 (8)
C1	0.35416 (16)	0.2500	0.6642 (7)	0.0379 (9)
C2	0.37872 (13)	0.1154 (3)	0.5815 (6)	0.0488 (7)
H2A	0.3624	0.0246	0.6398	0.059*
C3	0.42793 (13)	0.1177 (3)	0.4109 (6)	0.0557 (8)
H3A	0.4446	0.0268	0.3543	0.067*
C4	0.45334 (18)	0.2500	0.3212 (7)	0.0477 (10)
C5	0.5064 (2)	0.2500	0.1335 (11)	0.0714 (16)
H5B	0.505 (2)	0.320 (5)	0.013 (11)	0.14 (2)*
C6	0.23235 (16)	0.2500	0.5941 (7)	0.0383 (9)
H6A	0.2369	0.3385	0.4788	0.046*	0.50
H6B	0.2369	0.1615	0.4788	0.046*	0.50
C7	0.1292 (2)	0.2500	0.8320 (11)	0.0707 (14)
H5A	0.549 (2)	0.2500	0.242 (17)	0.21 (4)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0508 (6)	0.0300 (5)	0.0255 (4)	0.000	0.0031 (4)	0.000
O1	0.0676 (13)	0.0360 (10)	0.0349 (10)	0.0001 (9)	0.0045 (9)	0.0096 (7)
N1	0.051 (2)	0.0469 (19)	0.0467 (18)	0.000	0.0048 (17)	0.000
C1	0.044 (2)	0.0368 (19)	0.0330 (18)	0.000	−0.0023 (16)	0.000
C2	0.0551 (18)	0.0383 (15)	0.0531 (15)	−0.0007 (13)	0.0084 (14)	−0.0045 (12)
C3	0.0549 (19)	0.0551 (18)	0.0572 (18)	0.0105 (15)	0.0053 (15)	−0.0108 (15)
C4	0.040 (2)	0.065 (3)	0.039 (2)	0.000	−0.0021 (17)	0.000
C5	0.055 (3)	0.104 (5)	0.056 (3)	0.000	0.012 (3)	0.000
C6	0.051 (2)	0.0355 (18)	0.0288 (17)	0.000	0.0018 (16)	0.000
C7	0.066 (3)	0.059 (3)	0.087 (4)	0.000	0.008 (3)	0.000

Geometric parameters (Å, º)

S1—O1i	1.4340 (16)	C2—H2A	0.9300
S1—O1	1.4341 (16)	C3—C4	1.375 (4)
S1—C1	1.748 (4)	C3—H3A	0.9300
S1—C6	1.794 (4)	C4—C3i	1.375 (4)
N1—C7	1.154 (5)	C4—C5	1.494 (6)
N1—C6	1.424 (5)	C5—H5B	0.85 (5)
C1—C2i	1.375 (3)	C5—H5A	1.095 (10)
C1—C2	1.375 (3)	C6—H6A	0.9700
C2—C3	1.376 (4)	C6—H6B	0.9700
O1i—S1—O1	118.66 (14)	C4—C3—H3A	118.9
O1i—S1—C1	110.03 (9)	C2—C3—H3A	118.9
O1—S1—C1	110.03 (9)	C3—C4—C3i	117.3 (4)
O1i—S1—C6	107.61 (10)	C3—C4—C5	121.33 (18)
O1—S1—C6	107.61 (10)	C3i—C4—C5	121.33 (18)
C1—S1—C6	101.45 (16)	C4—C5—H5B	113 (3)
C7—N1—C6	177.2 (4)	C4—C5—H5A	114 (5)
C2i—C1—C2	120.8 (3)	H5B—C5—H5A	111 (4)
C2i—C1—S1	119.56 (18)	N1—C6—S1	108.9 (2)
C2—C1—S1	119.56 (18)	N1—C6—H6A	109.9
C1—C2—C3	118.8 (3)	S1—C6—H6A	109.9
C1—C2—H2A	120.6	N1—C6—H6B	109.9
C3—C2—H2A	120.6	S1—C6—H6B	109.9
C4—C3—C2	122.2 (3)	H6A—C6—H6B	108.3
O1i—S1—C1—C2i	−25.6 (3)	S1—C1—C2—C3	175.2 (2)
O1—S1—C1—C2i	−158.2 (2)	C1—C2—C3—C4	0.2 (5)
C6—S1—C1—C2i	88.1 (3)	C2—C3—C4—C3i	0.6 (6)
O1i—S1—C1—C2	158.2 (2)	C2—C3—C4—C5	−179.3 (4)
O1—S1—C1—C2	25.6 (3)	O1i—S1—C6—N1	−64.47 (9)
C6—S1—C1—C2	−88.1 (3)	O1—S1—C6—N1	64.47 (9)
C2i—C1—C2—C3	−0.9 (6)	C1—S1—C6—N1	180.0

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O1ii	0.97	2.47	3.2519 (18)	138
C6—H6A···O1iii	0.97	2.54	3.296 (4)	135
C6—H6B···O1iv	0.97	2.54	3.296 (4)	135
C6—H6B···O1v	0.97	2.47	3.2519 (18)	138

Symmetry codes: (ii) −x+1/2, y+1/2, z−1/2; (iii) x, −y+1/2, z−1; (iv) x, y, z−1; (v) −x+1/2, −y, z−1/2.