4-[(1,3-Thia­zol-2-yl)sulfamo­yl]phenyl 2,2,2-trifluoro­acetate

Abstract

In the title compound, C₁₁H₇F₃N₂O₄S₂, the 1,3-thia­zol-2-amine residue is almost perpendicular to the central benzene ring [dihedral angle = 84.3 (2)°]. There is a small twist between the benzene ring and the ester group [C—O—C—C torsion angle = 9.8 (6)°]. Thus, the mol­ecule has an L-shape. Inversion-related dimers are connected in the crystal packing by pairs of N—H⋯N hydrogen bonds formed between the amine H and thia­zole N atom via eight-membered {⋯HNCN}₂ synthons.

Related literature  

For the biological efficacy of F and CF₃ in medicinal chemistry, see: Fokin & Kolomiyets (1988 ▶); Bonacorso et al. (2006 ▶). For background to the biological applications of sulfonamides, see: Croitoru et al. (2004 ▶); Dogruer et al. (2010 ▶). For related structures, see: Asiri et al. (2011 ▶, 2012 ▶).

Experimental  

Crystal data  

• C₁₁H₇F₃N₂O₄S₂

• M _r = 352.31

• Monoclinic,

• a = 8.7498 (5) Å

• b = 14.4343 (9) Å

• c = 10.7225 (5) Å

• β = 96.749 (5)°

• V = 1344.84 (13) ų

• Z = 4

• Mo Kα radiation

• μ = 0.45 mm⁻¹

• T = 100 K

• 0.30 × 0.30 × 0.10 mm

Data collection  

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.876, T _max = 0.956

• 12068 measured reflections

• 3105 independent reflections

• 2252 reflections with I > 2σ(I)

• R _int = 0.036

Refinement  

• R[F ² > 2σ(F ²)] = 0.071

• wR(F ²) = 0.215

• S = 1.06

• 3105 reflections

• 199 parameters

• H-atom parameters constrained

• Δρ_max = 0.69 e Å⁻³

• Δρ_min = −0.41 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812011683/hg5192Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1i	0.88	1.99	2.858 (5)	171

Symmetry code: (i) .

supplementary crystallographic information

Comment

The presence of fluoride and trifluoromethyl groups, in particular, has long been recognized in medicinal chemistry as a substituent of distinctive qualities (Fokin & Kolomiyets, 1988; Bonacorso et al., 2006) owing to their ability to alter the physico-chemical and biological characteristics of molecules. In connection with on-going studies of sulphonamides, biological (Croitoru et al., 2004; Dogruer et al., 2010) and crystallographic (Asiri et al., 2011; Asiri et al., 2012), the title CF₃-derivatized sulphonamide (I), was investigated.

In (I), Fig. 1, with reference to the central benzene ring, the 1,3-thiazol-2-amine residue occupies an almost perpendicular position with the N2—S2—C4—C5 torsion angle being 122.7 (3)°. The dihedral angle between the benzene and thiazol rings [r.m.s. deviation = 0.011 Å] is 84.3 (2)°. There is a small twist between the benzene ring and the ester group with the C10—O3—C7—C6 torsion angle being 9.8 (6)°. To a first approximation, the molecule of (I) has the shape of the letter L.

In the crystal packing, N—H···N hydrogen bonds are formed between the amine-H and thiazol-N atoms of centrosymmetrically related molecules to form eight-membered {···HNCN}₂ synthons, Fig. 2 and Table 1. Molecules pack with no specific intermolecular interactions between them.

Experimental

A mixture of sulfamerazine (2.6 g, 10 mmol) in THF (30 ml) and trifluroacetic anhydride (2.2 g, 11 mmol) was refluxed for 2 h. The solid which separated on cooling was recrystallized from ethanol. Yield: 68%. M.pt: 513–514 K.

Refinement

Carbon-bound H-atoms were placed in calculated positions [N—H = 0.88 Å and C—H = 0.95 Å; U_iso(H) = 1.2U_eq(N,C)] and were included in the refinement in the riding model approximation. Owing to poor agreement, the (0 2 1) reflection was omitted from the final cycles of refinement.

Figures

Fig. 1.

The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.

Fig. 2.

Centrosymmetric dimers in (I) sustained by N—H···N hydrogen bonds shown as blue dashed lines leading to eight-membered {···HNCN}2 synthons.

Crystal data

C11H7F3N2O4S2	F(000) = 712
Mr = 352.31	Dx = 1.740 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3265 reflections
a = 8.7498 (5) Å	θ = 2.3–27.5°
b = 14.4343 (9) Å	µ = 0.45 mm−1
c = 10.7225 (5) Å	T = 100 K
β = 96.749 (5)°	Irregular, light-yellow
V = 1344.84 (13) Å3	0.30 × 0.30 × 0.10 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	3105 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2252 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.036
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.4°
ω scan	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→18
Tmin = 0.876, Tmax = 0.956	l = −13→13
12068 measured reflections

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.215	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.1054P)2 + 2.1576P] where P = (Fo2 + 2Fc2)/3
3105 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.69 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.83675 (13)	0.46698 (8)	0.30886 (10)	0.0500 (3)
S2	0.55748 (13)	0.61673 (8)	0.24923 (9)	0.0454 (3)
F1	1.4449 (3)	0.9101 (2)	0.4037 (3)	0.0707 (8)
F2	1.2781 (3)	1.0011 (2)	0.4699 (3)	0.0679 (8)
F3	1.3609 (4)	1.0282 (2)	0.2933 (3)	0.0684 (8)
O1	0.4182 (4)	0.6682 (2)	0.2516 (3)	0.0549 (8)
O2	0.5788 (4)	0.5696 (2)	0.1331 (2)	0.0547 (8)
O3	1.0875 (4)	0.8720 (2)	0.3708 (3)	0.0540 (8)
O4	1.2090 (4)	0.8779 (3)	0.1895 (3)	0.0621 (9)
N1	0.6932 (4)	0.4364 (2)	0.4965 (3)	0.0429 (8)
N2	0.5655 (4)	0.5461 (2)	0.3653 (3)	0.0407 (8)
H2	0.4899	0.5458	0.4127	0.049*
C1	0.9139 (5)	0.3890 (3)	0.4238 (4)	0.0525 (11)
H1	1.0078	0.3563	0.4215	0.063*
C2	0.8241 (5)	0.3813 (3)	0.5146 (4)	0.0487 (10)
H2A	0.8471	0.3419	0.5853	0.058*
C3	0.6816 (5)	0.4886 (3)	0.3920 (3)	0.0393 (9)
C4	0.7160 (5)	0.6916 (3)	0.2825 (3)	0.0390 (9)
C5	0.8250 (5)	0.7001 (3)	0.1993 (3)	0.0444 (10)
H5	0.8150	0.6645	0.1242	0.053*
C6	0.9482 (5)	0.7601 (3)	0.2248 (3)	0.0422 (9)
H6	1.0222	0.7663	0.1672	0.051*
C7	0.9628 (4)	0.8114 (3)	0.3362 (3)	0.0356 (8)
C8	0.8530 (5)	0.8018 (3)	0.4203 (3)	0.0408 (9)
H8	0.8636	0.8362	0.4963	0.049*
C9	0.7304 (5)	0.7431 (3)	0.3940 (3)	0.0414 (9)
H9	0.6556	0.7374	0.4510	0.050*
C10	1.1941 (5)	0.8985 (3)	0.2972 (4)	0.0484 (10)
C11	1.3199 (6)	0.9613 (4)	0.3672 (5)	0.0544 (11)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0531 (7)	0.0573 (7)	0.0405 (6)	−0.0071 (5)	0.0083 (5)	−0.0031 (5)
S2	0.0539 (6)	0.0557 (6)	0.0244 (5)	−0.0088 (5)	−0.0045 (4)	0.0085 (4)
F1	0.0512 (16)	0.0725 (19)	0.086 (2)	0.0087 (14)	−0.0015 (14)	0.0160 (17)
F2	0.0624 (17)	0.081 (2)	0.0607 (17)	−0.0100 (15)	0.0071 (13)	−0.0193 (15)
F3	0.0685 (19)	0.0635 (18)	0.0730 (19)	−0.0053 (14)	0.0073 (15)	0.0189 (15)
O1	0.0508 (17)	0.073 (2)	0.0385 (15)	−0.0029 (15)	−0.0064 (13)	0.0167 (15)
O2	0.076 (2)	0.0631 (19)	0.0219 (13)	−0.0207 (17)	−0.0062 (13)	0.0018 (13)
O3	0.062 (2)	0.0564 (19)	0.0436 (16)	0.0032 (15)	0.0051 (14)	0.0015 (14)
O4	0.071 (2)	0.073 (2)	0.0442 (18)	−0.0039 (18)	0.0159 (15)	−0.0029 (16)
N1	0.059 (2)	0.0393 (18)	0.0288 (15)	0.0003 (16)	−0.0016 (14)	−0.0013 (13)
N2	0.0466 (18)	0.051 (2)	0.0247 (14)	−0.0051 (15)	0.0032 (13)	0.0077 (13)
C1	0.054 (3)	0.049 (2)	0.053 (3)	0.003 (2)	−0.002 (2)	−0.013 (2)
C2	0.063 (3)	0.042 (2)	0.038 (2)	0.003 (2)	−0.0043 (19)	−0.0034 (17)
C3	0.051 (2)	0.041 (2)	0.0248 (17)	−0.0051 (18)	−0.0011 (15)	−0.0027 (15)
C4	0.050 (2)	0.042 (2)	0.0229 (16)	−0.0013 (17)	−0.0038 (15)	0.0024 (15)
C5	0.063 (3)	0.048 (2)	0.0211 (16)	−0.004 (2)	0.0020 (16)	−0.0050 (15)
C6	0.054 (2)	0.047 (2)	0.0266 (17)	0.0037 (19)	0.0092 (16)	−0.0010 (16)
C7	0.046 (2)	0.0314 (18)	0.0282 (17)	0.0078 (16)	−0.0004 (15)	0.0033 (14)
C8	0.057 (2)	0.041 (2)	0.0239 (16)	0.0028 (18)	0.0035 (16)	−0.0042 (15)
C9	0.053 (2)	0.049 (2)	0.0231 (16)	−0.0024 (18)	0.0067 (15)	0.0023 (16)
C10	0.051 (2)	0.050 (2)	0.044 (2)	0.0062 (19)	0.0088 (19)	0.0039 (19)
C11	0.050 (3)	0.062 (3)	0.051 (3)	0.007 (2)	0.006 (2)	0.007 (2)

Geometric parameters (Å, º)

S1—C3	1.738 (4)	N2—H2	0.8800
S1—C1	1.745 (5)	C1—C2	1.326 (6)
S2—O1	1.430 (4)	C1—H1	0.9500
S2—O2	1.450 (3)	C2—H2A	0.9500
S2—N2	1.604 (3)	C4—C5	1.386 (6)
S2—C4	1.762 (4)	C4—C9	1.400 (5)
F1—C11	1.339 (5)	C5—C6	1.385 (6)
F2—C11	1.331 (5)	C5—H5	0.9500
F3—C11	1.325 (5)	C6—C7	1.398 (5)
O3—C10	1.346 (5)	C6—H6	0.9500
O3—C7	1.414 (5)	C7—C8	1.399 (5)
O4—C10	1.214 (5)	C8—C9	1.370 (6)
N1—C3	1.344 (5)	C8—H8	0.9500
N1—C2	1.389 (6)	C9—H9	0.9500
N2—C3	1.317 (5)	C10—C11	1.550 (7)
C3—S1—C1	90.8 (2)	C6—C5—C4	120.4 (3)
O1—S2—O2	117.08 (19)	C6—C5—H5	119.8
O1—S2—N2	106.00 (19)	C4—C5—H5	119.8
O2—S2—N2	111.73 (19)	C5—C6—C7	119.4 (4)
O1—S2—C4	109.3 (2)	C5—C6—H6	120.3
O2—S2—C4	106.50 (19)	C7—C6—H6	120.3
N2—S2—C4	105.72 (17)	C6—C7—C8	119.8 (4)
C10—O3—C7	126.0 (3)	C6—C7—O3	122.8 (3)
C3—N1—C2	114.7 (4)	C8—C7—O3	117.3 (3)
C3—N2—S2	122.1 (3)	C9—C8—C7	120.6 (3)
C3—N2—H2	119.0	C9—C8—H8	119.7
S2—N2—H2	119.0	C7—C8—H8	119.7
C2—C1—S1	111.0 (4)	C8—C9—C4	119.5 (4)
C2—C1—H1	124.5	C8—C9—H9	120.2
S1—C1—H1	124.5	C4—C9—H9	120.2
C1—C2—N1	113.6 (4)	O4—C10—O3	130.4 (5)
C1—C2—H2A	123.2	O4—C10—C11	117.0 (4)
N1—C2—H2A	123.2	O3—C10—C11	112.6 (4)
N2—C3—N1	121.0 (4)	F3—C11—F2	107.4 (4)
N2—C3—S1	129.1 (3)	F3—C11—F1	107.9 (4)
N1—C3—S1	109.9 (3)	F2—C11—F1	106.9 (4)
C5—C4—C9	120.2 (4)	F3—C11—C10	111.3 (4)
C5—C4—S2	120.6 (3)	F2—C11—C10	113.9 (4)
C9—C4—S2	119.2 (3)	F1—C11—C10	109.2 (4)
O1—S2—N2—C3	−178.9 (3)	S2—C4—C5—C6	179.0 (3)
O2—S2—N2—C3	52.5 (4)	C4—C5—C6—C7	0.7 (6)
C4—S2—N2—C3	−63.0 (4)	C5—C6—C7—C8	−0.1 (6)
C3—S1—C1—C2	0.9 (4)	C5—C6—C7—O3	178.1 (3)
S1—C1—C2—N1	−0.1 (5)	C10—O3—C7—C6	9.8 (6)
C3—N1—C2—C1	−1.1 (5)	C10—O3—C7—C8	−171.9 (4)
S2—N2—C3—N1	173.6 (3)	C6—C7—C8—C9	−0.6 (6)
S2—N2—C3—S1	−6.0 (5)	O3—C7—C8—C9	−178.9 (3)
C2—N1—C3—N2	−178.0 (4)	C7—C8—C9—C4	0.7 (6)
C2—N1—C3—S1	1.7 (4)	C5—C4—C9—C8	−0.1 (6)
C1—S1—C3—N2	178.2 (4)	S2—C4—C9—C8	−179.7 (3)
C1—S1—C3—N1	−1.5 (3)	C7—O3—C10—O4	−0.2 (8)
O1—S2—C4—C5	−123.6 (3)	C7—O3—C10—C11	−176.8 (3)
O2—S2—C4—C5	3.7 (4)	O4—C10—C11—F3	41.5 (6)
N2—S2—C4—C5	122.7 (3)	O3—C10—C11—F3	−141.4 (4)
O1—S2—C4—C9	56.0 (4)	O4—C10—C11—F2	163.1 (4)
O2—S2—C4—C9	−176.7 (3)	O3—C10—C11—F2	−19.8 (5)
N2—S2—C4—C9	−57.7 (4)	O4—C10—C11—F1	−77.6 (5)
C9—C4—C5—C6	−0.6 (6)	O3—C10—C11—F1	99.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1i	0.88	1.99	2.858 (5)	171

Symmetry code: (i) −x+1, −y+1, −z+1.