Crystal structure of 2-amino-3-ethyl-4,5-di-hydro-1,3-thia-zol-3-ium 3-chloro-benzo-ate.

The title salt, C5H11N2S(+)·C7H4ClO2 (-), comprises a 2-amino-3-ethyl-4,5-di-hydro-1,3-thia-zol-3-ium cation in which the five-membered ring adopts an envelope conformation with the methyl-ene C adjacent to the S atom being the flap, and a planar 3-chloro-benzoate anion (r.m.s. deviation for the 10 non-H atoms = 0.021 Å). The most prominent feature of the crystal packing are N-H⋯O hydrogen bonds whereby the two amine H atoms bridge two carboxyl-ate O atoms resulting in the formation of a centrosymmetric 12-membered {⋯HNH⋯OCO}2 synthon involving two cations and two anions. These aggregates are linked by C-H⋯O inter-actions to form a supra-molecular chain along the a-axis direction.

Related literature

For the crystal structure of a related compound, see: Yamin & Zulkifli (2011 ▸).

Experimental

Crystal data

C5H11N2S+·C7H4ClO2 −

M = 286.77

Triclinic,

a = 7.3376 (7) Å

b = 8.7987 (9) Å

c = 11.7068 (11) Å

α = 70.728 (3)°

β = 80.269 (3)°

γ = 71.531 (3)°

V = 674.95 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.43 mm−1

T = 296 K

0.37 × 0.32 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.856, T max = 0.975

16295 measured reflections

3430 independent reflections

1957 reflections with I > 2σ(I)

R int = 0.064

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.142

S = 1.02

3430 reflections

171 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.26 e Å−3

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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015008385/tk5367sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008385/tk5367Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015008385/tk5367Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015008385/tk5367fig1.tif

The mol­ecular structure of the title salt with displacement ellipsoids drawn at 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015008385/tk5367fig2.tif

A view of the crystal packing of the title salt viewed down b axis. The dashed lines indicate hydrogen bonds.

CCDC reference: 1062249

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

C5H11N2S+·C7H4ClO2−	Z = 2
Mr = 286.77	F(000) = 300
Triclinic, P1	Dx = 1.411 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3376 (7) Å	Cell parameters from 6990 reflections
b = 8.7987 (9) Å	θ = 2.9–28.6°
c = 11.7068 (11) Å	µ = 0.43 mm−1
α = 70.728 (3)°	T = 296 K
β = 80.269 (3)°	Slab, colourless
γ = 71.531 (3)°	0.37 × 0.32 × 0.06 mm
V = 674.95 (11) Å3

Bruker SMART APEX CCD area-detector diffractometer	3430 independent reflections
Radiation source: fine-focus sealed tube	1957 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
Detector resolution: 83.66 pixels mm-1	θmax = 28.6°, θmin = 2.9°
ω scan	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −11→11
Tmin = 0.856, Tmax = 0.975	l = −15→15
16295 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0715P)2] where P = (Fo2 + 2Fc2)/3
3430 reflections	(Δ/σ)max < 0.001
171 parameters	Δρmax = 0.31 e Å−3
2 restraints	Δρmin = −0.26 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	1.18120 (11)	−0.25267 (10)	1.66658 (6)	0.0724 (3)
S1	0.48369 (9)	0.37155 (8)	0.90259 (5)	0.0493 (2)
O1	1.0531 (3)	−0.2998 (2)	1.16212 (16)	0.0570 (5)
O2	0.9540 (3)	−0.0771 (3)	1.22844 (19)	0.0855 (7)
N1	0.4326 (3)	0.1591 (3)	1.10804 (19)	0.0523 (6)
N2	0.7549 (3)	0.1491 (3)	1.0431 (2)	0.0514 (6)
H2B	0.835 (3)	0.189 (3)	0.9867 (19)	0.064 (9)*
H2C	0.810 (3)	0.068 (2)	1.1024 (17)	0.059 (8)*
C1	1.1263 (3)	−0.3301 (3)	1.3595 (2)	0.0383 (5)
C2	1.2154 (3)	−0.4996 (3)	1.3822 (2)	0.0459 (6)
H2A	1.2237	−0.5512	1.3230	0.055*
C3	1.2921 (4)	−0.5927 (3)	1.4918 (2)	0.0545 (7)
H3A	1.3509	−0.7072	1.5065	0.065*
C4	1.2829 (4)	−0.5184 (3)	1.5798 (2)	0.0523 (7)
H4A	1.3353	−0.5812	1.6537	0.063*
C5	1.1949 (3)	−0.3501 (3)	1.5564 (2)	0.0441 (6)
C6	1.1164 (3)	−0.2547 (3)	1.4475 (2)	0.0416 (6)
H6A	1.0571	−0.1405	1.4335	0.050*
C7	1.0367 (3)	−0.2280 (3)	1.2403 (2)	0.0468 (6)
C8	0.5708 (3)	0.2094 (3)	1.0315 (2)	0.0406 (6)
C9	0.2384 (4)	0.2374 (4)	1.0666 (3)	0.0713 (9)
H9A	0.1472	0.2595	1.1336	0.086*
H9B	0.2010	0.1635	1.0351	0.086*
C10	0.2390 (3)	0.3967 (4)	0.9701 (3)	0.0609 (8)
H10A	0.1996	0.4898	1.0043	0.073*
H10B	0.1511	0.4184	0.9096	0.073*
C11	0.4633 (5)	0.0131 (4)	1.2191 (3)	0.0694 (9)
H11A	0.3912	−0.0612	1.2173	0.083*
H11B	0.5988	−0.0486	1.2200	0.083*
C12	0.4029 (5)	0.0639 (4)	1.3300 (3)	0.0829 (10)
H12A	0.4251	−0.0338	1.3995	0.124*
H12B	0.2683	0.1232	1.3303	0.124*
H12C	0.4758	0.1357	1.3330	0.124*

	U11	U22	U33	U12	U13	U23
Cl1	0.0822 (6)	0.0905 (6)	0.0555 (5)	−0.0246 (5)	−0.0093 (4)	−0.0333 (4)
S1	0.0453 (4)	0.0562 (4)	0.0395 (4)	−0.0020 (3)	−0.0132 (3)	−0.0117 (3)
O1	0.0605 (11)	0.0701 (13)	0.0473 (10)	−0.0239 (9)	−0.0116 (9)	−0.0172 (10)
O2	0.1099 (18)	0.0587 (14)	0.0682 (14)	0.0216 (12)	−0.0489 (13)	−0.0156 (10)
N1	0.0438 (12)	0.0556 (14)	0.0474 (12)	−0.0072 (10)	−0.0040 (10)	−0.0085 (10)
N2	0.0411 (13)	0.0547 (15)	0.0449 (13)	0.0008 (11)	−0.0117 (11)	−0.0065 (11)
C1	0.0318 (12)	0.0416 (14)	0.0396 (13)	−0.0133 (10)	−0.0043 (10)	−0.0060 (10)
C2	0.0431 (14)	0.0437 (15)	0.0527 (15)	−0.0128 (11)	−0.0046 (12)	−0.0154 (12)
C3	0.0549 (16)	0.0369 (15)	0.0627 (18)	−0.0070 (12)	−0.0120 (14)	−0.0050 (13)
C4	0.0476 (15)	0.0547 (18)	0.0445 (14)	−0.0119 (13)	−0.0136 (12)	0.0011 (13)
C5	0.0371 (13)	0.0566 (16)	0.0417 (14)	−0.0189 (12)	−0.0008 (11)	−0.0138 (12)
C6	0.0366 (13)	0.0378 (13)	0.0473 (14)	−0.0087 (10)	−0.0045 (11)	−0.0096 (11)
C7	0.0361 (13)	0.0573 (18)	0.0436 (14)	−0.0125 (12)	−0.0091 (11)	−0.0080 (13)
C8	0.0463 (15)	0.0370 (13)	0.0376 (13)	−0.0010 (11)	−0.0101 (11)	−0.0167 (11)
C9	0.0454 (17)	0.095 (2)	0.0659 (19)	−0.0181 (16)	−0.0046 (14)	−0.0148 (18)
C10	0.0399 (15)	0.0683 (19)	0.0718 (19)	−0.0033 (13)	−0.0153 (14)	−0.0231 (16)
C11	0.074 (2)	0.0483 (17)	0.068 (2)	−0.0075 (15)	−0.0001 (16)	−0.0059 (15)
C12	0.100 (3)	0.075 (2)	0.063 (2)	−0.0175 (19)	−0.0161 (19)	−0.0080 (18)

Cl1—C5	1.743 (3)	C3—H3A	0.9300
S1—C8	1.746 (2)	C4—C5	1.368 (4)
S1—C10	1.811 (3)	C4—H4A	0.9300
O1—C7	1.245 (3)	C5—C6	1.377 (3)
O2—C7	1.243 (3)	C6—H6A	0.9300
N1—C8	1.320 (3)	C9—C10	1.483 (4)
N1—C9	1.460 (3)	C9—H9A	0.9700
N1—C11	1.485 (3)	C9—H9B	0.9700
N2—C8	1.298 (3)	C10—H10A	0.9700
N2—H2B	0.866 (10)	C10—H10B	0.9700
N2—H2C	0.862 (10)	C11—C12	1.465 (4)
C1—C6	1.379 (3)	C11—H11A	0.9700
C1—C2	1.379 (3)	C11—H11B	0.9700
C1—C7	1.514 (3)	C12—H12A	0.9600
C2—C3	1.376 (3)	C12—H12B	0.9600
C2—H2A	0.9300	C12—H12C	0.9600
C3—C4	1.373 (4)
C8—S1—C10	90.90 (12)	N2—C8—N1	126.9 (2)
C8—N1—C9	115.4 (2)	N2—C8—S1	120.1 (2)
C8—N1—C11	125.1 (2)	N1—C8—S1	112.98 (17)
C9—N1—C11	118.6 (2)	N1—C9—C10	107.9 (2)
C8—N2—H2B	120.1 (19)	N1—C9—H9A	110.1
C8—N2—H2C	126.2 (18)	C10—C9—H9A	110.1
H2B—N2—H2C	114 (3)	N1—C9—H9B	110.1
C6—C1—C2	119.3 (2)	C10—C9—H9B	110.1
C6—C1—C7	120.2 (2)	H9A—C9—H9B	108.4
C2—C1—C7	120.5 (2)	C9—C10—S1	106.45 (18)
C3—C2—C1	120.3 (2)	C9—C10—H10A	110.4
C3—C2—H2A	119.8	S1—C10—H10A	110.4
C1—C2—H2A	119.8	C9—C10—H10B	110.4
C4—C3—C2	120.7 (2)	S1—C10—H10B	110.4
C4—C3—H3A	119.7	H10A—C10—H10B	108.6
C2—C3—H3A	119.7	C12—C11—N1	112.1 (3)
C5—C4—C3	118.6 (2)	C12—C11—H11A	109.2
C5—C4—H4A	120.7	N1—C11—H11A	109.2
C3—C4—H4A	120.7	C12—C11—H11B	109.2
C4—C5—C6	121.6 (2)	N1—C11—H11B	109.2
C4—C5—Cl1	119.55 (19)	H11A—C11—H11B	107.9
C6—C5—Cl1	118.8 (2)	C11—C12—H12A	109.5
C5—C6—C1	119.5 (2)	C11—C12—H12B	109.5
C5—C6—H6A	120.3	H12A—C12—H12B	109.5
C1—C6—H6A	120.3	C11—C12—H12C	109.5
O2—C7—O1	125.3 (2)	H12A—C12—H12C	109.5
O2—C7—C1	116.6 (2)	H12B—C12—H12C	109.5
O1—C7—C1	118.1 (2)
C6—C1—C2—C3	0.5 (4)	C2—C1—C7—O1	−3.0 (3)
C7—C1—C2—C3	−178.3 (2)	C9—N1—C8—N2	−174.0 (3)
C1—C2—C3—C4	−0.6 (4)	C11—N1—C8—N2	−5.0 (4)
C2—C3—C4—C5	0.3 (4)	C9—N1—C8—S1	4.8 (3)
C3—C4—C5—C6	0.0 (4)	C11—N1—C8—S1	173.7 (2)
C3—C4—C5—Cl1	179.99 (19)	C10—S1—C8—N2	−171.3 (2)
C4—C5—C6—C1	−0.1 (4)	C10—S1—C8—N1	9.8 (2)
Cl1—C5—C6—C1	179.95 (18)	C8—N1—C9—C10	−20.9 (4)
C2—C1—C6—C5	−0.2 (3)	C11—N1—C9—C10	169.4 (3)
C7—C1—C6—C5	178.6 (2)	N1—C9—C10—S1	26.1 (3)
C6—C1—C7—O2	−1.0 (3)	C8—S1—C10—C9	−20.7 (2)
C2—C1—C7—O2	177.8 (2)	C8—N1—C11—C12	112.8 (3)
C6—C1—C7—O1	178.2 (2)	C9—N1—C11—C12	−78.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1i	0.87 (2)	1.89 (2)	2.730 (3)	164 (2)
N2—H2C···O2	0.86 (2)	1.83 (2)	2.680 (3)	169 (2)
C10—H10B···O1ii	0.97	2.46	3.297 (4)	145

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2BO1i	0.87(2)	1.89(2)	2.730(3)	164(2)
N2H2CO2	0.86(2)	1.83(2)	2.680(3)	169(2)
C10H10BO1ii	0.97	2.46	3.297(4)	145

Symmetry codes: (i) ; (ii) .