(3RS)-S-[1-(3-Chloro-phen-yl)-2-oxopyr-roli-din-3-yl]thio-uronium bromide.

In the title molecular salt, C(11)H(13)ClN(3)OS(+)·Br(-), the C-N bond lengths in the -S-C(NH(2))(2) fragment indicate partial double-bond character of these bonds. The constituent ions are connected by N-H⋯Br bridges into Z-shaped chains. The supra-molecular architecture of the structure can be described by being composed of these chains inter-locked by additional C-H⋯Br short contacts. An intra-molecular N-H⋯O=C bridge, as well as weak C-H⋯O hydrogen bonds, are also present in the structure.

Related literature

For the preparation and reactivity of isothiuronium salts, see: Hanusek et al. (2004 ▶); Sedlák et al. (2002 ▶, 2003 ▶). For related structures, see: Bel’skii et al. (1985 ▶); Cotton et al. (2006 ▶); Hanusek et al. (2009 ▶); Ishii et al. (2000 ▶); L’abbe et al. (1980 ▶); Luger et al. (1996 ▶); Rovnyak et al. (1995 ▶); Vijayan & Mani (1977 ▶).

Experimental

Crystal data

C11H13ClN3OS+·Br−

M = 350.66

Monoclinic,

a = 15.7379 (9) Å

b = 6.4250 (5) Å

c = 15.0531 (7) Å

β = 117.329 (5)°

V = 1352.22 (16) Å3

Z = 4

Mo Kα radiation

μ = 3.38 mm−1

T = 150 (2) K

0.29 × 0.12 × 0.03 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

Absorption correction: gaussian (Coppens, 1970 ▶) T min = 0.542, T max = 0.873

15769 measured reflections

3095 independent reflections

2214 reflections with I > 2σ(I)

R int = 0.097

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.096

S = 1.15

3095 reflections

164 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.47 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶) and DENZO (Otwin­owski & Minor, 1997 ▶); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001603/fb2122sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001603/fb2122Isup2.hkl

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

C11H13ClN3OS+·Br−	F(000) = 704
Mr = 350.66	Dx = 1.722 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15779 reflections
a = 15.7379 (9) Å	θ = 1–27.5°
b = 6.4250 (5) Å	µ = 3.38 mm−1
c = 15.0531 (7) Å	T = 150 K
β = 117.329 (5)°	Plate, colourless
V = 1352.22 (16) Å3	0.29 × 0.12 × 0.03 mm
Z = 4

Bruker–Nonius KappaCCD diffractometer	3095 independent reflections
Radiation source: fine-focus sealed tube	2214 reflections with I > 2σ(I)
graphite	Rint = 0.097
Detector resolution: 9.091 pixels mm-1	θmax = 27.5°, θmin = 2.9°
φ and ω scans	h = −20→20
Absorption correction: gaussian (Coppens, 1970)	k = −7→8
Tmin = 0.542, Tmax = 0.873	l = −19→19
15769 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050	H-atom parameters constrained
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0236P)2 + 1.6718P] where P = (Fo2 + 2Fc2)/3
S = 1.15	(Δ/σ)max < 0.001
3095 reflections	Δρmax = 0.48 e Å−3
164 parameters	Δρmin = −0.47 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
52 constraints	Extinction coefficient: 0.0036 (5)
Primary atom site location: structure-invariant direct methods

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br1	0.48049 (3)	0.45589 (6)	0.65892 (3)	0.04086 (16)
S1	0.34553 (7)	0.14593 (15)	0.41198 (8)	0.0339 (2)
Cl1	−0.19436 (7)	0.30572 (19)	−0.02926 (9)	0.0532 (3)
O1	0.21265 (19)	−0.2562 (4)	0.2711 (2)	0.0450 (7)
C5	0.0464 (3)	0.0076 (6)	0.1482 (3)	0.0295 (8)
C6	−0.0184 (3)	0.1577 (6)	0.0890 (3)	0.0330 (9)
H6	0.0040	0.2871	0.0774	0.040*
C4	0.3119 (3)	0.0455 (6)	0.2870 (3)	0.0346 (9)
H4	0.3640	−0.0404	0.2852	0.042*
C11	0.3880 (2)	−0.0716 (6)	0.4901 (3)	0.0291 (8)
C2	0.1792 (3)	0.2598 (6)	0.1780 (3)	0.0372 (10)
H2A	0.1660	0.3657	0.2179	0.045*
H2B	0.1480	0.3027	0.1069	0.045*
C1	0.2191 (3)	−0.0747 (6)	0.2493 (3)	0.0329 (9)
C10	0.0120 (3)	−0.1790 (7)	0.1662 (3)	0.0398 (10)
H10	0.0552	−0.2828	0.2072	0.048*
C8	−0.1500 (3)	−0.0645 (7)	0.0639 (3)	0.0422 (10)
H8	−0.2169	−0.0891	0.0349	0.051*
C7	−0.1148 (3)	0.1186 (7)	0.0473 (3)	0.0375 (9)
C9	−0.0854 (3)	−0.2119 (7)	0.1239 (3)	0.0459 (11)
H9	−0.1085	−0.3394	0.1364	0.055*
C3	0.2862 (3)	0.2309 (7)	0.2163 (3)	0.0410 (10)
H3A	0.3216	0.3568	0.2522	0.049*
H3B	0.3012	0.2018	0.1605	0.049*
N2A	0.4287 (2)	−0.0308 (5)	0.5862 (2)	0.0359 (8)
H2AA	0.4517	−0.1329	0.6299	0.043*
H2AB	0.4331	0.0986	0.6070	0.043*
N1	0.1455 (2)	0.0527 (5)	0.1902 (2)	0.0301 (7)
N3A	0.3800 (2)	−0.2598 (5)	0.4563 (3)	0.0387 (8)
H3AA	0.4023	−0.3650	0.4982	0.046*
H3AB	0.3523	−0.2825	0.3914	0.046*

	U11	U22	U33	U12	U13	U23
Br1	0.0583 (3)	0.0267 (2)	0.0360 (2)	−0.00529 (19)	0.0203 (2)	−0.00053 (19)
S1	0.0371 (5)	0.0258 (5)	0.0328 (5)	0.0008 (4)	0.0109 (4)	−0.0016 (4)
Cl1	0.0390 (6)	0.0562 (7)	0.0584 (7)	0.0075 (5)	0.0172 (5)	0.0116 (6)
O1	0.0468 (17)	0.0269 (16)	0.0439 (18)	−0.0033 (13)	0.0059 (13)	0.0010 (13)
C5	0.032 (2)	0.030 (2)	0.027 (2)	−0.0057 (15)	0.0133 (16)	−0.0075 (16)
C6	0.036 (2)	0.030 (2)	0.034 (2)	−0.0026 (17)	0.0161 (17)	0.0017 (17)
C4	0.034 (2)	0.037 (2)	0.032 (2)	−0.0007 (18)	0.0144 (17)	0.0001 (19)
C11	0.0234 (18)	0.025 (2)	0.039 (2)	−0.0001 (15)	0.0141 (16)	−0.0007 (17)
C2	0.037 (2)	0.030 (2)	0.040 (2)	−0.0071 (17)	0.0141 (18)	0.0067 (18)
C1	0.038 (2)	0.030 (2)	0.027 (2)	0.0000 (17)	0.0123 (17)	−0.0043 (17)
C10	0.040 (2)	0.036 (2)	0.038 (2)	−0.0058 (18)	0.0143 (19)	0.0043 (19)
C8	0.035 (2)	0.056 (3)	0.034 (2)	−0.014 (2)	0.0140 (18)	−0.002 (2)
C7	0.038 (2)	0.043 (2)	0.033 (2)	0.0007 (19)	0.0176 (18)	−0.0003 (19)
C9	0.048 (2)	0.041 (3)	0.047 (3)	−0.015 (2)	0.020 (2)	0.004 (2)
C3	0.038 (2)	0.048 (3)	0.038 (2)	−0.0066 (19)	0.0177 (19)	0.007 (2)
N2A	0.0434 (19)	0.0261 (16)	0.0307 (19)	−0.0003 (15)	0.0104 (15)	−0.0017 (15)
N1	0.0291 (16)	0.0265 (16)	0.0319 (18)	−0.0045 (14)	0.0116 (14)	−0.0010 (14)
N3A	0.049 (2)	0.0262 (18)	0.0327 (19)	0.0049 (15)	0.0117 (16)	−0.0026 (15)

S1—C11	1.749 (4)	C2—H2A	0.9900
S1—C4	1.822 (4)	C2—H2B	0.9900
Cl1—C7	1.737 (4)	C1—N1	1.363 (5)
O1—C1	1.228 (4)	C10—C9	1.379 (6)
C5—C6	1.389 (5)	C10—H10	0.9500
C5—C10	1.392 (5)	C8—C7	1.371 (6)
C5—N1	1.418 (4)	C8—C9	1.380 (6)
C6—C7	1.374 (5)	C8—H8	0.9500
C6—H6	0.9500	C9—H9	0.9500
C4—C1	1.514 (5)	C3—H3A	0.9900
C4—C3	1.523 (5)	C3—H3B	0.9900
C4—H4	1.0000	N2A—H2AA	0.8800
C11—N3A	1.296 (5)	N2A—H2AB	0.8800
C11—N2A	1.312 (5)	N3A—H3AA	0.8800
C2—N1	1.475 (5)	N3A—H3AB	0.8800
C2—C3	1.520 (5)
C11—S1—C4	104.56 (18)	C9—C10—H10	120.3
C6—C5—C10	119.1 (3)	C5—C10—H10	120.3
C6—C5—N1	118.5 (3)	C7—C8—C9	118.0 (4)
C10—C5—N1	122.4 (3)	C7—C8—H8	121.0
C7—C6—C5	119.9 (4)	C9—C8—H8	121.0
C7—C6—H6	120.1	C8—C7—C6	121.9 (4)
C5—C6—H6	120.1	C8—C7—Cl1	119.1 (3)
C1—C4—C3	103.7 (3)	C6—C7—Cl1	119.0 (3)
C1—C4—S1	109.9 (3)	C10—C9—C8	121.8 (4)
C3—C4—S1	107.6 (3)	C10—C9—H9	119.1
C1—C4—H4	111.8	C8—C9—H9	119.1
C3—C4—H4	111.8	C2—C3—C4	104.7 (3)
S1—C4—H4	111.8	C2—C3—H3A	110.8
N3A—C11—N2A	122.0 (4)	C4—C3—H3A	110.8
N3A—C11—S1	122.9 (3)	C2—C3—H3B	110.8
N2A—C11—S1	115.1 (3)	C4—C3—H3B	110.8
N1—C2—C3	104.0 (3)	H3A—C3—H3B	108.9
N1—C2—H2A	111.0	C11—N2A—H2AA	120.0
C3—C2—H2A	111.0	C11—N2A—H2AB	120.0
N1—C2—H2B	111.0	H2AA—N2A—H2AB	120.0
C3—C2—H2B	111.0	C1—N1—C5	126.8 (3)
H2A—C2—H2B	109.0	C1—N1—C2	112.1 (3)
O1—C1—N1	126.5 (4)	C5—N1—C2	120.9 (3)
O1—C1—C4	124.6 (4)	C11—N3A—H3AA	120.0
N1—C1—C4	108.8 (3)	C11—N3A—H3AB	120.0
C9—C10—C5	119.4 (4)	H3AA—N3A—H3AB	120.0

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AB···Br1	0.88	2.43	3.290 (3)	166
N2A—H2AA···Br1i	0.88	2.68	3.452 (3)	147
N2A—H2AA···Br1ii	0.88	2.91	3.426 (3)	119
N3A—H3AA···Br1i	0.88	2.44	3.273 (3)	158
N3A—H3AB···O1	0.88	2.12	2.823 (4)	137
C2—H2A···O1iii	0.99	2.57	3.352 (5)	137
C3—H3B···Br1iv	0.99	3.01	3.737 (4)	131
C10—H10···O1	0.95	2.22	2.852 (5)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AB⋯Br1	0.88	2.43	3.290 (3)	166
N2A—H2AA⋯Br1i	0.88	2.68	3.452 (3)	147
N2A—H2AA⋯Br1ii	0.88	2.91	3.426 (3)	119
N3A—H3AA⋯Br1i	0.88	2.44	3.273 (3)	158
N3A—H3AB⋯O1	0.88	2.12	2.823 (4)	137
C2—H2A⋯O1iii	0.99	2.57	3.352 (5)	137
C3—H3B⋯Br1iv	0.99	3.01	3.737 (4)	131
C10—H10⋯O1	0.95	2.22	2.852 (5)	124

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