7-Benzyl-3-methyl-6-phenyl­imidazo[2,1-b][1,3]thia­zol-7-ium chloride 0.75-hydrate

Guo-Li, H.; Bo, L.; Jun-Feng, K.

doi:10.1107/S1600536813018795

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages o1247-o1248

doi:10.1107/S1600536813018795

Open

access

7-Benzyl-3-methyl-6-phenylimidazo[2,1-b][1,3]thiazol-7-ium chloride 0.75-hydrate

Huang Guo-Li,^a ^* Liu Bo ^a and Kou Jun-Feng ^a

^aSchool of Chemistry and Chemical Engineering, Yunnan Normal University, Knuming 650050, People's Republic of China
^*Correspondence e-mail: hgli2005@126.com

(Received 13 April 2013; accepted 8 July 2013; online 13 July 2013)

Theasymmetric unit of the title salt, C₁₉H₁₇N₂S⁺·Cl⁻·0.75H₂O, contains two symmetrically independent formula units of the carbenium salt along with three water molecules. The water molecules are only 50% occupated, and one of them is positioned in a hydrophobic pocket not forming any hydrogen bonds. The conformation of the independent cations is very similar, with dihedral angles of 61.0 (2) and 61.5 (3)° between the benzene rings. They form quasi-centrosymmetric couples via π–π stacking interactions between the benzene and imidazo[2,1-b]thiazole rings [centroid–centroid distances = 3.718 (3) and 3.663 (3) Å]. In the crystal, O—H⋯Cl hydrogen bonds lead to the formation of a helical anion–water chain along the c-axis direction. The cations connect to the anion–water chain through C—H⋯Cl interactions, generating a three-dimensional supramolecular network. O—H⋯S hydrogen bonds and C—H⋯O interactions also occur.

Related literature

For applications in catalysis of abnormal N-heterocyclic carbenes, see: Mattson et al. (2006 ); Liu et al. (2008 ); Padmanaban et al. (2011 ). For related structures, see: Huang et al. (2011 ); Akkurt et al. (2011 , 2007 ); Song et al. (2008 ).

Experimental

Crystal data

C₁₉H₁₇N₂S⁺·Cl⁻·0.75H₂O
M_r = 354.37
Trigonal, P 3₂
a = 13.211 (1) Å
c = 19.555 (3) Å
V = 2955.7 (6) Å³
Z = 6
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 291 K
0.28 × 0.24 × 0.22 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.919, T_max = 0.936
16250 measured reflections
6594 independent reflections
4827 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.123
S = 1.00
6594 reflections
476 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 )
Flack parameter: 0.04 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯Cl1ⁱ	0.94	2.75	3.208 (6)	111
O1W—H1WA⋯S2ⁱⁱ	0.94	2.88	3.819 (6)	174
O1W—H1WB⋯Cl2	0.86	2.61	3.240 (7)	132
O3W—H3WA⋯Cl2ⁱⁱⁱ	0.85	2.68	3.275 (10)	129
O3W—H3WB⋯Cl1ⁱ	0.85	2.60	3.301 (10)	141
C8—H8⋯Cl1	0.93	2.78	3.664 (5)	159
C10—H10⋯Cl1^iv	0.93	2.72	3.390 (5)	130
C18—H18⋯O3W^v	0.93	2.52	3.320 (9)	144
C27—H27⋯Cl1	0.93	2.72	3.642 (5)	175
Symmetry codes: (i) x, y+1, z; (ii) $[-x+y, -x+1, z+{\script{1\over 3}}]$ ; (iii) $[-y+1, x-y+1, z-{\script{1\over 3}}]$ ; (iv) $[-x+y+1, -x+1, z+{\script{1\over 3}}]$ ; (v) x+1, y, z.

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813018795/ld2101sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813018795/ld2101Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813018795/ld2101Isup3.tif

Supporting information file. DOI: 10.1107/S1600536813018795/ld2101Isup4.tif

Supporting information file. DOI: 10.1107/S1600536813018795/ld2101Isup5.tif

checkCIF report

Comment top

N-Heterocyclic carbenes (NHCs) have become ubiquitous ligands in organometallic chemistry and also serve as excellent organocatalysts primarily due to their inherent strong σ-donor ability and nucleophilicity. Recently, Mattson et al. (2006), Liu et al. (2008), Padmanaban et al. (2011) and other researchers have designed new abnormal NHCs compounds and used them as organocatalysts to catalyze umpolung reactions. According to the reports on the synthesis of imidazo[2,1-b]thiazoles (Akkurt et al. (2011, 2007), Huang et al. (2011), Song et al. (2008)), herein we report the synthesis and structure of the title compound. The molecular structure of the title compound is depicted in Fig. 1. The crystallographic asymmetric unit of I, contains two 7-benzyl-3-methyl-6-phenyl-imidazo[2,1-b]thiazol-7-ium cation, two chlorine anion and three water molecule. As shown in Fig.2, the dihedral angle between benzene ring A and B is 60.85, while C and D is 61.66, indicating the two cations in the unit cell are not equivalent. The two symmetrically independent cations are stabilized by π–π stacking interactions, with a separation of 3.718 and 3.663 Å between the centroids of the benzene and thiazole rings. Another interesting part of the structure of title compound is the helical chain (Cl1—O3w—Cl2—O1w) formed entirely by the O—H···Cl hydrogen-bonding interactions (Fig.3 & Fig.4) hydrogen-bonding interactions along c axis in this molecule. O(3w) and O(1w) atoms bridges Cl(1) and Cl(2) atoms with the bond distances of O(3w)···Cl(1) 3.300 (2) Å, O(3w)···Cl(2) 3.275 (1) Å, O(1w)···Cl(1) 3.203 (6) Å, O(1w)···Cl(2) 3.236 (6) Å, while O(2w) doesn't involve in the formation of the helical chain. Probably because O2W water molecules is disordered and isolated, lead to some OH groups without acceptor and can't form hydrogen bonds. The cations connect to the anion-water chain through C—H···Cl hydrogen bonds, and each chloride ion binds to four cations with the average bond distances of 3.389 Å. Thus in the solid-state of title compound, the cation binds to the helical anion-water chain linked by intermolecular hydrogen bonds of O—H···Cl, generating a three-dimensional supramolecular network, and the space between them are occupied by some lattice water molecules.

Related literature top

For applications in catalysis of abnormal N-heterocyclic carbenes, see: Mattson et al. (2006); Liu et al. (2008); Padmanaban et al. (2011). For related structures, see: Huang et al. (2011); Akkurt et al. (2011, 2007); Song et al. (2008).

Experimental top

A mixture of 3-methyl-6-phenylimidazo[2,1-b]thiazole (1.071 g, 5.0 mmol) and benzyl chorlide (0.759 g, 6.0 mmol,1.2 equiv) was dissolved in CH3CN, and stirred under reflux for 12 h. The solvent was then removed under vacuum. The white solids obtained were washed with diethyl ether and the crude product was re-crystallized from chloroform / toluene. The yield was 1.45 g, 85%. 1H NMR (δ, 300 MHz, CDCl3): 8.35 (s, 1H), 7.71–7.68 (m, 2H), 7.54–7.52 (m, 3H), 7.41–7.29 (m, 6H), 5.53 (s, 2H), 2.64 (d, J = 1.2 Hz, 3H); 13 C NMR (δ, 75 MHz, CDCl3) 146.9, 140.3, 131.0, 130.8, 130.7, 130.1, 129.8, 129.4, 129.3, 129.1, 125.2, 114.4, 112.3, 51.5, 13.0.

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids.
	Fig. 2. The pi···pi stacking between two symmetrically independent cations.
	Fig. 3. The hydrogen bonded helical anion-water chain and the hydrogen bonding between Cl- ion and the cations.

7-Benzyl-3-methyl-6-phenylimidazo[2,1-b][1,3]thiazol-7-ium chloride 0.75-hydrate top

Crystal data top

C₁₉H₁₇N₂S⁺·Cl⁻·0.75H₂O	D_x = 1.195 Mg m⁻³
M_r = 354.37	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3₂	Cell parameters from 25 reflections
Hall symbol: P 32	θ = 1.8–26.0°
a = 13.211 (1) Å	µ = 0.31 mm⁻¹
c = 19.555 (3) Å	T = 291 K
V = 2955.7 (6) Å³	Block, colourless
Z = 6	0.28 × 0.24 × 0.22 mm
F(000) = 1113

Data collection top

Bruker SMART APEX CCD diffractometer	6594 independent reflections
Radiation source: fine-focus sealed tube	4827 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
phi and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −16→13
T_min = 0.919, T_max = 0.936	k = −14→16
16250 measured reflections	l = −24→16

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.060	w = 1/[σ²(F_o²) + (0.0606P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.123	(Δ/σ)_max < 0.001
S = 1.00	Δρ_max = 0.30 e Å⁻³
6594 reflections	Δρ_min = −0.28 e Å⁻³
476 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
15 restraints	Extinction coefficient: 0.0045 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.04 (7)

Crystal data top

C₁₉H₁₇N₂S⁺·Cl⁻·0.75H₂O	Z = 6
M_r = 354.37	Mo Kα radiation
Trigonal, P3₂	µ = 0.31 mm⁻¹
a = 13.211 (1) Å	T = 291 K
c = 19.555 (3) Å	0.28 × 0.24 × 0.22 mm
V = 2955.7 (6) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	6594 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	4827 reflections with I > 2σ(I)
T_min = 0.919, T_max = 0.936	R_int = 0.053
16250 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.123	Δρ_max = 0.30 e Å⁻³
S = 1.00	Δρ_min = −0.28 e Å⁻³
6594 reflections	Absolute structure: Flack (1983)
476 parameters	Absolute structure parameter: 0.04 (7)
15 restraints

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.4467 (3)	0.4753 (4)	0.1467 (2)	0.0415 (10)
C2	0.4721 (4)	0.4083 (4)	0.1030 (3)	0.0456 (11)
H2	0.5182	0.3774	0.1174	0.09 (2)*
C3	0.4258 (4)	0.3880 (4)	0.0358 (3)	0.0523 (12)
H3	0.4434	0.3455	0.0049	0.068 (17)*
C4	0.3542 (4)	0.4317 (4)	0.0161 (3)	0.0517 (12)
H4	0.3223	0.4168	−0.0276	0.035 (11)*
C5	0.3301 (4)	0.4974 (4)	0.0613 (2)	0.0464 (11)
H5	0.2827	0.5270	0.0474	0.039 (12)*
C6	0.3763 (3)	0.5200 (4)	0.1282 (2)	0.0437 (10)
H6	0.3597	0.5636	0.1588	0.073 (17)*
C7	0.4878 (4)	0.4879 (4)	0.2189 (2)	0.0454 (11)
C8	0.4919 (4)	0.4010 (4)	0.2554 (3)	0.0457 (11)
H8	0.4673	0.3255	0.2403	0.040 (12)*
C9	0.5679 (4)	0.4122 (4)	0.3779 (3)	0.0441 (10)
C10	0.6201 (4)	0.5055 (4)	0.4246 (3)	0.0436 (10)
H10	0.6468	0.4985	0.4674	0.08 (2)*
C11	0.5674 (4)	0.5640 (4)	0.3202 (3)	0.0527 (12)
C12	0.5438 (4)	0.2894 (4)	0.3879 (3)	0.0521 (12)
H12A	0.4609	0.2366	0.3882	0.069 (17)*
H12B	0.5765	0.2840	0.4307	0.047 (13)*
H12C	0.5787	0.2690	0.3513	0.12 (3)*
C13	0.5599 (4)	0.7050 (4)	0.2358 (3)	0.0517 (13)
H13A	0.5181	0.7308	0.2653	0.051 (14)*
H13B	0.5305	0.6991	0.1897	0.057 (15)*
C14	0.6892 (4)	0.7956 (4)	0.2372 (2)	0.0466 (11)
C15	0.7271 (4)	0.8950 (4)	0.2777 (3)	0.0501 (12)
H15	0.6742	0.9077	0.3022	0.075 (18)*
C16	0.8460 (4)	0.9743 (4)	0.2803 (3)	0.0566 (14)
H16	0.8730	1.0408	0.3073	0.068 (17)*
C17	0.9239 (4)	0.9570 (4)	0.2442 (3)	0.0577 (13)
H17	1.0033	1.0116	0.2460	0.077 (18)*
C18	0.8834 (5)	0.8563 (5)	0.2042 (3)	0.0560 (13)
H18	0.9361	0.8432	0.1795	0.10 (2)*
C19	0.7675 (4)	0.7778 (4)	0.2014 (2)	0.0510 (11)
H19	0.7411	0.7110	0.1747	0.043 (12)*
C20	0.2128 (4)	0.2665 (4)	0.3611 (2)	0.0458 (10)
H20	0.1764	0.1878	0.3495	0.072 (17)*
C21	0.2639 (4)	0.3027 (4)	0.4241 (3)	0.0495 (11)
H21	0.2614	0.2479	0.4549	0.046 (13)*
C22	0.3199 (4)	0.4213 (4)	0.4430 (2)	0.0425 (10)
H22	0.3551	0.4450	0.4857	0.078 (19)*
C23	0.3219 (3)	0.5016 (4)	0.3973 (2)	0.0393 (9)
H23	0.3570	0.5800	0.4096	0.072 (17)*
C24	0.2720 (4)	0.4666 (4)	0.3328 (2)	0.0456 (11)
H24	0.2763	0.5222	0.3020	0.044 (13)*
C25	0.2153 (3)	0.3487 (3)	0.3139 (2)	0.0399 (9)
C26	0.1701 (4)	0.3145 (4)	0.2445 (2)	0.0413 (10)
C27	0.1880 (3)	0.2417 (4)	0.2030 (2)	0.0403 (10)
H27	0.2297	0.2044	0.2139	0.056 (15)*
C28	0.1186 (4)	0.1747 (4)	0.0804 (2)	0.0423 (10)
C29	0.0565 (4)	0.2059 (4)	0.0319 (2)	0.0423 (10)
H29	0.0403	0.1797	−0.0130	0.054 (14)*
C30	0.0853 (3)	0.3017 (4)	0.1444 (2)	0.0378 (7)
C31	0.1685 (4)	0.0966 (4)	0.0659 (3)	0.0487 (11)
H31A	0.2388	0.1226	0.0920	0.073*
H31B	0.1860	0.0996	0.0181	0.073*
H31C	0.1126	0.0178	0.0785	0.073*
C32	0.0523 (4)	0.4200 (4)	0.2318 (3)	0.0473 (12)
H32A	0.0913	0.4940	0.2076	0.09 (2)*
H32B	0.0730	0.4372	0.2797	0.069 (17)*
C33	−0.0755 (4)	0.3745 (4)	0.2263 (3)	0.0472 (11)
C34	−0.1550 (4)	0.2597 (4)	0.2394 (2)	0.0462 (11)
H34	−0.1282	0.2097	0.2530	0.040 (12)*
C35	−0.2734 (4)	0.2163 (4)	0.2330 (3)	0.0538 (13)
H35	−0.3259	0.1375	0.2404	0.064 (16)*
C36	−0.3133 (4)	0.2921 (4)	0.2153 (3)	0.0510 (12)
H36	−0.3932	0.2651	0.2137	0.056 (15)*
C37	−0.2339 (4)	0.4087 (4)	0.1998 (3)	0.0505 (12)
H37	−0.2602	0.4586	0.1854	0.040 (12)*
C38	−0.1169 (4)	0.4485 (4)	0.2061 (3)	0.0542 (13)
H38	−0.0638	0.5265	0.1968	0.060 (15)*
Cl1	0.34178 (9)	0.08248 (9)	0.23677 (6)	0.0415 (2)
Cl2	0.50410 (9)	0.85717 (10)	0.41839 (6)	0.0492 (3)
N1	0.5403 (3)	0.4474 (3)	0.3202 (2)	0.0499 (9)
N2	0.5361 (3)	0.5880 (3)	0.2585 (2)	0.0486 (10)
N3	0.1327 (3)	0.2340 (3)	0.14208 (19)	0.0392 (8)
N4	0.1037 (3)	0.3502 (3)	0.20746 (19)	0.0383 (6)
O1W	0.4476 (5)	0.9150 (5)	0.2668 (3)	0.0474 (15)	0.50
H1WA	0.4076	0.9367	0.2979	0.057*	0.50
H1WB	0.4754	0.8780	0.2884	0.057*	0.50
O2W	0.7938 (8)	0.2009 (7)	0.4080 (5)	0.072 (2)	0.50
H2WA	0.8587	0.2262	0.3857	0.087*	0.50
H2WB	0.7494	0.2272	0.3924	0.087*	0.50
O3W	0.1192 (8)	0.8296 (9)	0.1880 (6)	0.100 (3)	0.50
H3WA	0.1196	0.7654	0.1890	0.121*	0.50
H3WB	0.1634	0.8744	0.2194	0.121*	0.50
S1	0.63072 (10)	0.63434 (11)	0.39577 (6)	0.0498 (3)
S2	0.01587 (10)	0.30059 (9)	0.07018 (6)	0.0448 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.032 (2)	0.037 (2)	0.043 (2)	0.0083 (18)	0.0137 (18)	0.0120 (18)
C2	0.038 (2)	0.044 (2)	0.049 (3)	0.016 (2)	0.0088 (19)	0.022 (2)
C3	0.048 (3)	0.040 (2)	0.049 (3)	0.008 (2)	0.026 (2)	0.015 (2)
C4	0.041 (2)	0.044 (2)	0.046 (3)	0.004 (2)	0.018 (2)	0.016 (2)
C5	0.043 (2)	0.040 (2)	0.043 (3)	0.0101 (19)	0.011 (2)	0.024 (2)
C6	0.0264 (19)	0.035 (2)	0.052 (3)	0.0021 (17)	0.0154 (19)	0.007 (2)
C7	0.031 (2)	0.037 (2)	0.047 (3)	0.0011 (17)	0.0121 (19)	−0.0010 (19)
C8	0.041 (2)	0.042 (2)	0.050 (3)	0.018 (2)	−0.012 (2)	−0.009 (2)
C9	0.035 (2)	0.041 (2)	0.056 (3)	0.0188 (18)	−0.007 (2)	0.012 (2)
C10	0.033 (2)	0.036 (2)	0.048 (3)	0.0079 (18)	0.0031 (19)	0.0041 (19)
C11	0.039 (2)	0.047 (3)	0.069 (3)	0.019 (2)	−0.014 (2)	−0.010 (2)
C12	0.051 (3)	0.036 (2)	0.043 (3)	0.002 (2)	0.016 (2)	0.007 (2)
C13	0.051 (3)	0.028 (2)	0.068 (4)	0.014 (2)	0.016 (2)	0.020 (2)
C14	0.041 (2)	0.035 (2)	0.051 (3)	0.0094 (19)	−0.002 (2)	0.011 (2)
C15	0.042 (2)	0.051 (3)	0.047 (3)	0.015 (2)	0.006 (2)	0.020 (2)
C16	0.048 (3)	0.042 (3)	0.059 (3)	0.008 (2)	−0.028 (2)	−0.002 (2)
C17	0.035 (2)	0.055 (3)	0.063 (3)	0.007 (2)	0.007 (2)	0.023 (3)
C18	0.053 (3)	0.067 (3)	0.051 (3)	0.032 (3)	0.000 (2)	0.002 (2)
C19	0.052 (3)	0.053 (3)	0.037 (3)	0.017 (2)	−0.002 (2)	−0.005 (2)
C20	0.034 (2)	0.043 (2)	0.050 (3)	0.0107 (18)	−0.0118 (19)	−0.0110 (19)
C21	0.054 (3)	0.040 (2)	0.042 (3)	0.015 (2)	−0.001 (2)	0.005 (2)
C22	0.041 (2)	0.040 (2)	0.041 (3)	0.0166 (18)	−0.0011 (19)	0.0033 (18)
C23	0.032 (2)	0.037 (2)	0.041 (2)	0.0120 (18)	−0.0115 (18)	−0.0145 (18)
C24	0.040 (2)	0.033 (2)	0.046 (3)	0.0052 (18)	0.0034 (19)	−0.0038 (19)
C25	0.034 (2)	0.034 (2)	0.044 (2)	0.0115 (17)	0.0133 (18)	0.0089 (17)
C26	0.038 (2)	0.034 (2)	0.040 (2)	0.0092 (18)	−0.0019 (18)	0.0015 (18)
C27	0.0193 (17)	0.048 (2)	0.039 (2)	0.0055 (17)	0.0006 (16)	−0.0057 (19)
C28	0.049 (2)	0.042 (2)	0.033 (2)	0.0211 (19)	0.0004 (19)	0.0074 (18)
C29	0.040 (2)	0.041 (2)	0.038 (2)	0.0144 (18)	−0.0121 (18)	−0.0122 (18)
C30	0.0324 (14)	0.0343 (14)	0.0412 (16)	0.0124 (12)	−0.0032 (13)	0.0015 (12)
C31	0.053 (3)	0.051 (3)	0.044 (3)	0.028 (2)	−0.012 (2)	−0.013 (2)
C32	0.035 (2)	0.055 (3)	0.055 (3)	0.025 (2)	−0.019 (2)	−0.027 (2)
C33	0.043 (2)	0.041 (2)	0.056 (3)	0.020 (2)	−0.024 (2)	−0.018 (2)
C34	0.047 (3)	0.031 (2)	0.056 (3)	0.0168 (19)	−0.017 (2)	−0.011 (2)
C35	0.048 (3)	0.047 (3)	0.048 (3)	0.010 (2)	−0.008 (2)	−0.016 (2)
C36	0.048 (3)	0.043 (2)	0.055 (3)	0.018 (2)	−0.006 (2)	−0.020 (2)
C37	0.047 (3)	0.054 (3)	0.050 (3)	0.025 (2)	−0.014 (2)	−0.011 (2)
C38	0.051 (3)	0.045 (3)	0.058 (3)	0.018 (2)	−0.016 (2)	−0.018 (2)
Cl1	0.0466 (6)	0.0407 (5)	0.0405 (5)	0.0243 (5)	0.0168 (4)	0.0141 (4)
Cl2	0.0390 (5)	0.0467 (6)	0.0495 (7)	0.0121 (5)	−0.0010 (5)	0.0196 (5)
N1	0.046 (2)	0.046 (2)	0.048 (2)	0.0151 (17)	0.0070 (17)	0.0076 (17)
N2	0.0363 (19)	0.0349 (19)	0.066 (3)	0.0113 (16)	−0.0117 (18)	−0.0056 (18)
N3	0.0315 (17)	0.0290 (16)	0.048 (2)	0.0081 (14)	0.0022 (14)	−0.0012 (15)
N4	0.0330 (13)	0.0344 (14)	0.0434 (15)	0.0137 (11)	−0.0028 (12)	−0.0029 (11)
O1W	0.055 (4)	0.043 (3)	0.046 (4)	0.026 (3)	0.011 (3)	0.001 (3)
O2W	0.092 (6)	0.058 (4)	0.078 (6)	0.045 (4)	−0.012 (5)	−0.007 (4)
O3W	0.069 (5)	0.114 (7)	0.138 (9)	0.060 (6)	0.011 (5)	−0.027 (7)
S1	0.0370 (6)	0.0464 (6)	0.0500 (7)	0.0089 (5)	0.0067 (5)	0.0070 (5)
S2	0.0416 (6)	0.0377 (5)	0.0446 (6)	0.0119 (5)	−0.0134 (5)	−0.0021 (5)

Geometric parameters (Å, º) top

C1—C6	1.376 (7)	C21—C22	1.406 (6)
C1—C2	1.387 (7)	C21—H21	0.9300
C1—C7	1.493 (6)	C22—C23	1.378 (6)
C2—C3	1.417 (7)	C22—H22	0.9300
C2—H2	0.9300	C23—C24	1.389 (6)
C3—C4	1.385 (7)	C23—H23	0.9300
C3—H3	0.9300	C24—C25	1.399 (6)
C4—C5	1.383 (7)	C24—H24	0.9300
C4—H4	0.9300	C25—C26	1.460 (6)
C5—C6	1.411 (7)	C26—C27	1.365 (6)
C5—H5	0.9300	C26—N4	1.390 (6)
C6—H6	0.9300	C27—N3	1.374 (6)
C7—C8	1.376 (7)	C27—H27	0.9300
C7—N2	1.382 (6)	C28—N3	1.399 (6)
C8—N1	1.413 (6)	C28—C29	1.441 (6)
C8—H8	0.9300	C28—C31	1.504 (7)
C9—N1	1.339 (6)	C29—S2	1.756 (5)
C9—C10	1.407 (7)	C29—H29	0.9300
C9—C12	1.502 (6)	C30—N3	1.324 (5)
C10—S1	1.731 (5)	C30—N4	1.354 (6)
C10—H10	0.9300	C30—S2	1.713 (4)
C11—N2	1.363 (7)	C31—H31A	0.9600
C11—N1	1.395 (6)	C31—H31B	0.9600
C11—S1	1.723 (5)	C31—H31C	0.9600
C12—H12A	0.9600	C32—N4	1.471 (5)
C12—H12B	0.9600	C32—C33	1.486 (6)
C12—H12C	0.9600	C32—H32A	0.9700
C13—N2	1.483 (6)	C32—H32B	0.9700
C13—C14	1.519 (6)	C33—C34	1.370 (6)
C13—H13A	0.9700	C33—C38	1.393 (7)
C13—H13B	0.9700	C34—C35	1.377 (7)
C14—C19	1.362 (7)	C34—H34	0.9300
C14—C15	1.396 (7)	C35—C36	1.388 (8)
C15—C16	1.386 (7)	C35—H35	0.9300
C15—H15	0.9300	C36—C37	1.396 (7)
C16—C17	1.358 (8)	C36—H36	0.9300
C16—H16	0.9300	C37—C38	1.367 (7)
C17—C18	1.399 (8)	C37—H37	0.9300
C17—H17	0.9300	C38—H38	0.9300
C18—C19	1.355 (7)	O1W—H1WA	0.9407
C18—H18	0.9300	O1W—H1WB	0.8555
C19—H19	0.9300	O2W—H2WA	0.8657
C20—C21	1.370 (6)	O2W—H2WB	0.8731
C20—C25	1.414 (6)	O3W—H3WA	0.8501
C20—H20	0.9300	O3W—H3WB	0.8502

C6—C1—C2	122.9 (4)	C22—C23—C24	120.6 (4)
C6—C1—C7	119.1 (4)	C22—C23—H23	119.7
C2—C1—C7	117.7 (4)	C24—C23—H23	119.7
C1—C2—C3	118.2 (4)	C23—C24—C25	120.8 (4)
C1—C2—H2	120.9	C23—C24—H24	119.6
C3—C2—H2	120.9	C25—C24—H24	119.6
C4—C3—C2	119.9 (5)	C24—C25—C20	118.4 (4)
C4—C3—H3	120.1	C24—C25—C26	120.0 (4)
C2—C3—H3	120.1	C20—C25—C26	121.3 (4)
C5—C4—C3	120.3 (5)	C27—C26—N4	106.9 (4)
C5—C4—H4	119.9	C27—C26—C25	125.7 (4)
C3—C4—H4	119.9	N4—C26—C25	127.5 (4)
C4—C5—C6	120.9 (5)	C26—C27—N3	107.2 (4)
C4—C5—H5	119.5	C26—C27—H27	126.4
C6—C5—H5	119.5	N3—C27—H27	126.4
C1—C6—C5	117.8 (5)	N3—C28—C29	110.0 (4)
C1—C6—H6	121.1	N3—C28—C31	124.4 (4)
C5—C6—H6	121.1	C29—C28—C31	125.5 (4)
C8—C7—N2	108.4 (4)	C28—C29—S2	110.1 (3)
C8—C7—C1	124.2 (4)	C28—C29—H29	124.9
N2—C7—C1	127.3 (4)	S2—C29—H29	124.9
C7—C8—N1	107.5 (4)	N3—C30—N4	108.5 (4)
C7—C8—H8	126.2	N3—C30—S2	113.4 (3)
N1—C8—H8	126.2	N4—C30—S2	138.1 (3)
N1—C9—C10	110.0 (4)	C28—C31—H31A	109.5
N1—C9—C12	122.6 (4)	C28—C31—H31B	109.5
C10—C9—C12	127.4 (4)	H31A—C31—H31B	109.5
C9—C10—S1	114.4 (4)	C28—C31—H31C	109.5
C9—C10—H10	122.8	H31A—C31—H31C	109.5
S1—C10—H10	122.8	H31B—C31—H31C	109.5
N2—C11—N1	108.4 (4)	N4—C32—C33	120.7 (4)
N2—C11—S1	139.0 (4)	N4—C32—H32A	107.2
N1—C11—S1	112.5 (4)	C33—C32—H32A	107.2
C9—C12—H12A	109.5	N4—C32—H32B	107.2
C9—C12—H12B	109.5	C33—C32—H32B	107.2
H12A—C12—H12B	109.5	H32A—C32—H32B	106.8
C9—C12—H12C	109.5	C34—C33—C38	118.5 (4)
H12A—C12—H12C	109.5	C34—C33—C32	121.4 (4)
H12B—C12—H12C	109.5	C38—C33—C32	120.1 (4)
N2—C13—C14	112.6 (4)	C33—C34—C35	121.7 (5)
N2—C13—H13A	109.1	C33—C34—H34	119.2
C14—C13—H13A	109.1	C35—C34—H34	119.2
N2—C13—H13B	109.1	C34—C35—C36	119.0 (5)
C14—C13—H13B	109.1	C34—C35—H35	120.5
H13A—C13—H13B	107.8	C36—C35—H35	120.5
C19—C14—C15	120.5 (4)	C35—C36—C37	120.2 (5)
C19—C14—C13	120.5 (4)	C35—C36—H36	119.9
C15—C14—C13	118.9 (4)	C37—C36—H36	119.9
C16—C15—C14	118.0 (5)	C38—C37—C36	119.1 (5)
C16—C15—H15	121.0	C38—C37—H37	120.5
C14—C15—H15	121.0	C36—C37—H37	120.5
C17—C16—C15	121.4 (5)	C37—C38—C33	121.4 (5)
C17—C16—H16	119.3	C37—C38—H38	119.3
C15—C16—H16	119.3	C33—C38—H38	119.3
C16—C17—C18	119.3 (5)	C9—N1—C11	114.8 (4)
C16—C17—H17	120.3	C9—N1—C8	138.3 (4)
C18—C17—H17	120.3	C11—N1—C8	106.9 (4)
C19—C18—C17	119.9 (5)	C11—N2—C7	108.8 (4)
C19—C18—H18	120.0	C11—N2—C13	125.2 (4)
C17—C18—H18	120.0	C7—N2—C13	125.8 (4)
C18—C19—C14	120.8 (5)	C30—N3—C27	109.5 (4)
C18—C19—H19	119.6	C30—N3—C28	115.6 (4)
C14—C19—H19	119.6	C27—N3—C28	134.9 (4)
C21—C20—C25	120.1 (4)	C30—N4—C26	107.9 (3)
C21—C20—H20	120.0	C30—N4—C32	124.2 (4)
C25—C20—H20	120.0	C26—N4—C32	127.7 (4)
C20—C21—C22	121.2 (4)	H1WA—O1W—H1WB	108.8
C20—C21—H21	119.4	H2WA—O2W—H2WB	113.8
C22—C21—H21	119.4	H3WA—O3W—H3WB	109.5
C23—C22—C21	118.9 (4)	C11—S1—C10	88.3 (2)
C23—C22—H22	120.5	C30—S2—C29	90.8 (2)
C21—C22—H22	120.5

C6—C1—C2—C3	1.9 (6)	C36—C37—C38—C33	1.3 (8)
C7—C1—C2—C3	175.1 (3)	C34—C33—C38—C37	0.4 (8)
C1—C2—C3—C4	−2.1 (6)	C32—C33—C38—C37	179.2 (5)
C2—C3—C4—C5	1.6 (6)	C10—C9—N1—C11	−0.8 (6)
C3—C4—C5—C6	−0.8 (6)	C12—C9—N1—C11	179.1 (4)
C2—C1—C6—C5	−1.1 (6)	C10—C9—N1—C8	177.4 (5)
C7—C1—C6—C5	−174.2 (3)	C12—C9—N1—C8	−2.7 (9)
C4—C5—C6—C1	0.5 (6)	N2—C11—N1—C9	179.3 (4)
C6—C1—C7—C8	138.1 (5)	S1—C11—N1—C9	0.0 (5)
C2—C1—C7—C8	−35.4 (6)	N2—C11—N1—C8	0.6 (5)
C6—C1—C7—N2	−47.5 (6)	S1—C11—N1—C8	−178.7 (3)
C2—C1—C7—N2	138.9 (5)	C7—C8—N1—C9	−179.9 (5)
N2—C7—C8—N1	2.0 (5)	C7—C8—N1—C11	−1.6 (5)
C1—C7—C8—N1	177.3 (4)	N1—C11—N2—C7	0.7 (5)
N1—C9—C10—S1	1.3 (5)	S1—C11—N2—C7	179.6 (5)
C12—C9—C10—S1	−178.6 (4)	N1—C11—N2—C13	−174.3 (4)
N2—C13—C14—C19	56.6 (6)	S1—C11—N2—C13	4.6 (9)
N2—C13—C14—C15	−120.9 (5)	C8—C7—N2—C11	−1.7 (5)
C19—C14—C15—C16	0.0 (7)	C1—C7—N2—C11	−176.8 (4)
C13—C14—C15—C16	177.5 (4)	C8—C7—N2—C13	173.3 (4)
C14—C15—C16—C17	0.6 (7)	C1—C7—N2—C13	−1.8 (7)
C15—C16—C17—C18	−0.9 (8)	C14—C13—N2—C11	57.4 (6)
C16—C17—C18—C19	0.6 (8)	C14—C13—N2—C7	−116.8 (5)
C17—C18—C19—C14	0.0 (8)	N4—C30—N3—C27	−2.9 (4)
C15—C14—C19—C18	−0.3 (8)	S2—C30—N3—C27	179.0 (3)
C13—C14—C19—C18	−177.7 (5)	N4—C30—N3—C28	178.4 (3)
C25—C20—C21—C22	−0.3 (7)	S2—C30—N3—C28	0.3 (5)
C20—C21—C22—C23	0.7 (7)	C26—C27—N3—C30	1.9 (4)
C21—C22—C23—C24	−1.6 (7)	C26—C27—N3—C28	−179.8 (4)
C22—C23—C24—C25	2.1 (7)	C29—C28—N3—C30	1.7 (5)
C23—C24—C25—C20	−1.7 (6)	C31—C28—N3—C30	177.9 (4)
C23—C24—C25—C26	−176.0 (4)	C29—C28—N3—C27	−176.5 (4)
C21—C20—C25—C24	0.8 (7)	C31—C28—N3—C27	−0.3 (7)
C21—C20—C25—C26	175.0 (4)	N3—C30—N4—C26	2.8 (4)
C24—C25—C26—C27	131.4 (4)	S2—C30—N4—C26	−179.8 (4)
C20—C25—C26—C27	−42.8 (6)	N3—C30—N4—C32	−172.8 (4)
C24—C25—C26—N4	−47.3 (6)	S2—C30—N4—C32	4.6 (7)
C20—C25—C26—N4	138.6 (4)	C27—C26—N4—C30	−1.6 (4)
N4—C26—C27—N3	−0.1 (4)	C25—C26—N4—C30	177.2 (4)
C25—C26—C27—N3	−179.0 (4)	C27—C26—N4—C32	173.7 (4)
N3—C28—C29—S2	−2.9 (4)	C25—C26—N4—C32	−7.4 (7)
C31—C28—C29—S2	−179.1 (4)	C33—C32—N4—C30	51.6 (7)
N4—C32—C33—C34	40.2 (7)	C33—C32—N4—C26	−123.1 (5)
N4—C32—C33—C38	−138.5 (5)	N2—C11—S1—C10	−178.3 (6)
C38—C33—C34—C35	0.2 (7)	N1—C11—S1—C10	0.6 (4)
C32—C33—C34—C35	−178.6 (5)	C9—C10—S1—C11	−1.0 (4)
C33—C34—C35—C36	−2.5 (7)	N3—C30—S2—C29	−1.8 (3)
C34—C35—C36—C37	4.2 (7)	N4—C30—S2—C29	−179.1 (5)
C35—C36—C37—C38	−3.7 (7)	C28—C29—S2—C30	2.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Cl1ⁱ	0.94	2.75	3.208 (6)	111
O1W—H1WA···S2ⁱⁱ	0.94	2.88	3.819 (6)	174
O1W—H1WB···Cl2	0.86	2.61	3.240 (7)	132
O3W—H3WA···Cl2ⁱⁱⁱ	0.85	2.68	3.275 (10)	129
O3W—H3WB···Cl1ⁱ	0.85	2.60	3.301 (10)	141
C8—H8···Cl1	0.93	2.78	3.664 (5)	159
C10—H10···Cl1^iv	0.93	2.72	3.390 (5)	130
C18—H18···O3W^v	0.93	2.52	3.320 (9)	144
C27—H27···Cl1	0.93	2.72	3.642 (5)	175

Symmetry codes: (i) x, y+1, z; (ii) −x+y, −x+1, z+1/3; (iii) −y+1, x−y+1, z−1/3; (iv) −x+y+1, −x+1, z+1/3; (v) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₇N₂S⁺·Cl⁻·0.75H₂O
M_r	354.37
Crystal system, space group	Trigonal, P3₂
Temperature (K)	291
a, c (Å)	13.211 (1), 19.555 (3)
V (Å³)	2955.7 (6)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.28 × 0.24 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.919, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	16250, 6594, 4827
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.123, 1.00
No. of reflections	6594
No. of parameters	476
No. of restraints	15
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.28
Absolute structure	Flack (1983)
Absolute structure parameter	0.04 (7)

Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Cl1ⁱ	0.94	2.75	3.208 (6)	110.8
O1W—H1WA···S2ⁱⁱ	0.94	2.88	3.819 (6)	173.7
O1W—H1WB···Cl2	0.86	2.61	3.240 (7)	132.0
O3W—H3WA···Cl2ⁱⁱⁱ	0.85	2.68	3.275 (10)	128.7
O3W—H3WB···Cl1ⁱ	0.85	2.60	3.301 (10)	140.9
C8—H8···Cl1	0.93	2.78	3.664 (5)	158.9
C10—H10···Cl1^iv	0.93	2.72	3.390 (5)	129.5
C18—H18···O3W^v	0.93	2.52	3.320 (9)	144.4
C27—H27···Cl1	0.93	2.72	3.642 (5)	175.1

Symmetry codes: (i) x, y+1, z; (ii) −x+y, −x+1, z+1/3; (iii) −y+1, x−y+1, z−1/3; (iv) −x+y+1, −x+1, z+1/3; (v) x+1, y, z.

Acknowledgements

The authors thank the Scientific Researching Fund Projects of Yunnan Educational Department (grant No. 22012Z017) and the Youth Scientific Fund Projects of Yunnan Normal University for financial support.

References

Akkurt, M., Güzeldemirci, N. U., Karaman, B. & Büyükgüngör, O. (2011). Acta Cryst. E67, o184–o185. Web of Science CrossRef CAS IUCr Journals Google Scholar
Akkurt, M., Yalçın, Ş. P., Gürsoy, E., Güzeldemirci, N. U. & Büyükgüngör, O. (2007). Acta Cryst. E63, o3103. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Huang, G. L., Sun, H. S., Qiu, X. J., Jin, C., Lin, C., Shen, Y. Z., Jiang, J. L. & Wang, L. Y. (2011). Org. Lett. 13, 5224–5227. Web of Science CSD CrossRef CAS PubMed Google Scholar
Liu, Q., Perreault, S. & Rovis, R. (2008). J. Am. Chem. Soc. 130, 14066–14067. Web of Science CSD CrossRef PubMed CAS Google Scholar
Mattson, A. E., Zuhl, A. M., Reynolds, T. E. & Scheidt, K. A. (2006). J. Am. Chem. Soc. 128, 4932–4933. Web of Science CSD CrossRef PubMed CAS Google Scholar
Padmanaban, M., Biju, A. T. & Glorius, F. (2011). Org. Lett. 13, 98–101. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, G. Y., Zhang, Y. & Li, X. W. (2008). Organometallics, 13, 1936-1943. Web of Science CSD CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages o1247-o1248

doi:10.1107/S1600536813018795

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

7-Benzyl-3-methyl-6-phenyl­imidazo[2,1-b][1,3]thia­zol-7-ium chloride 0.75-hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

7-Benzyl-3-methyl-6-phenylimidazo[2,1-b][1,3]thiazol-7-ium chloride 0.75-hydrate