1-Benzyl-3-methyl­imidazolium chloride 0.25-hydrate

Ji, X.; Cheng, B.; Song, J.; Liu, C.

doi:10.1107/S1600536809053306

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o218

doi:10.1107/S1600536809053306

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1-Benzyl-3-methylimidazolium chloride 0.25-hydrate

Xiujie Ji,^a Bowen Cheng,^a ^* Jun Song ^a and Chao Liu ^b

^aTianjin Municipal Key Laboratory of Fiber Modification and Functional Fibers, Tianjin Polytechnic University, Tianjin 300160, People's Republic of China, and ^bSchool of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, People's Republic of China
^*Correspondence e-mail: bowen15@tjpu.edu.cn

(Received 4 November 2009; accepted 10 December 2009; online 19 December 2009)

The asymmetric unit of the title compound, C₁₁H₁₃N₂⁺·Cl⁻, contains two independent ion pairs and and half a solvent water molecule (m site symmetry for the O atom). The imidazole ring is oriented at dihedral angles of 66.61 (3) and 89.17 (3)° with respect to the aromatic ring in the two cations. In the crystal, O—H⋯(O,Cl) hydrogen bonds and π–π stacking interactions between the imidazole ring of one molecule and the aromatic ring of another [perpendicular distance = 3.4 (4) Å] link the molecules.

Related literature

For general background to ionic liquids, see: Fukaya et al. (2006 ); Ranu et al. (2005 ); Chen et al. (2005 ); Blanchard et al. (2001 ); Zhang et al. (2006 ); Katayanagi et al. (2004 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₃N₂⁺·Cl⁻·0.25H₂O
M_r = 213.19
Orthorhombic, P b c a
a = 11.452 (2) Å
b = 11.410 (2) Å
c = 34.867 (7) Å
V = 4555.8 (16) Å³
Z = 16
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 113 K
0.22 × 0.20 × 0.16 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 ) T_min = 0.937, T_max = 0.953
30046 measured reflections
4022 independent reflections
3619 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.119
S = 1.08
4022 reflections
268 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1E⋯O1ⁱ	0.86 (1)	1.81 (4)	2.434 (7)	128 (4)
O1—H1E⋯Cl2ⁱ	0.86 (1)	2.51 (3)	3.179 (3)	135 (4)
Symmetry code: (i) -x+1, -y+2, -z+1.

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053306/bq2176sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053306/bq2176Isup2.hkl

checkCIF report

Comment top

Ionic liquids (ILs) are a class of compounds composed of organic cations and organic or inorganic anions and have attracted significant attention due to their beneficial properties and their low impact on environment. Many investigations have been dedicated to their use as new media for synthetic chemistry (Fukaya et al., 2006), catalysts for organic synthesis (Ranu et al., 2005; Chen et al., 2005), extractants for separation science (Blanchard et al., 2001) and electrolytes for electrochemistry (Zhang et al., 2006) as well as other areas due to their peculiar physical properties such as a wide liquid range, non-volatility, chemical stability and large windows of electrochemistry. Because it is technically difficult for ionic liquid to grow single crystal and to select suitable sample for single crystal x-ray diffraction at low temperature, so far a few crystal structures have been determined by x-ray diffraction (Katayanagi et al., 2004). We have synthesized a numer of ionic liquids. The title compound is one of the products, and we report herein its crystal structure.

In the molecule of the title compound (Fig. 1) the bond lengths (Allen et al., 1987) and angles are within normal ranges. The imidazole ring is oriented with respect to the aromatic ring at a dihedral angle of 89.17 (3)° and 66.61 (3)°, respectively. The hydrogen bond are formed between one Cl and H₂O (Table 1). In the crystal structure, π-π packing between the imidazole ring of one molecule and the aromatic ring of the other [perpendicular distance = 3.4 (4)Å] link the molecules. The packing diagram of the O-H···Cl bonds is shown in Fig. 2.

Related literature top

For general background to ionic liquids, see: Fukaya et al. (2006); Ranu et al. (2005); Chen et al. (2005); Blanchard et al. (2001); Zhang et al. (2006); Katayanagi et al. (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, N-methylimidazole (8.2 g, 0.1 mol) was dissolved in dry acetonitrile (30 ml). Benzyl chloride (12.7 g, 0.1 mol) was added to this solution, the reaction was stirred under reflux for 7 h. The reaction mixture was extracted with ethyl acetate. After concentration, the residue was purified by recrystallization from chloroform (yield; 19.4 g, 93%, m.p. 251 K). Spectroscopic analysis: IR (KBr, ν, cm^-1): 3415, 3085, 2927, 1634, 1571, 1455, 1160, 824, 722. Analysis required for C₂₂H₂₇Cl₂N₄O_0.5: C 61.97; H 6.38; N 13.14%. Found: C 61.92; H 6.40; N 13.10%.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The packing diagram of (I).

1-Benzyl-3-methylimidazolium chloride 0.25-hydrate top

Crystal data top

C₁₁H₁₃N₂⁺·Cl⁻·0.25(H₂O)	D_x = 1.243 Mg m⁻³
M_r = 213.19	Melting point: 251 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6089 reflections
a = 11.452 (2) Å	θ = 2.1–27.9°
b = 11.410 (2) Å	µ = 0.30 mm⁻¹
c = 34.867 (7) Å	T = 113 K
V = 4555.8 (16) Å³	Block, colorless
Z = 16	0.22 × 0.20 × 0.16 mm
F(000) = 1800

Data collection top

Rigaku Saturn diffractometer	4022 independent reflections
Radiation source: rotating anode	3619 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.041
ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	h = −13→13
T_min = 0.937, T_max = 0.953	k = −13→11
30046 measured reflections	l = −41→39

Refinement top

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0667P)² + 2.0145P] where P = (F_o² + 2F_c²)/3
4022 reflections	(Δ/σ)_max = 0.001
268 parameters	Δρ_max = 0.30 e Å⁻³
3 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₁H₁₃N₂⁺·Cl⁻·0.25(H₂O)	V = 4555.8 (16) Å³
M_r = 213.19	Z = 16
Orthorhombic, Pbca	Mo Kα radiation
a = 11.452 (2) Å	µ = 0.30 mm⁻¹
b = 11.410 (2) Å	T = 113 K
c = 34.867 (7) Å	0.22 × 0.20 × 0.16 mm

Data collection top

Rigaku Saturn diffractometer	4022 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	3619 reflections with I > 2σ(I)
T_min = 0.937, T_max = 0.953	R_int = 0.041
30046 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	3 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.30 e Å⁻³
4022 reflections	Δρ_min = −0.28 e Å⁻³
268 parameters

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)
Cl1	0.47805 (4)	1.03154 (4)	0.348689 (12)	0.02641 (15)
Cl2	0.55772 (5)	0.75655 (5)	0.519211 (14)	0.03879 (17)
N1	0.76243 (14)	0.70800 (14)	0.42512 (4)	0.0275 (4)
N2	0.77675 (14)	0.78892 (14)	0.36959 (4)	0.0279 (4)
N3	0.30575 (13)	0.63833 (13)	0.43738 (4)	0.0242 (3)
N4	0.27524 (13)	0.73929 (13)	0.38612 (4)	0.0230 (3)
C1	0.7808 (2)	0.6275 (2)	0.45759 (6)	0.0454 (6)
H1A	0.7798	0.5481	0.4485	0.068*
H1B	0.7196	0.6382	0.4761	0.068*
H1C	0.8549	0.6437	0.4693	0.068*
C2	0.81984 (17)	0.70586 (17)	0.39202 (5)	0.0290 (4)
H2	0.8801	0.6547	0.3857	0.035*
C3	0.68949 (18)	0.84657 (18)	0.38902 (6)	0.0315 (5)
H3	0.6446	0.9085	0.3799	0.038*
C4	0.68136 (17)	0.79632 (18)	0.42386 (6)	0.0312 (5)
H4	0.6303	0.8175	0.4434	0.037*
C5	0.8163 (2)	0.8133 (2)	0.33005 (6)	0.0432 (6)
H5A	0.8946	0.7825	0.3267	0.052*
H5B	0.8197	0.8975	0.3263	0.052*
C6	0.73773 (18)	0.76060 (18)	0.30011 (5)	0.0284 (4)
C7	0.76298 (19)	0.6509 (2)	0.28553 (6)	0.0393 (5)
H7	0.8274	0.6097	0.2946	0.047*
C8	0.6929 (2)	0.6021 (2)	0.25757 (7)	0.0520 (7)
H8	0.7101	0.5280	0.2480	0.062*
C9	0.5978 (2)	0.6625 (2)	0.24371 (6)	0.0494 (7)
H9	0.5519	0.6302	0.2244	0.059*
C10	0.5710 (2)	0.7711 (2)	0.25864 (7)	0.0474 (6)
H10	0.5061	0.8116	0.2496	0.057*
C11	0.6401 (2)	0.82016 (19)	0.28689 (6)	0.0374 (5)
H11	0.6211	0.8931	0.2970	0.045*
C12	0.2976 (2)	0.54811 (19)	0.46704 (6)	0.0358 (5)
H12A	0.2647	0.5814	0.4899	0.054*
H12B	0.3742	0.5182	0.4726	0.054*
H12C	0.2487	0.4854	0.4582	0.054*
C13	0.24416 (16)	0.64328 (16)	0.40510 (5)	0.0239 (4)
H13	0.1888	0.5888	0.3972	0.029*
C14	0.35863 (16)	0.79782 (16)	0.40711 (5)	0.0271 (4)
H14	0.3952	0.8677	0.4004	0.032*
C15	0.37723 (16)	0.73477 (17)	0.43921 (5)	0.0272 (4)
H15	0.4288	0.7531	0.4589	0.033*
C16	0.22392 (18)	0.77900 (18)	0.34989 (5)	0.0291 (4)
H16A	0.1832	0.7141	0.3379	0.035*
H16B	0.2859	0.8036	0.3327	0.035*
C17	0.13971 (17)	0.87942 (16)	0.35559 (5)	0.0251 (4)
C18	0.12909 (19)	0.96458 (18)	0.32750 (6)	0.0350 (5)
H18	0.1755	0.9605	0.3057	0.042*
C19	0.0500 (2)	1.05586 (19)	0.33155 (7)	0.0457 (6)
H19	0.0432	1.1120	0.3123	0.055*
C20	−0.0183 (2)	1.0634 (2)	0.36397 (8)	0.0463 (6)
H20	−0.0710	1.1249	0.3668	0.056*
C21	−0.00839 (19)	0.9798 (2)	0.39217 (7)	0.0389 (5)
H21	−0.0541	0.9852	0.4141	0.047*
C22	0.06960 (17)	0.88692 (17)	0.38806 (5)	0.0282 (4)
H22	0.0748	0.8299	0.4070	0.034*
O1	0.4899 (3)	0.9725 (3)	0.46644 (11)	0.0506 (9)	0.50
H1D	0.504 (5)	0.998 (4)	0.4438 (6)	0.061*	0.50
H1E	0.474 (5)	1.026 (3)	0.4830 (9)	0.061*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0257 (3)	0.0269 (3)	0.0266 (2)	0.00190 (18)	0.00007 (17)	0.00296 (17)
Cl2	0.0373 (3)	0.0435 (3)	0.0356 (3)	0.0013 (2)	−0.0102 (2)	0.0026 (2)
N1	0.0301 (9)	0.0269 (9)	0.0255 (8)	−0.0025 (7)	−0.0035 (6)	0.0001 (6)
N2	0.0274 (9)	0.0304 (9)	0.0259 (8)	−0.0078 (7)	−0.0030 (6)	−0.0001 (7)
N3	0.0244 (8)	0.0234 (8)	0.0249 (8)	0.0034 (6)	0.0008 (6)	0.0020 (6)
N4	0.0228 (8)	0.0213 (8)	0.0249 (8)	0.0025 (6)	−0.0010 (6)	−0.0013 (6)
C1	0.0541 (15)	0.0445 (14)	0.0377 (11)	−0.0041 (11)	−0.0141 (10)	0.0141 (10)
C2	0.0242 (10)	0.0304 (11)	0.0325 (10)	0.0018 (8)	−0.0028 (8)	−0.0064 (8)
C3	0.0285 (10)	0.0271 (10)	0.0387 (11)	0.0012 (8)	−0.0084 (8)	−0.0028 (8)
C4	0.0241 (10)	0.0355 (11)	0.0339 (10)	0.0015 (8)	0.0009 (8)	−0.0080 (9)
C5	0.0435 (13)	0.0593 (15)	0.0270 (10)	−0.0251 (12)	0.0001 (9)	0.0043 (10)
C6	0.0309 (11)	0.0318 (10)	0.0225 (9)	−0.0094 (8)	0.0019 (8)	0.0029 (8)
C7	0.0292 (11)	0.0429 (13)	0.0457 (12)	0.0009 (10)	0.0079 (9)	−0.0036 (10)
C8	0.0530 (15)	0.0537 (15)	0.0493 (14)	−0.0125 (13)	0.0188 (12)	−0.0275 (12)
C9	0.0505 (15)	0.0755 (18)	0.0221 (10)	−0.0270 (14)	0.0028 (10)	−0.0111 (11)
C10	0.0398 (13)	0.0664 (17)	0.0360 (12)	−0.0086 (12)	−0.0101 (10)	0.0171 (12)
C11	0.0461 (13)	0.0303 (11)	0.0359 (11)	−0.0011 (10)	0.0002 (10)	0.0042 (9)
C12	0.0386 (12)	0.0356 (12)	0.0330 (10)	0.0047 (9)	0.0031 (9)	0.0123 (9)
C13	0.0224 (9)	0.0213 (9)	0.0279 (9)	−0.0004 (7)	0.0001 (7)	−0.0006 (7)
C14	0.0227 (9)	0.0226 (9)	0.0359 (10)	−0.0027 (8)	−0.0021 (8)	−0.0016 (8)
C15	0.0231 (10)	0.0285 (10)	0.0301 (10)	−0.0001 (8)	−0.0035 (8)	−0.0041 (8)
C16	0.0346 (11)	0.0323 (11)	0.0204 (9)	0.0038 (9)	0.0000 (8)	0.0003 (8)
C17	0.0264 (10)	0.0223 (9)	0.0267 (9)	−0.0013 (8)	−0.0067 (7)	0.0000 (7)
C18	0.0414 (12)	0.0306 (11)	0.0329 (10)	−0.0063 (9)	−0.0096 (9)	0.0080 (8)
C19	0.0552 (15)	0.0241 (11)	0.0580 (15)	−0.0024 (10)	−0.0319 (12)	0.0087 (10)
C20	0.0380 (13)	0.0302 (12)	0.0708 (17)	0.0085 (10)	−0.0283 (12)	−0.0149 (12)
C21	0.0266 (11)	0.0421 (13)	0.0479 (13)	0.0042 (9)	−0.0087 (9)	−0.0178 (11)
C22	0.0274 (10)	0.0285 (10)	0.0287 (9)	−0.0012 (8)	−0.0045 (8)	−0.0019 (8)
O1	0.055 (2)	0.041 (2)	0.056 (2)	−0.0050 (17)	0.0031 (18)	−0.0113 (16)

Geometric parameters (Å, º) top

N1—C2	1.328 (2)	C9—C10	1.379 (4)
N1—C4	1.371 (3)	C9—H9	0.9300
N1—C1	1.473 (2)	C10—C11	1.382 (3)
N2—C2	1.324 (3)	C10—H10	0.9300
N2—C3	1.375 (3)	C11—H11	0.9300
N2—C5	1.478 (2)	C12—H12A	0.9600
N3—C13	1.329 (2)	C12—H12B	0.9600
N3—C15	1.373 (2)	C12—H12C	0.9600
N3—C12	1.462 (2)	C13—H13	0.9300
N4—C13	1.328 (2)	C14—C15	1.348 (3)
N4—C14	1.376 (2)	C14—H14	0.9300
N4—C16	1.465 (2)	C15—H15	0.9300
C1—H1A	0.9600	C16—C17	1.511 (3)
C1—H1B	0.9600	C16—H16A	0.9700
C1—H1C	0.9600	C16—H16B	0.9700
C2—H2	0.9300	C17—C18	1.385 (3)
C3—C4	1.347 (3)	C17—C22	1.391 (3)
C3—H3	0.9300	C18—C19	1.387 (3)
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.504 (3)	C19—C20	1.378 (4)
C5—H5A	0.9700	C19—H19	0.9300
C5—H5B	0.9700	C20—C21	1.375 (4)
C6—C7	1.382 (3)	C20—H20	0.9300
C6—C11	1.387 (3)	C21—C22	1.393 (3)
C7—C8	1.380 (3)	C21—H21	0.9300
C7—H7	0.9300	C22—H22	0.9300
C8—C9	1.376 (4)	O1—H1D	0.860 (10)
C8—H8	0.9300	O1—H1E	0.857 (10)

C2—N1—C4	108.72 (16)	C9—C10—H10	119.8
C2—N1—C1	125.85 (18)	C11—C10—H10	119.8
C4—N1—C1	125.42 (18)	C10—C11—C6	120.0 (2)
C2—N2—C3	108.79 (16)	C10—C11—H11	120.0
C2—N2—C5	124.87 (19)	C6—C11—H11	120.0
C3—N2—C5	126.34 (18)	N3—C12—H12A	109.5
C13—N3—C15	108.77 (15)	N3—C12—H12B	109.5
C13—N3—C12	126.51 (17)	H12A—C12—H12B	109.5
C15—N3—C12	124.70 (16)	N3—C12—H12C	109.5
C13—N4—C14	108.73 (15)	H12A—C12—H12C	109.5
C13—N4—C16	125.25 (16)	H12B—C12—H12C	109.5
C14—N4—C16	125.93 (16)	N4—C13—N3	108.34 (16)
N1—C1—H1A	109.5	N4—C13—H13	125.8
N1—C1—H1B	109.5	N3—C13—H13	125.8
H1A—C1—H1B	109.5	C15—C14—N4	107.00 (17)
N1—C1—H1C	109.5	C15—C14—H14	126.5
H1A—C1—H1C	109.5	N4—C14—H14	126.5
H1B—C1—H1C	109.5	C14—C15—N3	107.15 (16)
N2—C2—N1	108.40 (17)	C14—C15—H15	126.4
N2—C2—H2	125.8	N3—C15—H15	126.4
N1—C2—H2	125.8	N4—C16—C17	112.14 (15)
C4—C3—N2	106.93 (18)	N4—C16—H16A	109.2
C4—C3—H3	126.5	C17—C16—H16A	109.2
N2—C3—H3	126.5	N4—C16—H16B	109.2
C3—C4—N1	107.16 (17)	C17—C16—H16B	109.2
C3—C4—H4	126.4	H16A—C16—H16B	107.9
N1—C4—H4	126.4	C18—C17—C22	118.81 (19)
N2—C5—C6	112.86 (17)	C18—C17—C16	119.67 (18)
N2—C5—H5A	109.0	C22—C17—C16	121.50 (17)
C6—C5—H5A	109.0	C17—C18—C19	120.8 (2)
N2—C5—H5B	109.0	C17—C18—H18	119.6
C6—C5—H5B	109.0	C19—C18—H18	119.6
H5A—C5—H5B	107.8	C20—C19—C18	120.1 (2)
C7—C6—C11	119.36 (19)	C20—C19—H19	120.0
C7—C6—C5	119.5 (2)	C18—C19—H19	120.0
C11—C6—C5	121.1 (2)	C21—C20—C19	119.8 (2)
C8—C7—C6	120.2 (2)	C21—C20—H20	120.1
C8—C7—H7	119.9	C19—C20—H20	120.1
C6—C7—H7	119.9	C20—C21—C22	120.5 (2)
C9—C8—C7	120.5 (2)	C20—C21—H21	119.8
C9—C8—H8	119.8	C22—C21—H21	119.8
C7—C8—H8	119.8	C17—C22—C21	120.04 (19)
C8—C9—C10	119.5 (2)	C17—C22—H22	120.0
C8—C9—H9	120.2	C21—C22—H22	120.0
C10—C9—H9	120.2	H1D—O1—H1E	114.7 (19)
C9—C10—C11	120.4 (2)

C3—N2—C2—N1	0.4 (2)	C14—N4—C13—N3	−0.5 (2)
C5—N2—C2—N1	−178.98 (17)	C16—N4—C13—N3	−177.32 (16)
C4—N1—C2—N2	−0.8 (2)	C15—N3—C13—N4	0.7 (2)
C1—N1—C2—N2	177.98 (18)	C12—N3—C13—N4	178.88 (17)
C2—N2—C3—C4	0.2 (2)	C13—N4—C14—C15	0.1 (2)
C5—N2—C3—C4	179.59 (18)	C16—N4—C14—C15	176.88 (16)
N2—C3—C4—N1	−0.7 (2)	N4—C14—C15—N3	0.4 (2)
C2—N1—C4—C3	1.0 (2)	C13—N3—C15—C14	−0.7 (2)
C1—N1—C4—C3	−177.85 (18)	C12—N3—C15—C14	−178.89 (17)
C2—N2—C5—C6	99.5 (2)	C13—N4—C16—C17	103.1 (2)
C3—N2—C5—C6	−79.8 (3)	C14—N4—C16—C17	−73.2 (2)
N2—C5—C6—C7	−93.2 (2)	N4—C16—C17—C18	147.06 (18)
N2—C5—C6—C11	86.7 (3)	N4—C16—C17—C22	−34.8 (3)
C11—C6—C7—C8	1.2 (3)	C22—C17—C18—C19	0.0 (3)
C5—C6—C7—C8	−178.9 (2)	C16—C17—C18—C19	178.16 (19)
C6—C7—C8—C9	0.5 (3)	C17—C18—C19—C20	0.7 (3)
C7—C8—C9—C10	−1.6 (4)	C18—C19—C20—C21	−0.4 (3)
C8—C9—C10—C11	1.1 (3)	C19—C20—C21—C22	−0.5 (3)
C9—C10—C11—C6	0.7 (3)	C18—C17—C22—C21	−0.9 (3)
C7—C6—C11—C10	−1.8 (3)	C16—C17—C22—C21	−179.04 (18)
C5—C6—C11—C10	178.28 (19)	C20—C21—C22—C17	1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1E···O1ⁱ	0.86 (1)	1.81 (4)	2.434 (7)	128 (4)
O1—H1E···Cl2ⁱ	0.86 (1)	2.51 (3)	3.179 (3)	135 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃N₂⁺·Cl⁻·0.25(H₂O)
M_r	213.19
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	113
a, b, c (Å)	11.452 (2), 11.410 (2), 34.867 (7)
V (Å³)	4555.8 (16)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.22 × 0.20 × 0.16

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2000)
T_min, T_max	0.937, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	30046, 4022, 3619
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.119, 1.08
No. of reflections	4022
No. of parameters	268
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.28

Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1E···O1ⁱ	0.857 (10)	1.81 (4)	2.434 (7)	128 (4)
O1—H1E···Cl2ⁱ	0.857 (10)	2.51 (3)	3.179 (3)	135 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

We thank the China Postdoctoral Science Foundation (No. 20080440684), the Tianjin Municipal Natural Science Foundation (No. 09JCZDJC22700) and the Hebei Province Natural Science Foundation (No. E2009000081) for financial support.

References

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