1,3-Bis(4-methoxy­phen­yl)imidazolidium chloride monohydrate

Wan, Y.; Xin, H.; Chen, X.; Xu, H.; Wu, H.

doi:10.1107/S1600536808033965

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2159

doi:10.1107/S1600536808033965

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1,3-Bis(4-methoxyphenyl)imidazolidium chloride monohydrate

Yu Wan,^a Haiqiang Xin,^a Xiumei Chen,^a Huahong Xu ^a and Hui Wu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou 221116, People's Republic of China
^*Correspondence e-mail: wuhui72@yahoo.com.cn

(Received 27 September 2008; accepted 17 October 2008; online 22 October 2008)

The asymmetric unit of the title compound, C₁₇H₁₇N₂O₂⁺·Cl⁻·H₂O, contains one-half of the cation, one-half of a water molecule and a chloride anion. The complete cation is generated by crystallographic two-fold symmetry, with one C atom lying on the rotation axis. The O and Cl atoms have site symmetry 2. The imidazolidium ring is oriented at a dihedral angle of 4.15 (3)° with respect to the 4-methoxyphenyl ring and an intramolecular C—H⋯O interaction occurs. In the crystal structure, intermolecular O—H⋯Cl and C—H⋯Cl hydrogen bonds link the molecules. There is a π–π contact between the imidazolidium and 4-methoxyphenyl rings [centroid-to-centroid distance = 3.625(3 Å]. There is also a C—H⋯π contact between the methyl group and the 4-methoxyphenyl ring.

Related literature

For general background, see: Lin & Vasam (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₇H₁₇N₂O₂⁺·Cl⁻·H₂O
M_r = 334.79
Monoclinic, C 2
a = 15.6706 (19) Å
b = 9.4198 (9) Å
c = 5.4026 (4) Å
β = 90.156 (1)°
V = 797.50 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 (2) K
0.20 × 0.11 × 0.09 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.951, T_max = 0.977
2026 measured reflections
749 independent reflections
688 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.076
S = 1.01
749 reflections
107 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C3–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯Cl1	0.85	2.29	3.133 (3)	173
C1—H1⋯O2	0.93	2.13	3.060 (3)	180
C2—H2A⋯Cl1ⁱ	0.93	2.69	3.474 (3)	142
C4—H4⋯O2	0.93	2.47	3.391 (3)	170
C9—H9C⋯Cg2ⁱⁱ	0.96	2.91	3.629 (3)	133
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) x, y, z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033965/hk2542sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808033965/hk2542Isup2.hkl

checkCIF report

Comment top

Imidazole and its derivatives such as imidazolium cation are important compounds playing important roles in medical, organic and material chemistry (Lin & Vasam, 2005). A broad application of imidazolium now is to synthesize ionic liquids. Recently, ionic liquids are attracting much attention as alternative reaction media for synthesis and catalysis. Its applications in many different areas including separation processes, catalyst, electrochemistry, electrolytes in solar cells and lubricants are widely recognized. Therefore, the need of ionic liquids with specific chemical and physical properties become stronger. We report herein the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) contains one half-molecule, one half-water molecule and a chloride atom. The bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N1/N1'/C1/C2/C2') and B (C3–C8) are, of course, planar and the dihedral angle between them is A/B = 4.15 (3)° [symmetry code: (') -x, y, -z]. Intramolecular C—H···O and O—H···Cl hydrogen bonds (Table 1) link the molecules.

In the crystal structure, intramolecular C—H···O and O—H···Cl and intermolecular C—H···Cl hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contact between the imidazolidium and 4-methoxyphenyl rings, Cg1···Cg2ⁱ [symmetry code: (i) 1 - x, y, 1 - z, where Cg1 and Cg2 are the centroids of the rings A (N1/N1'/C1/C2/C2') and B (C3–C8), respectively] may further stabilize the structure, with centroid-centroid distance of 3.625 (3) Å. There also exist a C—H···π contact (Table 1) between the methyl group and the 4-methoxyphenyl ring.

Related literature top

For general background, see: Lin & Vasam (2005). For bond-length data, see: Allen et al. (1987).

Experimental top

The reaction of 4-methoxybenzenamine (2 mmol) with formaldehyde (aq. 37%, 1 mmol) and glyoxal (aq. 40%, 1 mmol) in ethanol (95%) at 273–278 K for 8 h afforded 1-(2,3-diethoxy-4-(4-methoxyphenyl)cyclopentyl)-4-methoxybenzene (yield; 89%). The title compound was obtained through the oxidization of 1-(2,3-diethoxy-4-(4-methoxyphenyl)cyclopentyl)-4-methoxybenzene by phosgene in DMF at 268–273 K (yield 95%).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme [symmetry code: (') -x, y, -z].
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines.

1,3-Bis(4-methoxyphenyl)imidazolidium chloride monohydrate top

Crystal data top

C₁₇H₁₇N₂O₂⁺·Cl⁻·H₂O	F(000) = 352
M_r = 334.79	D_x = 1.394 Mg m⁻³
Monoclinic, C2	Melting point = 492–494 K
Hall symbol: -C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 15.6706 (19) Å	Cell parameters from 1340 reflections
b = 9.4198 (9) Å	θ = 2.5–28.3°
c = 5.4026 (4) Å	µ = 0.26 mm⁻¹
β = 90.156 (1)°	T = 298 K
V = 797.50 (14) Å³	Block, colourless
Z = 2	0.20 × 0.11 × 0.09 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	749 independent reflections
Radiation source: fine-focus sealed tube	688 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→13
T_min = 0.951, T_max = 0.977	k = −9→11
2026 measured reflections	l = −6→6

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0503P)² + 0.1521P] where P = (F_o² + 2F_c²)/3
749 reflections	(Δ/σ)_max < 0.001
107 parameters	Δρ_max = 0.11 e Å⁻³
1 restraint	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₇H₁₇N₂O₂⁺·Cl⁻·H₂O	V = 797.50 (14) Å³
M_r = 334.79	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 15.6706 (19) Å	µ = 0.26 mm⁻¹
b = 9.4198 (9) Å	T = 298 K
c = 5.4026 (4) Å	0.20 × 0.11 × 0.09 mm
β = 90.156 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	749 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	688 reflections with I > 2σ(I)
T_min = 0.951, T_max = 0.977	R_int = 0.021
2026 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	1 restraint
wR(F²) = 0.076	H-atom parameters constrained
S = 1.01	Δρ_max = 0.11 e Å⁻³
749 reflections	Δρ_min = −0.22 e Å⁻³
107 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
Cl1	0.5000	0.84927 (12)	0.5000	0.0800 (5)
O1	0.24434 (13)	0.4740 (2)	0.9080 (3)	0.0519 (5)
O2	0.5000	0.6808 (3)	0.0000	0.0567 (8)
H2	0.5000	0.7335	0.1277	0.068*
N1	0.45802 (12)	0.27396 (19)	0.1594 (3)	0.0334 (5)
C1	0.5000	0.3560 (4)	0.0000	0.0350 (7)
H1	0.5000	0.4547	0.0000	0.042*
C2	0.47435 (17)	0.1342 (3)	0.0983 (5)	0.0444 (6)
H2A	0.4534	0.0545	0.1795	0.053*
C3	0.40340 (14)	0.3225 (3)	0.3567 (4)	0.0335 (5)
C4	0.39574 (17)	0.4670 (3)	0.4036 (5)	0.0420 (6)
H4	0.4262	0.5322	0.3094	0.050*
C5	0.34270 (17)	0.5135 (3)	0.5903 (5)	0.0449 (6)
H5	0.3378	0.6101	0.6225	0.054*
C6	0.29642 (15)	0.4164 (3)	0.7309 (5)	0.0386 (6)
C7	0.30558 (17)	0.2728 (3)	0.6859 (5)	0.0446 (6)
H7	0.2758	0.2073	0.7812	0.054*
C8	0.35934 (16)	0.2262 (3)	0.4979 (5)	0.0440 (6)
H8	0.3654	0.1296	0.4678	0.053*
C9	0.19340 (19)	0.3780 (4)	1.0497 (5)	0.0580 (8)
H9A	0.1588	0.3219	0.9402	0.087*
H9B	0.1573	0.4309	1.1594	0.087*
H9C	0.2299	0.3168	1.1447	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1591 (13)	0.0423 (5)	0.0387 (5)	0.000	0.0069 (6)	0.000
O1	0.0545 (11)	0.0522 (12)	0.0491 (11)	0.0011 (9)	0.0158 (9)	0.0059 (9)
O2	0.092 (2)	0.0344 (15)	0.0434 (14)	0.000	0.0109 (14)	0.000
N1	0.0365 (11)	0.0278 (10)	0.0358 (10)	−0.0015 (8)	−0.0027 (8)	0.0024 (8)
C1	0.0400 (18)	0.0271 (15)	0.0379 (15)	0.000	0.0009 (14)	0.000
C2	0.0572 (16)	0.0300 (13)	0.0461 (13)	−0.0031 (11)	0.0030 (11)	0.0012 (11)
C3	0.0319 (12)	0.0362 (13)	0.0323 (10)	−0.0010 (10)	−0.0018 (9)	0.0024 (10)
C4	0.0473 (15)	0.0333 (14)	0.0455 (14)	−0.0024 (11)	0.0086 (11)	0.0080 (11)
C5	0.0510 (15)	0.0339 (13)	0.0499 (14)	0.0029 (12)	0.0085 (11)	0.0012 (12)
C6	0.0356 (14)	0.0442 (15)	0.0360 (12)	−0.0008 (11)	0.0001 (11)	0.0027 (11)
C7	0.0480 (15)	0.0421 (16)	0.0438 (14)	−0.0081 (12)	0.0045 (11)	0.0072 (12)
C8	0.0518 (16)	0.0319 (13)	0.0484 (15)	−0.0044 (12)	0.0012 (13)	0.0019 (12)
C9	0.0485 (16)	0.069 (2)	0.0566 (16)	−0.0036 (14)	0.0137 (13)	0.0109 (15)

Geometric parameters (Å, º) top

O1—C6	1.371 (3)	C4—C5	1.380 (4)
O1—C9	1.430 (3)	C4—H4	0.9300
O2—H2	0.8500	C5—C6	1.394 (4)
N1—C1	1.332 (3)	C5—H5	0.9300
N1—C2	1.382 (3)	C6—C7	1.382 (4)
N1—C3	1.443 (3)	C7—C8	1.392 (4)
C1—N1ⁱ	1.332 (3)	C7—H7	0.9300
C1—H1	0.9300	C8—H8	0.9300
C2—C2ⁱ	1.334 (5)	C9—H9A	0.9600
C2—H2A	0.9300	C9—H9B	0.9600
C3—C8	1.372 (3)	C9—H9C	0.9600
C3—C4	1.390 (4)

C6—O1—C9	117.2 (2)	C4—C5—H5	119.8
C1—N1—C2	107.8 (2)	C6—C5—H5	119.8
C1—N1—C3	126.1 (2)	O1—C6—C7	124.9 (2)
C2—N1—C3	126.1 (2)	O1—C6—C5	115.6 (2)
N1ⁱ—C1—N1	109.1 (3)	C7—C6—C5	119.5 (2)
N1ⁱ—C1—H1	125.5	C6—C7—C8	120.0 (2)
N1—C1—H1	125.5	C6—C7—H7	120.0
C2ⁱ—C2—N1	107.63 (14)	C8—C7—H7	120.0
C2ⁱ—C2—H2A	126.2	C3—C8—C7	120.2 (2)
N1—C2—H2A	126.2	C3—C8—H8	119.9
C8—C3—C4	120.1 (2)	C7—C8—H8	119.9
C8—C3—N1	120.1 (2)	O1—C9—H9A	109.5
C4—C3—N1	119.8 (2)	O1—C9—H9B	109.5
C5—C4—C3	119.8 (2)	H9A—C9—H9B	109.5
C5—C4—H4	120.1	O1—C9—H9C	109.5
C3—C4—H4	120.1	H9A—C9—H9C	109.5
C4—C5—C6	120.4 (2)	H9B—C9—H9C	109.5

C2—N1—C1—N1ⁱ	0.12 (13)	C3—C4—C5—C6	−0.4 (4)
C3—N1—C1—N1ⁱ	−178.4 (2)	C9—O1—C6—C7	−2.5 (4)
C1—N1—C2—C2ⁱ	−0.3 (3)	C9—O1—C6—C5	177.7 (2)
C3—N1—C2—C2ⁱ	178.2 (2)	C4—C5—C6—O1	−178.7 (2)
C1—N1—C3—C8	175.65 (18)	C4—C5—C6—C7	1.5 (4)
C2—N1—C3—C8	−2.6 (3)	O1—C6—C7—C8	178.9 (2)
C1—N1—C3—C4	−4.5 (3)	C5—C6—C7—C8	−1.3 (4)
C2—N1—C3—C4	177.3 (2)	C4—C3—C8—C7	1.1 (3)
C8—C3—C4—C5	−0.9 (4)	N1—C3—C8—C7	−179.0 (2)
N1—C3—C4—C5	179.2 (2)	C6—C7—C8—C3	0.0 (4)

Symmetry code: (i) −x+1, y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Cl1	0.85	2.29	3.133 (3)	173
C1—H1···O2	0.93	2.13	3.060 (3)	180
C2—H2A···Cl1ⁱⁱ	0.93	2.69	3.474 (3)	142
C4—H4···O2	0.93	2.47	3.391 (3)	170
C9—H9C···Cg2ⁱⁱⁱ	0.96	2.91	3.629 (3)	133

Symmetry codes: (ii) x+1/2, y−1/2, z; (iii) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₇N₂O₂⁺·Cl⁻·H₂O
M_r	334.79
Crystal system, space group	Monoclinic, C2
Temperature (K)	298
a, b, c (Å)	15.6706 (19), 9.4198 (9), 5.4026 (4)
β (°)	90.156 (1)
V (Å³)	797.50 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.20 × 0.11 × 0.09

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.951, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	2026, 749, 688
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.076, 1.01
No. of reflections	749
No. of parameters	107
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.22

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Cl1	0.85	2.29	3.133 (3)	173
C1—H1···O2	0.93	2.13	3.060 (3)	180
C2—H2A···Cl1ⁱ	0.93	2.69	3.474 (3)	142
C4—H4···O2	0.93	2.47	3.391 (3)	170
C9—H9C···Cg2ⁱⁱ	0.96	2.91	3.629 (3)	133

Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x, y, z+1.

Acknowledgements

The authors are grateful to the National Natural Science Foundation of China (grant No. 20772103), the Natural Science Foundation of Jiangsu Province (grant No. BK 2007028) and the Surpassing Project of Jiangsu Province (grant No. CX07S_016z) for financial support.

References

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