1-(3-Ammonio­methyl-2,4,6-trimethyl­benz­yl)-3-(2,4,6-trimethyl­phen­yl)imidazol-1-ium dibromide monohydrate

Zhang, C.; Ren, Y.; Luo, M.-M.

doi:10.1107/S1600536809012811

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages o1023-o1024

doi:10.1107/S1600536809012811

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1-(3-Ammoniomethyl-2,4,6-trimethylbenzyl)-3-(2,4,6-trimethylphenyl)imidazol-1-ium dibromide monohydrate

Chao Zhang,^a Yong Ren ^b and Mei-Ming Luo ^a ^*

^aKey Laboratory of Green Chemistry and Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China, and ^bJiangsu Key Laboratory for Supramolecular Medicinal Materials and Applications, College of Life Science, Nanjing Normal University, No. 1 Wenyuan Road, Nanjing 210046, People's Republic of China
^*Correspondence e-mail: luomm@scu.edu.cn

(Received 23 February 2009; accepted 4 April 2009; online 10 April 2009)

In the title compound, C₂₅H₃₅N₃²⁺·2Br⁻·H₂O, the dihedral angles between the imidazole ring and the two outer benzene rings are 80.16 (16) and 69.40 (18)°. The component species are linked by N—H⋯Br, O—H⋯Br and C—H⋯Br hydrogen bonds.

Related literature

For carbene ligands and complexes, see: Alcalde et al. (2007 ); Douthwaite et al. (2004 ); Magill et al. (2001 ). For phosphine ligands and complexes, see: Cao et al. (2000 ); Liou et al. (1995 ); Rybtchinski et al. (1996 , 1999 , 2001 ). For a related synthesis, see: Gandelman et al. (1997 ). For related literature, see: Caddick et al. (2004 ); Hahn (2006 ).

Experimental

Crystal data

C₂₅H₃₅N₃²⁺·2Br⁻·H₂O
M_r = 555.40
Triclinic, $[P \overline 1]$
a = 10.594 (4) Å
b = 10.800 (3) Å
c = 13.193 (4) Å
α = 66.48 (4)°
β = 70.26 (4)°
γ = 80.58 (3)°
V = 1302.0 (9) Å³
Z = 2
Mo Kα radiation
μ = 3.13 mm⁻¹
T = 294 K
0.50 × 0.46 × 0.40 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: spherical (Farrugia, 1999 ) T_min = 0.303, T_max = 0.367
4856 measured reflections
4745 independent reflections
2966 reflections with I > 2σ(I)
R_int = 0.007
3 standard reflections every 300 reflections intensity decay: 2.7%

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.203
S = 1.09
4745 reflections
300 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯Br1	0.81 (6)	2.58 (3)	3.355 (6)	160 (8)
O1—H1O2⋯Br2	0.82 (6)	2.49 (6)	3.283 (6)	165 (7)
N1—H1N⋯Br2	0.90 (5)	2.40 (3)	3.238 (5)	154 (6)
C9—H9B⋯Br2ⁱ	0.96	2.85	3.792 (7)	167
C12—H12A⋯Br2	0.96	2.82	3.765 (7)	168
C14—H14⋯Br1ⁱⁱ	0.93	2.79	3.436 (6)	128
C16—H16⋯Br2ⁱⁱⁱ	0.93	2.81	3.597 (6)	143
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, z; (iii) -x+1, -y+1, -z.

Data collection: DIFRAC (Gabe et al., 1993 ); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ); 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, 1999); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012811/zl2182sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012811/zl2182Isup2.hkl

checkCIF report

Comment top

Transition metal complexes bearing N-heterocyclic carbene (NHC) ligands have attracted considerable attention in organometallic chemistry and catalysis. Compared to widely used phosphine complexes, the NHC complexes have been shown to be remarkably stable towards heat, air and moisture (Hahn, 2006). Rencently, phosphine complexes and phosphine-amido complexes were found to be active catalysts for the selective metal insertion into strong unstrained aryl-methyl bonds under very mild conditions (Cao et al., 2000; Gandelman et al., 1997; Liou et al., 1995; Rybtchinski et al., 1996; Rybtchinski et al., 1999; Rybtchinski et al., 2001). This prompted us to investigate whether NHC-amido complexes could provide different reactivity from phosphine-amido complexes in the aryl-methyl bond activation process. The title compound, a stable precursor of an NHC-amido ligand, was synthesized in moderate yield by reacting 1-[3-(bromomethyl)-2,4,6-trimethylbenzyl]-3-(2,4,6-trimethylphenyl)-1H-imidazol-3-ium bromide with a 10-fold excess of dimethylamine in methanol.

In the title compound (Fig. 1), the dihedral angles between the imidazole ring and the two outer benzene rings are 80.16 (16)° and 69.40 (18)°. A solvate water molecule and the bromide anions are linked to the main molecule via N—H···Br, O—H···Br and C—H···Br hydrogen bonds, and these intramolecular hydrogen bonds help to stabilize the crystal structure (Fig. 2).

Related literature top

For carbene ligands and complexes, see: Alcalde et al. (2007); Douthwaite et al. (2004); Magill et al. (2001). For phosphine ligands and complexes, see: Cao et al. (2000); Liou et al. (1995); Rybtchinski et al. (1996, 1999, 2001). For a related synthesis, see: Gandelman et al. (1997). For related literature, see: Caddick et al. (2004); Hahn (2006).

Experimental top

A mixture of 1-mesityl-1H-imidazole (2.79 g, 15.0 mmol) and 2,6-bis(bromomethyl)mesitylene (4.82 g, 15.0 mmol) in dioxane (30 ml) was heated under reflex with stirring for 0.5 h. After this the mixture was cooled to room temperature, the white precipitate was filtered and washed with ether to remove unreacted starting material. The resulting mixture of the monoimidazolium (4.42 g, 59.9%) and diimidazolium salts was separated by flash chromatography (CH₂Cl₂/CH₃OH (10/1, v/v)). Then, the monoimidazolium salt was dissovled in 35 ml of methanol and a 10-fold excess of dimethylamine (4.04 g, 89.8 mmol) was added. The resulting reaction mixture was heated for 6 h at 333 K. The product was obtained as a white powder (3.99 g, 82.8%) after the solvent removal under vacuum. Crystallization by slow evaporation of the solvent from a dichloromethane solution at ambient temperature afforded colorless crystals over a period of several days. m.p. 501 K. ¹H NMR (400 MHz, CDCl₃): δ = 10.68 (brs, 1H, N-H), 10.31 (s, 1H, Imi-H), 8.30 (s, 1H, Imi-H), 7.09 (s, 1H, Imi-H), 6.98 (m, 3H, Ar-H), 6.00 (s, 2H, Imi-CH₂), 4.58 (s, 2H, NHCH₂), 2.97 (s, 6H, NHCH₃), 2.69 (s, 3H, ArCH₃), 2.47 (s, 3H, ArCH₃), 2.33 (s, 3H, ArCH₃), 2.31 (s, 3H, ArCH₃), 2.06 (s, 3H, ArCH₃), 2.04 (s, 3H, ArCH₃). ¹³C NMR (400 MHz, CDCl₃): δ = 141.2, 140.7, 140.5, 139.9, 137.2, 134.1, 132.0, 130.7, 129.8, 128.5, 126.2, 123.9, 123.5, 56.1, 48.6, 21.2, 21.1, 20.2, 18.4, 17.6. MS (ESI) m/z = 455.5 [M - H₂O - HBr]⁺_,376.1 [M - H₂O - HBr - Br]⁺_.

Computing details top

Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); data reduction: NRCVAX (Gabe et al., 1989); 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, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding are omitted.

1-(3-Ammoniomethyl-2,4,6-trimethylbenzyl)-3-(2,4,6-trimethylphenyl)imidazol- 1-ium dibromide monohydrate top

Crystal data top

C₂₅H₃₅N₃²⁺·2Br⁻·H₂O	Z = 2
M_r = 555.40	F(000) = 572
Triclinic, P1	D_x = 1.417 Mg m⁻³
Hall symbol: -P 1	Melting point: 501 K
a = 10.594 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.800 (3) Å	Cell parameters from 23 reflections
c = 13.193 (4) Å	θ = 4.5–7.8°
α = 66.48 (4)°	µ = 3.13 mm⁻¹
β = 70.26 (4)°	T = 294 K
γ = 80.58 (3)°	Block, colourless
V = 1302.0 (9) Å³	0.50 × 0.46 × 0.40 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	2966 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.007
Graphite monochromator	θ_max = 25.6°, θ_min = 1.8°
ω/2θ scans	h = −12→12
Absorption correction: for a sphere (Farrugia, 1999)	k = −4→13
T_min = 0.303, T_max = 0.367	l = −14→15
4856 measured reflections	3 standard reflections every 300 reflections
4745 independent reflections	intensity decay: 2.7%

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)] = 0.065	Hydrogen site location: mixed
wR(F²) = 0.203	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.12P)² + 0.3033P] where P = (F_o² + 2F_c²)/3
4745 reflections	(Δ/σ)_max < 0.001
300 parameters	Δρ_max = 1.01 e Å⁻³
4 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

C₂₅H₃₅N₃²⁺·2Br⁻·H₂O	γ = 80.58 (3)°
M_r = 555.40	V = 1302.0 (9) Å³
Triclinic, P1	Z = 2
a = 10.594 (4) Å	Mo Kα radiation
b = 10.800 (3) Å	µ = 3.13 mm⁻¹
c = 13.193 (4) Å	T = 294 K
α = 66.48 (4)°	0.50 × 0.46 × 0.40 mm
β = 70.26 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2966 reflections with I > 2σ(I)
Absorption correction: for a sphere (Farrugia, 1999)	R_int = 0.007
T_min = 0.303, T_max = 0.367	3 standard reflections every 300 reflections
4856 measured reflections	intensity decay: 2.7%
4745 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	4 restraints
wR(F²) = 0.203	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 1.01 e Å⁻³
4745 reflections	Δρ_min = −0.58 e Å⁻³
300 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
Br1	0.05853 (7)	0.78890 (7)	0.34382 (7)	0.0653 (3)
Br2	0.53218 (8)	0.62059 (8)	0.28647 (7)	0.0652 (3)
O1	0.3386 (6)	0.7953 (7)	0.1251 (4)	0.0685 (14)
H1O1	0.272 (4)	0.815 (8)	0.170 (4)	0.07 (3)*
H1O2	0.397 (5)	0.764 (8)	0.157 (5)	0.07 (3)*
N1	0.3013 (5)	0.4016 (4)	0.4497 (4)	0.0341 (10)
H1N	0.383 (3)	0.438 (6)	0.413 (5)	0.056 (19)*
N2	0.3043 (4)	0.0868 (4)	0.1764 (4)	0.0308 (9)
N3	0.1566 (4)	0.2120 (4)	0.0972 (4)	0.0336 (10)
C1	0.3488 (5)	0.1091 (5)	0.3941 (5)	0.0326 (11)
C2	0.4293 (5)	0.0520 (5)	0.3132 (4)	0.0303 (11)
C3	0.5697 (5)	0.0588 (5)	0.2778 (5)	0.0339 (12)
C4	0.6263 (5)	0.1238 (5)	0.3225 (5)	0.0342 (12)
H4	0.7193	0.1254	0.3010	0.041*
C5	0.5505 (5)	0.1865 (5)	0.3978 (4)	0.0301 (11)
C6	0.4093 (5)	0.1809 (5)	0.4329 (4)	0.0305 (11)
C7	0.3254 (5)	0.2517 (5)	0.5130 (5)	0.0341 (12)
H7A	0.3699	0.2408	0.5694	0.041*
H7B	0.2395	0.2089	0.5548	0.041*
C8	0.2255 (6)	0.4298 (6)	0.3664 (5)	0.0455 (14)
H8A	0.2643	0.3772	0.3187	0.068*
H8B	0.2294	0.5241	0.3183	0.068*
H8C	0.1336	0.4064	0.4081	0.068*
C9	0.2247 (6)	0.4663 (6)	0.5380 (6)	0.0473 (15)
H9A	0.2131	0.5616	0.4984	0.071*
H9B	0.2745	0.4511	0.5909	0.071*
H9C	0.1384	0.4267	0.5802	0.071*
C10	0.1998 (5)	0.0854 (6)	0.4431 (5)	0.0398 (13)
H10A	0.1537	0.1555	0.3948	0.060*
H10B	0.1678	0.0864	0.5201	0.060*
H10C	0.1833	−0.0006	0.4455	0.060*
C11	0.6620 (6)	−0.0024 (6)	0.1924 (5)	0.0444 (14)
H11A	0.6464	−0.0971	0.2215	0.067*
H11B	0.7537	0.0100	0.1826	0.067*
H11C	0.6444	0.0413	0.1191	0.067*
C12	0.6214 (6)	0.2566 (6)	0.4402 (5)	0.0385 (12)
H12A	0.6090	0.3526	0.4046	0.058*
H12B	0.7154	0.2326	0.4202	0.058*
H12C	0.5850	0.2292	0.5229	0.058*
C13	0.3650 (6)	−0.0154 (5)	0.2643 (5)	0.0351 (12)
H13A	0.4318	−0.0707	0.2286	0.042*
H13B	0.2960	−0.0741	0.3265	0.042*
C14	0.1737 (5)	0.1112 (5)	0.1895 (4)	0.0302 (11)
H14	0.1052	0.0644	0.2539	0.036*
C15	0.3735 (6)	0.1725 (6)	0.0688 (5)	0.0421 (14)
H15	0.4663	0.1750	0.0371	0.050*
C16	0.2853 (6)	0.2512 (6)	0.0174 (5)	0.0437 (14)
H16	0.3042	0.3187	−0.0562	0.052*
C17	0.0284 (5)	0.2702 (5)	0.0807 (5)	0.0350 (12)
C18	−0.0477 (5)	0.3458 (6)	0.1462 (5)	0.0378 (12)
C19	−0.1741 (6)	0.3945 (6)	0.1334 (5)	0.0417 (13)
H19	−0.2271	0.4449	0.1764	0.050*
C20	−0.2221 (5)	0.3696 (6)	0.0589 (5)	0.0414 (13)
C21	−0.1385 (6)	0.3010 (6)	−0.0093 (6)	0.0489 (15)
H21	−0.1682	0.2895	−0.0636	0.059*
C22	−0.0132 (6)	0.2492 (6)	−0.0001 (5)	0.0423 (13)
C23	0.0000 (7)	0.3743 (7)	0.2297 (6)	0.0521 (16)
H23A	−0.0364	0.4603	0.2334	0.078*
H23B	0.0963	0.3757	0.2037	0.078*
H23C	−0.0292	0.3050	0.3052	0.078*
C24	−0.3623 (7)	0.4168 (8)	0.0498 (8)	0.066 (2)
H24A	−0.4166	0.4323	0.1187	0.099*
H24B	−0.4016	0.3488	0.0413	0.099*
H24C	−0.3575	0.4993	−0.0164	0.099*
C25	0.0750 (8)	0.1756 (9)	−0.0766 (8)	0.073 (2)
H25A	0.0258	0.1644	−0.1215	0.109*
H25B	0.1022	0.0886	−0.0293	0.109*
H25C	0.1529	0.2271	−0.1278	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0458 (4)	0.0520 (4)	0.0827 (6)	−0.0118 (3)	0.0013 (3)	−0.0227 (4)
Br2	0.0657 (5)	0.0598 (5)	0.0600 (5)	−0.0090 (3)	−0.0138 (4)	−0.0137 (4)
O1	0.058 (3)	0.106 (4)	0.053 (3)	−0.005 (3)	−0.016 (3)	−0.039 (3)
N1	0.036 (2)	0.034 (2)	0.040 (3)	−0.0018 (19)	−0.012 (2)	−0.020 (2)
N2	0.037 (2)	0.028 (2)	0.032 (2)	0.0007 (18)	−0.0126 (19)	−0.0136 (19)
N3	0.033 (2)	0.034 (2)	0.030 (2)	−0.0029 (18)	−0.0117 (19)	−0.0063 (19)
C1	0.031 (3)	0.030 (3)	0.034 (3)	−0.004 (2)	−0.010 (2)	−0.009 (2)
C2	0.035 (3)	0.024 (2)	0.033 (3)	−0.004 (2)	−0.012 (2)	−0.008 (2)
C3	0.036 (3)	0.026 (3)	0.037 (3)	0.003 (2)	−0.011 (2)	−0.009 (2)
C4	0.028 (3)	0.030 (3)	0.042 (3)	−0.003 (2)	−0.012 (2)	−0.009 (2)
C5	0.037 (3)	0.022 (2)	0.033 (3)	−0.004 (2)	−0.019 (2)	−0.003 (2)
C6	0.037 (3)	0.028 (3)	0.027 (3)	−0.006 (2)	−0.011 (2)	−0.007 (2)
C7	0.042 (3)	0.032 (3)	0.031 (3)	−0.001 (2)	−0.014 (2)	−0.011 (2)
C8	0.061 (4)	0.035 (3)	0.050 (4)	0.004 (3)	−0.036 (3)	−0.012 (3)
C9	0.051 (3)	0.044 (3)	0.056 (4)	0.004 (3)	−0.011 (3)	−0.033 (3)
C10	0.034 (3)	0.047 (3)	0.048 (3)	0.000 (2)	−0.013 (3)	−0.027 (3)
C11	0.037 (3)	0.050 (3)	0.053 (4)	0.000 (3)	−0.009 (3)	−0.030 (3)
C12	0.042 (3)	0.034 (3)	0.046 (3)	−0.007 (2)	−0.018 (3)	−0.015 (3)
C13	0.043 (3)	0.027 (3)	0.040 (3)	0.001 (2)	−0.020 (2)	−0.013 (2)
C14	0.027 (3)	0.033 (3)	0.029 (3)	−0.007 (2)	−0.007 (2)	−0.009 (2)
C15	0.029 (3)	0.052 (3)	0.033 (3)	−0.004 (3)	−0.005 (2)	−0.007 (3)
C16	0.037 (3)	0.052 (3)	0.033 (3)	−0.012 (3)	−0.008 (2)	−0.005 (3)
C17	0.033 (3)	0.036 (3)	0.033 (3)	−0.005 (2)	−0.010 (2)	−0.009 (2)
C18	0.039 (3)	0.037 (3)	0.033 (3)	−0.004 (2)	−0.011 (2)	−0.009 (2)
C19	0.040 (3)	0.037 (3)	0.039 (3)	0.001 (2)	−0.010 (3)	−0.008 (3)
C20	0.034 (3)	0.036 (3)	0.051 (4)	−0.006 (2)	−0.017 (3)	−0.007 (3)
C21	0.054 (4)	0.047 (3)	0.056 (4)	−0.004 (3)	−0.034 (3)	−0.013 (3)
C22	0.045 (3)	0.043 (3)	0.045 (3)	−0.003 (3)	−0.019 (3)	−0.017 (3)
C23	0.050 (4)	0.067 (4)	0.045 (4)	0.007 (3)	−0.018 (3)	−0.027 (3)
C24	0.049 (4)	0.057 (4)	0.099 (6)	0.004 (3)	−0.044 (4)	−0.021 (4)
C25	0.075 (5)	0.090 (6)	0.084 (6)	0.022 (4)	−0.042 (4)	−0.059 (5)

Geometric parameters (Å, º) top

O1—H1O1	0.81 (6)	C10—H10C	0.9600
O1—H1O2	0.82 (6)	C11—H11A	0.9600
N1—C8	1.482 (7)	C11—H11B	0.9600
N1—C7	1.521 (7)	C11—H11C	0.9600
N1—C9	1.526 (7)	C12—H12A	0.9600
N1—H1N	0.90 (5)	C12—H12B	0.9600
N2—C14	1.330 (6)	C12—H12C	0.9600
N2—C15	1.371 (7)	C13—H13A	0.9700
N2—C13	1.492 (7)	C13—H13B	0.9700
N3—C14	1.314 (6)	C14—H14	0.9300
N3—C16	1.418 (7)	C15—C16	1.328 (8)
N3—C17	1.449 (7)	C15—H15	0.9300
C1—C6	1.405 (7)	C16—H16	0.9300
C1—C2	1.409 (7)	C17—C22	1.387 (8)
C1—C10	1.512 (7)	C17—C18	1.393 (8)
C2—C3	1.406 (7)	C18—C19	1.396 (8)
C2—C13	1.497 (7)	C18—C23	1.503 (8)
C3—C4	1.380 (8)	C19—C20	1.376 (9)
C3—C11	1.517 (7)	C19—H19	0.9300
C4—C5	1.382 (7)	C20—C21	1.386 (9)
C4—H4	0.9300	C20—C24	1.518 (8)
C5—C6	1.412 (7)	C21—C22	1.379 (8)
C5—C12	1.503 (7)	C21—H21	0.9300
C6—C7	1.510 (7)	C22—C25	1.511 (9)
C7—H7A	0.9700	C23—H23A	0.9600
C7—H7B	0.9700	C23—H23B	0.9600
C8—H8A	0.9600	C23—H23C	0.9600
C8—H8B	0.9600	C24—H24A	0.9600
C8—H8C	0.9600	C24—H24B	0.9600
C9—H9A	0.9600	C24—H24C	0.9600
C9—H9B	0.9600	C25—H25A	0.9600
C9—H9C	0.9600	C25—H25B	0.9600
C10—H10A	0.9600	C25—H25C	0.9600
C10—H10B	0.9600

H1O1—O1—H1O2	109 (6)	H11A—C11—H11C	109.5
C8—N1—C7	113.5 (4)	H11B—C11—H11C	109.5
C8—N1—C9	108.8 (4)	C5—C12—H12A	109.5
C7—N1—C9	109.4 (4)	C5—C12—H12B	109.5
C8—N1—H1N	111 (4)	H12A—C12—H12B	109.5
C7—N1—H1N	107 (4)	C5—C12—H12C	109.5
C9—N1—H1N	108 (4)	H12A—C12—H12C	109.5
C14—N2—C15	108.3 (4)	H12B—C12—H12C	109.5
C14—N2—C13	125.8 (4)	N2—C13—C2	110.9 (4)
C15—N2—C13	125.9 (4)	N2—C13—H13A	109.5
C14—N3—C16	107.7 (4)	C2—C13—H13A	109.5
C14—N3—C17	125.5 (4)	N2—C13—H13B	109.5
C16—N3—C17	126.7 (4)	C2—C13—H13B	109.5
C6—C1—C2	119.5 (5)	H13A—C13—H13B	108.1
C6—C1—C10	120.9 (5)	N3—C14—N2	109.3 (4)
C2—C1—C10	119.5 (5)	N3—C14—H14	125.3
C3—C2—C1	120.1 (5)	N2—C14—H14	125.3
C3—C2—C13	120.0 (5)	C16—C15—N2	108.4 (5)
C1—C2—C13	119.9 (5)	C16—C15—H15	125.8
C4—C3—C2	118.8 (5)	N2—C15—H15	125.8
C4—C3—C11	118.5 (5)	C15—C16—N3	106.2 (5)
C2—C3—C11	122.7 (5)	C15—C16—H16	126.9
C3—C4—C5	122.7 (5)	N3—C16—H16	126.9
C3—C4—H4	118.6	C22—C17—C18	122.7 (5)
C5—C4—H4	118.6	C22—C17—N3	118.7 (5)
C4—C5—C6	118.7 (5)	C18—C17—N3	118.6 (5)
C4—C5—C12	118.8 (5)	C17—C18—C19	117.4 (5)
C6—C5—C12	122.6 (5)	C17—C18—C23	122.8 (5)
C1—C6—C5	120.0 (4)	C19—C18—C23	119.7 (5)
C1—C6—C7	120.9 (5)	C20—C19—C18	121.6 (5)
C5—C6—C7	119.1 (4)	C20—C19—H19	119.2
C6—C7—N1	113.2 (4)	C18—C19—H19	119.2
C6—C7—H7A	108.9	C19—C20—C21	118.3 (5)
N1—C7—H7A	108.9	C19—C20—C24	121.4 (6)
C6—C7—H7B	108.9	C21—C20—C24	120.4 (6)
N1—C7—H7B	108.9	C22—C21—C20	122.9 (6)
H7A—C7—H7B	107.8	C22—C21—H21	118.6
N1—C8—H8A	109.5	C20—C21—H21	118.6
N1—C8—H8B	109.5	C21—C22—C17	116.9 (5)
H8A—C8—H8B	109.5	C21—C22—C25	121.1 (6)
N1—C8—H8C	109.5	C17—C22—C25	122.0 (5)
H8A—C8—H8C	109.5	C18—C23—H23A	109.5
H8B—C8—H8C	109.5	C18—C23—H23B	109.5
N1—C9—H9A	109.5	H23A—C23—H23B	109.5
N1—C9—H9B	109.5	C18—C23—H23C	109.5
H9A—C9—H9B	109.5	H23A—C23—H23C	109.5
N1—C9—H9C	109.5	H23B—C23—H23C	109.5
H9A—C9—H9C	109.5	C20—C24—H24A	109.5
H9B—C9—H9C	109.5	C20—C24—H24B	109.5
C1—C10—H10A	109.5	H24A—C24—H24B	109.5
C1—C10—H10B	109.5	C20—C24—H24C	109.5
H10A—C10—H10B	109.5	H24A—C24—H24C	109.5
C1—C10—H10C	109.5	H24B—C24—H24C	109.5
H10A—C10—H10C	109.5	C22—C25—H25A	109.5
H10B—C10—H10C	109.5	C22—C25—H25B	109.5
C3—C11—H11A	109.5	H25A—C25—H25B	109.5
C3—C11—H11B	109.5	C22—C25—H25C	109.5
H11A—C11—H11B	109.5	H25A—C25—H25C	109.5
C3—C11—H11C	109.5	H25B—C25—H25C	109.5

C6—C1—C2—C3	4.4 (7)	C17—N3—C14—N2	−178.2 (5)
C10—C1—C2—C3	−172.1 (5)	C15—N2—C14—N3	−2.5 (6)
C6—C1—C2—C13	−175.3 (5)	C13—N2—C14—N3	176.9 (4)
C10—C1—C2—C13	8.2 (7)	C14—N2—C15—C16	1.5 (6)
C1—C2—C3—C4	−0.9 (7)	C13—N2—C15—C16	−177.9 (5)
C13—C2—C3—C4	178.8 (5)	N2—C15—C16—N3	0.0 (7)
C1—C2—C3—C11	179.1 (5)	C14—N3—C16—C15	−1.5 (6)
C13—C2—C3—C11	−1.3 (8)	C17—N3—C16—C15	179.2 (5)
C2—C3—C4—C5	−2.2 (8)	C14—N3—C17—C22	−110.0 (6)
C11—C3—C4—C5	177.8 (5)	C16—N3—C17—C22	69.2 (7)
C3—C4—C5—C6	1.7 (8)	C14—N3—C17—C18	70.5 (7)
C3—C4—C5—C12	−179.0 (5)	C16—N3—C17—C18	−110.3 (6)
C2—C1—C6—C5	−4.9 (7)	C22—C17—C18—C19	4.0 (8)
C10—C1—C6—C5	171.5 (5)	N3—C17—C18—C19	−176.5 (5)
C2—C1—C6—C7	175.7 (4)	C22—C17—C18—C23	−177.0 (6)
C10—C1—C6—C7	−7.9 (8)	N3—C17—C18—C23	2.5 (8)
C4—C5—C6—C1	1.9 (7)	C17—C18—C19—C20	−0.3 (8)
C12—C5—C6—C1	−177.4 (5)	C23—C18—C19—C20	−179.3 (6)
C4—C5—C6—C7	−178.6 (5)	C18—C19—C20—C21	−3.7 (9)
C12—C5—C6—C7	2.1 (7)	C18—C19—C20—C24	176.9 (6)
C1—C6—C7—N1	−97.4 (6)	C19—C20—C21—C22	4.4 (9)
C5—C6—C7—N1	83.1 (6)	C24—C20—C21—C22	−176.3 (6)
C8—N1—C7—C6	62.4 (6)	C20—C21—C22—C17	−0.9 (9)
C9—N1—C7—C6	−175.9 (4)	C20—C21—C22—C25	−179.7 (7)
C14—N2—C13—C2	−109.4 (6)	C18—C17—C22—C21	−3.4 (9)
C15—N2—C13—C2	69.9 (6)	N3—C17—C22—C21	177.1 (5)
C3—C2—C13—N2	−104.4 (5)	C18—C17—C22—C25	175.4 (6)
C1—C2—C13—N2	75.3 (6)	N3—C17—C22—C25	−4.1 (9)
C16—N3—C14—N2	2.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···Br1	0.81 (6)	2.58 (3)	3.355 (6)	160 (8)
O1—H1O2···Br2	0.82 (6)	2.49 (6)	3.283 (6)	165 (7)
N1—H1N···Br2	0.90 (5)	2.40 (3)	3.238 (5)	154 (6)
C9—H9B···Br2ⁱ	0.96	2.85	3.792 (7)	167
C12—H12A···Br2	0.96	2.82	3.765 (7)	168
C14—H14···Br1ⁱⁱ	0.93	2.79	3.436 (6)	128
C16—H16···Br2ⁱⁱⁱ	0.93	2.81	3.597 (6)	143

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

Experimental details

Crystal data
Chemical formula	C₂₅H₃₅N₃²⁺·2Br⁻·H₂O
M_r	555.40
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	10.594 (4), 10.800 (3), 13.193 (4)
α, β, γ (°)	66.48 (4), 70.26 (4), 80.58 (3)
V (Å³)	1302.0 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.13
Crystal size (mm)	0.50 × 0.46 × 0.40

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	For a sphere (Farrugia, 1999)
T_min, T_max	0.303, 0.367
No. of measured, independent and observed [I > 2σ(I)] reflections	4856, 4745, 2966
R_int	0.007
(sin θ/λ)_max (Å⁻¹)	0.607

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.203, 1.09
No. of reflections	4745
No. of parameters	300
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.58

Computer programs: DIFRAC (Gabe et al., 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···Br1	0.81 (6)	2.58 (3)	3.355 (6)	160 (8)
O1—H1O2···Br2	0.82 (6)	2.49 (6)	3.283 (6)	165 (7)
N1—H1N···Br2	0.90 (5)	2.40 (3)	3.238 (5)	154 (6)
C9—H9B···Br2ⁱ	0.96	2.85	3.792 (7)	167
C12—H12A···Br2	0.96	2.82	3.765 (7)	168
C14—H14···Br1ⁱⁱ	0.93	2.79	3.436 (6)	128
C16—H16···Br2ⁱⁱⁱ	0.93	2.81	3.597 (6)	143

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

Acknowledgements

Financial support for this work by the Natural Science Foundation of China is gratefully acknowledged.

References

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Volume 65| Part 5| May 2009| Pages o1023-o1024

doi:10.1107/S1600536809012811

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

1-(3-Ammonio­methyl-2,4,6-tri­methyl­benz­yl)-3-(2,4,6-tri­methyl­phen­yl)imidazol-1-ium dibromide monohydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-(3-Ammoniomethyl-2,4,6-trimethylbenzyl)-3-(2,4,6-trimethylphenyl)imidazol-1-ium dibromide monohydrate