1-(4-tert-Butyl­benz­yl)-3-(3,4,5-tri­methoxy­benz­yl)benzimidazolium bromide monohydrate

Arslan, H.; VanDerveer, D.; Demir, S.; Özdemir, İ.; Çetinkaya, B.

doi:10.1107/S1600536808043250

organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages o208-o209

doi:10.1107/S1600536808043250

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1-(4-tert-Butylbenzyl)-3-(3,4,5-trimethoxybenzyl)benzimidazolium bromide monohydrate

Hakan Arslan,^a,^b ^* Don VanDerveer,^c Serpil Demir,^d İsmail Özdemir ^d and Bekir Çetinkaya ^e

^aDepartment of Natural Sciences, Fayetteville State University, Fayetteville, NC 28301, USA, ^bDepartment of Chemistry, Faculty of Pharmacy, Mersin University, Mersin, TR 33169, Turkey, ^cDepartment of Chemistry, Clemson University, Clemson, SC 29634, USA, ^dDepartment of Chemistry, Faculty of Science and Arts, İnönü University, Malatya, TR 44280, Turkey, and ^eDepartment of Chemistry, Faculty of Science, Ege University, Bornova-İzmir, TR 35100, Turkey
^*Correspondence e-mail: hakan.arslan.acad@gmail.com

(Received 11 December 2008; accepted 18 December 2008; online 24 December 2008)

A novel N-heterocyclic carbene derivative, C₂₈H₃₃N₂O₃⁺·Br⁻·H₂O, was synthesized and characterized by elemental analysis, ¹H and ¹³C-NMR and IR spectroscopy and a single-crystal X-ray diffraction study. Ions of the title compound are linked by π⋯π stacking interactions (face–face separation 3.441 Å) and C—H⋯Br and O—H⋯Br interactions. Intra- and intermolecular C—H⋯O interactions are also present. The C—N bond lengths for the compound [1.329 (3), 1.325 (3), 1.389 (3) and 1.391 (3) Å] are all shorter than the average single C—N bond length of 1.48 Å, thus showing varying degrees of double-bond character.

Related literature

For the synthesis, see: Yaşar et al. (2008 ). For general background, see: Herrmann (2002 ); Arduengo & Krafczyc (1998 ); Herrmann et al. (1995 , 1998 ); Navarro et al. (2006 ). For related compounds, see: Yaşar et al. (2008); Arslan et al. (2009 and references therein). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₈H₃₃N₂O₃⁺·Br⁻·H₂O
M_r = 543.49
Triclinic, $[P \overline 1]$
a = 10.389 (2) Å
b = 10.436 (2) Å
c = 14.038 (3) Å
α = 109.79 (3)°
β = 90.70 (3)°
γ = 103.57 (3)°
V = 1385.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.52 mm⁻¹
T = 298 (2) K
0.48 × 0.29 × 0.26 mm

Data collection

Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.514, T_max = 0.673
11938 measured reflections
4860 independent reflections
3921 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.112
S = 1.08
4860 reflections
328 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯Br1ⁱ	0.87 (3)	2.54 (3)	3.393 (3)	169 (5)
O4—H4B⋯Br1ⁱⁱ	0.88 (5)	2.52 (5)	3.399 (3)	176 (5)
C1—H1⋯Br1	0.96	2.65	3.587 (3)	165
C3—H3⋯O2ⁱⁱⁱ	0.96	2.57	3.294 (4)	132
C6—H6⋯O4	0.96	2.38	3.305 (5)	161
C10—H10⋯O4	0.96	2.59	3.463 (5)	152
C14—H14⋯Br1	0.96	2.88	3.823 (3)	167
C18—H18A⋯Br1^iv	0.96	2.82	3.718 (3)	155
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, z; (iii) x+1, y, z; (iv) -x+2, -y+2, -z+1.

Data collection: CrystalClear (Rigaku/MSC, 2001 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536808043250/hg2459sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808043250/hg2459Isup2.hkl

checkCIF report

Comment top

N-heterocyclic carbenes have attracted much interest as a new class of compound in organometallic chemistry. The applications of N-heterocyclic carbenes were first reported by Herrmann in 1998 (Herrmann et al., 1998). Recently, Herrmann et al. and other researchers have designed new N-heterocyclic carbene compounds and have used them to prepare new catalysts for Suzuki-Miyura, Sonogashira, Stille and Heck reactions (Herrmann, 2002; Herrmann et al., 1995; Navarro et al., 2006; Arduengo & Krafczyc, 1998).

Recently, we have focused on the synthesis, characterization and use of palladium, platinum and ruthenium N-heterocyclic carbene complexes as catalysts for Suzuki-Miyura and Heck reactions (Yaşar et al., 2008; Arslan et al., 2009, and references therein).

In the present work, we report the preparation and characterization of a novel N-heterocyclic carbene derivative, 1-(4-tert-butylbenzyl)-3-(3,4,5-trimethoxybenzyl)benzimidazolium bromide monohydrate, (I). The compound was purified by re-crystallization from ethanol:diethylether mixture (1:1) and characterized by elemental analysis, ¹H and ¹³C-NMR and IR spectroscopy. The analytical and spectroscopic data are consistent with the proposed structure given in Scheme 1.

The molecular structure of the title compound is depicted in Figure 1. The crystal structure is composed of a 1-(4-tert-butylbenzyl)-3-(3,4,5-trimethoxybenzyl)benzimidazolium cation, a Br anion and solvent water molecules. All bond lengths in (I) are in normal ranges (Allen et al.,1987). The benzimidazole ring is almost coplanar with a maximum and a minimum deviation of 0.016 (2) Å for atom C2 and, 0.002 (2) Å for atom C6, respectively. In the crystal structure, π···π stacking interactions occurs between parallel benzimidazole rings, with a face-face separation of 3.441 Å (Figure 2) (Macrae et al., 2006). The dihedral angle between the benzimidazole ring and 4-tert-butylbenzyl and 3,4,5-trimethoxybenzyl groups are 70.23 (3)° and 73.48 (3) ^o, respectively.

The C—N bond lengths for the investigated compound are all shorter than the average single C—N bond length of 1.48 Å, being N1—C1 = 1.329 (3) Å, N2—C1 =1.325 (3) Å, N1—C7 = 1.389 (3) Å, and N2—C2 = 1.391 (3) Å thus showing varying degrees of double bond character in these C—N bonds. The other CN bond lengths are in agreement with the expected 1.48 Å C—N single bond lengths. This information indicates a partial electron delocalization within the C7—N1—C1—N2—C2 fragment. The N1—C1—N2 bond angle is also consistent with this hypothesis.

The crystal packing is shown in Figure 3. The intermolecular C—H···Br and O—H···Br hydrogen bonds (Figure 4, Table 1) and π···π stacking interactions link the molecules of the title compound.

Related literature top

For the synthesis, see: Yaşar et al. (2008). For general background, see: Herrmann (2002); Arduengo & Krafczyc (1998); Herrmann et al. (1995, 1998); Navarro et al. (2006). For related compounds, see: Yaşar et al. (2008); Arslan et al. (2009 and references therein). For bond-length data, see: Allen et al. (1987).

Experimental top

4-tertbutylbenzyl bromide (2.27 g, 10.0 mmol) was slowly added to a solution of 1-(3,4,5-trimethoxylbenzyl) benzimidazole (II) (2.98 g, 10.0 mmol) in DMF (5 mL) and the resulting mixture was stirred at room temperature for 5 h (Scheme 2). Diethylether (10 ml) was added to obtain a white crystalline solid which was filtered off. The solid was washed with diethylether (3 x 10 ml) dried under vacuum and the crude product was re-crystallized from ethanole/diethylether. M.p. = 246–247°C; yield 4.47 g, 85%; ν_(CN) = 1594 cm^{-1. 1}H NMR (δ, 200.13 MHz, CDCl₃): 1.25 (s, 9H, CH₂C₆H₄C(CH₃)₃-p); 3.86 and 3.79 (s, 9H, CH₂C₆H₂(OCH₃)₃-3,4,5); 5.81 (s,4H, CH₂C₆H₂(OCH₃)₃-3,4,5 and CH₂C₆H₄C(CH₃)₃-p); 6.90 (s, 2H, CH₂C₆H₂(OCH₃)₃-3,4,5); 7.33 and 7.48 (m, 8H, NC₆H₄N and CH₂C₆H₄C(CH₃)₃-p); 11.64 (s, 1H, NCHN). ¹³C NMR (δ, 50 MHz, CDCl₃): 31.6 (CH₂C₆H₄C(CH₃)₃-p); 35.1 (CH₂C₆H₄C(CH₃)₃-p); 51.6 (CH₂C₆H₄C(CH₃)₃-p); 52.1 (CH₂C₆H₂(OCH₃)₃-3,4,5); 57.2 and 61.2 (CH₂C₆H₂(OCH₃)₃-3,4,5); 106.5, 131.7, 138.9 and 152.9 (CH₂C₆H₂(OCH₃)₃-3,4,5); 114.2, 127.5, 128.7, 130.1, 131.8 and 143.2 (NC₆H₄N); 114.1, 126.7, 128.5 and 130.9 (CH₂C₆H₄C(CH₃)₃-p); 154.2 (NCHN). Anal. Found: C, 63.96; H, 6.28; N: 5.35. Calc. for C₂₈H₃₃N₂O₃Br: C, 64.00; H, 6.33; N, 5.33.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalClear (Rigaku/MSC, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram for (I).
	Fig. 3. A packing diagram for (I).
	Fig. 4. Hydrogen bonding for (I). Symmetry: O4A = x, 1 + y, z; O4B =1 - x,1 - y,1 - z; Br1A, etc. = 1 - x, 2 - y, 1 - z.
	Fig. 5. The preparation of the title compound.

1-(4-tert-Butylbenzyl)-3-(3,4,5-trimethoxybenzyl)benzimidazolium bromide monohydrate top

Crystal data top

C₂₈H₃₃N₂O₃⁺·Br⁻·H₂O	Z = 2
M_r = 543.49	F(000) = 568
Triclinic, P1	D_x = 1.303 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.389 (2) Å	Cell parameters from 4659 reflections
b = 10.436 (2) Å	θ = 3.2–26.4°
c = 14.038 (3) Å	µ = 1.52 mm⁻¹
α = 109.79 (3)°	T = 298 K
β = 90.70 (3)°	Rod, colorless
γ = 103.57 (3)°	0.48 × 0.29 × 0.26 mm
V = 1385.1 (6) Å³

Data collection top

Mercury CCD diffractometer	4860 independent reflections
Radiation source: Sealed Tube	3921 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.022
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
ω scans	h = −12→12
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −12→12
T_min = 0.514, T_max = 0.673	l = −16→16
11938 measured reflections

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) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0505P)² + 0.6557P] where P = (F_o² + 2F_c²)/3
4860 reflections	(Δ/σ)_max = 0.001
328 parameters	Δρ_max = 0.31 e Å⁻³
2 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₂₈H₃₃N₂O₃⁺·Br⁻·H₂O	γ = 103.57 (3)°
M_r = 543.49	V = 1385.1 (6) Å³
Triclinic, P1	Z = 2
a = 10.389 (2) Å	Mo Kα radiation
b = 10.436 (2) Å	µ = 1.52 mm⁻¹
c = 14.038 (3) Å	T = 298 K
α = 109.79 (3)°	0.48 × 0.29 × 0.26 mm
β = 90.70 (3)°

Data collection top

Mercury CCD diffractometer	4860 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	3921 reflections with I > 2σ(I)
T_min = 0.514, T_max = 0.673	R_int = 0.022
11938 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	2 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.31 e Å⁻³
4860 reflections	Δρ_min = −0.55 e Å⁻³
328 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	0.75295 (3)	0.93707 (4)	0.51515 (3)	0.06917 (15)
N1	0.8315 (2)	0.5830 (2)	0.57685 (15)	0.0384 (5)
N2	1.0326 (2)	0.7189 (2)	0.62364 (16)	0.0407 (5)
C1	0.9118 (3)	0.7064 (3)	0.5843 (2)	0.0439 (6)
H1	0.8858	0.7766	0.5640	0.053*
C2	1.0322 (2)	0.5974 (2)	0.64403 (18)	0.0363 (5)
C3	1.1313 (3)	0.5558 (3)	0.6834 (2)	0.0497 (7)
H3	1.2196	0.6159	0.7050	0.060*
C4	1.0966 (3)	0.4233 (3)	0.6901 (2)	0.0609 (8)
H4	1.1626	0.3902	0.7168	0.073*
C5	0.9681 (3)	0.3364 (3)	0.6591 (2)	0.0573 (7)
H5	0.9483	0.2449	0.6650	0.069*
C6	0.8695 (3)	0.3772 (3)	0.6207 (2)	0.0449 (6)
H6	0.7811	0.3170	0.5997	0.054*
C7	0.9039 (2)	0.5104 (2)	0.61354 (18)	0.0351 (5)
C8	0.6876 (2)	0.5379 (3)	0.5428 (2)	0.0454 (6)
H8A	0.6617	0.4377	0.5084	0.054*
H8B	0.6699	0.5814	0.4955	0.054*
C9	0.6061 (2)	0.5776 (3)	0.6319 (2)	0.0438 (6)
C10	0.5443 (3)	0.4785 (3)	0.6729 (2)	0.0456 (6)
H10	0.5523	0.3835	0.6449	0.055*
C11	0.4705 (3)	0.5178 (3)	0.7550 (2)	0.0521 (7)
C12	0.4583 (3)	0.6547 (3)	0.7952 (2)	0.0537 (7)
C13	0.5222 (3)	0.7534 (3)	0.7543 (2)	0.0553 (7)
C14	0.5963 (3)	0.7155 (3)	0.6720 (2)	0.0508 (7)
H14	0.6399	0.7839	0.6435	0.061*
C15	0.4234 (4)	0.2906 (4)	0.7695 (3)	0.0873 (12)
H15A	0.3873	0.2414	0.6998	0.131*
H15B	0.3783	0.2416	0.8112	0.131*
H15C	0.5166	0.2951	0.7756	0.131*
C16	0.4304 (4)	0.7401 (6)	0.9699 (3)	0.1083 (17)
H16A	0.4738	0.6735	0.9805	0.162*
H16B	0.3620	0.7526	1.0150	0.162*
H16C	0.4944	0.8286	0.9835	0.162*
C17	0.5773 (7)	0.9936 (4)	0.7672 (4)	0.119 (2)
H17A	0.6705	0.9984	0.7736	0.179*
H17B	0.5622	1.0823	0.8082	0.179*
H17C	0.5478	0.9731	0.6973	0.179*
C18	1.1457 (3)	0.8450 (3)	0.6461 (2)	0.0536 (7)
H18A	1.1451	0.8826	0.5925	0.064*
H18B	1.2277	0.8182	0.6483	0.064*
C19	1.1387 (3)	0.9570 (3)	0.7460 (2)	0.0450 (6)
C20	1.0657 (4)	1.0516 (3)	0.7490 (2)	0.0671 (9)
H20	1.0205	1.0466	0.6873	0.081*
C21	1.0563 (4)	1.1546 (3)	0.8403 (2)	0.0677 (9)
H21	1.0048	1.2198	0.8403	0.081*
C22	1.1192 (3)	1.1659 (3)	0.9317 (2)	0.0452 (6)
C23	1.1931 (3)	1.0704 (3)	0.9268 (2)	0.0532 (7)
H23	1.2390	1.0752	0.9883	0.064*
C24	1.2033 (3)	0.9667 (3)	0.8350 (2)	0.0533 (7)
H24	1.2558	0.9019	0.8342	0.064*
C25	1.1111 (3)	1.2836 (3)	1.0308 (2)	0.0591 (8)
C26	0.9702 (4)	1.3046 (5)	1.0365 (3)	0.0903 (13)
H26A	0.9665	1.3779	1.0993	0.135*
H26B	0.9085	1.2186	1.0334	0.135*
H26C	0.9472	1.3306	0.9804	0.135*
C27	1.2089 (5)	1.4190 (4)	1.0328 (4)	0.1013 (15)
H27A	1.2976	1.4066	1.0315	0.152*
H27B	1.2037	1.4947	1.0937	0.152*
H27C	1.1868	1.4408	0.9745	0.152*
C28	1.1443 (4)	1.2485 (5)	1.1241 (3)	0.0840 (11)
H28A	1.2353	1.2435	1.1266	0.126*
H28B	1.0870	1.1594	1.1196	0.126*
H28C	1.1315	1.3204	1.1846	0.126*
O1	0.4055 (2)	0.4294 (3)	0.80195 (18)	0.0717 (6)
O2	0.3740 (2)	0.6898 (3)	0.86948 (17)	0.0741 (7)
O3	0.5058 (3)	0.8868 (3)	0.8002 (2)	0.0870 (8)
O4	0.5832 (3)	0.1696 (3)	0.4946 (3)	0.0969 (10)
H4A	0.499 (2)	0.144 (6)	0.501 (4)	0.145*
H4B	0.623 (5)	0.107 (5)	0.501 (4)	0.145*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0556 (2)	0.0784 (2)	0.0980 (3)	0.02072 (16)	0.01227 (17)	0.0592 (2)
N1	0.0361 (11)	0.0451 (11)	0.0394 (12)	0.0158 (9)	0.0067 (9)	0.0176 (9)
N2	0.0412 (12)	0.0386 (11)	0.0437 (12)	0.0106 (9)	0.0121 (9)	0.0156 (9)
C1	0.0482 (15)	0.0452 (14)	0.0470 (15)	0.0210 (12)	0.0139 (12)	0.0208 (12)
C2	0.0364 (12)	0.0393 (12)	0.0342 (13)	0.0132 (10)	0.0078 (10)	0.0117 (10)
C3	0.0378 (14)	0.0634 (17)	0.0469 (16)	0.0149 (13)	0.0004 (12)	0.0169 (13)
C4	0.0558 (18)	0.073 (2)	0.067 (2)	0.0308 (16)	−0.0007 (15)	0.0315 (16)
C5	0.067 (2)	0.0494 (16)	0.0648 (19)	0.0205 (15)	0.0037 (15)	0.0284 (14)
C6	0.0463 (15)	0.0391 (13)	0.0477 (15)	0.0082 (11)	0.0045 (12)	0.0148 (11)
C7	0.0348 (12)	0.0396 (12)	0.0330 (12)	0.0147 (10)	0.0060 (10)	0.0119 (10)
C8	0.0360 (13)	0.0599 (16)	0.0433 (15)	0.0190 (12)	0.0027 (11)	0.0173 (12)
C9	0.0329 (13)	0.0567 (15)	0.0432 (14)	0.0176 (12)	0.0004 (11)	0.0155 (12)
C10	0.0366 (13)	0.0535 (15)	0.0483 (16)	0.0120 (12)	0.0020 (11)	0.0195 (12)
C11	0.0363 (14)	0.0673 (18)	0.0546 (17)	0.0098 (13)	0.0039 (12)	0.0260 (14)
C12	0.0355 (14)	0.079 (2)	0.0471 (16)	0.0209 (14)	0.0077 (12)	0.0187 (14)
C13	0.0541 (17)	0.0633 (18)	0.0550 (17)	0.0314 (15)	0.0114 (14)	0.0175 (14)
C14	0.0493 (16)	0.0589 (17)	0.0537 (17)	0.0222 (13)	0.0107 (13)	0.0260 (13)
C15	0.091 (3)	0.081 (3)	0.099 (3)	0.006 (2)	0.019 (2)	0.054 (2)
C16	0.078 (3)	0.170 (5)	0.054 (2)	0.022 (3)	0.013 (2)	0.016 (3)
C17	0.195 (6)	0.063 (2)	0.112 (4)	0.055 (3)	0.059 (4)	0.030 (2)
C18	0.0514 (16)	0.0446 (15)	0.0592 (18)	0.0025 (12)	0.0187 (14)	0.0175 (13)
C19	0.0452 (14)	0.0382 (13)	0.0515 (16)	0.0060 (11)	0.0132 (12)	0.0184 (11)
C20	0.097 (3)	0.0610 (19)	0.0488 (18)	0.0340 (18)	−0.0027 (17)	0.0174 (14)
C21	0.097 (3)	0.0613 (19)	0.0550 (19)	0.0438 (19)	0.0010 (18)	0.0179 (15)
C22	0.0462 (15)	0.0448 (14)	0.0458 (15)	0.0110 (12)	0.0085 (12)	0.0176 (12)
C23	0.0498 (16)	0.0567 (17)	0.0518 (17)	0.0147 (13)	−0.0032 (13)	0.0170 (13)
C24	0.0456 (15)	0.0498 (15)	0.0653 (19)	0.0185 (13)	0.0051 (14)	0.0170 (14)
C25	0.0622 (19)	0.0573 (17)	0.0523 (18)	0.0180 (15)	0.0122 (15)	0.0103 (14)
C26	0.091 (3)	0.113 (3)	0.072 (3)	0.056 (3)	0.024 (2)	0.018 (2)
C27	0.127 (4)	0.053 (2)	0.093 (3)	0.002 (2)	0.024 (3)	0.000 (2)
C28	0.087 (3)	0.112 (3)	0.0454 (19)	0.032 (2)	0.0076 (18)	0.0146 (19)
O1	0.0604 (14)	0.0848 (16)	0.0758 (16)	0.0089 (12)	0.0203 (12)	0.0416 (13)
O2	0.0492 (12)	0.1158 (19)	0.0554 (14)	0.0316 (13)	0.0177 (10)	0.0202 (13)
O3	0.111 (2)	0.0785 (16)	0.0900 (19)	0.0592 (16)	0.0421 (16)	0.0286 (14)
O4	0.0533 (14)	0.0568 (14)	0.174 (3)	0.0082 (12)	−0.0014 (18)	0.0367 (17)

Geometric parameters (Å, º) top

N1—C1	1.329 (3)	C16—H16A	0.9599
N1—C7	1.389 (3)	C16—H16B	0.9599
N1—C8	1.478 (3)	C16—H16C	0.9599
N2—C1	1.325 (3)	C17—O3	1.407 (5)
N2—C2	1.391 (3)	C17—H17A	0.9599
N2—C18	1.481 (3)	C17—H17B	0.9599
C1—H1	0.9600	C17—H17C	0.9599
C2—C3	1.382 (4)	C18—C19	1.507 (4)
C2—C7	1.393 (3)	C18—H18A	0.9600
C3—C4	1.380 (4)	C18—H18B	0.9600
C3—H3	0.9600	C19—C20	1.370 (4)
C4—C5	1.394 (5)	C19—C24	1.372 (4)
C4—H4	0.9600	C20—C21	1.389 (4)
C5—C6	1.368 (4)	C20—H20	0.9600
C5—H5	0.9600	C21—C22	1.388 (4)
C6—C7	1.390 (3)	C21—H21	0.9600
C6—H6	0.9600	C22—C23	1.380 (4)
C8—C9	1.513 (4)	C22—C25	1.532 (4)
C8—H8A	0.9600	C23—C24	1.399 (4)
C8—H8B	0.9600	C23—H23	0.9600
C9—C10	1.383 (4)	C24—H24	0.9600
C9—C14	1.386 (4)	C25—C27	1.526 (5)
C10—C11	1.390 (4)	C25—C26	1.529 (5)
C10—H10	0.9600	C25—C28	1.530 (5)
C11—O1	1.369 (3)	C26—H26A	0.9599
C11—C12	1.385 (4)	C26—H26B	0.9599
C12—O2	1.380 (3)	C26—H26C	0.9599
C12—C13	1.385 (4)	C27—H27A	0.9599
C13—O3	1.374 (4)	C27—H27B	0.9599
C13—C14	1.392 (4)	C27—H27C	0.9599
C14—H14	0.9600	C28—H28A	0.9599
C15—O1	1.422 (5)	C28—H28B	0.9599
C15—H15A	0.9599	C28—H28C	0.9599
C15—H15B	0.9599	O4—H4A	0.87 (2)
C15—H15C	0.9599	O4—H4B	0.88 (5)
C16—O2	1.394 (5)

C1—N1—C7	108.2 (2)	H16A—C16—H16C	109.5
C1—N1—C8	125.0 (2)	H16B—C16—H16C	109.5
C7—N1—C8	126.6 (2)	O3—C17—H17A	109.5
C1—N2—C2	108.4 (2)	O3—C17—H17B	109.5
C1—N2—C18	124.9 (2)	H17A—C17—H17B	109.5
C2—N2—C18	126.6 (2)	O3—C17—H17C	109.5
N2—C1—N1	110.5 (2)	H17A—C17—H17C	109.5
N2—C1—H1	124.8	H17B—C17—H17C	109.5
N1—C1—H1	124.8	N2—C18—C19	111.7 (2)
C3—C2—N2	132.0 (2)	N2—C18—H18A	109.3
C3—C2—C7	121.6 (2)	C19—C18—H18A	109.3
N2—C2—C7	106.3 (2)	N2—C18—H18B	109.3
C4—C3—C2	116.5 (3)	C19—C18—H18B	109.3
C4—C3—H3	121.7	H18A—C18—H18B	107.9
C2—C3—H3	121.7	C20—C19—C24	118.7 (3)
C3—C4—C5	121.6 (3)	C20—C19—C18	119.6 (3)
C3—C4—H4	119.2	C24—C19—C18	121.7 (3)
C5—C4—H4	119.2	C19—C20—C21	120.7 (3)
C6—C5—C4	122.1 (3)	C19—C20—H20	119.7
C6—C5—H5	118.9	C21—C20—H20	119.7
C4—C5—H5	118.9	C22—C21—C20	121.9 (3)
C5—C6—C7	116.5 (3)	C22—C21—H21	119.1
C5—C6—H6	121.8	C20—C21—H21	119.1
C7—C6—H6	121.8	C23—C22—C21	116.4 (3)
N1—C7—C6	131.8 (2)	C23—C22—C25	122.7 (3)
N1—C7—C2	106.6 (2)	C21—C22—C25	120.8 (3)
C6—C7—C2	121.6 (2)	C22—C23—C24	121.9 (3)
N1—C8—C9	111.2 (2)	C22—C23—H23	119.1
N1—C8—H8A	109.4	C24—C23—H23	119.1
C9—C8—H8A	109.4	C19—C24—C23	120.4 (3)
N1—C8—H8B	109.4	C19—C24—H24	119.8
C9—C8—H8B	109.4	C23—C24—H24	119.8
H8A—C8—H8B	108.0	C27—C25—C26	109.6 (3)
C10—C9—C14	120.8 (2)	C27—C25—C28	110.0 (3)
C10—C9—C8	120.6 (2)	C26—C25—C28	107.1 (3)
C14—C9—C8	118.6 (2)	C27—C25—C22	108.2 (3)
C9—C10—C11	119.5 (3)	C26—C25—C22	110.5 (3)
C9—C10—H10	120.3	C28—C25—C22	111.5 (3)
C11—C10—H10	120.3	C25—C26—H26A	109.5
O1—C11—C12	114.9 (3)	C25—C26—H26B	109.5
O1—C11—C10	124.7 (3)	H26A—C26—H26B	109.5
C12—C11—C10	120.4 (3)	C25—C26—H26C	109.5
O2—C12—C11	120.2 (3)	H26A—C26—H26C	109.5
O2—C12—C13	120.0 (3)	H26B—C26—H26C	109.5
C11—C12—C13	119.6 (3)	C25—C27—H27A	109.5
O3—C13—C12	115.3 (3)	C25—C27—H27B	109.5
O3—C13—C14	124.1 (3)	H27A—C27—H27B	109.5
C12—C13—C14	120.6 (3)	C25—C27—H27C	109.5
C9—C14—C13	119.1 (3)	H27A—C27—H27C	109.5
C9—C14—H14	120.5	H27B—C27—H27C	109.5
C13—C14—H14	120.5	C25—C28—H28A	109.5
O1—C15—H15A	109.5	C25—C28—H28B	109.5
O1—C15—H15B	109.5	H28A—C28—H28B	109.5
H15A—C15—H15B	109.5	C25—C28—H28C	109.5
O1—C15—H15C	109.5	H28A—C28—H28C	109.5
H15A—C15—H15C	109.5	H28B—C28—H28C	109.5
H15B—C15—H15C	109.5	C11—O1—C15	117.4 (3)
O2—C16—H16A	109.5	C12—O2—C16	116.4 (3)
O2—C16—H16B	109.5	C13—O3—C17	117.6 (3)
H16A—C16—H16B	109.5	H4A—O4—H4B	110 (5)
O2—C16—H16C	109.5

C2—N2—C1—N1	−0.4 (3)	O2—C12—C13—O3	6.4 (4)
C18—N2—C1—N1	−177.7 (2)	C11—C12—C13—O3	−179.1 (3)
C7—N1—C1—N2	0.1 (3)	O2—C12—C13—C14	−173.2 (3)
C8—N1—C1—N2	175.6 (2)	C11—C12—C13—C14	1.4 (5)
C1—N2—C2—C3	179.0 (3)	C10—C9—C14—C13	−0.4 (4)
C18—N2—C2—C3	−3.8 (4)	C8—C9—C14—C13	−179.7 (3)
C1—N2—C2—C7	0.6 (3)	O3—C13—C14—C9	179.9 (3)
C18—N2—C2—C7	177.8 (2)	C12—C13—C14—C9	−0.5 (4)
N2—C2—C3—C4	−177.6 (3)	C1—N2—C18—C19	81.3 (3)
C7—C2—C3—C4	0.5 (4)	C2—N2—C18—C19	−95.5 (3)
C2—C3—C4—C5	−0.3 (4)	N2—C18—C19—C20	−86.2 (3)
C3—C4—C5—C6	−0.1 (5)	N2—C18—C19—C24	93.5 (3)
C4—C5—C6—C7	0.2 (4)	C24—C19—C20—C21	−0.5 (5)
C1—N1—C7—C6	−178.2 (3)	C18—C19—C20—C21	179.1 (3)
C8—N1—C7—C6	6.3 (4)	C19—C20—C21—C22	−0.3 (6)
C1—N1—C7—C2	0.3 (3)	C20—C21—C22—C23	0.8 (5)
C8—N1—C7—C2	−175.2 (2)	C20—C21—C22—C25	177.9 (3)
C5—C6—C7—N1	178.4 (3)	C21—C22—C23—C24	−0.6 (4)
C5—C6—C7—C2	0.0 (4)	C25—C22—C23—C24	−177.7 (3)
C3—C2—C7—N1	−179.1 (2)	C20—C19—C24—C23	0.7 (4)
N2—C2—C7—N1	−0.5 (2)	C18—C19—C24—C23	−178.9 (3)
C3—C2—C7—C6	−0.4 (4)	C22—C23—C24—C19	−0.1 (4)
N2—C2—C7—C6	178.2 (2)	C23—C22—C25—C27	98.5 (4)
C1—N1—C8—C9	−90.8 (3)	C21—C22—C25—C27	−78.4 (4)
C7—N1—C8—C9	84.0 (3)	C23—C22—C25—C26	−141.5 (3)
N1—C8—C9—C10	−100.3 (3)	C21—C22—C25—C26	41.6 (4)
N1—C8—C9—C14	78.9 (3)	C23—C22—C25—C28	−22.5 (4)
C14—C9—C10—C11	0.5 (4)	C21—C22—C25—C28	160.6 (3)
C8—C9—C10—C11	179.7 (2)	C12—C11—O1—C15	−175.0 (3)
C9—C10—C11—O1	−179.8 (3)	C10—C11—O1—C15	5.2 (5)
C9—C10—C11—C12	0.3 (4)	C11—C12—O2—C16	92.8 (4)
O1—C11—C12—O2	−6.6 (4)	C13—C12—O2—C16	−92.7 (4)
C10—C11—C12—O2	173.3 (3)	C12—C13—O3—C17	175.0 (4)
O1—C11—C12—C13	178.9 (3)	C14—C13—O3—C17	−5.5 (6)
C10—C11—C12—C13	−1.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···Br1ⁱ	0.87 (3)	2.54 (3)	3.393 (3)	169 (5)
O4—H4B···Br1ⁱⁱ	0.88 (5)	2.52 (5)	3.399 (3)	176 (5)
C1—H1···Br1	0.96	2.65	3.587 (3)	165
C3—H3···O2ⁱⁱⁱ	0.96	2.57	3.294 (4)	132
C6—H6···O4	0.96	2.38	3.305 (5)	161
C10—H10···O4	0.96	2.59	3.463 (5)	152
C14—H14···Br1	0.96	2.88	3.823 (3)	167
C18—H18A···Br1^iv	0.96	2.82	3.718 (3)	155

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

Experimental details

Crystal data
Chemical formula	C₂₈H₃₃N₂O₃⁺·Br⁻·H₂O
M_r	543.49
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.389 (2), 10.436 (2), 14.038 (3)
α, β, γ (°)	109.79 (3), 90.70 (3), 103.57 (3)
V (Å³)	1385.1 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.52
Crystal size (mm)	0.48 × 0.29 × 0.26

Data collection
Diffractometer	Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.514, 0.673
No. of measured, independent and observed [I > 2σ(I)] reflections	11938, 4860, 3921
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.112, 1.08
No. of reflections	4860
No. of parameters	328
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.55

Computer programs: CrystalClear (Rigaku/MSC, 2001), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···Br1ⁱ	0.87 (3)	2.54 (3)	3.393 (3)	169 (5)
O4—H4B···Br1ⁱⁱ	0.88 (5)	2.52 (5)	3.399 (3)	176 (5)
C1—H1···Br1	0.96	2.65	3.587 (3)	165
C3—H3···O2ⁱⁱⁱ	0.96	2.57	3.294 (4)	132
C6—H6···O4	0.96	2.38	3.305 (5)	161
C10—H10···O4	0.96	2.59	3.463 (5)	152
C14—H14···Br1	0.96	2.88	3.823 (3)	167
C18—H18A···Br1^iv	0.96	2.82	3.718 (3)	155

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

Acknowledgements

We thank the Technological and Scientific Research Council of Turkey TÜBİTAK-CNRS [TBAG-U/181 (106 T716)] and İnönü University Research Fund (İÜ BAP: 2008/Güdümlü 3) for financial support.

References

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Volume 65| Part 1| January 2009| Pages o208-o209

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

1-(4-tert-Butyl­benz­yl)-3-(3,4,5-tri­meth­oxy­benz­yl)benzimidazolium bromide monohydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-(4-tert-Butylbenzyl)-3-(3,4,5-trimethoxybenzyl)benzimidazolium bromide monohydrate