Crystal structure of 1,3-bis-(4-methyl-benz-yl)-1H-1,3-benzimidazol-3-ium bromide monohydrate.

In the title hydrated symetrically substituted 1,3-bis-(4-methyl-benz-yl)benzimidazolium salt, C23H23N2 (+)·Br(-)·H2O, the dihedral angles between the benzimidazole ring system (r.m.s. deviation = 0.003 Å) and the pendant benzene rings are 73.18 (16) and 77.52 (16)°. Both benzene rings lie to the same side of the benzimidazole ring system, giving the cation an overall U-shape. In the crystal, the cation is linked to the water mol-ecule by a short C-H⋯O hydrogen bond and the water mol-ecule forms O-H⋯Br hydrogen bonds. Together, these inter-actions lead to [010] chains. The packing is consolidated by C-H⋯Br hydrogen bonds and aromatic π-π stacking inter-actions [centroid-centroid distances = 3.5401 (17) and 3.8815 (18) Å], generating a three-dimensional network.

Related literature

For general background to N-heterocyclic carbenes (NHCs), which have been frequently used as ligands in organometallic and coordination chemistry, see: Arduengo et al. (1991 ▸); Akkoç & Gök (2013 ▸); Akkoç et al. (2014 ▸); Berding et al. (2009 ▸); Gök et al. (2014 ▸). For related structures, see: Akkurt et al. (2011 ▸, 2012 ▸).

Experimental

Crystal data

C23H23N2 +·Br−·H2O

M = 425.35

Triclinic,

a = 9.3846 (3) Å

b = 9.7174 (3) Å

c = 12.5603 (4) Å

α = 76.405 (2)°

β = 84.739 (2)°

γ = 72.696 (2)°

V = 1062.65 (6) Å3

Z = 2

Mo Kα radiation

μ = 1.95 mm−1

T = 296 K

0.15 × 0.10 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer

22302 measured reflections

4342 independent reflections

3144 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.135

S = 1.06

4342 reflections

252 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.15 e Å−3

Δρmin = −0.49 e Å−3

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014025857/hb7325sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025857/hb7325Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989014025857/hb7325Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989014025857/hb7325fig1.tif

Perspective view of the mol­ecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

Click here for additional data file.

a . DOI: 10.1107/S2056989014025857/hb7325fig2.tif

View of the hydrogen bonding and mol­ecular packing of the title compound along a axis. Only H atoms involved in H bonding are shown.

CCDC reference: 1036037

Additional supporting information: crystallographic information; 3D view; checkCIF report

C23H23N2+·Br−·H2O	Z = 2
Mr = 425.35	F(000) = 440
Triclinic, P1	Dx = 1.329 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3846 (3) Å	Cell parameters from 7459 reflections
b = 9.7174 (3) Å	θ = 2.3–27.0°
c = 12.5603 (4) Å	µ = 1.95 mm−1
α = 76.405 (2)°	T = 296 K
β = 84.739 (2)°	Plane, colourless
γ = 72.696 (2)°	0.15 × 0.10 × 0.06 mm
V = 1062.65 (6) Å3

Bruker APEXII CCD diffractometer	3144 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.035
Graphite monochromator	θmax = 26.4°, θmin = 1.7°
φ and ω scans	h = −11→11
22302 measured reflections	k = −12→12
4342 independent reflections	l = −15→15

Refinement on F2	2 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.048	w = 1/[σ2(Fo2) + (0.0735P)2 + 0.2354P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.135	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 1.15 e Å−3
4342 reflections	Δρmin = −0.49 e Å−3
252 parameters

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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.

	x	y	z	Uiso*/Ueq
Br1	0.15363 (4)	0.70096 (4)	0.47065 (3)	0.0746 (2)
N1	0.2897 (3)	0.1364 (3)	0.36229 (18)	0.0512 (8)
N2	0.4267 (3)	0.2795 (2)	0.37164 (18)	0.0501 (8)
C1	0.5241 (3)	0.1441 (3)	0.3623 (2)	0.0474 (8)
C2	0.6799 (4)	0.0955 (4)	0.3603 (3)	0.0597 (11)
C3	0.7420 (4)	−0.0495 (4)	0.3526 (3)	0.0730 (12)
C4	0.6544 (4)	−0.1407 (4)	0.3469 (3)	0.0714 (13)
C5	0.5022 (4)	−0.0930 (3)	0.3487 (2)	0.0601 (10)
C6	0.4383 (3)	0.0537 (3)	0.3562 (2)	0.0484 (9)
C7	0.2888 (3)	0.2699 (3)	0.3712 (2)	0.0532 (9)
C8	0.4673 (4)	0.4144 (3)	0.3749 (3)	0.0599 (11)
C9	0.4849 (3)	0.5039 (3)	0.2621 (3)	0.0543 (10)
C10	0.3662 (4)	0.5668 (4)	0.1937 (3)	0.0768 (14)
C11	0.3829 (5)	0.6477 (4)	0.0897 (3)	0.0781 (12)
C12	0.5159 (5)	0.6716 (4)	0.0512 (3)	0.0731 (14)
C13	0.6324 (5)	0.6105 (6)	0.1209 (4)	0.0969 (17)
C14	0.6195 (4)	0.5281 (5)	0.2240 (4)	0.0828 (16)
C15	0.5316 (6)	0.7626 (6)	−0.0641 (4)	0.1146 (19)
C16	0.1558 (4)	0.0910 (4)	0.3505 (3)	0.0629 (11)
C17	0.1196 (3)	0.1227 (3)	0.2314 (3)	0.0552 (10)
C18	0.1778 (4)	0.0197 (4)	0.1693 (3)	0.0744 (14)
C19	0.1519 (5)	0.0524 (5)	0.0591 (3)	0.0863 (17)
C20	0.0658 (4)	0.1912 (5)	0.0063 (3)	0.0724 (14)
C21	0.0054 (5)	0.2899 (4)	0.0696 (3)	0.0795 (16)
C22	0.0303 (4)	0.2586 (4)	0.1806 (3)	0.0724 (12)
C23	0.0438 (6)	0.2267 (7)	−0.1146 (3)	0.110 (2)
O1	−0.0190 (4)	0.5308 (3)	0.3474 (2)	0.0850 (11)
H2	0.73790	0.15690	0.36400	0.0720*
H3	0.84540	−0.08750	0.35110	0.0880*
H4	0.70140	−0.23780	0.34160	0.0850*
H5	0.44440	−0.15460	0.34530	0.0720*
H7	0.20290	0.34660	0.37630	0.0640*
H8A	0.56020	0.38660	0.41330	0.0720*
H8B	0.39050	0.47440	0.41540	0.0720*
H10	0.27300	0.55480	0.21780	0.0920*
H11	0.30080	0.68710	0.04450	0.0940*
H13	0.72460	0.62560	0.09750	0.1160*
H14	0.70230	0.48810	0.26850	0.0990*
H15A	0.49850	0.86580	−0.06310	0.1710*
H15B	0.47190	0.74250	−0.11340	0.1710*
H15C	0.63430	0.73670	−0.08800	0.1710*
H16A	0.07180	0.14440	0.38980	0.0760*
H16B	0.17390	−0.01380	0.38180	0.0760*
H18	0.23590	−0.07390	0.20220	0.0890*
H19	0.19270	−0.01960	0.01880	0.1030*
H21	−0.05540	0.38250	0.03730	0.0950*
H22	−0.01330	0.32970	0.22130	0.0870*
H23A	−0.02220	0.17570	−0.13060	0.1660*
H23B	0.13840	0.19600	−0.15140	0.1660*
H23C	0.00120	0.33120	−0.13950	0.1660*
H1W	−0.069 (5)	0.490 (6)	0.395 (4)	0.1280*
H2W	0.017 (6)	0.582 (5)	0.374 (4)	0.1280*

	U11	U22	U33	U12	U13	U23
Br1	0.0632 (3)	0.0626 (2)	0.1010 (3)	−0.0181 (2)	0.0024 (2)	−0.0249 (2)
N1	0.0516 (14)	0.0507 (14)	0.0456 (13)	−0.0114 (11)	0.0027 (10)	−0.0053 (11)
N2	0.0516 (14)	0.0446 (13)	0.0468 (13)	−0.0021 (11)	−0.0055 (10)	−0.0095 (10)
C1	0.0533 (16)	0.0431 (14)	0.0398 (14)	−0.0032 (13)	−0.0048 (12)	−0.0097 (12)
C2	0.0523 (18)	0.0612 (19)	0.0595 (18)	−0.0036 (15)	−0.0088 (14)	−0.0147 (15)
C3	0.057 (2)	0.075 (2)	0.072 (2)	0.0122 (18)	−0.0080 (16)	−0.0248 (18)
C4	0.082 (3)	0.0510 (18)	0.067 (2)	0.0066 (18)	−0.0042 (18)	−0.0176 (16)
C5	0.076 (2)	0.0452 (16)	0.0528 (18)	−0.0091 (15)	−0.0026 (15)	−0.0087 (13)
C6	0.0527 (16)	0.0470 (15)	0.0345 (14)	−0.0045 (13)	0.0010 (12)	−0.0009 (12)
C7	0.0515 (17)	0.0480 (16)	0.0491 (16)	−0.0014 (13)	0.0014 (13)	−0.0071 (13)
C8	0.0619 (19)	0.0480 (16)	0.069 (2)	−0.0058 (14)	−0.0113 (15)	−0.0205 (15)
C9	0.0537 (17)	0.0420 (15)	0.069 (2)	−0.0103 (13)	−0.0042 (14)	−0.0187 (14)
C10	0.0524 (19)	0.074 (2)	0.089 (3)	−0.0164 (17)	−0.0051 (17)	0.010 (2)
C11	0.073 (2)	0.074 (2)	0.079 (2)	−0.0242 (19)	−0.0078 (19)	0.006 (2)
C12	0.079 (3)	0.058 (2)	0.083 (2)	−0.0247 (18)	0.017 (2)	−0.0174 (18)
C13	0.072 (3)	0.115 (3)	0.111 (3)	−0.051 (3)	0.018 (2)	−0.015 (3)
C14	0.057 (2)	0.092 (3)	0.103 (3)	−0.027 (2)	−0.012 (2)	−0.017 (2)
C15	0.140 (4)	0.101 (3)	0.096 (3)	−0.049 (3)	0.037 (3)	−0.005 (3)
C16	0.0608 (19)	0.066 (2)	0.060 (2)	−0.0262 (16)	0.0099 (15)	−0.0038 (16)
C17	0.0481 (16)	0.0573 (18)	0.0625 (19)	−0.0224 (14)	0.0055 (14)	−0.0104 (15)
C18	0.080 (2)	0.060 (2)	0.081 (3)	−0.0076 (18)	−0.0144 (19)	−0.0222 (18)
C19	0.086 (3)	0.095 (3)	0.085 (3)	−0.017 (2)	−0.001 (2)	−0.045 (2)
C20	0.068 (2)	0.092 (3)	0.065 (2)	−0.039 (2)	−0.0019 (17)	−0.011 (2)
C21	0.084 (3)	0.067 (2)	0.081 (3)	−0.020 (2)	−0.017 (2)	0.000 (2)
C22	0.073 (2)	0.064 (2)	0.074 (2)	−0.0070 (18)	−0.0038 (18)	−0.0185 (18)
C23	0.112 (4)	0.165 (5)	0.069 (3)	−0.072 (3)	−0.004 (2)	−0.012 (3)
O1	0.102 (2)	0.0815 (19)	0.0707 (17)	−0.0267 (15)	−0.0048 (14)	−0.0135 (14)

N1—C6	1.393 (4)	C21—C22	1.382 (5)
N1—C7	1.326 (4)	C2—H2	0.9300
N1—C16	1.480 (5)	C3—H3	0.9300
N2—C1	1.385 (4)	C4—H4	0.9300
N2—C7	1.326 (4)	C5—H5	0.9300
N2—C8	1.480 (4)	C7—H7	0.9300
C1—C2	1.396 (5)	C8—H8A	0.9700
C1—C6	1.375 (4)	C8—H8B	0.9700
C2—C3	1.378 (5)	C10—H10	0.9300
C3—C4	1.393 (5)	C11—H11	0.9300
C4—C5	1.364 (5)	C13—H13	0.9300
C5—C6	1.395 (4)	C14—H14	0.9300
C8—C9	1.501 (5)	C15—H15A	0.9600
C9—C10	1.370 (5)	C15—H15B	0.9600
C9—C14	1.376 (5)	C15—H15C	0.9600
C10—C11	1.379 (5)	C16—H16A	0.9700
C11—C12	1.362 (7)	C16—H16B	0.9700
C12—C13	1.364 (7)	C18—H18	0.9300
C12—C15	1.529 (6)	C19—H19	0.9300
C13—C14	1.369 (7)	C21—H21	0.9300
C16—C17	1.504 (5)	C22—H22	0.9300
C17—C18	1.368 (5)	C23—H23A	0.9600
C17—C22	1.377 (5)	C23—H23B	0.9600
C18—C19	1.373 (5)	C23—H23C	0.9600
C19—C20	1.393 (6)	O1—H1W	0.83 (5)
C20—C21	1.351 (6)	O1—H2W	0.82 (5)
C20—C23	1.496 (5)
C6—N1—C7	107.4 (3)	C5—C4—H4	119.00
C6—N1—C16	127.1 (3)	C4—C5—H5	122.00
C7—N1—C16	125.2 (3)	C6—C5—H5	122.00
C1—N2—C7	107.8 (2)	N1—C7—H7	125.00
C1—N2—C8	126.7 (3)	N2—C7—H7	125.00
C7—N2—C8	125.5 (2)	N2—C8—H8A	109.00
N2—C1—C2	130.8 (3)	N2—C8—H8B	109.00
N2—C1—C6	107.0 (3)	C9—C8—H8A	109.00
C2—C1—C6	122.3 (3)	C9—C8—H8B	109.00
C1—C2—C3	115.6 (3)	H8A—C8—H8B	108.00
C2—C3—C4	121.9 (4)	C9—C10—H10	120.00
C3—C4—C5	122.5 (3)	C11—C10—H10	120.00
C4—C5—C6	116.1 (3)	C10—C11—H11	119.00
N1—C6—C1	106.9 (3)	C12—C11—H11	119.00
N1—C6—C5	131.3 (3)	C12—C13—H13	119.00
C1—C6—C5	121.8 (3)	C14—C13—H13	119.00
N1—C7—N2	110.9 (3)	C9—C14—H14	120.00
N2—C8—C9	112.0 (3)	C13—C14—H14	120.00
C8—C9—C10	121.0 (3)	C12—C15—H15A	109.00
C8—C9—C14	121.6 (3)	C12—C15—H15B	109.00
C10—C9—C14	117.4 (4)	C12—C15—H15C	109.00
C9—C10—C11	120.9 (4)	H15A—C15—H15B	110.00
C10—C11—C12	122.0 (4)	H15A—C15—H15C	109.00
C11—C12—C13	116.4 (4)	H15B—C15—H15C	110.00
C11—C12—C15	121.1 (4)	N1—C16—H16A	110.00
C13—C12—C15	122.5 (4)	N1—C16—H16B	110.00
C12—C13—C14	122.8 (4)	C17—C16—H16A	110.00
C9—C14—C13	120.4 (4)	C17—C16—H16B	110.00
N1—C16—C17	110.1 (3)	H16A—C16—H16B	108.00
C16—C17—C18	121.3 (3)	C17—C18—H18	120.00
C16—C17—C22	120.8 (3)	C19—C18—H18	119.00
C18—C17—C22	117.9 (3)	C18—C19—H19	119.00
C17—C18—C19	121.0 (4)	C20—C19—H19	119.00
C18—C19—C20	121.5 (4)	C20—C21—H21	119.00
C19—C20—C21	116.7 (3)	C22—C21—H21	119.00
C19—C20—C23	120.7 (4)	C17—C22—H22	120.00
C21—C20—C23	122.7 (4)	C21—C22—H22	120.00
C20—C21—C22	122.5 (4)	C20—C23—H23A	110.00
C17—C22—C21	120.4 (3)	C20—C23—H23B	109.00
C1—C2—H2	122.00	C20—C23—H23C	109.00
C3—C2—H2	122.00	H23A—C23—H23B	109.00
C2—C3—H3	119.00	H23A—C23—H23C	109.00
C4—C3—H3	119.00	H23B—C23—H23C	109.00
C3—C4—H4	119.00	H1W—O1—H2W	109 (5)
C7—N1—C6—C1	0.2 (3)	C4—C5—C6—C1	−0.5 (4)
C16—N1—C6—C1	174.8 (3)	N2—C8—C9—C14	−117.1 (4)
C7—N1—C6—C5	178.4 (3)	N2—C8—C9—C10	64.0 (4)
C16—N1—C6—C5	−7.0 (5)	C8—C9—C14—C13	−179.8 (4)
C6—N1—C7—N2	−0.2 (3)	C8—C9—C10—C11	−179.3 (3)
C16—N1—C7—N2	−174.9 (3)	C14—C9—C10—C11	1.7 (5)
C6—N1—C16—C17	−85.5 (4)	C10—C9—C14—C13	−0.9 (6)
C7—N1—C16—C17	88.2 (3)	C9—C10—C11—C12	−1.5 (6)
C1—N2—C8—C9	86.2 (3)	C10—C11—C12—C15	−179.6 (4)
C7—N2—C8—C9	−89.9 (3)	C10—C11—C12—C13	0.3 (6)
C7—N2—C1—C6	0.1 (3)	C11—C12—C13—C14	0.6 (7)
C8—N2—C1—C6	−176.6 (3)	C15—C12—C13—C14	−179.6 (5)
C7—N2—C1—C2	−179.0 (3)	C12—C13—C14—C9	−0.3 (8)
C8—N2—C1—C2	4.4 (5)	N1—C16—C17—C18	90.4 (4)
C1—N2—C7—N1	0.1 (3)	N1—C16—C17—C22	−87.5 (4)
C8—N2—C7—N1	176.8 (3)	C16—C17—C18—C19	−175.9 (4)
N2—C1—C2—C3	178.5 (3)	C22—C17—C18—C19	2.1 (6)
C2—C1—C6—C5	0.6 (4)	C16—C17—C22—C21	175.9 (4)
N2—C1—C6—C5	−178.5 (2)	C18—C17—C22—C21	−2.1 (5)
C6—C1—C2—C3	−0.5 (5)	C17—C18—C19—C20	0.1 (7)
C2—C1—C6—N1	179.0 (3)	C18—C19—C20—C21	−2.1 (7)
N2—C1—C6—N1	−0.2 (3)	C18—C19—C20—C23	177.6 (4)
C1—C2—C3—C4	0.2 (5)	C19—C20—C21—C22	2.0 (7)
C2—C3—C4—C5	−0.1 (6)	C23—C20—C21—C22	−177.6 (4)
C3—C4—C5—C6	0.2 (5)	C20—C21—C22—C17	0.0 (7)
C4—C5—C6—N1	−178.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···Br1i	0.83 (5)	2.47 (5)	3.261 (3)	162 (5)
O1—H2W···Br1	0.82 (5)	2.51 (5)	3.318 (3)	171 (4)
C7—H7···O1	0.93	2.30	3.210 (4)	166
C8—H8B···Br1	0.97	2.79	3.730 (3)	163
C16—H16A···Br1i	0.97	2.91	3.875 (4)	173
C16—H16B···Br1ii	0.97	2.79	3.741 (4)	167

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O1H1WBr1i	0.83(5)	2.47(5)	3.261(3)	162(5)
O1H2WBr1	0.82(5)	2.51(5)	3.318(3)	171(4)
C7H7O1	0.93	2.30	3.210(4)	166
C8H8BBr1	0.97	2.79	3.730(3)	163
C16H16ABr1i	0.97	2.91	3.875(4)	173
C16H16BBr1ii	0.97	2.79	3.741(4)	167

Symmetry codes: (i) ; (ii) .