1,3-Bis(4-tert-butyl­benz­yl)-4,5-dihydro­imidazolium chloride monohydrate

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

doi:10.1107/S1600536809000452

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Pages o310-o311

doi:10.1107/S1600536809000452

Open

access

1,3-Bis(4-tert-butylbenzyl)-4,5-dihydroimidazolium chloride monohydrate

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

^aDepartment of Natural Sciences, Fayetteville State University, Fayetteville, NC 28301, USA, ^b Department 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, nönü University, Malatya, TR 44280, Turkey, and ^eDepartment of Chemistry, Faculty of Science, Ege University, Bornova-zmir, TR 35100, Turkey
^*Correspondence e-mail: hakan.arslan.acad@gmail.com

(Received 11 December 2008; accepted 6 January 2009; online 14 January 2009)

In the title compound, C₂₅H₃₅N₂⁺·Cl⁻·H₂O, the imidazolidine ring adopts a twisted conformation, with a pseudo-twofold axis passing through the N—C—N carbon and the opposite C—C bond. The N—C—N fragment of the imidazolidine ring shows some degree of both double- and single-bond character due to partial electron delocalization. One of the tert-butyl groups is disordered over two conformations with occupancies of 0.714 (8) and 0.286 (8). In the crystal, O—H⋯Cl and C—H⋯O hydrogen bonds help to establish the packing.

Related literature

For synthesis, see: Yaşar et al. (2008 ); Özdemir et al. (2004a , 2004b ). For general background, see: Herrmann et al. (1998 ); Glorius (2007 ); Nolan (2006 ). For related compounds, see: Arslan et al. (2009a ,b ) and references therein. For bond-length data, see: Allen et al. (1987 ). For puckering and asymmetry parameters, see: Cremer & Pople (1975 ); Nardelli (1983 ).

Experimental

Crystal data

C₂₅H₃₅N₂⁺·Cl⁻·H₂O
M_r = 417.02
Monoclinic, P 2₁ /c
a = 18.205 (4) Å
b = 10.148 (2) Å
c = 13.452 (3) Å
β = 100.01 (3)°
V = 2447.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 153 (2) K
0.43 × 0.17 × 0.05 mm

Data collection

Rigaku AFC 8S Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.929, T_max = 0.991
17800 measured reflections
4297 independent reflections
2886 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.207
S = 1.03
4297 reflections
299 parameters
50 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl1ⁱ	0.86 (4)	2.36 (4)	3.206 (3)	174 (4)
C3—H3B⋯O1ⁱⁱ	0.96	2.53	3.304 (4)	138
C17—H17⋯O1ⁱ	0.96	2.47	3.423 (5)	175
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2006 ); 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; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000452/hg2460sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809000452/hg2460Isup2.hkl

checkCIF report

Comment top

The first report of the application of N-heterocyclic carbenes compounds to various reactions was in 1998 (Herrmann et al., 1998). The metal complexes of N-heterocyclic carbene ligands have revealed excellent catalytic properties in a wide range of metal-catalyzed transformations such as Heck, Suzuki and Sonogashira couplings, Buchwald Hartwig amination, and olefin metathesis (Glorius, 2007; Nolan, 2006).

The use and characterization of an in situ formed imidazolidin-2-ylidene, tetrahydropyrimidin-2-ylidene, and the tetrahydrodiazepin-2-ylidene/palladium(II) system, which exhibits high activity in various coupling reactions of aryl bromides and aryl chlorides has been previously reported by our team (Yaşar et al., 2008; Arslan et al., 2009a, 2009b, and references therein). In order to obtain a more stable, efficient and active system, we have also investigated benzo-annelated derivatives (Özdemir et al., 2004a, 2004b; Yaşar et al., 2008). In the present work, we report the preparation and characterization of one of them, 1,3-bis(4-tert-butylbenzyl)-4,5-dihydroimidazolium chloride monohydrate, (I). The title compound was purified by re-crystallization from an ethanol:dichloromethane 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 Fig. 1. The crystal structure is composed of a 1,3-bis(4-tert-butylbenzyl)-4,5-dihydroimidazolium cation, a Cl^- anion and a water molecule. The imidazolidine ring adopts a twisted conformation with a pseudo-twofold axis passing through C1 and the C2—C3 bond. The puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameter (Nardelli, 1983) for the imidazolidine ring are q₂ = 0.073 (3) Å, ϕ₂= 306 (3)^oand ΔC₂(C1) = 0.1 (3), ΔC_s(C1) = 9.6 (3). The largest deviations from the mean plane of C1—N1—C3—C2—N2 ring are 0.044 (4) Å and 0.044 (3) Å for atom C2 and C3 atoms, respectively. One of the t-butyl groups is disordered over two conformations, with occupancies of 0.714 (8) and 0.286 (8).

The C—N bond lengths of N1—C1 and N2—C1 are shorter than the average single C—N bond length of 1.48 Å, being N1—C1 =1.319 (4) Å, N2—C1 = 1.312 (4) Å. The other C—N bond lengths (N1—C3 = 1.463 (4) Å, N2—C2 = 1.475 (4), N1—C4 = 1.458 (4) Å and N2—C15 = 1.449 (4) Å) are very close the average single C—N bond lengths. Therefore, we can easily say that the bonds in the N1—C1—N2 fragment of the imidazolidine ring are between double and single bond in character with partial electron delocalization. In addition, the sum of the bond angles around N1 (358.7°) and N2 (359.6°) indicate sp² hybridization. The other bond lengths in (I) are in the normal ranges (Allen et al., 1987).

The crystal packing is shown in Fig. 2. Although there are no intramolecular D—H···A contacts, intermolecular C—H···O and O—H···Cl hydrogen bonds link the molecules of (I) into one-dimensional chains extending along the [010] direction (Table 1).

Related literature top

For synthesis, see: Yaşar et al. (2008); Özdemir et al. (2004a, 2004b). For general background, see: Herrmann et al. (1998); Glorius (2007); Nolan (2006). For related compounds, see: Arslan et al. (2009a,b) and references therein. For bond-length data, see: Allen et al. (1987). For puckering and asymmetry parameters, see: Cremer & Pople (1975); Nardelli (1983).

Experimental top

The 4-tert-buthylbenzaldehyde (20 mmol) and the ethylenediamine (10 mmol) were stirred overnight in methanol. The diimine was collected as a white solid, filtrated and recrystallized in an alcohol/ether mixture. The diimine (10 mmol) was subsequently reduced by NaBH₄(30 mmol) in CH₃OH (30 ml). The solution was then treated with 1 N HCl, and the organic phase was extracted with CH₂Cl₂(3x30mL). After drying over MgSO₄ and evaporation, the diamine was isolated as a solid. The diamine was then treated in a large excess of triethylorthoformate (50 ml) in the presence of 10 mmol of NH₄Cl at 110 °C in a distillation apparatus until all of the ethanol was removed. Upon cooling to room temperature a colourless solid precipitated, which was collected by filtration and dried under vacuum. The crude product was recrystallized from absolute ethanol to give colourless needles and the solid was washed with diethyl ether (2x10 ml) and dried under vacuum. Yield: 3.53 g; 94%. M.p.: 294–295 °C; ν_(CN): 1669 cm^{-1. 1}H NMR (δ, CDCl₃): 1.24 (s, 18H, CH₂C₆H₄(CCH₃)₃-4), 3.73 (s, 4H, NCH₂CH₂N), 4.80 (s, 4H, CH₂C₆H₄(CCH₃)₃-4), 7.19–7.32 (m, 8H, CH₂C₆H₄(CCH₃)₃-4), 10.20 (s, 1H, NCHN). ¹³C NMR (δ, CDCl₃): 31.4 (CH₂C₆H₄(CCH₃)₃-4), 34.9 (CH₂C₆H₄(CCH₃)₃-4), 52.2 (CH₂C₆H₄(CCH₃)₃-4), 126.3, 128.9, 129.8 and 152.3 (CH₂C₆H₄(CCH₃)₃-4), 158.9 (NCHN). Anal. Calcd. for C₂₅H₃₅N₂Cl: C,75.25; H, 8.84; N, 7.02%. Found: C, 75.20; H, 8.83; N, 7.0%.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2006); cell refinement: CrystalClear (Rigaku/MSC, 2006); data reduction: CrystalClear (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); 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. The formation of the title compound.

1,3-Bis(4-tert-butylbenzyl)-4,5-dihydroimidazolium chloride monohydrate top

Crystal data top

C₂₅H₃₅N₂⁺·Cl⁻·H₂O	F(000) = 904
M_r = 417.02	D_x = 1.132 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5990 reflections
a = 18.205 (4) Å	θ = 2.3–26.7°
b = 10.148 (2) Å	µ = 0.17 mm⁻¹
c = 13.452 (3) Å	T = 153 K
β = 100.01 (3)°	Plate, colorless
V = 2447.3 (9) Å³	0.43 × 0.17 × 0.05 mm
Z = 4

Data collection top

Rigaku AFC 8S Mercury CCD diffractometer	4297 independent reflections
Radiation source: Sealed Tube	2886 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.072
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.0°, θ_min = 2.3°
ω scans	h = −15→21
Absorption correction: multi-scan (Jacobson, 1998)	k = −12→12
T_min = 0.929, T_max = 0.991	l = −16→16
17800 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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.207	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0868P)² + 3.6749P] where P = (F_o² + 2F_c²)/3
4297 reflections	(Δ/σ)_max < 0.001
299 parameters	Δρ_max = 0.28 e Å⁻³
50 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₅H₃₅N₂⁺·Cl⁻·H₂O	V = 2447.3 (9) Å³
M_r = 417.02	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.205 (4) Å	µ = 0.17 mm⁻¹
b = 10.148 (2) Å	T = 153 K
c = 13.452 (3) Å	0.43 × 0.17 × 0.05 mm
β = 100.01 (3)°

Data collection top

Rigaku AFC 8S Mercury CCD diffractometer	4297 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	2886 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.991	R_int = 0.072
17800 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	50 restraints
wR(F²) = 0.207	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.28 e Å⁻³
4297 reflections	Δρ_min = −0.26 e Å⁻³
299 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	0.55770 (5)	0.59372 (8)	0.69855 (6)	0.0407 (2)
C1	0.44642 (19)	0.3585 (3)	0.5584 (2)	0.0329 (7)
H1	0.4673	0.4424	0.5810	0.040*
C2	0.3626 (2)	0.2034 (3)	0.4864 (3)	0.0408 (8)
H2A	0.3513	0.1950	0.4143	0.049*
H2B	0.3225	0.1667	0.5152	0.049*
C3	0.43716 (19)	0.1369 (3)	0.5294 (2)	0.0348 (7)
H3A	0.4319	0.0779	0.5835	0.042*
H3B	0.4564	0.0890	0.4781	0.042*
C4	0.56104 (19)	0.2349 (3)	0.6223 (2)	0.0358 (8)
H4A	0.5607	0.1721	0.6756	0.043*
H4B	0.5765	0.3181	0.6530	0.043*
C5	0.61762 (19)	0.1916 (3)	0.5590 (2)	0.0328 (7)
C6	0.61032 (19)	0.2201 (3)	0.4561 (2)	0.0362 (8)
H6	0.5660	0.2627	0.4218	0.043*
C7	0.6664 (2)	0.1874 (4)	0.4035 (3)	0.0402 (8)
H7	0.6597	0.2071	0.3327	0.048*
C8	0.73238 (19)	0.1271 (3)	0.4493 (3)	0.0360 (8)
C9	0.7385 (2)	0.0989 (4)	0.5517 (3)	0.0422 (8)
H9	0.7831	0.0576	0.5863	0.051*
C10	0.6820 (2)	0.1288 (4)	0.6052 (3)	0.0433 (9)
H10	0.6877	0.1055	0.6753	0.052*
C11	0.7948 (2)	0.0960 (4)	0.3890 (3)	0.0421 (8)
C12	0.7640 (4)	0.0329 (9)	0.2899 (5)	0.073 (2)	0.714 (8)
H12A	0.7393	−0.0478	0.3016	0.109*	0.714 (8)
H12B	0.8039	0.0146	0.2538	0.109*	0.714 (8)
H12C	0.7289	0.0916	0.2508	0.109*	0.714 (8)
C12'	0.7917 (13)	−0.0488 (16)	0.367 (2)	0.109 (9)	0.286 (8)
H12D	0.7449	−0.0699	0.3251	0.164*	0.286 (8)
H12E	0.7963	−0.0969	0.4293	0.164*	0.286 (8)
H12F	0.8319	−0.0724	0.3328	0.164*	0.286 (8)
C13	0.8549 (4)	0.0036 (8)	0.4466 (5)	0.072 (2)	0.714 (8)
H13A	0.8746	0.0411	0.5112	0.108*	0.714 (8)
H13B	0.8944	−0.0073	0.4084	0.108*	0.714 (8)
H13C	0.8331	−0.0807	0.4559	0.108*	0.714 (8)
C13'	0.8687 (10)	0.148 (3)	0.4447 (14)	0.109 (10)	0.286 (8)
H13D	0.8605	0.1968	0.5031	0.164*	0.286 (8)
H13E	0.8905	0.2053	0.4008	0.164*	0.286 (8)
H13F	0.9017	0.0759	0.4654	0.164*	0.286 (8)
C14	0.8337 (4)	0.2256 (7)	0.3712 (7)	0.072 (2)	0.714 (8)
H14A	0.8539	0.2650	0.4350	0.108*	0.714 (8)
H14B	0.7982	0.2847	0.3332	0.108*	0.714 (8)
H14C	0.8732	0.2084	0.3341	0.108*	0.714 (8)
C14'	0.7827 (11)	0.1702 (19)	0.2853 (13)	0.080 (6)	0.286 (8)
H14D	0.7322	0.1582	0.2516	0.121*	0.286 (8)
H14E	0.8162	0.1355	0.2440	0.121*	0.286 (8)
H14F	0.7923	0.2625	0.2967	0.121*	0.286 (8)
C15	0.3209 (2)	0.4448 (4)	0.4915 (3)	0.0431 (9)
H15A	0.3039	0.4452	0.4198	0.052*
H15B	0.3433	0.5288	0.5102	0.052*
C16	0.2551 (2)	0.4253 (3)	0.5442 (3)	0.0377 (8)
C17	0.2655 (2)	0.4019 (5)	0.6469 (3)	0.0528 (10)
H17	0.3153	0.3980	0.6849	0.063*
C18	0.2052 (2)	0.3841 (5)	0.6957 (3)	0.0532 (11)
H18	0.2142	0.3690	0.7673	0.064*
C19	0.1325 (2)	0.3875 (3)	0.6443 (3)	0.0382 (8)
C20	0.1231 (2)	0.4119 (5)	0.5426 (3)	0.0550 (11)
H20	0.0734	0.4161	0.5043	0.066*
C21	0.1835 (2)	0.4307 (5)	0.4932 (3)	0.0549 (11)
H21	0.1746	0.4478	0.4219	0.066*
C22	0.0654 (2)	0.3722 (4)	0.6988 (3)	0.0459 (9)
C23	0.0852 (3)	0.2921 (5)	0.7956 (3)	0.0615 (11)
H23A	0.1047	0.2080	0.7805	0.092*
H23B	0.0414	0.2794	0.8251	0.092*
H23C	0.1221	0.3386	0.8424	0.092*
C24	0.0407 (3)	0.5107 (5)	0.7246 (4)	0.0754 (15)
H24A	−0.0034	0.5045	0.7543	0.113*
H24B	0.0303	0.5626	0.6641	0.113*
H24C	0.0798	0.5517	0.7714	0.113*
C25	0.0003 (2)	0.3024 (5)	0.6312 (4)	0.0649 (12)
H25A	0.0168	0.2187	0.6103	0.097*
H25B	−0.0170	0.3557	0.5729	0.097*
H25C	−0.0397	0.2892	0.6684	0.097*
N1	0.48540 (15)	0.2483 (3)	0.5661 (2)	0.0333 (6)
N2	0.37630 (16)	0.3421 (3)	0.5169 (2)	0.0353 (6)
O1	0.55870 (15)	0.5901 (2)	0.2126 (2)	0.0442 (6)
H1A	0.525 (2)	0.546 (4)	0.235 (3)	0.066*
H1B	0.556 (3)	0.6725 (19)	0.209 (3)	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0513 (5)	0.0360 (4)	0.0371 (4)	−0.0030 (4)	0.0140 (4)	−0.0004 (3)
C1	0.0419 (18)	0.0288 (16)	0.0323 (16)	−0.0043 (14)	0.0180 (14)	−0.0020 (13)
C2	0.0445 (19)	0.0341 (18)	0.047 (2)	−0.0023 (15)	0.0157 (16)	−0.0088 (15)
C3	0.0415 (19)	0.0288 (16)	0.0351 (17)	−0.0036 (14)	0.0090 (15)	−0.0034 (13)
C4	0.0428 (18)	0.0371 (18)	0.0269 (16)	−0.0023 (14)	0.0043 (14)	−0.0020 (13)
C5	0.0401 (18)	0.0248 (15)	0.0344 (17)	−0.0064 (13)	0.0090 (14)	−0.0005 (12)
C6	0.0362 (17)	0.0407 (18)	0.0309 (17)	0.0022 (14)	0.0040 (14)	0.0005 (14)
C7	0.046 (2)	0.046 (2)	0.0277 (17)	−0.0003 (16)	0.0047 (15)	−0.0005 (14)
C8	0.0364 (18)	0.0312 (17)	0.0402 (18)	−0.0057 (14)	0.0059 (15)	−0.0048 (13)
C9	0.043 (2)	0.047 (2)	0.0370 (19)	0.0046 (16)	0.0062 (15)	0.0041 (15)
C10	0.048 (2)	0.055 (2)	0.0267 (17)	0.0061 (17)	0.0065 (15)	0.0049 (15)
C11	0.0412 (19)	0.046 (2)	0.042 (2)	0.0009 (16)	0.0138 (16)	−0.0027 (16)
C12	0.063 (4)	0.099 (6)	0.059 (4)	0.001 (4)	0.019 (3)	−0.028 (4)
C12'	0.127 (18)	0.048 (10)	0.19 (2)	−0.011 (11)	0.117 (18)	−0.025 (12)
C13	0.059 (4)	0.091 (5)	0.073 (5)	0.039 (4)	0.030 (3)	0.012 (4)
C13'	0.047 (10)	0.22 (3)	0.065 (12)	−0.012 (14)	0.020 (9)	−0.004 (16)
C14	0.059 (4)	0.063 (4)	0.105 (6)	−0.009 (3)	0.045 (4)	0.004 (4)
C14'	0.099 (14)	0.085 (13)	0.071 (11)	0.030 (11)	0.054 (10)	0.024 (9)
C15	0.042 (2)	0.0412 (19)	0.047 (2)	0.0041 (15)	0.0108 (17)	0.0045 (16)
C16	0.0409 (19)	0.0320 (17)	0.0409 (19)	0.0025 (14)	0.0090 (15)	−0.0021 (14)
C17	0.0345 (19)	0.084 (3)	0.040 (2)	0.0040 (19)	0.0053 (16)	−0.0035 (19)
C18	0.040 (2)	0.084 (3)	0.0345 (19)	0.005 (2)	0.0060 (16)	−0.0025 (19)
C19	0.0384 (19)	0.0323 (17)	0.0443 (19)	0.0036 (14)	0.0082 (15)	−0.0051 (14)
C20	0.038 (2)	0.076 (3)	0.048 (2)	0.004 (2)	0.0007 (17)	0.011 (2)
C21	0.050 (2)	0.074 (3)	0.040 (2)	0.004 (2)	0.0046 (18)	0.0118 (19)
C22	0.041 (2)	0.041 (2)	0.058 (2)	0.0041 (16)	0.0158 (18)	0.0008 (17)
C23	0.062 (3)	0.066 (3)	0.062 (3)	−0.009 (2)	0.023 (2)	0.007 (2)
C24	0.080 (3)	0.052 (3)	0.109 (4)	0.010 (2)	0.058 (3)	−0.001 (3)
C25	0.045 (2)	0.069 (3)	0.079 (3)	−0.010 (2)	0.007 (2)	0.012 (2)
N1	0.0390 (15)	0.0285 (13)	0.0340 (14)	−0.0035 (11)	0.0107 (12)	−0.0051 (11)
N2	0.0404 (16)	0.0305 (14)	0.0373 (15)	−0.0010 (12)	0.0130 (12)	−0.0010 (11)
O1	0.0508 (15)	0.0368 (13)	0.0481 (15)	−0.0018 (12)	0.0171 (12)	0.0024 (11)

Geometric parameters (Å, º) top

C1—N2	1.312 (4)	C13—H13C	0.9600
C1—N1	1.319 (4)	C13'—H13D	0.9600
C1—H1	0.9600	C13'—H13E	0.9600
C2—N2	1.475 (4)	C13'—H13F	0.9600
C2—C3	1.536 (5)	C14—H14A	0.9600
C2—H2A	0.9600	C14—H14B	0.9600
C2—H2B	0.9600	C14—H14C	0.9600
C3—N1	1.463 (4)	C14'—H14D	0.9600
C3—H3A	0.9600	C14'—H14E	0.9600
C3—H3B	0.9600	C14'—H14F	0.9600
C4—N1	1.458 (4)	C15—N2	1.449 (4)
C4—C5	1.511 (5)	C15—C16	1.506 (5)
C4—H4A	0.9600	C15—H15A	0.9600
C4—H4B	0.9600	C15—H15B	0.9600
C5—C10	1.383 (5)	C16—C21	1.365 (5)
C5—C6	1.398 (5)	C16—C17	1.381 (5)
C6—C7	1.380 (5)	C17—C18	1.386 (6)
C6—H6	0.9600	C17—H17	0.9600
C7—C8	1.392 (5)	C18—C19	1.383 (5)
C7—H7	0.9600	C18—H18	0.9600
C8—C9	1.392 (5)	C19—C20	1.372 (5)
C8—C11	1.539 (5)	C19—C22	1.538 (5)
C9—C10	1.387 (5)	C20—C21	1.393 (6)
C9—H9	0.9600	C20—H20	0.9600
C10—H10	0.9600	C21—H21	0.9600
C11—C12	1.497 (7)	C22—C23	1.525 (6)
C11—C12'	1.498 (16)	C22—C24	1.534 (6)
C11—C13'	1.517 (18)	C22—C25	1.535 (6)
C11—C14	1.532 (7)	C23—H23A	0.9599
C11—C13	1.544 (7)	C23—H23B	0.9599
C11—C14'	1.567 (15)	C23—H23C	0.9599
C12—H12A	0.9600	C24—H24A	0.9599
C12—H12B	0.9600	C24—H24B	0.9599
C12—H12C	0.9600	C24—H24C	0.9599
C12'—H12D	0.9600	C25—H25A	0.9599
C12'—H12E	0.9600	C25—H25B	0.9599
C12'—H12F	0.9600	C25—H25C	0.9599
C13—H13A	0.9600	O1—H1A	0.85 (3)
C13—H13B	0.9600	O1—H1B	0.839 (18)

N2—C1—N1	113.4 (3)	H13D—C13'—H13E	109.5
N2—C1—H1	123.3	C11—C13'—H13F	109.5
N1—C1—H1	123.3	H13D—C13'—H13F	109.5
N2—C2—C3	102.7 (3)	H13E—C13'—H13F	109.5
N2—C2—H2A	111.2	C11—C14—H14A	109.5
C3—C2—H2A	111.2	C11—C14—H14B	109.5
N2—C2—H2B	111.2	H14A—C14—H14B	109.5
C3—C2—H2B	111.2	C11—C14—H14C	109.5
H2A—C2—H2B	109.1	H14A—C14—H14C	109.5
N1—C3—C2	103.1 (3)	H14B—C14—H14C	109.5
N1—C3—H3A	111.1	C11—C14'—H14D	109.5
C2—C3—H3A	111.1	C11—C14'—H14E	109.5
N1—C3—H3B	111.1	H14D—C14'—H14E	109.5
C2—C3—H3B	111.1	C11—C14'—H14F	109.5
H3A—C3—H3B	109.1	H14D—C14'—H14F	109.5
N1—C4—C5	114.2 (3)	H14E—C14'—H14F	109.5
N1—C4—H4A	108.7	N2—C15—C16	111.9 (3)
C5—C4—H4A	108.7	N2—C15—H15A	109.2
N1—C4—H4B	108.7	C16—C15—H15A	109.2
C5—C4—H4B	108.7	N2—C15—H15B	109.2
H4A—C4—H4B	107.6	C16—C15—H15B	109.2
C10—C5—C6	117.9 (3)	H15A—C15—H15B	107.9
C10—C5—C4	119.2 (3)	C21—C16—C17	117.6 (4)
C6—C5—C4	122.8 (3)	C21—C16—C15	121.7 (3)
C7—C6—C5	120.4 (3)	C17—C16—C15	120.7 (3)
C7—C6—H6	119.8	C16—C17—C18	120.9 (4)
C5—C6—H6	119.8	C16—C17—H17	119.5
C6—C7—C8	122.5 (3)	C18—C17—H17	119.5
C6—C7—H7	118.8	C19—C18—C17	121.9 (4)
C8—C7—H7	118.8	C19—C18—H18	119.1
C9—C8—C7	116.2 (3)	C17—C18—H18	119.1
C9—C8—C11	122.7 (3)	C20—C19—C18	116.5 (4)
C7—C8—C11	121.1 (3)	C20—C19—C22	121.4 (3)
C10—C9—C8	122.0 (3)	C18—C19—C22	122.0 (3)
C10—C9—H9	119.0	C19—C20—C21	121.9 (4)
C8—C9—H9	119.0	C19—C20—H20	119.1
C5—C10—C9	121.0 (3)	C21—C20—H20	119.1
C5—C10—H10	119.5	C16—C21—C20	121.3 (4)
C9—C10—H10	119.5	C16—C21—H21	119.4
C12'—C11—C13'	116.1 (15)	C20—C21—H21	119.4
C12—C11—C14	109.9 (5)	C23—C22—C24	109.3 (4)
C12—C11—C8	111.1 (4)	C23—C22—C25	107.7 (3)
C12'—C11—C8	107.4 (8)	C24—C22—C25	109.3 (4)
C13'—C11—C8	109.9 (8)	C23—C22—C19	111.8 (3)
C14—C11—C8	108.1 (4)	C24—C22—C19	107.7 (3)
C12—C11—C13	108.1 (5)	C25—C22—C19	111.1 (3)
C14—C11—C13	107.1 (5)	C22—C23—H23A	109.5
C8—C11—C13	112.6 (4)	C22—C23—H23B	109.5
C12'—C11—C14'	107.6 (13)	H23A—C23—H23B	109.5
C13'—C11—C14'	104.3 (12)	C22—C23—H23C	109.5
C8—C11—C14'	111.6 (7)	H23A—C23—H23C	109.5
C11—C12—H12A	109.5	H23B—C23—H23C	109.5
C11—C12—H12B	109.5	C22—C24—H24A	109.5
H12A—C12—H12B	109.5	C22—C24—H24B	109.5
C11—C12—H12C	109.5	H24A—C24—H24B	109.5
H12A—C12—H12C	109.5	C22—C24—H24C	109.5
H12B—C12—H12C	109.5	H24A—C24—H24C	109.5
C11—C12'—H12D	109.5	H24B—C24—H24C	109.5
C11—C12'—H12E	109.5	C22—C25—H25A	109.5
H12D—C12'—H12E	109.5	C22—C25—H25B	109.5
C11—C12'—H12F	109.5	H25A—C25—H25B	109.5
H12D—C12'—H12F	109.5	C22—C25—H25C	109.5
H12E—C12'—H12F	109.5	H25A—C25—H25C	109.5
C11—C13—H13A	109.5	H25B—C25—H25C	109.5
C11—C13—H13B	109.5	C1—N1—C4	124.5 (3)
H13A—C13—H13B	109.5	C1—N1—C3	110.2 (3)
C11—C13—H13C	109.5	C4—N1—C3	124.1 (3)
H13A—C13—H13C	109.5	C1—N2—C15	126.6 (3)
H13B—C13—H13C	109.5	C1—N2—C2	110.1 (3)
C11—C13'—H13D	109.5	C15—N2—C2	122.9 (3)
C11—C13'—H13E	109.5	H1A—O1—H1B	120 (5)

N2—C2—C3—N1	−7.2 (3)	C15—C16—C17—C18	179.9 (4)
N1—C4—C5—C10	−155.8 (3)	C16—C17—C18—C19	0.7 (7)
N1—C4—C5—C6	28.6 (4)	C17—C18—C19—C20	−1.2 (6)
C10—C5—C6—C7	−0.8 (5)	C17—C18—C19—C22	−178.0 (4)
C4—C5—C6—C7	174.8 (3)	C18—C19—C20—C21	0.8 (6)
C5—C6—C7—C8	−0.8 (5)	C22—C19—C20—C21	177.6 (4)
C6—C7—C8—C9	1.1 (5)	C17—C16—C21—C20	−0.7 (6)
C6—C7—C8—C11	−178.1 (3)	C15—C16—C21—C20	179.7 (4)
C7—C8—C9—C10	0.2 (5)	C19—C20—C21—C16	0.2 (7)
C11—C8—C9—C10	179.3 (3)	C20—C19—C22—C23	156.2 (4)
C6—C5—C10—C9	2.1 (5)	C18—C19—C22—C23	−27.1 (5)
C4—C5—C10—C9	−173.7 (3)	C20—C19—C22—C24	−83.8 (5)
C8—C9—C10—C5	−1.8 (6)	C18—C19—C22—C24	92.9 (5)
C9—C8—C11—C12	134.6 (5)	C20—C19—C22—C25	35.9 (5)
C7—C8—C11—C12	−46.3 (6)	C18—C19—C22—C25	−147.4 (4)
C9—C8—C11—C12'	77.5 (13)	N2—C1—N1—C4	−170.4 (3)
C7—C8—C11—C12'	−103.5 (13)	N2—C1—N1—C3	−2.6 (4)
C9—C8—C11—C13'	−49.7 (13)	C5—C4—N1—C1	−120.4 (3)
C7—C8—C11—C13'	129.4 (13)	C5—C4—N1—C3	73.4 (4)
C9—C8—C11—C14	−104.8 (5)	C2—C3—N1—C1	6.3 (3)
C7—C8—C11—C14	74.3 (5)	C2—C3—N1—C4	174.2 (3)
C9—C8—C11—C13	13.3 (6)	N1—C1—N2—C15	−175.2 (3)
C7—C8—C11—C13	−167.7 (5)	N1—C1—N2—C2	−2.6 (4)
C9—C8—C11—C14'	−164.9 (9)	C16—C15—N2—C1	−121.4 (4)
C7—C8—C11—C14'	14.2 (10)	C16—C15—N2—C2	66.8 (4)
N2—C15—C16—C21	−130.9 (4)	C3—C2—N2—C1	6.2 (4)
N2—C15—C16—C17	49.5 (5)	C3—C2—N2—C15	179.2 (3)
C21—C16—C17—C18	0.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1ⁱ	0.86 (4)	2.36 (4)	3.206 (3)	174 (4)
C3—H3B···O1ⁱⁱ	0.96	2.53	3.304 (4)	138
C17—H17···O1ⁱ	0.96	2.47	3.423 (5)	175

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

Experimental details

Crystal data
Chemical formula	C₂₅H₃₅N₂⁺·Cl⁻·H₂O
M_r	417.02
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	153
a, b, c (Å)	18.205 (4), 10.148 (2), 13.452 (3)
β (°)	100.01 (3)
V (Å³)	2447.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.43 × 0.17 × 0.05

Data collection
Diffractometer	Rigaku AFC 8S Mercury CCD diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.929, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	17800, 4297, 2886
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.207, 1.03
No. of reflections	4297
No. of parameters	299
No. of restraints	50
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.26

Computer programs: CrystalClear (Rigaku/MSC, 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1ⁱ	0.86 (4)	2.36 (4)	3.206 (3)	174 (4)
C3—H3B···O1ⁱⁱ	0.96	2.53	3.304 (4)	138
C17—H17···O1ⁱ	0.96	2.47	3.423 (5)	175

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

Acknowledgements

We thank the Technological and Scientific Research Council of Turkey TÜBİTAK-CNRS [TBAG-U/181 (106 T716)] and İnönü University Research Fund (BAP: 2008-Güdümlü3) for financial support.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Arslan, H., VanDerveer, D., Gök, Y., Özdemir, I. & Çetinkaya, B. (2009a). Acta Cryst. E65, o109–o110. Web of Science CSD CrossRef IUCr Journals Google Scholar
Arslan, H., VanDerveer, D., Yaşar, S., Özdemir, İ. & Çetinkaya, B. (2009b). Acta Cryst. E65, o121–o122. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Glorius, F. (2007). Topics in Organometallic Chemistry Vol. 21, N-Heterocyclic Carbenes in Transition Metal Catalysis. Heidelberg: Springer. Google Scholar
Herrmann, W. A., Reisinger, C. P. & Spiegler, M. (1998). J. Organomet. Chem. 557, 93–96. CAS Google Scholar
Jacobson, R. (1998). REQAB. Molecular Structure Corporation, The Woodlands, Texas, USA. Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Nolan, S. P. (2006). N-Heterocyclic Carbenes in Synthesis. Weinheim: Wiley. Google Scholar
Özdemir, I., Alıcı, B., Gürbüz, N., Çetinkaya, E. & Çetinkaya, B. (2004b). J. Mol. Catal. A Chem. 217, 37–40. Google Scholar
Özdemir, I., Gök, Y., Gürbüz, N., Çetinkaya, E. & Çetinkaya, B. (2004a). Heteroat. Chem. 15, 419–423. Google Scholar
Rigaku/MSC (2006). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yaşar, S., Özdemir, I., Çetinkaya, B., Renaud, J. L. & Bruneau, C. (2008). Eur. J. Org. Chem. 12, 2142–2149. Google Scholar