1,3-Bis[4-(meth­oxy­carbon­yl)benz­yl]benzimidazolium bromide monohydrate

Huang, H.-R.; Wen-Jiao, G.; Du, Z.-Y.; Fang, Y.-X.; Zhang, K.

doi:10.1107/S1600536810041929

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3064

https://doi.org/10.1107/S1600536810041929

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1,3-Bis[4-(methoxycarbonyl)benzyl]benzimidazolium bromide monohydrate

Hua-Rong Huang,^a ^* Guo Wen-Jiao,^a Zhi-Yun Du,^a Yan-Xiong Fang ^a and Kun Zhang ^a

^aGuangdong University of Technology, Faculty of Chemical Engineering and Light Industry, Guangzhou 510006, Guangdong, People's Republic of China
^*Correspondence e-mail: corihhr@yahoo.cn

(Received 6 October 2010; accepted 16 October 2010; online 6 November 2010)

In the title compound, C₂₅H₂₃N₂O₄⁺·Br⁻·H₂O, the dihedral angles between the benzimidazole ring system and the two benzene rings are 87.77 (11) and 63.05 (11)°; the dihedral angle between the two benzene rings is 66.25 (13)°. The crystal structure exhibits C—H⋯O and O—H⋯Br interactions; it is also stabilized by π–π stacking interactions, with a face-to-face separation of 3.456 Å between parallel benzimidazole ring systems.

Related literature

For general background to and the therapeutic properties of benzimidazole derivatives, see: Herrmann (2002 ); Herrmann et al. (1995 , 1998 ); Navarro et al. (2006 ). For related structures, see: Akkurt et al. (2005 ); Pınar et al. (2006 ); Arslan et al. (2009 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₅H₂₃N₂O₄⁺·Br⁻·H₂O
M_r = 513.38
Monoclinic, P 2₁ /c
a = 13.604 (2) Å
b = 9.3537 (16) Å
c = 18.962 (3) Å
β = 107.006 (3)°
V = 2307.4 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.82 mm⁻¹
T = 110 K
0.39 × 0.36 × 0.35 mm

Data collection

Bruker SMART CCD 1K area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.537, T_max = 0.568
13524 measured reflections
5002 independent reflections
3422 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.096
S = 1.05
5002 reflections
300 parameters
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1W	0.95	2.14	3.083 (3)	175
O1W—H1A⋯Br1	0.85	2.49	3.332 (2)	173
O1W—H1B⋯Br1ⁱ	0.84	2.43	3.269 (2)	173
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810041929/wn2412sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041929/wn2412Isup2.hkl

checkCIF report

Comment top

As a new class of compounds in organometallic chemistry, N-heterocyclic carbenes have attracted much interest; they have often been applied as catalysts for Suzuki-Miyura, Sonogashira, Stille and Heck reactions (Herrmann, 2002; Herrmann et al., 1995; Navarro et al., 2006).

In this work, we report the structure of a new N-heterocyclic carbene derivative, 1,3-bis(4-(methoxycarbonyl)benzyl)benzimidazolium bromide monohydrate. The molecular structure of the title compound is depicted in Fig. 1. All bond lengths are in normal ranges (Allen et al.,1987).

The dihedral angles between the benzimidazole ring system and the two (C9–C14) and (C18–C23) benzene rings are 87.77 (11)° and 63.05 (11)°, respectively; the dihedral angle between the two benzene rings is 66.25 (13)°.

The bromide anions and water molecules form infinite meso-helical chains parallel to the b axis via O—H···Br hydrogen bonds, and the cations are linked to water molecules by C—H···O hydrogen bonds (Fig. 2, Table 1). In the crystal structure, π–π stacking interactions occurs between parallel benzimidazole rings, with a face-to-face separation of 3.456 Å (Fig. 2).

The crystal structures of three very similar benzimidazolium halide monohydrates have been published in recent years (Akkurt et al., 2005; Pınar et al., 2006; Arslan et al., 2009;),

Related literature top

For general background to and the therapeutic properties of benzimidazole derivatives, see: Herrmann (2002); Herrmann et al. (1995, 1998); Navarro et al. (2006). For related structures, see: Akkurt et al. (2005); Pınar et al. (2006); Arslan et al. (2009). For reference bond lengths, see: Allen et al. (1987).

Experimental top

4-(Methoxycarbonyl)benzyl bromide (2.28 g, 10.0 mmol) was slowly added to a solution of benzimidazole (0.59 g, 5.0 mmol) in acetone (25 ml) and the resulting mixture was stirred under reflux for over a period of of 24 h. The volume of solvent was concentrated by ca 10 ml and then cooled to rt. The resulting precipitate was collected, washed with acetone, and dried to afford a white powder. The crude product was recrystallized from methanol/water. Yield 1.81 g, 73.2%. Elemental analysis, calcd (%) for C₂₅H₂₅N₂BrO₅: C 58.49, H 4.91; found(%): C 58.52, H 4.85. The FAB mass spectrum showed ions at 496.

Structure description top

The crystal structures of three very similar benzimidazolium halide monohydrates have been published in recent years (Akkurt et al., 2005; Pınar et al., 2006; Arslan et al., 2009;),

For general background to and the therapeutic properties of benzimidazole derivatives, see: Herrmann (2002); Herrmann et al. (1995, 1998); Navarro et al. (2006). For related structures, see: Akkurt et al. (2005); Pınar et al. (2006); Arslan et al. (2009). For reference bond lengths, see: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective view showing 30% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen atoms have been omitted.
	Fig. 2. Crystal packing of the title compound. Dashed lines indicate hydrogen bonds. Symmetry: A = -x + 1, y - 1/2, -z + 3/2; B = -x + 1, y + 1/2, -z + 3/2. H atoms not involved in the hydrogen bond interactions have been omitted for clarity.

1,3-Bis[4-(methoxycarbonyl)benzyl]benzimidazolium bromide monohydrate top

Crystal data top

C₂₅H₂₃N₂O₄⁺·Br⁻·H₂O	F(000) = 1056
M_r = 513.38	D_x = 1.478 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3740 reflections
a = 13.604 (2) Å	θ = 2.3–26.8°
b = 9.3537 (16) Å	µ = 1.82 mm⁻¹
c = 18.962 (3) Å	T = 110 K
β = 107.006 (3)°	Block, colorless
V = 2307.4 (7) Å³	0.39 × 0.36 × 0.35 mm
Z = 4

Data collection top

Bruker SMART CCD 1K area-detector diffractometer	5002 independent reflections
Radiation source: fine-focus sealed tube	3422 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
φ and ω scans	θ_max = 27.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→15
T_min = 0.537, T_max = 0.568	k = −11→11
13524 measured reflections	l = −18→24

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0417P)² + 0.4447P] where P = (F_o² + 2F_c²)/3
5002 reflections	(Δ/σ)_max < 0.001
300 parameters	Δρ_max = 0.78 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₂₅H₂₃N₂O₄⁺·Br⁻·H₂O	V = 2307.4 (7) Å³
M_r = 513.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.604 (2) Å	µ = 1.82 mm⁻¹
b = 9.3537 (16) Å	T = 110 K
c = 18.962 (3) Å	0.39 × 0.36 × 0.35 mm
β = 107.006 (3)°

Data collection top

Bruker SMART CCD 1K area-detector diffractometer	5002 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3422 reflections with I > 2σ(I)
T_min = 0.537, T_max = 0.568	R_int = 0.046
13524 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.05	Δρ_max = 0.78 e Å⁻³
5002 reflections	Δρ_min = −0.35 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	0.51077 (2)	0.40648 (3)	0.834559 (16)	0.02439 (10)
C1	0.6347 (2)	0.3275 (3)	0.63706 (15)	0.0175 (6)
H1	0.6346	0.2667	0.6772	0.021*
C2	0.6389 (2)	0.5212 (3)	0.57082 (15)	0.0145 (6)
C3	0.63019 (19)	0.4021 (3)	0.52566 (14)	0.0137 (6)
C4	0.6237 (2)	0.4155 (3)	0.45119 (15)	0.0178 (6)
H4	0.6179	0.3347	0.4198	0.021*
C5	0.6263 (2)	0.5528 (3)	0.42594 (16)	0.0233 (7)
H5	0.6223	0.5668	0.3756	0.028*
C6	0.6346 (2)	0.6733 (3)	0.47144 (16)	0.0214 (7)
H6	0.6357	0.7658	0.4511	0.026*
C7	0.6410 (2)	0.6601 (3)	0.54498 (16)	0.0201 (7)
H7	0.6466	0.7410	0.5762	0.024*
C8	0.6423 (2)	0.5565 (3)	0.70503 (15)	0.0200 (7)
H8A	0.6190	0.4961	0.7399	0.024*
H8B	0.5916	0.6346	0.6886	0.024*
C9	0.7443 (2)	0.6214 (3)	0.74563 (15)	0.0175 (6)
C10	0.8378 (2)	0.5707 (3)	0.74080 (15)	0.0198 (7)
H10	0.8398	0.4923	0.7094	0.024*
C11	0.9281 (2)	0.6342 (3)	0.78168 (16)	0.0209 (7)
H11	0.9919	0.5990	0.7780	0.025*
C12	0.9273 (2)	0.7487 (3)	0.82806 (15)	0.0172 (6)
C13	0.8336 (2)	0.7982 (3)	0.83393 (16)	0.0229 (7)
H13	0.8317	0.8746	0.8665	0.027*
C14	0.7432 (2)	0.7356 (3)	0.79225 (16)	0.0237 (7)
H14	0.6793	0.7713	0.7955	0.028*
C15	1.0268 (2)	0.8163 (3)	0.86905 (16)	0.0202 (7)
C16	1.1068 (2)	0.9863 (4)	0.96014 (18)	0.0311 (8)
H16A	1.1500	0.9130	0.9913	0.047*
H16B	1.0889	1.0592	0.9914	0.047*
H16C	1.1443	1.0309	0.9290	0.047*
C17	0.6111 (2)	0.1329 (3)	0.54368 (16)	0.0180 (6)
H17A	0.5744	0.1315	0.4902	0.022*
H17B	0.5669	0.0846	0.5696	0.022*
C18	0.7096 (2)	0.0511 (3)	0.55708 (16)	0.0183 (6)
C19	0.7559 (2)	−0.0094 (3)	0.62603 (16)	0.0198 (7)
H19	0.7242	0.0011	0.6643	0.024*
C20	0.8467 (2)	−0.0841 (3)	0.63950 (16)	0.0203 (6)
H20	0.8774	−0.1250	0.6867	0.024*
C21	0.8938 (2)	−0.0994 (3)	0.58324 (17)	0.0221 (7)
C22	0.8476 (2)	−0.0409 (3)	0.51461 (17)	0.0246 (7)
H22	0.8788	−0.0526	0.4762	0.029*
C23	0.7567 (2)	0.0343 (3)	0.50129 (17)	0.0238 (7)
H23	0.7260	0.0747	0.4540	0.029*
C24	0.9937 (2)	−0.1754 (3)	0.5955 (2)	0.0281 (8)
C25	1.1340 (2)	−0.2807 (4)	0.6830 (2)	0.0410 (9)
H25A	1.1294	−0.3672	0.6531	0.061*
H25B	1.1572	−0.3061	0.7354	0.061*
H25C	1.1832	−0.2141	0.6720	0.061*
N1	0.64248 (17)	0.4697 (2)	0.64073 (12)	0.0159 (5)
N2	0.62711 (17)	0.2832 (2)	0.56895 (12)	0.0150 (5)
O1	1.10918 (15)	0.7850 (2)	0.86183 (11)	0.0258 (5)
O2	1.01338 (14)	0.9206 (2)	0.91378 (11)	0.0246 (5)
O3	1.03392 (18)	−0.1982 (3)	0.54791 (14)	0.0406 (6)
O4	1.03454 (16)	−0.2138 (2)	0.66612 (12)	0.0312 (5)
O1W	0.63208 (16)	0.1475 (2)	0.77270 (11)	0.0273 (5)
H1A	0.5960	0.2114	0.7851	0.041*
H1B	0.5933	0.0829	0.7485	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02588 (17)	0.02610 (17)	0.02259 (17)	0.00320 (15)	0.00927 (12)	0.00488 (14)
C1	0.0135 (15)	0.0212 (16)	0.0173 (16)	0.0022 (12)	0.0037 (12)	0.0028 (13)
C2	0.0114 (14)	0.0154 (15)	0.0157 (15)	−0.0003 (11)	0.0027 (11)	0.0001 (12)
C3	0.0089 (13)	0.0144 (13)	0.0162 (14)	−0.0020 (12)	0.0012 (10)	0.0015 (12)
C4	0.0184 (15)	0.0191 (15)	0.0160 (14)	−0.0049 (13)	0.0052 (11)	−0.0032 (13)
C5	0.0225 (16)	0.0270 (17)	0.0200 (16)	−0.0031 (13)	0.0054 (13)	0.0037 (13)
C6	0.0181 (16)	0.0179 (16)	0.0272 (17)	−0.0026 (13)	0.0054 (13)	0.0061 (13)
C7	0.0178 (16)	0.0163 (15)	0.0261 (17)	−0.0013 (12)	0.0065 (13)	−0.0001 (13)
C8	0.0220 (16)	0.0240 (16)	0.0159 (15)	0.0011 (13)	0.0087 (12)	−0.0054 (12)
C9	0.0186 (15)	0.0216 (16)	0.0140 (15)	−0.0008 (12)	0.0073 (12)	0.0011 (12)
C10	0.0236 (16)	0.0175 (15)	0.0183 (15)	0.0029 (13)	0.0062 (12)	−0.0007 (12)
C11	0.0163 (15)	0.0210 (16)	0.0259 (17)	0.0043 (12)	0.0069 (13)	0.0042 (13)
C12	0.0175 (15)	0.0193 (15)	0.0142 (14)	−0.0014 (12)	0.0040 (12)	0.0016 (12)
C13	0.0238 (17)	0.0246 (17)	0.0218 (17)	−0.0007 (13)	0.0091 (13)	−0.0083 (13)
C14	0.0150 (15)	0.0323 (18)	0.0256 (17)	0.0026 (13)	0.0084 (13)	−0.0106 (14)
C15	0.0177 (16)	0.0213 (16)	0.0213 (16)	0.0019 (13)	0.0051 (12)	0.0041 (13)
C16	0.0222 (18)	0.041 (2)	0.0300 (19)	−0.0085 (15)	0.0067 (14)	−0.0140 (16)
C17	0.0208 (16)	0.0119 (14)	0.0199 (16)	−0.0027 (12)	0.0039 (12)	−0.0001 (12)
C18	0.0184 (15)	0.0118 (14)	0.0246 (16)	−0.0042 (12)	0.0060 (12)	−0.0025 (12)
C19	0.0216 (16)	0.0175 (15)	0.0223 (16)	−0.0033 (13)	0.0097 (13)	−0.0007 (13)
C20	0.0196 (15)	0.0146 (14)	0.0248 (16)	−0.0036 (13)	0.0033 (12)	−0.0004 (13)
C21	0.0208 (15)	0.0135 (14)	0.0333 (18)	−0.0008 (13)	0.0100 (13)	−0.0006 (14)
C22	0.0268 (17)	0.0201 (16)	0.0306 (18)	−0.0003 (14)	0.0145 (14)	−0.0017 (14)
C23	0.0291 (18)	0.0193 (16)	0.0238 (17)	0.0008 (14)	0.0089 (14)	0.0044 (13)
C24	0.0225 (17)	0.0198 (17)	0.045 (2)	−0.0019 (14)	0.0142 (16)	0.0007 (15)
C25	0.0204 (18)	0.034 (2)	0.064 (3)	0.0094 (16)	0.0054 (17)	−0.0011 (19)
N1	0.0152 (13)	0.0175 (12)	0.0161 (13)	0.0005 (10)	0.0061 (10)	−0.0024 (10)
N2	0.0146 (12)	0.0133 (12)	0.0163 (13)	−0.0014 (10)	0.0029 (10)	0.0017 (10)
O1	0.0178 (12)	0.0253 (12)	0.0345 (13)	0.0012 (9)	0.0077 (9)	−0.0024 (10)
O2	0.0154 (10)	0.0332 (13)	0.0247 (11)	−0.0023 (10)	0.0050 (8)	−0.0103 (10)
O3	0.0364 (14)	0.0392 (15)	0.0547 (17)	0.0107 (12)	0.0267 (13)	0.0050 (12)
O4	0.0196 (11)	0.0291 (12)	0.0432 (15)	0.0067 (10)	0.0065 (10)	0.0029 (11)
O1W	0.0282 (12)	0.0296 (12)	0.0249 (12)	−0.0060 (10)	0.0092 (10)	−0.0058 (10)

Geometric parameters (Å, º) top

C1—N2	1.331 (3)	C15—O1	1.205 (3)
C1—N1	1.334 (3)	C15—O2	1.340 (3)
C1—H1	0.9500	C16—O2	1.453 (3)
C2—C3	1.389 (4)	C16—H16A	0.9800
C2—C7	1.392 (4)	C16—H16B	0.9800
C2—N1	1.398 (3)	C16—H16C	0.9800
C3—N2	1.390 (3)	C17—N2	1.481 (3)
C3—C4	1.394 (4)	C17—C18	1.499 (4)
C4—C5	1.375 (4)	C17—H17A	0.9900
C4—H4	0.9500	C17—H17B	0.9900
C5—C6	1.403 (4)	C18—C19	1.394 (4)
C5—H5	0.9500	C18—C23	1.396 (4)
C6—C7	1.377 (4)	C19—C20	1.378 (4)
C6—H6	0.9500	C19—H19	0.9500
C7—H7	0.9500	C20—C21	1.403 (4)
C8—N1	1.466 (3)	C20—H20	0.9500
C8—C9	1.504 (4)	C21—C22	1.382 (4)
C8—H8A	0.9900	C21—C24	1.490 (4)
C8—H8B	0.9900	C22—C23	1.381 (4)
C9—C10	1.385 (4)	C22—H22	0.9500
C9—C14	1.390 (4)	C23—H23	0.9500
C10—C11	1.381 (4)	C24—O3	1.204 (4)
C10—H10	0.9500	C24—O4	1.340 (4)
C11—C12	1.388 (4)	C25—O4	1.439 (4)
C11—H11	0.9500	C25—H25A	0.9800
C12—C13	1.391 (4)	C25—H25B	0.9800
C12—C15	1.490 (4)	C25—H25C	0.9800
C13—C14	1.382 (4)	O1W—H1A	0.8490
C13—H13	0.9500	O1W—H1B	0.8441
C14—H14	0.9500

N2—C1—N1	110.0 (3)	O2—C16—H16A	109.5
N2—C1—H1	125.0	O2—C16—H16B	109.5
N1—C1—H1	125.0	H16A—C16—H16B	109.5
C3—C2—C7	122.6 (3)	O2—C16—H16C	109.5
C3—C2—N1	106.3 (2)	H16A—C16—H16C	109.5
C7—C2—N1	131.1 (3)	H16B—C16—H16C	109.5
C2—C3—N2	106.8 (2)	N2—C17—C18	112.9 (2)
C2—C3—C4	121.4 (2)	N2—C17—H17A	109.0
N2—C3—C4	131.8 (2)	C18—C17—H17A	109.0
C5—C4—C3	115.9 (3)	N2—C17—H17B	109.0
C5—C4—H4	122.1	C18—C17—H17B	109.0
C3—C4—H4	122.1	H17A—C17—H17B	107.8
C4—C5—C6	122.8 (3)	C19—C18—C23	118.9 (3)
C4—C5—H5	118.6	C19—C18—C17	120.1 (3)
C6—C5—H5	118.6	C23—C18—C17	121.0 (3)
C7—C6—C5	121.4 (3)	C20—C19—C18	120.9 (3)
C7—C6—H6	119.3	C20—C19—H19	119.5
C5—C6—H6	119.3	C18—C19—H19	119.5
C6—C7—C2	116.0 (3)	C19—C20—C21	119.7 (3)
C6—C7—H7	122.0	C19—C20—H20	120.2
C2—C7—H7	122.0	C21—C20—H20	120.2
N1—C8—C9	115.1 (2)	C22—C21—C20	119.5 (3)
N1—C8—H8A	108.5	C22—C21—C24	118.6 (3)
C9—C8—H8A	108.5	C20—C21—C24	121.9 (3)
N1—C8—H8B	108.5	C23—C22—C21	120.7 (3)
C9—C8—H8B	108.5	C23—C22—H22	119.7
H8A—C8—H8B	107.5	C21—C22—H22	119.7
C10—C9—C14	119.1 (3)	C22—C23—C18	120.2 (3)
C10—C9—C8	123.8 (3)	C22—C23—H23	119.9
C14—C9—C8	117.1 (2)	C18—C23—H23	119.9
C11—C10—C9	120.0 (3)	O3—C24—O4	123.7 (3)
C11—C10—H10	120.0	O3—C24—C21	124.2 (3)
C9—C10—H10	120.0	O4—C24—C21	112.2 (3)
C10—C11—C12	121.1 (3)	O4—C25—H25A	109.5
C10—C11—H11	119.4	O4—C25—H25B	109.5
C12—C11—H11	119.4	H25A—C25—H25B	109.5
C11—C12—C13	119.0 (3)	O4—C25—H25C	109.5
C11—C12—C15	118.9 (3)	H25A—C25—H25C	109.5
C13—C12—C15	122.1 (3)	H25B—C25—H25C	109.5
C14—C13—C12	119.8 (3)	C1—N1—C2	108.3 (2)
C14—C13—H13	120.1	C1—N1—C8	125.2 (2)
C12—C13—H13	120.1	C2—N1—C8	126.1 (2)
C13—C14—C9	121.0 (3)	C1—N2—C3	108.5 (2)
C13—C14—H14	119.5	C1—N2—C17	124.8 (2)
C9—C14—H14	119.5	C3—N2—C17	126.5 (2)
O1—C15—O2	123.5 (3)	C15—O2—C16	115.7 (2)
O1—C15—C12	124.8 (3)	C24—O4—C25	115.3 (3)
O2—C15—C12	111.6 (2)	H1A—O1W—H1B	109.6

C7—C2—C3—N2	−178.0 (2)	C19—C20—C21—C22	−0.9 (4)
N1—C2—C3—N2	0.9 (3)	C19—C20—C21—C24	178.2 (3)
C7—C2—C3—C4	0.5 (4)	C20—C21—C22—C23	1.1 (4)
N1—C2—C3—C4	179.4 (2)	C24—C21—C22—C23	−178.0 (3)
C2—C3—C4—C5	−0.1 (4)	C21—C22—C23—C18	−0.6 (4)
N2—C3—C4—C5	177.9 (3)	C19—C18—C23—C22	−0.2 (4)
C3—C4—C5—C6	−0.2 (4)	C17—C18—C23—C22	179.8 (3)
C4—C5—C6—C7	0.2 (4)	C22—C21—C24—O3	−5.4 (5)
C5—C6—C7—C2	0.1 (4)	C20—C21—C24—O3	175.5 (3)
C3—C2—C7—C6	−0.4 (4)	C22—C21—C24—O4	173.7 (3)
N1—C2—C7—C6	−179.1 (3)	C20—C21—C24—O4	−5.3 (4)
N1—C8—C9—C10	−20.6 (4)	N2—C1—N1—C2	0.5 (3)
N1—C8—C9—C14	161.6 (3)	N2—C1—N1—C8	173.9 (2)
C14—C9—C10—C11	−0.4 (4)	C3—C2—N1—C1	−0.9 (3)
C8—C9—C10—C11	−178.1 (3)	C7—C2—N1—C1	177.9 (3)
C9—C10—C11—C12	0.1 (4)	C3—C2—N1—C8	−174.2 (2)
C10—C11—C12—C13	1.0 (4)	C7—C2—N1—C8	4.6 (5)
C10—C11—C12—C15	−178.0 (3)	C9—C8—N1—C1	108.2 (3)
C11—C12—C13—C14	−1.8 (4)	C9—C8—N1—C2	−79.5 (3)
C15—C12—C13—C14	177.2 (3)	N1—C1—N2—C3	0.1 (3)
C12—C13—C14—C9	1.6 (5)	N1—C1—N2—C17	−176.2 (2)
C10—C9—C14—C13	−0.5 (4)	C2—C3—N2—C1	−0.7 (3)
C8—C9—C14—C13	177.4 (3)	C4—C3—N2—C1	−178.9 (3)
C11—C12—C15—O1	4.8 (4)	C2—C3—N2—C17	175.5 (2)
C13—C12—C15—O1	−174.2 (3)	C4—C3—N2—C17	−2.7 (5)
C11—C12—C15—O2	−177.2 (2)	C18—C17—N2—C1	−86.9 (3)
C13—C12—C15—O2	3.9 (4)	C18—C17—N2—C3	97.5 (3)
N2—C17—C18—C19	83.0 (3)	O1—C15—O2—C16	−6.2 (4)
N2—C17—C18—C23	−96.9 (3)	C12—C15—O2—C16	175.7 (2)
C23—C18—C19—C20	0.4 (4)	O3—C24—O4—C25	2.5 (5)
C17—C18—C19—C20	−179.6 (3)	C21—C24—O4—C25	−176.6 (3)
C18—C19—C20—C21	0.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1W	0.95	2.14	3.083 (3)	175
O1W—H1A···Br1	0.85	2.49	3.332 (2)	173
O1W—H1B···Br1ⁱ	0.84	2.43	3.269 (2)	173

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₂₅H₂₃N₂O₄⁺·Br⁻·H₂O
M_r	513.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	110
a, b, c (Å)	13.604 (2), 9.3537 (16), 18.962 (3)
β (°)	107.006 (3)
V (Å³)	2307.4 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.82
Crystal size (mm)	0.39 × 0.36 × 0.35

Data collection
Diffractometer	Bruker SMART CCD 1K area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.537, 0.568
No. of measured, independent and observed [I > 2σ(I)] reflections	13524, 5002, 3422
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.096, 1.05
No. of reflections	5002
No. of parameters	300
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.35

Computer programs: SMART (Bruker, 1999), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1W	0.95	2.14	3.083 (3)	174.7
O1W—H1A···Br1	0.85	2.49	3.332 (2)	172.6
O1W—H1B···Br1ⁱ	0.84	2.43	3.269 (2)	172.6

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Acknowledgements

This work was funded by the 211 project of Guangdong Province.

References

Akkurt, M., Karaca, S., Küçükbay, H., Orhan, E. & Büyükgüngör, O. (2005). Acta Cryst. E61, o2452–o2454. Web of Science CSD CrossRef IUCr Journals Google Scholar
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. CSD CrossRef Web of Science Google Scholar
Arslan, H., VanDerveer, D., Demir, S., Özdemir, İ. & Çetinkaya, B. (2009). Acta Cryst. E65, o208–o209. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (1999). SMART and SAINT-Plus. Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Herrmann, W. A. (2002). Angew. Chem. Int. Ed. 41, 1290–1309. Web of Science CrossRef CAS Google Scholar
Herrmann, W. A., Elison, M., Fischer, J., Köcher, C. & Artus, G. R. J. (1995). Angew. Chem. Int. Ed. Engl. 34, 2371–2374. CrossRef CAS Web of Science Google Scholar
Herrmann, W. A., Reisinger, C. P. & Spiegler, M. (1998). J. Organomet. Chem. 557, 93–96. CAS Google Scholar
Navarro, O., Marion, N., Oonishi, Y., Kelly, R. A. & Nolan, S. P. (2006). J. Org. Chem. 71, 685–692. Web of Science CrossRef PubMed CAS Google Scholar
Pınar, Ş., Akkurt, M., Küçükbay, H., Şireci, N. & Büyükgüngör, O. (2006). Acta Cryst. E62, o2223–o2225. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar