(E)-1,1′-Bis[(E)-but-2-en­yl]-3,3′-(propane-1,3-di­yl)bis­(1H-benzimidazol-3-ium) dibromide monohydrate

Akkurt, M.; Yıldırım, S.Ö.; Şireci, N.; Küçükbay, H.; Büyükgüngör, O.

doi:10.1107/S160053680803095X

(E)-1,1′-Bis[(E)-but-2-enyl]-3,3′-(propane-1,3-diyl)bis(1H-benzimidazol-3-ium) dibromide monohydrate

M. Akkurt, S. Ö. Yıldırım, N. Şireci, H. Küçükbay and O. Büyükgüngör

The title compound, C₂₅H₃₀N₄²⁺·2Br⁻·H₂O, was synthesized from 1,1′-propylenedibenzimidazole and (E)-1-bromobut-2-ene in dimethylformamide solution. The two benzimidazole ring systems are essentially planar, with maximum deviations of 0.011 (4) and 0.023 (3) Å. The dihedral angle between these two ring systems is 25.87 (15)°. The crystal structure is stabilized by intermolecular O—H

Br and C—H

Br hydrogen-bonding interactions. Atmospheric water was incorporated into the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680803095X/sj2540sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680803095X/sj2540Isup2.hkl Contains datablock I

CCDC reference: 709372

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.009 Å
R factor = 0.054
wR factor = 0.124
Data-to-parameter ratio = 20.8

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT220_ALERT_2_A Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       8.87 Ratio

Author Response: The -CH2CHCHCH3 groups show high thermal parameters but they were not refinable in terms of disordered substituents.

PLAT222_ALERT_3_A Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       9.61 Ratio

Author Response: The -CH2CHCHCH3 groups show high thermal parameters but they were not refinable in terms of disordered substituents.


Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         C4
PLAT362_ALERT_2_B Short  C(sp3)-C(sp2) Bond  C1     -   C2     ...       1.27 Ang.

Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT213_ALERT_2_C Atom C1      has ADP max/min Ratio .............       3.10 prola
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9
PLAT368_ALERT_2_C Short  C(sp2)-C(sp2) Bond  C2     -   C3     ...       1.16 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  Br1    ..  C21     ..       3.34 Ang.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        800 Deg.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C1
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C25
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels ..........          2

   2 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In the light of the general importance of benzimidazole compounds, the study of bisbenzimidazoles and their related derivatives has remained an active area of research despite extensive investigation. They are present in various naturally occurring drugs such as omeprazole, astemizole and emedastine difumarate (Sakai et al., 1989). Substituted benzimidazole compounds are established pharmacophores in parasitic chemotheraphy. They also show antiviral (Tidwell et al., 1993), antimicrobial (Küçükbay et al., 1995; Küçükbay et al., 2001), antitumor (Turner and Denny, 1996), antihistaminic, anticoagulant and anti-inflammatory activities (Hall et al., 1998). The objective of this study was to elucidate the crystal structure of the title compound (I) and to compare the results obtained with our previous studies on related bis-benzimidazole compounds (Öztürk et al., 2003; Akkurt et al., 2003; Akkurt et al., 2006).

In (I) (Fig. 1), the bond lengths and angles are generally within normal ranges (Allen et al., 1987). The two benzimidazole ring systems of (I), A (N1/N2/C5–C11) and B (N3/N4/C15–C21), are essentially planar, with maximum deviations of 0.011 (4) Å for C10 and -0.10 (5) Å for C11 in A, and 0.023 (3) Å for N3 and 0.016 (5) Å for C19 in B. The dihedral angle between these two ring systems A and B is 25.87 (15) °. This angle is 31.84 (11)° in 3,30-bis(cyclohexylmethyl)- 1,10-propylenedibenzimidazolium dibromide monohydrate (Akkurt et al., 2006) and 88.42 (4)° in 3,30-bis(3- cyanopropyl)-1,10-propylene- di(benzimidazolium) dichloride dihydrate (Akkurt et al., 2003). This divergence may be due to the interactions of the different substituents bounded to the benzimidazole ring system.

The crystal structure of (I) is stabilized by inter and intramolecular O—H···Br and C—H···Br hydrogen bonding interactions, involving the H atoms of the water molecule (Table 1 and Fig. 2).

Related literature top

For bond-length data, see: Allen et al. (1987). For general background, see: Sakai et al. (1989); Tidwell et al. (1993); Küçükbay et al. (1995, 2001); Turner & Denny (1996); Hall et al. (1998). For related structures, see, for example: Öztürk et al. (2003); Akkurt et al. (2003, 2006).

Experimental top

A mixture of 1,1'-propylenedibenzimidazole (0.9 g, 3.26 mmol) and (E)-1-bromobut-2-ene (1.2 g, 6.78 mmol) in dimethylformamide (5 ml) was heated under reflux for 3 h. The mixture was then cooled and the volatiles were removed in vacuo. The residue was crystallized from a DMF/EtOH (1:3) mixture [Yield: 1.39 g, 78%. Mp. 479–481°K].

Analysis, calculated for C₂₅H₃₂N₄OBr₂: C53.19, H 5.67, N 9.93%; found: C 53.95, H 5.42, N 10.11%. ¹H-NMR (DMSO-d₆): δ (p.p.m.) 8.24 (s, 2-CH, 2H), 2.64 (t, bridge, 2H), 4.83 (t, bridge, 4H), 1.86 (d, methyl, 6H), 5.14 (d, methylene, 4H), 5.77 (m, =CH, 4H), 7.70–8.05 (m, Ar—H, 8H). ¹³C-NMR (DMSO-d₆): δ (p.p.m.) 13.28, 17.56, 28.28, 43.70, 48.44, 113.74, 122.22, 123.37, 126.50, 130.89, 131.52, 132.89, 142.18.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP view of (I), with the atom-numbering scheme and 10% probability displacement ellipsoids.
	Fig. 2. The packing and hydrogen bonding of (I), viewed down the b axis. Hydrogen bonds are drawn as dashed lines and H atoms not involved in these interactions have been omitted for clarity.

(E)-1,1'-Bis[(E)-but-2-enyl]-3,3'-(propane-1,3-diyl)bis(1H-benzimidazol-3-ium) dibromide monohydrate top

Crystal data top

C₂₅H₃₀N₄²⁺·2Br⁻·H₂O	Z = 2
M_r = 564.35	F(000) = 576
Triclinic, P1	D_x = 1.420 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7989 (9) Å	Cell parameters from 25470 reflections
b = 11.1878 (13) Å	θ = 2.0–28.0°
c = 14.8813 (14) Å	µ = 3.09 mm⁻¹
α = 106.381 (8)°	T = 296 K
β = 96.490 (8)°	Prismatic plate, light yellow
γ = 106.227 (8)°	0.53 × 0.45 × 0.31 mm
V = 1319.9 (3) Å³

Data collection top

Stoe IPDSII diffractometer	6181 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	4101 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.063
Detector resolution: 6.67 pixels mm^-1	θ_max = 27.7°, θ_min = 2.5°
ω scans	h = −11→11
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −14→13
T_min = 0.291, T_max = 0.447	l = −18→19
16109 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0416P)² + 0.9807P] where P = (F_o² + 2F_c²)/3
6181 reflections	(Δ/σ)_max < 0.001
297 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₂₅H₃₀N₄²⁺·2Br⁻·H₂O	γ = 106.227 (8)°
M_r = 564.35	V = 1319.9 (3) Å³
Triclinic, P1	Z = 2
a = 8.7989 (9) Å	Mo Kα radiation
b = 11.1878 (13) Å	µ = 3.09 mm⁻¹
c = 14.8813 (14) Å	T = 296 K
α = 106.381 (8)°	0.53 × 0.45 × 0.31 mm
β = 96.490 (8)°

Data collection top

Stoe IPDSII diffractometer	6181 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	4101 reflections with I > 2σ(I)
T_min = 0.291, T_max = 0.447	R_int = 0.063
16109 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.57 e Å⁻³
6181 reflections	Δρ_min = −0.41 e Å⁻³
297 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.7390 (4)	0.6064 (4)	0.4072 (2)	0.0525 (10)
N2	0.4931 (4)	0.5116 (3)	0.3227 (2)	0.0495 (10)
N3	0.1559 (4)	0.3113 (3)	0.0400 (2)	0.0463 (10)
N4	0.2504 (4)	0.1820 (4)	−0.0600 (2)	0.0557 (11)
C1	1.1336 (19)	0.851 (2)	0.3031 (16)	0.400 (19)
C2	1.0601 (14)	0.774 (2)	0.3445 (13)	0.292 (12)
C3	0.9949 (10)	0.7489 (12)	0.4033 (10)	0.177 (6)
C4	0.9166 (5)	0.6413 (6)	0.4322 (3)	0.0707 (18)
C5	0.6392 (5)	0.6485 (4)	0.4651 (3)	0.0485 (12)
C6	0.6724 (5)	0.7321 (4)	0.5592 (3)	0.0572 (14)
C7	0.5407 (6)	0.7523 (5)	0.5946 (3)	0.0661 (16)
C8	0.3830 (6)	0.6909 (5)	0.5413 (3)	0.0673 (17)
C9	0.3504 (5)	0.6076 (4)	0.4486 (3)	0.0559 (14)
C10	0.4821 (5)	0.5886 (4)	0.4116 (2)	0.0451 (11)
C11	0.6481 (5)	0.5246 (4)	0.3234 (3)	0.0546 (14)
C12	0.3576 (5)	0.4279 (4)	0.2430 (3)	0.0524 (12)
C13	0.3047 (5)	0.5057 (4)	0.1841 (3)	0.0536 (12)
C14	0.1475 (5)	0.4283 (4)	0.1120 (3)	0.0547 (14)
C15	0.0246 (5)	0.2004 (4)	−0.0130 (2)	0.0462 (11)
C16	−0.1379 (5)	0.1681 (5)	−0.0101 (3)	0.0607 (16)
C17	−0.2356 (6)	0.0474 (5)	−0.0719 (4)	0.0730 (17)
C18	−0.1753 (7)	−0.0361 (5)	−0.1343 (4)	0.0756 (17)
C19	−0.0147 (6)	−0.0054 (5)	−0.1380 (3)	0.0692 (18)
C20	0.0849 (5)	0.1169 (4)	−0.0768 (3)	0.0528 (14)
C21	0.2866 (5)	0.2959 (4)	0.0079 (3)	0.0520 (14)
C22	0.3684 (7)	0.1338 (7)	−0.1103 (3)	0.084 (2)
C23	0.3596 (8)	0.1486 (7)	−0.2051 (4)	0.094 (3)
C24	0.3622 (10)	0.0582 (8)	−0.2808 (5)	0.116 (3)
C25	0.3606 (14)	0.0664 (10)	−0.3775 (6)	0.162 (5)
O1	0.5845 (5)	0.2069 (5)	0.1612 (4)	0.0878 (16)
Br1	0.70894 (5)	0.46584 (5)	0.08608 (3)	0.0654 (2)
Br2	−0.05435 (5)	0.30445 (5)	0.30568 (3)	0.0648 (2)
H1A	1.16160	0.80090	0.24750	0.5960*
H1B	1.23030	0.91410	0.34640	0.5960*
H1C	1.06430	0.89630	0.28420	0.5960*
H2	1.05770	0.69140	0.30580	0.3530*
H3	0.99330	0.82660	0.44670	0.2120*
H4A	0.95090	0.66410	0.50090	0.0840*
H4B	0.94770	0.56570	0.40120	0.0840*
H6	0.77720	0.77180	0.59580	0.0680*
H7	0.55760	0.80940	0.65670	0.0800*
H8	0.29780	0.70650	0.56900	0.0810*
H9	0.24520	0.56620	0.41270	0.0670*
H11	0.68710	0.48220	0.27240	0.0660*
H12A	0.26710	0.38660	0.26790	0.0630*
H12B	0.38910	0.35850	0.20210	0.0630*
H13A	0.29250	0.58410	0.22700	0.0650*
H13B	0.38890	0.53390	0.15050	0.0650*
H14A	0.06290	0.40110	0.14570	0.0660*
H14B	0.11790	0.48530	0.07980	0.0660*
H16	−0.17850	0.22470	0.03130	0.0730*
H17	−0.34570	0.02090	−0.07200	0.0870*
H18	−0.24680	−0.11630	−0.17550	0.0910*
H19	0.02510	−0.06320	−0.17900	0.0830*
H21	0.38980	0.35770	0.03050	0.0620*
H22A	0.47680	0.18260	−0.07220	0.1010*
H22B	0.34740	0.04150	−0.11690	0.1010*
H23	0.35180	0.22730	−0.21120	0.1130*
H24	0.36530	−0.02080	−0.27320	0.1390*
H25A	0.36370	−0.01500	−0.41980	0.2430*
H25B	0.45340	0.13740	−0.37610	0.2430*
H25C	0.26380	0.08230	−0.39980	0.2430*
HW1	0.625 (9)	0.268 (7)	0.143 (5)	0.11 (3)*
HW2	0.677 (10)	0.224 (7)	0.201 (5)	0.12 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0407 (17)	0.070 (2)	0.0457 (17)	0.0218 (17)	0.0100 (13)	0.0135 (16)
N2	0.0431 (18)	0.058 (2)	0.0410 (16)	0.0144 (15)	0.0074 (13)	0.0091 (14)
N3	0.0391 (16)	0.055 (2)	0.0418 (16)	0.0164 (15)	0.0081 (12)	0.0107 (14)
N4	0.052 (2)	0.074 (2)	0.0436 (17)	0.0306 (18)	0.0127 (14)	0.0120 (17)
C1	0.177 (14)	0.60 (4)	0.59 (4)	0.059 (18)	0.041 (18)	0.53 (3)
C2	0.089 (8)	0.50 (3)	0.40 (2)	0.047 (12)	0.045 (10)	0.37 (2)
C3	0.057 (5)	0.233 (12)	0.288 (14)	0.033 (6)	0.035 (6)	0.173 (11)
C4	0.043 (2)	0.108 (4)	0.061 (3)	0.032 (3)	0.0097 (19)	0.021 (3)
C5	0.044 (2)	0.058 (2)	0.045 (2)	0.0184 (19)	0.0102 (16)	0.0173 (18)
C6	0.055 (2)	0.068 (3)	0.043 (2)	0.024 (2)	0.0019 (17)	0.0093 (19)
C7	0.074 (3)	0.079 (3)	0.046 (2)	0.037 (3)	0.014 (2)	0.009 (2)
C8	0.063 (3)	0.087 (3)	0.057 (3)	0.038 (3)	0.023 (2)	0.014 (2)
C9	0.046 (2)	0.067 (3)	0.057 (2)	0.021 (2)	0.0142 (18)	0.020 (2)
C10	0.045 (2)	0.048 (2)	0.0401 (18)	0.0142 (17)	0.0084 (15)	0.0125 (16)
C11	0.046 (2)	0.069 (3)	0.043 (2)	0.018 (2)	0.0134 (16)	0.0088 (19)
C12	0.046 (2)	0.050 (2)	0.047 (2)	0.0062 (18)	0.0038 (16)	0.0061 (17)
C13	0.052 (2)	0.054 (2)	0.046 (2)	0.0144 (19)	0.0048 (17)	0.0080 (18)
C14	0.051 (2)	0.063 (3)	0.046 (2)	0.024 (2)	0.0077 (17)	0.0073 (18)
C15	0.046 (2)	0.053 (2)	0.0389 (18)	0.0184 (18)	0.0054 (15)	0.0133 (16)
C16	0.042 (2)	0.073 (3)	0.065 (3)	0.020 (2)	0.0046 (19)	0.021 (2)
C17	0.046 (3)	0.076 (3)	0.088 (3)	0.011 (2)	−0.003 (2)	0.029 (3)
C18	0.072 (3)	0.059 (3)	0.071 (3)	0.006 (3)	−0.021 (2)	0.013 (2)
C19	0.080 (4)	0.062 (3)	0.055 (2)	0.031 (3)	−0.005 (2)	0.003 (2)
C20	0.052 (2)	0.063 (3)	0.043 (2)	0.023 (2)	0.0033 (17)	0.0151 (18)
C21	0.040 (2)	0.068 (3)	0.043 (2)	0.0157 (19)	0.0085 (15)	0.0129 (19)
C22	0.073 (3)	0.117 (5)	0.063 (3)	0.051 (3)	0.025 (2)	0.007 (3)
C23	0.100 (5)	0.096 (4)	0.080 (4)	0.030 (4)	0.044 (3)	0.013 (3)
C24	0.159 (7)	0.124 (6)	0.082 (4)	0.058 (5)	0.042 (4)	0.042 (4)
C25	0.221 (11)	0.175 (9)	0.114 (6)	0.072 (8)	0.071 (7)	0.061 (6)
O1	0.054 (2)	0.091 (3)	0.103 (3)	0.006 (2)	0.007 (2)	0.030 (2)
Br1	0.0531 (3)	0.0932 (4)	0.0649 (3)	0.0309 (3)	0.0197 (2)	0.0390 (3)
Br2	0.0507 (3)	0.0840 (4)	0.0557 (3)	0.0243 (2)	0.0134 (2)	0.0140 (2)

Geometric parameters (Å, º) top

O1—HW2	0.89 (9)	C23—C24	1.292 (10)
O1—HW1	0.81 (8)	C24—C25	1.466 (12)
N1—C11	1.324 (5)	C1—H1C	0.9600
N1—C4	1.476 (6)	C1—H1A	0.9600
N1—C5	1.382 (6)	C1—H1B	0.9600
N2—C11	1.329 (6)	C2—H2	0.9300
N2—C12	1.461 (5)	C3—H3	0.9300
N2—C10	1.391 (4)	C4—H4A	0.9700
N3—C21	1.330 (6)	C4—H4B	0.9700
N3—C14	1.466 (5)	C6—H6	0.9300
N3—C15	1.392 (5)	C7—H7	0.9300
N4—C22	1.480 (7)	C8—H8	0.9300
N4—C20	1.391 (6)	C9—H9	0.9300
N4—C21	1.312 (6)	C11—H11	0.9300
C1—C2	1.27 (3)	C12—H12A	0.9700
C2—C3	1.16 (2)	C12—H12B	0.9700
C3—C4	1.416 (15)	C13—H13A	0.9700
C5—C6	1.392 (6)	C13—H13B	0.9700
C5—C10	1.388 (6)	C14—H14A	0.9700
C6—C7	1.374 (7)	C14—H14B	0.9700
C7—C8	1.392 (7)	C16—H16	0.9300
C8—C9	1.375 (6)	C17—H17	0.9300
C9—C10	1.381 (6)	C18—H18	0.9300
C12—C13	1.519 (6)	C19—H19	0.9300
C13—C14	1.512 (6)	C21—H21	0.9300
C15—C16	1.382 (7)	C22—H22B	0.9700
C15—C20	1.395 (6)	C22—H22A	0.9700
C16—C17	1.371 (8)	C23—H23	0.9300
C17—C18	1.384 (8)	C24—H24	0.9300
C18—C19	1.369 (8)	C25—H25C	0.9600
C19—C20	1.384 (7)	C25—H25A	0.9600
C22—C23	1.462 (8)	C25—H25B	0.9600

Br1···C21	3.550 (5)	C19···H1Cⁱ	2.8300
Br1···O1	3.342 (6)	C21···H12B	2.7500
Br1···C11	3.536 (4)	C21···H13B	2.7300
Br1···C14ⁱ	3.696 (4)	C22···H19	3.0600
Br1···C21ⁱ	3.335 (5)	HW1···H11	2.4900
Br1···N3ⁱ	3.555 (3)	HW1···Br1	2.54 (8)
Br2···O1ⁱⁱ	3.333 (5)	HW1···H16ⁱⁱⁱ	2.5800
Br1···HW1	2.54 (8)	H1C···C19ⁱ	2.8300
Br1···H11	2.7600	H2···H4B	2.3700
Br1···H21	2.6500	HW2···Br2ⁱⁱⁱ	2.45 (8)
Br1···H16ⁱⁱⁱ	3.0600	H4A···H6	2.5200
Br1···H14Bⁱ	3.1400	H4A···C6	2.9100
Br1···H21ⁱ	3.2000	H4A···Br2^iv	2.8100
Br2···H14A	3.0500	H4B···H2	2.3700
Br2···HW2ⁱⁱ	2.45 (8)	H4B···H11	2.5700
Br2···H4Bⁱⁱ	2.8600	H4B···Br2ⁱⁱⁱ	2.8600
Br2···H4A^iv	2.8100	H6···Br2^iv	3.1400
Br2···H6^iv	3.1400	H6···C4	3.0400
Br2···H8^v	2.9900	H6···H4A	2.5200
Br2···H19^vi	2.9200	H8···Br2^v	2.9900
Br2···H9	3.1900	H9···H12A	2.5700
Br2···H12A	2.8900	H9···C12	2.9900
O1···Br2ⁱⁱⁱ	3.333 (5)	H9···Br2	3.1900
O1···C17^vi	3.369 (8)	H11···Br1	2.7600
O1···Br1	3.342 (6)	H11···H4B	2.5700
O1···H12B	2.7400	H11···O1	2.8800
O1···H22B^vii	2.9200	H11···HW1	2.4900
O1···H11	2.8800	H11···H12B	2.5300
O1···H18^vi	2.9100	H12A···C9	2.9400
O1···H17^vi	2.6700	H12A···H9	2.5700
N1···N2	2.177 (5)	H12A···Br2	2.8900
N2···N1	2.177 (5)	H12A···H14A	2.4800
N3···Br1ⁱ	3.555 (3)	H12B···N3	2.8000
N3···N4	2.176 (5)	H12B···O1	2.7400
N4···N3	2.176 (5)	H12B···H18^vi	2.5400
N3···H12B	2.8000	H12B···H21	2.5500
C1···C19ⁱ	3.60 (2)	H12B···H11	2.5300
C5···C9^iv	3.473 (6)	H12B···C21	2.7500
C8···C11^iv	3.526 (7)	H13A···C10	3.0300
C9···C5^iv	3.473 (6)	H13B···H21	2.2600
C11···C8^iv	3.526 (7)	H13B···C21	2.7300
C11···Br1	3.536 (4)	H14A···Br2	3.0500
C12···C21	3.300 (6)	H14A···C16	2.9000
C14···Br1ⁱ	3.696 (4)	H14A···H12A	2.4800
C15···C18^vi	3.594 (7)	H14A···H16	2.5000
C15···C19^vi	3.538 (6)	H14B···Br1ⁱ	3.1400
C16···C19^vi	3.596 (7)	H16···C14	2.9800
C17···O1^vi	3.369 (8)	H16···Br1ⁱⁱ	3.0600
C18···C20^vi	3.572 (7)	H16···HW1ⁱⁱ	2.5800
C18···C15^vi	3.594 (7)	H16···H14A	2.5000
C19···C16^vi	3.596 (7)	H17···O1^vi	2.6700
C19···C15^vi	3.538 (6)	H18···H12B^vi	2.5400
C19···C1ⁱ	3.60 (2)	H18···O1^vi	2.9100
C20···C18^vi	3.572 (7)	H19···C22	3.0600
C21···Br1	3.550 (5)	H19···Br2^vi	2.9200
C21···C12	3.300 (6)	H21···Br1	2.6500
C21···Br1ⁱ	3.335 (5)	H21···C13	2.7300
C4···H6	3.0400	H21···H12B	2.5500
C6···H4A	2.9100	H21···H13B	2.2600
C9···H12A	2.9400	H21···H22A	2.4800
C10···H13A	3.0300	H21···Br1ⁱ	3.2000
C12···H9	2.9900	H22A···H21	2.4800
C13···H21	2.7300	H22B···C19	3.0400
C14···H16	2.9800	H22B···H24	2.2700
C16···H14A	2.9000	H22B···O1^vii	2.9200
C19···H22B	3.0400	H24···H22B	2.2700

HW1—O1—HW2	91 (7)	N1—C4—H4B	109.00
C4—N1—C11	124.1 (4)	C3—C4—H4B	109.00
C5—N1—C11	108.5 (4)	H4A—C4—H4B	108.00
C4—N1—C5	127.4 (3)	C3—C4—H4A	109.00
C10—N2—C11	108.2 (3)	C5—C6—H6	122.00
C11—N2—C12	125.7 (3)	C7—C6—H6	122.00
C10—N2—C12	126.1 (4)	C6—C7—H7	119.00
C14—N3—C15	125.6 (4)	C8—C7—H7	119.00
C15—N3—C21	107.6 (3)	C9—C8—H8	119.00
C14—N3—C21	126.6 (4)	C7—C8—H8	119.00
C20—N4—C21	108.8 (4)	C10—C9—H9	122.00
C20—N4—C22	126.5 (4)	C8—C9—H9	122.00
C21—N4—C22	124.7 (4)	N1—C11—H11	125.00
C1—C2—C3	155 (2)	N2—C11—H11	125.00
C2—C3—C4	142.0 (16)	N2—C12—H12A	109.00
N1—C4—C3	111.2 (6)	N2—C12—H12B	109.00
N1—C5—C10	106.8 (3)	C13—C12—H12B	109.00
C6—C5—C10	121.5 (4)	H12A—C12—H12B	108.00
N1—C5—C6	131.7 (4)	C13—C12—H12A	109.00
C5—C6—C7	115.8 (4)	C12—C13—H13A	109.00
C6—C7—C8	122.6 (4)	C14—C13—H13A	109.00
C7—C8—C9	121.4 (5)	C14—C13—H13B	109.00
C8—C9—C10	116.4 (4)	C12—C13—H13B	109.00
N2—C10—C5	106.3 (4)	H13A—C13—H13B	108.00
C5—C10—C9	122.1 (3)	N3—C14—H14B	109.00
N2—C10—C9	131.6 (4)	C13—C14—H14A	109.00
N1—C11—N2	110.2 (4)	C13—C14—H14B	109.00
N2—C12—C13	111.9 (4)	H14A—C14—H14B	108.00
C12—C13—C14	113.4 (4)	N3—C14—H14A	109.00
N3—C14—C13	113.3 (4)	C17—C16—H16	122.00
N3—C15—C16	131.2 (4)	C15—C16—H16	122.00
C16—C15—C20	122.0 (4)	C16—C17—H17	119.00
N3—C15—C20	106.8 (4)	C18—C17—H17	119.00
C15—C16—C17	116.0 (4)	C19—C18—H18	119.00
C16—C17—C18	121.9 (5)	C17—C18—H18	119.00
C17—C18—C19	122.7 (5)	C18—C19—H19	122.00
C18—C19—C20	115.9 (5)	C20—C19—H19	122.00
N4—C20—C15	105.8 (4)	N3—C21—H21	125.00
N4—C20—C19	132.7 (4)	N4—C21—H21	125.00
C15—C20—C19	121.4 (4)	N4—C22—H22B	109.00
N3—C21—N4	110.9 (4)	C23—C22—H22A	109.00
N4—C22—C23	111.9 (5)	C23—C22—H22B	109.00
C22—C23—C24	123.5 (7)	H22A—C22—H22B	108.00
C23—C24—C25	127.2 (9)	N4—C22—H22A	109.00
C2—C1—H1A	110.00	C24—C23—H23	118.00
C2—C1—H1B	109.00	C22—C23—H23	118.00
H1A—C1—H1B	109.00	C23—C24—H24	116.00
H1A—C1—H1C	109.00	C25—C24—H24	116.00
H1B—C1—H1C	109.00	C24—C25—H25B	109.00
C2—C1—H1C	109.00	C24—C25—H25C	110.00
C3—C2—H2	103.00	C24—C25—H25A	109.00
C1—C2—H2	103.00	H25A—C25—H25C	110.00
C2—C3—H3	109.00	H25B—C25—H25C	109.00
C4—C3—H3	109.00	H25A—C25—H25B	110.00
N1—C4—H4A	109.00

C11—N1—C5—C10	−0.5 (5)	C22—N4—C20—C19	2.6 (8)
C4—N1—C11—N2	179.3 (4)	C22—N4—C20—C15	−179.7 (4)
C5—N1—C4—C3	−94.8 (8)	C1—C2—C3—C4	179 (3)
C11—N1—C4—C3	86.9 (8)	C2—C3—C4—N1	−102.2 (19)
C4—N1—C5—C6	0.2 (8)	C6—C5—C10—C9	−0.5 (7)
C11—N1—C5—C6	178.8 (5)	C6—C5—C10—N2	−179.2 (4)
C4—N1—C5—C10	−179.1 (5)	C10—C5—C6—C7	−0.8 (7)
C5—N1—C11—N2	0.7 (5)	N1—C5—C6—C7	−180.0 (5)
C11—N2—C10—C9	−178.3 (5)	N1—C5—C10—C9	178.9 (4)
C12—N2—C10—C9	0.1 (7)	N1—C5—C10—N2	0.2 (5)
C10—N2—C11—N1	−0.5 (5)	C5—C6—C7—C8	1.6 (7)
C12—N2—C11—N1	−179.0 (4)	C6—C7—C8—C9	−1.2 (8)
C10—N2—C12—C13	83.4 (5)	C7—C8—C9—C10	−0.1 (7)
C11—N2—C12—C13	−98.4 (5)	C8—C9—C10—C5	0.9 (7)
C12—N2—C10—C5	178.7 (4)	C8—C9—C10—N2	179.3 (5)
C11—N2—C10—C5	0.2 (5)	N2—C12—C13—C14	−169.9 (4)
C21—N3—C14—C13	−29.1 (6)	C12—C13—C14—N3	−62.0 (5)
C15—N3—C14—C13	156.7 (4)	N3—C15—C20—N4	−0.6 (4)
C14—N3—C15—C16	−3.4 (7)	N3—C15—C16—C17	−178.5 (4)
C15—N3—C21—N4	−1.7 (5)	C20—C15—C16—C17	1.7 (7)
C14—N3—C21—N4	−176.7 (4)	C16—C15—C20—C19	−2.7 (7)
C14—N3—C15—C20	176.4 (4)	N3—C15—C20—C19	177.6 (4)
C21—N3—C15—C20	1.4 (4)	C16—C15—C20—N4	179.3 (4)
C21—N3—C15—C16	−178.4 (5)	C15—C16—C17—C18	−0.9 (8)
C21—N4—C20—C15	−0.4 (5)	C16—C17—C18—C19	0.9 (9)
C22—N4—C21—N3	−179.4 (4)	C17—C18—C19—C20	−1.6 (8)
C20—N4—C22—C23	77.2 (7)	C18—C19—C20—N4	180.0 (5)
C20—N4—C21—N3	1.3 (5)	C18—C19—C20—C15	2.5 (7)
C21—N4—C22—C23	−101.9 (6)	N4—C22—C23—C24	−136.1 (8)
C21—N4—C20—C19	−178.2 (5)	C22—C23—C24—C25	−177.3 (9)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—HW1···Br1	0.81 (8)	2.54 (8)	3.342 (6)	171 (8)
O1—HW2···Br2ⁱⁱⁱ	0.89 (9)	2.45 (8)	3.333 (5)	171 (7)
C4—H4A···Br2^iv	0.97	2.81	3.773 (4)	172
C4—H4B···Br2ⁱⁱⁱ	0.97	2.86	3.802 (6)	164
C11—H11···Br1	0.93	2.76	3.536 (4)	142
C12—H12A···Br2	0.97	2.89	3.822 (5)	161
C19—H19···Br2^vi	0.93	2.92	3.816 (5)	162
C21—H21···Br1	0.93	2.65	3.550 (5)	162

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

Experimental details

Crystal data
Chemical formula	C₂₅H₃₀N₄²⁺·2Br⁻·H₂O
M_r	564.35
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.7989 (9), 11.1878 (13), 14.8813 (14)
α, β, γ (°)	106.381 (8), 96.490 (8), 106.227 (8)
V (Å³)	1319.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.09
Crystal size (mm)	0.53 × 0.45 × 0.31

Data collection
Diffractometer	Stoe IPDSII diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.291, 0.447
No. of measured, independent and observed [I > 2σ(I)] reflections	16109, 6181, 4101
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.124, 1.05
No. of reflections	6181
No. of parameters	297
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.41

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).