2,2′-(Decane-1,10-di­yl)dibenz­imid­azo­lium dichloride trihydrate

Yi, J.-M.; Zhang, Y.-Q.; Xue, S.-F.; Zhu, Q.-J.

doi:10.1107/S160053680800617X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o696

doi:10.1107/S160053680800617X

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2,2′-(Decane-1,10-diyl)dibenzimidazolium dichloride trihydrate

Jun-Ming Yi,^a Yun-Qian Zhang,^b ^* Sai-Feng Xue ^b and Qian-Jiang Zhu ^c

^aCenter for Research & Development of Fine Chemicals Guizhou University, Guiyang 550025, People's Republic of China, ^bKey Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, People's Republic of China, and ^cInstitute of Applied Chemistry Guizhou University, Guiyang 550025, People's Republic of China
^*Correspondence e-mail: sci.yqzhang@gzu.edu.cn

(Received 17 February 2008; accepted 6 March 2008; online 12 March 2008)

The organic cation in the title compound, C₂₄H₃₂N₄²⁺·2Cl⁻·3H₂O, is situated on an inversion centre. The cations, anions and water molecules are linked via N—H⋯O, N—H⋯Cl, O—H⋯O and O—H⋯Cl hydrogen bonds and C—H⋯π interactions, forming a three-dimensional framework.

Related literature

For general background, see: Day & Arnold (2000 ); Day et al. (2002 ); Freeman et al. (1981 ); Kim et al. (2000 ); Wang & Joullie (1957 ).

Experimental

Crystal data

C₂₄H₃₂N₄²⁺·2Cl⁻·3H₂O
M_r = 501.48
Triclinic, $[P \overline 1]$
a = 10.8482 (6) Å
b = 11.5089 (6) Å
c = 11.9503 (6) Å
α = 77.619 (2)°
β = 71.501 (2)°
γ = 76.030 (2)°
V = 1357.58 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 (2) K
0.29 × 0.24 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.926, T_max = 0.958
13250 measured reflections
4702 independent reflections
3802 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.089
S = 1.06
4702 reflections
298 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3W	0.86	1.88	2.7142 (19)	162
N2—H2A⋯O2W	0.86	1.94	2.7500 (19)	157
N3—H3A⋯O1Wⁱ	0.86	1.88	2.7322 (18)	173
N4—H4A⋯Cl2	0.86	2.25	3.0823 (15)	163
O1W—H1WA⋯Cl1ⁱⁱ	0.87	2.25	3.1027 (13)	168
O1W—H1WB⋯Cl1ⁱⁱⁱ	0.89	2.21	3.0804 (13)	166
O2W—H2WA⋯O1W	0.97	1.96	2.8763 (18)	158
O2W—H2WB⋯Cl2^iv	0.90	2.28	3.1703 (13)	170
O3W—H3WB⋯Cl1	0.93	2.20	3.0912 (13)	162
O3W—H3WA⋯Cl2	0.92	2.21	3.1229 (13)	172
C11—H11B⋯Cg2	0.97	3.17	3.847 (3)	128
C22—H22A⋯Cg1^v	0.97	2.92	3.863 (3)	165
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y-1, z; (iii) -x+1, -y+1, -z; (iv) x+1, y, z; (v) -x+1, -y+1, -z+1. Cg1, Cg2 are the centroids of the C1–C6 and C13–C18 benzene rings, respectively.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800617X/rk2079sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680800617X/rk2079Isup2.hkl

checkCIF report

Comment top

We prepared and present a new 'axle' polyaromatic compound (I) containing multiple functional groups that can develop strong intermolecular interactions with cucurbit[n]urils (CB[n]) (Freeman et al., 1981; Day & Arnold, 2000; Day et al., 2002; Kim et al., 2000).

The structure of I, [C₂₄H₃₂N₄]²⁺.2Cl^-.3(H₂O), contains two independent molecules, which occupy the center of symmetry positions in the middle of C12–C12ⁱ and C24–C24ⁱⁱ bonds, respectively (symmetry codes: (i) -x + 2, -y + 3, -z, (ii) -x, -y, -z + 2). The angle between the plane of the phenyl rings and the plane through C10, C11, C12, C12ⁱ, C11ⁱ, C10ⁱ chain is 86.74 (9) Å, and the plane through C22, C23, C24, C24ⁱⁱ, C23ⁱⁱ, C22ⁱⁱ chain is 89.26 (10) Å. The cations, anions and water molecules are linked via N–H···O, N–H···Cl, O–H···O, O–H···Cl hydrogen bonds and C—H···π intreactions forming three–dimensional framework (see table, Cg1, Cg2 are the centroid of the C1/C6–benzene ring and C13/C18–benzene ring, respectively).

Related literature top

For general background, see: Day & Arnold (2000); Day et al. (2002); Freeman et al. (1981); Kim et al. (2000); Wang & Joullie (1957).

Experimental top

A solution of o–phenylenedimine (5.40 g, 0.05 mol) and 1,10–decanedicarboxylic acid (5.80 g, 0.025 mol) were reflux for 12 h in 70 ml of 4M HCl, the reaction mixture was cooled for one day and the crystals of I was removed by filtration and dried. The crystals of the title compound suitable for X–ray diffraction were obtained by dissolving in water and standing at room temperature after several days (Wang & Joullie, 1957). Yield: 25%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of I with the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius.

2,2'-(Decane-1,10-diyl)dibenzimidazolium dichloride trihydrate top

Crystal data top

C₂₄H₃₂N₄²⁺·2Cl⁻·3H₂O	Z = 2
M_r = 501.48	F(000) = 536
Triclinic, P1	D_x = 1.227 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.8482 (6) Å	Cell parameters from 13250 reflections
b = 11.5089 (6) Å	θ = 1.8–25.0°
c = 11.9503 (6) Å	µ = 0.27 mm⁻¹
α = 77.619 (2)°	T = 293 K
β = 71.501 (2)°	Prism, colourless
γ = 76.030 (2)°	0.29 × 0.24 × 0.16 mm
V = 1357.58 (13) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	4702 independent reflections
Radiation source: Fine–focus sealed tube	3802 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
T_min = 0.926, T_max = 0.958	k = −12→13
13250 measured reflections	l = −11→14

Refinement top

Refinement on F²	Primary atom site location: Direct
Least-squares matrix: Full	Secondary atom site location: Difmap
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: Geom
wR(F²) = 0.089	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0377P)² + 0.299P] where P = (F_o² + 2F_c²)/3
4702 reflections	(Δ/σ)_max < 0.001
298 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₄H₃₂N₄²⁺·2Cl⁻·3H₂O	γ = 76.030 (2)°
M_r = 501.48	V = 1357.58 (13) Å³
Triclinic, P1	Z = 2
a = 10.8482 (6) Å	Mo Kα radiation
b = 11.5089 (6) Å	µ = 0.27 mm⁻¹
c = 11.9503 (6) Å	T = 293 K
α = 77.619 (2)°	0.29 × 0.24 × 0.16 mm
β = 71.501 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4702 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	3802 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.958	R_int = 0.024
13250 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.06	Δρ_max = 0.22 e Å⁻³
4702 reflections	Δρ_min = −0.18 e Å⁻³
298 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 RR–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
C1	0.64008 (18)	0.65504 (16)	0.11143 (15)	0.0407 (4)
C2	0.6254 (2)	0.78026 (18)	0.09401 (19)	0.0572 (5)
H2	0.5447	0.8308	0.0923	0.069*
C3	0.7371 (2)	0.8257 (2)	0.07942 (19)	0.0624 (6)
H3	0.7317	0.9091	0.0668	0.075*
C4	0.8579 (2)	0.7500 (2)	0.08310 (17)	0.0570 (6)
H4	0.9307	0.7845	0.0729	0.068*
C5	0.87257 (19)	0.62624 (19)	0.10132 (16)	0.0487 (5)
H5	0.9530	0.5759	0.1043	0.058*
C6	0.76037 (17)	0.58019 (16)	0.11513 (15)	0.0387 (4)
C7	0.61491 (17)	0.46486 (15)	0.13702 (15)	0.0364 (4)
C8	0.55400 (18)	0.35944 (16)	0.14626 (17)	0.0418 (4)
H8A	0.5851	0.3315	0.0693	0.050*
H8B	0.4589	0.3864	0.1634	0.050*
C9	0.58230 (18)	0.25312 (15)	0.24031 (15)	0.0392 (4)
H9A	0.5473	0.2783	0.3186	0.047*
H9B	0.6772	0.2260	0.2255	0.047*
C10	0.51925 (18)	0.14950 (16)	0.23773 (16)	0.0409 (4)
H10A	0.4243	0.1771	0.2548	0.049*
H10B	0.5514	0.1281	0.1579	0.049*
C11	0.54728 (18)	0.03713 (16)	0.32589 (16)	0.0415 (4)
H11A	0.6422	0.0092	0.3085	0.050*
H11B	0.5093	−0.0263	0.3148	0.050*
C12	0.49251 (16)	0.05731 (15)	0.45552 (15)	0.0384 (4)
H12A	0.5374	0.1144	0.4686	0.046*
H12B	0.3994	0.0935	0.4705	0.046*
C13	0.16012 (15)	−0.00823 (15)	0.50147 (15)	0.0340 (4)
C14	0.19499 (17)	−0.13242 (16)	0.50035 (18)	0.0430 (4)
H14	0.1875	−0.1877	0.5703	0.052*
C15	0.24119 (18)	−0.16880 (18)	0.38967 (19)	0.0484 (5)
H15	0.2662	−0.2511	0.3848	0.058*
C16	0.25169 (17)	−0.08601 (18)	0.28440 (18)	0.0463 (5)
H16	0.2826	−0.1148	0.2116	0.056*
C17	0.21752 (16)	0.03697 (17)	0.28543 (16)	0.0405 (4)
H17	0.2246	0.0921	0.2153	0.049*
C18	0.17194 (15)	0.07423 (15)	0.39687 (15)	0.0329 (4)
C19	0.09620 (15)	0.17706 (16)	0.55014 (15)	0.0353 (4)
C20	0.04445 (17)	0.27781 (17)	0.62225 (17)	0.0454 (5)
H20A	0.0525	0.2469	0.7023	0.055*
H20B	−0.0489	0.3056	0.6283	0.055*
C21	0.11453 (17)	0.38577 (16)	0.57205 (17)	0.0436 (4)
H21A	0.1086	0.4154	0.4912	0.052*
H21B	0.0685	0.4502	0.6194	0.052*
C22	0.25918 (16)	0.35777 (15)	0.57035 (17)	0.0398 (4)
H22A	0.2659	0.3266	0.6507	0.048*
H22B	0.3064	0.2952	0.5210	0.048*
C23	0.32401 (18)	0.46815 (16)	0.52292 (18)	0.0463 (5)
H23A	0.2725	0.5324	0.5688	0.056*
H23B	0.3220	0.4959	0.4408	0.056*
C24	0.46640 (18)	0.44573 (17)	0.52768 (17)	0.0453 (5)
H24A	0.4678	0.4235	0.6103	0.054*
H24B	0.5167	0.3778	0.4864	0.054*
Cl1	0.18425 (5)	0.85742 (4)	0.02569 (4)	0.04826 (14)
Cl2	0.16011 (5)	0.39667 (4)	0.21933 (4)	0.05033 (15)
N1	0.55187 (14)	0.57926 (12)	0.12641 (13)	0.0397 (4)
H1	0.4698	0.6027	0.1285	0.048*
N2	0.73979 (14)	0.46237 (13)	0.13165 (13)	0.0400 (4)
H2A	0.7986	0.3979	0.1375	0.048*
N3	0.11251 (13)	0.06012 (13)	0.59441 (12)	0.0362 (3)
H3A	0.0962	0.0311	0.6691	0.043*
N4	0.13153 (13)	0.18871 (12)	0.43127 (12)	0.0355 (3)
H4A	0.1296	0.2562	0.3835	0.043*
O1W	0.95820 (12)	0.03649 (11)	0.16974 (10)	0.0452 (3)
H1WA	1.0290	−0.0060	0.1285	0.054*
H1WB	0.9039	0.0643	0.1235	0.054*
O3W	0.28364 (12)	0.62540 (11)	0.18261 (12)	0.0529 (4)
H3WA	0.2395	0.5627	0.1963	0.063*
H3WB	0.2443	0.6840	0.1315	0.063*
O2W	0.92820 (12)	0.28229 (11)	0.20533 (12)	0.0494 (3)
H2WA	0.9616	0.2021	0.1829	0.059*
H2WB	0.9970	0.3157	0.1996	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0453 (10)	0.0372 (10)	0.0372 (10)	−0.0113 (8)	−0.0083 (8)	−0.0014 (8)
C2	0.0637 (13)	0.0390 (12)	0.0617 (14)	−0.0091 (10)	−0.0123 (11)	−0.0012 (10)
C3	0.0850 (17)	0.0438 (12)	0.0578 (14)	−0.0296 (12)	−0.0094 (12)	−0.0023 (10)
C4	0.0653 (14)	0.0640 (14)	0.0463 (12)	−0.0362 (12)	−0.0062 (10)	−0.0053 (10)
C5	0.0473 (11)	0.0588 (13)	0.0423 (11)	−0.0208 (10)	−0.0090 (9)	−0.0059 (9)
C6	0.0433 (10)	0.0390 (10)	0.0324 (10)	−0.0116 (8)	−0.0085 (8)	−0.0016 (8)
C7	0.0371 (9)	0.0377 (10)	0.0343 (10)	−0.0082 (8)	−0.0114 (8)	−0.0013 (7)
C8	0.0403 (10)	0.0391 (10)	0.0481 (11)	−0.0069 (8)	−0.0169 (8)	−0.0044 (8)
C9	0.0433 (10)	0.0389 (10)	0.0368 (10)	−0.0119 (8)	−0.0108 (8)	−0.0044 (8)
C10	0.0404 (10)	0.0415 (10)	0.0437 (11)	−0.0131 (8)	−0.0119 (8)	−0.0062 (8)
C11	0.0398 (10)	0.0373 (10)	0.0492 (11)	−0.0105 (8)	−0.0119 (8)	−0.0079 (8)
C12	0.0334 (9)	0.0320 (9)	0.0507 (11)	−0.0080 (8)	−0.0123 (8)	−0.0050 (8)
C13	0.0280 (8)	0.0401 (10)	0.0370 (10)	−0.0090 (7)	−0.0113 (7)	−0.0061 (8)
C14	0.0382 (10)	0.0393 (11)	0.0549 (12)	−0.0098 (8)	−0.0197 (9)	−0.0012 (9)
C15	0.0408 (10)	0.0416 (11)	0.0704 (14)	−0.0061 (9)	−0.0215 (10)	−0.0174 (10)
C16	0.0375 (10)	0.0571 (13)	0.0533 (12)	−0.0097 (9)	−0.0144 (9)	−0.0235 (10)
C17	0.0351 (9)	0.0524 (12)	0.0382 (10)	−0.0133 (8)	−0.0123 (8)	−0.0068 (8)
C18	0.0266 (8)	0.0361 (10)	0.0392 (10)	−0.0091 (7)	−0.0113 (7)	−0.0058 (8)
C19	0.0247 (8)	0.0436 (11)	0.0397 (10)	−0.0099 (7)	−0.0085 (7)	−0.0080 (8)
C20	0.0326 (9)	0.0541 (12)	0.0511 (12)	−0.0083 (8)	−0.0063 (8)	−0.0192 (9)
C21	0.0388 (10)	0.0386 (10)	0.0543 (12)	−0.0002 (8)	−0.0137 (9)	−0.0163 (9)
C22	0.0382 (10)	0.0346 (10)	0.0471 (11)	−0.0055 (8)	−0.0121 (8)	−0.0087 (8)
C23	0.0490 (11)	0.0386 (11)	0.0537 (12)	−0.0111 (9)	−0.0149 (9)	−0.0084 (9)
C24	0.0477 (11)	0.0462 (11)	0.0463 (11)	−0.0153 (9)	−0.0126 (9)	−0.0093 (9)
Cl1	0.0498 (3)	0.0453 (3)	0.0464 (3)	0.0017 (2)	−0.0178 (2)	−0.0055 (2)
Cl2	0.0542 (3)	0.0429 (3)	0.0557 (3)	−0.0152 (2)	−0.0192 (2)	0.0017 (2)
N1	0.0358 (8)	0.0348 (9)	0.0464 (9)	−0.0034 (7)	−0.0143 (7)	−0.0009 (7)
N2	0.0367 (8)	0.0351 (8)	0.0469 (9)	−0.0047 (6)	−0.0129 (7)	−0.0037 (7)
N3	0.0331 (8)	0.0430 (9)	0.0337 (8)	−0.0114 (6)	−0.0105 (6)	−0.0015 (7)
N4	0.0336 (7)	0.0336 (8)	0.0386 (9)	−0.0086 (6)	−0.0103 (6)	−0.0012 (6)
O1W	0.0441 (7)	0.0501 (8)	0.0374 (7)	0.0007 (6)	−0.0125 (6)	−0.0075 (6)
O3W	0.0435 (7)	0.0373 (7)	0.0740 (10)	−0.0072 (6)	−0.0192 (7)	0.0034 (6)
O2W	0.0416 (7)	0.0412 (7)	0.0683 (9)	−0.0058 (6)	−0.0202 (6)	−0.0092 (6)

Geometric parameters (Å, º) top

C1—C6	1.387 (3)	C15—C16	1.397 (3)
C1—C2	1.388 (3)	C15—H15	0.9300
C1—N1	1.391 (2)	C16—C17	1.376 (3)
C2—C3	1.380 (3)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.388 (2)
C3—C4	1.396 (3)	C17—H17	0.9300
C3—H3	0.9300	C18—N4	1.391 (2)
C4—C5	1.372 (3)	C19—N3	1.327 (2)
C4—H4	0.9300	C19—N4	1.334 (2)
C5—C6	1.392 (2)	C19—C20	1.486 (2)
C5—H5	0.9300	C20—C21	1.526 (2)
C6—N2	1.390 (2)	C20—H20A	0.9700
C7—N1	1.329 (2)	C20—H20B	0.9700
C7—N2	1.329 (2)	C21—C22	1.518 (2)
C7—C8	1.485 (2)	C21—H21A	0.9700
C8—C9	1.517 (2)	C21—H21B	0.9700
C8—H8A	0.9700	C22—C23	1.516 (2)
C8—H8B	0.9700	C22—H22A	0.9700
C9—C10	1.521 (2)	C22—H22B	0.9700
C9—H9A	0.9700	C23—C24	1.521 (3)
C9—H9B	0.9700	C23—H23A	0.9700
C10—C11	1.518 (2)	C23—H23B	0.9700
C10—H10A	0.9700	C24—C24ⁱⁱ	1.520 (3)
C10—H10B	0.9700	C24—H24A	0.9700
C11—C12	1.520 (2)	C24—H24B	0.9700
C11—H11A	0.9700	N1—H1	0.8600
C11—H11B	0.9700	N2—H2A	0.8600
C12—C12ⁱ	1.517 (3)	N3—H3A	0.8600
C12—H12A	0.9700	N4—H4A	0.8600
C12—H12B	0.9700	O1W—H1WA	0.8680
C13—C18	1.388 (2)	O1W—H1WB	0.8916
C13—C14	1.389 (2)	O3W—H3WA	0.9188
C13—N3	1.390 (2)	O3W—H3WB	0.9275
C14—C15	1.375 (3)	O2W—H2WA	0.9681
C14—H14	0.9300	O2W—H2WB	0.8971

C6—C1—C2	121.54 (18)	C16—C15—H15	119.0
C6—C1—N1	106.43 (15)	C17—C16—C15	121.84 (18)
C2—C1—N1	132.02 (18)	C17—C16—H16	119.1
C3—C2—C1	116.3 (2)	C15—C16—H16	119.1
C3—C2—H2	121.8	C16—C17—C18	116.30 (17)
C1—C2—H2	121.8	C16—C17—H17	121.8
C2—C3—C4	121.9 (2)	C18—C17—H17	121.8
C2—C3—H3	119.0	C17—C18—C13	121.77 (16)
C4—C3—H3	119.0	C17—C18—N4	131.94 (16)
C5—C4—C3	121.93 (19)	C13—C18—N4	106.29 (14)
C5—C4—H4	119.0	N3—C19—N4	108.88 (15)
C3—C4—H4	119.0	N3—C19—C20	125.13 (16)
C4—C5—C6	116.28 (19)	N4—C19—C20	125.99 (16)
C4—C5—H5	121.9	C19—C20—C21	114.39 (15)
C6—C5—H5	121.9	C19—C20—H20A	108.7
C1—C6—N2	106.09 (15)	C21—C20—H20A	108.7
C1—C6—C5	121.99 (17)	C19—C20—H20B	108.7
N2—C6—C5	131.91 (17)	C21—C20—H20B	108.7
N1—C7—N2	109.12 (15)	H20A—C20—H20B	107.6
N1—C7—C8	123.98 (15)	C22—C21—C20	114.17 (15)
N2—C7—C8	126.82 (16)	C22—C21—H21A	108.7
C7—C8—C9	115.36 (15)	C20—C21—H21A	108.7
C7—C8—H8A	108.4	C22—C21—H21B	108.7
C9—C8—H8A	108.4	C20—C21—H21B	108.7
C7—C8—H8B	108.4	H21A—C21—H21B	107.6
C9—C8—H8B	108.4	C23—C22—C21	112.45 (15)
H8A—C8—H8B	107.5	C23—C22—H22A	109.1
C8—C9—C10	110.33 (14)	C21—C22—H22A	109.1
C8—C9—H9A	109.6	C23—C22—H22B	109.1
C10—C9—H9A	109.6	C21—C22—H22B	109.1
C8—C9—H9B	109.6	H22A—C22—H22B	107.8
C10—C9—H9B	109.6	C22—C23—C24	114.00 (16)
H9A—C9—H9B	108.1	C22—C23—H23A	108.8
C11—C10—C9	113.90 (14)	C24—C23—H23A	108.8
C11—C10—H10A	108.8	C22—C23—H23B	108.8
C9—C10—H10A	108.8	C24—C23—H23B	108.8
C11—C10—H10B	108.8	H23A—C23—H23B	107.6
C9—C10—H10B	108.8	C24ⁱⁱ—C24—C23	113.7 (2)
H10A—C10—H10B	107.7	C24ⁱⁱ—C24—H24A	108.8
C10—C11—C12	113.70 (15)	C23—C24—H24A	108.8
C10—C11—H11A	108.8	C24ⁱⁱ—C24—H24B	108.8
C12—C11—H11A	108.8	C23—C24—H24B	108.8
C10—C11—H11B	108.8	H24A—C24—H24B	107.7
C12—C11—H11B	108.8	C7—N1—C1	109.03 (14)
H11A—C11—H11B	107.7	C7—N1—H1	125.5
C12ⁱ—C12—C11	113.96 (18)	C1—N1—H1	125.5
C12ⁱ—C12—H12A	108.8	C7—N2—C6	109.33 (15)
C11—C12—H12A	108.8	C7—N2—H2A	125.3
C12ⁱ—C12—H12B	108.8	C6—N2—H2A	125.3
C11—C12—H12B	108.8	C19—N3—C13	109.52 (14)
H12A—C12—H12B	107.7	C19—N3—H3A	125.2
C18—C13—C14	121.89 (16)	C13—N3—H3A	125.2
C18—C13—N3	106.14 (14)	C19—N4—C18	109.17 (14)
C14—C13—N3	131.96 (16)	C19—N4—H4A	125.4
C15—C14—C13	116.09 (17)	C18—N4—H4A	125.4
C15—C14—H14	122.0	H1WA—O1W—H1WB	107.0
C13—C14—H14	122.0	H3WA—O3W—H3WB	103.3
C14—C15—C16	122.10 (18)	H2WA—O2W—H2WB	108.7
C14—C15—H15	119.0

C6—C1—C2—C3	0.7 (3)	N3—C13—C18—C17	179.89 (14)
N1—C1—C2—C3	−178.45 (19)	C14—C13—C18—N4	−178.69 (14)
C1—C2—C3—C4	−0.6 (3)	N3—C13—C18—N4	0.28 (16)
C2—C3—C4—C5	0.1 (3)	N3—C19—C20—C21	140.24 (17)
C3—C4—C5—C6	0.4 (3)	N4—C19—C20—C21	−41.0 (2)
C2—C1—C6—N2	−179.04 (17)	C19—C20—C21—C22	−64.7 (2)
N1—C1—C6—N2	0.27 (19)	C20—C21—C22—C23	−178.49 (16)
C2—C1—C6—C5	−0.2 (3)	C21—C22—C23—C24	176.07 (16)
N1—C1—C6—C5	179.12 (16)	C22—C23—C24—C24ⁱⁱ	176.07 (19)
C4—C5—C6—C1	−0.4 (3)	N2—C7—N1—C1	1.0 (2)
C4—C5—C6—N2	178.15 (18)	C8—C7—N1—C1	−175.79 (16)
N1—C7—C8—C9	−136.00 (18)	C6—C1—N1—C7	−0.79 (19)
N2—C7—C8—C9	47.8 (2)	C2—C1—N1—C7	178.4 (2)
C7—C8—C9—C10	−177.80 (16)	N1—C7—N2—C6	−0.9 (2)
C8—C9—C10—C11	177.68 (15)	C8—C7—N2—C6	175.85 (16)
C9—C10—C11—C12	62.6 (2)	C1—C6—N2—C7	0.35 (19)
C10—C11—C12—C12ⁱ	173.94 (17)	C5—C6—N2—C7	−178.35 (19)
C18—C13—C14—C15	−0.3 (2)	N4—C19—N3—C13	−0.13 (17)
N3—C13—C14—C15	−178.99 (16)	C20—C19—N3—C13	178.79 (15)
C13—C14—C15—C16	−0.4 (3)	C18—C13—N3—C19	−0.10 (17)
C14—C15—C16—C17	0.6 (3)	C14—C13—N3—C19	178.73 (17)
C15—C16—C17—C18	−0.1 (2)	N3—C19—N4—C18	0.31 (17)
C16—C17—C18—C13	−0.7 (2)	C20—C19—N4—C18	−178.60 (15)
C16—C17—C18—N4	178.80 (16)	C17—C18—N4—C19	−179.93 (17)
C14—C13—C18—C17	0.9 (2)	C13—C18—N4—C19	−0.37 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3W	0.86	1.88	2.7142 (19)	162
N2—H2A···O2W	0.86	1.94	2.7500 (19)	157
N3—H3A···O1Wⁱ	0.86	1.88	2.7322 (18)	173
N4—H4A···Cl2	0.86	2.25	3.0823 (15)	163
O1W—H1WA···Cl1ⁱⁱⁱ	0.87	2.25	3.1027 (13)	168
O1W—H1WB···Cl1^iv	0.89	2.21	3.0804 (13)	166
O2W—H2WA···O1W	0.97	1.96	2.8763 (18)	158
O2W—H2WB···Cl2^v	0.90	2.28	3.1703 (13)	170
O3W—H3WB···Cl1	0.93	2.20	3.0912 (13)	162
O3W—H3WA···Cl2	0.92	2.21	3.1229 (13)	172
C11—H11B···Cg2	0.97	3.17	3.847 (3)	128
C22—H22A···Cg1ⁱⁱ	0.97	2.92	3.863 (3)	165

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

Experimental details

Crystal data
Chemical formula	C₂₄H₃₂N₄²⁺·2Cl⁻·3H₂O
M_r	501.48
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.8482 (6), 11.5089 (6), 11.9503 (6)
α, β, γ (°)	77.619 (2), 71.501 (2), 76.030 (2)
V (Å³)	1357.58 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.29 × 0.24 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.926, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	13250, 4702, 3802
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.089, 1.06
No. of reflections	4702
No. of parameters	298
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.18

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3W	0.86	1.88	2.7142 (19)	161.5
N2—H2A···O2W	0.86	1.94	2.7500 (19)	156.6
N3—H3A···O1Wⁱ	0.86	1.88	2.7322 (18)	173.1
N4—H4A···Cl2	0.86	2.25	3.0823 (15)	163.2
O1W—H1WA···Cl1ⁱⁱ	0.87	2.25	3.1027 (13)	168.1
O1W—H1WB···Cl1ⁱⁱⁱ	0.89	2.21	3.0804 (13)	165.5
O2W—H2WA···O1W	0.97	1.96	2.8763 (18)	157.9
O2W—H2WB···Cl2^iv	0.90	2.28	3.1703 (13)	170.3
O3W—H3WB···Cl1	0.93	2.20	3.0912 (13)	162.1
O3W—H3WA···Cl2	0.92	2.21	3.1229 (13)	172.2
C11—H11B···Cg2	0.97	3.17	3.847 (3)	128.0
C22—H22A···Cg1^v	0.97	2.92	3.863 (3)	164.6

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

Acknowledgements

We acknowledge the support of the National Natural Science Foundation of China (No. 20662003), the International Collaborative Project of the Ministry of Science and Technology (No. 2007400108) and the Foundation of the Governor of Guizhou Province, China.

References

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