2,2′-(Heptane-1,7-di­yl)dibenz­imidazo­lium chloride nitrate monohydrate

Zeng, J.-P.; Zhang, Y.-Q.; Xue, S.-F.; Zhu, Q.-J.; Tao, Z.

doi:10.1107/S1600536809006370

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o620

doi:10.1107/S1600536809006370

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2,2′-(Heptane-1,7-diyl)dibenzimidazolium chloride nitrate monohydrate

Jin-Ping Zeng,^a Yun-Qian Zhang,^a Sai-Feng Xue,^a ^* Qian-Jiang Zhu ^a and Zhu Tao ^a,^b

^aKey Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, People's Republic of China, and ^bInstitute of Applied Chemistry, Guizhou University, Guiyang 550025, People's Republic of China
^*Correspondence e-mail: sci.yqzhang@gzu.edu.cn

(Received 8 January 2009; accepted 21 February 2009; online 28 February 2009)

In the title compound, C₂₁H₂₆N₄²⁺·Cl⁻·NO₃⁻·H₂O, the organic cations, anions and water molecules are linked through N—H⋯Cl, N—H⋯O, N—H⋯N and O—H⋯Cl hydrogen bonds, forming a three-dimensional framework, assisted by C—H⋯π interactions.

Related literature

For general background regarding interactions of linear polyaromatic compounds with cucurbit[n]urils, see: Day & Arnold (2000 ); Day et al. (2002 ); Freeman et al. (1981 ); Kim et al. (2000 ). For the synthesis, see: Wang & Joullié (1957 ).

Experimental

Crystal data

C₂₁H₂₆N₄²⁺·Cl⁻·NO₃⁻·H₂O
M_r = 449.93
Orthorhombic, P c a 2₁
a = 24.462 (10) Å
b = 5.102 (2) Å
c = 18.210 (7) Å
V = 2272.5 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 293 K
0.31 × 0.22 × 0.18 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.939, T_max = 0.964
14275 measured reflections
2086 independent reflections
1619 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.084
S = 1.03
2086 reflections
288 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.86	2.22	3.066 (3)	168
N2—H2A⋯O3ⁱ	0.86	1.94	2.778 (4)	164
N2—H2A⋯O1ⁱ	0.86	2.53	3.243 (4)	141
N2—H2A⋯N5ⁱ	0.86	2.59	3.436 (5)	168
N3—H3A⋯O2ⁱⁱ	0.86	1.95	2.807 (4)	177
N4—H4A⋯O1Wⁱⁱⁱ	0.86	1.87	2.730 (4)	173
O1W—H1WA⋯Cl1	0.927 (19)	2.19 (2)	3.088 (4)	163 (4)
O1W—H1WB⋯Cl1^iv	0.83 (2)	2.31 (3)	3.099 (3)	159 (5)
C10—H10A⋯Cg3^v	0.97	3.36	4.148 (4)	140
C11—H11B⋯Cg4^vi	0.97	3.21	4.047 (4)	146
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y, z-{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (iv) x, y+1, z; (v) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (vi) $[-x, -y+1, z-{\script{1\over 2}}]$ . Cg3 and Cg4 are the centroids of the C1–C6 and C16–C21 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 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006370/ez2159sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006370/ez2159Isup2.hkl

checkCIF report

Comment top

This paper describes the preparation and structure of a new linear polyaromatic compound (I) in which the multiple functional groups 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 molecular structure of (I), shown in Fig. 1, consists of one organic cation, one Cl^- anion, one NO₃^- anion and one lattice water molecule. The two benzimidazole groups of the organic cation are not co-planar, but are oriented at a dihedral angle of 78.42 (6) ° with respect to each other. Molecules are linked via an N1—H1A···Cl1, N2—H2A···O3, N2—H2A···O1, N2—H2A···N5, N3—H3A···O2, N4—H4A···O1W and O1W—H1WA···Cl1 network of hydrogen bonds (Table 1) forming a three-dimensional framework. In addition, C—H···π interactions occur between adjacent organic cations (Table 1, Cg(3) and Cg(4) are the centroids of the C1—C6 and C16—C21 benzene rings, respectively).

Related literature top

For general background regarding interactions of linear polyaromatic compounds with cucurbit[n]urils, see: Day & Arnold (2000); Day et al. (2002); Freeman et al. (1981); Kim et al. (2000). For the synthesis, see: Wang & Joullié (1957). Cg(3) and Cg(4) are the centroids of the C1–C6 and C16–C21 benzene rings, respectively.

Experimental top

A solution of o-phenylenediamine (5.40 g, 0.05 mol) and azelaic acid (4.71 g, 0.025 mol) were refluxed for twelve hours in 50 ml of 4M HCl. The reaction mixture was then cooled for one day and the blue crystalline 2,2'-(Heptane-1,7-diyl)dibenzimidazolium dihydrochloride which separated was removed by filtration and dried (Wang et al., 1957). Yield: 31%. The dihydrochloride (2.03 g, 5 mmol) and lanthanum nitrate (3.25 g, 10 mmol) were refluxed for three h in 50 ml water, and the mixture was cooled and filtered. Upon standing at room temperature, crystals of title compound (I) were obtained after several days.

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 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of (I), shown with the atom-labelling scheme and 50% probability displacement ellipsoids.

2,2'-(Heptane-1,7-diyl)dibenzimidazolium chloride nitrate monohydrate top

Crystal data top

C₂₁H₂₆N₄²⁺·Cl⁻·NO₃⁻·H₂O	F(000) = 952
M_r = 449.93	D_x = 1.315 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 3986 reflections
a = 24.462 (10) Å	θ = 1.7–25.1°
b = 5.102 (2) Å	µ = 0.21 mm⁻¹
c = 18.210 (7) Å	T = 293 K
V = 2272.5 (15) Å³	Prism, colorless
Z = 4	0.31 × 0.22 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2086 independent reflections
Radiation source: fine-focus sealed tube	1619 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −26→29
T_min = 0.939, T_max = 0.964	k = −6→6
14275 measured reflections	l = −21→21

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0385P)² + 0.1227P] where P = (F_o² + 2F_c²)/3
2086 reflections	(Δ/σ)_max < 0.001
288 parameters	Δρ_max = 0.19 e Å⁻³
5 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₁H₂₆N₄²⁺·Cl⁻·NO₃⁻·H₂O	V = 2272.5 (15) Å³
M_r = 449.93	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 24.462 (10) Å	µ = 0.21 mm⁻¹
b = 5.102 (2) Å	T = 293 K
c = 18.210 (7) Å	0.31 × 0.22 × 0.18 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2086 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1619 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.964	R_int = 0.063
14275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	5 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.19 e Å⁻³
2086 reflections	Δρ_min = −0.17 e Å⁻³
288 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
C1	0.31252 (16)	0.2574 (8)	0.5321 (2)	0.0467 (10)
H1	0.3358	0.1258	0.5156	0.056*
C2	0.28978 (16)	0.4345 (8)	0.4846 (2)	0.0538 (11)
H2	0.2975	0.4226	0.4347	0.065*
C3	0.25529 (18)	0.6318 (8)	0.5097 (3)	0.0548 (11)
H3	0.2410	0.7496	0.4758	0.066*
C4	0.24142 (16)	0.6603 (7)	0.5822 (3)	0.0504 (11)
H4	0.2180	0.7923	0.5981	0.061*
C5	0.26436 (14)	0.4805 (7)	0.6308 (2)	0.0409 (9)
C6	0.29941 (15)	0.2824 (7)	0.60581 (19)	0.0391 (9)
C7	0.29322 (16)	0.2498 (7)	0.7275 (2)	0.0397 (9)
C8	0.30248 (17)	0.1623 (8)	0.8034 (2)	0.0487 (10)
H8A	0.3179	−0.0129	0.8023	0.058*
H8B	0.2675	0.1516	0.8282	0.058*
C9	0.34010 (15)	0.3376 (7)	0.8482 (2)	0.0443 (10)
H9A	0.3235	0.5092	0.8537	0.053*
H9B	0.3745	0.3594	0.8224	0.053*
C10	0.35076 (16)	0.2195 (7)	0.9238 (2)	0.0440 (10)
H10A	0.3159	0.1796	0.9466	0.053*
H10B	0.3703	0.0555	0.9176	0.053*
C11	0.38324 (16)	0.3936 (8)	0.9753 (2)	0.0445 (10)
H11A	0.3640	0.5584	0.9818	0.053*
H11B	0.4185	0.4316	0.9534	0.053*
C12	0.39191 (15)	0.2656 (7)	1.0503 (2)	0.0478 (11)
H12A	0.3571	0.1985	1.0675	0.057*
H12B	0.4163	0.1173	1.0442	0.057*
C13	0.41530 (16)	0.4448 (8)	1.1086 (2)	0.0479 (10)
H13A	0.3891	0.5820	1.1197	0.057*
H13B	0.4483	0.5271	1.0901	0.057*
C14	0.42850 (16)	0.2939 (7)	1.1783 (2)	0.0475 (9)
H14A	0.3978	0.1810	1.1899	0.057*
H14B	0.4598	0.1819	1.1688	0.057*
C15	0.44061 (15)	0.4573 (7)	1.2432 (2)	0.0415 (9)
C16	0.47804 (15)	0.7535 (7)	1.3163 (2)	0.0424 (9)
C17	0.44065 (15)	0.6095 (8)	1.3572 (2)	0.0442 (10)
C18	0.43226 (17)	0.6605 (9)	1.4312 (2)	0.0579 (12)
H18	0.4077	0.5627	1.4589	0.070*
C19	0.46186 (18)	0.8618 (10)	1.4617 (3)	0.0627 (12)
H19	0.4571	0.9006	1.5112	0.075*
C20	0.4989 (2)	1.0102 (10)	1.4205 (3)	0.0607 (12)
H20	0.5176	1.1473	1.4428	0.073*
C21	0.50813 (17)	0.9566 (8)	1.3469 (2)	0.0528 (11)
H21	0.5333	1.0519	1.3194	0.063*
N1	0.31566 (11)	0.1448 (6)	0.66844 (17)	0.0403 (7)
H1A	0.3371	0.0113	0.6685	0.048*
N2	0.26120 (12)	0.4500 (6)	0.70671 (16)	0.0417 (8)
H2A	0.2418	0.5447	0.7357	0.050*
N3	0.41815 (12)	0.4278 (6)	1.30898 (16)	0.0429 (8)
H3A	0.3935	0.3142	1.3201	0.051*
N4	0.47645 (12)	0.6521 (6)	1.24534 (17)	0.0430 (8)
H4A	0.4956	0.7069	1.2088	0.052*
N5	0.32105 (13)	0.8845 (7)	1.2993 (2)	0.0466 (8)
O1	0.32896 (15)	0.9063 (7)	1.23308 (19)	0.0857 (11)
O2	0.34026 (11)	1.0441 (6)	1.34445 (16)	0.0608 (8)
O1W	0.46016 (12)	0.2164 (7)	0.62756 (17)	0.0558 (8)
O3	0.29200 (12)	0.6979 (5)	1.32219 (16)	0.0584 (8)
Cl1	0.40293 (4)	−0.28231 (18)	0.68522 (7)	0.0628 (3)
H1WA	0.4422 (19)	0.087 (7)	0.654 (3)	0.11 (2)*
H1WB	0.4403 (18)	0.347 (6)	0.633 (3)	0.10 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.039 (2)	0.050 (2)	0.051 (3)	−0.0075 (19)	0.001 (2)	−0.007 (2)
C2	0.052 (3)	0.058 (3)	0.051 (3)	−0.013 (2)	−0.005 (2)	0.001 (2)
C3	0.055 (3)	0.058 (3)	0.052 (3)	−0.014 (2)	−0.015 (2)	0.010 (2)
C4	0.041 (2)	0.039 (2)	0.072 (3)	−0.0037 (18)	−0.011 (2)	0.003 (2)
C5	0.038 (2)	0.042 (2)	0.042 (2)	−0.0061 (18)	−0.0078 (19)	−0.0017 (19)
C6	0.034 (2)	0.040 (2)	0.043 (2)	−0.0050 (17)	−0.0119 (18)	−0.0048 (18)
C7	0.036 (2)	0.040 (2)	0.043 (2)	−0.0067 (18)	−0.0029 (18)	0.0000 (18)
C8	0.047 (2)	0.049 (2)	0.050 (3)	−0.009 (2)	−0.0036 (19)	0.003 (2)
C9	0.044 (2)	0.040 (2)	0.049 (2)	−0.0033 (18)	−0.0060 (19)	0.0042 (19)
C10	0.043 (2)	0.041 (2)	0.048 (2)	−0.0021 (18)	−0.0019 (19)	0.0014 (19)
C11	0.039 (2)	0.050 (2)	0.045 (2)	0.0013 (18)	−0.0053 (18)	0.0036 (19)
C12	0.046 (3)	0.048 (3)	0.049 (3)	−0.0009 (19)	−0.001 (2)	0.004 (2)
C13	0.046 (2)	0.044 (2)	0.053 (2)	−0.0043 (19)	−0.006 (2)	0.004 (2)
C14	0.055 (2)	0.043 (2)	0.044 (2)	0.0017 (18)	−0.004 (2)	−0.001 (2)
C15	0.039 (2)	0.040 (2)	0.046 (2)	0.0059 (18)	−0.0013 (19)	0.004 (2)
C16	0.035 (2)	0.044 (2)	0.049 (2)	0.0078 (18)	−0.0055 (19)	−0.002 (2)
C17	0.037 (2)	0.049 (2)	0.046 (2)	0.0086 (19)	−0.002 (2)	−0.005 (2)
C18	0.049 (3)	0.075 (3)	0.050 (3)	0.008 (2)	0.002 (2)	−0.004 (2)
C19	0.056 (3)	0.076 (3)	0.055 (3)	0.010 (3)	−0.009 (2)	−0.022 (3)
C20	0.058 (3)	0.052 (3)	0.072 (3)	0.007 (2)	−0.025 (2)	−0.010 (2)
C21	0.042 (2)	0.050 (3)	0.066 (3)	0.005 (2)	−0.015 (2)	0.000 (2)
N1	0.0339 (16)	0.0401 (17)	0.047 (2)	0.0016 (14)	−0.0051 (16)	−0.0020 (16)
N2	0.0368 (17)	0.0398 (18)	0.049 (2)	0.0008 (15)	−0.0004 (15)	−0.0055 (15)
N3	0.0347 (17)	0.0455 (19)	0.048 (2)	0.0013 (15)	0.0025 (15)	0.0002 (17)
N4	0.0441 (19)	0.0424 (18)	0.043 (2)	0.0015 (15)	−0.0007 (16)	0.0003 (15)
N5	0.0362 (18)	0.042 (2)	0.062 (2)	0.0067 (16)	−0.0008 (18)	0.0029 (19)
O1	0.105 (3)	0.096 (3)	0.056 (2)	−0.042 (2)	0.014 (2)	−0.002 (2)
O2	0.0548 (18)	0.0584 (18)	0.069 (2)	−0.0157 (15)	0.0000 (16)	−0.0166 (17)
O1W	0.0483 (18)	0.058 (2)	0.061 (2)	−0.0063 (16)	0.0040 (15)	−0.0109 (17)
O3	0.0575 (18)	0.0548 (18)	0.0628 (19)	−0.0141 (15)	−0.0010 (16)	0.0030 (15)
Cl1	0.0477 (6)	0.0446 (5)	0.0960 (9)	0.0035 (5)	−0.0071 (6)	0.0021 (6)

Geometric parameters (Å, º) top

C1—C2	1.369 (5)	C13—C14	1.519 (5)
C1—C6	1.385 (5)	C13—H13A	0.9700
C1—H1	0.9300	C13—H13B	0.9700
C2—C3	1.391 (6)	C14—C15	1.477 (5)
C2—H2	0.9300	C14—H14A	0.9700
C3—C4	1.372 (6)	C14—H14B	0.9700
C3—H3	0.9300	C15—N3	1.326 (5)
C4—C5	1.393 (5)	C15—N4	1.326 (5)
C4—H4	0.9300	C16—C21	1.387 (5)
C5—N2	1.393 (4)	C16—C17	1.389 (5)
C5—C6	1.402 (5)	C16—N4	1.393 (5)
C6—N1	1.397 (4)	C17—C18	1.388 (5)
C7—N1	1.320 (5)	C17—N3	1.390 (5)
C7—N2	1.341 (4)	C18—C19	1.374 (6)
C7—C8	1.471 (5)	C18—H18	0.9300
C8—C9	1.520 (5)	C19—C20	1.398 (7)
C8—H8A	0.9700	C19—H19	0.9300
C8—H8B	0.9700	C20—C21	1.387 (6)
C9—C10	1.527 (5)	C20—H20	0.9300
C9—H9A	0.9700	C21—H21	0.9300
C9—H9B	0.9700	N1—H1A	0.8600
C10—C11	1.516 (5)	N2—H2A	0.8600
C10—H10A	0.9700	N3—H3A	0.8600
C10—H10B	0.9700	N4—H4A	0.8600
C11—C12	1.528 (5)	N5—O1	1.227 (4)
C11—H11A	0.9700	N5—O2	1.248 (4)
C11—H11B	0.9700	N5—O3	1.259 (4)
C12—C13	1.514 (5)	O1W—H1WA	0.927 (19)
C12—H12A	0.9700	O1W—H1WB	0.83 (2)
C12—H12B	0.9700

C2—C1—C6	117.2 (4)	H12A—C12—H12B	107.5
C2—C1—H1	121.4	C12—C13—C14	111.1 (3)
C6—C1—H1	121.4	C12—C13—H13A	109.4
C1—C2—C3	121.1 (4)	C14—C13—H13A	109.4
C1—C2—H2	119.4	C12—C13—H13B	109.4
C3—C2—H2	119.4	C14—C13—H13B	109.4
C4—C3—C2	122.9 (4)	H13A—C13—H13B	108.0
C4—C3—H3	118.6	C15—C14—C13	115.2 (3)
C2—C3—H3	118.6	C15—C14—H14A	108.5
C3—C4—C5	116.3 (4)	C13—C14—H14A	108.5
C3—C4—H4	121.9	C15—C14—H14B	108.5
C5—C4—H4	121.9	C13—C14—H14B	108.5
N2—C5—C4	133.0 (4)	H14A—C14—H14B	107.5
N2—C5—C6	106.0 (3)	N3—C15—N4	109.5 (3)
C4—C5—C6	121.0 (4)	N3—C15—C14	125.2 (4)
C1—C6—N1	132.7 (4)	N4—C15—C14	125.4 (4)
C1—C6—C5	121.5 (4)	C21—C16—C17	122.0 (4)
N1—C6—C5	105.7 (3)	C21—C16—N4	131.6 (4)
N1—C7—N2	108.8 (3)	C17—C16—N4	106.4 (3)
N1—C7—C8	125.3 (4)	C18—C17—C16	121.2 (4)
N2—C7—C8	125.9 (4)	C18—C17—N3	132.8 (4)
C7—C8—C9	114.7 (3)	C16—C17—N3	106.0 (3)
C7—C8—H8A	108.6	C19—C18—C17	117.1 (4)
C9—C8—H8A	108.6	C19—C18—H18	121.5
C7—C8—H8B	108.6	C17—C18—H18	121.5
C9—C8—H8B	108.6	C18—C19—C20	121.9 (4)
H8A—C8—H8B	107.6	C18—C19—H19	119.0
C8—C9—C10	110.8 (3)	C20—C19—H19	119.0
C8—C9—H9A	109.5	C21—C20—C19	121.2 (4)
C10—C9—H9A	109.5	C21—C20—H20	119.4
C8—C9—H9B	109.5	C19—C20—H20	119.4
C10—C9—H9B	109.5	C20—C21—C16	116.6 (4)
H9A—C9—H9B	108.1	C20—C21—H21	121.7
C11—C10—C9	114.6 (3)	C16—C21—H21	121.7
C11—C10—H10A	108.6	C7—N1—C6	110.0 (3)
C9—C10—H10A	108.6	C7—N1—H1A	125.0
C11—C10—H10B	108.6	C6—N1—H1A	125.0
C9—C10—H10B	108.6	C7—N2—C5	109.4 (3)
H10A—C10—H10B	107.6	C7—N2—H2A	125.3
C10—C11—C12	112.0 (3)	C5—N2—H2A	125.3
C10—C11—H11A	109.2	C15—N3—C17	109.3 (3)
C12—C11—H11A	109.2	C15—N3—H3A	125.3
C10—C11—H11B	109.2	C17—N3—H3A	125.3
C12—C11—H11B	109.2	C15—N4—C16	108.9 (3)
H11A—C11—H11B	107.9	C15—N4—H4A	125.6
C13—C12—C11	114.9 (3)	C16—N4—H4A	125.6
C13—C12—H12A	108.5	O1—N5—O2	121.9 (4)
C11—C12—H12A	108.5	O1—N5—O3	118.9 (4)
C13—C12—H12B	108.5	O2—N5—O3	119.2 (4)
C11—C12—H12B	108.5	H1WA—O1W—H1WB	104 (4)

C6—C1—C2—C3	0.4 (5)	N4—C16—C17—N3	−0.1 (4)
C1—C2—C3—C4	−0.8 (6)	C16—C17—C18—C19	1.0 (6)
C2—C3—C4—C5	0.6 (6)	N3—C17—C18—C19	−179.2 (4)
C3—C4—C5—N2	178.3 (4)	C17—C18—C19—C20	0.1 (6)
C3—C4—C5—C6	−0.2 (5)	C18—C19—C20—C21	−1.3 (7)
C2—C1—C6—N1	−178.1 (4)	C19—C20—C21—C16	1.4 (6)
C2—C1—C6—C5	0.0 (5)	C17—C16—C21—C20	−0.3 (5)
N2—C5—C6—C1	−179.0 (3)	N4—C16—C21—C20	178.8 (4)
C4—C5—C6—C1	−0.1 (5)	N2—C7—N1—C6	1.5 (4)
N2—C5—C6—N1	−0.4 (4)	C8—C7—N1—C6	−177.9 (3)
C4—C5—C6—N1	178.5 (3)	C1—C6—N1—C7	177.7 (4)
N1—C7—C8—C9	104.1 (4)	C5—C6—N1—C7	−0.7 (4)
N2—C7—C8—C9	−75.1 (5)	N1—C7—N2—C5	−1.8 (4)
C7—C8—C9—C10	−175.5 (3)	C8—C7—N2—C5	177.6 (3)
C8—C9—C10—C11	−174.1 (3)	C4—C5—N2—C7	−177.4 (4)
C9—C10—C11—C12	179.3 (3)	C6—C5—N2—C7	1.3 (4)
C10—C11—C12—C13	−169.9 (3)	N4—C15—N3—C17	−0.8 (4)
C11—C12—C13—C14	−173.5 (3)	C14—C15—N3—C17	177.8 (3)
C12—C13—C14—C15	−167.8 (3)	C18—C17—N3—C15	−179.2 (4)
C13—C14—C15—N3	130.3 (4)	C16—C17—N3—C15	0.5 (4)
C13—C14—C15—N4	−51.3 (5)	N3—C15—N4—C16	0.7 (4)
C21—C16—C17—C18	−0.9 (6)	C14—C15—N4—C16	−177.9 (3)
N4—C16—C17—C18	179.7 (3)	C21—C16—N4—C15	−179.7 (4)
C21—C16—C17—N3	179.3 (3)	C17—C16—N4—C15	−0.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.86	2.22	3.066 (3)	168
N2—H2A···O3ⁱ	0.86	1.94	2.778 (4)	164
N2—H2A···O1ⁱ	0.86	2.53	3.243 (4)	141
N2—H2A···N5ⁱ	0.86	2.59	3.436 (5)	168
N3—H3A···O2ⁱⁱ	0.86	1.95	2.807 (4)	177
N4—H4A···O1Wⁱⁱⁱ	0.86	1.87	2.730 (4)	173
O1W—H1WA···Cl1	0.93 (2)	2.19 (2)	3.088 (4)	163 (4)
O1W—H1WB···Cl1^iv	0.83 (2)	2.31 (3)	3.099 (3)	159 (5)
C10—H10A···Cg(3)^v	0.97	3.36	4.148 (4)	140
C11—H11B···Cg(4)^vi	0.97	3.21	4.047 (4)	146

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

Experimental details

Crystal data
Chemical formula	C₂₁H₂₆N₄²⁺·Cl⁻·NO₃⁻·H₂O
M_r	449.93
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	293
a, b, c (Å)	24.462 (10), 5.102 (2), 18.210 (7)
V (Å³)	2272.5 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.31 × 0.22 × 0.18

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.939, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	14275, 2086, 1619
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.084, 1.03
No. of reflections	2086
No. of parameters	288
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.86	2.22	3.066 (3)	167.8
N2—H2A···O3ⁱ	0.86	1.94	2.778 (4)	163.7
N2—H2A···O1ⁱ	0.86	2.53	3.243 (4)	140.9
N2—H2A···N5ⁱ	0.86	2.59	3.436 (5)	168.3
N3—H3A···O2ⁱⁱ	0.86	1.95	2.807 (4)	177.3
N4—H4A···O1Wⁱⁱⁱ	0.86	1.87	2.730 (4)	173.0
O1W—H1WA···Cl1	0.927 (19)	2.19 (2)	3.088 (4)	163 (4)
O1W—H1WB···Cl1^iv	0.83 (2)	2.31 (3)	3.099 (3)	159 (5)
C10—H10A···Cg(3)^v	0.9700	3.3590	4.148 (4)	139.92
C11—H11B···Cg(4)^vi	0.9700	3.2056	4.047 (4)	146.08

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

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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