Bis[(4-cyano­benz­yl)ammonium] bis­(perchlorate) monohydrate

Huang, Y.

doi:10.1107/S1600536811048884

organic compounds

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Volume 67| Part 12| December 2011| Page o3431

https://doi.org/10.1107/S1600536811048884

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Bis[(4-cyanobenzyl)ammonium] bis(perchlorate) monohydrate

Yao Huang ^a ^*

^aSchool of Chemical Engineering, Yunnan Radio and TV University, Kunming 650023, People's Republic of China
^*Correspondence e-mail: huangyao308sys@yahoo.com.cn

(Received 14 October 2011; accepted 16 November 2011; online 25 November 2011)

The asymmetric unit of the title compound, 2C₈H₉N₂⁺·2ClO₄⁻·H₂O, consists of two (4-cyanobenzyl)>ammonium cations, two disordered ClO₄⁻ anions and one water molecule. The differences in the two cations are reflected in the N—C—C—C torsion angles [−94.7 (3) and −115.9 (3)°]. In addition, the cations show different hydrogen-bonding patterns as one N atom bonds to two O atoms of ClO₄⁻ ions, while the other N atom is involved in hydrogen bonding with the O atoms of the ClO₄⁻ ions and water molecules. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds result in a three-dimensional network. An O atom in each of the anions is disordered over two positions of equal occupancy.

Related literature

For a related structure, see: Shahwar et al. (2009 ).

Experimental

Crystal data

2C₈H₉N₂⁺·2ClO₄⁻·H₂O
M_r = 483.26
Triclinic, $[P \overline 1]$
a = 5.0305 (10) Å
b = 13.616 (3) Å
c = 16.695 (3) Å
α = 66.79 (3)°
β = 86.17 (3)°
γ = 88.97 (3)°
V = 1048.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 293 K
0.29 × 0.25 × 0.21 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.8, T_max = 0.9
10950 measured reflections
4796 independent reflections
3490 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.179
S = 1.00
4796 reflections
285 parameters
62 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O1ⁱ	0.89	2.32	2.77 (3)	111
N2—H2C⋯O2ⁱⁱ	0.89	2.34	3.015 (4)	133
N2—H2C⋯O1′ⁱ	0.89	2.42	2.96 (3)	120
N2—H2C⋯O5′ⁱ	0.89	2.46	2.905 (9)	112
N2—H2C⋯O5ⁱ	0.89	2.55	3.036 (9)	115
N2—H2E⋯O7ⁱⁱⁱ	0.89	2.43	3.306 (5)	167
N2—H2E⋯O5ⁱⁱⁱ	0.89	2.45	3.176 (8)	139
N4—H4C⋯O1W^iv	0.89	1.96	2.845 (4)	177
N4—H4D⋯O3^iv	0.89	2.15	3.002 (5)	159
O1W—H1WA⋯O6^v	0.82 (1)	2.02 (1)	2.839 (5)	173 (5)
O1W—H1WB⋯O7ⁱⁱ	0.82 (1)	2.21 (2)	2.991 (4)	160 (4)
O1W—H1WB⋯Cl2ⁱⁱ	0.82 (1)	2.98 (3)	3.593 (3)	133 (4)
N2—H2D⋯O2	0.89	2.25	3.096 (5)	158
N2—H2D⋯O3	0.89	2.40	3.154 (5)	143
N4—H4B⋯O1W	0.89	2.25	3.011 (4)	143
N4—H4B⋯O1′	0.89	2.50	3.04 (3)	119
N4—H4B⋯O5′	0.89	2.66	3.225 (8)	123
N4—H4D⋯O4	0.89	2.63	3.202 (5)	123
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) x+1, y, z; (iii) -x+1, -y+1, -z+1; (iv) x-1, y, z; (v) -x+1, -y, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811048884/pv2463sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048884/pv2463Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811048884/pv2463Isup3.cml

checkCIF report

Comment top

Recently, the crystal structure phenylmethanaminium chloroacetate (Shahwar et al., 2009) has been reported. In our laboratory, a compound containing protonated 4-(aminomethyl)benzonitrile, ClO₄^- anions and water molecule has been synthesized. In this paper, we report the crystal structure of the title compound.

The asymmetric unit of the title compound, consists of two independent 4-(aminomethyl)benzonitrile cations, two disorder ClO₄^- anions and a water molecule. The dihedral angle between the 4-(aminomethyl)benzonitrile planes in the two cations is 7.25(9 )°. The atoms N2 and N4 are displaced out of these planes (C9–C16/N1 and C1–C8/N3) by 1.93 (3) and 1.325 (3) Å, respectively, with torsion angles C9/C12—C14/N2 and C6/C5—C2/N4 being -94.7 (3) and -115.9 (3) °, respectively.

The cations show different hydrogen bonding patterns as N2 atom bonds to two O atoms of ClO₄^- ions, while N2 atom is involved in hydrogen bonding with the O atoms of the ClO₄^- ions and H₂O of hydration. In the crystal structure, intermolecular hydrogen bonds of the types N—H···O and O—H···O result in a three-dimensional network thus stabilizing the structure. (Tab. 1 & Fig. 2).

Related literature top

For a related structure, see: Shahwar et al. (2009).

Experimental top

4-(Aminomethyl)benzonitrile (20 mmol, 2.64 g) and 10% aqueous HClO₄ in a molar ratio of 1:1 were mixed and dissolved in 50 ml water by heating to 363 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, block crystals of the title compound were formed after five days.

Structure description top

For a related structure, see: Shahwar et al. (2009).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 30% probability level. The oxygen atoms of the anions O1/O1' and O5/O5' were disordered in a 1:1 ratio.
	Fig. 2. The packing viewed along the a-axis. Hydrogen bonds are drawn as dashed lines

Bis[(4-cyanobenzyl)ammonium] bis(perchlorate) monohydrate top

Crystal data top

2C₈H₉N₂⁺·2ClO₄⁻·H₂O	Z = 2
M_r = 483.26	F(000) = 500
Triclinic, P1	D_x = 1.531 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0305 (10) Å	Cell parameters from 3490 reflections
b = 13.616 (3) Å	θ = 3.3–27.5°
c = 16.695 (3) Å	µ = 0.37 mm⁻¹
α = 66.79 (3)°	T = 293 K
β = 86.17 (3)°	Block, colorless
γ = 88.97 (3)°	0.29 × 0.25 × 0.21 mm
V = 1048.6 (4) Å³

Data collection top

Rigaku SCXmini diffractometer	4796 independent reflections
Radiation source: fine-focus sealed tube	3490 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
T_min = 0.8, T_max = 0.9	l = −21→21
10950 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.066	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.179	w = 1/[σ²(F_o²) + (0.0699P)² + 1.794P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
4796 reflections	Δρ_max = 0.70 e Å⁻³
285 parameters	Δρ_min = −0.70 e Å⁻³
62 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.047 (4)

Crystal data top

2C₈H₉N₂⁺·2ClO₄⁻·H₂O	γ = 88.97 (3)°
M_r = 483.26	V = 1048.6 (4) Å³
Triclinic, P1	Z = 2
a = 5.0305 (10) Å	Mo Kα radiation
b = 13.616 (3) Å	µ = 0.37 mm⁻¹
c = 16.695 (3) Å	T = 293 K
α = 66.79 (3)°	0.29 × 0.25 × 0.21 mm
β = 86.17 (3)°

Data collection top

Rigaku SCXmini diffractometer	4796 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	3490 reflections with I > 2σ(I)
T_min = 0.8, T_max = 0.9	R_int = 0.038
10950 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	62 restraints
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.70 e Å⁻³
4796 reflections	Δρ_min = −0.70 e Å⁻³
285 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)
N1	0.5034 (8)	0.8947 (3)	−0.0455 (3)	0.0622 (10)
N2	1.2660 (6)	0.6834 (3)	0.36264 (19)	0.0446 (7)
H2C	1.3892	0.6573	0.4013	0.067*
H2D	1.1463	0.6327	0.3702	0.067*
H2E	1.1855	0.7382	0.3702	0.067*
C11	1.0956 (8)	0.6906 (3)	0.1705 (2)	0.0445 (9)
H11A	1.1534	0.6202	0.1906	0.053*
C15	1.1073 (8)	0.8638 (3)	0.1743 (2)	0.0431 (8)
H15A	1.1737	0.9104	0.1966	0.052*
C13	0.8291 (7)	0.8294 (3)	0.0775 (2)	0.0367 (7)
C10	1.1925 (7)	0.7590 (3)	0.2048 (2)	0.0363 (7)
C14	0.9249 (8)	0.8999 (3)	0.1109 (2)	0.0441 (8)
H14A	0.8668	0.9702	0.0909	0.053*
C9	1.3941 (7)	0.7202 (3)	0.2730 (2)	0.0474 (9)
H9A	1.4938	0.6618	0.2666	0.057*
H9B	1.5188	0.7777	0.2641	0.057*
C16	0.6445 (8)	0.8667 (3)	0.0090 (2)	0.0444 (8)
C12	0.9149 (8)	0.7251 (3)	0.1071 (2)	0.0443 (8)
H12A	0.8510	0.6785	0.0844	0.053*
N3	−0.4792 (8)	0.3873 (3)	−0.0191 (2)	0.0595 (9)
N4	0.3279 (6)	0.2507 (3)	0.37842 (19)	0.0423 (7)
H4B	0.4520	0.2284	0.4171	0.063*
H4C	0.1783	0.2134	0.4011	0.063*
H4D	0.2968	0.3197	0.3653	0.063*
C3	0.1437 (8)	0.3734 (3)	0.1900 (2)	0.0444 (8)
H3A	0.2187	0.4246	0.2058	0.053*
C1	0.4220 (7)	0.2352 (3)	0.2980 (2)	0.0459 (9)
H1A	0.4646	0.1605	0.3133	0.055*
H1B	0.5839	0.2767	0.2733	0.055*
C8	−0.3365 (8)	0.3600 (3)	0.0352 (2)	0.0433 (8)
C6	−0.0743 (8)	0.2218 (3)	0.1421 (3)	0.0458 (9)
H6A	−0.1469	0.1706	0.1258	0.055*
C2	0.2180 (7)	0.2681 (3)	0.2300 (2)	0.0371 (7)
C7	0.1075 (8)	0.1923 (3)	0.2058 (3)	0.0464 (9)
H7A	0.1560	0.1210	0.2326	0.056*
C4	−0.0396 (8)	0.4042 (3)	0.1271 (2)	0.0438 (8)
H4A	−0.0901	0.4753	0.1013	0.053*
C5	−0.1485 (7)	0.3278 (3)	0.1025 (2)	0.0375 (7)
Cl1	0.81260 (16)	0.45679 (7)	0.38569 (6)	0.0390 (2)
O1	0.771 (5)	0.356 (3)	0.4610 (17)	0.068 (5)	0.50
O1'	0.709 (6)	0.363 (3)	0.4491 (18)	0.073 (5)	0.50
O2	0.7525 (6)	0.5448 (3)	0.4098 (2)	0.0673 (9)
O3	1.0947 (6)	0.4613 (3)	0.3634 (2)	0.0665 (9)
O4	0.6749 (6)	0.4664 (3)	0.3112 (2)	0.0647 (8)
Cl2	0.23525 (17)	0.09462 (7)	0.62797 (6)	0.0409 (2)
O6	0.3449 (6)	0.0479 (3)	0.5708 (2)	0.0705 (5)
O7	−0.0484 (6)	0.0887 (3)	0.6317 (2)	0.0705 (5)
O8	0.3295 (6)	0.0431 (3)	0.7120 (2)	0.0705 (5)
O5	0.2648 (14)	0.2074 (7)	0.6001 (5)	0.0705 (5)	0.50
O5'	0.3568 (14)	0.1992 (7)	0.5835 (5)	0.0705 (5)	0.50
O1W	0.8375 (6)	0.1387 (3)	0.4461 (2)	0.0520 (7)
H1WA	0.799 (10)	0.083 (2)	0.442 (3)	0.075 (17)*
H1WB	0.827 (9)	0.128 (4)	0.4981 (8)	0.059 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.070 (2)	0.057 (2)	0.063 (2)	0.0166 (18)	−0.035 (2)	−0.0242 (18)
N2	0.0431 (17)	0.0548 (19)	0.0367 (16)	−0.0024 (14)	−0.0109 (13)	−0.0175 (14)
C11	0.053 (2)	0.0374 (19)	0.044 (2)	0.0122 (16)	−0.0147 (17)	−0.0160 (16)
C15	0.050 (2)	0.0426 (19)	0.0417 (19)	0.0012 (16)	−0.0097 (16)	−0.0209 (16)
C13	0.0365 (17)	0.0427 (19)	0.0316 (17)	0.0051 (14)	−0.0069 (13)	−0.0150 (14)
C10	0.0326 (17)	0.0454 (19)	0.0301 (16)	0.0022 (14)	−0.0032 (13)	−0.0138 (14)
C14	0.052 (2)	0.0365 (19)	0.045 (2)	0.0070 (16)	−0.0091 (16)	−0.0166 (16)
C9	0.0368 (19)	0.067 (3)	0.0360 (19)	0.0068 (17)	−0.0091 (15)	−0.0168 (18)
C16	0.047 (2)	0.043 (2)	0.044 (2)	0.0073 (16)	−0.0117 (17)	−0.0164 (16)
C12	0.054 (2)	0.0408 (19)	0.043 (2)	0.0017 (16)	−0.0142 (17)	−0.0193 (16)
N3	0.069 (2)	0.060 (2)	0.057 (2)	0.0119 (18)	−0.0292 (19)	−0.0274 (18)
N4	0.0353 (15)	0.0513 (18)	0.0396 (16)	−0.0022 (13)	−0.0093 (12)	−0.0159 (14)
C3	0.050 (2)	0.0411 (19)	0.046 (2)	−0.0003 (16)	−0.0115 (16)	−0.0202 (16)
C1	0.0342 (18)	0.060 (2)	0.044 (2)	0.0085 (16)	−0.0076 (15)	−0.0213 (18)
C8	0.047 (2)	0.045 (2)	0.042 (2)	0.0020 (16)	−0.0067 (17)	−0.0199 (17)
C6	0.050 (2)	0.043 (2)	0.051 (2)	−0.0010 (16)	−0.0124 (17)	−0.0240 (17)
C2	0.0331 (17)	0.047 (2)	0.0338 (17)	0.0030 (14)	−0.0021 (13)	−0.0184 (15)
C7	0.053 (2)	0.0351 (19)	0.051 (2)	0.0074 (16)	−0.0103 (17)	−0.0154 (16)
C4	0.051 (2)	0.0361 (18)	0.044 (2)	0.0040 (16)	−0.0105 (16)	−0.0151 (16)
C5	0.0357 (18)	0.0453 (19)	0.0314 (16)	0.0024 (14)	−0.0042 (13)	−0.0149 (15)
Cl1	0.0360 (4)	0.0405 (5)	0.0415 (5)	0.0010 (3)	−0.0033 (3)	−0.0172 (4)
O1	0.090 (12)	0.056 (5)	0.042 (8)	−0.005 (7)	−0.005 (8)	−0.004 (6)
O1'	0.100 (12)	0.061 (8)	0.043 (6)	−0.033 (8)	−0.028 (6)	0.000 (5)
O2	0.0622 (19)	0.066 (2)	0.094 (2)	0.0170 (15)	−0.0153 (17)	−0.0525 (19)
O3	0.0370 (15)	0.077 (2)	0.095 (2)	0.0056 (14)	−0.0030 (15)	−0.0434 (19)
O4	0.0577 (18)	0.087 (2)	0.0553 (18)	−0.0067 (16)	−0.0151 (14)	−0.0324 (17)
Cl2	0.0403 (5)	0.0452 (5)	0.0388 (5)	−0.0029 (4)	−0.0029 (3)	−0.0181 (4)
O6	0.0604 (11)	0.0881 (12)	0.0651 (11)	0.0018 (9)	−0.0026 (8)	−0.0325 (9)
O7	0.0604 (11)	0.0881 (12)	0.0651 (11)	0.0018 (9)	−0.0026 (8)	−0.0325 (9)
O8	0.0604 (11)	0.0881 (12)	0.0651 (11)	0.0018 (9)	−0.0026 (8)	−0.0325 (9)
O5	0.0604 (11)	0.0881 (12)	0.0651 (11)	0.0018 (9)	−0.0026 (8)	−0.0325 (9)
O5'	0.0604 (11)	0.0881 (12)	0.0651 (11)	0.0018 (9)	−0.0026 (8)	−0.0325 (9)
O1W	0.0477 (16)	0.0612 (19)	0.0485 (17)	−0.0074 (14)	−0.0066 (13)	−0.0222 (15)

Geometric parameters (Å, º) top

N1—C16	1.132 (5)	C3—H3A	0.9300
N2—C9	1.482 (5)	C1—C2	1.510 (5)
N2—H2C	0.8900	C1—H1A	0.9700
N2—H2D	0.8900	C1—H1B	0.9700
N2—H2E	0.8900	C8—C5	1.444 (5)
C11—C12	1.374 (5)	C6—C7	1.382 (5)
C11—C10	1.380 (5)	C6—C5	1.386 (5)
C11—H11A	0.9300	C6—H6A	0.9300
C15—C14	1.381 (5)	C2—C7	1.384 (5)
C15—C10	1.384 (5)	C7—H7A	0.9300
C15—H15A	0.9300	C4—C5	1.392 (5)
C13—C12	1.379 (5)	C4—H4A	0.9300
C13—C14	1.393 (5)	Cl1—O1'	1.38 (3)
C13—C16	1.447 (5)	Cl1—O4	1.423 (3)
C10—C9	1.506 (5)	Cl1—O2	1.428 (3)
C14—H14A	0.9300	Cl1—O3	1.439 (3)
C9—H9A	0.9700	Cl1—O1	1.45 (3)
C9—H9B	0.9700	Cl2—O8	1.410 (3)
C12—H12A	0.9300	Cl2—O6	1.420 (3)
N3—C8	1.135 (5)	Cl2—O5	1.426 (9)
N4—C1	1.486 (5)	Cl2—O7	1.426 (3)
N4—H4B	0.8900	Cl2—O5'	1.445 (9)
N4—H4C	0.8900	O5—O5'	0.557 (8)
N4—H4D	0.8900	O1W—H1WA	0.820 (2)
C3—C4	1.377 (5)	O1W—H1WB	0.820 (2)
C3—C2	1.379 (5)

C9—N2—H2C	109.5	N4—C1—H1B	109.1
C9—N2—H2D	109.5	C2—C1—H1B	109.1
H2C—N2—H2D	109.5	H1A—C1—H1B	107.8
C9—N2—H2E	109.5	N3—C8—C5	178.1 (5)
H2C—N2—H2E	109.5	C7—C6—C5	119.9 (3)
H2D—N2—H2E	109.5	C7—C6—H6A	120.0
C12—C11—C10	120.8 (3)	C5—C6—H6A	120.0
C12—C11—H11A	119.6	C3—C2—C7	119.3 (3)
C10—C11—H11A	119.6	C3—C2—C1	120.8 (3)
C14—C15—C10	120.6 (3)	C7—C2—C1	119.9 (3)
C14—C15—H15A	119.7	C6—C7—C2	120.4 (3)
C10—C15—H15A	119.7	C6—C7—H7A	119.8
C12—C13—C14	120.5 (3)	C2—C7—H7A	119.8
C12—C13—C16	119.6 (3)	C3—C4—C5	119.4 (3)
C14—C13—C16	119.8 (3)	C3—C4—H4A	120.3
C11—C10—C15	119.4 (3)	C5—C4—H4A	120.3
C11—C10—C9	120.1 (3)	C6—C5—C4	119.8 (3)
C15—C10—C9	120.5 (3)	C6—C5—C8	120.5 (3)
C15—C14—C13	119.0 (3)	C4—C5—C8	119.6 (3)
C15—C14—H14A	120.5	O1'—Cl1—O4	102.7 (9)
C13—C14—H14A	120.5	O1'—Cl1—O2	110.4 (14)
N2—C9—C10	111.8 (3)	O4—Cl1—O2	110.4 (2)
N2—C9—H9A	109.3	O1'—Cl1—O3	117.5 (13)
C10—C9—H9A	109.3	O4—Cl1—O3	108.8 (2)
N2—C9—H9B	109.3	O2—Cl1—O3	106.82 (19)
C10—C9—H9B	109.3	O1'—Cl1—O1	14.8 (18)
H9A—C9—H9B	107.9	O4—Cl1—O1	115.4 (10)
N1—C16—C13	178.5 (4)	O2—Cl1—O1	110.3 (11)
C11—C12—C13	119.6 (3)	O3—Cl1—O1	104.6 (11)
C11—C12—H12A	120.2	O8—Cl2—O6	110.8 (2)
C13—C12—H12A	120.2	O8—Cl2—O5	109.5 (4)
C1—N4—H4B	109.5	O6—Cl2—O5	117.2 (3)
C1—N4—H4C	109.5	O8—Cl2—O7	110.7 (2)
H4B—N4—H4C	109.5	O6—Cl2—O7	109.4 (2)
C1—N4—H4D	109.5	O5—Cl2—O7	98.7 (3)
H4B—N4—H4D	109.5	O8—Cl2—O5'	110.7 (4)
H4C—N4—H4D	109.5	O6—Cl2—O5'	97.5 (3)
C4—C3—C2	121.1 (3)	O5—Cl2—O5'	22.3 (3)
C4—C3—H3A	119.4	O7—Cl2—O5'	117.1 (3)
C2—C3—H3A	119.4	O5'—O5—Cl2	80.8 (15)
N4—C1—C2	112.7 (3)	O5—O5'—Cl2	76.9 (15)
N4—C1—H1A	109.1	H1WA—O1W—H1WB	108 (5)
C2—C1—H1A	109.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O1ⁱ	0.89	2.32	2.77 (3)	111
N2—H2C···O2ⁱⁱ	0.89	2.34	3.015 (4)	133
N2—H2C···O1′ⁱ	0.89	2.42	2.96 (3)	120
N2—H2C···O5′ⁱ	0.89	2.46	2.905 (9)	112
N2—H2C···O5ⁱ	0.89	2.55	3.036 (9)	115
N2—H2E···O7ⁱⁱⁱ	0.89	2.43	3.306 (5)	167
N2—H2E···O5ⁱⁱⁱ	0.89	2.45	3.176 (8)	139
N4—H4C···O1W^iv	0.89	1.96	2.845 (4)	177
N4—H4D···O3^iv	0.89	2.15	3.002 (5)	159
O1W—H1WA···O6^v	0.82 (1)	2.02 (1)	2.839 (5)	173 (5)
O1W—H1WB···O7ⁱⁱ	0.82 (1)	2.21 (2)	2.991 (4)	160 (4)
O1W—H1WB···Cl2ⁱⁱ	0.82 (1)	2.98 (3)	3.593 (3)	133 (4)
N2—H2D···O2	0.89	2.25	3.096 (5)	158
N2—H2D···O3	0.89	2.40	3.154 (5)	143
N4—H4B···O1W	0.89	2.25	3.011 (4)	143
N4—H4B···O1′	0.89	2.50	3.04 (3)	119
N4—H4B···O5′	0.89	2.66	3.225 (8)	123
N4—H4D···O4	0.89	2.63	3.202 (5)	123

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

Experimental details

Crystal data
Chemical formula	2C₈H₉N₂⁺·2ClO₄⁻·H₂O
M_r	483.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.0305 (10), 13.616 (3), 16.695 (3)
α, β, γ (°)	66.79 (3), 86.17 (3), 88.97 (3)
V (Å³)	1048.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.29 × 0.25 × 0.21

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.8, 0.9
No. of measured, independent and observed [I > 2σ(I)] reflections	10950, 4796, 3490
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.179, 1.00
No. of reflections	4796
No. of parameters	285
No. of restraints	62
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.70

Computer programs: CrystalClear (Rigaku, 2005), 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
N2—H2C···O1ⁱ	0.89	2.32	2.77 (3)	111.1
N2—H2C···O2ⁱⁱ	0.89	2.34	3.015 (4)	132.8
N2—H2C···O1'ⁱ	0.89	2.42	2.96 (3)	119.7
N2—H2C···O5'ⁱ	0.89	2.46	2.905 (9)	111.5
N2—H2C···O5ⁱ	0.89	2.55	3.036 (9)	115.2
N2—H2E···O7ⁱⁱⁱ	0.89	2.43	3.306 (5)	167.0
N2—H2E···O5ⁱⁱⁱ	0.89	2.45	3.176 (8)	139.0
N4—H4C···O1W^iv	0.89	1.96	2.845 (4)	176.5
N4—H4D···O3^iv	0.89	2.15	3.002 (5)	159.1
O1W—H1WA···O6^v	0.820 (2)	2.024 (9)	2.839 (5)	173 (5)
O1W—H1WB···O7ⁱⁱ	0.820 (2)	2.209 (17)	2.991 (4)	160 (4)
O1W—H1WB···Cl2ⁱⁱ	0.820 (2)	2.98 (3)	3.593 (3)	133 (4)
N2—H2D···O2	0.89	2.25	3.096 (5)	157.9
N2—H2D···O3	0.89	2.40	3.154 (5)	142.7
N4—H4B···O1W	0.89	2.25	3.011 (4)	143.3
N4—H4B···O1'	0.89	2.50	3.04 (3)	119.3
N4—H4B···O5'	0.89	2.66	3.225 (8)	122.6
N4—H4D···O4	0.89	2.63	3.202 (5)	123.1

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

Acknowledgements

This work was supported by a start-up grant from the Yunnan Radio and TV University.

References

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Shahwar, D., Tahir, M. N., Ahmad, N., Khan, M. A. & Yasmeen, A. (2009). Acta Cryst. E65, o1312. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar