4-[(4-Chloro­phen­yl)(phen­yl)­meth­yl]­piperazin-1-ium picrate monohydrate

Song, Y.; Chidan Kumar, C.S.; Chandraju, S.; Naveen, S.; Li, H.

doi:10.1107/S1600536812031984

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2486

https://doi.org/10.1107/S1600536812031984

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4-[(4-Chlorophenyl)(phenyl)methyl]piperazin-1-ium picrate monohydrate

Yanxi Song,^a C. S. Chidan Kumar,^b S. Chandraju,^c S. Naveen ^d and Hongqi Li ^e ^*

^aSchool of Environmental Science and Engineering, Donghua University, Shanghai 201620, People's Repulic of China, ^bDepartment of Chemistry, G. Madegowda Institute of Technology, Bharathi Nagar 571 422, India, ^cDepartment of Sugar Technology, University of Mysore, Sir. M. V. PG Center, Tubinakere 571 402, India, ^dDepartment of Physics, School of Engineering and Technology, Jain University, Bangalore 562 112, India, and ^eCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, People's Repulic of China
^*Correspondence e-mail: hongqili@dhu.edu.cn

(Received 22 June 2012; accepted 13 July 2012; online 18 July 2012)

The asymmetric unit of the title compound, C₁₇H₂₀ClN₂⁺·C₆H₂N₃O₇⁻·H₂O, contains a piperazin-1-ium cation, a picrate anion and one solvent water molecule. The piperazene ring is protonated at one N atom and adopts a highly distorted chair conformation with the chloropheny(phenyl)methyl substituent on the second N atom in an equatorial position. The crystal structure is stabilized by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For the biological activity of 1-benzylpiperazine, see: Campbell et al. (1973 ). For related structures, see: Jasinski et al. (2011 ); Song et al. (2012 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₇H₂₀ClN₂⁺·C₆H₂N₃O₇⁻·H₂O
M_r = 533.92
Monoclinic, C 2/c
a = 21.144 (2) Å
b = 8.2997 (8) Å
c = 28.528 (3) Å
β = 93.029 (1)°
V = 4999.3 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.949, T_max = 0.985
12567 measured reflections
4417 independent reflections
2996 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.175
S = 1.04
4417 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1Wⁱ	0.90	2.03	2.850 (4)	151
N2—H2B⋯O1ⁱⁱ	0.90	1.96	2.819 (3)	160
N2—H2B⋯O2ⁱⁱ	0.90	2.42	3.017 (4)	124
O1W—H1WA⋯O1	0.85	1.97	2.805 (3)	168
C16—H16B⋯O5ⁱⁱⁱ	0.97	2.34	3.166 (4)	143
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x, y, z-1; (iii) -x+2, -y+1, -z+1.

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: 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/S1600536812031984/sj5246sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031984/sj5246Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031984/sj5246Isup3.cml

checkCIF report

Comment top

1-Benzylpiperazine was originally synthesized as a potential anthelmintic (Campbell et al., 1973) and its derivatives were found to possess excellent pharmacological activities. These include vasodilator, hypotensive and antiviral activity, the ability to increase cerebral blood flow and broad pharmacological action on central nervous system. In the course of our studies on the salts of piperazines (Jasinski et al., 2011; Song et al., 2012) and in view of the importance of piperazines, the paper reports the crystal and molecular structure of the title piperazin-1-ium salt.

The molecular structure and atom numbering scheme of the title compound are shown in Fig 1. In the title compound, the piperazine group is protonated at the N2 atom and adopts a highly distorted chair conformation with puckering parameters Q, θ and φ having values of 0.595 (3) °, 6.4 (3) ° and 342 (3) °, respectively. For an ideal chair conformation, θ has a value of 0 or 180°. The bond lengths (Allen et al., 1987) and bond angles are in good agreement with standard values. The crystal structure is stabilized by intermolecular O–H···O, N–H···O and C–H···O hydrogen bonds.

Related literature top

For the biological activity of 1-benzylpiperazine, see: Campbell et al. (1973). For related structures, see: Jasinski et al. (2011); Song et al. (2012). For bond-length data, see: Allen et al. (1987).

Experimental top

1-((4-Chlorophenyl)(phenyl)methyl)piperazine (2.88 g, 0.01 mol) and picric acid (2.99 g, 0.01 mol) were dissolved separately in methanol. Both the solutions were mixed together and stirred for a few minutes at room temperature. The precipitate was collected by filtration and purified by recrystallization from methanol. On recrystallization with DMF after 15 days, good quality single crystals were obtained by the slow evaporation method. (M.P.: 441–445 K).

Structure description top

For the biological activity of 1-benzylpiperazine, see: Campbell et al. (1973). For related structures, see: Jasinski et al. (2011); Song et al. (2012). For bond-length data, see: Allen et al. (1987).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

4-[(4-Chlorophenyl)(phenyl)methyl]piperazin-1-ium 2,4,6-trinitrophenolate monohydrate top

Crystal data top

C₁₇H₂₀ClN₂⁺·C₆H₂N₃O₇⁻·H₂O	F(000) = 2224
M_r = 533.92	D_x = 1.419 Mg m⁻³
Monoclinic, C2/c	Melting point = 441–445 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 21.144 (2) Å	Cell parameters from 2514 reflections
b = 8.2997 (8) Å	θ = 2.3–21.0°
c = 28.528 (3) Å	µ = 0.21 mm⁻¹
β = 93.029 (1)°	T = 296 K
V = 4999.3 (8) Å³	Block, yellow
Z = 8	0.25 × 0.22 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	4417 independent reflections
Radiation source: fine-focus sealed tube	2996 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 25.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −25→20
T_min = 0.949, T_max = 0.985	k = −9→8
12567 measured reflections	l = −31→33

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0837P)² + 4.3115P] where P = (F_o² + 2F_c²)/3
4417 reflections	(Δ/σ)_max < 0.001
334 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₇H₂₀ClN₂⁺·C₆H₂N₃O₇⁻·H₂O	V = 4999.3 (8) Å³
M_r = 533.92	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.144 (2) Å	µ = 0.21 mm⁻¹
b = 8.2997 (8) Å	T = 296 K
c = 28.528 (3) Å	0.25 × 0.22 × 0.07 mm
β = 93.029 (1)°

Data collection top

Bruker APEXII CCD diffractometer	4417 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2996 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.985	R_int = 0.026
12567 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.04	Δρ_max = 0.63 e Å⁻³
4417 reflections	Δρ_min = −0.46 e Å⁻³
334 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	0.4904 (2)	0.8333 (6)	0.18443 (11)	0.0783 (11)
C2	0.5527 (2)	0.8799 (4)	0.19014 (11)	0.0737 (10)
H2	0.5633	0.9873	0.1955	0.088*
C3	0.59944 (16)	0.7637 (4)	0.18770 (10)	0.0606 (8)
H3	0.6418	0.7938	0.1915	0.073*
C4	0.58414 (13)	0.6039 (4)	0.17965 (9)	0.0490 (7)
C5	0.52105 (16)	0.5623 (5)	0.17391 (12)	0.0700 (9)
H5	0.5100	0.4553	0.1682	0.084*
C6	0.47386 (18)	0.6774 (7)	0.17651 (14)	0.0917 (13)
H6	0.4314	0.6481	0.1729	0.110*
C7	0.63529 (13)	0.4768 (3)	0.17948 (9)	0.0471 (7)
H7	0.6158	0.3740	0.1699	0.057*
C8	0.66452 (14)	0.4592 (3)	0.22959 (9)	0.0472 (7)
C9	0.63449 (16)	0.3611 (4)	0.26056 (10)	0.0609 (8)
H9	0.5991	0.3016	0.2503	0.073*
C10	0.65702 (19)	0.3512 (4)	0.30690 (11)	0.0749 (10)
H10	0.6356	0.2884	0.3279	0.090*
C11	0.7106 (2)	0.4329 (4)	0.32234 (11)	0.0766 (11)
H11	0.7259	0.4240	0.3534	0.092*
C12	0.74098 (18)	0.5272 (4)	0.29149 (11)	0.0683 (9)
H12	0.7776	0.5820	0.3015	0.082*
C13	0.71784 (15)	0.5421 (3)	0.24554 (10)	0.0572 (8)
H13	0.7385	0.6089	0.2251	0.069*
C14	0.65583 (14)	0.5363 (4)	0.09816 (9)	0.0526 (7)
H14A	0.6220	0.6154	0.0980	0.063*
H14B	0.6379	0.4345	0.0874	0.063*
C15	0.70566 (15)	0.5901 (4)	0.06551 (10)	0.0569 (8)
H15A	0.6869	0.5989	0.0338	0.068*
H15B	0.7213	0.6956	0.0750	0.068*
C16	0.78429 (15)	0.4460 (4)	0.11470 (10)	0.0624 (8)
H16A	0.8031	0.5443	0.1274	0.075*
H16B	0.8170	0.3640	0.1148	0.075*
C17	0.73229 (14)	0.3923 (4)	0.14476 (10)	0.0535 (7)
H17A	0.7135	0.2937	0.1321	0.064*
H17B	0.7495	0.3703	0.1763	0.064*
C18	0.89491 (14)	0.6145 (3)	0.98892 (9)	0.0476 (7)
C19	0.92823 (13)	0.7277 (3)	1.01969 (9)	0.0458 (6)
C20	0.98723 (13)	0.7849 (3)	1.01257 (9)	0.0478 (7)
H20	1.0065	0.8563	1.0340	0.057*
C21	1.01856 (13)	0.7372 (3)	0.97362 (9)	0.0463 (6)
C22	0.98998 (13)	0.6302 (3)	0.94120 (9)	0.0473 (7)
H22	1.0111	0.5966	0.9151	0.057*
C23	0.93097 (14)	0.5763 (3)	0.94855 (8)	0.0456 (6)
Cl1	0.43227 (7)	0.9810 (2)	0.18712 (4)	0.1402 (6)
N1	0.68382 (10)	0.5177 (2)	0.14618 (7)	0.0434 (5)
N2	0.75908 (12)	0.4746 (3)	0.06606 (8)	0.0579 (7)
H2A	0.7458	0.3808	0.0531	0.069*
H2B	0.7900	0.5140	0.0488	0.069*
N3	0.89901 (14)	0.7854 (3)	1.06134 (9)	0.0658 (7)
N4	1.08105 (12)	0.7960 (3)	0.96648 (9)	0.0631 (7)
N5	0.90198 (15)	0.4691 (3)	0.91305 (9)	0.0638 (7)
O1	0.84301 (10)	0.5503 (3)	0.99573 (7)	0.0664 (6)
O2	0.84210 (16)	0.7700 (4)	1.06424 (12)	0.1309 (14)
O3	0.92957 (14)	0.8649 (4)	1.08951 (9)	0.1129 (11)
O4	1.10570 (11)	0.8886 (3)	0.99550 (9)	0.0830 (7)
O5	1.10730 (11)	0.7526 (4)	0.93145 (9)	0.0903 (8)
O6	0.93478 (15)	0.3624 (3)	0.89779 (9)	0.0927 (9)
O7	0.84749 (14)	0.4966 (4)	0.89915 (9)	0.0922 (9)
O1W	0.74452 (12)	0.3604 (3)	0.95584 (11)	0.0996 (9)
H1WA	0.7756	0.4210	0.9638	0.100*
H1WB	0.7219	0.4009	0.9333	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.076 (3)	0.113 (3)	0.0465 (18)	0.037 (2)	0.0071 (17)	0.008 (2)
C2	0.104 (3)	0.069 (2)	0.0476 (18)	0.020 (2)	0.0063 (18)	−0.0020 (16)
C3	0.063 (2)	0.066 (2)	0.0534 (17)	0.0055 (16)	0.0062 (14)	−0.0042 (15)
C4	0.0517 (17)	0.0633 (19)	0.0323 (13)	−0.0009 (14)	0.0060 (11)	0.0012 (12)
C5	0.057 (2)	0.086 (2)	0.066 (2)	−0.0055 (18)	−0.0042 (16)	0.0045 (18)
C6	0.053 (2)	0.139 (4)	0.083 (3)	0.013 (2)	−0.0016 (19)	0.021 (3)
C7	0.0550 (17)	0.0479 (16)	0.0390 (14)	−0.0083 (13)	0.0066 (12)	−0.0017 (12)
C8	0.0609 (18)	0.0451 (15)	0.0362 (14)	0.0050 (13)	0.0099 (12)	0.0016 (12)
C9	0.070 (2)	0.0621 (19)	0.0514 (17)	−0.0011 (16)	0.0138 (15)	0.0072 (15)
C10	0.102 (3)	0.078 (2)	0.0464 (18)	0.010 (2)	0.0210 (18)	0.0172 (17)
C11	0.114 (3)	0.074 (2)	0.0407 (17)	0.022 (2)	−0.0060 (18)	−0.0037 (17)
C12	0.092 (3)	0.059 (2)	0.0517 (19)	0.0035 (18)	−0.0103 (17)	−0.0110 (16)
C13	0.076 (2)	0.0493 (17)	0.0459 (16)	−0.0060 (15)	0.0015 (14)	0.0000 (13)
C14	0.0597 (18)	0.0622 (18)	0.0360 (14)	−0.0025 (14)	0.0050 (12)	0.0029 (13)
C15	0.068 (2)	0.0625 (19)	0.0413 (15)	−0.0056 (15)	0.0105 (13)	0.0058 (13)
C16	0.0562 (19)	0.077 (2)	0.0551 (18)	0.0061 (16)	0.0105 (14)	−0.0074 (16)
C17	0.0615 (18)	0.0558 (17)	0.0437 (15)	0.0042 (14)	0.0074 (13)	−0.0004 (13)
C18	0.0596 (18)	0.0456 (15)	0.0377 (14)	−0.0050 (13)	0.0036 (12)	0.0050 (12)
C19	0.0569 (18)	0.0463 (15)	0.0349 (13)	−0.0004 (13)	0.0105 (12)	−0.0017 (11)
C20	0.0556 (18)	0.0469 (15)	0.0407 (14)	0.0011 (13)	0.0000 (12)	−0.0056 (12)
C21	0.0450 (16)	0.0524 (16)	0.0416 (14)	0.0024 (12)	0.0037 (12)	−0.0032 (12)
C22	0.0587 (18)	0.0481 (16)	0.0357 (14)	0.0051 (13)	0.0066 (12)	0.0004 (12)
C23	0.0615 (18)	0.0420 (15)	0.0332 (13)	−0.0034 (13)	0.0002 (12)	−0.0011 (11)
Cl1	0.1339 (11)	0.1911 (15)	0.0945 (9)	0.1027 (11)	−0.0038 (7)	0.0031 (8)
N1	0.0497 (13)	0.0483 (13)	0.0329 (11)	0.0007 (10)	0.0079 (9)	0.0009 (9)
N2	0.0628 (16)	0.0653 (16)	0.0474 (14)	−0.0124 (13)	0.0204 (11)	−0.0090 (12)
N3	0.073 (2)	0.0739 (18)	0.0525 (15)	−0.0172 (15)	0.0207 (14)	−0.0167 (13)
N4	0.0517 (16)	0.0783 (18)	0.0599 (16)	−0.0023 (13)	0.0082 (13)	−0.0124 (14)
N5	0.083 (2)	0.0657 (18)	0.0430 (14)	−0.0191 (16)	0.0051 (14)	−0.0043 (13)
O1	0.0707 (15)	0.0780 (15)	0.0518 (12)	−0.0294 (12)	0.0165 (10)	−0.0060 (10)
O2	0.110 (2)	0.157 (3)	0.134 (3)	−0.068 (2)	0.080 (2)	−0.084 (2)
O3	0.096 (2)	0.176 (3)	0.0682 (16)	−0.019 (2)	0.0176 (14)	−0.0608 (19)
O4	0.0640 (15)	0.1024 (19)	0.0827 (16)	−0.0237 (14)	0.0053 (12)	−0.0275 (15)
O5	0.0620 (15)	0.131 (2)	0.0809 (17)	−0.0089 (15)	0.0277 (13)	−0.0341 (16)
O6	0.142 (3)	0.0651 (15)	0.0704 (16)	−0.0023 (16)	0.0001 (16)	−0.0268 (13)
O7	0.0768 (18)	0.135 (2)	0.0642 (16)	−0.0288 (17)	−0.0021 (13)	−0.0199 (15)
O1W	0.0735 (17)	0.0920 (19)	0.133 (2)	−0.0152 (14)	0.0024 (16)	−0.0241 (17)

Geometric parameters (Å, º) top

C1—C6	1.356 (6)	C15—H15B	0.9700
C1—C2	1.376 (5)	C16—N2	1.479 (4)
C1—Cl1	1.740 (4)	C16—C17	1.497 (4)
C2—C3	1.384 (5)	C16—H16A	0.9700
C2—H2	0.9300	C16—H16B	0.9700
C3—C4	1.382 (4)	C17—N1	1.463 (3)
C3—H3	0.9300	C17—H17A	0.9700
C4—C5	1.379 (4)	C17—H17B	0.9700
C4—C7	1.511 (4)	C18—O1	1.244 (3)
C5—C6	1.386 (5)	C18—C19	1.444 (4)
C5—H5	0.9300	C18—C23	1.449 (4)
C6—H6	0.9300	C19—C20	1.360 (4)
C7—N1	1.474 (3)	C19—N3	1.449 (4)
C7—C8	1.534 (4)	C20—C21	1.381 (4)
C7—H7	0.9800	C20—H20	0.9300
C8—C13	1.378 (4)	C21—C22	1.397 (4)
C8—C9	1.381 (4)	C21—N4	1.433 (4)
C9—C10	1.384 (4)	C22—C23	1.352 (4)
C9—H9	0.9300	C22—H22	0.9300
C10—C11	1.372 (5)	C23—N5	1.459 (4)
C10—H10	0.9300	N2—H2A	0.9000
C11—C12	1.364 (5)	N2—H2B	0.9000
C11—H11	0.9300	N3—O3	1.202 (3)
C12—C13	1.380 (4)	N3—O2	1.217 (4)
C12—H12	0.9300	N4—O5	1.223 (3)
C13—H13	0.9300	N4—O4	1.226 (3)
C14—N1	1.471 (3)	N5—O6	1.219 (4)
C14—C15	1.510 (4)	N5—O7	1.220 (4)
C14—H14A	0.9700	O1W—H1WA	0.8501
C14—H14B	0.9700	O1W—H1WA	0.8501
C15—N2	1.481 (4)	O1W—H1WB	0.8502
C15—H15A	0.9700

C6—C1—C2	121.6 (3)	H15A—C15—H15B	108.0
C6—C1—Cl1	120.2 (4)	N2—C16—C17	110.2 (2)
C2—C1—Cl1	118.2 (4)	N2—C16—H16A	109.6
C1—C2—C3	118.7 (4)	C17—C16—H16A	109.6
C1—C2—H2	120.6	N2—C16—H16B	109.6
C3—C2—H2	120.6	C17—C16—H16B	109.6
C4—C3—C2	121.0 (3)	H16A—C16—H16B	108.1
C4—C3—H3	119.5	N1—C17—C16	109.9 (2)
C2—C3—H3	119.5	N1—C17—H17A	109.7
C5—C4—C3	118.5 (3)	C16—C17—H17A	109.7
C5—C4—C7	120.9 (3)	N1—C17—H17B	109.7
C3—C4—C7	120.6 (3)	C16—C17—H17B	109.7
C4—C5—C6	121.0 (4)	H17A—C17—H17B	108.2
C4—C5—H5	119.5	O1—C18—C19	126.1 (3)
C6—C5—H5	119.5	O1—C18—C23	122.4 (2)
C1—C6—C5	119.2 (4)	C19—C18—C23	111.4 (2)
C1—C6—H6	120.4	C20—C19—C18	123.9 (2)
C5—C6—H6	120.4	C20—C19—N3	116.2 (2)
N1—C7—C4	111.4 (2)	C18—C19—N3	119.9 (3)
N1—C7—C8	111.3 (2)	C19—C20—C21	120.2 (2)
C4—C7—C8	108.5 (2)	C19—C20—H20	119.9
N1—C7—H7	108.6	C21—C20—H20	119.9
C4—C7—H7	108.6	C20—C21—C22	120.4 (3)
C8—C7—H7	108.6	C20—C21—N4	120.1 (2)
C13—C8—C9	118.6 (3)	C22—C21—N4	119.5 (2)
C13—C8—C7	122.8 (2)	C23—C22—C21	118.6 (2)
C9—C8—C7	118.5 (3)	C23—C22—H22	120.7
C8—C9—C10	120.0 (3)	C21—C22—H22	120.7
C8—C9—H9	120.0	C22—C23—C18	125.4 (2)
C10—C9—H9	120.0	C22—C23—N5	116.8 (2)
C11—C10—C9	120.9 (3)	C18—C23—N5	117.7 (3)
C11—C10—H10	119.5	C17—N1—C14	107.3 (2)
C9—C10—H10	119.5	C17—N1—C7	111.5 (2)
C12—C11—C10	119.1 (3)	C14—N1—C7	111.4 (2)
C12—C11—H11	120.5	C16—N2—C15	110.5 (2)
C10—C11—H11	120.5	C16—N2—H2A	109.5
C11—C12—C13	120.6 (3)	C15—N2—H2A	109.5
C11—C12—H12	119.7	C16—N2—H2B	109.5
C13—C12—H12	119.7	C15—N2—H2B	109.5
C8—C13—C12	120.8 (3)	H2A—N2—H2B	108.1
C8—C13—H13	119.6	O3—N3—O2	120.7 (3)
C12—C13—H13	119.6	O3—N3—C19	119.5 (3)
N1—C14—C15	110.2 (2)	O2—N3—C19	119.1 (3)
N1—C14—H14A	109.6	O5—N4—O4	122.8 (3)
C15—C14—H14A	109.6	O5—N4—C21	118.5 (3)
N1—C14—H14B	109.6	O4—N4—C21	118.7 (2)
C15—C14—H14B	109.6	O6—N5—O7	124.4 (3)
H14A—C14—H14B	108.1	O6—N5—C23	117.7 (3)
N2—C15—C14	111.0 (2)	O7—N5—C23	117.8 (3)
N2—C15—H15A	109.4	H1WA—O1W—H1WA	0.0
C14—C15—H15A	109.4	H1WA—O1W—H1WB	111.4
N2—C15—H15B	109.4	H1WA—O1W—H1WB	111.4
C14—C15—H15B	109.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1Wⁱ	0.90	2.03	2.850 (4)	151
N2—H2B···O1ⁱⁱ	0.90	1.96	2.819 (3)	160
N2—H2B···O2ⁱⁱ	0.90	2.42	3.017 (4)	124
O1W—H1WA···O1	0.85	1.97	2.805 (3)	168
C16—H16B···O5ⁱⁱⁱ	0.97	2.34	3.166 (4)	143

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) x, y, z−1; (iii) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₂₀ClN₂⁺·C₆H₂N₃O₇⁻·H₂O
M_r	533.92
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	21.144 (2), 8.2997 (8), 28.528 (3)
β (°)	93.029 (1)
V (Å³)	4999.3 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.25 × 0.22 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.949, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	12567, 4417, 2996
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.175, 1.04
No. of reflections	4417
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.46

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 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—H2A···O1Wⁱ	0.90	2.03	2.850 (4)	150.9
N2—H2B···O1ⁱⁱ	0.90	1.96	2.819 (3)	160.4
N2—H2B···O2ⁱⁱ	0.90	2.42	3.017 (4)	123.8
O1W—H1WA···O1	0.85	1.97	2.805 (3)	168.0
C16—H16B···O5ⁱⁱⁱ	0.97	2.34	3.166 (4)	143

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) x, y, z−1; (iii) −x+2, −y+1, −z+1.

Acknowledgements

This work was supported in part by the Council for the Chemical Sciences of the Netherlands Organization for Scientific Research. YS and HL acknowledge financial support by the Fundamental Research Funds for the Central Universities.

References

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