2-Amino-3-carb­oxy­pyridinium chloride hemihydrate

Bouchene, R.; Bouacida, S.; Berrah, F.; Daran, J.-C.

doi:10.1107/S1600536812017230

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1493-o1494

doi:10.1107/S1600536812017230

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2-Amino-3-carboxypyridinium chloride hemihydrate

Rafika Bouchene,^a,^b Sofiane Bouacida,^c,^a ^* Fadila Berrah ^a,^b and Jean-Claude Daran ^d

^aLaboratoire de Chimie Appliquée et Technologie des Matériaux (LCATM), Université Oum El Bouaghi, Algeria, ^bDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria, ^cUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université Mentouri–Constantine, 25000 Algeria, and ^dLaboratoire de Chimie de Coodination, UPR–CNRS 8241, 205 route de Narbonne, 31077 Toulouse Cedex 04, France
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

(Received 15 April 2012; accepted 18 April 2012; online 21 April 2012)

The asymmetric unit of the title compound, C₆H₇N₂O₂⁺·Cl⁻·0.5H₂O, consists of two protonated 2-amino-3-carboxypyridine cations, two chloride anions and one molecule of water. The crystal packing can be described as alternating layers of cations and anions parallel to (110), which are linked together by O_w—H⋯Cl interactions. In the crystal, four types of classical hydrogen bonds are observed, viz. cation–anion (O—H⋯Cl and N—H⋯Cl), cation–cation (N—H⋯O), cation–water (N—H⋯O_w) and water–anion (O_w—H⋯Cl), resulting in the formation of an infinite three-dimensional network.

Related literature

For applications of hybrid organic–inorganic compounds, see: Bouacida (2008 ); Kickelbick (2007 ); Mitzi et al. (1998 ); Asaji et al. (2007 ); Lynch & Jones (2004 ). For related structures, see: Beatty (2003 ); Sengupta et al. (2001 ); Berrah et al. (2011a ,b ,c ); Akriche & Rzaigui (2007 ).

Experimental

Crystal data

C₆H₇N₂O₂⁺·Cl⁻·0.5H₂O
M_r = 183.60
Triclinic, $[P \overline 1]$
a = 7.8949 (4) Å
b = 9.1639 (5) Å
c = 11.0285 (6) Å
α = 81.392 (4)°
β = 81.276 (3)°
γ = 81.682 (4)°
V = 773.68 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 180 K
0.1 × 0.08 × 0.06 mm

Data collection

Agilent Xcalibur Sapphire1 long-nozzle diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.831, T_max = 1
14449 measured reflections
3600 independent reflections
2857 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.08
S = 1.01
3600 reflections
214 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯Cl1	0.85 (1)	2.24 (1)	3.0887 (12)	173 (2)
O1W—H2W⋯Cl2	0.84 (2)	2.33 (2)	3.1639 (12)	170 (2)
O2A—H2A⋯Cl1ⁱ	0.82	2.18	2.9948 (11)	177
O2B—H2B⋯O1Wⁱ	0.82	1.78	2.5818 (15)	166
N3B—H3B2⋯O1B	0.86	2.10	2.7176 (17)	128
N3B—H3B2⋯O1Aⁱⁱ	0.86	2.25	2.9903 (17)	144
N3A—H3A2⋯O1A	0.86	2.04	2.6644 (16)	129
N3A—H3A2⋯O1Bⁱⁱ	0.86	2.17	2.8781 (17)	140
N3A—H3A1⋯Cl2ⁱⁱⁱ	0.86	2.34	3.1447 (13)	156
N4A—H4A⋯Cl2ⁱⁱⁱ	0.86	2.44	3.2265 (12)	152
N4B—H4B⋯Cl2	0.86	2.21	3.0510 (13)	166
Symmetry codes: (i) x, y, z-1; (ii) -x, -y+1, -z; (iii) -x, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia,1997 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812017230/bq2352sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017230/bq2352Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812017230/bq2352Isup3.cml

checkCIF report

Comment top

Organic-inorganic hybrid compounds represent one of the most important developments in materials chemistry in recent years. The tremendous possibilities of combination of different properties in one material initiated an explosion of ideas about potential materials and applications (Bouacida, 2008; Kickelbick, 2007; Mitzi et al., 1998). Hybrid structures including substituted pyridines organic units have drawn increasing attention due to their potential applications in biological and industrial fields (Asaji et al., 2007; Lynch & Jones, 2004), nitrogen in the pyridine ring has a lone pair of electrons which is not delocalized with the aromatic π-electron system and is easily available for protonation (Berrah et al., 2011a). In the presence of a carboxylic acid substituent, they are recognized as efficient N–O donors exhibiting diverse mode of coordination (Beatty, 2003; Sengupta et al., 2001). Their fascinating structures are rich in H-bonds wich have a potential importance in crystal stability (Berrah et al., 2011a,b,c; Akriche & Rzaigui, 2007).

In continuation of our search to enrich the varieties in such kinds of hybrid compounds and to investigate the influence of hydrogen bonds on the structural features, we report here the synthesis and crystal structure of 2-amino-3-carboxypyridinium chloride hemi hydrate, (I).

The asymmetric unit in this compound consists of two protonated, "2-amino-3-carboxypyridine", amino acids cations (A and B), two chloride anions and one molecule of water. The molecular geometry and the atom-numbering scheme of (I) are shown in Fig. 1. Bond distances and angles observed in the different entities, present no unusual features and are consistent with those reported previously (Berrah et al., 2011b). The crystal packing can be described as alternating layers parallel to (110) plane, which are linked together by O1W—H···Cl interactions involving molecule of water and anions chloride (Fig.2). In this structure, four types of classical hydrogen bonds are observed, viz. cation-anion [O—H···Cl & N—H···Cl], cation-cation [N—H···O], cation-water [N—H···O1W] and water-anion [O1W—H···Cl] (Fig. 3). All these interactions bonds link the molecules within the layers and also link the layers together, forming a three-dimensional network and reinforcing the cohesion of the structure. Additional hydrogen bond parameters are listed in table 1.

Related literature top

For applications of hybrid compounds, see: Bouacida (2008); Kickelbick (2007); Mitzi et al. (1998); Asaji et al. (2007); Lynch & Jones (2004). For related structures, see: Beatty (2003); Sengupta et al. (2001); Berrah et al. (2011a,b,c); Akriche & Rzaigui (2007).

Experimental top

The title compound was synthesized by reacting 3-amino-pyridine-2-carboxylic acid (3 mmol) with InCl₃ (1 mmol)in an aqueous solution of hydrochloric acid. The solutions were slowly evaporated to dryness for a couple of weeks. Some colorless crystals were carefully isolated under polarizing microscope for analysis by X-ray diffraction.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia,1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of (I) with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. (Brandenburg & Berndt, 2001) Partial packing viewed via c axis showing layers parallel to (110) plane, which are connected with O—H···Cl Hydrogen bonds, shown as dashed lines.
	Fig. 3. (Brandenburg & Berndt, 2001) Partial packing viewed via b axis showing Hydrogen bonds interactions, as dashed lines, cation-anion [O—H···Cl & N—H···Cl], cation-cation [N—H···O], cation-water [N—H···O1W] and water-anion [O1W—H···Cl].

2-Amino-3-carboxypyridinium chloride hemihydrate top

Crystal data top

C₆H₇N₂O₂⁺·Cl⁻·0.5H₂O	Z = 4
M_r = 183.60	F(000) = 380
Triclinic, P1	D_x = 1.576 Mg m⁻³
a = 7.8949 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.1639 (5) Å	Cell parameters from 8921 reflections
c = 11.0285 (6) Å	θ = 3.0–28.3°
α = 81.392 (4)°	µ = 0.45 mm⁻¹
β = 81.276 (3)°	T = 180 K
γ = 81.682 (4)°	Box, colourless
V = 773.68 (7) Å³	0.1 × 0.08 × 0.06 mm

Data collection top

Agilent Xcalibur Sapphire1 long-nozzle diffractometer	3600 independent reflections
Radiation source: fine-focus sealed tube	2857 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 8.2632 pixels mm^-1	θ_max = 28.4°, θ_min = 3.0°
ω scans	h = −10→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→12
T_min = 0.831, T_max = 1	l = −13→14
14449 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.08	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0442P)² + 0.1332P] where P = (F_o² + 2F_c²)/3
3600 reflections	(Δ/σ)_max = 0.006
214 parameters	Δρ_max = 0.26 e Å⁻³
3 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₆H₇N₂O₂⁺·Cl⁻·0.5H₂O	γ = 81.682 (4)°
M_r = 183.60	V = 773.68 (7) Å³
Triclinic, P1	Z = 4
a = 7.8949 (4) Å	Mo Kα radiation
b = 9.1639 (5) Å	µ = 0.45 mm⁻¹
c = 11.0285 (6) Å	T = 180 K
α = 81.392 (4)°	0.1 × 0.08 × 0.06 mm
β = 81.276 (3)°

Data collection top

Agilent Xcalibur Sapphire1 long-nozzle diffractometer	3600 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2857 reflections with I > 2σ(I)
T_min = 0.831, T_max = 1	R_int = 0.033
14449 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	3 restraints
wR(F²) = 0.08	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.26 e Å⁻³
3600 reflections	Δρ_min = −0.28 e Å⁻³
214 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
N3A	−0.02482 (16)	0.24894 (14)	0.18532 (11)	0.0277 (3)
H3A1	−0.0772	0.2962	0.2448	0.033*
H3A2	−0.0497	0.2761	0.1114	0.033*
N3B	0.13489 (17)	0.59931 (14)	0.23112 (12)	0.0291 (3)
H3B1	0.0857	0.6432	0.2933	0.035*
H3B2	0.1053	0.6298	0.1588	0.035*
O1W	0.33167 (15)	0.38876 (12)	0.72134 (10)	0.0306 (2)
H1W	0.287 (2)	0.3146 (14)	0.7070 (17)	0.046*
H2W	0.280 (2)	0.4650 (14)	0.6834 (16)	0.046*
Cl1	0.19706 (5)	0.11808 (4)	0.64870 (3)	0.03012 (11)
Cl2	0.14081 (5)	0.65043 (4)	0.55111 (3)	0.03071 (11)
O1A	0.05136 (14)	0.18895 (12)	−0.04721 (9)	0.0301 (2)
O2A	0.26652 (14)	0.01182 (12)	−0.09112 (9)	0.0287 (2)
H2A	0.2445	0.0392	−0.1619	0.043*
O1B	0.20803 (14)	0.54951 (12)	−0.00916 (10)	0.0333 (3)
N4A	0.12830 (15)	0.09603 (13)	0.32534 (10)	0.0220 (2)
H4A	0.074	0.1486	0.3809	0.026*
N4B	0.29795 (16)	0.44117 (14)	0.36162 (11)	0.0259 (3)
H4B	0.2425	0.488	0.4204	0.031*
C2B	0.34601 (17)	0.40270 (14)	0.15203 (12)	0.0193 (3)
C2A	0.19059 (17)	0.05053 (15)	0.11658 (12)	0.0196 (3)
C3A	0.09315 (17)	0.13510 (15)	0.20751 (12)	0.0201 (3)
C5A	0.24283 (19)	−0.01981 (16)	0.36061 (13)	0.0256 (3)
H5A	0.2593	−0.0421	0.4434	0.031*
C7A	0.30817 (19)	−0.06680 (16)	0.15319 (13)	0.0238 (3)
H7A	0.372	−0.1227	0.0942	0.029*
C1A	0.16107 (18)	0.09171 (15)	−0.01399 (12)	0.0210 (3)
O2B	0.38993 (13)	0.34859 (11)	−0.05118 (9)	0.0272 (2)
H2B	0.3638	0.3747	−0.1211	0.041*
C1B	0.30608 (17)	0.44226 (15)	0.02359 (12)	0.0209 (3)
C7B	0.47068 (18)	0.28766 (16)	0.18251 (13)	0.0227 (3)
H7B	0.5304	0.2339	0.1208	0.027*
C3B	0.25557 (18)	0.48538 (15)	0.24663 (13)	0.0218 (3)
C5B	0.4206 (2)	0.32921 (17)	0.39066 (14)	0.0279 (3)
H5B	0.4441	0.3064	0.4719	0.033*
C6B	0.51055 (19)	0.24892 (17)	0.30269 (13)	0.0264 (3)
H6B	0.5956	0.171	0.322	0.032*
C6A	0.3345 (2)	−0.10448 (17)	0.27672 (14)	0.0281 (3)
H6A	0.413	−0.1856	0.3008	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3A	0.0289 (7)	0.0298 (7)	0.0217 (6)	0.0094 (6)	−0.0026 (5)	−0.0084 (5)
N3B	0.0302 (7)	0.0268 (6)	0.0280 (7)	0.0051 (6)	−0.0008 (5)	−0.0080 (5)
O1W	0.0410 (7)	0.0254 (6)	0.0259 (5)	0.0005 (5)	−0.0104 (5)	−0.0036 (4)
Cl1	0.0377 (2)	0.0322 (2)	0.02155 (18)	−0.00542 (16)	−0.00607 (15)	−0.00379 (14)
Cl2	0.0382 (2)	0.0302 (2)	0.02172 (18)	0.00677 (16)	−0.00392 (15)	−0.00771 (14)
O1A	0.0310 (6)	0.0335 (6)	0.0227 (5)	0.0100 (5)	−0.0058 (4)	−0.0049 (4)
O2A	0.0349 (6)	0.0301 (6)	0.0179 (5)	0.0084 (5)	−0.0028 (4)	−0.0059 (4)
O1B	0.0351 (6)	0.0326 (6)	0.0278 (6)	0.0113 (5)	−0.0065 (5)	−0.0024 (4)
N4A	0.0249 (6)	0.0228 (6)	0.0185 (5)	−0.0021 (5)	−0.0001 (5)	−0.0062 (4)
N4B	0.0261 (6)	0.0306 (7)	0.0208 (6)	−0.0008 (5)	0.0008 (5)	−0.0093 (5)
C2B	0.0190 (6)	0.0178 (6)	0.0209 (6)	−0.0034 (5)	−0.0004 (5)	−0.0032 (5)
C2A	0.0190 (7)	0.0188 (6)	0.0209 (7)	−0.0021 (5)	−0.0015 (5)	−0.0042 (5)
C3A	0.0193 (7)	0.0216 (7)	0.0197 (6)	−0.0041 (5)	−0.0017 (5)	−0.0033 (5)
C5A	0.0304 (8)	0.0265 (7)	0.0202 (7)	−0.0028 (6)	−0.0061 (6)	−0.0014 (6)
C7A	0.0250 (7)	0.0223 (7)	0.0232 (7)	0.0005 (6)	−0.0013 (6)	−0.0055 (5)
C1A	0.0211 (7)	0.0212 (7)	0.0204 (7)	−0.0028 (6)	−0.0003 (5)	−0.0045 (5)
O2B	0.0330 (6)	0.0277 (5)	0.0197 (5)	0.0050 (5)	−0.0058 (4)	−0.0058 (4)
C1B	0.0191 (7)	0.0204 (7)	0.0225 (7)	−0.0017 (6)	−0.0007 (5)	−0.0039 (5)
C7B	0.0224 (7)	0.0227 (7)	0.0232 (7)	−0.0025 (6)	−0.0009 (6)	−0.0058 (5)
C3B	0.0201 (7)	0.0217 (7)	0.0239 (7)	−0.0049 (6)	−0.0005 (5)	−0.0043 (5)
C5B	0.0284 (8)	0.0344 (8)	0.0210 (7)	−0.0043 (7)	−0.0050 (6)	−0.0024 (6)
C6B	0.0247 (7)	0.0269 (7)	0.0264 (7)	0.0007 (6)	−0.0059 (6)	−0.0013 (6)
C6A	0.0300 (8)	0.0249 (7)	0.0273 (7)	0.0049 (6)	−0.0070 (6)	−0.0018 (6)

Geometric parameters (Å, º) top

N3A—C3A	1.3143 (18)	C2B—C7B	1.3738 (19)
N3A—H3A1	0.86	C2B—C3B	1.4236 (19)
N3A—H3A2	0.86	C2B—C1B	1.4785 (18)
N3B—C3B	1.3172 (18)	C2A—C7A	1.3695 (19)
N3B—H3B1	0.86	C2A—C3A	1.4227 (19)
N3B—H3B2	0.86	C2A—C1A	1.4778 (18)
O1W—H1W	0.854 (9)	C5A—C6A	1.353 (2)
O1W—H2W	0.843 (9)	C5A—H5A	0.93
O1A—C1A	1.2058 (17)	C7A—C6A	1.394 (2)
O2A—C1A	1.3221 (16)	C7A—H7A	0.93
O2A—H2A	0.82	O2B—C1B	1.3179 (16)
O1B—C1B	1.2058 (17)	O2B—H2B	0.82
N4A—C5A	1.3420 (18)	C7B—C6B	1.3911 (19)
N4A—C3A	1.3548 (17)	C7B—H7B	0.93
N4A—H4A	0.86	C5B—C6B	1.357 (2)
N4B—C5B	1.342 (2)	C5B—H5B	0.93
N4B—C3B	1.3491 (18)	C6B—H6B	0.93
N4B—H4B	0.86	C6A—H6A	0.93

C3A—N3A—H3A1	120	C2A—C7A—C6A	121.60 (13)
C3A—N3A—H3A2	120	C2A—C7A—H7A	119.2
H3A1—N3A—H3A2	120	C6A—C7A—H7A	119.2
C3B—N3B—H3B1	120	O1A—C1A—O2A	123.10 (12)
C3B—N3B—H3B2	120	O1A—C1A—C2A	123.28 (12)
H3B1—N3B—H3B2	120	O2A—C1A—C2A	113.62 (12)
H1W—O1W—H2W	106.3 (15)	C1B—O2B—H2B	109.5
C1A—O2A—H2A	109.5	O1B—C1B—O2B	123.72 (13)
C5A—N4A—C3A	123.91 (12)	O1B—C1B—C2B	123.43 (12)
C5A—N4A—H4A	118	O2B—C1B—C2B	112.84 (12)
C3A—N4A—H4A	118	C2B—C7B—C6B	122.19 (13)
C5B—N4B—C3B	124.58 (13)	C2B—C7B—H7B	118.9
C5B—N4B—H4B	117.7	C6B—C7B—H7B	118.9
C3B—N4B—H4B	117.7	N3B—C3B—N4B	118.05 (13)
C7B—C2B—C3B	118.77 (12)	N3B—C3B—C2B	125.61 (13)
C7B—C2B—C1B	121.29 (12)	N4B—C3B—C2B	116.33 (13)
C3B—C2B—C1B	119.94 (12)	N4B—C5B—C6B	120.70 (13)
C7A—C2A—C3A	118.82 (12)	N4B—C5B—H5B	119.7
C7A—C2A—C1A	122.21 (12)	C6B—C5B—H5B	119.7
C3A—C2A—C1A	118.96 (12)	C5B—C6B—C7B	117.41 (14)
N3A—C3A—N4A	118.07 (12)	C5B—C6B—H6B	121.3
N3A—C3A—C2A	125.06 (12)	C7B—C6B—H6B	121.3
N4A—C3A—C2A	116.85 (12)	C5A—C6A—C7A	118.20 (14)
N4A—C5A—C6A	120.56 (13)	C5A—C6A—H6A	120.9
N4A—C5A—H5A	119.7	C7A—C6A—H6A	120.9
C6A—C5A—H5A	119.7

C5A—N4A—C3A—N3A	178.44 (13)	C7B—C2B—C1B—O2B	5.75 (18)
C5A—N4A—C3A—C2A	−2.8 (2)	C3B—C2B—C1B—O2B	−174.82 (12)
C7A—C2A—C3A—N3A	−179.18 (14)	C3B—C2B—C7B—C6B	0.4 (2)
C1A—C2A—C3A—N3A	0.5 (2)	C1B—C2B—C7B—C6B	179.82 (13)
C7A—C2A—C3A—N4A	2.20 (19)	C5B—N4B—C3B—N3B	−178.55 (13)
C1A—C2A—C3A—N4A	−178.08 (12)	C5B—N4B—C3B—C2B	1.8 (2)
C3A—N4A—C5A—C6A	1.4 (2)	C7B—C2B—C3B—N3B	179.06 (13)
C3A—C2A—C7A—C6A	−0.2 (2)	C1B—C2B—C3B—N3B	−0.4 (2)
C1A—C2A—C7A—C6A	−179.93 (14)	C7B—C2B—C3B—N4B	−1.36 (19)
C7A—C2A—C1A—O1A	175.54 (13)	C1B—C2B—C3B—N4B	179.19 (12)
C3A—C2A—C1A—O1A	−4.2 (2)	C3B—N4B—C5B—C6B	−1.3 (2)
C7A—C2A—C1A—O2A	−4.50 (19)	N4B—C5B—C6B—C7B	0.1 (2)
C3A—C2A—C1A—O2A	175.79 (12)	C2B—C7B—C6B—C5B	0.3 (2)
C7B—C2B—C1B—O1B	−173.77 (14)	N4A—C5A—C6A—C7A	0.8 (2)
C3B—C2B—C1B—O1B	5.7 (2)	C2A—C7A—C6A—C5A	−1.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···Cl1	0.85 (1)	2.24 (1)	3.0887 (12)	173 (2)
O1W—H2W···Cl2	0.84 (2)	2.33 (2)	3.1639 (12)	170 (2)
O2A—H2A···Cl1ⁱ	0.82	2.18	2.9948 (11)	177
O2B—H2B···O1Wⁱ	0.82	1.78	2.5818 (15)	166
N3B—H3B2···O1B	0.86	2.10	2.7176 (17)	128
N3B—H3B2···O1Aⁱⁱ	0.86	2.25	2.9903 (17)	144
N3A—H3A2···O1A	0.86	2.04	2.6644 (16)	129
N3A—H3A2···O1Bⁱⁱ	0.86	2.17	2.8781 (17)	140
N3A—H3A1···Cl2ⁱⁱⁱ	0.86	2.34	3.1447 (13)	156
N4A—H4A···Cl2ⁱⁱⁱ	0.86	2.44	3.2265 (12)	152
N4B—H4B···Cl2	0.86	2.21	3.0510 (13)	166
C5A—H5A···Cl1	0.93	2.82	3.5417 (15)	135
C6A—H6A···O1W^iv	0.93	2.55	3.427 (2)	158
C7A—H7A···O2A	0.93	2.42	2.7397 (17)	100
C7B—H7B···O2B	0.93	2.37	2.7065 (17)	101

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

Experimental details

Crystal data
Chemical formula	C₆H₇N₂O₂⁺·Cl⁻·0.5H₂O
M_r	183.60
Crystal system, space group	Triclinic, P1
Temperature (K)	180
a, b, c (Å)	7.8949 (4), 9.1639 (5), 11.0285 (6)
α, β, γ (°)	81.392 (4), 81.276 (3), 81.682 (4)
V (Å³)	773.68 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.1 × 0.08 × 0.06

Data collection
Diffractometer	Agilent Xcalibur Sapphire1 long-nozzle diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.831, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	14449, 3600, 2857
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.08, 1.01
No. of reflections	3600
No. of parameters	214
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.28

Computer programs: CrysAlis PRO (Agilent, 2011), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia,1997) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···Cl1	0.854 (14)	2.240 (14)	3.0887 (12)	172.6 (16)
O1W—H2W···Cl2	0.844 (15)	2.330 (15)	3.1639 (12)	170.1 (15)
O2A—H2A···Cl1ⁱ	0.8200	2.1800	2.9948 (11)	177.00
O2B—H2B···O1Wⁱ	0.8200	1.7800	2.5818 (15)	166.00
N3B—H3B2···O1B	0.8600	2.1000	2.7176 (17)	128.00
N3B—H3B2···O1Aⁱⁱ	0.8600	2.2500	2.9903 (17)	144.00
N3A—H3A2···O1A	0.8600	2.0400	2.6644 (16)	129.00
N3A—H3A2···O1Bⁱⁱ	0.8600	2.1700	2.8781 (17)	140.00
N3A—H3A1···Cl2ⁱⁱⁱ	0.8600	2.3400	3.1447 (13)	156.00
N4A—H4A···Cl2ⁱⁱⁱ	0.8600	2.4400	3.2265 (12)	152.00
N4B—H4B···Cl2	0.8600	2.2100	3.0510 (13)	166.00

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

Acknowledgements

We are grateful to all personel of the LCATM laboratory, Université Oum El Bouaghi, Algérie for their assistance. Thanks are due to MESRS and ANDRU (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique et l'Agence Nationale pour le Développement de la Recherche Universitaire (ANDRU) - Algérie) via the PNR programme for financial support.

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