Adeninium 3-carboxy­anilinium bis­(perchlorate) trihydrate

Bendjeddou, L.; Cherouana, A.; Hadjadj, N.; Dahaoui, S.; Lecomte, C.

doi:10.1107/S1600536809034199

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Pages o2303-o2304

doi:10.1107/S1600536809034199

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Adeninium 3-carboxyanilinium bis(perchlorate) trihydrate

Lamia Bendjeddou,^a ^* Aouatef Cherouana,^a Nasreddine Hadjadj,^a Slimane Dahaoui ^b and Claude Lecomte ^b

^aLaboratoire de Chimie Moléculaire, du Contrôle de l'Environnement et des Mesures Physico-Chimiques, Faculté des Sciences Exactes, Département de Chimie, Université Mentouri de Constantine, 25000 Constantine, Algeria, and ^bCristallographie, Résonance Magnétique et Modélisation (CRM2), Université Henri Poincaré, Nancy 1, Faculté des Sciences, BP 70239, 54506 Vandoeuvre lès Nancy CEDEX, France
^*Correspondence e-mail: Lamiabendjeddou@yahoo.fr

(Received 25 August 2009; accepted 26 August 2009; online 5 September 2009)

In the title salt, C₅H₆N₅⁺·C₇H₈NO₂⁺·2ClO₄⁻·3H₂O, the 3-carboxyanilinium and adeninium cations are monoprotonated at the amino group and at a pyrimidine N atom respectively. In the crystal, the components are involved in extensive three-dimensional hydrogen-bonding networks composed of O—H⋯O, N—H⋯O, O—H⋯N, N—H⋯N and C—H⋯O interactions. Bifurcated hydrogen bonds are observed between perchlorate O atoms and adeninium cations.

Related literature

For hydrogen bonds in hybrid compounds, see: Baker et al. (1992 ); Richards et al. (1972 ). Hydrogen-bonding patterns involving aminopyrimidine and carboxylates have been observed in drug-receptor interactions, protein-nucleic acid interactions and supramolecular architectures, see: Perutz & Ten Eyck (1972 ). For their applications in drug design and the crystal engineering of pharmaceuticals, see: Desiraju (1989 ). For the use of aminopyrimidine derivatives as antifolate drugs, see: Stanley et al. (2005 ); Hunt et al. (1980 ). For studies of cation–anion hydrogen-bonding in organic salts of carboxylic acids, see: Bendjeddou et al. (2003 , 2009 ); Cherouana et al. (2003 ); Moussa Slimane et al. (2009 ). For the dependence of bond lengths and angles in adeninium cations on the degree of protonation, see: Hingerty et al. (1981 ); Langer & Huml (1978 ). For bond angles in unprotonated adenine, see: Voet & Rich (1970 ). For the hydrogen-bonding pattern in adeninium perchlorate adenine dihydrate, see: Zeleňák et al. (2004 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For a description of the Cambridge Structural Database, see: Allen et al. (1987 ).

Experimental

Crystal data

C₅H₆N₅⁺·C₇H₈NO₂⁺·2ClO₄⁻·3H₂O
M_r = 527.24
Triclinic, $[P \overline 1]$
a = 8.95610 (10) Å
b = 10.5563 (2) Å
c = 11.7362 (2) Å
α = 71.431 (7)°
β = 85.800 (5)°
γ = 78.192 (4)°
V = 1029.52 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 120 K
0.16 × 0.1 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
55756 measured reflections
6914 independent reflections
5822 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.098
S = 0.97
6914 reflections
316 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯O2W	0.86	2.03	2.8135 (13)	151
N1A—H1A⋯O6	0.86	2.54	3.0145 (14)	115
O1M—H1M⋯N7Aⁱ	0.82	1.86	2.6676 (14)	167
N1—H1N⋯O1Wⁱⁱ	0.89	1.86	2.7381 (15)	171
N1—H2N⋯O2W	0.89	1.92	2.8111 (14)	174
N1—H3N⋯O7ⁱⁱⁱ	0.89	2.00	2.8539 (14)	162
N9A—H9A⋯N3A^iv	0.86	2.07	2.9013 (14)	163
O3W—H13W⋯O1^v	0.868 (15)	2.297 (14)	3.0378 (18)	143.5 (13)
O3W—H13W⋯O1Mⁱⁱⁱ	0.868 (15)	2.548 (16)	3.0127 (14)	114.5 (11)
O1W—H21W⋯O4ⁱⁱ	0.843 (15)	2.149 (13)	2.9329 (14)	154.6 (18)
O1W—H21W⋯O7^vi	0.843 (15)	2.49 (2)	3.0553 (14)	124.9 (14)
O2W—H22W⋯O3	0.841 (14)	2.466 (15)	2.9164 (16)	114.5 (13)
O2W—H22W⋯O3ⁱⁱ	0.841 (14)	2.161 (15)	2.9627 (16)	159.3 (16)
O3W—H23W⋯O6	0.869 (17)	2.062 (17)	2.9199 (14)	169.5 (16)
N6A—H61⋯O1W	0.86	2.46	2.9458 (15)	116
N6A—H61⋯O8^vi	0.86	2.33	3.0126 (15)	137
N6A—H62⋯O2M^vii	0.86	1.97	2.8187 (14)	167
C2A—H2A⋯O6	0.93	2.50	3.0047 (15)	115
C2A—H2A⋯O7ⁱⁱⁱ	0.93	2.48	3.2166 (15)	136
C5M—H5M⋯O1ⁱⁱ	0.93	2.52	3.3883 (17)	156
C8A—H8A⋯O5^viii	0.93	2.58	3.2881 (15)	133
C8A—H8A⋯O3W^ix	0.93	2.42	3.1994 (16)	142
Symmetry codes: (i) x-1, y, z+1; (ii) -x+1, -y, -z+1; (iii) -x, -y+1, -z+1; (iv) -x, -y+1, -z; (v) x, y+1, z; (vi) -x+1, -y+1, -z+1; (vii) x+1, y, z-1; (viii) x, y, z-1; (ix) -x+1, -y+1, -z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); 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 ), PARST97 (Nardelli, 1995 ), Mercury (Macrae et al., 2006 ) and POVRay (Persistence of Vision Team, 2004 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034199/at2870sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034199/at2870Isup2.hkl

checkCIF report

Comment top

Hydrogen bonds of hybrid compounds are of interest because of their widespread biological occurrence (Baker et al., 1992), Richards et al., 1972). Hydrogen-bonding patterns involving aminopyrimidine and carboxylates have been observed in drug-receptor interactions, protein-nucleic acid interactions and supramolecular architectures (Perutz et al., 1972). Studies of such interactions are also of current interest because of their applications in drug design and the crystal engineering of pharmaceuticals (Desiraju et al., 1989). Pyrimidine and aminopyrimidine derivatives are biologically important as they occur in nature as components of nucleic acid. Some aminopyrimidine derivatives are used as antifolate drugs (Stanley et al., 2005; Hunt et al., 1980). The supramolecular networks become especially interesting when the cation and anion can participate in hydrogen-bonding. In this regard previous studies have been concerned with organic salts of carboxylic acids (Bendjeddou et al., 2003; 2009; Cherouana et al., 2003; Moussa Slimane et al., 2009)

Our investigations have focused on the use of perchloric, amino acids and/or nitrogen base acid as a structural building in the synthesis of hydrogen-bonded patterns inorganic-organic high-dimensional structure.

The asymmetric unit of (I) consists of two different monoprotonated adeninium and m-carboxyanilinium cations, two perchlorate anions and three water molecules (Fig. 1). A proton transfer from the perchloric acid to atom N1A of the imidazolyl moiety of adenine base and N1 of m-carboxyalinine acid resulted in the formation of salts. Adeninium cations can be either mono- or diprotonated and the bond lengths and angles are dependent on the degree of protonation (Hingerty et al., 1981; Langer & Huml, 1978). This form contains three basic N atoms, the most basic site is N1, which accepts the first proton, and the next protonation occurs at N7 and then at N3. In the title compound (I), only atom N1 is protonated. This is evident from the increase in the ring angle at the site of protonation, namely N1. The internal angles at N1 is increased from the reported values of 119.8 in unprotonated adenine (Voet & Rich, 1970). The bond lengths and angles of m-carboxyanilinium cation correspond to those expected for the atom types and the type of hybridization (Allen et al., 1987). All bond lengths and angles shows that the two perchlorate anions are tetrahedral.

The title compound is built on the basis of alternating cations and anions chains, the water molecules are sandwiched between them (Fig. 2). In (I), the cationic entities are connected into a two-dimensional hydrogen-bonded network via O—H..N, N—H···N and N—H···O hydrogen bonds, thus generating double layers, the junction between them is ensured by a N1A—H1A···O2w and N1—H2N···O2w hydrogen bonds via a water molecule (H2O(2)), forming a centrosymmetric rings a long [100] axe which can be described by the graph-set motif of R₆³(34) (Bernstein et al., 1995) (Fig. 3a).

The carbonyl O and the carboxyl H atoms participates in hydrogen bonding with a neighbouring adeninium cation through an N—H···O and O—H···N hydrogen bond. The combination of these two hydrogen bonds generates a noncentrosymmetric fused rings which can be described by the graph-set motif of R₂²(9). The adeninium cations are linked by two independents N—H···N hydrogen bonds (Table 3), atom N9A (x, y, z) acts as a hydrogen-bond donor to atom N3A at (-x, 1 - y,-z), so generating a Centrosymmetric ring R₂²(8). A similar pattern was also observed in the crystal structure of adeninium perchlorate adenine dihydrate (Zeleňák, et al., 2004) (Fig. 3 b).

The water molecules plays a pivotal role, they bridges the perchlorate anions as shown in Fig.4, so forming an alternating of R₂²(4) and an R₄⁴(12) rings running parallel to the [100] direction at a = 1/2 & 0 respectively.

The H atoms respectively from protonated atom N1 and atom C2A are involved in bifurcated hydrogen bonding with perchlorate atom O6 to form a five-membered hydrogen-bonded R₂¹(5) ring into a two-dimensional network (Fig.5).

Related literature top

For hydrogen bonds in hybrid compounds, see: Baker et al. (1992); Richards et al. (1972). Hydrogen-bonding patterns involving aminopyrimidine and carboxylates have been observed in drug-receptor interactions, protein-nucleic acid interactions and supramolecular architectures, see: Perutz & Ten Eyck (1972). Studies of such interactions are also of current interest because of their applications in drug design and the crystal engineering of pharmaceuticals, sse: Desiraju (1989). For the use of aminopyrimidine derivatives as antifolate drugs, see: Stanley et al. (2005); Hunt et al. (1980). For studies of cation–anion hydrogen-bonding in organic salts of carboxylic acids, see: Bendjeddou et al. (2003, 2009); Cherouana et al. (2003); Moussa Slimane et al. (2009). For the dependence of bond lengths and angles in adeninium cations on the degree of protonation, see: Hingerty et al. (1981); Langer & Huml (1978). For bond angles in unprotonated adenine, see: Voet & Rich (1970). For the hydrogen-bonding pattern in adeninium perchlorate adenine dihydrate, see: Zeleňák et al. (2004). For hydrogen-bond motifs, see: Bernstein et al. (1995). For a description of the Cambridge Structural Database, see: Allen et al. (1987).

Experimental top

The compound was obtained as colourless crystals, after few days, by slow evaporation from an aqueous solution of adenine, m-carboxyphenyl ammonium and perchloric acid in stoechiometric ratio of 1:1:1.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); 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), PARST97 (Nardelli, 1995), Mercury (Macrae et al., 2006) and POVRay (Persistence of Vision Team, 2004).

Figures top

	Fig. 1. The asymmetric unit of (I), showing the atom-labelling scheme and the hydrogen bonds within the selected asymmetric unit (dashed lines). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram for the title compound, viewed along the a axis, showing the formation of layers.
	Fig. 3. View of the two-dimensional hydrogen-bonded network parallel to the (001) and (101) planes of (I), showing the aggregation of R²₂(8), R²₂(9) and R⁴₂(34) hydrogen-bonding motifs. Atoms marked with a star (*), a hash symbol (#), an ampersand (&) or an at sign (@), are at the symmetry positions (-1 + x, y, 1 + z), (-1 + x, y, z), (x, 1 - y, z), (1 + x, y - 1 + z), respectively.
	Fig. 4. Part of the crystal structure, showing the aggregation of R⁴₄(12) and R²₂(4) motifs via O—H···O hydrogen bonds. Atoms marked with a hash symbol (#), an ampersand (&), dollar sign ($), or a star (*) are at the symmetry positions (-1 + x, y, z), (1 - x, -y, 1 - z), (x, -1 + y, z), (-x, -y, 1 - z), respectively.
	Fig. 5. Bifurcate hydrogen bonding

Adeninium 3-carboxyanilinium bis(perchlorate) trihydrate top

Crystal data top

C₅H₆N₅⁺·C₇H₈NO₂⁺·2ClO₄⁻·3H₂O	Z = 2
M_r = 527.24	F(000) = 544
Triclinic, P1	D_x = 1.701 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9561 (1) Å	Cell parameters from 55756 reflections
b = 10.5563 (2) Å	θ = 1.0–31.6°
c = 11.7362 (2) Å	µ = 0.40 mm⁻¹
α = 71.431 (7)°	T = 120 K
β = 85.800 (5)°	Needle, brown
γ = 78.192 (4)°	0.16 × 0.1 × 0.08 mm
V = 1029.52 (5) Å³

Data collection top

Nonius KappaCCD diffractometer	5822 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 31.6°, θ_min = 2.8°
ω scans	h = 0→13
55756 measured reflections	k = −14→15
6914 independent reflections	l = −17→17

Refinement top

Refinement on F²	9 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0626P)² + 0.328P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max = 0.001
S = 0.97	Δρ_max = 0.70 e Å⁻³
6914 reflections	Δρ_min = −0.64 e Å⁻³
316 parameters

Crystal data top

C₅H₆N₅⁺·C₇H₈NO₂⁺·2ClO₄⁻·3H₂O	γ = 78.192 (4)°
M_r = 527.24	V = 1029.52 (5) Å³
Triclinic, P1	Z = 2
a = 8.9561 (1) Å	Mo Kα radiation
b = 10.5563 (2) Å	µ = 0.40 mm⁻¹
c = 11.7362 (2) Å	T = 120 K
α = 71.431 (7)°	0.16 × 0.1 × 0.08 mm
β = 85.800 (5)°

Data collection top

Nonius KappaCCD diffractometer	5822 reflections with I > 2σ(I)
55756 measured reflections	R_int = 0.028
6914 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	9 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.70 e Å⁻³
6914 reflections	Δρ_min = −0.64 e Å⁻³
316 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl2	0.19523 (3)	0.56122 (3)	0.55586 (2)	0.01535 (6)
Cl1	0.26532 (3)	0.01925 (3)	0.32829 (3)	0.01919 (7)
O4	0.18456 (11)	−0.09092 (10)	0.38018 (9)	0.02546 (19)
O8	0.32466 (10)	0.59734 (10)	0.59496 (9)	0.02321 (18)
O2	0.15769 (12)	0.14560 (10)	0.28846 (11)	0.0331 (2)
O5	0.16150 (11)	0.43814 (9)	0.64068 (9)	0.0262 (2)
O6	0.22752 (11)	0.54327 (10)	0.43911 (8)	0.0256 (2)
O1W	0.84304 (11)	0.11571 (10)	0.36340 (9)	0.02322 (18)
H11W	0.9191 (16)	0.1428 (19)	0.3222 (14)	0.035*
H21W	0.848 (2)	0.1307 (19)	0.4293 (11)	0.035*
O2M	−0.17505 (10)	0.23783 (10)	1.07286 (8)	0.02331 (18)
O3	0.36504 (13)	0.02378 (12)	0.41750 (10)	0.0337 (2)
O3W	0.46761 (11)	0.68985 (11)	0.31943 (9)	0.02467 (19)
H23W	0.4054 (18)	0.6368 (16)	0.3575 (16)	0.037*
H13W	0.4085 (18)	0.7627 (12)	0.2763 (15)	0.037*
O2W	0.41376 (10)	0.23763 (9)	0.51016 (8)	0.01987 (17)
H22W	0.4707 (17)	0.1627 (12)	0.5132 (16)	0.03*
H12W	0.4495 (19)	0.2689 (16)	0.5578 (14)	0.03*
O7	0.06388 (10)	0.66963 (9)	0.54746 (8)	0.02176 (18)
O1M	−0.27521 (10)	0.26982 (10)	0.89398 (8)	0.02123 (18)
H1M	−0.3543	0.2954	0.9269	0.032*
O1	0.35415 (12)	−0.00416 (13)	0.22739 (10)	0.0358 (3)
N3A	0.11767 (11)	0.45851 (10)	0.13693 (9)	0.01576 (17)
N9A	0.19753 (11)	0.44133 (10)	−0.06160 (8)	0.01525 (17)
H9A	0.1122	0.4736	−0.0989	0.018*
N1A	0.32637 (11)	0.37745 (10)	0.27036 (8)	0.01595 (18)
H1A	0.355	0.3641	0.3423	0.019*
N7A	0.44549 (11)	0.35292 (10)	−0.02915 (9)	0.01645 (18)
N1	0.15132 (11)	0.14796 (10)	0.62650 (9)	0.01761 (18)
H3N	0.0719	0.2065	0.5864	0.026*
H1N	0.1521	0.0656	0.6211	0.026*
H2N	0.2373	0.1751	0.5951	0.026*
N6A	0.57570 (11)	0.29041 (11)	0.22322 (9)	0.0204 (2)
H61	0.6025	0.2766	0.2957	0.024*
H62	0.642	0.2695	0.1721	0.024*
C4A	0.22236 (12)	0.42565 (11)	0.05563 (10)	0.01409 (19)
C2M	−0.01192 (12)	0.18475 (11)	0.91804 (10)	0.01548 (19)
C6M	0.25407 (13)	0.08172 (13)	0.94549 (11)	0.0204 (2)
H6M	0.3389	0.0453	0.9949	0.025*
C5M	0.26698 (13)	0.08683 (12)	0.82521 (11)	0.0194 (2)
H5M	0.3596	0.0535	0.7939	0.023*
C5A	0.37585 (12)	0.37129 (11)	0.07482 (10)	0.01494 (19)
C1M	−0.16129 (13)	0.23298 (12)	0.96985 (10)	0.0169 (2)
C4M	0.13915 (13)	0.14247 (11)	0.75291 (10)	0.01572 (19)
C6A	0.43380 (13)	0.34339 (11)	0.19055 (10)	0.0158 (2)
C3M	−0.00021 (13)	0.19153 (11)	0.79698 (10)	0.01574 (19)
H3M	−0.0846	0.2284	0.7471	0.019*
C2A	0.17701 (13)	0.43122 (12)	0.24266 (10)	0.0168 (2)
H2A	0.1123	0.45	0.3034	0.02*
C7M	0.11526 (13)	0.13073 (12)	0.99212 (11)	0.0182 (2)
H7M	0.1073	0.1275	1.0724	0.022*
C8A	0.33410 (13)	0.39600 (12)	−0.10839 (10)	0.0164 (2)
H8A	0.3475	0.3954	−0.1876	0.02*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl2	0.01578 (12)	0.01495 (12)	0.01556 (12)	−0.00305 (9)	−0.00132 (8)	−0.00477 (9)
Cl1	0.01813 (12)	0.01781 (13)	0.02080 (13)	−0.00179 (9)	−0.00226 (9)	−0.00546 (10)
O4	0.0315 (5)	0.0199 (4)	0.0263 (5)	−0.0088 (4)	−0.0028 (4)	−0.0060 (4)
O8	0.0197 (4)	0.0283 (5)	0.0253 (4)	−0.0077 (3)	−0.0044 (3)	−0.0105 (4)
O2	0.0240 (5)	0.0175 (4)	0.0522 (7)	0.0008 (4)	−0.0025 (4)	−0.0057 (4)
O5	0.0276 (5)	0.0169 (4)	0.0291 (5)	−0.0063 (3)	−0.0021 (4)	0.0013 (3)
O6	0.0291 (5)	0.0330 (5)	0.0210 (4)	−0.0087 (4)	0.0028 (4)	−0.0161 (4)
O1W	0.0230 (4)	0.0241 (4)	0.0248 (4)	−0.0031 (3)	−0.0008 (3)	−0.0114 (4)
O2M	0.0197 (4)	0.0324 (5)	0.0181 (4)	−0.0018 (4)	0.0001 (3)	−0.0103 (4)
O3	0.0338 (5)	0.0363 (6)	0.0382 (6)	−0.0078 (4)	−0.0126 (4)	−0.0182 (5)
O3W	0.0210 (4)	0.0292 (5)	0.0232 (4)	−0.0015 (4)	−0.0013 (3)	−0.0093 (4)
O2W	0.0203 (4)	0.0218 (4)	0.0183 (4)	−0.0027 (3)	−0.0025 (3)	−0.0077 (3)
O7	0.0185 (4)	0.0191 (4)	0.0241 (4)	0.0018 (3)	−0.0016 (3)	−0.0047 (3)
O1M	0.0134 (4)	0.0311 (5)	0.0186 (4)	0.0004 (3)	−0.0002 (3)	−0.0100 (4)
O1	0.0268 (5)	0.0494 (7)	0.0241 (5)	0.0021 (5)	0.0032 (4)	−0.0080 (5)
N3A	0.0147 (4)	0.0177 (4)	0.0152 (4)	−0.0025 (3)	0.0004 (3)	−0.0061 (3)
N9A	0.0131 (4)	0.0185 (4)	0.0136 (4)	−0.0010 (3)	−0.0019 (3)	−0.0051 (3)
N1A	0.0154 (4)	0.0217 (5)	0.0120 (4)	−0.0044 (3)	−0.0003 (3)	−0.0065 (3)
N7A	0.0143 (4)	0.0204 (4)	0.0146 (4)	−0.0018 (3)	0.0006 (3)	−0.0066 (3)
N1	0.0159 (4)	0.0186 (4)	0.0170 (4)	−0.0014 (3)	0.0008 (3)	−0.0051 (4)
N6A	0.0153 (4)	0.0295 (5)	0.0152 (4)	−0.0007 (4)	−0.0030 (3)	−0.0069 (4)
C4A	0.0145 (4)	0.0140 (4)	0.0136 (4)	−0.0024 (4)	−0.0011 (4)	−0.0041 (4)
C2M	0.0147 (5)	0.0150 (5)	0.0164 (5)	−0.0032 (4)	0.0001 (4)	−0.0044 (4)
C6M	0.0160 (5)	0.0218 (5)	0.0207 (5)	−0.0010 (4)	−0.0038 (4)	−0.0036 (4)
C5M	0.0149 (5)	0.0196 (5)	0.0213 (5)	−0.0011 (4)	−0.0001 (4)	−0.0044 (4)
C5A	0.0139 (4)	0.0170 (5)	0.0141 (5)	−0.0027 (4)	−0.0008 (4)	−0.0051 (4)
C1M	0.0162 (5)	0.0166 (5)	0.0176 (5)	−0.0028 (4)	−0.0005 (4)	−0.0047 (4)
C4M	0.0154 (5)	0.0152 (5)	0.0158 (5)	−0.0030 (4)	0.0002 (4)	−0.0038 (4)
C6A	0.0161 (5)	0.0167 (5)	0.0149 (5)	−0.0038 (4)	0.0004 (4)	−0.0050 (4)
C3M	0.0141 (4)	0.0151 (5)	0.0174 (5)	−0.0021 (4)	−0.0009 (4)	−0.0044 (4)
C2A	0.0152 (5)	0.0194 (5)	0.0162 (5)	−0.0034 (4)	0.0005 (4)	−0.0064 (4)
C7M	0.0176 (5)	0.0187 (5)	0.0171 (5)	−0.0032 (4)	−0.0021 (4)	−0.0038 (4)
C8A	0.0161 (5)	0.0188 (5)	0.0143 (5)	−0.0023 (4)	0.0002 (4)	−0.0059 (4)

Geometric parameters (Å, º) top

Cl2—O5	1.4363 (9)	N7A—C8A	1.3220 (14)
Cl2—O8	1.4387 (9)	N7A—C5A	1.3804 (14)
Cl2—O6	1.4429 (9)	N1—C4M	1.4630 (15)
Cl2—O7	1.4483 (9)	N1—H3N	0.89
Cl1—O1	1.4367 (11)	N1—H1N	0.89
Cl1—O2	1.4386 (10)	N1—H2N	0.89
Cl1—O4	1.4405 (10)	N6A—C6A	1.3110 (15)
Cl1—O3	1.4432 (10)	N6A—H61	0.86
O1W—H11W	0.851 (9)	N6A—H62	0.86
O1W—H21W	0.843 (9)	C4A—C5A	1.3819 (15)
O2M—C1M	1.2225 (14)	C2M—C7M	1.3936 (16)
O3W—H23W	0.869 (9)	C2M—C3M	1.3969 (16)
O3W—H13W	0.868 (9)	C2M—C1M	1.4893 (16)
O2W—H22W	0.840 (9)	C6M—C7M	1.3894 (17)
O2W—H12W	0.843 (9)	C6M—C5M	1.3925 (17)
O1M—C1M	1.3173 (14)	C6M—H6M	0.93
O1M—H1M	0.82	C5M—C4M	1.3876 (16)
N3A—C2A	1.3082 (14)	C5M—H5M	0.93
N3A—C4A	1.3625 (14)	C5A—C6A	1.4096 (15)
N9A—C4A	1.3618 (14)	C4M—C3M	1.3802 (15)
N9A—C8A	1.3623 (14)	C3M—H3M	0.93
N9A—H9A	0.86	C2A—H2A	0.93
N1A—C2A	1.3612 (14)	C7M—H7M	0.93
N1A—C6A	1.3687 (14)	C8A—H8A	0.93
N1A—H1A	0.86

O5—Cl2—O8	110.25 (6)	N3A—C4A—C5A	127.04 (10)
O5—Cl2—O6	110.09 (6)	C7M—C2M—C3M	120.44 (10)
O8—Cl2—O6	109.38 (6)	C7M—C2M—C1M	119.27 (10)
O5—Cl2—O7	108.72 (6)	C3M—C2M—C1M	120.28 (10)
O8—Cl2—O7	109.21 (6)	C7M—C6M—C5M	120.43 (11)
O6—Cl2—O7	109.17 (6)	C7M—C6M—H6M	119.8
O1—Cl1—O2	109.41 (7)	C5M—C6M—H6M	119.8
O1—Cl1—O4	108.98 (7)	C4M—C5M—C6M	118.80 (11)
O2—Cl1—O4	109.54 (6)	C4M—C5M—H5M	120.6
O1—Cl1—O3	109.60 (7)	C6M—C5M—H5M	120.6
O2—Cl1—O3	110.26 (7)	C4A—C5A—N7A	110.32 (9)
O4—Cl1—O3	109.03 (6)	C4A—C5A—C6A	118.20 (10)
H11W—O1W—H21W	105.5 (15)	N7A—C5A—C6A	131.47 (10)
H23W—O3W—H13W	104.3 (14)	O2M—C1M—O1M	123.91 (11)
H22W—O2W—H12W	107.2 (14)	O2M—C1M—C2M	122.61 (11)
C1M—O1M—H1M	109.5	O1M—C1M—C2M	113.47 (10)
C2A—N3A—C4A	112.44 (10)	C3M—C4M—C5M	121.97 (11)
C4A—N9A—C8A	106.73 (9)	C3M—C4M—N1	118.77 (10)
C4A—N9A—H9A	126.6	C5M—C4M—N1	119.25 (10)
C8A—N9A—H9A	126.6	N6A—C6A—N1A	120.99 (10)
C2A—N1A—C6A	123.92 (10)	N6A—C6A—C5A	125.47 (10)
C2A—N1A—H1A	118	N1A—C6A—C5A	113.54 (10)
C6A—N1A—H1A	118	C4M—C3M—C2M	118.65 (10)
C8A—N7A—C5A	104.25 (9)	C4M—C3M—H3M	120.7
C4M—N1—H3N	109.5	C2M—C3M—H3M	120.7
C4M—N1—H1N	109.5	N3A—C2A—N1A	124.84 (10)
H3N—N1—H1N	109.5	N3A—C2A—H2A	117.6
C4M—N1—H2N	109.5	N1A—C2A—H2A	117.6
H3N—N1—H2N	109.5	C6M—C7M—C2M	119.70 (11)
H1N—N1—H2N	109.5	C6M—C7M—H7M	120.2
C6A—N6A—H61	120	C2M—C7M—H7M	120.2
C6A—N6A—H62	120	N7A—C8A—N9A	112.76 (10)
H61—N6A—H62	120	N7A—C8A—H8A	123.6
N9A—C4A—N3A	127.02 (10)	N9A—C8A—H8A	123.6
N9A—C4A—C5A	105.94 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O2W	0.86	2.03	2.8135 (13)	151
N1A—H1A···O6	0.86	2.54	3.0145 (14)	115
O1M—H1M···N7Aⁱ	0.82	1.86	2.6676 (14)	167
N1—H1N···O1Wⁱⁱ	0.89	1.86	2.7381 (15)	171
N1—H2N···O2W	0.89	1.92	2.8111 (14)	174
N1—H3N···O7ⁱⁱⁱ	0.89	2.00	2.8539 (14)	162
N9A—H9A···N3A^iv	0.86	2.07	2.9013 (14)	163
O3W—H13W···O1^v	0.87 (2)	2.30 (1)	3.0378 (18)	144 (1)
O3W—H13W···O1Mⁱⁱⁱ	0.87 (2)	2.55 (2)	3.0127 (14)	115 (1)
O1W—H21W···O4ⁱⁱ	0.84 (2)	2.15 (1)	2.9329 (14)	155 (2)
O1W—H21W···O7^vi	0.84 (2)	2.49 (2)	3.0553 (14)	125 (1)
O2W—H22W···O3	0.84 (1)	2.47 (2)	2.9164 (16)	115 (1)
O2W—H22W···O3ⁱⁱ	0.84 (1)	2.16 (2)	2.9627 (16)	159 (2)
O3W—H23W···O6	0.87 (2)	2.06 (2)	2.9199 (14)	170 (2)
N6A—H61···O1W	0.86	2.46	2.9458 (15)	116
N6A—H61···O8^vi	0.86	2.33	3.0126 (15)	137
N6A—H62···O2M^vii	0.86	1.97	2.8187 (14)	167
C2A—H2A···O6	0.93	2.50	3.0047 (15)	115
C2A—H2A···O7ⁱⁱⁱ	0.93	2.48	3.2166 (15)	136
C5M—H5M···O1ⁱⁱ	0.93	2.52	3.3883 (17)	156
C8A—H8A···O5^viii	0.93	2.58	3.2881 (15)	133
C8A—H8A···O3W^ix	0.93	2.42	3.1994 (16)	142

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

Experimental details

Crystal data
Chemical formula	C₅H₆N₅⁺·C₇H₈NO₂⁺·2ClO₄⁻·3H₂O
M_r	527.24
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.9561 (1), 10.5563 (2), 11.7362 (2)
α, β, γ (°)	71.431 (7), 85.800 (5), 78.192 (4)
V (Å³)	1029.52 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.16 × 0.1 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	55756, 6914, 5822
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.737

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.098, 0.97
No. of reflections	6914
No. of parameters	316
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.64

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999), PARST97 (Nardelli, 1995), Mercury (Macrae et al., 2006) and POVRay (Persistence of Vision Team, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O2W	0.8600	2.0300	2.8135 (13)	151.00
N1A—H1A···O6	0.8600	2.5400	3.0145 (14)	115.00
O1M—H1M···N7Aⁱ	0.8200	1.8600	2.6676 (14)	167.00
N1—H1N···O1Wⁱⁱ	0.8900	1.8600	2.7381 (15)	171.00
N1—H2N···O2W	0.8900	1.9200	2.8111 (14)	174.00
N1—H3N···O7ⁱⁱⁱ	0.8900	2.0000	2.8539 (14)	162.00
N9A—H9A···N3A^iv	0.8600	2.0700	2.9013 (14)	163.00
O3W—H13W···O1^v	0.868 (15)	2.297 (14)	3.0378 (18)	143.5 (13)
O3W—H13W···O1Mⁱⁱⁱ	0.868 (15)	2.548 (16)	3.0127 (14)	114.5 (11)
O1W—H21W···O4ⁱⁱ	0.843 (15)	2.149 (13)	2.9329 (14)	154.6 (18)
O1W—H21W···O7^vi	0.843 (15)	2.49 (2)	3.0553 (14)	124.9 (14)
O2W—H22W···O3	0.841 (14)	2.466 (15)	2.9164 (16)	114.5 (13)
O2W—H22W···O3ⁱⁱ	0.841 (14)	2.161 (15)	2.9627 (16)	159.3 (16)
O3W—H23W···O6	0.869 (17)	2.062 (17)	2.9199 (14)	169.5 (16)
N6A—H61···O1W	0.8600	2.4600	2.9458 (15)	116.00
N6A—H61···O8^vi	0.8600	2.3300	3.0126 (15)	137.00
N6A—H62···O2M^vii	0.8600	1.9700	2.8187 (14)	167.00
C2A—H2A···O6	0.9300	2.5000	3.0047 (15)	115.00
C2A—H2A···O7ⁱⁱⁱ	0.9300	2.4800	3.2166 (15)	136.00
C5M—H5M···O1ⁱⁱ	0.9300	2.5200	3.3883 (17)	156.00
C8A—H8A···O5^viii	0.9300	2.5800	3.2881 (15)	133.00
C8A—H8A···O3W^ix	0.9300	2.4200	3.1994 (16)	142.00

Acknowledgements

Technical support (X-ray measurements at SCDRX) from Université Henry Poincaré, Nancy 1 is gratefully acknowledged.

References

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