Adeninium 3-carboxy-anilinium bis-(perchlorate) trihydrate.

In the title salt, C(5)H(6)N(5) (+)·C(7)H(8)NO(2) (+)·2ClO(4) (-)·3H(2)O, the 3-carboxy-anilinium 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 inter-actions. 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 = 527.24

Triclinic,

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[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.098

S = 0.97

6914 reflections

316 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.70 e Å−3

Δρmin = −0.64 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C5H6N5+·C7H8NO2+·2ClO4−·3H2O	Z = 2
Mr = 527.24	F(000) = 544
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0626P)2 + 0.328P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.098	(Δ/σ)max = 0.001
S = 0.97	Δρmax = 0.70 e Å−3
6914 reflections	Δρmin = −0.64 e Å−3
316 parameters

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···N3Aiv	0.86	2.07	2.9013 (14)	163
O3W—H13W···O1v	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···O7vi	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···O8vi	0.86	2.33	3.0126 (15)	137
N6A—H62···O2Mvii	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···O5viii	0.93	2.58	3.2881 (15)	133
C8A—H8A···O3Wix	0.93	2.42	3.1994 (16)	142

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⋯N3Aiv	0.86	2.07	2.9013 (14)	163
O3W—H13W⋯O1v	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⋯O7vi	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⋯O8vi	0.86	2.33	3.0126 (15)	137
N6A—H62⋯O2Mvii	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⋯O5viii	0.93	2.58	3.2881 (15)	133
C8A—H8A⋯O3Wix	0.93	2.42	3.1994 (16)	142

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .