Bis(2,3-diamino-pyridinium) phthalate dihydrate.

The complete anion of the title hydrated mol-ecular salt, 2C(5)H(8)N(3) (+)·C(8)H(4)O(4) (-)·2H(2)O, is generated by a crystallographic twofold axis. In the crystal, the cations, anions and water mol-ecules are connected by N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional network. The crystal structure also features C-H⋯π inter-actions.

Related literature

For background to hydrogen-bonding patterns of 2-amino­pyridine derivatives, see: Gellert & Hsu (1988 ▶); Banerjee & Murugavel (2004 ▶). For related structures, see: Hemamalini & Fun (2010a ▶,b ▶,c ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

2C5H8N3 +·C8H4O4 −·2H2O

M = 420.43

Monoclinic,

a = 15.795 (5) Å

b = 13.083 (4) Å

c = 11.012 (4) Å

β = 115.194 (5)°

V = 2059.2 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.42 × 0.36 × 0.03 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.958, T max = 0.997

10343 measured reflections

2955 independent reflections

2148 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.125

S = 1.04

2955 reflections

184 parameters

All H-atom parameters refined

Δρmax = 0.33 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811055838/hb6574sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811055838/hb6574Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811055838/hb6574Isup3.cml

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

2C5H8N3+·C8H4O4−·2H2O	F(000) = 888
Mr = 420.43	Dx = 1.356 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3390 reflections
a = 15.795 (5) Å	θ = 2.8–29.8°
b = 13.083 (4) Å	µ = 0.10 mm−1
c = 11.012 (4) Å	T = 100 K
β = 115.194 (5)°	Plate, brown
V = 2059.2 (11) Å3	0.42 × 0.36 × 0.03 mm
Z = 4

Bruker APEXII DUO CCD diffractometer	2955 independent reflections
Radiation source: fine-focus sealed tube	2148 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 29.9°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −22→22
Tmin = 0.958, Tmax = 0.997	k = −18→18
10343 measured reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	All H-atom parameters refined
S = 1.03	w = 1/[σ2(Fo2) + (0.0653P)2 + 0.7423P] where P = (Fo2 + 2Fc2)/3
2955 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

	x	y	z	Uiso*/Ueq
N1	0.23077 (8)	0.94380 (9)	1.03746 (11)	0.0227 (3)
N2	0.30262 (8)	0.94315 (10)	0.89459 (13)	0.0256 (3)
N3	0.17815 (10)	0.78666 (11)	0.74285 (14)	0.0330 (3)
C1	0.23819 (9)	0.90400 (10)	0.93023 (13)	0.0192 (3)
C2	0.17516 (9)	0.82430 (9)	0.85688 (13)	0.0210 (3)
C3	0.11106 (9)	0.79131 (11)	0.90331 (14)	0.0249 (3)
C4	0.10585 (11)	0.83570 (13)	1.01540 (15)	0.0313 (3)
C5	0.16621 (11)	0.91224 (13)	1.08149 (15)	0.0310 (3)
O1	0.43751 (6)	0.07071 (7)	0.10193 (9)	0.0225 (2)
O2	0.32273 (6)	0.12167 (7)	0.15491 (9)	0.0225 (2)
C6	0.45346 (10)	0.41720 (10)	0.20469 (14)	0.0242 (3)
C7	0.40590 (9)	0.32537 (10)	0.16012 (13)	0.0201 (3)
C8	0.45249 (8)	0.23274 (9)	0.20552 (12)	0.0160 (2)
C9	0.40094 (8)	0.13405 (9)	0.15149 (12)	0.0168 (2)
O1W	0.45043 (8)	0.10881 (8)	0.86130 (12)	0.0315 (3)
H1	0.3388 (12)	0.3242 (12)	0.0959 (17)	0.028 (4)*
H2	0.0692 (11)	0.7346 (13)	0.8557 (17)	0.026 (4)*
H3	0.4209 (12)	0.4807 (14)	0.1749 (17)	0.032 (4)*
H4	0.1689 (13)	0.9496 (15)	1.160 (2)	0.043 (5)*
H5	0.3138 (13)	0.9165 (14)	0.8275 (19)	0.033 (5)*
H6	0.2697 (12)	1.0029 (15)	1.0806 (18)	0.036 (5)*
H7	0.3468 (13)	0.9879 (15)	0.9506 (19)	0.039 (5)*
H8	0.0557 (13)	0.8149 (14)	1.044 (2)	0.042 (5)*
H9	0.1404 (14)	0.7328 (17)	0.712 (2)	0.046 (5)*
H10	0.2265 (14)	0.7967 (14)	0.723 (2)	0.040 (5)*
H11	0.4555 (16)	0.1035 (17)	0.950 (3)	0.064 (7)*
H12	0.4828 (16)	0.0542 (18)	0.850 (2)	0.062 (7)*

	U11	U22	U33	U12	U13	U23
N1	0.0235 (6)	0.0244 (6)	0.0181 (5)	−0.0068 (5)	0.0070 (4)	−0.0020 (4)
N2	0.0237 (6)	0.0281 (6)	0.0260 (6)	−0.0104 (5)	0.0116 (5)	−0.0096 (5)
N3	0.0323 (7)	0.0332 (7)	0.0364 (7)	−0.0153 (6)	0.0174 (6)	−0.0188 (6)
C1	0.0186 (6)	0.0182 (6)	0.0175 (6)	−0.0001 (4)	0.0043 (5)	0.0016 (4)
C2	0.0195 (6)	0.0181 (6)	0.0197 (6)	−0.0001 (5)	0.0028 (5)	0.0004 (5)
C3	0.0232 (6)	0.0223 (6)	0.0224 (6)	−0.0060 (5)	0.0033 (5)	0.0024 (5)
C4	0.0312 (7)	0.0392 (8)	0.0237 (7)	−0.0138 (6)	0.0119 (6)	0.0001 (6)
C5	0.0348 (8)	0.0393 (8)	0.0223 (7)	−0.0128 (6)	0.0153 (6)	−0.0043 (6)
O1	0.0229 (5)	0.0220 (5)	0.0222 (5)	−0.0006 (4)	0.0093 (4)	−0.0059 (4)
O2	0.0205 (4)	0.0227 (5)	0.0253 (5)	−0.0041 (4)	0.0106 (4)	−0.0029 (4)
C6	0.0252 (7)	0.0173 (6)	0.0297 (7)	0.0038 (5)	0.0113 (6)	0.0033 (5)
C7	0.0191 (6)	0.0200 (6)	0.0196 (6)	0.0017 (5)	0.0068 (5)	0.0022 (4)
C8	0.0180 (6)	0.0171 (6)	0.0140 (5)	−0.0005 (4)	0.0078 (4)	−0.0002 (4)
C9	0.0178 (5)	0.0173 (6)	0.0124 (5)	0.0007 (4)	0.0036 (4)	0.0006 (4)
O1W	0.0361 (6)	0.0276 (6)	0.0363 (6)	0.0102 (4)	0.0208 (5)	0.0120 (4)

N1—C1	1.3404 (17)	C4—H8	1.01 (2)
N1—C5	1.3663 (18)	C5—H4	0.98 (2)
N1—H6	0.98 (2)	O1—C9	1.2596 (15)
N2—C1	1.3388 (17)	O2—C9	1.2623 (15)
N2—H5	0.899 (19)	C6—C6i	1.382 (3)
N2—H7	0.92 (2)	C6—C7	1.3910 (19)
N3—C2	1.3683 (19)	C6—H3	0.959 (18)
N3—H9	0.89 (2)	C7—C8	1.3954 (17)
N3—H10	0.89 (2)	C7—H1	0.993 (17)
C1—C2	1.4304 (18)	C8—C8i	1.400 (2)
C2—C3	1.383 (2)	C8—C9	1.5072 (17)
C3—C4	1.398 (2)	O1W—H11	0.95 (3)
C3—H2	0.983 (17)	O1W—H12	0.91 (2)
C4—C5	1.360 (2)
C1—N1—C5	123.61 (12)	C5—C4—H8	119.7 (11)
C1—N1—H6	117.6 (11)	C3—C4—H8	121.0 (11)
C5—N1—H6	118.5 (10)	C4—C5—N1	119.44 (14)
C1—N2—H5	122.2 (12)	C4—C5—H4	126.7 (11)
C1—N2—H7	120.2 (11)	N1—C5—H4	113.8 (11)
H5—N2—H7	116.0 (16)	C6i—C6—C7	120.25 (8)
C2—N3—H9	111.0 (13)	C6i—C6—H3	119.9 (10)
C2—N3—H10	122.9 (13)	C7—C6—H3	119.8 (10)
H9—N3—H10	121.6 (18)	C6—C7—C8	120.03 (12)
N2—C1—N1	118.16 (12)	C6—C7—H1	121.1 (10)
N2—C1—C2	123.13 (12)	C8—C7—H1	118.9 (10)
N1—C1—C2	118.67 (12)	C7—C8—C8i	119.70 (7)
N3—C2—C3	122.93 (12)	C7—C8—C9	119.26 (11)
N3—C2—C1	119.54 (12)	C8i—C8—C9	120.95 (6)
C3—C2—C1	117.49 (12)	O1—C9—O2	124.30 (11)
C2—C3—C4	121.61 (13)	O1—C9—C8	117.67 (11)
C2—C3—H2	118.0 (10)	O2—C9—C8	117.99 (11)
C4—C3—H2	120.4 (10)	H11—O1W—H12	105.6 (19)
C5—C4—C3	119.14 (13)
C5—N1—C1—N2	178.22 (13)	C3—C4—C5—N1	−0.3 (2)
C5—N1—C1—C2	0.2 (2)	C1—N1—C5—C4	0.6 (2)
N2—C1—C2—N3	−1.5 (2)	C6i—C6—C7—C8	−0.9 (2)
N1—C1—C2—N3	176.36 (12)	C6—C7—C8—C8i	−0.9 (2)
N2—C1—C2—C3	−179.27 (13)	C6—C7—C8—C9	−177.35 (12)
N1—C1—C2—C3	−1.39 (18)	C7—C8—C9—O1	126.40 (13)
N3—C2—C3—C4	−175.91 (14)	C8i—C8—C9—O1	−50.01 (19)
C1—C2—C3—C4	1.8 (2)	C7—C8—C9—O2	−51.38 (16)
C2—C3—C4—C5	−0.9 (2)	C8i—C8—C9—O2	132.22 (15)

Cg1 and Cg2 are the centroids of the C6–C8/C6A–C8A and N1/C1–C5 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H5···O2ii	0.90 (2)	2.03 (2)	2.9155 (19)	169.0 (18)
N1—H6···O2iii	0.98 (2)	1.790 (19)	2.7565 (18)	170.3 (19)
N2—H7···O1iii	0.92 (2)	1.99 (2)	2.8976 (19)	168.1 (19)
N3—H9···O1Wiv	0.89 (2)	2.09 (2)	2.978 (2)	179 (3)
N3—H10···O2ii	0.89 (2)	2.23 (2)	3.078 (2)	158.8 (17)
O1W—H11···O1v	0.95 (3)	1.86 (3)	2.7878 (18)	165 (3)
O1W—H12···O1vi	0.92 (2)	1.99 (2)	2.8641 (18)	158.2 (19)
C3—H2···O1Wvii	0.984 (17)	2.516 (18)	3.369 (2)	145.0 (14)
C4—H8···Cg1iv	1.01 (2)	2.76 (2)	3.629 (2)	144.3 (15)
C6—H3···Cg2viii	0.959 (18)	2.568 (18)	3.497 (2)	163.4 (14)

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C6–C8/C6A–C8A and N1/C1–C5 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H5⋯O2i	0.90 (2)	2.03 (2)	2.9155 (19)	169.0 (18)
N1—H6⋯O2ii	0.98 (2)	1.790 (19)	2.7565 (18)	170.3 (19)
N2—H7⋯O1ii	0.92 (2)	1.99 (2)	2.8976 (19)	168.1 (19)
N3—H9⋯O1Wiii	0.89 (2)	2.09 (2)	2.978 (2)	179 (3)
N3—H10⋯O2i	0.89 (2)	2.23 (2)	3.078 (2)	158.8 (17)
O1W—H11⋯O1iv	0.95 (3)	1.86 (3)	2.7878 (18)	165 (3)
O1W—H12⋯O1v	0.92 (2)	1.99 (2)	2.8641 (18)	158.2 (19)
C3—H2⋯O1Wvi	0.984 (17)	2.516 (18)	3.369 (2)	145.0 (14)
C4—H8⋯Cg1iii	1.01 (2)	2.76 (2)	3.629 (2)	144.3 (15)
C6—H3⋯Cg2vii	0.959 (18)	2.568 (18)	3.497 (2)	163.4 (14)

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