Bis(2,6-diamino-pyridinium) hydrogen phthalate nitrate monohydrate.

The title hydrated salt, 2C(5)H(8)N(3) (+)·C(8)H(5)O(4) (-)·NO(3) (-)·H(2)O, was obtained fortuitously from the reaction between 2,6-diamino-pyridine, phthalic acid and Co(NO(3))(2)·6H(2)O at 343 K. The asymmetric unit consists of two crystallographically independent 2,6-diamino-pyridinium cations, a hydrogen phthalate anion, a nitrate ion and a water mol-ecule of crystallization which in the crystal structure are linked by inter-molecular O-H⋯O and N-H⋯O hydrogen bonds into a three-dimensional network. In the hydrogen phthalate anion, there is a very strong intra-molecular O-H⋯O hydrogen bond.

Related literature

For a related structure, see: Al-Dajani et al. (2009 ▶). For a study of strong O—H⋯O hydrogen bonds, see: Gilli et al. (1994 ▶).

Experimental

Crystal data

2C5H8N3 +·C8H5O4 −·NO3 −·H2O

M = 465.43

Monoclinic,

a = 3.6923 (3) Å

b = 37.857 (3) Å

c = 14.8415 (10) Å

β = 95.111 (2)°

V = 2066.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 120 K

0.29 × 0.26 × 0.22 mm

Data collection

Bruker SMART 1000 diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.966, T max = 0.974

15097 measured reflections

2737 independent reflections

2309 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.093

S = 1.01

2737 reflections

298 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004150/lh2987sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004150/lh2987Isup2.hkl

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

2C5H8N3+·C8H5O4−·NO3−·H2O	F(000) = 976
Mr = 465.43	Dx = 1.496 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5008 reflections
a = 3.6923 (3) Å	θ = 2.2–27.2°
b = 37.857 (3) Å	µ = 0.12 mm−1
c = 14.8415 (10) Å	T = 120 K
β = 95.111 (2)°	Prism, colorless
V = 2066.3 (3) Å3	0.29 × 0.26 × 0.22 mm
Z = 4

Bruker SMART 1000 diffractometer	2737 independent reflections
Radiation source: fine-focus sealed tube	2309 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 29.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
Tmin = 0.966, Tmax = 0.974	k = −50→49
15097 measured reflections	l = −20→20

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)] = 0.046	Hydrogen site location: mixed
wR(F2) = 0.093	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.02P)2 + 3.5P] where P = (Fo2 + 2Fc2)/3
2737 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.26 e Å−3
2 restraints	Δρmin = −0.19 e Å−3

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

	x	y	z	Uiso*/Ueq
N1	0.6231 (8)	0.17540 (6)	0.49397 (18)	0.0283 (6)
H1NA	0.4475	0.1658	0.4557	0.034*
H1NB	0.6041	0.1721	0.5534	0.034*
N2	0.6881 (7)	0.22109 (6)	0.39298 (16)	0.0229 (5)
H2NA	0.5601	0.2072	0.3525	0.027*
N3	0.7201 (9)	0.26246 (7)	0.28055 (19)	0.0355 (7)
H3NB	0.7787	0.2848	0.2672	0.043*
H3NA	0.6032	0.2454	0.2473	0.043*
C1	0.7408 (8)	0.20826 (8)	0.4790 (2)	0.0229 (6)
C2	0.9210 (9)	0.22967 (8)	0.5452 (2)	0.0268 (6)
H2A	0.9646	0.2217	0.6059	0.032*
C3	1.0348 (8)	0.26286 (8)	0.5202 (2)	0.0274 (6)
H3A	1.1589	0.2775	0.5649	0.033*
C4	0.9751 (8)	0.27550 (8)	0.4329 (2)	0.0269 (6)
H4A	1.0539	0.2984	0.4177	0.032*
C5	0.7960 (8)	0.25365 (8)	0.3679 (2)	0.0253 (6)
N4	0.5267 (8)	0.09027 (7)	0.51218 (19)	0.0296 (6)
H4NA	0.6869	0.0988	0.4753	0.036*
H4NB	0.5352	0.1036	0.5625	0.036*
N5	0.4276 (7)	0.03920 (7)	0.42957 (18)	0.0258 (5)
H5NA	0.5180	0.0520	0.3857	0.031*
N6	0.3504 (8)	−0.00825 (7)	0.33294 (19)	0.0331 (6)
H6NB	0.2189	−0.0275	0.3158	0.040*
H6NA	0.4457	0.0043	0.2893	0.040*
C6	0.4164 (8)	0.05637 (8)	0.5096 (2)	0.0251 (6)
C7	0.2886 (9)	0.03842 (8)	0.5820 (2)	0.0283 (6)
H7A	0.2777	0.0497	0.6389	0.034*
C8	0.1770 (8)	0.00351 (9)	0.5693 (2)	0.0295 (7)
H8A	0.0886	−0.0090	0.6184	0.035*
C9	0.1914 (9)	−0.01353 (9)	0.4870 (2)	0.0294 (7)
H9A	0.1147	−0.0374	0.4797	0.035*
C10	0.3200 (8)	0.00492 (8)	0.4155 (2)	0.0255 (6)
O1	0.1534 (7)	0.15535 (7)	0.33076 (16)	0.0377 (6)
H1	0.0380	0.1279	0.3375	0.057*
O2	0.3398 (7)	0.19199 (6)	0.23096 (17)	0.0367 (6)
O3	−0.1237 (7)	0.09909 (7)	0.34030 (16)	0.0388 (6)
O4	−0.3587 (7)	0.05715 (7)	0.25269 (18)	0.0429 (6)
C11	0.1856 (8)	0.16417 (8)	0.2484 (2)	0.0269 (6)
C12	0.0332 (7)	0.14044 (8)	0.1715 (2)	0.0204 (6)
C13	0.0674 (8)	0.15452 (8)	0.0853 (2)	0.0232 (6)
H13A	0.1735	0.1773	0.0811	0.028*
C14	−0.0452 (8)	0.13698 (8)	0.0067 (2)	0.0263 (6)
H14A	−0.0135	0.1472	−0.0505	0.032*
C15	−0.2063 (8)	0.10402 (8)	0.0126 (2)	0.0273 (6)
H15A	−0.2905	0.0916	−0.0409	0.033*
C16	−0.2436 (8)	0.08934 (8)	0.0964 (2)	0.0248 (6)
H16A	−0.3498	0.0666	0.0994	0.030*
C17	−0.1311 (8)	0.10676 (8)	0.1768 (2)	0.0225 (6)
C18	−0.2081 (9)	0.08613 (9)	0.2609 (2)	0.0295 (7)
N7	0.5255 (8)	0.14787 (7)	0.72886 (18)	0.0307 (6)
O5	0.4868 (8)	0.17644 (6)	0.68613 (17)	0.0419 (6)
O6	0.6450 (7)	0.12132 (6)	0.69036 (16)	0.0392 (6)
O7	0.4512 (7)	0.14595 (6)	0.80893 (16)	0.0380 (6)
O1W	0.0932 (8)	0.07824 (6)	0.81011 (18)	0.0400 (6)
H1WA	−0.0387	0.0932	0.7797	0.060*
H1WB	0.2333	0.0959	0.8075	0.060*

	U11	U22	U33	U12	U13	U23
N1	0.0383 (15)	0.0226 (13)	0.0237 (13)	−0.0027 (11)	0.0010 (11)	0.0000 (10)
N2	0.0276 (13)	0.0200 (12)	0.0211 (12)	−0.0015 (10)	0.0019 (10)	−0.0023 (10)
N3	0.0520 (18)	0.0264 (14)	0.0270 (14)	−0.0091 (13)	−0.0020 (13)	0.0015 (11)
C1	0.0223 (14)	0.0206 (14)	0.0261 (15)	0.0022 (11)	0.0042 (11)	−0.0003 (11)
C2	0.0310 (16)	0.0269 (15)	0.0221 (14)	0.0018 (13)	−0.0002 (12)	−0.0017 (12)
C3	0.0277 (16)	0.0256 (15)	0.0285 (16)	0.0016 (12)	−0.0001 (12)	−0.0091 (12)
C4	0.0264 (15)	0.0223 (15)	0.0324 (16)	−0.0007 (12)	0.0044 (12)	−0.0023 (13)
C5	0.0285 (15)	0.0226 (15)	0.0254 (15)	0.0014 (12)	0.0056 (12)	0.0002 (12)
N4	0.0385 (15)	0.0230 (13)	0.0276 (13)	−0.0039 (11)	0.0042 (11)	−0.0019 (10)
N5	0.0293 (13)	0.0210 (12)	0.0273 (13)	−0.0020 (10)	0.0030 (10)	0.0032 (10)
N6	0.0440 (17)	0.0260 (14)	0.0295 (14)	−0.0065 (12)	0.0047 (12)	−0.0026 (11)
C6	0.0248 (15)	0.0225 (14)	0.0282 (15)	0.0034 (11)	0.0025 (12)	0.0022 (12)
C7	0.0304 (16)	0.0299 (16)	0.0247 (15)	0.0028 (13)	0.0038 (12)	0.0012 (13)
C8	0.0273 (16)	0.0299 (17)	0.0318 (16)	0.0018 (13)	0.0053 (13)	0.0099 (13)
C9	0.0306 (17)	0.0255 (15)	0.0322 (16)	−0.0006 (13)	0.0035 (13)	0.0053 (13)
C10	0.0239 (14)	0.0231 (15)	0.0292 (16)	0.0027 (12)	0.0016 (11)	0.0030 (12)
O1	0.0485 (15)	0.0380 (13)	0.0262 (12)	−0.0022 (11)	0.0012 (10)	−0.0044 (10)
O2	0.0404 (14)	0.0301 (12)	0.0397 (14)	−0.0112 (10)	0.0042 (11)	−0.0086 (10)
O3	0.0516 (16)	0.0393 (14)	0.0259 (12)	−0.0030 (12)	0.0065 (11)	0.0062 (11)
O4	0.0471 (15)	0.0370 (14)	0.0444 (15)	−0.0143 (12)	0.0021 (12)	0.0138 (12)
C11	0.0233 (15)	0.0267 (15)	0.0307 (16)	0.0016 (12)	0.0028 (12)	−0.0067 (13)
C12	0.0178 (13)	0.0211 (13)	0.0224 (13)	0.0033 (10)	0.0010 (10)	−0.0017 (11)
C13	0.0225 (14)	0.0206 (13)	0.0269 (14)	0.0023 (11)	0.0040 (11)	0.0025 (12)
C14	0.0276 (16)	0.0293 (15)	0.0224 (14)	0.0060 (12)	0.0039 (12)	0.0036 (12)
C15	0.0258 (15)	0.0299 (16)	0.0257 (15)	0.0043 (12)	−0.0012 (12)	−0.0067 (12)
C16	0.0226 (15)	0.0195 (13)	0.0316 (16)	0.0001 (11)	−0.0014 (12)	−0.0008 (12)
C17	0.0212 (14)	0.0238 (14)	0.0232 (14)	0.0028 (11)	0.0049 (11)	0.0007 (11)
C18	0.0257 (16)	0.0310 (16)	0.0318 (16)	0.0052 (13)	0.0021 (12)	0.0072 (13)
N7	0.0372 (16)	0.0307 (14)	0.0239 (14)	0.0012 (12)	0.0004 (11)	−0.0044 (11)
O5	0.0644 (18)	0.0302 (13)	0.0324 (13)	0.0097 (12)	0.0118 (12)	0.0070 (10)
O6	0.0564 (16)	0.0311 (13)	0.0299 (13)	0.0120 (11)	0.0019 (11)	−0.0063 (10)
O7	0.0551 (17)	0.0352 (14)	0.0243 (11)	−0.0027 (12)	0.0071 (11)	−0.0020 (10)
O1W	0.0516 (16)	0.0255 (12)	0.0431 (14)	0.0061 (11)	0.0053 (12)	0.0075 (10)

N1—C1	1.343 (4)	C8—C9	1.386 (5)
N1—H1NA	0.8999	C8—H8A	0.9500
N1—H1NB	0.9001	C9—C10	1.390 (4)
N2—C5	1.358 (4)	C9—H9A	0.9500
N2—C1	1.364 (4)	O1—C11	1.283 (4)
N2—H2NA	0.9000	O1—H1	1.1299
N3—C5	1.343 (4)	O2—C11	1.235 (4)
N3—H3NB	0.8998	O3—C18	1.289 (4)
N3—H3NA	0.8998	O3—H1	1.2468
C1—C2	1.396 (4)	O4—C18	1.231 (4)
C2—C3	1.386 (4)	C11—C12	1.520 (4)
C2—H2A	0.9500	C12—C13	1.402 (4)
C3—C4	1.379 (4)	C12—C17	1.417 (4)
C3—H3A	0.9500	C13—C14	1.374 (4)
C4—C5	1.393 (4)	C13—H13A	0.9500
C4—H4A	0.9500	C14—C15	1.389 (5)
N4—C6	1.346 (4)	C14—H14A	0.9500
N4—H4NA	0.9000	C15—C16	1.381 (4)
N4—H4NB	0.9001	C15—H15A	0.9500
N5—C6	1.358 (4)	C16—C17	1.393 (4)
N5—C10	1.368 (4)	C16—H16A	0.9500
N5—H5NA	0.9000	C17—C18	1.520 (4)
N6—C10	1.336 (4)	N7—O7	1.245 (3)
N6—H6NB	0.8996	N7—O6	1.255 (3)
N6—H6NA	0.8999	N7—O5	1.256 (4)
C6—C7	1.389 (4)	O1W—H1WA	0.8497
C7—C8	1.392 (5)	O1W—H1WB	0.8496
C7—H7A	0.9500
C1—N1—H1NA	119.7	C9—C8—C7	121.8 (3)
C1—N1—H1NB	110.2	C9—C8—H8A	119.1
H1NA—N1—H1NB	116.7	C7—C8—H8A	119.1
C5—N2—C1	124.0 (3)	C8—C9—C10	118.8 (3)
C5—N2—H2NA	119.7	C8—C9—H9A	120.6
C1—N2—H2NA	116.2	C10—C9—H9A	120.6
C5—N3—H3NB	114.3	N6—C10—N5	116.6 (3)
C5—N3—H3NA	113.5	N6—C10—C9	125.1 (3)
H3NB—N3—H3NA	131.9	N5—C10—C9	118.3 (3)
N1—C1—N2	117.6 (3)	C11—O1—H1	113.1
N1—C1—C2	124.3 (3)	C18—O3—H1	112.4
N2—C1—C2	118.1 (3)	O2—C11—O1	120.4 (3)
C3—C2—C1	118.4 (3)	O2—C11—C12	119.5 (3)
C3—C2—H2A	120.8	O1—C11—C12	120.1 (3)
C1—C2—H2A	120.8	C13—C12—C17	117.8 (3)
C4—C3—C2	122.6 (3)	C13—C12—C11	113.8 (3)
C4—C3—H3A	118.7	C17—C12—C11	128.5 (3)
C2—C3—H3A	118.7	C14—C13—C12	123.1 (3)
C3—C4—C5	118.1 (3)	C14—C13—H13A	118.5
C3—C4—H4A	120.9	C12—C13—H13A	118.5
C5—C4—H4A	120.9	C13—C14—C15	118.7 (3)
N3—C5—N2	116.7 (3)	C13—C14—H14A	120.7
N3—C5—C4	124.5 (3)	C15—C14—H14A	120.7
N2—C5—C4	118.8 (3)	C16—C15—C14	119.7 (3)
C6—N4—H4NA	122.5	C16—C15—H15A	120.1
C6—N4—H4NB	123.2	C14—C15—H15A	120.1
H4NA—N4—H4NB	109.1	C15—C16—C17	122.3 (3)
C6—N5—C10	123.8 (3)	C15—C16—H16A	118.8
C6—N5—H5NA	114.7	C17—C16—H16A	118.8
C10—N5—H5NA	121.5	C16—C17—C12	118.4 (3)
C10—N6—H6NB	118.3	C16—C17—C18	113.4 (3)
C10—N6—H6NA	122.2	C12—C17—C18	128.3 (3)
H6NB—N6—H6NA	117.4	O4—C18—O3	120.0 (3)
N4—C6—N5	116.7 (3)	O4—C18—C17	119.5 (3)
N4—C6—C7	124.5 (3)	O3—C18—C17	120.5 (3)
N5—C6—C7	118.8 (3)	O7—N7—O6	120.3 (3)
C6—C7—C8	118.5 (3)	O7—N7—O5	120.5 (3)
C6—C7—H7A	120.8	O6—N7—O5	119.2 (3)
C8—C7—H7A	120.8	H1WA—O1W—H1WB	76.9
C5—N2—C1—N1	−179.3 (3)	O2—C11—C12—C13	−3.8 (4)
C5—N2—C1—C2	−0.9 (4)	O1—C11—C12—C13	176.1 (3)
N1—C1—C2—C3	178.7 (3)	O2—C11—C12—C17	175.6 (3)
N2—C1—C2—C3	0.4 (4)	O1—C11—C12—C17	−4.5 (5)
C1—C2—C3—C4	0.4 (5)	C17—C12—C13—C14	−1.0 (4)
C2—C3—C4—C5	−0.6 (5)	C11—C12—C13—C14	178.5 (3)
C1—N2—C5—N3	−179.3 (3)	C12—C13—C14—C15	1.1 (4)
C1—N2—C5—C4	0.7 (4)	C13—C14—C15—C16	−1.2 (4)
C3—C4—C5—N3	−179.9 (3)	C14—C15—C16—C17	1.3 (5)
C3—C4—C5—N2	0.1 (4)	C15—C16—C17—C12	−1.2 (4)
C10—N5—C6—N4	−179.0 (3)	C15—C16—C17—C18	178.4 (3)
C10—N5—C6—C7	0.0 (4)	C13—C12—C17—C16	1.0 (4)
N4—C6—C7—C8	178.8 (3)	C11—C12—C17—C16	−178.4 (3)
N5—C6—C7—C8	−0.1 (4)	C13—C12—C17—C18	−178.5 (3)
C6—C7—C8—C9	0.2 (5)	C11—C12—C17—C18	2.1 (5)
C7—C8—C9—C10	−0.2 (5)	C16—C17—C18—O4	−0.5 (4)
C6—N5—C10—N6	−179.5 (3)	C12—C17—C18—O4	179.0 (3)
C6—N5—C10—C9	0.0 (4)	C16—C17—C18—O3	−179.1 (3)
C8—C9—C10—N6	179.6 (3)	C12—C17—C18—O3	0.4 (5)
C8—C9—C10—N5	0.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3	1.13	1.25	2.373 (4)	173
N1—H1NA···O1	0.90	2.10	2.950 (4)	157
N1—H1NB···O5	0.90	2.06	2.940 (4)	165
N2—H2NA···O1	0.90	2.48	3.259 (4)	146
N2—H2NA···O2	0.90	2.00	2.846 (3)	157
N3—H3NB···O5i	0.90	2.09	2.921 (4)	154
N3—H3NA···O2	0.90	2.25	3.074 (4)	153
N4—H4NA···O3ii	0.90	2.18	2.979 (4)	147
N4—H4NB···O6	0.90	2.02	2.891 (4)	163
N5—H5NA···O3ii	0.90	2.35	3.167 (4)	150
N5—H5NA···O4ii	0.90	2.07	2.889 (4)	150
N6—H6NB···O1Wiii	0.90	1.98	2.825 (4)	157
N6—H6NA···O4ii	0.90	2.21	2.988 (4)	144
O1W—H1WA···O6iv	0.85	1.99	2.834 (4)	169
O1W—H1WB···O6	0.85	2.59	3.258 (4)	136
O1W—H1WB···O7	0.85	2.06	2.885 (3)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3	1.13	1.25	2.373 (4)	173
N1—H1NA⋯O1	0.90	2.10	2.950 (4)	157
N1—H1NB⋯O5	0.90	2.06	2.940 (4)	165
N2—H2NA⋯O1	0.90	2.48	3.259 (4)	146
N2—H2NA⋯O2	0.90	2.00	2.846 (3)	157
N3—H3NB⋯O5i	0.90	2.09	2.921 (4)	154
N3—H3NA⋯O2	0.90	2.25	3.074 (4)	153
N4—H4NA⋯O3ii	0.90	2.18	2.979 (4)	147
N4—H4NB⋯O6	0.90	2.02	2.891 (4)	163
N5—H5NA⋯O3ii	0.90	2.35	3.167 (4)	150
N5—H5NA⋯O4ii	0.90	2.07	2.889 (4)	150
N6—H6NB⋯O1Wiii	0.90	1.98	2.825 (4)	157
N6—H6NA⋯O4ii	0.90	2.21	2.988 (4)	144
O1W—H1WA⋯O6iv	0.85	1.99	2.834 (4)	169
O1W—H1WB⋯O6	0.85	2.59	3.258 (4)	136
O1W—H1WB⋯O7	0.85	2.06	2.885 (3)	165

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .