Butane-1,4-diammonium bis-(pyridine-2-carboxyl-ate) monohydrate.

The asymmetric unit of the title compound, C(4)H(14)N(2) (2+)·2C(6)H(4)NO(2) (-)·H(2)O, consists of half of a doubly protonated tetra-methyl-enediammonium dication, a pyridine-2-carboxyl-ate anion and half of a solvent water mol-ecule; the dication is located on a centre of inversion and a twofold rotation axis passes through the O atom of the water mol-ecule. The carboxyl-ate group of the anion appears to be delocalized on the basis of the C-O bond lengths. In the crystal structure, the components are linked by inter-molecular N-H⋯O, N-H⋯N and O-H⋯O hydrogen bonds.

Related literature

For the crystal structures of some butane-1,4-diammonium compounds, see: n class="Chemical">Natarajan & Cheetham (1997 ▶); Zheng et al. (1999 ▶); Sediri et al. (2002 ▶); Srinivasan et al. (2005 ▶); Lemmerer & Billing (2006 ▶); van Blerk & Kruger (2007 ▶, 2008 ▶); Jayasundera et al. (2008 ▶). For the structure of pyridine-2-carboxylic acid, see: Hamazaki et al. (1998 ▶). For a related hexane-1,6-diammonium compound, see: Kim & Ha (2009 ▶).

Experimental

Crystal data

C4H14N2 2+·2n class="CellLine">C6H4NO2 −·H2O

M = 352.39

Monoclinic,

a = 20.655 (3) Å

b = 7.6170 (11) Å

c = 12.910 (2) Å

β = 113.789 (4)°

V = 1858.5 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.27 × 0.21 × 0.16 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (; Bruker, 2000 ▶) T min = 0.740, T max = 0.985

6674 measured reflections

2298 independent reflections

1040 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.152

S = 0.99

2298 reflections

162 parameters

All H-atom parameters refined

Δρmax = 0.18 e Å−3

Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031493/is2449sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031493/is2449Isup2.hkl

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

C4H14N22+·2C6H4NO2−·H2O	F(000) = 752
Mr = 352.39	Dx = 1.259 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1114 reflections
a = 20.655 (3) Å	θ = 2.9–22.5°
b = 7.6170 (11) Å	µ = 0.10 mm−1
c = 12.910 (2) Å	T = 296 K
β = 113.789 (4)°	Block, colorless
V = 1858.5 (5) Å3	0.27 × 0.21 × 0.16 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	2298 independent reflections
Radiation source: fine-focus sealed tube	1040 reflections with I > 2σ(I)
graphite	Rint = 0.048
φ and ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −27→27
Tmin = 0.740, Tmax = 0.985	k = −10→9
6674 measured reflections	l = −17→15

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	All H-atom parameters refined
S = 0.99	w = 1/[σ2(Fo2) + (0.0576P)2] where P = (Fo2 + 2Fc2)/3
2298 reflections	(Δ/σ)max < 0.001
162 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.42900 (8)	0.4778 (2)	0.55250 (14)	0.0629 (6)
O2	0.36511 (9)	0.6362 (3)	0.61996 (15)	0.0793 (7)
N1	0.31266 (9)	0.3696 (3)	0.37672 (16)	0.0541 (6)
C1	0.25453 (15)	0.3005 (4)	0.2959 (2)	0.0663 (8)
H1	0.2608 (13)	0.230 (4)	0.235 (2)	0.089 (9)*
C2	0.18842 (15)	0.3185 (4)	0.2948 (3)	0.0685 (8)
H2	0.1484 (13)	0.262 (3)	0.233 (2)	0.073 (8)*
C3	0.18017 (14)	0.4148 (4)	0.3778 (3)	0.0646 (8)
H3	0.1342 (14)	0.439 (3)	0.380 (2)	0.085 (9)*
C4	0.23908 (13)	0.4901 (4)	0.4606 (2)	0.0547 (7)
H4	0.2350 (11)	0.556 (3)	0.517 (2)	0.055 (7)*
C5	0.30461 (11)	0.4623 (3)	0.45825 (18)	0.0429 (6)
C6	0.37158 (13)	0.5323 (3)	0.5513 (2)	0.0483 (6)
N2	0.05485 (12)	0.8325 (3)	0.15154 (19)	0.0463 (5)
H2A	0.0797 (12)	0.853 (3)	0.234 (2)	0.072 (8)*
H2B	0.0116 (14)	0.898 (3)	0.121 (2)	0.070 (8)*
H2C	0.0864 (14)	0.863 (4)	0.117 (2)	0.091 (10)*
C7	0.00642 (18)	0.5974 (3)	0.0102 (2)	0.0599 (8)
H7A	−0.0362 (16)	0.665 (4)	−0.025 (3)	0.106 (11)*
H7B	0.0374 (16)	0.642 (4)	−0.025 (3)	0.116 (12)*
C8	0.04043 (18)	0.6425 (4)	0.1318 (2)	0.0612 (8)
H8A	0.0144 (16)	0.604 (4)	0.173 (3)	0.113 (13)*
H8B	0.0889 (17)	0.577 (4)	0.175 (3)	0.127 (13)*
O3	0.0000	0.2467 (4)	0.2500	0.0872 (10)
H3O	0.018 (2)	0.173 (5)	0.311 (3)	0.176 (18)*

	U11	U22	U33	U12	U13	U23
O1	0.0443 (9)	0.0705 (12)	0.0630 (12)	−0.0030 (9)	0.0102 (8)	−0.0125 (9)
O2	0.0782 (13)	0.0863 (15)	0.0542 (12)	0.0161 (11)	0.0066 (10)	−0.0263 (11)
N1	0.0472 (12)	0.0625 (14)	0.0459 (12)	−0.0017 (10)	0.0117 (10)	−0.0095 (10)
C1	0.0599 (18)	0.0692 (19)	0.0532 (17)	−0.0025 (15)	0.0056 (14)	−0.0149 (14)
C2	0.0483 (17)	0.0638 (19)	0.068 (2)	−0.0074 (14)	−0.0032 (14)	0.0020 (15)
C3	0.0429 (16)	0.073 (2)	0.071 (2)	0.0037 (14)	0.0156 (15)	0.0136 (16)
C4	0.0538 (16)	0.0597 (18)	0.0500 (16)	0.0119 (13)	0.0202 (13)	0.0062 (13)
C5	0.0462 (13)	0.0407 (13)	0.0368 (13)	0.0041 (11)	0.0116 (10)	0.0035 (10)
C6	0.0527 (14)	0.0423 (14)	0.0412 (14)	0.0048 (12)	0.0097 (12)	0.0015 (11)
N2	0.0456 (12)	0.0466 (13)	0.0425 (13)	0.0015 (10)	0.0134 (11)	−0.0049 (10)
C7	0.082 (2)	0.0495 (16)	0.0436 (15)	−0.0082 (16)	0.0205 (15)	−0.0045 (12)
C8	0.089 (2)	0.0471 (17)	0.0409 (15)	−0.0074 (15)	0.0191 (15)	−0.0047 (12)
O3	0.108 (2)	0.072 (2)	0.063 (2)	0.000	0.0152 (18)	0.000

O1—C6	1.251 (3)	C5—C6	1.517 (3)
O2—C6	1.235 (3)	N2—C8	1.479 (3)
N1—C5	1.332 (3)	N2—H2A	0.99 (3)
N1—C1	1.341 (3)	N2—H2B	0.96 (3)
C1—C2	1.367 (4)	N2—H2C	0.95 (3)
C1—H1	1.01 (3)	C7—C8	1.478 (3)
C2—C3	1.364 (4)	C7—C7i	1.512 (5)
C2—H2	0.98 (2)	C7—H7A	0.96 (3)
C3—C4	1.380 (4)	C7—H7B	0.98 (3)
C3—H3	0.98 (3)	C8—H8A	0.95 (3)
C4—C5	1.383 (3)	C8—H8B	1.05 (3)
C4—H4	0.91 (2)	O3—H3O	0.92 (4)
C5—N1—C1	117.7 (2)	C8—N2—H2A	108.6 (15)
N1—C1—C2	123.1 (3)	C8—N2—H2B	110.4 (14)
N1—C1—H1	117.5 (15)	H2A—N2—H2B	111 (2)
C2—C1—H1	119.4 (15)	C8—N2—H2C	106.6 (17)
C3—C2—C1	119.1 (3)	H2A—N2—H2C	108 (2)
C3—C2—H2	122.5 (15)	H2B—N2—H2C	112 (2)
C1—C2—H2	118.4 (15)	C8—C7—C7i	112.8 (3)
C2—C3—C4	118.8 (3)	C8—C7—H7A	109.3 (19)
C2—C3—H3	123.6 (16)	C7i—C7—H7A	112.5 (19)
C4—C3—H3	117.5 (16)	C8—C7—H7B	106.8 (19)
C3—C4—C5	119.0 (3)	C7i—C7—H7B	111.1 (19)
C3—C4—H4	120.6 (14)	H7A—C7—H7B	104 (2)
C5—C4—H4	120.4 (14)	C7—C8—N2	112.7 (2)
N1—C5—C4	122.3 (2)	C7—C8—H8A	113.3 (19)
N1—C5—C6	116.6 (2)	N2—C8—H8A	108.9 (19)
C4—C5—C6	121.1 (2)	C7—C8—H8B	113.5 (17)
O2—C6—O1	125.5 (2)	N2—C8—H8B	106.6 (17)
O2—C6—C5	117.7 (2)	H8A—C8—H8B	101 (3)
O1—C6—C5	116.8 (2)
C5—N1—C1—C2	−1.1 (4)	C3—C4—C5—C6	−176.1 (2)
N1—C1—C2—C3	1.7 (5)	N1—C5—C6—O2	171.3 (2)
C1—C2—C3—C4	−0.4 (4)	C4—C5—C6—O2	−10.4 (3)
C2—C3—C4—C5	−1.4 (4)	N1—C5—C6—O1	−9.5 (3)
C1—N1—C5—C4	−0.8 (4)	C4—C5—C6—O1	168.8 (2)
C1—N1—C5—C6	177.5 (2)	C7i—C7—C8—N2	178.3 (3)
C3—C4—C5—N1	2.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ii	0.99 (3)	1.77 (3)	2.749 (3)	170 (2)
N2—H2B···O1iii	0.96 (3)	1.84 (3)	2.792 (3)	176 (2)
N2—H2C···O1iv	0.95 (3)	2.26 (3)	2.997 (3)	134 (2)
N2—H2C···N1iv	0.95 (3)	2.06 (3)	2.917 (3)	149 (2)
O3—H3O···O1v	0.92 (4)	2.02 (4)	2.926 (3)	172 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2i	0.99 (3)	1.77 (3)	2.749 (3)	170 (2)
N2—H2B⋯O1ii	0.96 (3)	1.84 (3)	2.792 (3)	176 (2)
N2—H2C⋯O1iii	0.95 (3)	2.26 (3)	2.997 (3)	134 (2)
N2—H2C⋯N1iii	0.95 (3)	2.06 (3)	2.917 (3)	149 (2)
O3—H3O⋯O1iv	0.92 (4)	2.02 (4)	2.926 (3)	172 (4)

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