Propane-1,3-diaminium bis-(pyridine-4-carboxyl-ate) monohydrate.

The asymmetric unit of the title compound, C(3)H(12)N(2) (2+)·2C(6)H(4)NO(2) (-)·H(2)O, consists of half of a doubly protonated propane-1,3-diammonium dication, a pyridine-4-carboxyl-ate anion and half of a solvent water mol-ecule; the dication and the solvent water are located on a twofold rotation axis which passes through the central C atom of the dication and the water O atom. The carboxyl-ate group of the anion appears to be delocalized on the basis of the C-O bond lengths. In the crystal, the components are linked by inter-molecular N-H⋯O, N-H⋯N and O-H⋯O hydrogen bonds.

Related literature

For related compounds with a propane-1,3- diammonium dication which exhibit an all-trans zigzag conformation, see: Turner & Batten (2010 ▶); Aghabozorg et al., (2011 ▶). For the preparation of the flexible ligand, see: Brito et al. (2010 ▶, 2011 ▶).

Experimental

Crystal data

C3H12N2 2+·2C6H4NO2 −·H2O

M = 338.37

Monoclinic,

a = 15.360 (3) Å

b = 12.508 (3) Å

c = 10.593 (2) Å

β = 122.67 (3)°

V = 1713.2 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 295 K

0.27 × 0.25 × 0.21 mm

Data collection

Nonius KappaCCD area-detector diffractometer

11720 measured reflections

2119 independent reflections

1871 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.122

S = 1.06

2119 reflections

115 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.24 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶; cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶ ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811033502/om2459sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033502/om2459Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811033502/om2459Isup3.cml

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

C3H12N22+·2C6H4NO2−·H2O	F(000) = 720
Mr = 338.37	Dx = 1.312 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9511 reflections
a = 15.360 (3) Å	θ = 3.9–28.5°
b = 12.508 (3) Å	µ = 0.10 mm−1
c = 10.593 (2) Å	T = 295 K
β = 122.67 (3)°	Block, colourless
V = 1713.2 (8) Å3	0.27 × 0.25 × 0.21 mm
Z = 4

Nonius KappaCCD area-detector diffractometer	1871 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.050
graphite	θmax = 28.5°, θmin = 4.0°
φ and ω scans with κ offsets	h = −20→20
11720 measured reflections	k = −16→16
2119 independent reflections	l = −14→11

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: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0545P)2 + 1.0503P] where P = (Fo2 + 2Fc2)/3
2119 reflections	(Δ/σ)max = 0.003
115 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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	Occ. (<1)
O1	0.87262 (8)	0.51431 (8)	0.82722 (12)	0.0447 (3)
O2	0.81345 (8)	0.36420 (8)	0.86906 (13)	0.0480 (3)
O3	0.5000	0.90541 (13)	0.7500	0.0712 (6)
H3	0.4617 (17)	0.9452 (17)	0.766 (2)	0.072 (6)*
N1	0.60893 (9)	0.65138 (10)	0.92600 (13)	0.0405 (3)
N2	0.48117 (8)	0.79864 (8)	0.46730 (12)	0.0340 (3)
H2A	0.4411	0.8559	0.4258	0.041*
H2B	0.5458	0.8194	0.5334	0.041*
H2C	0.4579	0.7600	0.5136	0.041*
C1	0.64814 (10)	0.69083 (11)	0.84955 (15)	0.0389 (3)
H1	0.6312	0.7605	0.8136	0.047*
C2	0.71275 (10)	0.63306 (11)	0.82123 (14)	0.0355 (3)
H2	0.7383	0.6636	0.7675	0.043*
C3	0.73892 (9)	0.52889 (10)	0.87425 (13)	0.0301 (3)
C4	0.69716 (10)	0.48635 (11)	0.95152 (16)	0.0386 (3)
H4	0.7115	0.4163	0.9866	0.046*
C5	0.63370 (11)	0.55061 (13)	0.97516 (17)	0.0437 (3)
H5	0.6068	0.5220	1.0282	0.052*
C6	0.81423 (9)	0.46330 (10)	0.85422 (14)	0.0339 (3)
C7	0.47907 (13)	0.73319 (11)	0.34918 (17)	0.0431 (3)
H7B	0.4119	0.6993	0.2884	0.052*
H7A	0.5309	0.6773	0.3956	0.052*
C8	0.5000	0.80121 (15)	0.2500	0.0401 (4)
H8A	0.4408	0.8468	0.1876	0.048*	0.50
H8B	0.5592	0.8468	0.3124	0.048*	0.50

	U11	U22	U33	U12	U13	U23
O1	0.0438 (5)	0.0454 (6)	0.0626 (7)	0.0006 (4)	0.0402 (5)	−0.0077 (5)
O2	0.0492 (6)	0.0347 (5)	0.0702 (7)	0.0085 (4)	0.0389 (6)	−0.0020 (5)
O3	0.0961 (14)	0.0306 (8)	0.146 (2)	0.000	0.1046 (16)	0.000
N1	0.0363 (6)	0.0498 (7)	0.0401 (6)	0.0113 (5)	0.0237 (5)	−0.0029 (5)
N2	0.0406 (6)	0.0330 (5)	0.0414 (6)	−0.0052 (4)	0.0306 (5)	0.0008 (4)
C1	0.0392 (7)	0.0383 (7)	0.0402 (7)	0.0127 (5)	0.0220 (6)	0.0027 (5)
C2	0.0361 (6)	0.0375 (7)	0.0393 (6)	0.0060 (5)	0.0246 (5)	0.0030 (5)
C3	0.0264 (5)	0.0332 (6)	0.0320 (6)	0.0027 (4)	0.0165 (5)	−0.0045 (4)
C4	0.0402 (7)	0.0371 (7)	0.0469 (7)	0.0049 (5)	0.0289 (6)	0.0036 (5)
C5	0.0438 (7)	0.0528 (8)	0.0483 (7)	0.0067 (6)	0.0340 (6)	0.0031 (6)
C6	0.0298 (6)	0.0366 (6)	0.0371 (6)	0.0048 (5)	0.0194 (5)	−0.0049 (5)
C7	0.0649 (9)	0.0301 (6)	0.0561 (8)	−0.0059 (6)	0.0469 (8)	−0.0024 (6)
C8	0.0597 (12)	0.0308 (9)	0.0484 (10)	0.000	0.0413 (10)	0.000

O1—C6	1.2531 (16)	C2—H2	0.9300
O2—C6	1.2503 (17)	C3—C4	1.3896 (18)
O3—H3	0.85 (2)	C3—C6	1.5237 (15)
N1—C1	1.3373 (18)	C4—C5	1.3865 (18)
N1—C5	1.338 (2)	C4—H4	0.9300
N2—C7	1.4809 (17)	C5—H5	0.9300
N2—H2A	0.8900	C7—C8	1.5151 (16)
N2—H2B	0.8900	C7—H7B	0.9700
N2—H2C	0.8900	C7—H7A	0.9700
C1—C2	1.3851 (17)	C8—C7i	1.5151 (16)
C1—H1	0.9300	C8—H8A	0.9700
C2—C3	1.3897 (18)	C8—H8B	0.9700
C1—N1—C5	117.18 (11)	N1—C5—C4	123.75 (13)
C7—N2—H2A	109.5	N1—C5—H5	118.1
C7—N2—H2B	109.5	C4—C5—H5	118.1
H2A—N2—H2B	109.5	O2—C6—O1	126.17 (11)
C7—N2—H2C	109.5	O2—C6—C3	117.18 (11)
H2A—N2—H2C	109.5	O1—C6—C3	116.64 (12)
H2B—N2—H2C	109.5	N2—C7—C8	111.07 (11)
N1—C1—C2	123.24 (13)	N2—C7—H7B	109.4
N1—C1—H1	118.4	C8—C7—H7B	109.4
C2—C1—H1	118.4	N2—C7—H7A	109.4
C1—C2—C3	119.10 (12)	C8—C7—H7A	109.4
C1—C2—H2	120.5	H7B—C7—H7A	108.0
C3—C2—H2	120.5	C7i—C8—C7	111.68 (15)
C4—C3—C2	118.18 (11)	C7i—C8—H8A	109.3
C4—C3—C6	120.16 (12)	C7—C8—H8A	109.3
C2—C3—C6	121.62 (11)	C7i—C8—H8B	109.3
C5—C4—C3	118.52 (13)	C7—C8—H8B	109.3
C5—C4—H4	120.7	H8A—C8—H8B	107.9
C3—C4—H4	120.7
C5—N1—C1—C2	−0.7 (2)	C3—C4—C5—N1	0.9 (2)
N1—C1—C2—C3	−0.1 (2)	C4—C3—C6—O2	20.19 (18)
C1—C2—C3—C4	1.19 (19)	C2—C3—C6—O2	−162.03 (12)
C1—C2—C3—C6	−176.62 (12)	C4—C3—C6—O1	−158.46 (13)
C2—C3—C4—C5	−1.6 (2)	C2—C3—C6—O1	19.31 (17)
C6—C3—C4—C5	176.26 (12)	N2—C7—C8—C7i	167.76 (14)
C1—N1—C5—C4	0.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ii	0.89	1.91	2.7901 (16)	170
N2—H2B···O2iii	0.89	1.91	2.779 (2)	165
N2—H2C···N1iv	0.89	2.00	2.877 (2)	166
O3—H3···O1v	0.85 (2)	2.00 (3)	2.8426 (17)	169 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1i	0.89	1.91	2.7901 (16)	170
N2—H2B⋯O2ii	0.89	1.91	2.779 (2)	165
N2—H2C⋯N1iii	0.89	2.00	2.877 (2)	166
O3—H3⋯O1iv	0.85 (2)	2.00 (3)	2.8426 (17)	169 (2)

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