Propane-1,3-diaminium bis­(pyridine-4-carboxyl­ate) monohydrate

Brito, I.; Vallejos, J.; Cárdenas, A.; López-Rodríguez, M.

doi:10.1107/S1600536811033502

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2423

doi:10.1107/S1600536811033502

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Propane-1,3-diaminium bis(pyridine-4-carboxylate) monohydrate

Iván Brito,^a ^* Javier Vallejos,^a Alejandro Cárdenas ^b and Matías López-Rodríguez ^c

^aDepartamento de Química, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, ^bDepartamento de Física, Facultad de Ciencias Básicas, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile, and ^cInstituto de Bio-Orgánica 'Antonio González', Universidad de La Laguna, Astrofísico Francisco Sánchez N°2, La Laguna, Tenerife, Spain
^*Correspondence e-mail: ivanbritob@yahoo.com

(Received 8 August 2011; accepted 17 August 2011; online 27 August 2011)

The asymmetric unit of the title compound, C₃H₁₂N₂²⁺·2C₆H₄NO₂⁻·H₂O, consists of half of a doubly protonated propane-1,3-diammonium dication, a pyridine-4-carboxylate anion and half of a solvent water molecule; 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 carboxylate 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 intermolecular 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

C₃H₁₂N₂²⁺·2C₆H₄NO₂⁻·H₂O
M_r = 338.37
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.046
wR(F²) = 0.122
S = 1.06
2119 reflections
115 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.24 e Å⁻³

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⋯O1^iv	0.85 (2)	2.00 (3)	2.8426 (17)	169 (2)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811033502/om2459sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811033502/om2459Isup3.cml

checkCIF report

Comment top

This paper forms part of our continuing study of the synthesis and structural characterization of a flexible ligand for preparation of coordination polymers (Brito et al., 2010; 2011 and references therein). The title compound was isolated during attempts to synthesize a flexible ligand by a condensation reaction between 4-pyridinecarboxylic acid and 1,3-diaminopropane. A notable feature of the structure is the extensive network of the hydrogen bonds between the ammonium H and pyridine-carboxylate N, O atoms. The hydrogen-bonding network involves all of the ammonium H and pyridine-carboxylate O,N atoms, forming a three-dimensional network Fig.2, Table 1. The water H are linked to two carboxylate O atoms at (-1/2 + x, 1/2 + y, z) and at (3/2 - x,1/2 + y, 3/2 - z) respectively, forming a two-dimensional network. Propane-1,3-diammonium dication has a fully extended all-trans zigzag conformation (N/C/C/C torsion angle 167.57 (13)°). The bond distances and angles for dication and anion are in normal range (Aghabozorg et al., 2011; Turner & Batten 2010, as representative examples).

Related literature top

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 top

To a solution of 4-pyridinecarboxylic acid (12.3 g, 0.1 mol) in pyridine (40 ml) was added 1,3-diaminopropane (3.71 g, 0,05 mol) in pyridine (20 ml). The solution was stirred gently for 15 min, forming a white precipitate. The resultant solution was then heated with stirring on the steam bath for 4 h. On cooling of the mixture, a white solid crystalline was obtained. Yield 15.8 g (92.9%). Analysis calculated for C₁₅H₂₂N₄O₅ (338.37 Dalton): C: 53.22, H: 6.52, N: 16.53; found: C: 52.97, H: 6.50, N: 16.90. IR (KBr, cm^-1): (NH₃⁺) 1664 m, (C=C) 1600 m, (NH₃⁺) 1500 m, (CH₂) 1378 w, (NH₃⁺) 1155 m

Computing details top

Data collection: COLLECT (Nonius, 2000; cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); 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).

Figures top

	Fig. 1. A view of the molecular structure of title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code i: 1 - x, y, 1/2 - z].
	Fig. 2. A view of title compound showing the hydrogen bonds and are indicated by dashed lines. [Symmetry codes: (i) x - 1/2, -y + 3/2, z - 1/2; (ii) -x + 3/2, y + 1/2, -z + 3/2; (iii) -x + 1, y, -z + 3/2; (iv) x - 1/2, y + 1/2, z]

Propane-1,3-diaminium bis(pyridine-4-carboxylate) monohydrate top

Crystal data top

C₃H₁₂N₂²⁺·2C₆H₄NO₂⁻·H₂O	F(000) = 720
M_r = 338.37	D_x = 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

Data collection top

Nonius KappaCCD area-detector diffractometer	1871 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 28.5°, θ_min = 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 top

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(F_o²) + (0.0545P)² + 1.0503P] where P = (F_o² + 2F_c²)/3
2119 reflections	(Δ/σ)_max = 0.003
115 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₃H₁₂N₂²⁺·2C₆H₄NO₂⁻·H₂O	V = 1713.2 (8) Å³
M_r = 338.37	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 15.360 (3) Å	µ = 0.10 mm⁻¹
b = 12.508 (3) Å	T = 295 K
c = 10.593 (2) Å	0.27 × 0.25 × 0.21 mm
β = 122.67 (3)°

Data collection top

Nonius KappaCCD area-detector diffractometer	1871 reflections with I > 2σ(I)
11720 measured reflections	R_int = 0.050
2119 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.32 e Å⁻³
2119 reflections	Δρ_min = −0.24 e Å⁻³
115 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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···N1^iv	0.89	2.00	2.877 (2)	166
O3—H3···O1^v	0.85 (2)	2.00 (3)	2.8426 (17)	169 (2)

Symmetry codes: (ii) x−1/2, −y+3/2, z−1/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+1, y, −z+3/2; (v) x−1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₃H₁₂N₂²⁺·2C₆H₄NO₂⁻·H₂O
M_r	338.37
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	15.360 (3), 12.508 (3), 10.593 (2)
β (°)	122.67 (3)
V (Å³)	1713.2 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.27 × 0.25 × 0.21

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11720, 2119, 1871
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.122, 1.06
No. of reflections	2119
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.24

Computer programs: COLLECT (Nonius, 2000, DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.85 (2)	2.00 (3)	2.8426 (17)	169 (2)

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+1, y, −z+3/2; (iv) x−1/2, y+1/2, z.

Acknowledgements

We thank the Spanish Research Council (CSIC) for providing us with a free-of-charge licence for the CSD system. JV thanks the Universidad de Antofagasta for PhD fellowships.

References

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