Butane-1,4-diammonium bis­(pyridine-2-carboxyl­ate) monohydrate

Kim, N.-H.; Ha, K.

doi:10.1107/S1600536809031493

organic compounds

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Volume 65| Part 9| September 2009| Page o2151

doi:10.1107/S1600536809031493

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Butane-1,4-diammonium bis(pyridine-2-carboxylate) monohydrate

Nam-Ho Kim ^a and Kwang Ha ^a ^*

^aSchool of Applied Chemical Engineering, the Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 10 August 2009; accepted 10 August 2009; online 15 August 2009)

The asymmetric unit of the title compound, C₄H₁₄N₂²⁺·2C₆H₄NO₂⁻·H₂O, consists of half of a doubly protonated tetramethylenediammonium dication, a pyridine-2-carboxylate anion and half of a solvent water molecule; the dication is located on a centre of inversion and a twofold rotation axis passes through the O atom of the water molecule. The carboxylate 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 intermolecular 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: 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

C₄H₁₄N₂²⁺·2C₆H₄NO₂⁻·H₂O
M_r = 352.39
Monoclinic, C 2/c
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 (SADABS; 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[F² > 2σ(F²)] = 0.056
wR(F²) = 0.152
S = 0.99
2298 reflections
162 parameters
All H-atom parameters refined
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³

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⋯O1^iv	0.92 (4)	2.02 (4)	2.926 (3)	172 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

The title compound, C₄H₁₄N₂²⁺.2C₆H₄NO₂^-.H₂O, consists of a doubly protonated tetramethylenediammonium dication, two pyridine-2-carboxylate anions and a solvent water molecule and the asymmetric unit contains one half of the formula unit (Fig. 1); a centre of inversion is located at the mid-point of the dication and the water molecule is disposed about a twofold rotation axis through O atom with the special position at (0, y, 1/4) (Wyckoff letter e). The carboxylate groups of the anions appear to be delocalized on the basis of the C—O bond lengths [C—O: 1.235 (3) and 1.251 (3) Å]. The torsion angles within the dication reveal that all N and C atoms of the dication display the anti conformation. In the crystal structure, the components are linked by intermolecular N—H···O, N—H···N and O—H···O hydrogen bonds (Table 1 and Fig. 2). There may also be intermolecular π–π interactions between adjacent pyridine rings, with a centroid-centroid distance of 3.796 (2) Å.

Related literature top

For the crystal structures of some butane-1,4-diammonium compounds, see: 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 top

A solution of 1,4-diaminobutane (0.200 g, 2.269 mmol) and pyridine-2-carboxylic acid (1.173 g, 9.528 mmol) in H₂O (20 ml) was stirred for 3 h at 60 °C. The solvent was removed under vacuum and the residue was washed with acetone/ether, to give a white powder (0.830 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from an acetone solution.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 40% probability level for non-H atoms. The superscript a corresponds to symmetry code: -x, -y + 1, -z.
	Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.

Butane-1,4-diammonium bis(pyridine-2-carboxylate) monohydrate top

Crystal data top

C₄H₁₄N₂²⁺·2C₆H₄NO₂⁻·H₂O	F(000) = 752
M_r = 352.39	D_x = 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

Data collection top

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

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	All H-atom parameters refined
S = 0.99	w = 1/[σ²(F_o²) + (0.0576P)²] where P = (F_o² + 2F_c²)/3
2298 reflections	(Δ/σ)_max < 0.001
162 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₄H₁₄N₂²⁺·2C₆H₄NO₂⁻·H₂O	V = 1858.5 (5) Å³
M_r = 352.39	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.655 (3) Å	µ = 0.10 mm⁻¹
b = 7.6170 (11) Å	T = 296 K
c = 12.910 (2) Å	0.27 × 0.21 × 0.16 mm
β = 113.789 (4)°

Data collection top

Bruker SMART 1000 CCD diffractometer	2298 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1040 reflections with I > 2σ(I)
T_min = 0.740, T_max = 0.985	R_int = 0.048
6674 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.152	All H-atom parameters refined
S = 0.99	Δρ_max = 0.18 e Å⁻³
2298 reflections	Δρ_min = −0.16 e Å⁻³
162 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.95 (3)	2.26 (3)	2.997 (3)	134 (2)
N2—H2C···N1^iv	0.95 (3)	2.06 (3)	2.917 (3)	149 (2)
O3—H3O···O1^v	0.92 (4)	2.02 (4)	2.926 (3)	172 (4)

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

Experimental details

Crystal data
Chemical formula	C₄H₁₄N₂²⁺·2C₆H₄NO₂⁻·H₂O
M_r	352.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	20.655 (3), 7.6170 (11), 12.910 (2)
β (°)	113.789 (4)
V (Å³)	1858.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.27 × 0.21 × 0.16

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.740, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	6674, 2298, 1040
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.152, 0.99
No. of reflections	2298
No. of parameters	162
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.16

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.92 (4)	2.02 (4)	2.926 (3)	172 (4)

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

Acknowledgements

This work was supported by a Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).

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