Hexane-1,6-diammonium bis-(pyridine-2-carboxyl-ate).

The title compound, C(6)H(18)N(2) (2+)·2C(6)H(4)NO(2) (-), consists of a doubly protonated hexa-methyl-enediammonium dication and two pyridine-2-carboxyl-ate anions. These ions inter-act by means of inter-molecular N-H⋯O and N-H⋯N hydrogen bonds to form a two-dimensional array. The carboxyl-ate groups of the anions appear to be delocalized on the basis of the C-O bond lengths.

Related literature

For the crystal structures of (C6H18N2)X 2 (X = Cl, Br or I), see: Binnie & Robertson (1949a ▶,b ▶); Borkakoti et al. (1978 ▶); van Blerk & Kruger (2008 ▶). For details of some other hexane-1,6-diammonium compounds, see: Phan Thanh et al. (2000 ▶); Mousdis et al. (2000 ▶); Rakovský et al. (2002 ▶); Dammak et al. (2007 ▶); Sun et al. (2007 ▶); Yang et al. (2007 ▶); Wilkinson & Harrison (2007 ▶); Wang & Wei (2007 ▶). For the structure of pyridine-2-carboxylic acid, see: Hamazaki et al. (1998 ▶).

Experimental

Crystal data

C6H18N2 2+·2C6H4NO2 −

M = 362.43

Monoclinic,

a = 9.8182 (7) Å

b = 9.1569 (7) Å

c = 21.6423 (17) Å

β = 99.038 (2)°

V = 1921.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.33 × 0.25 × 0.18 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.685, T max = 0.984

13964 measured reflections

4752 independent reflections

1740 reflections with I > 2σ(I)

R int = 0.089

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.124

S = 0.93

4752 reflections

339 parameters

All H-atom parameters refined

Δρmax = 0.15 e Å−3

Δρmin = −0.15 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/S1600536809019424/tk2459sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019424/tk2459Isup2.hkl

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

C6H18N22+·2C6H4NO2−	F(000) = 776
Mr = 362.43	Dx = 1.253 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1472 reflections
a = 9.8182 (7) Å	θ = 2.6–24.0°
b = 9.1569 (7) Å	µ = 0.09 mm−1
c = 21.6423 (17) Å	T = 296 K
β = 99.038 (2)°	Block, colourless
V = 1921.6 (3) Å3	0.33 × 0.25 × 0.18 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	4752 independent reflections
Radiation source: fine-focus sealed tube	1740 reflections with I > 2σ(I)
graphite	Rint = 0.089
φ and ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
Tmin = 0.685, Tmax = 0.984	k = −12→12
13964 measured reflections	l = −21→28

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	All H-atom parameters refined
S = 0.93	w = 1/[σ2(Fo2) + (0.0318P)2] where P = (Fo2 + 2Fc2)/3
4752 reflections	(Δ/σ)max < 0.001
339 parameters	Δρmax = 0.15 e Å−3
0 restraints	Δρmin = −0.15 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	0.39197 (19)	0.3983 (2)	0.43294 (9)	0.0607 (6)
O2	0.3440 (2)	0.1705 (2)	0.40142 (11)	0.0809 (7)
N1	0.5671 (2)	0.4287 (2)	0.34905 (10)	0.0514 (6)
C1	0.6534 (3)	0.4405 (4)	0.30699 (15)	0.0632 (9)
H1	0.704 (3)	0.538 (3)	0.3085 (12)	0.078 (10)*
C2	0.6711 (3)	0.3335 (4)	0.26461 (16)	0.0684 (9)
H2	0.739 (3)	0.351 (3)	0.2336 (14)	0.100 (11)*
C3	0.5975 (4)	0.2072 (4)	0.26545 (16)	0.0702 (10)
H3	0.605 (3)	0.128 (3)	0.2356 (13)	0.080 (10)*
C4	0.5110 (3)	0.1905 (3)	0.30952 (14)	0.0586 (8)
H4	0.458 (2)	0.099 (3)	0.3141 (12)	0.061 (8)*
C5	0.4980 (3)	0.3030 (3)	0.35030 (12)	0.0428 (6)
C6	0.4034 (3)	0.2901 (3)	0.39927 (14)	0.0508 (7)
O3	0.1328 (2)	0.4425 (2)	0.07130 (9)	0.0654 (6)
O4	0.2162 (2)	0.2478 (2)	0.12601 (10)	0.0760 (7)
N2	0.0026 (2)	0.5187 (3)	0.16852 (11)	0.0617 (7)
C7	−0.0394 (4)	0.5760 (4)	0.21915 (18)	0.0749 (10)
H7	−0.127 (3)	0.630 (3)	0.2088 (13)	0.084 (10)*
C8	0.0265 (4)	0.5565 (4)	0.27899 (17)	0.0718 (10)
H8	−0.010 (3)	0.603 (3)	0.3131 (14)	0.080 (10)*
C9	0.1416 (4)	0.4708 (4)	0.28807 (15)	0.0653 (9)
H9	0.195 (3)	0.456 (3)	0.3287 (12)	0.066 (9)*
C10	0.1851 (3)	0.4064 (3)	0.23713 (14)	0.0545 (8)
H10	0.268 (3)	0.344 (3)	0.2409 (13)	0.083 (10)*
C11	0.1141 (3)	0.4333 (3)	0.17813 (13)	0.0443 (7)
C12	0.1582 (3)	0.3693 (3)	0.12002 (14)	0.0479 (7)
N3	0.4265 (3)	0.1748 (3)	0.06174 (13)	0.0505 (7)
H3A	0.334 (3)	0.200 (3)	0.0800 (14)	0.114 (12)*
H3B	0.467 (3)	0.090 (3)	0.0830 (15)	0.095 (12)*
H3C	0.415 (3)	0.154 (3)	0.0194 (16)	0.092 (12)*
N4	1.1032 (3)	0.3355 (3)	−0.04832 (13)	0.0487 (6)
H4A	1.046 (3)	0.403 (3)	−0.0754 (12)	0.068 (10)*
H4B	1.117 (3)	0.372 (3)	−0.0007 (16)	0.099 (11)*
H4C	1.196 (4)	0.333 (3)	−0.0672 (15)	0.126 (13)*
C13	0.5150 (3)	0.3063 (4)	0.07920 (18)	0.0655 (9)
H13A	0.500 (3)	0.334 (3)	0.1259 (15)	0.101 (11)*
H13B	0.475 (3)	0.388 (3)	0.0459 (14)	0.099 (11)*
C14	0.6652 (4)	0.2789 (4)	0.07806 (17)	0.0676 (10)
H14A	0.718 (3)	0.372 (3)	0.0970 (13)	0.086 (10)*
H14B	0.697 (3)	0.194 (3)	0.1038 (14)	0.090 (12)*
C15	0.6995 (3)	0.2449 (4)	0.01361 (16)	0.0600 (9)
H15A	0.654 (3)	0.150 (3)	−0.0029 (13)	0.073 (9)*
H15B	0.654 (3)	0.336 (3)	−0.0184 (14)	0.100 (11)*
C16	0.8544 (3)	0.2304 (4)	0.01326 (16)	0.0578 (8)
H16A	0.895 (3)	0.153 (3)	0.0455 (12)	0.072 (9)*
H16B	0.898 (2)	0.328 (3)	0.0250 (12)	0.070 (9)*
C17	0.8877 (3)	0.1893 (4)	−0.05053 (16)	0.0623 (9)
H17A	0.841 (3)	0.261 (3)	−0.0839 (13)	0.075 (10)*
H17B	0.851 (3)	0.083 (3)	−0.0641 (14)	0.103 (11)*
C18	1.0393 (4)	0.1871 (4)	−0.05523 (19)	0.0660 (9)
H18A	1.054 (3)	0.150 (3)	−0.1001 (15)	0.110 (12)*
H18B	1.088 (3)	0.123 (3)	−0.0212 (15)	0.102 (13)*

	U11	U22	U33	U12	U13	U23
O1	0.0655 (13)	0.0674 (13)	0.0506 (12)	0.0062 (11)	0.0135 (11)	−0.0096 (11)
O2	0.0771 (15)	0.0718 (15)	0.1046 (19)	−0.0218 (12)	0.0482 (14)	−0.0166 (14)
N1	0.0577 (15)	0.0545 (15)	0.0435 (14)	−0.0030 (12)	0.0132 (12)	−0.0014 (12)
C1	0.077 (2)	0.062 (2)	0.053 (2)	−0.0093 (19)	0.0165 (19)	−0.0003 (19)
C2	0.069 (2)	0.079 (3)	0.062 (2)	−0.006 (2)	0.0240 (19)	−0.007 (2)
C3	0.083 (2)	0.071 (2)	0.061 (2)	0.008 (2)	0.026 (2)	−0.019 (2)
C4	0.065 (2)	0.0547 (19)	0.058 (2)	−0.0009 (17)	0.0143 (17)	−0.0086 (18)
C5	0.0387 (15)	0.0484 (16)	0.0397 (16)	0.0027 (14)	0.0009 (13)	0.0009 (15)
C6	0.0406 (17)	0.0568 (19)	0.0536 (19)	0.0032 (16)	0.0037 (15)	−0.0004 (17)
O3	0.0893 (16)	0.0646 (13)	0.0413 (12)	0.0046 (11)	0.0075 (11)	0.0000 (12)
O4	0.0864 (16)	0.0717 (14)	0.0775 (16)	0.0331 (13)	0.0361 (13)	0.0103 (13)
N2	0.0638 (17)	0.0723 (17)	0.0496 (16)	0.0235 (14)	0.0108 (14)	0.0054 (14)
C7	0.076 (3)	0.083 (3)	0.066 (2)	0.031 (2)	0.014 (2)	0.005 (2)
C8	0.088 (3)	0.073 (2)	0.060 (2)	0.010 (2)	0.029 (2)	−0.002 (2)
C9	0.077 (3)	0.077 (2)	0.041 (2)	−0.001 (2)	0.0073 (19)	0.007 (2)
C10	0.0522 (19)	0.062 (2)	0.0489 (19)	0.0088 (16)	0.0048 (17)	0.0112 (18)
C11	0.0437 (17)	0.0441 (16)	0.0447 (17)	0.0016 (14)	0.0055 (14)	0.0061 (15)
C12	0.0424 (17)	0.0504 (18)	0.0510 (19)	−0.0023 (14)	0.0073 (15)	0.0037 (16)
N3	0.0516 (16)	0.0521 (16)	0.0487 (17)	0.0030 (14)	0.0111 (14)	0.0051 (15)
N4	0.0480 (15)	0.0531 (16)	0.0445 (15)	0.0048 (13)	0.0060 (14)	0.0050 (14)
C13	0.066 (2)	0.055 (2)	0.079 (3)	−0.0051 (18)	0.021 (2)	−0.008 (2)
C14	0.063 (2)	0.070 (2)	0.072 (3)	−0.010 (2)	0.016 (2)	−0.013 (2)
C15	0.052 (2)	0.066 (2)	0.063 (2)	−0.0077 (18)	0.0128 (18)	0.000 (2)
C16	0.052 (2)	0.058 (2)	0.064 (2)	−0.0051 (17)	0.0086 (17)	0.0004 (19)
C17	0.059 (2)	0.069 (2)	0.061 (2)	−0.0086 (19)	0.0140 (18)	−0.008 (2)
C18	0.069 (2)	0.060 (2)	0.074 (3)	−0.0004 (19)	0.025 (2)	−0.010 (2)

O1—C6	1.245 (3)	N3—C13	1.498 (4)
O2—C6	1.245 (3)	N3—H3A	1.07 (3)
N1—C5	1.339 (3)	N3—H3B	0.96 (3)
N1—C1	1.341 (3)	N3—H3C	0.92 (3)
C1—C2	1.371 (4)	N4—C18	1.495 (4)
C1—H1	1.02 (3)	N4—H4A	0.97 (3)
C2—C3	1.365 (4)	N4—H4B	1.07 (3)
C2—H2	1.03 (3)	N4—H4C	1.05 (3)
C3—C4	1.381 (4)	C13—C14	1.500 (4)
C3—H3	0.98 (3)	C13—H13A	1.08 (3)
C4—C5	1.375 (3)	C13—H13B	1.07 (3)
C4—H4	1.00 (2)	C14—C15	1.518 (4)
C5—C6	1.520 (3)	C14—H14A	1.05 (3)
O3—C12	1.241 (3)	C14—H14B	0.98 (3)
O4—C12	1.247 (3)	C15—C16	1.528 (4)
N2—C11	1.335 (3)	C15—H15A	1.01 (3)
N2—C7	1.337 (4)	C15—H15B	1.13 (3)
C7—C8	1.365 (4)	C16—C17	1.515 (4)
C7—H7	0.99 (3)	C16—H16A	1.03 (3)
C8—C9	1.365 (4)	C16—H16B	1.01 (3)
C8—H8	0.97 (3)	C17—C18	1.508 (4)
C9—C10	1.376 (4)	C17—H17A	1.03 (3)
C9—H9	0.96 (3)	C17—H17B	1.06 (3)
C10—C11	1.378 (4)	C18—H18A	1.06 (3)
C10—H10	0.99 (3)	C18—H18B	1.01 (3)
C11—C12	1.512 (4)
C5—N1—C1	117.3 (3)	H3B—N3—H3C	107 (3)
N1—C1—C2	123.8 (3)	C18—N4—H4A	108.7 (15)
N1—C1—H1	114.0 (15)	C18—N4—H4B	111.5 (16)
C2—C1—H1	122.2 (15)	H4A—N4—H4B	111 (2)
C3—C2—C1	118.2 (3)	C18—N4—H4C	108.3 (18)
C3—C2—H2	122.6 (17)	H4A—N4—H4C	104 (2)
C1—C2—H2	119.1 (17)	H4B—N4—H4C	113 (2)
C2—C3—C4	119.1 (3)	N3—C13—C14	113.3 (3)
C2—C3—H3	121.3 (16)	N3—C13—H13A	105.3 (16)
C4—C3—H3	119.6 (16)	C14—C13—H13A	109.7 (16)
C5—C4—C3	119.3 (3)	N3—C13—H13B	104.9 (16)
C5—C4—H4	117.4 (15)	C14—C13—H13B	111.3 (16)
C3—C4—H4	123.3 (15)	H13A—C13—H13B	112 (2)
N1—C5—C4	122.2 (3)	C13—C14—C15	114.2 (3)
N1—C5—C6	116.6 (2)	C13—C14—H14A	106.5 (15)
C4—C5—C6	121.2 (3)	C15—C14—H14A	111.1 (15)
O2—C6—O1	126.3 (3)	C13—C14—H14B	110.6 (18)
O2—C6—C5	115.8 (3)	C15—C14—H14B	105.3 (18)
O1—C6—C5	117.9 (3)	H14A—C14—H14B	109 (2)
C11—N2—C7	116.9 (3)	C14—C15—C16	112.8 (3)
N2—C7—C8	124.4 (3)	C14—C15—H15A	110.5 (15)
N2—C7—H7	112.3 (17)	C16—C15—H15A	108.0 (15)
C8—C7—H7	123.2 (17)	C14—C15—H15B	106.8 (15)
C9—C8—C7	118.0 (3)	C16—C15—H15B	111.0 (14)
C9—C8—H8	122.6 (17)	H15A—C15—H15B	108 (2)
C7—C8—H8	119.4 (17)	C17—C16—C15	112.5 (3)
C8—C9—C10	119.0 (3)	C17—C16—H16A	109.2 (14)
C8—C9—H9	122.0 (16)	C15—C16—H16A	109.9 (14)
C10—C9—H9	118.9 (16)	C17—C16—H16B	107.8 (15)
C9—C10—C11	119.4 (3)	C15—C16—H16B	107.9 (14)
C9—C10—H10	122.4 (17)	H16A—C16—H16B	110 (2)
C11—C10—H10	118.2 (17)	C18—C17—C16	114.9 (3)
N2—C11—C10	122.2 (3)	C18—C17—H17A	107.2 (15)
N2—C11—C12	115.7 (3)	C16—C17—H17A	110.3 (15)
C10—C11—C12	122.2 (3)	C18—C17—H17B	105.3 (16)
O3—C12—O4	126.7 (3)	C16—C17—H17B	111.6 (16)
O3—C12—C11	116.8 (3)	H17A—C17—H17B	107 (2)
O4—C12—C11	116.5 (3)	N4—C18—C17	112.6 (3)
C13—N3—H3A	103.1 (16)	N4—C18—H18A	105.7 (17)
C13—N3—H3B	110.6 (18)	C17—C18—H18A	110.1 (17)
H3A—N3—H3B	108 (2)	N4—C18—H18B	108.5 (18)
C13—N3—H3C	113.2 (19)	C17—C18—H18B	108.7 (18)
H3A—N3—H3C	115 (3)	H18A—C18—H18B	111 (2)
C5—N1—C1—C2	2.0 (4)	C8—C9—C10—C11	1.9 (5)
N1—C1—C2—C3	−0.5 (5)	C7—N2—C11—C10	−1.1 (4)
C1—C2—C3—C4	−1.4 (5)	C7—N2—C11—C12	179.5 (3)
C2—C3—C4—C5	1.8 (5)	C9—C10—C11—N2	−0.9 (4)
C1—N1—C5—C4	−1.5 (4)	C9—C10—C11—C12	178.5 (3)
C1—N1—C5—C6	178.6 (2)	N2—C11—C12—O3	30.2 (3)
C3—C4—C5—N1	−0.3 (4)	C10—C11—C12—O3	−149.2 (3)
C3—C4—C5—C6	179.6 (3)	N2—C11—C12—O4	−149.6 (2)
N1—C5—C6—O2	−177.3 (3)	C10—C11—C12—O4	31.0 (4)
C4—C5—C6—O2	2.8 (4)	N3—C13—C14—C15	64.9 (4)
N1—C5—C6—O1	2.9 (4)	C13—C14—C15—C16	175.1 (3)
C4—C5—C6—O1	−177.0 (3)	C14—C15—C16—C17	177.3 (3)
C11—N2—C7—C8	2.2 (5)	C15—C16—C17—C18	174.6 (3)
N2—C7—C8—C9	−1.2 (6)	C16—C17—C18—N4	−66.6 (4)
C7—C8—C9—C10	−0.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O4	1.07 (3)	1.70 (3)	2.747 (3)	165 (3)
N3—H3B···O1i	0.96 (3)	2.29 (3)	3.088 (3)	140 (2)
N3—H3B···N1i	0.96 (3)	2.15 (3)	2.962 (3)	142 (2)
N3—H3C···O1ii	0.92 (3)	1.91 (3)	2.835 (3)	177 (3)
N4—H4A···O3iii	0.97 (3)	2.27 (3)	3.064 (3)	139 (2)
N4—H4A···N2iii	0.97 (3)	2.12 (3)	2.963 (3)	144 (2)
N4—H4B···O3iv	1.07 (3)	1.67 (3)	2.740 (3)	175 (3)
N4—H4C···O2v	1.05 (3)	1.70 (4)	2.754 (3)	179 (3)
C1—H1···O4vi	1.02 (3)	2.45 (3)	3.328 (4)	145 (2)
C16—H16B···O3iv	1.01 (3)	2.58 (3)	3.426 (4)	140.8 (18)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O4	1.07 (3)	1.70 (3)	2.747 (3)	165 (3)
N3—H3B⋯O1i	0.96 (3)	2.29 (3)	3.088 (3)	140 (2)
N3—H3B⋯N1i	0.96 (3)	2.15 (3)	2.962 (3)	142 (2)
N3—H3C⋯O1ii	0.92 (3)	1.91 (3)	2.835 (3)	177 (3)
N4—H4A⋯O3iii	0.97 (3)	2.27 (3)	3.064 (3)	139 (2)
N4—H4A⋯N2iii	0.97 (3)	2.12 (3)	2.963 (3)	144 (2)
N4—H4B⋯O3iv	1.07 (3)	1.67 (3)	2.740 (3)	175 (3)
N4—H4C⋯O2v	1.05 (3)	1.70 (4)	2.754 (3)	179 (3)
C1—H1⋯O4vi	1.02 (3)	2.45 (3)	3.328 (4)	145 (2)
C16—H16B⋯O3iv	1.01 (3)	2.58 (3)	3.426 (4)	140.8 (18)

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