Cyclo-hexane-1,2-diammonium bis-(pyridine-2-carboxyl-ate).

In the dication of the title salt, C(6)H(16)N(2) (2+)·2C(6)H(4)NO(2) (-), the two ammonium groups are in the equatorial positions of the chair-shaped cyclo-hexyl ring. In the crystal, the cations and anions are linked by N-H⋯O and N-H⋯N hydrogen bonds, forming a layer network parallel to the ac plane. Weak π-π inter-actions between adjacent pyridine rings with a centroid-centroid distance of 3.589 (2) Å are also present.

Related literature

For the syntheses and structures of cyclo­hexane-1,2-diammonium compounds, see: Lin & Lii (1998 ▶); Lin & Wang (2000 ▶). For the crystal structures of pyridine-2-carboxyl­ates, see: Kim & Ha (2009a ▶,b ▶,c ▶).

Experimental

Crystal data

C6H16N2 2+·2C6H4NO2 −

M = 360.41

Monoclinic,

a = 9.2942 (11) Å

b = 20.329 (2) Å

c = 10.2189 (11) Å

β = 101.775 (3)°

V = 1890.1 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: none

11005 measured reflections

3854 independent reflections

1741 reflections with I > 2σ(I)

R int = 0.064

Refinement

R[F 2 > 2σ(F 2)] = 0.064

wR(F 2) = 0.171

S = 0.98

3854 reflections

237 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.17 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/S1600536809038689/ng2649sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038689/ng2649Isup2.hkl

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

C6H16N22+·2C6H4NO2−	F(000) = 768
Mr = 360.41	Dx = 1.267 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 784 reflections
a = 9.2942 (11) Å	θ = 2.3–17.2°
b = 20.329 (2) Å	µ = 0.09 mm−1
c = 10.2189 (11) Å	T = 293 K
β = 101.775 (3)°	Rod, colorless
V = 1890.1 (4) Å3	0.20 × 0.10 × 0.10 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	1741 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
graphite	θmax = 26.4°, θmin = 2.3°
φ and ω scans	h = −11→11
11005 measured reflections	k = −25→25
3854 independent reflections	l = −12→7

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.171	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0581P)2] where P = (Fo2 + 2Fc2)/3
3854 reflections	(Δ/σ)max < 0.001
237 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	0.5813 (2)	0.56693 (10)	0.5900 (2)	0.0580 (6)
O2	0.6448 (3)	0.60901 (12)	0.7932 (2)	0.0874 (9)
O3	0.9341 (2)	0.53730 (12)	1.1294 (2)	0.0629 (7)
O4	0.7329 (2)	0.53120 (12)	1.2114 (2)	0.0705 (7)
N1	0.7776 (2)	0.49308 (12)	0.8877 (2)	0.0497 (7)
H1A	0.8252	0.5093	0.9617	0.060*
H1B	0.7247	0.5233	0.8425	0.060*
H1C	0.8387	0.4780	0.8423	0.060*
N2	0.5142 (2)	0.44461 (12)	0.6901 (2)	0.0515 (7)
H2A	0.4887	0.4232	0.6164	0.062*
H2B	0.5633	0.4790	0.6768	0.062*
H2C	0.4370	0.4563	0.7182	0.062*
N3	0.4687 (3)	0.68504 (14)	0.4928 (3)	0.0660 (8)
N4	1.1006 (3)	0.56390 (14)	1.3686 (3)	0.0606 (8)
C1	0.6809 (3)	0.43883 (15)	0.9164 (3)	0.0469 (8)
H1	0.6048	0.4573	0.9593	0.056*
C2	0.6076 (3)	0.40179 (15)	0.7922 (3)	0.0494 (8)
H2	0.6844	0.3820	0.7519	0.059*
C3	0.5124 (4)	0.34650 (16)	0.8301 (3)	0.0646 (10)
H3A	0.4353	0.3652	0.8698	0.078*
H3B	0.4664	0.3227	0.7503	0.078*
C4	0.6042 (4)	0.29907 (18)	0.9290 (4)	0.0789 (11)
H4A	0.5408	0.2657	0.9550	0.095*
H4B	0.6754	0.2772	0.8865	0.095*
C5	0.6839 (5)	0.33547 (18)	1.0523 (3)	0.0802 (12)
H5A	0.6128	0.3529	1.1007	0.096*
H5B	0.7474	0.3052	1.1108	0.096*
C6	0.7750 (4)	0.39129 (16)	1.0134 (3)	0.0625 (10)
H6A	0.8516	0.3733	0.9722	0.075*
H6B	0.8219	0.4150	1.0931	0.075*
C7	0.4020 (5)	0.74176 (19)	0.4510 (4)	0.0801 (12)
H7	0.3641	0.7465	0.3600	0.096*
C8	0.3859 (5)	0.79253 (18)	0.5318 (4)	0.0832 (12)
H8	0.3372	0.8307	0.4977	0.100*
C9	0.4430 (5)	0.78617 (18)	0.6647 (4)	0.0863 (13)
H9	0.4344	0.8203	0.7231	0.104*
C10	0.5136 (4)	0.72897 (17)	0.7119 (3)	0.0668 (10)
H10	0.5546	0.7241	0.8024	0.080*
C11	0.5224 (3)	0.67897 (15)	0.6232 (3)	0.0493 (8)
C12	0.5894 (3)	0.61329 (16)	0.6723 (4)	0.0542 (9)
C13	1.1815 (4)	0.58402 (19)	1.4852 (4)	0.0769 (11)
H13	1.2833	0.5832	1.4958	0.092*
C14	1.1234 (4)	0.60559 (18)	1.5892 (4)	0.0715 (11)
H14	1.1846	0.6196	1.6678	0.086*
C15	0.9757 (5)	0.60653 (18)	1.5775 (4)	0.0723 (11)
H15	0.9338	0.6212	1.6474	0.087*
C16	0.8879 (4)	0.58488 (17)	1.4573 (3)	0.0646 (10)
H16	0.7861	0.5843	1.4463	0.078*
C17	0.9540 (3)	0.56461 (14)	1.3564 (3)	0.0452 (8)
C18	0.8658 (4)	0.54258 (15)	1.2225 (3)	0.0496 (8)

	U11	U22	U33	U12	U13	U23
O1	0.0663 (15)	0.0528 (14)	0.0526 (14)	0.0046 (11)	0.0071 (11)	−0.0075 (11)
O2	0.126 (2)	0.0742 (18)	0.0482 (16)	0.0264 (16)	−0.0142 (15)	−0.0071 (12)
O3	0.0525 (14)	0.0915 (18)	0.0459 (14)	−0.0065 (12)	0.0128 (11)	−0.0127 (12)
O4	0.0427 (14)	0.102 (2)	0.0660 (17)	−0.0010 (13)	0.0095 (12)	−0.0170 (13)
N1	0.0466 (16)	0.0592 (17)	0.0403 (15)	0.0014 (13)	0.0018 (12)	−0.0019 (12)
N2	0.0448 (15)	0.0642 (18)	0.0444 (16)	−0.0042 (13)	0.0061 (12)	−0.0097 (13)
N3	0.077 (2)	0.062 (2)	0.053 (2)	0.0113 (16)	−0.0005 (15)	−0.0010 (14)
N4	0.0504 (18)	0.078 (2)	0.0512 (18)	−0.0100 (15)	0.0052 (14)	−0.0030 (14)
C1	0.0436 (18)	0.055 (2)	0.0424 (19)	−0.0030 (16)	0.0109 (15)	0.0000 (15)
C2	0.0467 (18)	0.057 (2)	0.0450 (19)	0.0038 (16)	0.0096 (15)	−0.0014 (15)
C3	0.069 (2)	0.065 (2)	0.062 (2)	−0.014 (2)	0.0177 (19)	−0.0052 (18)
C4	0.105 (3)	0.061 (2)	0.072 (3)	−0.006 (2)	0.021 (2)	0.007 (2)
C5	0.111 (3)	0.069 (3)	0.061 (3)	0.002 (2)	0.018 (2)	0.013 (2)
C6	0.073 (2)	0.062 (2)	0.050 (2)	0.0062 (19)	0.0045 (17)	0.0067 (17)
C7	0.104 (3)	0.070 (3)	0.058 (3)	0.012 (2)	−0.002 (2)	0.001 (2)
C8	0.107 (3)	0.056 (3)	0.083 (3)	0.012 (2)	0.011 (3)	0.004 (2)
C9	0.132 (4)	0.048 (2)	0.081 (3)	0.005 (2)	0.025 (3)	−0.016 (2)
C10	0.086 (3)	0.054 (2)	0.058 (2)	−0.002 (2)	0.0076 (19)	−0.0057 (18)
C11	0.0482 (19)	0.050 (2)	0.050 (2)	−0.0064 (16)	0.0087 (16)	−0.0029 (16)
C12	0.052 (2)	0.057 (2)	0.052 (2)	−0.0021 (17)	0.0063 (17)	−0.0047 (18)
C13	0.059 (2)	0.106 (3)	0.062 (3)	−0.019 (2)	0.004 (2)	−0.004 (2)
C14	0.079 (3)	0.088 (3)	0.045 (2)	−0.022 (2)	0.006 (2)	−0.0053 (19)
C15	0.083 (3)	0.083 (3)	0.056 (3)	0.001 (2)	0.028 (2)	−0.0101 (19)
C16	0.054 (2)	0.087 (3)	0.056 (2)	−0.0048 (19)	0.0173 (19)	−0.0143 (19)
C17	0.046 (2)	0.0454 (19)	0.043 (2)	−0.0001 (15)	0.0074 (15)	0.0047 (14)
C18	0.044 (2)	0.053 (2)	0.051 (2)	0.0054 (16)	0.0081 (17)	−0.0018 (16)

O1—C12	1.255 (3)	C4—H4A	0.9700
O2—C12	1.241 (3)	C4—H4B	0.9700
O3—C18	1.251 (3)	C5—C6	1.517 (5)
O4—C18	1.239 (3)	C5—H5A	0.9700
N1—C1	1.489 (3)	C5—H5B	0.9700
N1—H1A	0.8600	C6—H6A	0.9700
N1—H1B	0.8600	C6—H6B	0.9700
N1—H1C	0.8600	C7—C8	1.349 (5)
N2—C2	1.493 (3)	C7—H7	0.9300
N2—H2A	0.8600	C8—C9	1.359 (5)
N2—H2B	0.8600	C8—H8	0.9300
N2—H2C	0.8600	C9—C10	1.374 (5)
N3—C11	1.330 (4)	C9—H9	0.9300
N3—C7	1.337 (4)	C10—C11	1.376 (4)
N4—C13	1.337 (4)	C10—H10	0.9300
N4—C17	1.343 (4)	C11—C12	1.515 (4)
C1—C2	1.513 (4)	C13—C14	1.359 (5)
C1—C6	1.526 (4)	C13—H13	0.9300
C1—H1	0.9800	C14—C15	1.353 (5)
C2—C3	1.528 (4)	C14—H14	0.9300
C2—H2	0.9800	C15—C16	1.400 (4)
C3—C4	1.525 (4)	C15—H15	0.9300
C3—H3A	0.9700	C16—C17	1.368 (4)
C3—H3B	0.9700	C16—H16	0.9300
C4—C5	1.517 (5)	C17—C18	1.512 (4)
C1—N1—H1A	109.5	H5A—C5—H5B	108.1
C1—N1—H1B	109.5	C5—C6—C1	111.6 (3)
H1A—N1—H1B	109.5	C5—C6—H6A	109.3
C1—N1—H1C	109.5	C1—C6—H6A	109.3
H1A—N1—H1C	109.5	C5—C6—H6B	109.3
H1B—N1—H1C	109.5	C1—C6—H6B	109.3
C2—N2—H2A	109.5	H6A—C6—H6B	108.0
C2—N2—H2B	109.5	N3—C7—C8	124.5 (4)
H2A—N2—H2B	109.5	N3—C7—H7	117.8
C2—N2—H2C	109.5	C8—C7—H7	117.8
H2A—N2—H2C	109.5	C7—C8—C9	118.0 (4)
H2B—N2—H2C	109.5	C7—C8—H8	121.0
C11—N3—C7	117.1 (3)	C9—C8—H8	121.0
C13—N4—C17	117.1 (3)	C8—C9—C10	119.5 (3)
N1—C1—C2	112.9 (2)	C8—C9—H9	120.2
N1—C1—C6	108.0 (2)	C10—C9—H9	120.2
C2—C1—C6	109.3 (3)	C9—C10—C11	118.8 (3)
N1—C1—H1	108.9	C9—C10—H10	120.6
C2—C1—H1	108.9	C11—C10—H10	120.6
C6—C1—H1	108.9	N3—C11—C10	122.1 (3)
N2—C2—C1	113.2 (2)	N3—C11—C12	117.3 (3)
N2—C2—C3	108.8 (2)	C10—C11—C12	120.6 (3)
C1—C2—C3	109.8 (2)	O2—C12—O1	124.8 (3)
N2—C2—H2	108.3	O2—C12—C11	116.8 (3)
C1—C2—H2	108.3	O1—C12—C11	118.4 (3)
C3—C2—H2	108.3	N4—C13—C14	123.7 (4)
C4—C3—C2	111.0 (3)	N4—C13—H13	118.2
C4—C3—H3A	109.4	C14—C13—H13	118.2
C2—C3—H3A	109.4	C15—C14—C13	119.6 (3)
C4—C3—H3B	109.4	C15—C14—H14	120.2
C2—C3—H3B	109.4	C13—C14—H14	120.2
H3A—C3—H3B	108.0	C14—C15—C16	118.2 (3)
C5—C4—C3	110.7 (3)	C14—C15—H15	120.9
C5—C4—H4A	109.5	C16—C15—H15	120.9
C3—C4—H4A	109.5	C17—C16—C15	119.0 (3)
C5—C4—H4B	109.5	C17—C16—H16	120.5
C3—C4—H4B	109.5	C15—C16—H16	120.5
H4A—C4—H4B	108.1	N4—C17—C16	122.4 (3)
C6—C5—C4	110.6 (3)	N4—C17—C18	115.7 (3)
C6—C5—H5A	109.5	C16—C17—C18	121.9 (3)
C4—C5—H5A	109.5	O4—C18—O3	124.4 (3)
C6—C5—H5B	109.5	O4—C18—C17	119.0 (3)
C4—C5—H5B	109.5	O3—C18—C17	116.6 (3)
N1—C1—C2—N2	−59.0 (3)	C9—C10—C11—C12	−175.5 (3)
C6—C1—C2—N2	−179.2 (2)	N3—C11—C12—O2	177.0 (3)
N1—C1—C2—C3	179.2 (2)	C10—C11—C12—O2	−5.3 (5)
C6—C1—C2—C3	59.0 (3)	N3—C11—C12—O1	−5.1 (4)
N2—C2—C3—C4	177.0 (3)	C10—C11—C12—O1	172.6 (3)
C1—C2—C3—C4	−58.6 (4)	C17—N4—C13—C14	−0.9 (5)
C2—C3—C4—C5	56.3 (4)	N4—C13—C14—C15	0.9 (6)
C3—C4—C5—C6	−54.9 (4)	C13—C14—C15—C16	0.1 (6)
C4—C5—C6—C1	56.8 (4)	C14—C15—C16—C17	−0.9 (5)
N1—C1—C6—C5	177.9 (3)	C13—N4—C17—C16	0.1 (5)
C2—C1—C6—C5	−58.9 (4)	C13—N4—C17—C18	179.1 (3)
C11—N3—C7—C8	−0.1 (6)	C15—C16—C17—N4	0.8 (5)
N3—C7—C8—C9	1.0 (7)	C15—C16—C17—C18	−178.1 (3)
C7—C8—C9—C10	−0.4 (6)	N4—C17—C18—O4	167.7 (3)
C8—C9—C10—C11	−1.0 (6)	C16—C17—C18—O4	−13.2 (5)
C7—N3—C11—C10	−1.5 (5)	N4—C17—C18—O3	−12.5 (4)
C7—N3—C11—C12	176.2 (3)	C16—C17—C18—O3	166.5 (3)
C9—C10—C11—N3	2.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.86	1.89	2.749 (3)	175
N1—H1B···O2	0.86	1.92	2.743 (3)	160
N1—H1C···O3i	0.86	2.10	2.790 (3)	137
N1—H1C···N4i	0.86	2.49	3.271 (4)	152
N2—H2A···O1ii	0.86	2.09	2.828 (3)	144
N2—H2A···N3ii	0.86	2.53	3.254 (4)	142
N2—H2B···O1	0.86	2.02	2.807 (3)	152
N2—H2C···O4iii	0.86	1.88	2.734 (3)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.86	1.89	2.749 (3)	175
N1—H1B⋯O2	0.86	1.92	2.743 (3)	160
N1—H1C⋯O3i	0.86	2.10	2.790 (3)	137
N1—H1C⋯N4i	0.86	2.49	3.271 (4)	152
N2—H2A⋯O1ii	0.86	2.09	2.828 (3)	144
N2—H2A⋯N3ii	0.86	2.53	3.254 (4)	142
N2—H2B⋯O1	0.86	2.02	2.807 (3)	152
N2—H2C⋯O4iii	0.86	1.88	2.734 (3)	171

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