Cyclo­hexane-1,2-diammonium bis­(pyridine-2-carboxyl­ate)

Kim, N.-H.; Hwang, I.-C.; Ha, K.

doi:10.1107/S1600536809038689

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2571

doi:10.1107/S1600536809038689

Open

access

Cyclohexane-1,2-diammonium bis(pyridine-2-carboxylate)

Nam-Ho Kim,^a In-Chul Hwang ^b and Kwang Ha ^a ^*

^aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea, and ^bInstitute of Basic Sciences, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 23 September 2009; accepted 24 September 2009; online 30 September 2009)

In the dication of the title salt, C₆H₁₆N₂²⁺·2C₆H₄NO₂⁻, the two ammonium groups are in the equatorial positions of the chair-shaped cyclohexyl 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 interactions 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

C₆H₁₆N₂²⁺·2C₆H₄NO₂⁻
M_r = 360.41
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.064
wR(F²) = 0.171
S = 0.98
3854 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

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) -x+2, -y+1, -z+2; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+1, -z+2.

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/S1600536809038689/ng2649sup1.cif

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

checkCIF report

Comment top

The title compound, C₆H₁₆N₂²⁺.2C₆H₄NO₂^-, consists of a doubly protonated cyclohexane-1,2-diammonium dication and two pyridine-2-carboxylate anions (Fig. 1). The dication has two chiral carbon atoms (C1 and C2), and is one of four possible stereoisomers. Both chiral atoms have R configuration. The cyclohexane ring of the dication adopts a strain-free chair conformation. The C—C—C bond angles lie in the range of 109.3 (3)°–111.6 (3)°, close to the ideal tetrahedral angle, and all neighboring C—H bonds are staggered. The diammonium groups within the dication are on opposite faces of the cyclohexane ring, that is, trans with respect to each other, and therefore the dication exists in the diequatorial conformation. The N1—C1—C2—N2 torsion angle of -59.0 (3)° displays the gauche conformation for the four atoms and there is a gauche interaction between the two NH₃⁺ groups. The carboxylate groups of the anions appear to be delocalized on the basis of the C—O bond lengths [C—O: 1.239 (3)–1.255 (3) Å]. In the crystal structure, the component ions interact by means of many intermolecular N—H···O and N—H···N hydrogen bonds to form a two-dimensional network parallel to the ac plane (Table 1 and Fig. 2). There may also be intermolecular π-π interactions between adjacent pyridine rings, with a centroid-centroid distance of 3.589 (2) Å.

Related literature top

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 top

A solution of a mixture of cis and trans isomers of 1,2-diaminocyclohexane (0.202 g, 1.769 mmol) and pyridine-2-carboxylic acid (0.294 g, 2.388 mmol) in H₂O (10 ml) was stirred for 3 h at 60 °C. The solvent was removed under vacuum and the residue was washed with ether/acetone/CHCl₃, to give a white powder (0.112 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN 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 30% probability level for non-H atoms.
	Fig. 2. View of the unit-cell contents of the title compound. Hydrogen-bond interactions are drawn with dashed lines.

Cyclohexane-1,2-diammonium bis(pyridine-2-carboxylate) top

Crystal data top

C₆H₁₆N₂²⁺·2C₆H₄NO₂⁻	F(000) = 768
M_r = 360.41	D_x = 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

Data collection top

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

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.171	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0581P)²] where P = (F_o² + 2F_c²)/3
3854 reflections	(Δ/σ)_max < 0.001
237 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₆H₁₆N₂²⁺·2C₆H₄NO₂⁻	V = 1890.1 (4) Å³
M_r = 360.41	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.2942 (11) Å	µ = 0.09 mm⁻¹
b = 20.329 (2) Å	T = 293 K
c = 10.2189 (11) Å	0.20 × 0.10 × 0.10 mm
β = 101.775 (3)°

Data collection top

Bruker SMART 1000 CCD diffractometer	1741 reflections with I > 2σ(I)
11005 measured reflections	R_int = 0.064
3854 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 0.98	Δρ_max = 0.18 e Å⁻³
3854 reflections	Δρ_min = −0.17 e Å⁻³
237 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	0.5813 (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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+2, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₆H₁₆N₂²⁺·2C₆H₄NO₂⁻
M_r	360.41
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.2942 (11), 20.329 (2), 10.2189 (11)
β (°)	101.775 (3)
V (Å³)	1890.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11005, 3854, 1741
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.171, 0.98
No. of reflections	3854
No. of parameters	237
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.17

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
N1—H1A···O3	0.86	1.89	2.749 (3)	175.0
N1—H1B···O2	0.86	1.92	2.743 (3)	159.5
N1—H1C···O3ⁱ	0.86	2.10	2.790 (3)	137.4
N1—H1C···N4ⁱ	0.86	2.49	3.271 (4)	151.8
N2—H2A···O1ⁱⁱ	0.86	2.09	2.828 (3)	144.0
N2—H2A···N3ⁱⁱ	0.86	2.53	3.254 (4)	141.8
N2—H2B···O1	0.86	2.02	2.807 (3)	152.1
N2—H2C···O4ⁱⁱⁱ	0.86	1.88	2.734 (3)	171.4

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

Acknowledgements

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

References

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kim, N.-H. & Ha, K. (2009a). Acta Cryst. E65, o1415. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kim, N.-H. & Ha, K. (2009b). Acta Cryst. E65, o2151. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kim, N.-H. & Ha, K. (2009c). Acta Cryst. E65, o2504. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lin, H.-M. & Lii, K.-H. (1998). Inorg. Chem. 37, 4220–4222. Web of Science CSD CrossRef PubMed CAS Google Scholar
Lin, C.-H. & Wang, S.-L. (2000). Chem. Mater. 12, 3617–3623. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar