Hexane-1,6-diammonium bis­(pyridine-2-carboxyl­ate)

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

doi:10.1107/S1600536809019424

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1415

doi:10.1107/S1600536809019424

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Hexane-1,6-diammonium bis(pyridine-2-carboxylate)

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

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

(Received 20 May 2009; accepted 22 May 2009; online 29 May 2009)

The title compound, C₆H₁₈N₂²⁺·2C₆H₄NO₂⁻, consists of a doubly protonated hexamethylenediammonium dication and two pyridine-2-carboxylate anions. These ions interact by means of intermolecular N—H⋯O and N—H⋯N hydrogen bonds to form a two-dimensional array. The carboxylate 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)X₂ (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

C₆H₁₈N₂²⁺·2C₆H₄NO₂⁻
M_r = 362.43
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.057
wR(F²) = 0.124
S = 0.93
4752 reflections
339 parameters
All H-atom parameters refined
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

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⋯O3^iv	1.07 (3)	1.67 (3)	2.740 (3)	175 (3)
N4—H4C⋯O2^v	1.05 (3)	1.70 (4)	2.754 (3)	179 (3)
C1—H1⋯O4^vi	1.02 (3)	2.45 (3)	3.328 (4)	145 (2)
C16—H16B⋯O3^iv	1.01 (3)	2.58 (3)	3.426 (4)	140.8 (18)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z; (iv) x+1, y, z; (v) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536809019424/tk2459sup1.cif

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

checkCIF report

Comment top

The title compound, C₆H₁₈N₂²⁺.2C₆H₄NO₂^-, consists of a doubly protonated hexamethylenediammonium dication and two pyridinecarboxylate anions (Fig. 1). The carboxylate groups of the anions appear to be delocalized on the basis of the C—O bond lengths (C—O: 1.241 (3)–1.247 (3) Å). The N3—C13—C14—C15 and C16—C17—C18—N4 torsion angles [64.9 (4)° and -66.6 (4)°, respectively] display the gauche conformation for the two groups within the dication, whereas C13—C14—C15—C16, C14—C15—C16—C17 and C15—C16—C17—C18 atoms show the anti conformation [their torsion angles lie in the range of 174.6 (3)°–177.3 (3)°]. In the crystal, the component ions interact by means of many intermolecular N—H···O and N—H···N hydrogen bonds and C—H···O contacts to form a 2-D array (Table 1 and Fig. 2).

Related literature top

For the crystal structures of (C₆H₁₈N₂)X₂ (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 top

A solution of 1,6-diaminohexane (0.200 g, 1.721 mmol) and pyridine-2-carboxylic acid (1.180 g, 8.606 mmol) in H₂O (20 ml) was stirred for 2 h at 333 K. The solvent was removed under vacuum and the residue was washed with acetone to give a white powder (0.5972 g). Crystals were obtained by slow evaporation from an ethanol 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 molecular structures of the components (I), with displacement ellipsoids drawn at the 30% probability level for non-H atoms.
	Fig. 2. View of the unit-cell contents for (I). Hydrogen-bond interactions are drawn with dashed lines.

Hexane-1,6-diammonium bis(pyridine-2-carboxylate) top

Crystal data top

C₆H₁₈N₂²⁺·2C₆H₄NO₂⁻	F(000) = 776
M_r = 362.43	D_x = 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

Data collection top

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

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	All H-atom parameters refined
S = 0.93	w = 1/[σ²(F_o²) + (0.0318P)²] where P = (F_o² + 2F_c²)/3
4752 reflections	(Δ/σ)_max < 0.001
339 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₆H₁₈N₂²⁺·2C₆H₄NO₂⁻	V = 1921.6 (3) Å³
M_r = 362.43	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.8182 (7) Å	µ = 0.09 mm⁻¹
b = 9.1569 (7) Å	T = 296 K
c = 21.6423 (17) Å	0.33 × 0.25 × 0.18 mm
β = 99.038 (2)°

Data collection top

Bruker SMART 1000 CCD diffractometer	4752 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1740 reflections with I > 2σ(I)
T_min = 0.685, T_max = 0.984	R_int = 0.089
13964 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.124	All H-atom parameters refined
S = 0.93	Δρ_max = 0.15 e Å⁻³
4752 reflections	Δρ_min = −0.15 e Å⁻³
339 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	0.39197 (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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O3^iv	1.07 (3)	1.67 (3)	2.740 (3)	175 (3)
N4—H4C···O2^v	1.05 (3)	1.70 (4)	2.754 (3)	179 (3)
C1—H1···O4^vi	1.02 (3)	2.45 (3)	3.328 (4)	145 (2)
C16—H16B···O3^iv	1.01 (3)	2.58 (3)	3.426 (4)	140.8 (18)

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

Experimental details

Crystal data
Chemical formula	C₆H₁₈N₂²⁺·2C₆H₄NO₂⁻
M_r	362.43
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.8182 (7), 9.1569 (7), 21.6423 (17)
β (°)	99.038 (2)
V (Å³)	1921.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.33 × 0.25 × 0.18

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.685, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	13964, 4752, 1740
R_int	0.089
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.124, 0.93
No. of reflections	4752
No. of parameters	339
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.15

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
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···O3^iv	1.07 (3)	1.67 (3)	2.740 (3)	175 (3)
N4—H4C···O2^v	1.05 (3)	1.70 (4)	2.754 (3)	179 (3)
C1—H1···O4^vi	1.02 (3)	2.45 (3)	3.328 (4)	145 (2)
C16—H16B···O3^iv	1.01 (3)	2.58 (3)	3.426 (4)	140.8 (18)

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

Acknowledgements

This work was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (grant No. KRF-2007–412-J02001).

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