3-Carb­oxy-2-(2-cyclo­propyl­amino-4-methyl­pyridinium-3-yl­amino)­pyridinium dinitrate dihydrate

Dong, Q.; Jin, S.; Tong, K.; He, H.; Yu, Y.Q.

doi:10.1107/S1600536811040323

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2864

doi:10.1107/S1600536811040323

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3-Carboxy-2-(2-cyclopropylamino-4-methylpyridinium-3-ylamino)pyridinium dinitrate dihydrate

Qiong Dong,^a Shouwen Jin,^b ^* Kai Tong,^a Haidong He ^a and YuanQi Yu ^a

^aFaculty of Science ZheJiang A & F University, Lin'An 311300, People's Republic of China, and ^bTianmu College of ZheJiang A & F University, Lin'An 311300, People's Republic of China
^*Correspondence e-mail: JINSWw@yahoo.cn

(Received 28 August 2011; accepted 30 September 2011; online 8 October 2011)

The two benzene rings in the cation of the title compound, C₁₅H₁₈N₄O₂²⁺·2NO₃⁻·2H₂O, are almost perpendicular [dihedral angle = 91.6 (2)°]. In the crystal, the components are linked by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For general background to hydrogen-bonding interactions, see: Lam & Mak (2000 ); Desiraju (2002 ); Liu et al. (2008 ); Biswas et al. (2009 ); Jin et al. (2010 ).

Experimental

Crystal data

C₁₅H₁₈N₄O₂²⁺·2NO₃⁻·2H₂O
M_r = 446.39
Orthorhombic, P b c a
a = 7.4463 (6) Å
b = 15.0032 (14) Å
c = 35.975 (2) Å
V = 4019.0 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.44 × 0.36 × 0.34 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.947, T_max = 0.958
18931 measured reflections
3540 independent reflections
1964 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.295
S = 1.04
3540 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10D⋯O8ⁱ	0.85	2.10	2.942 (8)	171
O10—H10C⋯O4ⁱⁱ	0.85	2.19	3.037 (7)	172
O9—H9D⋯O5ⁱⁱⁱ	0.85	2.55	3.089 (7)	123
O9—H9D⋯O4ⁱⁱⁱ	0.85	2.07	2.916 (6)	174
O9—H9C⋯O1^iv	0.85	1.96	2.809 (5)	173
O2—H2A⋯O9^v	0.82	1.73	2.535 (5)	168
N4—H4⋯O7^vi	0.86	1.94	2.787 (6)	166
N3—H3⋯O6	0.86	2.01	2.746 (6)	143
N2—H2⋯O3	0.86	1.98	2.810 (5)	163
N1—H1⋯O10	0.86	2.22	2.900 (6)	136
N1—H1⋯O1	0.86	2.05	2.697 (4)	131
C4—H4A⋯O5^vii	0.93	2.34	3.162 (7)	147
C6—H6⋯O3^iv	0.93	2.26	3.161 (6)	162
C11—H11⋯O8^vi	0.93	2.57	3.252 (8)	131
C15—H15A⋯O3ⁱⁱ	0.96	2.58	3.533 (7)	174
Symmetry codes: (i) x-1, y, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) x+1, y, z; (v) -x+1, -y+1, -z+1; (vi) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ ; (vii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811040323/jh2324sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040323/jh2324Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811040323/jh2324Isup3.cml

checkCIF report

Comment top

Intermolecular interactions are responsible for crystal packing and gaining an understanding of them allows us to comprehend collective properties and permits the design of new crystals with specific physical and chemical properties (Lam & Mak, 2000). Hydrogen bonding is one of the most important noncovalent interactions that determines and controls the assembly of molecules and ions (Desiraju, 2002, Liu et al., 2008, Biswas et al., 2009).

Organic salts based on hydrogen bonding are also a research field receiving great attention in recent years. As an extension of our study concentrating on hydrogen bonded assembly of organic acid and organic base (Jin et al., 2010), herein we report the crystal structure of 2-(2-(cyclopropylamino)-4-methylpyridinium-3-ylamino) nicotinic acid dinitrate dihydrate.

The crystal of the title compound of the formula C₁₅H₂₂N₆O₁₀ was obtained by recrystallization of 2-(2-(cyclopropylamino)-4-methylpyridin-3-ylamino) nicotinic acid from aqueous solution of HNO₃.

The asymmetric unit of the compound consists of one dication, two nitrate anions, and two free water molecules (Fig. 1), respectively.

The compound is an organic salt. At every cation there are bound two nitrate anions through the N—H···O hydrogen bond. And the two water molecules were connected with carbonyl and OH of the carboxyl group of the cation rspectively via the O—H···O hydrogen bond. Under these interactions the cation, the anions, and the water molecules form a pentacomponent adduct. Such kind of adducts were connected together by the N—H···O, O—H···O, O-pi, and CH₂—O interactions to form a one-dimensional chain running along the a axis direction. Two such chains were joined together via the CH—O, and CH₂—O interactions to form double chain structure (Fig. 2). The double chains were linked together via the water molecule that is bound with the carboxyl group to form two-dimensional sheet extending along the ac plane. The two-dimensional sheets further stacked along the b axis direction through the nitrate group to form three-dimensional layer network structure.

Related literature top

For general background to hydrogen-bonding interactions, see: Lam & Mak (2000); Desiraju (2002); Liu et al. (2008); Biswas et al. (2009); Jin et al. (2010).

Experimental top

A solution of 2-(2-(cyclopropylamino)-4-methylpyridin-3-ylamino) nicotinic acid (28.4 mg, 0.1 mmol) was dissolved in 5 ml of water and 1 ml of conc. HNO₃ under continuous stirring. The solution was stirred for about 1 h at room temperature, then the solution was filtered into a test tube. The solution was left standing at room temperature for several days, colorless block crystals were isolated after slow evaporation of the solution in air at ambient temperature. The crystals were collected and dried in air to give the title compound.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The one-dimensional doublechain formed through CH—O, and CH₂—O interactions running along the a axis direction.

3-Carboxy-2-(2-cyclopropylamino-4-methylpyridinium-3-ylamino)pyridinium dinitrate dihydrate top

Crystal data top

C₁₅H₁₈N₄O₂²⁺·2NO₃⁻·2H₂O	D_x = 1.475 Mg m⁻³
M_r = 446.39	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 887 reflections
a = 7.4463 (6) Å	θ = 2.7–20.4°
b = 15.0032 (14) Å	µ = 0.13 mm⁻¹
c = 35.975 (2) Å	T = 298 K
V = 4019.0 (6) Å³	Block, colorless
Z = 8	0.44 × 0.36 × 0.34 mm
F(000) = 1872

Data collection top

Bruker SMART CCD diffractometer	3540 independent reflections
Radiation source: fine-focus sealed tube	1964 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
T_min = 0.947, T_max = 0.958	k = −17→17
18931 measured reflections	l = −33→42

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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.295	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1827P)²] where P = (F_o² + 2F_c²)/3
3540 reflections	(Δ/σ)_max = 0.001
281 parameters	Δρ_max = 1.01 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₁₅H₁₈N₄O₂²⁺·2NO₃⁻·2H₂O	V = 4019.0 (6) Å³
M_r = 446.39	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.4463 (6) Å	µ = 0.13 mm⁻¹
b = 15.0032 (14) Å	T = 298 K
c = 35.975 (2) Å	0.44 × 0.36 × 0.34 mm

Data collection top

Bruker SMART CCD diffractometer	3540 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1964 reflections with I > 2σ(I)
T_min = 0.947, T_max = 0.958	R_int = 0.062
18931 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.084	0 restraints
wR(F²) = 0.295	H-atom parameters constrained
S = 1.04	Δρ_max = 1.01 e Å⁻³
3540 reflections	Δρ_min = −0.56 e Å⁻³
281 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
N1	0.4596 (5)	0.5310 (2)	0.60657 (9)	0.0449 (9)
H1	0.3541	0.5202	0.5979	0.054*
N2	0.3878 (5)	0.6437 (2)	0.66673 (11)	0.0551 (11)
H2	0.3653	0.6592	0.6442	0.066*
N3	0.7403 (5)	0.5937 (2)	0.59845 (10)	0.0467 (9)
H3	0.7653	0.5784	0.6209	0.056*
N4	0.4826 (5)	0.5354 (3)	0.70757 (10)	0.0529 (10)
H4	0.4567	0.5709	0.7256	0.064*
N5	0.3305 (7)	0.7673 (3)	0.58219 (12)	0.0604 (11)
N6	0.9273 (8)	0.5859 (4)	0.69535 (14)	0.0758 (14)
O1	0.2512 (4)	0.5323 (2)	0.54524 (9)	0.0611 (10)
O2	0.3557 (5)	0.6001 (2)	0.49541 (8)	0.0666 (10)
H2A	0.2583	0.5853	0.4868	0.100*
O3	0.2495 (5)	0.7115 (3)	0.59976 (12)	0.0820 (13)
O4	0.4801 (6)	0.7916 (3)	0.59228 (13)	0.0889 (13)
O5	0.2641 (9)	0.7961 (4)	0.55453 (15)	0.143 (2)
O6	0.8651 (6)	0.6237 (4)	0.66917 (13)	0.1026 (15)
O7	0.8916 (9)	0.6246 (4)	0.72714 (14)	0.139 (2)
O8	1.0224 (9)	0.5242 (4)	0.69928 (17)	0.128 (2)
O9	0.9337 (5)	0.4322 (3)	0.53919 (11)	0.0792 (12)
H9C	1.0258	0.4656	0.5397	0.095*
H9D	0.9505	0.3895	0.5543	0.095*
O10	0.0912 (7)	0.4787 (3)	0.62102 (13)	0.1114 (17)
H10C	0.0673	0.4250	0.6152	0.134*
H10D	0.0670	0.4862	0.6439	0.134*
C1	0.3673 (6)	0.5733 (3)	0.52926 (12)	0.0470 (11)
C2	0.5772 (6)	0.5728 (3)	0.58415 (11)	0.0397 (10)
C3	0.5404 (6)	0.5972 (3)	0.54734 (11)	0.0417 (10)
C4	0.6701 (6)	0.6429 (3)	0.52733 (12)	0.0502 (11)
H4A	0.6464	0.6598	0.5030	0.060*
C5	0.8353 (7)	0.6638 (3)	0.54316 (13)	0.0564 (12)
H5	0.9221	0.6947	0.5298	0.068*
C6	0.8655 (6)	0.6383 (3)	0.57803 (13)	0.0529 (12)
H6	0.9758	0.6514	0.5889	0.063*
C7	0.4545 (6)	0.5623 (3)	0.67250 (12)	0.0474 (11)
C8	0.4974 (6)	0.5038 (3)	0.64316 (11)	0.0424 (10)
C9	0.5662 (6)	0.4192 (3)	0.65037 (13)	0.0492 (12)
C10	0.5932 (7)	0.3961 (3)	0.68769 (15)	0.0611 (14)
H10	0.6408	0.3405	0.6935	0.073*
C11	0.5509 (7)	0.4537 (4)	0.71544 (14)	0.0612 (14)
H11	0.5688	0.4370	0.7401	0.073*
C12	0.3515 (8)	0.7062 (3)	0.69516 (15)	0.0675 (15)
H12	0.2439	0.6942	0.7100	0.081*
C13	0.4961 (10)	0.7496 (4)	0.7146 (2)	0.0862 (19)
H13A	0.6180	0.7342	0.7076	0.103*
H13B	0.4794	0.7625	0.7408	0.103*
C14	0.3883 (10)	0.7997 (4)	0.6879 (2)	0.091 (2)
H14A	0.3044	0.8434	0.6975	0.110*
H14B	0.4431	0.8151	0.6643	0.110*
C15	0.6116 (8)	0.3554 (4)	0.62113 (16)	0.0719 (16)
H15A	0.5122	0.3158	0.6172	0.108*
H15B	0.7152	0.3216	0.6285	0.108*
H15C	0.6374	0.3869	0.5985	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.042 (2)	0.058 (2)	0.0342 (19)	−0.0082 (18)	−0.0056 (16)	0.0035 (17)
N2	0.067 (3)	0.053 (2)	0.045 (2)	0.005 (2)	−0.0016 (19)	−0.0010 (18)
N3	0.041 (2)	0.053 (2)	0.046 (2)	−0.0064 (17)	−0.0023 (17)	−0.0017 (17)
N4	0.059 (3)	0.065 (3)	0.035 (2)	−0.003 (2)	−0.0017 (18)	0.0049 (19)
N5	0.066 (3)	0.058 (2)	0.058 (3)	−0.004 (2)	−0.005 (2)	0.005 (2)
N6	0.077 (4)	0.097 (4)	0.054 (3)	−0.022 (3)	−0.015 (3)	0.007 (3)
O1	0.051 (2)	0.088 (2)	0.0446 (18)	−0.0183 (18)	−0.0130 (16)	0.0122 (17)
O2	0.065 (2)	0.097 (3)	0.0374 (19)	−0.0155 (19)	−0.0153 (16)	0.0130 (17)
O3	0.072 (3)	0.076 (2)	0.098 (3)	−0.018 (2)	−0.026 (2)	0.032 (2)
O4	0.077 (3)	0.097 (3)	0.092 (3)	−0.028 (2)	−0.005 (2)	−0.003 (2)
O5	0.155 (6)	0.173 (5)	0.102 (4)	−0.018 (4)	−0.050 (4)	0.071 (4)
O6	0.100 (4)	0.142 (4)	0.066 (3)	0.002 (3)	−0.023 (3)	0.007 (3)
O7	0.174 (6)	0.179 (5)	0.064 (3)	0.041 (5)	−0.020 (3)	−0.015 (3)
O8	0.143 (5)	0.115 (4)	0.126 (5)	0.025 (4)	0.030 (4)	0.040 (4)
O9	0.076 (3)	0.079 (2)	0.083 (3)	−0.015 (2)	−0.037 (2)	0.016 (2)
O10	0.128 (4)	0.121 (4)	0.085 (3)	−0.014 (3)	0.004 (3)	−0.013 (3)
C1	0.050 (3)	0.057 (3)	0.034 (2)	−0.002 (2)	−0.005 (2)	−0.001 (2)
C2	0.037 (2)	0.044 (2)	0.037 (2)	−0.0040 (19)	−0.0001 (18)	−0.0010 (18)
C3	0.042 (2)	0.046 (2)	0.037 (2)	−0.0034 (19)	−0.0008 (19)	−0.0001 (19)
C4	0.053 (3)	0.059 (3)	0.039 (2)	−0.006 (2)	−0.001 (2)	0.007 (2)
C5	0.049 (3)	0.064 (3)	0.056 (3)	−0.010 (2)	0.006 (2)	0.006 (2)
C6	0.040 (3)	0.064 (3)	0.055 (3)	−0.009 (2)	−0.005 (2)	−0.002 (2)
C7	0.051 (3)	0.051 (3)	0.040 (3)	−0.003 (2)	−0.003 (2)	0.002 (2)
C8	0.040 (2)	0.052 (3)	0.035 (2)	−0.006 (2)	−0.0019 (19)	0.0020 (19)
C9	0.052 (3)	0.050 (3)	0.046 (3)	−0.004 (2)	−0.001 (2)	0.002 (2)
C10	0.064 (3)	0.056 (3)	0.062 (3)	0.009 (2)	−0.008 (3)	0.014 (3)
C11	0.072 (4)	0.070 (3)	0.041 (3)	−0.001 (3)	−0.005 (2)	0.013 (3)
C12	0.069 (4)	0.067 (3)	0.066 (3)	0.001 (3)	0.003 (3)	−0.015 (3)
C13	0.091 (5)	0.074 (4)	0.093 (5)	0.000 (3)	−0.007 (4)	−0.022 (3)
C14	0.113 (6)	0.067 (4)	0.095 (5)	0.019 (4)	−0.011 (4)	−0.018 (3)
C15	0.080 (4)	0.067 (3)	0.069 (4)	0.006 (3)	0.011 (3)	−0.008 (3)

Geometric parameters (Å, º) top

N1—C2	1.346 (5)	C2—C3	1.401 (6)
N1—C8	1.406 (5)	C3—C4	1.386 (6)
N1—H1	0.8600	C4—C5	1.392 (7)
N2—C7	1.335 (6)	C4—H4A	0.9300
N2—C12	1.414 (6)	C5—C6	1.331 (6)
N2—H2	0.8600	C5—H5	0.9300
N3—C2	1.356 (5)	C6—H6	0.9300
N3—C6	1.363 (6)	C7—C8	1.410 (6)
N3—H3	0.8600	C8—C9	1.393 (6)
N4—C7	1.341 (5)	C9—C10	1.401 (7)
N4—C11	1.358 (6)	C9—C15	1.462 (7)
N4—H4	0.8600	C10—C11	1.357 (7)
N5—O5	1.192 (6)	C10—H10	0.9300
N5—O3	1.210 (5)	C11—H11	0.9300
N5—O4	1.227 (6)	C12—C13	1.440 (8)
N6—O8	1.174 (7)	C12—C14	1.452 (8)
N6—O6	1.193 (6)	C12—H12	0.9800
N6—O7	1.310 (7)	C13—C14	1.460 (9)
O1—C1	1.207 (5)	C13—H13A	0.9700
O2—C1	1.285 (5)	C13—H13B	0.9700
O2—H2A	0.8200	C14—H14A	0.9700
O9—H9C	0.8500	C14—H14B	0.9700
O9—H9D	0.8501	C15—H15A	0.9600
O10—H10C	0.8499	C15—H15B	0.9600
O10—H10D	0.8501	C15—H15C	0.9600
C1—C3	1.488 (6)

C2—N1—C8	124.4 (4)	N2—C7—N4	118.7 (4)
C2—N1—H1	117.8	N2—C7—C8	122.5 (4)
C8—N1—H1	117.8	N4—C7—C8	118.8 (4)
C7—N2—C12	124.4 (4)	C9—C8—N1	120.8 (4)
C7—N2—H2	117.8	C9—C8—C7	120.7 (4)
C12—N2—H2	117.8	N1—C8—C7	118.4 (4)
C2—N3—C6	121.5 (4)	C8—C9—C10	117.2 (4)
C2—N3—H3	119.3	C8—C9—C15	123.2 (4)
C6—N3—H3	119.3	C10—C9—C15	119.6 (5)
C7—N4—C11	121.8 (4)	C11—C10—C9	120.9 (5)
C7—N4—H4	119.1	C11—C10—H10	119.5
C11—N4—H4	119.1	C9—C10—H10	119.5
O5—N5—O3	118.6 (5)	C10—C11—N4	120.6 (4)
O5—N5—O4	121.1 (5)	C10—C11—H11	119.7
O3—N5—O4	120.3 (5)	N4—C11—H11	119.7
O8—N6—O6	134.8 (7)	N2—C12—C13	120.6 (5)
O8—N6—O7	111.5 (6)	N2—C12—C14	118.3 (5)
O6—N6—O7	113.5 (6)	C13—C12—C14	60.6 (4)
C1—O2—H2A	109.5	N2—C12—H12	115.4
H9C—O9—H9D	108.2	C13—C12—H12	115.4
H10C—O10—H10D	108.6	C14—C12—H12	115.4
O1—C1—O2	124.3 (4)	C12—C13—C14	60.1 (4)
O1—C1—C3	122.4 (4)	C12—C13—H13A	117.8
O2—C1—C3	113.4 (4)	C14—C13—H13A	117.8
N1—C2—N3	117.6 (4)	C12—C13—H13B	117.8
N1—C2—C3	124.1 (4)	C14—C13—H13B	117.8
N3—C2—C3	118.3 (4)	H13A—C13—H13B	114.9
C4—C3—C2	118.9 (4)	C12—C14—C13	59.3 (4)
C4—C3—C1	119.7 (4)	C12—C14—H14A	117.8
C2—C3—C1	121.3 (4)	C13—C14—H14A	117.8
C3—C4—C5	121.0 (4)	C12—C14—H14B	117.8
C3—C4—H4A	119.5	C13—C14—H14B	117.8
C5—C4—H4A	119.5	H14A—C14—H14B	115.0
C6—C5—C4	118.1 (4)	C9—C15—H15A	109.5
C6—C5—H5	121.0	C9—C15—H15B	109.5
C4—C5—H5	121.0	H15A—C15—H15B	109.5
C5—C6—N3	122.3 (4)	C9—C15—H15C	109.5
C5—C6—H6	118.9	H15A—C15—H15C	109.5
N3—C6—H6	118.9	H15B—C15—H15C	109.5

C8—N1—C2—N3	−3.2 (6)	C11—N4—C7—C8	−0.1 (7)
C8—N1—C2—C3	178.0 (4)	C2—N1—C8—C9	−90.6 (5)
C6—N3—C2—N1	−178.0 (4)	C2—N1—C8—C7	93.0 (5)
C6—N3—C2—C3	0.9 (6)	N2—C7—C8—C9	−179.7 (4)
N1—C2—C3—C4	177.7 (4)	N4—C7—C8—C9	0.6 (7)
N3—C2—C3—C4	−1.1 (6)	N2—C7—C8—N1	−3.3 (6)
N1—C2—C3—C1	−3.7 (6)	N4—C7—C8—N1	177.0 (4)
N3—C2—C3—C1	177.5 (4)	N1—C8—C9—C10	−177.4 (4)
O1—C1—C3—C4	178.8 (4)	C7—C8—C9—C10	−1.1 (7)
O2—C1—C3—C4	−1.0 (6)	N1—C8—C9—C15	3.1 (7)
O1—C1—C3—C2	0.2 (7)	C7—C8—C9—C15	179.4 (5)
O2—C1—C3—C2	−179.5 (4)	C8—C9—C10—C11	1.1 (7)
C2—C3—C4—C5	0.5 (7)	C15—C9—C10—C11	−179.5 (5)
C1—C3—C4—C5	−178.0 (4)	C9—C10—C11—N4	−0.5 (8)
C3—C4—C5—C6	0.3 (7)	C7—N4—C11—C10	0.0 (8)
C4—C5—C6—N3	−0.6 (7)	C7—N2—C12—C13	71.3 (7)
C2—N3—C6—C5	0.0 (7)	C7—N2—C12—C14	142.1 (6)
C12—N2—C7—N4	3.0 (7)	N2—C12—C13—C14	107.4 (6)
C12—N2—C7—C8	−176.6 (5)	N2—C12—C14—C13	−111.1 (6)
C11—N4—C7—N2	−179.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10D···O8ⁱ	0.85	2.10	2.942 (8)	171
O10—H10C···O4ⁱⁱ	0.85	2.19	3.037 (7)	172
O9—H9D···O5ⁱⁱⁱ	0.85	2.55	3.089 (7)	123
O9—H9D···O4ⁱⁱⁱ	0.85	2.07	2.916 (6)	174
O9—H9C···O1^iv	0.85	1.96	2.809 (5)	173
O2—H2A···O9^v	0.82	1.73	2.535 (5)	168
N4—H4···O7^vi	0.86	1.94	2.787 (6)	166
N3—H3···O6	0.86	2.01	2.746 (6)	143
N2—H2···O3	0.86	1.98	2.810 (5)	163
N1—H1···O10	0.86	2.22	2.900 (6)	136
N1—H1···O1	0.86	2.05	2.697 (4)	131
C4—H4A···O5^vii	0.93	2.34	3.162 (7)	147
C6—H6···O3^iv	0.93	2.26	3.161 (6)	162
C11—H11···O8^vi	0.93	2.57	3.252 (8)	131
C15—H15A···O3ⁱⁱ	0.96	2.58	3.533 (7)	174

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₈N₄O₂²⁺·2NO₃⁻·2H₂O
M_r	446.39
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	7.4463 (6), 15.0032 (14), 35.975 (2)
V (Å³)	4019.0 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.44 × 0.36 × 0.34

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.947, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	18931, 3540, 1964
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.084, 0.295, 1.04
No. of reflections	3540
No. of parameters	281
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.56

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10D···O8ⁱ	0.85	2.10	2.942 (8)	171.4
O10—H10C···O4ⁱⁱ	0.85	2.19	3.037 (7)	171.7
O9—H9D···O5ⁱⁱⁱ	0.85	2.55	3.089 (7)	122.7
O9—H9D···O4ⁱⁱⁱ	0.85	2.07	2.916 (6)	173.5
O9—H9C···O1^iv	0.85	1.96	2.809 (5)	172.9
O2—H2A···O9^v	0.82	1.73	2.535 (5)	168.0
N4—H4···O7^vi	0.86	1.94	2.787 (6)	166.2
N3—H3···O6	0.86	2.01	2.746 (6)	143.4
N2—H2···O3	0.86	1.98	2.810 (5)	162.5
N1—H1···O10	0.86	2.22	2.900 (6)	136.4
N1—H1···O1	0.86	2.05	2.697 (4)	131.1
C4—H4A···O5^vii	0.93	2.34	3.162 (7)	147
C6—H6···O3^iv	0.93	2.26	3.161 (6)	162
C11—H11···O8^vi	0.93	2.57	3.252 (8)	131
C15—H15A···O3ⁱⁱ	0.96	2.58	3.533 (7)	174

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

Acknowledgements

We gratefully acknowledge financial support by the Education Office Foundation of ZheJiang Province (project No. Y201017321) and the Innovation Project of ZheJiang A & F University.

References

Biswas, C., Drew, M. G. B., Escudero, D., Frontera, A. & Ghosh, A. (2009). Eur. J. Inorg. Chem. pp. 2238–2246. Web of Science CSD CrossRef Google Scholar
Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565–573. Web of Science CrossRef PubMed CAS Google Scholar
Jin, S. W., Zhang, W. B., Liu, L., Gao, H. F., Wang, D. Q., Chen, R. P. & Xu, X. L. (2010). J. Mol. Struct. 975, 128–136. Web of Science CSD CrossRef CAS Google Scholar
Lam, C. K. & Mak, T. C. W. (2000). Tetrahedron, 56, 6657–6665. Web of Science CSD CrossRef CAS Google Scholar
Liu, J. Q., Wang, Y. Y., Ma, L. F., Zhang, W. H., Zeng, X. R., Zhong, F., Shi, Q. Z. & Peng, S. M. (2008). Inorg. Chim. Acta, 361, 173–182. Web of Science CSD CrossRef CAS Google Scholar
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Volume 67| Part 11| November 2011| Page o2864

doi:10.1107/S1600536811040323

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3-Carb­­oxy-2-(2-cyclo­propyl­amino-4-methyl­pyridinium-3-yl­amino)­pyridinium dinitrate dihydrate

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Experimental

Crystal data

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organic compounds

3-Carboxy-2-(2-cyclopropylamino-4-methylpyridinium-3-ylamino)pyridinium dinitrate dihydrate