2-(Aminocarbonyl)hydrazin-1-ium 6-carboxy-picolinate.

In the crystal structure of the title proton-transfer compound, CH(6)N(3)O(+)·C(7)H(4)NO(4) (-), O-H⋯O and N-H⋯O hydrogen bonds are formed respectively between the cations and the anions, each component affording a supra-molecular chain along the c axis. The cation and anion chains are further linked by N-H⋯O and N-H⋯N hydrogen bonds. A π-π inter-action is also observed between the pyridine rings; the inter-planar separation and the centroid-centroid distance are 3.3425 (6) and 4.6256 (11) Å, respectively.

Related literature

For general background, see: Desiraju (1997 ▶); Braga et al. (1998 ▶). For related structures of proton-transfer compounds, see: Moghimi et al. (2002 ▶, 2003 ▶, 2007 ▶); Aghabozorg et al. (2008 ▶); Soleimannejad et al. (2008 ▶).

Experimental

Crystal data

CH6N3O+·C7H4NO4 −

M = 242.20

Monoclinic,

a = 7.9553 (11) Å

b = 14.965 (2) Å

c = 8.5510 (11) Å

β = 97.305 (2)°

V = 1009.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 293 K

0.30 × 0.28 × 0.25 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (; Sheldrick, 2004 ▶) T min = 0.961, T max = 0.967

10168 measured reflections

1980 independent reflections

1865 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.102

S = 0.85

1980 reflections

170 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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: SHELXTL.

Crystal structure: contains datablocks I, Global. DOI: 10.1107/S1600536809020601/is2423sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020601/is2423Isup2.hkl

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

CH6N3O+·C7H4NO4−	F(000) = 504
Mr = 242.20	Dx = 1.593 Mg m−3
Monoclinic, P21/c	Melting point: 475 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.9553 (11) Å	Cell parameters from 7532 reflections
b = 14.965 (2) Å	θ = 2.6–26.0°
c = 8.5510 (11) Å	µ = 0.13 mm−1
β = 97.305 (2)°	T = 293 K
V = 1009.7 (2) Å3	Block, colorless
Z = 4	0.30 × 0.28 × 0.25 mm

Bruker SMART CCD diffractometer	1980 independent reflections
Radiation source: fine-focus sealed tube	1865 reflections with I > 2σ(I)
graphite	Rint = 0.023
phi and ω scans	θmax = 26.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
Tmin = 0.961, Tmax = 0.967	k = −18→18
10168 measured reflections	l = −10→10

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 0.85	w = 1/[σ2(Fo2) + (0.0606P)2 + 0.7523P] where P = (Fo2 + 2Fc2)/3
1980 reflections	(Δ/σ)max < 0.001
170 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.25 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
C1	0.47854 (19)	0.35088 (10)	0.52831 (17)	0.0322 (3)
C2	0.37085 (18)	0.41208 (10)	0.41520 (17)	0.0312 (3)
C3	0.2536 (2)	0.47012 (12)	0.46794 (19)	0.0383 (4)
H3	0.2400	0.4728	0.5743	0.046*
C4	0.1580 (2)	0.52359 (13)	0.3594 (2)	0.0444 (4)
H4	0.0805	0.5639	0.3919	0.053*
C5	0.1785 (2)	0.51663 (12)	0.2019 (2)	0.0400 (4)
H5	0.1142	0.5512	0.1262	0.048*
C6	0.29775 (18)	0.45658 (10)	0.15969 (17)	0.0316 (3)
C7	0.31929 (19)	0.44623 (10)	−0.01161 (18)	0.0325 (3)
C8	0.99077 (19)	0.22252 (10)	0.68173 (17)	0.0330 (3)
N1	0.39422 (15)	0.40574 (8)	0.26364 (14)	0.0302 (3)
N2	0.70619 (16)	0.17789 (9)	0.68390 (15)	0.0335 (3)
H01A	0.6308	0.1692	0.7509	0.050*
H01B	0.7228	0.1269	0.6346	0.050*
H01C	0.6675	0.2192	0.6134	0.050*
N3	0.86050 (17)	0.20697 (11)	0.76760 (17)	0.0426 (4)
N4	1.1225 (2)	0.26456 (12)	0.75923 (19)	0.0475 (4)
O1	0.59699 (15)	0.31012 (8)	0.47629 (13)	0.0395 (3)
O2	0.44050 (16)	0.34339 (9)	0.66510 (13)	0.0463 (3)
O3	0.42447 (16)	0.38249 (9)	−0.03960 (14)	0.0448 (3)
O4	0.24379 (16)	0.49243 (8)	−0.11360 (14)	0.0452 (3)
O5	0.98177 (14)	0.19620 (8)	0.54419 (13)	0.0407 (3)
H04	1.205 (3)	0.2741 (15)	0.711 (3)	0.057 (6)*
H06	1.114 (3)	0.2797 (14)	0.857 (3)	0.054 (6)*
H08	0.853 (3)	0.2351 (14)	0.857 (3)	0.053 (6)*
H09	0.429 (3)	0.3798 (15)	−0.137 (3)	0.057 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0362 (8)	0.0364 (8)	0.0250 (7)	−0.0052 (6)	0.0080 (6)	−0.0025 (6)
C2	0.0300 (7)	0.0367 (8)	0.0280 (7)	−0.0046 (6)	0.0081 (6)	−0.0038 (6)
C3	0.0362 (8)	0.0488 (9)	0.0319 (8)	0.0001 (7)	0.0116 (6)	−0.0065 (7)
C4	0.0383 (9)	0.0506 (10)	0.0463 (10)	0.0095 (7)	0.0132 (7)	−0.0057 (8)
C5	0.0342 (8)	0.0458 (9)	0.0399 (9)	0.0051 (7)	0.0040 (7)	0.0013 (7)
C6	0.0292 (7)	0.0353 (8)	0.0306 (8)	−0.0035 (6)	0.0046 (6)	−0.0012 (6)
C7	0.0308 (7)	0.0361 (8)	0.0299 (8)	−0.0055 (6)	0.0016 (6)	0.0002 (6)
C8	0.0336 (8)	0.0387 (8)	0.0277 (7)	0.0037 (6)	0.0078 (6)	0.0043 (6)
N1	0.0303 (6)	0.0354 (7)	0.0256 (6)	−0.0017 (5)	0.0065 (5)	−0.0016 (5)
N2	0.0306 (7)	0.0398 (7)	0.0314 (7)	−0.0036 (5)	0.0087 (5)	0.0008 (5)
N3	0.0344 (7)	0.0675 (10)	0.0273 (7)	−0.0105 (7)	0.0095 (5)	−0.0106 (7)
N4	0.0356 (8)	0.0707 (11)	0.0383 (8)	−0.0115 (7)	0.0125 (6)	−0.0101 (7)
O1	0.0437 (7)	0.0467 (7)	0.0301 (6)	0.0099 (5)	0.0128 (5)	0.0059 (5)
O2	0.0561 (8)	0.0610 (8)	0.0245 (6)	0.0025 (6)	0.0153 (5)	0.0014 (5)
O3	0.0514 (7)	0.0597 (8)	0.0233 (6)	0.0161 (6)	0.0053 (5)	−0.0021 (5)
O4	0.0549 (7)	0.0471 (7)	0.0323 (6)	0.0058 (6)	0.0009 (5)	0.0057 (5)
O5	0.0393 (6)	0.0584 (7)	0.0262 (6)	−0.0001 (5)	0.0107 (4)	−0.0009 (5)

C1—O2	1.2499 (18)	C7—O4	1.2107 (19)
C1—O1	1.2507 (19)	C7—O3	1.311 (2)
C1—C2	1.516 (2)	C8—O5	1.2338 (19)
C2—N1	1.3358 (19)	C8—N4	1.326 (2)
C2—C3	1.391 (2)	C8—N3	1.364 (2)
C3—C4	1.379 (2)	N2—N3	1.4090 (19)
C3—H3	0.9300	N2—H01A	0.8900
C4—C5	1.381 (2)	N2—H01B	0.8900
C4—H4	0.9300	N2—H01C	0.8900
C5—C6	1.387 (2)	N3—H08	0.88 (2)
C5—H5	0.9300	N4—H04	0.83 (2)
C6—N1	1.336 (2)	N4—H06	0.88 (2)
C6—C7	1.504 (2)	O3—H09	0.84 (2)
O2—C1—O1	124.90 (15)	O4—C7—C6	122.35 (15)
O2—C1—C2	117.83 (14)	O3—C7—C6	114.02 (13)
O1—C1—C2	117.25 (13)	O5—C8—N4	125.06 (15)
N1—C2—C3	122.73 (15)	O5—C8—N3	120.18 (15)
N1—C2—C1	116.04 (13)	N4—C8—N3	114.74 (14)
C3—C2—C1	121.22 (13)	C2—N1—C6	117.78 (13)
C4—C3—C2	118.65 (15)	N3—N2—H01A	109.5
C4—C3—H3	120.7	N3—N2—H01B	109.5
C2—C3—H3	120.7	H01A—N2—H01B	109.5
C3—C4—C5	119.29 (15)	N3—N2—H01C	109.5
C3—C4—H4	120.4	H01A—N2—H01C	109.5
C5—C4—H4	120.4	H01B—N2—H01C	109.5
C4—C5—C6	118.16 (15)	C8—N3—N2	116.86 (13)
C4—C5—H5	120.9	C8—N3—H08	121.6 (14)
C6—C5—H5	120.9	N2—N3—H08	116.0 (14)
N1—C6—C5	123.36 (14)	C8—N4—H04	117.1 (16)
N1—C6—C7	117.54 (13)	C8—N4—H06	116.7 (14)
C5—C6—C7	119.09 (14)	H04—N4—H06	126 (2)
O4—C7—O3	123.62 (15)	C7—O3—H09	108.9 (15)
O2—C1—C2—N1	−167.83 (14)	N1—C6—C7—O4	−176.25 (14)
O1—C1—C2—N1	10.7 (2)	C5—C6—C7—O4	4.7 (2)
O2—C1—C2—C3	11.3 (2)	N1—C6—C7—O3	4.6 (2)
O1—C1—C2—C3	−170.13 (15)	C5—C6—C7—O3	−174.44 (14)
N1—C2—C3—C4	−0.3 (2)	C3—C2—N1—C6	−1.2 (2)
C1—C2—C3—C4	−179.36 (15)	C1—C2—N1—C6	177.91 (13)
C2—C3—C4—C5	1.4 (3)	C5—C6—N1—C2	1.6 (2)
C3—C4—C5—C6	−1.1 (3)	C7—C6—N1—C2	−177.39 (13)
C4—C5—C6—N1	−0.5 (2)	O5—C8—N3—N2	−13.1 (2)
C4—C5—C6—C7	178.52 (15)	N4—C8—N3—N2	168.50 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H01A···O1i	0.89	2.00	2.7551 (17)	141
N2—H01A···N1i	0.89	2.21	2.9361 (17)	139
N2—H01B···O4ii	0.89	2.04	2.8781 (19)	156
N2—H01C···O1	0.89	1.84	2.7258 (18)	176
N4—H04···O2iii	0.83 (2)	2.22 (2)	2.993 (2)	155 (2)
N3—H08···O5i	0.88 (2)	2.06 (2)	2.8362 (19)	146.2 (19)
N3—H08···O1i	0.88 (2)	2.49 (2)	2.9319 (18)	112.0 (16)
O3—H09···O2iv	0.84 (2)	1.79 (2)	2.6109 (16)	165 (2)
N4—H06···O5i	0.88 (2)	2.05 (2)	2.869 (2)	153.5 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H01A⋯O1i	0.89	2.00	2.7551 (17)	141
N2—H01A⋯N1i	0.89	2.21	2.9361 (17)	139
N2—H01B⋯O4ii	0.89	2.04	2.8781 (19)	156
N2—H01C⋯O1	0.89	1.84	2.7258 (18)	176
N4—H04⋯O2iii	0.83 (2)	2.22 (2)	2.993 (2)	155 (2)
N3—H08⋯O5i	0.88 (2)	2.06 (2)	2.8362 (19)	146.2 (19)
N3—H08⋯O1i	0.88 (2)	2.49 (2)	2.9319 (18)	112.0 (16)
O3—H09⋯O2iv	0.84 (2)	1.79 (2)	2.6109 (16)	165 (2)
N4—H06⋯O5i	0.88 (2)	2.05 (2)	2.869 (2)	153.5 (19)

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