Hydrazinediium bis-(6-carboxy-pyridazine-3-carboxyl-ate) dihydrate.

The triclinic unit cell of the title compound, N(2)H(6) (2+)·2C(6)H(3)N(2)O(4) (-)·2H(2)O, contains one doubly protonated hydrazine cation which lies on an inversion centre, two symmetry-related singly deprotonated 6-carboxy-pyridazine-3-carboxyl-ate anions and two symmetry-related solvent water mol-ecules. The anions inter-act via hydrogen bonds to form double ribbons which are bridged by hydrogen bonds donated by hydrazinediium cations and water molecules.

Related literature

For the crystal structures of two polymorphs of the hydrazine adduct of pyrazole-3,5-dicarboxylic acid, see Kumar et al. (2007 ▶). Singly protonated hydrazine cations and di(aqua-O)bis­(pyridazine-3,6-dicarboxyl­ato-N,O)magnesium(II) anions have also been observed (Gryz et al., 2004 ▶). For related literature, see: Starosta & Leciejewicz (2004 ▶); Sueur et al. (1987 ▶).

Experimental

Crystal data

N2H6 2+·2C6H3N2O4 −·2H2O

M = 404.31

Triclinic,

a = 5.1727 (10) Å

b = 6.6257 (13) Å

c = 12.271 (3) Å

α = 102.08 (3)°

β = 93.92 (3)°

γ = 107.44 (3)°

V = 388.47 (17) Å3

Z = 1

Mo Kα radiation

μ = 0.15 mm−1

T = 293 (2) K

0.16 × 0.08 × 0.07 mm

Data collection

Kuma KM-4 four-circle diffractometer

Absorption correction: none

2512 measured reflections

2279 independent reflections

1431 reflections with I > 2σ(I)

R int = 0.017

3 standard reflections every 200 reflections intensity decay: 3.72%

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.133

S = 1.02

2279 reflections

159 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.23 e Å−3

Data collection: KM-4 Software (Kuma, 1996 ▶); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001037/at2534sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001037/at2534Isup2.hkl

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

N2H62+·2C6H3N2O4–·2H2O	Z = 1
Mr = 404.31	F000 = 210
Triclinic, P1	Dx = 1.728 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 5.1727 (10) Å	Cell parameters from 25 reflections
b = 6.6257 (13) Å	θ = 6–15º
c = 12.271 (3) Å	µ = 0.15 mm−1
α = 102.08 (3)º	T = 293 (2) K
β = 93.92 (3)º	Rectangular plate, colourless
γ = 107.44 (3)º	0.16 × 0.08 × 0.07 mm
V = 388.47 (17) Å3

Kuma KM-4 four-circle diffractometer	Rint = 0.017
Radiation source: fine-focus sealed tube	θmax = 30.1º
Monochromator: graphite	θmin = 1.7º
T = 293(2) K	h = −7→0
profile data from ω/2θ scans	k = −8→9
Absorption correction: none	l = −17→17
2512 measured reflections	3 standard reflections
2279 independent reflections	every 200 reflections
1431 reflections with I > 2σ(I)	intensity decay: 3.7%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.133	w = 1/[σ2(Fo2) + (0.092P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2279 reflections	Δρmax = 0.52 e Å−3
159 parameters	Δρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
O2	0.0745 (3)	1.1260 (2)	0.19096 (9)	0.0301 (3)
O3	0.6795 (3)	0.37197 (19)	0.35261 (9)	0.0292 (3)
O4	0.7130 (3)	0.4033 (2)	0.17502 (10)	0.0319 (3)
O1	−0.0377 (3)	1.1253 (2)	0.36330 (10)	0.0315 (3)
N2	0.3236 (3)	0.8346 (2)	0.19854 (10)	0.0248 (3)
N1	0.4514 (3)	0.6882 (2)	0.19574 (10)	0.0261 (3)
C6	0.4853 (3)	0.6120 (2)	0.28600 (11)	0.0198 (3)
C3	0.2223 (3)	0.9032 (2)	0.29085 (11)	0.0191 (3)
C7	0.0773 (3)	1.0655 (2)	0.27720 (12)	0.0212 (3)
C4	0.2473 (3)	0.8274 (2)	0.38706 (12)	0.0238 (3)
C8	0.6396 (3)	0.4472 (2)	0.26852 (12)	0.0215 (3)
C5	0.3863 (4)	0.6784 (3)	0.38484 (12)	0.0250 (3)
O6	0.1862 (3)	0.3212 (2)	0.98874 (10)	0.0295 (3)
N3	0.3528 (3)	0.9661 (2)	0.99354 (11)	0.0233 (3)
H5	0.169 (4)	0.871 (3)	0.4510 (18)	0.031 (5)*
H6	0.411 (4)	0.628 (3)	0.4471 (19)	0.037 (6)*
H62	0.268 (6)	0.416 (5)	1.044 (2)	0.059 (8)*
H51	0.288 (5)	0.840 (4)	0.9317 (19)	0.038 (6)*
H61	0.223 (5)	0.395 (4)	0.927 (2)	0.045 (6)*
H53	0.307 (5)	0.924 (3)	1.0576 (18)	0.035 (5)*
H52	0.288 (5)	1.098 (4)	0.9885 (18)	0.036 (5)*
H1	−0.136 (8)	1.234 (6)	0.350 (3)	0.117 (14)*

	U11	U22	U33	U12	U13	U23
O2	0.0426 (8)	0.0379 (6)	0.0231 (5)	0.0268 (6)	0.0091 (5)	0.0143 (4)
O3	0.0400 (7)	0.0348 (6)	0.0259 (5)	0.0261 (5)	0.0095 (5)	0.0130 (4)
O4	0.0465 (8)	0.0369 (6)	0.0248 (5)	0.0295 (6)	0.0119 (5)	0.0082 (4)
O1	0.0459 (8)	0.0394 (7)	0.0263 (5)	0.0315 (6)	0.0165 (5)	0.0148 (5)
N2	0.0362 (8)	0.0282 (6)	0.0197 (5)	0.0208 (6)	0.0089 (5)	0.0098 (5)
N1	0.0382 (8)	0.0294 (7)	0.0215 (6)	0.0231 (6)	0.0105 (5)	0.0092 (5)
C6	0.0237 (7)	0.0200 (6)	0.0200 (6)	0.0123 (5)	0.0051 (5)	0.0055 (5)
C3	0.0225 (7)	0.0199 (6)	0.0184 (6)	0.0109 (5)	0.0044 (5)	0.0056 (5)
C7	0.0238 (7)	0.0222 (7)	0.0210 (6)	0.0119 (6)	0.0037 (5)	0.0053 (5)
C4	0.0339 (8)	0.0279 (7)	0.0179 (6)	0.0194 (6)	0.0084 (6)	0.0077 (5)
C8	0.0249 (8)	0.0202 (6)	0.0231 (6)	0.0124 (6)	0.0036 (5)	0.0058 (5)
C5	0.0373 (9)	0.0284 (7)	0.0190 (6)	0.0206 (7)	0.0081 (6)	0.0102 (5)
O6	0.0375 (7)	0.0290 (6)	0.0237 (6)	0.0128 (5)	0.0049 (5)	0.0070 (4)
N3	0.0225 (7)	0.0293 (7)	0.0220 (6)	0.0121 (5)	0.0057 (5)	0.0084 (5)

O2—C7	1.2082 (18)	C3—C7	1.5128 (18)
O3—C8	1.2666 (17)	C4—C5	1.382 (2)
O4—C8	1.2376 (18)	C4—H5	0.94 (2)
O1—C7	1.2956 (18)	C5—H6	0.91 (2)
O1—H1	1.03 (4)	O6—H62	0.81 (3)
N2—N1	1.3241 (17)	O6—H61	0.98 (3)
N2—C3	1.3313 (18)	N3—N3i	1.440 (3)
N1—C6	1.3317 (17)	N3—H51	0.96 (2)
C6—C5	1.387 (2)	N3—H53	0.91 (2)
C6—C8	1.5236 (18)	N3—H52	1.04 (2)
C3—C4	1.3889 (19)
C7—O1—H1	111 (2)	C3—C4—H5	122.1 (13)
N1—N2—C3	120.23 (12)	O4—C8—O3	127.45 (13)
N2—N1—C6	120.34 (12)	O4—C8—C6	116.92 (12)
N1—C6—C5	122.08 (13)	O3—C8—C6	115.63 (12)
N1—C6—C8	113.36 (12)	C4—C5—C6	117.66 (13)
C5—C6—C8	124.56 (12)	C4—C5—H6	119.8 (14)
N2—C3—C4	122.16 (13)	C6—C5—H6	122.5 (14)
N2—C3—C7	112.66 (12)	H62—O6—H61	103 (2)
C4—C3—C7	125.17 (13)	N3i—N3—H51	106.7 (14)
O2—C7—O1	126.02 (13)	N3i—N3—H53	105.3 (14)
O2—C7—C3	119.91 (13)	H51—N3—H53	108 (2)
O1—C7—C3	114.07 (12)	N3i—N3—H52	109.5 (13)
C5—C4—C3	117.50 (13)	H51—N3—H52	117.5 (18)
C5—C4—H5	120.3 (13)	H53—N3—H52	109.0 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H62···N1ii	0.81 (3)	2.23 (3)	3.031 (2)	174 (3)
N3—H51···O4iii	0.96 (2)	1.85 (2)	2.770 (2)	160 (2)
O6—H61···O4iii	0.98 (3)	1.99 (3)	2.9581 (18)	168 (2)
O6—H61···N1iii	0.98 (3)	2.45 (2)	3.039 (2)	118.5 (18)
N3—H53···N2ii	0.91 (2)	1.95 (2)	2.8287 (18)	163 (2)
N3—H53···O2ii	0.91 (2)	2.50 (2)	3.0627 (19)	120.7 (17)
N3—H52···O6iv	1.04 (2)	1.71 (2)	2.7473 (18)	176.6 (19)
O1—H1···O3v	1.03 (4)	1.51 (4)	2.5152 (16)	165 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H62⋯N1i	0.81 (3)	2.23 (3)	3.031 (2)	174 (3)
N3—H51⋯O4ii	0.96 (2)	1.85 (2)	2.770 (2)	160 (2)
O6—H61⋯O4ii	0.98 (3)	1.99 (3)	2.9581 (18)	168 (2)
O6—H61⋯N1ii	0.98 (3)	2.45 (2)	3.039 (2)	118.5 (18)
N3—H53⋯N2i	0.91 (2)	1.95 (2)	2.8287 (18)	163 (2)
N3—H53⋯O2i	0.91 (2)	2.50 (2)	3.0627 (19)	120.7 (17)
N3—H52⋯O6iii	1.04 (2)	1.71 (2)	2.7473 (18)	176.6 (19)
O1—H1⋯O3iv	1.03 (4)	1.51 (4)	2.5152 (16)	165 (3)

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