Hydrazinediium bis­(6-carboxy­pyridazine-3-carboxyl­ate) dihydrate

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536808001037

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o461

doi:10.1107/S1600536808001037

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Hydrazinediium bis(6-carboxypyridazine-3-carboxylate) dihydrate

Wojciech Starosta ^a and Janusz Leciejewicz ^a ^*

^aInstitute of Nuclear Chemistry and Technology, ul. Dorodna 16, 03-195 Warszawa, Poland
^*Correspondence e-mail: jlec@ichtj.waw.pl

(Received 8 January 2008; accepted 10 January 2008; online 16 January 2008)

The triclinic unit cell of the title compound, N₂H₆²⁺·2C₆H₃N₂O₄⁻·2H₂O, contains one doubly protonated hydrazine cation which lies on an inversion centre, two symmetry-related singly deprotonated 6-carboxypyridazine-3-carboxylate anions and two symmetry-related solvent water molecules. The anions interact 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

N₂H₆²⁺·2C₆H₃N₂O₄⁻·2H₂O
M_r = 404.31
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.133
S = 1.02
2279 reflections
159 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.23 e Å⁻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⋯O3^iv	1.03 (4)	1.51 (4)	2.5152 (16)	165 (3)
Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) x, y+1, z; (iv) x-1, y+1, z.

Data collection: KM-4 Software (Kuma, 1996 $[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 $[Kuma (2001). DATAPROC. Version 10.0.7. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); 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 I, global. DOI: 10.1107/S1600536808001037/at2534sup1.cif

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

checkCIF report

Comment top

The structure of the title compound (I) is composed of one doubly-protonated hydrazine cation having its geometrical centre on an inversion centre at 1/2,0,0, two symmetry related singly-deprotonated pyridazine-3,6-dicarboxylate anions and a pair of symmetry related solvent water molecules. Fig.1 shows the asymetric unit with atom labelling scheme. Atoms forming the pyridazine ring are coplanar (r.m.s.0.057 Å). The carboxylate moiety (C7/O1/O2) makes an angle of 3.8 (1) ° with the pyridazine ring, while the (C8/O3/O4) group makes an angle of 1.1 (1) °. Bond lengths and bond angles within the title anion agree well with those reported in the structures of both modifications of the parent acid (Sueur et al., 1987, Starosta & Leciejewicz, 2004). A fairly strong hydrogen bond of 2.515 (2) Å is observed between the protonated O atom of the carboxylic group acting as a donor and the deprotonated carboxylate O atom in the adjacent anion giving rise to polyionic ribbons composed of pairs of anions (Fig. 2). The ribbons are bridged by weaker bonds in which the hydrazine cations and solvation water molecules are the donors and the anions' O atoms and hetero-ring N atoms act as acceptors.

Related literature top

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 top

In the course of experiments aiming to obtain single crystals of a calcium complex with pyridazine-3,6-dicarboxylate ligand, single crystals of either the triclinic modification of the pyridazine-3,6-dicarboxylic acid dihydrate (Starosta & Leciejewicz, 2004) or of the title compound were found in the mass of polycrystalline material. The crystals of the title compound appeared when hydrazine was used to maintain the acidicity of the initial solution.

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit with atom labelling scheme and 50% probability displacement ellipsoids. The hydrazine cation is symmetry complete (symmetry code: (A) -x + 1, -y + 1, -z + 1).
	Fig. 2. Packing diagram of the structure of (I).

Hydrazinediium bis(6-carboxypyridazine-3-carboxylate) dihydrate top

Crystal data top

N₂H₆²⁺·2C₆H₃N₂O₄⁻·2H₂O	Z = 1
M_r = 404.31	F(000) = 210
Triclinic, P1	D_x = 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 = 6–15°
c = 12.271 (3) Å	µ = 0.15 mm⁻¹
α = 102.08 (3)°	T = 293 K
β = 93.92 (3)°	Rectangular plate, colourless
γ = 107.44 (3)°	0.16 × 0.08 × 0.07 mm
V = 388.47 (17) Å³

Data collection top

Kuma KM-4 four-circle diffractometer	R_int = 0.017
Radiation source: fine-focus sealed tube	θ_max = 30.1°, θ_min = 1.7°
Graphite monochromator	h = −7→0
profile data from ω/2θ scans	k = −8→9
2512 measured reflections	l = −17→17
2279 independent reflections	3 standard reflections every 200 reflections
1431 reflections with I > 2σ(I)	intensity decay: 3.7%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.092P)²] where P = (F_o² + 2F_c²)/3
2279 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

N₂H₆²⁺·2C₆H₃N₂O₄⁻·2H₂O	γ = 107.44 (3)°
M_r = 404.31	V = 388.47 (17) Å³
Triclinic, P1	Z = 1
a = 5.1727 (10) Å	Mo Kα radiation
b = 6.6257 (13) Å	µ = 0.15 mm⁻¹
c = 12.271 (3) Å	T = 293 K
α = 102.08 (3)°	0.16 × 0.08 × 0.07 mm
β = 93.92 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	R_int = 0.017
2512 measured reflections	3 standard reflections every 200 reflections
2279 independent reflections	intensity decay: 3.7%
1431 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.52 e Å⁻³
2279 reflections	Δρ_min = −0.23 e Å⁻³
159 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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

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···O6^iv	1.04 (2)	1.71 (2)	2.7473 (18)	176.6 (19)
O1—H1···O3^v	1.03 (4)	1.51 (4)	2.5152 (16)	165 (3)

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

Experimental details

Crystal data
Chemical formula	N₂H₆²⁺·2C₆H₃N₂O₄⁻·2H₂O
M_r	404.31
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.1727 (10), 6.6257 (13), 12.271 (3)
α, β, γ (°)	102.08 (3), 93.92 (3), 107.44 (3)
V (Å³)	388.47 (17)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.16 × 0.08 × 0.07

Data collection
Diffractometer	Kuma KM-4 four-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2512, 2279, 1431
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.133, 1.02
No. of reflections	2279
No. of parameters	159
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.23

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), 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
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···O3^iv	1.03 (4)	1.51 (4)	2.5152 (16)	165 (3)

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

References

Gryz, M., Starosta, W. & Leciejewicz, J. (2004). J. Coord. Chem. 57, 917–922. Web of Science CSD CrossRef CAS Google Scholar
Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Kuma (2001). DATAPROC. Version 10.0.7. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Kumar, V. S. S., Premkumar, T., Rath, N. P. & Govindarajan, S. (2007). Indian J. Chem. Sect B, 46, 141–147. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2004). J. Coord. Chem. 57, 1151–1156. Web of Science CSD CrossRef CAS Google Scholar
Sueur, S., Lagrengee, M., Abraham, F. & Brenard, C. (1987). J. Heterocycl. Chem. 24, 1285–1289. CrossRef CAS Google Scholar

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doi:10.1107/S1600536808001037

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