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BY 4.0 license Open Access Published by De Gruyter (O) June 22, 2019

Crystal structure of dihydrazinium 1H-pyrazole-3,5-dicarboxylate, C5H12N6O4

Nedeljko Latinović, Sladjana B. Novaković, Goran A. Bogdanović, Vlatko Kastratović, Gerald Giester and Željko K. Jaćimović

Abstract

C5H12N6O4, monoclinic, P21/n (no. 14), a = 4.3368(6) Å, b = 15.483(2) Å, c = 13.8852(19) Å, β = 97.714(3)°, V = 923.9(2) Å3, Z = 4, Rgt(F) = 0.0411, wRref(F2) = 0.1109, T = 200(2) K.

CCDC no.: 1910983

The asymmetric unit of the title crystal structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Yellow prism
Size:0.22 × 0.16 × 0.07 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:0.14 mm−1
Diffractometer, scan mode:Bruker APEX-II, φ and ω-scans
θmax, completeness:33.4°, >99%
N(hkl)measured, N(hkl)unique, Rint:32710, 3560, 0.039
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2985
N(param)refined:184
Programs:Bruker programs [1], SHELX [2], [3]

Table 2:

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

AtomxyzUiso*/Ueq
O11.0208(2)0.37998(5)0.00034(6)0.02391(18)
O20.95263(19)0.27289(5)0.10278(5)0.01774(16)
O30.3217(2)0.57757(5)0.34723(6)0.02178(17)
O40.3622(2)0.43877(6)0.39166(6)0.02606(19)
N10.7665(2)0.49729(5)0.12136(6)0.01619(17)
N20.6304(2)0.54007(5)0.18837(6)0.01656(17)
N30.4105(2)0.19896(6)0.30831(7)0.01824(17)
N40.0802(2)0.21603(6)0.29600(7)0.01688(17)
N5−0.1350(2)0.31100(6)0.45979(7)0.01783(17)
N60.0646(2)0.36462(6)0.52751(6)0.01631(17)
C10.7787(2)0.41106(6)0.13768(7)0.01305(17)
C20.6380(2)0.39651(6)0.21949(7)0.01395(17)
C30.5512(2)0.47861(6)0.24878(7)0.01327(17)
C40.9279(2)0.35062(6)0.07503(7)0.01376(17)
C50.3981(2)0.50030(6)0.33578(7)0.01423(17)
H10.836(4)0.5238(11)0.0767(13)0.028(4)*
H20.601(3)0.3413(10)0.2477(11)0.019(3)*
H310.448(4)0.1762(11)0.3700(13)0.028(4)*
H320.428(4)0.1547(11)0.2676(12)0.027(4)*
H410.035(4)0.2515(11)0.3457(13)0.026(4)*
H420.032(4)0.2416(11)0.2356(13)0.027(4)*
H43−0.042(4)0.1653(12)0.3002(12)0.031(4)*
H510.216(4)0.3295(11)0.5599(11)0.023(4)*
H52−0.046(4)0.3928(11)0.5707(13)0.032(4)*
H530.163(4)0.4018(11)0.4929(13)0.031(4)*
H61−0.290(4)0.3452(11)0.4301(12)0.027(4)*
H62−0.218(4)0.2750(11)0.4960(13)0.031(4)*

Source of material

In an attempt to synthesize the intermediates of 1H-pyrazole-3,5-dicarbohydrazide with direct synthesis starting from 3,5-pyrazoledicarboxylic acid monohydrate and hydrazine monohydrate in a stoichiometric relationship, a microcrystalline light yellow mixture was obtained with a pair of monocrystals that were mechanically isolated from the mixture and prepared for X-ray analysis.

Experimental details

All hydrogen atoms were identified in difference Fourier map and were refined isotropically.

Discussion

Pyrazole-related molecules have attracted much attention because of their diverse pharmacological properties [4], and also because of their increased use in the synthesis of new functional materials [5]. The derivatives of 3,5-pyrazoledicarboxylic acid (H3PZDC) are known as building components of either purely organic or organometallic materials. As ligands the H3PZDC derivatives can display up to six metal coordination sites and various bridging modes [6] that is utilized for the synthesis of polynuclear magnetic solids [7] and MOFs [8]. On the other hand, the uncoordinated H3PZDC possesses multiple hydrogen bonding sites and can generate extensive hydrogen bonding important for supramolecular organic networks. [9] As a continuation of our research on pyrazole-derived molecules [10], [11], the present work describes the crystal structure of novel hydrazinium(+1) salt of 3,5-pyrazoledicarboxylic acid, (N2H5)2⋅HPZDC.

The crystal structures of two hydrazine salts of H3PZDC have been reported previously. These salts are of the type N2H6⋅(H2PZDC)2 [12] and N2H5⋅H2PZDC⋅H2O [9] and both contain the monocarboxylate H2PZDC anion. The asymmetric unit of title salt (N2H5)2⋅HPZDC contains the dicarboxylate dianion of H3PZDC and two hydrazinium counterions. In comparison to previous structures [12], [13] the geometry of species shows expected differences arising from their different protonation states. The crystal structure is stabilized by extensive N—H⋯O and N—H⋯N hydrogen bonding between the charged species with H⋯A distances ranging from 1.84(2) to 2.32(2) Å. The HPZDC anions alone form N1—H1⋯O1 centrosymmetric dimer [N1—H1⋯O1i = 161(2)°, H1⋯O1 = 1.98(2) Å, (i) = 2 − x, 1 − x, −z].

Acknowledgements

N⋅L. and Ž⋅K⋅J. thank to the Ministry of Science of the Republic of Montenegro for financial support (Innovative Project-Bioextra); G⋅A⋅B and S⋅B⋅N thank to the Ministry of Education, Science and Technological Development of the Republic of Serbia for financial support (Project Nos. 172014 and 172035).

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Received: 2019-03-06
Accepted: 2019-04-18
Published Online: 2019-06-22
Published in Print: 2019-09-25

©2019 Nedeljko Latinović et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 Public License.