3,5-Dimethyl­pyrazolium 3,5-dinitro­salicylate

Shuaishuai Wei; Shouwen Jin; Zhaofeng Hu; Yong Zhou; Yingping Zhou

doi:10.1107/S1600536812041906

. 2012 Oct 13;68(Pt 11):o3117. doi: 10.1107/S1600536812041906

3,5-Dimethylpyrazolium 3,5-dinitrosalicylate

Shuaishuai Wei ^a, Shouwen Jin ^a,^*, Zhaofeng Hu ^a, Yong Zhou ^a, Yingping Zhou ^a

PMCID: PMC3515222 PMID: 23284442

Abstract

In the title molecular salt, C₅H₉N₂ ⁺·C₇H₃N₂O₇ ⁻, the roughly planar anion (r.m.s. deviation = 0.120 Å) has been deprotonated at the phenol group. An intramolecular O—H⋯O hydrogen bond in the anion generates an S(6) ring. In the crystal, the components are linked by cation-to-anion N—H⋯O and N—H⋯(O,O) hydrogen bonds, generating [010] double chains. Weak C—H⋯O interactions consolidate the packing.

Related literature

For a related structure and background to hydrogen-bonding interactions, see: Jin et al. (2010 ▶). For another related structure, see: Smith et al. (2011 ▶).

Experimental

Crystal data

C₅H₉N₂ ⁺·C₇H₃N₂O₇ ⁻
M _r = 324.26
Monoclinic,
a = 8.1183 (7) Å
b = 6.0636 (5) Å
c = 14.1453 (11) Å
β = 91.904 (1)°
V = 695.93 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.40 × 0.27 × 0.11 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.959, T _max = 0.986
3523 measured reflections
2301 independent reflections
1659 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.105
S = 1.02
2301 reflections
208 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

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: SHELXTL.

Supplementary Material

Click here for additional data file.^{(18KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812041906/hb6958sup1.cif

e-68-o3117-sup1.cif^{(18KB, cif)}

Click here for additional data file.^{(113.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041906/hb6958Isup2.hkl

e-68-o3117-Isup2.hkl^{(113.1KB, hkl)}

Click here for additional data file.^{(5.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812041906/hb6958Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O7ⁱ	0.86	2.09	2.859 (4)	148
N1—H1⋯O1ⁱ	0.86	2.16	2.809 (4)	132
N2—H2⋯O3	0.86	1.88	2.684 (3)	156
O2—H2A⋯O1	0.82	1.72	2.481 (3)	154
C1—H1A⋯O7ⁱ	0.96	2.32	3.166 (5)	147
C5—H5B⋯O4ⁱⁱ	0.96	2.49	3.414 (5)	160
C10—H10⋯O6ⁱⁱⁱ	0.93	2.48	3.379 (4)	164

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

We gratefully acknowledge the financial support of the Education Office Foundation of Zhejiang Province (project No. Y201017321) and the innovation project of Zhejiang A & F University.

supplementary crystallographic information

Comment

Organic acid-base adducts based on hydrogen bonding are 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 3,5-dimethylpyrazolium 3,5-dinitrosalicylate.

The crystal of the title compound of the formula C₁₂H₁₂N₄O₇ was obtained by recrystallization of the mixture of 3,5-dimethylpyrazole and 3,5-dinitrosalicylic acid acid from the MeOH solution.

In this case (Fig. 1) it is the phenol H that has been deprotonated. The C—O distance 1.284 (4) Å concerning the phenolate is similar to the proton transfer compound bearing the 3,5-dinitrosalicylate in which only the phenol group has been deprotonated (Smith et al., 2011). The C—O distances O(2)—C(6), 1.300 (4) Å, O(3)—C(6), 1.223 (4) Å; in the COOH show characteristic C—O, and C=O distances which are also confirming the reliability of adding H atoms experimentally by different electron density onto O atoms.

One anion is bonded to one cation via N—H···O, and CH₃—O associations to form a heteroadduct.

For the presence of these interactions, there are close joint motifs with descriptors of R₂1(6), and R₁2(6). The usual intramolecular hydrogen bond is found between the phenolate and the carboxyl group to exhibit a S₁1(6) graph. The heteroadducts were linked together by the CH₃—O association between the methyl group of the pyrazole and the 5-nitro group with C—O distance of 3.415 Å to form one-dimensional chain running along the direction that made an angle of ca 60° with the a axis (Fig. 2). The chains were further stacked along the direction that is perpendicular with its extending direction via the interchain N-π interaction between the 5-nitro group and the phenyl ring of the anion with N—Cg distance of 3.236 Å to form two-dimensional sheet extending parallel to the ab plane. The sheets were further stacked along the c axis direction by the CH—O, N—H···O, and O—H···O associations to form three-dimensional ABAB layer network structure. Herein the chains at adjacent layers intersect at an angle of ca 120° with each other.

Experimental

A solution of 3,5-dimethyl pyrazole (19.2 mg, 0.2 mmol) in 5 ml of MeOH was added to a MeOH solution (6 ml) containing 3,5-dinitrosalicylic acid (22.8 mg, 0.1 mmol) 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, yellow blocks 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.