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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1808–o1809.
Published online 2008 August 23. doi:  10.1107/S1600536808026378
PMCID: PMC2960540

Ethyl­enediammonium bis­(5-methyl-3-oxo-2-phenyl-2,3-dihydro­pyrazol-1-ide): a hydrogen-bond-supported supra­molecular ionic assembly

Abstract

The title compound, C2H10N2 2+·2C10H9N2O, is composed of deprotonated 5-methyl-2-phenyl-1H-pyrazol-3(2H)-one anions (PMP) and protonated ethyl­enediamine cations (H2en2+). The ethyl­enediammonium ion is located on a crystallographic inversion center. The dihedral angle between the phenyl and pyrazole rings is 39.73 (8)°. The two components are connected through N—H(...)O and N—H(...)N hydrogen bonds, forming an infinite three-dimensional network.

Related literature

For related literature on pyrazolones, see: Cerchiaro et al. (2006 [triangle]). For conductivity data for ionic electrolytes, see: Kwak et al. (2004 [triangle]); Allmann et al. (1990 [triangle]). For background information on hydrogen bonds and their importance and applications, see: Fu et al. (2004 [triangle]); Hernández-Galindo et al. (2007 [triangle]); Hu et al. (2004 [triangle]); Li & Wang (2007 [triangle]); Peng et al. (2005 [triangle]); Yang et al. (2002 [triangle], 2005 [triangle], 2006 [triangle]); Zhou et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1808-scheme1.jpg

Experimental

Crystal data

  • C2H10N2 2+·2C10H9N2O
  • M r = 408.50
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-64-o1808-efi1.jpg
  • a = 17.179 (2) Å
  • c = 7.0929 (15) Å
  • V = 2093.2 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 (2) K
  • 0.24 × 0.22 × 0.17 mm

Data collection

  • Siemens SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 10541 measured reflections
  • 1856 independent reflections
  • 1284 reflections with I > 2σ(I)
  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.141
  • S = 1.04
  • 1856 reflections
  • 136 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808026378/zl2127sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026378/zl2127Isup2.hkl

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

Acknowledgments

This project was supported by the Key Project for Fundamental Research of the Jiangsu Provincial Educational Committee (07 K J A150011) and the Natural Science Foundation of the Jiangsu Provincial Educational Committee (05KJB150003)

supplementary crystallographic information

Comment

Hydrogen bonds (H-bonds) are of importance in a large number of chemical and biological processes and in many practical applications (Li et al., 2007; Peng et al., 2005; Yang et al., 2006; Yang et al., 2002). Many interesting two- and three-dimensional frameworks have been designed and produced based on H-bonds (Fu et al., 2004; Hu et al., 2004; Zhou et al., 2006). The chemistry of pyrazylone and its derivatives is particularly interesting because of their potential application in medicinal chemistry (Cerchiaro et al., 2006), so 1-phenyl-3-methyl-pyrazole-5-one (PMP), which contains imino and carbonyl groups in its heterocycle, was choosen to react with the amino groups of ethylene diamine (en). The synthesis and crystal structure of the product of this reaction are reported here.

The title compound (Fig. 1) contains two crystallographically independent ions: the [H2en]2+ cation which has two cationic ammonium groups, and the [PMP]- anion. In the [PMP]- anion, the bond length of C(1)—O(1) is 1.288 (3) Å, much shorter than that of C—O (1.43 Å), but close to that of C═O (1.22 Å) (Yang et al., 2005), indicating that the pyrazole-one ring of the title compound is present in the keto form, not the enol form. The N(2) atom of the deprotonated imino group of PMP is electron rich, therefore, the O atom of the carbonyl group and the N(2) atom of the pyrazole-one ring of the PMP molecule can be expected to be good hydrogen bond acceptors, while the H atoms of the [H2en]2+ ammonium cations are expected to be good hydrogen donors. The Jeffrey criterion for H-bonds used by the International Union of Crystallography defines the largest distance between the hydrogen and the acceptor atoms as 2.60 Å for H···O and 2.63 Å for H···N, respectively (Hernández-Galindo et al., 2007). Compared to these data, the distances of H(3)···O(1) (-x+1, -y+1/2, -z) and H(3)···N(2)(x,-y+1/2, -z+1/2) for the title compound, respectively being 1.786 Å (or 1.940 Å) and 2.039 Å, are much shorter than the above-mentioned largest limit, providing a powerful evidence of the formation of H-bonds between these separate components.

There are no covalent interactions between the separate components of the title compound, but electrostatic and H-bonding interactions are present. All H atoms of the ammonium group, the O atom of the carbonyl group and the N atom of the deprotonated imino group in the title compound are engaged in intermolecular H-bonds which link the molecule into an extended three-dimensional network (Fig. 2). The H-bonds can be clearly seen in Fig. 2 to Fig. 5, and are summarized in Table 1. There are two kinds of H-bonds in the crystal structure: N—H···O and N—H···N. As shown in Fig. 3, the oxygen atom of the carbonyl group from [PMP]- takes part in the H-bonding to the terminal nitrogen of [H2en]2+, forming intermolecular N—H···O H-bonds that result in the formation of 8-membered rings. Each of the two ammonium groups of the [H2en]2+ cation engages in these 8—membered rings, further linking the [H2en]2+ and [PMP]- ions into a two-dimensional network via these N—H···O H-bonds (Fig. 4). It can be seen from Fig. 5 that the nitrogen atom of the deprotonated imino group of [PMP]- takes part in the H-bonding to the terminal nitrogen of [H2en]2+, forming intermolecular N—H···N H-bonds. Therefore, through intermolecular N—H···O and N—H···N H-bonding interactions, each [PMP]- anion is linked to three [H2en]2+ cations and each [H2en]2+ cation to six adjacent [PMP]- anions. The two components thus construct a supramolecular assembly with a three-dimensional hydrogen bonded framework.

Experimental

A solution of PMP (2 mmol in 10 ml anhydrous methanol) was added dropwise with constant stirring to the solution of en (2 mmol in 10 ml anhydrous methanol) at 323 K for 2 h. The resulting mixture was filtrated. After cooling, the filtrate was evaporated at ambient environment. Several days later, pink blocky crystals suitable for X-ray analysis were collected and washed with a small amount of methanol and dried at room temperature (yield 67%. m.p. 438–441 K). Anal. Calcd (%) for C22H28N6O2 (Mr = 408.5): C, 64.69; H, 6.91; N, 20.57. Found (%): C, 64.73; H, 6.97; N, 20.52. UV-vis (methanol): λmax = 239 nm, ε = 2.655. The molar conductance of the compound in anhydrous methanol was 45.1 Ω-1cm2mol-1, much lower than that expected for a 1:2 electrolyte, indicating that the compound is forming ion pairs and larger assemblies tightly bonded to each other by e.g. hydrogen bonds (Allmann et al., 1990; Kwak et al., 2004).

Refinement

H atoms were placed in calculated positions with C—H = 0.92Å (pyrazolyl), 0.93 Å (phenyl), 0.96 Å (methyl), 0.97 Å (methylene) and N—H = 0.89 Å (amino), and were refined in riding mode with Uiso(H) = 1.5 Ueq(C) (methyl) and Uiso(H) = 1.2 Ueq(C, N) (pyrazolyl, phenyl, methylene and amino).

Figures

Fig. 1.
ORTEP drawing of the structure of the title compound with the atomic numbering scheme.
Fig. 2.
Stereoview and packing diagram for the title compound viewed along the c-axis.
Fig. 3.
Part of the crystal structure of the title compound, showing the 8-membered rings formed by N—H···O interactions. Dashed lines indicate H-bonds.
Fig. 4.
The crystal structure of title compound, showing the two-dimensional network parallel to the bc plane formed through N—H···O H-bond interactions. H-bonds are shown as dashed lines.
Fig. 5.
Part of the crystal structure of the title compound, showing the intermolecular N—H···N interactions. Dashed lines indicate H-bonds.

Crystal data

C2H10N22+·2(C10H9N2O1)F000 = 872
Mr = 408.50Dx = 1.296 Mg m3
Tetragonal, P42/nMelting point = 441–438 K
a = 17.179 (2) ÅMo Kα radiation λ = 0.71073 Å
b = 17.179 (2) ÅCell parameters from 2381 reflections
c = 7.0929 (15) Åθ = 3.1–24.1º
α = 90ºµ = 0.09 mm1
β = 90ºT = 298 (2) K
γ = 90ºBlock, pink
V = 2093.2 (6) Å30.24 × 0.22 × 0.17 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer1284 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.046
Monochromator: graphiteθmax = 25.0º
T = 298(2) Kθmin = 1.7º
[var phi] and ω scansh = −18→20
Absorption correction: nonek = −15→20
10541 measured reflectionsl = −8→8
1856 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.141  w = 1/[σ2(Fo2) + (0.0642P)2 + 1.1449P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1856 reflectionsΔρmax = 0.22 e Å3
136 parametersΔρmin = −0.16 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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.

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

xyzUiso*/Ueq
N10.50902 (11)0.26458 (10)0.1311 (3)0.0316 (5)
N20.55431 (11)0.19843 (11)0.0995 (3)0.0363 (5)
N30.45643 (11)0.51464 (11)0.2591 (3)0.0329 (5)
H3A0.46110.46620.21610.049*
H3B0.46790.54810.16750.049*
H3C0.40780.52260.29770.049*
O10.50279 (10)0.39457 (9)0.0303 (2)0.0428 (5)
C10.53354 (13)0.32631 (13)0.0203 (3)0.0320 (5)
C20.59414 (14)0.29704 (13)−0.0881 (3)0.0354 (6)
H20.62250.3239−0.17880.042*
C30.60418 (14)0.21958 (13)−0.0345 (3)0.0364 (6)
C40.66173 (18)0.16275 (17)−0.1105 (4)0.0579 (8)
H4A0.65330.1128−0.05330.087*
H4B0.71350.1804−0.08250.087*
H4C0.65540.1585−0.24460.087*
C50.46305 (12)0.26868 (12)0.2962 (3)0.0298 (5)
C60.39474 (13)0.31290 (14)0.2980 (3)0.0373 (6)
H60.37780.33800.18930.045*
C70.35267 (15)0.31879 (15)0.4635 (4)0.0444 (7)
H70.30770.34890.46610.053*
C80.37619 (15)0.28079 (15)0.6244 (4)0.0451 (7)
H80.34760.28570.73510.054*
C90.44250 (15)0.23530 (14)0.6208 (4)0.0414 (6)
H90.45780.20850.72850.050*
C100.48621 (13)0.22946 (13)0.4580 (3)0.0349 (6)
H100.53110.19930.45670.042*
C110.51023 (13)0.52621 (14)0.4182 (3)0.0349 (6)
H11A0.50800.58010.45880.042*
H11B0.56300.51530.37730.042*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0388 (11)0.0248 (10)0.0314 (10)0.0026 (8)0.0055 (9)0.0014 (8)
N20.0446 (12)0.0273 (10)0.0370 (11)0.0061 (9)0.0070 (9)0.0007 (8)
N30.0364 (11)0.0309 (10)0.0313 (10)0.0010 (8)0.0033 (8)0.0021 (8)
O10.0609 (11)0.0284 (9)0.0391 (10)0.0102 (8)0.0137 (8)0.0063 (7)
C10.0414 (13)0.0280 (12)0.0266 (11)−0.0013 (10)−0.0001 (10)0.0003 (9)
C20.0432 (14)0.0328 (13)0.0300 (12)0.0004 (11)0.0083 (10)0.0022 (10)
C30.0410 (14)0.0358 (13)0.0324 (13)0.0055 (11)0.0017 (11)−0.0037 (10)
C40.070 (2)0.0500 (17)0.0532 (17)0.0183 (15)0.0204 (15)0.0015 (14)
C50.0292 (12)0.0264 (12)0.0338 (12)−0.0034 (9)0.0014 (10)0.0002 (9)
C60.0349 (13)0.0371 (13)0.0398 (14)0.0024 (11)−0.0013 (11)0.0043 (11)
C70.0378 (14)0.0427 (15)0.0526 (16)0.0072 (11)0.0107 (12)0.0049 (13)
C80.0450 (15)0.0485 (16)0.0417 (15)−0.0008 (12)0.0152 (12)0.0036 (12)
C90.0452 (15)0.0442 (15)0.0349 (14)−0.0008 (12)0.0026 (11)0.0083 (11)
C100.0334 (13)0.0324 (13)0.0388 (14)0.0009 (10)−0.0004 (11)0.0020 (10)
C110.0321 (12)0.0387 (14)0.0340 (13)−0.0020 (10)−0.0003 (10)0.0026 (10)

Geometric parameters (Å, °)

N1—C11.385 (3)C4—H4C0.9600
N1—N21.395 (2)C5—C101.388 (3)
N1—C51.414 (3)C5—C61.398 (3)
N2—C31.330 (3)C6—C71.382 (3)
N3—C111.472 (3)C6—H60.9300
N3—H3A0.8900C7—C81.375 (4)
N3—H3B0.8900C7—H70.9300
N3—H3C0.8900C8—C91.382 (4)
O1—C11.288 (3)C8—H80.9300
C1—C21.389 (3)C9—C101.381 (3)
C2—C31.394 (3)C9—H90.9300
C2—H20.9300C10—H100.9300
C3—C41.490 (3)C11—C11i1.510 (4)
C4—H4A0.9600C11—H11A0.9700
C4—H4B0.9600C11—H11B0.9700
C1—N1—N2111.27 (17)C10—C5—C6119.8 (2)
C1—N1—C5126.97 (18)C10—C5—N1120.0 (2)
N2—N1—C5119.01 (17)C6—C5—N1120.2 (2)
C3—N2—N1104.56 (18)C7—C6—C5119.1 (2)
C11—N3—H3A109.5C7—C6—H6120.5
C11—N3—H3B109.5C5—C6—H6120.5
H3A—N3—H3B109.5C8—C7—C6121.1 (2)
C11—N3—H3C109.5C8—C7—H7119.5
H3A—N3—H3C109.5C6—C7—H7119.5
H3B—N3—H3C109.5C7—C8—C9119.7 (2)
O1—C1—N1122.8 (2)C7—C8—H8120.2
O1—C1—C2131.9 (2)C9—C8—H8120.2
N1—C1—C2105.35 (19)C10—C9—C8120.3 (2)
C1—C2—C3106.7 (2)C10—C9—H9119.8
C1—C2—H2126.6C8—C9—H9119.8
C3—C2—H2126.6C9—C10—C5120.0 (2)
N2—C3—C2112.1 (2)C9—C10—H10120.0
N2—C3—C4120.4 (2)C5—C10—H10120.0
C2—C3—C4127.5 (2)N3—C11—C11i111.2 (2)
C3—C4—H4A109.5N3—C11—H11A109.4
C3—C4—H4B109.5C11i—C11—H11A109.4
H4A—C4—H4B109.5N3—C11—H11B109.4
C3—C4—H4C109.5C11i—C11—H11B109.4
H4A—C4—H4C109.5H11A—C11—H11B108.0
H4B—C4—H4C109.5
C1—N1—N2—C3−2.0 (2)C1—N1—C5—C10−130.8 (2)
C5—N1—N2—C3−164.5 (2)N2—N1—C5—C1028.7 (3)
N2—N1—C1—O1−177.0 (2)C1—N1—C5—C648.4 (3)
C5—N1—C1—O1−16.3 (4)N2—N1—C5—C6−152.1 (2)
N2—N1—C1—C22.0 (2)C10—C5—C6—C72.1 (3)
C5—N1—C1—C2162.8 (2)N1—C5—C6—C7−177.1 (2)
O1—C1—C2—C3177.8 (2)C5—C6—C7—C8−1.2 (4)
N1—C1—C2—C3−1.2 (3)C6—C7—C8—C9−0.6 (4)
N1—N2—C3—C21.3 (3)C7—C8—C9—C101.6 (4)
N1—N2—C3—C4−178.4 (2)C8—C9—C10—C5−0.8 (4)
C1—C2—C3—N2−0.1 (3)C6—C5—C10—C9−1.1 (3)
C1—C2—C3—C4179.6 (2)N1—C5—C10—C9178.1 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3A···O10.891.942.743 (2)149
N3—H3B···O1ii0.891.792.672 (2)173
N3—H3C···N2iii0.892.042.924 (3)173

Symmetry codes: (ii) −x+1, −y+1, −z; (iii) −y+1/2, x, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2127).

References

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