Ethyl-enediammonium bis-(5-methyl-3-oxo-2-phenyl-2,3-dihydro-pyrazol-1-ide): a hydrogen-bond-supported supra-molecular ionic assembly.

The title compound, C(2)H(10)N(2) (2+)·2C(10)H(9)N(2)O(-), is composed of deprotonated 5-methyl-2-phenyl-1H-pyrazol-3(2H)-one anions (PMP(-)) and protonated ethyl-enediamine cations (H(2)en(2+)). The ethyl-enediammonium 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 ▶). For conductivity data for ionic electrolytes, see: Kwak et al. (2004 ▶); Allmann et al. (1990 ▶). For background information on n class="Chemical">hydrogen bonds and their importance and applications, see: Fu et al. (2004 ▶); Hernández-Galindo et al. (2007 ▶); Hu et al. (2004 ▶); Li & Wang (2007 ▶); Peng et al. (2005 ▶); Yang et al. (2002 ▶, 2005 ▶, 2006 ▶); Zhou et al. (2006 ▶).

Experimental

Crystal data

C2H10N2 2+·2C10H9N2O−

M = 408.50

Tetragonal,

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 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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.

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

C2H10N22+·2(C10H9N2O1–)	F000 = 872
Mr = 408.50	Dx = 1.296 Mg m−3
Tetragonal, P42/n	Melting point = 441–438 K
a = 17.179 (2) Å	Mo Kα radiation λ = 0.71073 Å
b = 17.179 (2) Å	Cell parameters from 2381 reflections
c = 7.0929 (15) Å	θ = 3.1–24.1º
α = 90º	µ = 0.09 mm−1
β = 90º	T = 298 (2) K
γ = 90º	Block, pink
V = 2093.2 (6) Å3	0.24 × 0.22 × 0.17 mm
Z = 4

Siemens SMART CCD area-detector diffractometer	1284 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.046
Monochromator: graphite	θmax = 25.0º
T = 298(2) K	θmin = 1.7º
φ and ω scans	h = −18→20
Absorption correction: none	k = −15→20
10541 measured reflections	l = −8→8
1856 independent reflections

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)] = 0.043	H-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 reflections	Δρmax = 0.22 e Å−3
136 parameters	Δρmin = −0.16 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 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.

	x	y	z	Uiso*/Ueq
N1	0.50902 (11)	0.26458 (10)	0.1311 (3)	0.0316 (5)
N2	0.55431 (11)	0.19843 (11)	0.0995 (3)	0.0363 (5)
N3	0.45643 (11)	0.51464 (11)	0.2591 (3)	0.0329 (5)
H3A	0.4611	0.4662	0.2161	0.049*
H3B	0.4679	0.5481	0.1675	0.049*
H3C	0.4078	0.5226	0.2977	0.049*
O1	0.50279 (10)	0.39457 (9)	0.0303 (2)	0.0428 (5)
C1	0.53354 (13)	0.32631 (13)	0.0203 (3)	0.0320 (5)
C2	0.59414 (14)	0.29704 (13)	−0.0881 (3)	0.0354 (6)
H2	0.6225	0.3239	−0.1788	0.042*
C3	0.60418 (14)	0.21958 (13)	−0.0345 (3)	0.0364 (6)
C4	0.66173 (18)	0.16275 (17)	−0.1105 (4)	0.0579 (8)
H4A	0.6533	0.1128	−0.0533	0.087*
H4B	0.7135	0.1804	−0.0825	0.087*
H4C	0.6554	0.1585	−0.2446	0.087*
C5	0.46305 (12)	0.26868 (12)	0.2962 (3)	0.0298 (5)
C6	0.39474 (13)	0.31290 (14)	0.2980 (3)	0.0373 (6)
H6	0.3778	0.3380	0.1893	0.045*
C7	0.35267 (15)	0.31879 (15)	0.4635 (4)	0.0444 (7)
H7	0.3077	0.3489	0.4661	0.053*
C8	0.37619 (15)	0.28079 (15)	0.6244 (4)	0.0451 (7)
H8	0.3476	0.2857	0.7351	0.054*
C9	0.44250 (15)	0.23530 (14)	0.6208 (4)	0.0414 (6)
H9	0.4578	0.2085	0.7285	0.050*
C10	0.48621 (13)	0.22946 (13)	0.4580 (3)	0.0349 (6)
H10	0.5311	0.1993	0.4567	0.042*
C11	0.51023 (13)	0.52621 (14)	0.4182 (3)	0.0349 (6)
H11A	0.5080	0.5801	0.4588	0.042*
H11B	0.5630	0.5153	0.3773	0.042*

	U11	U22	U33	U12	U13	U23
N1	0.0388 (11)	0.0248 (10)	0.0314 (10)	0.0026 (8)	0.0055 (9)	0.0014 (8)
N2	0.0446 (12)	0.0273 (10)	0.0370 (11)	0.0061 (9)	0.0070 (9)	0.0007 (8)
N3	0.0364 (11)	0.0309 (10)	0.0313 (10)	0.0010 (8)	0.0033 (8)	0.0021 (8)
O1	0.0609 (11)	0.0284 (9)	0.0391 (10)	0.0102 (8)	0.0137 (8)	0.0063 (7)
C1	0.0414 (13)	0.0280 (12)	0.0266 (11)	−0.0013 (10)	−0.0001 (10)	0.0003 (9)
C2	0.0432 (14)	0.0328 (13)	0.0300 (12)	0.0004 (11)	0.0083 (10)	0.0022 (10)
C3	0.0410 (14)	0.0358 (13)	0.0324 (13)	0.0055 (11)	0.0017 (11)	−0.0037 (10)
C4	0.070 (2)	0.0500 (17)	0.0532 (17)	0.0183 (15)	0.0204 (15)	0.0015 (14)
C5	0.0292 (12)	0.0264 (12)	0.0338 (12)	−0.0034 (9)	0.0014 (10)	0.0002 (9)
C6	0.0349 (13)	0.0371 (13)	0.0398 (14)	0.0024 (11)	−0.0013 (11)	0.0043 (11)
C7	0.0378 (14)	0.0427 (15)	0.0526 (16)	0.0072 (11)	0.0107 (12)	0.0049 (13)
C8	0.0450 (15)	0.0485 (16)	0.0417 (15)	−0.0008 (12)	0.0152 (12)	0.0036 (12)
C9	0.0452 (15)	0.0442 (15)	0.0349 (14)	−0.0008 (12)	0.0026 (11)	0.0083 (11)
C10	0.0334 (13)	0.0324 (13)	0.0388 (14)	0.0009 (10)	−0.0004 (11)	0.0020 (10)
C11	0.0321 (12)	0.0387 (14)	0.0340 (13)	−0.0020 (10)	−0.0003 (10)	0.0026 (10)

N1—C1	1.385 (3)	C4—H4C	0.9600
N1—N2	1.395 (2)	C5—C10	1.388 (3)
N1—C5	1.414 (3)	C5—C6	1.398 (3)
N2—C3	1.330 (3)	C6—C7	1.382 (3)
N3—C11	1.472 (3)	C6—H6	0.9300
N3—H3A	0.8900	C7—C8	1.375 (4)
N3—H3B	0.8900	C7—H7	0.9300
N3—H3C	0.8900	C8—C9	1.382 (4)
O1—C1	1.288 (3)	C8—H8	0.9300
C1—C2	1.389 (3)	C9—C10	1.381 (3)
C2—C3	1.394 (3)	C9—H9	0.9300
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.490 (3)	C11—C11i	1.510 (4)
C4—H4A	0.9600	C11—H11A	0.9700
C4—H4B	0.9600	C11—H11B	0.9700
C1—N1—N2	111.27 (17)	C10—C5—C6	119.8 (2)
C1—N1—C5	126.97 (18)	C10—C5—N1	120.0 (2)
N2—N1—C5	119.01 (17)	C6—C5—N1	120.2 (2)
C3—N2—N1	104.56 (18)	C7—C6—C5	119.1 (2)
C11—N3—H3A	109.5	C7—C6—H6	120.5
C11—N3—H3B	109.5	C5—C6—H6	120.5
H3A—N3—H3B	109.5	C8—C7—C6	121.1 (2)
C11—N3—H3C	109.5	C8—C7—H7	119.5
H3A—N3—H3C	109.5	C6—C7—H7	119.5
H3B—N3—H3C	109.5	C7—C8—C9	119.7 (2)
O1—C1—N1	122.8 (2)	C7—C8—H8	120.2
O1—C1—C2	131.9 (2)	C9—C8—H8	120.2
N1—C1—C2	105.35 (19)	C10—C9—C8	120.3 (2)
C1—C2—C3	106.7 (2)	C10—C9—H9	119.8
C1—C2—H2	126.6	C8—C9—H9	119.8
C3—C2—H2	126.6	C9—C10—C5	120.0 (2)
N2—C3—C2	112.1 (2)	C9—C10—H10	120.0
N2—C3—C4	120.4 (2)	C5—C10—H10	120.0
C2—C3—C4	127.5 (2)	N3—C11—C11i	111.2 (2)
C3—C4—H4A	109.5	N3—C11—H11A	109.4
C3—C4—H4B	109.5	C11i—C11—H11A	109.4
H4A—C4—H4B	109.5	N3—C11—H11B	109.4
C3—C4—H4C	109.5	C11i—C11—H11B	109.4
H4A—C4—H4C	109.5	H11A—C11—H11B	108.0
H4B—C4—H4C	109.5
C1—N1—N2—C3	−2.0 (2)	C1—N1—C5—C10	−130.8 (2)
C5—N1—N2—C3	−164.5 (2)	N2—N1—C5—C10	28.7 (3)
N2—N1—C1—O1	−177.0 (2)	C1—N1—C5—C6	48.4 (3)
C5—N1—C1—O1	−16.3 (4)	N2—N1—C5—C6	−152.1 (2)
N2—N1—C1—C2	2.0 (2)	C10—C5—C6—C7	2.1 (3)
C5—N1—C1—C2	162.8 (2)	N1—C5—C6—C7	−177.1 (2)
O1—C1—C2—C3	177.8 (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—C2	1.3 (3)	C7—C8—C9—C10	1.6 (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—C4	179.6 (2)	N1—C5—C10—C9	178.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.89	1.94	2.743 (2)	149
N3—H3B···O1ii	0.89	1.79	2.672 (2)	173
N3—H3C···N2iii	0.89	2.04	2.924 (3)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.89	1.94	2.743 (2)	149
N3—H3B⋯O1i	0.89	1.79	2.672 (2)	173
N3—H3C⋯N2ii	0.89	2.04	2.924 (3)	173

Symmetry codes: (i) ; (ii) .