N-(5-Phenyl-1H-pyrazol-3-yl)benzene-1,2-diamine

Doumbia, M.L.; Bouhfid, R.; Essassi, E.M.; El Ammari, L.

doi:10.1107/S1600536810009104

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o841

doi:10.1107/S1600536810009104

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N-(5-Phenyl-1H-pyrazol-3-yl)benzene-1,2-diamine

Mohamadou Lamine Doumbia,^a Rachid Bouhfid,^b El Mokhtar Essassi ^a ^*‡ and Lahcen El Ammari ^c

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences, Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V-Agdal, Rabat, Morocco, ^bInstitute of Nanomaterials and Nanotechnology, Avenue Armée Royale, Rabat, Morocco, and ^cLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: emessassi@yahoo.fr

(Received 9 March 2010; accepted 10 March 2010; online 17 March 2010)

In the title compound, C₁₅H₁₄N₄, the phenyl and pyrazole rings are essentially coplanar, being twisted relative to each other by a dihedral of only 3.68 (11)°. The benzene ring makes a dihedral angle of 64.47 (11)° with the pyrazole ring. The crystal structure is stabilized by two intermolecular N—H⋯N hydrogen-bonds, which build a two-dimensional network developing parallel to (100). An intramolecular N—H⋯N hydrogen bond also occurs.

Related literature

For the pharmacological applications of N-(3-phenyl-1H-pyrazol-5-yl)benzene-1, 2-diamine, see: Sharon et al. (2005 ); Barsoum et al. (2006 ); Cunico et al. (2006 ). For the use of pyrazole derivatives as chelating agents, see: Onishi et al. (2006 ) and as corrosion inibitors, see: Tebbji et al. (2005 ).

Experimental

Crystal data

C₁₅H₁₄N₄
M_r = 250.30
Monoclinic, P 2₁ /c
a = 13.2357 (8) Å
b = 5.8473 (4) Å
c = 16.4039 (10) Å
β = 92.074 (4)°
V = 1268.72 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.32 × 0.27 × 0.19 mm

Data collection

Bruker X8 APEXII CCD area-detector diffractometer
11640 measured reflections
2333 independent reflections
1527 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.127
S = 1.02
2333 reflections
228 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2ⁱ	0.97 (2)	2.14 (3)	3.048 (2)	157 (2)
N3—H3⋯N4ⁱⁱ	0.89 (2)	2.27 (2)	3.122 (2)	160 (2)
N4—H4B⋯N2	0.95 (3)	2.36 (3)	3.086 (2)	132 (2)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+2, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810009104/dn2548sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810009104/dn2548Isup2.hkl

checkCIF report

Comment top

Pyrazole derivatives have attracted particular interest during the last years due to the use of such ring systems as the core structure of many drug substances, covering wide range of pharmacological applications. They were reported to possess antihyperglycemic (Sharon et al., 2005), anti-inflammatory (Barsoum et al., 2006) and antimalarial activitys (Cunico et al., 2006). Further, pyrazole derivatives is also, used as chelating agent (Onishi et al., 2006) and inhibitor of the corrosion of the steel (Tebbji et al., 2005).

The N-(3-phenyl-1H-pyrazol-5-yl)benzene-1,2-diamine molecule structure is built up from three rings (phenyl, pyrazol and benzene) interconnected like linear chain as schown in Fig. 1. The phenyl and pyrazol rings are essentially planar and are only twisted to each other by a dihedral of 3.68 (11)°. As schown in Fig. 1, the molecule is not planar and the dihedral angle between the phenyl and pyrazol rings mean plane and the benzene ring is 64.21 (9)°. Two intermolecular N—H···N hydrogen bonds ensures the cohesion of the crystal structure building up a two dimensional network parallel to the (1 0 0) plane (Table 1, Fig.2).

Related literature top

For the pharmacological applications of N-(3-phenyl-1H-pyrazol-5-yl)benzene-1, 2-diamine, see: Sharon et al. (2005); Barsoum et al. (2006); Cunico et al. (2006). For the use of pyrazole derivatives as chelating agents, see: Onishi et al. (2006) and as corrosion inibitors, see: Tebbji et al. (2005).

Experimental top

A solution of (1 g, 3,96 mmol) 4-phenyl-1,5-benzodiazepine-2-thione and (1.1 ml, 15.85 mmol) of hydrate bhydrazine in 20 ml of ethanol was refluxed for 4 h. The solvent was removed in vaccuo and the residue was washed with 60 ml of water. The resulting product was recrystallized from ethanol to give N-(3-phenyl-1H-pyrazol-5-yl)benzene-1,2-diamine in 60% yield..

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. : The title molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small sphere of arbitray radii.
	Fig. 2. : Packing view showing the N—H···N interactions as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x+2, y-1/2, -z+3/2; (ii) -x+2, -y+2, -z+1]

N-(5-Phenyl-1H-pyrazol-3-yl)benzene-1,2-diamine top

Crystal data top

C₁₅H₁₄N₄	F(000) = 528
M_r = 250.30	D_x = 1.310 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 12462 reflections
a = 13.2357 (8) Å	θ = 25.4–2.5°
b = 5.8473 (4) Å	µ = 0.08 mm⁻¹
c = 16.4039 (10) Å	T = 298 K
β = 92.074 (4)°	Parallelepiped, clear pale yellow
V = 1268.72 (14) Å³	0.32 × 0.27 × 0.19 mm
Z = 4

Data collection top

Bruker X8 APEX CCD area-detector diffractometer	1527 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 25.4°, θ_min = 2.5°
ϕ and ω scans	h = −15→15
11640 measured reflections	k = −7→6
2333 independent reflections	l = −19→19

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0719P)²] where P = (F_o² + 2F_c²)/3
2333 reflections	(Δ/σ)_max < 0.001
228 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₅H₁₄N₄	V = 1268.72 (14) Å³
M_r = 250.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2357 (8) Å	µ = 0.08 mm⁻¹
b = 5.8473 (4) Å	T = 298 K
c = 16.4039 (10) Å	0.32 × 0.27 × 0.19 mm
β = 92.074 (4)°

Data collection top

Bruker X8 APEX CCD area-detector diffractometer	1527 reflections with I > 2σ(I)
11640 measured reflections	R_int = 0.056
2333 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.15 e Å⁻³
2333 reflections	Δρ_min = −0.15 e Å⁻³
228 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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) top

	x	y	z	U_iso*/U_eq
N1	0.92397 (12)	0.5307 (3)	0.69736 (9)	0.0414 (4)
N2	1.00286 (12)	0.6719 (3)	0.67931 (9)	0.0423 (4)
N3	1.01564 (13)	1.0130 (3)	0.60311 (9)	0.0426 (4)
N4	1.10392 (16)	0.6520 (3)	0.51288 (11)	0.0507 (5)
C1	0.95922 (14)	0.8361 (3)	0.63347 (10)	0.0369 (5)
C2	0.85506 (15)	0.8033 (4)	0.62309 (11)	0.0416 (5)
C3	0.83439 (14)	0.6054 (3)	0.66539 (10)	0.0385 (5)
C4	0.73944 (15)	0.4805 (4)	0.67390 (11)	0.0421 (5)
C5	0.73429 (19)	0.2767 (4)	0.71726 (13)	0.0541 (6)
C6	0.6440 (2)	0.1608 (5)	0.72155 (16)	0.0669 (7)
C7	0.55732 (19)	0.2441 (5)	0.68386 (16)	0.0684 (7)
C8	0.56061 (19)	0.4460 (5)	0.64097 (17)	0.0695 (7)
C9	0.65081 (17)	0.5631 (5)	0.63635 (14)	0.0576 (6)
C10	1.12135 (15)	1.0028 (3)	0.59179 (10)	0.0396 (5)
C11	1.16551 (15)	0.8230 (3)	0.54840 (11)	0.0424 (5)
C12	1.26837 (18)	0.8308 (5)	0.53560 (13)	0.0561 (6)
C13	1.32666 (19)	1.0142 (5)	0.56121 (15)	0.0662 (7)
C14	1.2833 (2)	1.1923 (5)	0.60222 (14)	0.0619 (7)
C15	1.18167 (18)	1.1845 (4)	0.61841 (12)	0.0498 (6)
H15	1.1477 (16)	1.308 (4)	0.6454 (13)	0.056 (6)*
H1	0.9384 (19)	0.389 (4)	0.7256 (16)	0.083 (8)*
H2	0.8072 (16)	0.894 (4)	0.5930 (13)	0.054 (6)*
H3	0.9810 (18)	1.130 (4)	0.5814 (15)	0.070 (8)*
H4A	1.1389 (18)	0.521 (5)	0.4963 (15)	0.073 (8)*
H4B	1.052 (2)	0.591 (5)	0.5453 (18)	0.092 (9)*
H5	0.7973 (19)	0.217 (4)	0.7414 (15)	0.075 (7)*
H6	0.6439 (18)	0.011 (5)	0.7494 (16)	0.082 (8)*
H7	0.4918 (19)	0.165 (4)	0.6883 (15)	0.074 (7)*
H8	0.498 (2)	0.513 (4)	0.6133 (16)	0.089 (8)*
H9	0.6532 (19)	0.707 (5)	0.6077 (16)	0.082 (8)*
H12	1.2969 (19)	0.700 (4)	0.5093 (15)	0.074 (8)*
H13	1.4002 (19)	1.025 (4)	0.5512 (15)	0.074 (7)*
H14	1.3233 (18)	1.322 (4)	0.6203 (14)	0.067 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0454 (10)	0.0454 (11)	0.0333 (8)	−0.0028 (8)	−0.0006 (7)	0.0066 (8)
N2	0.0474 (10)	0.0455 (11)	0.0338 (8)	−0.0027 (8)	−0.0025 (7)	0.0044 (7)
N3	0.0481 (11)	0.0403 (11)	0.0392 (9)	0.0005 (9)	0.0011 (7)	0.0042 (8)
N4	0.0659 (13)	0.0445 (12)	0.0418 (10)	−0.0001 (11)	0.0015 (9)	−0.0055 (8)
C1	0.0472 (12)	0.0379 (12)	0.0255 (9)	−0.0001 (9)	0.0006 (7)	−0.0004 (8)
C2	0.0474 (13)	0.0451 (13)	0.0320 (9)	0.0064 (10)	−0.0016 (8)	0.0016 (9)
C3	0.0431 (11)	0.0461 (13)	0.0261 (9)	0.0016 (9)	−0.0008 (8)	−0.0016 (8)
C4	0.0469 (12)	0.0469 (14)	0.0326 (9)	−0.0004 (10)	0.0021 (8)	−0.0056 (9)
C5	0.0567 (15)	0.0555 (16)	0.0498 (12)	−0.0048 (12)	−0.0028 (10)	0.0050 (11)
C6	0.0655 (17)	0.0678 (19)	0.0673 (16)	−0.0164 (14)	0.0007 (13)	0.0101 (14)
C7	0.0525 (16)	0.082 (2)	0.0707 (16)	−0.0185 (15)	0.0025 (12)	0.0020 (14)
C8	0.0454 (15)	0.088 (2)	0.0750 (17)	−0.0034 (14)	−0.0012 (12)	0.0110 (15)
C9	0.0491 (14)	0.0641 (17)	0.0593 (14)	0.0001 (12)	−0.0010 (10)	0.0074 (13)
C10	0.0480 (12)	0.0425 (13)	0.0280 (9)	−0.0022 (10)	−0.0028 (8)	0.0044 (8)
C11	0.0518 (13)	0.0447 (13)	0.0305 (9)	−0.0017 (10)	−0.0018 (8)	0.0053 (9)
C12	0.0562 (15)	0.0675 (17)	0.0447 (12)	0.0069 (14)	0.0018 (10)	0.0055 (12)
C13	0.0498 (15)	0.090 (2)	0.0590 (15)	−0.0070 (15)	−0.0007 (12)	0.0108 (14)
C14	0.0614 (16)	0.0685 (19)	0.0551 (14)	−0.0175 (15)	−0.0079 (12)	0.0046 (13)
C15	0.0586 (15)	0.0505 (15)	0.0400 (11)	−0.0076 (12)	−0.0035 (10)	0.0028 (10)

Geometric parameters (Å, º) top

N1—C3	1.352 (2)	C6—C7	1.372 (4)
N1—N2	1.372 (2)	C6—H6	0.99 (3)
N1—H1	0.96 (3)	C7—C8	1.376 (4)
N2—C1	1.338 (2)	C7—H7	0.99 (2)
N3—C1	1.379 (2)	C8—C9	1.381 (3)
N3—C10	1.419 (2)	C8—H8	1.01 (3)
N3—H3	0.89 (2)	C9—H9	0.96 (3)
N4—C11	1.404 (3)	C10—C15	1.390 (3)
N4—H4A	0.94 (3)	C10—C11	1.408 (3)
N4—H4B	0.96 (3)	C11—C12	1.386 (3)
C1—C2	1.396 (3)	C12—C13	1.378 (4)
C2—C3	1.382 (3)	C12—H12	0.96 (2)
C2—H2	0.95 (2)	C13—C14	1.376 (4)
C3—C4	1.465 (3)	C13—H13	1.00 (2)
C4—C5	1.391 (3)	C14—C15	1.382 (3)
C4—C9	1.392 (3)	C14—H14	0.97 (3)
C5—C6	1.378 (3)	C15—H15	0.96 (2)
C5—H5	0.97 (3)

C3—N1—N2	112.68 (17)	C6—C7—C8	119.6 (3)
C3—N1—H1	128.2 (16)	C6—C7—H7	121.5 (14)
N2—N1—H1	118.8 (15)	C8—C7—H7	118.9 (14)
C1—N2—N1	103.70 (15)	C7—C8—C9	119.8 (2)
C1—N3—C10	124.40 (17)	C7—C8—H8	121.6 (15)
C1—N3—H3	116.4 (15)	C9—C8—H8	118.6 (15)
C10—N3—H3	118.3 (15)	C8—C9—C4	121.3 (2)
C11—N4—H4A	114.5 (15)	C8—C9—H9	120.2 (15)
C11—N4—H4B	117.1 (16)	C4—C9—H9	118.4 (15)
H4A—N4—H4B	103 (2)	C15—C10—C11	119.0 (2)
N2—C1—N3	120.85 (17)	C15—C10—N3	118.98 (19)
N2—C1—C2	111.97 (17)	C11—C10—N3	121.78 (17)
N3—C1—C2	127.18 (18)	C12—C11—N4	121.3 (2)
C3—C2—C1	105.46 (17)	C12—C11—C10	118.7 (2)
C3—C2—H2	125.9 (13)	N4—C11—C10	119.76 (19)
C1—C2—H2	128.6 (13)	C13—C12—C11	121.5 (2)
N1—C3—C2	106.18 (18)	C13—C12—H12	122.1 (15)
N1—C3—C4	123.06 (18)	C11—C12—H12	116.4 (15)
C2—C3—C4	130.67 (18)	C14—C13—C12	120.0 (2)
C5—C4—C9	117.9 (2)	C14—C13—H13	117.3 (14)
C5—C4—C3	122.29 (19)	C12—C13—H13	122.7 (14)
C9—C4—C3	119.8 (2)	C13—C14—C15	119.7 (3)
C6—C5—C4	120.4 (2)	C13—C14—H14	120.9 (14)
C6—C5—H5	122.4 (15)	C15—C14—H14	119.5 (14)
C4—C5—H5	117.2 (15)	C14—C15—C10	121.1 (2)
C7—C6—C5	121.0 (3)	C14—C15—H15	122.5 (13)
C7—C6—H6	120.6 (15)	C10—C15—H15	116.3 (13)
C5—C6—H6	118.3 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.97 (2)	2.14 (3)	3.048 (2)	157 (2)
N3—H3···N4ⁱⁱ	0.89 (2)	2.27 (2)	3.122 (2)	160 (2)
N4—H4B···N2	0.95 (3)	2.36 (3)	3.086 (2)	132 (2)

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₄
M_r	250.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	13.2357 (8), 5.8473 (4), 16.4039 (10)
β (°)	92.074 (4)
V (Å³)	1268.72 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.27 × 0.19

Data collection
Diffractometer	Bruker X8 APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11640, 2333, 1527
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 1.02
No. of reflections	2333
No. of parameters	228
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.15

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2ⁱ	0.97 (2)	2.14 (3)	3.048 (2)	157 (2)
N3—H3···N4ⁱⁱ	0.89 (2)	2.27 (2)	3.122 (2)	160 (2)
N4—H4B···N2	0.95 (3)	2.36 (3)	3.086 (2)	132 (2)

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y+2, −z+1.

Footnotes

‡Present address: Institute of Nanomaterials and Nanotechnology, Avenue de l'Armée Royale, Rabat, Morocco.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for making possible the present work. They also thank H. Zouihri for his technical assistance during the X-ray measurements.

References

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