A second polymorph of (Z)-3-amino-4-(2-phenyl­hydrazinyl­idene)-1H-pyrazol-5(4H)-one

Elgazwy, A.-S.S.H.; Jones, P.G.

doi:10.1107/S1600536814000427

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 2| February 2014| Pages o141-o142

doi:10.1107/S1600536814000427

Open

access

A second polymorph of (Z)-3-amino-4-(2-phenylhydrazinylidene)-1H-pyrazol-5(4H)-one

Abdel-Sattar S. Hamad Elgazwy ^a and Peter G. Jones ^b ^*

^aChemistry Department, Faculty of Science, Ain Shams University, Abbassia 11566, Cairo, Egypt, and ^bInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Postfach 3329, 38023 Braunschweig, Germany
^*Correspondence e-mail: p.jones@tu-bs.de

(Received 6 January 2014; accepted 8 January 2014; online 15 January 2014)

The molecule of the title compound, C₉H₉N₅O, is approximately planar (the r.m.s. deviation of all non-H atoms is 0.08 Å). The amine substituent is pyramidal at the N atom. An intramolecular N—H_hydrazine⋯O=C hydrogen bond is present. In the crystal, molecules are connected via N—H⋯N and N—H⋯O hydrogen bonds, forming infinite layers parallel to (010). This polymorph is triclinic, space group P-1, whereas the previously reported form was monoclinic, space group P2₁/c [Elgemeie et al. (2013 ). Acta Cryst. E69, o187], with stepped layers and a significantly lower density.

CCDC reference: 980594

Related literature

Synthetic purine (Hamad & Derbala, 2001 ) and pyrazole (Elgazwy, 2003 ; Madkour & Elgazwy, 2007 ) analogues find numerous applications in clinical medicine and medical research. For the synthesis, chemistry, medicinal chemistry and biological activity of related compounds, see: Elgazwy et al. (2012a ,b , 2013 ); Arnost et al. (2010 ). For the monoclinic polymorph of the title compound, see: Elgemeie et al. (2013, 2014 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₉H₉N₅O
M_r = 203.21
Triclinic, $[P \overline 1]$
a = 6.4433 (4) Å
b = 7.4563 (5) Å
c = 10.1989 (6) Å
α = 80.005 (5)°
β = 81.271 (5)°
γ = 70.512 (5)°
V = 452.57 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.40 × 0.35 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.948, T_max = 1.000
31042 measured reflections
2848 independent reflections
2649 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.107
S = 1.04
2848 reflections
152 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H05⋯O1	0.920 (14)	2.164 (14)	2.8524 (9)	130.9 (11)
N5—H05⋯O1ⁱ	0.920 (14)	2.266 (14)	3.0176 (10)	138.6 (12)
N1—H01⋯N2ⁱⁱ	0.931 (14)	2.089 (14)	2.9272 (10)	149.0 (12)
N1—H01⋯N1ⁱⁱ	0.931 (14)	2.547 (14)	3.0692 (14)	115.8 (10)
N3—H031⋯N2ⁱⁱⁱ	0.899 (16)	2.369 (16)	3.2424 (10)	163.9 (13)
N3—H032⋯O1^iv	0.893 (15)	2.185 (15)	3.0428 (10)	161.0 (13)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x, -y+1, -z+2; (iii) -x+1, -y+1, -z+2; (iv) x+1, y, z.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 980594

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814000427/zq2216sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000427/zq2216Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814000427/zq2216Isup3.cml

checkCIF report

Comment top

Synthetic purine (Hamad & Derbala, 2001) and pyrazole (Elgazwy, 2003; Madkour & Elgazwy, 2007) analogues find numerous applications in clinical medicine and medical research. As part of our work directed towards the synthesis of pyrazolones (Elgazwy et al., 2012a, 2012b), we have recently reported various successful approaches to the syntheses of pyrazolone analogues that are interesting for biochemical reactions. The title compound (Z)-3-amino-4-(2-phenylhydrazono)-1H-pyrazol-5(4H)-one (I) was prepared in the course of these investigations.

By chance, compound I was also prepared and structurally investigated during a collaboration with a different group (Elgemeie et al., 2013, 2014; regrettably, the stereochemistry was erroneously described as E). The current structure proved to be a different polymorph of I, being triclinic (space group P1; henceforth It) rather than monoclinic (space group P2₁/c; henceforth Im).

The molecule of It is shown in Fig. 1. Molecular dimensions, such as the bond lengths C4═N4 1.3070 (10) and N4—N5 1.3128 (9) Å, may be regarded as normal. A search of the Cambridge Database (Allen, 2002; Version 1.15) for the same five-membered ring with C═O and C═N—N substituents gave average bond lengths of 1.309 (8) and 1.318 (10) Å respectively for these bonds (35 hits, 39 fragments excluding one obvious outlier). The nitrogen N3 of the amine substituent is pyramidal, lying 0.224 (8) Å out of the plane of its substituents. The entire molecule is planar to within an r.m.s. deviation of 0.08 Å for the non-H atoms, with no torsion angle deviating by more than 6.5 ° from 0/180 °; this is in part attributable to the intramolecular hydrogen bond N5—H05···O1. A more detailed analysis shows two planar units (i) C11–16 with substituent N5 and (ii) the five-membered ring, both with r.m.s.d. 0.004 Å, that subtend an interplanar angle of 8.51 (4) °. The substituents O1, N4 and N3 all lie slightly but significantly out of the plane of the five-membered ring, by 0.057 (1), 0.095 (1) and 0.069 (1) Å respectively, all to the same side. A comparison with Im shows that the molecules are closely similar except for a slight difference in the orientation of the phenyl ring; a least-squares fit excluding the non-ipso phenyl carbon atoms gives an r.m.s. deviation of 0.04 Å. However, there are some significant differences such as the N1—C5 bond length, which is 1.3387 (13) Å in Im but 1.3489 (10) Å in It.

The molecules of It are connected by hydrogen bonds (Table 1) to form infinite layers (one per b translation) parallel to the ac plane (Fig. 2). There are two three-centre interactions (N5—H05···O1 intra- and intermolecular, N1—H01···N1/N2) and two two-centre interactions involving the NH₂ H atoms (with N2 and O1 as acceptors). In Im, one of the N3 H atoms forms a three-centre system with N1 and N2, the N5—H05···O1 interaction is purely two-centre, N1—H01 and N3—H03A are two-centre donors to O1. The packing of Im is a stepped layer structure that intuitively seems to display a less efficient packing than that of It; consistent with this are the crystallographic densities of 1.464 and 1.491 g cm^-3, respectively, but we have carried out no further calculations or experiments to test this hypothesis.

Related literature top

Synthetic purine (Hamad & Derbala, 2001) and pyrazole (Elgazwy, 2003; Madkour & Elgazwy, 2007) analogues find numerous applications in clinical medicine and medical research. For the synthesis, chemistry, medicinal chemistry and biological activity of related compounds, see: Elgazwy et al. (2012a,b, 2013); Arnost et al. (2010). For the monoclinic polymorph of the title compound, see: Elgemeie et al. (2013, 2014). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The title compound was obtained according to the following general procedure (Arnost et al., 2010): 3-amino-1H-pyrazol-5(4H)-one was prepared by refluxing an ethanolic solution of sodium cyanoacetate and sodium ethoxide containing a few drops of hydrazine hydrate for 1 h. After cooling, the precipitate was filtered off and recrystallized from ethanol. A solution of freshly prepared phenyldiazonium chloride (2.66 mmol) was added to the pyrazolone (1 equiv in 50% aqueous EtOH, 3 ml/mmol)and potassium acetate (6 equiv) and the mixture stirred at 0 °C for a further 30 min. The precipitate was filtered, washed with water and dried to give (Z)-3-amino-4-(2-phenylhydrazono)-1H-pyrazol-5(4H)-one (I). Recrystallization from ethanol afforded reddish-brown crystals in 87% yield; m.p. 119–120 °C (dec). Red single crystals of I were obtained by slow diffusion of water into a ethanol solution. Most crystals were swallowtail twins; single crystalline fragments could be separated using a razor blade. IR (KBr, ν (cm^-1): 3449, 3350, 3330, 3300 (NH₂, 2NH), 1702, 1668 (C═O), 1627 (C═N), 1475 (N═N); ¹H NMR (300 MHz, DMSO-d6): δ 6.85 (s, br, 2H, NH₂), 7.41–7.92 (m, 5H, Ph), 10.71 (s, br, 1H, NH, pyrazole), 14.18 (br, 1H, NH, hydrazone); ¹³C-NMR (DMSO-d6): δ 175.9 (C═O), 162.2 (C-5), 154.3 (C-3), 154.2 (C-4), 143.2 (C-i), 129.7 (C-m), 120.0 (C-p), 117.9 (C-o). Anal. Calcd for for C₉H₉N₅O (203); C, 53.20; H, 4.46; N, 34.47. Found: C, 53.27; H, 4.51; N, 34.12%.

Structure description top

Synthetic purine (Hamad & Derbala, 2001) and pyrazole (Elgazwy, 2003; Madkour & Elgazwy, 2007) analogues find numerous applications in clinical medicine and medical research. As part of our work directed towards the synthesis of pyrazolones (Elgazwy et al., 2012a, 2012b), we have recently reported various successful approaches to the syntheses of pyrazolone analogues that are interesting for biochemical reactions. The title compound (Z)-3-amino-4-(2-phenylhydrazono)-1H-pyrazol-5(4H)-one (I) was prepared in the course of these investigations.

Synthetic purine (Hamad & Derbala, 2001) and pyrazole (Elgazwy, 2003; Madkour & Elgazwy, 2007) analogues find numerous applications in clinical medicine and medical research. For the synthesis, chemistry, medicinal chemistry and biological activity of related compounds, see: Elgazwy et al. (2012a,b, 2013); Arnost et al. (2010). For the monoclinic polymorph of the title compound, see: Elgemeie et al. (2013, 2014). For a description of the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecule of the title compound in the crystal; ellipsoids represent 50% probability levels.

Fig. 2. Packing diagram of the title compound viewed perpendicular to the ac plane. Phenyl rings are reduced to the ipso carbons for clarity. Intramolecular hydrogen bonds are drawn as thin and intermolecular hydrogen bonds as thick dashed lines; the latter are numbered according to their order in the relevant Table. H bonds #4 are omitted because they represent the weak components of asymmetric three-centre interactions.

(Z)-3-Amino-4-(2-phenylhydrazinylidene)-1H-pyrazol-5(4H)-one top

Crystal data top

C₉H₉N₅O	Z = 2
M_r = 203.21	F(000) = 212
Triclinic, P1	D_x = 1.491 Mg m⁻³
Hall symbol: -P 1	Melting point = 120–119 K
a = 6.4433 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.4563 (5) Å	Cell parameters from 18469 reflections
c = 10.1989 (6) Å	θ = 2.9–31.4°
α = 80.005 (5)°	µ = 0.11 mm⁻¹
β = 81.271 (5)°	T = 100 K
γ = 70.512 (5)°	Tablet, brown-orange dichroic
V = 452.57 (5) Å³	0.40 × 0.35 × 0.15 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2848 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2649 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 16.1419 pixels mm^-1	θ_max = 31.5°, θ_min = 2.9°
ω–scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −10→10
T_min = 0.948, T_max = 1.000	l = −14→14
31042 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0618P)² + 0.1329P] where P = (F_o² + 2F_c²)/3
2848 reflections	(Δ/σ)_max < 0.001
152 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₉H₉N₅O	γ = 70.512 (5)°
M_r = 203.21	V = 452.57 (5) Å³
Triclinic, P1	Z = 2
a = 6.4433 (4) Å	Mo Kα radiation
b = 7.4563 (5) Å	µ = 0.11 mm⁻¹
c = 10.1989 (6) Å	T = 100 K
α = 80.005 (5)°	0.40 × 0.35 × 0.15 mm
β = 81.271 (5)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2848 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	2649 reflections with I > 2σ(I)
T_min = 0.948, T_max = 1.000	R_int = 0.022
31042 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.54 e Å⁻³
2848 reflections	Δρ_min = −0.19 e Å⁻³
152 parameters

Special details top

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

1.7900 (0.0023) x + 6.5551 (0.0012) y - 3.2198 (0.0028) z = 1.0389 (0.0022)

* -0.0005 (0.0005) N5 * 0.0026 (0.0007) C11 * -0.0059 (0.0007) C12 * 0.0039 (0.0006) C13 * 0.0020 (0.0007) C14 * -0.0064 (0.0006) C15 * 0.0043 (0.0007) C16

Rms deviation of fitted atoms = 0.0041

1.7459 (0.0026) x + 6.9955 (0.0012) y - 1.8138 (0.0040) z = 1.9727 (0.0038)

Angle to previous plane (with approximate e.s.d.) = 8.51 (0.04)

* 0.0048 (0.0005) C4 * -0.0057 (0.0005) C5 * 0.0045 (0.0005) N1 * -0.0011 (0.0005) N2 * -0.0025 (0.0005) C3 - 0.0571 (0.0012) O1 - 0.0953 (0.0013) N4 - 0.0691 (0.0013) N3

Rms deviation of fitted atoms = 0.0041

0.9251 (0.0393) x + 7.1132 (0.0235) y - 0.8552 (0.1393) z = 2.4580 (0.1235)

Angle to previous plane (with approximate e.s.d.) = 10.20 (0.77)

* 0.0000 (0.0001) C3 * 0.0000 (0.0001) H031 * 0.0000 (0.0000) H032 - 0.2236 (0.0081) N3

Rms deviation of fitted atoms = 0.0000

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	0.07044 (12)	0.48559 (11)	0.85055 (7)	0.01658 (16)
H01	−0.069 (2)	0.523 (2)	0.8985 (14)	0.026 (3)*
N2	0.26071 (11)	0.45453 (11)	0.91700 (7)	0.01619 (15)
C3	0.43103 (13)	0.38930 (11)	0.83013 (8)	0.01377 (16)
C4	0.36028 (13)	0.37553 (11)	0.70490 (8)	0.01289 (15)
C5	0.11746 (13)	0.43979 (11)	0.72476 (8)	0.01381 (16)
C11	0.53773 (13)	0.20424 (11)	0.39128 (8)	0.01417 (16)
C12	0.43303 (15)	0.18095 (12)	0.28826 (9)	0.01816 (17)
H12	0.2761	0.2239	0.2922	0.022*
C13	0.56037 (17)	0.09431 (13)	0.17965 (9)	0.02246 (19)
H13	0.4900	0.0798	0.1085	0.027*
C14	0.78986 (17)	0.02890 (13)	0.17463 (9)	0.0239 (2)
H14	0.8762	−0.0305	0.1004	0.029*
C15	0.89267 (16)	0.05055 (13)	0.27848 (10)	0.02299 (19)
H15	1.0495	0.0042	0.2754	0.028*
C16	0.76831 (14)	0.13954 (12)	0.38721 (9)	0.01822 (17)
H16	0.8392	0.1559	0.4574	0.022*
N3	0.64559 (12)	0.33318 (11)	0.85693 (7)	0.01741 (16)
H031	0.671 (3)	0.370 (2)	0.9308 (16)	0.035 (4)*
H032	0.743 (2)	0.343 (2)	0.7861 (15)	0.032 (4)*
N4	0.49280 (11)	0.30196 (10)	0.60388 (7)	0.01314 (14)
N5	0.40314 (11)	0.29333 (10)	0.49879 (7)	0.01411 (15)
H05	0.253 (2)	0.345 (2)	0.4940 (14)	0.027 (3)*
O1	−0.01526 (10)	0.44520 (9)	0.64628 (6)	0.01777 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0113 (3)	0.0266 (4)	0.0117 (3)	−0.0051 (3)	0.0009 (2)	−0.0060 (3)
N2	0.0118 (3)	0.0242 (3)	0.0130 (3)	−0.0053 (3)	−0.0002 (2)	−0.0054 (3)
C3	0.0129 (3)	0.0170 (3)	0.0117 (3)	−0.0054 (3)	0.0003 (3)	−0.0029 (3)
C4	0.0116 (3)	0.0157 (3)	0.0113 (3)	−0.0046 (3)	0.0007 (3)	−0.0024 (3)
C5	0.0121 (3)	0.0168 (3)	0.0117 (3)	−0.0042 (3)	0.0011 (3)	−0.0024 (3)
C11	0.0160 (3)	0.0135 (3)	0.0116 (3)	−0.0037 (3)	0.0017 (3)	−0.0027 (3)
C12	0.0208 (4)	0.0175 (4)	0.0155 (4)	−0.0041 (3)	−0.0021 (3)	−0.0041 (3)
C13	0.0330 (5)	0.0195 (4)	0.0143 (4)	−0.0069 (3)	−0.0007 (3)	−0.0051 (3)
C14	0.0314 (5)	0.0192 (4)	0.0179 (4)	−0.0064 (3)	0.0084 (3)	−0.0069 (3)
C15	0.0204 (4)	0.0210 (4)	0.0243 (4)	−0.0045 (3)	0.0078 (3)	−0.0073 (3)
C16	0.0157 (4)	0.0194 (4)	0.0181 (4)	−0.0039 (3)	0.0021 (3)	−0.0050 (3)
N3	0.0124 (3)	0.0268 (4)	0.0137 (3)	−0.0062 (3)	−0.0001 (2)	−0.0057 (3)
N4	0.0139 (3)	0.0142 (3)	0.0113 (3)	−0.0050 (2)	0.0003 (2)	−0.0020 (2)
N5	0.0124 (3)	0.0177 (3)	0.0116 (3)	−0.0034 (2)	0.0005 (2)	−0.0044 (2)
O1	0.0138 (3)	0.0252 (3)	0.0137 (3)	−0.0046 (2)	−0.0017 (2)	−0.0037 (2)

Geometric parameters (Å, º) top

N1—C5	1.3489 (10)	C12—H12	0.9500
N1—N2	1.4227 (10)	C13—C14	1.3898 (15)
N1—H01	0.931 (14)	C13—H13	0.9500
N2—C3	1.3130 (10)	C14—C15	1.3894 (14)
C3—N3	1.3602 (10)	C14—H14	0.9500
C3—C4	1.4502 (11)	C15—C16	1.3939 (12)
C4—N4	1.3070 (10)	C15—H15	0.9500
C4—C5	1.4682 (11)	C16—H16	0.9500
C5—O1	1.2438 (10)	N3—H031	0.899 (16)
C11—C12	1.3949 (11)	N3—H032	0.893 (15)
C11—C16	1.3970 (12)	N4—N5	1.3128 (9)
C11—N5	1.4055 (10)	N5—H05	0.920 (14)
C12—C13	1.3916 (12)

C5—N1—N2	113.92 (7)	C14—C13—C12	120.35 (9)
C5—N1—H01	127.2 (9)	C14—C13—H13	119.8
N2—N1—H01	118.6 (9)	C12—C13—H13	119.8
C3—N2—N1	105.54 (7)	C15—C14—C13	119.81 (8)
N2—C3—N3	124.13 (7)	C15—C14—H14	120.1
N2—C3—C4	111.24 (7)	C13—C14—H14	120.1
N3—C3—C4	124.56 (7)	C14—C15—C16	120.74 (9)
N4—C4—C3	124.84 (7)	C14—C15—H15	119.6
N4—C4—C5	129.43 (7)	C16—C15—H15	119.6
C3—C4—C5	105.40 (7)	C15—C16—C11	118.91 (8)
O1—C5—N1	127.60 (8)	C15—C16—H16	120.5
O1—C5—C4	128.47 (7)	C11—C16—H16	120.5
N1—C5—C4	103.89 (7)	C3—N3—H031	116.3 (10)
C12—C11—C16	120.73 (8)	C3—N3—H032	115.2 (9)
C12—C11—N5	117.65 (7)	H031—N3—H032	114.2 (14)
C16—C11—N5	121.62 (8)	C4—N4—N5	117.74 (7)
C13—C12—C11	119.44 (8)	N4—N5—C11	119.81 (7)
C13—C12—H12	120.3	N4—N5—H05	121.2 (9)
C11—C12—H12	120.3	C11—N5—H05	119.0 (9)

C5—N1—N2—C3	0.58 (10)	C16—C11—C12—C13	−0.78 (13)
N1—N2—C3—N3	−176.87 (8)	N5—C11—C12—C13	179.67 (7)
N1—N2—C3—C4	0.11 (9)	C11—C12—C13—C14	0.95 (13)
N2—C3—C4—N4	−174.62 (8)	C12—C13—C14—C15	−0.15 (14)
N3—C3—C4—N4	2.34 (13)	C13—C14—C15—C16	−0.83 (14)
N2—C3—C4—C5	−0.68 (9)	C14—C15—C16—C11	0.99 (14)
N3—C3—C4—C5	176.29 (8)	C12—C11—C16—C15	−0.18 (13)
N2—N1—C5—O1	176.90 (8)	N5—C11—C16—C15	179.36 (8)
N2—N1—C5—C4	−0.97 (9)	C3—C4—N4—N5	177.60 (7)
N4—C4—C5—O1	−3.32 (15)	C5—C4—N4—N5	5.17 (13)
C3—C4—C5—O1	−176.89 (8)	C4—N4—N5—C11	−175.90 (7)
N4—C4—C5—N1	174.52 (8)	C12—C11—N5—N4	173.50 (7)
C3—C4—C5—N1	0.96 (8)	C16—C11—N5—N4	−6.05 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H05···O1	0.920 (14)	2.164 (14)	2.8524 (9)	130.9 (11)
N5—H05···O1ⁱ	0.920 (14)	2.266 (14)	3.0176 (10)	138.6 (12)
N1—H01···N2ⁱⁱ	0.931 (14)	2.089 (14)	2.9272 (10)	149.0 (12)
N1—H01···N1ⁱⁱ	0.931 (14)	2.547 (14)	3.0692 (14)	115.8 (10)
N3—H031···N2ⁱⁱⁱ	0.899 (16)	2.369 (16)	3.2424 (10)	163.9 (13)
N3—H032···O1^iv	0.893 (15)	2.185 (15)	3.0428 (10)	161.0 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H05···O1	0.920 (14)	2.164 (14)	2.8524 (9)	130.9 (11)
N5—H05···O1ⁱ	0.920 (14)	2.266 (14)	3.0176 (10)	138.6 (12)
N1—H01···N2ⁱⁱ	0.931 (14)	2.089 (14)	2.9272 (10)	149.0 (12)
N1—H01···N1ⁱⁱ	0.931 (14)	2.547 (14)	3.0692 (14)	115.8 (10)
N3—H031···N2ⁱⁱⁱ	0.899 (16)	2.369 (16)	3.2424 (10)	163.9 (13)
N3—H032···O1^iv	0.893 (15)	2.185 (15)	3.0428 (10)	161.0 (13)

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

Acknowledgements

The authors acknowledge the financial support of the Ain Shams University, established and supported under the Egyptian Government Cooperative Research Centers Program.

References

Agilent (2010). CrysAlis PRO. Agilent Technologies Ltd, Yarnton, England. Google Scholar
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Arnost, M., Pierce, A., ter Haar, E., Lauffer, D., Madden, J., Tanner, K. & Green, J. (2010). Bioorg. Med. Chem. Lett. 20, 1661–1664. Web of Science CrossRef CAS PubMed Google Scholar
Elgazwy, A.-S. S. H. (2003). Tetrahedron, 59, 7445–7463. Google Scholar
Elgazwy, A.-S. S. H., Nassar, I. F. & Jones, P. G. (2013). Acta Cryst. E69, o1376. CSD CrossRef IUCr Journals Google Scholar
Elgazwy, A.-S. S. H., Nassar, E. & Zaki, M. Y. (2012a). Org. Chem. Curr. Res. 1, 1–112. Google Scholar
Elgazwy, A.-S. S. H., Soliman, D. H. S., Atta-Allah, S. R. & Ibrahim, D. A. (2012b). Chem. Cent. J. 6, 1–18. Web of Science PubMed Google Scholar
Elgemeie, G. H., Sayed, S. H. & Jones, P. G. (2013). Acta Cryst. E69, o187. CSD CrossRef IUCr Journals Google Scholar
Elgemeie, G. H., Sayed, S. H. & Jones, P. G. (2014). Acta Cryst. E70, e1. CrossRef IUCr Journals Google Scholar
Hamad, A. S. & Derbala, H. A. Y. (2001). J. Heterocycl. Chem, 38, 939–944. CrossRef CAS Google Scholar
Madkour, H. M. F. & Elgazwy, A.-S. S. H. (2007). Curr. Org. Chem. 11, 853–903. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 2| February 2014| Pages o141-o142

doi:10.1107/S1600536814000427

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

A second polymorph of (Z)-3-amino-4-(2-phenyl­hydrazinyl­­idene)-1H-pyrazol-5(4H)-one

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

A second polymorph of (Z)-3-amino-4-(2-phenylhydrazinylidene)-1H-pyrazol-5(4H)-one