A second polymorph of (Z)-3-amino-4-(2-phenyl-hydrazinyl-idene)-1H-pyrazol-5(4H)-one.

The mol-ecule 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 intra-molecular N-Hhydrazine⋯O=C hydrogen bond is present. In the crystal, mol-ecules 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.

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 = 203.21

Triclinic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.107

S = 1.04

2848 reflections

152 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.19 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814000427/zq2216sup1.cif

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

Click here for additional data file.

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

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C9H9N5O	Z = 2
Mr = 203.21	F(000) = 212
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0618P)2 + 0.1329P] where P = (Fo2 + 2Fc2)/3
2848 reflections	(Δ/σ)max < 0.001
152 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

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) C16Rms deviation of fitted atoms = 0.00411.7459 (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) N3Rms deviation of fitted atoms = 0.00410.9251 (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) N3Rms 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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···O1iv	0.893 (15)	2.185 (15)	3.0428 (10)	161.0 (13)

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⋯O1iv	0.893 (15)	2.185 (15)	3.0428 (10)	161.0 (13)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .