N'-Acetyl-5-amino-1-methyl-1H-pyrazole-4-carbohydrazonamide dihydrate.

In the title compound, C(7)H(12)N(6)O·2H(2)O, the Z configuration of the hydrazone fragment is stabilized by an intra-molecular N-H⋯N hydrogen bond involving one of the amino groups. In the crystal structure, the hydrazonamide mol-ecules are connected via inter-molecular N-H⋯O=C hydrogen bonds, forming C(7) chains running along [010]. The chains form sheets parallel to the (01). The chains are cross-linked by water mol-ecules to form a three-dimensional hydrogen-bonded network.

Related literature

For bioactive pyrazoles, see: Elguero et al. (2002 ▶); Lamberth (2007 ▶). For the use of pyrazoles as synthons in heterocyclic chemistry, see: Schenone et al. (2007 ▶); Dolzhenko et al. (2008 ▶). For the use of pyrazoles in metal-organic chemistry, see: Mukherjee (2000 ▶); Halcrow (2009 ▶). For the crystal structures of related 5-amino-1H-pyrazole-4-carboxylic acid derivatives, see: Zia-ur-Rehman et al. (2008 ▶, 2009 ▶); Caruso et al. (2009 ▶). For the crystal structure of N′-acetyl-2-phenyl­ethane­hydra­zo­namide, see: Ianelli et al. (2001 ▶). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C7H12N6O·2H2O

M = 232.26

Triclinic,

a = 7.5496 (9) Å

b = 7.6208 (9) Å

c = 11.2518 (13) Å

α = 102.645 (2)°

β = 101.440 (2)°

γ = 110.810 (2)°

V = 562.75 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 223 K

0.45 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.953, T max = 0.989

3963 measured reflections

2548 independent reflections

2174 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.141

S = 1.05

2548 reflections

183 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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/S1600536810015357/ci5086sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015357/ci5086Isup2.hkl

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

C7H12N6O·2H2O	Z = 2
Mr = 232.26	F(000) = 248
Triclinic, P1	Dx = 1.371 Mg m−3
Hall symbol: -P 1	Melting point: 513 K
a = 7.5496 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6208 (9) Å	Cell parameters from 1515 reflections
c = 11.2518 (13) Å	θ = 3.0–27.5°
α = 102.645 (2)°	µ = 0.11 mm−1
β = 101.440 (2)°	T = 223 K
γ = 110.810 (2)°	Rod, colourless
V = 562.75 (11) Å3	0.45 × 0.12 × 0.10 mm

Bruker SMART APEX CCD diffractometer	2548 independent reflections
Radiation source: fine-focus sealed tube	2174 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −9→9
Tmin = 0.953, Tmax = 0.989	k = −9→9
3963 measured reflections	l = −14→13

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0711P)2 + 0.1961P] where P = (Fo2 + 2Fc2)/3
2548 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

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 > 2σ(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
O1	0.3615 (2)	0.89463 (19)	0.14623 (12)	0.0421 (4)
N1	0.7337 (2)	0.3950 (2)	0.48625 (14)	0.0306 (4)
N2	0.7791 (2)	0.5933 (2)	0.51428 (13)	0.0264 (3)
N3	0.7066 (3)	0.8221 (2)	0.42298 (16)	0.0302 (4)
H31	0.748 (3)	0.907 (3)	0.495 (2)	0.036 (6)*
H32	0.613 (3)	0.821 (3)	0.365 (2)	0.039 (6)*
N4	0.3308 (2)	0.2471 (2)	0.11287 (15)	0.0297 (4)
H41	0.350 (3)	0.158 (3)	0.132 (2)	0.032 (5)*
H42	0.260 (3)	0.223 (3)	0.034 (2)	0.040 (6)*
N5	0.4378 (2)	0.5945 (2)	0.18078 (13)	0.0294 (4)
N6	0.3198 (2)	0.5816 (2)	0.06398 (13)	0.0267 (3)
H6N	0.269 (3)	0.479 (3)	0.000 (2)	0.037 (6)*
C1	0.6808 (2)	0.6344 (2)	0.41838 (15)	0.0239 (4)
C2	0.5664 (2)	0.4541 (2)	0.32050 (15)	0.0236 (4)
C3	0.6068 (3)	0.3143 (3)	0.37018 (16)	0.0272 (4)
H3	0.5496	0.1780	0.3256	0.033*
C4	0.9204 (3)	0.7328 (3)	0.63443 (17)	0.0359 (4)
H4A	1.0140	0.8443	0.6188	0.054*
H4C	0.9916	0.6687	0.6766	0.054*
H4D	0.8504	0.7791	0.6886	0.054*
C5	0.4374 (2)	0.4304 (2)	0.19753 (15)	0.0225 (3)
C6	0.2965 (3)	0.7431 (3)	0.05365 (16)	0.0278 (4)
C7	0.1873 (3)	0.7318 (3)	−0.07661 (17)	0.0354 (4)
H7A	0.0729	0.7603	−0.0721	0.053*
H7B	0.1431	0.6000	−0.1353	0.053*
H7C	0.2751	0.8278	−0.1066	0.053*
O1W	0.8443 (2)	0.7733 (2)	0.15574 (13)	0.0380 (4)
H1W	0.752 (5)	0.757 (4)	0.186 (3)	0.069 (9)*
H2W	0.949 (5)	0.780 (4)	0.213 (3)	0.065 (8)*
O2W	0.1806 (2)	0.8169 (2)	0.34309 (14)	0.0393 (4)
H3W	0.253 (4)	0.812 (4)	0.294 (3)	0.064 (9)*
H4W	0.189 (4)	0.731 (4)	0.381 (3)	0.060 (8)*

	U11	U22	U33	U12	U13	U23
O1	0.0739 (10)	0.0235 (7)	0.0262 (7)	0.0259 (7)	0.0028 (7)	0.0046 (5)
N1	0.0382 (8)	0.0292 (8)	0.0260 (8)	0.0170 (7)	0.0052 (6)	0.0107 (6)
N2	0.0311 (7)	0.0255 (7)	0.0195 (7)	0.0118 (6)	0.0023 (6)	0.0060 (6)
N3	0.0413 (9)	0.0219 (7)	0.0218 (8)	0.0130 (7)	0.0021 (7)	0.0032 (6)
N4	0.0436 (9)	0.0173 (7)	0.0228 (8)	0.0136 (6)	−0.0018 (6)	0.0053 (6)
N5	0.0403 (8)	0.0219 (7)	0.0197 (7)	0.0141 (6)	−0.0034 (6)	0.0043 (6)
N6	0.0375 (8)	0.0195 (7)	0.0174 (7)	0.0128 (6)	−0.0022 (6)	0.0029 (6)
C1	0.0268 (8)	0.0265 (8)	0.0186 (7)	0.0119 (7)	0.0058 (6)	0.0071 (6)
C2	0.0286 (8)	0.0225 (8)	0.0199 (8)	0.0119 (6)	0.0046 (6)	0.0072 (6)
C3	0.0342 (9)	0.0228 (8)	0.0241 (8)	0.0138 (7)	0.0037 (7)	0.0076 (6)
C4	0.0374 (10)	0.0406 (11)	0.0206 (8)	0.0142 (8)	−0.0003 (7)	0.0043 (8)
C5	0.0274 (8)	0.0211 (8)	0.0188 (7)	0.0114 (6)	0.0045 (6)	0.0061 (6)
C6	0.0353 (9)	0.0264 (8)	0.0217 (8)	0.0143 (7)	0.0048 (7)	0.0085 (7)
C7	0.0447 (11)	0.0370 (10)	0.0273 (9)	0.0227 (9)	0.0026 (8)	0.0136 (8)
O1W	0.0406 (8)	0.0395 (8)	0.0236 (7)	0.0125 (6)	0.0021 (6)	0.0044 (6)
O2W	0.0518 (9)	0.0414 (8)	0.0299 (7)	0.0253 (7)	0.0082 (7)	0.0145 (6)

O1—C6	1.236 (2)	C1—C2	1.401 (2)
N1—C3	1.317 (2)	C2—C3	1.402 (2)
N1—N2	1.372 (2)	C2—C5	1.459 (2)
N2—C1	1.344 (2)	C3—H3	0.94
N2—C4	1.445 (2)	C4—H4A	0.97
N3—C1	1.362 (2)	C4—H4C	0.97
N3—H31	0.83 (2)	C4—H4D	0.97
N3—H32	0.86 (2)	C6—C7	1.500 (2)
N4—C5	1.350 (2)	C7—H7A	0.97
N4—H41	0.81 (2)	C7—H7B	0.97
N4—H42	0.88 (2)	C7—H7C	0.97
N5—C5	1.303 (2)	O1W—H1W	0.81 (3)
N5—N6	1.3953 (19)	O1W—H2W	0.89 (3)
N6—C6	1.330 (2)	O2W—H3W	0.86 (3)
N6—H6N	0.84 (2)	O2W—H4W	0.87 (3)
C3—N1—N2	104.63 (14)	C2—C3—H3	123.7
C1—N2—N1	112.10 (14)	N2—C4—H4A	109.5
C1—N2—C4	127.04 (15)	N2—C4—H4C	109.5
N1—N2—C4	120.85 (14)	H4A—C4—H4C	109.5
C1—N3—H31	117.5 (15)	N2—C4—H4D	109.5
C1—N3—H32	110.8 (16)	H4A—C4—H4D	109.5
H31—N3—H32	119 (2)	H4C—C4—H4D	109.5
C5—N4—H41	116.7 (15)	N5—C5—N4	126.14 (15)
C5—N4—H42	123.9 (15)	N5—C5—C2	114.92 (14)
H41—N4—H42	118 (2)	N4—C5—C2	118.95 (15)
C5—N5—N6	117.52 (14)	O1—C6—N6	121.90 (15)
C6—N6—N5	117.50 (14)	O1—C6—C7	121.68 (16)
C6—N6—H6N	119.6 (15)	N6—C6—C7	116.42 (15)
N5—N6—H6N	122.8 (15)	C6—C7—H7A	109.5
N2—C1—N3	122.61 (15)	C6—C7—H7B	109.5
N2—C1—C2	106.59 (14)	H7A—C7—H7B	109.5
N3—C1—C2	130.72 (15)	C6—C7—H7C	109.5
C1—C2—C3	104.15 (14)	H7A—C7—H7C	109.5
C1—C2—C5	125.02 (15)	H7B—C7—H7C	109.5
C3—C2—C5	130.83 (15)	H1W—O1W—H2W	110 (3)
N1—C3—C2	112.53 (15)	H3W—O2W—H4W	103 (3)
N1—C3—H3	123.7
C3—N1—N2—C1	0.66 (19)	N2—N1—C3—C2	−0.1 (2)
C3—N1—N2—C4	−178.36 (16)	C1—C2—C3—N1	−0.5 (2)
C5—N5—N6—C6	170.14 (16)	C5—C2—C3—N1	179.83 (17)
N1—N2—C1—N3	−177.99 (15)	N6—N5—C5—N4	−1.0 (3)
C4—N2—C1—N3	1.0 (3)	N6—N5—C5—C2	178.89 (14)
N1—N2—C1—C2	−0.95 (19)	C1—C2—C5—N5	1.9 (2)
C4—N2—C1—C2	178.00 (16)	C3—C2—C5—N5	−178.43 (17)
N2—C1—C2—C3	0.82 (18)	C1—C2—C5—N4	−178.18 (16)
N3—C1—C2—C3	177.53 (18)	C3—C2—C5—N4	1.5 (3)
N2—C1—C2—C5	−179.44 (15)	N5—N6—C6—O1	−6.2 (3)
N3—C1—C2—C5	−2.7 (3)	N5—N6—C6—C7	173.75 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H4W···N1i	0.87 (3)	2.04 (3)	2.884 (2)	162 (3)
O2W—H3W···O1	0.86 (3)	2.11 (3)	2.885 (2)	150 (3)
O1W—H2W···O2Wii	0.89 (3)	1.93 (3)	2.824 (2)	175 (3)
O1W—H1W···N5	0.81 (3)	2.24 (3)	2.982 (2)	153 (3)
N6—H6N···O1Wiii	0.84 (2)	2.07 (2)	2.905 (2)	177 (2)
N4—H42···O1Wiii	0.88 (2)	2.14 (3)	2.995 (2)	165 (2)
N4—H41···O1iv	0.81 (2)	2.08 (2)	2.874 (2)	169 (2)
N3—H32···N5	0.86 (2)	2.18 (2)	2.791 (2)	128 (2)
N3—H31···O2Wv	0.83 (2)	2.27 (2)	3.082 (2)	163 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H4W⋯N1i	0.87 (3)	2.04 (3)	2.884 (2)	162 (3)
O2W—H3W⋯O1	0.86 (3)	2.11 (3)	2.885 (2)	150 (3)
O1W—H2W⋯O2Wii	0.89 (3)	1.93 (3)	2.824 (2)	175 (3)
O1W—H1W⋯N5	0.81 (3)	2.24 (3)	2.982 (2)	153 (3)
N6—H6N⋯O1Wiii	0.84 (2)	2.07 (2)	2.905 (2)	177 (2)
N4—H42⋯O1Wiii	0.88 (2)	2.14 (3)	2.995 (2)	165 (2)
N4—H41⋯O1iv	0.81 (2)	2.08 (2)	2.874 (2)	169 (2)
N3—H32⋯N5	0.86 (2)	2.18 (2)	2.791 (2)	128 (2)
N3—H31⋯O2Wv	0.83 (2)	2.27 (2)	3.082 (2)	163 (2)

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