The molecules of methyl 3-(2-nitrophenylhydrazono)butanoate, C
11H
13N
3O
4, (I), and methyl 3-(2,4-dinitrophenylhydrazono)butanoate, C
11H
12N
4O
6, (II), both prepared from methyl 3-oxobutanoate and the corresponding nitrophenylhydrazine, exhibit polarized molecular electronic structures; in each of (I) and (II), the molecules are linked into chains by a single C-H
O hydrogen bond. The molecules of 5-hydroxy-3-methyl-1-phenyl-1
H-pyrazole, C
10H
10N
2O, (III), prepared by the reaction of methyl 3-oxobutanoate and phenylhydrazine, are linked into chains by a single O-H
N hydrogen bond. The reaction between methyl 3-oxobutanoate and 3-nitrophenylhydrazine yields 5-hydroxy-3-methyl-1-(3-nitrophenyl)-1
H-pyrazole, (IV), which when crystallized from acetone yields 4-isopropylidene-3-methyl-1-(3-nitrophenyl)-1
H-pyrazol-5(4
H)-one, C
13H
13N
3O
3, (V).
Supporting information
CCDC references: 659129; 659130; 659131; 659132
For the synthesis of compound (I), a solution of methyl acetoacetate (1 mmol)
and 2-nitrophenylhydrazine (1 mmol) in methanol (10 ml) was heated under
reflux for 30 min; the solution was cooled to ambient temperature and then
evaporated to dryness. The product, (I), was recrystallized from ethanol. IR
(KBr, cm-1): 3330, 1731, 1613, 1575. Heating a solution of (I) in ethanol
for 1 h at reflux temperature led to no cyclization or other change. Compound
(II) was similarly prepared from methyl acetoacetate and
2,4-dinitrophenylhydrazine, but the heating time was 90 min; compound (II) was
recrystallized from ethanol. IR (KBr, cm-1): 3327, 1740, 1620, 1594.
Compound (III) was prepared from the reaction of methyl acetoacetate and
phenylhydrazine, exactly as for (I). The product was recrystallized from
ethanol [m.p. 398–400 K; literature m.p. 400 K (Singh, 2005)]. IR (KBr,
cm-1): 3130–2700, 1569, 1534. For the synthesis of (IV), a solution of
methyl acetoacetate (1 mmol) and 3-nitrophenylhydrazine hydrochloride (1 mmol)
in methanol (20 ml) was heated under reflux for 30 min; the solution was
cooled to ambient temperature and then evaporated to dryness. The residue was
recrystallized from ethanol, but this material was not suitable for
single-crystal X-ray diffraction. IR (KBr, cm-1): 3120, 3100–2300, 1591,
1556, 1530. Further recrystallization of (IV) from acetone gave (V). IR (KBr,
cm-1): 1688, 1614, 1529.
For compounds (I), (II) and (V), respectively, the space groups
P21/n, Pbca and P21/c were uniquely
assigned from the systematic absences. For compound (III), the systematic
absences permitted Pca21 and Pbcm (= Pcam) as possible
space groups; Pca21 was selected, and confirmed by the successful
structure analysis. All H atoms were located in difference maps and then
treated as riding atoms. H atoms bonded to C atoms were placed in
geometrically idealized positions and allowed to ride with C—H distances of
0.95 Å (aromatic and pyrazole), 0.98 Å (CH3) or 0.99 Å (CH2), and
with Uiso(H) = kUeq(C), where k = 1.5 for the methyl
groups and k = 1.2 otherwise. H atoms bonded to N or O atoms were
allowed to ride at the distances deduced from the difference maps [N—H =
0.88 Å in (I) or 0.93 Å in (II), and O—H = 0.84 Å, with
Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O)]. In the absence
of significant resonant scattering it was not possible to establish the
correct orientation of the structure of (III) with respect to the polar axis
direction; accordingly, the Friedel-equivalent reflections were merged prior
to the final refinements. Compound (IV) has unit-cell dimensions a =
25.648 (4) Å, b = 3.8259 (6) Å, c = 24.790 (5) Å, β =
118.739 (14)° in space group P2/c; the compound was crystallized
from ethanol as a hemihydrochloride salt,
[(C10H9.5N3O3)+0.5]2·Cl- and the crystals were twinned, as
well as exhibiting very poor overall quality.
For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
(I) Methyl 3-(2-nitrophenylhydrazono)butanoate
top
Crystal data top
C11H13N3O4 | F(000) = 528 |
Mr = 251.24 | Dx = 1.463 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2617 reflections |
a = 12.1494 (4) Å | θ = 3.4–27.6° |
b = 5.1355 (2) Å | µ = 0.11 mm−1 |
c = 18.6969 (6) Å | T = 120 K |
β = 102.079 (2)° | Plate, colourless |
V = 1140.73 (7) Å3 | 0.28 × 0.22 × 0.04 mm |
Z = 4 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2617 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1931 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.6°, θmin = 3.4° |
ϕ & ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −6→6 |
Tmin = 0.975, Tmax = 0.995 | l = −24→24 |
13943 measured reflections | |
Refinement top
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)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0411P)2 + 0.6763P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2617 reflections | Δρmax = 0.26 e Å−3 |
166 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.011 (2) |
Crystal data top
C11H13N3O4 | V = 1140.73 (7) Å3 |
Mr = 251.24 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.1494 (4) Å | µ = 0.11 mm−1 |
b = 5.1355 (2) Å | T = 120 K |
c = 18.6969 (6) Å | 0.28 × 0.22 × 0.04 mm |
β = 102.079 (2)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 2617 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1931 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.995 | Rint = 0.053 |
13943 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.26 e Å−3 |
2617 reflections | Δρmin = −0.29 e Å−3 |
166 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.45922 (13) | 0.3031 (3) | 0.33540 (8) | 0.0184 (4) | |
C2 | 0.57012 (13) | 0.3105 (3) | 0.32352 (9) | 0.0194 (4) | |
N12 | 0.65264 (11) | 0.4910 (3) | 0.36133 (8) | 0.0225 (3) | |
O22 | 0.75021 (10) | 0.4772 (3) | 0.35191 (8) | 0.0349 (4) | |
O21 | 0.62525 (10) | 0.6564 (2) | 0.40332 (7) | 0.0257 (3) | |
C3 | 0.60631 (14) | 0.1370 (4) | 0.27520 (9) | 0.0228 (4) | |
C4 | 0.53425 (15) | −0.0463 (4) | 0.23858 (9) | 0.0252 (4) | |
C5 | 0.42442 (14) | −0.0596 (3) | 0.25068 (9) | 0.0233 (4) | |
C6 | 0.38764 (14) | 0.1084 (3) | 0.29745 (9) | 0.0222 (4) | |
N1 | 0.42133 (11) | 0.4699 (3) | 0.38180 (8) | 0.0204 (3) | |
N2 | 0.31239 (11) | 0.4447 (3) | 0.39129 (8) | 0.0198 (3) | |
C13 | 0.27959 (13) | 0.6086 (3) | 0.43426 (9) | 0.0189 (4) | |
C14 | 0.34938 (14) | 0.8266 (3) | 0.47396 (10) | 0.0236 (4) | |
C12 | 0.16198 (13) | 0.5701 (3) | 0.44509 (9) | 0.0209 (4) | |
C11 | 0.08386 (13) | 0.7894 (3) | 0.41402 (9) | 0.0197 (4) | |
O12 | 0.10607 (10) | 0.9629 (2) | 0.37597 (7) | 0.0251 (3) | |
O11 | −0.01560 (9) | 0.7650 (2) | 0.43366 (6) | 0.0232 (3) | |
C15 | −0.09780 (14) | 0.9636 (4) | 0.40543 (10) | 0.0256 (4) | |
H3 | 0.6813 | 0.1469 | 0.2679 | 0.027* | |
H4 | 0.5583 | −0.1627 | 0.2054 | 0.030* | |
H5 | 0.3744 | −0.1881 | 0.2259 | 0.028* | |
H6 | 0.3127 | 0.0941 | 0.3046 | 0.027* | |
H1 | 0.4658 | 0.5914 | 0.4053 | 0.024* | |
H14A | 0.3598 | 0.9613 | 0.4388 | 0.035* | |
H14B | 0.4230 | 0.7590 | 0.4987 | 0.035* | |
H14C | 0.3109 | 0.9016 | 0.5103 | 0.035* | |
H12A | 0.1320 | 0.4049 | 0.4215 | 0.025* | |
H12B | 0.1637 | 0.5546 | 0.4981 | 0.025* | |
H15A | −0.1174 | 0.9525 | 0.3519 | 0.038* | |
H15B | −0.0661 | 1.1358 | 0.4200 | 0.038* | |
H15C | −0.1655 | 0.9370 | 0.4252 | 0.038* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0215 (8) | 0.0177 (9) | 0.0163 (8) | 0.0026 (6) | 0.0049 (6) | 0.0025 (6) |
C2 | 0.0209 (8) | 0.0187 (9) | 0.0182 (8) | −0.0004 (6) | 0.0032 (6) | 0.0021 (7) |
N12 | 0.0216 (7) | 0.0236 (8) | 0.0232 (8) | 0.0001 (6) | 0.0069 (6) | 0.0025 (6) |
O22 | 0.0199 (6) | 0.0397 (8) | 0.0484 (9) | −0.0047 (6) | 0.0148 (6) | −0.0075 (7) |
O21 | 0.0252 (6) | 0.0259 (7) | 0.0270 (7) | −0.0027 (5) | 0.0080 (5) | −0.0055 (5) |
C3 | 0.0218 (8) | 0.0268 (9) | 0.0208 (9) | 0.0041 (7) | 0.0067 (7) | 0.0032 (7) |
C4 | 0.0310 (9) | 0.0251 (9) | 0.0203 (9) | 0.0062 (8) | 0.0069 (7) | −0.0007 (7) |
C5 | 0.0266 (9) | 0.0216 (9) | 0.0203 (9) | 0.0003 (7) | 0.0019 (7) | −0.0013 (7) |
C6 | 0.0217 (8) | 0.0232 (9) | 0.0217 (9) | 0.0015 (7) | 0.0044 (7) | 0.0007 (7) |
N1 | 0.0180 (7) | 0.0201 (7) | 0.0239 (8) | −0.0023 (6) | 0.0064 (6) | −0.0034 (6) |
N2 | 0.0172 (7) | 0.0190 (7) | 0.0241 (8) | 0.0005 (6) | 0.0065 (6) | 0.0010 (6) |
C13 | 0.0215 (8) | 0.0175 (8) | 0.0180 (8) | 0.0019 (7) | 0.0051 (6) | 0.0028 (7) |
C14 | 0.0250 (9) | 0.0213 (9) | 0.0253 (9) | −0.0008 (7) | 0.0070 (7) | −0.0025 (7) |
C12 | 0.0232 (8) | 0.0190 (8) | 0.0216 (9) | −0.0003 (7) | 0.0073 (7) | 0.0002 (7) |
C11 | 0.0205 (8) | 0.0190 (9) | 0.0201 (8) | −0.0021 (7) | 0.0056 (6) | −0.0053 (7) |
O12 | 0.0248 (6) | 0.0196 (6) | 0.0322 (7) | −0.0006 (5) | 0.0088 (5) | 0.0036 (5) |
O11 | 0.0197 (6) | 0.0241 (6) | 0.0274 (7) | 0.0018 (5) | 0.0086 (5) | 0.0032 (5) |
C15 | 0.0212 (8) | 0.0243 (9) | 0.0318 (10) | 0.0040 (7) | 0.0064 (7) | −0.0010 (8) |
Geometric parameters (Å, º) top
C1—N1 | 1.366 (2) | N2—C13 | 1.283 (2) |
C1—C2 | 1.411 (2) | C13—C12 | 1.498 (2) |
C1—C6 | 1.414 (2) | C13—C14 | 1.503 (2) |
C2—C3 | 1.403 (2) | C14—H14A | 0.98 |
C2—N12 | 1.438 (2) | C14—H14B | 0.98 |
N12—O22 | 1.2363 (17) | C14—H14C | 0.98 |
N12—O21 | 1.2482 (18) | C12—C11 | 1.508 (2) |
C3—C4 | 1.368 (3) | C12—H12A | 0.99 |
C3—H3 | 0.95 | C12—H12B | 0.99 |
C4—C5 | 1.401 (2) | C11—O12 | 1.206 (2) |
C4—H4 | 0.95 | C11—O11 | 1.3402 (19) |
C5—C6 | 1.368 (2) | O11—C15 | 1.448 (2) |
C5—H5 | 0.95 | C15—H15A | 0.98 |
C6—H6 | 0.95 | C15—H15B | 0.98 |
N1—N2 | 1.3778 (18) | C15—H15C | 0.98 |
N1—H1 | 0.88 | | |
| | | |
N1—C1—C2 | 122.88 (15) | N2—C13—C12 | 115.36 (15) |
N1—C1—C6 | 120.55 (15) | N2—C13—C14 | 125.49 (15) |
C2—C1—C6 | 116.56 (15) | C12—C13—C14 | 119.14 (14) |
C3—C2—C1 | 121.49 (15) | C13—C14—H14A | 109.5 |
C3—C2—N12 | 116.46 (14) | C13—C14—H14B | 109.5 |
C1—C2—N12 | 122.04 (14) | H14A—C14—H14B | 109.5 |
O22—N12—O21 | 121.22 (14) | C13—C14—H14C | 109.5 |
O22—N12—C2 | 118.92 (14) | H14A—C14—H14C | 109.5 |
O21—N12—C2 | 119.85 (13) | H14B—C14—H14C | 109.5 |
C4—C3—C2 | 120.35 (16) | C13—C12—C11 | 113.01 (14) |
C4—C3—H3 | 119.8 | C13—C12—H12B | 109.0 |
C2—C3—H3 | 119.8 | C11—C12—H12B | 109.0 |
C3—C4—C5 | 118.97 (16) | C13—C12—H12A | 109.0 |
C3—C4—H4 | 120.5 | C11—C12—H12A | 109.0 |
C5—C4—H4 | 120.5 | H12B—C12—H12A | 107.8 |
C6—C5—C4 | 121.45 (16) | O12—C11—O11 | 123.83 (15) |
C6—C5—H5 | 119.3 | O12—C11—C12 | 125.35 (15) |
C4—C5—H5 | 119.3 | O11—C11—C12 | 110.82 (14) |
C5—C6—C1 | 121.16 (16) | C11—O11—C15 | 115.27 (13) |
C5—C6—H6 | 119.4 | O11—C15—H15A | 109.5 |
C1—C6—H6 | 119.4 | O11—C15—H15B | 109.5 |
C1—N1—N2 | 118.91 (13) | H15A—C15—H15B | 109.5 |
C1—N1—H1 | 120.5 | O11—C15—H15C | 109.5 |
N2—N1—H1 | 120.5 | H15A—C15—H15C | 109.5 |
C13—N2—N1 | 116.85 (14) | H15B—C15—H15C | 109.5 |
| | | |
N1—C1—C2—C3 | −179.71 (16) | N1—C1—C6—C5 | 179.85 (16) |
C6—C1—C2—C3 | 1.4 (2) | C2—C1—C6—C5 | −1.2 (2) |
N1—C1—C2—N12 | 1.8 (2) | C2—C1—N1—N2 | −178.57 (14) |
C6—C1—C2—N12 | −177.08 (14) | C6—C1—N1—N2 | 0.3 (2) |
C3—C2—N12—O22 | −3.0 (2) | C1—N1—N2—C13 | −178.70 (15) |
C1—C2—N12—O22 | 175.59 (15) | N1—N2—C13—C12 | −178.15 (13) |
C3—C2—N12—O21 | 177.67 (15) | N1—N2—C13—C14 | 0.9 (2) |
C1—C2—N12—O21 | −3.8 (2) | N2—C13—C12—C11 | −113.65 (17) |
C1—C2—C3—C4 | −0.5 (3) | C14—C13—C12—C11 | 67.19 (19) |
N12—C2—C3—C4 | 178.09 (15) | C13—C12—C11—O12 | 9.2 (2) |
C2—C3—C4—C5 | −0.7 (3) | C13—C12—C11—O11 | −171.48 (13) |
C3—C4—C5—C6 | 0.8 (3) | O12—C11—O11—C15 | 0.4 (2) |
C4—C5—C6—C1 | 0.1 (3) | C12—C11—O11—C15 | −178.88 (13) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O21 | 0.88 | 1.97 | 2.6077 (17) | 128 |
C12—H12A···O12i | 0.99 | 2.42 | 3.3894 (19) | 166 |
Symmetry code: (i) x, y−1, z. |
(II) Methyl 3-(2,4-dinitrophenylhydrazono)butanoate
top
Crystal data top
C11H12N4O6 | F(000) = 1232 |
Mr = 296.25 | Dx = 1.483 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 3033 reflections |
a = 10.6100 (3) Å | θ = 3.2–27.5° |
b = 12.1878 (4) Å | µ = 0.12 mm−1 |
c = 20.522 (2) Å | T = 120 K |
V = 2653.7 (3) Å3 | Block, yellow |
Z = 8 | 0.43 × 0.35 × 0.14 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 3033 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 2289 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ & ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −15→15 |
Tmin = 0.961, Tmax = 0.983 | l = −24→26 |
20035 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0551P)2 + 0.817P] where P = (Fo2 + 2Fc2)/3 |
3033 reflections | (Δ/σ)max < 0.001 |
192 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C11H12N4O6 | V = 2653.7 (3) Å3 |
Mr = 296.25 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.6100 (3) Å | µ = 0.12 mm−1 |
b = 12.1878 (4) Å | T = 120 K |
c = 20.522 (2) Å | 0.43 × 0.35 × 0.14 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 3033 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2289 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.983 | Rint = 0.061 |
20035 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.27 e Å−3 |
3033 reflections | Δρmin = −0.25 e Å−3 |
192 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O11 | 0.01578 (11) | 0.55193 (10) | 0.69090 (6) | 0.0297 (3) | |
O12 | 0.13782 (15) | 0.43776 (15) | 0.74791 (7) | 0.0606 (5) | |
O21 | 0.66390 (10) | 0.26911 (9) | 0.64925 (6) | 0.0230 (3) | |
O22 | 0.85592 (10) | 0.32760 (10) | 0.65229 (7) | 0.0311 (3) | |
O41 | 0.98648 (10) | 0.63378 (10) | 0.52622 (6) | 0.0301 (3) | |
O42 | 0.84785 (11) | 0.75212 (10) | 0.49240 (6) | 0.0302 (3) | |
N1 | 0.48258 (11) | 0.40416 (11) | 0.61533 (7) | 0.0177 (3) | |
N2 | 0.36163 (11) | 0.44540 (11) | 0.61213 (6) | 0.0180 (3) | |
N12 | 0.74485 (12) | 0.33937 (10) | 0.63681 (7) | 0.0192 (3) | |
N14 | 0.87653 (13) | 0.66549 (11) | 0.52018 (7) | 0.0222 (3) | |
C1 | 0.57946 (13) | 0.46822 (12) | 0.59429 (7) | 0.0162 (3) | |
C2 | 0.70780 (14) | 0.43794 (12) | 0.60203 (8) | 0.0161 (3) | |
C3 | 0.80473 (14) | 0.50226 (13) | 0.57740 (8) | 0.0179 (3) | |
C4 | 0.77522 (14) | 0.59849 (12) | 0.54603 (8) | 0.0179 (3) | |
C5 | 0.65006 (15) | 0.63349 (12) | 0.53913 (8) | 0.0191 (3) | |
C6 | 0.55446 (15) | 0.56928 (12) | 0.56314 (8) | 0.0184 (3) | |
C11 | 0.10115 (16) | 0.47250 (15) | 0.69668 (9) | 0.0270 (4) | |
C12 | 0.14400 (14) | 0.43223 (14) | 0.63058 (8) | 0.0233 (4) | |
C13 | 0.27347 (14) | 0.38216 (14) | 0.63305 (8) | 0.0206 (4) | |
C14 | 0.29115 (17) | 0.26882 (15) | 0.65951 (11) | 0.0339 (5) | |
C15 | −0.0374 (2) | 0.59322 (18) | 0.75140 (10) | 0.0469 (6) | |
H1 | 0.5001 | 0.3380 | 0.6364 | 0.021* | |
H3 | 0.8901 | 0.4801 | 0.5822 | 0.022* | |
H5 | 0.6316 | 0.7010 | 0.5181 | 0.023* | |
H6 | 0.4697 | 0.5933 | 0.5587 | 0.022* | |
H12A | 0.0834 | 0.3769 | 0.6143 | 0.028* | |
H12B | 0.1444 | 0.4945 | 0.5996 | 0.028* | |
H14A | 0.3444 | 0.2264 | 0.6297 | 0.051* | |
H14B | 0.2089 | 0.2329 | 0.6638 | 0.051* | |
H14C | 0.3317 | 0.2729 | 0.7023 | 0.051* | |
H15A | −0.0849 | 0.5346 | 0.7730 | 0.070* | |
H15B | −0.0939 | 0.6548 | 0.7419 | 0.070* | |
H15C | 0.0307 | 0.6180 | 0.7801 | 0.070* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O11 | 0.0326 (7) | 0.0331 (7) | 0.0234 (7) | 0.0096 (5) | 0.0052 (5) | 0.0064 (5) |
O12 | 0.0645 (10) | 0.0938 (13) | 0.0236 (8) | 0.0502 (10) | 0.0066 (7) | 0.0142 (8) |
O21 | 0.0207 (6) | 0.0194 (5) | 0.0288 (7) | −0.0020 (5) | 0.0041 (5) | 0.0045 (5) |
O22 | 0.0152 (6) | 0.0305 (7) | 0.0478 (8) | 0.0045 (5) | −0.0027 (5) | 0.0118 (6) |
O41 | 0.0168 (6) | 0.0334 (7) | 0.0401 (8) | −0.0032 (5) | 0.0059 (5) | 0.0052 (6) |
O42 | 0.0328 (7) | 0.0231 (6) | 0.0347 (7) | −0.0047 (5) | 0.0030 (6) | 0.0092 (5) |
N1 | 0.0112 (6) | 0.0198 (7) | 0.0222 (7) | 0.0012 (5) | 0.0012 (5) | 0.0031 (5) |
N2 | 0.0109 (6) | 0.0257 (7) | 0.0175 (7) | 0.0010 (5) | 0.0002 (5) | −0.0015 (5) |
N12 | 0.0151 (7) | 0.0189 (6) | 0.0236 (7) | 0.0013 (5) | 0.0029 (6) | 0.0002 (5) |
N14 | 0.0223 (8) | 0.0226 (7) | 0.0216 (8) | −0.0048 (6) | 0.0038 (6) | 0.0000 (6) |
C1 | 0.0146 (7) | 0.0193 (7) | 0.0148 (8) | −0.0010 (6) | 0.0014 (6) | −0.0031 (6) |
C2 | 0.0160 (8) | 0.0154 (7) | 0.0170 (8) | 0.0014 (6) | −0.0002 (6) | 0.0002 (6) |
C3 | 0.0146 (7) | 0.0200 (7) | 0.0192 (8) | −0.0004 (6) | 0.0012 (6) | −0.0023 (6) |
C4 | 0.0178 (8) | 0.0196 (7) | 0.0164 (8) | −0.0046 (6) | 0.0016 (6) | −0.0011 (6) |
C5 | 0.0217 (8) | 0.0185 (7) | 0.0169 (8) | 0.0000 (6) | −0.0015 (6) | 0.0006 (6) |
C6 | 0.0157 (8) | 0.0218 (8) | 0.0177 (8) | 0.0016 (6) | −0.0023 (6) | −0.0004 (6) |
C11 | 0.0197 (8) | 0.0369 (10) | 0.0245 (10) | 0.0049 (7) | 0.0035 (7) | 0.0072 (8) |
C12 | 0.0137 (8) | 0.0338 (9) | 0.0223 (9) | 0.0002 (7) | 0.0004 (7) | 0.0031 (7) |
C13 | 0.0155 (8) | 0.0284 (8) | 0.0178 (8) | −0.0004 (6) | 0.0005 (6) | 0.0011 (6) |
C14 | 0.0203 (9) | 0.0323 (9) | 0.0492 (13) | −0.0007 (7) | 0.0059 (8) | 0.0145 (9) |
C15 | 0.0582 (14) | 0.0531 (12) | 0.0292 (11) | 0.0294 (11) | 0.0164 (10) | 0.0099 (10) |
Geometric parameters (Å, º) top
C1—N1 | 1.3612 (19) | C15—H15A | 0.98 |
C1—C6 | 1.413 (2) | C15—H15B | 0.98 |
C1—C2 | 1.420 (2) | C15—H15C | 0.98 |
N1—N2 | 1.3797 (17) | C2—C3 | 1.388 (2) |
N1—H1 | 0.9337 | C2—N12 | 1.4517 (19) |
N2—C13 | 1.286 (2) | N12—O22 | 1.2290 (16) |
C13—C14 | 1.496 (2) | N12—O21 | 1.2394 (16) |
C13—C12 | 1.504 (2) | C3—C4 | 1.374 (2) |
C14—H14A | 0.98 | C3—H3 | 0.95 |
C14—H14B | 0.98 | C4—C5 | 1.402 (2) |
C14—H14C | 0.98 | C4—N14 | 1.4503 (19) |
C12—C11 | 1.512 (2) | N14—O41 | 1.2352 (17) |
C12—H12A | 0.99 | N14—O42 | 1.2378 (18) |
C12—H12B | 0.99 | C5—C6 | 1.373 (2) |
C11—O12 | 1.198 (2) | C5—H5 | 0.95 |
C11—O11 | 1.331 (2) | C6—H6 | 0.95 |
O11—C15 | 1.454 (2) | | |
| | | |
N1—C1—C6 | 120.12 (13) | O11—C15—H15B | 109.5 |
N1—C1—C2 | 122.67 (14) | H15A—C15—H15B | 109.5 |
C6—C1—C2 | 117.21 (13) | O11—C15—H15C | 109.5 |
C1—N1—N2 | 118.57 (12) | H15A—C15—H15C | 109.5 |
C1—N1—H1 | 119.5 | H15B—C15—H15C | 109.5 |
N2—N1—H1 | 121.5 | C3—C2—C1 | 121.54 (14) |
C13—N2—N1 | 116.25 (13) | C3—C2—N12 | 116.47 (13) |
N2—C13—C14 | 125.69 (15) | C1—C2—N12 | 121.99 (13) |
N2—C13—C12 | 114.21 (14) | O22—N12—O21 | 122.04 (13) |
C14—C13—C12 | 120.09 (14) | O22—N12—C2 | 118.91 (12) |
C13—C14—H14A | 109.5 | O21—N12—C2 | 119.04 (12) |
C13—C14—H14B | 109.5 | C4—C3—C2 | 118.93 (14) |
H14A—C14—H14B | 109.5 | C4—C3—H3 | 120.5 |
C13—C14—H14C | 109.5 | C2—C3—H3 | 120.5 |
H14A—C14—H14C | 109.5 | C3—C4—C5 | 121.52 (14) |
H14B—C14—H14C | 109.5 | C3—C4—N14 | 118.89 (14) |
C13—C12—C11 | 112.09 (14) | C5—C4—N14 | 119.58 (14) |
C13—C12—H12A | 109.2 | O41—N14—O42 | 123.04 (13) |
C11—C12—H12A | 109.2 | O41—N14—C4 | 119.15 (13) |
C13—C12—H12B | 109.2 | O42—N14—C4 | 117.81 (13) |
C11—C12—H12B | 109.2 | C6—C5—C4 | 119.36 (14) |
H12A—C12—H12B | 107.9 | C6—C5—H5 | 120.3 |
O12—C11—O11 | 123.78 (17) | C4—C5—H5 | 120.3 |
O12—C11—C12 | 125.07 (16) | C5—C6—C1 | 121.38 (14) |
O11—C11—C12 | 111.14 (14) | C5—C6—H6 | 119.3 |
C11—O11—C15 | 116.10 (14) | C1—C6—H6 | 119.3 |
O11—C15—H15A | 109.5 | | |
| | | |
C6—C1—N1—N2 | −7.1 (2) | C1—C2—N12—O22 | −166.82 (14) |
C2—C1—N1—N2 | 173.08 (13) | C3—C2—N12—O21 | −166.83 (14) |
C1—N1—N2—C13 | −179.46 (14) | C1—C2—N12—O21 | 14.1 (2) |
N1—N2—C13—C14 | −0.7 (2) | C1—C2—C3—C4 | 1.4 (2) |
N1—N2—C13—C12 | 178.09 (13) | N12—C2—C3—C4 | −177.75 (14) |
N2—C13—C12—C11 | −101.57 (17) | C2—C3—C4—C5 | 0.8 (2) |
C14—C13—C12—C11 | 77.3 (2) | C2—C3—C4—N14 | −179.85 (14) |
C13—C12—C11—O12 | −25.3 (3) | C3—C4—N14—O41 | 0.9 (2) |
C13—C12—C11—O11 | 155.12 (14) | C5—C4—N14—O41 | −179.68 (14) |
O12—C11—O11—C15 | −2.7 (3) | C3—C4—N14—O42 | −179.63 (15) |
C12—C11—O11—C15 | 176.87 (16) | C5—C4—N14—O42 | −0.3 (2) |
N1—C1—C2—C3 | 176.91 (15) | C3—C4—C5—C6 | −1.3 (2) |
C6—C1—C2—C3 | −2.9 (2) | N14—C4—C5—C6 | 179.38 (14) |
N1—C1—C2—N12 | −4.0 (2) | C4—C5—C6—C1 | −0.4 (2) |
C6—C1—C2—N12 | 176.14 (13) | N1—C1—C6—C5 | −177.40 (15) |
C3—C2—N12—O22 | 12.3 (2) | C2—C1—C6—C5 | 2.4 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O21 | 0.93 | 1.95 | 2.6258 (17) | 128 |
C6—H6···O42i | 0.95 | 2.51 | 3.293 (2) | 139 |
Symmetry code: (i) x−1/2, −y+3/2, −z+1. |
(III) 5-Hydroxy-3-methyl-1-phenyl-1
H-pyrazole
top
Crystal data top
C10H10N2O | F(000) = 368 |
Mr = 174.20 | Dx = 1.330 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 1051 reflections |
a = 15.0138 (9) Å | θ = 3.3–27.5° |
b = 5.2952 (3) Å | µ = 0.09 mm−1 |
c = 10.9469 (6) Å | T = 120 K |
V = 870.29 (9) Å3 | Needle, colourless |
Z = 4 | 0.22 × 0.09 × 0.02 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 1051 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 913 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ & ω scans | h = −19→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −6→6 |
Tmin = 0.974, Tmax = 0.998 | l = −12→14 |
8739 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0482P)2 + 0.1089P] where P = (Fo2 + 2Fc2)/3 |
1051 reflections | (Δ/σ)max < 0.001 |
120 parameters | Δρmax = 0.17 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
Crystal data top
C10H10N2O | V = 870.29 (9) Å3 |
Mr = 174.20 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 15.0138 (9) Å | µ = 0.09 mm−1 |
b = 5.2952 (3) Å | T = 120 K |
c = 10.9469 (6) Å | 0.22 × 0.09 × 0.02 mm |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 1051 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 913 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.998 | Rint = 0.057 |
8739 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 1 restraint |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.17 e Å−3 |
1051 reflections | Δρmin = −0.21 e Å−3 |
120 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.64367 (15) | 0.3886 (4) | 0.6963 (2) | 0.0195 (5) | |
C2 | 0.61493 (16) | 0.3673 (5) | 0.8171 (2) | 0.0232 (5) | |
C3 | 0.55513 (17) | 0.5448 (5) | 0.8625 (2) | 0.0274 (6) | |
C4 | 0.52322 (19) | 0.7370 (5) | 0.7897 (3) | 0.0292 (6) | |
C5 | 0.55078 (18) | 0.7531 (5) | 0.6698 (3) | 0.0274 (6) | |
C6 | 0.61146 (16) | 0.5798 (4) | 0.6215 (2) | 0.0239 (6) | |
N1 | 0.70654 (13) | 0.2088 (4) | 0.65099 (17) | 0.0198 (4) | |
N2 | 0.75777 (13) | 0.0691 (3) | 0.73189 (18) | 0.0206 (5) | |
C11 | 0.72202 (15) | 0.1281 (4) | 0.5345 (2) | 0.0205 (5) | |
O11 | 0.67794 (12) | 0.2304 (3) | 0.44157 (17) | 0.0273 (4) | |
C12 | 0.78441 (15) | −0.0624 (4) | 0.5395 (2) | 0.0218 (5) | |
C13 | 0.80393 (16) | −0.0922 (4) | 0.6631 (2) | 0.0208 (5) | |
C14 | 0.86558 (17) | −0.2775 (5) | 0.7216 (3) | 0.0274 (6) | |
H2 | 0.6359 | 0.2339 | 0.8675 | 0.028* | |
H3 | 0.5360 | 0.5333 | 0.9450 | 0.033* | |
H4 | 0.4826 | 0.8574 | 0.8219 | 0.035* | |
H5 | 0.5281 | 0.8841 | 0.6192 | 0.033* | |
H6 | 0.6304 | 0.5925 | 0.5389 | 0.029* | |
H11 | 0.6993 | 0.1773 | 0.3755 | 0.041* | |
H12 | 0.8089 | −0.1539 | 0.4728 | 0.026* | |
H14A | 0.8637 | −0.2565 | 0.8105 | 0.041* | |
H14B | 0.9264 | −0.2482 | 0.6923 | 0.041* | |
H14C | 0.8471 | −0.4495 | 0.7003 | 0.041* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0176 (12) | 0.0198 (12) | 0.0210 (12) | −0.0020 (9) | 0.0002 (9) | −0.0052 (9) |
C2 | 0.0244 (13) | 0.0271 (13) | 0.0181 (11) | −0.0035 (10) | 0.0005 (10) | −0.0026 (10) |
C3 | 0.0258 (13) | 0.0331 (14) | 0.0231 (13) | −0.0054 (11) | 0.0045 (10) | −0.0089 (11) |
C4 | 0.0254 (12) | 0.0267 (14) | 0.0355 (15) | −0.0023 (11) | 0.0048 (11) | −0.0111 (11) |
C5 | 0.0266 (14) | 0.0216 (13) | 0.0341 (14) | −0.0003 (9) | −0.0013 (11) | −0.0015 (11) |
C6 | 0.0259 (13) | 0.0232 (13) | 0.0226 (13) | −0.0029 (10) | 0.0017 (9) | −0.0027 (10) |
N1 | 0.0208 (10) | 0.0234 (10) | 0.0150 (10) | 0.0010 (8) | −0.0016 (8) | 0.0007 (8) |
N2 | 0.0240 (10) | 0.0245 (11) | 0.0134 (9) | 0.0006 (9) | −0.0027 (8) | 0.0004 (8) |
C11 | 0.0218 (12) | 0.0257 (12) | 0.0139 (11) | −0.0026 (10) | −0.0004 (9) | −0.0004 (10) |
O11 | 0.0309 (10) | 0.0393 (11) | 0.0117 (7) | 0.0100 (8) | −0.0012 (7) | −0.0001 (8) |
C12 | 0.0216 (12) | 0.0246 (12) | 0.0193 (11) | 0.0010 (10) | 0.0021 (10) | −0.0008 (11) |
C13 | 0.0197 (12) | 0.0216 (11) | 0.0210 (12) | −0.0030 (9) | 0.0014 (9) | 0.0022 (10) |
C14 | 0.0291 (14) | 0.0261 (13) | 0.0269 (14) | 0.0018 (10) | −0.0019 (11) | 0.0040 (11) |
Geometric parameters (Å, º) top
C1—C6 | 1.389 (3) | N1—C11 | 1.364 (3) |
C1—C2 | 1.396 (3) | N1—N2 | 1.387 (3) |
C1—N1 | 1.430 (3) | N2—C13 | 1.333 (3) |
C2—C3 | 1.391 (4) | C11—O11 | 1.329 (3) |
C2—H2 | 0.95 | C11—C12 | 1.378 (3) |
C3—C4 | 1.378 (4) | O11—H11 | 0.84 |
C3—H3 | 0.95 | C12—C13 | 1.394 (3) |
C4—C5 | 1.379 (4) | C12—H12 | 0.95 |
C4—H4 | 0.95 | C13—C14 | 1.493 (3) |
C5—C6 | 1.397 (4) | C14—H14A | 0.98 |
C5—H5 | 0.95 | C14—H14B | 0.98 |
C6—H6 | 0.95 | C14—H14C | 0.98 |
| | | |
C6—C1—C2 | 120.7 (2) | C11—N1—C1 | 130.2 (2) |
C6—C1—N1 | 120.7 (2) | N2—N1—C1 | 119.99 (18) |
C2—C1—N1 | 118.6 (2) | C13—N2—N1 | 105.63 (19) |
C3—C2—C1 | 118.9 (2) | O11—C11—N1 | 120.2 (2) |
C3—C2—H2 | 120.6 | O11—C11—C12 | 131.8 (2) |
C1—C2—H2 | 120.6 | N1—C11—C12 | 108.0 (2) |
C4—C3—C2 | 121.1 (2) | C11—O11—H11 | 109.5 |
C4—C3—H3 | 119.4 | C11—C12—C13 | 105.3 (2) |
C2—C3—H3 | 119.4 | C11—C12—H12 | 127.3 |
C3—C4—C5 | 119.4 (2) | C13—C12—H12 | 127.3 |
C3—C4—H4 | 120.3 | N2—C13—C12 | 111.5 (2) |
C5—C4—H4 | 120.3 | N2—C13—C14 | 120.1 (2) |
C4—C5—C6 | 121.0 (3) | C12—C13—C14 | 128.4 (2) |
C4—C5—H5 | 119.5 | C13—C14—H14A | 109.5 |
C6—C5—H5 | 119.5 | C13—C14—H14B | 109.5 |
C1—C6—C5 | 118.9 (2) | H14A—C14—H14B | 109.5 |
C1—C6—H6 | 120.6 | C13—C14—H14C | 109.5 |
C5—C6—H6 | 120.6 | H14A—C14—H14C | 109.5 |
C11—N1—N2 | 109.59 (18) | H14B—C14—H14C | 109.5 |
| | | |
C6—C1—C2—C3 | −1.6 (3) | C11—N1—N2—C13 | 0.5 (2) |
N1—C1—C2—C3 | 178.7 (2) | C1—N1—N2—C13 | 175.4 (2) |
C1—C2—C3—C4 | 1.0 (4) | N2—N1—C11—O11 | 178.0 (2) |
C2—C3—C4—C5 | 0.3 (4) | C1—N1—C11—O11 | 3.7 (4) |
C3—C4—C5—C6 | −0.9 (4) | N2—N1—C11—C12 | −0.8 (3) |
C2—C1—C6—C5 | 1.0 (3) | C1—N1—C11—C12 | −175.0 (2) |
N1—C1—C6—C5 | −179.4 (2) | O11—C11—C12—C13 | −177.8 (2) |
C4—C5—C6—C1 | 0.3 (4) | N1—C11—C12—C13 | 0.7 (3) |
C6—C1—N1—C11 | −25.5 (4) | N1—N2—C13—C12 | 0.0 (3) |
C2—C1—N1—C11 | 154.2 (2) | N1—N2—C13—C14 | −178.8 (2) |
C6—C1—N1—N2 | 160.8 (2) | C11—C12—C13—N2 | −0.4 (3) |
C2—C1—N1—N2 | −19.6 (3) | C11—C12—C13—C14 | 178.2 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O11 | 0.95 | 2.31 | 2.881 (3) | 118 |
O11—H11···N2i | 0.84 | 1.79 | 2.633 (3) | 178 |
Symmetry code: (i) −x+3/2, y, z−1/2. |
(V) 4-isopropylidene-3-methyl-1-(3-nitrophenyl)-1
H-pyrazol-5(4
H)-one
top
Crystal data top
C13H13N3O3 | F(000) = 544 |
Mr = 259.26 | Dx = 1.437 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2752 reflections |
a = 8.8910 (3) Å | θ = 3.5–27.5° |
b = 10.1699 (6) Å | µ = 0.11 mm−1 |
c = 13.4731 (7) Å | T = 120 K |
β = 100.415 (3)° | Block, red |
V = 1198.17 (10) Å3 | 0.36 × 0.24 × 0.14 mm |
Z = 4 | |
Data collection top
Bruker-Nonius KappaCCD diffractometer | 2752 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 1840 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.5° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003) | k = −13→13 |
Tmin = 0.958, Tmax = 0.985 | l = −17→17 |
15923 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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0789P)2 + 0.7324P] where P = (Fo2 + 2Fc2)/3 |
2752 reflections | (Δ/σ)max < 0.001 |
175 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C13H13N3O3 | V = 1198.17 (10) Å3 |
Mr = 259.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.8910 (3) Å | µ = 0.11 mm−1 |
b = 10.1699 (6) Å | T = 120 K |
c = 13.4731 (7) Å | 0.36 × 0.24 × 0.14 mm |
β = 100.415 (3)° | |
Data collection top
Bruker-Nonius KappaCCD diffractometer | 2752 independent reflections |
Absorption correction: multi-scan SADABS 2.10 (Sheldrick, 2003) | 1840 reflections with I > 2σ(I) |
Tmin = 0.958, Tmax = 0.985 | Rint = 0.057 |
15923 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.53 e Å−3 |
2752 reflections | Δρmin = −0.27 e Å−3 |
175 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.6412 (2) | 0.3896 (2) | 0.58841 (16) | 0.0251 (5) | |
C2 | 0.5480 (2) | 0.2940 (2) | 0.53563 (16) | 0.0261 (5) | |
C3 | 0.4712 (2) | 0.2100 (2) | 0.59011 (16) | 0.0266 (5) | |
N3 | 0.3745 (2) | 0.10745 (18) | 0.53370 (14) | 0.0296 (4) | |
O31 | 0.37429 (19) | 0.09546 (17) | 0.44281 (12) | 0.0372 (4) | |
O32 | 0.29733 (18) | 0.03864 (17) | 0.58002 (13) | 0.0384 (4) | |
C4 | 0.4805 (2) | 0.2175 (2) | 0.69288 (16) | 0.0308 (5) | |
C5 | 0.5737 (3) | 0.3139 (2) | 0.74368 (17) | 0.0340 (6) | |
C6 | 0.6550 (2) | 0.3989 (2) | 0.69307 (16) | 0.0285 (5) | |
N1 | 0.7228 (2) | 0.47471 (19) | 0.53473 (13) | 0.0270 (4) | |
N2 | 0.7157 (2) | 0.45083 (19) | 0.42918 (14) | 0.0310 (5) | |
C11 | 0.8088 (3) | 0.5830 (2) | 0.56848 (18) | 0.0318 (5) | |
O11 | 0.8279 (2) | 0.62522 (18) | 0.65341 (12) | 0.0415 (5) | |
C12 | 0.8663 (2) | 0.6299 (2) | 0.47662 (17) | 0.0286 (5) | |
C13 | 0.7981 (2) | 0.5402 (2) | 0.39738 (18) | 0.0313 (5) | |
C14 | 0.8126 (3) | 0.5385 (3) | 0.28851 (18) | 0.0395 (6) | |
C15 | 0.9605 (2) | 0.7355 (2) | 0.47696 (19) | 0.0348 (6) | |
C16 | 1.0160 (3) | 0.8131 (3) | 0.5715 (2) | 0.0433 (6) | |
C17 | 1.0143 (3) | 0.7835 (3) | 0.38357 (19) | 0.0389 (6) | |
H2 | 0.5372 | 0.2865 | 0.4644 | 0.031* | |
H4 | 0.4250 | 0.1588 | 0.7276 | 0.037* | |
H5 | 0.5822 | 0.3218 | 0.8147 | 0.041* | |
H6 | 0.7200 | 0.4634 | 0.7294 | 0.034* | |
H14A | 0.7449 | 0.4709 | 0.2529 | 0.059* | |
H14B | 0.9186 | 0.5188 | 0.2829 | 0.059* | |
H14C | 0.7837 | 0.6246 | 0.2584 | 0.059* | |
H16A | 0.9291 | 0.8571 | 0.5929 | 0.065* | |
H16B | 1.0902 | 0.8791 | 0.5583 | 0.065* | |
H16C | 1.0648 | 0.7536 | 0.6250 | 0.065* | |
H17A | 1.0159 | 0.7100 | 0.3368 | 0.058* | |
H17B | 1.1175 | 0.8202 | 0.4022 | 0.058* | |
H17C | 0.9445 | 0.8517 | 0.3509 | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0236 (10) | 0.0255 (12) | 0.0270 (11) | 0.0048 (8) | 0.0066 (8) | 0.0035 (9) |
C2 | 0.0224 (10) | 0.0299 (12) | 0.0262 (11) | 0.0057 (9) | 0.0048 (8) | 0.0022 (9) |
C3 | 0.0232 (10) | 0.0264 (12) | 0.0298 (12) | 0.0029 (8) | 0.0038 (8) | 0.0004 (9) |
N3 | 0.0274 (10) | 0.0296 (11) | 0.0313 (11) | 0.0020 (8) | 0.0037 (8) | 0.0023 (8) |
O31 | 0.0415 (9) | 0.0402 (10) | 0.0289 (9) | −0.0038 (7) | 0.0038 (7) | −0.0031 (7) |
O32 | 0.0383 (9) | 0.0354 (10) | 0.0424 (11) | −0.0076 (7) | 0.0093 (8) | 0.0056 (8) |
C4 | 0.0345 (12) | 0.0301 (12) | 0.0284 (12) | −0.0001 (9) | 0.0077 (9) | 0.0044 (10) |
C5 | 0.0426 (13) | 0.0354 (14) | 0.0246 (12) | 0.0004 (11) | 0.0082 (9) | 0.0034 (10) |
C6 | 0.0314 (11) | 0.0274 (12) | 0.0263 (12) | 0.0017 (9) | 0.0044 (9) | −0.0005 (9) |
N1 | 0.0285 (9) | 0.0291 (10) | 0.0233 (10) | −0.0009 (8) | 0.0048 (7) | 0.0028 (8) |
N2 | 0.0298 (10) | 0.0361 (11) | 0.0281 (10) | 0.0017 (8) | 0.0080 (8) | 0.0076 (8) |
C11 | 0.0308 (12) | 0.0302 (12) | 0.0331 (13) | 0.0037 (10) | 0.0025 (9) | 0.0038 (10) |
O11 | 0.0517 (11) | 0.0402 (10) | 0.0310 (10) | −0.0116 (8) | 0.0028 (7) | −0.0001 (8) |
C12 | 0.0228 (10) | 0.0283 (12) | 0.0336 (12) | 0.0016 (9) | 0.0022 (8) | 0.0073 (10) |
C13 | 0.0276 (11) | 0.0328 (13) | 0.0329 (13) | 0.0053 (9) | 0.0039 (9) | 0.0007 (10) |
C14 | 0.0417 (14) | 0.0467 (16) | 0.0303 (13) | 0.0011 (11) | 0.0068 (10) | 0.0026 (11) |
C15 | 0.0279 (11) | 0.0336 (13) | 0.0413 (14) | 0.0038 (10) | 0.0020 (9) | 0.0078 (11) |
C16 | 0.0387 (13) | 0.0387 (15) | 0.0485 (16) | −0.0070 (11) | −0.0023 (11) | −0.0028 (12) |
C17 | 0.0321 (12) | 0.0371 (14) | 0.0486 (15) | −0.0018 (10) | 0.0099 (10) | 0.0119 (12) |
Geometric parameters (Å, º) top
C1—C2 | 1.387 (3) | C11—O11 | 1.205 (3) |
C1—C6 | 1.396 (3) | C11—C12 | 1.500 (3) |
C1—N1 | 1.410 (3) | C12—C15 | 1.361 (3) |
C2—C3 | 1.384 (3) | C12—C13 | 1.452 (3) |
C2—H2 | 0.95 | C13—C14 | 1.496 (3) |
C3—C4 | 1.374 (3) | C14—H14A | 0.98 |
C3—N3 | 1.473 (3) | C14—H14B | 0.98 |
N3—O32 | 1.226 (2) | C14—H14C | 0.98 |
N3—O31 | 1.230 (2) | C15—C16 | 1.504 (4) |
C4—C5 | 1.382 (3) | C15—C17 | 1.506 (3) |
C4—H4 | 0.95 | C16—H16A | 0.98 |
C5—C6 | 1.383 (3) | C16—H16B | 0.98 |
C5—H5 | 0.95 | C16—H16C | 0.98 |
C6—H6 | 0.95 | C17—H17A | 0.98 |
N1—C11 | 1.371 (3) | C17—H17B | 0.98 |
N1—N2 | 1.433 (3) | C17—H17C | 0.98 |
N2—C13 | 1.288 (3) | | |
| | | |
C2—C1—C6 | 120.0 (2) | C15—C12—C13 | 132.3 (2) |
C2—C1—N1 | 118.84 (19) | C15—C12—C11 | 123.3 (2) |
C6—C1—N1 | 121.1 (2) | C13—C12—C11 | 104.33 (19) |
C3—C2—C1 | 117.8 (2) | N2—C13—C12 | 112.7 (2) |
C3—C2—H2 | 121.1 | N2—C13—C14 | 118.2 (2) |
C1—C2—H2 | 121.1 | C12—C13—C14 | 129.0 (2) |
C4—C3—C2 | 123.7 (2) | C13—C14—H14A | 109.5 |
C4—C3—N3 | 118.8 (2) | C13—C14—H14B | 109.5 |
C2—C3—N3 | 117.48 (19) | H14A—C14—H14B | 109.5 |
O32—N3—O31 | 123.34 (19) | C13—C14—H14C | 109.5 |
O32—N3—C3 | 118.01 (18) | H14A—C14—H14C | 109.5 |
O31—N3—C3 | 118.65 (18) | H14B—C14—H14C | 109.5 |
C3—C4—C5 | 117.4 (2) | C12—C15—C16 | 121.6 (2) |
C3—C4—H4 | 121.3 | C12—C15—C17 | 122.8 (2) |
C5—C4—H4 | 121.3 | C16—C15—C17 | 115.7 (2) |
C4—C5—C6 | 121.3 (2) | C15—C16—H16A | 109.5 |
C4—C5—H5 | 119.4 | C15—C16—H16B | 109.5 |
C6—C5—H5 | 119.4 | H16A—C16—H16B | 109.5 |
C5—C6—C1 | 119.8 (2) | C15—C16—H16C | 109.5 |
C5—C6—H6 | 120.1 | H16A—C16—H16C | 109.5 |
C1—C6—H6 | 120.1 | H16B—C16—H16C | 109.5 |
C11—N1—C1 | 129.13 (19) | C15—C17—H17A | 109.5 |
C11—N1—N2 | 112.79 (17) | C15—C17—H17B | 109.5 |
C1—N1—N2 | 118.07 (17) | H17A—C17—H17B | 109.5 |
C13—N2—N1 | 106.55 (19) | C15—C17—H17C | 109.5 |
O11—C11—N1 | 125.1 (2) | H17A—C17—H17C | 109.5 |
O11—C11—C12 | 131.3 (2) | H17B—C17—H17C | 109.5 |
N1—C11—C12 | 103.58 (19) | | |
| | | |
C6—C1—C2—C3 | −0.1 (3) | C1—N1—N2—C13 | 179.97 (18) |
N1—C1—C2—C3 | 178.84 (18) | C1—N1—C11—O11 | −0.7 (4) |
C1—C2—C3—C4 | 1.0 (3) | N2—N1—C11—O11 | 177.7 (2) |
C1—C2—C3—N3 | −179.00 (17) | C1—N1—C11—C12 | 179.6 (2) |
C4—C3—N3—O32 | 5.1 (3) | N2—N1—C11—C12 | −2.0 (2) |
C2—C3—N3—O32 | −174.84 (19) | O11—C11—C12—C15 | 1.8 (4) |
C4—C3—N3—O31 | −175.27 (19) | N1—C11—C12—C15 | −178.5 (2) |
C2—C3—N3—O31 | 4.8 (3) | O11—C11—C12—C13 | −177.8 (2) |
C2—C3—C4—C5 | −0.8 (3) | N1—C11—C12—C13 | 1.9 (2) |
N3—C3—C4—C5 | 179.19 (19) | N1—N2—C13—C12 | 0.0 (2) |
C3—C4—C5—C6 | −0.3 (3) | N1—N2—C13—C14 | 179.47 (18) |
C4—C5—C6—C1 | 1.2 (3) | C15—C12—C13—N2 | 179.3 (2) |
C2—C1—C6—C5 | −1.0 (3) | C11—C12—C13—N2 | −1.2 (2) |
N1—C1—C6—C5 | −179.9 (2) | C15—C12—C13—C14 | −0.1 (4) |
C2—C1—N1—C11 | 173.0 (2) | C11—C12—C13—C14 | 179.4 (2) |
C6—C1—N1—C11 | −8.1 (3) | C13—C12—C15—C16 | −179.9 (2) |
C2—C1—N1—N2 | −5.3 (3) | C11—C12—C15—C16 | 0.7 (3) |
C6—C1—N1—N2 | 173.58 (18) | C13—C12—C15—C17 | 1.0 (4) |
C11—N1—N2—C13 | 1.4 (2) | C11—C12—C15—C17 | −178.5 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O11 | 0.95 | 2.24 | 2.871 (3) | 123 |
Experimental details
| (I) | (II) | (III) | (V) |
Crystal data |
Chemical formula | C11H13N3O4 | C11H12N4O6 | C10H10N2O | C13H13N3O3 |
Mr | 251.24 | 296.25 | 174.20 | 259.26 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pbca | Orthorhombic, Pca21 | Monoclinic, P21/c |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 12.1494 (4), 5.1355 (2), 18.6969 (6) | 10.6100 (3), 12.1878 (4), 20.522 (2) | 15.0138 (9), 5.2952 (3), 10.9469 (6) | 8.8910 (3), 10.1699 (6), 13.4731 (7) |
α, β, γ (°) | 90, 102.079 (2), 90 | 90, 90, 90 | 90, 90, 90 | 90, 100.415 (3), 90 |
V (Å3) | 1140.73 (7) | 2653.7 (3) | 870.29 (9) | 1198.17 (10) |
Z | 4 | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.11 | 0.12 | 0.09 | 0.11 |
Crystal size (mm) | 0.28 × 0.22 × 0.04 | 0.43 × 0.35 × 0.14 | 0.22 × 0.09 × 0.02 | 0.36 × 0.24 × 0.14 |
|
Data collection |
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker-Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan SADABS 2.10 (Sheldrick, 2003) |
Tmin, Tmax | 0.975, 0.995 | 0.961, 0.983 | 0.974, 0.998 | 0.958, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13943, 2617, 1931 | 20035, 3033, 2289 | 8739, 1051, 913 | 15923, 2752, 1840 |
Rint | 0.053 | 0.061 | 0.057 | 0.057 |
(sin θ/λ)max (Å−1) | 0.651 | 0.649 | 0.650 | 0.651 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.117, 1.05 | 0.044, 0.116, 1.05 | 0.039, 0.093, 1.12 | 0.060, 0.165, 1.04 |
No. of reflections | 2617 | 3033 | 1051 | 2752 |
No. of parameters | 166 | 192 | 120 | 175 |
No. of restraints | 0 | 0 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.29 | 0.27, −0.25 | 0.17, −0.21 | 0.53, −0.27 |
Selected bond distances and torsion angles
(Å, °) for compounds (I) and (II) topParameter | (I) | (II) |
C1-C2 | 1.411 (2) | 1.420 (2) |
C2-C3 | 1.403 (2) | 1.388 (2) |
C3-C4 | 1.368 (3) | 1.374 (2) |
C4-C5 | 1.401 (2) | 1.402 (2) |
C5-C6 | 1.368 (2) | 1.373 (2) |
C6-C1 | 1.414 (2) | 1.413 (2) |
C1-N1 | 1.366 (2) | 1.3612 (19) |
C2-N12 | 1.438 (2) | 1.4517 (19) |
N12-O21 | 1.2482 (18) | 1.2394 (16) |
N12-O22 | 1.2363 (17) | 1.2290 (16) |
C4-N14 | | 1.4503 (19) |
N14-O41 | | 1.2352 (17) |
N14-O42 | | 1.2378 (17) |
C2-C1-N1-N2 | -178.57 (14) | 173.08 (13) |
C1-N1-N2-C13 | -178.70 (15) | -179.46 (14) |
N1-N2-C13-C12 | -178.15 (13) | 178.09 (13) |
N2-C13-C12-C11 | -113.65 (17) | -101.57 (17) |
C13-C12-C11-O11 | -171.48 (13) | 155.12 (14) |
C12-C11-O11-C15 | -178.88 (13) | 176.87 (16) |
C1-C2-N12-O21 | -3.8 (2) | 14.1 (2) |
C3-C4-N14-O41 | | 0.9 (2) |
Selected bond lengths (Å) in compounds (III) and (V) topParameter | (III) | (V) |
N1-N2 | 1.387 (3) | 1.433 (3) |
N2-C13 | 1.333 (3) | 1.288 (3) |
C13-C12 | 1.394 (3) | 1.452 (3) |
C12-C11 | 1.378 (3) | 1.500 (3) |
C11-N1 | 1.364 (3) | 1.371 (3) |
C11-O11 | 1.329 (3) | 1.205 (3) |
C12-C15 | | 1.361 (3) |
Hydrogen bonds and short intramolecular contacts (Å, °)
for compounds (I)–(III) and (V) topD-H···A | D-H | H···A | D···A | D-H···A |
(I) | | | | |
N1-H1···O21 | 0.88 | 1.97 | 2.6077 (19) | 128 |
C12-H12A···O12i | 0.99 | 2.42 | 3.3894 (19) | 166 |
(II) | | | | |
N1-H1···O21 | 0.93 | 1.95 | 2.6258 (17) | 128 |
C6-H6···O42ii | 0.95 | 2.51 | 3.293 (2) | 139 |
(III) | | | | |
O11-H11···N2iii | 0.84 | 1.79 | 2.633 (3) | 178 |
C6-H6···O1 | 0.95 | 2.31 | 2.881 (3) | 118 |
(V) | | | | |
C6-H6···O1 | 0.95 | 2.24 | 2.871 (3) | 123 |
Symmetry codes:
(i) x, y -1, z; (ii) x - 1/2, -y + 3/2, -z +1;
(iii) -x + 3/2, y, z - 1/2. |
We have for a number of years been interested in the structures of hydrazones (for examples, see Glidewell et al., 2003, 2004, 2006; Peralta et al., 2007; Wardell et al., 2005). As a part of this wider study, we have now investigated the reactions of methyl 3-oxobutanoate (methyl acetoacetate) with a range of simple arylhydrazines. The reaction products include the acyclic 3-arylhydrazinobutanoate esters (I) and (II); the cyclized 1-aryl-5-hydroxypyrazoles (III) and (IV); and the condensation products (V) + ?, initially obtained during attempts to crystallize the pyrazole derivatives from ketonic solvents (Scheme 1). Here we report the structures of compounds (I)–(III) and (V), and we integrate the various structural types into a single mechanistic scheme. The structure of compound (III) reported here represents a second polymorph of this compound; a monoclinic polymorph crystallizes with Z' = 2 in space group P21/c (Bechtel et al., 1973a; Chmutova et al., 2001).
Compounds (I)–(III) (Figs. 1–3) were readily obtained from the reactions between methyl 3-oxobutanoate and the appropriate arylhydrazines, viz. 2-nitrophenylhydrazine for (I), 2,4-dinitrophenlhydrazine for (II) and phenylhydrazine for (III). The analogous reaction using 3-nitrophenylhydrazine gave the product (IV), but the crystal initially obtained from methanol solution were of very poor quality and they were twinned. The diffraction data obtained from these crystals were correspondingly poor, and we have been unable to reduce R significantly below 0.11; thus we do not report the structure of (IV) in detail here. Nonetheless, the atom connectivity revealed by these very poor data unambiguously corresponds to that of compound (IV), directly analogous to compound (III). Attempted recrystallization of compound (IV) from acetone solution yielded instead the condensation product (V) (Fig. 4), evidently a product of the reaction between (IV) itself and the acetone solvent.
The bond lengths in the aryl rings of compounds (I) and (II) show significant variation (Table 1). In particular, the C3—C4 and C5—C6 bonds are substantially shorter than the other ring bonds; in addition, the C2—N12 and C4—N14 bonds are long for their type, while the nitro N—O bonds are all long (Allen et al., 1987). The observations indicate that the polarized quinonoid forms (Ia), and (IIa) and (IIb), respectively (Scheme 2), are significant contributors to the overall electronic structures of compounds (I) and (II). This behaviour is typical of that observed in 2-nitroanilines and 4-nitroanilines, but not in 3-nitroanilines (Cannon et al., 2001; Garden et al., 2001, 2002; Glidewell et al., 2001; Zakaria et al., 2001), and it indicates a reduction in the basicity and nucleophilicity of atom N1 in such 2- and 4-substituted species as compared with both the 3-nitro derivatives and the un-nitrated analogues. The aryl rings in (I) and (II) are almost coplanar with the chain-extended fragment between atoms C1 and C13 (Figs. 1 and 2), and the nitro groups are nearly coplanar with the rings as shown by the relevant torsion angles (Table 1). These nearly planar conformations may be influenced by the intramolecular N—H···O interactions (Table 2). The ester fragments between atoms C12 and C15 are also nearly planar but in each compound there is a substantial bend in the side chain at the C12—C13 bond.
The heterocyclic rings in compounds (III) and (V) exhibit very different bond lengths (Table 2), consistent with significant π-delocalization in (III) and complete bond fixation in (V). The exocyclic C—O bond lengths, in particular, are consistent with the location of the hydroxyl H atom in (III) as deduced from difference maps. The inter-ring dihedral angle is 22.0 (2)° in (III) and 6.2 (2)° in (V), where the nitro group makes a dihedral angle of only 4.9 (2)° with the aryl ring.
The formation of the various products arising from the reactions of methyl acetoacetate with aryl hydrazines can readily be envisaged in terms of an initial condensation to form the acyclic (E)-hydrazone of type (A) (Scheme 3), exemplified here by compounds (I) and (II). Provided that the hydrazine atom N1 is sufficiently nucleophilic then the intermediate (B) can readily cyclize, with loss of methanol, to form (C), whose tautomer (D) is exemplified by (III). Intermediate (B) is simply the Z isomer of (A) and its formation most plausibly involves the tautomer (A'), in which effectively free rotation about the N2—C13 bond is possible. Condensation of (C) with carbonyl compounds yields the exo-methylene derivatives (E), exemplified here by compound (V). We have noted above the evidence for the significance of polarized electronic forms in compounds (I) and (II), and an important consequence of such charge separation is the reduction in nucleophilicity of atom N1 when the aryl group contains 2-nitro and/or 4-nitro substituents. The structural evidence from compounds (I) and (II) is thus consistent with the failure of these two compounds to undergo cyclization under the reaction conditions that produce compounds (III) and (IV). When atom N1 is more nucleophilic, as in the presence of either an unsubstituted phenyl ring or a 3-nitrophenyl ring, cyclization to form (C) and (D) is thus feasible.
While there are no direction-specific interactions of any kind in the structure of (V), the molecules in (I), (II) and (III) are all linked into chains; in each of (I) and (II), the chain is built from a single C—H···O hydrogen bond, and that in (III) by a single O—H···N hydrogen bond. In (I), methylene atom C12 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the carbonyl atom O12 in the molecule at (x, -1 + y, z), so generating by translation a C(4) (Bernstein et al., 1995) chain running parallel to the [010] direction (Fig. 5). In (II), the hydrogen-bond donor and acceptor are both different from those utilized in (I). In (II), aryl atom C6 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the nitro atom O42 in the molecule at (-1/2 + x, 3/2 - y, 1 - z), so forming a C(6) chain running parallel to [100] and generated by the 21 screw axis along (x, 3/4, 1/2) (Fig. 6). In (III), hydroxy atom O11 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the pyrazole atom N2 in the molecule at (3/2 - x, y, -1/2 + z), so forming a C(5) chain running parallel to the [001] direction and generated by the c-glide plane at x = 0.75 (Fig. 7). There are no direction-specific interactions between the chains in compounds (I) and (III), but those in (II) are weakly linked by a dipolar carbonyl–nitro interaction. Carbonyl atom O12 in the molecule at (x, y, z), which forms part of the hydrogen-bonded chain along (x, 3/4, 1/2), makes a nearly linear contact with the nitro atom N12 in the molecule at (-1/2 + x, y, 1.5 - z), which lies in the hydrogen-bonded chain along (x, 3/4, 1) [O···Ni = 2.885 (2) Å and C—O···Ni 173.7 (2)°; symmetry code: (i) -1/2 + x, y, 3/2 - z)], and the effect of this contact is to link the [100] chains weakly into a sheet parallel to (010).
The monoclinic polymorph of (III) (Bechtel et al., 1973a; Chmutova et al., 2001) is, in fact, a 1:1 cocrystal of the two tautomeric forms 5-hydroxy-3-methyl-1-phenylpyrazole and 3-methyl-1-phenyl-2H-pyrazolin-5-one [(IIIa), Scheme 1), and the molecules are linked by alternating O—H···O and N—H···N hydrogen bonds into C22(10) chains. By contrast, the sulfur analogue of (II) exists in the crystalline state solely as the thione tautomer (Chmutova et al., 2001). Isomeric with compound (III) is 3-hydroxy-5-methyl-1-phenylpyrazole, (VI), which exists in the crystalline state as a single tautomer; the compound crystallizes with Z' = 2 in space group Pbca and the molecules are linked by two independent O—H···N hydrogen bonds into R22(8) dimers, which do not exhibit even approximate symmetry (Bechtel et al., 1973b).