(3
Z)-3-{1-[(5-Phenyl-1
H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3
H)-one, C
15H
15N
3O
2, (I), and the stoichiometric adduct (3
Z)-3-{1-[(5-methyl-1
H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3
H)-one–6-(2-hydroxyethyl)-2,5-dimethylpyrazolo[1,5-
a]pyrimidin-7(4
H)-one (1/1), C
10H
13N
3O
2·C
10H
13N
3O
2, (II), in which the two components have the same composition but different constitutions, are formed in the reactions of 2-acetyl-4-butyrolactone with 5-amino-3-phenyl-1
H-pyrazole and 5-amino-3-methyl-1
H-pyrazole, respectively. In each compound, the furanone component contains an intramolecular N—H
O hydrogen bond. The molecules of (I) are linked into a chain by a single intermolecular N—H
O hydrogen bond, while in (II), a combination of one O—H
N hydrogen bond, within the selected asymmetric unit, and two N—H
O hydrogen bonds link the molecular components into a ribbon containing alternating centrosymmetric
R44(20) and
R66(22) rings.
Supporting information
CCDC references: 765471; 765472
For the synthesis of compound (I), a mixture of 2-acetyl-4-butyrolactone (1 mmol), 5-amino-3-phenyl-1H-pyrazole (1 mmol) and 4-toluenesulfonic acid
(0.01 mmol) in ethanol (15 ml) was heated under reflux with magnetic stirring
for 18 h. The mixture was cooled to ambient temperature and the solvent was
removed under reduced pressure. The resulting solid product was recrystallized
from dimethylformamide to yield (I) as colourless crystals (yield 63%, m.p.
595–596 K). Analysis: MS (70 eV) m/z (%) 269 (5, M+),
251 (35), 104 (25), 18 (100).
For the synthesis of compound (II), a mixture of 2-acetyl-4-butyrolactone (1 mmol), 5-amino-3-methyl-1H-pyrazole (1 mmol) and 4-toluenesulfonic acid
(0.01 mmol) in ethanol (15 ml) was heated under reflux with magnetic stirring
for 23 h. The reaction mixture was cooled to ambient temperature and the
solvent was removed under reduced pressure. The resulting solid product was
recrystallized from dimethylformamide to yield (II) as colourless crystals
(yield 48%, m.p. 493–494 K). Analysis: MS (70 eV) m/z (%) 207
(6, M+), 189 (23), 152 (8), 86 (41), 43 (100).
All H atoms were located in difference maps. H atoms bonded to C or N atoms were
then treated as riding in geometrically idealized positions, with C—H = 0.95
(aromatic or pyrazole), 0.98 (CH3) or 0.99 Å (CH2) and N—H = 0.88 Å,
and with Uiso(H) = kUeq(carrier), where k = 1.5 for
the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for
all other H atoms bonded to C or N atoms. The H atom bonded to an O atom in
compound (II) was permitted to ride at the position deduced from the
difference maps, with Uiso(H) = 1.5Ueq(O), giving an O—H
distance of 0.86 Å.
For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
(I) (3
Z)-3-{1-[(5-phenyl-1
H-pyrazol-3-yl)amino]ethylidene}-4,5-
dihydrofuran-2(3
H)-one
top
Crystal data top
C15H15N3O2 | F(000) = 568 |
Mr = 269.30 | Dx = 1.385 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2536 reflections |
a = 10.4969 (17) Å | θ = 3.3–26.1° |
b = 9.8550 (9) Å | µ = 0.10 mm−1 |
c = 12.6739 (16) Å | T = 120 K |
β = 99.883 (9)° | Block, colourless |
V = 1291.6 (3) Å3 | 0.39 × 0.25 × 0.14 mm |
Z = 4 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 2536 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1704 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
Detector resolution: 9.091 pixels mm-1 | θmax = 26.1°, θmin = 3.3° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −11→12 |
Tmin = 0.964, Tmax = 0.987 | l = −15→15 |
19109 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0499P)2 + 0.7664P] where P = (Fo2 + 2Fc2)/3 |
2536 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C15H15N3O2 | V = 1291.6 (3) Å3 |
Mr = 269.30 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.4969 (17) Å | µ = 0.10 mm−1 |
b = 9.8550 (9) Å | T = 120 K |
c = 12.6739 (16) Å | 0.39 × 0.25 × 0.14 mm |
β = 99.883 (9)° | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 2536 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1704 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.987 | Rint = 0.056 |
19109 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.22 e Å−3 |
2536 reflections | Δρmin = −0.26 e Å−3 |
182 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.24565 (15) | 0.99120 (16) | 0.48162 (13) | 0.0398 (4) | |
C2 | 0.3290 (2) | 0.8906 (2) | 0.51543 (18) | 0.0321 (5) | |
C3 | 0.40566 (19) | 0.8586 (2) | 0.43747 (16) | 0.0269 (5) | |
C4 | 0.3659 (2) | 0.9450 (2) | 0.34120 (18) | 0.0363 (6) | |
H4A | 0.3342 | 0.8894 | 0.2770 | 0.044* | |
H4B | 0.4382 | 1.0029 | 0.3269 | 0.044* | |
C5 | 0.2574 (2) | 1.0299 (2) | 0.37378 (19) | 0.0377 (6) | |
H5A | 0.2780 | 1.1277 | 0.3710 | 0.045* | |
H5B | 0.1751 | 1.0126 | 0.3244 | 0.045* | |
O2 | 0.33004 (15) | 0.84051 (17) | 0.60463 (12) | 0.0397 (4) | |
C6 | 0.50234 (19) | 0.7638 (2) | 0.45348 (16) | 0.0260 (5) | |
C61 | 0.5851 (2) | 0.7370 (2) | 0.37190 (17) | 0.0320 (5) | |
H61A | 0.6753 | 0.7580 | 0.4020 | 0.048* | |
H61B | 0.5568 | 0.7941 | 0.3089 | 0.048* | |
H61C | 0.5778 | 0.6412 | 0.3509 | 0.048* | |
N7 | 0.52487 (16) | 0.69449 (18) | 0.54559 (14) | 0.0298 (4) | |
H7 | 0.4737 | 0.7167 | 0.5910 | 0.036* | |
N11 | 0.69552 (16) | 0.45224 (18) | 0.69836 (13) | 0.0291 (4) | |
H11 | 0.7092 | 0.4029 | 0.7571 | 0.035* | |
N12 | 0.59966 (17) | 0.54334 (18) | 0.67646 (14) | 0.0305 (4) | |
C13 | 0.61353 (19) | 0.5946 (2) | 0.58251 (16) | 0.0267 (5) | |
C14 | 0.71760 (19) | 0.5361 (2) | 0.54421 (16) | 0.0275 (5) | |
H14 | 0.7470 | 0.5555 | 0.4790 | 0.033* | |
C15 | 0.76826 (19) | 0.4442 (2) | 0.62139 (16) | 0.0257 (5) | |
C51 | 0.87557 (19) | 0.3499 (2) | 0.62863 (16) | 0.0267 (5) | |
C52 | 0.9272 (2) | 0.3170 (2) | 0.53853 (18) | 0.0344 (6) | |
H52 | 0.8947 | 0.3597 | 0.4722 | 0.041* | |
C53 | 1.0251 (2) | 0.2229 (2) | 0.54399 (19) | 0.0392 (6) | |
H53 | 1.0586 | 0.2004 | 0.4812 | 0.047* | |
C54 | 1.0744 (2) | 0.1618 (2) | 0.63896 (19) | 0.0366 (6) | |
H54 | 1.1417 | 0.0966 | 0.6423 | 0.044* | |
C55 | 1.0261 (2) | 0.1953 (2) | 0.72947 (18) | 0.0375 (6) | |
H55 | 1.0606 | 0.1540 | 0.7960 | 0.045* | |
C56 | 0.9278 (2) | 0.2888 (2) | 0.72418 (17) | 0.0343 (5) | |
H56 | 0.8953 | 0.3116 | 0.7874 | 0.041* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0343 (9) | 0.0378 (9) | 0.0484 (10) | 0.0083 (8) | 0.0103 (7) | −0.0040 (8) |
C2 | 0.0293 (12) | 0.0279 (12) | 0.0387 (14) | −0.0009 (10) | 0.0046 (10) | −0.0060 (10) |
C3 | 0.0265 (11) | 0.0250 (11) | 0.0298 (12) | −0.0024 (9) | 0.0064 (9) | −0.0035 (9) |
C4 | 0.0338 (12) | 0.0352 (13) | 0.0406 (13) | 0.0022 (11) | 0.0080 (10) | 0.0015 (11) |
C5 | 0.0306 (12) | 0.0302 (13) | 0.0513 (15) | 0.0017 (10) | 0.0037 (10) | −0.0027 (12) |
O2 | 0.0406 (9) | 0.0484 (10) | 0.0325 (9) | 0.0030 (8) | 0.0133 (7) | −0.0049 (8) |
C6 | 0.0259 (11) | 0.0249 (11) | 0.0275 (11) | −0.0052 (9) | 0.0055 (8) | −0.0035 (9) |
C61 | 0.0309 (11) | 0.0339 (13) | 0.0330 (12) | 0.0033 (10) | 0.0109 (9) | 0.0033 (10) |
N7 | 0.0311 (10) | 0.0312 (10) | 0.0287 (10) | 0.0043 (8) | 0.0100 (8) | −0.0024 (8) |
N11 | 0.0326 (10) | 0.0284 (10) | 0.0269 (9) | 0.0006 (8) | 0.0071 (8) | 0.0012 (8) |
N12 | 0.0338 (10) | 0.0301 (10) | 0.0288 (10) | 0.0004 (9) | 0.0087 (8) | −0.0023 (8) |
C13 | 0.0270 (11) | 0.0260 (11) | 0.0274 (11) | −0.0041 (9) | 0.0052 (9) | −0.0037 (9) |
C14 | 0.0264 (11) | 0.0310 (12) | 0.0256 (11) | −0.0005 (10) | 0.0059 (9) | −0.0004 (9) |
C15 | 0.0268 (11) | 0.0252 (11) | 0.0247 (11) | −0.0057 (9) | 0.0038 (9) | −0.0030 (9) |
C51 | 0.0250 (10) | 0.0244 (11) | 0.0303 (12) | −0.0032 (9) | 0.0037 (9) | 0.0005 (9) |
C52 | 0.0312 (12) | 0.0398 (14) | 0.0324 (13) | 0.0055 (11) | 0.0060 (9) | 0.0056 (10) |
C53 | 0.0330 (12) | 0.0467 (15) | 0.0402 (13) | 0.0070 (11) | 0.0127 (10) | 0.0025 (12) |
C54 | 0.0267 (11) | 0.0349 (13) | 0.0474 (15) | 0.0040 (10) | 0.0042 (10) | 0.0034 (11) |
C55 | 0.0372 (13) | 0.0360 (14) | 0.0363 (13) | 0.0039 (11) | −0.0021 (10) | 0.0064 (11) |
C56 | 0.0370 (12) | 0.0358 (13) | 0.0294 (12) | 0.0011 (11) | 0.0034 (10) | 0.0001 (10) |
Geometric parameters (Å, º) top
O1—C2 | 1.343 (3) | N11—H11 | 0.8800 |
O1—C5 | 1.444 (3) | N12—C13 | 1.324 (3) |
C2—O2 | 1.232 (3) | C13—C14 | 1.394 (3) |
C2—C3 | 1.413 (3) | C14—C15 | 1.371 (3) |
C3—C6 | 1.369 (3) | C15—N11 | 1.340 (2) |
C3—C4 | 1.488 (3) | C14—H14 | 0.9500 |
C4—C5 | 1.527 (3) | C15—C51 | 1.451 (3) |
C4—H4A | 0.9900 | C51—C56 | 1.379 (3) |
C4—H4B | 0.9900 | C51—C52 | 1.384 (3) |
C5—H5A | 0.9900 | C52—C53 | 1.377 (3) |
C5—H5B | 0.9900 | C52—H52 | 0.9500 |
C6—N7 | 1.338 (3) | C53—C54 | 1.366 (3) |
C6—C61 | 1.484 (3) | C53—H53 | 0.9500 |
C61—H61A | 0.9800 | C54—C55 | 1.372 (3) |
C61—H61B | 0.9800 | C54—H54 | 0.9500 |
C61—H61C | 0.9800 | C55—C56 | 1.376 (3) |
N7—C13 | 1.380 (3) | C55—H55 | 0.9500 |
N7—H7 | 0.8800 | C56—H56 | 0.9500 |
N11—N12 | 1.341 (2) | | |
| | | |
C2—O1—C5 | 109.89 (17) | C15—N11—N12 | 112.93 (17) |
O2—C2—O1 | 119.42 (19) | C15—N11—H11 | 123.5 |
O2—C2—C3 | 129.5 (2) | N12—N11—H11 | 123.5 |
O1—C2—C3 | 111.1 (2) | C13—N12—N11 | 104.32 (16) |
C6—C3—C2 | 123.1 (2) | N12—C13—N7 | 113.91 (18) |
C6—C3—C4 | 127.50 (18) | N12—C13—C14 | 111.62 (19) |
C2—C3—C4 | 109.43 (18) | N7—C13—C14 | 134.45 (19) |
C3—C4—C5 | 102.06 (18) | C15—C14—C13 | 104.84 (18) |
C3—C4—H4A | 111.4 | C15—C14—H14 | 127.6 |
C5—C4—H4A | 111.4 | C13—C14—H14 | 127.6 |
C3—C4—H4B | 111.4 | N11—C15—C14 | 106.29 (18) |
C5—C4—H4B | 111.4 | N11—C15—C51 | 121.66 (18) |
H4A—C4—H4B | 109.2 | C14—C15—C51 | 132.04 (19) |
O1—C5—C4 | 107.46 (18) | C56—C51—C52 | 118.0 (2) |
O1—C5—H5A | 110.2 | C56—C51—C15 | 121.50 (19) |
C4—C5—H5A | 110.2 | C52—C51—C15 | 120.51 (19) |
O1—C5—H5B | 110.2 | C53—C52—C51 | 120.7 (2) |
C4—C5—H5B | 110.2 | C53—C52—H52 | 119.6 |
H5A—C5—H5B | 108.5 | C51—C52—H52 | 119.6 |
N7—C6—C3 | 119.55 (18) | C54—C53—C52 | 120.5 (2) |
N7—C6—C61 | 118.72 (18) | C54—C53—H53 | 119.7 |
C3—C6—C61 | 121.72 (19) | C52—C53—H53 | 119.7 |
C6—C61—H61A | 109.5 | C53—C54—C55 | 119.4 (2) |
C6—C61—H61B | 109.5 | C53—C54—H54 | 120.3 |
H61A—C61—H61B | 109.5 | C55—C54—H54 | 120.3 |
C6—C61—H61C | 109.5 | C54—C55—C56 | 120.2 (2) |
H61A—C61—H61C | 109.5 | C54—C55—H55 | 119.9 |
H61B—C61—H61C | 109.5 | C56—C55—H55 | 119.9 |
C6—N7—C13 | 131.88 (17) | C55—C56—C51 | 121.1 (2) |
C6—N7—H7 | 114.1 | C55—C56—H56 | 119.4 |
C13—N7—H7 | 114.1 | C51—C56—H56 | 119.4 |
| | | |
C5—O1—C2—O2 | −177.4 (2) | C6—N7—C13—C14 | 6.1 (4) |
C5—O1—C2—C3 | 2.7 (2) | N12—C13—C14—C15 | −0.1 (2) |
O2—C2—C3—C6 | −2.8 (4) | N7—C13—C14—C15 | 178.4 (2) |
O1—C2—C3—C6 | 177.02 (19) | N12—N11—C15—C14 | 0.3 (2) |
O2—C2—C3—C4 | 178.5 (2) | N12—N11—C15—C51 | −178.84 (17) |
O1—C2—C3—C4 | −1.6 (2) | C13—C14—C15—N11 | −0.1 (2) |
C6—C3—C4—C5 | −178.6 (2) | C13—C14—C15—C51 | 178.9 (2) |
C2—C3—C4—C5 | −0.1 (2) | N11—C15—C51—C56 | −16.1 (3) |
C2—O1—C5—C4 | −2.7 (2) | C14—C15—C51—C56 | 165.1 (2) |
C3—C4—C5—O1 | 1.6 (2) | N11—C15—C51—C52 | 162.8 (2) |
C2—C3—C6—N7 | 1.8 (3) | C14—C15—C51—C52 | −16.1 (3) |
C4—C3—C6—N7 | −179.9 (2) | C56—C51—C52—C53 | 1.9 (3) |
C2—C3—C6—C61 | −177.1 (2) | C15—C51—C52—C53 | −177.0 (2) |
C4—C3—C6—C61 | 1.2 (3) | C51—C52—C53—C54 | −1.0 (4) |
C3—C6—N7—C13 | 179.6 (2) | C52—C53—C54—C55 | −0.4 (4) |
C61—C6—N7—C13 | −1.5 (3) | C53—C54—C55—C56 | 0.7 (4) |
C15—N11—N12—C13 | −0.3 (2) | C54—C55—C56—C51 | 0.3 (3) |
N11—N12—C13—N7 | −178.57 (16) | C52—C51—C56—C55 | −1.6 (3) |
N11—N12—C13—C14 | 0.3 (2) | C15—C51—C56—C55 | 177.4 (2) |
C6—N7—C13—N12 | −175.4 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O2 | 0.88 | 1.97 | 2.709 (2) | 141 |
N11—H11···O2i | 0.88 | 1.97 | 2.784 (2) | 154 |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
(II) (3
Z)-3-{1-[(5-methyl-1
H-pyrazol-3-yl)amino]ethylidene}-4,5-
dihydrofuran-2(3
H)-one–6-(2-hydroxyethyl)-2,5-
dimethylpyrazolo[1,5-
a]pyrimidin-7(4
H)-one (1/1)
top
Crystal data top
C10H13N3O2·C10H13N3O2 | Z = 2 |
Mr = 414.46 | F(000) = 440 |
Triclinic, P1 | Dx = 1.401 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0402 (11) Å | Cell parameters from 3857 reflections |
b = 8.2025 (17) Å | θ = 2.7–26.1° |
c = 15.348 (3) Å | µ = 0.10 mm−1 |
α = 91.999 (14)° | T = 120 K |
β = 99.785 (12)° | Block, colourless |
γ = 99.172 (15)° | 0.38 × 0.23 × 0.16 mm |
V = 982.7 (3) Å3 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 3857 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2739 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
Detector resolution: 9.091 pixels mm-1 | θmax = 26.1°, θmin = 2.7° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −10→10 |
Tmin = 0.963, Tmax = 0.984 | l = −18→18 |
21688 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0572P)2 + 0.4084P] where P = (Fo2 + 2Fc2)/3 |
3857 reflections | (Δ/σ)max = 0.001 |
275 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
C10H13N3O2·C10H13N3O2 | γ = 99.172 (15)° |
Mr = 414.46 | V = 982.7 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0402 (11) Å | Mo Kα radiation |
b = 8.2025 (17) Å | µ = 0.10 mm−1 |
c = 15.348 (3) Å | T = 120 K |
α = 91.999 (14)° | 0.38 × 0.23 × 0.16 mm |
β = 99.785 (12)° | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 3857 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2739 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.984 | Rint = 0.044 |
21688 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.23 e Å−3 |
3857 reflections | Δρmin = −0.33 e Å−3 |
275 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N11 | 0.9005 (2) | 0.1184 (2) | 0.36250 (10) | 0.0249 (4) | |
C12 | 1.0571 (3) | 0.0890 (2) | 0.36009 (13) | 0.0244 (4) | |
C13 | 1.1747 (3) | 0.1491 (2) | 0.43683 (13) | 0.0249 (4) | |
H13 | 1.2929 | 0.1414 | 0.4499 | 0.030* | |
C13A | 1.0813 (2) | 0.2210 (2) | 0.48849 (12) | 0.0217 (4) | |
N14 | 1.1170 (2) | 0.30378 (19) | 0.56890 (10) | 0.0231 (4) | |
H14 | 1.2225 | 0.3127 | 0.5982 | 0.028* | |
C15 | 0.9955 (2) | 0.3690 (2) | 0.60250 (12) | 0.0223 (4) | |
C16 | 0.8319 (2) | 0.3509 (2) | 0.55720 (13) | 0.0237 (4) | |
C17 | 0.7841 (2) | 0.2612 (2) | 0.47338 (13) | 0.0236 (4) | |
N17A | 0.9174 (2) | 0.20143 (19) | 0.44295 (10) | 0.0217 (4) | |
C121 | 1.0913 (3) | 0.0033 (3) | 0.28026 (13) | 0.0310 (5) | |
H12A | 0.9833 | −0.0341 | 0.2393 | 0.046* | |
H12B | 1.1455 | −0.0924 | 0.2974 | 0.046* | |
H12C | 1.1679 | 0.0796 | 0.2512 | 0.046* | |
C151 | 1.0544 (3) | 0.4591 (3) | 0.69134 (13) | 0.0275 (5) | |
H15A | 1.1753 | 0.4528 | 0.7120 | 0.041* | |
H15B | 0.9859 | 0.4085 | 0.7334 | 0.041* | |
H15C | 1.0407 | 0.5753 | 0.6869 | 0.041* | |
C161 | 0.6935 (2) | 0.4238 (3) | 0.59071 (13) | 0.0256 (5) | |
H16A | 0.6182 | 0.4613 | 0.5401 | 0.031* | |
H16B | 0.7460 | 0.5218 | 0.6313 | 0.031* | |
C162 | 0.5871 (2) | 0.3018 (3) | 0.63883 (14) | 0.0258 (5) | |
H16C | 0.5456 | 0.1986 | 0.6007 | 0.031* | |
H16D | 0.6597 | 0.2742 | 0.6933 | 0.031* | |
O16 | 0.44467 (16) | 0.36457 (17) | 0.66201 (9) | 0.0270 (3) | |
H16 | 0.4797 | 0.4536 | 0.6957 | 0.041* | |
O17 | 0.64014 (17) | 0.23687 (19) | 0.42772 (9) | 0.0319 (4) | |
O21 | 0.92873 (18) | 0.16357 (17) | 0.97582 (9) | 0.0295 (3) | |
C22 | 0.8563 (2) | 0.2870 (2) | 0.93740 (14) | 0.0243 (4) | |
C23 | 0.8047 (2) | 0.3886 (2) | 1.00196 (13) | 0.0235 (4) | |
C24 | 0.8599 (3) | 0.3285 (3) | 1.09152 (13) | 0.0264 (5) | |
H24A | 0.7641 | 0.3109 | 1.1249 | 0.032* | |
H24B | 0.9563 | 0.4070 | 1.1266 | 0.032* | |
C25 | 0.9152 (3) | 0.1659 (3) | 1.06832 (14) | 0.0311 (5) | |
H25A | 1.0269 | 0.1577 | 1.1051 | 0.037* | |
H25B | 0.8296 | 0.0714 | 1.0793 | 0.037* | |
O22 | 0.84505 (18) | 0.29913 (17) | 0.85764 (9) | 0.0285 (3) | |
C26 | 0.7314 (2) | 0.5236 (2) | 0.98163 (13) | 0.0233 (4) | |
C261 | 0.6909 (3) | 0.6317 (3) | 1.05154 (13) | 0.0282 (5) | |
H26A | 0.6896 | 0.5724 | 1.1058 | 0.042* | |
H26B | 0.5783 | 0.6625 | 1.0318 | 0.042* | |
H26C | 0.7780 | 0.7318 | 1.0633 | 0.042* | |
N27 | 0.6965 (2) | 0.5611 (2) | 0.89575 (11) | 0.0253 (4) | |
H27 | 0.7340 | 0.4987 | 0.8582 | 0.030* | |
N31 | 0.4713 (2) | 0.7896 (2) | 0.75191 (11) | 0.0263 (4) | |
H31 | 0.4145 | 0.8030 | 0.6991 | 0.032* | |
N32 | 0.5371 (2) | 0.6517 (2) | 0.77339 (11) | 0.0266 (4) | |
C33 | 0.6110 (2) | 0.6823 (2) | 0.85791 (13) | 0.0236 (4) | |
C34 | 0.5931 (2) | 0.8381 (2) | 0.88960 (13) | 0.0248 (4) | |
H34 | 0.6351 | 0.8887 | 0.9475 | 0.030* | |
C35 | 0.5016 (2) | 0.9032 (2) | 0.81927 (13) | 0.0247 (4) | |
C351 | 0.4410 (3) | 1.0634 (3) | 0.81029 (15) | 0.0313 (5) | |
H35A | 0.3677 | 1.0630 | 0.7523 | 0.047* | |
H35B | 0.5395 | 1.1528 | 0.8155 | 0.047* | |
H35C | 0.3754 | 1.0808 | 0.8571 | 0.047* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N11 | 0.0298 (9) | 0.0260 (9) | 0.0201 (9) | 0.0066 (7) | 0.0064 (7) | −0.0006 (7) |
C12 | 0.0301 (11) | 0.0209 (10) | 0.0251 (11) | 0.0079 (9) | 0.0088 (9) | 0.0058 (8) |
C13 | 0.0239 (10) | 0.0260 (11) | 0.0264 (11) | 0.0074 (9) | 0.0056 (8) | 0.0033 (9) |
C13A | 0.0234 (10) | 0.0214 (10) | 0.0210 (10) | 0.0045 (8) | 0.0044 (8) | 0.0040 (8) |
N14 | 0.0208 (8) | 0.0261 (9) | 0.0230 (9) | 0.0065 (7) | 0.0034 (7) | 0.0021 (7) |
C15 | 0.0270 (10) | 0.0193 (10) | 0.0216 (10) | 0.0037 (8) | 0.0065 (8) | 0.0049 (8) |
C16 | 0.0272 (10) | 0.0242 (10) | 0.0216 (10) | 0.0060 (9) | 0.0076 (8) | 0.0047 (8) |
C17 | 0.0235 (10) | 0.0273 (11) | 0.0220 (10) | 0.0075 (9) | 0.0060 (8) | 0.0064 (8) |
N17A | 0.0244 (9) | 0.0236 (9) | 0.0184 (8) | 0.0063 (7) | 0.0051 (7) | 0.0008 (7) |
C121 | 0.0378 (12) | 0.0337 (12) | 0.0251 (11) | 0.0129 (10) | 0.0096 (9) | 0.0006 (9) |
C151 | 0.0283 (11) | 0.0294 (11) | 0.0249 (11) | 0.0037 (9) | 0.0067 (9) | −0.0010 (9) |
C161 | 0.0261 (10) | 0.0275 (11) | 0.0254 (11) | 0.0098 (9) | 0.0056 (8) | 0.0025 (9) |
C162 | 0.0223 (10) | 0.0280 (11) | 0.0297 (11) | 0.0090 (9) | 0.0078 (8) | 0.0019 (9) |
O16 | 0.0202 (7) | 0.0296 (8) | 0.0314 (8) | 0.0057 (6) | 0.0055 (6) | −0.0070 (6) |
O17 | 0.0239 (8) | 0.0478 (10) | 0.0245 (8) | 0.0100 (7) | 0.0021 (6) | 0.0005 (7) |
O21 | 0.0348 (8) | 0.0268 (8) | 0.0284 (8) | 0.0089 (6) | 0.0062 (6) | 0.0028 (6) |
C22 | 0.0195 (10) | 0.0227 (11) | 0.0292 (11) | 0.0003 (8) | 0.0029 (8) | 0.0019 (9) |
C23 | 0.0202 (10) | 0.0255 (11) | 0.0232 (10) | 0.0003 (8) | 0.0027 (8) | −0.0006 (8) |
C24 | 0.0248 (10) | 0.0297 (11) | 0.0238 (11) | 0.0016 (9) | 0.0041 (8) | 0.0035 (9) |
C25 | 0.0344 (12) | 0.0301 (12) | 0.0275 (11) | 0.0012 (9) | 0.0049 (9) | 0.0055 (9) |
O22 | 0.0341 (8) | 0.0291 (8) | 0.0228 (8) | 0.0063 (6) | 0.0059 (6) | −0.0011 (6) |
C26 | 0.0169 (9) | 0.0276 (11) | 0.0237 (10) | −0.0009 (8) | 0.0034 (8) | −0.0010 (8) |
C261 | 0.0277 (11) | 0.0315 (12) | 0.0258 (11) | 0.0075 (9) | 0.0040 (9) | −0.0002 (9) |
N27 | 0.0275 (9) | 0.0269 (9) | 0.0227 (9) | 0.0077 (7) | 0.0052 (7) | −0.0001 (7) |
N31 | 0.0276 (9) | 0.0271 (9) | 0.0237 (9) | 0.0071 (8) | 0.0010 (7) | 0.0014 (7) |
N32 | 0.0283 (9) | 0.0268 (9) | 0.0249 (9) | 0.0083 (8) | 0.0026 (7) | 0.0002 (7) |
C33 | 0.0193 (10) | 0.0275 (11) | 0.0238 (10) | 0.0023 (8) | 0.0046 (8) | 0.0018 (8) |
C34 | 0.0236 (10) | 0.0252 (11) | 0.0239 (11) | 0.0009 (8) | 0.0035 (8) | −0.0023 (8) |
C35 | 0.0222 (10) | 0.0240 (11) | 0.0278 (11) | −0.0006 (8) | 0.0088 (8) | 0.0009 (8) |
C351 | 0.0322 (12) | 0.0261 (11) | 0.0360 (12) | 0.0032 (9) | 0.0088 (10) | 0.0024 (9) |
Geometric parameters (Å, º) top
N11—C12 | 1.325 (2) | O21—C22 | 1.351 (2) |
C12—C13 | 1.399 (3) | O21—C25 | 1.442 (2) |
C12—C121 | 1.479 (3) | C22—O22 | 1.221 (2) |
C13—C13A | 1.361 (3) | C22—C23 | 1.429 (3) |
C13—H13 | 0.9500 | C23—C26 | 1.356 (3) |
C13A—N14 | 1.351 (2) | C23—C24 | 1.496 (3) |
N14—C15 | 1.351 (2) | C24—C25 | 1.521 (3) |
N14—H14 | 0.8800 | C24—H24A | 0.9900 |
C15—C16 | 1.362 (3) | C24—H24B | 0.9900 |
C15—C151 | 1.493 (3) | C25—H25A | 0.9900 |
C16—C17 | 1.422 (3) | C25—H25B | 0.9900 |
C16—C161 | 1.499 (3) | C26—N27 | 1.357 (2) |
C17—N17A | 1.389 (2) | C26—C261 | 1.479 (3) |
N17A—N11 | 1.364 (2) | C261—H26A | 0.9800 |
C13A—N17A | 1.365 (2) | C261—H26B | 0.9800 |
C17—O17 | 1.229 (2) | C261—H26C | 0.9800 |
C121—H12A | 0.9800 | N27—C33 | 1.386 (2) |
C121—H12B | 0.9800 | N27—H27 | 0.8800 |
C121—H12C | 0.9800 | N31—N32 | 1.351 (2) |
C151—H15A | 0.9800 | N31—H31 | 0.8800 |
C151—H15B | 0.9800 | N32—C33 | 1.329 (3) |
C151—H15C | 0.9800 | C33—C34 | 1.389 (3) |
C161—C162 | 1.508 (3) | C34—C35 | 1.374 (3) |
C161—H16A | 0.9900 | C35—N31 | 1.331 (3) |
C161—H16B | 0.9900 | C34—H34 | 0.9500 |
C162—O16 | 1.420 (2) | C35—C351 | 1.476 (3) |
C162—H16C | 0.9900 | C351—H35A | 0.9800 |
C162—H16D | 0.9900 | C351—H35B | 0.9800 |
O16—H16 | 0.8600 | C351—H35C | 0.9800 |
| | | |
C12—N11—N17A | 103.52 (16) | C22—O21—C25 | 109.65 (15) |
N11—C12—C13 | 113.19 (17) | O22—C22—O21 | 119.58 (18) |
N11—C12—C121 | 119.53 (18) | O22—C22—C23 | 129.65 (18) |
C13—C12—C121 | 127.27 (18) | O21—C22—C23 | 110.76 (17) |
C13A—C13—C12 | 104.29 (17) | C26—C23—C22 | 123.07 (18) |
C13A—C13—H13 | 127.9 | C26—C23—C24 | 128.30 (18) |
C12—C13—H13 | 127.9 | C22—C23—C24 | 108.40 (17) |
N14—C13A—C13 | 134.67 (18) | C23—C24—C25 | 102.06 (16) |
N14—C13A—N17A | 118.01 (16) | C23—C24—H24A | 111.4 |
C13—C13A—N17A | 107.31 (17) | C25—C24—H24A | 111.4 |
C13A—N14—C15 | 121.18 (16) | C23—C24—H24B | 111.4 |
C13A—N14—H14 | 117.0 | C25—C24—H24B | 111.4 |
C15—N14—H14 | 121.8 | H24A—C24—H24B | 109.2 |
N14—C15—C16 | 121.14 (18) | O21—C25—C24 | 107.28 (16) |
N14—C15—C151 | 115.15 (17) | O21—C25—H25A | 110.3 |
C16—C15—C151 | 123.71 (18) | C24—C25—H25A | 110.3 |
C15—C16—C17 | 120.70 (18) | O21—C25—H25B | 110.3 |
C15—C16—C161 | 123.19 (18) | C24—C25—H25B | 110.3 |
C17—C16—C161 | 116.11 (17) | H25A—C25—H25B | 108.5 |
O17—C17—N17A | 119.91 (18) | C23—C26—N27 | 119.41 (18) |
O17—C17—C16 | 125.70 (18) | C23—C26—C261 | 121.15 (18) |
N17A—C17—C16 | 114.38 (17) | N27—C26—C261 | 119.43 (17) |
N11—N17A—C13A | 111.70 (15) | C26—C261—H26A | 109.5 |
N11—N17A—C17 | 123.74 (16) | C26—C261—H26B | 109.5 |
C13A—N17A—C17 | 124.54 (16) | H26A—C261—H26B | 109.5 |
C12—C121—H12A | 109.5 | C26—C261—H26C | 109.5 |
C12—C121—H12B | 109.5 | H26A—C261—H26C | 109.5 |
H12A—C121—H12B | 109.5 | H26B—C261—H26C | 109.5 |
C12—C121—H12C | 109.5 | C26—N27—C33 | 130.19 (17) |
H12A—C121—H12C | 109.5 | C26—N27—H27 | 114.9 |
H12B—C121—H12C | 109.5 | C33—N27—H27 | 114.9 |
C15—C151—H15A | 109.5 | C35—N31—N32 | 112.72 (16) |
C15—C151—H15B | 109.5 | C35—N31—H31 | 123.6 |
H15A—C151—H15B | 109.5 | N32—N31—H31 | 123.6 |
C15—C151—H15C | 109.5 | C33—N32—N31 | 104.27 (16) |
H15A—C151—H15C | 109.5 | N32—C33—N27 | 116.05 (18) |
H15B—C151—H15C | 109.5 | N32—C33—C34 | 111.33 (18) |
C16—C161—C162 | 112.21 (16) | N27—C33—C34 | 132.52 (18) |
C16—C161—H16A | 109.2 | C35—C34—C33 | 105.15 (18) |
C162—C161—H16A | 109.2 | C35—C34—H34 | 127.4 |
C16—C161—H16B | 109.2 | C33—C34—H34 | 127.4 |
C162—C161—H16B | 109.2 | N31—C35—C34 | 106.53 (17) |
H16A—C161—H16B | 107.9 | N31—C35—C351 | 121.70 (18) |
O16—C162—C161 | 112.20 (16) | C34—C35—C351 | 131.77 (19) |
O16—C162—H16C | 109.2 | C35—C351—H35A | 109.5 |
C161—C162—H16C | 109.2 | C35—C351—H35B | 109.5 |
O16—C162—H16D | 109.2 | H35A—C351—H35B | 109.5 |
C161—C162—H16D | 109.2 | C35—C351—H35C | 109.5 |
H16C—C162—H16D | 107.9 | H35A—C351—H35C | 109.5 |
C162—O16—H16 | 109.8 | H35B—C351—H35C | 109.5 |
| | | |
N17A—N11—C12—C13 | 0.5 (2) | C17—C16—C161—C162 | 85.3 (2) |
N17A—N11—C12—C121 | −178.29 (17) | C16—C161—C162—O16 | −173.50 (16) |
N11—C12—C13—C13A | −0.6 (2) | C25—O21—C22—O22 | −175.33 (18) |
C121—C12—C13—C13A | 178.13 (19) | C25—O21—C22—C23 | 5.5 (2) |
C12—C13—C13A—N14 | −178.4 (2) | O22—C22—C23—C26 | −0.5 (3) |
C12—C13—C13A—N17A | 0.3 (2) | O21—C22—C23—C26 | 178.64 (18) |
C13—C13A—N14—C15 | 177.0 (2) | O22—C22—C23—C24 | −175.4 (2) |
N17A—C13A—N14—C15 | −1.7 (3) | O21—C22—C23—C24 | 3.7 (2) |
C13A—N14—C15—C16 | 1.3 (3) | C26—C23—C24—C25 | 174.9 (2) |
C13A—N14—C15—C151 | −179.10 (17) | C22—C23—C24—C25 | −10.4 (2) |
N14—C15—C16—C17 | 0.6 (3) | C22—O21—C25—C24 | −12.2 (2) |
C151—C15—C16—C17 | −178.99 (18) | C23—C24—C25—O21 | 13.5 (2) |
N14—C15—C16—C161 | −178.69 (17) | C22—C23—C26—N27 | 3.5 (3) |
C151—C15—C16—C161 | 1.7 (3) | C24—C23—C26—N27 | 177.42 (18) |
C15—C16—C17—O17 | 179.45 (19) | C22—C23—C26—C261 | −175.78 (18) |
C161—C16—C17—O17 | −1.2 (3) | C24—C23—C26—C261 | −1.8 (3) |
C15—C16—C17—N17A | −1.9 (3) | C23—C26—N27—C33 | 174.17 (19) |
C161—C16—C17—N17A | 177.45 (16) | C261—C26—N27—C33 | −6.5 (3) |
C12—N11—N17A—C13A | −0.3 (2) | C35—N31—N32—C33 | 0.1 (2) |
C12—N11—N17A—C17 | 178.48 (17) | N31—N32—C33—N27 | −177.14 (16) |
N14—C13A—N17A—N11 | 178.95 (16) | N31—N32—C33—C34 | −0.3 (2) |
C13—C13A—N17A—N11 | −0.1 (2) | C26—N27—C33—N32 | −154.14 (19) |
N14—C13A—N17A—C17 | 0.2 (3) | C26—N27—C33—C34 | 29.9 (3) |
C13—C13A—N17A—C17 | −178.79 (17) | N32—C33—C34—C35 | 0.4 (2) |
O17—C17—N17A—N11 | 1.7 (3) | N27—C33—C34—C35 | 176.6 (2) |
C16—C17—N17A—N11 | −177.07 (16) | N32—N31—C35—C34 | 0.2 (2) |
O17—C17—N17A—C13A | −179.74 (18) | N32—N31—C35—C351 | −179.95 (17) |
C16—C17—N17A—C13A | 1.5 (3) | C33—C34—C35—N31 | −0.3 (2) |
C15—C16—C161—C162 | −95.4 (2) | C33—C34—C35—C351 | 179.8 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O16—H16···N32 | 0.86 | 1.93 | 2.784 (2) | 175 |
N27—H27···O22 | 0.88 | 1.99 | 2.712 (2) | 139 |
N14—H14···O16i | 0.88 | 1.86 | 2.736 (2) | 172 |
N31—H31···O17ii | 0.88 | 1.93 | 2.740 (2) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C15H15N3O2 | C10H13N3O2·C10H13N3O2 |
Mr | 269.30 | 414.46 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 10.4969 (17), 9.8550 (9), 12.6739 (16) | 8.0402 (11), 8.2025 (17), 15.348 (3) |
α, β, γ (°) | 90, 99.883 (9), 90 | 91.999 (14), 99.785 (12), 99.172 (15) |
V (Å3) | 1291.6 (3) | 982.7 (3) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.39 × 0.25 × 0.14 | 0.38 × 0.23 × 0.16 |
|
Data collection |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.964, 0.987 | 0.963, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19109, 2536, 1704 | 21688, 3857, 2739 |
Rint | 0.056 | 0.044 |
(sin θ/λ)max (Å−1) | 0.618 | 0.618 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.128, 1.07 | 0.046, 0.123, 1.07 |
No. of reflections | 2536 | 3857 |
No. of parameters | 182 | 275 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.26 | 0.23, −0.33 |
Selected bond lengths (Å) for (I) topC2—O2 | 1.232 (3) | N11—N12 | 1.341 (2) |
C2—C3 | 1.413 (3) | N12—C13 | 1.324 (3) |
C3—C6 | 1.369 (3) | C13—C14 | 1.394 (3) |
C6—N7 | 1.338 (3) | C14—C15 | 1.371 (3) |
N7—C13 | 1.380 (3) | C15—N11 | 1.340 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O2 | 0.88 | 1.97 | 2.709 (2) | 141 |
N11—H11···O2i | 0.88 | 1.97 | 2.784 (2) | 154 |
Symmetry code: (i) −x+1, y−1/2, −z+3/2. |
Selected bond lengths (Å) for (II) topN11—C12 | 1.325 (2) | C22—O22 | 1.221 (2) |
C12—C13 | 1.399 (3) | C22—C23 | 1.429 (3) |
C13—C13A | 1.361 (3) | C23—C26 | 1.356 (3) |
C13A—N14 | 1.351 (2) | C26—N27 | 1.357 (2) |
N14—C15 | 1.351 (2) | N27—C33 | 1.386 (2) |
C15—C16 | 1.362 (3) | N31—N32 | 1.351 (2) |
C16—C17 | 1.422 (3) | N32—C33 | 1.329 (3) |
C17—N17A | 1.389 (2) | C33—C34 | 1.389 (3) |
N17A—N11 | 1.364 (2) | C34—C35 | 1.374 (3) |
C13A—N17A | 1.365 (2) | C35—N31 | 1.331 (3) |
C17—O17 | 1.229 (2) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O16—H16···N32 | 0.86 | 1.93 | 2.784 (2) | 175 |
N27—H27···O22 | 0.88 | 1.99 | 2.712 (2) | 139 |
N14—H14···O16i | 0.88 | 1.86 | 2.736 (2) | 172 |
N31—H31···O17ii | 0.88 | 1.93 | 2.740 (2) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1. |
The condensation reactions between substituted aminopyrazoles and dicarbonyl compounds provide a potentially very versatile route for the synthesis of new fused heterocyclic compounds with precisely defined regiochemistry (Portilla et al., 2008), and fused pyrazole derivatives are potentially valuable for drug and pesticide applications (Elguero, 1984,1996). Here, we report the structures of the two title compounds, (I) and (II) (Figs. 1 and 2), which result from the condensation reactions between 2-acetyl-4-butyrolactone and two 5-amino-1H-pyrazoles carrying different hydrocarbyl substituents at position 3 (see reaction scheme).
The reaction between equimolar quantities of the lactone and 5-amino-3-phenyl-1H-pyrazole provides (3Z)-3-{1-[(5-phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one, (I), which apparently results from a simple condensation involving only the 2-acetyl substituent in the lactone reagent, to form a product in which the lactone ring survives intact (see reaction scheme). By contrast, the corresponding reaction between the same lactone reagent and 5-amino-3-methyl-1H-pyrazole proceeds along two different reaction pathways. One of these pathways is entirely analogous to that which forms compound (I), leading to the product denoted (A) in the reaction scheme. The second pathway involves both carbonyl functions in the lactone component, which itself undergoes ring opening, so that this pathway is indeed a cyclocondensation reaction giving a fused heterocyclic system in the product denoted (B) in the reaction scheme. The product (II) which crystallizes from the reaction between 5-amino-3-methyl-1H-pyrazole and the lactone is a 1:1 hydrogen-bonded adduct formed by the primary products (A) and (B), which are, in fact, isomeric with one another despite their very different constitutions.
Within the molecule of compound (I), the C2—O2 and C3—C6 bonds (Table 1) are both long for their types [mean values (Allen et al., 1987) 1.201 and 1.340 Å, respectively, upper quartile values 1.206 and 1.348 Å, respectively] and the C2—C3 bond is short for its type (mean value 1.464 Å, lower quartile value 1.453 Å), while the N7—C6 bond is significantly shorter than the N7—C13 bond. These values provide evidence for electronic polarization in the vinylogous amide fragment of (I), indicating that the form (Ia) is a significant contributor to the overall electronic structure. A similar pattern of distances is found in component (A) of compound (II) (Table 3), but the deviations from the expected values are all somewhat smaller in (II), indicative of a lesser degree of electronic polarization in this component. A similar pattern is found also in the vinylogous amide fragment in component (B) of (II), indicating a contribution from the form (IIa). Consistent with this observation concerning component (B) of (II), the C12—C13 and C13—C13A bonds in (II) differ in length by almost 0.04 Å, while the corresponding differences in (I) and in component (A) of (II) are no more than half of this value. In addition, the C13A—N17A bond in (II) is rather longer than the corresponding bonds in the unfused pyrazole rings of both (I) and (II), indicating stronger bond fixation in the fused pyrazole ring than in either of the unfused pyrazole rings.
The molecules of (I) contain an intramolecular N—H···O hydrogen bond (Table 2, Fig. 1) forming an S(6) motif (Bernstein et al., 1995), and molecules related by the 21 screw axis along (1/2, y, 3/4) are linked into chains by a second N—H···O hydrogen bond to form an S(6)C(9)C12(7) chain of rings running parallel to the [010] direction (Fig. 3). Two chains of this type, related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent chains. In particular, there are neither C—H···π(arene) hydrogen bonds nor aromatic π–π stacking interactions in the structure of (I).
Within the selected asymmetric unit of (II) (Fig. 2), the two components are linked by a fairly short and almost linear O—H···N hydrogen bond (Table 4), and there is also an intramolecular N—H···O hydrogen bond, analogous to that in (I). Two further N—H···O hydrogen bonds then link the bimolecular aggregates into a ribbon containing two types of centrosymmetric ring and running parallel to the [100] direction. Within the ribbon, R44(20) rings centred at (n + 1/2, 1/2, 1/2), where n represents an integer, alternate with R66(22) rings centred at (n, 1/2, 1/2) where n again represents an integer (Fig. 4).