There are both weak and strong hydrogen bonds in the title compound, C
19H
13N
3O
2, The strong bond is an O—H
O intramolecular bond which forms an
S(6) ring motif, whereas the weak C—H
N bond forms a
C(9) motif forming chains which run parallel to the
b axis.
Supporting information
CCDC reference: 159764
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.002 Å
- R factor = 0.046
- wR factor = 0.136
- Data-to-parameter ratio = 14.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 27.53
From the CIF: _reflns_number_total 3032
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 3302
Completeness (_total/calc) 91.82%
Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
An equimolar mixture of 3-formylchromone and 5-amino-3-phenylpyrazol in ethanol
was heated to reflux for 10 min. The title compound precipitated, was
separated by filtration and recrystallized from DMF, affording crystals
suitable for X-ray diffraction. M.p. 290–291 K, yield: 86%.
H atoms were treated as riding atoms with C—H distances in the range
0.90–0.95 Å and an O—H distance of 1.02 Å.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
6-(2-hydroxybenzoyl)-2-phenylpyrazolo[1,5-
a]pyrimidine
top
Crystal data top
C19H13N3O2 | Dx = 1.463 Mg m−3 |
Mr = 315.32 | Melting point: 590 K |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 5.6606 (2) Å | Cell parameters from 9215 reflections |
b = 11.7048 (5) Å | θ = 1.0–27.5° |
c = 21.6815 (10) Å | µ = 0.10 mm−1 |
β = 94.7970 (15)° | T = 150 K |
V = 1431.50 (10) Å3 | Needle, yellow |
Z = 4 | 0.44 × 0.10 × 0.08 mm |
F(000) = 656 | |
Data collection top
KappaCCD diffractometer | 3032 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2168 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ϕ and ω scans with κ offsets | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −6→6 |
Tmin = 0.958, Tmax = 0.992 | k = −14→15 |
12852 measured reflections | l = −28→28 |
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) = 0.136 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0846P)2] where P = (Fo2 + 2Fc2)/3 |
3032 reflections | (Δ/σ)max = 0.002 |
217 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C19H13N3O2 | V = 1431.50 (10) Å3 |
Mr = 315.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.6606 (2) Å | µ = 0.10 mm−1 |
b = 11.7048 (5) Å | T = 150 K |
c = 21.6815 (10) Å | 0.44 × 0.10 × 0.08 mm |
β = 94.7970 (15)° | |
Data collection top
KappaCCD diffractometer | 3032 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2168 reflections with I > 2σ(I) |
Tmin = 0.958, Tmax = 0.992 | Rint = 0.051 |
12852 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.26 e Å−3 |
3032 reflections | Δρmin = −0.27 e Å−3 |
217 parameters | |
Special details top
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm
(Fox & Holmes, 1966) which effectively corrects for absorption effects. High
redundancy data were used in the scaling program hence the 'multi-scan' code
word was used. no transmission coefficients are available from the program
(only scale factors for each frame). The scale factors in the experimental
table are calculated from the 'size' command in the SHELXL97 input
file. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.8503 (2) | −0.07565 (12) | 0.40296 (6) | 0.0266 (3) | |
C2 | 1.0571 (3) | −0.09435 (14) | 0.43675 (7) | 0.0259 (4) | |
C21 | 1.0833 (3) | −0.19334 (14) | 0.47804 (7) | 0.0263 (4) | |
C22 | 0.9007 (3) | −0.27172 (15) | 0.48181 (7) | 0.0298 (4) | |
C23 | 0.9261 (3) | −0.36321 (16) | 0.52165 (8) | 0.0335 (4) | |
C24 | 1.1334 (3) | −0.37829 (16) | 0.55898 (8) | 0.0342 (4) | |
C25 | 1.3157 (3) | −0.30119 (16) | 0.55611 (8) | 0.0347 (4) | |
C26 | 1.2923 (3) | −0.20985 (16) | 0.51590 (7) | 0.0317 (4) | |
C3 | 1.2266 (3) | −0.01047 (14) | 0.42730 (7) | 0.0265 (4) | |
C3A | 1.1175 (3) | 0.06478 (14) | 0.38585 (7) | 0.0245 (4) | |
N4 | 1.1882 (2) | 0.16338 (12) | 0.36037 (6) | 0.0290 (3) | |
C5 | 1.0311 (3) | 0.21521 (15) | 0.32270 (7) | 0.0276 (4) | |
C6 | 0.7988 (3) | 0.17334 (14) | 0.30481 (7) | 0.0260 (4) | |
C67 | 0.6385 (3) | 0.24735 (15) | 0.26531 (7) | 0.0273 (4) | |
O61 | 0.6629 (2) | 0.35226 (10) | 0.27246 (6) | 0.0374 (3) | |
C61 | 0.4552 (3) | 0.20198 (14) | 0.22000 (7) | 0.0252 (4) | |
C62 | 0.2709 (3) | 0.27456 (14) | 0.19630 (7) | 0.0256 (4) | |
O62 | 0.2589 (2) | 0.38546 (10) | 0.21305 (5) | 0.0320 (3) | |
C63 | 0.0882 (3) | 0.23229 (15) | 0.15627 (7) | 0.0317 (4) | |
C64 | 0.0907 (3) | 0.12000 (16) | 0.13801 (8) | 0.0348 (4) | |
C65 | 0.2743 (3) | 0.04757 (16) | 0.15900 (7) | 0.0326 (4) | |
C66 | 0.4545 (3) | 0.08862 (15) | 0.19963 (7) | 0.0288 (4) | |
C7 | 0.7311 (3) | 0.07319 (14) | 0.33052 (7) | 0.0251 (4) | |
N7A | 0.8902 (2) | 0.02183 (12) | 0.37149 (6) | 0.0240 (3) | |
H22 | 0.7566 | −0.2620 | 0.4566 | 0.036* | |
H23 | 0.8001 | −0.4164 | 0.5235 | 0.040* | |
H24 | 1.1501 | −0.4415 | 0.5865 | 0.041* | |
H25 | 1.4583 | −0.3109 | 0.5819 | 0.042* | |
H26 | 1.4199 | −0.1576 | 0.5139 | 0.038* | |
H3 | 1.3845 | −0.0066 | 0.4458 | 0.032* | |
H5 | 1.0749 | 0.2863 | 0.3059 | 0.033* | |
H62 | 0.4183 | 0.4016 | 0.2377 | 0.038* | |
H63 | −0.0386 | 0.2809 | 0.1415 | 0.038* | |
H64 | −0.0352 | 0.0914 | 0.1106 | 0.042* | |
H65 | 0.2757 | −0.0296 | 0.1455 | 0.039* | |
H66 | 0.5802 | 0.0391 | 0.2140 | 0.035* | |
H7 | 0.5789 | 0.0411 | 0.3201 | 0.030* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0244 (7) | 0.0275 (8) | 0.0274 (7) | −0.0009 (5) | −0.0015 (5) | 0.0010 (6) |
C2 | 0.0239 (9) | 0.0311 (10) | 0.0225 (8) | 0.0026 (7) | −0.0003 (6) | −0.0070 (7) |
C21 | 0.0257 (8) | 0.0311 (10) | 0.0217 (8) | 0.0038 (7) | 0.0003 (6) | −0.0054 (7) |
C22 | 0.0261 (9) | 0.0357 (11) | 0.0266 (8) | 0.0010 (7) | −0.0036 (6) | −0.0023 (7) |
C23 | 0.0333 (9) | 0.0343 (11) | 0.0326 (9) | 0.0003 (7) | 0.0004 (7) | 0.0008 (8) |
C24 | 0.0392 (10) | 0.0338 (11) | 0.0293 (9) | 0.0092 (8) | 0.0015 (7) | 0.0027 (8) |
C25 | 0.0311 (9) | 0.0407 (11) | 0.0312 (9) | 0.0079 (8) | −0.0046 (7) | −0.0020 (8) |
C26 | 0.0252 (9) | 0.0369 (11) | 0.0321 (9) | 0.0027 (7) | −0.0032 (7) | −0.0045 (8) |
C3 | 0.0205 (8) | 0.0336 (10) | 0.0247 (8) | −0.0001 (7) | −0.0020 (6) | −0.0041 (7) |
C3A | 0.0173 (7) | 0.0324 (10) | 0.0239 (8) | −0.0031 (6) | 0.0016 (6) | −0.0081 (7) |
N4 | 0.0270 (8) | 0.0330 (9) | 0.0268 (7) | −0.0033 (6) | 0.0007 (6) | −0.0022 (6) |
C5 | 0.0285 (9) | 0.0286 (10) | 0.0258 (8) | −0.0028 (7) | 0.0027 (6) | −0.0041 (7) |
C6 | 0.0269 (8) | 0.0283 (10) | 0.0224 (8) | −0.0001 (7) | 0.0007 (6) | −0.0043 (7) |
C67 | 0.0285 (9) | 0.0262 (10) | 0.0274 (8) | −0.0015 (7) | 0.0038 (6) | 0.0003 (7) |
O61 | 0.0395 (7) | 0.0268 (8) | 0.0443 (7) | −0.0022 (5) | −0.0066 (5) | −0.0002 (6) |
C61 | 0.0284 (9) | 0.0250 (9) | 0.0223 (8) | −0.0003 (7) | 0.0030 (6) | 0.0026 (7) |
C62 | 0.0318 (9) | 0.0234 (9) | 0.0221 (8) | 0.0017 (7) | 0.0050 (6) | 0.0049 (7) |
O62 | 0.0406 (7) | 0.0241 (7) | 0.0305 (6) | 0.0041 (5) | −0.0013 (5) | 0.0007 (5) |
C63 | 0.0319 (9) | 0.0328 (10) | 0.0294 (9) | 0.0054 (7) | −0.0038 (7) | 0.0036 (7) |
C64 | 0.0389 (10) | 0.0333 (11) | 0.0303 (9) | −0.0011 (8) | −0.0082 (7) | 0.0010 (8) |
C65 | 0.0399 (10) | 0.0262 (10) | 0.0306 (9) | 0.0015 (7) | −0.0039 (7) | −0.0010 (7) |
C66 | 0.0327 (9) | 0.0279 (10) | 0.0254 (8) | 0.0049 (7) | 0.0001 (7) | 0.0021 (7) |
C7 | 0.0185 (8) | 0.0307 (10) | 0.0256 (8) | 0.0011 (6) | −0.0013 (6) | −0.0048 (7) |
N7A | 0.0198 (7) | 0.0271 (8) | 0.0244 (7) | −0.0010 (5) | −0.0011 (5) | −0.0031 (6) |
Geometric parameters (Å, º) top
N1—C2 | 1.3459 (19) | C5—C6 | 1.426 (2) |
N1—N7A | 1.3580 (19) | C5—H5 | 0.9500 |
C2—C3 | 1.400 (2) | C6—C7 | 1.367 (2) |
C2—C21 | 1.464 (2) | C6—C67 | 1.476 (2) |
C21—C22 | 1.389 (2) | C67—O61 | 1.2439 (19) |
C21—C26 | 1.396 (2) | C67—C61 | 1.467 (2) |
C22—C23 | 1.376 (2) | C61—C66 | 1.398 (2) |
C22—H22 | 0.9500 | C61—C62 | 1.409 (2) |
C23—C24 | 1.380 (2) | C62—O62 | 1.3512 (19) |
C23—H23 | 0.9500 | C62—C63 | 1.385 (2) |
C24—C25 | 1.376 (3) | O62—H62 | 1.0275 |
C24—H24 | 0.9500 | C63—C64 | 1.373 (2) |
C25—C26 | 1.379 (2) | C63—H63 | 0.9500 |
C25—H25 | 0.9500 | C64—C65 | 1.388 (2) |
C26—H26 | 0.9500 | C64—H64 | 0.9500 |
C3—C3A | 1.368 (2) | C65—C66 | 1.377 (2) |
C3—H3 | 0.9500 | C65—H65 | 0.9500 |
C3A—N4 | 1.354 (2) | C66—H66 | 0.9500 |
C3A—N7A | 1.3922 (19) | C7—N7A | 1.3519 (19) |
N4—C5 | 1.306 (2) | C7—H7 | 0.9500 |
| | | |
C2—N1—N7A | 103.67 (12) | C7—C6—C5 | 117.87 (15) |
N1—C2—C3 | 112.45 (14) | C7—C6—C67 | 124.08 (15) |
N1—C2—C21 | 120.02 (14) | C5—C6—C67 | 117.67 (15) |
C3—C2—C21 | 127.53 (14) | O61—C67—C61 | 120.37 (15) |
C22—C21—C26 | 118.17 (16) | O61—C67—C6 | 116.79 (14) |
C22—C21—C2 | 121.39 (14) | C61—C67—C6 | 122.83 (15) |
C26—C21—C2 | 120.43 (15) | C66—C61—C62 | 118.32 (14) |
C23—C22—C21 | 120.78 (15) | C66—C61—C67 | 122.56 (14) |
C23—C22—H22 | 119.6 | C62—C61—C67 | 119.11 (15) |
C21—C22—H22 | 119.6 | O62—C62—C63 | 117.37 (14) |
C22—C23—C24 | 120.46 (16) | O62—C62—C61 | 122.27 (14) |
C22—C23—H23 | 119.8 | C63—C62—C61 | 120.31 (15) |
C24—C23—H23 | 119.8 | C62—O62—H62 | 104.8 |
C25—C24—C23 | 119.59 (17) | C64—C63—C62 | 119.83 (15) |
C25—C24—H24 | 120.2 | C64—C63—H63 | 120.1 |
C23—C24—H24 | 120.2 | C62—C63—H63 | 120.1 |
C24—C25—C26 | 120.27 (16) | C63—C64—C65 | 121.03 (16) |
C24—C25—H25 | 119.9 | C63—C64—H64 | 119.5 |
C26—C25—H25 | 119.9 | C65—C64—H64 | 119.5 |
C25—C26—C21 | 120.73 (16) | C66—C65—C64 | 119.39 (17) |
C25—C26—H26 | 119.6 | C66—C65—H65 | 120.3 |
C21—C26—H26 | 119.6 | C64—C65—H65 | 120.3 |
C3A—C3—C2 | 105.70 (14) | C65—C66—C61 | 121.04 (15) |
C3A—C3—H3 | 127.1 | C65—C66—H66 | 119.5 |
C2—C3—H3 | 127.1 | C61—C66—H66 | 119.5 |
N4—C3A—C3 | 133.16 (15) | N7A—C7—C6 | 117.09 (15) |
N4—C3A—N7A | 121.04 (14) | N7A—C7—H7 | 121.5 |
C3—C3A—N7A | 105.79 (14) | C6—C7—H7 | 121.5 |
C5—N4—C3A | 116.24 (14) | C7—N7A—N1 | 125.03 (13) |
N4—C5—C6 | 125.08 (16) | C7—N7A—C3A | 122.59 (14) |
N4—C5—H5 | 117.5 | N1—N7A—C3A | 112.37 (12) |
C6—C5—H5 | 117.5 | | |
| | | |
N7A—N1—C2—C3 | 0.12 (17) | C5—C6—C67—C61 | 149.14 (14) |
N7A—N1—C2—C21 | 179.46 (13) | O61—C67—C61—C66 | 164.67 (15) |
N1—C2—C21—C22 | 2.2 (2) | C6—C67—C61—C66 | −16.2 (2) |
C3—C2—C21—C22 | −178.52 (15) | O61—C67—C61—C62 | −16.0 (2) |
N1—C2—C21—C26 | −176.31 (14) | C6—C67—C61—C62 | 163.18 (14) |
C3—C2—C21—C26 | 2.9 (2) | C66—C61—C62—O62 | −179.45 (14) |
C26—C21—C22—C23 | −0.2 (2) | C67—C61—C62—O62 | 1.2 (2) |
C2—C21—C22—C23 | −178.80 (15) | C66—C61—C62—C63 | 3.2 (2) |
C21—C22—C23—C24 | 0.5 (3) | C67—C61—C62—C63 | −176.21 (14) |
C22—C23—C24—C25 | −0.1 (3) | O62—C62—C63—C64 | −179.62 (14) |
C23—C24—C25—C26 | −0.5 (3) | C61—C62—C63—C64 | −2.1 (2) |
C24—C25—C26—C21 | 0.7 (3) | C62—C63—C64—C65 | −0.1 (3) |
C22—C21—C26—C25 | −0.4 (2) | C63—C64—C65—C66 | 1.1 (3) |
C2—C21—C26—C25 | 178.24 (15) | C64—C65—C66—C61 | 0.0 (2) |
N1—C2—C3—C3A | 0.61 (18) | C62—C61—C66—C65 | −2.1 (2) |
C21—C2—C3—C3A | −178.67 (15) | C67—C61—C66—C65 | 177.26 (15) |
C2—C3—C3A—N4 | 178.17 (16) | C5—C6—C7—N7A | 0.5 (2) |
C2—C3—C3A—N7A | −1.05 (16) | C67—C6—C7—N7A | −172.32 (14) |
C3—C3A—N4—C5 | −178.38 (16) | C6—C7—N7A—N1 | 177.63 (14) |
N7A—C3A—N4—C5 | 0.7 (2) | C6—C7—N7A—C3A | −2.5 (2) |
C3A—N4—C5—C6 | −2.9 (2) | C2—N1—N7A—C7 | 179.05 (13) |
N4—C5—C6—C7 | 2.4 (2) | C2—N1—N7A—C3A | −0.82 (16) |
N4—C5—C6—C67 | 175.64 (14) | N4—C3A—N7A—C7 | 2.0 (2) |
C7—C6—C67—O61 | 141.11 (16) | C3—C3A—N7A—C7 | −178.66 (13) |
C5—C6—C67—O61 | −31.7 (2) | N4—C3A—N7A—N1 | −178.12 (13) |
C7—C6—C67—C61 | −38.1 (2) | C3—C3A—N7A—N1 | 1.22 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C63—H63···N1i | 0.95 | 2.56 | 3.512 (2) | 174 |
O62—H62···O61 | 1.03 | 1.62 | 2.559 (2) | 149 |
Symmetry code: (i) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | C19H13N3O2 |
Mr | 315.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 5.6606 (2), 11.7048 (5), 21.6815 (10) |
β (°) | 94.7970 (15) |
V (Å3) | 1431.50 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.44 × 0.10 × 0.08 |
|
Data collection |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.958, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12852, 3032, 2168 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.136, 1.04 |
No. of reflections | 3032 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.27 |
Selected geometric parameters (Å, º) topN1—C2 | 1.3459 (19) | C3A—N7A | 1.3922 (19) |
N1—N7A | 1.3580 (19) | N4—C5 | 1.306 (2) |
C3A—N4 | 1.354 (2) | C7—N7A | 1.3519 (19) |
| | | |
C2—N1—N7A | 103.67 (12) | C7—N7A—C3A | 122.59 (14) |
C5—N4—C3A | 116.24 (14) | N1—N7A—C3A | 112.37 (12) |
C7—N7A—N1 | 125.03 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C63—H63···N1i | 0.95 | 2.56 | 3.512 (2) | 174 |
O62—H62···O61 | 1.03 | 1.62 | 2.559 (2) | 149 |
Symmetry code: (i) −x+1/2, y+1/2, −z+1/2. |
Since becoming readily available, 3-formylchromone has been used to prepare a variety of heterocyclic systems (Jones & Albrecht., 1976; Haas et al., 1981; Pene & Hubert-Habart., 1980; Sigg et al., 1982). In our investigation of pyrazolo[1,5-a]pyrimidines, we have established that the cyclocondensation reaction of 5-amino-1H-pyrazoles with α,β-unsaturated aromatic ketones is a versatile and efficient method for the preparation of these compounds (Orlov et al., 1988; Quiroga et al., 1994, 1999), but the reaction with 3-formylchromone was not previously investigated. We have recently applied above methodology to prepare several pyrazolo[1,5-a]pyrimidines starting from 3-formylchromone.
Geometric parameters for the title compound, (I), are given in Table 1 and a view of the molecule is shown in Fig. 1. A strong intramolecular hydrogen bond, O62—H62···O61, forms an S(6) (Bernstein et al., 1995) ring motif. The molecules are linked into chains by the weak C63–H63···N1i hydrogen bond, which form a C(9) motif [symmetry code: (i) -x + 1/2, y + 1/2, -z + 1/2]. A series of antiparallel chains run parallel to the b axis. Details of the hydrogen bonds are given in Table 2.
Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.