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The structure of C19H12N4O4 contains one strong intramolecular O—H....O bond giving an S(6) motif. The mol­ecules are linked together by weak C—H...O and C—H...N hydrogen bonds, forming a complex three-dimensional network of chain and ring motifs.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001696/na6044sup1.cif
Contains datablocks global, 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001696/na6044Isup2.hkl
Contains datablock I

CCDC reference: 159762

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.047
  • wR factor = 0.124
  • Data-to-parameter ratio = 8.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_707 Alert C D...A Calc 3.306(4), Rep 3.301(4), Dev. 1.25 Sigma C5 -O62 1.555 1.455 General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.44 From the CIF: _reflns_number_total 2022 Count of symmetry unique reflns 2042 Completeness (_total/calc) 99.02% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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 hydrogen-bond parameters are given in Table 2. The three-dimensional hydrogen-bonding network produced by the weak intermolecular C—H···O and C—H···N hydrogen bonds is very complex, the simpler motifs being three infinite chains based on the following motifs; a C(7) motif (Bernstein et al., 1995) involving C5—H5···O62i, a C(5) motif in which C66—H66···O67iii and a C22(12) motif in which C66—H66···O67iii and C63—H63···N1ii [symmetry codes: (i) x - 1, y, z; (iii) 1 - x, y + 1/2, -z + 1/2]. The chains produced by repeat of these motifs creates ring motifs which in turn produce a three-dimensional network. A view of the molecule is shown in Fig. 1.

Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.

Experimental top

An equimolar mixture of 3-formylchromone and 5-amino-3-(4-nitrophenyl)pyrazole 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. 553–555 K, yield: 90%.

Refinement top

H atoms were treated as riding with distances C—H = 0.95 Å and O—-H = 0.90 Å.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
6-(2-Hydroxybenzoyl)-2-(4-nitrophenyl)pyrazolo[1,5-a]pyrimidine top
Crystal data top
C19H12N4O4Dx = 1.566 Mg m3
Mr = 360.33Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 7067 reflections
a = 5.5421 (2) Åθ = 1.0–27.5°
b = 11.5858 (5) ŵ = 0.11 mm1
c = 23.8057 (13) ÅT = 150 K
V = 1528.56 (12) Å3Needle, yellow
Z = 40.20 × 0.08 × 0.07 mm
F(000) = 744
Data collection top
KappaCCD
diffractometer
2022 independent reflections
Radiation source: fine-focus sealed X-ray tube1364 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ϕ and ω scans with κ offsetsθmax = 27.4°, θmin = 1.7°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 77
Tmin = 0.978, Tmax = 0.992k = 1515
7572 measured reflectionsl = 3030
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.048P)2 + 0.3279P]
where P = (Fo2 + 2Fc2)/3
2022 reflections(Δ/σ)max = 0.005
244 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C19H12N4O4V = 1528.56 (12) Å3
Mr = 360.33Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.5421 (2) ŵ = 0.11 mm1
b = 11.5858 (5) ÅT = 150 K
c = 23.8057 (13) Å0.20 × 0.08 × 0.07 mm
Data collection top
KappaCCD
diffractometer
2022 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
1364 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.992Rint = 0.037
7572 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.124H-atom parameters constrained
S = 1.07Δρmax = 0.25 e Å3
2022 reflectionsΔρmin = 0.27 e Å3
244 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
xyzUiso*/Ueq
N10.4216 (5)0.2523 (2)0.38267 (13)0.0246 (7)
C20.2294 (6)0.2706 (3)0.41569 (16)0.0231 (8)
C210.2235 (7)0.3756 (3)0.45031 (16)0.0236 (8)
C220.4135 (7)0.4528 (3)0.44951 (17)0.0292 (9)
C230.4127 (7)0.5509 (3)0.48185 (18)0.0313 (9)
C240.2193 (7)0.5701 (3)0.51646 (16)0.0270 (9)
N240.2188 (7)0.6734 (3)0.55150 (15)0.0354 (9)
O210.3823 (6)0.7435 (2)0.54588 (14)0.0465 (8)
O220.0492 (6)0.6874 (2)0.58380 (14)0.0490 (9)
C250.0268 (7)0.4960 (3)0.51892 (17)0.0299 (9)
C260.0278 (6)0.3979 (3)0.48571 (16)0.0261 (8)
C30.0589 (6)0.1814 (3)0.41285 (16)0.0242 (8)
C3A0.1556 (6)0.1025 (3)0.37594 (16)0.0235 (8)
N40.0807 (6)0.0027 (2)0.35731 (14)0.0267 (8)
C50.2270 (7)0.0559 (3)0.32334 (16)0.0270 (9)
C60.4488 (7)0.0104 (3)0.30287 (17)0.0260 (9)
C670.6017 (6)0.0860 (3)0.26614 (17)0.0274 (9)
O670.5901 (5)0.1918 (2)0.27446 (13)0.0364 (7)
C610.7653 (6)0.0379 (3)0.22383 (16)0.0244 (9)
C620.9607 (7)0.1058 (3)0.20466 (16)0.0261 (9)
O620.9951 (5)0.21614 (19)0.22193 (11)0.0292 (6)
C631.1303 (7)0.0592 (3)0.16808 (16)0.0295 (9)
C641.0969 (7)0.0512 (3)0.14697 (17)0.0312 (9)
C650.8972 (8)0.1152 (3)0.16177 (17)0.0324 (10)
C660.7353 (7)0.0720 (3)0.20037 (16)0.0284 (9)
C70.5201 (7)0.0945 (3)0.32124 (15)0.0241 (8)
N7A0.3740 (5)0.1493 (2)0.35832 (13)0.0227 (7)
H220.54830.43760.42600.035*
H230.54280.60420.48030.038*
H250.10550.51180.54310.036*
H260.10440.34570.48700.031*
H30.09070.17650.43220.029*
H50.18240.13100.31120.032*
H620.85970.23750.23990.035*
H631.26830.10280.15760.035*
H641.21300.08310.12200.037*
H650.87110.18890.14540.039*
H660.60090.11770.21130.034*
H70.66660.12850.30870.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0256 (16)0.0248 (16)0.0234 (17)0.0000 (13)0.0001 (15)0.0026 (15)
C20.0191 (18)0.030 (2)0.0200 (19)0.0002 (15)0.0006 (17)0.0047 (17)
C210.0227 (19)0.024 (2)0.024 (2)0.0025 (15)0.0004 (17)0.0001 (16)
C220.026 (2)0.031 (2)0.031 (2)0.0024 (17)0.0068 (18)0.0041 (19)
C230.028 (2)0.031 (2)0.035 (2)0.0028 (17)0.000 (2)0.000 (2)
C240.032 (2)0.026 (2)0.023 (2)0.0011 (17)0.0002 (18)0.0008 (18)
N240.044 (2)0.037 (2)0.0248 (19)0.0028 (18)0.0022 (19)0.0056 (17)
O210.0533 (19)0.0376 (17)0.049 (2)0.0140 (16)0.0074 (17)0.0150 (16)
O220.064 (2)0.0443 (18)0.0391 (19)0.0021 (16)0.0189 (19)0.0096 (15)
C250.030 (2)0.034 (2)0.025 (2)0.0036 (18)0.0060 (18)0.0030 (19)
C260.0226 (18)0.029 (2)0.026 (2)0.0028 (17)0.0020 (17)0.0010 (18)
C30.0219 (18)0.031 (2)0.020 (2)0.0003 (16)0.0001 (17)0.0012 (17)
C3A0.0190 (18)0.028 (2)0.023 (2)0.0011 (15)0.0028 (16)0.0037 (19)
N40.0250 (16)0.0268 (17)0.0282 (19)0.0032 (14)0.0016 (15)0.0020 (15)
C50.028 (2)0.027 (2)0.026 (2)0.0041 (17)0.0028 (18)0.0009 (17)
C60.0273 (19)0.024 (2)0.026 (2)0.0001 (16)0.0025 (18)0.0008 (17)
C670.025 (2)0.029 (2)0.028 (2)0.0009 (17)0.0043 (17)0.0038 (17)
O670.0444 (17)0.0226 (14)0.0423 (19)0.0017 (13)0.0068 (15)0.0004 (13)
C610.0216 (18)0.028 (2)0.023 (2)0.0006 (16)0.0005 (18)0.0033 (17)
C620.0297 (19)0.023 (2)0.025 (2)0.0008 (16)0.0075 (17)0.0054 (17)
O620.0362 (15)0.0234 (13)0.0281 (15)0.0051 (11)0.0010 (14)0.0003 (12)
C630.028 (2)0.035 (2)0.026 (2)0.0050 (18)0.0034 (18)0.0044 (19)
C640.037 (2)0.031 (2)0.026 (2)0.0025 (18)0.0044 (19)0.0040 (19)
C650.046 (2)0.025 (2)0.027 (2)0.0009 (19)0.003 (2)0.0006 (18)
C660.034 (2)0.027 (2)0.025 (2)0.0059 (17)0.0038 (19)0.0054 (17)
C70.0209 (18)0.028 (2)0.023 (2)0.0006 (16)0.0021 (16)0.0020 (16)
N7A0.0208 (15)0.0235 (16)0.0237 (17)0.0009 (13)0.0001 (14)0.0008 (14)
Geometric parameters (Å, º) top
N1—C21.341 (5)N4—C51.300 (5)
N1—N7A1.353 (4)C5—C61.424 (5)
C2—C31.402 (5)C5—H50.9500
C2—C211.470 (5)C6—C71.351 (5)
C21—C221.382 (5)C6—C671.500 (5)
C21—C261.397 (5)C67—O671.244 (4)
C22—C231.373 (5)C67—C611.465 (5)
C22—H220.9500C61—C661.401 (5)
C23—C241.370 (5)C61—C621.415 (5)
C23—H230.9500C62—O621.356 (4)
C24—C251.371 (5)C62—C631.390 (5)
C24—N241.460 (5)O62—H620.8980
N24—O211.224 (4)C63—C641.387 (6)
N24—O221.225 (4)C63—H630.9500
C25—C261.385 (5)C64—C651.377 (5)
C25—H250.9500C64—H640.9500
C26—H260.9500C65—C661.378 (5)
C3—C3A1.377 (5)C65—H650.9500
C3—H30.9500C66—H660.9500
C3A—N41.362 (5)C7—N7A1.356 (5)
C3A—N7A1.391 (5)C7—H70.9500
C2—N1—N7A103.6 (3)N4—C5—H5117.4
N1—C2—C3113.0 (3)C6—C5—H5117.4
N1—C2—C21118.5 (3)C7—C6—C5118.4 (4)
C3—C2—C21128.5 (3)C7—C6—C67123.3 (3)
C22—C21—C26118.7 (3)C5—C6—C67118.1 (3)
C22—C21—C2120.7 (3)O67—C67—C61121.1 (3)
C26—C21—C2120.6 (3)O67—C67—C6117.0 (3)
C23—C22—C21121.7 (4)C61—C67—C6121.9 (3)
C23—C22—H22119.1C66—C61—C62117.9 (4)
C21—C22—H22119.1C66—C61—C67123.1 (3)
C24—C23—C22118.3 (4)C62—C61—C67119.0 (3)
C24—C23—H23120.9O62—C62—C63117.5 (3)
C22—C23—H23120.9O62—C62—C61122.3 (3)
C23—C24—C25122.2 (4)C63—C62—C61120.2 (3)
C23—C24—N24118.6 (4)C62—O62—H62106.6
C25—C24—N24119.2 (4)C64—C63—C62119.7 (4)
O21—N24—O22123.3 (3)C64—C63—H63120.2
O21—N24—C24118.7 (3)C62—C63—H63120.2
O22—N24—C24118.0 (3)C65—C64—C63120.7 (4)
C24—C25—C26119.1 (4)C65—C64—H64119.7
C24—C25—H25120.4C63—C64—H64119.7
C26—C25—H25120.4C66—C65—C64119.9 (4)
C25—C26—C21119.9 (3)C66—C65—H65120.0
C25—C26—H26120.0C64—C65—H65120.0
C21—C26—H26120.0C65—C66—C61121.2 (4)
C3A—C3—C2105.0 (3)C65—C66—H66119.4
C3A—C3—H3127.5C61—C66—H66119.4
C2—C3—H3127.5C6—C7—N7A117.2 (3)
N4—C3A—C3133.1 (3)C6—C7—H7121.4
N4—C3A—N7A121.1 (3)N7A—C7—H7121.4
C3—C3A—N7A105.8 (3)N1—N7A—C7125.1 (3)
C5—N4—C3A115.9 (3)N1—N7A—C3A112.6 (3)
N4—C5—C6125.2 (4)C7—N7A—C3A122.2 (3)
N7A—N1—C2—C30.2 (4)C7—C6—C67—O67143.9 (4)
N7A—N1—C2—C21178.4 (3)C5—C6—C67—O6730.4 (5)
N1—C2—C21—C221.0 (5)C7—C6—C67—C6133.7 (6)
C3—C2—C21—C22177.3 (4)C5—C6—C67—C61152.0 (4)
N1—C2—C21—C26179.5 (4)O67—C67—C61—C66159.5 (4)
C3—C2—C21—C261.1 (6)C6—C67—C61—C6623.0 (6)
C26—C21—C22—C231.0 (6)O67—C67—C61—C6219.3 (6)
C2—C21—C22—C23179.5 (4)C6—C67—C61—C62158.2 (3)
C21—C22—C23—C241.5 (6)C66—C61—C62—O62175.4 (3)
C22—C23—C24—C251.2 (6)C67—C61—C62—O623.5 (5)
C22—C23—C24—N24179.2 (4)C66—C61—C62—C636.5 (5)
C23—C24—N24—O215.2 (5)C67—C61—C62—C63174.7 (3)
C25—C24—N24—O21174.4 (4)O62—C62—C63—C64176.8 (3)
C23—C24—N24—O22177.3 (4)C61—C62—C63—C645.0 (6)
C25—C24—N24—O223.1 (5)C62—C63—C64—C650.1 (6)
C23—C24—C25—C260.5 (6)C63—C64—C65—C663.7 (6)
N24—C24—C25—C26179.9 (3)C64—C65—C66—C612.1 (6)
C24—C25—C26—C210.0 (5)C62—C61—C66—C653.0 (5)
C22—C21—C26—C250.2 (6)C67—C61—C66—C65178.2 (4)
C2—C21—C26—C25178.7 (3)C5—C6—C7—N7A0.1 (5)
N1—C2—C3—C3A0.7 (4)C67—C6—C7—N7A174.1 (3)
C21—C2—C3—C3A177.7 (4)C2—N1—N7A—C7179.6 (3)
C2—C3—C3A—N4177.6 (4)C2—N1—N7A—C3A0.4 (4)
C2—C3—C3A—N7A0.9 (4)C6—C7—N7A—N1177.2 (3)
C3—C3A—N4—C5177.3 (4)C6—C7—N7A—C3A1.9 (5)
N7A—C3A—N4—C51.1 (5)N4—C3A—N7A—N1177.9 (3)
C3A—N4—C5—C63.0 (5)C3—C3A—N7A—N10.9 (4)
N4—C5—C6—C72.5 (6)N4—C3A—N7A—C71.3 (5)
N4—C5—C6—C67177.0 (4)C3—C3A—N7A—C7179.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O62i0.952.563.301 (4)135
C63—H63···N1ii0.952.583.519 (5)168
C66—H66···O67iii0.952.473.332 (4)150
O62—H62···O670.901.782.583 (4)147
Symmetry codes: (i) x1, y, z; (ii) x+2, y1/2, z+1/2; (iii) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC19H12N4O4
Mr360.33
Crystal system, space groupOrthorhombic, P212121
Temperature (K)150
a, b, c (Å)5.5421 (2), 11.5858 (5), 23.8057 (13)
V3)1528.56 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.20 × 0.08 × 0.07
Data collection
DiffractometerKappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.978, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections
7572, 2022, 1364
Rint0.037
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.124, 1.07
No. of reflections2022
No. of parameters244
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.27

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2000), SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
N1—C21.341 (5)C3A—N41.362 (5)
N1—N7A1.353 (4)C3A—N7A1.391 (5)
C24—N241.460 (5)C7—N7A1.356 (5)
C2—N1—N7A103.6 (3)C5—N4—C3A115.9 (3)
O21—N24—O22123.3 (3)N1—N7A—C7125.1 (3)
O21—N24—C24118.7 (3)N1—N7A—C3A112.6 (3)
O22—N24—C24118.0 (3)C7—N7A—C3A122.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O62i0.952.563.301 (4)135
C63—H63···N1ii0.952.583.519 (5)168
C66—H66···O67iii0.952.473.332 (4)150
O62—H62···O670.901.782.583 (4)147
Symmetry codes: (i) x1, y, z; (ii) x+2, y1/2, z+1/2; (iii) x+1, y+1/2, z+1/2.
 

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