organic compounds
2-[4-(Piperidin-1-yl)-5H-chromeno[2,3-d]pyrimidin-2-yl]phenol
aPost-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and bLaboratory of Natural Products & Organic Synthesis, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235, West Bengal, India
*Correspondence e-mail: vivek_gupta2k2@hotmail.com
In the title compound, C22H21N3O2, the pyrimidine ring is essentially planar [maximum deviation = 0.018 (2) Å] and forms dihedral angles of 22.70 (8) and 0.97 (7)°, respectively, with the fused benzene ring and the hydroxy-substituted benzene ring. The piperidine ring has a chair conformation and the pyran ring has a flattened twist-boat conformation. The hydroxy group was refined as disordered over two sets of sites in a 0.702 (4):0.298 (4) ratio. The disorder corresponds to a rotation of approxomiately 180° about the C—C bond connecting the phenol group to the pyrimidine ring and hence, both the major and minor components of disorder form intramolecular O—H⋯N hydrogen bonds. In the crystal, pairs of weak C—H⋯π interactions form inversion dimers. In addition, π–π interactions are observed between the pyrimidine ring and the hydroxy-substituted benzene ring [centroid–centroid separation = 3.739 (2) Å].
CCDC reference: 975917
Related literature
For applications of benzopyrano[2,3-d]pyrimidines, see: Hadfield et al. (1999); Bruno et al. (2001, 2004). For general background to benzopyrano[2,3-d]pyrimidines, see: Brahmachari & Das (2014). For a related structure, see: Gajera et al. (2013). For standard bond-length data, see: Allen et al. (1987). For see: Duax & Norton (1975).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON.
Supporting information
CCDC reference: 975917
10.1107/S1600536814005625/lh5695sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005625/lh5695Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814005625/lh5695Isup3.cml
Infrared spectra were recorded using a Shimadzu (FT—IR 8400S) FT—IR spectrophotometer using KBr disc. 1H and 13 C NMR spectra was obtained at 400 and 100 MHz, respectively, using Bruker DRX spectrometer and CDCl3 and DMSO-d6 as solvents. Elemental analysis was performed with an Elementar Vario EL III Carlo Erba 1108 micro-analyzer instrument. Melting point was recorded on a Sunvic melting point apparatus and is uncorrected. TLC was performed using silica gel 60 F254 (Merck) plates. An oven-dried screw cap test tube was charged with a magnetic stir bar, salicylaldehyde (2 mmol), malononitrile (1 mmol), piperidine (1 mmol), and sodium formate (10 mol%) in 4 ml e thanol. The reaction mixture was stirred at room temperature for 12 h. On completion of the reaction as monitored by TLC, the product was precipitated out and filtered; the filtrate was preserved for reuse. The crude residue was washed with water followed by ethanol to obtain pure product 1, characterized by elemental analyses as well as spectral studies including FT—IR, 1H-NMR and 13 C-NMR. The title compound (50 mg) was dissolved in 10 ml DMSO and left for several days at ambient temperature which yielded single crystals suitable for X-ray diffraction.
All H atoms were geometrically fixed and allowed to ride on their parent atoms, with C—H distances of 0.93–0.97 Å, O—H = 0.82Å and with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(O).
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).Fig. 1. The molecular structure of (I) with ellipsoids drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii. Both disorder components are shown. | |
Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines. Only the H atoms involved in hydrogen bonds and weak C—H···π interactions are shown. |
C22H21N3O2 | F(000) = 760 |
Mr = 359.42 | Dx = 1.307 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4022 reflections |
a = 9.9826 (5) Å | θ = 3.4–29.1° |
b = 15.8773 (7) Å | µ = 0.09 mm−1 |
c = 12.2197 (6) Å | T = 293 K |
β = 109.381 (6)° | Block, colourless |
V = 1827.03 (15) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 3576 independent reflections |
Radiation source: fine-focus sealed tube | 1918 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 16.1049 pixels mm-1 | θmax = 26.0°, θmin = 3.4° |
ω scans | h = −12→10 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | k = −19→19 |
Tmin = 0.975, Tmax = 0.983 | l = −15→15 |
13349 measured reflections |
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) = 0.133 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0481P)2 + 0.0647P] where P = (Fo2 + 2Fc2)/3 |
3576 reflections | (Δ/σ)max < 0.001 |
254 parameters | Δρmax = 0.13 e Å−3 |
12 restraints | Δρmin = −0.16 e Å−3 |
C22H21N3O2 | V = 1827.03 (15) Å3 |
Mr = 359.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.9826 (5) Å | µ = 0.09 mm−1 |
b = 15.8773 (7) Å | T = 293 K |
c = 12.2197 (6) Å | 0.30 × 0.20 × 0.20 mm |
β = 109.381 (6)° |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 3576 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | 1918 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.983 | Rint = 0.048 |
13349 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 12 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.13 e Å−3 |
3576 reflections | Δρmin = −0.16 e Å−3 |
254 parameters |
Experimental. CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01–02-2013 CrysAlis171. NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C2 | 0.1453 (2) | 0.07319 (14) | 0.0435 (2) | 0.0477 (6) | |
C4 | 0.3129 (2) | −0.03037 (14) | 0.1148 (2) | 0.0463 (6) | |
C5 | 0.3928 (2) | −0.06426 (14) | 0.33523 (19) | 0.0507 (6) | |
H5A | 0.3894 | −0.1235 | 0.3152 | 0.061* | |
H5B | 0.4916 | −0.0469 | 0.3622 | 0.061* | |
C6 | 0.3630 (3) | −0.10672 (16) | 0.5247 (2) | 0.0647 (8) | |
H6 | 0.4218 | −0.1527 | 0.5280 | 0.078* | |
C7 | 0.3085 (3) | −0.09410 (19) | 0.6134 (2) | 0.0742 (9) | |
H7 | 0.3312 | −0.1312 | 0.6758 | 0.089* | |
C8 | 0.2209 (3) | −0.0268 (2) | 0.6095 (3) | 0.0756 (9) | |
H8 | 0.1837 | −0.0185 | 0.6691 | 0.091* | |
C9 | 0.1882 (3) | 0.02815 (18) | 0.5177 (2) | 0.0658 (8) | |
H9 | 0.1296 | 0.0742 | 0.5147 | 0.079* | |
C11 | 0.3132 (2) | −0.01433 (14) | 0.2289 (2) | 0.0443 (6) | |
C12 | 0.3321 (3) | −0.05240 (15) | 0.4307 (2) | 0.0499 (6) | |
C13 | 0.2437 (3) | 0.01392 (16) | 0.4299 (2) | 0.0522 (7) | |
C14 | 0.2228 (3) | 0.04870 (15) | 0.2367 (2) | 0.0483 (6) | |
C16 | 0.3602 (3) | −0.11949 (17) | −0.0314 (2) | 0.0693 (8) | |
H16A | 0.4132 | −0.0854 | −0.0688 | 0.083* | |
H16B | 0.2598 | −0.1115 | −0.0730 | 0.083* | |
C17 | 0.3982 (3) | −0.21068 (17) | −0.0359 (2) | 0.0731 (9) | |
H17A | 0.3828 | −0.2264 | −0.1159 | 0.088* | |
H17B | 0.3360 | −0.2449 | −0.0078 | 0.088* | |
C18 | 0.5505 (3) | −0.22899 (19) | 0.0357 (3) | 0.0843 (10) | |
H18A | 0.6137 | −0.2019 | 0.0009 | 0.101* | |
H18B | 0.5674 | −0.2892 | 0.0374 | 0.101* | |
C19 | 0.5809 (3) | −0.19662 (19) | 0.1583 (2) | 0.0783 (9) | |
H19A | 0.5263 | −0.2288 | 0.1963 | 0.094* | |
H19B | 0.6808 | −0.2040 | 0.2020 | 0.094* | |
C20 | 0.5425 (3) | −0.10490 (16) | 0.1567 (2) | 0.0618 (7) | |
H20A | 0.5606 | −0.0853 | 0.2355 | 0.074* | |
H20B | 0.6010 | −0.0723 | 0.1229 | 0.074* | |
C21 | 0.0531 (2) | 0.12112 (13) | −0.0572 (2) | 0.0488 (6) | |
C22 | 0.0519 (3) | 0.10222 (18) | −0.1690 (2) | 0.0599 (7) | |
H22 | 0.1079 | 0.0582 | −0.1794 | 0.072* | 0.702 (4) |
O27A | 0.1226 (5) | 0.0461 (3) | −0.1909 (5) | 0.076 (3) | 0.298 (4) |
H27A | 0.1672 | 0.0216 | −0.1308 | 0.114* | 0.298 (4) |
C23 | −0.0300 (3) | 0.14697 (19) | −0.2643 (3) | 0.0711 (8) | |
H23 | −0.0277 | 0.1340 | −0.3379 | 0.085* | |
C24 | −0.1140 (3) | 0.2101 (2) | −0.2497 (3) | 0.0745 (9) | |
H24 | −0.1694 | 0.2404 | −0.3140 | 0.089* | |
C25 | −0.1190 (3) | 0.23027 (16) | −0.1420 (3) | 0.0728 (9) | |
H25 | −0.1787 | 0.2729 | −0.1336 | 0.087* | |
C26 | −0.0337 (3) | 0.18620 (15) | −0.0448 (3) | 0.0604 (7) | |
H26 | −0.0350 | 0.2006 | 0.0286 | 0.072* | 0.298 (4) |
O27B | −0.0379 (3) | 0.21092 (14) | 0.0561 (2) | 0.0703 (11) | 0.702 (4) |
H27B | 0.0250 | 0.1872 | 0.1079 | 0.105* | 0.702 (4) |
N1 | 0.1407 (2) | 0.09492 (12) | 0.14824 (18) | 0.0522 (5) | |
N3 | 0.2261 (2) | 0.01277 (12) | 0.02367 (17) | 0.0499 (5) | |
N15 | 0.3930 (2) | −0.09248 (12) | 0.08946 (17) | 0.0536 (6) | |
O10 | 0.20328 (18) | 0.07135 (10) | 0.33851 (15) | 0.0621 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C2 | 0.0481 (15) | 0.0410 (14) | 0.0520 (16) | −0.0057 (12) | 0.0137 (12) | −0.0011 (12) |
C4 | 0.0432 (14) | 0.0424 (14) | 0.0499 (15) | −0.0060 (12) | 0.0107 (12) | −0.0062 (12) |
C5 | 0.0486 (15) | 0.0474 (15) | 0.0501 (16) | 0.0009 (12) | 0.0083 (12) | −0.0074 (12) |
C6 | 0.0749 (19) | 0.0566 (18) | 0.0548 (18) | −0.0014 (14) | 0.0110 (15) | −0.0021 (15) |
C7 | 0.095 (2) | 0.071 (2) | 0.0508 (18) | −0.0174 (19) | 0.0165 (16) | 0.0041 (15) |
C8 | 0.082 (2) | 0.093 (2) | 0.055 (2) | −0.0225 (19) | 0.0271 (17) | −0.0147 (18) |
C9 | 0.0647 (19) | 0.073 (2) | 0.0583 (19) | −0.0039 (15) | 0.0189 (15) | −0.0157 (16) |
C11 | 0.0454 (14) | 0.0373 (13) | 0.0461 (15) | −0.0035 (11) | 0.0099 (12) | −0.0056 (11) |
C12 | 0.0515 (15) | 0.0461 (15) | 0.0446 (15) | −0.0074 (13) | 0.0061 (12) | −0.0082 (12) |
C13 | 0.0559 (16) | 0.0523 (16) | 0.0424 (15) | −0.0050 (13) | 0.0082 (13) | −0.0069 (13) |
C14 | 0.0527 (15) | 0.0434 (14) | 0.0469 (15) | −0.0046 (12) | 0.0139 (12) | −0.0095 (12) |
C16 | 0.080 (2) | 0.0724 (19) | 0.0500 (17) | 0.0152 (16) | 0.0138 (14) | −0.0087 (14) |
C17 | 0.084 (2) | 0.0658 (19) | 0.0637 (19) | 0.0169 (16) | 0.0171 (16) | −0.0174 (15) |
C18 | 0.085 (2) | 0.080 (2) | 0.081 (2) | 0.0266 (18) | 0.0185 (18) | −0.0180 (17) |
C19 | 0.0648 (19) | 0.087 (2) | 0.072 (2) | 0.0243 (17) | 0.0071 (15) | −0.0029 (17) |
C20 | 0.0479 (16) | 0.075 (2) | 0.0596 (17) | −0.0004 (14) | 0.0144 (13) | −0.0148 (14) |
C21 | 0.0495 (15) | 0.0381 (14) | 0.0547 (16) | −0.0058 (12) | 0.0117 (12) | 0.0047 (12) |
C22 | 0.0549 (17) | 0.0660 (19) | 0.0544 (18) | −0.0102 (15) | 0.0121 (14) | 0.0054 (15) |
O27A | 0.057 (4) | 0.109 (6) | 0.061 (4) | 0.019 (4) | 0.017 (3) | 0.009 (4) |
C23 | 0.0653 (19) | 0.079 (2) | 0.0622 (19) | −0.0111 (17) | 0.0115 (15) | 0.0125 (17) |
C24 | 0.070 (2) | 0.070 (2) | 0.069 (2) | −0.0155 (17) | 0.0042 (16) | 0.0223 (17) |
C25 | 0.0633 (19) | 0.0512 (18) | 0.092 (2) | 0.0057 (14) | 0.0092 (17) | 0.0127 (17) |
C26 | 0.0659 (18) | 0.0452 (16) | 0.0648 (19) | −0.0019 (14) | 0.0146 (15) | 0.0029 (14) |
O27B | 0.083 (2) | 0.0662 (18) | 0.061 (2) | 0.0287 (14) | 0.0220 (14) | 0.0006 (14) |
N1 | 0.0570 (13) | 0.0442 (12) | 0.0518 (13) | 0.0029 (10) | 0.0132 (10) | −0.0018 (10) |
N3 | 0.0503 (12) | 0.0461 (12) | 0.0507 (13) | 0.0030 (10) | 0.0132 (10) | −0.0030 (10) |
N15 | 0.0529 (13) | 0.0540 (13) | 0.0486 (13) | 0.0093 (10) | 0.0097 (10) | −0.0106 (10) |
O10 | 0.0786 (13) | 0.0545 (11) | 0.0527 (11) | 0.0138 (9) | 0.0208 (9) | −0.0054 (9) |
C2—N3 | 1.326 (3) | C17—C18 | 1.509 (4) |
C2—N1 | 1.341 (3) | C17—H17A | 0.9700 |
C2—C21 | 1.479 (3) | C17—H17B | 0.9700 |
C4—N3 | 1.349 (3) | C18—C19 | 1.517 (3) |
C4—N15 | 1.368 (3) | C18—H18A | 0.9700 |
C4—C11 | 1.416 (3) | C18—H18B | 0.9700 |
C5—C12 | 1.495 (3) | C19—C20 | 1.504 (3) |
C5—C11 | 1.504 (3) | C19—H19A | 0.9700 |
C5—H5A | 0.9700 | C19—H19B | 0.9700 |
C5—H5B | 0.9700 | C20—N15 | 1.458 (3) |
C6—C7 | 1.379 (4) | C20—H20A | 0.9700 |
C6—C12 | 1.387 (3) | C20—H20B | 0.9700 |
C6—H6 | 0.9300 | C21—C26 | 1.388 (3) |
C7—C8 | 1.371 (4) | C21—C22 | 1.395 (3) |
C7—H7 | 0.9300 | C22—O27A | 1.220 (5) |
C8—C9 | 1.373 (4) | C22—C23 | 1.378 (3) |
C8—H8 | 0.9300 | C22—H22 | 0.9300 |
C9—C13 | 1.379 (3) | O27A—H27A | 0.8200 |
C9—H9 | 0.9300 | C23—C24 | 1.357 (4) |
C11—C14 | 1.372 (3) | C23—H23 | 0.9300 |
C12—C13 | 1.371 (3) | C24—C25 | 1.371 (4) |
C13—O10 | 1.394 (3) | C24—H24 | 0.9300 |
C14—N1 | 1.338 (3) | C25—C26 | 1.397 (4) |
C14—O10 | 1.370 (3) | C25—H25 | 0.9300 |
C16—N15 | 1.467 (3) | C26—O27B | 1.309 (3) |
C16—C17 | 1.503 (3) | C26—H26 | 0.9300 |
C16—H16A | 0.9700 | O27B—H27B | 0.8200 |
C16—H16B | 0.9700 | ||
N3—C2—N1 | 125.1 (2) | C17—C18—C19 | 109.9 (2) |
N3—C2—C21 | 118.0 (2) | C17—C18—H18A | 109.7 |
N1—C2—C21 | 116.9 (2) | C19—C18—H18A | 109.7 |
N3—C4—N15 | 116.3 (2) | C17—C18—H18B | 109.7 |
N3—C4—C11 | 120.8 (2) | C19—C18—H18B | 109.7 |
N15—C4—C11 | 122.8 (2) | H18A—C18—H18B | 108.2 |
C12—C5—C11 | 111.9 (2) | C20—C19—C18 | 110.4 (2) |
C12—C5—H5A | 109.2 | C20—C19—H19A | 109.6 |
C11—C5—H5A | 109.2 | C18—C19—H19A | 109.6 |
C12—C5—H5B | 109.2 | C20—C19—H19B | 109.6 |
C11—C5—H5B | 109.2 | C18—C19—H19B | 109.6 |
H5A—C5—H5B | 107.9 | H19A—C19—H19B | 108.1 |
C7—C6—C12 | 121.5 (3) | N15—C20—C19 | 110.3 (2) |
C7—C6—H6 | 119.2 | N15—C20—H20A | 109.6 |
C12—C6—H6 | 119.2 | C19—C20—H20A | 109.6 |
C8—C7—C6 | 120.0 (3) | N15—C20—H20B | 109.6 |
C8—C7—H7 | 120.0 | C19—C20—H20B | 109.6 |
C6—C7—H7 | 120.0 | H20A—C20—H20B | 108.1 |
C7—C8—C9 | 120.0 (3) | C26—C21—C22 | 117.6 (2) |
C7—C8—H8 | 120.0 | C26—C21—C2 | 122.1 (2) |
C9—C8—H8 | 120.0 | C22—C21—C2 | 120.3 (2) |
C8—C9—C13 | 118.9 (3) | O27A—C22—C23 | 114.5 (4) |
C8—C9—H9 | 120.5 | O27A—C22—C21 | 123.7 (4) |
C13—C9—H9 | 120.5 | C23—C22—C21 | 121.8 (3) |
C14—C11—C4 | 114.4 (2) | C23—C22—H22 | 119.1 |
C14—C11—C5 | 119.7 (2) | C21—C22—H22 | 119.1 |
C4—C11—C5 | 125.7 (2) | C22—O27A—H27A | 109.5 |
C13—C12—C6 | 116.7 (2) | C24—C23—C22 | 119.3 (3) |
C13—C12—C5 | 121.2 (2) | C24—C23—H23 | 120.4 |
C6—C12—C5 | 122.1 (2) | C22—C23—H23 | 120.4 |
C12—C13—C9 | 122.9 (3) | C23—C24—C25 | 121.3 (3) |
C12—C13—O10 | 121.5 (2) | C23—C24—H24 | 119.3 |
C9—C13—O10 | 115.6 (2) | C25—C24—H24 | 119.3 |
N1—C14—O10 | 110.9 (2) | C24—C25—C26 | 119.5 (3) |
N1—C14—C11 | 125.8 (2) | C24—C25—H25 | 120.2 |
O10—C14—C11 | 123.3 (2) | C26—C25—H25 | 120.2 |
N15—C16—C17 | 110.1 (2) | O27B—C26—C21 | 122.8 (3) |
N15—C16—H16A | 109.6 | O27B—C26—C25 | 116.7 (3) |
C17—C16—H16A | 109.6 | C21—C26—C25 | 120.5 (3) |
N15—C16—H16B | 109.6 | C21—C26—H26 | 119.8 |
C17—C16—H16B | 109.6 | C25—C26—H26 | 119.8 |
H16A—C16—H16B | 108.2 | C26—O27B—H27B | 109.5 |
C16—C17—C18 | 112.5 (2) | C14—N1—C2 | 115.1 (2) |
C16—C17—H17A | 109.1 | C2—N3—C4 | 118.7 (2) |
C18—C17—H17A | 109.1 | C4—N15—C20 | 122.37 (19) |
C16—C17—H17B | 109.1 | C4—N15—C16 | 119.1 (2) |
C18—C17—H17B | 109.1 | C20—N15—C16 | 111.89 (19) |
H17A—C17—H17B | 107.8 | C14—O10—C13 | 117.75 (19) |
C12—C6—C7—C8 | 0.4 (4) | C26—C21—C22—C23 | 1.1 (2) |
C6—C7—C8—C9 | −0.4 (4) | C2—C21—C22—C23 | −178.3 (2) |
C7—C8—C9—C13 | 0.6 (4) | O27A—C22—C23—C24 | 179.2 (2) |
N3—C4—C11—C14 | −1.7 (3) | C21—C22—C23—C24 | −1.3 (3) |
N15—C4—C11—C14 | −178.1 (2) | C22—C23—C24—C25 | 0.0 (4) |
N3—C4—C11—C5 | 173.0 (2) | C23—C24—C25—C26 | 1.4 (4) |
N15—C4—C11—C5 | −3.4 (4) | C22—C21—C26—O27B | −177.9 (2) |
C12—C5—C11—C14 | 15.2 (3) | C2—C21—C26—O27B | 1.5 (3) |
C12—C5—C11—C4 | −159.2 (2) | C22—C21—C26—C25 | 0.3 (3) |
C7—C6—C12—C13 | −0.6 (4) | C2—C21—C26—C25 | 179.8 (2) |
C7—C6—C12—C5 | 178.7 (2) | C24—C25—C26—O27B | 176.8 (2) |
C11—C5—C12—C13 | −17.3 (3) | C24—C25—C26—C21 | −1.5 (4) |
C11—C5—C12—C6 | 163.5 (2) | O10—C14—N1—C2 | −175.57 (18) |
C6—C12—C13—C9 | 0.8 (4) | C11—C14—N1—C2 | 3.3 (3) |
C5—C12—C13—C9 | −178.4 (2) | N3—C2—N1—C14 | −2.0 (3) |
C6—C12—C13—O10 | −178.6 (2) | C21—C2—N1—C14 | 178.36 (19) |
C5—C12—C13—O10 | 2.1 (3) | N1—C2—N3—C4 | −0.9 (3) |
C8—C9—C13—C12 | −0.8 (4) | C21—C2—N3—C4 | 178.68 (18) |
C8—C9—C13—O10 | 178.7 (2) | N15—C4—N3—C2 | 179.44 (19) |
C4—C11—C14—N1 | −1.5 (3) | C11—C4—N3—C2 | 2.9 (3) |
C5—C11—C14—N1 | −176.5 (2) | N3—C4—N15—C20 | 137.0 (2) |
C4—C11—C14—O10 | 177.2 (2) | C11—C4—N15—C20 | −46.5 (3) |
C5—C11—C14—O10 | 2.2 (3) | N3—C4—N15—C16 | −12.1 (3) |
N15—C16—C17—C18 | −54.4 (3) | C11—C4—N15—C16 | 164.4 (2) |
C16—C17—C18—C19 | 53.0 (3) | C19—C20—N15—C4 | 148.4 (2) |
C17—C18—C19—C20 | −54.2 (3) | C19—C20—N15—C16 | −60.5 (3) |
C18—C19—C20—N15 | 58.2 (3) | C17—C16—N15—C4 | −149.8 (2) |
N3—C2—C21—C26 | −179.10 (19) | C17—C16—N15—C20 | 58.0 (3) |
N1—C2—C21—C26 | 0.6 (3) | N1—C14—O10—C13 | 160.0 (2) |
N3—C2—C21—C22 | 0.4 (3) | C11—C14—O10—C13 | −18.9 (3) |
N1—C2—C21—C22 | −179.98 (17) | C12—C13—O10—C14 | 16.6 (3) |
C26—C21—C22—O27A | −179.45 (14) | C9—C13—O10—C14 | −162.9 (2) |
C2—C21—C22—O27A | 1.1 (2) |
Cg is the centroid of the C6–C9/C12/C13 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O27A—H27A···N3 | 0.82 | 1.78 | 2.535 (3) | 151 |
O27B—H27B···N1 | 0.82 | 1.83 | 2.551 (3) | 146 |
C5—H5B···Cgi | 0.97 | 2.67 | 3.59 | 159 |
Symmetry code: (i) −x, −y+1, −z. |
Cg is the centroid of the C6–C9/C12/C13 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O27A—H27A···N3 | 0.82 | 1.78 | 2.535 (3) | 151 |
O27B—H27B···N1 | 0.82 | 1.83 | 2.551 (3) | 146 |
C5—H5B···Cgi | 0.97 | 2.67 | 3.59 | 159 |
Symmetry code: (i) −x, −y+1, −z. |
Acknowledgements
RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. GB is thankful to the CSIR, New Delhi, for financial support [grant No. 02 (110)/12/EMR-II]. SD is grateful to the UGC, New Delhi, for the award of a Junior Research Fellowship.
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Benzopyrano[2,3-d]pyrimidines have gained much attention as significant medicinal scaffolds due to their inherent and multidirectional pharmaceutical potentials that include anti-inflammatory, analgesic, and anti-aggregating activities (Bruno et al., 2001,2004). More importantly, such chemical entities have been found to exhibit potent in vivo antitumor as well as in vitro cytotoxic activity against various cancer cell lines causing considerable degree of perturbation in cell cycle kinetics (Hadfield et al., 1999). Very recently, we have developed a straight forward and efficient pseudo four-component one-pot synthesis of diverse benzopyrano[2,3-d]pyrimidine scaffolds in good yields using commercially available sodium formate as an inexpensive and non-toxic catalyst (Brahmachari & Das, 2014). Herein, we wish to report the environmentally benign one-pot synthesis and X-ray crystal structure of 2-(4-(piperidin-1-yl)-5H-chromeno[2,3-d]pyrimidin-2-yl)phenol.
The molecular structure of the title compound (I) is shown in Fig. 1. In (I), the expected values for the bond-lengths are observed (Allen et al., 1987) and the distances are comparable to a closely related structure (Gajera et al., 2013). The pyrimidine ring (A) is essentially planar with a maximum deviation of 0.019 (2) Å for C4. This ring forms dihedral angles of 22.70 (8)° and 0.97 (7)°, respectively, with the fused benzene ring (B) and hydroxy-substituted benzene ring (E). The pyran ring (C) adopts a flattened twist-boat conformation with asymmetry parameters [ΔCs(C5—C10)=2.61, ΔC2(C11—C14)=2.66] and the piperidine ring (D) adopts chair conformation with asymmetry parameters [ΔCs(C17—C20)=2.67, ΔC2(C17—C8)=0.2] (Duax & Norton, 1975). The hydroxy group was refined as disordered over two sets of sites in a 0.702 (4): 0.298 (4) ratio. The disorder corresponds to a rotation of approxomiately 180° about the C2—C21 bond and hence, both the major and minor components of disorder form intramolecular O—H···N hydrogen bonds (see Table 1). In the crystal, pairs of weak C—H···π interactions form inversion dimers. In addition, π–π interactions are observed between the pyrimidine ring and hydroxy-substituted benzene ring [centroid–centroid seperation = 3.739 (2) Å, interplanar spacing = 3.534 Å, centriod shift = 1.22 Å, symmetry code: 1 - x,1 - y,1 - z]. The crystal packing is shown in Fig. 2.