2-[4-(Piperidin-1-yl)-5H-chromeno[2,3-d]pyrimidin-2-yl]phenol.

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 hy-droxy-substituted benzene ring. The piperidine ring has a chair conformation and the pyran ring has a flattened twist-boat conformation. The hy-droxy 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 intra-molecular O-H⋯N hydrogen bonds. In the crystal, pairs of weak C-H⋯π inter-actions form inversion dimers. In addition, π-π inter-actions are observed between the pyrimidine ring and the hy-droxy-substituted benzene ring [centroid-centroid separation = 3.739 (2) Å].

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 conformational analysis, see: Duax & Norton (1975 ▶).

Experimental

Crystal data

C22H21N3O2

M = 359.42

Monoclinic,

a = 9.9826 (5) Å

b = 15.8773 (7) Å

c = 12.2197 (6) Å

β = 109.381 (6)°

V = 1827.03 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.975, T max = 0.983

13349 measured reflections

3576 independent reflections

1918 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.133

S = 1.03

3576 reflections

254 parameters

12 restraints

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.16 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: 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.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814005625/lh5695sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814005625/lh5695Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814005625/lh5695Isup3.cml

CCDC reference: 975917

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

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)

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

Table 1

Hydrogen-bond geometry (Å, °)

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⋯Cg i	0.97	2.67	3.59	159

Symmetry code: (i) .