6-Hy-droxy-5-[(2-hy-droxy-4,4-dimethyl-6-oxo-cyclo-hex-1-en-yl)(4-nitro-phen-yl)meth-yl]-1,3-di-methyl-pyrimidine-2,4(1H,3H)-dione.

In the title compound, C21H23N3O7, the pyrimidine-dione ring adopts a screw-boat conformation, whereas the cyclo-hexenone ring adopts an envelope conformation, with the C atom bearing the methyl groups as the flap atom. The dihedral angle between the mean planes of the pyrimidine-dione and cyclo-hexenone rings is 58.78 (2)°. The pyrimidine-dione and cyclo-hexenone rings form dihedral angles of 59.94 (3) and 54.73 (2)°, respectively, with the 4-nitro-phenyl ring. Relatively strong intra-molecular O-H⋯O hydrogen bonds are observed. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming a chain along the c-axis direction.

Related literature

For related syntheses, see: Horning & Horning (1946 ▶); Kaupp et al. (2003 ▶). For biological and pharmaceutical properties of pyrimidine derivatives, see: Ibrahim & El-Metwally (2010 ▶); Kappe (1993 ▶); Campbell et al. (1988 ▶); Elinson et al. (2006 ▶); Sun et al. (2006 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the crystal structure of a related bis­dimedone derivative, see: Sughanya & Sureshbabu (2012 ▶). For the assignment of ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C21H23N3O7

M = 429.42

Monoclinic,

a = 12.7470 (2) Å

b = 14.0577 (3) Å

c = 11.7639 (2) Å

β = 99.752 (1)°

V = 2077.55 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.953, T max = 0.996

19038 measured reflections

3655 independent reflections

2930 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.111

S = 1.03

3655 reflections

284 parameters

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813028584/is5316sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028584/is5316Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813028584/is5316Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H23N3O7	F(000) = 904
Mr = 429.42	Dx = 1.373 Mg m−3
Monoclinic, P21/c	Melting point: 446 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.7470 (2) Å	Cell parameters from 6971 reflections
b = 14.0577 (3) Å	θ = 2.3–31.1°
c = 11.7639 (2) Å	µ = 0.10 mm−1
β = 99.752 (1)°	T = 296 K
V = 2077.55 (7) Å3	Block, yellow
Z = 4	0.30 × 0.20 × 0.20 mm

Bruker Kappa APEXII CCD diffractometer	3655 independent reflections
Radiation source: fine-focus sealed tube	2930 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω and φ scan	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→15
Tmin = 0.953, Tmax = 0.996	k = −16→16
19038 measured reflections	l = −13→13

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0532P)2 + 0.7319P] where P = (Fo2 + 2Fc2)/3
3655 reflections	(Δ/σ)max < 0.001
284 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.43994 (13)	0.52617 (14)	0.32945 (15)	0.0463 (4)
C3	0.31661 (13)	0.58663 (12)	0.44572 (15)	0.0405 (4)
C4	0.28899 (12)	0.49692 (12)	0.47480 (14)	0.0379 (4)
C5	0.34740 (13)	0.41934 (12)	0.44258 (14)	0.0393 (4)
C7	0.47199 (16)	0.35565 (15)	0.32496 (18)	0.0574 (5)
H7A	0.4211	0.3198	0.2725	0.086*
H7B	0.5024	0.3158	0.3883	0.086*
H7C	0.5273	0.3781	0.2855	0.086*
C8	0.41348 (18)	0.69691 (15)	0.3370 (2)	0.0674 (6)
H8A	0.4819	0.6971	0.3132	0.101*
H8B	0.4142	0.7405	0.4000	0.101*
H8C	0.3600	0.7161	0.2736	0.101*
C9	0.19863 (12)	0.48072 (12)	0.54145 (14)	0.0367 (4)
H9	0.1586	0.5406	0.5336	0.044*
C10	0.23508 (12)	0.46936 (12)	0.67044 (14)	0.0372 (4)
C11	0.25023 (13)	0.55493 (12)	0.73689 (15)	0.0400 (4)
C12	0.28119 (16)	0.55040 (13)	0.86545 (16)	0.0503 (5)
H12A	0.2477	0.6030	0.8990	0.060*
H12B	0.3576	0.5589	0.8853	0.060*
C13	0.25105 (16)	0.45824 (14)	0.91944 (16)	0.0518 (5)
C14	0.29180 (17)	0.37709 (14)	0.85299 (16)	0.0541 (5)
H14A	0.3685	0.3730	0.8756	0.065*
H14B	0.2617	0.3180	0.8753	0.065*
C15	0.26648 (13)	0.38623 (12)	0.72543 (15)	0.0419 (4)
C16	0.3044 (2)	0.45346 (18)	1.04585 (18)	0.0775 (7)
H16A	0.3802	0.4564	1.0507	0.116*
H16B	0.2854	0.3949	1.0791	0.116*
H16C	0.2809	0.5061	1.0871	0.116*
C17	0.13041 (19)	0.45314 (18)	0.9135 (2)	0.0700 (6)
H17A	0.1071	0.5066	0.9533	0.105*
H17B	0.1123	0.3953	0.9490	0.105*
H17C	0.0961	0.4543	0.8343	0.105*
C18	0.11860 (12)	0.40589 (12)	0.48585 (14)	0.0368 (4)
C19	0.05242 (13)	0.35990 (13)	0.54975 (14)	0.0419 (4)
H19	0.0575	0.3744	0.6276	0.050*
C20	−0.02105 (13)	0.29298 (13)	0.50096 (14)	0.0410 (4)
H20	−0.0648	0.2624	0.5452	0.049*
C21	−0.02800 (12)	0.27259 (12)	0.38590 (14)	0.0391 (4)
C22	0.03304 (15)	0.31929 (15)	0.31838 (15)	0.0527 (5)
H22	0.0258	0.3061	0.2400	0.063*
C23	0.10532 (15)	0.38612 (15)	0.36873 (15)	0.0514 (5)
H23	0.1462	0.4188	0.3231	0.062*
N1	−0.10298 (12)	0.19886 (11)	0.33551 (13)	0.0476 (4)
N2	0.41894 (11)	0.43692 (11)	0.36855 (13)	0.0441 (4)
N3	0.38954 (11)	0.60059 (11)	0.37410 (13)	0.0464 (4)
O1	0.50086 (11)	0.53864 (11)	0.26191 (12)	0.0635 (4)
O2	0.27934 (10)	0.66554 (8)	0.48297 (11)	0.0500 (3)
H2	0.2621	0.6561	0.5461	0.075*
O3	0.33804 (10)	0.33569 (9)	0.47517 (11)	0.0483 (3)
O4	0.24328 (10)	0.63529 (9)	0.69037 (11)	0.0494 (3)
O5	0.27781 (11)	0.30563 (9)	0.67125 (11)	0.0527 (3)
H5	0.2868	0.3171	0.6052	0.079*
O6	−0.16084 (13)	0.16313 (11)	0.39533 (12)	0.0695 (4)
O7	−0.10407 (13)	0.17628 (13)	0.23596 (13)	0.0773 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0342 (9)	0.0604 (12)	0.0431 (10)	−0.0059 (8)	0.0029 (8)	0.0007 (9)
C3	0.0339 (8)	0.0411 (10)	0.0448 (9)	0.0020 (7)	0.0013 (7)	0.0043 (8)
C4	0.0329 (8)	0.0388 (9)	0.0410 (9)	−0.0012 (7)	0.0038 (7)	0.0008 (7)
C5	0.0344 (8)	0.0411 (10)	0.0408 (9)	−0.0026 (7)	0.0022 (7)	−0.0040 (8)
C7	0.0478 (11)	0.0640 (13)	0.0630 (12)	0.0038 (9)	0.0168 (9)	−0.0149 (10)
C8	0.0674 (14)	0.0561 (13)	0.0821 (15)	−0.0027 (11)	0.0222 (12)	0.0254 (11)
C9	0.0333 (8)	0.0342 (8)	0.0422 (9)	0.0034 (7)	0.0047 (7)	0.0004 (7)
C10	0.0318 (8)	0.0374 (9)	0.0418 (9)	0.0005 (7)	0.0044 (7)	−0.0016 (7)
C11	0.0331 (8)	0.0383 (10)	0.0477 (10)	0.0015 (7)	0.0044 (7)	−0.0010 (8)
C12	0.0535 (11)	0.0468 (11)	0.0480 (10)	−0.0034 (9)	0.0015 (9)	−0.0074 (8)
C13	0.0624 (12)	0.0499 (11)	0.0417 (10)	−0.0017 (9)	0.0050 (9)	−0.0013 (8)
C14	0.0667 (12)	0.0450 (11)	0.0481 (11)	0.0050 (9)	0.0024 (9)	0.0051 (9)
C15	0.0404 (9)	0.0384 (10)	0.0460 (10)	0.0021 (7)	0.0044 (7)	−0.0012 (8)
C16	0.109 (2)	0.0723 (16)	0.0466 (12)	0.0021 (14)	−0.0003 (12)	−0.0014 (11)
C17	0.0708 (14)	0.0786 (16)	0.0646 (14)	−0.0145 (12)	0.0228 (11)	−0.0096 (12)
C18	0.0305 (8)	0.0409 (9)	0.0383 (9)	0.0023 (7)	0.0036 (7)	0.0014 (7)
C19	0.0383 (9)	0.0539 (11)	0.0343 (8)	−0.0025 (8)	0.0085 (7)	−0.0039 (8)
C20	0.0361 (9)	0.0491 (10)	0.0391 (9)	−0.0044 (7)	0.0097 (7)	0.0024 (8)
C21	0.0322 (8)	0.0447 (10)	0.0398 (9)	−0.0003 (7)	0.0045 (7)	−0.0011 (7)
C22	0.0469 (10)	0.0786 (14)	0.0331 (9)	−0.0154 (10)	0.0080 (8)	−0.0053 (9)
C23	0.0448 (10)	0.0719 (13)	0.0382 (10)	−0.0171 (9)	0.0090 (8)	0.0042 (9)
N1	0.0424 (8)	0.0535 (9)	0.0461 (9)	−0.0038 (7)	0.0055 (7)	−0.0050 (7)
N2	0.0367 (8)	0.0493 (9)	0.0472 (8)	−0.0011 (6)	0.0099 (6)	−0.0063 (7)
N3	0.0399 (8)	0.0475 (9)	0.0522 (9)	−0.0033 (7)	0.0092 (7)	0.0095 (7)
O1	0.0520 (8)	0.0836 (11)	0.0597 (8)	−0.0101 (7)	0.0235 (7)	0.0018 (7)
O2	0.0524 (7)	0.0388 (7)	0.0599 (8)	0.0050 (6)	0.0123 (6)	0.0063 (6)
O3	0.0532 (7)	0.0369 (7)	0.0564 (8)	0.0026 (6)	0.0136 (6)	−0.0042 (6)
O4	0.0564 (8)	0.0358 (7)	0.0542 (8)	0.0024 (6)	0.0040 (6)	−0.0025 (6)
O5	0.0673 (9)	0.0386 (7)	0.0513 (7)	0.0102 (6)	0.0072 (6)	−0.0010 (6)
O6	0.0794 (10)	0.0691 (10)	0.0623 (9)	−0.0344 (8)	0.0185 (8)	−0.0005 (7)
O7	0.0736 (10)	0.1064 (13)	0.0537 (9)	−0.0336 (9)	0.0157 (7)	−0.0312 (9)

C1—O1	1.214 (2)	C13—C14	1.523 (3)
C1—N3	1.377 (2)	C13—C16	1.528 (3)
C1—N2	1.378 (2)	C13—C17	1.529 (3)
C3—O2	1.311 (2)	C14—C15	1.486 (2)
C3—C4	1.368 (2)	C14—H14A	0.9700
C3—N3	1.370 (2)	C14—H14B	0.9700
C4—C5	1.408 (2)	C15—O5	1.320 (2)
C4—C9	1.516 (2)	C16—H16A	0.9600
C5—O3	1.249 (2)	C16—H16B	0.9600
C5—N2	1.386 (2)	C16—H16C	0.9600
C7—N2	1.464 (2)	C17—H17A	0.9600
C7—H7A	0.9600	C17—H17B	0.9600
C7—H7B	0.9600	C17—H17C	0.9600
C7—H7C	0.9600	C18—C19	1.382 (2)
C8—N3	1.470 (2)	C18—C23	1.387 (2)
C8—H8A	0.9600	C19—C20	1.382 (2)
C8—H8B	0.9600	C19—H19	0.9300
C8—H8C	0.9600	C20—C21	1.372 (2)
C9—C10	1.518 (2)	C20—H20	0.9300
C9—C18	1.533 (2)	C21—C22	1.370 (2)
C9—H9	0.9800	C21—N1	1.465 (2)
C10—C15	1.363 (2)	C22—C23	1.378 (3)
C10—C11	1.430 (2)	C22—H22	0.9300
C11—O4	1.252 (2)	C23—H23	0.9300
C11—C12	1.498 (2)	N1—O7	1.2112 (19)
C12—C13	1.520 (3)	N1—O6	1.211 (2)
C12—H12A	0.9700	O2—H2	0.8200
C12—H12B	0.9700	O5—H5	0.8200
O1—C1—N3	122.09 (18)	C15—C14—H14A	108.6
O1—C1—N2	122.13 (18)	C13—C14—H14A	108.6
N3—C1—N2	115.77 (15)	C15—C14—H14B	108.6
O2—C3—C4	124.97 (16)	C13—C14—H14B	108.6
O2—C3—N3	113.98 (15)	H14A—C14—H14B	107.6
C4—C3—N3	121.04 (16)	O5—C15—C10	123.67 (16)
C3—C4—C5	118.45 (15)	O5—C15—C14	112.99 (15)
C3—C4—C9	121.19 (15)	C10—C15—C14	123.34 (16)
C5—C4—C9	120.36 (15)	C13—C16—H16A	109.5
O3—C5—N2	117.92 (15)	C13—C16—H16B	109.5
O3—C5—C4	124.36 (16)	H16A—C16—H16B	109.5
N2—C5—C4	117.72 (15)	C13—C16—H16C	109.5
N2—C7—H7A	109.5	H16A—C16—H16C	109.5
N2—C7—H7B	109.5	H16B—C16—H16C	109.5
H7A—C7—H7B	109.5	C13—C17—H17A	109.5
N2—C7—H7C	109.5	C13—C17—H17B	109.5
H7A—C7—H7C	109.5	H17A—C17—H17B	109.5
H7B—C7—H7C	109.5	C13—C17—H17C	109.5
N3—C8—H8A	109.5	H17A—C17—H17C	109.5
N3—C8—H8B	109.5	H17B—C17—H17C	109.5
H8A—C8—H8B	109.5	C19—C18—C23	117.61 (15)
N3—C8—H8C	109.5	C19—C18—C9	120.83 (14)
H8A—C8—H8C	109.5	C23—C18—C9	121.44 (15)
H8B—C8—H8C	109.5	C18—C19—C20	121.72 (15)
C4—C9—C10	113.70 (13)	C18—C19—H19	119.1
C4—C9—C18	113.04 (13)	C20—C19—H19	119.1
C10—C9—C18	115.04 (13)	C21—C20—C19	118.56 (15)
C4—C9—H9	104.5	C21—C20—H20	120.7
C10—C9—H9	104.5	C19—C20—H20	120.7
C18—C9—H9	104.5	C22—C21—C20	121.60 (16)
C15—C10—C11	117.41 (15)	C22—C21—N1	120.00 (15)
C15—C10—C9	125.47 (15)	C20—C21—N1	118.40 (15)
C11—C10—C9	116.62 (14)	C21—C22—C23	118.80 (16)
O4—C11—C10	121.82 (16)	C21—C22—H22	120.6
O4—C11—C12	117.81 (15)	C23—C22—H22	120.6
C10—C11—C12	120.28 (15)	C22—C23—C18	121.59 (16)
C11—C12—C13	114.57 (15)	C22—C23—H23	119.2
C11—C12—H12A	108.6	C18—C23—H23	119.2
C13—C12—H12A	108.6	O7—N1—O6	123.01 (16)
C11—C12—H12B	108.6	O7—N1—C21	118.45 (15)
C13—C12—H12B	108.6	O6—N1—C21	118.55 (15)
H12A—C12—H12B	107.6	C1—N2—C5	123.91 (15)
C12—C13—C14	106.95 (16)	C1—N2—C7	117.79 (15)
C12—C13—C16	109.98 (17)	C5—N2—C7	118.24 (15)
C14—C13—C16	109.41 (17)	C3—N3—C1	122.31 (15)
C12—C13—C17	110.12 (17)	C3—N3—C8	120.72 (16)
C14—C13—C17	111.65 (17)	C1—N3—C8	116.91 (16)
C16—C13—C17	108.70 (18)	C3—O2—H2	109.5
C15—C14—C13	114.76 (15)	C15—O5—H5	109.5
O2—C3—C4—C5	−170.34 (15)	C4—C9—C18—C19	159.10 (15)
N3—C3—C4—C5	8.5 (2)	C10—C9—C18—C19	26.2 (2)
O2—C3—C4—C9	8.9 (3)	C4—C9—C18—C23	−24.9 (2)
N3—C3—C4—C9	−172.22 (15)	C10—C9—C18—C23	−157.83 (16)
C3—C4—C5—O3	171.47 (16)	C23—C18—C19—C20	3.2 (3)
C9—C4—C5—O3	−7.8 (2)	C9—C18—C19—C20	179.29 (15)
C3—C4—C5—N2	−9.4 (2)	C18—C19—C20—C21	−0.3 (3)
C9—C4—C5—N2	171.30 (14)	C19—C20—C21—C22	−2.4 (3)
C3—C4—C9—C10	−96.64 (18)	C19—C20—C21—N1	177.59 (15)
C5—C4—C9—C10	82.59 (19)	C20—C21—C22—C23	2.1 (3)
C3—C4—C9—C18	129.82 (16)	N1—C21—C22—C23	−177.94 (17)
C5—C4—C9—C18	−51.0 (2)	C21—C22—C23—C18	1.0 (3)
C4—C9—C10—C15	−86.4 (2)	C19—C18—C23—C22	−3.5 (3)
C18—C9—C10—C15	46.2 (2)	C9—C18—C23—C22	−179.63 (18)
C4—C9—C10—C11	85.25 (17)	C22—C21—N1—O7	4.9 (3)
C18—C9—C10—C11	−142.16 (15)	C20—C21—N1—O7	−175.09 (18)
C15—C10—C11—O4	166.07 (16)	C22—C21—N1—O6	−175.25 (18)
C9—C10—C11—O4	−6.3 (2)	C20—C21—N1—O6	4.7 (2)
C15—C10—C11—C12	−10.5 (2)	O1—C1—N2—C5	−177.80 (16)
C9—C10—C11—C12	177.14 (14)	N3—C1—N2—C5	3.8 (2)
O4—C11—C12—C13	159.47 (16)	O1—C1—N2—C7	−0.6 (3)
C10—C11—C12—C13	−23.8 (2)	N3—C1—N2—C7	−179.05 (15)
C11—C12—C13—C14	50.5 (2)	O3—C5—N2—C1	−177.50 (15)
C11—C12—C13—C16	169.25 (18)	C4—C5—N2—C1	3.4 (2)
C11—C12—C13—C17	−71.0 (2)	O3—C5—N2—C7	5.4 (2)
C12—C13—C14—C15	−47.2 (2)	C4—C5—N2—C7	−173.79 (15)
C16—C13—C14—C15	−166.26 (18)	O2—C3—N3—C1	177.86 (15)
C17—C13—C14—C15	73.4 (2)	C4—C3—N3—C1	−1.1 (2)
C11—C10—C15—O5	−165.52 (16)	O2—C3—N3—C8	−5.1 (2)
C9—C10—C15—O5	6.1 (3)	C4—C3—N3—C8	175.86 (17)
C11—C10—C15—C14	14.3 (3)	O1—C1—N3—C3	176.59 (16)
C9—C10—C15—C14	−174.07 (16)	N2—C1—N3—C3	−5.0 (2)
C13—C14—C15—O5	−163.61 (17)	O1—C1—N3—C8	−0.5 (3)
C13—C14—C15—C10	16.5 (3)	N2—C1—N3—C8	177.89 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14B···O3i	0.97	2.57	3.328 (2)	135
C20—H20···O7i	0.93	2.53	3.153 (2)	125
O2—H2···O4	0.82	1.78	2.5932 (18)	172
O5—H5···O3	0.82	1.78	2.5863 (18)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯O3i	0.97	2.57	3.328 (2)	135
C20—H20⋯O7i	0.93	2.53	3.153 (2)	125
O2—H2⋯O4	0.82	1.78	2.5932 (18)	172
O5—H5⋯O3	0.82	1.78	2.5863 (18)	167

Symmetry code: (i) .