Crystal structure of ethyl (2S)-9-meth-oxy-2-methyl-4-oxo-3,4,5,6-tetra-hydro-2H- 2,6-methano-benzo[g][1,3,5]oxa-diazocine-11-carboxyl-ate.

In the title compound, C15H18N2O5, the meth-oxy-phenyl ring makes a dihedral angle of 84.70 (12)° with the mean plane of the tetra-hydro-pyrimidin-2(1H)-one ring. Both the pyran and tetra-hydro-pyrimidin-2(1H)-one rings have distorted envelope conformations with the carboxyl-ate-substituted C atom as the flap. In the crystal, mol-ecules are linked via pairs of N-H⋯O hydrogen bonds, forming zigzag chains propagating along [010], which enclose R (2) 2(8) ring motifs. The chains are linked by C-H⋯π inter-actions, forming a two-dimensional network parallel to (100).

Related literature

For the biological activity of di­hydro­pyrimidine derivatives, see: Hurst & Hull (1961 ▸); Ashok et al. (2007 ▸); Bahekar & Shinde (2004 ▸); Mayer et al. (1999 ▸); Kappe (2000 ▸); For the crystal structures of two very similar compounds, see: Jing et al. (2009 ▸); Yar et al. (2014 ▸; Liu et al. (2014 ▸).

Experimental

Crystal data

C15H18N2O5

M = 306.31

Monoclinic,

a = 9.6982 (14) Å

b = 7.4802 (12) Å

c = 10.8293 (17) Å

β = 111.252 (5)°

V = 732.2 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 295 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T min = 0.954, T max = 0.975

10886 measured reflections

3030 independent reflections

2029 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.071

wR(F 2) = 0.175

S = 1.14

3030 reflections

203 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.25 e Å−3

Absolute structure: Flack (1983 ▸), 1371 Friedel pairs

Absolute structure parameter: 0.01 (4)

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸, 2015 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015000559/su5057sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015000559/su5057Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015000559/su5057Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015000559/su5057fig1.tif

The mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015000559/su5057fig2.tif

The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1043105

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

C15H18N2O5	F(000) = 324
Mr = 306.31	Dx = 1.389 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3030 reflections
a = 9.6982 (14) Å	θ = 2.0–26.8°
b = 7.4802 (12) Å	µ = 0.11 mm−1
c = 10.8293 (17) Å	T = 295 K
β = 111.252 (5)°	Block, colourless
V = 732.2 (2) Å3	0.25 × 0.20 × 0.20 mm
Z = 2

Bruker APEXII CCD diffractometer	3030 independent reflections
Radiation source: fine-focus sealed tube	2029 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 0 pixels mm-1	θmax = 26.9°, θmin = 2.0°
ω and φ scans	h = −11→12
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→9
Tmin = 0.954, Tmax = 0.975	l = −13→13
10886 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.071	w = 1/[σ2(Fo2) + (0.0537P)2 + 0.7506P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.175	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 0.26 e Å−3
3030 reflections	Δρmin = −0.25 e Å−3
203 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
1 restraint	Extinction coefficient: 0.031 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1371 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.01 (4)

	x	y	z	Uiso*/Ueq
C1	0.9053 (5)	0.2379 (7)	0.5750 (5)	0.0437 (13)
C2	0.8132 (5)	0.0956 (7)	0.5239 (5)	0.0412 (12)
H2	0.8430	−0.0198	0.5535	0.049*
C3	0.6753 (5)	0.1257 (6)	0.4278 (4)	0.0325 (10)
C4	0.6293 (5)	0.2978 (6)	0.3837 (4)	0.0309 (10)
C5	0.7245 (6)	0.4362 (6)	0.4375 (5)	0.0375 (11)
H5	0.6948	0.5519	0.4085	0.045*
C6	0.8629 (6)	0.4105 (7)	0.5331 (5)	0.0455 (13)
H6	0.9257	0.5066	0.5682	0.055*
C7	0.4765 (5)	0.3254 (6)	0.2807 (4)	0.0299 (10)
H7	0.4353	0.4379	0.2984	0.036*
C8	0.4926 (4)	0.1772 (6)	0.0871 (4)	0.0302 (9)
C9	0.4544 (5)	0.0033 (6)	0.2670 (4)	0.0295 (10)
C10	0.3772 (4)	0.1706 (6)	0.2878 (4)	0.0308 (9)
H10	0.3722	0.1671	0.3765	0.037*
C11	0.2243 (5)	0.2001 (7)	0.1873 (5)	0.0412 (11)
C12	0.0178 (7)	0.3958 (9)	0.1308 (6)	0.0700 (19)
H12A	0.0121	0.3701	0.0413	0.084*
H12B	0.0123	0.5244	0.1396	0.084*
C13	−0.1071 (7)	0.3110 (11)	0.1540 (7)	0.088 (2)
H13A	−0.1119	0.1870	0.1299	0.132*
H13B	−0.1974	0.3693	0.1011	0.132*
H13C	−0.0937	0.3212	0.2460	0.132*
C14	0.3703 (5)	−0.1689 (6)	0.2594 (5)	0.0398 (12)
H14A	0.2826	−0.1685	0.1810	0.060*
H14B	0.3432	−0.1792	0.3361	0.060*
H14C	0.4316	−0.2683	0.2564	0.060*
C15	1.1301 (7)	0.3274 (10)	0.7503 (6)	0.074 (2)
H15A	1.1513	0.4157	0.6953	0.111*
H15B	1.2209	0.2756	0.8085	0.111*
H15C	1.0794	0.3828	0.8017	0.111*
N1	0.4778 (4)	0.3287 (5)	0.1464 (3)	0.0341 (9)
H1	0.4690	0.4288	0.1051	0.041*
N2	0.4908 (4)	0.0226 (4)	0.1509 (3)	0.0326 (9)
H2A	0.5136	−0.0733	0.1187	0.039*
O1	0.5875 (3)	−0.0211 (4)	0.3833 (3)	0.0343 (8)
O2	0.5039 (3)	0.1774 (4)	−0.0236 (3)	0.0383 (8)
O3	0.1709 (4)	0.1240 (6)	0.0862 (4)	0.0817 (15)
O4	0.1593 (4)	0.3304 (6)	0.2256 (4)	0.0650 (12)
O5	1.0392 (4)	0.1917 (6)	0.6693 (4)	0.0682 (12)

	U11	U22	U33	U12	U13	U23
C1	0.033 (3)	0.059 (3)	0.037 (3)	0.002 (2)	0.010 (2)	−0.003 (2)
C2	0.044 (3)	0.040 (3)	0.039 (3)	0.006 (2)	0.014 (2)	0.003 (2)
C3	0.040 (3)	0.028 (2)	0.031 (2)	−0.001 (2)	0.016 (2)	−0.0004 (18)
C4	0.039 (3)	0.028 (2)	0.028 (2)	0.003 (2)	0.015 (2)	0.0012 (19)
C5	0.046 (3)	0.033 (3)	0.038 (3)	−0.003 (2)	0.020 (2)	0.000 (2)
C6	0.046 (3)	0.044 (3)	0.048 (3)	−0.015 (3)	0.018 (3)	−0.008 (2)
C7	0.042 (3)	0.023 (2)	0.028 (2)	0.000 (2)	0.017 (2)	−0.0006 (18)
C8	0.039 (2)	0.026 (2)	0.029 (2)	0.001 (2)	0.0161 (18)	0.000 (2)
C9	0.037 (2)	0.025 (2)	0.028 (2)	0.000 (2)	0.013 (2)	0.0020 (18)
C10	0.036 (2)	0.031 (2)	0.030 (2)	0.001 (2)	0.0173 (18)	−0.002 (2)
C11	0.042 (3)	0.040 (3)	0.042 (3)	0.002 (2)	0.016 (2)	−0.004 (2)
C12	0.060 (4)	0.077 (4)	0.065 (4)	0.028 (4)	0.014 (3)	0.009 (3)
C13	0.060 (4)	0.084 (5)	0.099 (5)	0.006 (4)	0.003 (4)	0.011 (5)
C14	0.051 (3)	0.030 (2)	0.047 (3)	−0.007 (2)	0.028 (2)	−0.002 (2)
C15	0.057 (4)	0.089 (5)	0.055 (3)	−0.020 (4)	−0.006 (3)	0.004 (4)
N1	0.058 (3)	0.0218 (18)	0.0261 (19)	0.0069 (18)	0.0197 (18)	0.0055 (15)
N2	0.050 (2)	0.0202 (19)	0.036 (2)	0.0038 (17)	0.0244 (19)	0.0013 (15)
O1	0.0418 (18)	0.0264 (16)	0.0315 (16)	0.0019 (14)	0.0092 (14)	0.0033 (13)
O2	0.062 (2)	0.0286 (16)	0.0309 (15)	−0.0006 (17)	0.0244 (14)	0.0015 (14)
O3	0.058 (3)	0.089 (3)	0.071 (3)	0.019 (2)	−0.011 (2)	−0.041 (3)
O4	0.060 (2)	0.074 (3)	0.051 (2)	0.037 (2)	0.0092 (19)	−0.004 (2)
O5	0.044 (2)	0.073 (3)	0.066 (2)	0.007 (2)	−0.0064 (19)	−0.008 (2)

C1—C2	1.371 (7)	C9—C10	1.516 (6)
C1—O5	1.373 (6)	C10—C11	1.504 (6)
C1—C6	1.381 (7)	C10—H10	0.9800
C2—C3	1.383 (6)	C11—O3	1.174 (5)
C2—H2	0.9300	C11—O4	1.308 (6)
C3—O1	1.366 (5)	C12—O4	1.468 (7)
C3—C4	1.389 (6)	C12—C13	1.468 (9)
C4—C5	1.369 (6)	C12—H12A	0.9700
C4—C7	1.511 (6)	C12—H12B	0.9700
C5—C6	1.379 (7)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—N1	1.459 (5)	C14—H14A	0.9600
C7—C10	1.526 (6)	C14—H14B	0.9600
C7—H7	0.9800	C14—H14C	0.9600
C8—O2	1.242 (5)	C15—O5	1.420 (7)
C8—N1	1.336 (5)	C15—H15A	0.9600
C8—N2	1.351 (5)	C15—H15B	0.9600
C9—N2	1.431 (6)	C15—H15C	0.9600
C9—O1	1.452 (5)	N1—H1	0.8600
C9—C14	1.510 (6)	N2—H2A	0.8600
C2—C1—O5	114.0 (5)	C7—C10—H10	109.1
C2—C1—C6	121.3 (4)	O3—C11—O4	123.8 (5)
O5—C1—C6	124.6 (5)	O3—C11—C10	126.1 (4)
C1—C2—C3	119.3 (4)	O4—C11—C10	110.0 (4)
C1—C2—H2	120.4	O4—C12—C13	110.9 (5)
C3—C2—H2	120.4	O4—C12—H12A	109.5
O1—C3—C2	116.3 (4)	C13—C12—H12A	109.5
O1—C3—C4	122.9 (4)	O4—C12—H12B	109.5
C2—C3—C4	120.8 (4)	C13—C12—H12B	109.5
C5—C4—C3	118.1 (4)	H12A—C12—H12B	108.1
C5—C4—C7	122.8 (4)	C12—C13—H13A	109.5
C3—C4—C7	119.1 (4)	C12—C13—H13B	109.5
C4—C5—C6	122.5 (4)	H13A—C13—H13B	109.5
C4—C5—H5	118.8	C12—C13—H13C	109.5
C6—C5—H5	118.8	H13A—C13—H13C	109.5
C5—C6—C1	118.1 (5)	H13B—C13—H13C	109.5
C5—C6—H6	121.0	C9—C14—H14A	109.5
C1—C6—H6	121.0	C9—C14—H14B	109.5
N1—C7—C4	112.2 (4)	H14A—C14—H14B	109.5
N1—C7—C10	107.3 (3)	C9—C14—H14C	109.5
C4—C7—C10	109.1 (3)	H14A—C14—H14C	109.5
N1—C7—H7	109.4	H14B—C14—H14C	109.5
C4—C7—H7	109.4	O5—C15—H15A	109.5
C10—C7—H7	109.4	O5—C15—H15B	109.5
O2—C8—N1	121.7 (4)	H15A—C15—H15B	109.5
O2—C8—N2	121.1 (4)	O5—C15—H15C	109.5
N1—C8—N2	117.2 (3)	H15A—C15—H15C	109.5
N2—C9—O1	110.5 (3)	H15B—C15—H15C	109.5
N2—C9—C14	109.8 (3)	C8—N1—C7	120.4 (4)
O1—C9—C14	103.5 (3)	C8—N1—H1	119.8
N2—C9—C10	109.8 (3)	C7—N1—H1	119.8
O1—C9—C10	107.8 (3)	C8—N2—C9	126.1 (3)
C14—C9—C10	115.2 (4)	C8—N2—H2A	117.0
C11—C10—C9	115.1 (4)	C9—N2—H2A	117.0
C11—C10—C7	109.1 (4)	C3—O1—C9	116.7 (3)
C9—C10—C7	105.3 (3)	C11—O4—C12	117.5 (4)
C11—C10—H10	109.1	C1—O5—C15	119.1 (5)
C9—C10—H10	109.1
O5—C1—C2—C3	−179.8 (4)	N1—C7—C10—C9	64.6 (4)
C6—C1—C2—C3	0.4 (7)	C4—C7—C10—C9	−57.2 (4)
C1—C2—C3—O1	−178.5 (4)	C9—C10—C11—O3	−12.8 (7)
C1—C2—C3—C4	−0.5 (7)	C7—C10—C11—O3	105.3 (6)
O1—C3—C4—C5	178.2 (4)	C9—C10—C11—O4	170.0 (4)
C2—C3—C4—C5	0.4 (6)	C7—C10—C11—O4	−71.9 (5)
O1—C3—C4—C7	−0.9 (6)	O2—C8—N1—C7	−175.1 (4)
C2—C3—C4—C7	−178.7 (4)	N2—C8—N1—C7	6.6 (6)
C3—C4—C5—C6	−0.2 (7)	C4—C7—N1—C8	75.5 (5)
C7—C4—C5—C6	178.9 (4)	C10—C7—N1—C8	−44.2 (5)
C4—C5—C6—C1	0.0 (7)	O2—C8—N2—C9	−169.1 (4)
C2—C1—C6—C5	−0.2 (7)	N1—C8—N2—C9	9.1 (6)
O5—C1—C6—C5	−179.9 (5)	O1—C9—N2—C8	−103.2 (5)
C5—C4—C7—N1	87.0 (5)	C14—C9—N2—C8	143.3 (4)
C3—C4—C7—N1	−94.0 (5)	C10—C9—N2—C8	15.7 (6)
C5—C4—C7—C10	−154.3 (4)	C2—C3—O1—C9	−169.5 (4)
C3—C4—C7—C10	24.7 (5)	C4—C3—O1—C9	12.6 (6)
N2—C9—C10—C11	69.2 (5)	N2—C9—O1—C3	72.7 (4)
O1—C9—C10—C11	−170.3 (3)	C14—C9—O1—C3	−169.9 (4)
C14—C9—C10—C11	−55.3 (5)	C10—C9—O1—C3	−47.4 (5)
N2—C9—C10—C7	−50.9 (4)	O3—C11—O4—C12	−6.2 (8)
O1—C9—C10—C7	69.5 (4)	C10—C11—O4—C12	171.1 (5)
C14—C9—C10—C7	−175.5 (4)	C13—C12—O4—C11	96.3 (7)
N1—C7—C10—C11	−59.5 (4)	C2—C1—O5—C15	−166.0 (5)
C4—C7—C10—C11	178.8 (3)	C6—C1—O5—C15	13.8 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.86	2.12	2.962 (5)	168
N2—H2A···O2ii	0.86	2.11	2.936 (4)	162
C14—H14B···Cg1iii	0.96	2.62	3.570 (6)	171

Table 1

Hydrogen-bond geometry (, )

Cg1 is the centroid of the C1C6 ring.

DHA	DH	HA	D A	DHA
N1H1O2i	0.86	2.12	2.962(5)	168
N2H2AO2ii	0.86	2.11	2.936(4)	162
C14H14B Cg1iii	0.96	2.62	3.570(6)	171

Symmetry codes: (i) ; (ii) ; (iii) .