1-(2-Oxo-3,4-dihydro-2H-1,3-benzoxazin-4-yl)urea monohydrate

Kurbanova, M.M.; Novruzova, A.B.; Gurbanov, A.V.; Ismaylova, S.R.; Maharramov, A.M.

doi:10.1107/S1600536810032411

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2348

https://doi.org/10.1107/S1600536810032411

Open

access

1-(2-Oxo-3,4-dihydro-2H-1,3-benzoxazin-4-yl)urea monohydrate

Malahat M. Kurbanova,^a ^* Aysel B. Novruzova,^a Atash V. Gurbanov,^a Sheyda R. Ismaylova ^a and Abel M. Maharramov ^a

^aBaku State University, Z. Khalilov Street 23, Baku, AZ-1148, Azerbaijan
^*Correspondence e-mail: mkurbanova72@mail.ru

(Received 2 August 2010; accepted 11 August 2010; online 18 August 2010)

The organic molecule in the title hydrate, C₉H₉N₃O₃·H₂O, was obtained by the condenstation of salicylic aldehyde with urea in acetonitrile. The oxazine ring adopts a slightly distorted sofa conformation, with the N atom deviating from the plane passing through the other atoms of the ring by 0.267 (2) Å. The crystal structure displays intermolecular N—H⋯O and O—H⋯O hydrogen bonding.

Related literature

For details of the condensation of salicyl aldehyde with urea, see: Pandey et al. (2008 ); El-Hamouly et al. (2007 ); Bobowski & Shavel (1967 ).

Experimental

Crystal data

C₉H₉N₃O₃·H₂O
M_r = 225.21
Monoclinic, P 2₁ /n
a = 5.3393 (10) Å
b = 8.5465 (16) Å
c = 21.846 (4) Å
β = 95.472 (4)°
V = 992.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.965, T_max = 0.965
10468 measured reflections
2448 independent reflections
1942 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.117
S = 1.00
2448 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.90	2.05	2.946 (2)	174
N2—H2A⋯O3ⁱⁱ	0.90	2.41	3.088 (2)	132
N3—H3A⋯O4ⁱⁱⁱ	0.93	2.14	3.054 (2)	169
N3—H3B⋯O4	0.96	1.99	2.923 (2)	166
O4—H4A⋯O2^iv	0.94	1.91	2.774 (2)	153
O4—H4B⋯O3^v	0.94	1.94	2.842 (2)	161
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x-1, y, z; (iii) x+1, y, z; (iv) x-1, y-1, z; (v) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810032411/rk2226sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032411/rk2226Isup2.hkl

checkCIF report

Comment top

3,4-Dihydro-3-alkyl-2H-1,3-benzoxazin-2-ones, 4,4'-oxobis(3,4-dihydro-3-alkyl-2H-benzoxazin-2-ones), and 1-(3,4-dihydro-3-alkyl-2-oxo-2H-1,3-benzoxazin-4-yl-1,3-dialkylureas were obtained by the condensation of o-hydroxyaromatic aldehydes with alkylisocyanates (Bobowski & Shavel, 1967). The formation 1,1'-[(2-hydroxyphenyl)methylene]diurea by the condensation of salicyl aldehyde with two molecules of carbamide is well known from the literature (El-Hamouly et al., 2007; Pandey et al., 2008).

The title molecule contains a fused bicycle system containing two six-membered rings (benzene and oxazin) (Fig. 1). The oxazin cycle adopts a slightly distorted sofa conformation, with the nitrogen N1 atom deviating from plane passed through the other atoms of the cycle by 0.267 (2)Å. Such disposion of the nitrogen atom is defined by the intermolecular N1–H1···O2ⁱ hydrogen bonding (Table 1). Symmetry code: (i) -x+1, -y+2, -z+1. The nitrogen N1 atom has a pyramidalized configuration (sum of bond angles at the nitrogen N1 atom is 352.7°, the C2–N1–O1–C1 torsion angle is 22.4 (2)°). The carbamide substituent of the oxazin cycle is in axial position (the C9–N2–C2–N1 torsion angle is -64.31 (15)°).

Compound I possesses one asymmetric center at the C2, but the crystal of I is racemate.

In crystal of I, the organic molecules and solvate water molecules are bound into complex two-tier layers parallel to (0 0 1) by the hydrogen bonds (Fig. 2, Table 1).

Related literature top

For details of the condensation of salicyl aldehyde with urea, see: Pandey et al. (2008); El-Hamouly et al. (2007); Bobowski & Shavel (1967).

Experimental top

The solution of salicylic aldehyde (0.02 mol), urea (0.03 mol), 1 ml trichloroacetic acid, 3 ml AcOH in 15 ml acetonitril was mixed for 3-4 h (Fig. 3). Of a reaction course observed using thin layer chromatography (TLC) method. After cooling the product was filtered and washed out by ethanol. The target product was obtained by re-crystallization of a water solution of ethanol (1:3) as white crystals. M.p. = 498-500 K. IR, ν/cm^-1: 1456-1541 (C═C), 1646 (NH–C(O)–NH₂), 1710 (C(O)–O), 3349 (NH(lactam), associated), 3346 (C(O)–NH₂). Mass spectrum, m/z: 230 [M+Na]^{+. 1}H NMR ((CD₃)₂SO, 293 K): 8.5 (S, 1H, NH), 7.3(m, 2H, H6, H7), 7.15 (m, 2H, H3, H5),7.05 (d, 1H, H8, ³J = 7.2), 6.2 (d, 1H, H4, ³J = 7.5), 5.65 (S, 2H, NH₂). ¹³C NMR ((CD₃)₂SO, 293 K): δ = 164 (S, NH–C(O)–NH₂), 158 (S, C(O)–O), 150 (S, C9), 130 (S, C8), 127 (S, C5), 124.5 (S, C7), 121 (S, C10), 116 (S, C6), 58 (S, C4).

Structure description top

Compound I possesses one asymmetric center at the C2, but the crystal of I is racemate.

In crystal of I, the organic molecules and solvate water molecules are bound into complex two-tier layers parallel to (0 0 1) by the hydrogen bonds (Fig. 2, Table 1).

For details of the condensation of salicyl aldehyde with urea, see: Pandey et al. (2008); El-Hamouly et al. (2007); Bobowski & Shavel (1967).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of I with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% proabbility level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. Crystal packing of the molecules of I viewed down the a axis. Dashed lines show intermolecular hydrogen bonds.
	Fig. 3. Condensation of salicyl aldehyde with two molecules of urea with reception benzoxazin.

1-(2-Oxo-3,4-dihydro-2H-1,3-benzoxazin-4-yl)urea monohydrate top

Crystal data top

C₉H₉N₃O₃·H₂O	F(000) = 472
M_r = 225.21	D_x = 1.508 Mg m⁻³
Monoclinic, P2₁/n	Melting point: 499 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 5.3393 (10) Å	Cell parameters from 3341 reflections
b = 8.5465 (16) Å	θ = 2.6–28.2°
c = 21.846 (4) Å	µ = 0.12 mm⁻¹
β = 95.472 (4)°	T = 296 K
V = 992.3 (3) Å³	Prism, colourless
Z = 4	0.30 × 0.30 × 0.30 mm

Data collection top

Bruker APEXII CCD diffractometer	2448 independent reflections
Radiation source: fine-focus sealed tube	1942 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
φ and ω scans	θ_max = 28.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→7
T_min = 0.965, T_max = 0.965	k = −11→11
10468 measured reflections	l = −29→28

Refinement top

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)] = 0.043	Hydrogen site location: difference Fourier map
wR(F²) = 0.117	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0598P)² + 0.12P] where P = (F_o² + 2F_c²)/3
2448 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₉H₉N₃O₃·H₂O	V = 992.3 (3) Å³
M_r = 225.21	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.3393 (10) Å	µ = 0.12 mm⁻¹
b = 8.5465 (16) Å	T = 296 K
c = 21.846 (4) Å	0.30 × 0.30 × 0.30 mm
β = 95.472 (4)°

Data collection top

Bruker APEXII CCD diffractometer	2448 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1942 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.965	R_int = 0.058
10468 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.00	Δρ_max = 0.28 e Å⁻³
2448 reflections	Δρ_min = −0.29 e Å⁻³
145 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.72114 (16)	0.97940 (12)	0.35888 (4)	0.0372 (2)
O2	0.7419 (2)	1.05038 (14)	0.45587 (5)	0.0500 (3)
O3	0.74592 (16)	0.64789 (12)	0.40776 (4)	0.0377 (3)
N1	0.3995 (2)	0.91465 (14)	0.41776 (5)	0.0360 (3)
H1	0.3548	0.9179	0.4565	0.043*
N2	0.32112 (19)	0.63842 (14)	0.40155 (5)	0.0348 (3)
H2A	0.1839	0.5802	0.4065	0.042*
N3	0.5568 (2)	0.42106 (15)	0.43002 (6)	0.0420 (3)
H3A	0.7098	0.3794	0.4466	0.050*
H3B	0.4077	0.3652	0.4378	0.050*
C1	0.6227 (2)	0.98097 (16)	0.41376 (6)	0.0337 (3)
C2	0.2868 (2)	0.79512 (16)	0.37637 (6)	0.0322 (3)
H2	0.1054	0.8154	0.3709	0.039*
C3	0.3850 (2)	0.81370 (15)	0.31454 (6)	0.0316 (3)
C4	0.2696 (3)	0.74090 (18)	0.26224 (7)	0.0418 (3)
H4	0.1274	0.6796	0.2652	0.050*
C5	0.3641 (3)	0.7586 (2)	0.20596 (7)	0.0495 (4)
H5	0.2852	0.7098	0.1713	0.059*
C6	0.5756 (3)	0.8489 (2)	0.20131 (7)	0.0483 (4)
H6	0.6398	0.8600	0.1634	0.058*
C7	0.6926 (3)	0.92281 (19)	0.25240 (7)	0.0418 (3)
H7	0.8347	0.9842	0.2493	0.050*
C8	0.5943 (2)	0.90387 (16)	0.30837 (6)	0.0316 (3)
C9	0.5510 (2)	0.57119 (16)	0.41307 (5)	0.0306 (3)
O4	0.08489 (19)	0.29496 (14)	0.46692 (5)	0.0499 (3)
H4A	0.0070	0.1995	0.4555	0.075*
H4B	0.1116	0.2988	0.5099	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0276 (4)	0.0451 (6)	0.0392 (5)	−0.0083 (4)	0.0049 (4)	0.0007 (4)
O2	0.0477 (6)	0.0588 (7)	0.0432 (6)	−0.0203 (5)	0.0027 (5)	−0.0081 (5)
O3	0.0229 (4)	0.0452 (6)	0.0455 (5)	−0.0048 (4)	0.0059 (4)	0.0060 (4)
N1	0.0293 (5)	0.0432 (7)	0.0368 (6)	−0.0030 (5)	0.0093 (4)	−0.0067 (5)
N2	0.0218 (5)	0.0415 (6)	0.0419 (6)	−0.0091 (4)	0.0066 (4)	0.0025 (5)
N3	0.0385 (6)	0.0410 (7)	0.0477 (7)	−0.0032 (5)	0.0101 (5)	0.0076 (5)
C1	0.0295 (6)	0.0344 (7)	0.0371 (7)	−0.0026 (5)	0.0024 (5)	0.0001 (5)
C2	0.0177 (5)	0.0416 (7)	0.0375 (7)	−0.0009 (5)	0.0041 (5)	−0.0021 (5)
C3	0.0240 (5)	0.0363 (7)	0.0343 (6)	0.0033 (5)	0.0019 (5)	0.0020 (5)
C4	0.0352 (7)	0.0466 (8)	0.0423 (8)	−0.0025 (6)	−0.0023 (6)	−0.0008 (6)
C5	0.0556 (9)	0.0565 (10)	0.0349 (7)	0.0027 (7)	−0.0032 (6)	−0.0035 (7)
C6	0.0578 (9)	0.0539 (9)	0.0346 (7)	0.0087 (7)	0.0121 (6)	0.0041 (7)
C7	0.0385 (7)	0.0448 (8)	0.0437 (8)	0.0023 (6)	0.0125 (6)	0.0086 (6)
C8	0.0248 (5)	0.0350 (7)	0.0350 (6)	0.0040 (5)	0.0025 (5)	0.0023 (5)
C9	0.0269 (6)	0.0396 (7)	0.0260 (6)	−0.0056 (5)	0.0062 (4)	−0.0013 (5)
O4	0.0416 (6)	0.0568 (7)	0.0506 (6)	−0.0155 (5)	0.0009 (5)	0.0044 (5)

Geometric parameters (Å, º) top

O1—C1	1.3541 (16)	C2—H2	0.9800
O1—C8	1.3965 (16)	C3—C8	1.3746 (18)
O2—C1	1.2213 (17)	C3—C4	1.3919 (19)
O3—C9	1.2449 (15)	C4—C5	1.381 (2)
N1—C1	1.3300 (16)	C4—H4	0.9300
N1—C2	1.4558 (17)	C5—C6	1.380 (2)
N1—H1	0.9026	C5—H5	0.9300
N2—C9	1.3567 (17)	C6—C7	1.379 (2)
N2—C2	1.4527 (18)	C6—H6	0.9300
N2—H2A	0.9010	C7—C8	1.3853 (19)
N3—C9	1.3350 (19)	C7—H7	0.9300
N3—H3A	0.9321	O4—H4A	0.9390
N3—H3B	0.9572	O4—H4B	0.9361
C2—C3	1.5032 (18)

C1—O1—C8	120.28 (10)	C4—C3—C2	121.70 (12)
C1—N1—C2	125.32 (11)	C5—C4—C3	120.75 (14)
C1—N1—H1	111.6	C5—C4—H4	119.6
C2—N1—H1	118.3	C3—C4—H4	119.6
C9—N2—C2	122.67 (10)	C6—C5—C4	119.86 (14)
C9—N2—H2A	118.4	C6—C5—H5	120.1
C2—N2—H2A	118.7	C4—C5—H5	120.1
C9—N3—H3A	118.1	C7—C6—C5	120.49 (14)
C9—N3—H3B	122.1	C7—C6—H6	119.8
H3A—N3—H3B	117.0	C5—C6—H6	119.8
O2—C1—N1	124.29 (12)	C6—C7—C8	118.70 (14)
O2—C1—O1	116.96 (12)	C6—C7—H7	120.7
N1—C1—O1	118.66 (11)	C8—C7—H7	120.6
N2—C2—N1	112.46 (11)	C3—C8—C7	122.14 (13)
N2—C2—C3	113.30 (11)	C3—C8—O1	121.28 (11)
N1—C2—C3	108.97 (10)	C7—C8—O1	116.57 (12)
N2—C2—H2	107.3	O3—C9—N3	122.31 (12)
N1—C2—H2	107.3	O3—C9—N2	120.61 (12)
C3—C2—H2	107.3	N3—C9—N2	117.07 (11)
C8—C3—C4	118.06 (12)	H4A—O4—H4B	108.6
C8—C3—C2	120.24 (11)

C2—N1—C1—O2	−161.10 (14)	C3—C4—C5—C6	0.2 (2)
C2—N1—C1—O1	22.4 (2)	C4—C5—C6—C7	−0.5 (3)
C8—O1—C1—O2	−179.29 (12)	C5—C6—C7—C8	0.3 (2)
C8—O1—C1—N1	−2.56 (18)	C4—C3—C8—C7	−0.5 (2)
C9—N2—C2—N1	−64.31 (15)	C2—C3—C8—C7	179.31 (12)
C9—N2—C2—C3	59.82 (15)	C4—C3—C8—O1	−179.47 (12)
C1—N1—C2—N2	98.81 (15)	C2—C3—C8—O1	0.31 (19)
C1—N1—C2—C3	−27.67 (17)	C6—C7—C8—C3	0.2 (2)
N2—C2—C3—C8	−110.70 (13)	C6—C7—C8—O1	179.23 (13)
N1—C2—C3—C8	15.31 (16)	C1—O1—C8—C3	−8.08 (18)
N2—C2—C3—C4	69.07 (15)	C1—O1—C8—C7	172.86 (12)
N1—C2—C3—C4	−164.92 (12)	C2—N2—C9—O3	6.81 (19)
C8—C3—C4—C5	0.3 (2)	C2—N2—C9—N3	−173.09 (11)
C2—C3—C4—C5	−179.52 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.90	2.05	2.946 (2)	174
N2—H2A···O3ⁱⁱ	0.90	2.41	3.088 (2)	132
N3—H3A···O4ⁱⁱⁱ	0.93	2.14	3.054 (2)	169
N3—H3B···O4	0.96	1.99	2.923 (2)	166
O4—H4A···O2^iv	0.94	1.91	2.774 (2)	153
O4—H4B···O3^v	0.94	1.94	2.842 (2)	161

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x−1, y−1, z; (v) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₉N₃O₃·H₂O
M_r	225.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.3393 (10), 8.5465 (16), 21.846 (4)
β (°)	95.472 (4)
V (Å³)	992.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.30 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.965, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	10468, 2448, 1942
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.117, 1.00
No. of reflections	2448
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.29

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.90	2.05	2.946 (2)	174
N2—H2A···O3ⁱⁱ	0.90	2.41	3.088 (2)	132
N3—H3A···O4ⁱⁱⁱ	0.93	2.14	3.054 (2)	169
N3—H3B···O4	0.96	1.99	2.923 (2)	166
O4—H4A···O2^iv	0.94	1.91	2.774 (2)	153
O4—H4B···O3^v	0.94	1.94	2.842 (2)	161

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x−1, y−1, z; (v) −x+1, −y+1, −z+1.

Acknowledgements

The authors thank Dr Victor N. Khrustalev for fruitful discussions and help with this work.

References

Bobowski, G. & Shavel, J. (1967). J. Org. Chem. 32, 953–959. CrossRef CAS Web of Science Google Scholar
Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
El-Hamouly, W. S., Tawfeek, H. A. & Abbas, M. H. (2007). Egypt. J. Chem. 50, 97–104. CAS Google Scholar
Pandey, V. K., Mukesh, A. K. & Noopur, T. (2008). Indian J. Chem. Sect. B, 47, 1910–1914. Google Scholar
Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar