3-(2-Amino­ethyl)-2-anilinoquinazolin-4(3H)-one methanol hemisolvate

Gao, T.; Jiao, Y.-H.; Ng, S.W.

doi:10.1107/S1600536809045516

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o2989

doi:10.1107/S1600536809045516

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3-(2-Aminoethyl)-2-anilinoquinazolin-4(3H)-one methanol hemisolvate

Tao Gao,^a Yuan-Hong Jiao ^b and Seik Weng Ng ^c ^*

^aFaculty of Chemistry and Life Science, Xianning University, Xianning 437100, People's Republic of China, ^bSchool of Chemistry and Material Engineering, Huangshi Institute of Technology, Huangshi 435003, People's Republic of China, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 28 October 2009; accepted 29 October 2009; online 4 November 2009)

The title methanol hemisolvated quinazolin-(3H)-one, C₁₆H₁₆N₄O·0.5CH₃OH, has an anilino substituent in the 2-position and an aminoethyl substituent in the 3-position of the planar fused-ring system (r.m.s. deviation = 0.019 Å). The anilino N atom donates an intramolecular hydrogen bond to the aminoethyl N atom. The molecule and the solvent methanol molecule are linked by N—H⋯N, N—H⋯O and O—H⋯O hydrogen bonds. The methanol molecule is disordered over two equally occupied positions about a twofold rotation axis.

Related literature

For the synthesis of this class of compounds, see: Yang et al. (2008 ). For the crystal structure of a chlorine-substituted derivative, see: Yang et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₆N₄O·0.5CH₄O
M_r = 296.35
Monoclinic, C 2/c
a = 19.5972 (11) Å
b = 12.2035 (7) Å
c = 12.8681 (8) Å
β = 103.301 (1)°
V = 2994.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: none
14007 measured reflections
3399 independent reflections
2377 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.186
S = 1.09
3399 reflections
210 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 0.55 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
N3—H31⋯N4	0.88	2.04	2.811 (3)	146
N4—H41⋯O2ⁱ	0.88	2.13	2.990 (6)	168
O2—H2O⋯O1	0.84	2.01	2.755 (6)	147
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045516/bt5121sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045516/bt5121Isup2.hkl

checkCIF report

Related literature top

For the synthesis of this class of compounds, see: Yang et al. (2008). For the crystal structure of a chlorine-substituted derivative, see: Yang et al. (2009).

Experimental top

To a THF (10 ml) solution of 2-ethoxycarbonyliminophosphorane (1.27 g, 3.0 mmol) was added phenylisocyanate (0.36 g, 3.0 mmol). The solution was set aside undisturbed for 6 h at 273 K. To this solution was added ethanolamine (0.18 g, 3 mmol) in THF (5 ml). The mixture was stirred overnight. The solvent was removed and the solid recrystallized from a chloroform/methanol (1/1) mixture to give colorless crystals in 80% yield; m.p. 433–434 K.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of the title compound at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

3-(2-Aminoethyl)-2-anilinoquinazolin-4(3H)-one methanol hemisolvate top

Crystal data top

C₁₆H₁₆N₄O·0.5CH₄O	F(000) = 1256
M_r = 296.35	D_x = 1.314 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3816 reflections
a = 19.5972 (11) Å	θ = 2.4–25.9°
b = 12.2035 (7) Å	µ = 0.09 mm⁻¹
c = 12.8681 (8) Å	T = 295 K
β = 103.301 (1)°	Block, colorless
V = 2994.9 (3) Å³	0.30 × 0.20 × 0.10 mm
Z = 8

Data collection top

Bruker APEXII diffractometer	2377 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.073
Graphite monochromator	θ_max = 27.5°, θ_min = 2.0°
ω scans	h = −17→25
14007 measured reflections	k = −15→14
3399 independent reflections	l = −16→16

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.1044P)² + 0.1504P] where P = (F_o² + 2F_c²)/3
3399 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 0.55 e Å⁻³
13 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₆H₁₆N₄O·0.5CH₄O	V = 2994.9 (3) Å³
M_r = 296.35	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.5972 (11) Å	µ = 0.09 mm⁻¹
b = 12.2035 (7) Å	T = 295 K
c = 12.8681 (8) Å	0.30 × 0.20 × 0.10 mm
β = 103.301 (1)°

Data collection top

Bruker APEXII diffractometer	2377 reflections with I > 2σ(I)
14007 measured reflections	R_int = 0.073
3399 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	13 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 1.09	Δρ_max = 0.55 e Å⁻³
3399 reflections	Δρ_min = −0.29 e Å⁻³
210 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.68958 (7)	0.41303 (12)	0.81309 (11)	0.0573 (4)
N1	0.73674 (8)	0.41620 (12)	0.66714 (11)	0.0424 (4)
N2	0.84958 (8)	0.34284 (13)	0.67038 (11)	0.0458 (4)
N3	0.77752 (9)	0.40366 (13)	0.51241 (12)	0.0498 (4)
H31	0.7345	0.4239	0.4817	0.060*
N4	0.63136 (9)	0.37965 (16)	0.44490 (14)	0.0632 (5)
H41	0.6131	0.4263	0.3939	0.076*
H42	0.6131	0.3143	0.4284	0.076*
C1	0.80430 (10)	0.34133 (14)	0.83148 (13)	0.0414 (4)
C2	0.81360 (11)	0.31401 (16)	0.93932 (14)	0.0503 (5)
H2	0.7782	0.3290	0.9746	0.060*
C3	0.87449 (12)	0.26533 (18)	0.99341 (15)	0.0576 (6)
H3	0.8804	0.2465	1.0650	0.069*
C4	0.92707 (11)	0.24457 (19)	0.94030 (15)	0.0589 (6)
H4	0.9684	0.2115	0.9767	0.071*
C5	0.91908 (11)	0.27202 (19)	0.83510 (16)	0.0573 (6)
H5	0.9552	0.2579	0.8011	0.069*
C6	0.85720 (10)	0.32115 (15)	0.77791 (13)	0.0427 (5)
C7	0.73916 (10)	0.39143 (15)	0.77321 (14)	0.0437 (5)
C8	0.79099 (10)	0.38642 (15)	0.61962 (14)	0.0414 (4)
C9	0.82431 (10)	0.39287 (14)	0.44502 (14)	0.0426 (5)
C10	0.79487 (10)	0.36669 (15)	0.33875 (14)	0.0462 (5)
H10	0.7472	0.3515	0.3175	0.055*
C11	0.83579 (12)	0.36311 (17)	0.26507 (15)	0.0530 (5)
H11	0.8154	0.3462	0.1942	0.064*
C12	0.90627 (13)	0.38417 (19)	0.29508 (18)	0.0614 (6)
H12	0.9338	0.3820	0.2451	0.074*
C13	0.93592 (12)	0.40868 (19)	0.40098 (18)	0.0616 (6)
H13	0.9838	0.4225	0.4220	0.074*
C14	0.89551 (11)	0.41293 (17)	0.47595 (16)	0.0534 (5)
H14	0.9161	0.4292	0.5468	0.064*
C15	0.67613 (10)	0.48235 (17)	0.61029 (15)	0.0516 (5)
H15A	0.6922	0.5335	0.5634	0.062*
H15B	0.6587	0.5248	0.6624	0.062*
C16	0.61626 (11)	0.41579 (18)	0.54480 (17)	0.0586 (6)
H16A	0.6080	0.3524	0.5857	0.070*
H16B	0.5739	0.4599	0.5298	0.070*
O2	0.5495 (3)	0.4637 (6)	0.7850 (7)	0.176 (3)	0.50
H2O	0.5856	0.4244	0.8006	0.211*	0.50
C17	0.4883 (4)	0.3949 (6)	0.7344 (11)	0.101 (3)	0.50
H17A	0.4553	0.3937	0.7792	0.152*	0.50
H17B	0.5037	0.3216	0.7254	0.152*	0.50
H17C	0.4662	0.4250	0.6660	0.152*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0468 (8)	0.0701 (10)	0.0607 (8)	0.0019 (7)	0.0243 (7)	−0.0043 (6)
N1	0.0402 (9)	0.0437 (9)	0.0438 (8)	0.0002 (7)	0.0110 (7)	−0.0028 (6)
N2	0.0417 (9)	0.0570 (10)	0.0402 (8)	0.0011 (7)	0.0130 (7)	−0.0002 (6)
N3	0.0430 (9)	0.0665 (11)	0.0405 (8)	0.0019 (8)	0.0107 (7)	0.0053 (7)
N4	0.0614 (12)	0.0661 (12)	0.0558 (10)	0.0053 (9)	0.0006 (9)	−0.0015 (8)
C1	0.0435 (10)	0.0412 (10)	0.0411 (9)	−0.0070 (8)	0.0128 (8)	−0.0050 (7)
C2	0.0578 (13)	0.0540 (12)	0.0437 (10)	−0.0063 (10)	0.0214 (9)	−0.0038 (8)
C3	0.0697 (14)	0.0649 (13)	0.0384 (9)	−0.0019 (11)	0.0128 (10)	0.0028 (9)
C4	0.0490 (12)	0.0744 (15)	0.0494 (11)	0.0035 (11)	0.0035 (10)	0.0062 (9)
C5	0.0446 (12)	0.0782 (15)	0.0510 (11)	0.0058 (10)	0.0152 (9)	0.0035 (10)
C6	0.0424 (10)	0.0490 (11)	0.0378 (9)	−0.0038 (8)	0.0112 (8)	−0.0014 (7)
C7	0.0443 (11)	0.0438 (10)	0.0459 (10)	−0.0063 (8)	0.0164 (8)	−0.0070 (7)
C8	0.0413 (10)	0.0424 (10)	0.0415 (9)	−0.0040 (8)	0.0112 (8)	−0.0027 (7)
C9	0.0445 (11)	0.0432 (10)	0.0411 (9)	−0.0007 (8)	0.0122 (8)	0.0067 (7)
C10	0.0482 (11)	0.0448 (11)	0.0440 (9)	−0.0001 (8)	0.0072 (8)	0.0011 (7)
C11	0.0636 (14)	0.0570 (12)	0.0404 (9)	0.0007 (10)	0.0159 (9)	−0.0006 (8)
C12	0.0654 (15)	0.0711 (15)	0.0554 (12)	0.0043 (11)	0.0293 (11)	0.0041 (10)
C13	0.0466 (12)	0.0792 (16)	0.0620 (13)	−0.0042 (10)	0.0187 (10)	0.0085 (10)
C14	0.0490 (12)	0.0683 (14)	0.0423 (10)	−0.0097 (10)	0.0091 (9)	0.0032 (9)
C15	0.0507 (12)	0.0492 (12)	0.0548 (11)	0.0090 (9)	0.0119 (9)	−0.0007 (8)
C16	0.0445 (12)	0.0671 (14)	0.0618 (13)	0.0074 (10)	0.0071 (10)	0.0025 (10)
O2	0.109 (4)	0.189 (6)	0.231 (6)	−0.017 (4)	0.043 (4)	−0.115 (5)
C17	0.044 (6)	0.143 (5)	0.117 (8)	0.021 (4)	0.017 (5)	0.021 (5)

Geometric parameters (Å, º) top

O1—C7	1.227 (2)	C5—H5	0.9300
N1—C7	1.388 (2)	C9—C14	1.382 (3)
N1—C8	1.391 (2)	C9—C10	1.394 (2)
N1—C15	1.482 (2)	C10—C11	1.376 (3)
N2—C8	1.297 (2)	C10—H10	0.9300
N2—C6	1.383 (2)	C11—C12	1.370 (3)
N3—C8	1.360 (2)	C11—H11	0.9300
N3—C9	1.406 (2)	C12—C13	1.386 (3)
N3—H31	0.8800	C12—H12	0.9300
N4—C16	1.453 (3)	C13—C14	1.383 (3)
N4—H41	0.8800	C13—H13	0.9300
N4—H42	0.8800	C14—H14	0.9300
C1—C6	1.393 (3)	C15—C16	1.514 (3)
C1—C2	1.398 (2)	C15—H15A	0.9700
C1—C7	1.458 (3)	C15—H15B	0.9700
C2—C3	1.371 (3)	C16—H16A	0.9700
C2—H2	0.9300	C16—H16B	0.9700
C3—C4	1.385 (3)	O2—C17	1.486 (2)
C3—H3	0.9300	O2—H2O	0.8400
C4—C5	1.368 (3)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.400 (3)	C17—H17C	0.9600

C7—N1—C8	121.23 (15)	N2—C8—N1	124.28 (16)
C7—N1—C15	116.50 (15)	N3—C8—N1	114.57 (16)
C8—N1—C15	122.13 (15)	C14—C9—C10	119.07 (18)
C8—N2—C6	117.49 (16)	C14—C9—N3	124.37 (17)
C8—N3—C9	127.54 (17)	C10—C9—N3	116.44 (17)
C8—N3—H31	116.2	C11—C10—C9	120.53 (19)
C9—N3—H31	116.2	C11—C10—H10	119.7
C16—N4—H41	109.5	C9—C10—H10	119.7
C16—N4—H42	109.5	C12—C11—C10	120.61 (19)
H41—N4—H42	109.5	C12—C11—H11	119.7
C6—C1—C2	120.49 (17)	C10—C11—H11	119.7
C6—C1—C7	118.89 (16)	C11—C12—C13	119.0 (2)
C2—C1—C7	120.62 (18)	C11—C12—H12	120.5
C3—C2—C1	120.45 (19)	C13—C12—H12	120.5
C3—C2—H2	119.8	C14—C13—C12	121.1 (2)
C1—C2—H2	119.8	C14—C13—H13	119.5
C2—C3—C4	119.24 (17)	C12—C13—H13	119.5
C2—C3—H3	120.4	C9—C14—C13	119.66 (19)
C4—C3—H3	120.4	C9—C14—H14	120.2
C5—C4—C3	120.99 (19)	C13—C14—H14	120.2
C5—C4—H4	119.5	N1—C15—C16	114.39 (17)
C3—C4—H4	119.5	N1—C15—H15A	108.7
C4—C5—C6	120.9 (2)	C16—C15—H15A	108.7
C4—C5—H5	119.6	N1—C15—H15B	108.7
C6—C5—H5	119.6	C16—C15—H15B	108.7
N2—C6—C1	122.70 (17)	H15A—C15—H15B	107.6
N2—C6—C5	119.27 (17)	N4—C16—C15	111.46 (19)
C1—C6—C5	117.96 (16)	N4—C16—H16A	109.3
O1—C7—N1	120.87 (17)	C15—C16—H16A	109.3
O1—C7—C1	123.97 (17)	N4—C16—H16B	109.3
N1—C7—C1	115.15 (16)	C15—C16—H16B	109.3
N2—C8—N3	121.13 (18)	H16A—C16—H16B	108.0

C6—C1—C2—C3	−1.1 (3)	C6—N2—C8—N3	−175.64 (16)
C7—C1—C2—C3	178.97 (17)	C6—N2—C8—N1	2.5 (3)
C1—C2—C3—C4	0.7 (3)	C9—N3—C8—N2	−9.1 (3)
C2—C3—C4—C5	0.1 (3)	C9—N3—C8—N1	172.63 (16)
C3—C4—C5—C6	−0.5 (4)	C7—N1—C8—N2	−6.1 (3)
C8—N2—C6—C1	1.8 (3)	C15—N1—C8—N2	169.49 (18)
C8—N2—C6—C5	178.68 (18)	C7—N1—C8—N3	172.12 (15)
C2—C1—C6—N2	177.50 (16)	C15—N1—C8—N3	−12.3 (2)
C7—C1—C6—N2	−2.5 (3)	C8—N3—C9—C14	−31.8 (3)
C2—C1—C6—C5	0.6 (3)	C8—N3—C9—C10	152.29 (18)
C7—C1—C6—C5	−179.41 (17)	C14—C9—C10—C11	−1.4 (3)
C4—C5—C6—N2	−176.84 (19)	N3—C9—C10—C11	174.75 (17)
C4—C5—C6—C1	0.2 (3)	C9—C10—C11—C12	0.6 (3)
C8—N1—C7—O1	−176.29 (16)	C10—C11—C12—C13	0.3 (3)
C15—N1—C7—O1	7.9 (3)	C11—C12—C13—C14	−0.5 (3)
C8—N1—C7—C1	4.9 (2)	C10—C9—C14—C13	1.2 (3)
C15—N1—C7—C1	−170.91 (15)	N3—C9—C14—C13	−174.6 (2)
C6—C1—C7—O1	−179.64 (17)	C12—C13—C14—C9	−0.3 (3)
C2—C1—C7—O1	0.3 (3)	C7—N1—C15—C16	−96.6 (2)
C6—C1—C7—N1	−0.9 (2)	C8—N1—C15—C16	87.6 (2)
C2—C1—C7—N1	179.07 (16)	N1—C15—C16—N4	−77.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31···N4	0.88	2.04	2.811 (3)	146
N4—H41···O2ⁱ	0.88	2.13	2.990 (6)	168
O2—H2O···O1	0.84	2.01	2.755 (6)	147

Symmetry code: (i) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₄O·0.5CH₄O
M_r	296.35
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	19.5972 (11), 12.2035 (7), 12.8681 (8)
β (°)	103.301 (1)
V (Å³)	2994.9 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14007, 3399, 2377
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.186, 1.09
No. of reflections	3399
No. of parameters	210
No. of restraints	13
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H31···N4	0.88	2.04	2.811 (3)	146
N4—H41···O2ⁱ	0.88	2.13	2.990 (6)	168
O2—H2O···O1	0.84	2.01	2.755 (6)	147

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

We thank Xianning University, Huangshi Institute of Technology and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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