data reports
Monoclinic, P21 =c
a = 19.2953 (8) Å
b = 9.9889 (3) Å
c = 9.6341 (4) Å
= 96.667 (4)
V = 1844.31 (12) Å3
ISSN 1600-5368
Crystal structure of 4,4-dibutyl-2-phenyl3,4-dihydroquinazoline
Gamal A. El-Hiti,a* Keith Smith,b Amany S. Hegazy,b
Mohammed B. Alshammaric and Benson M. Kariukib*
a
Cornea Research Chair, Department of Optometry, College of Applied Medical
Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia,
b
School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff
CF10 3AT, Wales, and cChemistry Department, College of Sciences and Humanities,
Salman bin Abdulaziz University, PO Box 83, Al-Kharij 11942, Saudi Arabia.
*Correspondence e-mail: gelhiti@ksu.edu.sa, kariukib@cardiff.ac.uk
Received 4 September 2014; accepted 4 September 2014
Z=4
Cu K radiation
= 0.51 mm1
T = 150 K
0.41 0.13 0.04 mm
2.2. Data collection
SuperNova, Dual, Cu at zero, Atlas
diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
Tmin = 0.829, Tmax = 1.000
12894 measured reflections
3657 independent reflections
2866 reflections with I > 2(I)
Rint = 0.043
2.3. Refinement
R[F 2 > 2(F 2)] = 0.047
wR(F 2) = 0.129
S = 1.04
3657 reflections
219 parameters
H-atom parameters constrained
max = 0.23 e Å3
min = 0.17 e Å3
Table 1
Hydrogen-bond geometry (Å, ).
Edited by W. T. A. Harrison, University of Aberdeen, Scotland
D—H A
In the title compound, C22H28N2, the dihedral angle between
the planes of the phenyl ring and the dihydroquinazoline ring
system (r.m.s. deviation = 0.030 Å) is 24.95 (7) and both
n-butane chains assume all-trans conformations. In the crystal,
N—H N hydrogen bonds link the molecules into C(4) chains
propagating in the [001] direction.
Keywords: crystal structure; quinazoline; hydrogen bonding.
CCDC reference: 1022964
N1—H1 N2
i
D—H
H A
D A
D—H A
0.88
2.29
3.1239 (16)
157
Symmetry code: (i) x; y þ 12; z 12.
Data collection: CrysAlis PRO (Agilent, 2014); cell refinement:
CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to
solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to
refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics:
ORTEP-3 for Windows (Farrugia, 2012) and CHEMDRAW Ultra
(Cambridge Soft, 2001); software used to prepare material for
publication: SHELXL2013.
Acknowledgements
1. Related literature
For the synthesis of 4,4-dibutyl-2-phenyl-3,4-dihydroquinazoline, see: Smith et al. (2005); Plé et al. (1997). For the crystal
structures of related compounds, see Valkonen et al. (2011);
Derabli et al. (2013).
This project was supported by the Deanship of Scientific
Research at Salman bin Abdulaziz University under research
project 2013/01/8.
Supporting information for this paper is available from the IUCr
electronic archives (Reference: HB7281).
References
Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire,
England.
Cambridge Soft (2001). CHEMDRAW Ultra. Cambridge Soft Corporation,
Cambridge, Massachusetts, USA.
Derabli, C., Boulcina, R., Bouacida, S., Merazig, H. & Debache, A. (2013).
Acta Cryst. E69, o1653–o1654.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
Plé, N., Turck, A., Chapoulaud, V. & Quéguiner, G. (1997). Tetrahedron, 53,
2871–2890.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Smith, K., El-Hiti, G. A. & Hegazy, A. S. (2005). J. Sulfur Chem. 26, 121–131.
Valkonen, A., Kolehmainen, E., Zakrzewska, A., Skotnicka, A. & Gawinecki,
R. (2011). Acta Cryst. E67, o923–o924.
2. Experimental
2.1. Crystal data
C22H28N2
o1100
Mr = 320.46
El-Hiti et al.
doi:10.1107/S1600536814020017
Acta Cryst. (2014). E70, o1100
supporting information
supporting information
Acta Cryst. (2014). E70, o1100
[doi:10.1107/S1600536814020017]
Crystal structure of 4,4-dibutyl-2-phenyl-3,4-dihydroquinazoline
Gamal A. El-Hiti, Keith Smith, Amany S. Hegazy, Mohammed B. Alshammari and Benson M.
Kariuki
S1. Chemical context
S2. Structural commentary
In the molecule of C22H28N2 (Fig. 1), the phenyl ring is twisted by 24.95 (7) from the plane of the dihydroquinazoline
group. Both n-butane chains assume all-trans conformation. N—H···N hydrogen bonds between neigbouring molecules
form chains parallel to the c-axis (Fig. 2).
4,4-Dibutyl-2-phenyl-3,4-dihydroquinazoline can be obtained from reaction of two mole equivalents of n-butyllithium
with 4-(methylthio)-2-phenylquinazoline at –78°C in anhydrous THF [Smith et al. (2005); Plé et al. (1997)]. The reaction
involves initial addition of n-butyllithium at the 4-position of quinazoline ring followed by elimination of methanethiolate
anion and then further addition of n-butyllithium (Smith et al., 2005). For the X-ray structures of related compounds, see
Valkonen et al. (2011); Derabli et al. (2013).
S3. Supramolecular features
S4. Database survey
S5. Synthesis and crystallization
4,4-Dibutyl-2-phenyl-3,4-dihydroquinazoline
A solution of n-butyllithium in hexane (1.76 mL, 2.5 M, 4.4 mmol) was added to a cold (–78 οC), stirred solution of
4-(methylthio)-2-phenylquinazoline (0.50 g, 2.0 mmol) in anhydrous THF (10 mL) under N2. The reaction mixture was
stirred at –78 οC for 1 h then removed from the cooling bath and allowed to warm to room temperature, diluted with diethyl ether (10 mL), then quenched with aqueous saturated NH4Cl (10 mL). The organic layer was separated, washed
with water (2 x 10 mL), dried (MgSO4), and evaporated under reduced pressure. The residue obtained was purified by
column chromatography (silica gel; diethyl ether–hexane, 1:4 by volume) to give 4,4-dibutyl-2-phenyl-3,4-dihydroquinazoline in 96% yield, m.p. 161 οC [lit. 161 οC: Smith et al. (2005); 154–155 οC: Plé et al. (1997)]. Crystallization
from a mixture of ethyl acetate and diethyl ether (1:3 by volume) gave the title compound as colorless crystals. The
spectroscopic data for the title compound, including NMR and low and high resolution mass spectra, were consistent
with those reported [Smith et al. (2005)].
S6. Refinement
H atoms were positioned geometrically and refined using a riding model, with Uiso(H) constrained to be 1.2 times Ueq for
the bonded atom except for methyl groups where Uiso(H) was 1.5 times and free rotation about the C—C bond was
allowed. Crystal data, data collection and structure refinement details are summarized in the table.
Acta Cryst. (2014). E70, o1100
sup-1
supporting information
Figure 1
The asymmetric unit of the title compound with 50% probability displacement ellipsoids.
Figure 2
Packing in the crystal structure showing N—H···N contacts as dotted lines with hydrogen atoms omitted for clarity.
Acta Cryst. (2014). E70, o1100
sup-2
supporting information
4,4-Dibutyl-2-phenyl-3,4-dihydroquinazoline
Crystal data
F(000) = 696
Dx = 1.154 Mg m−3
Cu Kα radiation, λ = 1.5418 Å
Cell parameters from 3898 reflections
θ = 4.6–73.6°
µ = 0.51 mm−1
T = 150 K
Plate, colourless
0.41 × 0.13 × 0.04 mm
C22H28N2
Mr = 320.46
Monoclinic, P21/c
a = 19.2953 (8) Å
b = 9.9889 (3) Å
c = 9.6341 (4) Å
β = 96.667 (4)°
V = 1844.31 (12) Å3
Z=4
Data collection
3657 independent reflections
2866 reflections with I > 2σ(I)
Rint = 0.043
θmax = 73.6°, θmin = 4.6°
h = −23→23
k = −12→12
l = −11→11
SuperNova, Dual, Cu at zero, Atlas
diffractometer
ω scans
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2014)
Tmin = 0.829, Tmax = 1.000
12894 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.047
wR(F2) = 0.129
S = 1.04
3657 reflections
219 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0587P)2 + 0.3637P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.23 e Å−3
Δρmin = −0.17 e Å−3
Special details
Experimental. Absorption correction: CrysAlisPro, 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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
C1
C2
C3
C4
C5
H5
C6
H6
x
y
z
Uiso*/Ueq
0.28102 (8)
0.18929 (7)
0.26279 (8)
0.29777 (8)
0.28292 (9)
0.2592
0.33672 (9)
0.3500
0.40404 (13)
0.30261 (13)
0.45814 (13)
0.48405 (13)
0.52724 (14)
0.5103
0.61972 (15)
0.6650
0.14783 (14)
0.27980 (14)
0.39845 (15)
0.28214 (15)
0.52321 (16)
0.6025
0.53300 (17)
0.6187
0.0259 (3)
0.0246 (3)
0.0272 (3)
0.0273 (3)
0.0314 (3)
0.038*
0.0356 (4)
0.043*
Acta Cryst. (2014). E70, o1100
sup-3
supporting information
C7
H7
C8
H8
C9
C10
H10
C11
H11
C12
H12
C13
H13
C14
H14
C15
H15A
H15B
C16
H16A
H16B
C17
H17A
H17B
C18
H18A
H18B
H18C
C19
H19A
H19B
C20
H20A
H20B
C21
H21A
H21B
C22
H22A
H22B
H22C
N1
H1
N2
0.37112 (9)
0.4078
0.35142 (8)
0.3750
0.12820 (8)
0.11781 (8)
0.1501
0.06087 (9)
0.0544
0.01348 (9)
−0.0251
0.02269 (9)
−0.0099
0.07937 (9)
0.0851
0.26253 (8)
0.3044
0.2520
0.20181 (9)
0.2107
0.1586
0.19140 (8)
0.2352
0.1817
0.13220 (9)
0.0880
0.1300
0.1404
0.34439 (8)
0.3305
0.3820
0.37407 (8)
0.3375
0.3877
0.43742 (9)
0.4249
0.4755
0.46367 (11)
0.4806
0.5018
0.4255
0.22079 (6)
0.2042
0.20764 (7)
Acta Cryst. (2014). E70, o1100
0.64606 (15)
0.7099
0.57829 (15)
0.5966
0.20985 (13)
0.10256 (14)
0.0869
0.01805 (15)
−0.0546
0.03893 (17)
−0.0198
0.14620 (18)
0.1616
0.23099 (16)
0.3045
0.49478 (14)
0.5479
0.4366
0.59109 (15)
0.6483
0.5394
0.67945 (14)
0.7288
0.6217
0.77946 (17)
0.7313
0.8369
0.8347
0.31704 (14)
0.2605
0.3773
0.22668 (15)
0.1632
0.2818
0.14803 (16)
0.0997
0.2115
0.0478 (2)
0.0958
−0.0049
−0.0121
0.31594 (12)
0.2684
0.36574 (12)
0.41752 (18)
0.4232
0.29334 (17)
0.2142
0.27592 (14)
0.18380 (16)
0.1183
0.18637 (17)
0.1225
0.28127 (18)
0.2837
0.37290 (18)
0.4378
0.36999 (17)
0.4328
0.01923 (15)
0.0049
−0.0637
0.02432 (16)
0.1084
0.0319
−0.10553 (16)
−0.1141
−0.1891
−0.10306 (19)
−0.1029
−0.1859
−0.0187
0.12029 (15)
0.0373
0.0966
0.23908 (16)
0.2613
0.3233
0.20321 (18)
0.1141
0.1894
0.3163 (2)
0.4023
0.2851
0.3343
0.16295 (12)
0.0897
0.39726 (12)
0.0358 (4)
0.043*
0.0326 (3)
0.039*
0.0259 (3)
0.0293 (3)
0.035*
0.0347 (4)
0.042*
0.0369 (4)
0.044*
0.0399 (4)
0.048*
0.0346 (4)
0.041*
0.0286 (3)
0.034*
0.034*
0.0322 (3)
0.039*
0.039*
0.0309 (3)
0.037*
0.037*
0.0410 (4)
0.061*
0.061*
0.061*
0.0284 (3)
0.034*
0.034*
0.0322 (3)
0.039*
0.039*
0.0380 (4)
0.046*
0.046*
0.0534 (5)
0.080*
0.080*
0.080*
0.0269 (3)
0.032*
0.0281 (3)
sup-4
supporting information
Atomic displacement parameters (Å2)
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
N1
N2
U11
U22
U33
U12
U13
U23
0.0316 (8)
0.0291 (7)
0.0328 (8)
0.0322 (7)
0.0408 (9)
0.0445 (9)
0.0369 (9)
0.0376 (8)
0.0297 (7)
0.0344 (8)
0.0389 (9)
0.0320 (8)
0.0338 (9)
0.0366 (9)
0.0349 (8)
0.0378 (8)
0.0358 (8)
0.0396 (9)
0.0334 (8)
0.0380 (8)
0.0387 (9)
0.0478 (11)
0.0345 (7)
0.0352 (7)
0.0222 (6)
0.0207 (6)
0.0205 (6)
0.0201 (6)
0.0265 (7)
0.0260 (7)
0.0247 (7)
0.0256 (7)
0.0240 (6)
0.0264 (7)
0.0254 (7)
0.0353 (8)
0.0490 (10)
0.0372 (8)
0.0257 (7)
0.0286 (7)
0.0264 (7)
0.0356 (8)
0.0265 (7)
0.0292 (7)
0.0322 (8)
0.0497 (11)
0.0247 (6)
0.0253 (6)
0.0253 (7)
0.0248 (7)
0.0285 (7)
0.0297 (7)
0.0273 (7)
0.0349 (8)
0.0456 (9)
0.0357 (8)
0.0243 (7)
0.0287 (7)
0.0404 (9)
0.0440 (9)
0.0398 (9)
0.0313 (8)
0.0265 (7)
0.0313 (8)
0.0305 (8)
0.0477 (10)
0.0267 (7)
0.0301 (8)
0.0443 (9)
0.0628 (12)
0.0227 (6)
0.0248 (6)
−0.0012 (5)
0.0044 (5)
0.0035 (5)
0.0024 (5)
0.0023 (6)
0.0018 (6)
−0.0037 (6)
−0.0009 (6)
0.0022 (5)
0.0016 (6)
−0.0018 (6)
−0.0029 (6)
−0.0008 (7)
0.0006 (6)
−0.0016 (6)
0.0019 (6)
−0.0011 (6)
0.0043 (7)
−0.0005 (6)
0.0036 (6)
0.0047 (7)
0.0166 (9)
−0.0036 (5)
−0.0012 (5)
0.0088 (6)
0.0060 (5)
0.0049 (6)
0.0045 (6)
0.0054 (6)
−0.0013 (7)
0.0032 (7)
0.0089 (7)
0.0049 (6)
0.0104 (6)
0.0070 (7)
0.0068 (7)
0.0168 (7)
0.0101 (6)
0.0092 (6)
0.0083 (6)
0.0036 (6)
0.0053 (7)
0.0094 (6)
0.0075 (6)
0.0095 (7)
0.0060 (9)
0.0084 (5)
0.0079 (5)
0.0013 (5)
0.0031 (5)
0.0009 (5)
0.0022 (5)
−0.0007 (6)
−0.0062 (6)
−0.0020 (6)
0.0010 (6)
0.0050 (5)
0.0019 (5)
−0.0001 (6)
0.0066 (7)
−0.0003 (7)
−0.0039 (6)
0.0023 (5)
0.0035 (6)
0.0011 (6)
0.0087 (7)
0.0009 (5)
0.0020 (6)
0.0024 (7)
0.0133 (9)
−0.0009 (4)
−0.0002 (5)
Geometric parameters (Å, º)
C1—N1
C1—C4
C1—C15
C1—C19
C2—N2
C2—N1
C2—C9
C3—C4
C3—C5
C3—N2
C4—C8
C5—C6
C5—H5
C6—C7
C6—H6
C7—C8
C7—H7
C8—H8
Acta Cryst. (2014). E70, o1100
1.4783 (18)
1.523 (2)
1.5432 (19)
1.5480 (19)
1.3079 (19)
1.3466 (18)
1.496 (2)
1.398 (2)
1.401 (2)
1.4078 (19)
1.394 (2)
1.385 (2)
0.9500
1.385 (2)
0.9500
1.389 (2)
0.9500
0.9500
C13—H13
C14—H14
C15—C16
C15—H15A
C15—H15B
C16—C17
C16—H16A
C16—H16B
C17—C18
C17—H17A
C17—H17B
C18—H18A
C18—H18B
C18—H18C
C19—C20
C19—H19A
C19—H19B
C20—C21
0.9500
0.9500
1.521 (2)
0.9900
0.9900
1.525 (2)
0.9900
0.9900
1.520 (2)
0.9900
0.9900
0.9800
0.9800
0.9800
1.517 (2)
0.9900
0.9900
1.526 (2)
sup-5
supporting information
C9—C10
C9—C14
C10—C11
C10—H10
C11—C12
C11—H11
C12—C13
C12—H12
C13—C14
1.391 (2)
1.397 (2)
1.388 (2)
0.9500
1.382 (2)
0.9500
1.387 (2)
0.9500
1.386 (2)
C20—H20A
C20—H20B
C21—C22
C21—H21A
C21—H21B
C22—H22A
C22—H22B
C22—H22C
N1—H1
0.9900
0.9900
1.523 (2)
0.9900
0.9900
0.9800
0.9800
0.9800
0.8800
N1—C1—C4
N1—C1—C15
C4—C1—C15
N1—C1—C19
C4—C1—C19
C15—C1—C19
N2—C2—N1
N2—C2—C9
N1—C2—C9
C4—C3—C5
C4—C3—N2
C5—C3—N2
C8—C4—C3
C8—C4—C1
C3—C4—C1
C6—C5—C3
C6—C5—H5
C3—C5—H5
C5—C6—C7
C5—C6—H6
C7—C6—H6
C6—C7—C8
C6—C7—H7
C8—C7—H7
C7—C8—C4
C7—C8—H8
C4—C8—H8
C10—C9—C14
C10—C9—C2
C14—C9—C2
C11—C10—C9
C11—C10—H10
C9—C10—H10
C12—C11—C10
C12—C11—H11
C10—C11—H11
C11—C12—C13
C11—C12—H12
108.69 (11)
108.52 (12)
112.35 (11)
109.17 (11)
110.25 (12)
107.80 (11)
124.93 (13)
116.96 (12)
118.10 (12)
119.01 (14)
123.35 (13)
117.64 (13)
119.10 (14)
120.17 (13)
120.61 (13)
121.19 (14)
119.4
119.4
119.83 (15)
120.1
120.1
119.38 (15)
120.3
120.3
121.49 (14)
119.3
119.3
118.18 (14)
123.21 (12)
118.61 (13)
120.86 (13)
119.6
119.6
120.39 (15)
119.8
119.8
119.48 (15)
120.3
C1—C15—H15B
H15A—C15—H15B
C15—C16—C17
C15—C16—H16A
C17—C16—H16A
C15—C16—H16B
C17—C16—H16B
H16A—C16—H16B
C18—C17—C16
C18—C17—H17A
C16—C17—H17A
C18—C17—H17B
C16—C17—H17B
H17A—C17—H17B
C17—C18—H18A
C17—C18—H18B
H18A—C18—H18B
C17—C18—H18C
H18A—C18—H18C
H18B—C18—H18C
C20—C19—C1
C20—C19—H19A
C1—C19—H19A
C20—C19—H19B
C1—C19—H19B
H19A—C19—H19B
C19—C20—C21
C19—C20—H20A
C21—C20—H20A
C19—C20—H20B
C21—C20—H20B
H20A—C20—H20B
C22—C21—C20
C22—C21—H21A
C20—C21—H21A
C22—C21—H21B
C20—C21—H21B
H21A—C21—H21B
108.1
107.3
111.60 (12)
109.3
109.3
109.3
109.3
108.0
113.28 (13)
108.9
108.9
108.9
108.9
107.7
109.5
109.5
109.5
109.5
109.5
109.5
116.19 (12)
108.2
108.2
108.2
108.2
107.4
112.19 (12)
109.2
109.2
109.2
109.2
107.9
112.66 (14)
109.1
109.1
109.1
109.1
107.8
Acta Cryst. (2014). E70, o1100
sup-6
supporting information
C13—C12—H12
C14—C13—C12
C14—C13—H13
C12—C13—H13
C13—C14—C9
C13—C14—H14
C9—C14—H14
C16—C15—C1
C16—C15—H15A
C1—C15—H15A
C16—C15—H15B
120.3
120.16 (14)
119.9
119.9
120.92 (15)
119.5
119.5
116.92 (12)
108.1
108.1
108.1
C21—C22—H22A
C21—C22—H22B
H22A—C22—H22B
C21—C22—H22C
H22A—C22—H22C
H22B—C22—H22C
C2—N1—C1
C2—N1—H1
C1—N1—H1
C2—N2—C3
109.5
109.5
109.5
109.5
109.5
109.5
125.27 (12)
117.4
117.4
116.84 (12)
Hydrogen-bond geometry (Å, º)
D—H···A
N1—H1···N2
i
D—H
H···A
D···A
D—H···A
0.88
2.29
3.1239 (16)
157
Symmetry code: (i) x, −y+1/2, z−1/2.
Acta Cryst. (2014). E70, o1100
sup-7