3-[(1-Isobutyl-1H-imidazo[4,5-c]quinolin-4-yl)amino]­benzoic acid

Fun, H.-K.; Shahani, T.; Dinesh; Kayarmar, R.; Nagaraja, G.K.

doi:10.1107/S1600536811028765

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2150

doi:10.1107/S1600536811028765

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3-[(1-Isobutyl-1H-imidazo[4,5-c]quinolin-4-yl)amino]benzoic acid

Hoong-Kun Fun,^a ^*‡ Tara Shahani,^a Dinesh,^b Reshma Kayarmar ^b and G. K. Nagaraja ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Chemistry, Mangalore University, Karnataka, India
^*Correspondence e-mail: hkfun@usm.my

(Received 15 July 2011; accepted 17 July 2011; online 30 July 2011)

In the title compound, C₂₁H₂₀N₄O₂, the statistically planar 1H-limidazole ring [maximum deviation = 0.003 (1) Å] makes dihedral angles of 1.33 (9) and 8.23 (7)°, respectively, with the essentially planar fused pyridine ring [maximum devation = 0.018 (1) Å] and the pendant benzene ring, which is attached to the pyridine ring by an —NH— group. An intramolecular C—H⋯N interaction, which generates an S(6) ring, helps to estalish the molecular conformation. In the crystal, the molecules are linked by N—H⋯O, C—H⋯O and O—H—N hydrogen bonds, which generate bifurcated R¹₂(6) and R²₂(9) ring motifs, resulting in supramolecular [001] chains. The crystal structure also features weak π–π stacking [centroid–centroid distance = 3.5943 (9) Å] and C—H⋯π interactions.

Related literature

For our previous study of a related structure and background references, see: Loh et al. (2011 ). For a further related structure, see: Rasmussen et al. (2009 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For reference bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₁H₂₀N₄O₂
M_r = 360.41
Monoclinic, P 2₁ /c
a = 9.6440 (1) Å
b = 15.1496 (2) Å
c = 14.5286 (2) Å
β = 123.927 (1)°
V = 1761.28 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.41 × 0.26 × 0.22 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.964, T_max = 0.980
23777 measured reflections
5859 independent reflections
4504 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.140
S = 1.04
5859 reflections
254 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ⁱ	0.860 (16)	2.114 (17)	2.9436 (14)	161.8 (15)
O2—H1O2⋯N4ⁱⁱ	0.99 (2)	1.71 (2)	2.6926 (13)	172 (2)
C3—H3A⋯O1ⁱ	0.93	2.42	3.1998 (15)	142
C5—H5A⋯N2	0.93	2.21	2.8337 (16)	123
C1—H1A⋯Cg2ⁱⁱⁱ	0.93	2.94	3.3877 (14)	111
Symmetry codes: (i) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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 and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811028765/hb5954sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028765/hb5954Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028765/hb5954Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies of imidazoquinoline derivatives with possible pharmacological activity (Loh et al., 2011), we now report the synthesis and structure of the title compound, (I).

The asymmetric unit of the title compound is shown in Fig. 1. The essentially planar 1H-limidazole ring (N3/N4/C15–C17) [maximum deviation = 0.003 (1) Å for atom C16] makes dihedral angles of 1.33 (9)° and 8.23 (7)° respectively with the essentially planar pyridine ring (N2/C8/C9/C14–C16 [maximum devation = 0.018 (1) Å for atom C8] and benzene ring (C1–C6) which is attached to the pridine ring by dimethylamine group (N1/C4/C8). The bond lengths (Allen et al., 1987) and angles are within normal ranges and is comparable to a closely the related structure (Rasmussen et al., 2009).

In the crystal structure (Fig. 2), the molecules are linked by intermolecular N1—H1N1···O1, C3—H3A···O1 and C5—H5A···N2 hydrogen bonds generating bifurcated R¹₂(6) and R²₂(9) ring motifs, resulting in supramolecular [001] chains. Furthermore, the crystal structure is stabilized by weak π···π interactions between 1H-limidazole andpyridine rings [centroid–centroid distance = 3.5943 (9) Å; 1 - x, -y, 1 - z] and C—H···π interactions, involving Cg1 (N3/N4/C15–C17) and Cg2 (C9–C14) rings.

Related literature top

For our previous study of a related structure and background references, see: Loh et al. (2011). For a further related structure, see: Rasmussen et al. (2009). For hydrogen-bond motifs, see: Bernstein et al. (1995). For reference bond-length data, see: Allen et al. (1987).

Experimental top

To a solution of 4-chloro-1-(2-metylpropyl)-1H-imidazo [4,5-c] quinoline (0.1 mol) in ethanol (30 ml), 3-Aminobenzoic acid (0.1 mol) was added and the reaction mixture was refluxed for 24 h. It was then concentrated, cooled and poured over crushed ice to get the precipitate which was filtered, washed with water and recrystallized from ethanol to yield colourless blocks of (I). Mp: 485–487 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. The intramolecular hydrogen bond is shown by a dashed line.
	Fig. 2. The crystal packing of the title compound, viewed approximately along a axis. Intermolecular hydrogen bonds link the molecules into chains along [001].

3-[(1-Isobutyl-1H-imidazo[4,5-c]quinolin-4-yl)amino]benzoic acid top

Crystal data top

C₂₁H₂₀N₄O₂	F(000) = 760
M_r = 360.41	D_x = 1.359 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5489 reflections
a = 9.6440 (1) Å	θ = 2.2–32.1°
b = 15.1496 (2) Å	µ = 0.09 mm⁻¹
c = 14.5286 (2) Å	T = 296 K
β = 123.927 (1)°	Block, colourless
V = 1761.28 (4) Å³	0.41 × 0.26 × 0.22 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD diffractometer	5859 independent reflections
Radiation source: fine-focus sealed tube	4504 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 31.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→14
T_min = 0.964, T_max = 0.980	k = −20→22
23777 measured reflections	l = −21→18

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0764P)² + 0.3392P] where P = (F_o² + 2F_c²)/3
5859 reflections	(Δ/σ)_max < 0.001
254 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₁H₂₀N₄O₂	V = 1761.28 (4) Å³
M_r = 360.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.6440 (1) Å	µ = 0.09 mm⁻¹
b = 15.1496 (2) Å	T = 296 K
c = 14.5286 (2) Å	0.41 × 0.26 × 0.22 mm
β = 123.927 (1)°

Data collection top

Bruker APEXII DUO CCD diffractometer	5859 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4504 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.980	R_int = 0.035
23777 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.51 e Å⁻³
5859 reflections	Δρ_min = −0.22 e Å⁻³
254 parameters

Special details top

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.

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	0.14729 (12)	−0.33971 (6)	0.12947 (8)	0.0215 (2)
O2	0.15417 (11)	−0.47845 (6)	0.18402 (7)	0.01792 (19)
N1	0.16268 (13)	−0.15414 (6)	0.43284 (9)	0.0156 (2)
N2	0.24570 (13)	−0.09564 (6)	0.32204 (8)	0.0155 (2)
N3	0.33813 (12)	0.13649 (6)	0.49615 (8)	0.0148 (2)
N4	0.22805 (13)	0.02550 (7)	0.53736 (8)	0.0153 (2)
C1	0.07884 (15)	−0.42262 (8)	0.33507 (10)	0.0170 (2)
H1A	0.0624	−0.4821	0.3160	0.020*
C2	0.05934 (17)	−0.39045 (8)	0.41686 (11)	0.0206 (3)
H2A	0.0269	−0.4287	0.4516	0.025*
C3	0.08756 (16)	−0.30209 (8)	0.44747 (10)	0.0188 (2)
H3A	0.0752	−0.2822	0.5030	0.023*
C4	0.13454 (14)	−0.24239 (7)	0.39563 (10)	0.0142 (2)
C5	0.15066 (14)	−0.27426 (8)	0.31152 (9)	0.0142 (2)
H5A	0.1794	−0.2358	0.2748	0.017*
C6	0.12366 (14)	−0.36354 (7)	0.28254 (9)	0.0136 (2)
C7	0.14233 (14)	−0.39209 (8)	0.19153 (9)	0.0144 (2)
C8	0.21835 (14)	−0.08493 (7)	0.40042 (9)	0.0141 (2)
C9	0.30995 (14)	−0.02752 (8)	0.29402 (10)	0.0149 (2)
C10	0.33503 (16)	−0.04493 (8)	0.20876 (10)	0.0190 (2)
H10A	0.3056	−0.0997	0.1740	0.023*
C11	0.40222 (16)	0.01784 (8)	0.17665 (11)	0.0207 (3)
H11A	0.4170	0.0056	0.1199	0.025*
C12	0.44865 (16)	0.10040 (8)	0.22899 (11)	0.0198 (2)
H12A	0.4963	0.1422	0.2078	0.024*
C13	0.42430 (15)	0.12010 (8)	0.31138 (10)	0.0173 (2)
H13A	0.4547	0.1753	0.3451	0.021*
C14	0.35331 (14)	0.05705 (8)	0.34531 (9)	0.0143 (2)
C15	0.31713 (14)	0.06692 (7)	0.42760 (9)	0.0135 (2)
C16	0.24962 (14)	−0.00111 (8)	0.45501 (9)	0.0139 (2)
C17	0.28305 (15)	0.10753 (8)	0.55894 (10)	0.0163 (2)
H17A	0.2841	0.1423	0.6121	0.020*
C18	0.41403 (15)	0.22270 (8)	0.50622 (10)	0.0168 (2)
H18A	0.5132	0.2142	0.5056	0.020*
H18B	0.4490	0.2484	0.5772	0.020*
C19	0.29783 (15)	0.28790 (8)	0.41406 (10)	0.0175 (2)
H19A	0.2461	0.2576	0.3425	0.021*
C20	0.40172 (18)	0.36485 (9)	0.41590 (13)	0.0277 (3)
H20A	0.4829	0.3431	0.4029	0.041*
H20B	0.4579	0.3934	0.4869	0.041*
H20C	0.3297	0.4064	0.3590	0.041*
C21	0.15965 (15)	0.31946 (8)	0.42709 (11)	0.0211 (3)
H21A	0.0850	0.3575	0.3663	0.032*
H21B	0.2080	0.3513	0.4956	0.032*
H21C	0.0989	0.2695	0.4276	0.032*
H1N1	0.1529 (19)	−0.1435 (11)	0.4871 (14)	0.021 (4)*
H1O2	0.171 (3)	−0.4938 (15)	0.1246 (18)	0.052 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0341 (5)	0.0166 (4)	0.0218 (5)	0.0039 (4)	0.0207 (4)	0.0028 (3)
O2	0.0250 (4)	0.0134 (4)	0.0200 (4)	0.0004 (3)	0.0155 (4)	−0.0017 (3)
N1	0.0232 (5)	0.0119 (4)	0.0170 (5)	−0.0023 (4)	0.0145 (4)	−0.0020 (3)
N2	0.0192 (5)	0.0131 (5)	0.0163 (5)	0.0004 (4)	0.0112 (4)	0.0007 (3)
N3	0.0184 (5)	0.0110 (4)	0.0150 (5)	−0.0013 (3)	0.0094 (4)	−0.0002 (3)
N4	0.0184 (5)	0.0141 (5)	0.0147 (4)	−0.0001 (3)	0.0100 (4)	0.0003 (3)
C1	0.0215 (5)	0.0135 (5)	0.0182 (5)	−0.0030 (4)	0.0125 (5)	−0.0018 (4)
C2	0.0298 (6)	0.0166 (6)	0.0220 (6)	−0.0062 (5)	0.0186 (5)	−0.0018 (4)
C3	0.0265 (6)	0.0170 (6)	0.0200 (6)	−0.0043 (4)	0.0174 (5)	−0.0031 (4)
C4	0.0149 (5)	0.0123 (5)	0.0148 (5)	−0.0012 (4)	0.0079 (4)	−0.0009 (4)
C5	0.0162 (5)	0.0125 (5)	0.0151 (5)	−0.0001 (4)	0.0094 (4)	0.0002 (4)
C6	0.0145 (5)	0.0135 (5)	0.0130 (5)	0.0005 (4)	0.0077 (4)	−0.0002 (4)
C7	0.0136 (5)	0.0143 (5)	0.0146 (5)	0.0008 (4)	0.0074 (4)	−0.0017 (4)
C8	0.0153 (5)	0.0119 (5)	0.0144 (5)	−0.0002 (4)	0.0078 (4)	0.0006 (4)
C9	0.0160 (5)	0.0141 (5)	0.0149 (5)	0.0015 (4)	0.0087 (4)	0.0020 (4)
C10	0.0236 (6)	0.0170 (6)	0.0196 (6)	0.0031 (4)	0.0141 (5)	0.0015 (4)
C11	0.0257 (6)	0.0214 (6)	0.0198 (6)	0.0050 (5)	0.0158 (5)	0.0049 (5)
C12	0.0207 (6)	0.0195 (6)	0.0226 (6)	0.0030 (4)	0.0143 (5)	0.0073 (5)
C13	0.0177 (5)	0.0153 (5)	0.0192 (6)	0.0008 (4)	0.0106 (5)	0.0033 (4)
C14	0.0140 (5)	0.0142 (5)	0.0142 (5)	0.0014 (4)	0.0077 (4)	0.0023 (4)
C15	0.0145 (5)	0.0112 (5)	0.0140 (5)	0.0004 (4)	0.0075 (4)	0.0003 (4)
C16	0.0155 (5)	0.0131 (5)	0.0134 (5)	0.0008 (4)	0.0082 (4)	0.0006 (4)
C17	0.0209 (5)	0.0138 (5)	0.0155 (5)	−0.0009 (4)	0.0111 (5)	−0.0005 (4)
C18	0.0182 (5)	0.0119 (5)	0.0189 (6)	−0.0029 (4)	0.0094 (5)	−0.0003 (4)
C19	0.0194 (5)	0.0134 (5)	0.0197 (6)	0.0002 (4)	0.0109 (5)	0.0022 (4)
C20	0.0284 (7)	0.0178 (6)	0.0411 (8)	0.0009 (5)	0.0220 (6)	0.0083 (5)
C21	0.0194 (6)	0.0175 (6)	0.0245 (6)	−0.0001 (4)	0.0111 (5)	−0.0006 (5)

Geometric parameters (Å, º) top

O1—C7	1.2219 (15)	C9—C10	1.4131 (17)
O2—C7	1.3231 (14)	C9—C14	1.4225 (16)
O2—H1O2	0.99 (2)	C10—C11	1.3709 (18)
N1—C8	1.3755 (15)	C10—H10A	0.9300
N1—C4	1.4106 (15)	C11—C12	1.4012 (18)
N1—H1N1	0.860 (16)	C11—H11A	0.9300
N2—C8	1.3145 (15)	C12—C13	1.3750 (18)
N2—C9	1.3771 (15)	C12—H12A	0.9300
N3—C17	1.3592 (15)	C13—C14	1.4146 (16)
N3—C15	1.3852 (14)	C13—H13A	0.9300
N3—C18	1.4641 (15)	C14—C15	1.4280 (17)
N4—C17	1.3185 (15)	C15—C16	1.3907 (16)
N4—C16	1.3838 (15)	C17—H17A	0.9300
C1—C2	1.3908 (17)	C18—C19	1.5327 (16)
C1—C6	1.3923 (16)	C18—H18A	0.9700
C1—H1A	0.9300	C18—H18B	0.9700
C2—C3	1.3887 (17)	C19—C21	1.5238 (18)
C2—H2A	0.9300	C19—C20	1.5276 (18)
C3—C4	1.4041 (16)	C19—H19A	0.9800
C3—H3A	0.9300	C20—H20A	0.9600
C4—C5	1.4008 (16)	C20—H20B	0.9600
C5—C6	1.3973 (16)	C20—H20C	0.9600
C5—H5A	0.9300	C21—H21A	0.9600
C6—C7	1.4945 (16)	C21—H21B	0.9600
C8—C16	1.4371 (16)	C21—H21C	0.9600

C7—O2—H1O2	111.6 (13)	C13—C12—C11	120.54 (11)
C8—N1—C4	128.29 (10)	C13—C12—H12A	119.7
C8—N1—H1N1	115.8 (11)	C11—C12—H12A	119.7
C4—N1—H1N1	115.7 (11)	C12—C13—C14	120.52 (11)
C8—N2—C9	120.30 (10)	C12—C13—H13A	119.7
C17—N3—C15	106.38 (10)	C14—C13—H13A	119.7
C17—N3—C18	125.57 (10)	C13—C14—C9	118.92 (11)
C15—N3—C18	127.95 (10)	C13—C14—C15	127.81 (11)
C17—N4—C16	104.21 (10)	C9—C14—C15	113.27 (10)
C2—C1—C6	118.33 (11)	N3—C15—C16	105.18 (10)
C2—C1—H1A	120.8	N3—C15—C14	132.51 (11)
C6—C1—H1A	120.8	C16—C15—C14	122.30 (10)
C3—C2—C1	121.03 (11)	N4—C16—C15	110.61 (10)
C3—C2—H2A	119.5	N4—C16—C8	130.39 (11)
C1—C2—H2A	119.5	C15—C16—C8	118.97 (11)
C2—C3—C4	120.89 (11)	N4—C17—N3	113.62 (11)
C2—C3—H3A	119.6	N4—C17—H17A	123.2
C4—C3—H3A	119.6	N3—C17—H17A	123.2
C5—C4—C3	118.17 (11)	N3—C18—C19	113.99 (10)
C5—C4—N1	124.73 (10)	N3—C18—H18A	108.8
C3—C4—N1	117.10 (11)	C19—C18—H18A	108.8
C6—C5—C4	120.25 (11)	N3—C18—H18B	108.8
C6—C5—H5A	119.9	C19—C18—H18B	108.8
C4—C5—H5A	119.9	H18A—C18—H18B	107.6
C1—C6—C5	121.31 (11)	C21—C19—C20	111.64 (11)
C1—C6—C7	121.77 (10)	C21—C19—C18	110.94 (10)
C5—C6—C7	116.91 (10)	C20—C19—C18	108.90 (10)
O1—C7—O2	122.72 (11)	C21—C19—H19A	108.4
O1—C7—C6	122.59 (10)	C20—C19—H19A	108.4
O2—C7—C6	114.69 (10)	C18—C19—H19A	108.4
N2—C8—N1	120.53 (10)	C19—C20—H20A	109.5
N2—C8—C16	120.36 (10)	C19—C20—H20B	109.5
N1—C8—C16	119.10 (10)	H20A—C20—H20B	109.5
N2—C9—C10	116.40 (11)	C19—C20—H20C	109.5
N2—C9—C14	124.70 (11)	H20A—C20—H20C	109.5
C10—C9—C14	118.89 (11)	H20B—C20—H20C	109.5
C11—C10—C9	120.90 (12)	C19—C21—H21A	109.5
C11—C10—H10A	119.6	C19—C21—H21B	109.5
C9—C10—H10A	119.6	H21A—C21—H21B	109.5
C10—C11—C12	120.20 (12)	C19—C21—H21C	109.5
C10—C11—H11A	119.9	H21A—C21—H21C	109.5
C12—C11—H11A	119.9	H21B—C21—H21C	109.5

C6—C1—C2—C3	−1.50 (19)	N2—C9—C14—C13	177.58 (11)
C1—C2—C3—C4	0.8 (2)	C10—C9—C14—C13	−1.70 (16)
C2—C3—C4—C5	0.58 (18)	N2—C9—C14—C15	−2.51 (16)
C2—C3—C4—N1	−179.23 (12)	C10—C9—C14—C15	178.21 (10)
C8—N1—C4—C5	−3.85 (19)	C17—N3—C15—C16	−0.25 (12)
C8—N1—C4—C3	175.94 (11)	C18—N3—C15—C16	176.10 (11)
C3—C4—C5—C6	−1.29 (17)	C17—N3—C15—C14	−179.22 (12)
N1—C4—C5—C6	178.50 (11)	C18—N3—C15—C14	−2.9 (2)
C2—C1—C6—C5	0.77 (18)	C13—C14—C15—N3	0.0 (2)
C2—C1—C6—C7	−178.19 (11)	C9—C14—C15—N3	−179.85 (11)
C4—C5—C6—C1	0.63 (17)	C13—C14—C15—C16	−178.78 (11)
C4—C5—C6—C7	179.64 (10)	C9—C14—C15—C16	1.32 (16)
C1—C6—C7—O1	164.52 (12)	C17—N4—C16—C15	−0.49 (13)
C5—C6—C7—O1	−14.48 (16)	C17—N4—C16—C8	177.45 (12)
C1—C6—C7—O2	−15.91 (16)	N3—C15—C16—N4	0.46 (13)
C5—C6—C7—O2	165.09 (10)	C14—C15—C16—N4	179.56 (10)
C9—N2—C8—N1	−176.50 (10)	N3—C15—C16—C8	−177.74 (10)
C9—N2—C8—C16	2.20 (16)	C14—C15—C16—C8	1.36 (17)
C4—N1—C8—N2	3.04 (18)	N2—C8—C16—N4	178.96 (11)
C4—N1—C8—C16	−175.68 (11)	N1—C8—C16—N4	−2.32 (18)
C8—N2—C9—C10	−179.91 (10)	N2—C8—C16—C15	−3.25 (16)
C8—N2—C9—C14	0.79 (17)	N1—C8—C16—C15	175.47 (10)
N2—C9—C10—C11	−178.40 (11)	C16—N4—C17—N3	0.33 (13)
C14—C9—C10—C11	0.94 (18)	C15—N3—C17—N4	−0.05 (13)
C9—C10—C11—C12	0.58 (19)	C18—N3—C17—N4	−176.51 (10)
C10—C11—C12—C13	−1.35 (19)	C17—N3—C18—C19	−104.71 (13)
C11—C12—C13—C14	0.55 (18)	C15—N3—C18—C19	79.60 (15)
C12—C13—C14—C9	0.97 (17)	N3—C18—C19—C21	71.13 (13)
C12—C13—C14—C15	−178.92 (11)	N3—C18—C19—C20	−165.62 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.860 (16)	2.114 (17)	2.9436 (14)	161.8 (15)
O2—H1O2···N4ⁱⁱ	0.99 (2)	1.71 (2)	2.6926 (13)	172 (2)
C3—H3A···O1ⁱ	0.93	2.42	3.1998 (15)	142
C5—H5A···N2	0.93	2.21	2.8337 (16)	123
C1—H1A···Cg2ⁱⁱⁱ	0.93	2.94	3.3877 (14)	111

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

Experimental details

Crystal data
Chemical formula	C₂₁H₂₀N₄O₂
M_r	360.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.6440 (1), 15.1496 (2), 14.5286 (2)
β (°)	123.927 (1)
V (Å³)	1761.28 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.41 × 0.26 × 0.22

Data collection
Diffractometer	Bruker APEXII DUO CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.964, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	23777, 5859, 4504
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.735

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.140, 1.04
No. of reflections	5859
No. of parameters	254
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.22

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1ⁱ	0.860 (16)	2.114 (17)	2.9436 (14)	161.8 (15)
O2—H1O2···N4ⁱⁱ	0.99 (2)	1.71 (2)	2.6926 (13)	172 (2)
C3—H3A···O1ⁱ	0.93	2.42	3.1998 (15)	142
C5—H5A···N2	0.93	2.21	2.8337 (16)	123
C1—H1A···Cg2ⁱⁱⁱ	0.93	2.94	3.3877 (14)	111

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and TSH thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (1001/PF121K/811012). VV is grateful to the DST-India for funding through the Young Scientist Scheme (Fast Track Proposal).

References

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