N-[(9-Ethyl-9H-carbazol-3-yl)methyl­idene]-3,4-dimethyl­isoxazol-5-amine

Asiri, A.M.; Khan, S.A.; Tan, K.W.; Ng, S.W.

doi:10.1107/S1600536810027686

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2046

https://doi.org/10.1107/S1600536810027686

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N-[(9-Ethyl-9H-carbazol-3-yl)methylidene]-3,4-dimethylisoxazol-5-amine

Abdullah M. Asiri,^a Salman A. Khan,^a Kong Wai Tan ^b and Seik Weng Ng ^b ^*

^aChemistry Department, Faculty of Science, King Abdul Aziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 17 June 2010; accepted 12 July 2010; online 17 July 2010)

The azomethine double bond in the title Schiff base, C₂₀H₁₉N₃O, has an E configuration. The 13-membered carbazolyl fused ring system [r.m.s. deviation = 0.023 (9) Å] is nearly coplanar with the five-membered pyrazole ring [r.m.s. deviation = 0.003 (4) Å]; the dihedral angle between the two systems is 10.8 (2)°. The crystal studied was a non-merohedral twin having a 35% minor component.

Related literature

For the synthesis and spectroscopic characterization of the title compound, see: Asiri et al. (2010 ). For the treatment of non-merohedral twins, see: Spek (2009 ).

Experimental

Crystal data

C₂₀H₁₉N₃O
M_r = 317.38
Monoclinic, P 2₁ /c
a = 8.0575 (9) Å
b = 13.4483 (15) Å
c = 14.8488 (16) Å
β = 94.049 (2)°
V = 1605.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
11993 measured reflections
2811 independent reflections
2286 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.089
wR(F²) = 0.262
S = 1.11
2811 reflections
221 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810027686/rk2213sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810027686/rk2213Isup2.hkl

checkCIF report

Comment top

We have recently reported the synthesis and characterization of this Schiff base (Asiri et al., 2010). The azomethine double-bond of the Schiff base (Scheme, Fig. 1) has an E-configuration. The 13-membered carbazolyl fused-ring (r.m.s. deviation 0.023 (9)Å) is nearly coplanar with 5-membered pyrazolyl ring (r.m.s. deviation 0.003 (4)Å) (dihedral angle between the two systems 10.8 (2)°).

Related literature top

For the synthesis and spectroscopic characterization of this Schiff base, see: Asiri et al. (2010). For the treatment of non-merohedral twins, see: Spek (2009).

Experimental top

Crystals of the compound were synthesized as reported (Asiri et al., 2010).

Structure description top

For the synthesis and spectroscopic characterization of this Schiff base, see: Asiri et al. (2010). For the treatment of non-merohedral twins, see: Spek (2009).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 2010).

Figures top

Fig. 1. The molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 70% probability level. Hydrogen atoms are drawn as a small spheres of arbitrary radius.

N-[(9-Ethyl-9H-carbazol-3-yl)methylidene]-3,4- dimethylisoxazol-5-amine top

Crystal data top

C₂₀H₁₉N₃O	F(000) = 672
M_r = 317.38	D_x = 1.313 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3958 reflections
a = 8.0575 (9) Å	θ = 2.5–27.4°
b = 13.4483 (15) Å	µ = 0.08 mm⁻¹
c = 14.8488 (16) Å	T = 100 K
β = 94.049 (2)°	Prism, yellow
V = 1605.0 (3) Å³	0.20 × 0.15 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2286 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.057
Graphite monochromator	θ_max = 25.0°, θ_min = 2.1°
ω scans	h = −9→8
11993 measured reflections	k = −15→15
2811 independent reflections	l = −17→17

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)] = 0.089	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.262	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.1086P)² + 4.6936P] where P = (F_o² + 2F_c²)/3
2811 reflections	(Δ/σ)_max = 0.001
221 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

C₂₀H₁₉N₃O	V = 1605.0 (3) Å³
M_r = 317.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0575 (9) Å	µ = 0.08 mm⁻¹
b = 13.4483 (15) Å	T = 100 K
c = 14.8488 (16) Å	0.20 × 0.15 × 0.05 mm
β = 94.049 (2)°

Data collection top

Bruker SMART APEX diffractometer	2286 reflections with I > 2σ(I)
11993 measured reflections	R_int = 0.057
2811 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.089	0 restraints
wR(F²) = 0.262	H-atom parameters constrained
S = 1.11	Δρ_max = 0.55 e Å⁻³
2811 reflections	Δρ_min = −0.54 e Å⁻³
221 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	0.2910 (4)	0.3151 (2)	0.1571 (2)	0.0238 (8)
N1	1.1980 (5)	0.1389 (3)	0.4076 (3)	0.0219 (9)
N2	0.4716 (5)	0.1815 (3)	0.2053 (3)	0.0216 (9)
N3	0.1279 (5)	0.3252 (3)	0.1158 (3)	0.0253 (9)
C1	1.1728 (6)	0.3018 (3)	0.3684 (3)	0.0187 (10)
C2	1.2291 (6)	0.3999 (3)	0.3616 (3)	0.0215 (10)
H2	1.1602	0.4489	0.3320	0.026*
C3	1.3860 (6)	0.4244 (3)	0.3984 (3)	0.0257 (11)
H3	1.4247	0.4909	0.3947	0.031*
C4	1.4879 (6)	0.3522 (4)	0.4411 (3)	0.0257 (11)
H4	1.5947	0.3708	0.4667	0.031*
C5	1.4375 (6)	0.2540 (4)	0.4472 (3)	0.0248 (11)
H5	1.5084	0.2049	0.4753	0.030*
C6	1.2794 (6)	0.2302 (3)	0.4105 (3)	0.0185 (10)
C7	1.2634 (6)	0.0460 (3)	0.4467 (3)	0.0239 (11)
H7A	1.1712	0.0081	0.4710	0.029*
H7B	1.3453	0.0614	0.4976	0.029*
C8	1.3456 (7)	−0.0178 (4)	0.3792 (4)	0.0336 (13)
H8A	1.3818	−0.0805	0.4078	0.050*
H8B	1.4423	0.0174	0.3583	0.050*
H8C	1.2662	−0.0315	0.3277	0.050*
C9	1.0436 (6)	0.1505 (3)	0.3641 (3)	0.0175 (10)
C10	1.0204 (6)	0.2514 (3)	0.3393 (3)	0.0180 (10)
C11	0.8678 (6)	0.2813 (3)	0.2978 (3)	0.0193 (10)
H11	0.8495	0.3491	0.2821	0.023*
C12	0.7420 (6)	0.2112 (3)	0.2796 (3)	0.0212 (10)
C13	0.7718 (6)	0.1102 (3)	0.3024 (3)	0.0212 (10)
H13	0.6869	0.0627	0.2875	0.025*
C14	0.9185 (6)	0.0784 (3)	0.3453 (3)	0.0228 (11)
H14	0.9354	0.0107	0.3616	0.027*
C15	0.5842 (6)	0.2432 (3)	0.2365 (3)	0.0205 (10)
H15	0.5625	0.3124	0.2311	0.025*
C16	0.3229 (6)	0.2162 (3)	0.1664 (3)	0.0186 (10)
C17	0.1911 (6)	0.1619 (3)	0.1324 (3)	0.0207 (10)
C18	0.0728 (6)	0.2352 (3)	0.1022 (3)	0.0197 (10)
C19	0.1746 (6)	0.0520 (3)	0.1276 (3)	0.0253 (11)
H19A	0.2802	0.0211	0.1493	0.038*
H19B	0.1463	0.0320	0.0650	0.038*
H19C	0.0866	0.0304	0.1655	0.038*
C20	−0.0982 (6)	0.2179 (4)	0.0589 (3)	0.0280 (11)
H20A	−0.1665	0.1847	0.1020	0.042*
H20B	−0.0911	0.1758	0.0054	0.042*
H20C	−0.1488	0.2818	0.0410	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0252 (18)	0.0164 (16)	0.0296 (18)	−0.0002 (14)	0.0004 (14)	0.0000 (13)
N1	0.026 (2)	0.0186 (19)	0.021 (2)	0.0010 (17)	0.0022 (17)	0.0028 (15)
N2	0.023 (2)	0.0176 (19)	0.024 (2)	−0.0013 (17)	0.0046 (17)	0.0003 (15)
N3	0.024 (2)	0.024 (2)	0.028 (2)	0.0035 (18)	0.0010 (18)	0.0026 (17)
C1	0.022 (2)	0.019 (2)	0.015 (2)	−0.0006 (19)	0.0041 (18)	−0.0030 (17)
C2	0.021 (2)	0.016 (2)	0.027 (2)	0.0013 (19)	0.002 (2)	−0.0006 (18)
C3	0.024 (3)	0.019 (2)	0.034 (3)	−0.003 (2)	0.004 (2)	−0.003 (2)
C4	0.021 (2)	0.031 (3)	0.024 (2)	−0.001 (2)	0.001 (2)	−0.004 (2)
C5	0.029 (3)	0.027 (2)	0.019 (2)	0.009 (2)	0.001 (2)	0.0007 (19)
C6	0.021 (2)	0.018 (2)	0.017 (2)	0.0017 (19)	0.0020 (18)	−0.0010 (17)
C7	0.031 (3)	0.016 (2)	0.025 (2)	0.003 (2)	−0.002 (2)	0.0036 (18)
C8	0.037 (3)	0.027 (3)	0.037 (3)	0.009 (2)	0.000 (2)	0.002 (2)
C9	0.021 (2)	0.016 (2)	0.015 (2)	0.0030 (18)	0.0046 (19)	0.0001 (17)
C10	0.024 (3)	0.014 (2)	0.016 (2)	−0.0009 (18)	0.0040 (19)	−0.0010 (16)
C11	0.023 (3)	0.017 (2)	0.018 (2)	0.0014 (19)	0.0032 (19)	−0.0007 (17)
C12	0.024 (3)	0.021 (2)	0.019 (2)	−0.003 (2)	0.0043 (19)	−0.0026 (18)
C13	0.025 (3)	0.017 (2)	0.022 (2)	−0.0061 (19)	0.005 (2)	−0.0020 (18)
C14	0.030 (3)	0.013 (2)	0.025 (2)	−0.001 (2)	0.005 (2)	0.0007 (18)
C15	0.021 (2)	0.017 (2)	0.024 (2)	−0.0023 (19)	0.005 (2)	−0.0019 (18)
C16	0.023 (2)	0.014 (2)	0.019 (2)	0.0001 (18)	0.0054 (19)	0.0019 (17)
C17	0.021 (2)	0.019 (2)	0.022 (2)	−0.0016 (19)	0.0039 (19)	−0.0006 (18)
C18	0.021 (2)	0.020 (2)	0.018 (2)	−0.0012 (19)	0.0040 (19)	0.0003 (18)
C19	0.024 (3)	0.016 (2)	0.036 (3)	−0.002 (2)	−0.003 (2)	0.0011 (19)
C20	0.025 (3)	0.033 (3)	0.026 (3)	0.000 (2)	0.000 (2)	0.001 (2)

Geometric parameters (Å, º) top

O1—C16	1.360 (5)	C8—H8B	0.9800
O1—N3	1.417 (5)	C8—H8C	0.9800
N1—C9	1.369 (6)	C9—C14	1.412 (6)
N1—C6	1.391 (6)	C9—C10	1.416 (6)
N1—C7	1.461 (6)	C10—C11	1.395 (6)
N2—C15	1.291 (6)	C11—C12	1.397 (6)
N2—C16	1.375 (6)	C11—H11	0.9500
N3—C18	1.300 (6)	C12—C13	1.416 (6)
C1—C2	1.400 (6)	C12—C15	1.448 (7)
C1—C6	1.407 (6)	C13—C14	1.371 (7)
C1—C10	1.443 (6)	C13—H13	0.9500
C2—C3	1.381 (7)	C14—H14	0.9500
C2—H2	0.9500	C15—H15	0.9500
C3—C4	1.395 (7)	C16—C17	1.357 (6)
C3—H3	0.9500	C17—C18	1.422 (6)
C4—C5	1.386 (7)	C17—C19	1.485 (6)
C4—H4	0.9500	C18—C20	1.496 (7)
C5—C6	1.387 (7)	C19—H19A	0.9800
C5—H5	0.9500	C19—H19B	0.9800
C7—C8	1.507 (7)	C19—H19C	0.9800
C7—H7A	0.9900	C20—H20A	0.9800
C7—H7B	0.9900	C20—H20B	0.9800
C8—H8A	0.9800	C20—H20C	0.9800

C16—O1—N3	107.5 (3)	C11—C10—C9	119.2 (4)
C9—N1—C6	109.0 (4)	C11—C10—C1	134.6 (4)
C9—N1—C7	125.1 (4)	C9—C10—C1	106.2 (4)
C6—N1—C7	125.9 (4)	C10—C11—C12	119.7 (4)
C15—N2—C16	120.1 (4)	C10—C11—H11	120.1
C18—N3—O1	105.9 (4)	C12—C11—H11	120.1
C2—C1—C6	119.1 (4)	C11—C12—C13	119.5 (4)
C2—C1—C10	134.0 (4)	C11—C12—C15	119.2 (4)
C6—C1—C10	107.0 (4)	C13—C12—C15	121.3 (4)
C3—C2—C1	119.2 (4)	C14—C13—C12	122.4 (4)
C3—C2—H2	120.4	C14—C13—H13	118.8
C1—C2—H2	120.4	C12—C13—H13	118.8
C2—C3—C4	120.4 (4)	C13—C14—C9	117.3 (4)
C2—C3—H3	119.8	C13—C14—H14	121.4
C4—C3—H3	119.8	C9—C14—H14	121.4
C5—C4—C3	121.8 (5)	N2—C15—C12	122.7 (4)
C5—C4—H4	119.1	N2—C15—H15	118.6
C3—C4—H4	119.1	C12—C15—H15	118.6
C4—C5—C6	117.3 (4)	C17—C16—O1	110.6 (4)
C4—C5—H5	121.3	C17—C16—N2	127.6 (4)
C6—C5—H5	121.3	O1—C16—N2	121.9 (4)
C5—C6—N1	129.3 (4)	C16—C17—C18	103.5 (4)
C5—C6—C1	122.1 (4)	C16—C17—C19	128.2 (4)
N1—C6—C1	108.6 (4)	C18—C17—C19	128.3 (4)
N1—C7—C8	112.7 (4)	N3—C18—C17	112.5 (4)
N1—C7—H7A	109.1	N3—C18—C20	120.4 (4)
C8—C7—H7A	109.1	C17—C18—C20	127.2 (4)
N1—C7—H7B	109.1	C17—C19—H19A	109.5
C8—C7—H7B	109.1	C17—C19—H19B	109.5
H7A—C7—H7B	107.8	H19A—C19—H19B	109.5
C7—C8—H8A	109.5	C17—C19—H19C	109.5
C7—C8—H8B	109.5	H19A—C19—H19C	109.5
H8A—C8—H8B	109.5	H19B—C19—H19C	109.5
C7—C8—H8C	109.5	C18—C20—H20A	109.5
H8A—C8—H8C	109.5	C18—C20—H20B	109.5
H8B—C8—H8C	109.5	H20A—C20—H20B	109.5
N1—C9—C14	128.9 (4)	C18—C20—H20C	109.5
N1—C9—C10	109.3 (4)	H20A—C20—H20C	109.5
C14—C9—C10	121.8 (4)	H20B—C20—H20C	109.5

C16—O1—N3—C18	−0.6 (5)	C2—C1—C10—C9	178.0 (5)
C6—C1—C2—C3	−1.7 (6)	C6—C1—C10—C9	−1.0 (5)
C10—C1—C2—C3	179.5 (5)	C9—C10—C11—C12	−1.5 (6)
C1—C2—C3—C4	0.6 (7)	C1—C10—C11—C12	−179.1 (5)
C2—C3—C4—C5	0.9 (7)	C10—C11—C12—C13	−0.8 (6)
C3—C4—C5—C6	−1.2 (7)	C10—C11—C12—C15	180.0 (4)
C4—C5—C6—N1	−179.6 (4)	C11—C12—C13—C14	2.5 (7)
C4—C5—C6—C1	0.1 (7)	C15—C12—C13—C14	−178.3 (4)
C9—N1—C6—C5	−179.6 (4)	C12—C13—C14—C9	−1.8 (7)
C7—N1—C6—C5	2.0 (7)	N1—C9—C14—C13	178.3 (4)
C9—N1—C6—C1	0.6 (5)	C10—C9—C14—C13	−0.6 (6)
C7—N1—C6—C1	−177.8 (4)	C16—N2—C15—C12	178.9 (4)
C2—C1—C6—C5	1.3 (6)	C11—C12—C15—N2	169.3 (4)
C10—C1—C6—C5	−179.6 (4)	C13—C12—C15—N2	−9.9 (7)
C2—C1—C6—N1	−178.9 (4)	N3—O1—C16—C17	0.9 (5)
C10—C1—C6—N1	0.2 (5)	N3—O1—C16—N2	−179.4 (4)
C9—N1—C7—C8	86.7 (6)	C15—N2—C16—C17	−178.4 (4)
C6—N1—C7—C8	−95.2 (5)	C15—N2—C16—O1	2.0 (6)
C6—N1—C9—C14	179.8 (4)	O1—C16—C17—C18	−0.9 (5)
C7—N1—C9—C14	−1.9 (7)	N2—C16—C17—C18	179.5 (4)
C6—N1—C9—C10	−1.2 (5)	O1—C16—C17—C19	178.9 (4)
C7—N1—C9—C10	177.1 (4)	N2—C16—C17—C19	−0.7 (8)
N1—C9—C10—C11	−176.9 (4)	O1—N3—C18—C17	0.1 (5)
C14—C9—C10—C11	2.2 (6)	O1—N3—C18—C20	−179.9 (4)
N1—C9—C10—C1	1.4 (5)	C16—C17—C18—N3	0.5 (5)
C14—C9—C10—C1	−179.6 (4)	C19—C17—C18—N3	−179.3 (5)
C2—C1—C10—C11	−4.2 (9)	C16—C17—C18—C20	−179.5 (4)
C6—C1—C10—C11	176.8 (5)	C19—C17—C18—C20	0.7 (8)

Experimental details

Crystal data
Chemical formula	C₂₀H₁₉N₃O
M_r	317.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.0575 (9), 13.4483 (15), 14.8488 (16)
β (°)	94.049 (2)
V (Å³)	1605.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.15 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11993, 2811, 2286
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.089, 0.262, 1.11
No. of reflections	2811
No. of parameters	221
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.54

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank King Abdul Aziz University and the University of Malaya for supporting this study.

References

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