4-{[4-(Dimethylamino)benzylidene]­amino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

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

doi:10.1107/S1600536810023536

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1751

doi:10.1107/S1600536810023536

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4-{[4-(Dimethylamino)benzylidene]amino}-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

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 17 June 2010; online 23 June 2010)

The azomethine double-bond in the title Schiff base, C₂₀H₂₂N₄O, has an E-configuration. The aromatic ring of the benzylidene portion (r.m.s. deviation 0.011 Å) and the five-membered pyrazolyl ring (r.m.s. deviation 0.033 Å) form a dihedral angle of 19.0 (1)°. The phenyl substituent is twisted by 55.0 (1)° with respect to the five-membered ring.

Related literature

For background to Schiff bases derived from 4-aminoantipyridine, see: Montalvo-González & Ariza-Castolo (2003 ).

Experimental

Crystal data

C₂₀H₂₂N₄O
M_r = 334.42
Monoclinic, C 2/c
a = 17.7275 (14) Å
b = 6.7552 (6) Å
c = 29.387 (2) Å
β = 101.426 (1)°
V = 3449.5 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.25 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
15916 measured reflections
3959 independent reflections
3146 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.101
S = 1.02
3959 reflections
230 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 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: 10.1107/S1600536810023536/kp2268sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023536/kp2268Isup2.hkl

checkCIF report

Comment top

4-Aminoantipyrine (4-amino-1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one) possesses a aminopyrazolone unit, a feature that allows the compound to condense with aromatic aldehydes to yield Schiff bases. The Schiff base derived from the benzaldehyde homolog has nearly coplanar phenyl and pyrazoly rings (Montalvo-González & Ariza-Castolo, 2003). The azomethine double-bond in the Schiff base, C₂₀H₂₂N₄O, has an E-configuration (Scheme 1, Fig. 1). The aromatic ring of the benzylidene portion (r.m.s. deviation 0.011 Å) and 5-membered pyrazolyl ring (r.m.s. deviation 0.033 Å) form the dihedral angle between of 19.0 (1) °. The phenyl substituent is twisted by 55.0 (1) ° with respect to the 5-membered ring.

Related literature top

For background to Schiff bases derived from 4-aminoantipyridine, see: Montalvo-González & Ariza-Castolo (2003).

Experimental top

N,N-Dimethylbenzaldehyde (0.32 g, 2.2 mmol) and 4-aminoantipyrine (0.45 g, 2.2 mmol) were heated in methanol (15 ml) for 5 h. A solution was set aside to cool slowly and after a day crystals were separated.

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. ORTEP drawing (Barbour, 2001) of the title molecule (I) with the displacement parameters at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-{[4-(Dimethylamino)benzylidene]amino}-1,5-dimethyl-2-phenyl- 1H-pyrazol-3(2H)-one top

Crystal data top

C₂₀H₂₂N₄O	F(000) = 1424
M_r = 334.42	D_x = 1.288 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3746 reflections
a = 17.7275 (14) Å	θ = 2.3–28.2°
b = 6.7552 (6) Å	µ = 0.08 mm⁻¹
c = 29.387 (2) Å	T = 100 K
β = 101.426 (1)°	Irregular, yellow
V = 3449.5 (5) Å³	0.25 × 0.20 × 0.10 mm
Z = 8

Data collection top

Bruker SMART APEX diffractometer	3146 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 27.5°, θ_min = 1.4°
ω scans	h = −22→22
15916 measured reflections	k = −8→8
3959 independent reflections	l = −38→38

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0456P)² + 1.6458P] where P = (F_o² + 2F_c²)/3
3959 reflections	(Δ/σ)_max = 0.001
230 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₀H₂₂N₄O	V = 3449.5 (5) Å³
M_r = 334.42	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 17.7275 (14) Å	µ = 0.08 mm⁻¹
b = 6.7552 (6) Å	T = 100 K
c = 29.387 (2) Å	0.25 × 0.20 × 0.10 mm
β = 101.426 (1)°

Data collection top

Bruker SMART APEX diffractometer	3146 reflections with I > 2σ(I)
15916 measured reflections	R_int = 0.043
3959 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.02	Δρ_max = 0.22 e Å⁻³
3959 reflections	Δρ_min = −0.22 e Å⁻³
230 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.44182 (5)	0.85565 (14)	0.62281 (3)	0.0206 (2)
N1	0.88210 (7)	0.91371 (18)	0.54534 (4)	0.0232 (3)
N2	0.58578 (6)	0.58777 (17)	0.61620 (4)	0.0173 (2)
N3	0.45341 (6)	0.41420 (16)	0.68429 (4)	0.0163 (2)
N4	0.41440 (6)	0.58791 (16)	0.66631 (4)	0.0166 (2)
C1	0.81084 (8)	0.8721 (2)	0.55470 (4)	0.0196 (3)
C2	0.79273 (8)	0.6806 (2)	0.56883 (4)	0.0204 (3)
H2	0.8292	0.5767	0.5700	0.024*
C3	0.72303 (8)	0.6430 (2)	0.58096 (4)	0.0194 (3)
H3	0.7125	0.5130	0.5903	0.023*
C4	0.66719 (8)	0.7900 (2)	0.57993 (4)	0.0182 (3)
C5	0.68396 (8)	0.9775 (2)	0.56453 (5)	0.0210 (3)
H5	0.6466	1.0795	0.5626	0.025*
C6	0.75351 (8)	1.0189 (2)	0.55193 (5)	0.0219 (3)
H6	0.7627	1.1477	0.5413	0.026*
C7	0.93806 (8)	0.7568 (2)	0.54517 (5)	0.0253 (3)
H7A	0.9402	0.6730	0.5726	0.038*
H7B	0.9889	0.8150	0.5457	0.038*
H7C	0.9229	0.6766	0.5171	0.038*
C8	0.89519 (9)	1.0978 (2)	0.52251 (5)	0.0267 (3)
H8A	0.8791	1.2096	0.5396	0.040*
H8B	0.8653	1.0975	0.4907	0.040*
H8C	0.9500	1.1105	0.5219	0.040*
C9	0.59614 (8)	0.7527 (2)	0.59633 (4)	0.0183 (3)
H9	0.5571	0.8510	0.5923	0.022*
C10	0.45790 (7)	0.68849 (19)	0.63871 (4)	0.0162 (3)
C11	0.52186 (8)	0.55737 (19)	0.63643 (4)	0.0160 (3)
C12	0.51466 (7)	0.39349 (19)	0.66245 (4)	0.0160 (3)
C13	0.56351 (8)	0.2136 (2)	0.66934 (5)	0.0206 (3)
H13A	0.6052	0.2271	0.6521	0.031*
H13B	0.5322	0.0975	0.6580	0.031*
H13C	0.5854	0.1973	0.7025	0.031*
C14	0.40306 (8)	0.2478 (2)	0.69032 (5)	0.0208 (3)
H14A	0.4343	0.1376	0.7054	0.031*
H14B	0.3744	0.2051	0.6599	0.031*
H14C	0.3668	0.2897	0.7097	0.031*
C16	0.36949 (7)	0.68935 (18)	0.69429 (4)	0.0154 (3)
C17	0.39115 (7)	0.68983 (19)	0.74243 (4)	0.0168 (3)
H17	0.4349	0.6172	0.7574	0.020*
C18	0.34793 (8)	0.79786 (19)	0.76822 (5)	0.0181 (3)
H18	0.3619	0.7977	0.8011	0.022*
C19	0.28464 (8)	0.90595 (19)	0.74637 (5)	0.0187 (3)
H19	0.2559	0.9817	0.7642	0.022*
C20	0.26332 (8)	0.9032 (2)	0.69835 (5)	0.0196 (3)
H20	0.2198	0.9770	0.6833	0.024*
C21	0.30522 (8)	0.7932 (2)	0.67215 (5)	0.0180 (3)
H21	0.2900	0.7890	0.6393	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0237 (5)	0.0167 (5)	0.0222 (5)	0.0029 (4)	0.0069 (4)	0.0043 (4)
N1	0.0196 (6)	0.0284 (7)	0.0230 (6)	−0.0015 (5)	0.0074 (5)	0.0046 (5)
N2	0.0160 (6)	0.0207 (6)	0.0153 (5)	−0.0014 (5)	0.0029 (4)	−0.0016 (4)
N3	0.0177 (6)	0.0124 (5)	0.0193 (5)	0.0016 (4)	0.0047 (5)	0.0016 (4)
N4	0.0183 (6)	0.0141 (5)	0.0180 (5)	0.0028 (4)	0.0053 (5)	0.0028 (4)
C1	0.0196 (7)	0.0273 (7)	0.0117 (6)	−0.0017 (6)	0.0027 (5)	0.0007 (5)
C2	0.0198 (7)	0.0249 (7)	0.0166 (6)	0.0024 (6)	0.0038 (5)	0.0014 (5)
C3	0.0217 (7)	0.0213 (7)	0.0152 (6)	−0.0014 (6)	0.0034 (5)	0.0018 (5)
C4	0.0192 (7)	0.0229 (7)	0.0123 (6)	−0.0011 (6)	0.0029 (5)	0.0006 (5)
C5	0.0219 (7)	0.0233 (7)	0.0178 (6)	0.0031 (6)	0.0042 (6)	0.0026 (5)
C6	0.0249 (8)	0.0220 (7)	0.0193 (7)	−0.0031 (6)	0.0060 (6)	0.0034 (6)
C7	0.0196 (7)	0.0347 (8)	0.0226 (7)	−0.0002 (6)	0.0067 (6)	0.0001 (6)
C8	0.0270 (8)	0.0313 (8)	0.0229 (7)	−0.0074 (7)	0.0079 (6)	0.0021 (6)
C9	0.0198 (7)	0.0206 (7)	0.0141 (6)	0.0005 (5)	0.0024 (5)	−0.0009 (5)
C10	0.0167 (7)	0.0173 (7)	0.0145 (6)	−0.0032 (5)	0.0026 (5)	−0.0016 (5)
C11	0.0161 (7)	0.0178 (7)	0.0138 (6)	−0.0004 (5)	0.0023 (5)	−0.0020 (5)
C12	0.0152 (7)	0.0166 (6)	0.0150 (6)	−0.0008 (5)	0.0005 (5)	−0.0036 (5)
C13	0.0211 (7)	0.0184 (7)	0.0224 (7)	0.0016 (6)	0.0044 (6)	0.0000 (5)
C14	0.0232 (7)	0.0164 (7)	0.0238 (7)	−0.0026 (5)	0.0072 (6)	0.0008 (5)
C16	0.0157 (6)	0.0128 (6)	0.0191 (6)	−0.0022 (5)	0.0066 (5)	−0.0012 (5)
C17	0.0145 (7)	0.0155 (6)	0.0196 (6)	−0.0006 (5)	0.0017 (5)	0.0018 (5)
C18	0.0207 (7)	0.0168 (7)	0.0168 (6)	−0.0032 (5)	0.0039 (5)	0.0006 (5)
C19	0.0193 (7)	0.0147 (6)	0.0242 (7)	0.0000 (5)	0.0095 (6)	−0.0009 (5)
C20	0.0161 (7)	0.0166 (6)	0.0258 (7)	0.0019 (5)	0.0036 (6)	0.0032 (5)
C21	0.0179 (7)	0.0183 (7)	0.0176 (6)	−0.0009 (5)	0.0025 (5)	0.0019 (5)

Geometric parameters (Å, º) top

O1—C10	1.2337 (16)	C8—H8A	0.9800
N1—C1	1.3743 (18)	C8—H8B	0.9800
N1—C7	1.4523 (19)	C8—H8C	0.9800
N1—C8	1.4533 (19)	C9—H9	0.9500
N2—C9	1.2877 (17)	C10—C11	1.4509 (18)
N2—C11	1.3950 (17)	C11—C12	1.3657 (18)
N3—C12	1.3735 (17)	C12—C13	1.4825 (18)
N3—N4	1.4106 (15)	C13—H13A	0.9800
N3—C14	1.4676 (17)	C13—H13B	0.9800
N4—C10	1.4007 (16)	C13—H13C	0.9800
N4—C16	1.4279 (16)	C14—H14A	0.9800
C1—C6	1.410 (2)	C14—H14B	0.9800
C1—C2	1.415 (2)	C14—H14C	0.9800
C2—C3	1.3758 (19)	C16—C21	1.3855 (18)
C2—H2	0.9500	C16—C17	1.3905 (18)
C3—C4	1.3982 (19)	C17—C18	1.3872 (18)
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.3969 (19)	C18—C19	1.3853 (19)
C4—C9	1.4569 (19)	C18—H18	0.9500
C5—C6	1.3842 (19)	C19—C20	1.3867 (19)
C5—H5	0.9500	C19—H19	0.9500
C6—H6	0.9500	C20—C21	1.3871 (19)
C7—H7A	0.9800	C20—H20	0.9500
C7—H7B	0.9800	C21—H21	0.9500
C7—H7C	0.9800

C1—N1—C7	120.48 (12)	N2—C9—H9	119.7
C1—N1—C8	120.29 (12)	C4—C9—H9	119.7
C7—N1—C8	116.83 (12)	O1—C10—N4	123.44 (12)
C9—N2—C11	121.43 (12)	O1—C10—C11	131.70 (12)
C12—N3—N4	106.50 (10)	N4—C10—C11	104.81 (11)
C12—N3—C14	122.31 (11)	C12—C11—N2	122.13 (12)
N4—N3—C14	114.67 (10)	C12—C11—C10	107.96 (11)
C10—N4—N3	109.57 (10)	N2—C11—C10	129.65 (12)
C10—N4—C16	122.30 (11)	C11—C12—N3	110.45 (11)
N3—N4—C16	118.13 (10)	C11—C12—C13	128.60 (12)
N1—C1—C6	121.69 (13)	N3—C12—C13	120.93 (12)
N1—C1—C2	121.11 (13)	C12—C13—H13A	109.5
C6—C1—C2	117.18 (12)	C12—C13—H13B	109.5
C3—C2—C1	120.83 (13)	H13A—C13—H13B	109.5
C3—C2—H2	119.6	C12—C13—H13C	109.5
C1—C2—H2	119.6	H13A—C13—H13C	109.5
C2—C3—C4	122.11 (13)	H13B—C13—H13C	109.5
C2—C3—H3	118.9	N3—C14—H14A	109.5
C4—C3—H3	118.9	N3—C14—H14B	109.5
C5—C4—C3	117.13 (12)	H14A—C14—H14B	109.5
C5—C4—C9	121.16 (12)	N3—C14—H14C	109.5
C3—C4—C9	121.64 (12)	H14A—C14—H14C	109.5
C6—C5—C4	121.84 (13)	H14B—C14—H14C	109.5
C6—C5—H5	119.1	C21—C16—C17	120.82 (12)
C4—C5—H5	119.1	C21—C16—N4	118.22 (11)
C5—C6—C1	120.84 (13)	C17—C16—N4	120.92 (12)
C5—C6—H6	119.6	C18—C17—C16	119.08 (12)
C1—C6—H6	119.6	C18—C17—H17	120.5
N1—C7—H7A	109.5	C16—C17—H17	120.5
N1—C7—H7B	109.5	C19—C18—C17	120.55 (12)
H7A—C7—H7B	109.5	C19—C18—H18	119.7
N1—C7—H7C	109.5	C17—C18—H18	119.7
H7A—C7—H7C	109.5	C18—C19—C20	119.82 (12)
H7B—C7—H7C	109.5	C18—C19—H19	120.1
N1—C8—H8A	109.5	C20—C19—H19	120.1
N1—C8—H8B	109.5	C19—C20—C21	120.27 (13)
H8A—C8—H8B	109.5	C19—C20—H20	119.9
N1—C8—H8C	109.5	C21—C20—H20	119.9
H8A—C8—H8C	109.5	C16—C21—C20	119.44 (12)
H8B—C8—H8C	109.5	C16—C21—H21	120.3
N2—C9—C4	120.66 (13)	C20—C21—H21	120.3

C12—N3—N4—C10	−8.61 (13)	C9—N2—C11—C10	1.4 (2)
C14—N3—N4—C10	−147.15 (11)	O1—C10—C11—C12	176.26 (14)
C12—N3—N4—C16	−155.05 (11)	N4—C10—C11—C12	−1.17 (14)
C14—N3—N4—C16	66.41 (14)	O1—C10—C11—N2	2.2 (2)
C7—N1—C1—C6	−175.50 (12)	N4—C10—C11—N2	−175.21 (12)
C8—N1—C1—C6	−13.63 (19)	N2—C11—C12—N3	170.36 (11)
C7—N1—C1—C2	6.28 (19)	C10—C11—C12—N3	−4.23 (15)
C8—N1—C1—C2	168.15 (13)	N2—C11—C12—C13	−8.4 (2)
N1—C1—C2—C3	175.89 (12)	C10—C11—C12—C13	177.05 (12)
C6—C1—C2—C3	−2.41 (19)	N4—N3—C12—C11	7.87 (14)
C1—C2—C3—C4	0.1 (2)	C14—N3—C12—C11	142.49 (12)
C2—C3—C4—C5	1.99 (19)	N4—N3—C12—C13	−173.29 (11)
C2—C3—C4—C9	−175.04 (12)	C14—N3—C12—C13	−38.67 (18)
C3—C4—C5—C6	−1.7 (2)	C10—N4—C16—C21	68.38 (16)
C9—C4—C5—C6	175.37 (12)	N3—N4—C16—C21	−149.66 (12)
C4—C5—C6—C1	−0.7 (2)	C10—N4—C16—C17	−109.37 (14)
N1—C1—C6—C5	−175.58 (12)	N3—N4—C16—C17	32.58 (17)
C2—C1—C6—C5	2.7 (2)	C21—C16—C17—C18	−0.70 (19)
C11—N2—C9—C4	173.20 (12)	N4—C16—C17—C18	177.00 (11)
C5—C4—C9—N2	−170.60 (12)	C16—C17—C18—C19	−0.84 (19)
C3—C4—C9—N2	6.3 (2)	C17—C18—C19—C20	1.3 (2)
N3—N4—C10—O1	−171.71 (12)	C18—C19—C20—C21	−0.2 (2)
C16—N4—C10—O1	−26.94 (19)	C17—C16—C21—C20	1.8 (2)
N3—N4—C10—C11	5.99 (13)	N4—C16—C21—C20	−175.97 (12)
C16—N4—C10—C11	150.76 (11)	C19—C20—C21—C16	−1.3 (2)
C9—N2—C11—C12	−171.88 (12)

Experimental details

Crystal data
Chemical formula	C₂₀H₂₂N₄O
M_r	334.42
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	17.7275 (14), 6.7552 (6), 29.387 (2)
β (°)	101.426 (1)
V (Å³)	3449.5 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	15916, 3959, 3146
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.101, 1.02
No. of reflections	3959
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

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

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Montalvo-González, R. & Ariza-Castolo, A. (2003). J. Mol. Struct. 655, 375–389. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43. Submitted. Google Scholar

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