4-[(3,4-Dimeth­oxy­benzyl­idene)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/S1600536810023238

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1732

doi:10.1107/S1600536810023238

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4-[(3,4-Dimethoxybenzylidene)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 15 June 2010; accepted 16 June 2010; online 23 June 2010)

The imino–carbon double-bond in the title Schiff base, C₂₀H₂₁N₃O₃, has an E configuration; the six-membered aromatic substituent (r.m.s. deviation = 0.012 Å) is nearly coplanar with five-membered pyrazole substituent (r.m.s. deviation = 0.031 Å), the dihedral angle between the two systems being 11.4 (1)°]. The phenyl ring connected to the pyrazole ring is aligned at 45.5 (1)° with respect to this five-membered ring. The N atoms in the ring show pyramidal coordinations.

Related literature

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

Experimental

Crystal data

C₂₀H₂₁N₃O₃
M_r = 351.40
Monoclinic, P 2₁ /c
a = 12.5584 (8) Å
b = 10.4752 (7) Å
c = 14.6002 (9) Å
β = 109.039 (1)°
V = 1815.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.35 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
16900 measured reflections
4164 independent reflections
3442 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.103
S = 1.00
4164 reflections
239 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.24 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/S1600536810023238/cv2733sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023238/cv2733Isup2.hkl

checkCIF report

Comment top

4-Aminoantipyrine (4-amino-1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one) possesses an 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). In the title benzaldehyde analog (Scheme I, Fig. 1), the 6-membered ring is nearly coplanar with 5-membered pyrazolyl ring [dihedral angle between the two systems 11.4 (1) °]. The phenyl ring connected to the pyrazolyl ring is aligned at 45.5 (1)°.

Related literature top

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

Experimental top

3,4-Dimethoxybenzaldehyde (0.36 g, 2.2 mmol) and 4-aminoantipyrine (0.45 g, 2.2 mmol) here heated in methanol (15 ml) for 5 h to afford a colorless precipitate. The solid material was collected and recrystallized from methanol.

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. Displacement ellipsoid plot (Barbour, 2001) of C₂₀H₂₁N₃O₃ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-[(3,4-Dimethoxybenzylidene)amino]-1,5-dimethyl-2-phenyl- 1H-pyrazol-3(2H)-one top

Crystal data top

C₂₀H₂₁N₃O₃	F(000) = 744
M_r = 351.40	D_x = 1.286 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6153 reflections
a = 12.5584 (8) Å	θ = 2.4–28.2°
b = 10.4752 (7) Å	µ = 0.09 mm⁻¹
c = 14.6002 (9) Å	T = 100 K
β = 109.039 (1)°	Prism, colourless
V = 1815.6 (2) Å³	0.35 × 0.25 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3442 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 27.5°, θ_min = 1.7°
ω scans	h = −16→16
16900 measured reflections	k = −13→12
4164 independent reflections	l = −18→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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0548P)² + 0.5659P] where P = (F_o² + 2F_c²)/3
4164 reflections	(Δ/σ)_max = 0.001
239 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₂₀H₂₁N₃O₃	V = 1815.6 (2) Å³
M_r = 351.40	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.5584 (8) Å	µ = 0.09 mm⁻¹
b = 10.4752 (7) Å	T = 100 K
c = 14.6002 (9) Å	0.35 × 0.25 × 0.15 mm
β = 109.039 (1)°

Data collection top

Bruker SMART APEX diffractometer	3442 reflections with I > 2σ(I)
16900 measured reflections	R_int = 0.031
4164 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.00	Δρ_max = 0.23 e Å⁻³
4164 reflections	Δρ_min = −0.24 e Å⁻³
239 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.28425 (6)	0.77513 (8)	0.59527 (6)	0.01980 (19)
O2	0.86240 (7)	0.62990 (8)	0.50221 (6)	0.02147 (19)
O3	0.86452 (8)	0.84966 (8)	0.42541 (7)	0.0292 (2)
N1	0.26678 (8)	0.60441 (9)	0.69085 (7)	0.0185 (2)
N2	0.33485 (8)	0.50111 (9)	0.73701 (7)	0.0190 (2)
N3	0.50498 (8)	0.62594 (9)	0.60372 (7)	0.0187 (2)
C1	0.18777 (9)	0.65675 (11)	0.73138 (8)	0.0189 (2)
C2	0.09077 (9)	0.71284 (11)	0.66951 (9)	0.0204 (2)
H2	0.0778	0.7155	0.6017	0.025*
C3	0.01286 (10)	0.76508 (12)	0.70792 (9)	0.0235 (3)
H3	−0.0530	0.8052	0.6662	0.028*
C4	0.03033 (10)	0.75915 (12)	0.80662 (9)	0.0252 (3)
H4	−0.0240	0.7936	0.8323	0.030*
C5	0.12751 (11)	0.70267 (13)	0.86781 (9)	0.0258 (3)
H5	0.1394	0.6982	0.9354	0.031*
C6	0.20713 (10)	0.65278 (12)	0.83089 (9)	0.0230 (3)
H6	0.2745	0.6161	0.8731	0.028*
C7	0.31965 (9)	0.67280 (11)	0.63587 (8)	0.0171 (2)
C8	0.41934 (9)	0.59911 (11)	0.64197 (8)	0.0173 (2)
C9	0.42229 (9)	0.49573 (11)	0.70009 (8)	0.0179 (2)
C10	0.50361 (10)	0.38826 (12)	0.72347 (9)	0.0231 (3)
H10A	0.5663	0.4077	0.6996	0.035*
H10B	0.4657	0.3102	0.6924	0.035*
H10C	0.5326	0.3759	0.7938	0.035*
C11	0.27490 (10)	0.38645 (11)	0.75111 (9)	0.0225 (3)
H11A	0.2343	0.4054	0.7965	0.034*
H11B	0.3292	0.3177	0.7774	0.034*
H11C	0.2212	0.3597	0.6888	0.034*
C12	0.49724 (9)	0.72136 (11)	0.54678 (8)	0.0191 (2)
H12	0.4304	0.7713	0.5274	0.023*
C13	0.59014 (9)	0.75419 (11)	0.51128 (8)	0.0187 (2)
C14	0.68242 (9)	0.67130 (11)	0.52633 (8)	0.0182 (2)
H14	0.6838	0.5919	0.5582	0.022*
C15	0.77102 (9)	0.70504 (11)	0.49495 (8)	0.0186 (2)
C16	0.77122 (10)	0.82494 (11)	0.45064 (9)	0.0213 (2)
C17	0.68007 (11)	0.90626 (12)	0.43516 (9)	0.0241 (3)
H17	0.6794	0.9867	0.4049	0.029*
C18	0.58924 (10)	0.86946 (11)	0.46420 (9)	0.0222 (3)
H18	0.5257	0.9242	0.4515	0.027*
C19	0.87115 (10)	0.51317 (11)	0.55464 (9)	0.0229 (3)
H19A	0.9404	0.4687	0.5564	0.034*
H19B	0.8060	0.4590	0.5226	0.034*
H19C	0.8730	0.5316	0.6209	0.034*
C20	0.86692 (15)	0.96944 (14)	0.37878 (14)	0.0452 (4)
H20A	0.9381	0.9775	0.3652	0.068*
H20B	0.8605	1.0393	0.4213	0.068*
H20C	0.8038	0.9735	0.3179	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0190 (4)	0.0167 (4)	0.0230 (4)	0.0009 (3)	0.0060 (3)	0.0034 (3)
O2	0.0217 (4)	0.0182 (4)	0.0269 (4)	0.0041 (3)	0.0112 (3)	0.0044 (3)
O3	0.0333 (5)	0.0184 (4)	0.0463 (6)	0.0023 (4)	0.0273 (4)	0.0066 (4)
N1	0.0171 (4)	0.0173 (5)	0.0208 (5)	0.0008 (4)	0.0060 (4)	0.0036 (4)
N2	0.0183 (4)	0.0165 (5)	0.0216 (5)	0.0006 (4)	0.0057 (4)	0.0036 (4)
N3	0.0178 (4)	0.0192 (5)	0.0192 (5)	−0.0019 (4)	0.0062 (4)	−0.0020 (4)
C1	0.0170 (5)	0.0173 (5)	0.0228 (6)	−0.0038 (4)	0.0071 (4)	−0.0013 (5)
C2	0.0188 (5)	0.0214 (6)	0.0208 (6)	−0.0040 (4)	0.0060 (4)	−0.0001 (5)
C3	0.0176 (5)	0.0232 (6)	0.0293 (6)	−0.0018 (5)	0.0071 (5)	−0.0010 (5)
C4	0.0241 (6)	0.0237 (6)	0.0319 (7)	−0.0058 (5)	0.0147 (5)	−0.0083 (5)
C5	0.0302 (6)	0.0271 (7)	0.0212 (6)	−0.0061 (5)	0.0097 (5)	−0.0051 (5)
C6	0.0220 (6)	0.0236 (6)	0.0211 (6)	−0.0021 (5)	0.0039 (5)	−0.0013 (5)
C7	0.0164 (5)	0.0169 (5)	0.0167 (5)	−0.0032 (4)	0.0038 (4)	−0.0016 (4)
C8	0.0163 (5)	0.0172 (5)	0.0174 (5)	−0.0008 (4)	0.0042 (4)	−0.0013 (4)
C9	0.0169 (5)	0.0179 (5)	0.0170 (5)	−0.0012 (4)	0.0030 (4)	−0.0019 (4)
C10	0.0232 (6)	0.0190 (6)	0.0258 (6)	0.0036 (5)	0.0064 (5)	0.0027 (5)
C11	0.0249 (6)	0.0185 (6)	0.0251 (6)	−0.0033 (5)	0.0096 (5)	0.0031 (5)
C12	0.0184 (5)	0.0198 (6)	0.0189 (5)	0.0007 (4)	0.0060 (4)	−0.0012 (4)
C13	0.0207 (5)	0.0190 (6)	0.0171 (5)	−0.0008 (4)	0.0070 (4)	−0.0022 (4)
C14	0.0219 (5)	0.0160 (5)	0.0170 (5)	−0.0006 (4)	0.0069 (4)	0.0001 (4)
C15	0.0206 (5)	0.0161 (5)	0.0192 (5)	0.0017 (4)	0.0069 (4)	−0.0019 (4)
C16	0.0250 (6)	0.0184 (6)	0.0253 (6)	−0.0005 (5)	0.0149 (5)	−0.0008 (5)
C17	0.0325 (6)	0.0166 (6)	0.0284 (6)	0.0030 (5)	0.0169 (5)	0.0034 (5)
C18	0.0256 (6)	0.0191 (6)	0.0241 (6)	0.0046 (5)	0.0113 (5)	0.0006 (5)
C19	0.0246 (6)	0.0176 (6)	0.0273 (6)	0.0028 (5)	0.0095 (5)	0.0041 (5)
C20	0.0552 (9)	0.0222 (7)	0.0797 (12)	0.0092 (7)	0.0513 (9)	0.0175 (7)

Geometric parameters (Å, º) top

O1—C7	1.2354 (14)	C9—C10	1.4830 (16)
O2—C15	1.3669 (14)	C10—H10A	0.9800
O2—C19	1.4277 (14)	C10—H10B	0.9800
O3—C16	1.3627 (14)	C10—H10C	0.9800
O3—C20	1.4326 (16)	C11—H11A	0.9800
N1—C7	1.3950 (14)	C11—H11B	0.9800
N1—N2	1.4072 (13)	C11—H11C	0.9800
N1—C1	1.4206 (15)	C12—C13	1.4638 (16)
N2—C9	1.3731 (15)	C12—H12	0.9500
N2—C11	1.4673 (14)	C13—C18	1.3876 (17)
N3—C12	1.2833 (15)	C13—C14	1.4067 (16)
N3—C8	1.3926 (14)	C14—C15	1.3804 (16)
C1—C2	1.3883 (16)	C14—H14	0.9500
C1—C6	1.3933 (17)	C15—C16	1.4132 (16)
C2—C3	1.3890 (17)	C16—C17	1.3851 (17)
C2—H2	0.9500	C17—C18	1.3946 (17)
C3—C4	1.3865 (18)	C17—H17	0.9500
C3—H3	0.9500	C18—H18	0.9500
C4—C5	1.3879 (19)	C19—H19A	0.9800
C4—H4	0.9500	C19—H19B	0.9800
C5—C6	1.3839 (18)	C19—H19C	0.9800
C5—H5	0.9500	C20—H20A	0.9800
C6—H6	0.9500	C20—H20B	0.9800
C7—C8	1.4486 (15)	C20—H20C	0.9800
C8—C9	1.3688 (16)

C15—O2—C19	116.78 (9)	H10B—C10—H10C	109.5
C16—O3—C20	116.62 (10)	N2—C11—H11A	109.5
C7—N1—N2	109.98 (9)	N2—C11—H11B	109.5
C7—N1—C1	124.72 (10)	H11A—C11—H11B	109.5
N2—N1—C1	119.67 (9)	N2—C11—H11C	109.5
C9—N2—N1	106.39 (9)	H11A—C11—H11C	109.5
C9—N2—C11	122.28 (10)	H11B—C11—H11C	109.5
N1—N2—C11	115.93 (9)	N3—C12—C13	120.78 (10)
C12—N3—C8	120.78 (10)	N3—C12—H12	119.6
C2—C1—C6	120.57 (11)	C13—C12—H12	119.6
C2—C1—N1	118.44 (10)	C18—C13—C14	119.19 (11)
C6—C1—N1	120.99 (10)	C18—C13—C12	120.08 (10)
C1—C2—C3	119.23 (11)	C14—C13—C12	120.71 (10)
C1—C2—H2	120.4	C15—C14—C13	120.15 (11)
C3—C2—H2	120.4	C15—C14—H14	119.9
C4—C3—C2	120.56 (11)	C13—C14—H14	119.9
C4—C3—H3	119.7	O2—C15—C14	125.03 (10)
C2—C3—H3	119.7	O2—C15—C16	114.87 (10)
C3—C4—C5	119.73 (11)	C14—C15—C16	120.10 (10)
C3—C4—H4	120.1	O3—C16—C17	125.23 (11)
C5—C4—H4	120.1	O3—C16—C15	115.00 (10)
C6—C5—C4	120.37 (12)	C17—C16—C15	119.77 (11)
C6—C5—H5	119.8	C16—C17—C18	119.66 (11)
C4—C5—H5	119.8	C16—C17—H17	120.2
C5—C6—C1	119.50 (11)	C18—C17—H17	120.2
C5—C6—H6	120.2	C13—C18—C17	121.05 (11)
C1—C6—H6	120.2	C13—C18—H18	119.5
O1—C7—N1	123.87 (10)	C17—C18—H18	119.5
O1—C7—C8	131.33 (10)	O2—C19—H19A	109.5
N1—C7—C8	104.77 (9)	O2—C19—H19B	109.5
C9—C8—N3	122.68 (10)	H19A—C19—H19B	109.5
C9—C8—C7	107.92 (10)	O2—C19—H19C	109.5
N3—C8—C7	129.26 (10)	H19A—C19—H19C	109.5
C8—C9—N2	110.34 (10)	H19B—C19—H19C	109.5
C8—C9—C10	128.36 (11)	O3—C20—H20A	109.5
N2—C9—C10	121.31 (10)	O3—C20—H20B	109.5
C9—C10—H10A	109.5	H20A—C20—H20B	109.5
C9—C10—H10B	109.5	O3—C20—H20C	109.5
H10A—C10—H10B	109.5	H20A—C20—H20C	109.5
C9—C10—H10C	109.5	H20B—C20—H20C	109.5
H10A—C10—H10C	109.5

C7—N1—N2—C9	−8.00 (12)	C7—C8—C9—N2	−3.61 (13)
C1—N1—N2—C9	−162.78 (10)	N3—C8—C9—C10	−8.03 (19)
C7—N1—N2—C11	−147.65 (10)	C7—C8—C9—C10	175.83 (11)
C1—N1—N2—C11	57.57 (13)	N1—N2—C9—C8	7.08 (12)
C7—N1—C1—C2	58.12 (15)	C11—N2—C9—C8	143.54 (11)
N2—N1—C1—C2	−151.03 (10)	N1—N2—C9—C10	−172.41 (10)
C7—N1—C1—C6	−121.50 (12)	C11—N2—C9—C10	−35.94 (16)
N2—N1—C1—C6	29.34 (16)	C8—N3—C12—C13	176.26 (10)
C6—C1—C2—C3	−0.05 (17)	N3—C12—C13—C18	−168.62 (11)
N1—C1—C2—C3	−179.68 (10)	N3—C12—C13—C14	9.85 (17)
C1—C2—C3—C4	−1.31 (18)	C18—C13—C14—C15	0.35 (17)
C2—C3—C4—C5	1.22 (18)	C12—C13—C14—C15	−178.13 (10)
C3—C4—C5—C6	0.25 (19)	C19—O2—C15—C14	−6.31 (16)
C4—C5—C6—C1	−1.59 (19)	C19—O2—C15—C16	174.22 (10)
C2—C1—C6—C5	1.50 (18)	C13—C14—C15—O2	−177.20 (10)
N1—C1—C6—C5	−178.89 (11)	C13—C14—C15—C16	2.23 (17)
N2—N1—C7—O1	−172.69 (10)	C20—O3—C16—C17	−0.3 (2)
C1—N1—C7—O1	−19.46 (17)	C20—O3—C16—C15	178.96 (13)
N2—N1—C7—C8	5.75 (12)	O2—C15—C16—O3	−2.53 (15)
C1—N1—C7—C8	158.98 (10)	C14—C15—C16—O3	177.98 (11)
C12—N3—C8—C9	177.56 (11)	O2—C15—C16—C17	176.81 (11)
C12—N3—C8—C7	−7.18 (18)	C14—C15—C16—C17	−2.68 (18)
O1—C7—C8—C9	176.90 (12)	O3—C16—C17—C18	179.80 (12)
N1—C7—C8—C9	−1.37 (12)	C15—C16—C17—C18	0.52 (19)
O1—C7—C8—N3	1.1 (2)	C14—C13—C18—C17	−2.54 (18)
N1—C7—C8—N3	−177.18 (11)	C12—C13—C18—C17	175.95 (11)
N3—C8—C9—N2	172.54 (10)	C16—C17—C18—C13	2.10 (19)

Experimental details

Crystal data
Chemical formula	C₂₀H₂₁N₃O₃
M_r	351.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	12.5584 (8), 10.4752 (7), 14.6002 (9)
β (°)	109.039 (1)
V (Å³)	1815.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	16900, 4164, 3442
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.103, 1.00
No. of reflections	4164
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24

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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