4-[(E)-(2,4,5-Trimeth-oxy-benzyl-idene)amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one.

The title compound, C(21)H(23)N(3)O(4), adopts an E configuration about the central C=N double bond and the pyrazolone ring is almost planar, with a maximum deviation of 0.042 (1) Å. The central pyrazolone ring makes dihedral angles of 51.96 (5) and 3.82 (5)° with the attached phenyl and the trimeth-oxy-substituted benzene rings, respectively. The dihedral angle between the phenyl ring and the trimeth-oxy-substituted benzene ring is 50.19 (5)° and an intra-molecular C-H⋯O hydrogen bond generates an S(6) ring motif. The crystal structure is stabilized by inter-molecular C-H⋯O and C-H⋯N hydrogen bonds.

Related literature

For background to the applications of Schiff bases, see: Vukovic et al. (2010 ▶); Ramesh & Maheswaran (2003 ▶); Dongfang et al. (2008 ▶); Sastry & Rao (1988 ▶); Kamel et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C21H23N3O4

M = 381.42

Monoclinic,

a = 21.0128 (10) Å

b = 7.4242 (4) Å

c = 12.5194 (6) Å

β = 98.675 (1)°

V = 1930.72 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.67 × 0.27 × 0.15 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.941, T max = 0.987

23600 measured reflections

5614 independent reflections

4779 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.123

S = 1.04

5614 reflections

345 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.23 e Å−3

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810021586/hb5480sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021586/hb5480Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H23N3O4	F(000) = 808
Mr = 381.42	Dx = 1.312 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8559 reflections
a = 21.0128 (10) Å	θ = 2.9–34.8°
b = 7.4242 (4) Å	µ = 0.09 mm−1
c = 12.5194 (6) Å	T = 100 K
β = 98.675 (1)°	Blcok, yellow
V = 1930.72 (17) Å3	0.67 × 0.27 × 0.15 mm
Z = 4

Bruker APEXII DUO CCD diffractometer	5614 independent reflections
Radiation source: fine-focus sealed tube	4779 reflections with I > 2σ(I)
graphite	Rint = 0.031
φ and ω scans	θmax = 30.0°, θmin = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −29→29
Tmin = 0.941, Tmax = 0.987	k = −10→10
23600 measured reflections	l = −17→17

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0771P)2 + 0.3259P] where P = (Fo2 + 2Fc2)/3
5614 reflections	(Δ/σ)max < 0.001
345 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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 > 2σ(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.

	x	y	z	Uiso*/Ueq
O1	0.36912 (3)	−0.05337 (10)	0.48796 (5)	0.01654 (15)
O2	0.02634 (3)	0.14809 (11)	0.14482 (6)	0.02325 (17)
O3	0.06645 (3)	0.44390 (11)	0.06868 (6)	0.02140 (17)
O4	0.27842 (3)	0.35928 (10)	0.27787 (6)	0.01722 (15)
N1	0.35715 (4)	−0.34299 (11)	0.55298 (6)	0.01452 (16)
N2	0.30506 (4)	−0.45837 (11)	0.56225 (6)	0.01459 (16)
N3	0.22306 (4)	−0.11616 (11)	0.39236 (6)	0.01426 (16)
C1	0.47358 (5)	−0.34082 (14)	0.59345 (8)	0.01773 (19)
C2	0.52970 (5)	−0.35703 (15)	0.66770 (9)	0.0216 (2)
C3	0.52678 (5)	−0.39395 (14)	0.77564 (8)	0.0205 (2)
C4	0.46740 (5)	−0.41126 (14)	0.81062 (8)	0.01797 (19)
C5	0.41087 (5)	−0.39230 (14)	0.73777 (7)	0.01641 (18)
C6	0.41448 (4)	−0.35847 (13)	0.62948 (7)	0.01427 (18)
C7	0.25240 (4)	−0.38702 (13)	0.49748 (7)	0.01383 (18)
C8	0.26770 (4)	−0.22283 (13)	0.45728 (7)	0.01270 (17)
C9	0.33566 (4)	−0.18791 (13)	0.49592 (7)	0.01293 (17)
C10	0.24207 (4)	0.03035 (13)	0.35116 (7)	0.01384 (17)
C11	0.19674 (4)	0.14168 (13)	0.27961 (7)	0.01385 (18)
C12	0.13242 (4)	0.08699 (14)	0.24831 (7)	0.01533 (18)
C13	0.08971 (4)	0.18970 (14)	0.17891 (8)	0.01645 (18)
C14	0.11121 (4)	0.35193 (14)	0.13731 (7)	0.01642 (19)
C15	0.17427 (4)	0.40938 (14)	0.16780 (7)	0.01589 (18)
C16	0.21674 (4)	0.30561 (13)	0.24024 (7)	0.01424 (17)
C17	0.32012 (5)	−0.65126 (14)	0.55935 (8)	0.0194 (2)
C18	0.18985 (5)	−0.48412 (14)	0.47905 (8)	0.01728 (19)
C19	0.00170 (5)	−0.00727 (18)	0.19178 (11)	0.0293 (3)
C20	0.08640 (5)	0.61077 (16)	0.02644 (9)	0.0223 (2)
C21	0.29988 (5)	0.52608 (14)	0.23842 (8)	0.01750 (19)
H1A	0.4749 (7)	−0.319 (2)	0.5178 (11)	0.025 (3)*
H2A	0.5716 (7)	−0.342 (2)	0.6413 (11)	0.027 (4)*
H3A	0.5674 (7)	−0.413 (2)	0.8265 (12)	0.028 (4)*
H4A	0.4646 (6)	−0.4380 (19)	0.8855 (11)	0.020 (3)*
H5A	0.3683 (7)	−0.407 (2)	0.7601 (11)	0.024 (3)*
H10A	0.2859 (6)	0.0685 (18)	0.3651 (10)	0.016 (3)*
H12A	0.1206 (7)	−0.025 (2)	0.2767 (11)	0.022 (3)*
H15A	0.1878 (7)	0.520 (2)	0.1400 (11)	0.020 (3)*
H17A	0.2798 (7)	−0.723 (2)	0.5642 (11)	0.024 (3)*
H17B	0.3365 (7)	−0.684 (2)	0.4918 (12)	0.027 (4)*
H17C	0.3507 (7)	−0.673 (2)	0.6234 (12)	0.030 (4)*
H18A	0.1555 (7)	−0.411 (2)	0.4352 (12)	0.030 (4)*
H18B	0.1925 (8)	−0.601 (2)	0.4416 (12)	0.033 (4)*
H18C	0.1744 (7)	−0.511 (2)	0.5471 (12)	0.032 (4)*
H19A	−0.0437 (8)	−0.018 (2)	0.1586 (13)	0.037 (4)*
H19B	0.0243 (8)	−0.119 (2)	0.1720 (13)	0.038 (4)*
H19C	0.0082 (8)	0.003 (3)	0.2715 (14)	0.042 (4)*
H20A	0.1208 (7)	0.586 (2)	−0.0182 (11)	0.024 (3)*
H20B	0.1018 (7)	0.696 (2)	0.0873 (12)	0.032 (4)*
H20C	0.0475 (7)	0.656 (2)	−0.0181 (11)	0.026 (4)*
H21A	0.3011 (7)	0.515 (2)	0.1612 (12)	0.023 (3)*
H21B	0.3418 (7)	0.545 (2)	0.2761 (11)	0.025 (4)*
H21C	0.2732 (7)	0.626 (2)	0.2555 (11)	0.024 (3)*

	U11	U22	U33	U12	U13	U23
O1	0.0170 (3)	0.0133 (3)	0.0192 (3)	−0.0013 (3)	0.0023 (2)	0.0031 (3)
O2	0.0125 (3)	0.0240 (4)	0.0322 (4)	−0.0015 (3)	0.0001 (3)	0.0114 (3)
O3	0.0138 (3)	0.0224 (4)	0.0272 (4)	0.0030 (3)	0.0007 (3)	0.0132 (3)
O4	0.0142 (3)	0.0164 (3)	0.0202 (3)	−0.0017 (3)	−0.0002 (2)	0.0061 (3)
N1	0.0139 (3)	0.0120 (4)	0.0170 (3)	−0.0004 (3)	0.0000 (3)	0.0033 (3)
N2	0.0149 (3)	0.0111 (4)	0.0172 (3)	−0.0007 (3)	0.0004 (3)	0.0030 (3)
N3	0.0153 (3)	0.0137 (4)	0.0137 (3)	0.0033 (3)	0.0020 (3)	0.0020 (3)
C1	0.0173 (4)	0.0173 (5)	0.0189 (4)	0.0029 (4)	0.0038 (3)	0.0031 (4)
C2	0.0151 (4)	0.0213 (5)	0.0281 (5)	0.0019 (4)	0.0027 (4)	0.0041 (4)
C3	0.0190 (4)	0.0159 (4)	0.0243 (5)	0.0007 (4)	−0.0041 (3)	0.0008 (4)
C4	0.0218 (4)	0.0150 (4)	0.0158 (4)	0.0018 (4)	−0.0013 (3)	−0.0005 (3)
C5	0.0173 (4)	0.0151 (4)	0.0166 (4)	0.0019 (3)	0.0020 (3)	−0.0005 (3)
C6	0.0148 (4)	0.0110 (4)	0.0163 (4)	0.0020 (3)	−0.0001 (3)	0.0004 (3)
C7	0.0153 (4)	0.0132 (4)	0.0130 (4)	0.0014 (3)	0.0023 (3)	0.0005 (3)
C8	0.0140 (4)	0.0119 (4)	0.0122 (3)	0.0020 (3)	0.0020 (3)	0.0007 (3)
C9	0.0149 (4)	0.0119 (4)	0.0122 (3)	0.0023 (3)	0.0026 (3)	0.0010 (3)
C10	0.0145 (4)	0.0131 (4)	0.0138 (4)	0.0025 (3)	0.0018 (3)	0.0012 (3)
C11	0.0146 (4)	0.0132 (4)	0.0140 (4)	0.0023 (3)	0.0027 (3)	0.0024 (3)
C12	0.0149 (4)	0.0143 (4)	0.0171 (4)	0.0020 (3)	0.0037 (3)	0.0038 (3)
C13	0.0122 (4)	0.0176 (4)	0.0197 (4)	0.0017 (3)	0.0031 (3)	0.0039 (4)
C14	0.0144 (4)	0.0175 (4)	0.0176 (4)	0.0043 (3)	0.0030 (3)	0.0056 (3)
C15	0.0155 (4)	0.0154 (4)	0.0171 (4)	0.0023 (3)	0.0035 (3)	0.0051 (3)
C16	0.0131 (4)	0.0150 (4)	0.0147 (4)	0.0013 (3)	0.0024 (3)	0.0019 (3)
C17	0.0216 (4)	0.0111 (4)	0.0244 (5)	0.0012 (4)	−0.0003 (4)	0.0034 (4)
C18	0.0166 (4)	0.0155 (4)	0.0196 (4)	−0.0020 (3)	0.0025 (3)	0.0013 (3)
C19	0.0165 (4)	0.0268 (6)	0.0443 (7)	−0.0026 (4)	0.0037 (4)	0.0137 (5)
C20	0.0179 (4)	0.0221 (5)	0.0268 (5)	0.0031 (4)	0.0028 (4)	0.0124 (4)
C21	0.0194 (4)	0.0139 (4)	0.0194 (4)	−0.0017 (4)	0.0036 (3)	0.0029 (3)

O1—C9	1.2341 (12)	C8—C9	1.4603 (12)
O2—C13	1.3709 (11)	C10—C11	1.4613 (12)
O2—C19	1.4268 (14)	C10—H10A	0.954 (13)
O3—C14	1.3583 (11)	C11—C16	1.4011 (13)
O3—C20	1.4342 (13)	C11—C12	1.4090 (13)
O4—C16	1.3698 (11)	C12—C13	1.3808 (13)
O4—C21	1.4311 (12)	C12—H12A	0.949 (15)
N1—C9	1.3937 (12)	C13—C14	1.4130 (14)
N1—N2	1.4084 (11)	C14—C15	1.3897 (13)
N1—C6	1.4261 (11)	C15—C16	1.4029 (12)
N2—C7	1.3754 (11)	C15—H15A	0.953 (15)
N2—C17	1.4683 (13)	C17—H17A	1.008 (14)
N3—C10	1.2927 (12)	C17—H17B	0.990 (14)
N3—C8	1.3918 (11)	C17—H17C	0.963 (15)
C1—C6	1.3898 (13)	C18—H18A	1.000 (16)
C1—C2	1.3923 (13)	C18—H18B	0.990 (17)
C1—H1A	0.965 (14)	C18—H18C	0.977 (15)
C2—C3	1.3893 (15)	C19—H19A	0.986 (17)
C2—H2A	0.992 (15)	C19—H19B	1.006 (17)
C3—C4	1.3892 (15)	C19—H19C	0.990 (18)
C3—H3A	0.995 (15)	C20—H20A	0.996 (14)
C4—C5	1.3913 (13)	C20—H20B	1.007 (16)
C4—H4A	0.969 (13)	C20—H20C	0.976 (15)
C5—C6	1.3921 (13)	C21—H21A	0.974 (14)
C5—H5A	0.984 (14)	C21—H21B	0.945 (14)
C7—C8	1.3753 (13)	C21—H21C	0.972 (15)
C7—C18	1.4863 (13)
C13—O2—C19	116.72 (8)	C13—C12—H12A	122.3 (8)
C14—O3—C20	117.04 (8)	C11—C12—H12A	116.3 (8)
C16—O4—C21	117.65 (7)	O2—C13—C12	125.46 (9)
C9—N1—N2	110.43 (7)	O2—C13—C14	115.26 (8)
C9—N1—C6	125.90 (8)	C12—C13—C14	119.28 (8)
N2—N1—C6	118.94 (7)	O3—C14—C15	124.05 (9)
C7—N2—N1	106.45 (7)	O3—C14—C13	115.62 (8)
C7—N2—C17	121.21 (8)	C15—C14—C13	120.33 (8)
N1—N2—C17	114.72 (8)	C14—C15—C16	119.75 (9)
C10—N3—C8	119.36 (8)	C14—C15—H15A	119.3 (8)
C6—C1—C2	118.90 (9)	C16—C15—H15A	120.9 (8)
C6—C1—H1A	119.6 (8)	O4—C16—C11	116.75 (8)
C2—C1—H1A	121.5 (8)	O4—C16—C15	122.63 (9)
C3—C2—C1	120.62 (9)	C11—C16—C15	120.61 (8)
C3—C2—H2A	121.2 (8)	N2—C17—H17A	109.0 (8)
C1—C2—H2A	118.2 (8)	N2—C17—H17B	111.4 (9)
C4—C3—C2	119.89 (9)	H17A—C17—H17B	108.9 (12)
C4—C3—H3A	120.6 (9)	N2—C17—H17C	105.3 (9)
C2—C3—H3A	119.4 (9)	H17A—C17—H17C	108.8 (12)
C3—C4—C5	120.18 (9)	H17B—C17—H17C	113.3 (12)
C3—C4—H4A	120.8 (8)	C7—C18—H18A	111.7 (9)
C5—C4—H4A	119.0 (8)	C7—C18—H18B	112.7 (9)
C4—C5—C6	119.34 (9)	H18A—C18—H18B	107.7 (13)
C4—C5—H5A	121.7 (8)	C7—C18—H18C	111.5 (9)
C6—C5—H5A	118.9 (8)	H18A—C18—H18C	106.4 (12)
C1—C6—C5	121.05 (8)	H18B—C18—H18C	106.5 (13)
C1—C6—N1	118.69 (8)	O2—C19—H19A	106.4 (10)
C5—C6—N1	120.26 (8)	O2—C19—H19B	110.6 (9)
C8—C7—N2	110.21 (8)	H19A—C19—H19B	106.9 (14)
C8—C7—C18	128.54 (8)	O2—C19—H19C	110.6 (11)
N2—C7—C18	121.25 (8)	H19A—C19—H19C	114.1 (14)
C7—C8—N3	122.95 (8)	H19B—C19—H19C	108.1 (14)
C7—C8—C9	107.87 (8)	O3—C20—H20A	109.0 (9)
N3—C8—C9	129.17 (8)	O3—C20—H20B	110.2 (9)
O1—C9—N1	124.44 (8)	H20A—C20—H20B	111.3 (12)
O1—C9—C8	131.11 (8)	O3—C20—H20C	104.0 (9)
N1—C9—C8	104.37 (8)	H20A—C20—H20C	111.0 (11)
N3—C10—C11	120.57 (8)	H20B—C20—H20C	111.1 (12)
N3—C10—H10A	121.7 (8)	O4—C21—H21A	109.1 (9)
C11—C10—H10A	117.8 (8)	O4—C21—H21B	105.8 (9)
C16—C11—C12	118.58 (8)	H21A—C21—H21B	110.2 (12)
C16—C11—C10	120.31 (8)	O4—C21—H21C	111.1 (8)
C12—C11—C10	121.11 (8)	H21A—C21—H21C	112.6 (12)
C13—C12—C11	121.40 (9)	H21B—C21—H21C	107.8 (12)
C9—N1—N2—C7	8.54 (10)	C7—C8—C9—O1	−173.56 (9)
C6—N1—N2—C7	165.59 (8)	N3—C8—C9—O1	5.87 (16)
C9—N1—N2—C17	145.49 (8)	C7—C8—C9—N1	3.25 (10)
C6—N1—N2—C17	−57.45 (11)	N3—C8—C9—N1	−177.33 (9)
C6—C1—C2—C3	1.32 (16)	C8—N3—C10—C11	177.82 (8)
C1—C2—C3—C4	−1.34 (17)	N3—C10—C11—C16	176.26 (8)
C2—C3—C4—C5	0.21 (16)	N3—C10—C11—C12	−4.03 (14)
C3—C4—C5—C6	0.91 (16)	C16—C11—C12—C13	1.10 (14)
C2—C1—C6—C5	−0.17 (15)	C10—C11—C12—C13	−178.61 (9)
C2—C1—C6—N1	−179.57 (9)	C19—O2—C13—C12	5.04 (16)
C4—C5—C6—C1	−0.93 (15)	C19—O2—C13—C14	−175.23 (10)
C4—C5—C6—N1	178.45 (9)	C11—C12—C13—O2	−179.44 (9)
C9—N1—C6—C1	−65.96 (13)	C11—C12—C13—C14	0.83 (15)
N2—N1—C6—C1	140.85 (9)	C20—O3—C14—C15	−0.36 (14)
C9—N1—C6—C5	114.64 (11)	C20—O3—C14—C13	178.96 (9)
N2—N1—C6—C5	−38.55 (13)	O2—C13—C14—O3	−0.49 (13)
N1—N2—C7—C8	−6.30 (10)	C12—C13—C14—O3	179.26 (9)
C17—N2—C7—C8	−139.83 (9)	O2—C13—C14—C15	178.86 (9)
N1—N2—C7—C18	173.92 (8)	C12—C13—C14—C15	−1.40 (15)
C17—N2—C7—C18	40.39 (13)	O3—C14—C15—C16	179.28 (9)
N2—C7—C8—N3	−177.54 (8)	C13—C14—C15—C16	0.00 (15)
C18—C7—C8—N3	2.22 (15)	C21—O4—C16—C11	179.81 (8)
N2—C7—C8—C9	1.93 (10)	C21—O4—C16—C15	−1.66 (13)
C18—C7—C8—C9	−178.31 (9)	C12—C11—C16—O4	176.04 (8)
C10—N3—C8—C7	−174.99 (8)	C10—C11—C16—O4	−4.24 (13)
C10—N3—C8—C9	5.66 (14)	C12—C11—C16—C15	−2.52 (14)
N2—N1—C9—O1	169.88 (8)	C10—C11—C16—C15	177.20 (8)
C6—N1—C9—O1	14.78 (14)	C14—C15—C16—O4	−176.49 (9)
N2—N1—C9—C8	−7.20 (9)	C14—C15—C16—C11	1.98 (14)
C6—N1—C9—C8	−162.30 (8)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1	0.954 (13)	2.331 (13)	3.0112 (11)	127.8 (10)
C4—H4A···O1i	0.969 (13)	2.541 (13)	3.2628 (12)	131.4 (10)
C20—H20A···N3ii	0.996 (14)	2.577 (14)	3.5383 (13)	162.1 (12)
C20—H20C···O2iii	0.977 (14)	2.509 (14)	3.4470 (13)	160.8 (12)
C20—H20C···O3iii	0.977 (14)	2.495 (15)	3.2779 (13)	137.0 (11)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O1	0.954 (13)	2.331 (13)	3.0112 (11)	127.8 (10)
C4—H4A⋯O1i	0.969 (13)	2.541 (13)	3.2628 (12)	131.4 (10)
C20—H20A⋯N3ii	0.996 (14)	2.577 (14)	3.5383 (13)	162.1 (12)
C20—H20C⋯O2iii	0.977 (14)	2.509 (14)	3.4470 (13)	160.8 (12)
C20—H20C⋯O3iii	0.977 (14)	2.495 (15)	3.2779 (13)	137.0 (11)

Symmetry codes: (i) ; (ii) ; (iii) .