4-[(Z)-(n-Butyl-amino)(phenyl)methyl-idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one.

The title compound, C(21)H(23)N(3)O, exists in an enamine-keto form with the amino group involved in an intra-molecular N-H⋯O hydrogen bond. The dihedral angle between the phenyl rings is 73.59 (6)°. The five-membered ring is nearly planar, the largest deviation being 0.0004 (7) Å, and makes dihedral angles of 4.81 (6) and 69.81 (5)° wth the phenyl rings. In the crystal, pairs of weak C-H⋯O inter-actions link the mol-ecules into centrosymmetric dimers.

Related literature

For applications of Schiff bases derived from 4-acyl­pyrazolo­nes, see: Bernardino et al. (2006 ▶); Zhang et al. (2008 ▶). For related structures, see: Zhang et al. (2007 ▶); Chi et al. (2010 ▶); Zhen & Han (2005 ▶); Wang (2010 ▶).

Experimental

Crystal data

C21H23N3O

M = 333.42

Monoclinic,

a = 9.5215 (9) Å

b = 14.7867 (14) Å

c = 12.8055 (12) Å

β = 100.645 (2)°

V = 1771.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.08 mm−1

T = 296 K

0.28 × 0.20 × 0.16 mm

Data collection

Bruker SMART 1000 CCD diffractometer

16506 measured reflections

4368 independent reflections

3362 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.103

S = 1.01

4368 reflections

232 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812009166/cv5252sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009166/cv5252Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812009166/cv5252Isup3.cml

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

C21H23N3O	F(000) = 712.0
Mr = 333.42	Dx = 1.250 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3753 reflections
a = 9.5215 (9) Å	θ = 2.6–28.1°
b = 14.7867 (14) Å	µ = 0.08 mm−1
c = 12.8055 (12) Å	T = 296 K
β = 100.645 (2)°	Block, yellow
V = 1771.9 (3) Å3	0.28 × 0.20 × 0.16 mm
Z = 4

Bruker SMART 1000 CCD diffractometer	3362 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.035
Graphite monochromator	θmax = 28.3°, θmin = 2.6°
phi and ω scans	h = −12→12
16506 measured reflections	k = −19→19
4368 independent reflections	l = −17→16

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) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0499P)2 + 0.4177P] where P = (Fo2 + 2Fc2)/3
4368 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.21783 (12)	0.26068 (9)	0.88837 (9)	0.0167 (2)
C2	0.10538 (13)	0.21696 (9)	0.92399 (9)	0.0204 (3)
H2	0.1013	0.1541	0.9255	0.024*
C3	−0.00037 (13)	0.26856 (9)	0.95714 (10)	0.0218 (3)
H3	−0.0742	0.2397	0.9824	0.026*
C4	0.00239 (13)	0.36198 (9)	0.95320 (9)	0.0218 (3)
H4	−0.0699	0.3957	0.9744	0.026*
C5	0.11413 (13)	0.40483 (9)	0.91726 (10)	0.0220 (3)
H5	0.1166	0.4676	0.9144	0.026*
C6	0.22209 (13)	0.35488 (9)	0.88561 (9)	0.0193 (3)
H6	0.2973	0.3842	0.8626	0.023*
C7	0.35303 (12)	0.11883 (8)	0.85902 (9)	0.0158 (2)
C8	0.48777 (12)	0.10785 (8)	0.82441 (9)	0.0159 (2)
C9	0.53156 (12)	0.19778 (8)	0.80232 (9)	0.0168 (2)
C10	0.66208 (13)	0.22991 (9)	0.76371 (10)	0.0217 (3)
H10A	0.6553	0.2136	0.6904	0.033*
H10B	0.7453	0.2023	0.8052	0.033*
H10C	0.6693	0.2945	0.7708	0.033*
C11	0.55372 (12)	0.02287 (8)	0.82705 (9)	0.0152 (2)
C12	0.69661 (12)	0.00963 (8)	0.79819 (9)	0.0153 (2)
C13	0.81099 (13)	−0.01709 (9)	0.87666 (9)	0.0185 (3)
H13	0.7970	−0.0279	0.9456	0.022*
C14	0.94570 (13)	−0.02752 (9)	0.85151 (10)	0.0221 (3)
H14	1.0223	−0.0446	0.9038	0.027*
C15	0.96628 (13)	−0.01252 (9)	0.74855 (10)	0.0228 (3)
H15	1.0567	−0.0195	0.7319	0.027*
C16	0.85241 (14)	0.01285 (9)	0.67051 (10)	0.0212 (3)
H16	0.8663	0.0221	0.6013	0.025*
C17	0.71793 (13)	0.02451 (8)	0.69496 (9)	0.0179 (2)
H17	0.6419	0.0423	0.6425	0.021*
C18	0.53117 (13)	−0.14295 (8)	0.85933 (9)	0.0177 (2)
H18A	0.6204	−0.1519	0.9088	0.021*
H18B	0.5456	−0.1600	0.7889	0.021*
C19	0.41494 (13)	−0.20109 (8)	0.89147 (9)	0.0172 (2)
H19A	0.4043	−0.1852	0.9631	0.021*
H19B	0.3250	−0.1886	0.8444	0.021*
C20	0.44787 (13)	−0.30125 (9)	0.88723 (10)	0.0197 (3)
H20A	0.5401	−0.3132	0.9316	0.024*
H20B	0.4540	−0.3177	0.8149	0.024*
C21	0.33508 (15)	−0.35963 (9)	0.92449 (11)	0.0262 (3)
H21A	0.3317	−0.3456	0.9972	0.039*
H21B	0.3589	−0.4223	0.9188	0.039*
H21C	0.2435	−0.3478	0.8810	0.039*
H3A	0.4031 (17)	−0.0341 (11)	0.8798 (12)	0.030 (4)*
N1	0.32840 (10)	0.21097 (7)	0.85512 (8)	0.0172 (2)
N2	0.43854 (10)	0.25859 (7)	0.82022 (8)	0.0182 (2)
N3	0.48854 (11)	−0.04789 (7)	0.85966 (8)	0.0172 (2)
O1	0.27412 (9)	0.06007 (6)	0.88848 (7)	0.0195 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0156 (5)	0.0187 (6)	0.0152 (5)	0.0023 (5)	0.0014 (4)	−0.0004 (4)
C2	0.0197 (6)	0.0187 (6)	0.0231 (6)	0.0020 (5)	0.0050 (5)	0.0022 (5)
C3	0.0188 (6)	0.0255 (7)	0.0219 (6)	0.0013 (5)	0.0058 (5)	0.0014 (5)
C4	0.0203 (6)	0.0251 (7)	0.0204 (6)	0.0061 (5)	0.0048 (5)	−0.0026 (5)
C5	0.0249 (6)	0.0175 (7)	0.0234 (6)	0.0020 (5)	0.0042 (5)	−0.0032 (5)
C6	0.0189 (6)	0.0180 (6)	0.0209 (6)	−0.0008 (5)	0.0034 (4)	−0.0002 (5)
C7	0.0163 (5)	0.0158 (6)	0.0149 (5)	−0.0001 (5)	0.0019 (4)	0.0002 (4)
C8	0.0150 (5)	0.0171 (6)	0.0157 (5)	−0.0013 (4)	0.0034 (4)	0.0005 (4)
C9	0.0165 (5)	0.0171 (6)	0.0167 (5)	−0.0003 (5)	0.0026 (4)	0.0004 (4)
C10	0.0200 (6)	0.0174 (6)	0.0293 (6)	−0.0020 (5)	0.0088 (5)	0.0009 (5)
C11	0.0156 (5)	0.0171 (6)	0.0128 (5)	−0.0014 (5)	0.0019 (4)	0.0000 (4)
C12	0.0154 (5)	0.0129 (6)	0.0184 (5)	−0.0009 (4)	0.0050 (4)	−0.0011 (4)
C13	0.0184 (6)	0.0186 (6)	0.0188 (5)	−0.0011 (5)	0.0042 (4)	0.0005 (5)
C14	0.0162 (6)	0.0213 (7)	0.0282 (6)	−0.0001 (5)	0.0024 (5)	0.0004 (5)
C15	0.0170 (6)	0.0209 (7)	0.0333 (7)	−0.0030 (5)	0.0116 (5)	−0.0056 (5)
C16	0.0261 (6)	0.0189 (6)	0.0208 (6)	−0.0054 (5)	0.0106 (5)	−0.0040 (5)
C17	0.0197 (6)	0.0159 (6)	0.0183 (5)	−0.0023 (5)	0.0038 (4)	−0.0010 (5)
C18	0.0181 (5)	0.0142 (6)	0.0216 (5)	0.0010 (5)	0.0055 (4)	0.0006 (5)
C19	0.0181 (5)	0.0159 (6)	0.0182 (5)	−0.0007 (5)	0.0051 (4)	0.0012 (4)
C20	0.0218 (6)	0.0153 (6)	0.0224 (6)	−0.0006 (5)	0.0047 (5)	0.0012 (5)
C21	0.0324 (7)	0.0190 (7)	0.0283 (6)	−0.0056 (6)	0.0087 (5)	0.0008 (5)
N1	0.0159 (5)	0.0149 (5)	0.0218 (5)	0.0002 (4)	0.0064 (4)	0.0020 (4)
N2	0.0164 (5)	0.0168 (5)	0.0226 (5)	−0.0020 (4)	0.0068 (4)	0.0016 (4)
N3	0.0165 (5)	0.0142 (5)	0.0224 (5)	0.0007 (4)	0.0073 (4)	0.0009 (4)
O1	0.0180 (4)	0.0168 (5)	0.0252 (4)	−0.0018 (3)	0.0082 (3)	0.0018 (3)

C1—C6	1.3942 (18)	C12—C13	1.3956 (16)
C1—C2	1.3975 (17)	C13—C14	1.3876 (17)
C1—N1	1.4125 (15)	C13—H13	0.9300
C2—C3	1.3906 (18)	C14—C15	1.3861 (18)
C2—H2	0.9300	C14—H14	0.9300
C3—C4	1.3827 (19)	C15—C16	1.3838 (18)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.3879 (19)	C16—C17	1.3840 (17)
C4—H4	0.9300	C16—H16	0.9300
C5—C6	1.3858 (18)	C17—H17	0.9300
C5—H5	0.9300	C18—N3	1.4633 (16)
C6—H6	0.9300	C18—C19	1.5171 (16)
C7—O1	1.2516 (15)	C18—H18A	0.9700
C7—N1	1.3819 (16)	C18—H18B	0.9700
C7—C8	1.4418 (16)	C19—C20	1.5169 (17)
C8—C11	1.4023 (17)	C19—H19A	0.9700
C8—C9	1.4373 (17)	C19—H19B	0.9700
C9—N2	1.3117 (16)	C20—C21	1.5218 (18)
C9—C10	1.4971 (16)	C20—H20A	0.9700
C10—H10A	0.9600	C20—H20B	0.9700
C10—H10B	0.9600	C21—H21A	0.9600
C10—H10C	0.9600	C21—H21B	0.9600
C11—N3	1.3230 (15)	C21—H21C	0.9600
C11—C12	1.4872 (16)	N1—N2	1.4030 (14)
C12—C17	1.3914 (16)	N3—H3A	0.921 (16)
C6—C1—C2	119.87 (11)	C15—C14—H14	119.9
C6—C1—N1	119.04 (11)	C13—C14—H14	119.9
C2—C1—N1	121.09 (11)	C16—C15—C14	120.05 (11)
C3—C2—C1	119.18 (13)	C16—C15—H15	120.0
C3—C2—H2	120.4	C14—C15—H15	120.0
C1—C2—H2	120.4	C15—C16—C17	120.31 (11)
C4—C3—C2	121.15 (12)	C15—C16—H16	119.8
C4—C3—H3	119.4	C17—C16—H16	119.8
C2—C3—H3	119.4	C16—C17—C12	119.91 (11)
C3—C4—C5	119.28 (12)	C16—C17—H17	120.0
C3—C4—H4	120.4	C12—C17—H17	120.0
C5—C4—H4	120.4	N3—C18—C19	109.09 (10)
C6—C5—C4	120.60 (13)	N3—C18—H18A	109.9
C6—C5—H5	119.7	C19—C18—H18A	109.9
C4—C5—H5	119.7	N3—C18—H18B	109.9
C5—C6—C1	119.90 (12)	C19—C18—H18B	109.9
C5—C6—H6	120.0	H18A—C18—H18B	108.3
C1—C6—H6	120.0	C20—C19—C18	112.19 (10)
O1—C7—N1	126.02 (11)	C20—C19—H19A	109.2
O1—C7—C8	129.22 (12)	C18—C19—H19A	109.2
N1—C7—C8	104.75 (10)	C20—C19—H19B	109.2
C11—C8—C9	133.54 (11)	C18—C19—H19B	109.2
C11—C8—C7	120.89 (11)	H19A—C19—H19B	107.9
C9—C8—C7	105.26 (10)	C19—C20—C21	112.34 (11)
N2—C9—C8	111.72 (11)	C19—C20—H20A	109.1
N2—C9—C10	117.95 (11)	C21—C20—H20A	109.1
C8—C9—C10	130.33 (11)	C19—C20—H20B	109.1
C9—C10—H10A	109.5	C21—C20—H20B	109.1
C9—C10—H10B	109.5	H20A—C20—H20B	107.9
H10A—C10—H10B	109.5	C20—C21—H21A	109.5
C9—C10—H10C	109.5	C20—C21—H21B	109.5
H10A—C10—H10C	109.5	H21A—C21—H21B	109.5
H10B—C10—H10C	109.5	C20—C21—H21C	109.5
N3—C11—C8	118.83 (11)	H21A—C21—H21C	109.5
N3—C11—C12	118.58 (11)	H21B—C21—H21C	109.5
C8—C11—C12	122.56 (11)	C7—N1—N2	111.99 (9)
C17—C12—C13	119.83 (11)	C7—N1—C1	129.28 (10)
C17—C12—C11	121.06 (10)	N2—N1—C1	118.52 (10)
C13—C12—C11	119.10 (10)	C9—N2—N1	106.27 (10)
C14—C13—C12	119.75 (11)	C11—N3—C18	127.75 (10)
C14—C13—H13	120.1	C11—N3—H3A	113.8 (10)
C12—C13—H13	120.1	C18—N3—H3A	118.3 (10)
C15—C14—C13	120.14 (11)
C6—C1—C2—C3	−0.55 (16)	C11—C12—C13—C14	−178.40 (11)
N1—C1—C2—C3	179.27 (10)	C12—C13—C14—C15	−0.77 (19)
C1—C2—C3—C4	1.43 (17)	C13—C14—C15—C16	0.0 (2)
C2—C3—C4—C5	−1.14 (18)	C14—C15—C16—C17	0.8 (2)
C3—C4—C5—C6	−0.03 (18)	C15—C16—C17—C12	−0.76 (19)
C4—C5—C6—C1	0.89 (17)	C13—C12—C17—C16	−0.06 (18)
C2—C1—C6—C5	−0.60 (17)	C11—C12—C17—C16	179.14 (11)
N1—C1—C6—C5	179.59 (10)	N3—C18—C19—C20	176.92 (9)
O1—C7—C8—C11	−4.43 (18)	C18—C19—C20—C21	177.25 (10)
N1—C7—C8—C11	174.38 (10)	O1—C7—N1—N2	178.95 (10)
O1—C7—C8—C9	−178.92 (11)	C8—C7—N1—N2	0.09 (12)
N1—C7—C8—C9	−0.11 (11)	O1—C7—N1—C1	4.41 (19)
C11—C8—C9—N2	−173.37 (12)	C8—C7—N1—C1	−174.45 (10)
C7—C8—C9—N2	0.10 (13)	C6—C1—N1—C7	174.10 (11)
C11—C8—C9—C10	6.6 (2)	C2—C1—N1—C7	−5.72 (17)
C7—C8—C9—C10	−179.93 (11)	C6—C1—N1—N2	−0.14 (15)
C9—C8—C11—N3	174.20 (12)	C2—C1—N1—N2	−179.96 (10)
C7—C8—C11—N3	1.54 (16)	C8—C9—N2—N1	−0.04 (12)
C9—C8—C11—C12	−3.62 (19)	C10—C9—N2—N1	179.98 (9)
C7—C8—C11—C12	−176.27 (10)	C7—N1—N2—C9	−0.03 (12)
N3—C11—C12—C17	116.65 (13)	C1—N1—N2—C9	175.16 (9)
C8—C11—C12—C17	−65.53 (16)	C8—C11—N3—C18	173.83 (11)
N3—C11—C12—C13	−64.14 (15)	C12—C11—N3—C18	−8.27 (17)
C8—C11—C12—C13	113.67 (13)	C19—C18—N3—C11	−173.20 (11)
C17—C12—C13—C14	0.82 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.921 (16)	1.873 (16)	2.6704 (14)	143.5 (14)
C13—H13···O1i	0.93	2.39	3.3175 (15)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.921 (16)	1.873 (16)	2.6704 (14)	143.5 (14)
C13—H13⋯O1i	0.93	2.39	3.3175 (15)	172

Symmetry code: (i) .