(4Z)-4-[(2,6-Diisopropyl­anilino)(phen­yl)methyl­idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Lai, S.-L.; Chang, C.-Y.

doi:10.1107/S1600536811000602

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o324

doi:10.1107/S1600536811000602

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(4Z)-4-[(2,6-Diisopropylanilino)(phenyl)methylidene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Shu-Ling Lai ^a and Ching-Yao Chang ^b ^*

^aDepartment of Media and Design, Asia University, Taichung 413, Taiwan, and ^bDepartment of Biotechnology, Asia University, Taichung 413, Taiwan
^*Correspondence e-mail: cychang@asia.edu.tw

(Received 10 December 2010; accepted 5 January 2011; online 12 January 2011)

In the title compound, C₂₉H₃₁N₃O, the three terminal benzene rings are oriented at dihedral angles of 20.7 (3), 65.8 (3) and 72.6 (3)° with respect to the central pyrazolone ring. Intramolecular N—H⋯O hydrogen bonding occurs between the imine and carbonyl groups. Intermolecular C—H⋯π interactions are present in the crystal structure.

Related literature

For the catalysis of olefins polymerization by complexes containing N,O-bidentate ligands, see: Wang et al. (1998 ); Connor et al. (2003 ); Sun et al. (2003 ); Lü et al. (2006 ). For related structures, see: Wang et al. (2003 ); Li et al. (2009 ); Xu et al. (2010 ).

Experimental

Crystal data

C₂₉H₃₁N₃O
M_r = 437.57
Orthorhombic, P n a 2₁
a = 12.9094 (6) Å
b = 10.6947 (5) Å
c = 17.9676 (8) Å
V = 2480.6 (2) Å³
Z = 4
Cu Kα radiation
μ = 0.56 mm⁻¹
T = 110 K
0.6 × 0.5 × 0.4 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.702, T_max = 1.00
8437 measured reflections
3755 independent reflections
3643 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.09
3755 reflections
302 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 1293 Friedel pairs
Flack parameter: 0.2 (2)

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C18–C23 and N1,N2,C1–C3 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O	0.80 (2)	1.95 (2)	2.6734 (17)	149 (3)
C9—H9A⋯Cg1ⁱ	0.95	2.73	3.601 (2)	153
C14—H14A⋯Cg2ⁱⁱ	0.96	2.76	3.467 (2)	132
Symmetry codes: (i) $[-x+2, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); data reduction: CrysAlis RED; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811000602/xu5120sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000602/xu5120Isup2.hkl

checkCIF report

Comment top

β-Ketoimine is an important family of N,O-bidentate ligands because of their ease of preparation and modification of steric and electronic effects. They are particularly interested for catalysis. For instance, their Cu complexes have shown to be effective in norbornene (NBE) polymerization (Lü et al., 2006) in the presence of MAO and the Ni-based systems are used in ethylene polymerization (Wang et al., 1998; Connor et al., 2003; Sun et al., 2003). As part of this work, the title compound (I) was prepared from β-diketone and 2,6-diisopropylaniline.

The molecular structure of (I) is shown in Fig. 1. The dihedral angles between the pyrazolone ring and C5–C10, C12–C17 and C18–C23 phenyl rings are 20.7 (3), 65.8 (3) and 72.6 (3)°, respectively. The C11–N3 distance of 1.333 (3) Å is similar to that for a C–N single bond (1.338 (8) Å (Li et al., 2009) but is much longer than that for a C=N double bond (1.318 (3)Å) (Lü et al., 2006) in pyrazolone compounds.

A strong intramolecular N(3)—H(3 A)···O hydrogen bond (Table 1.) is observed with N···O distance of 2.672 (2) Å, which is much shorter than their van der Waals radius. The intermolecular C—H···π interactions are present in the crystal structure (Table 1).

Related literature top

For the catalysis of olefins polymerization by complexes containing N,O-bidentate ligands, see: Wang et al. (1998); Connor et al. (2003); Sun et al. (2003); Lü et al. (2006). For related structures, see: Wang et al. (2003); Li et al. (2009); Xu et al. (2010).

Experimental top

The title compound was synthesized by refluxing a mixture of 1-phenyl-3-methyl-4-benzoylpyrazol-5-one (10 mmol) and 2,6-diisopropylaniline (10 mmol) in ethanol (60 ml) for 16 h. Volatile materials were removed under vacuum and the residue was washed twice from cold ethanol solution to give yellow solids. The resulting solids were recrystallized from ethanol solution to yield yellow crystals after 2 d.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), thermal ellipsoids for non-H atoms are shown at 25% probability levels.

(4Z)-4-[(2,6-Diisopropylanilino)(phenyl)methylidene]-3-methyl- 1-phenyl-1H-pyrazol-5(4H)-one top

Crystal data top

C₂₉H₃₁N₃O	F(000) = 936
M_r = 437.57	D_x = 1.172 Mg m⁻³
Orthorhombic, Pna2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2n	Cell parameters from 7431 reflections
a = 12.9094 (6) Å	θ = 4.1–71.6°
b = 10.6947 (5) Å	µ = 0.56 mm⁻¹
c = 17.9676 (8) Å	T = 110 K
V = 2480.6 (2) Å³	Parallelpiped, yellow
Z = 4	0.6 × 0.5 × 0.4 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 Gemini diffractometer	3755 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3643 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 16.0690 pixels mm^-1	θ_max = 71.6°, θ_min = 4.8°
ω scans	h = −12→15
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −13→12
T_min = 0.702, T_max = 1.00	l = −22→18
8437 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.080P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
3755 reflections	Δρ_max = 0.27 e Å⁻³
302 parameters	Δρ_min = −0.21 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1293 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (2)

Crystal data top

C₂₉H₃₁N₃O	V = 2480.6 (2) Å³
M_r = 437.57	Z = 4
Orthorhombic, Pna2₁	Cu Kα radiation
a = 12.9094 (6) Å	µ = 0.56 mm⁻¹
b = 10.6947 (5) Å	T = 110 K
c = 17.9676 (8) Å	0.6 × 0.5 × 0.4 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 Gemini diffractometer	3755 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	3643 reflections with I > 2σ(I)
T_min = 0.702, T_max = 1.00	R_int = 0.026
8437 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.100	Δρ_max = 0.27 e Å⁻³
S = 1.09	Δρ_min = −0.21 e Å⁻³
3755 reflections	Absolute structure: Flack (1983), 1293 Friedel pairs
302 parameters	Absolute structure parameter: 0.2 (2)
1 restraint

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O	0.91287 (8)	0.45238 (12)	0.24514 (7)	0.0298 (3)
N1	0.93713 (10)	0.44539 (12)	0.37452 (8)	0.0264 (3)
N2	0.87895 (11)	0.47065 (13)	0.43864 (8)	0.0277 (3)
N3	0.72027 (10)	0.52807 (13)	0.21416 (8)	0.0249 (3)
H3A	0.7776 (18)	0.502 (2)	0.2066 (14)	0.032 (5)*
C1	0.88237 (12)	0.46862 (13)	0.31018 (10)	0.0252 (3)
C2	0.78251 (11)	0.51329 (14)	0.33598 (10)	0.0243 (3)
C3	0.78841 (12)	0.50848 (14)	0.41567 (10)	0.0252 (3)
C4	0.70441 (13)	0.53150 (18)	0.47178 (11)	0.0333 (4)
H4A	0.7326	0.5214	0.5221	0.050*
H4B	0.6481	0.4714	0.4641	0.050*
H4C	0.6777	0.6167	0.4658	0.050*
C5	1.04093 (11)	0.40332 (14)	0.38254 (10)	0.0274 (3)
C6	1.08976 (13)	0.34062 (15)	0.32476 (11)	0.0316 (4)
H6A	1.0547	0.3269	0.2790	0.038*
C7	1.19107 (14)	0.29789 (16)	0.33456 (12)	0.0368 (4)
H7A	1.2252	0.2554	0.2951	0.044*
C8	1.24239 (13)	0.31699 (16)	0.40159 (11)	0.0361 (4)
H8A	1.3107	0.2861	0.4084	0.043*
C9	1.19329 (14)	0.38119 (17)	0.45825 (12)	0.0365 (4)
H9A	1.2288	0.3956	0.5038	0.044*
C10	1.09248 (13)	0.42494 (17)	0.44944 (10)	0.0326 (4)
H10A	1.0592	0.4691	0.4886	0.039*
C11	0.70334 (12)	0.54389 (14)	0.28638 (9)	0.0227 (3)
C12	0.59977 (12)	0.58874 (14)	0.31176 (9)	0.0250 (3)
C13	0.58906 (14)	0.70320 (16)	0.34759 (11)	0.0330 (4)
H13A	0.6477	0.7557	0.3542	0.040*
C14	0.49253 (15)	0.74109 (18)	0.37387 (12)	0.0407 (4)
H14A	0.4854	0.8194	0.3983	0.049*
C15	0.40749 (14)	0.6652 (2)	0.36452 (13)	0.0447 (5)
H15A	0.3418	0.6910	0.3827	0.054*
C16	0.41744 (14)	0.5512 (2)	0.32857 (13)	0.0438 (5)
H16A	0.3586	0.4989	0.3224	0.053*
C17	0.51324 (13)	0.51316 (17)	0.30150 (11)	0.0322 (4)
H17A	0.5196	0.4357	0.2761	0.039*
C18	0.65579 (11)	0.56969 (14)	0.15362 (9)	0.0234 (3)
C19	0.65238 (11)	0.69774 (14)	0.13647 (9)	0.0260 (3)
C20	0.59414 (11)	0.73324 (15)	0.07474 (10)	0.0285 (3)
H20A	0.5891	0.8193	0.0622	0.034*
C21	0.54324 (11)	0.64521 (16)	0.03119 (10)	0.0296 (3)
H21A	0.5043	0.6714	−0.0109	0.035*
C22	0.54908 (12)	0.51948 (16)	0.04900 (10)	0.0285 (3)
H22A	0.5144	0.4599	0.0187	0.034*
C23	0.60517 (11)	0.47919 (15)	0.11070 (9)	0.0253 (3)
C24	0.71736 (13)	0.79226 (16)	0.17900 (10)	0.0305 (4)
H24A	0.7239	0.7617	0.2314	0.037*
C25	0.82671 (14)	0.79704 (18)	0.14543 (12)	0.0387 (4)
H25A	0.8560	0.7126	0.1442	0.058*
H25B	0.8708	0.8512	0.1760	0.058*
H25C	0.8231	0.8304	0.0947	0.058*
C26	0.66815 (17)	0.92275 (18)	0.18176 (13)	0.0439 (5)
H26A	0.5986	0.9168	0.2034	0.066*
H26B	0.6633	0.9567	0.1312	0.066*
H26C	0.7110	0.9781	0.2124	0.066*
C27	0.61474 (14)	0.34042 (16)	0.12972 (11)	0.0331 (4)
H27A	0.6263	0.3337	0.1846	0.040*
C28	0.7098 (2)	0.2853 (2)	0.09084 (16)	0.0579 (6)
H28A	0.7712	0.3345	0.1038	0.087*
H28B	0.6994	0.2874	0.0368	0.087*
H28C	0.7197	0.1986	0.1070	0.087*
C29	0.5179 (2)	0.2645 (2)	0.11084 (16)	0.0581 (7)
H29A	0.5289	0.1769	0.1247	0.087*
H29B	0.5042	0.2701	0.0573	0.087*
H29C	0.4586	0.2980	0.1384	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0258 (5)	0.0416 (6)	0.0220 (6)	0.0060 (4)	−0.0012 (4)	0.0005 (5)
N1	0.0249 (6)	0.0309 (6)	0.0234 (7)	−0.0021 (5)	−0.0020 (5)	0.0028 (6)
N2	0.0303 (7)	0.0319 (7)	0.0208 (7)	−0.0063 (5)	−0.0024 (5)	0.0025 (6)
N3	0.0206 (6)	0.0307 (7)	0.0233 (7)	0.0047 (5)	−0.0019 (5)	−0.0008 (5)
C1	0.0231 (7)	0.0250 (7)	0.0274 (9)	−0.0023 (5)	−0.0018 (6)	0.0021 (6)
C2	0.0246 (7)	0.0242 (7)	0.0241 (9)	−0.0028 (5)	0.0005 (6)	0.0005 (6)
C3	0.0281 (7)	0.0252 (7)	0.0221 (8)	−0.0054 (6)	−0.0010 (6)	0.0009 (6)
C4	0.0324 (8)	0.0442 (10)	0.0232 (9)	−0.0026 (7)	0.0024 (7)	0.0020 (7)
C5	0.0267 (7)	0.0242 (6)	0.0314 (9)	−0.0038 (5)	−0.0055 (6)	0.0070 (6)
C6	0.0311 (8)	0.0282 (7)	0.0354 (10)	0.0029 (6)	−0.0109 (6)	−0.0003 (7)
C7	0.0336 (9)	0.0310 (8)	0.0459 (12)	0.0070 (7)	−0.0096 (8)	−0.0029 (8)
C8	0.0285 (8)	0.0316 (8)	0.0483 (12)	0.0022 (7)	−0.0113 (8)	0.0074 (7)
C9	0.0327 (8)	0.0411 (9)	0.0355 (10)	−0.0039 (7)	−0.0126 (7)	0.0075 (8)
C10	0.0298 (8)	0.0388 (9)	0.0292 (9)	−0.0037 (6)	−0.0039 (7)	0.0054 (7)
C11	0.0249 (7)	0.0207 (6)	0.0224 (8)	−0.0028 (5)	0.0003 (6)	−0.0002 (6)
C12	0.0266 (7)	0.0290 (7)	0.0194 (8)	0.0020 (5)	0.0012 (6)	0.0054 (6)
C13	0.0383 (9)	0.0283 (8)	0.0324 (9)	0.0034 (6)	0.0065 (7)	0.0028 (7)
C14	0.0475 (10)	0.0383 (8)	0.0363 (10)	0.0168 (7)	0.0092 (9)	0.0069 (9)
C15	0.0309 (9)	0.0629 (12)	0.0403 (11)	0.0185 (8)	0.0105 (7)	0.0127 (9)
C16	0.0273 (8)	0.0613 (12)	0.0428 (12)	−0.0018 (8)	0.0036 (7)	0.0079 (10)
C17	0.0279 (8)	0.0375 (8)	0.0310 (10)	−0.0024 (6)	0.0005 (7)	0.0020 (7)
C18	0.0198 (6)	0.0297 (7)	0.0205 (7)	0.0028 (5)	0.0020 (6)	0.0014 (6)
C19	0.0229 (7)	0.0300 (7)	0.0251 (8)	0.0009 (5)	0.0068 (6)	0.0015 (6)
C20	0.0272 (8)	0.0285 (7)	0.0297 (9)	0.0052 (6)	0.0074 (6)	0.0071 (7)
C21	0.0207 (7)	0.0421 (9)	0.0259 (8)	0.0055 (6)	−0.0001 (6)	0.0081 (7)
C22	0.0229 (7)	0.0365 (8)	0.0262 (9)	−0.0004 (6)	−0.0016 (6)	0.0002 (7)
C23	0.0224 (6)	0.0304 (8)	0.0231 (8)	0.0007 (5)	0.0014 (6)	0.0004 (6)
C24	0.0336 (8)	0.0295 (8)	0.0283 (9)	−0.0029 (6)	0.0052 (7)	−0.0005 (6)
C25	0.0325 (8)	0.0419 (9)	0.0418 (11)	−0.0094 (7)	0.0048 (8)	−0.0044 (8)
C26	0.0485 (11)	0.0328 (9)	0.0504 (13)	−0.0002 (7)	0.0082 (9)	−0.0057 (9)
C27	0.0433 (9)	0.0287 (8)	0.0272 (9)	−0.0015 (7)	−0.0068 (7)	0.0003 (7)
C28	0.0776 (16)	0.0373 (10)	0.0587 (16)	0.0200 (10)	0.0137 (12)	−0.0005 (10)
C29	0.0722 (15)	0.0434 (11)	0.0586 (15)	−0.0228 (10)	−0.0260 (12)	0.0142 (11)

Geometric parameters (Å, º) top

O—C1	1.245 (2)	C15—H15A	0.9500
N1—C1	1.378 (2)	C16—C17	1.390 (3)
N1—N2	1.402 (2)	C16—H16A	0.9500
N1—C5	1.421 (2)	C17—H17A	0.9500
N2—C3	1.304 (2)	C18—C19	1.404 (2)
N3—C11	1.327 (2)	C18—C23	1.400 (2)
N3—C18	1.440 (2)	C19—C20	1.393 (2)
N3—H3A	0.80 (2)	C19—C24	1.520 (2)
C1—C2	1.451 (2)	C20—C21	1.389 (3)
C2—C11	1.395 (2)	C20—H20A	0.9500
C2—C3	1.435 (2)	C21—C22	1.384 (2)
C3—C4	1.501 (2)	C21—H21A	0.9500
C4—H4A	0.9800	C22—C23	1.392 (2)
C4—H4B	0.9800	C22—H22A	0.9500
C4—H4C	0.9800	C23—C27	1.528 (2)
C5—C6	1.387 (3)	C24—C25	1.536 (2)
C5—C10	1.393 (2)	C24—C26	1.534 (2)
C6—C7	1.397 (2)	C24—H24A	1.0000
C6—H6A	0.9500	C25—H25A	0.9800
C7—C8	1.390 (3)	C25—H25B	0.9800
C7—H7A	0.9500	C25—H25C	0.9800
C8—C9	1.382 (3)	C26—H26A	0.9800
C8—H8A	0.9500	C26—H26B	0.9800
C9—C10	1.392 (3)	C26—H26C	0.9800
C9—H9A	0.9500	C27—C28	1.531 (3)
C10—H10A	0.9500	C27—C29	1.529 (3)
C11—C12	1.492 (2)	C27—H27A	1.0000
C12—C13	1.390 (2)	C28—H28A	0.9800
C12—C17	1.391 (2)	C28—H28B	0.9800
C13—C14	1.393 (2)	C28—H28C	0.9800
C13—H13A	0.9500	C29—H29A	0.9800
C14—C15	1.375 (3)	C29—H29B	0.9800
C14—H14A	0.9500	C29—H29C	0.9800
C15—C16	1.386 (3)

C1—N1—N2	112.33 (12)	C12—C17—C16	119.86 (18)
C1—N1—C5	128.77 (15)	C12—C17—H17A	120.1
N2—N1—C5	118.88 (14)	C16—C17—H17A	120.1
C3—N2—N1	106.26 (13)	C19—C18—C23	122.60 (14)
C11—N3—C18	127.16 (14)	C19—C18—N3	119.03 (14)
C11—N3—H3A	111.2 (18)	C23—C18—N3	118.19 (14)
C18—N3—H3A	120.9 (19)	C20—C19—C18	117.23 (15)
O—C1—N1	126.87 (14)	C20—C19—C24	121.14 (15)
O—C1—C2	128.80 (15)	C18—C19—C24	121.40 (14)
N1—C1—C2	104.32 (14)	C21—C20—C19	121.27 (15)
C11—C2—C3	133.22 (15)	C21—C20—H20A	119.4
C11—C2—C1	121.61 (16)	C19—C20—H20A	119.4
C3—C2—C1	105.06 (14)	C22—C21—C20	120.15 (15)
N2—C3—C2	112.00 (15)	C22—C21—H21A	119.9
N2—C3—C4	119.07 (16)	C20—C21—H21A	119.9
C2—C3—C4	128.76 (15)	C21—C22—C23	120.86 (15)
C3—C4—H4A	109.5	C21—C22—H22A	119.6
C3—C4—H4B	109.5	C23—C22—H22A	119.6
H4A—C4—H4B	109.5	C22—C23—C18	117.87 (15)
C3—C4—H4C	109.5	C22—C23—C27	121.38 (15)
H4A—C4—H4C	109.5	C18—C23—C27	120.71 (14)
H4B—C4—H4C	109.5	C19—C24—C25	109.39 (14)
C6—C5—C10	120.58 (15)	C19—C24—C26	113.12 (15)
C6—C5—N1	120.37 (15)	C25—C24—C26	111.28 (15)
C10—C5—N1	119.05 (16)	C19—C24—H24A	107.6
C5—C6—C7	119.29 (17)	C25—C24—H24A	107.6
C5—C6—H6A	120.4	C26—C24—H24A	107.6
C7—C6—H6A	120.4	C24—C25—H25A	109.5
C8—C7—C6	120.51 (19)	C24—C25—H25B	109.5
C8—C7—H7A	119.7	H25A—C25—H25B	109.5
C6—C7—H7A	119.7	C24—C25—H25C	109.5
C9—C8—C7	119.53 (16)	H25A—C25—H25C	109.5
C9—C8—H8A	120.2	H25B—C25—H25C	109.5
C7—C8—H8A	120.2	C24—C26—H26A	109.5
C8—C9—C10	120.80 (17)	C24—C26—H26B	109.5
C8—C9—H9A	119.6	H26A—C26—H26B	109.5
C10—C9—H9A	119.6	C24—C26—H26C	109.5
C9—C10—C5	119.27 (18)	H26A—C26—H26C	109.5
C9—C10—H10A	120.4	H26B—C26—H26C	109.5
C5—C10—H10A	120.4	C28—C27—C23	109.70 (16)
N3—C11—C2	118.31 (14)	C28—C27—C29	110.5 (2)
N3—C11—C12	119.19 (14)	C23—C27—C29	113.57 (16)
C2—C11—C12	122.46 (15)	C28—C27—H27A	107.6
C13—C12—C17	119.56 (15)	C23—C27—H27A	107.6
C13—C12—C11	120.92 (14)	C29—C27—H27A	107.6
C17—C12—C11	119.49 (15)	C27—C28—H28A	109.5
C12—C13—C14	120.14 (17)	C27—C28—H28B	109.5
C12—C13—H13A	119.9	H28A—C28—H28B	109.5
C14—C13—H13A	119.9	C27—C28—H28C	109.5
C15—C14—C13	120.07 (19)	H28A—C28—H28C	109.5
C15—C14—H14A	120.0	H28B—C28—H28C	109.5
C13—C14—H14A	120.0	C27—C29—H29A	109.5
C14—C15—C16	120.14 (17)	C27—C29—H29B	109.5
C14—C15—H15A	119.9	H29A—C29—H29B	109.5
C16—C15—H15A	119.9	C27—C29—H29C	109.5
C15—C16—C17	120.22 (18)	H29A—C29—H29C	109.5
C15—C16—H16A	119.9	H29B—C29—H29C	109.5
C17—C16—H16A	119.9

C1—N1—N2—C3	0.44 (16)	C2—C11—C12—C13	66.2 (2)
C5—N1—N2—C3	179.29 (13)	N3—C11—C12—C17	65.8 (2)
N2—N1—C1—O	−178.34 (15)	C2—C11—C12—C17	−111.77 (19)
C5—N1—C1—O	2.9 (2)	C17—C12—C13—C14	0.8 (3)
N2—N1—C1—C2	0.69 (15)	C11—C12—C13—C14	−177.13 (17)
C5—N1—C1—C2	−178.02 (13)	C12—C13—C14—C15	0.1 (3)
O—C1—C2—C11	0.8 (2)	C13—C14—C15—C16	−0.4 (3)
N1—C1—C2—C11	−178.21 (14)	C14—C15—C16—C17	−0.3 (3)
O—C1—C2—C3	177.56 (16)	C13—C12—C17—C16	−1.5 (3)
N1—C1—C2—C3	−1.45 (16)	C11—C12—C17—C16	176.53 (18)
N1—N2—C3—C2	−1.44 (17)	C15—C16—C17—C12	1.2 (3)
N1—N2—C3—C4	174.25 (14)	C11—N3—C18—C19	72.6 (2)
C11—C2—C3—N2	178.08 (16)	C11—N3—C18—C23	−112.15 (18)
C1—C2—C3—N2	1.86 (18)	C23—C18—C19—C20	1.2 (2)
C11—C2—C3—C4	2.9 (3)	N3—C18—C19—C20	176.16 (14)
C1—C2—C3—C4	−173.31 (15)	C23—C18—C19—C24	−173.31 (14)
C1—N1—C5—C6	−21.9 (2)	N3—C18—C19—C24	1.7 (2)
N2—N1—C5—C6	159.49 (14)	C18—C19—C20—C21	−1.2 (2)
C1—N1—C5—C10	158.71 (16)	C24—C19—C20—C21	173.28 (14)
N2—N1—C5—C10	−19.9 (2)	C19—C20—C21—C22	0.5 (2)
C10—C5—C6—C7	0.7 (3)	C20—C21—C22—C23	0.4 (2)
N1—C5—C6—C7	−178.67 (15)	C21—C22—C23—C18	−0.4 (2)
C5—C6—C7—C8	0.5 (3)	C21—C22—C23—C27	−178.27 (15)
C6—C7—C8—C9	−1.4 (3)	C19—C18—C23—C22	−0.4 (2)
C7—C8—C9—C10	1.2 (3)	N3—C18—C23—C22	−175.40 (14)
C8—C9—C10—C5	0.0 (3)	C19—C18—C23—C27	177.48 (15)
C6—C5—C10—C9	−1.0 (2)	N3—C18—C23—C27	2.5 (2)
N1—C5—C10—C9	178.42 (15)	C20—C19—C24—C25	−90.19 (18)
C18—N3—C11—C2	−170.51 (14)	C18—C19—C24—C25	84.08 (19)
C18—N3—C11—C12	11.8 (2)	C20—C19—C24—C26	34.5 (2)
C3—C2—C11—N3	−173.95 (17)	C18—C19—C24—C26	−151.26 (16)
C1—C2—C11—N3	1.8 (2)	C22—C23—C27—C28	89.8 (2)
C3—C2—C11—C12	3.7 (3)	C18—C23—C27—C28	−88.0 (2)
C1—C2—C11—C12	179.36 (13)	C22—C23—C27—C29	−34.4 (2)
N3—C11—C12—C13	−116.23 (18)	C18—C23—C27—C29	147.85 (19)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C18–C23 and N1,N2,C1–C3 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O	0.80 (2)	1.95 (2)	2.6734 (17)	149 (3)
C9—H9A···Cg1ⁱ	0.95	2.73	3.601 (2)	153
C14—H14A···Cg2ⁱⁱ	0.96	2.76	3.467 (2)	132

Symmetry codes: (i) −x+2, −y+1, z+1/2; (ii) x−1/2, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	C₂₉H₃₁N₃O
M_r	437.57
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	110
a, b, c (Å)	12.9094 (6), 10.6947 (5), 17.9676 (8)
V (Å³)	2480.6 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.6 × 0.5 × 0.4

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.702, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	8437, 3755, 3643
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.09
No. of reflections	3755
No. of parameters	302
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.21
Absolute structure	Flack (1983), 1293 Friedel pairs
Absolute structure parameter	0.2 (2)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C18–C23 and N1,N2,C1–C3 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O	0.80 (2)	1.95 (2)	2.6734 (17)	149 (3)
C9—H9A···Cg1ⁱ	0.95	2.73	3.601 (2)	153
C14—H14A···Cg2ⁱⁱ	0.96	2.76	3.467 (2)	132

Symmetry codes: (i) −x+2, −y+1, z+1/2; (ii) x−1/2, −y+3/2, z.

Acknowledgements

We gratefully acknowledge financial support in part from the National Science Council, Taiwan. Helpful comments from the reviewers are also greatly appreciated.

References

Connor, E. F., Younkin, T. R., Henderson, J. I., Waltman, A. W. & Grubbs, R. H. (2003). Chem. Commun. 18, 2272–2273. Web of Science CSD CrossRef Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Li, J., Li, J.-Z., Li, J.-Q., Zhang, H.-Q. & Li, J.-M. (2009). Acta Cryst. E65, o1824. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lü, X.-Q., Bao, F., Kang, B.-S., Wu, Q., Liu, H.-Q. & Zhu, F.-M. (2006). J. Organomet. Chem. 691, 821–828. Google Scholar
Oxford Diffraction (2005). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, W.-H., Yang, H., Li, Z. & Li, Y. (2003). Organometallics, 22, 3678–3683. Web of Science CSD CrossRef CAS Google Scholar
Wang, C.-M., Friedrich, S., Younkin, T.-R., Li, R.-T., Grubbs, R. H., Bansleben, D. A. & Day, M. W. (1998). Organometallics, 17, 3149–3151. Web of Science CSD CrossRef CAS Google Scholar
Wang, J.-L., Yang, Y., Zhang, X. & Miao, F.-M. (2003). Acta Cryst. E59, o430–o432. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, H.-Z., Yang, Y.-X. & Zhu, Y.-Q. (2010). Acta Cryst. E66, o1123. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 67| Part 2| February 2011| Page o324

doi:10.1107/S1600536811000602

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(4Z)-4-[(2,6-Diiso­propyl­anilino)(phen­yl)methyl­­idene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

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Experimental

Crystal data

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organic compounds

(4Z)-4-[(2,6-Diisopropylanilino)(phenyl)methylidene]-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one