1,5-Dimethyl-2-phenyl-1H-pyrazol-3(2H)-one–4,4′-(propane-2,2-di­yl)bis­[1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one] (1/1)

Lyczko, K.

doi:10.1107/S160053681205091X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Pages o127-o128

https://doi.org/10.1107/S160053681205091X

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1,5-Dimethyl-2-phenyl-1H-pyrazol-3(2H)-one–4,4′-(propane-2,2-diyl)bis[1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one] (1/1)

Krzysztof Lyczko ^a ^*

^aInstitute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland
^*Correspondence e-mail: k.lyczko@ichtj.waw.pl

(Received 5 November 2012; accepted 14 December 2012; online 22 December 2012)

The asymmetric unit of the title compound, C₁₁H₁₂N₂O·C₂₅H₂₈N₄O₂, contains two different molecules. The smaller is known as antipyrine [systematic name: 1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one] and the larger is built up from two antypirine molecules which are connected through a C atom of the pyrazolone ring to a central propanyl part [systematic name: 4,4′-(propane-2,2-diyl)bis[1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one]. Intramolecular C—H⋯O hydrogen bonds occur in the latter molecule. In the crystal, C—H⋯O hydrogen bonds link the molecules into a two-dimensional network parallel to (001).

Related literature

Structural data on metal complexes with antipyrine were reported by Vijayan & Viswamitra (1966 ); Biagini Cingi et al. (1972 ); Baker & Jeffery (1974 ); Brassy et al. (1974 ); Mahadevan et al. (1984 ); Rheingold & King (1989 ) and Su et al. (2000 ). For related structures, see: Singh & Vijayan (1973 ); Panneerselvam et al. (1996 ); Merz (2002 ); Yuchi et al. (1991 ). Some properties of antipyrine and its derivatives were described by Peter et al. (1991 ).

Experimental

Crystal data

C₁₁H₁₂N₂O·C₂₅H₂₈N₄O₂
M_r = 604.74
Monoclinic, P 2₁ /n
a = 11.1751 (3) Å
b = 7.4623 (2) Å
c = 37.2830 (8) Å
β = 91.570 (2)°
V = 3107.93 (14) Å³
Z = 4
Cu Kα radiation
μ = 0.67 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.15 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.938, T_max = 1.000
12009 measured reflections
6009 independent reflections
5366 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.099
S = 1.03
6009 reflections
414 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.95	2.50	3.2949 (17)	142
C5—H5C⋯O2	0.98	2.44	3.3930 (17)	163
C10—H10⋯O3ⁱⁱ	0.95	2.53	3.4670 (18)	171
C14—H14A⋯O3	0.98	2.45	3.1228 (17)	126
C14—H14B⋯O2	0.98	2.34	3.0275 (17)	126
C21—H21⋯O1ⁱⁱⁱ	0.95	2.49	3.3428 (18)	150
C25—H25⋯O2	0.95	2.37	2.8811 (17)	113
C29—H29B⋯O3^iv	0.98	2.38	3.2956 (17)	155
C30—H30A⋯O3^iv	0.98	2.32	3.3015 (16)	176
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y+1, z; (iii) x-1, y-1, z; (iv) x, y+1, z.

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681205091X/kj2216sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681205091X/kj2216Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681205091X/kj2216Isup3.cml

checkCIF report

Comment top

1,5-Dimethyl-2-phenyl-1H-pyrazol-3(2H)-one, known as antipyrine or phenazone, is an interesting synthetic compound from the medicinal (pharmaceutical) point of view because of its analgesic and antipyretic properties. It is also used as a probe of oxidative metabolism (Peter et al., 1991). Antipyrine is a bulky monodentate donor ligand. Its functional carbonyl group can coordinate to metal ions. Some structures of homoleptic antipyrine-metal complexes were punlished, such as [Pb(antipyrine)₆](ClO₄)₂ (Vijayan & Viswamitra, 1966), [Y(antipyrine)₆]I₃ (Baker & Jeffery, 1974), [Cd(antipyrine)₆](ClO₄)₂ (Mahadevan et al., 1984), [Tb(antipyrine)₆]I₃ (Rheingold & King, 1989) and [Tb(antipyrine)₆](ClO₄)₃ (Su et al., 2000). Moreover, the crystal structures of other complexes, e.g., [Zn(antipyrine)₂Cl₂] (Biagini Cingi et al., 1972) and [Cu(antipyrine)₂(NO₃)₂] (Brassy et al., 1974) have been reported.

The aim of this work was to crystallize the hexa-coordinated complex between Pb^II ions and antipyrine with nitrate as a counterion. Previously the hexakis(antipyrine)lead(II) perchlorate complex was successfully crystallized from a solution in water (Vijayan & Viswamitra, 1966). Unexpectedly, under the reaction conditions applied in this work (see Experimental), instead of the hexakis(antipyrine)lead(II) nitrate complex, two different organic molecules were co-crystallized (Fig. 1). The first one is antipyrine and the second one is 4,4'-propane-2,2-diyldiantipyrine - a compound containing two antipyrine molecules linked by a propanyl group. The molecules in the crystal structure are interacting together through very weak intermolecular C—H···O hydrogen bonds (Table 1, Fig. 2) forming a two-dimensional network parallel to (0 0 1). Additionally, the structure of 4,4'-propane-2,2-diyldiantipyrine is stabilized by three intramolecular C—H···O hydrogen bonds (Table 1, Fig. 2).

Previously antipyrine (Singh & Vijayan, 1973), 4-hydroxyantipyrine (Panneerselvam et al., 1996) and 4,4'-methylenediantipyrine (Merz, 2002), the similar compounds to 4,4'-propane-2,2-diyldiantipyrine, were crystallized. The reaction of 4,4'-methylenediantipyrine with titanium(IV) has been used for selective photometric determination of this cation. The structure of tris(4,4'-methylenediantipyrine)titanium(IV) perchlorate complex has been presented by Yuchi et al., (1991).

The presence of an antipyrine derivative in this crystal structure is extremely strange and in my opinion can probably be ascribed to the catalyzed conversion of antipyrine into such a complicated compound as in the presented reaction system.

Related literature top

Structural data on metal complexes with antipyrine were reported by Vijayan & Viswamitra (1966); Biagini Cingi et al. (1972); Baker & Jeffery (1974); Brassy et al. (1974); Mahadevan et al. (1984); Rheingold & King (1989) and Su et al. (2000). For related structures, see: Singh & Vijayan (1973); Panneerselvam et al. (1996); Merz (2002); Yuchi et al. (1991). Some properties of antipyrine and its derivatives were described by Peter et al. (1991).

Experimental top

The title compounds were crystallized unintentionally in an attempt to synthesize single crystals of the hexakis(antipyrine)lead(II) nitrate complex. Lead(II) nitrate (0.236 g, 0.712 mmol) and antipyrine (0.809 g, 4.293 mmol) were dissolved in 1.0 ml of water and methanol (1:1). Next about 1/5 of the solvent was evaporated off at a temperature of about 75°C. After one year of storage in the refrigerator some colourless block like crystals were found.

Structure description top

Structural data on metal complexes with antipyrine were reported by Vijayan & Viswamitra (1966); Biagini Cingi et al. (1972); Baker & Jeffery (1974); Brassy et al. (1974); Mahadevan et al. (1984); Rheingold & King (1989) and Su et al. (2000). For related structures, see: Singh & Vijayan (1973); Panneerselvam et al. (1996); Merz (2002); Yuchi et al. (1991). Some properties of antipyrine and its derivatives were described by Peter et al. (1991).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A molecular structure of the title compounds. Displacement ellipsoids of the non-hydrogen atoms are drawn at the 50% probability level.
	Fig. 2. A fragment of the crystal structure showing the intra- and intermolecular hydrogen bonds.

1,5-Dimethyl-2-phenyl-1H-pyrazol-3(2H)-one– 4,4'-(propane-2,2-diyl)bis[1,5-dimethyl-2-phenyl-1H- pyrazol-3(2H)-one] (1/1) top

Crystal data top

C₂₅H₂₈N₄O₂·C₁₁H₁₂N₂O	F(000) = 1288
M_r = 604.74	D_x = 1.292 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 5594 reflections
a = 11.1751 (3) Å	θ = 3.6–71.8°
b = 7.4623 (2) Å	µ = 0.67 mm⁻¹
c = 37.2830 (8) Å	T = 100 K
β = 91.570 (2)°	Block, colourless
V = 3107.93 (14) Å³	0.30 × 0.25 × 0.15 mm
Z = 4

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	6009 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	5366 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.018
Detector resolution: 16.0131 pixels mm^-1	θ_max = 72.0°, θ_min = 4.1°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −4→9
T_min = 0.938, T_max = 1.000	l = −45→42
12009 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0422P)² + 1.6129P] where P = (F_o² + 2F_c²)/3
6009 reflections	(Δ/σ)_max < 0.001
414 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₂₅H₂₈N₄O₂·C₁₁H₁₂N₂O	V = 3107.93 (14) Å³
M_r = 604.74	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 11.1751 (3) Å	µ = 0.67 mm⁻¹
b = 7.4623 (2) Å	T = 100 K
c = 37.2830 (8) Å	0.30 × 0.25 × 0.15 mm
β = 91.570 (2)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	6009 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	5366 reflections with I > 2σ(I)
T_min = 0.938, T_max = 1.000	R_int = 0.018
12009 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 1.03	Δρ_max = 0.26 e Å⁻³
6009 reflections	Δρ_min = −0.31 e Å⁻³
414 parameters

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
C1	0.73885 (12)	0.5494 (2)	0.19813 (4)	0.0176 (3)
C2	0.70121 (13)	0.4021 (2)	0.22001 (4)	0.0201 (3)
H2	0.7288	0.3775	0.2438	0.024*
C3	0.61974 (12)	0.30441 (19)	0.20087 (4)	0.0191 (3)
C4	0.55955 (15)	0.1333 (2)	0.21067 (4)	0.0281 (3)
H4A	0.5944	0.0341	0.1973	0.042*
H4B	0.4738	0.1418	0.2047	0.042*
H4C	0.5710	0.1117	0.2365	0.042*
C5	0.57888 (13)	0.2704 (2)	0.13580 (4)	0.0201 (3)
H5A	0.6543	0.2098	0.1306	0.030*
H5B	0.5546	0.3459	0.1154	0.030*
H5C	0.5167	0.1808	0.1400	0.030*
C6	0.65888 (12)	0.65797 (18)	0.13835 (3)	0.0160 (3)
C7	0.54464 (13)	0.69605 (19)	0.12467 (4)	0.0191 (3)
H7	0.4769	0.6379	0.1342	0.023*
C8	0.53013 (14)	0.8194 (2)	0.09705 (4)	0.0230 (3)
H8	0.4524	0.8436	0.0873	0.028*
C9	0.62883 (15)	0.9074 (2)	0.08366 (4)	0.0246 (3)
H9	0.6188	0.9905	0.0645	0.029*
C10	0.74213 (14)	0.87403 (19)	0.09827 (4)	0.0227 (3)
H10	0.8091	0.9375	0.0896	0.027*
C11	0.75846 (13)	0.74826 (19)	0.12551 (4)	0.0189 (3)
H11	0.8362	0.7241	0.1352	0.023*
N1	0.59546 (10)	0.38236 (16)	0.16795 (3)	0.0166 (2)
N2	0.67665 (10)	0.52572 (16)	0.16531 (3)	0.0161 (2)
O1	0.80765 (9)	0.67590 (15)	0.20421 (3)	0.0244 (2)
C12	0.26030 (12)	0.43381 (19)	0.11446 (4)	0.0179 (3)
H12A	0.2893	0.5128	0.0956	0.027*
H12B	0.3282	0.3712	0.1259	0.027*
H12C	0.2192	0.5053	0.1324	0.027*
C13	0.17264 (11)	0.29586 (17)	0.09789 (3)	0.0139 (3)
C14	0.24097 (12)	0.18958 (19)	0.06911 (4)	0.0182 (3)
H14A	0.1884	0.0971	0.0587	0.027*
H14B	0.3118	0.1329	0.0803	0.027*
H14C	0.2659	0.2716	0.0502	0.027*
C15	0.22095 (12)	0.04833 (18)	0.14514 (3)	0.0154 (3)
C16	0.13547 (11)	0.17061 (17)	0.12818 (3)	0.0137 (3)
C17	0.03074 (12)	0.15149 (18)	0.14544 (3)	0.0143 (3)
C18	−0.08452 (12)	0.2527 (2)	0.14323 (4)	0.0201 (3)
H18A	−0.0899	0.3321	0.1641	0.030*
H18B	−0.1516	0.1682	0.1430	0.030*
H18C	−0.0876	0.3244	0.1212	0.030*
C19	−0.01645 (13)	0.0347 (2)	0.20569 (4)	0.0209 (3)
H19A	0.0201	0.1378	0.2180	0.031*
H19B	−0.0029	−0.0736	0.2201	0.031*
H19C	−0.1027	0.0550	0.2024	0.031*
C20	0.19083 (12)	−0.20882 (18)	0.18707 (3)	0.0163 (3)
C21	0.10387 (13)	−0.3368 (2)	0.19420 (4)	0.0205 (3)
H21	0.0220	−0.3141	0.1883	0.025*
C22	0.13810 (15)	−0.4980 (2)	0.21008 (4)	0.0267 (3)
H22	0.0786	−0.5836	0.2158	0.032*
C23	0.25744 (15)	−0.5362 (2)	0.21774 (4)	0.0279 (3)
H23	0.2800	−0.6475	0.2283	0.034*
C24	0.34341 (14)	−0.4095 (2)	0.20980 (4)	0.0248 (3)
H24	0.4255	−0.4356	0.2145	0.030*
C25	0.31133 (13)	−0.2447 (2)	0.19507 (3)	0.0192 (3)
H25	0.3708	−0.1573	0.1905	0.023*
C26	−0.02192 (11)	0.26949 (18)	0.05944 (3)	0.0137 (3)
C27	0.06521 (11)	0.38047 (18)	0.07869 (3)	0.0135 (3)
C28	0.02835 (11)	0.55412 (18)	0.07508 (3)	0.0138 (3)
C29	0.08036 (13)	0.72665 (18)	0.08890 (4)	0.0189 (3)
H29A	0.0926	0.7190	0.1150	0.028*
H29B	0.0252	0.8252	0.0831	0.028*
H29C	0.1573	0.7486	0.0777	0.028*
C30	−0.10277 (12)	0.69931 (18)	0.02819 (3)	0.0169 (3)
H30A	−0.0781	0.8171	0.0373	0.025*
H30B	−0.1883	0.7018	0.0217	0.025*
H30C	−0.0568	0.6698	0.0070	0.025*
C31	−0.22286 (12)	0.34094 (18)	0.03238 (3)	0.0143 (3)
C32	−0.23650 (13)	0.20851 (19)	0.00621 (4)	0.0176 (3)
H32	−0.1684	0.1509	−0.0032	0.021*
C33	−0.35122 (13)	0.16203 (19)	−0.00586 (4)	0.0204 (3)
H33	−0.3616	0.0719	−0.0237	0.024*
C34	−0.45076 (13)	0.2464 (2)	0.00795 (4)	0.0217 (3)
H34	−0.5288	0.2144	−0.0005	0.026*
C35	−0.43591 (13)	0.37752 (19)	0.03412 (4)	0.0199 (3)
H35	−0.5040	0.4350	0.0436	0.024*
C36	−0.32209 (12)	0.42511 (19)	0.04652 (3)	0.0170 (3)
H36	−0.3120	0.5144	0.0645	0.020*
N3	0.03776 (10)	0.01203 (16)	0.17043 (3)	0.0154 (2)
N4	0.15874 (10)	−0.04046 (16)	0.17199 (3)	0.0160 (2)
N5	−0.08054 (10)	0.56315 (14)	0.05609 (3)	0.0137 (2)
N6	−0.10503 (10)	0.38756 (15)	0.04440 (3)	0.0142 (2)
O2	0.32678 (8)	0.01806 (14)	0.13877 (3)	0.0215 (2)
O3	−0.03072 (9)	0.10492 (12)	0.05679 (3)	0.0181 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0138 (6)	0.0231 (7)	0.0160 (6)	0.0009 (6)	0.0012 (5)	−0.0033 (5)
C2	0.0194 (7)	0.0249 (7)	0.0161 (6)	0.0009 (6)	0.0015 (5)	0.0000 (6)
C3	0.0176 (7)	0.0194 (7)	0.0204 (7)	0.0026 (6)	0.0028 (5)	0.0013 (5)
C4	0.0316 (8)	0.0238 (8)	0.0290 (8)	−0.0051 (7)	0.0001 (6)	0.0059 (6)
C5	0.0169 (7)	0.0216 (7)	0.0218 (7)	−0.0013 (6)	−0.0005 (5)	−0.0064 (6)
C6	0.0189 (7)	0.0148 (6)	0.0142 (6)	0.0003 (5)	0.0023 (5)	−0.0031 (5)
C7	0.0184 (7)	0.0203 (7)	0.0187 (6)	0.0008 (6)	0.0028 (5)	−0.0022 (5)
C8	0.0255 (8)	0.0229 (7)	0.0204 (7)	0.0082 (6)	−0.0002 (6)	−0.0022 (6)
C9	0.0395 (9)	0.0160 (7)	0.0184 (7)	0.0049 (6)	0.0045 (6)	0.0006 (6)
C10	0.0303 (8)	0.0162 (7)	0.0219 (7)	−0.0042 (6)	0.0093 (6)	−0.0041 (6)
C11	0.0191 (7)	0.0186 (7)	0.0193 (6)	−0.0010 (6)	0.0042 (5)	−0.0045 (5)
N1	0.0166 (6)	0.0151 (6)	0.0180 (5)	−0.0034 (5)	0.0004 (4)	−0.0011 (4)
N2	0.0150 (5)	0.0169 (6)	0.0162 (5)	−0.0033 (5)	−0.0002 (4)	0.0000 (4)
O1	0.0228 (5)	0.0292 (6)	0.0210 (5)	−0.0091 (5)	−0.0016 (4)	−0.0043 (4)
C12	0.0142 (6)	0.0164 (7)	0.0228 (7)	−0.0012 (5)	−0.0019 (5)	0.0007 (5)
C13	0.0128 (6)	0.0128 (6)	0.0161 (6)	−0.0007 (5)	0.0010 (5)	0.0002 (5)
C14	0.0174 (7)	0.0194 (7)	0.0180 (6)	0.0027 (6)	0.0029 (5)	0.0009 (5)
C15	0.0152 (6)	0.0139 (6)	0.0173 (6)	−0.0012 (5)	0.0005 (5)	0.0005 (5)
C16	0.0130 (6)	0.0123 (6)	0.0157 (6)	−0.0003 (5)	−0.0008 (5)	−0.0016 (5)
C17	0.0141 (6)	0.0147 (6)	0.0141 (6)	−0.0004 (5)	−0.0017 (5)	−0.0011 (5)
C18	0.0146 (7)	0.0243 (7)	0.0216 (7)	0.0044 (6)	0.0026 (5)	0.0007 (6)
C19	0.0245 (7)	0.0214 (7)	0.0171 (7)	0.0008 (6)	0.0062 (5)	0.0010 (5)
C20	0.0213 (7)	0.0147 (6)	0.0128 (6)	0.0009 (5)	0.0007 (5)	−0.0001 (5)
C21	0.0227 (7)	0.0203 (7)	0.0184 (7)	−0.0015 (6)	0.0017 (5)	−0.0003 (5)
C22	0.0382 (9)	0.0179 (7)	0.0242 (7)	−0.0038 (7)	0.0067 (6)	0.0026 (6)
C23	0.0435 (10)	0.0187 (7)	0.0218 (7)	0.0084 (7)	0.0039 (6)	0.0053 (6)
C24	0.0293 (8)	0.0279 (8)	0.0170 (7)	0.0104 (7)	−0.0005 (6)	0.0014 (6)
C25	0.0214 (7)	0.0209 (7)	0.0152 (6)	0.0012 (6)	−0.0006 (5)	0.0000 (5)
C26	0.0141 (6)	0.0138 (6)	0.0133 (6)	0.0003 (5)	0.0019 (5)	−0.0005 (5)
C27	0.0133 (6)	0.0135 (6)	0.0138 (6)	−0.0009 (5)	0.0020 (5)	−0.0007 (5)
C28	0.0129 (6)	0.0146 (6)	0.0140 (6)	−0.0012 (5)	0.0013 (5)	−0.0009 (5)
C29	0.0207 (7)	0.0119 (6)	0.0239 (7)	0.0001 (5)	−0.0048 (5)	−0.0016 (5)
C30	0.0207 (7)	0.0141 (6)	0.0159 (6)	0.0008 (5)	−0.0004 (5)	0.0023 (5)
C31	0.0159 (6)	0.0130 (6)	0.0138 (6)	−0.0021 (5)	−0.0018 (5)	0.0024 (5)
C32	0.0201 (7)	0.0157 (7)	0.0168 (6)	0.0004 (5)	0.0005 (5)	−0.0008 (5)
C33	0.0246 (7)	0.0174 (7)	0.0188 (6)	−0.0026 (6)	−0.0041 (5)	−0.0020 (5)
C34	0.0180 (7)	0.0223 (7)	0.0246 (7)	−0.0043 (6)	−0.0060 (5)	0.0030 (6)
C35	0.0165 (7)	0.0193 (7)	0.0239 (7)	0.0014 (6)	0.0009 (5)	0.0022 (6)
C36	0.0197 (7)	0.0158 (7)	0.0156 (6)	−0.0006 (5)	0.0002 (5)	−0.0005 (5)
N3	0.0116 (5)	0.0184 (6)	0.0162 (5)	0.0011 (4)	0.0017 (4)	0.0012 (4)
N4	0.0110 (5)	0.0175 (6)	0.0196 (6)	0.0004 (4)	0.0003 (4)	0.0025 (5)
N5	0.0162 (5)	0.0095 (5)	0.0154 (5)	−0.0006 (4)	−0.0011 (4)	−0.0007 (4)
N6	0.0154 (6)	0.0100 (5)	0.0170 (5)	−0.0006 (4)	−0.0016 (4)	−0.0012 (4)
O2	0.0123 (5)	0.0237 (5)	0.0287 (5)	0.0033 (4)	0.0038 (4)	0.0073 (4)
O3	0.0193 (5)	0.0114 (5)	0.0236 (5)	−0.0008 (4)	−0.0027 (4)	−0.0009 (4)

Geometric parameters (Å, º) top

C1—C2	1.439 (2)	C19—H19C	0.9800
C2—H2	0.9500	C20—C21	1.393 (2)
C3—C2	1.354 (2)	C20—C25	1.3972 (19)
C3—C4	1.493 (2)	C21—H21	0.9500
C4—H4A	0.9800	C22—C21	1.390 (2)
C4—H4B	0.9800	C22—C23	1.386 (2)
C4—H4C	0.9800	C22—H22	0.9500
C5—H5A	0.9800	C23—H23	0.9500
C5—H5B	0.9800	C24—C23	1.386 (2)
C5—H5C	0.9800	C24—C25	1.390 (2)
C6—C7	1.3909 (19)	C24—H24	0.9500
C7—H7	0.9500	C25—H25	0.9500
C8—C7	1.387 (2)	C27—C26	1.4529 (18)
C8—C9	1.389 (2)	C28—C27	1.3652 (19)
C8—H8	0.9500	C28—C29	1.4982 (18)
C9—H9	0.9500	C29—H29A	0.9800
C10—C9	1.387 (2)	C29—H29B	0.9800
C10—H10	0.9500	C29—H29C	0.9800
C11—C6	1.3966 (19)	C30—H30A	0.9800
C11—C10	1.391 (2)	C30—H30B	0.9800
C11—H11	0.9500	C30—H30C	0.9800
N1—C3	1.3785 (18)	C31—C32	1.3942 (18)
N1—C5	1.4683 (17)	C32—H32	0.9500
N2—C1	1.4018 (17)	C33—C32	1.391 (2)
N2—C6	1.4187 (17)	C33—C34	1.389 (2)
N2—N1	1.4079 (16)	C33—H33	0.9500
O1—C1	1.2342 (17)	C34—H34	0.9500
C12—H12A	0.9800	C35—C34	1.389 (2)
C12—H12B	0.9800	C35—H35	0.9500
C12—H12C	0.9800	C36—C31	1.3908 (19)
C13—C12	1.5388 (18)	C36—C35	1.3877 (19)
C13—C16	1.5318 (17)	C36—H36	0.9500
C13—C27	1.5185 (18)	N3—C17	1.3975 (17)
C14—C13	1.5519 (18)	N3—C19	1.4724 (16)
C14—H14A	0.9800	N4—C15	1.4009 (17)
C14—H14B	0.9800	N4—C20	1.4184 (17)
C14—H14C	0.9800	N4—N3	1.4072 (15)
C15—C16	1.4533 (18)	O2—C15	1.2335 (16)
C17—C16	1.3587 (18)	O3—C26	1.2357 (17)
C17—C18	1.4936 (18)	N5—C28	1.3926 (17)
C18—H18A	0.9800	N5—C30	1.4705 (16)
C18—H18B	0.9800	N5—N6	1.4054 (15)
C18—H18C	0.9800	N6—C26	1.3873 (17)
C19—H19A	0.9800	N6—C31	1.4225 (17)
C19—H19B	0.9800

O1—C1—C2	132.09 (13)	H18B—C18—H18C	109.5
O1—C1—N2	123.27 (13)	H19A—C19—H19B	109.5
N2—C1—C2	104.63 (12)	H19A—C19—H19C	109.5
C3—C2—C1	108.39 (12)	H19B—C19—H19C	109.5
C3—C2—H2	125.8	N3—C19—H19A	109.5
C1—C2—H2	125.8	N3—C19—H19B	109.5
C2—C3—C4	129.21 (13)	N3—C19—H19C	109.5
C2—C3—N1	110.80 (13)	C21—C20—C25	120.07 (13)
N1—C3—C4	119.98 (13)	C21—C20—N4	120.84 (12)
C3—C4—H4A	109.5	C25—C20—N4	119.09 (12)
C3—C4—H4B	109.5	C20—C21—H21	120.3
C3—C4—H4C	109.5	C22—C21—C20	119.30 (14)
H4A—C4—H4B	109.5	C22—C21—H21	120.3
H4A—C4—H4C	109.5	C21—C22—H22	119.4
H4B—C4—H4C	109.5	C23—C22—C21	121.17 (14)
H5A—C5—H5B	109.5	C23—C22—H22	119.4
H5A—C5—H5C	109.5	C22—C23—H23	120.5
H5B—C5—H5C	109.5	C24—C23—C22	119.00 (14)
N1—C5—H5A	109.5	C24—C23—H23	120.5
N1—C5—H5B	109.5	C23—C24—C25	121.01 (14)
N1—C5—H5C	109.5	C23—C24—H24	119.5
C7—C6—C11	120.51 (13)	C25—C24—H24	119.5
C7—C6—N2	120.73 (12)	C20—C25—H25	120.3
C11—C6—N2	118.75 (12)	C24—C25—C20	119.39 (14)
C6—C7—H7	120.2	C24—C25—H25	120.3
C8—C7—C6	119.67 (13)	N6—C26—C27	105.65 (11)
C8—C7—H7	120.2	O3—C26—C27	131.05 (13)
C7—C8—C9	120.20 (14)	O3—C26—N6	123.23 (12)
C7—C8—H8	119.9	C26—C27—C13	120.43 (11)
C9—C8—H8	119.9	C28—C27—C13	132.34 (12)
C8—C9—H9	120.0	C28—C27—C26	107.22 (11)
C10—C9—C8	119.95 (14)	C27—C28—C29	131.96 (12)
C10—C9—H9	120.0	C27—C28—N5	110.67 (11)
C9—C10—C11	120.53 (14)	N5—C28—C29	117.30 (12)
C9—C10—H10	119.7	C28—C29—H29A	109.5
C11—C10—H10	119.7	C28—C29—H29B	109.5
C6—C11—H11	120.5	C28—C29—H29C	109.5
C10—C11—C6	119.07 (13)	H29A—C29—H29B	109.5
C10—C11—H11	120.5	H29A—C29—H29C	109.5
C3—N1—C5	120.26 (12)	H29B—C29—H29C	109.5
C3—N1—N2	105.75 (11)	H30A—C30—H30B	109.5
N2—N1—C5	116.26 (11)	H30A—C30—H30C	109.5
C1—N2—C6	125.95 (12)	H30B—C30—H30C	109.5
C1—N2—N1	109.88 (11)	N5—C30—H30A	109.5
N1—N2—C6	120.01 (11)	N5—C30—H30B	109.5
C13—C12—H12A	109.5	N5—C30—H30C	109.5
C13—C12—H12B	109.5	C32—C31—N6	118.45 (12)
C13—C12—H12C	109.5	C36—C31—C32	120.83 (12)
H12A—C12—H12B	109.5	C36—C31—N6	120.72 (12)
H12A—C12—H12C	109.5	C31—C32—H32	120.5
H12B—C12—H12C	109.5	C33—C32—C31	119.03 (13)
C12—C13—C14	107.43 (11)	C33—C32—H32	120.5
C16—C13—C12	107.15 (10)	C32—C33—H33	119.8
C16—C13—C14	110.26 (11)	C34—C33—C32	120.48 (13)
C27—C13—C12	113.43 (11)	C34—C33—H33	119.8
C27—C13—C14	106.50 (10)	C33—C34—H34	120.1
C27—C13—C16	111.99 (10)	C35—C34—C33	119.89 (13)
C13—C14—H14A	109.5	C35—C34—H34	120.1
C13—C14—H14B	109.5	C34—C35—H35	119.8
C13—C14—H14C	109.5	C36—C35—C34	120.35 (13)
H14A—C14—H14B	109.5	C36—C35—H35	119.8
H14A—C14—H14C	109.5	C31—C36—H36	120.3
H14B—C14—H14C	109.5	C35—C36—C31	119.41 (13)
N4—C15—C16	105.96 (11)	C35—C36—H36	120.3
O2—C15—C16	130.79 (12)	C17—N3—C19	119.52 (11)
O2—C15—N4	123.24 (12)	C17—N3—N4	105.74 (10)
C15—C16—C13	121.04 (11)	N4—N3—C19	114.42 (10)
C17—C16—C13	131.90 (12)	C15—N4—C20	125.25 (11)
C17—C16—C15	106.99 (11)	C15—N4—N3	109.50 (10)
C16—C17—C18	132.34 (13)	N3—N4—C20	119.68 (11)
C16—C17—N3	111.14 (11)	C28—N5—C30	121.43 (11)
N3—C17—C18	116.50 (11)	C28—N5—N6	105.82 (10)
C17—C18—H18A	109.5	N6—N5—C30	113.40 (10)
C17—C18—H18B	109.5	C26—N6—C31	125.14 (11)
C17—C18—H18C	109.5	C26—N6—N5	110.14 (10)
H18A—C18—H18B	109.5	N5—N6—C31	119.77 (10)
H18A—C18—H18C	109.5

N2—C1—C2—C3	−1.74 (15)	C23—C22—C21—C20	−2.3 (2)
O1—C1—C2—C3	177.25 (15)	C21—C22—C23—C24	0.9 (2)
C4—C3—C2—C1	175.98 (14)	C25—C24—C23—C22	1.3 (2)
N1—C3—C2—C1	−3.07 (16)	C23—C24—C25—C20	−2.1 (2)
C11—C6—C7—C8	2.6 (2)	C13—C27—C26—N6	−178.31 (11)
N2—C6—C7—C8	−176.75 (12)	C13—C27—C26—O3	4.7 (2)
C9—C8—C7—C6	−1.5 (2)	C28—C27—C26—N6	1.73 (14)
C7—C8—C9—C10	−0.9 (2)	C28—C27—C26—O3	−175.24 (14)
C11—C10—C9—C8	2.1 (2)	C29—C28—C27—C13	−0.2 (2)
C10—C11—C6—C7	−1.4 (2)	C29—C28—C27—C26	179.77 (13)
C10—C11—C6—N2	177.97 (12)	N5—C28—C27—C13	−177.14 (12)
C6—C11—C10—C9	−1.0 (2)	N5—C28—C27—C26	2.81 (15)
C5—N1—C3—C2	140.75 (13)	C36—C31—C32—C33	0.4 (2)
C5—N1—C3—C4	−38.41 (19)	N6—C31—C32—C33	−179.81 (12)
N2—N1—C3—C2	6.58 (15)	C34—C33—C32—C31	0.0 (2)
N2—N1—C3—C4	−172.58 (12)	C32—C33—C34—C35	−0.3 (2)
C6—N2—C1—C2	162.62 (12)	C36—C35—C34—C33	0.1 (2)
C6—N2—C1—O1	−16.5 (2)	C35—C36—C31—C32	−0.6 (2)
N1—N2—C1—C2	5.83 (14)	C35—C36—C31—N6	179.63 (12)
N1—N2—C1—O1	−173.27 (12)	C31—C36—C35—C34	0.3 (2)
C1—N2—C6—C7	−127.36 (14)	C19—N3—C17—C16	139.18 (12)
C1—N2—C6—C11	53.23 (18)	C19—N3—C17—C18	−39.15 (17)
N1—N2—C6—C7	27.30 (18)	N4—N3—C17—C16	8.40 (14)
N1—N2—C6—C11	−152.11 (12)	N4—N3—C17—C18	−169.93 (11)
C1—N2—N1—C3	−7.69 (14)	C15—N4—C20—C21	−138.74 (14)
C1—N2—N1—C5	−143.99 (12)	C15—N4—C20—C25	41.86 (18)
C6—N2—N1—C3	−166.08 (11)	N3—N4—C20—C21	12.09 (18)
C6—N2—N1—C5	57.62 (16)	N3—N4—C20—C25	−167.32 (11)
C12—C13—C16—C15	−67.73 (15)	C20—N4—C15—C16	157.61 (12)
C12—C13—C16—C17	108.90 (16)	C20—N4—C15—O2	−21.5 (2)
C14—C13—C16—C15	48.90 (16)	N3—N4—C15—C16	4.31 (14)
C14—C13—C16—C17	−134.48 (15)	N3—N4—C15—O2	−174.79 (12)
C27—C13—C16—C15	167.29 (11)	C15—N4—N3—C17	−7.68 (14)
C27—C13—C16—C17	−16.1 (2)	C15—N4—N3—C19	−141.33 (12)
C12—C13—C27—C26	175.73 (11)	C20—N4—N3—C17	−162.70 (11)
C12—C13—C27—C28	−4.3 (2)	C20—N4—N3—C19	63.66 (15)
C14—C13—C27—C26	57.76 (15)	C30—N5—C28—C27	−137.23 (12)
C14—C13—C27—C28	−122.29 (15)	C30—N5—C28—C29	45.31 (17)
C16—C13—C27—C26	−62.84 (15)	N6—N5—C28—C27	−6.17 (14)
C16—C13—C27—C28	117.11 (15)	N6—N5—C28—C29	176.37 (11)
N4—C15—C16—C13	178.23 (11)	C28—N5—N6—C26	7.30 (13)
N4—C15—C16—C17	0.86 (14)	C28—N5—N6—C31	163.66 (11)
O2—C15—C16—C13	−2.8 (2)	C30—N5—N6—C26	142.79 (11)
O2—C15—C16—C17	179.86 (14)	C30—N5—N6—C31	−60.86 (15)
C18—C17—C16—C13	−4.8 (3)	C31—N6—C26—C27	−160.42 (11)
C18—C17—C16—C15	172.16 (14)	C31—N6—C26—O3	16.9 (2)
N3—C17—C16—C13	177.21 (12)	N5—N6—C26—C27	−5.62 (13)
N3—C17—C16—C15	−5.81 (15)	N5—N6—C26—O3	171.66 (12)
C25—C20—C21—C22	1.5 (2)	C26—N6—C31—C32	−57.86 (17)
N4—C20—C21—C22	−177.89 (12)	C26—N6—C31—C36	121.90 (14)
C21—C20—C25—C24	0.7 (2)	N5—N6—C31—C32	149.55 (12)
N4—C20—C25—C24	−179.91 (12)	N5—N6—C31—C36	−30.68 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.50	3.2949 (17)	142
C5—H5C···O2	0.98	2.44	3.3930 (17)	163
C10—H10···O3ⁱⁱ	0.95	2.53	3.4670 (18)	171
C14—H14A···O3	0.98	2.45	3.1228 (17)	126
C14—H14B···O2	0.98	2.34	3.0275 (17)	126
C21—H21···O1ⁱⁱⁱ	0.95	2.49	3.3428 (18)	150
C25—H25···O2	0.95	2.37	2.8811 (17)	113
C29—H29B···O3^iv	0.98	2.38	3.2956 (17)	155
C30—H30A···O3^iv	0.98	2.32	3.3015 (16)	176

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₈N₄O₂·C₁₁H₁₂N₂O
M_r	604.74
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.1751 (3), 7.4623 (2), 37.2830 (8)
β (°)	91.570 (2)
V (Å³)	3107.93 (14)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.30 × 0.25 × 0.15

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Eos)
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.938, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12009, 6009, 5366
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.099, 1.03
No. of reflections	6009
No. of parameters	414
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.31

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.50	3.2949 (17)	141.9
C5—H5C···O2	0.98	2.44	3.3930 (17)	162.8
C10—H10···O3ⁱⁱ	0.95	2.53	3.4670 (18)	170.7
C14—H14A···O3	0.98	2.45	3.1228 (17)	125.7
C14—H14B···O2	0.98	2.34	3.0275 (17)	126.1
C21—H21···O1ⁱⁱⁱ	0.95	2.49	3.3428 (18)	150.1
C25—H25···O2	0.95	2.37	2.8811 (17)	113.3
C29—H29B···O3^iv	0.98	2.38	3.2956 (17)	154.8
C30—H30A···O3^iv	0.98	2.32	3.3015 (16)	176.0

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

Acknowledgements

The author thanks the Institute of Nuclear Chemistry and Technology for financial support.

References

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Pages o127-o128

https://doi.org/10.1107/S160053681205091X

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

1,5-Di­methyl-2-phenyl-1H-pyrazol-3(2H)-one–4,4′-(propane-2,2-di­yl)bis­­[1,5-di­methyl-2-phenyl-1H-pyrazol-3(2H)-one] (1/1)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,5-Dimethyl-2-phenyl-1H-pyrazol-3(2H)-one–4,4′-(propane-2,2-diyl)bis[1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one] (1/1)