1,1′,5,5′-Tetra­methyl-2,2′-diphenyl-4,4′-[p-phenyl­enebis(methyl­idynenitrilo)]di-1H-pyrazol-3(2H)-one

Xiao, Y.; Bi, C.F.; Wang, A.D.; Fan, Y.H.; Zhang, X.; Xu, J.K.; Xie, S.T.

doi:10.1107/S1600536808021028

organic compounds

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Volume 64| Part 8| August 2008| Page o1479

doi:10.1107/S1600536808021028

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1,1′,5,5′-Tetramethyl-2,2′-diphenyl-4,4′-[p-phenylenebis(methylidynenitrilo)]di-1H-pyrazol-3(2H)-one

Yan Xiao,^a Cai Feng Bi,^a ^* Ai Dong Wang,^a Yu Hua Fan,^a Xia Zhang,^a Jia Kun Xu ^a and Si Tang Xie ^a

^aKey Laboratory of Marine Chemistry, Theory and Technology, Ministry of Education, College of Chemistry, Ocean University of China, Qingdao Shandong 266100, People's Republic of China
^*Correspondence e-mail: caifeng_bi@yahoo.com.cn

(Received 4 June 2008; accepted 7 July 2008; online 12 July 2008)

In the centrosymmetric title compound, C₃₀H₂₈N₆O₂, the dihedral angles between the antipyrine ring and the terminal phenyl and central benzene rings are 50.55 (10) and 14.62 (9)°, respectively. Some short intermolecular C—H⋯O interactions may help to establish the packing. An intramolecular C—H⋯O hydrogen bond is also present.

Related literature

For related structures, see: Guo et al. (2007 ); Selvakumar et al. (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₃₀H₂₈N₆O₂
M_r = 504.58
Monoclinic, P 2₁ /c
a = 6.0710 (2) Å
b = 22.2948 (7) Å
c = 9.8712 (3) Å
β = 95.147 (2)°
V = 1330.70 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 292 (2) K
0.18 × 0.10 × 0.09 mm

Data collection

Bruker APEX2 CCD diffractometer
Absorption correction: none
9162 measured reflections
3034 independent reflections
1545 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.141
S = 1.03
3034 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11C⋯O1ⁱ	0.96	2.36	3.321 (2)	179
C11—H11A⋯O1ⁱⁱ	0.96	2.47	3.375 (3)	157
C12—H12⋯O1	0.93	2.30	3.002 (2)	132
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x-1, y, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021028/hb2742sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021028/hb2742Isup2.hkl

checkCIF report

Comment top

Recently, some new Schiff bases of 4-aminoantipyrine have been reported (Guo et al., 2007; Selvakumar et al., 2007). We herein report the crystal structure of the related title compound, (I).

The complete molecule of (I) is generated by inversion and its bond lengths and angles are within normal ranges (Allen et al., 1987). The maximum deviation from the mean plane for the antipyrine ring (N1/N2/C7—C9) is 0.039 (2)Å for N2. The dihedral angles between the mean planes of the antipyrine ring and the terminal and central benzene rings are 50.55 (10)° and 14.62 (9)°, respectively.

In the crystal, weak intermolecular C—H···O hydrogen bonds (Table 1) lead to chains of molecules (Fig. 2).

Related literature top

For related structures, see: Guo et al. (2007); Selvakumar et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized according to the literature method (Selvakumar et al., 2007). Orange plates of (I) were obtained by slow evaporation of a dichloromethane solution at 292 K.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level for the non-hydrogen atoms. Atoms with the suffix a are generated by the symmetry operation (2-x, 1-y, 1-z).
	Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines.

1,1',5,5'-Tetramethyl-2,2'-diphenyl-4,4'-[p- phenylenebis(methylidynenitrilo)]di-1H-pyrazol-3(2H)-one top

Crystal data top

C₃₀H₂₈N₆O₂	F(000) = 532
M_r = 504.58	D_x = 1.259 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1828 reflections
a = 6.0710 (2) Å	θ = 2.3–22.5°
b = 22.2948 (7) Å	µ = 0.08 mm⁻¹
c = 9.8712 (3) Å	T = 292 K
β = 95.147 (2)°	Plate, orange
V = 1330.70 (7) Å³	0.18 × 0.10 × 0.09 mm
Z = 2

Data collection top

Bruker APEX2 CCD diffractometer	1545 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 27.5°, θ_min = 1.8°
ω scans	h = −7→7
9162 measured reflections	k = −28→17
3034 independent reflections	l = −12→9

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0656P)² + 0.0153P] where P = (F_o² + 2F_c²)/3
3034 reflections	(Δ/σ)_max = 0.001
174 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₃₀H₂₈N₆O₂	V = 1330.70 (7) Å³
M_r = 504.58	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0710 (2) Å	µ = 0.08 mm⁻¹
b = 22.2948 (7) Å	T = 292 K
c = 9.8712 (3) Å	0.18 × 0.10 × 0.09 mm
β = 95.147 (2)°

Data collection top

Bruker APEX2 CCD diffractometer	1545 reflections with I > 2σ(I)
9162 measured reflections	R_int = 0.027
3034 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.03	Δρ_max = 0.12 e Å⁻³
3034 reflections	Δρ_min = −0.18 e Å⁻³
174 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	0.5949 (3)	0.12139 (11)	0.32324 (19)	0.0767 (6)
H1	0.5483	0.1411	0.2427	0.092*
C2	0.6689 (3)	0.06296 (12)	0.3206 (2)	0.0898 (7)
H2	0.6696	0.0428	0.2382	0.108*
C3	0.7414 (4)	0.03451 (11)	0.4398 (3)	0.0976 (7)
H3	0.7902	−0.0050	0.4379	0.117*
C4	0.7420 (4)	0.06412 (12)	0.5614 (2)	0.0936 (7)
H4	0.7959	0.0450	0.6412	0.112*
C5	0.6643 (3)	0.12151 (11)	0.56657 (19)	0.0777 (6)
H5	0.6608	0.1410	0.6497	0.093*
C6	0.5907 (3)	0.15033 (9)	0.44679 (17)	0.0638 (5)
C7	0.6507 (3)	0.25841 (8)	0.49729 (18)	0.0680 (5)
C8	0.5528 (3)	0.31031 (9)	0.42952 (16)	0.0657 (5)
C9	0.3701 (3)	0.29191 (11)	0.34882 (16)	0.0677 (5)
C10	0.2076 (3)	0.32926 (10)	0.26424 (18)	0.0837 (6)
H10A	0.1999	0.3158	0.1715	0.126*
H10B	0.2536	0.3705	0.2689	0.126*
H10C	0.0646	0.3256	0.2978	0.126*
C11	0.1418 (3)	0.19847 (10)	0.3420 (2)	0.0868 (6)
H11A	0.0685	0.2043	0.4232	0.130*
H11B	0.1695	0.1565	0.3300	0.130*
H11C	0.0497	0.2133	0.2650	0.130*
C12	0.8174 (3)	0.38194 (9)	0.49480 (17)	0.0709 (5)
H12	0.8987	0.3517	0.5407	0.085*
C13	0.9078 (3)	0.44231 (9)	0.49655 (17)	0.0647 (5)
C14	0.7891 (3)	0.49092 (10)	0.44065 (18)	0.0758 (6)
H14	0.6464	0.4852	0.4000	0.091*
C15	0.8790 (3)	0.54686 (9)	0.44463 (19)	0.0782 (6)
H15	0.7957	0.5787	0.4070	0.094*
N1	0.5147 (2)	0.21053 (8)	0.45312 (14)	0.0699 (5)
N2	0.3520 (2)	0.23112 (8)	0.35370 (14)	0.0709 (5)
N3	0.6298 (2)	0.36905 (8)	0.43221 (14)	0.0692 (4)
O1	0.8196 (2)	0.25210 (6)	0.57570 (14)	0.0871 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0660 (11)	0.1017 (18)	0.0610 (13)	−0.0126 (11)	−0.0015 (9)	−0.0058 (11)
C2	0.0811 (14)	0.1034 (19)	0.0843 (16)	−0.0086 (13)	0.0044 (12)	−0.0195 (14)
C3	0.0867 (15)	0.0909 (17)	0.113 (2)	−0.0014 (12)	−0.0011 (14)	−0.0023 (16)
C4	0.0888 (15)	0.107 (2)	0.0824 (17)	0.0020 (13)	−0.0072 (12)	0.0115 (14)
C5	0.0653 (11)	0.1053 (18)	0.0605 (13)	−0.0029 (11)	−0.0064 (9)	−0.0020 (11)
C6	0.0466 (9)	0.0866 (15)	0.0563 (11)	−0.0086 (9)	−0.0051 (8)	−0.0048 (10)
C7	0.0526 (9)	0.0930 (15)	0.0554 (11)	−0.0021 (9)	−0.0110 (8)	−0.0130 (10)
C8	0.0527 (9)	0.0910 (15)	0.0509 (10)	0.0064 (10)	−0.0094 (8)	−0.0077 (9)
C9	0.0487 (9)	0.1015 (17)	0.0505 (10)	0.0041 (10)	−0.0086 (8)	−0.0064 (10)
C10	0.0628 (11)	0.1145 (17)	0.0696 (13)	0.0125 (10)	−0.0170 (9)	−0.0040 (11)
C11	0.0511 (10)	0.1288 (18)	0.0764 (13)	−0.0119 (10)	−0.0170 (9)	−0.0014 (12)
C12	0.0620 (11)	0.0919 (15)	0.0562 (11)	0.0073 (10)	−0.0099 (9)	−0.0055 (10)
C13	0.0590 (10)	0.0832 (14)	0.0497 (10)	0.0020 (9)	−0.0070 (8)	−0.0066 (9)
C14	0.0555 (10)	0.0959 (17)	0.0716 (12)	0.0021 (10)	−0.0187 (9)	−0.0014 (11)
C15	0.0643 (11)	0.0872 (16)	0.0781 (13)	0.0062 (11)	−0.0210 (10)	0.0021 (11)
N1	0.0542 (8)	0.0945 (13)	0.0571 (9)	0.0002 (8)	−0.0174 (7)	−0.0081 (8)
N2	0.0477 (8)	0.1039 (14)	0.0570 (9)	0.0000 (8)	−0.0175 (7)	−0.0055 (8)
N3	0.0579 (9)	0.0914 (13)	0.0557 (9)	0.0025 (8)	−0.0085 (7)	−0.0079 (8)
O1	0.0706 (8)	0.0991 (11)	0.0832 (9)	0.0021 (7)	−0.0401 (7)	−0.0085 (7)

Geometric parameters (Å, º) top

C1—C2	1.379 (3)	C9—C10	1.488 (2)
C1—C6	1.382 (2)	C10—H10A	0.9600
C1—H1	0.9300	C10—H10B	0.9600
C2—C3	1.373 (3)	C10—H10C	0.9600
C2—H2	0.9300	C11—N2	1.464 (2)
C3—C4	1.370 (3)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.366 (3)	C11—H11C	0.9600
C4—H4	0.9300	C12—N3	1.279 (2)
C5—C6	1.384 (2)	C12—C13	1.453 (3)
C5—H5	0.9300	C12—H12	0.9300
C6—N1	1.422 (2)	C13—C14	1.388 (2)
C7—O1	1.2360 (19)	C13—C15ⁱ	1.391 (2)
C7—N1	1.395 (2)	C14—C15	1.361 (2)
C7—C8	1.438 (2)	C14—H14	0.9300
C8—C9	1.369 (2)	C15—C13ⁱ	1.391 (2)
C8—N3	1.390 (2)	C15—H15	0.9300
C9—N2	1.361 (2)	N1—N2	1.4056 (17)

C2—C1—C6	119.3 (2)	H10A—C10—H10B	109.5
C2—C1—H1	120.4	C9—C10—H10C	109.5
C6—C1—H1	120.4	H10A—C10—H10C	109.5
C3—C2—C1	120.0 (2)	H10B—C10—H10C	109.5
C3—C2—H2	120.0	N2—C11—H11A	109.5
C1—C2—H2	120.0	N2—C11—H11B	109.5
C4—C3—C2	120.2 (2)	H11A—C11—H11B	109.5
C4—C3—H3	119.9	N2—C11—H11C	109.5
C2—C3—H3	119.9	H11A—C11—H11C	109.5
C5—C4—C3	120.7 (2)	H11B—C11—H11C	109.5
C5—C4—H4	119.7	N3—C12—C13	122.21 (17)
C3—C4—H4	119.7	N3—C12—H12	118.9
C4—C5—C6	119.3 (2)	C13—C12—H12	118.9
C4—C5—H5	120.4	C14—C13—C15ⁱ	117.43 (17)
C6—C5—H5	120.4	C14—C13—C12	122.44 (16)
C1—C6—C5	120.5 (2)	C15ⁱ—C13—C12	120.13 (17)
C1—C6—N1	120.73 (17)	C15—C14—C13	120.76 (16)
C5—C6—N1	118.80 (17)	C15—C14—H14	119.6
O1—C7—N1	122.90 (17)	C13—C14—H14	119.6
O1—C7—C8	131.90 (17)	C14—C15—C13ⁱ	121.81 (17)
N1—C7—C8	105.18 (15)	C14—C15—H15	119.1
C9—C8—N3	123.15 (18)	C13ⁱ—C15—H15	119.1
C9—C8—C7	108.00 (18)	C7—N1—N2	109.12 (15)
N3—C8—C7	128.68 (15)	C7—N1—C6	123.38 (14)
N2—C9—C8	109.98 (16)	N2—N1—C6	119.21 (14)
N2—C9—C10	121.68 (16)	C9—N2—N1	107.21 (13)
C8—C9—C10	128.3 (2)	C9—N2—C11	124.40 (15)
C9—C10—H10A	109.5	N1—N2—C11	116.47 (16)
C9—C10—H10B	109.5	C12—N3—C8	120.28 (16)

C6—C1—C2—C3	−1.3 (3)	C13—C14—C15—C13ⁱ	0.4 (3)
C1—C2—C3—C4	−0.5 (3)	O1—C7—N1—N2	−173.36 (16)
C2—C3—C4—C5	2.1 (3)	C8—C7—N1—N2	4.94 (18)
C3—C4—C5—C6	−2.0 (3)	O1—C7—N1—C6	−25.5 (3)
C2—C1—C6—C5	1.4 (3)	C8—C7—N1—C6	152.81 (15)
C2—C1—C6—N1	−179.78 (16)	C1—C6—N1—C7	−114.23 (18)
C4—C5—C6—C1	0.3 (3)	C5—C6—N1—C7	64.6 (2)
C4—C5—C6—N1	−178.63 (17)	C1—C6—N1—N2	30.6 (2)
O1—C7—C8—C9	177.28 (19)	C5—C6—N1—N2	−150.49 (15)
N1—C7—C8—C9	−0.80 (19)	C8—C9—N2—N1	6.81 (18)
O1—C7—C8—N3	2.0 (3)	C10—C9—N2—N1	−173.58 (15)
N1—C7—C8—N3	−176.11 (16)	C8—C9—N2—C11	147.84 (16)
N3—C8—C9—N2	171.85 (15)	C10—C9—N2—C11	−32.6 (2)
C7—C8—C9—N2	−3.78 (19)	C7—N1—N2—C9	−7.32 (18)
N3—C8—C9—C10	−7.7 (3)	C6—N1—N2—C9	−156.74 (15)
C7—C8—C9—C10	176.65 (17)	C7—N1—N2—C11	−151.89 (16)
N3—C12—C13—C14	5.7 (3)	C6—N1—N2—C11	58.7 (2)
N3—C12—C13—C15ⁱ	−174.14 (16)	C13—C12—N3—C8	177.92 (15)
C15ⁱ—C13—C14—C15	−0.4 (3)	C9—C8—N3—C12	−170.27 (17)
C12—C13—C14—C15	179.78 (18)	C7—C8—N3—C12	4.4 (3)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11C···O1ⁱⁱ	0.96	2.36	3.321 (2)	179
C11—H11A···O1ⁱⁱⁱ	0.96	2.47	3.375 (3)	157
C12—H12···O1	0.93	2.30	3.002 (2)	132

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

Experimental details

Crystal data
Chemical formula	C₃₀H₂₈N₆O₂
M_r	504.58
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	6.0710 (2), 22.2948 (7), 9.8712 (3)
β (°)	95.147 (2)
V (Å³)	1330.70 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.18 × 0.10 × 0.09

Data collection
Diffractometer	Bruker APEX2 CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9162, 3034, 1545
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.141, 1.03
No. of reflections	3034
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.18

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11C···O1ⁱ	0.96	2.36	3.321 (2)	179
C11—H11A···O1ⁱⁱ	0.96	2.47	3.375 (3)	157
C12—H12···O1	0.93	2.30	3.002 (2)	132

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

Acknowledgements

We thank Jian Dong Fan for collecting the data and Wei Huang for giving us a lot of help.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Guo, F., Bi, C. F., Fan, Y. H. & Xiao, Y. (2007). Asian J. Chem. 3, 1846–1852. Google Scholar
Selvakumar, P. M., Suresh, E. & Subramanian, P. S. (2007). Polyhedron, 26, 749–756. 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
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 64| Part 8| August 2008| Page o1479

doi:10.1107/S1600536808021028

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

1,1′,5,5′-Tetra­methyl-2,2′-di­phenyl-4,4′-[p-phenyl­enebis(methyl­­idyne­nitrilo)]di-1H-pyrazol-3(2H)-one

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,1′,5,5′-Tetramethyl-2,2′-diphenyl-4,4′-[p-phenylenebis(methylidynenitrilo)]di-1H-pyrazol-3(2H)-one