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)
aInstitute of Nuclear Chemistry and Technology, Dorodna 16, 03-195 Warsaw, Poland
*Correspondence e-mail: k.lyczko@ichtj.waw.pl
The 11H12N2O·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).
of the title compound, CRelated 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
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2010); cell 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
https://doi.org/10.1107/S160053681205091X/kj2216sup1.cif
contains datablocks global, I. DOI: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
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.
H atoms were placed in calculated positions with C—H = 0.98 (methyl) or 0.95 Å (aromatic) and were refined isotropically using a riding model with Uiso(H) = 1.5 Ueq(C) for methyl H atoms and Uiso(H) = 1.2 Ueq(C) for aromatic H atoms.
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 PbII 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
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
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.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).
Data collection: CrysAlis PRO (Agilent, 2010); cell
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).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. |
C25H28N4O2·C11H12N2O | F(000) = 1288 |
Mr = 604.74 | Dx = 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 |
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 | Rint = 0.018 |
Detector resolution: 16.0131 pixels mm-1 | θmax = 72.0°, θmin = 4.1° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −4→9 |
Tmin = 0.938, Tmax = 1.000 | l = −45→42 |
12009 measured reflections |
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(Fo2) + (0.0422P)2 + 1.6129P] where P = (Fo2 + 2Fc2)/3 |
6009 reflections | (Δ/σ)max < 0.001 |
414 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C25H28N4O2·C11H12N2O | V = 3107.93 (14) Å3 |
Mr = 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)° |
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) |
Tmin = 0.938, Tmax = 1.000 | Rint = 0.018 |
12009 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.26 e Å−3 |
6009 reflections | Δρmin = −0.31 e Å−3 |
414 parameters |
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 | 0.73885 (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) |
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) |
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) |
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···O3iv | 0.98 | 2.38 | 3.2956 (17) | 155 |
C30—H30A···O3iv | 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 |
Mr | 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) |
Tmin, Tmax | 0.938, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12009, 6009, 5366 |
Rint | 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 |
Δρmax, Δρmin (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).
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···O3iv | 0.98 | 2.38 | 3.2956 (17) | 154.8 |
C30—H30A···O3iv | 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
and Technology for financial support.References
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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 PbII 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.