organic compounds
of tetrakis(1-oxidopyridin-2-yl)methane methanol tetrasolvate
aInstitute of Natural Sciences, Senshu University, Higashimita 2-1-1, Kawasaki, Kanagawa 214-8580, Japan, and bDepartment of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
*Correspondence e-mail: matsumoto@isc.senshu-u.ac.jp
The 21H16N4O4·4CH3OH, consists of a quarter molecule of tetrakis(1-oxidopyridin-2-yl)methane and one methanol solvent molecule. In the crystal, the pyridine N-oxide derivative is located about a fourfold rotoinversion axis and exhibits S4 symmetry along the c axis. An intermolecular O—H⋯O hydrogen bond is observed between the O atom of the pyridine N-oxide and the OH group of the methanol. An intermolecular C—H⋯O bond is also observed between adjacent pyridine N-oxide rings.
of the title compound, CKeywords: crystal structure; pyridine N-oxide; S4 symmetry; hydrogen bonding.
CCDC reference: 1423138
1. Related literature
For aspects of pyridine N-oxides, see: Katritzky & Lagowski (1971). For reviews of metal complexes of pyridine N-oxides, see: Orchin & Schmidt (1968); Carlin & De Jongh (1986). For the synthesis of the title compound, see: Matsumoto et al. (2003). For coordination polymers of pyridine N-oxides, see: Henkelis et al. (2012). For structures of related molecules, see: Betz et al. (2011); Matsumoto et al. (2014). For the effect of the formation of hydrogen bonds on the N—O bond length of pyridine N-oxides, see: Eichhorn (1987).
2. Experimental
2.1. Crystal data
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2.2. Data collection
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2.3. Refinement
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Data collection: PROCESS-AUTO (Rigaku, 1998); cell PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Yadokari-XG 2009 (Wakita, 2001) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Yadokari-XG 2009 and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 1423138
10.1107/S2056989015016862/is5417sup1.cif
contains datablocks I, Global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016862/is5417Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015016862/is5417Isup3.cml
To a solution of tetrakis(pyridin-2-yl)methane (100 mg, 0.3 mmol) in acetic acid (4.5 mL) was added 30% aqueous solution of hydrogen peroxide (66 mmol). The mixture was heated to 90 °C for 2.5 hours. After cooling to room temperature, acetone (20 mL) was added. When the mixture was stirred a few minutes, white precipitates appeared. Collection of the precipitate by filtration gave the title compound (120 mg, 46%) as colourless solid. The single crystals were prepared by slow evaporation of a solution of the title compound in methanol. The obtained single crystals were highly efflorescent and the exposure of the crystal to the air should be avoided.
H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms, and with O—H = 0.84 Å and Uiso(H) = 1.5Ueq(O) for hydroxyl H atoms.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell
PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Yadokari-XG 2009 (Wakita, 2001) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Yadokari-XG 2009 (Wakita, 2001) and publCIF (Westrip, 2010).C21H16N4O4·4CH4O | Dx = 1.337 Mg m−3 |
Mr = 516.54 | Mo Kα radiation, λ = 0.71075 Å |
Tetragonal, I41/a | Cell parameters from 9662 reflections |
a = 14.4474 (4) Å | θ = 3.6–27.4° |
c = 12.2965 (5) Å | µ = 0.10 mm−1 |
V = 2566.62 (18) Å3 | T = 200 K |
Z = 4 | Prism, colourless |
F(000) = 1096 | 0.2 × 0.2 × 0.1 mm |
Rigaku R-AXIS RAPID diffractometer | Rint = 0.031 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.4°, θmin = 3.6° |
ω scans | h = −18→18 |
12321 measured reflections | k = −18→18 |
1470 independent reflections | l = −15→15 |
1289 reflections with I > 2σ(I) |
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) = 0.138 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0821P)2 + 1.7364P] where P = (Fo2 + 2Fc2)/3 |
1470 reflections | (Δ/σ)max < 0.001 |
86 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C21H16N4O4·4CH4O | Z = 4 |
Mr = 516.54 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.10 mm−1 |
a = 14.4474 (4) Å | T = 200 K |
c = 12.2965 (5) Å | 0.2 × 0.2 × 0.1 mm |
V = 2566.62 (18) Å3 |
Rigaku R-AXIS RAPID diffractometer | 1289 reflections with I > 2σ(I) |
12321 measured reflections | Rint = 0.031 |
1470 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.40 e Å−3 |
1470 reflections | Δρmin = −0.25 e Å−3 |
86 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 was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0000 | 0.2500 | 0.6250 | 0.0172 (5) | |
C2 | −0.06345 (8) | 0.18960 (8) | 0.69738 (9) | 0.0181 (3) | |
C3 | −0.15822 (8) | 0.17917 (8) | 0.68249 (10) | 0.0218 (3) | |
H1 | −0.1873 | 0.2091 | 0.6228 | 0.026* | |
C4 | −0.21147 (9) | 0.12608 (9) | 0.75266 (11) | 0.0263 (3) | |
H2 | −0.2762 | 0.1198 | 0.7416 | 0.032* | |
C5 | −0.16814 (10) | 0.08235 (10) | 0.83934 (12) | 0.0299 (4) | |
H3 | −0.2030 | 0.0458 | 0.8887 | 0.036* | |
C6 | −0.07458 (9) | 0.09250 (10) | 0.85293 (11) | 0.0276 (3) | |
H4 | −0.0449 | 0.0623 | 0.9120 | 0.033* | |
C7 | 0.14412 (17) | 0.16009 (17) | 1.05514 (18) | 0.0626 (6) | |
H6 | 0.0822 | 0.1835 | 1.0727 | 0.094* | |
H7 | 0.1792 | 0.2082 | 1.0169 | 0.094* | |
H8 | 0.1764 | 0.1433 | 1.1224 | 0.094* | |
N1 | −0.02328 (7) | 0.14510 (7) | 0.78324 (8) | 0.0211 (3) | |
O1 | 0.06661 (6) | 0.15169 (7) | 0.79946 (8) | 0.0279 (3) | |
O2 | 0.13633 (12) | 0.08248 (11) | 0.98897 (12) | 0.0639 (5) | |
H5 | 0.1193 | 0.0987 | 0.9265 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0179 (7) | 0.0179 (7) | 0.0159 (10) | 0.000 | 0.000 | 0.000 |
C2 | 0.0194 (6) | 0.0181 (5) | 0.0167 (6) | 0.0004 (4) | 0.0014 (4) | 0.0005 (4) |
C3 | 0.0202 (6) | 0.0224 (6) | 0.0230 (6) | 0.0003 (4) | −0.0006 (4) | −0.0001 (5) |
C4 | 0.0195 (6) | 0.0286 (7) | 0.0308 (7) | −0.0018 (5) | 0.0037 (5) | −0.0003 (5) |
C5 | 0.0275 (7) | 0.0321 (7) | 0.0300 (7) | −0.0014 (5) | 0.0095 (5) | 0.0067 (5) |
C6 | 0.0287 (7) | 0.0315 (7) | 0.0225 (6) | 0.0021 (5) | 0.0039 (5) | 0.0091 (5) |
C7 | 0.0630 (13) | 0.0783 (15) | 0.0464 (11) | −0.0129 (11) | −0.0033 (9) | −0.0051 (10) |
N1 | 0.0194 (5) | 0.0251 (5) | 0.0186 (5) | 0.0015 (4) | 0.0009 (4) | 0.0029 (4) |
O1 | 0.0183 (5) | 0.0382 (6) | 0.0271 (5) | 0.0004 (4) | −0.0033 (3) | 0.0090 (4) |
O2 | 0.0954 (12) | 0.0553 (9) | 0.0411 (8) | 0.0033 (7) | −0.0273 (7) | 0.0119 (6) |
C1—C2 | 1.5472 (11) | C5—C6 | 1.3698 (19) |
C1—C2i | 1.5472 (11) | C5—H3 | 0.9500 |
C1—C2ii | 1.5472 (11) | C6—N1 | 1.3643 (16) |
C1—C2iii | 1.5472 (11) | C6—H4 | 0.9500 |
C2—N1 | 1.3656 (16) | C7—O2 | 1.390 (3) |
C2—C3 | 1.3895 (16) | C7—H6 | 0.9800 |
C3—C4 | 1.3874 (18) | C7—H7 | 0.9800 |
C3—H1 | 0.9500 | C7—H8 | 0.9800 |
C4—C5 | 1.3881 (19) | N1—O1 | 1.3174 (14) |
C4—H2 | 0.9500 | O2—H5 | 0.8400 |
C2—C1—C2i | 109.77 (9) | C6—C5—H3 | 120.3 |
C2—C1—C2ii | 109.32 (4) | C4—C5—H3 | 120.3 |
C2i—C1—C2ii | 109.32 (4) | N1—C6—C5 | 121.26 (12) |
C2—C1—C2iii | 109.32 (4) | N1—C6—H4 | 119.4 |
C2i—C1—C2iii | 109.32 (4) | C5—C6—H4 | 119.4 |
C2ii—C1—C2iii | 109.77 (9) | O2—C7—H6 | 109.5 |
N1—C2—C3 | 118.00 (11) | O2—C7—H7 | 109.5 |
N1—C2—C1 | 117.29 (9) | H6—C7—H7 | 109.5 |
C3—C2—C1 | 124.69 (10) | O2—C7—H8 | 109.5 |
C4—C3—C2 | 121.63 (11) | H6—C7—H8 | 109.5 |
C4—C3—H1 | 119.2 | H7—C7—H8 | 109.5 |
C2—C3—H1 | 119.2 | O1—N1—C6 | 118.73 (10) |
C3—C4—C5 | 118.62 (12) | O1—N1—C2 | 120.13 (10) |
C3—C4—H2 | 120.7 | C6—N1—C2 | 121.13 (11) |
C5—C4—H2 | 120.7 | C7—O2—H5 | 109.5 |
C6—C5—C4 | 119.34 (12) | ||
C2i—C1—C2—N1 | −45.51 (8) | C3—C4—C5—C6 | −0.2 (2) |
C2ii—C1—C2—N1 | 74.40 (6) | C4—C5—C6—N1 | 0.3 (2) |
C2iii—C1—C2—N1 | −165.42 (10) | C5—C6—N1—O1 | −179.29 (12) |
C2i—C1—C2—C3 | 133.05 (13) | C5—C6—N1—C2 | 0.0 (2) |
C2ii—C1—C2—C3 | −107.04 (14) | C3—C2—N1—O1 | 178.83 (10) |
C2iii—C1—C2—C3 | 13.14 (11) | C1—C2—N1—O1 | −2.51 (15) |
N1—C2—C3—C4 | 0.59 (18) | C3—C2—N1—C6 | −0.48 (18) |
C1—C2—C3—C4 | −177.96 (10) | C1—C2—N1—C6 | 178.18 (10) |
C2—C3—C4—C5 | −0.2 (2) |
Symmetry codes: (i) −x, −y+1/2, z; (ii) −y+1/4, x+1/4, −z+5/4; (iii) y−1/4, −x+1/4, −z+5/4. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H5···O1 | 0.84 | 1.90 | 2.7285 (15) | 169 |
C4—H2···O1iv | 0.95 | 2.37 | 3.290 (2) | 163 |
Symmetry code: (iv) x−1/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H5···O1 | 0.84 | 1.90 | 2.7285 (15) | 169 |
C4—H2···O1i | 0.95 | 2.37 | 3.290 (2) | 163 |
Symmetry code: (i) x−1/2, y, −z+3/2. |
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Research (No. 24550049) from the Japan Society for the Promotion of Science.
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Pyridine N-oxides are one of the most common heterocyclic N-oxides and their physical and chemical properties are studied in detail (Katritzky & Lagowski, 1971). Pyridine N-oxides are the important compounds not only as the precursors of the substituted pyridine derivatives but also as the ligand molecules for the metal complexes (Orchin & Schmidt, 1968; Carlin & De Jongh, 1986). Recently, the bridging ligands containing more than two pyridine N-oxide groups were explored (Henkelis et al., 2012). In the course of our investigation of tetrakis(pyridin-2-yl)methane (Matsumoto et al., 2003), we are interested in the corresponding N-oxides as the bridging ligand and now we report the crystal structure of the title compound (Fig. 1). The bond lengths and angles of pyridine rings are similar to those of 2-methylpyridine N-oxide (Betz et al., 2011). The C1—C2 bond length [1.5472 (11) Å] is similar to that of tetrakis(pyridin-2-yl)methane [1.545 (2) Å] (Matsumoto et al., 2014) and the prominent C1—C2 bond elongation by N-oxidation is not observed. The N—O bond length [1.3174 (14) Å] is also normal value in considering the formation of hydrogen bond with methanol molecule (Eichhorn, 1987). The interatomic distance of hydrogen bond is O1···H5 = 1.90 Å [O1···O2 = 2.7285 (15) Å]. An intermolecular C—H···O bond is also observed between the adjacent pyridine N-oxide rings [C4···H2 = 2.37 Å, O1···O2 = 3.290 (2) Å; Table 1].