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4-Nitro­phenol and 4-methyl­pyridine form a 1:1 hydrogen-bonded dimer, C6H5NO3.C6H7N, with the mol­ecules linked by an O-H...N hydrogen bond [O...N 2.668 (2) Å]. The dihedral angle between the phenyl and pyridine ring is 57.8 (4)°. The dimers pack in a herring-bone structure in the crystal lattice.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100001074/qb0172sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001074/qb0172Isup2.hkl
Contains datablock I

CCDC reference: 142946

Comment top

The phenol–pyridine solution systems have been intensively studied by various means (Emsley, 1968; Moreau Descoings et al., 1985), focusing on the tautomerization (Ratajczak et al., 1965; Nouwen et al., 1973) between hydrogen bonds of O—H···N and N+—H···O. Of equivalently interesting is to reveal the hydrogen-bond patterns and their nature in solid state. As part of the investigation on the complex of pyridine with phenol in solid state, the crystal structure of the complex of 4-nitrophenol (NP) and 4-methylpyridine (MPy) has been determined, and reported herein.

In the crystallographic structure, the entities of NP and MPy are linked by an O1—HO1···N2 hydrogen bond [O1—N2 2.668 (2) Å, HO1···N2 1.74 (2) Å and O1—HO1···N2 174 (2)°]. The base of MPy does not appear to be protonated by the NP. In comparison with the original pyridine, while the angle of C—N—C in the ring of pyridinium is expanded, both of N—C—C are reduced. These feature are obviously showed in the 1:1 crystalline complexes (Malarski et al., 1987, 1996) of MPy and pentachlorophenol (MPy–PCP) respectively at 80 and 295 K. The bond angle values of C—N—C, N—-C–C in the 4-methylpyridinium of MPy–PCP at 80 K have been revealed to be 119.9 (2), 121.3 (2) and 121.4 (2)°, respectively, and in the MPy of MPy–PCP at 295 K to be 118.0 (4), 122.3 (4) and 122.5 (4)°, respectively. The 4-methylpyridinium in it's trifluoroacetate (Dega-Szafran et al., 1992) displays itself with angles of C—N—C [120.5 (3)°] and N—C—C [119.9 (4) and 120.4 (4)°]. The MPy in the title complex with angles of C11—N2—C7 [116.1 (2)°], N2—C7—C8 [123.6 (2)°] and N2—C11—C10 [123.7 (2)°] demonstrate obviously unprotonated features. The O1—C1 length value of 1.344 (2) %A, with a minute deviation from 1.351 Å for crystal NP (Coppens et al., 1965), is closed to the average C—O length value of 1.36 Å for phenol (Sakurai, 1962), and deviated obviously from average C—O value of 1.255 Å for phenolate (Sawka-Dobrowolska et al., 1995). Such a value for the C1—O1 bond length with the angle C1—O1—H [116.8°] point to some contribution of sp2 hybridization of the O atom and the double-bond character of the C1—O1 bond in the title complex. The N1—C4 bond length [1.449 (2) Å] with the angle sum around N1 (360°) indicate also some double-bond character (Kawai et al., 1976).

The geometrical arrangement in the crystal structure is characterized by the formation of herring-bone structure of MPy and NP. The nitro group is coplanar with the phenyl ring. The dihedral angle between phenol phenyl ring and pyridine ring is 57.8°. While, one molecule pair of NP and MPy are connected by hydrogen bond of O1—N2 to form such a structure with an orientation, another pair are arranged in the same fashion except for an inverse orientation to the former pair.

Experimental top

NP (0.01 mol) was dissolved in MPy (0.02 mol) by heating to a temperature where a clear solution resulted. Single crystals of the title complex was formed by standing of the resulting solution overnight at 293 K.

Refinement top

The carboxyl H-atom coordinates were refined isotropically; all other H atoms were treated as riding atoms.

Computing details top

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS (Siemens, 1991); data reduction: SHELXTL-Plus (Sheldrick, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 1990).

1:1 Complex of 4-Nitrophenol and 4-Methyl-Pyridine top
Crystal data top
C6H5NO3·C6H7NDx = 1.325 Mg m3
Mr = 232.24Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 29 reflections
a = 7.199 (1) Åθ = 3.3–17.3°
b = 12.896 (1) ŵ = 0.10 mm1
c = 25.077 (3) ÅT = 296 K
V = 2328.1 (5) Å3Prism, pale yellow
Z = 80.44 × 0.36 × 0.28 mm
F(000) = 976
Data collection top
Bruker P4
diffractometer
Rint = 0.024
Radiation source: normal-focus sealed tubeθmax = 26.0°, θmin = 1.6°
Graphite monochromatorh = 18
ω scansk = 115
3576 measured reflectionsl = 130
2280 independent reflections3 standard reflections every 97 reflections
893 reflections with I > 2σ(I) intensity decay: 3.9%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.077 w = 1/[σ2(Fo2) + (0.0265P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.81(Δ/σ)max = 0.001
2280 reflectionsΔρmax = 0.15 e Å3
160 parametersΔρmin = 0.13 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0071 (5)
Crystal data top
C6H5NO3·C6H7NV = 2328.1 (5) Å3
Mr = 232.24Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.199 (1) ŵ = 0.10 mm1
b = 12.896 (1) ÅT = 296 K
c = 25.077 (3) Å0.44 × 0.36 × 0.28 mm
Data collection top
Bruker P4
diffractometer
Rint = 0.024
3576 measured reflections3 standard reflections every 97 reflections
2280 independent reflections intensity decay: 3.9%
893 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.077H atoms treated by a mixture of independent and constrained refinement
S = 0.81Δρmax = 0.15 e Å3
2280 reflectionsΔρmin = 0.13 e Å3
160 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
xyzUiso*/Ueq
O10.0088 (2)0.05759 (13)0.16674 (6)0.0693 (5)
O20.2113 (3)0.25521 (14)0.01202 (6)0.0914 (7)
O30.3181 (3)0.11665 (12)0.04795 (6)0.0933 (7)
N10.2415 (3)0.16134 (17)0.01114 (8)0.0660 (6)
N20.0390 (3)0.26345 (13)0.17283 (8)0.0635 (6)
C10.0674 (3)0.00810 (17)0.12268 (9)0.0507 (6)
C20.0415 (3)0.09829 (16)0.12053 (8)0.0532 (6)
H20.01400.13240.14910.064*
C30.0971 (3)0.15370 (16)0.07665 (8)0.0528 (6)
H30.07720.22490.07490.063*
C40.1827 (3)0.10255 (16)0.03511 (8)0.0478 (6)
C50.2109 (3)0.00320 (18)0.03631 (8)0.0562 (6)
H50.26910.03670.00800.067*
C60.1515 (3)0.05842 (16)0.08014 (8)0.0560 (6)
H60.16780.12990.08120.067*
C70.0486 (3)0.3204 (2)0.13657 (9)0.0671 (8)
H70.10150.28670.10750.081*
C80.0654 (3)0.42668 (19)0.13959 (9)0.0621 (7)
H80.12670.46290.11280.074*
C90.0085 (3)0.47896 (16)0.18222 (9)0.0520 (6)
C100.0983 (3)0.42021 (18)0.22001 (8)0.0598 (7)
H100.14960.45190.24990.072*
C110.1121 (4)0.31479 (18)0.21363 (9)0.0640 (7)
H110.17630.27720.23930.077*
C120.0103 (4)0.59459 (15)0.18725 (8)0.0826 (8)
H12A0.08140.62020.21170.099*
H12B0.00760.62610.15300.099*
H12C0.13210.61130.20030.099*
H0.020 (4)0.1296 (18)0.1665 (9)0.109 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0913 (13)0.0506 (10)0.0661 (10)0.0026 (11)0.0165 (10)0.0085 (10)
O20.1372 (18)0.0547 (10)0.0824 (12)0.0053 (12)0.0092 (12)0.0144 (10)
O30.1336 (18)0.0831 (13)0.0632 (10)0.0157 (13)0.0272 (12)0.0060 (10)
N10.0791 (17)0.0646 (15)0.0542 (13)0.0135 (14)0.0015 (12)0.0033 (13)
N20.0741 (16)0.0534 (12)0.0630 (12)0.0018 (12)0.0046 (12)0.0065 (12)
C10.0505 (16)0.0491 (14)0.0525 (14)0.0003 (13)0.0029 (13)0.0014 (13)
C20.0544 (16)0.0479 (15)0.0574 (14)0.0045 (13)0.0020 (14)0.0047 (12)
C30.0564 (16)0.0424 (13)0.0594 (14)0.0003 (13)0.0090 (14)0.0015 (13)
C40.0521 (16)0.0475 (15)0.0440 (13)0.0051 (13)0.0040 (13)0.0025 (12)
C50.0599 (17)0.0556 (15)0.0532 (15)0.0008 (14)0.0027 (14)0.0076 (13)
C60.0658 (17)0.0436 (14)0.0587 (14)0.0052 (14)0.0009 (13)0.0032 (12)
C70.068 (2)0.0723 (19)0.0607 (17)0.0070 (16)0.0032 (15)0.0158 (14)
C80.0597 (18)0.0634 (17)0.0630 (16)0.0056 (15)0.0038 (14)0.0047 (13)
C90.0471 (14)0.0492 (14)0.0597 (14)0.0021 (13)0.0101 (13)0.0043 (13)
C100.0663 (18)0.0589 (16)0.0541 (15)0.0071 (15)0.0025 (14)0.0088 (13)
C110.0738 (19)0.0614 (17)0.0569 (16)0.0022 (16)0.0027 (15)0.0059 (13)
C120.092 (2)0.0558 (15)0.1002 (19)0.0003 (16)0.0133 (19)0.0093 (14)
Geometric parameters (Å, º) top
O1—C11.344 (2)C3—C41.379 (2)
O2—N11.230 (2)C4—C51.379 (3)
O3—N11.220 (2)C5—C61.378 (3)
N1—C41.449 (2)C7—C81.378 (3)
N2—C111.327 (2)C8—C91.371 (3)
N2—C71.328 (2)C9—C101.374 (3)
C1—C21.386 (2)C9—C121.503 (2)
C1—C61.388 (2)C10—C111.373 (2)
C2—C31.372 (2)
O3—N1—O2122.1 (2)C5—C4—N1119.5 (2)
O3—N1—C4119.4 (2)C6—C5—C4118.9 (2)
O2—N1—C4118.5 (2)C5—C6—C1120.5 (2)
C11—N2—C7116.1 (2)N2—C7—C8123.6 (2)
O1—C1—C2117.4 (2)C9—C8—C7119.9 (2)
O1—C1—C6123.2 (2)C8—C9—C10116.7 (2)
C2—C1—C6119.5 (2)C8—C9—C12121.2 (2)
C3—C2—C1120.5 (2)C10—C9—C12122.1 (2)
C2—C3—C4119.17 (19)C11—C10—C9120.0 (2)
C3—C4—C5121.5 (2)N2—C11—C10123.7 (2)
C3—C4—N1119.0 (2)
O1—C1—C2—C3179.66 (19)C4—C5—C6—C11.0 (3)
C6—C1—C2—C30.4 (3)O1—C1—C6—C5179.1 (2)
C1—C2—C3—C41.3 (3)C2—C1—C6—C50.8 (3)
C2—C3—C4—C51.1 (3)C11—N2—C7—C80.1 (4)
C2—C3—C4—N1179.92 (19)N2—C7—C8—C90.9 (4)
O3—N1—C4—C3179.7 (2)C7—C8—C9—C100.5 (3)
O2—N1—C4—C30.7 (3)C7—C8—C9—C12178.9 (2)
O3—N1—C4—C51.3 (3)C8—C9—C10—C110.7 (3)
O2—N1—C4—C5178.3 (2)C12—C9—C10—C11180.0 (2)
C3—C4—C5—C60.1 (3)C7—N2—C11—C101.2 (4)
N1—C4—C5—C6178.89 (19)C9—C10—C11—N21.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H···N20.93 (2)1.74 (2)2.668 (2)174 (2)

Experimental details

Crystal data
Chemical formulaC6H5NO3·C6H7N
Mr232.24
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)7.199 (1), 12.896 (1), 25.077 (3)
V3)2328.1 (5)
Z8
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.44 × 0.36 × 0.28
Data collection
DiffractometerBruker P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3576, 2280, 893
Rint0.024
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.077, 0.81
No. of reflections2280
No. of parameters160
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.15, 0.13

Computer programs: XSCANS (Siemens, 1991), SHELXTL-Plus (Sheldrick, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) top
O1—C11.344 (2)N1—C41.449 (2)
O2—N11.230 (2)N2—C111.327 (2)
O3—N11.220 (2)N2—C71.328 (2)
O3—N1—O2122.1 (2)C11—N2—C7116.1 (2)
O3—N1—C4119.4 (2)N2—C7—C8123.6 (2)
O2—N1—C4118.5 (2)N2—C11—C10123.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H···N20.93 (2)1.74 (2)2.668 (2)174 (2)
 

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