supplementary materials


ld2106 scheme

Acta Cryst. (2013). E69, o1164    [ doi:10.1107/S1600536813017145 ]

4-(4-Nitrobenzyl)pyridine

D. Taher, F. F. Awwadi and M. H. Kailani

Abstract top

The title compound, C12H10N2O2, has a twisted conformation, with a dihedral angle between the planes of the pyridine and benzene rings of 78.4 (2)°. The nitro group is coplanar with the attached benzene ring within experimental error. The molecules form centrosymmetric dimers via Car-H...O interactions (H...O = 2.49 Å) and the dimers are [pi]-stacked along the b axis [the separation between ring centroids is 3.788 (2) Å].

Comment top

X-Ray structure of the title compound was never reported before in its non-coordinated form, even though several works have been published on it's pyridiunium salts/adducts. The adducts with carboxilic acids were reported for 4-aminobenzoic (Smith et al., 1997) and 5-nitrosalicylic acid (Smith & Wermuth, 2010). Recently, a structure of an adduct with 3-carboxy-4-hydroxybenzenesulfonic acid was also determined (Smith & Wermuth, 2013). The structures of the adducts are dominated by N(pyridine)—H···O hydrogen bonding interactions. In addition, X-ray structure of a zinc complex of the title compound (Diiodidobis[4-(4-nitrobenzyl)pyridine-κN1]zinc) has also been determined (Smith et al., 2011).

The title compound (Fig. 1) gives colorless crystals. The angle between the planes of benzene and pyridine rings is 78.43° and the nitro group is coplanar with the benzene ring. The two aromatic planes are twisted relative to each other, which result in reduction of molecular symmetry from Cs to C1: the dihedral angle C2—C3···C7—C8 is 30.5 (2)°. Two molecular units of the title compound inter-associate through duplex C9—H···O2 hydrogen bonds to form a cyclic dimer (Fig. 2 and Table 1). Then, these dimers are stacked via π···π interactions between benzene rings to form ribbon structure extending parallel to b-axis (Fig. 3); the angle between the two planes, centroid-centroid distance and shift distance are 0°, 3.788 Å and 1.613 Å, respectively, as determined by Olex2 program package (Dolomanov et al., 2009). Subsequently, these ribbons are interdigitated to form the final three-dimensional structure (Fig. 4).

The nitro group of the title compound, was found to be a major factor in determining the interactions in the crystal form, unlike in the previously published structures where the pyridinic nitrogen was the main driving force for amolecular association.

Related literature top

For adducts of the title compound with different organic acids, see: Smith et al. (1997); Smith & Wermuth (2010, 2013). For a zinc complex of the title compound, see: Smith et al. (2011). For the analysis of π-stacking interactions, see: Dolomanov et al. (2009).

Experimental top

Crystals of the title compound were obtained by dissolving 1 mmol of 4-(4-nitrobenzyl) pyridine in 30 ml of hot 96% ethanol. Partial evaporation of the hot-filtered solution at room temperature yielded colourless crystals from which a block section was cleaved for the X-ray analysis.

Refinement top

The structure was solved by direct methods and refined by least squares method on F2 using the SHELXTL program package. All atoms were refined anisotropically. Hydrogen atoms were placed at the calculated positions using a riding model with C(aromatic)— H = 0.95 Å and Uiso(H) = 1.2Ueq(C), and with C(aliphatic)—H = 0.98 Å and Uiso(H) = 1.5Ueq(C). refinement details)

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular unit of the title compound. Thermal ellipsoids are shown at 50% probability.
[Figure 2] Fig. 2. Structure of the cyclic dimer.
[Figure 3] Fig. 3. Illustration of the ribbon structure of the title compound.
[Figure 4] Fig. 4. Illustration of the three dimensional structure of the title compound viewed along the b-axis.
4-(4-Nitrobenzyl)pyridine top
Crystal data top
C12H10N2O2F(000) = 448
Mr = 214.22Dx = 1.350 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 949 reflections
a = 11.4138 (9) Åθ = 3.3–29.0°
b = 6.1241 (5) ŵ = 0.09 mm1
c = 15.5812 (13) ÅT = 293 K
β = 104.561 (9)°Needle, white
V = 1054.13 (15) Å30.4 × 0.2 × 0.15 mm
Z = 4
Data collection top
Agilent Xcalibur Eos
diffractometer
2136 independent reflections
Radiation source: Enhance (Mo) X-ray Source1514 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
Detector resolution: 16.0534 pixels mm-1θmax = 26.3°, θmin = 3.6°
ω scansh = 1314
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 76
Tmin = 0.770, Tmax = 1.000l = 1919
4351 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0401P)2 + 0.1216P]
where P = (Fo2 + 2Fc2)/3
2136 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C12H10N2O2V = 1054.13 (15) Å3
Mr = 214.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.4138 (9) ŵ = 0.09 mm1
b = 6.1241 (5) ÅT = 293 K
c = 15.5812 (13) Å0.4 × 0.2 × 0.15 mm
β = 104.561 (9)°
Data collection top
Agilent Xcalibur Eos
diffractometer
2136 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
1514 reflections with I > 2σ(I)
Tmin = 0.770, Tmax = 1.000Rint = 0.018
4351 measured reflectionsθmax = 26.3°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.106Δρmax = 0.12 e Å3
S = 1.03Δρmin = 0.15 e Å3
2136 reflectionsAbsolute structure: ?
145 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
Special details top

Experimental. Absorption correction CrysAlis PRO (Agilent, 2011). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
N20.13729 (12)0.2522 (2)0.13717 (9)0.0459 (4)
C100.15049 (13)0.1215 (2)0.06150 (10)0.0361 (4)
C90.11079 (14)0.2054 (3)0.02263 (11)0.0413 (4)
H9A0.07570.34330.03170.050*
C70.17562 (14)0.1248 (3)0.08069 (10)0.0391 (4)
O20.09206 (12)0.4333 (2)0.12370 (9)0.0633 (4)
C110.20080 (14)0.0837 (3)0.07671 (11)0.0410 (4)
H11A0.22580.13900.13400.049*
C80.12404 (14)0.0808 (3)0.09329 (11)0.0427 (4)
H8A0.09780.13610.15050.051*
C120.21313 (14)0.2047 (3)0.00541 (11)0.0426 (4)
H12A0.24730.34330.01490.051*
C60.19074 (15)0.2601 (3)0.15842 (11)0.0496 (5)
H6A0.14570.39530.16070.059*
H6B0.15760.18090.21300.059*
O10.17074 (16)0.1747 (2)0.21073 (9)0.0835 (5)
C30.32183 (15)0.3119 (3)0.15136 (10)0.0445 (4)
C40.37349 (17)0.5080 (3)0.11888 (12)0.0555 (5)
H4A0.32630.61680.10280.067*
N10.56897 (15)0.3995 (3)0.13144 (12)0.0712 (5)
C20.39748 (17)0.1617 (3)0.17558 (13)0.0610 (5)
H2A0.36760.02740.19920.073*
C50.49444 (19)0.5428 (4)0.11034 (14)0.0670 (6)
H5A0.52630.67700.08810.080*
C10.51831 (19)0.2128 (4)0.16440 (15)0.0731 (6)
H1B0.56760.10880.18120.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N20.0485 (9)0.0470 (9)0.0436 (9)0.0015 (7)0.0142 (7)0.0001 (7)
C100.0327 (8)0.0392 (9)0.0376 (9)0.0024 (7)0.0108 (7)0.0001 (7)
C90.0387 (9)0.0401 (9)0.0448 (10)0.0031 (7)0.0098 (8)0.0074 (8)
C70.0308 (8)0.0477 (10)0.0398 (9)0.0043 (7)0.0104 (7)0.0016 (8)
O20.0808 (10)0.0477 (8)0.0618 (9)0.0179 (7)0.0189 (7)0.0018 (7)
C110.0430 (9)0.0428 (9)0.0363 (9)0.0032 (8)0.0086 (8)0.0070 (8)
C80.0424 (9)0.0498 (10)0.0350 (9)0.0003 (8)0.0082 (8)0.0064 (8)
C120.0396 (9)0.0385 (9)0.0494 (10)0.0037 (7)0.0109 (8)0.0026 (8)
C60.0413 (10)0.0621 (11)0.0455 (10)0.0024 (8)0.0113 (8)0.0088 (9)
O10.1380 (14)0.0749 (10)0.0378 (8)0.0326 (10)0.0224 (8)0.0078 (7)
C30.0436 (9)0.0551 (11)0.0361 (9)0.0042 (9)0.0126 (8)0.0120 (8)
C40.0519 (11)0.0561 (11)0.0601 (12)0.0023 (9)0.0172 (10)0.0061 (10)
N10.0481 (10)0.0950 (14)0.0719 (12)0.0042 (10)0.0176 (9)0.0145 (11)
C20.0540 (12)0.0668 (13)0.0653 (13)0.0035 (10)0.0211 (10)0.0019 (11)
C50.0585 (13)0.0708 (14)0.0692 (14)0.0117 (12)0.0114 (11)0.0119 (11)
C10.0535 (13)0.0956 (17)0.0759 (15)0.0169 (13)0.0271 (12)0.0053 (14)
Geometric parameters (Å, º) top
N2—O11.2101 (17)C6—C31.506 (2)
N2—O21.2194 (17)C6—H6A0.9700
N2—C101.464 (2)C6—H6B0.9700
C10—C91.374 (2)C3—C41.377 (2)
C10—C111.377 (2)C3—C21.378 (2)
C9—C81.379 (2)C4—C51.370 (3)
C9—H9A0.9300C4—H4A0.9300
C7—C81.383 (2)N1—C51.320 (3)
C7—C121.391 (2)N1—C11.325 (3)
C7—C61.513 (2)C2—C11.382 (3)
C11—C121.372 (2)C2—H2A0.9300
C11—H11A0.9300C5—H5A0.9300
C8—H8A0.9300C1—H1B0.9300
C12—H12A0.9300
O1—N2—O2122.59 (15)C3—C6—H6A109.3
O1—N2—C10118.47 (14)C7—C6—H6A109.3
O2—N2—C10118.93 (14)C3—C6—H6B109.3
C9—C10—C11121.90 (15)C7—C6—H6B109.3
C9—C10—N2119.20 (14)H6A—C6—H6B108.0
C11—C10—N2118.89 (14)C4—C3—C2116.31 (17)
C10—C9—C8118.60 (15)C4—C3—C6122.41 (16)
C10—C9—H9A120.7C2—C3—C6121.27 (17)
C8—C9—H9A120.7C5—C4—C3119.94 (18)
C8—C7—C12118.32 (15)C5—C4—H4A120.0
C8—C7—C6121.02 (15)C3—C4—H4A120.0
C12—C7—C6120.66 (15)C5—N1—C1115.11 (18)
C12—C11—C10118.48 (15)C3—C2—C1119.2 (2)
C12—C11—H11A120.8C3—C2—H2A120.4
C10—C11—H11A120.8C1—C2—H2A120.4
C9—C8—C7121.25 (15)N1—C5—C4124.7 (2)
C9—C8—H8A119.4N1—C5—H5A117.6
C7—C8—H8A119.4C4—C5—H5A117.6
C11—C12—C7121.44 (15)N1—C1—C2124.7 (2)
C11—C12—H12A119.3N1—C1—H1B117.7
C7—C12—H12A119.3C2—C1—H1B117.7
C3—C6—C7111.59 (13)
O1—N2—C10—C9178.75 (15)C6—C7—C12—C11179.59 (14)
O2—N2—C10—C90.5 (2)C8—C7—C6—C3119.47 (17)
O1—N2—C10—C110.3 (2)C12—C7—C6—C360.7 (2)
O2—N2—C10—C11179.55 (15)C7—C6—C3—C498.12 (19)
C11—C10—C9—C81.2 (2)C7—C6—C3—C280.4 (2)
N2—C10—C9—C8179.84 (13)C2—C3—C4—C51.5 (3)
C9—C10—C11—C121.2 (2)C6—C3—C4—C5177.18 (16)
N2—C10—C11—C12179.81 (13)C4—C3—C2—C11.4 (3)
C10—C9—C8—C70.2 (2)C6—C3—C2—C1177.24 (17)
C12—C7—C8—C90.6 (2)C1—N1—C5—C41.2 (3)
C6—C7—C8—C9179.57 (14)C3—C4—C5—N10.1 (3)
C10—C11—C12—C70.3 (2)C5—N1—C1—C21.3 (3)
C8—C7—C12—C110.6 (2)C3—C2—C1—N10.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9A···O2i0.932.493.302 (2)146
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC12H10N2O2
Mr214.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)11.4138 (9), 6.1241 (5), 15.5812 (13)
β (°) 104.561 (9)
V3)1054.13 (15)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.4 × 0.2 × 0.15
Data collection
DiffractometerAgilent Xcalibur Eos
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2011)
Tmin, Tmax0.770, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
4351, 2136, 1514
Rint0.018
(sin θ/λ)max1)0.624
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.106, 1.03
No. of reflections2136
No. of parameters145
No. of restraints0
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.12, 0.15

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9A···O2i0.9302.49263.3018 (20)145.57
Symmetry code: (i) x, y+1, z.
Acknowledgements top

The authors thank the University of Jordan and Hamdi Mango Center for Scientific Research for providing support and time to collect the single-crystal X-ray diffraction data set.

references
References top

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Smith, G., Lynch, D. E., Byriel, K. A. & Kennard, C. H. L. (1997). J. Chem. Crystallogr. 27, 307–317.

Smith, G. & Wermuth, U. D. (2010). Acta Cryst. E66, o1173.

Smith, G. & Wermuth, U. D. (2013). Acta Cryst. E69, o206.

Smith, G., Wermuth, U. D. & Williams, M. L. (2011). Acta Cryst. E67, m359.