Buy article online - an online subscription or single-article purchase is required to access this article.
A versatile approach for the synthesis of
N-(4-methylbenzyl)benzamide, C
15H
15NO, using CuI as catalyst has been reported. Single crystals of the synthesized compound were grown using the slow evaporation solution technique. The crystal structure of the
N-(4-methylbenzyl)benzamide crystals has been determined by single-crystal X-ray diffraction. The compound crystallizes in an orthorhombic lattice, noncentrosymmetric space group
Pna2
1. The crystal structure is stabilized by intermolecular N—H
O hydrogen bonds and weak C—H
π interactions to form layers parallel to the
a axis. A user-friendly approach based on centre of mass propagation vector theory was used to predict the crystal morphology. The framework developed here utilizes the concept of intermolecular bond strength to discern the crystal morphology. Fourier transform IR, NMR and high-resolution mass spectrometry analytical techniques were used for the identification of functional groups and confirmation of the structure of the title compound. All of the intermolecular interactions present in the crystal structure, including the C—H
π, C—H
O and N—H
O interactions, were investigated and confirmed by molecular Hirshfeld surface analysis. From linear optical spectroscopy, the transmittance, optical band gap and UV cutoff wavelength were determined. The photoluminescence emission spectrum was recorded for a grown crystal. Dielectric measurements were performed at room temperature for various frequencies. The mechanical strength of the (001) plane of the title compound was measured using the Vickers micro-hardness technique. A piezo-coefficient of 15 pC N
−1 was found along the (001) plane of the title crystals. The thermal stability and melting point were also investigated. In addition, density functional theory simulations were used to calculate the optimized molecular geometry and the UV–vis spectrum, and to determine the highest occupied molecular orbital/lowest unoccupied molecular orbital energy gap. The results show that
N-(4-methylbenzyl)benzamide is a potential candidate for multifunctional optical and piezoelectric crystals.
Supporting information
CCDC reference: 1524601
Program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).
Crystal data top
C15H15NO | Dx = 1.195 Mg m−3 |
Mr = 225.28 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 1346 reflections |
a = 9.5277 (8) Å | θ = 3.3–18.9° |
b = 11.1555 (11) Å | µ = 0.08 mm−1 |
c = 11.7848 (10) Å | T = 293 K |
V = 1252.6 (2) Å3 | Block, colourless |
Z = 4 | 0.5 × 0.5 × 0.5 mm |
F(000) = 480 | |
Data collection top
Xcalibur, Sapphire3 diffractometer | 1322 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.108 |
Absorption correction: multi-scan CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug 2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. | θmax = 29.5°, θmin = 3.3° |
Tmin = 0.713, Tmax = 1.000 | h = −12→11 |
16911 measured reflections | k = −14→14 |
3189 independent reflections | l = −16→16 |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.015P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.063 | (Δ/σ)max < 0.001 |
wR(F2) = 0.108 | Δρmax = 0.12 e Å−3 |
S = 0.97 | Δρmin = −0.12 e Å−3 |
3189 reflections | Extinction correction: SHELXL-2016/6 (Sheldrick 2016), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
156 parameters | Extinction coefficient: 0.0122 (14) |
1 restraint | Absolute structure: Flack x determined using 401 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −1.9 (10) |
Hydrogen site location: inferred from neighbouring sites | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. olex2_refinement_description
1. Fixed Uiso
At 1.2 times of:
All C(H) groups, All C(H,H) groups, All N(H) groups
At 1.5 times of:
All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
C8(H8A,H8B)
2.b Aromatic/amide H refined with riding coordinates:
C14(H14), N1(H1), C13(H13), C5(H5), C1(H1A), C10(H10), C11(H11), C3(H3),
C2(H2), C4(H4)
2.c Idealised Me refined as rotating group:
C15(H15A,H15B,H15C) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.0275 (3) | −0.6733 (3) | −0.3283 (3) | 0.0677 (10) | |
C6 | 0.1316 (5) | −0.6668 (4) | −0.1749 (4) | 0.0493 (12) | |
C14 | 0.3313 (5) | −0.7751 (4) | −0.6445 (4) | 0.0600 (13) | |
H14 | 0.314021 | −0.856900 | −0.650694 | 0.072* | |
C9 | 0.2651 (5) | −0.7104 (5) | −0.5608 (4) | 0.0537 (12) | |
N1 | 0.1902 (4) | −0.7411 (4) | −0.3621 (3) | 0.0627 (12) | |
H1 | 0.272632 | −0.752847 | −0.334489 | 0.075* | |
C13 | 0.4235 (5) | −0.7207 (5) | −0.7201 (4) | 0.0645 (15) | |
H13 | 0.466828 | −0.766568 | −0.775959 | 0.077* | |
C7 | 0.0919 (5) | −0.6947 (4) | −0.2950 (4) | 0.0544 (13) | |
C5 | 0.2463 (5) | −0.7184 (4) | −0.1217 (4) | 0.0679 (15) | |
H5 | 0.303957 | −0.770560 | −0.161953 | 0.081* | |
C1 | 0.0506 (5) | −0.5895 (4) | −0.1140 (5) | 0.0654 (14) | |
H1A | −0.026841 | −0.554057 | −0.148366 | 0.079* | |
C8 | 0.1647 (5) | −0.7730 (5) | −0.4807 (4) | 0.0661 (15) | |
H8A | 0.069162 | −0.751564 | −0.500657 | 0.079* | |
H8B | 0.174434 | −0.859003 | −0.489598 | 0.079* | |
C10 | 0.2939 (5) | −0.5903 (5) | −0.5534 (5) | 0.0679 (14) | |
H10 | 0.251583 | −0.544295 | −0.497188 | 0.082* | |
C12 | 0.4511 (5) | −0.6005 (6) | −0.7134 (4) | 0.0666 (15) | |
C11 | 0.3858 (6) | −0.5373 (5) | −0.6292 (5) | 0.0767 (17) | |
H11 | 0.403762 | −0.455626 | −0.622637 | 0.092* | |
C3 | 0.1947 (6) | −0.6146 (5) | 0.0502 (5) | 0.0813 (18) | |
H3 | 0.216023 | −0.596478 | 0.125256 | 0.098* | |
C2 | 0.0811 (6) | −0.5627 (5) | −0.0019 (5) | 0.0768 (17) | |
H2 | 0.024611 | −0.509477 | 0.038140 | 0.092* | |
C15 | 0.5490 (6) | −0.5395 (6) | −0.7953 (5) | 0.102 (2) | |
H15A | 0.591896 | −0.598406 | −0.843504 | 0.152* | |
H15B | 0.620461 | −0.497520 | −0.753825 | 0.152* | |
H15C | 0.497103 | −0.483577 | −0.840860 | 0.152* | |
C4 | 0.2758 (6) | −0.6931 (5) | −0.0095 (5) | 0.0846 (19) | |
H4 | 0.351754 | −0.729915 | 0.025656 | 0.102* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0413 (19) | 0.097 (3) | 0.065 (2) | 0.0048 (19) | −0.0082 (18) | 0.012 (2) |
C6 | 0.040 (3) | 0.056 (3) | 0.052 (3) | −0.004 (2) | −0.003 (2) | 0.007 (2) |
C14 | 0.066 (3) | 0.067 (3) | 0.047 (3) | −0.005 (3) | −0.012 (3) | −0.003 (3) |
C9 | 0.045 (3) | 0.073 (3) | 0.043 (3) | 0.002 (2) | −0.008 (2) | −0.003 (3) |
N1 | 0.038 (2) | 0.100 (3) | 0.051 (3) | −0.005 (2) | −0.008 (2) | −0.002 (2) |
C13 | 0.067 (4) | 0.084 (4) | 0.043 (3) | 0.005 (3) | 0.000 (3) | 0.003 (3) |
C7 | 0.043 (3) | 0.069 (4) | 0.052 (3) | −0.009 (3) | −0.002 (3) | 0.010 (3) |
C5 | 0.063 (4) | 0.092 (4) | 0.049 (3) | 0.010 (3) | −0.004 (3) | −0.001 (3) |
C1 | 0.062 (4) | 0.067 (4) | 0.068 (4) | 0.001 (3) | −0.007 (3) | −0.003 (3) |
C8 | 0.058 (4) | 0.096 (4) | 0.044 (3) | −0.007 (3) | 0.000 (3) | −0.008 (3) |
C10 | 0.067 (4) | 0.071 (4) | 0.065 (3) | 0.012 (3) | −0.006 (3) | −0.014 (3) |
C12 | 0.053 (4) | 0.088 (4) | 0.059 (4) | 0.001 (3) | −0.009 (3) | 0.018 (3) |
C11 | 0.076 (4) | 0.069 (4) | 0.085 (4) | −0.005 (3) | 0.003 (4) | 0.013 (4) |
C3 | 0.076 (4) | 0.104 (5) | 0.065 (4) | −0.006 (4) | −0.015 (4) | −0.010 (3) |
C2 | 0.073 (4) | 0.085 (4) | 0.072 (4) | −0.001 (3) | 0.008 (3) | −0.025 (3) |
C15 | 0.080 (5) | 0.134 (5) | 0.090 (5) | −0.015 (4) | −0.007 (4) | 0.039 (4) |
C4 | 0.075 (4) | 0.119 (6) | 0.059 (4) | 0.026 (4) | −0.015 (3) | −0.002 (4) |
Geometric parameters (Å, º) top
O1—C7 | 1.227 (5) | N1—C8 | 1.462 (5) |
C6—C7 | 1.498 (6) | C13—C12 | 1.369 (6) |
C6—C5 | 1.385 (6) | C5—C4 | 1.381 (6) |
C6—C1 | 1.361 (6) | C1—C2 | 1.386 (6) |
C14—C9 | 1.376 (6) | C10—C11 | 1.383 (6) |
C14—C13 | 1.390 (6) | C12—C11 | 1.367 (6) |
C9—C8 | 1.515 (6) | C12—C15 | 1.506 (6) |
C9—C10 | 1.370 (6) | C3—C2 | 1.371 (6) |
N1—C7 | 1.331 (5) | C3—C4 | 1.364 (6) |
| | | |
C5—C6—C7 | 122.7 (5) | C4—C5—C6 | 120.6 (5) |
C1—C6—C7 | 119.1 (5) | C6—C1—C2 | 121.3 (5) |
C1—C6—C5 | 118.2 (5) | N1—C8—C9 | 112.2 (4) |
C9—C14—C13 | 121.3 (5) | C9—C10—C11 | 120.3 (5) |
C14—C9—C8 | 119.6 (5) | C13—C12—C15 | 121.7 (5) |
C10—C9—C14 | 117.8 (5) | C11—C12—C13 | 117.4 (5) |
C10—C9—C8 | 122.5 (5) | C11—C12—C15 | 120.9 (6) |
C7—N1—C8 | 123.1 (4) | C12—C11—C10 | 122.4 (5) |
C12—C13—C14 | 120.8 (5) | C4—C3—C2 | 119.2 (5) |
O1—C7—C6 | 119.7 (5) | C3—C2—C1 | 120.1 (5) |
O1—C7—N1 | 122.6 (5) | C3—C4—C5 | 120.7 (5) |
N1—C7—C6 | 117.7 (4) | | |
Subscribe to Journal of Applied Crystallography
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.