2,4,6-Triphenyl­aniline

Ugono, O.; Cowin, S.; Beatty, A.M.

doi:10.1107/S160053681002338X

2,4,6-Triphenylaniline

Individual molecules of the title compound, C₂₄H₁₉N, do not participate in hydrogen-bonding interactions due to the steric bulk of the phenyl rings ortho to the amine. The dihedral angles between the central ring and the pendant rings are 68.26 (10), 55.28 (10) and 30.61 (11)°.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681002338X/hg2686sup1.cif Contains datablocks I, New_Global_Publ_Block
	Structure factor file (CIF format) https://doi.org/10.1107/S160053681002338X/hg2686Isup2.hkl Contains datablock I

CCDC reference: 786693

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.001 Å
R factor = 0.043
wR factor = 0.125
Data-to-parameter ratio = 29.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.14
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        341

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The reactions of equimolar amounts of pyrazole-3,5-dicarboxylic acid (HPzDCA) and primary amines have yielded ammonium carboxylate salts that adopt layered architectures (Ugono et al., 2009; Beatty et al., 2002a,b). The level of structural fidelity for these organic salts allows, from a crystal engineering point of view, for the tuning of material properties by changing the identity of the organic group for the amines employed in the reaction. The reaction of pyrazole-3,5-dicarboxylic acid and 2,4,6-triphenylaniline (TPA) does not produce appreciable amounts of the desired ammonium carboxylate salt. However, large colorless single crystals of the aniline were obtained and structurally characterized.

The title compound packs in the monoclinic space group P 2₁/c, with one molecule in the asymmetric unit. TPA does not self aggregate via intermolecular hydrogen bonds in the solid state. This lack of significant intermolecular hydrogen bonds appears to be due to the bulky ortho phenyl groups. These groups ensure that the distance requirements for hydrogen bond interactions are not satisfied, as potential participating hydrogen bonding donors and acceptors can not approach each other. This is not uncommon, as other amines, namely 2,6-bis(Benzofuran-2-yl)phenylamine (Lonkin et al., 2004) and (R,R)-2,6-bis(1-Phenylethyl)4-methylaniline (Cherian et al., 2005) among others, exhibit this characteristic for identical reasons.

Related literature top

The reaction of equimolar amounts of pyrazole-3,5-dicarboxylic acid (HPzDCA) and primary amines have yielded ammonium carboxylate salts that adopt layered architectures, see: Ugono et al. (2009); Beatty et al. (2002a,b). For other amines which do not exhibit intermolecular hydrogen bonding due to the bulky ortho phenyl groups, see: Cherian et al. (2005); Lonkin & Marshal (2004). For the preparation of 2,4,6-triphenylaniline, see: Basu et al. (2003); Paul & Clark (2003).

Experimental top

Into a 20 ml scintillation vial was placed 65 mg (37 mmol s) of pyrazole-3,5-dicarboxylic acid, 120 mg (37 mmol s) of 2,4,6-triphenylaniline (Basu et al., 2003; Paul & Clark, 2003) and 5 ml of a 3:2 ethanol:water mixture. The mixture was warmed gently until the solution became clear and then filtered. The filtrate was placed in another scintillation vial, and colorless single crystals of the title compound were obtained in 48 h.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot of 2,4,6-triphenylaniline at 50% probability.

2,4,6-Triphenylaniline top

Crystal data top

C₂₄H₁₉N	F(000) = 680
M_r = 321.40	D_x = 1.226 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 395–398 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.735 (2) Å	Cell parameters from 6695 reflections
b = 14.792 (3) Å	θ = 2.1–33.9°
c = 11.911 (2) Å	µ = 0.07 mm⁻¹
β = 113.02 (3)°	T = 100 K
V = 1740.7 (6) Å³	Prism, colorless
Z = 4	0.50 × 0.50 × 0.25 mm

Data collection top

Bruker SMART APEXII diffractometer	6695 independent reflections
Radiation source: fine-focus sealed tube	5813 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 33.9°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.966, T_max = 0.983	k = −23→23
44061 measured reflections	l = −18→18

Refinement top

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0697P)² + 0.5511P] where P = (F_o² + 2F_c²)/3
6695 reflections	(Δ/σ)_max = 0.001
226 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₂₄H₁₉N	V = 1740.7 (6) Å³
M_r = 321.40	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.735 (2) Å	µ = 0.07 mm⁻¹
b = 14.792 (3) Å	T = 100 K
c = 11.911 (2) Å	0.50 × 0.50 × 0.25 mm
β = 113.02 (3)°

Data collection top

Bruker SMART APEXII diffractometer	6695 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5813 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.983	R_int = 0.027
44061 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.02	Δρ_max = 0.48 e Å⁻³
6695 reflections	Δρ_min = −0.23 e Å⁻³
226 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

	x	y	z	U_iso*/U_eq
N1	−0.03946 (8)	0.31892 (6)	0.10628 (7)	0.02312 (15)
H1A	−0.0309	0.3532	0.1693	0.028*
H1B	−0.1086	0.2817	0.0760	0.028*
C1	0.05584 (7)	0.32362 (5)	0.05479 (6)	0.01365 (13)
C2	0.16729 (8)	0.38320 (5)	0.10276 (7)	0.01385 (13)
C3	0.26324 (8)	0.38694 (5)	0.05077 (7)	0.01493 (13)
H3	0.3376	0.4272	0.0842	0.018*
C4	0.25338 (7)	0.33322 (5)	−0.04924 (7)	0.01409 (13)
C5	0.14616 (7)	0.27160 (5)	−0.09177 (7)	0.01405 (13)
H5	0.1399	0.2322	−0.1567	0.017*
C6	0.04796 (7)	0.26577 (5)	−0.04244 (6)	0.01310 (13)
C7	0.18451 (8)	0.44422 (5)	0.20775 (7)	0.01407 (13)
C8	0.29191 (8)	0.43079 (5)	0.32071 (7)	0.01645 (14)
H8	0.3517	0.3812	0.3314	0.020*
C9	0.31156 (8)	0.48981 (6)	0.41751 (7)	0.01874 (15)
H9	0.3837	0.4796	0.4941	0.022*
C10	0.22601 (9)	0.56362 (6)	0.40238 (7)	0.01889 (15)
H10	0.2404	0.6042	0.4681	0.023*
C11	0.11933 (9)	0.57760 (6)	0.29049 (7)	0.01905 (15)
H11	0.0609	0.6280	0.2797	0.023*
C12	0.09793 (9)	0.51788 (5)	0.19407 (7)	0.01751 (14)
H12	0.0239	0.5273	0.1184	0.021*
C13	0.34837 (8)	0.34425 (5)	−0.11131 (7)	0.01444 (13)
C14	0.48238 (8)	0.37311 (6)	−0.04755 (7)	0.01809 (14)
H14	0.5146	0.3829	0.0380	0.022*
C15	0.56863 (8)	0.38749 (6)	−0.10796 (8)	0.02019 (15)
H15	0.6589	0.4071	−0.0633	0.024*
C16	0.52351 (9)	0.37333 (6)	−0.23338 (8)	0.02020 (15)
H16	0.5819	0.3842	−0.2747	0.024*
C17	0.39142 (9)	0.34296 (6)	−0.29744 (8)	0.01904 (15)
H17	0.3603	0.3318	−0.3826	0.023*
C18	0.30489 (8)	0.32897 (5)	−0.23725 (7)	0.01613 (14)
H18	0.2150	0.3088	−0.2821	0.019*
C19	−0.06390 (7)	0.19929 (5)	−0.09729 (6)	0.01294 (12)
C20	−0.19933 (8)	0.22763 (5)	−0.14897 (7)	0.01598 (14)
H20	−0.2206	0.2894	−0.1433	0.019*
C21	−0.30318 (8)	0.16641 (5)	−0.20861 (7)	0.01793 (14)
H21	−0.3944	0.1866	−0.2431	0.022*
C22	−0.27334 (8)	0.07567 (5)	−0.21765 (7)	0.01761 (14)
H22	−0.3438	0.0339	−0.2587	0.021*
C23	−0.13918 (8)	0.04676 (5)	−0.16595 (7)	0.01747 (14)
H23	−0.1184	−0.0151	−0.1715	0.021*
C24	−0.03506 (8)	0.10781 (5)	−0.10612 (7)	0.01537 (13)
H24	0.0559	0.0872	−0.0712	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0255 (3)	0.0285 (4)	0.0204 (3)	−0.0110 (3)	0.0144 (3)	−0.0100 (3)
C1	0.0160 (3)	0.0130 (3)	0.0116 (3)	−0.0006 (2)	0.0051 (2)	0.0004 (2)
C2	0.0169 (3)	0.0120 (3)	0.0117 (3)	−0.0010 (2)	0.0047 (2)	−0.0007 (2)
C3	0.0165 (3)	0.0133 (3)	0.0141 (3)	−0.0019 (2)	0.0050 (2)	−0.0016 (2)
C4	0.0147 (3)	0.0134 (3)	0.0139 (3)	−0.0009 (2)	0.0053 (2)	−0.0010 (2)
C5	0.0153 (3)	0.0124 (3)	0.0139 (3)	−0.0006 (2)	0.0052 (2)	−0.0015 (2)
C6	0.0146 (3)	0.0112 (3)	0.0123 (3)	−0.0006 (2)	0.0040 (2)	−0.0001 (2)
C7	0.0177 (3)	0.0130 (3)	0.0113 (3)	−0.0022 (2)	0.0054 (2)	−0.0006 (2)
C8	0.0166 (3)	0.0180 (3)	0.0134 (3)	−0.0012 (2)	0.0045 (2)	−0.0003 (2)
C9	0.0196 (3)	0.0231 (4)	0.0123 (3)	−0.0046 (3)	0.0049 (3)	−0.0016 (3)
C10	0.0253 (4)	0.0192 (3)	0.0140 (3)	−0.0058 (3)	0.0095 (3)	−0.0039 (3)
C11	0.0268 (4)	0.0151 (3)	0.0165 (3)	0.0002 (3)	0.0098 (3)	−0.0012 (2)
C12	0.0229 (3)	0.0148 (3)	0.0132 (3)	0.0011 (3)	0.0052 (3)	0.0004 (2)
C13	0.0153 (3)	0.0125 (3)	0.0155 (3)	−0.0007 (2)	0.0060 (2)	−0.0011 (2)
C14	0.0154 (3)	0.0195 (3)	0.0182 (3)	−0.0013 (2)	0.0054 (3)	−0.0018 (3)
C15	0.0159 (3)	0.0192 (3)	0.0262 (4)	−0.0002 (3)	0.0090 (3)	−0.0002 (3)
C16	0.0214 (4)	0.0173 (3)	0.0264 (4)	0.0023 (3)	0.0142 (3)	0.0026 (3)
C17	0.0245 (4)	0.0166 (3)	0.0186 (3)	0.0012 (3)	0.0112 (3)	0.0001 (3)
C18	0.0181 (3)	0.0144 (3)	0.0158 (3)	−0.0012 (2)	0.0065 (3)	−0.0017 (2)
C19	0.0153 (3)	0.0117 (3)	0.0117 (3)	−0.0009 (2)	0.0052 (2)	0.0001 (2)
C20	0.0162 (3)	0.0129 (3)	0.0166 (3)	0.0004 (2)	0.0041 (2)	0.0001 (2)
C21	0.0162 (3)	0.0162 (3)	0.0178 (3)	−0.0010 (2)	0.0028 (3)	0.0006 (2)
C22	0.0189 (3)	0.0152 (3)	0.0167 (3)	−0.0041 (2)	0.0048 (3)	−0.0012 (2)
C23	0.0204 (3)	0.0123 (3)	0.0204 (3)	−0.0017 (2)	0.0088 (3)	−0.0018 (2)
C24	0.0168 (3)	0.0124 (3)	0.0176 (3)	−0.0007 (2)	0.0075 (3)	−0.0006 (2)

Geometric parameters (Å, º) top

N1—C1	1.3850 (11)	C12—H12	0.9500
N1—H1A	0.8800	C13—C18	1.4040 (11)
N1—H1B	0.8800	C13—C14	1.4050 (11)
C1—C2	1.4142 (11)	C14—C15	1.3933 (12)
C1—C6	1.4156 (10)	C14—H14	0.9500
C2—C3	1.3951 (11)	C15—C16	1.3944 (13)
C2—C7	1.4939 (11)	C15—H15	0.9500
C3—C4	1.4010 (11)	C16—C17	1.3960 (13)
C3—H3	0.9500	C16—H16	0.9500
C4—C5	1.3987 (10)	C17—C18	1.3930 (12)
C4—C13	1.4841 (11)	C17—H17	0.9500
C5—C6	1.3959 (11)	C18—H18	0.9500
C5—H5	0.9500	C19—C24	1.4012 (11)
C6—C19	1.4907 (10)	C19—C20	1.4030 (11)
C7—C12	1.3997 (11)	C20—C21	1.3958 (11)
C7—C8	1.4020 (12)	C20—H20	0.9500
C8—C9	1.3950 (11)	C21—C22	1.3939 (12)
C8—H8	0.9500	C21—H21	0.9500
C9—C10	1.3923 (13)	C22—C23	1.3938 (12)
C9—H9	0.9500	C22—H22	0.9500
C10—C11	1.3916 (13)	C23—C24	1.3962 (11)
C10—H10	0.9500	C23—H23	0.9500
C11—C12	1.3949 (11)	C24—H24	0.9500
C11—H11	0.9500

C1—N1—H1A	120.0	C7—C12—H12	119.7
C1—N1—H1B	120.0	C18—C13—C14	117.95 (8)
H1A—N1—H1B	120.0	C18—C13—C4	120.56 (7)
N1—C1—C2	120.47 (7)	C14—C13—C4	121.46 (7)
N1—C1—C6	120.92 (7)	C15—C14—C13	120.93 (8)
C2—C1—C6	118.53 (7)	C15—C14—H14	119.5
C3—C2—C1	120.01 (7)	C13—C14—H14	119.5
C3—C2—C7	118.45 (7)	C14—C15—C16	120.51 (8)
C1—C2—C7	121.53 (7)	C14—C15—H15	119.7
C2—C3—C4	122.11 (7)	C16—C15—H15	119.7
C2—C3—H3	118.9	C15—C16—C17	119.14 (8)
C4—C3—H3	118.9	C15—C16—H16	120.4
C5—C4—C3	117.09 (7)	C17—C16—H16	120.4
C5—C4—C13	121.31 (7)	C18—C17—C16	120.38 (8)
C3—C4—C13	121.54 (7)	C18—C17—H17	119.8
C6—C5—C4	122.53 (7)	C16—C17—H17	119.8
C6—C5—H5	118.7	C17—C18—C13	121.06 (8)
C4—C5—H5	118.7	C17—C18—H18	119.5
C5—C6—C1	119.59 (7)	C13—C18—H18	119.5
C5—C6—C19	117.89 (6)	C24—C19—C20	118.49 (7)
C1—C6—C19	122.51 (7)	C24—C19—C6	120.41 (7)
C12—C7—C8	118.77 (7)	C20—C19—C6	120.94 (7)
C12—C7—C2	120.91 (7)	C21—C20—C19	120.92 (7)
C8—C7—C2	120.26 (7)	C21—C20—H20	119.5
C9—C8—C7	120.42 (8)	C19—C20—H20	119.5
C9—C8—H8	119.8	C22—C21—C20	120.14 (7)
C7—C8—H8	119.8	C22—C21—H21	119.9
C10—C9—C8	120.33 (8)	C20—C21—H21	119.9
C10—C9—H9	119.8	C23—C22—C21	119.36 (7)
C8—C9—H9	119.8	C23—C22—H22	120.3
C11—C10—C9	119.64 (7)	C21—C22—H22	120.3
C11—C10—H10	120.2	C22—C23—C24	120.65 (7)
C9—C10—H10	120.2	C22—C23—H23	119.7
C10—C11—C12	120.22 (8)	C24—C23—H23	119.7
C10—C11—H11	119.9	C23—C24—C19	120.44 (7)
C12—C11—H11	119.9	C23—C24—H24	119.8
C11—C12—C7	120.61 (8)	C19—C24—H24	119.8
C11—C12—H12	119.7

Experimental details

Crystal data
Chemical formula	C₂₄H₁₉N
M_r	321.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.735 (2), 14.792 (3), 11.911 (2)
β (°)	113.02 (3)
V (Å³)	1740.7 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.50 × 0.50 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.966, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	44061, 6695, 5813
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.784

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.125, 1.02
No. of reflections	6695
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.23

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

2,4,6-Triphenyl­aniline

Supporting information

Key indicators

checkCIF/PLATON results

2,4,6-Triphenylaniline