A triclinic polymorph of N-[5-(di­phenyl­amino)­penta-2,4-diyn-1-yl]benzamide

Ozaki, K.; Okuno, T.

doi:10.1107/S2414314619003717

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 4| April 2019| x190371

https://doi.org/10.1107/S2414314619003717

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A triclinic polymorph of N-[5-(diphenylamino)penta-2,4-diyn-1-yl]benzamide

Koji Ozaki ^a and Tsunehisa Okuno ^a ^*

^aDepartment of Systems Engineering, Wakayama University, Sakaedani, Wakayama, 640-8510, Japan
^*Correspondence e-mail: okuno@wakayama-u.ac.jp

Edited by J. Simpson, University of Otago, New Zealand (Received 4 March 2019; accepted 18 March 2019; online 2 April 2019)

The title compound, C₂₄H₁₈N₂O, was been described previously in the space group P2₁/c with Z = 4 [Kawashima & Okuno (2017 ). IUCrData, 2, x170277]. The current P $[\overline{1}]$ polymorph was obtained from a chloroform–ethanol solution. The molecular structure in this polymorph is slightly different from the previously reported structure, with different dihedral angles of the two N-phenyl groups to the ynamine plane; these are 79.99 (11) and 12.09 (11)° in the polymorph reported here. The molecules form dimers through four C—H⋯π interactions. Furthermore, in this polymorph, the molecules stack along the a axis to form a molecular arrangement that would be suitable to promote the solid-state polymerization of diacetylenes.

Keywords: polymorph diacetylene polymerization hydrogen bond C–H⋯π interaction; crystal structure.

CCDC reference: 1903693

Structure description

The title compound (Fig. 1) is a diacetylene derivative that has potential solid-state polymerization reactivity. Previously, it was isolated in a monoclinic P2₁/c polymorph with Z = 4 (Kawashima & Okuno, 2017). The current triclinic polymorph was obtained by recrystallizationfrom a mixed solution of chloroform–ethanol (1:1 v:v).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level and H atoms shown as small spheres.

In the title compound, the N1/C1/C7/C13 ynamine moiety has an almost planar structure (r.m.s. deviation = 0.0239 Å). The C1–C6 and C7–C12 phenyl groups subtend dihedral angles of 79.99 (11) and 12.09 (11)°, respectively, with this plane. This geometric situation is very similar to that reported for 5-(diphenylamino)penta-2,4-diyn-1-ol (Tokutome et al., 2012 ). However, those found in the previously reported polymorph are 52.99 (7) and 21.91 (7)°, showing significant variation from those found in the current structure.

In the crystal, molecules are connected by N—H⋯O hydrogen bonds to form one-dimensional stacks along the a axis (Fig. 2). According to Baughman's notation (Baughman, 1974 ), the repeating interval (the length of the a axis in this case) and inclination angle to the stacking axis (C16—C13—C13ⁱⁱ) are 5.033 (5) Å and 44.27 (7)° [symmetry code: (ii) x + 1, y, z], respectively. This molecular arrangement is suitable for the solid-state polymerization of diacetylenes and the title compound shows polymerization reactivity when exposed to heat or under irradiation by UV light. Weak intercolumnar C—H⋯π interactions are also detected between the stacks of molecules (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O1ⁱ	0.88 (3)	2.09 (3)	2.952 (4)	169 (2)
C11—H11⋯Cgⁱⁱ	0.95	2.97	3.822 (5)	150
Symmetry codes: (i) x-1, y, z; (ii) -x-1, -y, -z+2.

Figure 2
A view of the intermolecular interactions in the title compound [symmetry codes:(i) x − 1, y, z; (ii) x + 1, y, z; (iii) −x − 1, −y, −z + 2]. Chains of molecules along the a axis with hydrogen bonds are drawn as red dashed line. Ring centroids are shown as red spheres and C—H⋯π(ring) contacts are drawn as blue dashed lines.

Synthesis and crystallization

Preparation was carried out according to Tokutome et al. (2012), Tokutome & Okuno (2013 ) and Tabata et al. (2012 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₁₈N₂O
M_r	350.42
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	93
a, b, c (Å)	5.033 (5), 11.682 (10), 15.433 (15)
α, β, γ (°)	96.228 (19), 91.207 (14), 94.27 (2)
V (Å³)	899.2 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.10 × 0.07

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Numerical (NUMABS; Rigaku, 1999 )
T_min, T_max	0.988, 0.994
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	6092, 3091, 2235
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.136, 1.05
No. of reflections	3091
No. of parameters	248
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.21
Computer programs: CrystalClear (Rigaku, 2008 ), SIR92 (Altomare et al., 1994 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and CrystalStructure (Rigaku, 2014 ).

Structural data

CCDC reference: 1903693

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619003717/sj4201sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619003717/sj4201Isup2.hkl

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: CrystalStructure (Rigaku, 2014).

N-[5-(Diphenylamino)penta-2,4-diyn-1-yl]benzamide top

Crystal data top

C₂₄H₁₈N₂O	Z = 2
M_r = 350.42	F(000) = 368.00
Triclinic, P1	D_x = 1.294 Mg m⁻³
a = 5.033 (5) Å	Mo Kα radiation, λ = 0.71075 Å
b = 11.682 (10) Å	Cell parameters from 2799 reflections
c = 15.433 (15) Å	θ = 2.3–30.8°
α = 96.228 (19)°	µ = 0.08 mm⁻¹
β = 91.207 (14)°	T = 93 K
γ = 94.27 (2)°	Block, colorless
V = 899.2 (14) Å³	0.20 × 0.10 × 0.07 mm

Data collection top

Rigaku Saturn724+ diffractometer	2235 reflections with F² > 2.0σ(F²)
Detector resolution: 7.111 pixels mm^-1	R_int = 0.040
ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: numerical (NUMABS; Rigaku, 1999)	h = −5→5
T_min = 0.988, T_max = 0.994	k = −13→10
6092 measured reflections	l = −18→18
3091 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0496P)² + 0.5409P] where P = (F_o² + 2F_c²)/3
3091 reflections	(Δ/σ)_max < 0.001
248 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

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 sigma(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.3363 (3)	0.62279 (14)	0.63872 (12)	0.0291 (4)
N1	−0.0220 (4)	0.19512 (16)	0.87818 (13)	0.0207 (5)
N2	0.9003 (4)	0.57251 (17)	0.65461 (14)	0.0233 (5)
C1	−0.0880 (5)	0.08597 (19)	0.82601 (16)	0.0201 (5)
C2	−0.2982 (5)	0.0755 (2)	0.76636 (17)	0.0290 (6)
C3	−0.3651 (6)	−0.0291 (2)	0.71730 (17)	0.0311 (6)
C4	−0.2210 (5)	−0.1226 (2)	0.72699 (18)	0.0309 (6)
C5	−0.0093 (6)	−0.1117 (2)	0.7858 (2)	0.0360 (7)
C6	0.0576 (5)	−0.0074 (2)	0.83586 (19)	0.0296 (6)
C7	−0.1784 (5)	0.23177 (19)	0.94990 (15)	0.0193 (5)
C8	−0.1554 (5)	0.3459 (2)	0.98629 (16)	0.0247 (6)
C9	−0.3156 (5)	0.3812 (2)	1.05424 (17)	0.0266 (6)
C10	−0.4954 (5)	0.3033 (2)	1.08805 (17)	0.0268 (6)
C11	−0.5150 (5)	0.1893 (2)	1.05221 (17)	0.0265 (6)
C12	−0.3572 (5)	0.1530 (2)	0.98362 (16)	0.0225 (6)
C13	0.1717 (5)	0.26552 (19)	0.84948 (15)	0.0192 (5)
C14	0.3477 (5)	0.32555 (19)	0.82152 (16)	0.0201 (5)
C15	0.5552 (5)	0.39027 (19)	0.78986 (15)	0.0197 (5)
C16	0.7342 (5)	0.4456 (2)	0.75999 (16)	0.0228 (6)
C17	0.9673 (5)	0.5097 (2)	0.72805 (18)	0.0295 (6)
C18	1.1009 (5)	0.6262 (2)	0.61485 (16)	0.0212 (5)
C19	1.0257 (5)	0.6922 (2)	0.54136 (15)	0.0208 (5)
C20	1.1882 (5)	0.7891 (2)	0.52703 (17)	0.0280 (6)
C21	1.1243 (6)	0.8541 (3)	0.46038 (19)	0.0394 (7)
C22	0.9044 (6)	0.8206 (3)	0.40727 (19)	0.0435 (8)
C23	0.7433 (6)	0.7230 (3)	0.41991 (18)	0.0423 (8)
C24	0.8052 (5)	0.6589 (2)	0.48719 (17)	0.0296 (6)
H1	0.732 (5)	0.581 (2)	0.6428 (17)	0.024 (7)*
H2	−0.39701	0.14018	0.75897	0.0348*
H3	−0.51142	−0.03651	0.67667	0.0374*
H4	−0.26753	−0.19441	0.69317	0.0370*
H5	0.09163	−0.176	0.79211	0.0432*
H6	0.20311	−0.00024	0.8768	0.0355*
H8	−0.02988	0.39976	0.96463	0.0296*
H9	−0.30232	0.45995	1.07807	0.0319*
H10	−0.60344	0.32789	1.13519	0.0322*
H11	−0.63804	0.13527	1.07481	0.0317*
H12	−0.37127	0.07432	0.95969	0.0270*
H17A	1.04771	0.56518	0.77621	0.0354*
H17B	1.10183	0.45495	0.7098	0.0354*
H20	1.3434	0.81105	0.56283	0.0337*
H21	1.23292	0.92172	0.45164	0.0473*
H22	0.86219	0.86473	0.36137	0.0522*
H23	0.5914	0.70001	0.3828	0.0508*
H24	0.69529	0.59172	0.49603	0.0355*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0180 (10)	0.0335 (10)	0.0378 (11)	0.0014 (8)	0.0027 (8)	0.0134 (8)
N1	0.0225 (12)	0.0160 (10)	0.0231 (12)	−0.0025 (8)	0.0054 (9)	0.0010 (8)
N2	0.0148 (12)	0.0251 (12)	0.0316 (13)	0.0014 (9)	0.0025 (10)	0.0103 (9)
C1	0.0244 (14)	0.0133 (12)	0.0221 (13)	−0.0020 (10)	0.0076 (11)	0.0017 (10)
C2	0.0363 (16)	0.0226 (14)	0.0283 (15)	0.0074 (11)	0.0008 (12)	0.0000 (11)
C3	0.0362 (17)	0.0286 (15)	0.0260 (15)	−0.0009 (12)	−0.0026 (12)	−0.0054 (11)
C4	0.0357 (17)	0.0200 (14)	0.0343 (16)	−0.0034 (11)	0.0137 (13)	−0.0068 (11)
C5	0.0304 (16)	0.0195 (14)	0.058 (2)	0.0060 (11)	0.0070 (14)	0.0022 (13)
C6	0.0235 (14)	0.0228 (14)	0.0426 (17)	−0.0001 (11)	−0.0004 (12)	0.0054 (12)
C7	0.0196 (13)	0.0208 (13)	0.0175 (13)	0.0006 (10)	−0.0010 (10)	0.0034 (10)
C8	0.0277 (14)	0.0190 (13)	0.0262 (14)	−0.0060 (10)	0.0055 (11)	0.0012 (10)
C9	0.0347 (16)	0.0178 (13)	0.0257 (14)	0.0012 (11)	0.0035 (12)	−0.0044 (10)
C10	0.0293 (15)	0.0271 (14)	0.0241 (14)	0.0026 (11)	0.0063 (11)	0.0012 (11)
C11	0.0302 (15)	0.0216 (13)	0.0279 (15)	−0.0029 (11)	0.0081 (12)	0.0062 (11)
C12	0.0288 (14)	0.0143 (12)	0.0240 (14)	−0.0012 (10)	0.0036 (11)	0.0020 (10)
C13	0.0190 (13)	0.0191 (12)	0.0193 (13)	0.0017 (10)	0.0009 (10)	0.0019 (10)
C14	0.0218 (13)	0.0169 (12)	0.0217 (13)	0.0037 (10)	0.0011 (11)	0.0006 (10)
C15	0.0196 (13)	0.0203 (12)	0.0198 (13)	0.0030 (10)	0.0009 (10)	0.0034 (10)
C16	0.0221 (14)	0.0207 (13)	0.0267 (14)	0.0045 (10)	0.0014 (11)	0.0058 (10)
C17	0.0188 (14)	0.0348 (15)	0.0385 (17)	0.0033 (11)	0.0021 (12)	0.0192 (13)
C18	0.0186 (14)	0.0196 (13)	0.0251 (14)	0.0013 (10)	0.0056 (11)	0.0001 (10)
C19	0.0192 (13)	0.0246 (13)	0.0181 (13)	0.0038 (10)	0.0037 (10)	−0.0015 (10)
C20	0.0287 (15)	0.0295 (15)	0.0255 (15)	−0.0014 (11)	0.0006 (12)	0.0036 (11)
C21	0.0464 (19)	0.0396 (17)	0.0358 (17)	0.0045 (14)	0.0084 (14)	0.0175 (13)
C22	0.0411 (19)	0.069 (2)	0.0262 (17)	0.0170 (16)	0.0050 (14)	0.0219 (15)
C23	0.0315 (17)	0.076 (2)	0.0196 (15)	0.0056 (15)	−0.0010 (12)	0.0039 (14)
C24	0.0283 (15)	0.0388 (16)	0.0205 (14)	−0.0007 (12)	0.0050 (12)	−0.0002 (11)

Geometric parameters (Å, º) top

O1—C18	1.238 (3)	C19—C24	1.381 (4)
N1—C1	1.445 (3)	C20—C21	1.389 (4)
N1—C7	1.419 (3)	C21—C22	1.371 (4)
N1—C13	1.342 (3)	C22—C23	1.382 (5)
N2—C17	1.462 (4)	C23—C24	1.388 (4)
N2—C18	1.344 (3)	N2—H1	0.88 (3)
C1—C2	1.377 (4)	C2—H2	0.950
C1—C6	1.378 (4)	C3—H3	0.950
C2—C3	1.381 (3)	C4—H4	0.950
C3—C4	1.375 (4)	C5—H5	0.950
C4—C5	1.374 (4)	C6—H6	0.950
C5—C6	1.385 (4)	C8—H8	0.950
C7—C8	1.385 (3)	C9—H9	0.950
C7—C12	1.388 (3)	C10—H10	0.950
C8—C9	1.383 (4)	C11—H11	0.950
C9—C10	1.385 (4)	C12—H12	0.950
C10—C11	1.381 (3)	C17—H17A	0.990
C11—C12	1.386 (4)	C17—H17B	0.990
C13—C14	1.205 (3)	C20—H20	0.950
C14—C15	1.373 (3)	C21—H21	0.950
C15—C16	1.199 (3)	C22—H22	0.950
C16—C17	1.468 (4)	C23—H23	0.950
C18—C19	1.496 (4)	C24—H24	0.950
C19—C20	1.387 (4)

C1—N1—C7	120.96 (19)	C18—N2—H1	122.4 (17)
C1—N1—C13	117.0 (2)	C1—C2—H2	120.071
C7—N1—C13	121.57 (19)	C3—C2—H2	120.068
C17—N2—C18	118.0 (2)	C2—C3—H3	119.845
N1—C1—C2	119.6 (2)	C4—C3—H3	119.829
N1—C1—C6	120.4 (2)	C3—C4—H4	120.118
C2—C1—C6	120.1 (2)	C5—C4—H4	120.116
C1—C2—C3	119.9 (2)	C4—C5—H5	119.851
C2—C3—C4	120.3 (3)	C6—C5—H5	119.851
C3—C4—C5	119.8 (2)	C1—C6—H6	120.160
C4—C5—C6	120.3 (3)	C5—C6—H6	120.160
C1—C6—C5	119.7 (3)	C7—C8—H8	120.094
N1—C7—C8	120.5 (2)	C9—C8—H8	120.082
N1—C7—C12	119.9 (2)	C8—C9—H9	119.555
C8—C7—C12	119.6 (2)	C10—C9—H9	119.551
C7—C8—C9	119.8 (2)	C9—C10—H10	120.499
C8—C9—C10	120.9 (2)	C11—C10—H10	120.495
C9—C10—C11	119.0 (2)	C10—C11—H11	119.660
C10—C11—C12	120.7 (2)	C12—C11—H11	119.674
C7—C12—C11	119.9 (2)	C7—C12—H12	120.027
N1—C13—C14	177.7 (2)	C11—C12—H12	120.023
C13—C14—C15	177.6 (3)	N2—C17—H17A	109.084
C14—C15—C16	178.2 (2)	N2—C17—H17B	109.092
C15—C16—C17	175.6 (3)	C16—C17—H17A	109.078
N2—C17—C16	112.6 (2)	C16—C17—H17B	109.082
O1—C18—N2	121.6 (2)	H17A—C17—H17B	107.829
O1—C18—C19	121.6 (2)	C19—C20—H20	119.955
N2—C18—C19	116.7 (2)	C21—C20—H20	119.953
C18—C19—C20	118.0 (2)	C20—C21—H21	120.056
C18—C19—C24	122.5 (2)	C22—C21—H21	120.062
C20—C19—C24	119.5 (2)	C21—C22—H22	119.708
C19—C20—C21	120.1 (2)	C23—C22—H22	119.707
C20—C21—C22	119.9 (3)	C22—C23—H23	120.233
C21—C22—C23	120.6 (3)	C24—C23—H23	120.242
C22—C23—C24	119.5 (3)	C19—C24—H24	119.798
C19—C24—C23	120.4 (2)	C23—C24—H24	119.790
C17—N2—H1	119.1 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1···O1ⁱ	0.88 (3)	2.09 (3)	2.952 (4)	169 (2)
C11—H11···Cgⁱⁱ	0.95	2.97	3.822 (5)	150

Symmetry codes: (i) x−1, y, z; (ii) −x−1, −y, −z+2.

Acknowledgements

This work was supported by Research for Promoting Technological Seeds from Japan Science and Technology Agency (JST).

References

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