2-[(Prop-2-yn-1-yl)amino]­anilinium chloride

Essaghouani, A.; Boulhaoua, M.; El Hafi, M.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314617015838

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171583

https://doi.org/10.1107/S2414314617015838

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2-[(Prop-2-yn-1-yl)amino]anilinium chloride

Abdelhanine Essaghouani,^a ^* Mohammed Boulhaoua,^a Mohamed El Hafi,^a El Mokhtar Essassi ^a and Joel T. Mague ^b

^aLaboratoire de Chimie Organique Hétérocyclique, Centre de Recherche des Sciences des Médicaments, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta BP 1014, Faculté des Sciences Université Mohammed V Rabat, Morocco, and ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: hessaghouani@yahoo.fr

Edited by J. Simpson, University of Otago, New Zealand (Received 18 October 2017; accepted 31 October 2017; online 7 November 2017)

The title compound, C₉H₁₁N₂⁺·Cl⁻, is an anilinium chloride salt, in which the C_ar—N—C—C (ar = aromatic) torsion angle is −84.95 (18)°. In the crystal, a bilayer of cation–anion sheets runs parallel to (100), primarily through an extensive range of N—H⋯Cl hydrogen bonds. Weak offset π-stacking interactions between the benzene rings stack molecules along c.

Keywords: crystal structure; anilinium salt; hydrogen bond; offset π-stacking interactions.

CCDC reference: 1583039

Structure description

As a continuation of our studies of substituted 4-phenyl-1,5-benzodiazepin-2-one derivatives (Loughzail et al., 2011 ; Ballo et al., 2010 ), we have prepared the title compound (Fig. 1) by the action of hydroxylamine hydrochloride on 4-phenyl-1-(prop-2-yn-1-yl)-1H-1,5-benzodiazepin-2(3H)-one in ethanol.

Figure 1
The title molecule with the atom-labelling scheme and 50% probability displacement ellipsoids.

In the title anilinium chloride salt, the N1 atom of the NH₃⁺ substituent and the N2—H2A group lie in the plane of the benzene ring while the N2,C7,C8≡C9 substituent is inclined to the benzene ring at an angle of 81.57 (12)°.

In the crystal, the major packing interactions involve several N—H⋯Cl hydrogen bonds. Each of the H atoms of the NH₃⁺ cations and the amine group form N—H⋯Cl hydrogen bonds with N1—H1A acting as a bifurcated donor while the N1—H1B⋯Cl1 contact is supported by a weaker C5—H5⋯Cl hydrogen bond, Table 1, Fig. 2. Weak, offset π-stacking interactions between the benzene rings stack molecules along a with centroid–centroid distances of 3.951 (2) Å and a dihedral angle of 7.02 (7)° between the rings. These interactions form bilayers running along the caxis direction (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.90 (2)	2.72 (2)	3.2854 (17)	122.2 (17)
N1—H1A⋯Cl1ⁱⁱ	0.90 (2)	2.56 (2)	3.2903 (18)	138.6 (18)
N1—H1B⋯Cl1ⁱⁱⁱ	0.92 (2)	2.29 (2)	3.2011 (16)	174.6 (16)
N1—H1C⋯Cl1	0.86 (2)	2.44 (2)	3.2064 (17)	148.2 (16)
N2—H2A⋯Cl1ⁱⁱ	0.832 (17)	2.492 (17)	3.3148 (18)	170.1 (15)
C5—H5⋯Cl1ⁱⁱⁱ	0.996 (17)	2.935 (16)	3.7479 (19)	139.4 (12)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z.

Figure 2
Details of the cation–anion interactions, with hydrogen bonds shown as dashed lines and symmetry operations as in Table 1

Figure 3
Overall packing viewed along the b-axis direction with π–π stacking interactions shown as dashed orange lines.

Synthesis and crystallization

To a solution of 4-phenyl-1-(prop-2-yn-1-yl)-1H-1,5-benzodiazepin-2(3H)-one (10 mmol), was added hydroxylamine hydrochloride (20 mmol) in anhydrous ethanol (100 ml). The mixture was stirred at room temperature for 24 h. The solvent was removed under reduced pressure. The solid product was purified by recrystallization from ethanol solution to afford the title salt as colourless crystals.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₉H₁₁N₂⁺·Cl⁻
M_r	182.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.736 (6), 7.955 (3), 7.843 (3)
β (°)	94.502 (5)
V (Å³)	916.6 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.36
Crystal size (mm)	0.30 × 0.29 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.84, 0.97
No. of measured, independent and observed [I > 2σ(I)] reflections	8431, 2311, 1732
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.677

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.106, 1.00
No. of reflections	2311
No. of parameters	153
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.18
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1583039

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314617015838/sj4142sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617015838/sj4142Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617015838/sj4142Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617015838/sj4142Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2-[(Prop-2-yn-1-yl)amino]anilinium chloride top

Crystal data top

C₉H₁₁N₂⁺·Cl⁻	F(000) = 384
M_r = 182.65	D_x = 1.324 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.736 (6) Å	Cell parameters from 3191 reflections
b = 7.955 (3) Å	θ = 2.8–28.1°
c = 7.843 (3) Å	µ = 0.36 mm⁻¹
β = 94.502 (5)°	T = 296 K
V = 916.6 (7) Å³	Plate, colourless
Z = 4	0.30 × 0.29 × 0.08 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2311 independent reflections
Radiation source: fine-focus sealed tube	1732 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.7°, θ_min = 1.4°
φ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −10→10
T_min = 0.84, T_max = 0.97	l = −10→10
8431 measured reflections

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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F²) = 0.106	All H-atom parameters refined
S = 1.00	w = 1/[σ²(F_o²) + (0.0677P)²] where P = (F_o² + 2F_c²)/3
2311 reflections	(Δ/σ)_max = 0.002
153 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Special details top

Experimental. The diffraction data were collected in three sets of 363 frames (0.5° width in ω) at φ = 0, 120 and 240°. A scan time of 25 sec/frame was used.

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. 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 > 2sigma(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	0.08712 (9)	0.56842 (17)	0.23286 (19)	0.0323 (3)
H1A	0.0601 (16)	0.533 (3)	0.325 (3)	0.079 (7)*
H1B	0.0470 (13)	0.633 (3)	0.166 (2)	0.056 (5)*
H1C	0.1026 (12)	0.485 (3)	0.172 (3)	0.055 (6)*
N2	0.24881 (9)	0.42987 (16)	0.38629 (18)	0.0373 (3)
H2A	0.2005 (12)	0.383 (2)	0.407 (2)	0.040 (5)*
C1	0.24303 (9)	0.60397 (17)	0.36781 (18)	0.0296 (3)
C2	0.31409 (11)	0.7126 (2)	0.4199 (2)	0.0379 (4)
H2	0.3669 (12)	0.663 (2)	0.465 (2)	0.043 (4)*
C3	0.30463 (11)	0.8851 (2)	0.4016 (2)	0.0433 (4)
H3	0.3552 (12)	0.953 (2)	0.438 (2)	0.049 (5)*
C4	0.22475 (12)	0.9538 (2)	0.3278 (2)	0.0435 (4)
H4	0.2185 (13)	1.075 (2)	0.317 (2)	0.060 (5)*
C5	0.15423 (10)	0.84824 (19)	0.27104 (19)	0.0355 (3)
H5	0.0949 (11)	0.890 (2)	0.217 (2)	0.042 (4)*
C6	0.16362 (9)	0.67665 (17)	0.29098 (17)	0.0275 (3)
C7	0.32679 (10)	0.3572 (2)	0.4861 (2)	0.0412 (4)
H7A	0.3111 (15)	0.243 (3)	0.526 (3)	0.066 (6)*
H7B	0.3429 (11)	0.419 (2)	0.591 (2)	0.043 (4)*
C8	0.40509 (11)	0.3334 (2)	0.3858 (2)	0.0513 (5)
C9	0.46786 (16)	0.3128 (4)	0.3068 (3)	0.0850 (8)
H9	0.516 (3)	0.307 (5)	0.237 (5)	0.147 (13)*
Cl1	0.05771 (2)	0.22948 (5)	0.01428 (5)	0.03535 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0282 (6)	0.0321 (7)	0.0357 (7)	−0.0017 (5)	−0.0030 (5)	−0.0011 (6)
N2	0.0259 (6)	0.0294 (6)	0.0555 (8)	−0.0006 (5)	−0.0033 (6)	0.0061 (6)
C1	0.0260 (7)	0.0292 (7)	0.0337 (7)	−0.0007 (5)	0.0026 (5)	0.0011 (6)
C2	0.0275 (7)	0.0388 (8)	0.0466 (9)	−0.0024 (6)	−0.0026 (7)	0.0015 (7)
C3	0.0375 (9)	0.0367 (8)	0.0552 (10)	−0.0101 (7)	−0.0001 (7)	−0.0047 (7)
C4	0.0468 (9)	0.0279 (8)	0.0561 (10)	−0.0035 (7)	0.0049 (8)	−0.0003 (7)
C5	0.0330 (8)	0.0324 (8)	0.0408 (8)	0.0041 (6)	0.0015 (6)	0.0014 (6)
C6	0.0246 (6)	0.0287 (7)	0.0293 (7)	−0.0022 (5)	0.0028 (5)	−0.0016 (5)
C7	0.0364 (8)	0.0358 (9)	0.0498 (10)	0.0057 (7)	−0.0059 (7)	0.0011 (8)
C8	0.0362 (9)	0.0601 (11)	0.0553 (11)	0.0059 (8)	−0.0113 (8)	−0.0156 (9)
C9	0.0405 (11)	0.142 (2)	0.0713 (16)	0.0057 (13)	−0.0047 (11)	−0.0393 (16)
Cl1	0.0343 (2)	0.0347 (2)	0.0365 (2)	0.00367 (14)	−0.00021 (15)	−0.00251 (14)

Geometric parameters (Å, º) top

N1—C6	1.4626 (18)	C3—C4	1.383 (2)
N1—H1A	0.90 (2)	C3—H3	0.948 (19)
N1—H1B	0.92 (2)	C4—C5	1.382 (2)
N1—H1C	0.86 (2)	C4—H4	0.968 (19)
N2—C1	1.3945 (19)	C5—C6	1.380 (2)
N2—C7	1.4580 (19)	C5—H5	0.996 (17)
N2—H2A	0.832 (17)	C7—C8	1.459 (2)
C1—C2	1.394 (2)	C7—H7A	0.99 (2)
C1—C6	1.3986 (18)	C7—H7B	0.972 (17)
C2—C3	1.385 (2)	C8—C9	1.164 (3)
C2—H2	0.919 (17)	C9—H9	0.93 (4)

C6—N1—H1A	108.4 (15)	C5—C4—C3	119.21 (15)
C6—N1—H1B	107.3 (11)	C5—C4—H4	120.7 (12)
H1A—N1—H1B	109.3 (18)	C3—C4—H4	120.1 (12)
C6—N1—H1C	113.3 (12)	C6—C5—C4	119.90 (13)
H1A—N1—H1C	111.1 (19)	C6—C5—H5	116.9 (9)
H1B—N1—H1C	107.4 (17)	C4—C5—H5	123.2 (9)
C1—N2—C7	119.25 (13)	C5—C6—C1	122.07 (12)
C1—N2—H2A	115.0 (12)	C5—C6—N1	118.63 (12)
C7—N2—H2A	111.5 (11)	C1—C6—N1	119.29 (13)
C2—C1—N2	123.16 (13)	N2—C7—C8	112.68 (15)
C2—C1—C6	116.99 (13)	N2—C7—H7A	109.8 (13)
N2—C1—C6	119.84 (12)	C8—C7—H7A	105.2 (13)
C3—C2—C1	121.09 (14)	N2—C7—H7B	112.6 (10)
C3—C2—H2	122.9 (11)	C8—C7—H7B	111.8 (9)
C1—C2—H2	116.0 (11)	H7A—C7—H7B	104.1 (17)
C4—C3—C2	120.70 (15)	C9—C8—C7	179.3 (3)
C4—C3—H3	121.5 (11)	C8—C9—H9	174 (2)
C2—C3—H3	117.8 (11)

C7—N2—C1—C2	9.2 (2)	C4—C5—C6—C1	0.0 (2)
C7—N2—C1—C6	−172.05 (13)	C4—C5—C6—N1	178.74 (14)
N2—C1—C2—C3	−178.87 (14)	C2—C1—C6—C5	−1.7 (2)
C6—C1—C2—C3	2.3 (2)	N2—C1—C6—C5	179.43 (13)
C1—C2—C3—C4	−1.3 (2)	C2—C1—C6—N1	179.61 (13)
C2—C3—C4—C5	−0.5 (2)	N2—C1—C6—N1	0.7 (2)
C3—C4—C5—C6	1.1 (2)	C1—N2—C7—C8	−84.95 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.90 (2)	2.72 (2)	3.2854 (17)	122.2 (17)
N1—H1A···Cl1ⁱⁱ	0.90 (2)	2.56 (2)	3.2903 (18)	138.6 (18)
N1—H1B···Cl1ⁱⁱⁱ	0.92 (2)	2.29 (2)	3.2011 (16)	174.6 (16)
N1—H1C···Cl1	0.86 (2)	2.44 (2)	3.2064 (17)	148.2 (16)
N2—H2A···Cl1ⁱⁱ	0.832 (17)	2.492 (17)	3.3148 (18)	170.1 (15)
C5—H5···Cl1ⁱⁱⁱ	0.996 (17)	2.935 (16)	3.7479 (19)	139.4 (12)

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

Acknowledgements

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

References

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