(3E)-4-[(Naphthalen-1-yl)amino]­pent-3-en-2-one hemihydrate

Diop, A.; Diop, T.; Diop, C.A.K.; Tumanov, N.; Ennio, Z.; Sidibé, M.

doi:10.1107/S2414314621009895

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 9| September 2021| x210989

https://doi.org/10.1107/S2414314621009895

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(3E)-4-[(Naphthalen-1-yl)amino]pent-3-en-2-one hemihydrate

Aboubacar Diop,^a ^* Tidiane Diop,^a Cheikh Abdou Khadre Diop,^a Nikolay Tumanov,^b Zangrando Ennio ^c and Mamadou Sidibé ^a ^*

^aLaboratoire de Chimie Minérale et Analytique (LA.CHI.MI.A), Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, ^bDepartement de Chimie, Université de Namur ASBL, Rue de Bruxelles 61-5000 Namur, Belgium, and ^cDepartement of Chemical and Pharmaceutical Sciences, via Giorgieri, 34127-Trieste, Italy
^*Correspondence e-mail: aboubacar.diop@ucad.edu.sn, aboubacar.diop@ucad.edu.sn

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 2 September 2021; accepted 22 September 2021; online 30 September 2021)

The title compound, C₁₅H₁₅NO·0.5H₂O, was prepared from α-naphthylamine and 2,4-pentanedione in a 1:1 ratio. An intramolecular N—H⋯O hydrogen bond in the N-naphthylpent-3-en-2-one molecule involving the amine and carbonyl groups strengthens the structure. The water molecule interacts with two symmetry-related N-naphthylpent-3-en-2-one molecules viaby O—H⋯O hydrogen bonds.

Keywords: crystal structure; naphthalene; aminopentanone; N-naphthylpent-3-en-2-one; hydrogen bonding.

CCDC reference: 2111316

Structure description

Enaminones, which consist of an amino group linked by a carbon–carbon double bond to a carbonyl group, is an area of considerable opportunity (Montanile, 2003 ). In fact, enaminones are used in the synthesis of different heterocycles and biologically active analogues and also in the development of pharmaceuticals because of their role as organic intermediates (Esmaiel et al., 2018 ). It should be noted that the biological activity of enaminone compounds is attributed to the presence of the active N—C=C—C=O group within a ring system (Kale, 2016 ). Much work has been undertaken to explore new routes for the synthesis of enaminones. Azzoro et al. (1981 ) reported a simple method using amines and 1,3-diketones. Eddington et al. (2000 ) reported on the synthesis and anticonvulsant evaluations of some enaminones. In another method, β-chloro vinyl ketone was reacted with amines to synthesize these compounds (Pohland & Benson, 1966 ). Other methods of preparation include reactions between formamide dimethyl acetate and ketones (Abdulla & Brinkmeyer, 1979 ), acid chlorides with terminal alkynes and triethylamine (Karpov & Müller, 2003 ), primary amines and β-dicarbonyl compounds catalysed by copper nanoparticles (Kidwai et al., 2009 ). Lue & Greenhill (1996 ) functionalized enaminones by introducing different substituents on the nitrogen, α- and β-carbon atoms to the carbonyl group. These derivatives are used extensively for preserving natural products and analogues. Enaminones are also considered to be good chelating ligands for transition metals in coordination chemistry (Esmaiel et al., 2018). The anions produced from enaminone offer potential isoelectronic alternatives to cyclopentadienyl-based anions and therefore their transition-metal complexes can act as possible alternative catalysts for olefinic polymerization (Pešková et al., 2006 ). Imada et al. (1996 ) transformed β-amino ketones to enaminones using palladium while Tan et al. (2008 ) reported enaminone applications of rhodium compounds containing bidentate ligand systems.

In the title compound (Fig. 1), the dihedral angle formed by the mean planes through the naphthalene ring system and the aminopentanone group is 69.66 (9)°. This angle is determined by crystal-packing requirements. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. The water molecule, located on a crystallographic twofold axis, is linked to two symmetry-related N-naphthylpent-3-en-2-one molecules via O—H⋯O hydrogen bonds (Fig. 2 and Table 1). In addition, In addition, there are π–π interactions [centroid-to-centroid distance of 3.7975 (10) Å] between the naphthalene ring systems of symmetry-related molecules, generating chains of molecules running in the [100] direction.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.905 (17)	1.933 (17)	2.6765 (17)	138.2 (15)
O2—H2A⋯O1	0.85 (3)	2.02 (3)	2.8678 (15)	176 (3)

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 35% probability level. Hydrogen bonds are shown as light-blue dashed lines.

Figure 2
Crystal packing of the title compound viewed down the b axis. O—H⋯O hydrogen bonds are shown as light-green dashed lines. H atoms are omitted.

Synthesis and crystallization

A mixture of α-naphthylamine (0,143 g; 1 mmol) and 2,4-pentanedione (0,100 g; 1 mmol) in ethanol solvent was stirred for about 4 h and then filtered. Slow evaporation of the solution at room temperature was carried out, leading to grey crystals suitable for a single-crystal X-ray diffraction study (yield 63%).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO·0.5H₂O
M_r	234.29
Crystal system, space group	Monoclinic, I2/a
Temperature (K)	295
a, b, c (Å)	17.1405 (8), 8.3052 (4), 18.5156 (8)
β (°)	102.347 (4)
V (Å³)	2574.8 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.88 × 0.48 × 0.27

Data collection
Diffractometer	Oxford Diffraction Xcalibur, Ruby, Gemini Ultra
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.952, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	6527, 2637, 2045
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.05
No. of reflections	2637
No. of parameters	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.16
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ) and SHELXL2018/3 (Sheldrick, 2015b ).

Structural data

CCDC reference: 2111316

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621009895/xu4045sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621009895/xu4045Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314621009895/xu4045Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b).

(3E)-4-[(Naphthalen-1-yl)amino]pent-3-en-2-one hemihydrate top

Crystal data top

C₁₅H₁₅NO·0.5H₂O	F(000) = 1000
M_r = 234.29	D_x = 1.209 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 17.1405 (8) Å	Cell parameters from 2470 reflections
b = 8.3052 (4) Å	θ = 2.9–30.5°
c = 18.5156 (8) Å	µ = 0.08 mm⁻¹
β = 102.347 (4)°	T = 295 K
V = 2574.8 (2) Å³	Block, colourless
Z = 8	0.88 × 0.48 × 0.27 mm

Data collection top

Oxford Diffraction Xcalibur, Ruby, Gemini Ultra diffractometer	2637 independent reflections
Graphite monochromator	2045 reflections with I > 2σ(I)
Detector resolution: 10.3712 pixels mm^-1	R_int = 0.013
ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2018)	h = −21→13
T_min = 0.952, T_max = 0.981	k = −10→10
6527 measured reflections	l = −21→23

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: dual
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: difference Fourier map
wR(F²) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0578P)² + 0.6014P] where P = (F_o² + 2F_c²)/3
2637 reflections	(Δ/σ)_max = 0.002
168 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.35246 (7)	0.84680 (13)	0.60203 (6)	0.0697 (3)
N1	0.41810 (7)	0.55405 (15)	0.62641 (6)	0.0554 (3)
H1	0.4037 (10)	0.641 (2)	0.5971 (9)	0.067*
C1	0.54448 (8)	0.47503 (16)	0.59592 (7)	0.0487 (3)
C2	0.57433 (9)	0.63404 (19)	0.60622 (8)	0.0613 (4)
H2	0.542714	0.714959	0.619655	0.074*
C3	0.64878 (11)	0.6695 (3)	0.59665 (10)	0.0820 (5)
H3	0.667331	0.774862	0.602925	0.098*
C4	0.69744 (11)	0.5507 (3)	0.57766 (10)	0.0914 (6)
H4	0.748515	0.576743	0.571849	0.110*
C5	0.67113 (10)	0.3970 (3)	0.56749 (9)	0.0787 (5)
H5	0.704585	0.318524	0.554932	0.094*
C6	0.59393 (9)	0.35372 (18)	0.57560 (7)	0.0581 (4)
C7	0.56410 (11)	0.1952 (2)	0.56424 (9)	0.0716 (5)
H7	0.596165	0.114794	0.551045	0.086*
C8	0.48942 (12)	0.15854 (19)	0.57231 (10)	0.0747 (5)
H8	0.470690	0.053490	0.564663	0.090*
C9	0.44020 (10)	0.27831 (19)	0.59215 (8)	0.0654 (4)
H9	0.388734	0.252280	0.596803	0.079*
C10	0.46696 (8)	0.43196 (16)	0.60462 (7)	0.0511 (3)
C11	0.40408 (8)	0.57179 (17)	0.69445 (7)	0.0545 (3)
C12	0.42920 (14)	0.4398 (2)	0.74914 (10)	0.0870 (6)
H12A	0.395859	0.347308	0.734921	0.131*
H12B	0.424079	0.475343	0.797244	0.131*
H12C	0.483825	0.411805	0.750444	0.131*
C13	0.36721 (9)	0.70740 (18)	0.71367 (8)	0.0583 (4)
H13	0.357332	0.711308	0.761114	0.070*
C14	0.34324 (8)	0.84062 (17)	0.66740 (8)	0.0566 (4)
C15	0.30550 (13)	0.9813 (2)	0.69784 (11)	0.0864 (5)
H15A	0.297561	1.067498	0.662469	0.130*	0.5
H15B	0.339877	1.017109	0.742911	0.130*	0.5
H15C	0.254936	0.949261	0.707604	0.130*	0.5
H15D	0.297355	0.955081	0.746187	0.130*	0.5
H15E	0.255039	1.005469	0.665745	0.130*	0.5
H15F	0.339980	1.073318	0.701052	0.130*	0.5
O2	0.250000	1.0550 (2)	0.500000	0.1027 (7)
H2A	0.2805 (17)	0.990 (3)	0.5285 (16)	0.151 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0799 (8)	0.0721 (7)	0.0613 (7)	0.0141 (5)	0.0242 (5)	0.0081 (5)
N1	0.0566 (7)	0.0623 (7)	0.0506 (7)	0.0104 (5)	0.0184 (5)	0.0042 (5)
C1	0.0496 (7)	0.0604 (8)	0.0356 (6)	0.0035 (6)	0.0080 (5)	−0.0002 (6)
C2	0.0641 (9)	0.0675 (9)	0.0528 (8)	−0.0044 (7)	0.0141 (7)	−0.0035 (7)
C3	0.0744 (12)	0.0982 (13)	0.0744 (11)	−0.0283 (10)	0.0180 (9)	−0.0020 (9)
C4	0.0535 (10)	0.148 (2)	0.0751 (12)	−0.0135 (11)	0.0187 (8)	−0.0011 (12)
C5	0.0573 (10)	0.1225 (16)	0.0582 (9)	0.0216 (10)	0.0164 (7)	0.0010 (10)
C6	0.0596 (8)	0.0751 (10)	0.0395 (7)	0.0158 (7)	0.0108 (6)	0.0001 (6)
C7	0.0924 (13)	0.0661 (10)	0.0562 (9)	0.0226 (9)	0.0157 (8)	−0.0059 (7)
C8	0.1019 (14)	0.0539 (9)	0.0677 (10)	−0.0024 (8)	0.0170 (9)	−0.0089 (7)
C9	0.0687 (10)	0.0653 (9)	0.0634 (9)	−0.0095 (7)	0.0166 (7)	−0.0046 (7)
C10	0.0530 (8)	0.0566 (8)	0.0443 (7)	0.0043 (6)	0.0121 (6)	−0.0005 (6)
C11	0.0550 (8)	0.0613 (8)	0.0484 (7)	−0.0003 (6)	0.0137 (6)	−0.0007 (6)
C12	0.1277 (16)	0.0789 (11)	0.0574 (10)	0.0258 (11)	0.0262 (10)	0.0092 (9)
C13	0.0631 (9)	0.0657 (9)	0.0493 (8)	0.0026 (7)	0.0195 (6)	−0.0032 (7)
C14	0.0510 (8)	0.0618 (8)	0.0584 (9)	−0.0019 (6)	0.0151 (6)	−0.0055 (7)
C15	0.1069 (15)	0.0715 (10)	0.0870 (12)	0.0205 (10)	0.0350 (11)	−0.0041 (9)
O2	0.1283 (19)	0.0622 (11)	0.1037 (16)	0.000	−0.0062 (13)	0.000

Geometric parameters (Å, º) top

O1—C14	1.2548 (17)	C8—H8	0.9300
N1—C11	1.3403 (17)	C9—C10	1.359 (2)
N1—C10	1.4271 (17)	C9—H9	0.9300
N1—H1	0.904 (17)	C11—C13	1.375 (2)
C1—C2	1.414 (2)	C11—C12	1.492 (2)
C1—C10	1.4180 (18)	C12—H12A	0.9600
C1—C6	1.4183 (18)	C12—H12B	0.9600
C2—C3	1.358 (2)	C12—H12C	0.9600
C2—H2	0.9300	C13—C14	1.406 (2)
C3—C4	1.385 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.503 (2)
C4—C5	1.354 (3)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.410 (2)	C15—H15C	0.9600
C5—H5	0.9300	C15—H15D	0.9600
C6—C7	1.412 (2)	C15—H15E	0.9600
C7—C8	1.355 (2)	C15—H15F	0.9600
C7—H7	0.9300	O2—H2A	0.85 (3)
C8—C9	1.403 (2)	O2—H2Aⁱ	0.85 (3)

C11—N1—C10	125.30 (12)	C13—C11—C12	120.54 (13)
C11—N1—H1	113.3 (10)	C11—C12—H12A	109.5
C10—N1—H1	119.8 (10)	C11—C12—H12B	109.5
C2—C1—C10	122.75 (12)	H12A—C12—H12B	109.5
C2—C1—C6	118.65 (13)	C11—C12—H12C	109.5
C10—C1—C6	118.60 (13)	H12A—C12—H12C	109.5
C3—C2—C1	120.52 (15)	H12B—C12—H12C	109.5
C3—C2—H2	119.7	C11—C13—C14	125.27 (13)
C1—C2—H2	119.7	C11—C13—H13	117.4
C2—C3—C4	120.85 (18)	C14—C13—H13	117.4
C2—C3—H3	119.6	O1—C14—C13	122.64 (13)
C4—C3—H3	119.6	O1—C14—C15	118.90 (14)
C5—C4—C3	120.41 (16)	C13—C14—C15	118.46 (13)
C5—C4—H4	119.8	C14—C15—H15A	109.5
C3—C4—H4	119.8	C14—C15—H15B	109.5
C4—C5—C6	121.21 (17)	H15A—C15—H15B	109.5
C4—C5—H5	119.4	C14—C15—H15C	109.5
C6—C5—H5	119.4	H15A—C15—H15C	109.5
C5—C6—C7	122.70 (15)	H15B—C15—H15C	109.5
C5—C6—C1	118.35 (15)	C14—C15—H15D	109.5
C7—C6—C1	118.95 (14)	H15A—C15—H15D	141.1
C8—C7—C6	120.91 (14)	H15B—C15—H15D	56.3
C8—C7—H7	119.5	H15C—C15—H15D	56.3
C6—C7—H7	119.5	C14—C15—H15E	109.5
C7—C8—C9	120.32 (15)	H15A—C15—H15E	56.3
C7—C8—H8	119.8	H15B—C15—H15E	141.1
C9—C8—H8	119.8	H15C—C15—H15E	56.3
C10—C9—C8	120.68 (15)	H15D—C15—H15E	109.5
C10—C9—H9	119.7	C14—C15—H15F	109.5
C8—C9—H9	119.7	H15A—C15—H15F	56.3
C9—C10—C1	120.52 (13)	H15B—C15—H15F	56.3
C9—C10—N1	121.20 (13)	H15C—C15—H15F	141.1
C1—C10—N1	118.27 (12)	H15D—C15—H15F	109.5
N1—C11—C13	121.20 (13)	H15E—C15—H15F	109.5
N1—C11—C12	118.26 (13)	H2A—O2—H2Aⁱ	101 (4)

C10—C1—C2—C3	−179.47 (14)	C8—C9—C10—C1	1.7 (2)
C6—C1—C2—C3	0.1 (2)	C8—C9—C10—N1	−178.61 (14)
C1—C2—C3—C4	−0.9 (3)	C2—C1—C10—C9	178.20 (13)
C2—C3—C4—C5	0.7 (3)	C6—C1—C10—C9	−1.40 (19)
C3—C4—C5—C6	0.2 (3)	C2—C1—C10—N1	−1.53 (19)
C4—C5—C6—C7	178.95 (16)	C6—C1—C10—N1	178.86 (11)
C4—C5—C6—C1	−1.0 (2)	C11—N1—C10—C9	76.91 (19)
C2—C1—C6—C5	0.79 (19)	C11—N1—C10—C1	−103.36 (16)
C10—C1—C6—C5	−179.59 (12)	C10—N1—C11—C13	169.20 (13)
C2—C1—C6—C7	−179.15 (13)	C10—N1—C11—C12	−11.1 (2)
C10—C1—C6—C7	0.47 (19)	N1—C11—C13—C14	−2.3 (2)
C5—C6—C7—C8	−179.74 (15)	C12—C11—C13—C14	178.05 (16)
C1—C6—C7—C8	0.2 (2)	C11—C13—C14—O1	1.2 (2)
C6—C7—C8—C9	0.0 (3)	C11—C13—C14—C15	−178.45 (16)
C7—C8—C9—C10	−1.0 (3)

Symmetry code: (i) −x+1/2, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.905 (17)	1.933 (17)	2.6765 (17)	138.2 (15)
O2—H2A···O1	0.85 (3)	2.02 (3)	2.8678 (15)	176 (3)

Acknowledgements

The authors thank the crystallographic service of the Chemistry Department of Namur University (Belgium) for the data collection.

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