Syntheses and structures of 1-[2,2-di­chloro-1-hy­droxy-3-(4-methyl­phen­yl)-3-oxoprop­yl]urea and 1-[2,2-di­chloro-3-(4-fluoro­phen­yl)-1-hy­droxy-3-oxoprop­yl]urea

Guseinov, F.I.; Hökelek, T.; Afanaseva, K.A.; Shuvalova, E.V.; Glukhov, L.M.; Samigullina, A.I.; Belay, A.N.

doi:10.1107/S2056989025004359

research communications

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ISSN: 2056-9890

Volume 81| Part 6| June 2025| Pages 538-542

https://doi.org/10.1107/S2056989025004359

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Syntheses and structures of 1-[2,2-dichloro-1-hydroxy-3-(4-methylphenyl)-3-oxopropyl]urea and 1-[2,2-dichloro-3-(4-fluorophenyl)-1-hydroxy-3-oxopropyl]urea

Firudin I. Guseinov,^a,^b Tuncer Hökelek,^c Ksenia A. Afanaseva,^a,^b Elena V. Shuvalova,^b Lev M. Glukhov,^b Aida I. Samigullina ^b and Alebel N. Belay ^d ^*

^aKosygin State University of Russia, 117997 Moscow, Russian Federation, ^bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation, ^cHacettepe University, Department of Physics, 06800 Beytepe-Ankara, Türkiye, and ^dDepartment of Chemistry, Bahir Dar University, PO Box 79, Bahir Dar, Ethiopia
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 10 March 2025; accepted 14 May 2025; online 20 May 2025)

The title compounds, C₁₀H₉Cl₂FN₂O₃, (I), and C₁₁H₁₂Cl₂N₂O₃, (II), are α,α-dihalo-β-diketone urea derivatives, which contain 4-fluorophenyl and p-tolyl groups, respectively. The conformation about the C_O—C_Cl2—C_O—N_u (O = keto, Cl2 = dichloro, u = urea) bond is anti in (I) and gauche in (II). In the crystals of both compounds, O—H⋯O hydrogen bonds generate inversion dimers and the dimers are linked into (100) layers by N—H⋯O hydrogen bonds. The Hirshfeld surface analyses of the crystal structures indicate that the most important contributions for the crystal packings are from H⋯O/O⋯H (22.3%), H⋯H (20.9%), H⋯Cl/Cl⋯H (15.6%) and H⋯C/C⋯H (10.3%) for (I) and H⋯H (31.7%), H⋯O/O⋯H (25.1%), H⋯Cl/Cl⋯H (21.1%) and H⋯C/C⋯H (9.5%) for (II).

Keywords: crystal structure; hydrogen bonds; Hirshfeld surface analysis; α,α-dihalo-β-oxoaldehydes; urea.

CCDC references: 2451169; 2451168

1. Chemical context

The replacement of hydrogen atoms with halogen atoms at the active methylene group in β-diketones prevents keto–enol tautomerism and impacts on the reactivity of the corresponding α,α-dihalo-β- diketones (e.g., Guseinov et al., 2006 ). For instance, the reaction of α,α-dihalo-β-oxoaldehydes and their derivatives with N-nucleophilic reagents lead to hetero- or macrocyclic compounds (Guseinov et al., 2024 ). This class of compounds can be used in the spectrophotometric determination of metal ions (Aliyev et al., 2020 ), decoration of the secondary coordination sphere of metal complexes for catalysis (Aliyeva et al., 2024 ), crystal growth and design (Naghiyev et al., 2023 ) and heterogenous catalysis (Mahmudov et al., 2022 ). In fact, the use of N-compounds has many synthetic advantages (Khalilov, 2021 ), such as easy modification and functionalization (Huseynov et al., 2021 ), immobilization on solid materials through supramolecular interactions (Mamedov et al., 2006 ), and crystal engineering (Hajiyeva et al., 2024 ).

Herein, we describe the syntheses and crystal structures of the two title compounds, C₁₀H₉Cl₂FN₂O₃ (I) and C₁₁H₁₂Cl₂N₂O₃ (II), which differ in the substituent at the para position of the phenyl group.

2. Structural commentary

In (I) (Fig. 1), the dihedral angle between the C7–C12 phenyl group and the C2/N1/N3/O2 urea moiety is 65.19 (8)°. The key torsion angles for the backbone of the molecule are C7—C6—C5—C4 = −179.65 (13), C6—C5—C4—N3 = −171.20 (12), C4—C5—C6—O6 = 2.95 (19) and C6—C5—C4—O4 = 66.65 (15)°. Atom C4 is a stereogenic centre: in the arbitrarily chosen asymmetric unit it has R configuration, but crystal symmetry generates a racemic mixture. Atoms F1, C6, C5 are displaced by −0.0244 (11), −0.0602 (15) and −0.0879 (15) Å, respectively, from the plane of the phenyl group. The N1—C2—O2, N3—C4—O4, N3—C4—C5, Cl1—C5—Cl2 and C4—C5—C6 bond angles in (I) are enlarged, while the O2—C2—N3 bond angle in (I) is narrowed compared to the corresponding values in (II): these small differences might arise due to steric reasons or 'packing effects'.

Figure 1
The asymmetric units of compounds (a) (I) and (b) (II) with 50% probability ellipsoids.

In (II) (Fig. 1), the corresponding dihedral angle between the C7–C12 and C2/N1/N3/O2 planes is 62.70 (9)° and the equivalent backbone torsion angles are C7—C6—C5—C4 = 162.65 (14), C6—C5—C4—N3 = −62.41 (16), C4—C5—C6—O6 = −17.42 (19) and C6—C5—C4—O4 = 176.34 (12)°. Thus it may be seen that the conformation of the atoms about the C4—C5 bond is quite different in the two structures. The stereogenic atom C4 in (II) was arbitrarily assigned to have an R configuration, but crystal symmetry generates a racemic mixture.

3. Supramolecular features

In the crystals of both compounds, O—H⋯O hydrogen bonds (Tables 1 and 2) generate inversion dimers featuring R₂²(12) loops. In both structures, N—H⋯O hydrogen bonds link the dimers into (100) layers, although they are not isostuctural. The hydrogen-bond network encloses R₃³(14) loops in (I) (Fig. 2a) and R₂²(8) and R₃³(8) loops in (II) (Fig. 2b).

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.90 (3)	2.06 (3)	2.9488 (19)	172 (2)
N1—H1B⋯O2ⁱⁱ	0.86 (2)	2.48 (2)	3.297 (2)	158 (2)
N3—H3⋯O6ⁱⁱⁱ	0.87 (2)	2.06 (2)	2.9055 (18)	167 (2)
O4—H4⋯O2^iv	0.78 (3)	1.91 (3)	2.6596 (16)	161 (3)
Symmetry codes: (i) ; (ii) $[x, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) .

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.82 (3)	2.27 (3)	3.0261 (19)	153 (2)
N1—H1B⋯O4ⁱⁱ	0.84 (3)	2.14 (3)	2.9798 (18)	177 (2)
N3—H3⋯O2ⁱⁱⁱ	0.81 (3)	2.19 (3)	2.9445 (18)	156 (2)
O4—H4⋯O2^iv	0.78 (3)	1.83 (3)	2.5979 (16)	168 (3)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) .

Figure 2
The partial packing diagrams of compounds (a) (I) and (b) (II). Intermolecular O—H⋯O and N—H⋯O hydrogen bonds are shown as dashed lines. H atoms not involved in these interactions have been omitted for clarity.

4. Hirshfeld surface analysis

For visualizing the intermolecular interactions in the crystals of (I) and (II), Hirshfeld surface (HS) analyses were carried out using Crystal Explorer 17.5 (Spackman et al., 2021 ). In the HSs plotted over d_norm (Fig. 3a and b), the contact distances equal, shorter and longer with respect to the sum of van der Waals radii are shown by the white, red and blue colours, respectively. According to the two-dimensional fingerprint plots, H⋯O/O⋯H, H⋯H and H⋯Cl/Cl⋯H contacts make the most important contributions to the HSs (Table 3, Figs. 4 and 5), and they have significant differences due to the different numbers and values of the close contacts in (I) and (II).

Table 3
Comparison of the fingerprint percentages for compounds (I) and (II)

Contacts	(I)	(II)
H⋯O/O⋯H	22.3	25.1
H⋯H	20.9	31.7
H⋯Cl/Cl⋯H	15.6	21.1
H⋯C/C⋯H	10.3	9.5
H⋯F/F⋯H	8.3	–
C⋯Cl/Cl⋯C	6.4	2.8
C⋯F/F⋯C	3.1	–
F⋯Cl/Cl⋯F	2.8	–
Cl⋯Cl	2.4	1.9
H⋯N/N⋯H	2.4	1.3
C⋯C	1.8	3.0
O⋯O	1.4	–
F⋯F	0.7	–
O⋯Cl/Cl⋯O	0.7	0.2
C⋯O/O⋯C	0.6	1.9
N⋯O/O⋯N	0.3	0.1
C⋯N/N⋯C	0.1	–
N⋯Cl/Cl⋯N	0.1	1.3

Figure 3
Views of the three-dimensional Hirshfeld surfaces of compounds (a) (I) and (b) (II) plotted over d_norm.

Figure 4
The two-dimensional fingerprint plots for compound (I), showing (a) all interactions, and delineated into different contact types (b)–(i). The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

Figure 5
The two-dimensional fingerprint plots for compound (II), showing (a) all interactions, and delineated into different contact types (b)–(i). The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

5. Synthesis and crystallization

A solution of 2,2-dichloro-3-oxo-3-(p-tolyl)propanal (231 mg) for (I) or 2,2-dichloro-3-(4-fluorophenyl)-3-oxopropanal (235 mg) for (II) and urea (60 mg) in 15 ml of dry acetonitrile was stirred at room temperature for 6 h. The solvent was removed in vacuo, and the remaining white powder was recrystallized from acetone solution and the title compounds were isolated. The reaction scheme is shown in Fig. 6.

Figure 6
The synthesis of the title compounds.

(I): yield 82%; m.p. 378–380 K. Analysis calculated (%) for C₁₁H₁₂Cl₂N₂O₃: C 45.38, H 4.15, N 9.62; found C 45.36, H 4.11, N 9.60. ¹H NMR (300MHz, DMSO-d₆): 2.41 (s, CH₃), 5.94 (s, 2H, NH₂), 6.01–6.08 (d.d, CH), 6.72 (d, OH), 6.85 (d. NH), 7.38 (d. 2H, Ar), 7.95 (d, 2H, Ar). ¹³C NMR (75 MHz, DMSO-d₆): 21.32, 88.03, 104.05, 128.74, 128.91, 133.77, 142.81, 162.72, 186.95.

(II): yield 78%; m.p. 397–398 K. Analysis calculated (%) for C₁₀H₉Cl₂FN₂O₃: C 40.70, H 3.07, N 9.49; found C 40.65, H 3.02, N 9.45. ¹H NMR (300MHz, DMSO-d₆): 5.96 (s, 2H, NH₂), 6.03–6.08 (d.d, CH), 6.78 (d, OH), 6.93 (d, NH), 7.46 (t, 2H, Ar), 8.12 (d.d, 2H, Ar). ¹³C NMR (75 MHz, DMSO-d₆): 88.10, 104.12, 115.46, 130.49, 132.37, 162.74, 167.35, 186.92.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The OH and NH₂ hydrogen atoms were located in difference-Fourier maps, and refined isotropically. The C-bond hydrogen-atom positions were placed geometrically (C—H = 0.95–1.00 Å) and refined using a riding model by applying the constraint U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Table 4
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₀H₉Cl₂FN₂O₃	C₁₁H₁₂Cl₂N₂O₃
M_r	295.09	291.13
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	100	100
a, b, c (Å)	15.6136 (1), 7.2214 (1), 10.7929 (1)	12.62183 (13), 8.77585 (9), 11.59930 (11)
β (°)	104.622 (1)	94.8294 (9)
V (Å³)	1177.51 (2)	1280.26 (2)
Z	4	4
Radiation type	Cu Kα	Cu Kα
μ (mm⁻¹)	5.14	4.60
Crystal size (mm)	0.32 × 0.15 × 0.05	0.45 × 0.35 × 0.16

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Gaussian (CrysAlis PRO; Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.408, 1.000	0.277, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16149, 2562, 2494	17344, 2808, 2738
R_int	0.035	0.050
(sin θ/λ)_max (Å⁻¹)	0.640	0.640

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.082, 1.06	0.037, 0.104, 1.06
No. of reflections	2562	2808
No. of parameters	179	180
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.31	0.51, −0.43
Computer programs: CrysAlis PRO (Rigaku OD, 2024 $[Rigaku OD (2024). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 2451169; 2451168

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989025004359/hb8127sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989025004359/hb8127Isup4.cml

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025004359/hb8127Isup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025004359/hb8127IIsup5.cml

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989025004359/hb8127IIsup5.hkl

checkCIF report

Computing details top

1-[2,2-Dichloro-1-hydroxy-3-(4-methylphenyl)-3-oxopropyl]urea (I) top

Crystal data top

C₁₀H₉Cl₂FN₂O₃	F(000) = 600
M_r = 295.09	D_x = 1.665 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 15.6136 (1) Å	Cell parameters from 10775 reflections
b = 7.2214 (1) Å	θ = 2.9–80.5°
c = 10.7929 (1) Å	µ = 5.14 mm⁻¹
β = 104.622 (1)°	T = 100 K
V = 1177.51 (2) Å³	Prism, colorless
Z = 4	0.32 × 0.15 × 0.05 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2562 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2494 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.035
Detector resolution: 10.0000 pixels mm^-1	θ_max = 80.7°, θ_min = 2.9°
ω scans	h = −19→19
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2024)	k = −9→9
T_min = 0.408, T_max = 1.000	l = −10→13
16149 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: mixed
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0418P)² + 0.7639P] where P = (F_o² + 2F_c²)/3
2562 reflections	(Δ/σ)_max < 0.001
179 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.31 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
Cl1	0.75812 (2)	0.64065 (5)	0.20981 (3)	0.02166 (11)
Cl2	0.71108 (2)	0.90786 (5)	0.38664 (3)	0.02237 (11)
F1	0.45932 (7)	0.18867 (16)	0.44559 (10)	0.0321 (2)
O2	0.91429 (7)	1.16468 (16)	0.49959 (11)	0.0231 (2)
O4	0.93636 (8)	0.66517 (16)	0.38219 (11)	0.0216 (2)
H4	0.9848 (18)	0.692 (4)	0.417 (2)	0.038 (7)*
O6	0.83823 (7)	0.53628 (16)	0.55147 (10)	0.0220 (2)
N1	0.91321 (10)	1.2742 (2)	0.30188 (16)	0.0279 (3)
H1A	0.9206 (17)	1.389 (4)	0.334 (2)	0.040 (7)*
H1B	0.9071 (15)	1.259 (4)	0.221 (2)	0.032 (6)*
N3	0.88523 (9)	0.96745 (19)	0.32966 (13)	0.0222 (3)
H3	0.8796 (15)	0.958 (4)	0.248 (2)	0.035 (6)*
C2	0.90498 (10)	1.1385 (2)	0.38332 (16)	0.0204 (3)
C4	0.87990 (10)	0.8058 (2)	0.40405 (14)	0.0195 (3)
H4A	0.896975	0.839528	0.496915	0.023*
C5	0.78496 (10)	0.7248 (2)	0.37028 (13)	0.0185 (3)
C6	0.77450 (10)	0.5688 (2)	0.46381 (14)	0.0178 (3)
C7	0.68898 (10)	0.4691 (2)	0.45000 (14)	0.0187 (3)
C8	0.61114 (10)	0.5077 (2)	0.35608 (15)	0.0220 (3)
H8	0.611405	0.600113	0.293538	0.026*
C9	0.53355 (11)	0.4121 (2)	0.35358 (16)	0.0239 (3)
H9	0.480694	0.437166	0.289650	0.029*
C10	0.53522 (11)	0.2797 (2)	0.44634 (16)	0.0238 (3)
C11	0.61052 (11)	0.2368 (2)	0.54016 (16)	0.0261 (3)
H11	0.609462	0.144287	0.602320	0.031*
C12	0.68768 (11)	0.3321 (2)	0.54142 (15)	0.0228 (3)
H12	0.740343	0.304306	0.605008	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02614 (19)	0.0226 (2)	0.01572 (18)	−0.00771 (14)	0.00426 (13)	−0.00293 (12)
Cl2	0.02389 (19)	0.01773 (19)	0.0245 (2)	0.00268 (13)	0.00429 (14)	0.00032 (13)
F1	0.0255 (5)	0.0325 (6)	0.0395 (6)	−0.0097 (4)	0.0100 (4)	0.0007 (5)
O2	0.0221 (5)	0.0199 (6)	0.0272 (6)	−0.0036 (4)	0.0059 (4)	−0.0061 (4)
O4	0.0204 (5)	0.0172 (5)	0.0271 (6)	−0.0031 (4)	0.0057 (4)	−0.0057 (4)
O6	0.0226 (5)	0.0229 (6)	0.0188 (5)	0.0006 (4)	0.0023 (4)	0.0011 (4)
N1	0.0359 (8)	0.0167 (7)	0.0321 (8)	−0.0040 (6)	0.0103 (6)	−0.0020 (6)
N3	0.0285 (7)	0.0174 (7)	0.0200 (6)	−0.0056 (5)	0.0046 (5)	−0.0023 (5)
C2	0.0147 (6)	0.0177 (7)	0.0281 (8)	−0.0015 (5)	0.0041 (6)	−0.0038 (6)
C4	0.0219 (7)	0.0151 (7)	0.0210 (7)	−0.0024 (6)	0.0043 (5)	−0.0024 (6)
C5	0.0214 (7)	0.0158 (7)	0.0171 (6)	−0.0011 (6)	0.0029 (5)	−0.0017 (5)
C6	0.0215 (7)	0.0160 (7)	0.0164 (7)	0.0001 (5)	0.0057 (5)	−0.0024 (5)
C7	0.0218 (7)	0.0165 (7)	0.0186 (7)	−0.0008 (6)	0.0063 (5)	−0.0019 (5)
C8	0.0239 (7)	0.0211 (7)	0.0204 (7)	−0.0011 (6)	0.0045 (6)	0.0014 (6)
C9	0.0219 (7)	0.0254 (8)	0.0237 (7)	−0.0007 (6)	0.0042 (6)	−0.0014 (6)
C10	0.0236 (7)	0.0207 (8)	0.0285 (8)	−0.0058 (6)	0.0093 (6)	−0.0045 (6)
C11	0.0297 (8)	0.0227 (8)	0.0269 (8)	−0.0032 (7)	0.0088 (6)	0.0052 (6)
C12	0.0233 (7)	0.0210 (8)	0.0231 (7)	−0.0001 (6)	0.0040 (6)	0.0028 (6)

Geometric parameters (Å, º) top

Cl1—C5	1.7826 (14)	C4—C5	1.549 (2)
Cl2—C5	1.7923 (16)	C5—C6	1.549 (2)
F1—C10	1.3534 (18)	C6—C7	1.491 (2)
O2—C2	1.241 (2)	C7—C8	1.400 (2)
O4—H4	0.78 (3)	C7—C12	1.401 (2)
O4—C4	1.4032 (19)	C8—H8	0.9500
O6—C6	1.2103 (19)	C8—C9	1.389 (2)
N1—H1A	0.90 (3)	C9—H9	0.9500
N1—H1B	0.86 (2)	C9—C10	1.380 (2)
N1—C2	1.344 (2)	C10—C11	1.379 (2)
N3—H3	0.87 (2)	C11—H11	0.9500
N3—C2	1.366 (2)	C11—C12	1.385 (2)
N3—C4	1.431 (2)	C12—H12	0.9500
C4—H4A	1.0000

C4—O4—H4	108.1 (19)	O6—C6—C5	116.71 (13)
H1A—N1—H1B	119 (2)	O6—C6—C7	121.55 (14)
C2—N1—H1A	116.4 (17)	C7—C6—C5	121.69 (13)
C2—N1—H1B	124.6 (17)	C8—C7—C6	124.60 (14)
C2—N3—H3	117.2 (17)	C8—C7—C12	119.10 (14)
C2—N3—C4	122.60 (14)	C12—C7—C6	116.26 (14)
C4—N3—H3	120.1 (17)	C7—C8—H8	119.7
O2—C2—N1	122.99 (15)	C9—C8—C7	120.56 (15)
O2—C2—N3	121.50 (15)	C9—C8—H8	119.7
N1—C2—N3	115.50 (15)	C8—C9—H9	120.9
O4—C4—N3	111.59 (13)	C10—C9—C8	118.28 (15)
O4—C4—H4A	109.0	C10—C9—H9	120.9
O4—C4—C5	106.95 (12)	F1—C10—C9	118.43 (15)
N3—C4—H4A	109.0	F1—C10—C11	118.56 (15)
N3—C4—C5	111.33 (13)	C11—C10—C9	123.01 (15)
C5—C4—H4A	109.0	C10—C11—H11	120.9
Cl1—C5—Cl2	110.35 (8)	C10—C11—C12	118.29 (15)
C4—C5—Cl1	109.49 (10)	C12—C11—H11	120.9
C4—C5—Cl2	107.43 (10)	C7—C12—H12	119.6
C6—C5—Cl1	110.36 (10)	C11—C12—C7	120.75 (15)
C6—C5—Cl2	107.22 (10)	C11—C12—H12	119.6
C6—C5—C4	111.93 (12)

Cl1—C5—C6—O6	125.15 (13)	C4—N3—C2—O2	−4.3 (2)
Cl1—C5—C6—C7	−57.44 (16)	C4—N3—C2—N1	175.81 (14)
Cl2—C5—C6—O6	−114.62 (13)	C4—C5—C6—O6	2.95 (19)
Cl2—C5—C6—C7	62.78 (15)	C4—C5—C6—C7	−179.65 (13)
F1—C10—C11—C12	−179.17 (15)	C5—C6—C7—C8	−1.6 (2)
O4—C4—C5—Cl1	−56.04 (14)	C5—C6—C7—C12	−179.34 (13)
O4—C4—C5—Cl2	−175.90 (10)	C6—C7—C8—C9	−177.53 (15)
O4—C4—C5—C6	66.65 (15)	C6—C7—C12—C11	177.33 (15)
O6—C6—C7—C8	175.69 (15)	C7—C8—C9—C10	0.5 (2)
O6—C6—C7—C12	−2.1 (2)	C8—C7—C12—C11	−0.5 (2)
N3—C4—C5—Cl1	66.10 (14)	C8—C9—C10—F1	178.80 (15)
N3—C4—C5—Cl2	−53.75 (14)	C8—C9—C10—C11	−0.8 (3)
N3—C4—C5—C6	−171.20 (12)	C9—C10—C11—C12	0.4 (3)
C2—N3—C4—O4	−124.46 (15)	C10—C11—C12—C7	0.3 (3)
C2—N3—C4—C5	116.12 (15)	C12—C7—C8—C9	0.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.90 (3)	2.06 (3)	2.9488 (19)	172 (2)
N1—H1B···O2ⁱⁱ	0.86 (2)	2.48 (2)	3.297 (2)	158 (2)
N3—H3···O6ⁱⁱⁱ	0.87 (2)	2.06 (2)	2.9055 (18)	167 (2)
O4—H4···O2^iv	0.78 (3)	1.91 (3)	2.6596 (16)	161 (3)

Symmetry codes: (i) x, y+1, z; (ii) x, −y+5/2, z−1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+2, −y+2, −z+1.

1-[2,2-Dichloro-3-(4-fluorophenyl)-1-hydroxy-3-oxopropyl]urea (II) top

Crystal data top

C₁₁H₁₂Cl₂N₂O₃	F(000) = 600
M_r = 291.13	D_x = 1.510 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 12.62183 (13) Å	Cell parameters from 11708 reflections
b = 8.77585 (9) Å	θ = 3.5–80.3°
c = 11.59930 (11) Å	µ = 4.60 mm⁻¹
β = 94.8294 (9)°	T = 100 K
V = 1280.26 (2) Å³	Prism, colourless
Z = 4	0.45 × 0.35 × 0.16 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2808 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2738 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.050
Detector resolution: 10.0000 pixels mm^-1	θ_max = 80.7°, θ_min = 3.5°
ω scans	h = −13→16
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2024)	k = −11→11
T_min = 0.277, T_max = 1.000	l = −14→14
17344 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: mixed
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0655P)² + 0.6302P] where P = (F_o² + 2F_c²)/3
2808 reflections	(Δ/σ)_max = 0.001
180 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Cl1	0.22629 (3)	0.88241 (4)	0.40687 (3)	0.02066 (13)
Cl2	0.24819 (3)	0.70279 (5)	0.61915 (3)	0.02309 (13)
O2	0.02392 (10)	0.37516 (13)	0.31405 (10)	0.0221 (3)
O4	0.03286 (9)	0.72384 (13)	0.48926 (10)	0.0192 (2)
O6	0.27591 (10)	0.45882 (14)	0.39418 (11)	0.0259 (3)
N1	0.03826 (12)	0.49974 (17)	0.14562 (12)	0.0212 (3)
N3	0.08327 (11)	0.62287 (15)	0.31617 (12)	0.0180 (3)
C2	0.04683 (12)	0.49344 (18)	0.26185 (13)	0.0181 (3)
C4	0.10682 (12)	0.63031 (17)	0.43899 (13)	0.0176 (3)
H4A	0.103457	0.525355	0.472057	0.021*
C5	0.22071 (13)	0.69474 (17)	0.46569 (13)	0.0185 (3)
C6	0.30485 (13)	0.58690 (19)	0.41747 (13)	0.0204 (3)
C7	0.41441 (13)	0.6404 (2)	0.40165 (14)	0.0225 (3)
C8	0.46819 (15)	0.5634 (2)	0.31877 (16)	0.0279 (4)
H8	0.433483	0.484415	0.274165	0.033*
C9	0.57245 (15)	0.6024 (2)	0.30150 (17)	0.0321 (4)
H9	0.607516	0.551826	0.243057	0.039*
C10	0.62617 (15)	0.7138 (2)	0.36820 (18)	0.0325 (4)
C11	0.57243 (15)	0.7900 (2)	0.45141 (18)	0.0326 (4)
H11	0.608274	0.866470	0.497716	0.039*
C12	0.46717 (15)	0.7555 (2)	0.46742 (16)	0.0275 (4)
H12	0.431028	0.810101	0.523000	0.033*
C13	0.74130 (16)	0.7514 (3)	0.3535 (2)	0.0440 (5)
H13A	0.762750	0.702446	0.283178	0.066*
H13B	0.786149	0.713990	0.420656	0.066*
H13C	0.749543	0.862022	0.347188	0.066*
H1A	0.059 (2)	0.574 (3)	0.110 (2)	0.030 (6)*
H1B	0.0183 (19)	0.420 (3)	0.110 (2)	0.028 (6)*
H3	0.0725 (18)	0.701 (3)	0.280 (2)	0.023 (5)*
H4	0.014 (2)	0.683 (3)	0.543 (3)	0.034 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0239 (2)	0.0173 (2)	0.0211 (2)	−0.00221 (12)	0.00407 (14)	0.00018 (12)
Cl2	0.0263 (2)	0.0291 (2)	0.01385 (19)	0.00153 (14)	0.00155 (14)	−0.00215 (13)
O2	0.0313 (6)	0.0194 (6)	0.0164 (5)	−0.0060 (4)	0.0065 (4)	−0.0001 (4)
O4	0.0229 (5)	0.0207 (5)	0.0150 (5)	0.0016 (4)	0.0073 (4)	0.0021 (4)
O6	0.0270 (6)	0.0222 (6)	0.0290 (6)	0.0015 (5)	0.0057 (5)	−0.0049 (5)
N1	0.0304 (7)	0.0189 (6)	0.0144 (6)	−0.0061 (5)	0.0037 (5)	−0.0009 (5)
N3	0.0253 (6)	0.0152 (6)	0.0139 (6)	−0.0010 (5)	0.0032 (5)	0.0016 (5)
C2	0.0199 (7)	0.0179 (7)	0.0168 (7)	0.0003 (5)	0.0043 (5)	0.0001 (5)
C4	0.0217 (7)	0.0176 (7)	0.0139 (7)	−0.0012 (5)	0.0042 (5)	0.0008 (5)
C5	0.0225 (7)	0.0182 (7)	0.0150 (7)	−0.0007 (6)	0.0035 (5)	−0.0005 (5)
C6	0.0235 (7)	0.0226 (7)	0.0156 (7)	0.0027 (6)	0.0039 (5)	−0.0006 (6)
C7	0.0215 (7)	0.0258 (8)	0.0203 (7)	0.0026 (6)	0.0030 (6)	0.0021 (6)
C8	0.0277 (8)	0.0307 (9)	0.0258 (8)	0.0044 (7)	0.0061 (6)	−0.0006 (7)
C9	0.0279 (9)	0.0390 (10)	0.0308 (9)	0.0081 (8)	0.0105 (7)	0.0065 (7)
C10	0.0231 (8)	0.0377 (10)	0.0372 (10)	0.0018 (7)	0.0063 (7)	0.0162 (8)
C11	0.0269 (9)	0.0346 (10)	0.0358 (10)	−0.0041 (7)	0.0000 (7)	0.0040 (8)
C12	0.0263 (8)	0.0305 (9)	0.0260 (8)	−0.0010 (7)	0.0039 (6)	−0.0010 (7)
C13	0.0258 (10)	0.0529 (14)	0.0546 (13)	−0.0018 (9)	0.0104 (9)	0.0210 (11)

Geometric parameters (Å, º) top

Cl1—C5	1.7864 (16)	C6—C7	1.486 (2)
Cl2—C5	1.7861 (16)	C7—C8	1.397 (2)
O2—C2	1.248 (2)	C7—C12	1.400 (3)
O4—C4	1.4060 (18)	C8—H8	0.9500
O4—H4	0.78 (3)	C8—C9	1.390 (3)
O6—C6	1.205 (2)	C9—H9	0.9500
N1—C2	1.345 (2)	C9—C10	1.388 (3)
N1—H1A	0.82 (3)	C10—C11	1.396 (3)
N1—H1B	0.84 (3)	C10—C13	1.514 (2)
N3—C2	1.360 (2)	C11—H11	0.9500
N3—C4	1.432 (2)	C11—C12	1.390 (3)
N3—H3	0.81 (3)	C12—H12	0.9500
C4—H4A	1.0000	C13—H13A	0.9800
C4—C5	1.551 (2)	C13—H13B	0.9800
C5—C6	1.561 (2)	C13—H13C	0.9800

C4—O4—H4	109 (2)	C8—C7—C6	116.30 (16)
C2—N1—H1A	121.9 (18)	C8—C7—C12	119.18 (16)
C2—N1—H1B	117.0 (16)	C12—C7—C6	124.44 (15)
H1A—N1—H1B	121 (2)	C7—C8—H8	120.0
C2—N3—C4	122.18 (13)	C9—C8—C7	120.07 (18)
C2—N3—H3	115.9 (17)	C9—C8—H8	120.0
C4—N3—H3	118.9 (17)	C8—C9—H9	119.4
O2—C2—N1	121.23 (15)	C10—C9—C8	121.10 (18)
O2—C2—N3	123.58 (14)	C10—C9—H9	119.4
N1—C2—N3	115.19 (14)	C9—C10—C11	118.69 (17)
O4—C4—N3	110.47 (13)	C9—C10—C13	121.3 (2)
O4—C4—H4A	109.1	C11—C10—C13	120.0 (2)
O4—C4—C5	109.93 (12)	C10—C11—H11	119.6
N3—C4—H4A	109.1	C12—C11—C10	120.89 (19)
N3—C4—C5	109.05 (12)	C12—C11—H11	119.6
C5—C4—H4A	109.1	C7—C12—H12	120.0
Cl2—C5—Cl1	109.48 (8)	C11—C12—C7	120.02 (17)
C4—C5—Cl1	108.99 (11)	C11—C12—H12	120.0
C4—C5—Cl2	108.20 (10)	C10—C13—H13A	109.5
C4—C5—C6	110.76 (13)	C10—C13—H13B	109.5
C6—C5—Cl1	111.85 (11)	C10—C13—H13C	109.5
C6—C5—Cl2	107.47 (11)	H13A—C13—H13B	109.5
O6—C6—C5	116.31 (14)	H13A—C13—H13C	109.5
O6—C6—C7	122.32 (15)	H13B—C13—H13C	109.5
C7—C6—C5	121.38 (14)

Cl1—C5—C6—O6	−139.23 (13)	C4—N3—C2—N1	−173.78 (14)
Cl1—C5—C6—C7	40.85 (18)	C4—C5—C6—O6	−17.42 (19)
Cl2—C5—C6—O6	100.57 (15)	C4—C5—C6—C7	162.65 (14)
Cl2—C5—C6—C7	−79.35 (16)	C5—C6—C7—C8	−155.04 (15)
O4—C4—C5—Cl1	−60.19 (14)	C5—C6—C7—C12	28.2 (2)
O4—C4—C5—Cl2	58.79 (14)	C6—C7—C8—C9	−177.58 (17)
O4—C4—C5—C6	176.34 (12)	C6—C7—C12—C11	175.43 (17)
O6—C6—C7—C8	25.0 (2)	C7—C8—C9—C10	2.2 (3)
O6—C6—C7—C12	−151.71 (18)	C8—C7—C12—C11	−1.2 (3)
N3—C4—C5—Cl1	61.06 (14)	C8—C9—C10—C11	−1.9 (3)
N3—C4—C5—Cl2	−179.97 (10)	C8—C9—C10—C13	177.11 (18)
N3—C4—C5—C6	−62.41 (16)	C9—C10—C11—C12	−0.1 (3)
C2—N3—C4—O4	−110.90 (16)	C10—C11—C12—C7	1.6 (3)
C2—N3—C4—C5	128.18 (15)	C12—C7—C8—C9	−0.6 (3)
C4—N3—C2—O2	5.2 (2)	C13—C10—C11—C12	−179.03 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.82 (3)	2.27 (3)	3.0261 (19)	153 (2)
N1—H1B···O4ⁱⁱ	0.84 (3)	2.14 (3)	2.9798 (18)	177 (2)
N3—H3···O2ⁱⁱⁱ	0.81 (3)	2.19 (3)	2.9445 (18)	156 (2)
O4—H4···O2^iv	0.78 (3)	1.83 (3)	2.5979 (16)	168 (3)

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2; (iv) −x, −y+1, −z+1.

Comparison of the fingerprint percentages for compounds (I) and (II) top

Contacts	(I)	(II)
H···O/O···H	22.3	25.1
H···H	20.9	31.7
H···Cl/Cl···H	15.6	21.1
H···C/C···H	10.3	9.5
H···F/F···H	8.3	–
C···Cl/Cl···C	6.4	2.8
C···F/F···C	3.1	–
F···Cl/Cl···F	2.8	–
Cl···Cl	2.4	1.9
H···N/N···H	2.4	1.3
C···C	1.8	3.0
O···O	1.4	–
F···F	0.7	–
O···Cl/Cl···O	0.7	0.2
C···O/O···C	0.6	1.9
N···O/O···N	0.3	0.1
C···N/N···C	0.1	–
N···Cl/Cl···N	0.1	1.3

Acknowledgements

The crystal structure determinations were performed in the Department of Structural Studies of Zelinsky Institute of Organic Chemistry, Moscow. This work was supported by the Western Caspian University and Azerbaijan Medical University in Azerbaijan. The authors' contributions are as follows. Conceptualization, FIG, TH and ANB; synthesis, KAA, EVS and LMG; X-ray analysis, AIS; Hirshfeld surface analyses, crystal voids, interaction energies and energy frameworks, TH; writing (review and editing of the manuscript) FIG and TH; funding acquisition, KIH; supervision, FIG, TH and ANB.

References

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Volume 81| Part 6| June 2025| Pages 538-542

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Syntheses and structures of 1-[2,2-di­chloro-1-hy­dr­oxy-3-(4-methyl­phen­yl)-3-oxoprop­yl]urea and 1-[2,2-di­chloro-3-(4-fluoro­phen­yl)-1-hy­dr­oxy-3-oxoprop­yl]urea

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Syntheses and structures of 1-[2,2-dichloro-1-hydroxy-3-(4-methylphenyl)-3-oxopropyl]urea and 1-[2,2-dichloro-3-(4-fluorophenyl)-1-hydroxy-3-oxopropyl]urea

3. Supramolecular features