Synthesis, characterization, and crystal structures of N,N′-bis­(2-di­alkyl­amino­phen­yl)thio­ureas

Lee, K.

doi:10.1107/S2056989022012245

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 2| February 2023| Pages 60-64

https://doi.org/10.1107/S2056989022012245

Open

access

Synthesis, characterization, and crystal structures of N,N′-bis(2-dialkylaminophenyl)thioureas

Kyounghoon Lee ^a ^*

^aDepartment of Chemical Education and Research Institute of Natural Sciences, Gyeongsang National University, Gyeongsangnam-do 52828, Republic of Korea
^*Correspondence e-mail: klee1@gnu.ac.kr

Edited by V. Jancik, Universidad Nacional Autónoma de México, México (Received 2 November 2022; accepted 29 December 2022; online 6 January 2023)

N,N′-Bis[2-(dimethylamino)phenyl]thiourea, C₁₇H₂₂N₄S (1), and N,N′-bis[2-(diethylamino)phenyl]thiourea, C₂₁H₃₀N₄S (2), were prepared by the treatment of 1,1′-thiocarbonyldiimidazole and 2 equivalents of 2-amino-N,N′-dialkylaniline. Both compounds exhibit intramolecular hydrogen bonds between the N—H(thiourea) and NR₂ (R = Me, Et) groups. The other N—H bonds face the sulfur atoms of S=C bonds in an adjacent molecule, which forms an intermolecular interaction in the packed structure. The structural details match the spectroscopic data acquired from NMR and IR spectroscopy.

Keywords: crystal structure; aryl-substituted thiourea; hydrogen bond.

CCDC references: 2233350; 2233349

1. Chemical context

Thioureas and their derivatives are found in numerous organic and biological molecules (Schroeder, 1955 ; Kožurková et al., 2017 ; Khan et al., 2021 ; Ronchetti et al., 2021 ). Recent reviews pointed out that thioureas have been used in various research areas, such as catalysis (Doyle & Jacobsen, 2007 ; Zhang & Schreiner, 2009 ; Sun et al., 2017 ; Parvin et al., 2020 ), chemical sensing (Li et al., 2010 ; Khan et al., 2021; Al-Saidi & Khan, 2022 ), as ligands (Saeed et al., 2014 ; Zahra et al., 2022 ), etc. For example, strong hydrogen bonding in some thiourea compounds allows them to be using as organocatalysts in different chemical transformations. Furthermore, thioureas with chiral substituents are easily available and are used in asymmetric catalysis. Finally, thioureas substituted with functionalized aromatic rings can act as chemosensors.

Aryl-substituted thiourea compounds with amine groups in the ortho positions are expected to have versatile applications due to the unique hydrogen-bonding interactions, but so far, no such compounds have been reported. Diaryl thioureas with dimethylamine functional groups in the meta or para positions of the aryl substituents have been reported, but their crystal structures are unknown.

This report describes the preparation and crystal structures of N,N′-bis(2-dimethylaminophenyl)thiourea (1) and N,N′-bis(2-diethylaminophenyl)thiourea (2). Compounds 1 and 2 were prepared by treating 1,1′-thiocarbonyldiimidazole and two equivalents of 2-amino-N,N′-dialkylaniline in CH₂Cl₂. Methyl and NH resonances for 1 were observed at δ 2.64 and 8.82 ppm in the ¹H NMR spectrum, whereas singlets at δ 43.99 and 178.66 ppm in the ¹³C NMR spectrum match to methyl and C=S resonances (Figs. S1 and S2 in the supporting information). Ethyl and NH resonances for 2 were found at δ 0.89, 2.89, and 9.14 ppm in the ¹H NMR spectrum, while resonances at δ 12.47, 48.07, and 176.68 ppm in ¹³C NMR spectrum correspond to the ethyl and C=S groups (Figs. S3 and S4). In the IR spectra, the NH stretches were observed at 3165 and 3226 cm⁻¹ for 1 and 2, respectively (Figs. S5 and S6). High-resolution ESI–MS data confirmed the formation of 1 and 2 with the desired isotopic patterns (Figs. S7 and S8).

2. Structural commentary

One of the most noticeable features in both 1 and 2 is the intramolecular hydrogen bonding between one of the thiourea NH moieties and the NR₂ group (R = Me and Et) in the ortho position of the aromatic rings (Figs. 1 and 2). The N2—H2 bond distance of 0.896 (15) Å in 1 is slightly shorter (within error ranges) than the N2—H2 bond distance of 0.905 (15) Å in 2, whereas the N3⋯H2 distance of 1.957 (17) Å for 1 is more elongated than the N3⋯H2 distance of 1.864 (15) Å for 2. Bond distance analysis suggests that the hydrogen bonding interaction is stronger in 2, due to the increased basicity of amine with longer chains. The increased hydrogen bonding was also observed in the solution, as demonstrated with the deshielded NH resonance of 2 at δ 9.14 ppm compared to that for 1 at δ 8.82 ppm. It is worth noting that, contrary to what is expected, there are no hydrogen bonds between N4 and H2 in both 1 and 2 even as the corresponding N⋯H distances are 2.707 (12) and 2.641 (14) Å for 1 and 2, respectively.

Figure 1
Molecular structure of 1 with displacement ellipsoids at the 50% probability level. Hydrogen atoms attached to carbon were omitted from the figure.

Figure 2
Molecular structure of 2 with displacement ellipsoids at the 50% probability level. Hydrogen atoms attached to carbon were omitted from the figure.

Slightly asymmetric C1—N1 and C1—N2 bond distances are observed for the trigonal planar thiourea backbones, presumably due to the intramolecular hydrogen-bonding interactions. The C1—S1 bond distance of 1.6879 (11) Å in 1 is between the values for a double and a single bond, while the sum of bond angles around the thiourea carbon (C1) is 360.0°. In the thiourea backbone, the C1—N2 bond [1.3396 (14) Å] that is involved in intramolecular hydrogen bonding is slightly shorter than the C1—N1 bond [1.3621 (15) Å] without the intramolecular hydrogen bonding. The other C—N bond distances, such as C1—N1, C3—N3, C8—N2, and C9—N4 range from 1.41 to 1.43 Å. Similar bond distances and angles were observed for 2. The thiourea backbone contains the C1—S1 bond distance of 1.6921 (11) Å, and C1—N2 and C1—N1 bond distances of 1.3415 (14) and 1.3652 (14) Å, respectively, while the sum of the bond angles around C1 is 360.0°. Finally, the C1—N1, C3—N3, C8—N2, and C9—N4 bond distances range from 1.42 to 1.43 Å. Overall, a similar C1—S1 bond distance is observed within a variation of 0.01 Å between 1 and 2, while both structures exhibit a trigonal–planar geometry around the central carbon (C1). Furthermore, the C1—N2 bonds involved in intramolecular hydrogen bonds are 0.02 Å shorter than the C1—N1 bonds in 1 and 2 that do not participate in the hydrogen bonding.

3. Supramolecular features

Supramolecular features for 1 and 2 were investigated using Hirshfeld surface analysis with CrystalExplorer 21.5 (Spackman et al., 2021 ). Hirshfeld surfaces for 1 and 2 were mapped over d_norm in the range of −0.27 to 1.29 and −0.18 to 1.48 a.u. for 1 and 2, respectively (Figs. 3 and 4). The most intense red spots on the surface indicate the intermolecular H1⋯S1 interactions (Tables 1 and 2) with the graph-set descriptor R₂²(8) (Bernstein et al., 1995 ). The corresponding intermolecular distances of H1⋯S1 were measured to be 2.506 (14) and 2.677 (16) Å for 1 and 2, respectively. In addition, the acquired N—H stretch from IR spectra red shifted for 1 (3165 cm⁻¹) when compared to that of 2 (3226 cm⁻¹). This matches the elongated N1—H1 bond distance of 0.905 (15) Å and shorter H1⋯S1 interaction of 2.506 (14) Å for 1 when compared to those for 2 at 0.851 (16) and 2.677 (16) Å.

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.905 (15)	2.506 (14)	3.3814 (10)	163.4 (14)
N2—H2⋯N3	0.896 (15)	1.957 (17)	2.8018 (17)	156.8 (13)
Symmetry code: (i) .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.851 (16)	2.677 (16)	3.5017 (10)	163.6 (13)
N2—H2⋯N3	0.905 (15)	1.864 (15)	2.7366 (14)	161.4 (13)
Symmetry code: (i) .

Figure 3
(a) Hirshfeld surface mapped over d_norm in the range −0.27 to 1.29. (b) Partial packing plot of 1.

Figure 4
(a) Hirshfeld surface mapped over d_norm in the range −0.18 to 1.48. (b) Partial packing plot of 2.

Some weaker interactions were observed as faint red spots on the Hirshfeld surface. The spots in 1 correspond to the short contacts of C15—H15A⋯H15A—C15 and C5—H5⋯C9—C10 (Fig. 3). In addition, the spots in 2 correspond to C20—H20A⋯C15—H15B, C4—H4⋯C11, and C20—H20B⋯C5—C6 interactions (Fig. 4). No appreciable π–π interactions or hydrogen bonding associated with N4 atoms are observed for either 1 or 2. The Hirshfeld surface of 1 arises from H⋯H (64.8%), C⋯H/H⋯C (22.9%), and S⋯H/H⋯S (12.1%) contacts, whereas H⋯H (71.3%), C⋯H/H⋯C (14.4%), and S⋯H/H⋯S (11.4%) contacts contribute to the surface of 2. The minor contributions include N⋯H/H⋯N (0.2%) for 1 and C⋯C (2.0%) and N⋯H/H⋯N (1.0%) for 2.

4. Database survey

A search in the Cambridge Structural Database for structures 1 and 2 did not match any reported structures, including derivative searches. Similar compounds with dimethylamine at the meta or para position have been prepared, but the structures are unknown.

5. Synthesis and crystallization

Compounds 1 and 2 were prepared by treating 1,1′-thiocarbonyldiimidazole with two equivalents of 2-amino-N,N′-dialkylaniline in CH₂Cl₂ (Fig. 5) following the reported procedures (Ren et al., 2011 ; Thapa et al., 2020 ). Detailed procedures are described below. Single crystals were grown by diffusion of pentane vapor into a solution of 1 in THF or 2 in Et₂O, respectively. The relative intensities of IR bands were described as vw, w, m, s, and vs, corresponding to very weak, weak, medium, strong, and very strong, respectively.

Figure 5
Preparation of N,N′-bis(2-dimethylaminophenyl)thiourea (1) and N,N′-bis(2-diethylaminophenyl)thiourea (2).

N,N'-Bis(2-dimethylaminophenyl)thiourea (1). To a stirred solution of 1,1′-thiocarbonyldiimidazole (0.38 g, 2.2 mmol) in CH₂Cl₂ (5 mL) was added a solution of 2-amino-N,N′-dimethylaniline (0.58 g, 4.3 mmol) in CH₂Cl₂ (5 mL). The resulting solution was heated at 323 K overnight. CH₂Cl₂ (50 mL) was added to the pale-yellow solution, and the solution was washed with deionized (DI) water (60 mL) three times. The organic layer was dried over Na₂SO₄ and evaporated to dryness under vacuum. The obtained solid was solubilized in a minimum amount of CH₂Cl₂ (ca 5 mL) and excess amount of Et₂O was added before the solution was stored at 253 K. The product was obtained as an off-white powder. Yield: 0.47 g (70%). ¹H NMR (CDCl₃, 300 MHz): δ 8.82 (br s, NH, 2H), 7.96 (s, Ar, 2H), 7.19–7.13 (m, Ar, 2H), 7.13–7.06 (m, Ar, 4H), 2.64 (s, NMe₂, 12H). ¹³C{¹H} NMR (CDCl₃, 126 MHz): δ 178.66 (s, C—S), 146.26 (s, Ar), 132.49 (s, Ar), 126.25 (s, Ar), 124.16 (s, Ar), 123.56 (s, Ar), 119.71 (s, Ar), 44.00 [s, N(CH₃)₂]. IR (ATR, cm⁻¹): 3165 s (N—H stretch), 3068 w (C—H stretch), 2984 w (C—H stretch), 2936 w (C—H stretch), 2834 m (C—H stretch), 2788 w (C—H stretch), 1596 s, 1583 s, 1552 s, 1525 s, 1489 vs, 1451 m, 1429 w, 1405 w, 1362 s, 1297 m, 1259 s, 1215 s, 1159 w, 1150 m, 1100 s, 1045 vs, 935 vs, 855 vw, 809 m, 751 vs, 735 m, 644 m, 623 vs, 566 m, 558 m, 531 m, 507 m, 493 s. ESI–MS m/z: calculated for C₁₇H₂₃N₄S 315.1643; found 315.1644.

N,N'-Bis(2-diethylaminophenyl)thiourea (2). To a stirred solution of 1,1′-thiocarbonyldiimidazole (0.40 g, 2.2 mmol) in CH₂Cl₂ (5 mL) was added a solution of 2-amino-N,N′-dimethylaniline (0.74 g, 4.5 mmol) in CH₂Cl₂ (5 mL). The resulting solution was heated at 323 K overnight. CH₂Cl₂ (20 mL) was added to the pale-yellow solution, and the solution was washed with DI water (30 mL) three times. The organic layer was dried over Na₂SO₄ and evaporated to dryness under vacuum. The obtained solid was solubilized in a minimum amount of CH₂Cl₂ (ca 5 mL) and excess amount of Et₂O was added before the solution was stored at 253 K. The product was obtained as an off-white powder. Yield: 0.51 g (61%). ¹H NMR (CDCl₃, 300 MHz): δ 9.14 (br s, NH, 2H), 8.27 (s, Ar, 2H), 7.20–7.10 (m, Ar, 6H), 2.89 (q, NCH₂, 8H), 0.89 (t, CH₃, 12H). ¹³C{¹H} NMR (CDCl₃, 126 MHz): δ 176.68 (s, C—S), 141.93 (s, Ar), 135.14 (s, Ar), 125.03 (s, Ar), 124.59 (s, Ar), 123.19 (s, Ar), 121.78 (s, Ar), 48.07 [s, N(CH₂CH₃)₂], 12.47 [s, N(CH₂CH₃)₂]. IR (ATR, cm⁻¹): 3226 s (N—H stretch), 2977 s (C—H stretch), 2958 w (C—H stretch), 2936 w (C—H stretch), 2866 m (C—H stretch), 1600 s, 1577 m, 1556 s, 1523 s, 1485 vs, 1442 s, 1370 vs, 1347 m, 1336 w, 1302 m, 1285 m, 1275 m, 1257 m, 1236 s, 1203 s, 1162 s, 1088 s, 1066 m, 1015 s, 942 w, 901 w, 861 w, 828 m, 799 m, 766 w, 755 vs, 735 m, 692 m, 646 s, 623 s, 586 m, 555 m, 523 m, 506 s, 470 m, 463 m, 435 w. ESI–MS m/z: calculated for C₂₁H₃₁N₄S 371.2269; found 371.2273.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3. Upon scrutiny, no appreciable disorder was observed in either structure. The positions of hydrogen on nitrogen atoms were refined, whereas the other hydrogen atoms were optimized using riding models [C—H = 0.93–0.98 Å; U_iso(H) = 1.2–1.5U_eq(C)].

Table 3
Experimental details

	1	2
Crystal data
Chemical formula	C₁₇H₂₂N₄S	C₂₁H₃₀N₄S
M_r	314.44	370.55
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/n
Temperature (K)	173	296
a, b, c (Å)	7.6486 (1), 10.8964 (2), 10.9266 (2)	9.6159 (7), 16.0524 (11), 12.9462 (8)
α, β, γ (°)	78.086 (1), 70.863 (1), 81.135 (1)	90, 96.724 (3), 90
V (Å³)	838.10 (3)	1984.6 (2)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.20	0.18
Crystal size (mm)	0.41 × 0.33 × 0.16	0.63 × 0.46 × 0.33

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.705, 0.746	0.671, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	15212, 3820, 3496	19639, 4948, 4402
R_int	0.023	0.037
(sin θ/λ)_max (Å⁻¹)	0.649	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.089, 1.04	0.037, 0.095, 1.04
No. of reflections	3820	4948
No. of parameters	209	245
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)	0.24, −0.27	0.32, −0.26
Computer programs: APEX2 and SAINT (Bruker, 2012 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC references: 2233350; 2233349

Crystal structure: contains datablocks global, 1, 2. DOI: https://doi.org/10.1107/S2056989022012245/jq2024sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989022012245/jq20241sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989022012245/jq20242sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989022012245/jq20241sup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989022012245/jq20242sup5.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989022012245/jq2024sup6.docx

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

N,N'-Bis[2-(dimethylamino)phenyl]thiourea (1) top

Crystal data top

C₁₇H₂₂N₄S	Z = 2
M_r = 314.44	F(000) = 336
Triclinic, P1	D_x = 1.246 Mg m⁻³
a = 7.6486 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8964 (2) Å	Cell parameters from 8859 reflections
c = 10.9266 (2) Å	θ = 2.5–27.5°
α = 78.086 (1)°	µ = 0.20 mm⁻¹
β = 70.863 (1)°	T = 173 K
γ = 81.135 (1)°	BLOCK, colourless
V = 838.10 (3) Å³	0.41 × 0.33 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	3496 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.023
φ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
T_min = 0.705, T_max = 0.746	k = −14→14
15212 measured reflections	l = −13→14
3820 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0424P)² + 0.2821P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3820 reflections	Δρ_max = 0.24 e Å⁻³
209 parameters	Δρ_min = −0.26 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
S1	0.11704 (4)	0.46317 (3)	0.30114 (3)	0.02635 (10)
N2	0.38096 (14)	0.27534 (9)	0.32181 (9)	0.0225 (2)
H2	0.466 (2)	0.2452 (13)	0.3632 (14)	0.027*
N1	0.20935 (15)	0.34773 (9)	0.51263 (9)	0.0246 (2)
H1	0.115 (2)	0.4039 (14)	0.5467 (14)	0.030*
N4	0.71659 (14)	0.34986 (9)	0.14163 (10)	0.0256 (2)
N3	0.57747 (15)	0.21641 (10)	0.50554 (11)	0.0288 (2)
C9	0.59665 (16)	0.29364 (10)	0.09912 (11)	0.0216 (2)
C2	0.23764 (17)	0.23641 (10)	0.60252 (11)	0.0231 (2)
C3	0.41291 (17)	0.17201 (10)	0.60109 (11)	0.0241 (2)
C1	0.24274 (15)	0.35521 (10)	0.38108 (11)	0.0207 (2)
C8	0.42590 (15)	0.25953 (10)	0.18851 (11)	0.0206 (2)
C13	0.30914 (17)	0.19843 (11)	0.15256 (12)	0.0270 (3)
H13	0.193140	0.176791	0.214054	0.032*
C10	0.64498 (18)	0.26354 (11)	−0.02667 (12)	0.0280 (3)
H10	0.759573	0.286296	−0.089404	0.034*
C7	0.07808 (19)	0.19426 (12)	0.69835 (12)	0.0302 (3)
H7	−0.039053	0.239647	0.700428	0.036*
C4	0.4167 (2)	0.06285 (11)	0.69360 (12)	0.0319 (3)
H4	0.532617	0.015914	0.692284	0.038*
C12	0.36034 (19)	0.16861 (12)	0.02749 (13)	0.0329 (3)
H12	0.280371	0.126205	0.003170	0.039*
C11	0.5286 (2)	0.20110 (13)	−0.06139 (13)	0.0334 (3)
H11	0.564805	0.180434	−0.147111	0.040*
C17	0.65604 (19)	0.48128 (12)	0.15808 (15)	0.0360 (3)
H17A	0.677991	0.534802	0.071569	0.054*
H17B	0.726455	0.507818	0.207029	0.054*
H17C	0.523152	0.489167	0.206665	0.054*
C5	0.2567 (2)	0.02127 (12)	0.78690 (13)	0.0386 (3)
H5	0.263790	−0.053267	0.848686	0.046*
C16	0.91227 (18)	0.33728 (14)	0.06450 (15)	0.0385 (3)
H16A	0.951293	0.248938	0.054645	0.058*
H16B	0.987224	0.364986	0.109466	0.058*
H16C	0.929808	0.389445	−0.022427	0.058*
C6	0.0869 (2)	0.08720 (13)	0.79092 (13)	0.0385 (3)
H6	−0.023033	0.059693	0.856327	0.046*
C14	0.7454 (2)	0.12829 (15)	0.48739 (17)	0.0428 (3)
H14A	0.786992	0.115000	0.565347	0.064*
H14B	0.843493	0.163155	0.410108	0.064*
H14C	0.718103	0.047721	0.474562	0.064*
C15	0.6169 (2)	0.33902 (13)	0.52041 (17)	0.0435 (4)
H15A	0.504137	0.397587	0.530400	0.065*
H15B	0.715220	0.372392	0.442398	0.065*
H15C	0.657686	0.329057	0.598368	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02772 (17)	0.02673 (16)	0.02053 (15)	0.00853 (11)	−0.00787 (12)	−0.00237 (11)
N2	0.0221 (5)	0.0251 (5)	0.0180 (5)	0.0051 (4)	−0.0064 (4)	−0.0037 (4)
N1	0.0283 (5)	0.0220 (5)	0.0182 (5)	0.0087 (4)	−0.0052 (4)	−0.0030 (4)
N4	0.0226 (5)	0.0245 (5)	0.0292 (5)	−0.0008 (4)	−0.0079 (4)	−0.0042 (4)
N3	0.0261 (5)	0.0299 (5)	0.0324 (6)	0.0031 (4)	−0.0124 (4)	−0.0081 (4)
C9	0.0227 (6)	0.0182 (5)	0.0218 (5)	0.0038 (4)	−0.0080 (4)	−0.0014 (4)
C2	0.0313 (6)	0.0199 (5)	0.0174 (5)	0.0030 (4)	−0.0088 (5)	−0.0036 (4)
C3	0.0321 (6)	0.0209 (5)	0.0227 (5)	0.0027 (4)	−0.0127 (5)	−0.0074 (4)
C1	0.0203 (5)	0.0193 (5)	0.0199 (5)	−0.0006 (4)	−0.0044 (4)	−0.0015 (4)
C8	0.0218 (5)	0.0189 (5)	0.0191 (5)	0.0052 (4)	−0.0064 (4)	−0.0035 (4)
C13	0.0231 (6)	0.0274 (6)	0.0298 (6)	0.0005 (4)	−0.0080 (5)	−0.0055 (5)
C10	0.0283 (6)	0.0300 (6)	0.0201 (6)	0.0034 (5)	−0.0036 (5)	−0.0030 (5)
C7	0.0342 (7)	0.0288 (6)	0.0232 (6)	0.0025 (5)	−0.0053 (5)	−0.0041 (5)
C4	0.0462 (8)	0.0232 (6)	0.0307 (6)	0.0080 (5)	−0.0214 (6)	−0.0064 (5)
C12	0.0351 (7)	0.0337 (7)	0.0368 (7)	0.0016 (5)	−0.0179 (6)	−0.0134 (5)
C11	0.0409 (7)	0.0369 (7)	0.0237 (6)	0.0073 (6)	−0.0121 (5)	−0.0123 (5)
C17	0.0326 (7)	0.0269 (6)	0.0475 (8)	−0.0036 (5)	−0.0078 (6)	−0.0105 (6)
C5	0.0628 (10)	0.0221 (6)	0.0276 (7)	0.0026 (6)	−0.0155 (6)	0.0013 (5)
C16	0.0230 (6)	0.0416 (7)	0.0498 (8)	−0.0017 (5)	−0.0086 (6)	−0.0106 (6)
C6	0.0506 (9)	0.0308 (7)	0.0252 (6)	−0.0046 (6)	−0.0020 (6)	0.0001 (5)
C14	0.0306 (7)	0.0474 (8)	0.0546 (9)	0.0098 (6)	−0.0180 (7)	−0.0195 (7)
C15	0.0392 (8)	0.0329 (7)	0.0593 (10)	−0.0069 (6)	−0.0154 (7)	−0.0069 (7)

Geometric parameters (Å, º) top

S1—C1	1.6879 (11)	C7—H7	0.9500
N2—H2	0.896 (15)	C7—C6	1.3862 (17)
N2—C1	1.3396 (14)	C4—H4	0.9500
N2—C8	1.4235 (14)	C4—C5	1.380 (2)
N1—H1	0.905 (15)	C12—H12	0.9500
N1—C2	1.4316 (14)	C12—C11	1.380 (2)
N1—C1	1.3621 (15)	C11—H11	0.9500
N4—C9	1.4152 (15)	C17—H17A	0.9800
N4—C17	1.4645 (16)	C17—H17B	0.9800
N4—C16	1.4583 (17)	C17—H17C	0.9800
N3—C3	1.4233 (16)	C5—H5	0.9500
N3—C14	1.4636 (17)	C5—C6	1.376 (2)
N3—C15	1.4657 (17)	C16—H16A	0.9800
C9—C8	1.4004 (16)	C16—H16B	0.9800
C9—C10	1.3960 (16)	C16—H16C	0.9800
C2—C3	1.4109 (16)	C6—H6	0.9500
C2—C7	1.3903 (17)	C14—H14A	0.9800
C3—C4	1.3963 (16)	C14—H14B	0.9800
C8—C13	1.3843 (17)	C14—H14C	0.9800
C13—H13	0.9500	C15—H15A	0.9800
C13—C12	1.3855 (18)	C15—H15B	0.9800
C10—H10	0.9500	C15—H15C	0.9800
C10—C11	1.3835 (19)

C1—N2—H2	115.8 (9)	C5—C4—H4	119.1
C1—N2—C8	124.84 (10)	C13—C12—H12	120.3
C8—N2—H2	117.6 (9)	C11—C12—C13	119.35 (12)
C2—N1—H1	115.3 (9)	C11—C12—H12	120.3
C1—N1—H1	111.8 (9)	C10—C11—H11	119.7
C1—N1—C2	125.90 (10)	C12—C11—C10	120.53 (12)
C9—N4—C17	113.86 (10)	C12—C11—H11	119.7
C9—N4—C16	115.07 (10)	N4—C17—H17A	109.5
C16—N4—C17	110.25 (10)	N4—C17—H17B	109.5
C3—N3—C14	116.65 (11)	N4—C17—H17C	109.5
C3—N3—C15	113.45 (10)	H17A—C17—H17B	109.5
C14—N3—C15	110.35 (11)	H17A—C17—H17C	109.5
C8—C9—N4	119.15 (10)	H17B—C17—H17C	109.5
C10—C9—N4	122.93 (11)	C4—C5—H5	119.8
C10—C9—C8	117.82 (11)	C6—C5—C4	120.36 (12)
C3—C2—N1	124.50 (11)	C6—C5—H5	119.8
C7—C2—N1	115.61 (11)	N4—C16—H16A	109.5
C7—C2—C3	119.87 (11)	N4—C16—H16B	109.5
C2—C3—N3	120.27 (10)	N4—C16—H16C	109.5
C4—C3—N3	122.17 (11)	H16A—C16—H16B	109.5
C4—C3—C2	117.53 (12)	H16A—C16—H16C	109.5
N2—C1—S1	123.65 (9)	H16B—C16—H16C	109.5
N2—C1—N1	116.15 (10)	C7—C6—H6	120.4
N1—C1—S1	120.19 (8)	C5—C6—C7	119.19 (13)
C9—C8—N2	119.51 (10)	C5—C6—H6	120.4
C13—C8—N2	119.31 (10)	N3—C14—H14A	109.5
C13—C8—C9	120.82 (10)	N3—C14—H14B	109.5
C8—C13—H13	119.8	N3—C14—H14C	109.5
C8—C13—C12	120.45 (12)	H14A—C14—H14B	109.5
C12—C13—H13	119.8	H14A—C14—H14C	109.5
C9—C10—H10	119.5	H14B—C14—H14C	109.5
C11—C10—C9	121.03 (12)	N3—C15—H15A	109.5
C11—C10—H10	119.5	N3—C15—H15B	109.5
C2—C7—H7	119.4	N3—C15—H15C	109.5
C6—C7—C2	121.18 (12)	H15A—C15—H15B	109.5
C6—C7—H7	119.4	H15A—C15—H15C	109.5
C3—C4—H4	119.1	H15B—C15—H15C	109.5
C5—C4—C3	121.79 (12)

N2—C8—C13—C12	−172.36 (10)	C1—N1—C2—C7	−115.29 (13)
N1—C2—C3—N3	−0.24 (17)	C8—N2—C1—S1	−8.08 (16)
N1—C2—C3—C4	−178.48 (11)	C8—N2—C1—N1	173.53 (10)
N1—C2—C7—C6	179.76 (12)	C8—C9—C10—C11	−0.54 (17)
N4—C9—C8—N2	−3.56 (15)	C8—C13—C12—C11	−0.39 (19)
N4—C9—C8—C13	−176.63 (10)	C13—C12—C11—C10	−0.40 (19)
N4—C9—C10—C11	175.69 (11)	C10—C9—C8—N2	172.81 (10)
N3—C3—C4—C5	179.22 (11)	C10—C9—C8—C13	−0.25 (16)
C9—C8—C13—C12	0.72 (17)	C7—C2—C3—N3	−178.31 (11)
C9—C10—C11—C12	0.88 (19)	C7—C2—C3—C4	3.45 (17)
C2—N1—C1—S1	150.72 (10)	C4—C5—C6—C7	1.4 (2)
C2—N1—C1—N2	−30.83 (17)	C17—N4—C9—C8	−74.41 (13)
C2—C3—C4—C5	−2.57 (18)	C17—N4—C9—C10	109.41 (13)
C2—C7—C6—C5	−0.5 (2)	C16—N4—C9—C8	156.94 (11)
C3—C2—C7—C6	−2.01 (19)	C16—N4—C9—C10	−19.25 (16)
C3—C4—C5—C6	0.2 (2)	C14—N3—C3—C2	−164.03 (11)
C1—N2—C8—C9	114.58 (13)	C14—N3—C3—C4	14.13 (17)
C1—N2—C8—C13	−72.26 (15)	C15—N3—C3—C2	66.05 (15)
C1—N1—C2—C3	66.56 (17)	C15—N3—C3—C4	−115.79 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.905 (15)	2.506 (14)	3.3814 (10)	163.4 (14)
N2—H2···N3	0.896 (15)	1.957 (17)	2.8018 (17)	156.8 (13)

Symmetry code: (i) −x, −y+1, −z+1.

N,N'-Bis[2-(diethylamino)phenyl]thiourea (2) top

Crystal data top

C₂₁H₃₀N₄S	F(000) = 800
M_r = 370.55	D_x = 1.240 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.6159 (7) Å	Cell parameters from 8945 reflections
b = 16.0524 (11) Å	θ = 2.5–28.4°
c = 12.9462 (8) Å	µ = 0.18 mm⁻¹
β = 96.724 (3)°	T = 296 K
V = 1984.6 (2) Å³	Block, colourless
Z = 4	0.63 × 0.46 × 0.33 mm

Data collection top

Bruker APEXII CCD diffractometer	4402 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.037
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 28.4°, θ_min = 2.0°
T_min = 0.671, T_max = 0.746	h = −12→12
19639 measured reflections	k = −21→21
4948 independent reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0441P)² + 0.8116P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4948 reflections	Δρ_max = 0.32 e Å⁻³
245 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.02729 (3)	0.62006 (2)	0.58639 (3)	0.02352 (9)
N2	0.24439 (10)	0.69094 (6)	0.50659 (7)	0.01290 (18)
H2	0.2836 (15)	0.6950 (9)	0.4466 (11)	0.015*
N3	0.33323 (10)	0.67098 (6)	0.31488 (7)	0.01359 (19)
N1	0.17251 (10)	0.56268 (6)	0.44080 (7)	0.01455 (19)
H1	0.1150 (15)	0.5228 (10)	0.4448 (11)	0.017*
N4	0.20893 (10)	0.85320 (6)	0.42949 (7)	0.01425 (19)
C3	0.37577 (11)	0.58724 (7)	0.33846 (8)	0.0127 (2)
C9	0.25294 (11)	0.84099 (7)	0.53724 (8)	0.0131 (2)
C2	0.29696 (11)	0.53669 (7)	0.39875 (8)	0.0127 (2)
C8	0.25996 (11)	0.75917 (7)	0.57688 (8)	0.0129 (2)
C4	0.49907 (12)	0.55411 (7)	0.30729 (8)	0.0157 (2)
H4	0.554145	0.587217	0.269367	0.019*
C7	0.33721 (12)	0.45419 (7)	0.41875 (8)	0.0156 (2)
H7	0.281572	0.420032	0.454924	0.019*
C5	0.54073 (12)	0.47335 (8)	0.33161 (9)	0.0172 (2)
H5	0.624257	0.453287	0.311572	0.021*
C16	0.44184 (12)	0.72933 (7)	0.28857 (9)	0.0176 (2)
H16A	0.398226	0.781294	0.264119	0.021*
H16B	0.488678	0.706059	0.232742	0.021*
C10	0.29015 (12)	0.90660 (7)	0.60646 (9)	0.0164 (2)
H10	0.289327	0.960906	0.581382	0.020*
C12	0.32860 (12)	0.81178 (8)	0.75043 (9)	0.0168 (2)
H12	0.350995	0.802119	0.821254	0.020*
C13	0.29531 (11)	0.74547 (7)	0.68286 (8)	0.0152 (2)
H13	0.296695	0.691408	0.708783	0.018*
C1	0.15685 (11)	0.62606 (7)	0.50880 (8)	0.0142 (2)
C6	0.45841 (12)	0.42208 (7)	0.38581 (9)	0.0177 (2)
H6	0.484168	0.367023	0.399816	0.021*
C18	0.05902 (12)	0.83248 (7)	0.40160 (9)	0.0165 (2)
H18A	0.042289	0.777080	0.427390	0.020*
H18B	0.039633	0.830878	0.326388	0.020*
C14	0.20097 (12)	0.67896 (8)	0.24495 (9)	0.0177 (2)
H14A	0.161228	0.733438	0.255343	0.021*
H14B	0.135428	0.637633	0.264764	0.021*
C11	0.32826 (12)	0.89210 (8)	0.71185 (9)	0.0174 (2)
H11	0.353513	0.936423	0.756383	0.021*
C20	0.24384 (12)	0.93418 (7)	0.38573 (9)	0.0180 (2)
H20A	0.210396	0.978289	0.427696	0.022*
H20B	0.195027	0.939178	0.316070	0.022*
C17	0.54904 (13)	0.74644 (8)	0.38189 (10)	0.0211 (2)
H17A	0.614692	0.787422	0.363685	0.032*
H17B	0.597900	0.695884	0.402564	0.032*
H17C	0.502305	0.766842	0.438405	0.032*
C21	0.39972 (13)	0.94621 (8)	0.38091 (10)	0.0213 (2)
H21A	0.430684	0.908551	0.330719	0.032*
H21B	0.449937	0.935165	0.448033	0.032*
H21C	0.416989	1.002519	0.360919	0.032*
C15	0.21500 (15)	0.66843 (8)	0.13015 (9)	0.0251 (3)
H15A	0.123605	0.667487	0.091349	0.038*
H15B	0.262470	0.617064	0.119600	0.038*
H15C	0.267808	0.714092	0.106882	0.038*
C19	−0.04336 (13)	0.89250 (8)	0.44342 (10)	0.0229 (3)
H19A	−0.036737	0.946001	0.411224	0.034*
H19B	−0.020992	0.897916	0.517347	0.034*
H19C	−0.136942	0.871446	0.428077	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02364 (16)	0.01920 (16)	0.03137 (18)	−0.00753 (12)	0.01852 (13)	−0.00934 (12)
N2	0.0141 (4)	0.0115 (4)	0.0137 (4)	−0.0010 (3)	0.0045 (3)	−0.0009 (3)
N3	0.0141 (4)	0.0124 (5)	0.0147 (4)	−0.0004 (3)	0.0032 (3)	0.0012 (3)
N1	0.0136 (4)	0.0124 (5)	0.0188 (5)	−0.0030 (4)	0.0068 (3)	−0.0025 (4)
N4	0.0146 (4)	0.0123 (4)	0.0155 (4)	−0.0017 (4)	0.0001 (3)	0.0017 (3)
C3	0.0131 (5)	0.0134 (5)	0.0115 (5)	0.0001 (4)	0.0011 (4)	−0.0020 (4)
C9	0.0108 (5)	0.0131 (5)	0.0156 (5)	0.0000 (4)	0.0020 (4)	−0.0006 (4)
C2	0.0124 (5)	0.0142 (5)	0.0116 (5)	0.0002 (4)	0.0018 (4)	−0.0025 (4)
C8	0.0106 (5)	0.0122 (5)	0.0162 (5)	−0.0003 (4)	0.0034 (4)	−0.0022 (4)
C4	0.0143 (5)	0.0182 (6)	0.0150 (5)	−0.0018 (4)	0.0035 (4)	−0.0024 (4)
C7	0.0184 (5)	0.0141 (5)	0.0144 (5)	−0.0014 (4)	0.0021 (4)	−0.0007 (4)
C5	0.0137 (5)	0.0194 (6)	0.0183 (5)	0.0032 (4)	0.0015 (4)	−0.0043 (4)
C16	0.0204 (6)	0.0149 (5)	0.0187 (5)	−0.0030 (4)	0.0070 (4)	0.0004 (4)
C10	0.0157 (5)	0.0125 (5)	0.0210 (5)	−0.0008 (4)	0.0027 (4)	−0.0014 (4)
C12	0.0132 (5)	0.0230 (6)	0.0141 (5)	0.0026 (4)	0.0013 (4)	−0.0020 (4)
C13	0.0143 (5)	0.0151 (5)	0.0168 (5)	0.0021 (4)	0.0038 (4)	0.0013 (4)
C1	0.0134 (5)	0.0138 (5)	0.0159 (5)	0.0006 (4)	0.0038 (4)	0.0001 (4)
C6	0.0192 (6)	0.0148 (5)	0.0184 (5)	0.0039 (4)	−0.0008 (4)	−0.0020 (4)
C18	0.0152 (5)	0.0153 (5)	0.0184 (5)	−0.0009 (4)	−0.0011 (4)	−0.0011 (4)
C14	0.0168 (5)	0.0172 (6)	0.0186 (5)	0.0030 (4)	0.0003 (4)	0.0005 (4)
C11	0.0138 (5)	0.0182 (6)	0.0203 (5)	−0.0014 (4)	0.0016 (4)	−0.0064 (4)
C20	0.0203 (6)	0.0132 (5)	0.0202 (5)	−0.0014 (4)	0.0017 (4)	0.0035 (4)
C17	0.0195 (6)	0.0189 (6)	0.0255 (6)	−0.0044 (5)	0.0047 (5)	−0.0030 (5)
C21	0.0227 (6)	0.0164 (6)	0.0255 (6)	−0.0032 (5)	0.0061 (5)	0.0010 (5)
C15	0.0354 (7)	0.0219 (6)	0.0169 (6)	−0.0012 (5)	−0.0016 (5)	0.0007 (5)
C19	0.0163 (6)	0.0243 (7)	0.0281 (6)	0.0005 (5)	0.0031 (5)	−0.0038 (5)

Geometric parameters (Å, º) top

S1—C1	1.6921 (11)	C10—C11	1.3903 (16)
N2—H2	0.905 (15)	C12—H12	0.9300
N2—C8	1.4206 (14)	C12—C13	1.3910 (16)
N2—C1	1.3415 (14)	C12—C11	1.3826 (17)
N3—C3	1.4277 (14)	C13—H13	0.9300
N3—C16	1.4722 (14)	C6—H6	0.9300
N3—C14	1.4779 (14)	C18—H18A	0.9700
N1—H1	0.851 (16)	C18—H18B	0.9700
N1—C2	1.4335 (14)	C18—C19	1.5217 (17)
N1—C1	1.3652 (14)	C14—H14A	0.9700
N4—C9	1.4231 (14)	C14—H14B	0.9700
N4—C18	1.4822 (14)	C14—C15	1.5174 (17)
N4—C20	1.4724 (14)	C11—H11	0.9300
C3—C2	1.4072 (15)	C20—H20A	0.9700
C3—C4	1.4013 (15)	C20—H20B	0.9700
C9—C8	1.4089 (15)	C20—C21	1.5198 (17)
C9—C10	1.4018 (15)	C17—H17A	0.9600
C2—C7	1.3955 (16)	C17—H17B	0.9600
C8—C13	1.3919 (15)	C17—H17C	0.9600
C4—H4	0.9300	C21—H21A	0.9600
C4—C5	1.3822 (17)	C21—H21B	0.9600
C7—H7	0.9300	C21—H21C	0.9600
C7—C6	1.3865 (16)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C5—C6	1.3879 (17)	C15—H15C	0.9600
C16—H16A	0.9700	C19—H19A	0.9600
C16—H16B	0.9700	C19—H19B	0.9600
C16—C17	1.5186 (17)	C19—H19C	0.9600
C10—H10	0.9300

C8—N2—H2	118.1 (9)	N1—C1—S1	119.00 (8)
C1—N2—H2	113.5 (9)	C7—C6—C5	119.00 (11)
C1—N2—C8	127.18 (9)	C7—C6—H6	120.5
C3—N3—C16	117.08 (9)	C5—C6—H6	120.5
C3—N3—C14	114.65 (9)	N4—C18—H18A	108.5
C16—N3—C14	112.71 (9)	N4—C18—H18B	108.5
C2—N1—H1	112.4 (10)	N4—C18—C19	114.99 (10)
C1—N1—H1	113.5 (10)	H18A—C18—H18B	107.5
C1—N1—C2	128.45 (10)	C19—C18—H18A	108.5
C9—N4—C18	112.15 (9)	C19—C18—H18B	108.5
C9—N4—C20	116.34 (9)	N3—C14—H14A	108.5
C20—N4—C18	111.31 (9)	N3—C14—H14B	108.5
C2—C3—N3	120.14 (10)	N3—C14—C15	114.93 (10)
C4—C3—N3	121.78 (10)	H14A—C14—H14B	107.5
C4—C3—C2	118.01 (10)	C15—C14—H14A	108.5
C8—C9—N4	118.78 (10)	C15—C14—H14B	108.5
C10—C9—N4	123.20 (10)	C10—C11—H11	120.0
C10—C9—C8	118.02 (10)	C12—C11—C10	119.99 (11)
C3—C2—N1	124.79 (10)	C12—C11—H11	120.0
C7—C2—N1	115.56 (10)	N4—C20—H20A	108.9
C7—C2—C3	119.63 (10)	N4—C20—H20B	108.9
C9—C8—N2	119.24 (9)	N4—C20—C21	113.48 (10)
C13—C8—N2	120.32 (10)	H20A—C20—H20B	107.7
C13—C8—C9	120.14 (10)	C21—C20—H20A	108.9
C3—C4—H4	119.2	C21—C20—H20B	108.9
C5—C4—C3	121.52 (11)	C16—C17—H17A	109.5
C5—C4—H4	119.2	C16—C17—H17B	109.5
C2—C7—H7	119.3	C16—C17—H17C	109.5
C6—C7—C2	121.37 (11)	H17A—C17—H17B	109.5
C6—C7—H7	119.3	H17A—C17—H17C	109.5
C4—C5—H5	119.9	H17B—C17—H17C	109.5
C4—C5—C6	120.27 (11)	C20—C21—H21A	109.5
C6—C5—H5	119.9	C20—C21—H21B	109.5
N3—C16—H16A	109.3	C20—C21—H21C	109.5
N3—C16—H16B	109.3	H21A—C21—H21B	109.5
N3—C16—C17	111.40 (9)	H21A—C21—H21C	109.5
H16A—C16—H16B	108.0	H21B—C21—H21C	109.5
C17—C16—H16A	109.3	C14—C15—H15A	109.5
C17—C16—H16B	109.3	C14—C15—H15B	109.5
C9—C10—H10	119.3	C14—C15—H15C	109.5
C11—C10—C9	121.32 (11)	H15A—C15—H15B	109.5
C11—C10—H10	119.3	H15A—C15—H15C	109.5
C13—C12—H12	120.1	H15B—C15—H15C	109.5
C11—C12—H12	120.1	C18—C19—H19A	109.5
C11—C12—C13	119.72 (10)	C18—C19—H19B	109.5
C8—C13—H13	119.6	C18—C19—H19C	109.5
C12—C13—C8	120.71 (11)	H19A—C19—H19B	109.5
C12—C13—H13	119.6	H19A—C19—H19C	109.5
N2—C1—S1	124.35 (9)	H19B—C19—H19C	109.5
N2—C1—N1	116.61 (10)

N2—C8—C13—C12	171.57 (10)	C4—C3—C2—N1	176.86 (10)
N3—C3—C2—N1	−0.16 (16)	C4—C3—C2—C7	−4.85 (15)
N3—C3—C2—C7	178.13 (9)	C4—C5—C6—C7	−2.64 (17)
N3—C3—C4—C5	179.08 (10)	C16—N3—C3—C2	157.09 (10)
N1—C2—C7—C6	−177.58 (10)	C16—N3—C3—C4	−19.82 (14)
N4—C9—C8—N2	9.69 (15)	C16—N3—C14—C15	56.20 (13)
N4—C9—C8—C13	−176.53 (10)	C10—C9—C8—N2	−170.21 (10)
N4—C9—C10—C11	177.90 (10)	C10—C9—C8—C13	3.57 (16)
C3—N3—C16—C17	−67.54 (12)	C13—C12—C11—C10	2.17 (17)
C3—N3—C14—C15	−81.12 (12)	C1—N2—C8—C9	−128.51 (12)
C3—C2—C7—C6	3.98 (16)	C1—N2—C8—C13	57.73 (15)
C3—C4—C5—C6	1.66 (17)	C1—N1—C2—C3	−60.21 (16)
C9—N4—C18—C19	69.76 (13)	C1—N1—C2—C7	121.44 (12)
C9—N4—C20—C21	68.56 (13)	C18—N4—C9—C8	68.45 (13)
C9—C8—C13—C12	−2.13 (16)	C18—N4—C9—C10	−111.66 (12)
C9—C10—C11—C12	−0.65 (17)	C18—N4—C20—C21	−161.30 (10)
C2—N1—C1—S1	−153.44 (9)	C14—N3—C3—C2	−67.53 (13)
C2—N1—C1—N2	28.65 (17)	C14—N3—C3—C4	115.56 (11)
C2—C3—C4—C5	2.11 (16)	C14—N3—C16—C17	156.26 (10)
C2—C7—C6—C5	−0.18 (17)	C11—C12—C13—C8	−0.78 (17)
C8—N2—C1—S1	10.13 (16)	C20—N4—C9—C8	−161.81 (10)
C8—N2—C1—N1	−172.09 (10)	C20—N4—C9—C10	18.08 (15)
C8—C9—C10—C11	−2.20 (16)	C20—N4—C18—C19	−62.54 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.851 (16)	2.677 (16)	3.5017 (10)	163.6 (13)
N2—H2···N3	0.905 (15)	1.864 (15)	2.7366 (14)	161.4 (13)

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

Dr Ji-Eun Lee (Gyeongsang National University) is gratefully acknowledged for collecting the single-crystal XRD data.

Funding information

Funding for this research was provided by: National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (2021R1G1A1093332 and 2022R1F1A1064158).

References

Al-Saidi, H. M. & Khan, S. (2022). Crit. Rev. Anal. Chem. pp. 1–17. Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2012). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Doyle, A. G. & Jacobsen, E. N. (2007). Chem. Rev. 107, 5713–5743. Web of Science CrossRef PubMed CAS Google Scholar
Khan, E., Khan, S., Gul, Z. & Muhammad, M. (2021). Crit. Rev. Anal. Chem. 51, 812–834. Web of Science CAS PubMed Google Scholar
Kožurková, M., Sabolová, D. & Kristian, P. (2017). J. Appl. Toxicol. 37, 1132–1139. Web of Science PubMed Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Li, A.-F., Wang, J.-H., Wang, F. & Jiang, Y.-B. (2010). Chem. Soc. Rev. 39, 3729–3745. Web of Science CrossRef CAS PubMed Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parvin, T., Yadav, R. & Choudhury, L. H. (2020). Org. Biomol. Chem. 18, 5513–5532. Web of Science CrossRef CAS PubMed Google Scholar
Ren, P., Vechorkin, O., Csok, Z., Salihu, I., Scopelliti, R. & Hu, X. (2011). Dalton Trans. 40, 8906–8911. Web of Science CSD CrossRef CAS PubMed Google Scholar
Ronchetti, R., Moroni, G., Carotti, A., Gioiello, A. & Camaioni, E. (2021). RSC Med. Chem. 12, 1046–1064. Web of Science CrossRef CAS PubMed Google Scholar
Saeed, A., Flörke, U. & Erben, M. F. (2014). J. Sulfur Chem. 35, 318–355. Web of Science CrossRef CAS Google Scholar
Schroeder, D. C. (1955). Chem. Rev. 55, 181–228. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, Y.-L., Wei, Y. & Shi, M. (2017). ChemCatChem, 9, 718–727. Web of Science CrossRef CAS Google Scholar
Thapa, P., Palacios, P. M., Tran, T., Pierce, B. S. & Foss, F. W. (2020). J. Org. Chem. 85, 1991–2009. Web of Science CrossRef CAS PubMed Google Scholar
Zahra, U., Saeed, A., Abdul Fattah, T., Flörke, U. & Erben, M. F. (2022). RSC Adv. 12, 12710–12745. Web of Science CrossRef CAS PubMed Google Scholar
Zhang, Z. & Schreiner, P. R. (2009). Chem. Soc. Rev. 38, 1187–1198. Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 2| February 2023| Pages 60-64

https://doi.org/10.1107/S2056989022012245

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

Synthesis, characterization, and crystal structures of N,N′-bis­­(2-di­alkyl­amino­phen­yl)thio­ureas

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

Synthesis, characterization, and crystal structures of N,N′-bis(2-dialkylaminophenyl)thioureas

3. Supramolecular features