Crystal structure and Hirshfeld surface analysis of a new di­thio­glycoluril: 1,4-bis­(4-meth­oxy­phen­yl)-3a-methyl­tetra­hydro­imidazo[4,5-d]imidazole-2,5(1H,3H)-di­thione

Asegbeloyin, J.N.; Ifeanyieze, K.J.; Okpareke, O.C.; Oyeka, E.E.; Groutso, T.V.

doi:10.1107/S2056989019010764

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 75| Part 9| September 2019| Pages 1297-1300

https://doi.org/10.1107/S2056989019010764

Open

access

Crystal structure and Hirshfeld surface analysis of a new dithioglycoluril: 1,4-bis(4-methoxyphenyl)-3a-methyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dithione

Jonnie N. Asegbeloyin,^a Kenechukwu J. Ifeanyieze,^a Obinna C. Okpareke,^a ^* Ebube E. Oyeka ^a and Tatiana V. Groutso ^b

^aDepartment of Pure and Industrial Chemistry, University of Nigeria, Nsukka 410001, Enugu State, Nigeria, and ^bSchool of Chemical Sciences, the University of Auckland Private Bag 92019, Auckland 1142, New Zealand
^*Correspondence e-mail: obinna.okpareke@unn.edu.ng

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 8 May 2019; accepted 1 August 2019; online 6 August 2019)

In the title dithioglycoluril derivative, C₁₉H₂₀N₄O₃S₂, there is a difference in the torsion angles between the thioimidazole moiety and the methoxyphenyl groups on either side of the molecule [C—N—C_ar—C_ar = 116.9 (2) and −86.1 (3)°, respectively]. The N—C—N bond angle on one side of the dithioglycoluril moiety is slightly smaller compared to that on the opposite side, [110.9 (2)° cf. 112.0 (2)°], probably as a result of the steric effect of the methyl group. In the crystal, N—H⋯S hydrogen bonds link adjacent molecules to form chains propagating along the c-axis direction. The chains are linked by C—H⋯S hydrogen bonds, forming layers parallel to the bc plane. The layers are then linked by C—H⋯π interactions, leading to the formation of a three-dimensional supramolecular network. Hirshfeld surface analysis and two-dimensional fingerprint plots were used to investigate the molecular interactions in the crystal.

Keywords: crystal structure; thioglycoluril; imidazole; cinnamoyl chloride; isothiocyanate; N—H⋯S hydrogen bonding; C—H⋯π interactions.

CCDC reference: 1906113

1. Chemical context

Heterocycles with five-membered rings containing two nitrogen atoms in the 1,3 positions and three carbon atoms in the ring are known as imidazoles. Most imidazoles, except for the N-substituted derivatives, have a distinct pyrrole type and pyridine-type annular nitrogen atoms. The isolation of imidazole derivatives has been documented (Beyer et al., 2011 ; Zeng et al., 2003 ; Dawood et al., 2010 ). Glycolurils, tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-diones, are well-known imidazole derivatives of great research interest. As well as serving as building blocks in the preparation of many organic compounds and supramolecular synthons (Burnett et al., 2003 ; Kravchenko et al., 2018 ), they have also been reported to behave as nootropic (Ryzhkina et al., 2013 ), neurotropic (Berlyand et al., 2013 ) and anxiolytic agents (Kravchenko et al., 2018). Some derivatives are used as flame-resistant materials (Sal'keeva et al., 2016 ; Zharkov et al., 2015 ) and gelators (Tiefenbacher et al., 2011 ). While several glycoluril analogues have been synthesized and characterized, reports on dithioglycolurils are quite rare. In the course of our search for thioureas with bioactivity, we had intended to isolate (2E)-N-[(4-methoxyphenyl)carbamothioyl]-3-phenylprop-2-enamide using well-documented methods (Asegbeloyin et al., 2018 ; Douglass & Dains, 1934 ; Oyeka et al., 2018 ); however, we obtained crystals of 1,4-bis(4-methoxyphenyl)-3a-methyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dithione, a new dithioglycoluril. As a result of the importance of glucolurils and their analogues and our current interest in the construction of novel heterocycles with good bioactivity (Asegbeloyin et al., 2019 ), we decided to investigate the title compound, and we report herein on its synthesis, crystal structure and Hirshfeld surface analysis.

2. Structural commentary

The molecular structure and conformation of the title compound is shown in Fig. 1. The two imidazole rings, N1/N2/C1–C3 and N3/N4/C2/C3/C5, are inclined to each other by 62.16 (12)°, while the 4-methoxyphenyl rings (C6–C11 and C13–C18) are inclined to each other by 29.36 (12)°. The latter rings are inclined to the imidazole ring to which they are attached by 62.51 (11) and 89.16 (12)°, respectively. Hence, the two ends of the molecule are orientated differently, as shown by the difference in the torsion angles between the thioimidazole moiety and the methoxyphenyl groups; C2—N3—C6—C11 and C3—N1—C13—C14 are 116.9 (2) and −86.1 (3)°, respectively.

Figure 1
A view of the molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

The thione C=S bond lengths of 1.674 (2) Å are longer than those in previous reports where all N atoms were substituted (Deng et al., 2010 ; Wang et al., 2011 ; Wu & Sun, 2009 ; Zhang et al., 2011 ). The C—N bonds around the thione moiety [C1—N1, C1—N2, C5—N3 and C5—N4 = 1.350 (3), 1.357 (3), 1.355 (3) and 1.353 (3) Å, respectively] are significantly shorter than the average C—N single bond length of 1.48 Å (Oyeka et al., 2018), as has also been observed in other thioglycoluril systems (Wu & Sun, 2009; Zhang et al., 2011) and acyl thiourea derivatives (Asegbeloyin et al., 2018; Oyeka et al., 2018). This is probably due to the conjugation between the π-electrons on C=S and the lone pairs of electrons on the nitrogen atoms. The C—C bond lengths of the aromatic rings are typical of sp²-hybridized carbons while the C2—C3 bond of the thioglycoluril moiety [1.542 (3) Å] shows sp³ hybridization. These bond lengths are consistent with previous reports for thioglycourils and acylthioureas (Binzet et al., 2009 ; Oyeka et al., 2018; Wang & Xi, 2009 ; Yang, 2010 ). The imidazole carbon atoms, C2 and C3, each have a distorted tetrahedral geometry with the N1—C3—N4 and N2—C2—N3 bond angles being 112.0 (4) and 112.9 (2)°, respectively. The bond angles between the N-methoxyphenyl nitrogen atom and the aromatic ring, C5—N3—C6 and C1—N1—C13, are 124.8 (2) and 126.1 (2)°, respectively.

3. Supramolecular features

In the crystal, N—H⋯S hydrogen bonds link neighbouring molecules to form chains propagating along the c-axis direction (Table 1 and Fig. 2). The chains are linked by C—H⋯S hydrogen bonds, forming layers parallel to the bc plane (Fig. 3 and Table 1). In turn, the layers are linked by C—H⋯π interactions involving a methoxy methyl H atom (H12B) and a 4-methoxyphenyl ring (C13–C18); see Table 1. These interactions result in the formation of a supramolecular three-dimensional architecture (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C13–C18 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S2ⁱ	0.86	2.62	3.265 (2)	133
N4—H4⋯S1ⁱⁱ	0.86	2.57	3.382 (2)	157
C7—H7⋯S1ⁱⁱⁱ	0.93	2.87	3.786 (3)	170
C12—H12B⋯Cg^iv	0.96	2.99	3.893 (3)	157
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) x-1, y, z.

Figure 2
A view along the b axis of the N—H⋯S hydrogen-bonded chain in the crystal of the title compound.

Figure 3
A view along the b axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines and the C—H⋯π interactions are represented by blue arrows (see Table 1

for details). For clarity, H atoms not involved in these interactions have been omitted.

3.1. Hirshfeld Surface Analysis

The Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) were performed with CrystalExplorer17 (Turner et al., 2017 ). In the Hirshfeld surface mapped over d_norm (Fig. 4), the red spots indicate contacts shorter than the sum of the van der Waals radii with negative d_norm, blue regions represent contacts longer than the sum of van der Waals radii with negative d_norm, while white regions correspond to intermolecular distances close to the sum of the van der Waals radii with d_norm equal to zero. The most intense red spots on the surface of the title compound are found around the thione S and N—H groups of the compound, which play a role in the hydrogen bonding interactions in the crystal (Table 1 and Fig. 2). The less intense red spots (Fig. 4), are observed around the ring carbon atoms resulting from C—H⋯S and C—H⋯π short contacts. The two-dimensional fingerprint plots (Fig. 5) show the overall contribution of the various interactions and those delineated into H⋯H, S⋯H/H⋯S, C⋯H/H⋯C, O⋯H/H⋯O and N⋯H/H⋯N contacts. Apart from the non-directional H⋯H contacts (41.3%), the highest contribution to the Hirshfeld surface is from S⋯H/H⋯S contacts (26.1%).

Figure 4
The Hirshfeld surface of the title compound mapped over d_norm, with an arbitrary colour scale of −0.3207 to 1.4281.

Figure 5
(a) The full two-dimensional fingerprint plot of the title compound, and fingerprint plots delineated into (b) H⋯H, (c) S⋯H/H⋯S, (d) C⋯H/H⋯C, (e) O⋯H/H⋯O and (f) N⋯H/H⋯N contacts.

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.39, February 2019) for thioglycoluril found two molecules similar to the title compound: 1,6-dipivaloyl-3,3a,4,6a-tetramethyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dithione (refcode ADEMOL; Duspara et al., 2001 ) and 1,6-diacetyl-3,4,7,8-tetramethyl-2,5-dithiogylcoluril (SOLQIT; Cow, 1998 ). In both compounds, large polar groups are substituted on adjacent sides of the imidazole ring, resulting in steric hindrance and distortion of the C—N—C angles. The C—N—C bond angles between the thione carbon and the N-substituted groups are ca 119.8 and 125.4° in ADEMOL and 122.6 and 125.4° in SOLQIT. In the title compound, the C5—N3—C6 and C1—N1—C13 bond angles are 124.8 (2) and 126.1 (2)°, respectively, showing only little distortion. The thione bond lengths [C5=S2 and C1=S1 are both 1.674 (2) Å] in the title compound are longer than in the reference compounds (1.650–1.664 Å). This is probably due to the fact that all of the imidazole nitrogen atoms in the reference compounds are substituted. The presence of unsubstituted imidazole nitrogens in the title compound promotes conjugation between the lone pairs of electrons on the nitrogen atom and the C=S π-electrons and hence stretches the C=S bond. The C—N bond lengths around the thione group of the title compound [1.350 (3)–1.357 (3) Å] are shorter than the corresponding bonds in the reference compounds (ca 1.367–1.397 Å). The other C—N bonds and the C—C bonds in the thiogylcouril moiety are similar to those of the title compound.

5. Synthesis and crystallization

The title compound was synthesized according to the reported method (Asegbeloyin et al., 2018; Douglass & Dains, 1934; Oyeka et al., 2018). A solution of cinnamoyl chloride (0.02 mol) dissolved in 40 ml acetone was mixed with a 30 ml acetone solution of potassium thiocyanate (0.02 mol). The reaction mixture was refluxed for 30 min to give a suspension of cinnamoyl isothiocyanate, which was then left to cool to room temperature. 4-Methoxyaniline (0.02 mol) was dissolved in 40 ml of acetone and the resulting solution was mixed with the suspension of cinnamoyl isothiocyanate, and the mixture was stirred for 2 h. The resultant lemon–green solution was filtered and left at room temperature for 96 h to obtain colourless plate-like crystals of the title compound.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were placed at idealized positions (N—H = 0.86 Å, C—H = 0.93–0.98 Å) and refined using a riding model with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C,N) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₂₀N₄O₂S₂
M_r	400.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.1955 (3), 10.0157 (2), 14.5476 (3)
β (°)	98.329 (2)
V (Å³)	1902.36 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.73
Crystal size (mm)	0.12 × 0.05 × 0.01

Data collection
Diffractometer	Rigaku Oxford Diffraction XtaLAB Synergy, Dualflex, Pilatus 200K
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 $[Rigaku OD (2018). Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.735, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	25390, 3824, 3267
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.156, 1.22
No. of reflections	3824
No. of parameters	247
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.53
Computer programs: CrysAlis PRO (Rigaku OD, 2018 $[Rigaku OD (2018). Rigaku Oxford Diffraction, Yarnton, England.]$ ), olex2.solve (Bourhis et al., 2015 ), SHELXL2016/6 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1906113

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019010764/ex2021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019010764/ex2021Isup2.hkl

supporting information. DOI: https://doi.org/10.1107/S2056989019010764/ex2021sup3.docx

Supporting information file. DOI: https://doi.org/10.1107/S2056989019010764/ex2021Isup4.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: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

1,4-Bis(4-methoxyphenyl)-3a-methyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dithione top

Crystal data top

C₁₉H₂₀N₄O₂S₂	F(000) = 840
M_r = 400.51	D_x = 1.398 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 13.1955 (3) Å	Cell parameters from 11825 reflections
b = 10.0157 (2) Å	θ = 3.4–73.8°
c = 14.5476 (3) Å	µ = 2.73 mm⁻¹
β = 98.329 (2)°	T = 100 K
V = 1902.36 (7) Å³	Plate, clear colourless
Z = 4	0.12 × 0.05 × 0.01 mm

Data collection top

Rigaku Oxford Diffraction XtaLAB Synergy, Dualflex, Pilatus 200K diffractometer	3824 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3267 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.053
ω scans	θ_max = 74.2°, θ_min = 3.4°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	h = −16→15
T_min = 0.735, T_max = 1.000	k = −12→12
25390 measured reflections	l = −18→15

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.156	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.22	(Δ/σ)_max = 0.001
3824 reflections	Δρ_max = 0.63 e Å⁻³
247 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints

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
S2	0.42015 (4)	0.63758 (5)	0.56357 (4)	0.02883 (19)
S1	0.69303 (4)	0.64039 (6)	0.20550 (4)	0.03272 (19)
O2	0.05235 (12)	0.52239 (19)	0.24656 (13)	0.0411 (4)
O1	1.06251 (13)	0.6869 (2)	0.55605 (14)	0.0501 (5)
N3	0.42969 (13)	0.73812 (19)	0.39262 (13)	0.0282 (4)
N1	0.66847 (13)	0.76111 (19)	0.36715 (13)	0.0282 (4)
N4	0.56744 (13)	0.7746 (2)	0.49428 (13)	0.0302 (4)
H4	0.607926	0.773181	0.546222	0.036*
N2	0.52813 (13)	0.7489 (2)	0.26451 (13)	0.0321 (4)
H2	0.488712	0.728354	0.214118	0.039*
C6	0.33311 (15)	0.6860 (2)	0.35217 (14)	0.0278 (4)
C5	0.47370 (15)	0.7169 (2)	0.48150 (15)	0.0269 (4)
C13	0.77144 (15)	0.7412 (2)	0.41232 (15)	0.0285 (5)
C2	0.49454 (16)	0.8198 (2)	0.34048 (15)	0.0288 (5)
H2A	0.462130	0.905134	0.320659	0.035*
C9	0.14274 (16)	0.5846 (2)	0.27955 (16)	0.0326 (5)
C1	0.62924 (16)	0.7179 (2)	0.28148 (15)	0.0290 (4)
C3	0.59244 (16)	0.8391 (2)	0.41109 (16)	0.0294 (5)
C11	0.31898 (16)	0.5490 (2)	0.34585 (16)	0.0326 (5)
H11	0.373181	0.491552	0.365398	0.039*
C10	0.22374 (17)	0.4982 (2)	0.31029 (17)	0.0355 (5)
H10	0.213660	0.406289	0.306848	0.043*
C8	0.15769 (17)	0.7205 (3)	0.28276 (17)	0.0346 (5)
H8	0.104211	0.778010	0.261024	0.041*
C7	0.25360 (17)	0.7716 (3)	0.31882 (17)	0.0345 (5)
H7	0.264271	0.863400	0.320503	0.041*
C14	0.84562 (18)	0.8354 (3)	0.40334 (17)	0.0370 (5)
H14	0.829035	0.910173	0.366309	0.044*
C16	0.96858 (17)	0.7111 (3)	0.50581 (18)	0.0383 (6)
C15	0.94482 (18)	0.8197 (3)	0.44908 (17)	0.0393 (6)
H15	0.994904	0.882321	0.441325	0.047*
C18	0.79544 (19)	0.6308 (2)	0.4673 (2)	0.0383 (6)
H18	0.745801	0.566657	0.473044	0.046*
C4	0.62578 (19)	0.9834 (3)	0.42760 (19)	0.0391 (6)
H4A	0.685302	0.986734	0.474091	0.059*
H4B	0.571319	1.033392	0.448355	0.059*
H4C	0.641782	1.021121	0.370769	0.059*
C12	−0.03793 (18)	0.6032 (3)	0.2306 (2)	0.0427 (6)
H12A	−0.033051	0.663519	0.180189	0.064*
H12B	−0.044452	0.653243	0.285733	0.064*
H12C	−0.096868	0.546930	0.215268	0.064*
C17	0.8940 (2)	0.6156 (3)	0.5143 (2)	0.0432 (6)
H17	0.910343	0.541071	0.551726	0.052*
C19	1.14391 (19)	0.7756 (4)	0.5431 (2)	0.0588 (9)
H19A	1.151078	0.778830	0.478399	0.088*
H19B	1.206604	0.744313	0.578239	0.088*
H19C	1.128777	0.863354	0.563931	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0231 (3)	0.0352 (3)	0.0281 (3)	−0.00311 (18)	0.0035 (2)	0.00066 (19)
S1	0.0274 (3)	0.0385 (3)	0.0323 (3)	0.0050 (2)	0.0046 (2)	−0.0049 (2)
O2	0.0238 (8)	0.0425 (10)	0.0540 (11)	0.0022 (7)	−0.0052 (7)	−0.0128 (8)
O1	0.0242 (8)	0.0612 (13)	0.0617 (12)	0.0036 (8)	−0.0043 (8)	−0.0093 (10)
N3	0.0207 (8)	0.0359 (10)	0.0283 (9)	−0.0014 (7)	0.0043 (7)	0.0021 (7)
N1	0.0203 (8)	0.0334 (10)	0.0313 (9)	0.0005 (7)	0.0049 (7)	−0.0038 (7)
N4	0.0218 (8)	0.0410 (11)	0.0281 (9)	−0.0041 (7)	0.0050 (7)	−0.0020 (8)
N2	0.0223 (8)	0.0439 (11)	0.0298 (10)	0.0034 (8)	0.0028 (7)	−0.0014 (8)
C6	0.0218 (10)	0.0368 (12)	0.0245 (10)	0.0012 (8)	0.0031 (8)	−0.0011 (9)
C5	0.0219 (9)	0.0290 (10)	0.0299 (10)	0.0014 (8)	0.0037 (8)	−0.0034 (8)
C13	0.0230 (10)	0.0336 (11)	0.0294 (11)	−0.0037 (8)	0.0055 (8)	−0.0073 (9)
C2	0.0253 (10)	0.0321 (11)	0.0298 (11)	0.0019 (8)	0.0069 (8)	0.0021 (9)
C9	0.0251 (11)	0.0397 (12)	0.0319 (11)	0.0037 (9)	0.0006 (8)	−0.0074 (9)
C1	0.0279 (10)	0.0298 (10)	0.0295 (11)	−0.0001 (8)	0.0055 (8)	0.0012 (8)
C3	0.0261 (10)	0.0322 (11)	0.0318 (11)	−0.0005 (8)	0.0101 (8)	−0.0035 (9)
C11	0.0248 (10)	0.0362 (12)	0.0349 (12)	0.0074 (9)	−0.0020 (8)	−0.0034 (9)
C10	0.0291 (11)	0.0322 (12)	0.0430 (13)	0.0016 (9)	−0.0027 (9)	−0.0046 (10)
C8	0.0251 (10)	0.0397 (13)	0.0378 (12)	0.0081 (9)	0.0012 (9)	0.0006 (10)
C7	0.0286 (11)	0.0341 (12)	0.0397 (12)	0.0022 (9)	0.0010 (9)	0.0007 (10)
C14	0.0289 (11)	0.0451 (13)	0.0368 (12)	−0.0083 (10)	0.0041 (9)	0.0045 (10)
C16	0.0259 (11)	0.0487 (14)	0.0395 (13)	0.0019 (10)	0.0018 (9)	−0.0091 (11)
C15	0.0282 (11)	0.0519 (15)	0.0387 (13)	−0.0098 (10)	0.0074 (9)	−0.0026 (11)
C18	0.0281 (11)	0.0340 (12)	0.0517 (15)	−0.0039 (9)	0.0020 (10)	−0.0011 (10)
C4	0.0382 (12)	0.0334 (12)	0.0478 (14)	−0.0015 (10)	0.0128 (10)	−0.0048 (10)
C12	0.0240 (11)	0.0507 (15)	0.0518 (15)	0.0035 (10)	0.0002 (10)	−0.0070 (12)
C17	0.0343 (13)	0.0375 (13)	0.0557 (16)	0.0026 (10)	−0.0005 (11)	0.0040 (11)
C19	0.0237 (12)	0.103 (3)	0.0501 (16)	−0.0083 (14)	0.0054 (11)	−0.0106 (16)

Geometric parameters (Å, º) top

S2—C5	1.674 (2)	C9—C8	1.375 (4)
S1—C1	1.674 (2)	C3—C4	1.520 (3)
O2—C9	1.370 (3)	C11—H11	0.9300
O2—C12	1.431 (3)	C11—C10	1.385 (3)
O1—C16	1.366 (3)	C10—H10	0.9300
O1—C19	1.427 (4)	C8—H8	0.9300
N3—C6	1.423 (3)	C8—C7	1.395 (3)
N3—C5	1.355 (3)	C7—H7	0.9300
N3—C2	1.472 (3)	C14—H14	0.9300
N1—C13	1.435 (3)	C14—C15	1.389 (3)
N1—C1	1.350 (3)	C16—C15	1.374 (4)
N1—C3	1.487 (3)	C16—C17	1.391 (4)
N4—H4	0.8600	C15—H15	0.9300
N4—C5	1.353 (3)	C18—H18	0.9300
N4—C3	1.451 (3)	C18—C17	1.388 (4)
N2—H2	0.8600	C4—H4A	0.9600
N2—C2	1.437 (3)	C4—H4B	0.9600
N2—C1	1.357 (3)	C4—H4C	0.9600
C6—C11	1.386 (3)	C12—H12A	0.9600
C6—C7	1.387 (3)	C12—H12B	0.9600
C13—C14	1.379 (3)	C12—H12C	0.9600
C13—C18	1.374 (3)	C17—H17	0.9300
C2—H2A	0.9800	C19—H19A	0.9600
C2—C3	1.542 (3)	C19—H19B	0.9600
C9—C10	1.398 (3)	C19—H19C	0.9600

C9—O2—C12	117.5 (2)	C10—C11—H11	120.2
C16—O1—C19	117.4 (2)	C9—C10—H10	119.9
C6—N3—C2	122.93 (17)	C11—C10—C9	120.1 (2)
C5—N3—C6	124.84 (18)	C11—C10—H10	119.9
C5—N3—C2	112.21 (17)	C9—C8—H8	120.2
C13—N1—C3	121.96 (18)	C9—C8—C7	119.6 (2)
C1—N1—C13	126.11 (18)	C7—C8—H8	120.2
C1—N1—C3	111.89 (17)	C6—C7—C8	120.3 (2)
C5—N4—H4	123.6	C6—C7—H7	119.9
C5—N4—C3	112.89 (18)	C8—C7—H7	119.9
C3—N4—H4	123.6	C13—C14—H14	119.7
C2—N2—H2	123.9	C13—C14—C15	120.6 (2)
C1—N2—H2	123.9	C15—C14—H14	119.7
C1—N2—C2	112.18 (18)	O1—C16—C15	124.9 (2)
C11—C6—N3	119.63 (19)	O1—C16—C17	115.4 (2)
C11—C6—C7	120.1 (2)	C15—C16—C17	119.7 (2)
C7—C6—N3	120.3 (2)	C14—C15—H15	120.2
N3—C5—S2	126.03 (16)	C16—C15—C14	119.7 (2)
N4—C5—S2	125.21 (16)	C16—C15—H15	120.2
N4—C5—N3	108.73 (19)	C13—C18—H18	120.1
C14—C13—N1	119.9 (2)	C13—C18—C17	119.7 (2)
C18—C13—N1	120.11 (19)	C17—C18—H18	120.1
C18—C13—C14	119.9 (2)	C3—C4—H4A	109.5
N3—C2—H2A	112.0	C3—C4—H4B	109.5
N3—C2—C3	102.70 (17)	C3—C4—H4C	109.5
N2—C2—N3	112.86 (19)	H4A—C4—H4B	109.5
N2—C2—H2A	112.0	H4A—C4—H4C	109.5
N2—C2—C3	104.61 (17)	H4B—C4—H4C	109.5
C3—C2—H2A	112.0	O2—C12—H12A	109.5
O2—C9—C10	114.6 (2)	O2—C12—H12B	109.5
O2—C9—C8	125.1 (2)	O2—C12—H12C	109.5
C8—C9—C10	120.2 (2)	H12A—C12—H12B	109.5
N1—C1—S1	126.59 (16)	H12A—C12—H12C	109.5
N1—C1—N2	109.29 (19)	H12B—C12—H12C	109.5
N2—C1—S1	124.11 (17)	C16—C17—H17	119.8
N1—C3—C2	101.56 (17)	C18—C17—C16	120.3 (2)
N1—C3—C4	111.68 (18)	C18—C17—H17	119.8
N4—C3—N1	111.96 (19)	O1—C19—H19A	109.5
N4—C3—C2	103.31 (17)	O1—C19—H19B	109.5
N4—C3—C4	112.76 (19)	O1—C19—H19C	109.5
C4—C3—C2	114.8 (2)	H19A—C19—H19B	109.5
C6—C11—H11	120.2	H19A—C19—H19C	109.5
C10—C11—C6	119.7 (2)	H19B—C19—H19C	109.5

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C13–C18 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S2ⁱ	0.86	2.62	3.265 (2)	133
N4—H4···S1ⁱⁱ	0.86	2.57	3.382 (2)	157
C7—H7···S1ⁱⁱⁱ	0.93	2.87	3.786 (3)	170
C12—H12B···Cg^iv	0.96	2.99	3.893 (3)	157

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

Acknowledgements

The authors acknowledge the School of Chemical Sciences at the University of Auckland for X-ray intensity measurements.

References

Asegbeloyin, J. N., Izuogu, D. C., Oyeka, E. E., Okpareke, O. C. & Ibezim, A. (2019). J. Mol. Struct. 1175, 219–229. Web of Science CSD CrossRef CAS Google Scholar
Asegbeloyin, J. N., Oyeka, E. E., Okpareke, O. & Ibezim, A. (2018). J. Mol. Struct. 1153, 69–77. Web of Science CSD CrossRef CAS Google Scholar
Berlyand, A. S., Lebedev, O. V. & Prokopov, A. A. (2013). Pharm. Chem. J. 47, 176–178. Web of Science CrossRef CAS Google Scholar
Beyer, A., Reucher, C. M. M. & Bolm, C. (2011). Org. Lett. 13, 2876–2879. Web of Science CrossRef CAS PubMed Google Scholar
Binzet, G., Külcü, N., Flörke, U. & Arslan, H. (2009). J. Coord. Chem. 62, 3454–3462. Web of Science CSD CrossRef CAS Google Scholar
Bourhis, L. J., Dolomanov, O. V., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2015). Acta Cryst. A71, 59–75. Web of Science CrossRef IUCr Journals Google Scholar
Burnett, C. A., Lagona, J., Wu, A., Shaw, J. A., Coady, D., Fettinger, J. C., Day, A. I. & Isaacs, L. (2003). Tetrahedron, 59, 1961–1970. Web of Science CSD CrossRef CAS Google Scholar
Cow, C. N. (1998). Chem. Commun. pp. 1147–1148. Web of Science CSD CrossRef Google Scholar
Dawood, K. M., Elwan, N. M., Farahat, A. A. & Abdel-Wahab, B. F. (2010). J. Heterocycl. Chem. 47, 243-267. CAS Google Scholar
Deng, C., Shu, W. & Zhang, D. (2010). Acta Cryst. E66, o1524. Web of Science CSD CrossRef IUCr Journals 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
Douglass, I. B. & Dains, F. (1934). J. Am. Chem. Soc. 56, 719–721. CrossRef CAS Google Scholar
Duspara, P. A., Matta, C. F., Jenkins, S. I. & Harrison, P. H. (2001). Org. Lett. 3, 495–498. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kravchenko, A. N., Baranov, V. V. & Gazieva, G. A. (2018). Russ. Chem. Rev. 87, 89–108. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Oyeka, E. E., Asegbeloyin, J. N., Babahan, I., Eboma, B., Okpareke, O., Lane, J., Ibezim, A., Bıyık, H. H., Törün, B. & Izuogu, D. C. (2018). J. Mol. Struct. 1168, 153–164. Web of Science CSD CrossRef CAS Google Scholar
Rigaku OD (2018). Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Ryzhkina, I. S., Kiseleva, Y. V., Mishina, O. A., Timosheva, A. P., Sergeeva, S. Y., Kravchenko, A. N. & Konovalov, A. I. (2013). Mendeleev Commun. 23, 262–264. Web of Science CrossRef CAS Google Scholar
Sal'keeva, L., Bakibaev, A. A., Khasenova, G., Taishibekova, Y. K., Sugralina, L., Minaeva, Y. V. & Sal'keeva, A. (2016). Russ. J. Appl. Chem. 89, 132–139. CAS Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Jayatilaka, D. (2009). CrystEngComm, 11, 19–32. Web of Science CrossRef CAS Google Scholar
Tiefenbacher, K., Dube, H., Ajami, D. & Rebek, J. (2011). Chem. Commun. 47, 7341–7343. Web of Science CrossRef CAS Google Scholar
Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). CrystalExplorer17. University of Western Australia. https://hirshfeldsurface.net Google Scholar
Wang, M., Wang, J. & Xiang, J. (2011). Acta Cryst. E67, o2060. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, Z. & Xi, H. (2009). Acta Cryst. E65, o1426. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wu, Y. & Sun, Y. (2009). Acta Cryst. E65, o1715. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yang, Y. (2010). Acta Cryst. E66, o1673. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zeng, R.-S., Zou, J.-P., Zhi, S.-J., Chen, J. & Shen, Q. (2003). Org. Lett. 5, 1657–1659. Web of Science CrossRef PubMed CAS Google Scholar
Zhang, Q., Li, P., Chen, X., Wang, X. & Liu, H. (2011). Acta Cryst. E67, o1673. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zharkov, M. N., Kuchurov, I. V., Fomenkov, I. V., Zlotin, S. G. & Tartakovsky, V. A. (2015). Mendeleev Commun. 25, 15–16. Web of Science CrossRef 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 75| Part 9| September 2019| Pages 1297-1300

https://doi.org/10.1107/S2056989019010764

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

Crystal structure and Hirshfeld surface analysis of a new di­thio­glycoluril: 1,4-bis­­(4-meth­­oxy­phen­yl)-3a-methyl­tetra­hydro­imidazo[4,5-d]imidazole-2,5(1H,3H)-di­thione

1. Chemical context

2. Structural commentary

3. Supra­molecular features

3.1. Hirshfeld Surface Analysis

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure and Hirshfeld surface analysis of a new dithioglycoluril: 1,4-bis(4-methoxyphenyl)-3a-methyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dithione

3. Supramolecular features