4-[4-(4-Chloro-1,2,5-thia­diazol-3-yl)phen­yl]morpholine

Palme, P.R.; Goddard, R.; Richter, A.; Imming, P.; Seidel, R.W.

doi:10.1107/S2414314626004207

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 11| Part 5| May 2026| x260420

https://doi.org/10.1107/S2414314626004207

Open

access

4-[4-(4-Chloro-1,2,5-thiadiazol-3-yl)phenyl]morpholine

Paul R. Palme,^a Richard Goddard,^b Adrian Richter,^a Peter Imming ^a and Rüdiger W. Seidel ^a ^*

^aInstitut für Pharmazie, Martin-Luther-Universität Halle-Wittenberg, Wolfgang-Langenbeck-Str. 4, 06120 Halle (Saale), Germany, and ^bMax-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
^*Correspondence e-mail: [email protected]

Edited by M. Zeller, Purdue University, USA (Received 20 April 2026; accepted 21 April 2026; online 7 May 2026)

The title compound, C₁₂H₁₂ClN₃OS, was prepared using a Suzuki–Miyaura cross-coupling reaction. The compound was found to crystallize in the orthorhombic system (space group Pbca, Z = 8). The crystal structure was refined with non-spherical atomic form factors using Hirshfeld atom refinement. The mean planes through the thiadiazole ring and the benzene ring are inclined at an angle of 36.83 (2)°. The morpholine ring adopts a chair conformation with a markedly pyramidal bonding situation at the N atom. The crystal packing is dense, with a packing index of 75%.

Keywords: crystal structure; Hirshfeld atom refinement; Hirshfeld surface analysis; thiadiazole; morpholine; Suzuki coupling.

CCDC reference: 2548183

Structure description

The 1,2,5-thiadiazole heterocyclic system has gained importance in medicinal chemistry, as well as agricultural and materials science (Quiroga et al., 2025 ). The saturated six-membered morpholine heterocycle is part of many drug substances, adjusting the degree of polarity and ease of metabolism (Kumari & Singh, 2020 ). We prepared the title compound from (4-morpholinophenyl)boronic acid and 3,4-dichloro-1,2,5-thiadiazole by a Suzuki–Miyaura heteroaryl cross-coupling reaction (Meringdal & Menche, 2025 ). It has been demonstrated previously that 3,4-dichloro-1,2,5-thiadiazole undergoes Suzuki–Miyaura cross-coupling reactions to yield the corresponding mono-substituted derivatives, leaving one Cl atom for potential further functionalization (Merschaert & Gorissen, 2003 ). While the Cambridge Structural Database (CSD; Groom et al., 2016 ) contains a wide variety of crystal structures of 4-phenylmorpholine derivatives, a search using the WebCSD interface (Thomas et al., 2010 ) in April 2026 revealed only one crystallographically characterized compound containing a 4-chloro-1,2,5-thiadiazol-3-yl group, namely, 2-(4-chloro-1,2,5-thiadiazol-3-yl)quinazolin-4(3H)-one (CSD refcode UQOGIT; Kalogirou et al., 2021 ). The CSD entry DOCFEG features a 1,2,5-thiadiazolium-2-yl moiety in a pentafluoridoarsenate adduct (Roesky et al., 1986 ).

Fig. 1 shows the molecular structure of the title compound in the crystal. Table 1 lists geometric parameters within the 1,2,5-thiadiazole ring. These are comparable to those encountered in the above-mentioned UQOGIT and also resemble those in the structure of the parent 1,2,5-thiadiazole, as determined by electron diffraction in the gas phase (Momany & Bonham, 1964 ). As in UQOGIT, the electronegative Cl substituent increases the ipso N—C—C angle as compared with the aromatic substituent. The dihedral angle between the mean planes of the 1,2,5-thiadiazole ring and the benzene ring is 36.83 (2)°. The morpholine ring exhibits the expected low-energy chair conformation and is slightly twisted out of the plane of the benzene ring. The bonding situation at the morpholine N atom is markedly pyramidal, as indicated by Σ(C—N—C) = 343.21 (7)°, which is significantly smaller than the value of 360° in the case of a perfectly planar coordination. The pyramidal height, i.e. the perpendicular distance from N4 to the plane defined by C3, C5 and C7, is 0.3473 (4) Å. Fig. 2 depicts the arrangement of the molecules in the orthorhombic unit cell. A packing index of 75%, as calculated with PLATON (Spek, 2020 ), reveals a dense crystal packing (Kitajgorodskij, 1973 ).

Table 1
Selected geometric parameters (Å, °)

C13—C14	1.4364 (7)	N2—S1	1.6274 (4)
C13—N2	1.3298 (6)	N5—S1	1.6304 (5)
C14—N5	1.3133 (6)

N2—C13—C14	110.85 (4)	S1—N5—C14	106.12 (3)
N5—C14—C13	115.65 (4)	N5—S1—N2	99.09 (2)
S1—N2—C13	108.29 (3)

Figure 1
Displacement ellipsoid plot of the title compound (50% probability level). H atoms are shown as small spheres of arbitrary radius.

Figure 2
View of the orthorhombic unit cell of the title compound approximately along the a-axis direction. H atoms have been omitted for clarity. Colour scheme: C grey, Cl green, N blue, O red and S yellow.

To better understand the molecular environment of the title compound, we carried out a Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) using CrystalExplorer21 (Spackman et al., 2021 ). Fig. 3(a) shows the Hirshfeld surface for the title compound mapped with the normalized contact distance (d_norm), with the colours indicating intermolecular contacts shorter (red), approximately equal (white) or longer (blue) than the sum of the van der Waals radii (Bondi, 1964 ). Inspection of the d_norm plot reveals two large red concave areas associated with the C5—H5A⋯O1ⁱⁱ and C12—H12⋯O1ⁱⁱ intermolecular contacts, which can be regarded as weak hydrogen bonds (Table 2). A small red area arises from a short intermolecular H⋯H contact between the morpholine rings of adjacent molecules. In contrast, the H⋯A separation in the C3—H3A⋯N2ⁱ intermolecular contact (Table 2) is close to the sum of the corresponding van der Waals radii (bearing in mind that CrystalExplorer21 by default sets neutron-normalized X—H distances; Allen & Bruno, 2010 ) and is not associated with a red area in the d_norm plot. Fig. 3(b) shows the corresponding fingerprint plot. For H⋯H contacts (26.4% contribution of close contacts to the Hirshfeld surface), the tip on the diagonal occurs at d_e + d_i < 2.4 Å (i.e. less than two times the van der Waals radius of hydrogen) and corresponds to the small red spot in the d_norm plot in Fig. 3(a). Moverover, the fingerprint plot shows the two spikes for H⋯O/O⋯H contacts (6.4% contribution) from the C—H⋯O weak hydrogen bonds and wings associated with H⋯C/C⋯H contacts (13.8% contribution).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯N2ⁱ	1.107 (7)	2.608 (7)	3.6913 (7)	165.8 (5)
C5—H5A⋯O1ⁱⁱ	1.070 (7)	2.406 (7)	3.4529 (6)	165.6 (5)
C12—H12⋯O1ⁱⁱ	1.063 (6)	2.348 (7)	3.3275 (6)	152.6 (5)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 3
(a) Hirshfeld surface mapped with d_norm for the title compound and (b) the corresponding two-dimensional fingerprint plot, where d_i and d_e are the distances from a point on the Hirshfeld surface to the nearest atom inside and outside the surface, respectively. Dashed lines represent weak hydrogen bonds. Colour scheme for the atoms: C grey, H white, Cl green, N blue, O red and S yellow.

Synthesis and crystallization

Starting materials were purchased and used as received. NMR spectra were recorded on an Agilent Technologies 400 MHz VNMRS spectrometer. Chemical shifts are reported relative to the residual solvent signal of chloroform-d (δ_H = 7.26 ppm, δ_C = 77.16 ppm). Abbreviation: m = multiplet.

(4-Morpholinophenyl)boronic acid (615 mg, 2.97 mmol) was dissolved in toluene (40 ml), 1,4-dioxane (5 ml) and dimethylformamide (5 ml) in a 100 ml Schlenk flask. Caesium fluoride (1.83 g, 12.0 mmol) dissolved in approximately 0.5 ml of deionized water, tetrakis(triphenylphosphane)palladium(0) (231 mg, 0.20 mmol) and 3,4-dichloro-1,2,5-thiadiazole (620 mg, 4.00 mmol) were added under an argon atmosphere. Subsequently, the mixture was heated to 363 K for 12 h with magnetic stirring, whereupon the colour turned from yellow to red. After filtering through Celite, the solvents were removed under reduced pressure co-evaporation using toluene (2 × 20 ml of toluene were added to the residue and evaporated). The crude product was purified by flash chromatography (Interchim puriFlash 430) on silica gel using gradient elution (n-heptane with ethyl acetate 0 to 40% v/v) to yield the title compound as a yellow oil (167 mg, 0.59 mmol, 20%). ¹H NMR (402 MHz, chloroform-d) δ 7.55–7.46 (m, 2H), 6.90–6.83 (m, 2H), 3.88–3.81 (m, 4H), 3.31–3.24 (m, 4H) ppm. ¹³C{¹H} NMR (101 MHz, chloroform-d): δ 153.6, 133.6, 128.5, 120.0, 114.2, 101.1, 66.6, 47.5 ppm. Crystals suitable for X-ray diffraction analysis were obtained when a solution of the compound in chloroform-d was allowed to evaporate slowly under ambient conditions.

Refinement

Crystal data and refinement details are given in Table 3. Initial independent atom model (IAM) refinement was carried out with SHELXL (Sheldrick, 2015b ). The final model from IAM refinement was then used as the starting point for Hirshfeld atom refinement using NoSpherA2 (Kleemiss et al., 2021 ) in OLEX2 (Dolomanov et al., 2009 ). Within NoSpherA2, ORCA (Version 6.1; Neese, 2025 ) was used to calculate the electron density at the B3LYP/def2-TZVPP level of theory (Becke, 1993 ; Lee et al., 1988 ; Weigend & Ahlrichs, 2005 ), which was subsequently partitioned into Hirshfeld atoms and converted via Fourier transform into atomic form factors (Midgley et al., 2021 ). Least-squares refinements against the non-spherical atomic form factors so obtained were performed using olex2.refine (Bourhis et al., 2015 ). Anisotropic atomic displacement parameters (ADPs) were refined for all non-H atoms. The positions and isotropic ADPs of the H atoms were refined freely.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₂H₁₂ClN₃OS
M_r	281.77
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	7.5584 (4), 11.5187 (6), 27.5229 (16)
V (Å³)	2396.2 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.48
Crystal size (mm)	0.24 × 0.15 × 0.10

Data collection
Diffractometer	Bruker Kappa Mach3 APEXII
Absorption correction	Gaussian (SADABS; Krause et al., 2015 )
T_min, T_max	0.933, 0.963
No. of measured, independent and observed [I ≥ 2u(I)] reflections	89511, 5236, 4448
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.806

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.032, 1.04
No. of reflections	5236
No. of parameters	211
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.25
Computer programs: APEX3 (Bruker, 2016 ), SAINT (Bruker, 2004 ), SHELXT (Sheldrick, 2015a ), olex2.refine (Bourhis et al., 2015), SHELXL (Sheldrick, 2015b), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2548183

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314626004207/zl4097sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314626004207/zl4097Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314626004207/zl4097Isup3.cdx

1H and 13C NMR spectra of the title compound. DOI: https://doi.org/10.1107/S2414314626004207/zl4097sup3.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2414314626004207/zl4097Isup5.cml

checkCIF report

Computing details top

4-[4-(4-Chloro-1,2,5-thiadiazol-3-yl)phenyl]morpholine top

Crystal data top

C₁₂H₁₂ClN₃OS	D_x = 1.562 Mg m⁻³
M_r = 281.77	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9139 reflections
a = 7.5584 (4) Å	θ = 3.0–34.7°
b = 11.5187 (6) Å	µ = 0.48 mm⁻¹
c = 27.5229 (16) Å	T = 100 K
V = 2396.2 (2) Å³	Prism, yellow
Z = 8	0.24 × 0.15 × 0.10 mm
F(000) = 1170.773

Data collection top

Bruker Kappa Mach3 APEXII diffractometer	5236 independent reflections
Radiation source: IµS	4448 reflections with I ≥ 2u(I)
Incoatec Helios mirrors monochromator	R_int = 0.040
Detector resolution: 66.67 pixels mm^-1	θ_max = 35.0°, θ_min = 1.5°
φ– and ω–scans	h = −12→12
Absorption correction: gaussian (SADABS; Krause et al, 2015)	k = −18→18
T_min = 0.933, T_max = 0.963	l = −43→44
89511 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)] = 0.020	Hydrogen site location: difference Fourier map
wR(F²) = 0.032	All H-atom parameters refined
S = 1.03	w = 1/[σ²(F_o²) + (0.0074P)² + 0.278P] where P = (F_o² + 2F_c²)/3
5236 reflections	(Δ/σ)_max = −0.001
211 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³
0 constraints

Special details top

Experimental. Crystal mounted on a MiTeGen loop using Perfluoropolyether PFO-XR75

Refinement. Refinement using NoSpherA2, an implementation of NOn-SPHERical Atom-form-factors in Olex2. Please cite: F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021 NoSpherA2 implementation of HAR makes use of tailor-made aspherical atomic form factors calculated on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF wavefunction - either Hartree-Fock or DFT using selected funtionals - for a fragment of the crystal. This fragment can be embedded in an electrostatic crystal field by employing cluster charges or modelled using implicit solvation models, depending on the software used.

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

	x	y	z	U_iso*/U_eq
C2	0.38502 (7)	0.92641 (4)	0.425523 (18)	0.01240 (9)
H2A	0.5161 (10)	0.9672 (6)	0.4261 (2)	0.0279 (18)*
H2B	0.2929 (9)	0.9833 (6)	0.4074 (2)	0.0281 (17)*
C3	0.39295 (7)	0.81117 (4)	0.398916 (19)	0.01214 (9)
H3A	0.2567 (10)	0.7782 (6)	0.3937 (2)	0.0326 (19)*
H3B	0.4511 (9)	0.8271 (6)	0.3634 (3)	0.0293 (18)*
C5	0.45592 (7)	0.71994 (4)	0.476838 (18)	0.01125 (9)
H5A	0.5541 (9)	0.6714 (6)	0.4962 (2)	0.0286 (18)*
H5B	0.3287 (9)	0.6744 (6)	0.4811 (2)	0.0281 (18)*
C6	0.44555 (7)	0.83994 (4)	0.499362 (19)	0.01331 (9)
H6A	0.3980 (9)	0.8330 (6)	0.5368 (3)	0.0295 (18)*
H6B	0.5775 (9)	0.8807 (6)	0.4993 (2)	0.0307 (18)*
C7	0.52410 (6)	0.61898 (4)	0.401643 (17)	0.00858 (8)
C8	0.48098 (7)	0.60330 (4)	0.352314 (18)	0.01083 (9)
H8	0.4279 (9)	0.6729 (6)	0.3307 (2)	0.0271 (18)*
C9	0.50209 (7)	0.49617 (4)	0.329747 (18)	0.01090 (8)
H9	0.4654 (9)	0.4885 (6)	0.2924 (2)	0.0250 (17)*
C10	0.56536 (6)	0.39984 (4)	0.355300 (17)	0.00928 (8)
C11	0.61137 (7)	0.41537 (4)	0.404152 (17)	0.01015 (8)
H11	0.6638 (9)	0.3425 (6)	0.4246 (2)	0.0246 (17)*
C12	0.59249 (6)	0.52214 (4)	0.426911 (18)	0.00995 (8)
H12	0.6311 (9)	0.5284 (5)	0.4639 (2)	0.0238 (16)*
C13	0.57517 (6)	0.28349 (4)	0.333634 (17)	0.00958 (8)
C14	0.62143 (7)	0.25191 (4)	0.284770 (18)	0.01116 (8)
Cl1	0.687353 (18)	0.347856 (10)	0.240584 (5)	0.01629 (3)
N2	0.53607 (6)	0.18989 (3)	0.359801 (16)	0.01227 (8)
N4	0.50157 (6)	0.72611 (3)	0.425004 (14)	0.00921 (7)
N5	0.61572 (6)	0.14042 (4)	0.274917 (16)	0.01455 (8)
O1	0.32449 (5)	0.91267 (3)	0.474029 (13)	0.01268 (7)
S1	0.555918 (19)	0.076238 (10)	0.325098 (5)	0.01464 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0156 (2)	0.00861 (18)	0.0130 (2)	0.00196 (17)	0.00191 (18)	0.00020 (16)
C3	0.0170 (2)	0.00870 (18)	0.0108 (2)	0.00192 (17)	−0.00117 (18)	0.00038 (16)
C5	0.0144 (2)	0.00977 (18)	0.0096 (2)	0.00127 (17)	−0.00004 (18)	−0.00046 (15)
C6	0.0174 (2)	0.01161 (19)	0.0109 (2)	0.00261 (18)	−0.00030 (19)	−0.00234 (17)
C7	0.0102 (2)	0.00721 (17)	0.0084 (2)	−0.00005 (15)	−0.00072 (16)	−0.00013 (15)
C8	0.0161 (2)	0.00774 (18)	0.0086 (2)	0.00140 (16)	−0.00195 (17)	−0.00022 (15)
C9	0.0163 (2)	0.00841 (18)	0.0080 (2)	0.00109 (16)	−0.00197 (17)	−0.00071 (16)
C10	0.0122 (2)	0.00704 (17)	0.0086 (2)	0.00006 (15)	−0.00089 (17)	−0.00057 (14)
C11	0.0140 (2)	0.00743 (17)	0.0091 (2)	0.00062 (16)	−0.00205 (17)	−0.00002 (15)
C12	0.0134 (2)	0.00818 (18)	0.0083 (2)	0.00056 (15)	−0.00264 (17)	−0.00056 (15)
C13	0.0117 (2)	0.00786 (17)	0.0092 (2)	−0.00008 (15)	−0.00026 (16)	−0.00088 (15)
C14	0.0134 (2)	0.00995 (18)	0.0101 (2)	0.00038 (16)	0.00056 (17)	−0.00111 (16)
Cl1	0.02243 (6)	0.01487 (5)	0.01157 (5)	−0.00035 (5)	0.00489 (5)	0.00119 (4)
N2	0.0174 (2)	0.00820 (16)	0.0112 (2)	−0.00033 (15)	0.00177 (16)	−0.00013 (14)
N4	0.01069 (18)	0.00762 (15)	0.00932 (18)	0.00034 (13)	−0.00017 (14)	−0.00057 (13)
N5	0.0202 (2)	0.01077 (17)	0.0126 (2)	0.00121 (16)	0.00077 (17)	−0.00376 (15)
O1	0.01367 (17)	0.01125 (15)	0.01311 (17)	0.00307 (13)	0.00292 (13)	−0.00071 (12)
S1	0.02151 (6)	0.00717 (4)	0.01524 (6)	−0.00030 (4)	0.00130 (5)	−0.00138 (4)

Geometric parameters (Å, º) top

C2—H2A	1.096 (7)	C7—N4	1.4019 (6)
C2—H2B	1.078 (7)	C8—H8	1.075 (7)
C2—C3	1.5171 (7)	C8—C9	1.3907 (6)
C2—O1	1.4201 (6)	C9—H9	1.069 (7)
C3—H3A	1.107 (7)	C9—C10	1.3980 (6)
C3—H3B	1.088 (7)	C10—C11	1.4002 (7)
C3—N4	1.4661 (6)	C10—C13	1.4688 (6)
C5—H5A	1.070 (7)	C11—H11	1.085 (6)
C5—H5B	1.101 (7)	C11—C12	1.3875 (6)
C5—C6	1.5169 (7)	C12—H12	1.063 (6)
C5—N4	1.4695 (6)	C13—C14	1.4364 (7)
C6—H6A	1.094 (7)	C13—N2	1.3298 (6)
C6—H6B	1.102 (7)	C14—Cl1	1.7172 (5)
C6—O1	1.4231 (6)	C14—N5	1.3133 (6)
C7—C8	1.4079 (7)	N2—S1	1.6274 (4)
C7—C12	1.4125 (6)	N5—S1	1.6304 (5)

H2B—C2—H2A	109.2 (5)	C9—C8—C7	121.20 (4)
C3—C2—H2A	110.3 (4)	C9—C8—H8	117.2 (3)
C3—C2—H2B	109.5 (4)	H9—C9—C8	118.2 (3)
O1—C2—H2A	109.0 (3)	C10—C9—C8	121.25 (4)
O1—C2—H2B	107.1 (3)	C10—C9—H9	120.5 (3)
O1—C2—C3	111.65 (4)	C11—C10—C9	117.81 (4)
H3A—C3—C2	109.0 (4)	C13—C10—C9	122.49 (4)
H3B—C3—C2	107.6 (4)	C13—C10—C11	119.60 (4)
H3B—C3—H3A	108.5 (5)	H11—C11—C10	119.3 (3)
N4—C3—C2	111.74 (4)	C12—C11—C10	121.42 (4)
N4—C3—H3A	110.8 (4)	C12—C11—H11	119.3 (3)
N4—C3—H3B	109.0 (4)	C11—C12—C7	121.02 (4)
H5B—C5—H5A	107.7 (5)	H12—C12—C7	121.3 (3)
C6—C5—H5A	108.0 (4)	H12—C12—C11	117.7 (3)
C6—C5—H5B	110.2 (4)	C14—C13—C10	128.57 (4)
N4—C5—H5A	110.2 (4)	N2—C13—C10	120.58 (4)
N4—C5—H5B	109.4 (4)	N2—C13—C14	110.85 (4)
N4—C5—C6	111.39 (4)	Cl1—C14—C13	124.80 (4)
H6A—C6—C5	109.6 (4)	N5—C14—C13	115.65 (4)
H6B—C6—C5	109.9 (4)	N5—C14—Cl1	119.52 (4)
H6B—C6—H6A	109.2 (5)	S1—N2—C13	108.29 (3)
O1—C6—C5	111.68 (4)	C5—N4—C3	112.10 (4)
O1—C6—H6A	107.1 (4)	C7—N4—C3	115.57 (4)
O1—C6—H6B	109.3 (4)	C7—N4—C5	115.54 (4)
C12—C7—C8	117.27 (4)	S1—N5—C14	106.12 (3)
N4—C7—C8	121.81 (4)	C6—O1—C2	108.60 (4)
N4—C7—C12	120.92 (4)	N5—S1—N2	99.09 (2)
H8—C8—C7	121.6 (3)

C2—C3—N4—C5	48.09 (5)	C9—C10—C13—C14	37.71 (6)
C2—C3—N4—C7	−176.66 (4)	C9—C10—C13—N2	−141.29 (5)
C2—O1—C6—C5	−61.73 (4)	C10—C13—C14—Cl1	3.27 (6)
C3—C2—O1—C6	61.40 (5)	C10—C13—C14—N5	−178.58 (5)
C3—N4—C5—C6	−48.20 (4)	C10—C13—N2—S1	178.84 (4)
C3—N4—C7—C8	14.02 (5)	C11—C10—C13—C14	−145.91 (5)
C3—N4—C7—C12	−166.35 (4)	C11—C10—C13—N2	35.09 (5)
C5—N4—C7—C8	147.73 (4)	C11—C12—C7—N4	178.61 (4)
C5—N4—C7—C12	−32.64 (5)	C12—C11—C10—C13	−175.54 (5)
C6—C5—N4—C7	176.53 (4)	C13—C14—N5—S1	−0.41 (4)
C7—C8—C9—C10	0.59 (6)	C13—N2—S1—N5	0.09 (4)
C7—C12—C11—C10	0.70 (6)	C14—C13—N2—S1	−0.32 (4)
C8—C7—C12—C11	−1.74 (5)	C14—N5—S1—N2	0.19 (4)
C8—C9—C10—C11	−1.65 (6)	Cl1—C14—C13—N2	−177.66 (4)
C8—C9—C10—C13	174.79 (5)	Cl1—C14—N5—S1	177.85 (4)
C9—C8—C7—C12	1.11 (6)	N2—C13—C14—N5	0.50 (5)
C9—C8—C7—N4	−179.25 (5)	N4—C3—C2—O1	−55.33 (5)
C9—C10—C11—C12	1.01 (5)	N4—C5—C6—O1	55.67 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···N2ⁱ	1.107 (7)	2.608 (7)	3.6913 (7)	165.8 (5)
C5—H5A···O1ⁱⁱ	1.070 (7)	2.406 (7)	3.4529 (6)	165.6 (5)
C12—H12···O1ⁱⁱ	1.063 (6)	2.348 (7)	3.3275 (6)	152.6 (5)

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

Acknowledgements

We would like to thank Professor Christian W. Lehmann for providing access to the X-ray diffraction facility, Heike Salandin for technical assistance with the data collection and Dr Markus Leutzsch for helpful discussions. We acknowledge the financial support of the Open Access Publication Fund of the Martin-Luther-Universität Halle-Wittenberg.

References

Allen, F. H. & Bruno, I. J. (2010). Acta Cryst. B66, 380–386. Web of Science CrossRef CAS IUCr Journals Google Scholar
Becke, A. D. (1993). J. Chem. Phys. 98, 5648–5652. CrossRef CAS Web of Science Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–451. CrossRef CAS Web of Science 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
Bruker (2004). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2016). APEX3. 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
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Kalogirou, A. S., Kourtellaris, A. & Koutentis, P. A. (2021). J. Org. Chem. 86, 5702–5713. Web of Science CrossRef CAS PubMed Google Scholar
Kitajgorodskij, A. I. (1973). In Molecular crystals and molecules. London: Academic Press. Google Scholar
Kleemiss, F., Dolomanov, O. V., Bodensteiner, M., Peyerimhoff, N., Midgley, M., Bourhis, L. J., Genoni, A., Malaspina, L. A., Jayatilaka, D., Spencer, J. L., White, F., Grundkötter-Stock, B., Steinhauer, S., Lentz, D., Puschmann, H. & Grabowsky, S. (2021). Chem. Sci. 12, 1675–1692. Web of Science CSD CrossRef CAS 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
Kumari, A. & Singh, R. K. (2020). Bioorg. Chem. 96, 103578. Web of Science CrossRef PubMed Google Scholar
Lee, C., Yang, W. & Parr, R. G. (1988). Phys. Rev. B 37, 785–789. CrossRef CAS Web of Science 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
Meringdal, J. W. & Menche, D. (2025). Chem. Soc. Rev. 54, 5746–5765. Web of Science CrossRef CAS PubMed Google Scholar
Merschaert, A. & J. Gorissen, H. (2003). Heterocycles 60, 29. Google Scholar
Midgley, L., Bourhis, L. J., Dolomanov, O. V., Grabowsky, S., Kleemiss, F., Puschmann, H. & Peyerimhoff, N. (2021). Acta Cryst. A77, 519–533. Web of Science CrossRef IUCr Journals Google Scholar
Momany, F. A. & Bonham, R. A. (1964). J. Am. Chem. Soc. 86, 162–164. CrossRef CAS Web of Science Google Scholar
Neese, F. (2025). WIREs Comput. Mol. Sci. 15, e70019. Google Scholar
Quiroga, D., Rodríguez, D. & Coy-Barrera, E. (2025). Molecules 30, 4373. Web of Science CrossRef PubMed Google Scholar
Roesky, H. W., Sundermeyer, J., Schimkowiak, J., Gries, T., Noltemeyer, M. & Sheldrick, G. M. (1986). Z. Naturforsch. B 41, 162–166. CrossRef 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, M. A. & Jayatilaka, D. (2009). CrystEngComm 11, 19–32. Web of Science CrossRef CAS 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
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Thomas, I. R., Bruno, I. J., Cole, J. C., Macrae, C. F., Pidcock, E. & Wood, P. A. (2010). J. Appl. Cryst. 43, 362–366. Web of Science CrossRef CAS IUCr Journals Google Scholar
Weigend, F. & Ahlrichs, R. (2005). Phys. Chem. Chem. Phys. 7, 3297–3305. Web of Science CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar