(E)-2,4-Di­amino-5-{7-[(4-chloro­phen­yl)diazen­yl]-3,3-dimethyl-1-oxo-2,3,4,9-tetra­hydro-1H-xanthen-9-yl}-6-oxo-1,6-di­hydro­pyridine-3-carbo­nitrile di­methyl­formamide monosolvate

Elgemeie, G.H.; Metwally, N.H.; Abd Al-latif, E.S.M.; Jones, P.G.

doi:10.1107/S2414314625009393

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 11| November 2025| x250939

https://doi.org/10.1107/S2414314625009393

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(E)-2,4-Diamino-5-{7-[(4-chlorophenyl)diazenyl]-3,3-dimethyl-1-oxo-2,3,4,9-tetrahydro-1H-xanthen-9-yl}-6-oxo-1,6-dihydropyridine-3-carbonitrile dimethylformamide monosolvate

Galal H. Elgemeie,^a Nadia H. Metwally,^b El-shimaa S. M. Abd Al-latif ^b and Peter G. Jones ^c ^*

^aChemistry Department, Faculty of Science, Helwan University, Cairo, Egypt, ^bChemistry Department, Faculty of Science, Cairo University, Giza, Egypt, and ^cInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany
^*Correspondence e-mail: [email protected]

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 21 October 2025; accepted 24 October 2025; online 6 November 2025)

In the title compound, C₂₇H₂₃ClN₆O₃·C₃H₇NO, much of the molecule is approximately planar, excluding the pyridinic ring, which is almost perpendicular to this plane, and the sp³ atoms of the modified xanthene system. The diazene group is E-configured. In the extended structure, two hydrogen bonds of the type N—H⋯O and one N—H⋯Cl combine to form a layer structure parallel to (111). The solvent is severely disordered and this necessitated the use of SQUEEZE for a reliable refinement.

Keywords: diazene; xanthene; hydrogen bond; crystal structure.

CCDC reference: 2497635

Structure description

In a variety of chemical processes, activated nitriles, which involve active methylene groups, are used for the synthesis of heterocyclic, pharmaceutically significant compounds (Wang et al., 2016 ; Fleming & Wang, 2003 ; Zhang et al., 2023 ; Abu-Zaied et al., 2024a ,b ; Zhang et al., 2019 ). Using such nitriles as starting materials, we have published a number of new approaches for the synthesis of heterocycles (Elgemeie et al., 1998a ,b , 2010 ). Using dimedone as the starting material, we and others have continued this work by synthesizing a number of condensed carbocyclic pyridines and carbocyclic pyrans (Hebishy et al., 2022 , 2023 ; Tu et al., 2014 ). The current study describes a one-pot synthesis of a tetrahydroxanthene derivative by the reaction of dimedone with enamino nitriles and o-hydroxy aromatic aldehydes.

It was found (Fig. 1) that dimedone reacted with (4-chlorophenyl)diazenyl-2-hydroxybenzaldehyde) (1) and 2-aminoprop-1-ene-1,1,3-tricarbonitrile (2) in refluxing acetonitrile containing catalytic amounts of trimethylamine to give the condensation product (E)-5-{7-[(4-chlorophenyl)diazenyl]-2,3,4,9-tetrahydro-3,3-dimethyl-1-oxo-1H-xanthen-9-yl}-2,4-diamino-1,6-dihydro-6-oxopyridine-3-carbonitrile (9). The structure of 9 was suggested by elemental analysis and spectroscopic studies (¹H NMR, IR and MS). As a mechanism we propose a condensation reaction that consists of an initial Michael addition of the methylene group of the dimedone to the double bond of intermediate 3 to give a further intermediate 4, which then cyclizes to give the tetrahydroxanthene structure 9 rather than the alternative cyclization leading to the chromeno[2,3-b]pyridine structure 6. The same reaction has been carried out, under the same reaction conditions, by other researchers, who however stated that they obtained structure 6 as the sole product, but no X-ray single-crystal studies were performed (Vereshchagin et al., 2017 ; Ryzhkova et al., 2022 ). In order to establish the structure of the compound unambiguously, the crystal structure of 9 was determined and is presented here.

Figure 1
The reaction scheme and proposed mechanism for the formation of 9.

The structure of compound 9 (excluding solvent, see Refinement details) is shown in Figs. 2 and 3. Molecular dimensions, a brief selection of which are given in Table 1, may be regarded as normal. Despite the presence of sp³ carbon atoms and the possibility of rotation about the C—N bonds to the E-configured diazene group, much of the molecule is approximately planar (Fig. 3); excluding the pyridinic ring and the atoms C3, C27 and C28, the r.m.s. deviation from the best plane is 0.10 Å. The pyridinic ring (including substituents) has an r.m.s. deviation of 0.03 Å and subtends an interplanar angle of 88.66 (2)° with the main plane. The intramolecular hydrogen bond H051⋯O2, not drawn explicitly in Fig. 2 for reasons of clarity, is part of a three-centre system (Table 2).

Table 1
Selected geometric parameters (Å, °)

N1—N2	1.2572 (13)	N11—C16	1.3875 (12)
N1—C7	1.4217 (13)	C12—N3	1.3517 (14)
N2—C21	1.4224 (14)	C14—N5	1.3489 (12)
N11—C12	1.3483 (13)

N2—N1—C7	112.74 (9)	C12—N11—C16	124.32 (8)
N1—N2—C21	114.76 (9)

C7—N1—N2—C21	−179.90 (8)	C9A—C9—C15—C16	−64.70 (11)
C9A—C9—C15—C14	118.20 (10)	C8A—C9—C15—C16	57.63 (11)
C8A—C9—C15—C14	−119.47 (10)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H011⋯O3ⁱ	0.898 (17)	1.758 (17)	2.6558 (11)	178.7 (18)
N5—H051⋯O2	0.83 (1)	2.62 (2)	3.1939 (12)	128 (1)
N5—H051⋯Cl1ⁱⁱ	0.83 (1)	2.69 (1)	3.3709 (9)	141 (1)
N5—H052⋯O2ⁱⁱⁱ	0.85 (1)	2.08 (1)	2.8266 (11)	147 (2)
C4—H4A⋯N1^iv	0.99	2.66	3.5236 (14)	146
C5—H05⋯Cl1^v	0.95	2.82	3.6093 (10)	141
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 2
The molecule of compound 9 in the crystal (excluding the severely disordered solvent). Ellipsoids are drawn at the 50% probability level.

Figure 3
Side view of the molecule of 9 (excluding hydrogen atoms); radii are arbitrary.

The molecular packing may be analysed in terms of hydrogen bonds (Table 3). The hydrogen bonds N11—H011⋯O3′ and N5—H052⋯O2′ combine to form a one-dimensional array propagating in the [01 $[\overline{1}]$ ] direction (Fig. 4), whereas N11—H011⋯O3′ and N5—H051⋯Cl1′ form a one-dimensional array parallel to [10 $[\overline{1}]$ ] (Fig. 5). The zone law then suggests that the layer structure formed by all three hydrogen bonds should be parallel to (111), which is indeed the case (Fig. 6). We note that the potential hydrogen bond donors at N3 do not appear to form hydrogen bonds; in fact there are short contacts between these hydrogen atoms and the difference peaks arising from the severely disordered solvent.

Table 3
Experimental details

Crystal data
Chemical formula	C₂₇H₂₃ClN₆O₃·C₃H₇NO
M_r	588.06
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	11.0172 (3), 12.3285 (3), 12.6748 (4)
α, β, γ (°)	64.450 (3), 89.344 (3), 78.658 (2)
V (Å³)	1517.63 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.18
Crystal size (mm)	0.16 × 0.16 × 0.12

Data collection
Diffractometer	XtaLAB Synergy
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2025 )
T_min, T_max	0.872, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	100274, 11619, 9160
R_int	0.056
θ values (°)	θ_max = 33.2, θ_min = 2.4
(sin θ/λ)_max (Å⁻¹)	0.770

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.126, 1.07
No. of reflections	11619
No. of parameters	356
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.29
Computer programs: CrysAlis PRO (Rigaku OD, 2025), SHELXT (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b), XP (Bruker, 1998 ) and publCIF (Westrip, 2010 ).

Figure 4
Packing of compound 9 viewed parallel to the a axis (thick dashed lines indicate hydrogen bonds; atoms of the asymmetric unit are numbered). Hydrogen atoms not involved in the hydrogen bonds N11—H011⋯O3′ and N5—H052⋯O2′ are omitted. Labels indicate atoms of the asymmetric unit.

Figure 5
Packing of compound 9 viewed perpendicular to the ac plane (thick dashed lines indicate hydrogen bonds; atoms of the asymmetric unit are numbered). Hydrogen atoms not involved in the hydrogen bonds N11—H011⋯O3′ and N5—H051⋯Cl1′ are omitted. Labels indicate atoms of the asymmetric unit.

Figure 6
The layer structure of compound 9 viewed perpendicular to (111) (thick dashed lines indicate hydrogen bonds). Hydrogen atoms not involved in hydrogen bonds are omitted.

A search of the Cambridge Database (Version 2025.1.1; Groom et al., 2016 ) using the routine CONQUEST (Bruno et al., 2002 ) found no other examples of a similarly modified xanthene derivative either with a nitrogen substituent at C7 or a nitrogen heterocycle at C9.

Synthesis and crystallization

A mixture of 4-(chlorophenyldiazenyl)-2-hydroxybenzaldehyde 1 (2.6 g, 0.01 mmol), 2-aminoprop-1-ene-1,1,3-tricarbonitrile 2 (1.32 g, 0.01 mmol), 5,5-dimethylcyclohexane-1,3-dione (‘dimedone', 1.4 g, 0.01 mmol) and few drops of trimethylamine in acetonitrile (30 ml) was refluxed for 8 h. After cooling, the precipitate of compound 9 was collected by filtration and recrystallized from dimethylformamide (DMF) as large orange blocks. Yield 4.00 g (78%). For X-ray measurements, an irregular single crystalline fragment of suitable dimensions was cut from a larger block.

M.p.: above 573 K. ¹H NMR (400 MHz, DMSO-d₆): δH = 0.98 (s, 3H, CH₃), 1.06 (s, 3H, CH₃), 2.07 (d, 1H, J = 16.4 Hz, CH₂), 2.33 (d, 1H, J = 16.14 Hz, CH₂), 2.40–2.59 (m, 2H, CH₂), 4.94 (s, 1H, pyran-H), 6.35 (s, 2H, NH₂), 6.47 (s, 2H, NH₂), 7.14 (d, 1H, J = 8.64 Hz, Ar—H), 7.55 (s, 1H, Ar—H), 7.60 (d, 2H, J = 8.6 Hz, Ar—H), 7.67–7.69 (m, 1H, Ar—H), 7.85 (d, 2H, J = 8.6 Hz, Ar—H), 9.67 (s,1H, NH) p.p.m.. ¹³C NMR (100 MHz, DMSO-d₆): δC = 26.82, 27.60, 29.48, 31.24, 32.21, 50.82, 62.50, 99.39, 110.75, 116.73, 117.43, 121.98, 124.17, 124.55, 127.23, 129.95, 135.99, 148.50, 151.02, 153.27, 153.38, 155.05, 160.20, 162.77, 165.10, 196.91. Analysis calculated for C₂₇H₂₃ClN₆O₃ (514.96): C 62.97, H 4.50, Cl 6.88, N 16.32. Found: C 62.80, H 4.69, N 16.08%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Hydrogen atoms bonded to nitrogen were refined with an N—H distance restraint (SADI) for the NH₂ groups. Methyl groups were refined as idealized rigid groups allowed to rotate but not tip (‘AFIX 137’), with C—H = 0.98, H—C—H = 109.5°. Other hydrogen atoms were included using a riding model starting from calculated positions (C—H_methine = 1.00, C—H_methylene = 0.99 Å). The U_iso(H) values were fixed for methyl groups at 1.5 × U_eq, and for other H atoms at 1.2 × U_eq of the parent carbon atoms. Three badly-fitting reflections (deviations > 7.5σ) were omitted from the refinement. The weighting parameters a and b (Sheldrick, 2015b ) oscillated over a small range.

A region of residual electron density around the inversion centre at (0, 0, 1/2) was tentatively interpreted as several overlapping (and thus partially occupied) DMF sites (DMF was used for the recrystallization). One clear DMF position could be refined (with occupation 0.58) but the remaining difference peaks could not be interpreted satisfactorily; no suitable model of disordered DMF was found. It is possible that some other solvent, perhaps remaining from the synthesis, may be involved. The routine SQUEEZE (as implemented in the program system PLATON; Spek, 2020 ) was used to remove mathematically the effects of the disordered solvent. The electron content of the void was estimated as 98, corresponding to two DMF molecules per void (and thus per cell) and one DMF per asymmetric unit. This content was used to calculate the formula weight and other related quantities, but should be interpreted with caution. The number of parameters in the refinement was adjusted upwards by 55 (recommended by the SQUEEZE routine; command ‘L.S. 6 0 55') to allow for the solvent parameters when calculating su's. The use of SQUEEZE causes a long series of ‘G ALERTS' when the CIF file is analysed by checkCIF.

Structural data

CCDC reference: 2497635

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314625009393/bt4183sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625009393/bt4183Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625009393/bt4183Isup3.cml

checkCIF report

Computing details top

(E)-2,4-Diamino-5-{7-[(4-chlorophenyl)diazenyl]-3,3-dimethyl-1-oxo-2,3,4,9-tetrahydro-1H-xanthen-9-yl}-6-oxo-1,6-dihydropyridine-3-carbonitrile dimethylformamide monosolvate top

Crystal data top

C₂₇H₂₃ClN₆O₃·C₃H₇NO	Z = 2
M_r = 588.06	F(000) = 696
Triclinic, P1	D_x = 1.447 Mg m⁻³
a = 11.0172 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3285 (3) Å	Cell parameters from 38596 reflections
c = 12.6748 (4) Å	θ = 2.4–33.2°
α = 64.450 (3)°	µ = 0.18 mm⁻¹
β = 89.344 (3)°	T = 100 K
γ = 78.658 (2)°	Irregular, orange
V = 1517.63 (8) Å³	0.16 × 0.16 × 0.12 mm

Data collection top

XtaLAB Synergy diffractometer	11619 independent reflections
Radiation source: micro-focus sealed X-ray tube	9160 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.056
ω scans	θ_max = 33.2°, θ_min = 2.4°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2025)	h = −16→16
T_min = 0.872, T_max = 1.000	k = −18→18
100274 measured reflections	l = −19→19

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0676P)² + 0.2643P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
11619 reflections	Δρ_max = 0.56 e Å⁻³
356 parameters	Δρ_min = −0.29 e Å⁻³
6 restraints

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

	x	y	z	U_iso*/U_eq
N1	0.14828 (8)	0.65466 (8)	0.84932 (8)	0.02025 (17)
N2	0.10393 (9)	0.76856 (9)	0.80198 (9)	0.02349 (18)
O1	0.65579 (7)	0.52573 (6)	0.81948 (7)	0.01912 (14)
C1	0.72160 (9)	0.18661 (9)	0.93834 (8)	0.01572 (16)
O2	0.66692 (7)	0.10096 (7)	0.97332 (7)	0.02217 (15)
C2	0.86182 (9)	0.16316 (9)	0.94458 (9)	0.01906 (18)
H2A	0.893707	0.087344	0.934964	0.023*
H2B	0.893364	0.148495	1.023451	0.023*
C3	0.91361 (9)	0.26893 (10)	0.85173 (9)	0.01951 (18)
C4	0.85135 (9)	0.38947 (9)	0.85687 (9)	0.01856 (18)
H4A	0.885379	0.390258	0.928422	0.022*
H4B	0.871513	0.459764	0.788082	0.022*
C4A	0.71351 (9)	0.40505 (9)	0.85790 (8)	0.01557 (16)
C5	0.47856 (10)	0.67623 (10)	0.80104 (11)	0.0235 (2)
H05	0.530245	0.734582	0.776609	0.028*
C6	0.35346 (10)	0.71337 (10)	0.80853 (10)	0.0231 (2)
H06	0.318453	0.796859	0.790331	0.028*
C7	0.27887 (9)	0.62564 (9)	0.84350 (9)	0.01862 (18)
C8	0.33099 (9)	0.50313 (9)	0.87186 (8)	0.01639 (17)
H08	0.279648	0.444474	0.897171	0.020*
C8A	0.45709 (9)	0.46475 (8)	0.86387 (8)	0.01459 (16)
C8B	0.52913 (9)	0.55330 (9)	0.82927 (9)	0.01740 (17)
C9	0.51168 (8)	0.33465 (8)	0.88298 (8)	0.01328 (15)
H9	0.485321	0.276919	0.958844	0.016*
C9A	0.65145 (8)	0.31294 (8)	0.89250 (8)	0.01400 (15)
N11	0.42705 (9)	0.37815 (8)	0.57725 (7)	0.01944 (17)
H011	0.4374 (16)	0.4289 (16)	0.5031 (15)	0.036 (4)*
C12	0.35524 (10)	0.29688 (10)	0.59099 (9)	0.01940 (18)
C13	0.33734 (9)	0.21558 (9)	0.70441 (8)	0.01629 (17)
C14	0.39335 (8)	0.22110 (8)	0.80298 (8)	0.01318 (15)
C15	0.46177 (8)	0.31130 (8)	0.78490 (8)	0.01323 (15)
C16	0.48166 (9)	0.38942 (9)	0.66910 (8)	0.01586 (16)
N3	0.30702 (12)	0.29933 (11)	0.49221 (9)	0.0312 (2)
H031	0.3275 (16)	0.3486 (15)	0.4255 (12)	0.040 (5)*
H032	0.2477 (16)	0.2626 (18)	0.4947 (17)	0.058 (6)*
N4	0.21380 (11)	0.04876 (11)	0.73639 (10)	0.0322 (2)
N5	0.37648 (8)	0.14009 (8)	0.91206 (7)	0.01654 (15)
H051	0.4246 (14)	0.1289 (15)	0.9669 (12)	0.030 (4)*
H052	0.3407 (15)	0.0814 (14)	0.9237 (14)	0.037 (4)*
O3	0.54610 (7)	0.47042 (7)	0.64269 (6)	0.02039 (15)
C17	0.26884 (10)	0.12390 (10)	0.72123 (9)	0.02006 (19)
C21	−0.02659 (9)	0.80208 (10)	0.80584 (10)	0.02030 (19)
C22	−0.07321 (10)	0.92779 (10)	0.76723 (11)	0.0243 (2)
H22	−0.018664	0.983383	0.740749	0.029*
C23	−0.19902 (10)	0.97174 (10)	0.76743 (10)	0.0232 (2)
H23	−0.231313	1.057128	0.742361	0.028*
C24	−0.27692 (9)	0.88893 (9)	0.80484 (9)	0.01874 (18)
Cl1	−0.43554 (2)	0.94466 (2)	0.79962 (2)	0.02262 (6)
C25	−0.23163 (10)	0.76299 (10)	0.84473 (10)	0.0232 (2)
H25	−0.286433	0.707667	0.871535	0.028*
C26	−0.10597 (10)	0.71939 (10)	0.84486 (11)	0.0238 (2)
H26	−0.073774	0.633779	0.871307	0.029*
C27	1.05426 (10)	0.24386 (11)	0.87808 (12)	0.0273 (2)
H27A	1.072060	0.240009	0.955343	0.041*
H27B	1.087824	0.310192	0.818031	0.041*
H27C	1.092951	0.165326	0.877734	0.041*
C28	0.88616 (11)	0.27880 (11)	0.72925 (10)	0.0264 (2)
H28A	0.924472	0.201162	0.726918	0.040*
H28B	0.920329	0.345764	0.670810	0.040*
H28C	0.796121	0.295779	0.711728	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0175 (4)	0.0204 (4)	0.0240 (4)	0.0002 (3)	−0.0005 (3)	−0.0125 (3)
N2	0.0173 (4)	0.0198 (4)	0.0350 (5)	0.0001 (3)	−0.0013 (3)	−0.0151 (4)
O1	0.0146 (3)	0.0128 (3)	0.0298 (4)	−0.0040 (2)	0.0003 (3)	−0.0087 (3)
C1	0.0161 (4)	0.0144 (4)	0.0149 (4)	−0.0032 (3)	−0.0003 (3)	−0.0047 (3)
O2	0.0199 (3)	0.0128 (3)	0.0274 (4)	−0.0048 (3)	−0.0011 (3)	−0.0023 (3)
C2	0.0153 (4)	0.0164 (4)	0.0236 (5)	−0.0018 (3)	−0.0010 (3)	−0.0076 (4)
C3	0.0152 (4)	0.0191 (4)	0.0255 (5)	−0.0044 (3)	0.0029 (3)	−0.0106 (4)
C4	0.0144 (4)	0.0173 (4)	0.0253 (5)	−0.0056 (3)	0.0018 (3)	−0.0096 (4)
C4A	0.0149 (4)	0.0134 (4)	0.0187 (4)	−0.0036 (3)	0.0008 (3)	−0.0070 (3)
C5	0.0186 (4)	0.0145 (4)	0.0394 (6)	−0.0037 (3)	−0.0034 (4)	−0.0135 (4)
C6	0.0192 (4)	0.0170 (4)	0.0358 (6)	−0.0011 (4)	−0.0041 (4)	−0.0151 (4)
C7	0.0164 (4)	0.0186 (4)	0.0224 (5)	−0.0010 (3)	−0.0012 (3)	−0.0116 (4)
C8	0.0153 (4)	0.0165 (4)	0.0181 (4)	−0.0033 (3)	0.0008 (3)	−0.0083 (3)
C8A	0.0149 (4)	0.0137 (4)	0.0157 (4)	−0.0031 (3)	0.0000 (3)	−0.0069 (3)
C8B	0.0147 (4)	0.0152 (4)	0.0234 (5)	−0.0032 (3)	−0.0012 (3)	−0.0094 (3)
C9	0.0138 (4)	0.0120 (4)	0.0136 (4)	−0.0040 (3)	0.0009 (3)	−0.0047 (3)
C9A	0.0140 (4)	0.0128 (4)	0.0145 (4)	−0.0037 (3)	0.0005 (3)	−0.0049 (3)
N11	0.0263 (4)	0.0199 (4)	0.0129 (4)	−0.0135 (3)	0.0018 (3)	−0.0043 (3)
C12	0.0239 (5)	0.0202 (4)	0.0168 (4)	−0.0107 (4)	0.0018 (3)	−0.0081 (3)
C13	0.0187 (4)	0.0149 (4)	0.0173 (4)	−0.0079 (3)	0.0019 (3)	−0.0071 (3)
C14	0.0126 (4)	0.0103 (3)	0.0158 (4)	−0.0028 (3)	0.0022 (3)	−0.0048 (3)
C15	0.0143 (4)	0.0115 (4)	0.0136 (4)	−0.0048 (3)	0.0015 (3)	−0.0044 (3)
C16	0.0181 (4)	0.0150 (4)	0.0144 (4)	−0.0064 (3)	0.0010 (3)	−0.0052 (3)
N3	0.0444 (6)	0.0377 (6)	0.0177 (4)	−0.0260 (5)	0.0010 (4)	−0.0107 (4)
N4	0.0406 (6)	0.0320 (5)	0.0342 (5)	−0.0231 (5)	0.0075 (4)	−0.0174 (4)
N5	0.0189 (4)	0.0137 (3)	0.0152 (4)	−0.0076 (3)	0.0016 (3)	−0.0029 (3)
O3	0.0268 (4)	0.0201 (3)	0.0152 (3)	−0.0151 (3)	0.0024 (3)	−0.0044 (3)
C17	0.0236 (5)	0.0199 (4)	0.0201 (4)	−0.0095 (4)	0.0030 (4)	−0.0099 (4)
C21	0.0165 (4)	0.0191 (4)	0.0271 (5)	−0.0003 (3)	−0.0016 (4)	−0.0131 (4)
C22	0.0210 (5)	0.0165 (4)	0.0341 (6)	−0.0032 (4)	0.0020 (4)	−0.0102 (4)
C23	0.0211 (5)	0.0139 (4)	0.0329 (5)	−0.0002 (3)	0.0001 (4)	−0.0101 (4)
C24	0.0155 (4)	0.0190 (4)	0.0224 (4)	0.0002 (3)	−0.0027 (3)	−0.0112 (4)
Cl1	0.01652 (11)	0.02239 (12)	0.02925 (13)	0.00158 (8)	−0.00234 (8)	−0.01387 (10)
C25	0.0180 (4)	0.0177 (4)	0.0338 (6)	−0.0025 (4)	−0.0037 (4)	−0.0116 (4)
C26	0.0189 (5)	0.0163 (4)	0.0369 (6)	0.0001 (4)	−0.0048 (4)	−0.0138 (4)
C27	0.0155 (4)	0.0281 (5)	0.0401 (6)	−0.0049 (4)	0.0051 (4)	−0.0166 (5)
C28	0.0288 (6)	0.0290 (5)	0.0258 (5)	−0.0089 (4)	0.0075 (4)	−0.0151 (4)

Geometric parameters (Å, º) top

N1—N2	1.2572 (13)	N11—C16	1.3875 (12)
N1—C7	1.4217 (13)	N11—H011	0.898 (17)
N2—C21	1.4224 (14)	C12—N3	1.3517 (14)
O1—C4A	1.3657 (12)	C12—C13	1.3923 (14)
O1—C8B	1.3871 (12)	C13—C17	1.4200 (13)
C1—O2	1.2306 (12)	C13—C14	1.4331 (13)
C1—C9A	1.4549 (13)	C14—N5	1.3489 (12)
C1—C2	1.5112 (14)	C14—C15	1.4011 (12)
C2—C3	1.5377 (14)	C15—C16	1.4094 (12)
C2—H2A	0.9900	C16—O3	1.2642 (11)
C2—H2B	0.9900	N3—H031	0.861 (13)
C3—C27	1.5306 (15)	N3—H032	0.858 (14)
C3—C28	1.5328 (16)	N4—C17	1.1522 (14)
C3—C4	1.5378 (14)	N5—H051	0.825 (12)
C4—C4A	1.4933 (13)	N5—H052	0.848 (13)
C4—H4A	0.9900	C21—C22	1.3941 (15)
C4—H4B	0.9900	C21—C26	1.3980 (15)
C4A—C9A	1.3485 (13)	C22—C23	1.3859 (15)
C5—C6	1.3800 (15)	C22—H22	0.9500
C5—C8B	1.3928 (14)	C23—C24	1.3861 (15)
C5—H05	0.9500	C23—H23	0.9500
C6—C7	1.4033 (15)	C24—C25	1.3926 (14)
C6—H06	0.9500	C24—Cl1	1.7383 (10)
C7—C8	1.3911 (14)	C25—C26	1.3828 (15)
C8—C8A	1.3942 (13)	C25—H25	0.9500
C8—H08	0.9500	C26—H26	0.9500
C8A—C8B	1.3907 (13)	C27—H27A	0.9800
C8A—C9	1.5107 (13)	C27—H27B	0.9800
C9—C9A	1.5072 (13)	C27—H27C	0.9800
C9—C15	1.5223 (13)	C28—H28A	0.9800
C9—H9	1.0000	C28—H28B	0.9800
N11—C12	1.3483 (13)	C28—H28C	0.9800

N2—N1—C7	112.74 (9)	C12—N11—H011	116.4 (11)
N1—N2—C21	114.76 (9)	C16—N11—H011	119.3 (11)
C4A—O1—C8B	118.26 (7)	N11—C12—N3	116.93 (9)
O2—C1—C9A	120.10 (9)	N11—C12—C13	118.49 (9)
O2—C1—C2	121.11 (9)	N3—C12—C13	124.56 (9)
C9A—C1—C2	118.77 (8)	C12—C13—C17	119.55 (9)
C1—C2—C3	114.03 (8)	C12—C13—C14	119.79 (8)
C1—C2—H2A	108.7	C17—C13—C14	120.59 (8)
C3—C2—H2A	108.7	N5—C14—C15	121.31 (8)
C1—C2—H2B	108.7	N5—C14—C13	118.77 (8)
C3—C2—H2B	108.7	C15—C14—C13	119.90 (8)
H2A—C2—H2B	107.6	C14—C15—C16	118.79 (8)
C27—C3—C28	109.25 (9)	C14—C15—C9	123.90 (8)
C27—C3—C2	109.27 (9)	C16—C15—C9	117.25 (8)
C28—C3—C2	110.06 (9)	O3—C16—N11	117.22 (8)
C27—C3—C4	109.92 (9)	O3—C16—C15	124.23 (9)
C28—C3—C4	109.77 (9)	N11—C16—C15	118.55 (8)
C2—C3—C4	108.56 (8)	C12—N3—H031	118.6 (12)
C4A—C4—C3	112.29 (8)	C12—N3—H032	120.6 (13)
C4A—C4—H4A	109.1	H031—N3—H032	119.9 (17)
C3—C4—H4A	109.1	C14—N5—H051	118.2 (11)
C4A—C4—H4B	109.1	C14—N5—H052	121.7 (11)
C3—C4—H4B	109.1	H051—N5—H052	115.4 (16)
H4A—C4—H4B	107.9	N4—C17—C13	179.12 (12)
C9A—C4A—O1	123.10 (9)	C22—C21—C26	120.48 (10)
C9A—C4A—C4	125.22 (9)	C22—C21—N2	114.69 (9)
O1—C4A—C4	111.67 (8)	C26—C21—N2	124.83 (9)
C6—C5—C8B	120.08 (10)	C23—C22—C21	120.08 (10)
C6—C5—H05	120.0	C23—C22—H22	120.0
C8B—C5—H05	120.0	C21—C22—H22	120.0
C5—C6—C7	118.84 (10)	C22—C23—C24	118.84 (10)
C5—C6—H06	120.6	C22—C23—H23	120.6
C7—C6—H06	120.6	C24—C23—H23	120.6
C8—C7—C6	120.34 (9)	C23—C24—C25	121.77 (10)
C8—C7—N1	116.11 (9)	C23—C24—Cl1	118.85 (8)
C6—C7—N1	123.54 (9)	C25—C24—Cl1	119.37 (8)
C7—C8—C8A	121.30 (9)	C26—C25—C24	119.23 (10)
C7—C8—H08	119.4	C26—C25—H25	120.4
C8A—C8—H08	119.4	C24—C25—H25	120.4
C8B—C8A—C8	117.29 (9)	C25—C26—C21	119.59 (10)
C8B—C8A—C9	121.08 (8)	C25—C26—H26	120.2
C8—C8A—C9	121.47 (8)	C21—C26—H26	120.2
O1—C8B—C8A	122.45 (9)	C3—C27—H27A	109.5
O1—C8B—C5	115.40 (8)	C3—C27—H27B	109.5
C8A—C8B—C5	122.14 (9)	H27A—C27—H27B	109.5
C9A—C9—C8A	109.52 (7)	C3—C27—H27C	109.5
C9A—C9—C15	112.34 (7)	H27A—C27—H27C	109.5
C8A—C9—C15	110.07 (7)	H27B—C27—H27C	109.5
C9A—C9—H9	108.3	C3—C28—H28A	109.5
C8A—C9—H9	108.3	C3—C28—H28B	109.5
C15—C9—H9	108.3	H28A—C28—H28B	109.5
C4A—C9A—C1	119.03 (8)	C3—C28—H28C	109.5
C4A—C9A—C9	123.00 (8)	H28A—C28—H28C	109.5
C1—C9A—C9	117.95 (8)	H28B—C28—H28C	109.5
C12—N11—C16	124.32 (8)

C7—N1—N2—C21	−179.90 (8)	C2—C1—C9A—C9	177.87 (8)
O2—C1—C2—C3	153.20 (10)	C8A—C9—C9A—C4A	−16.02 (12)
C9A—C1—C2—C3	−28.24 (13)	C15—C9—C9A—C4A	106.62 (10)
C1—C2—C3—C27	171.41 (9)	C8A—C9—C9A—C1	165.67 (8)
C1—C2—C3—C28	−68.62 (11)	C15—C9—C9A—C1	−71.68 (10)
C1—C2—C3—C4	51.54 (11)	C16—N11—C12—N3	178.74 (11)
C27—C3—C4—C4A	−167.54 (9)	C16—N11—C12—C13	−2.26 (17)
C28—C3—C4—C4A	72.27 (11)	N11—C12—C13—C17	−175.92 (10)
C2—C3—C4—C4A	−48.07 (11)	N3—C12—C13—C17	2.99 (18)
C8B—O1—C4A—C9A	7.66 (14)	N11—C12—C13—C14	0.93 (15)
C8B—O1—C4A—C4	−172.08 (8)	N3—C12—C13—C14	179.84 (11)
C3—C4—C4A—C9A	22.81 (14)	C12—C13—C14—N5	−178.89 (9)
C3—C4—C4A—O1	−157.45 (8)	C17—C13—C14—N5	−2.08 (14)
C8B—C5—C6—C7	−0.76 (17)	C12—C13—C14—C15	2.50 (14)
C5—C6—C7—C8	1.04 (16)	C17—C13—C14—C15	179.31 (9)
C5—C6—C7—N1	−177.21 (10)	N5—C14—C15—C16	176.81 (9)
N2—N1—C7—C8	−167.33 (9)	C13—C14—C15—C16	−4.62 (14)
N2—N1—C7—C6	10.98 (15)	N5—C14—C15—C9	−6.13 (14)
C6—C7—C8—C8A	−1.49 (15)	C13—C14—C15—C9	172.43 (8)
N1—C7—C8—C8A	176.89 (9)	C9A—C9—C15—C14	118.20 (10)
C7—C8—C8A—C8B	1.58 (14)	C8A—C9—C15—C14	−119.47 (10)
C7—C8—C8A—C9	−173.89 (9)	C9A—C9—C15—C16	−64.70 (11)
C4A—O1—C8B—C8A	−7.51 (14)	C8A—C9—C15—C16	57.63 (11)
C4A—O1—C8B—C5	173.03 (9)	C12—N11—C16—O3	−179.59 (10)
C8—C8A—C8B—O1	179.27 (9)	C12—N11—C16—C15	0.09 (16)
C9—C8A—C8B—O1	−5.24 (14)	C14—C15—C16—O3	−176.96 (9)
C8—C8A—C8B—C5	−1.31 (15)	C9—C15—C16—O3	5.79 (15)
C9—C8A—C8B—C5	174.18 (9)	C14—C15—C16—N11	3.38 (14)
C6—C5—C8B—O1	−179.61 (10)	C9—C15—C16—N11	−173.87 (9)
C6—C5—C8B—C8A	0.93 (17)	N1—N2—C21—C22	172.06 (10)
C8B—C8A—C9—C9A	15.75 (12)	N1—N2—C21—C26	−7.68 (16)
C8—C8A—C9—C9A	−168.95 (8)	C26—C21—C22—C23	0.09 (17)
C8B—C8A—C9—C15	−108.23 (10)	N2—C21—C22—C23	−179.66 (10)
C8—C8A—C9—C15	67.07 (11)	C21—C22—C23—C24	−0.95 (17)
O1—C4A—C9A—C1	−176.54 (9)	C22—C23—C24—C25	1.60 (17)
C4—C4A—C9A—C1	3.17 (15)	C22—C23—C24—Cl1	−177.48 (9)
O1—C4A—C9A—C9	5.17 (15)	C23—C24—C25—C26	−1.34 (17)
C4—C4A—C9A—C9	−175.12 (9)	Cl1—C24—C25—C26	177.73 (9)
O2—C1—C9A—C4A	178.07 (9)	C24—C25—C26—C21	0.43 (17)
C2—C1—C9A—C4A	−0.51 (13)	C22—C21—C26—C25	0.18 (17)
O2—C1—C9A—C9	−3.56 (13)	N2—C21—C26—C25	179.90 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N11—H011···O3ⁱ	0.898 (17)	1.758 (17)	2.6558 (11)	178.7 (18)
N5—H051···O2	0.83 (1)	2.62 (2)	3.1939 (12)	128 (1)
N5—H051···Cl1ⁱⁱ	0.83 (1)	2.69 (1)	3.3709 (9)	141 (1)
N5—H052···O2ⁱⁱⁱ	0.85 (1)	2.08 (1)	2.8266 (11)	147 (2)
C4—H4A···N1^iv	0.99	2.66	3.5236 (14)	146
C5—H05···Cl1^v	0.95	2.82	3.6093 (10)	141

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

Acknowledgements

The authors acknowledge support by the Open Access Publication Funds of the Technical University of Braunschweig.

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