N,N′-[1,4-Phenyl­enebis(imino­carbon­yl)]bis­(l-phenyl­alanine) tetra­hydro­furan disolvate

In the crystal structure of the title bis-urea derivative, the host mol­ecules are linked by N—H⋯O=C hydrogen bonds and C—H⋯O contacts with (6) and (7) ring motifs.

Abstract

The title compound, C₂₆H₂₆N₄O₆·2C₄H₈O, representing a bis-urea with terminal phenyl­alanine units, crystallized with two tetra­hydro­furan (THF) mol­ecules. The main mol­ecule is located on a crystallographic twofold axis, while the solvent mol­ecule is disordered over two positions, with occupancies of 0.571 (15) and 0.429 (15). The host mol­ecules are linked by N—H⋯O=C hydrogen bonds and C—H⋯O contacts with R ₂ ¹(6) and R ₂ ¹(7) ring motifs. The THF mol­ecules enclosed in the crystal are connected to the bis-urea compound via O—H⋯O and C—H⋯O inter­actions.

Structure description

Bis-urea compounds containing a central 1,4-phenyl­ene unit have been shown to be suitable mol­ecules for anion recognition (Stapf et al., 2015 ▸; Casula et al., 2016 ▸; Manna et al., 2018 ▸; Manna & Das, 2019 ▸, 2020 ▸; Das et al., 2020 ▸). In this context, we introduced compounds combining this scaffold and various amino acids [such as l-valine, l-leucine, l-proline, (R)-3-piperidine­carb­oxy­lic acid, l-threonine or even l-phenyl­alanine], whose amino group is part of the urea moiety, among them the title compound, possessing l-phenyl­alanine units (Stapf et al., 2015 ▸). Furthermore, we have already reported the crystal structure of a supra­molecular coordination polymer of the title compound with lead(II) (Stapf et al., 2012 ▸). In the present article, we describe the crystal structure of the tetra­hydro­furan (THF) disolvate.

The title compound was found to crystallize in the tetra­gonal space group I4₁ with half a mol­ecule of the bis-urea compound and one THF mol­ecule (Fig. 1 ▸), which is disordered over two positions (57:43). Within a single mol­ecule possessing a twofold rotation axis, the plane of the phenyl­ene unit includes a dihedral angle with the peripheral arene rings of 88.4 (1)° and with the planes of the urea moieties of 19.4 (2)°. This small angle may be associated with an intra­molecular C—H⋯O inter­action (H⋯O = 2.35 Å) between the phenyl­ene core and the urea moiety. Furthermore, the carb­oxy group is almost perpendicular to the central aromatic ring, showing a dihedral angle of 82.9 (1)°, and the phenyl­ene units of adjacent mol­ecules are oriented orthogonal with respect to each other.

Figure 1.

The mol­ecular structure of the title compound, including the atom-numbering scheme. Atoms are drawn with displacement ellipsoids at the 50% probability level. The intra­molecular C—H⋯O inter­action, as well as the inter­molecular hydrogen bonding between the carb­oxy group and the THF mol­ecule, are shown as dashed lines. Both disordered parts (57:43) of the THF mol­ecule are displayed. Unlabelled atoms are generated by the symmetry operation −x + 1, −y, z.

The dominant inter­molecular inter­actions between urea moieties of neighbouring mol­ecules are inverse bifurcated hydrogen bonds of the N—H⋯O=C type [H⋯O = 2.08 (4) and 2.32 (3) Å; Table 1 ▸], which can be described by the graph set (6) (Etter, 1990 ▸; Fig. 2 ▸). Unlike in the previously published coordination polymer (Stapf et al., 2012 ▸), in which the urea groups form two-dimensional hydrogen-bridged ribbons (H⋯O = 2.06–2.26 Å), the structure presented here is characterized by supra­molecular chains [graph set C(4)]. The angle between the planes of adjacent urea moieties is 83.7 (1)°, thus they are nearly perpendicular to one other. Such a motif is also well known in the literature (for examples, see: Albrecht et al., 2002 ▸; Berkessel et al., 2006 ▸; Saxena et al., 2014 ▸; Shugrue et al., 2019 ▸). The N atoms do not act as acceptors for hydrogen bonds. Instead, the linkage of two adjacent mol­ecules is supported by the formation of C—H⋯O=C contacts (H⋯O = 2.55 and 2.70 Å) between the C—H groups of phenyl­alanine and an O atom of a carb­oxy group which acts as a bifurcated acceptor [graph set (7); Fig. 2 ▸].

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

Cg is defined as the centre of gravity of the rings: Cg1 is ring C1–C6 and Cg2 is C10/C11/C12/C10′/C11′/C12′, with primed atoms generated by the symmetry code (−x + 1, −y, z).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.84 (4)	2.32 (3)	3.091 (3)	153 (3)
N2—H2N⋯O1i	0.88 (3)	2.08 (4)	2.937 (3)	163 (3)
O3—H3O⋯O4A ii	0.90 (3)	1.73 (3)	2.623 (7)	175 (7)
C5—H5⋯O2iii	0.95	2.55	3.464 (4)	161
C8—H8⋯O2iii	1.00	2.70	3.629 (4)	155
C11—H11⋯O1	0.95	2.35	2.916 (3)	118
C14A—H14B⋯O3iv	0.99	2.78	3.581 (18)	139
C16A—H16A⋯Cg1v	0.99	2.61	3.497 (8)	149
C16B—H16D⋯Cg1v	0.99	2.82	3.449 (10)	122
C17A—H17B⋯Cg2vi	0.99	3.00	3.574 (8)	118

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Figure 2.

Excerpt of the crystal packing showing the (6) and (7) ring motifs of the N—H⋯O=C and C—H⋯O=C(OH) inter­actions drawn as dashed lines. The THF mol­ecules and the H atoms not involved in the inter­actions have been omitted for clarity.

The crystal structure exhibits cavities which are occupied by THF mol­ecules requiring about 961 ų (corresponding to about 29% of the unit-cell volume). The cavities are bounded by the nonpolar phenyl­ene and arene units of the title compound. In addition, the carb­oxy groups point into the inter­ior of these cavities and form O—H⋯O hydrogen bonds with the THF O atom [H⋯O = 1.73 (3) Å]. Further stabilization of the mol­ecular network, each involving the THF mol­ecules, is realized by C—H⋯O contacts with the carb­oxy group of an adjacent mol­ecule (H⋯O = 2.78 Å) and weak C—H⋯π contacts (H⋯Cg = 2.61–3.00 Å) with the central benzene core or peripheral arene substituents.

Synthesis and crystallization

The synthetic and spectroscopic details for the title compound have been reported previously (Stapf et al., 2012 ▸, 2015 ▸). Single crystals suitable for X-ray analysis were obtained as colourless prisms by slow evaporation of a saturated solution of the bis-urea compound in tetra­hydro­furan.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atoms at N1 and N2 were located in a difference Fourier map and refined freely. The H atom at O3 was also located in the difference Fourier map but refined using a DFIX restraint at 0.84 (2) Å. Other H atoms were included using a riding model starting from calculated positions (aromatic C—H = 0.95 Å, methyl­ene C—H = 0.99 Å, and alkyl C—H = 1.00 Å). The U _iso(H) values were fixed at 1.2 times the equivalent U _eq value of the parent C atoms. The THF solvent mol­ecule is disordered over at least two positions [refined occupancies 0.571 (15) and 0.429 (15)]. Therefore, the solvent mol­ecule was refined using ISOR for C16A, C16B, C17A and C17B (approximate isotropic behaviour) and SADI (same distances over pairs of bonded atoms) restraints (Sheldrick, 2015b ▸). The absolute structure of the title compound has been assigned by reference to an unchanging chiral centre in the synthetic procedure, not by anomalous dispersion effects in the diffraction experiment.

Table 2. Experimental details.

Crystal data
Chemical formula	C26H26N4O6·2C4H8O
M r	634.71
Crystal system, space group	Tetragonal, I41
Temperature (K)	153
a, c (Å)	13.632 (4), 17.507 (6)
V (Å3)	3253 (2)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.09
Crystal size (mm)	0.10 × 0.05 × 0.04
Data collection
Diffractometer	Stoe IPDS 2T
No. of measured, independent and observed [I > 2σ(I)] reflections	25670, 3554, 3269
R int	0.028
(sin θ/λ)max (Å−1)	0.639
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.040, 0.107, 1.05
No. of reflections	3554
No. of parameters	266
No. of restraints	95
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.31, −0.20

Computer programs: X-AREA (Stoe & Cie, 2009 ▸), X-RED (Stoe & Cie, 2009 ▸), SHELXT2018 (Sheldrick, 2015a ▸), SHELXL2018 (Sheldrick, 2015b ▸), XP (Sheldrick, 2008 ▸), WinGX (Farrugia, 2012 ▸), publCIF (Westrip, 2010 ▸) and shelXle (Hübschle et al., 2011 ▸).

Supplementary Material

CCDC reference: 2290568

Additional supporting information: crystallographic information; 3D view; checkCIF report

full crystallographic data

Crystal data

C26H26N4O6·2C4H8O	Dx = 1.296 Mg m−3
Mr = 634.71	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41	Cell parameters from 1266 reflections
a = 13.632 (4) Å	θ = 3.1–26.7°
c = 17.507 (6) Å	µ = 0.09 mm−1
V = 3253 (2) Å3	T = 153 K
Z = 4	Chunk, colourless
F(000) = 1352	0.10 × 0.05 × 0.04 mm

Data collection

STOE IPDS 2T diffractometer	3269 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	Rint = 0.028
Plane graphite monochromator	θmax = 27.0°, θmin = 3.0°
Detector resolution: 6.67 pixels mm-1	h = −17→17
rotation method scans	k = −17→17
25670 measured reflections	l = −22→22
3554 independent reflections

Refinement

Refinement on F2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	Hydrogen site location: mixed
wR(F2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0557P)2 + 2.0532P] where P = (Fo2 + 2Fc2)/3
3554 reflections	(Δ/σ)max = 0.002
266 parameters	Δρmax = 0.31 e Å−3
95 restraints	Δρmin = −0.20 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.38152 (16)	0.16933 (16)	0.54757 (12)	0.0285 (4)
H1N	0.376 (2)	0.194 (2)	0.504 (2)	0.030 (8)*
N2	0.27971 (16)	0.29428 (15)	0.58122 (12)	0.0278 (4)
H2N	0.285 (2)	0.310 (2)	0.533 (2)	0.034 (8)*
O1	0.31329 (14)	0.17368 (13)	0.66808 (10)	0.0302 (4)
O2	0.11068 (16)	0.19008 (15)	0.57508 (14)	0.0445 (5)
O3	0.02642 (16)	0.30373 (19)	0.63921 (15)	0.0529 (6)
H3O	−0.023 (4)	0.263 (4)	0.627 (5)	0.14 (3)*
C1	0.3225 (2)	0.5393 (2)	0.54681 (18)	0.0389 (6)
H1	0.302627	0.524528	0.496096	0.047*
C2	0.4061 (2)	0.5960 (2)	0.55894 (19)	0.0460 (7)
H2A	0.442763	0.619510	0.516591	0.055*
C3	0.4360 (2)	0.6185 (2)	0.6331 (2)	0.0497 (8)
H3	0.493013	0.657049	0.641531	0.060*
C4	0.3818 (3)	0.5840 (2)	0.69431 (19)	0.0466 (7)
H4	0.401726	0.599088	0.744967	0.056*
C5	0.2986 (2)	0.5276 (2)	0.68217 (16)	0.0380 (6)
H5	0.262005	0.504595	0.724742	0.046*
C6	0.26774 (19)	0.50397 (18)	0.60822 (16)	0.0313 (5)
C7	0.17887 (19)	0.44008 (19)	0.59624 (15)	0.0327 (6)
H7A	0.161232	0.440197	0.541378	0.039*
H7B	0.122863	0.467660	0.625126	0.039*
C8	0.19711 (18)	0.33349 (18)	0.62249 (14)	0.0283 (5)
H8	0.213017	0.333795	0.678256	0.034*
C9	0.32327 (17)	0.20934 (17)	0.60329 (13)	0.0252 (5)
C10	0.43982 (17)	0.08384 (17)	0.55283 (14)	0.0250 (5)
C11	0.47052 (18)	0.04159 (18)	0.62133 (14)	0.0275 (5)
H11	0.450935	0.069967	0.668486	0.033*
C12	0.4700 (2)	0.0413 (2)	0.48385 (14)	0.0341 (6)
H12	0.449394	0.068988	0.436734	0.041*
C13	0.1072 (2)	0.2663 (2)	0.60914 (15)	0.0370 (6)
O4A	0.6924 (5)	0.1252 (4)	0.3577 (7)	0.048 (2)	0.571 (15)
C14A	0.5578 (8)	0.2254 (9)	0.3317 (12)	0.062 (5)	0.571 (15)
H14A	0.519420	0.224367	0.379670	0.074*	0.571 (15)
H14B	0.515206	0.247603	0.289262	0.074*	0.571 (15)
C15A	0.6031 (10)	0.1256 (10)	0.3148 (10)	0.046 (4)	0.571 (15)
H15A	0.559079	0.071968	0.331644	0.055*	0.571 (15)
H15B	0.616352	0.118003	0.259558	0.055*	0.571 (15)
C16A	0.7185 (6)	0.2206 (5)	0.3801 (6)	0.057 (2)	0.571 (15)
H16A	0.787187	0.234862	0.365513	0.068*	0.571 (15)
H16B	0.711966	0.228135	0.436102	0.068*	0.571 (15)
C17A	0.6488 (4)	0.2893 (4)	0.3391 (4)	0.0483 (19)	0.571 (15)
H17A	0.674677	0.308654	0.288402	0.058*	0.571 (15)
H17B	0.635496	0.348937	0.369627	0.058*	0.571 (15)
O4B	0.6865 (10)	0.1184 (7)	0.3439 (12)	0.081 (5)	0.429 (15)
C14B	0.5595 (10)	0.2278 (11)	0.3178 (12)	0.043 (4)	0.429 (15)
H14C	0.491571	0.225648	0.337787	0.052*	0.429 (15)
H14D	0.560401	0.268410	0.270882	0.052*	0.429 (15)
C15B	0.5969 (15)	0.1248 (10)	0.3012 (13)	0.046 (4)	0.429 (15)
H15C	0.549184	0.074772	0.318503	0.056*	0.429 (15)
H15D	0.609168	0.115831	0.245904	0.056*	0.429 (15)
C16B	0.7256 (7)	0.2178 (7)	0.3503 (8)	0.053 (3)	0.429 (15)
H16C	0.748952	0.243547	0.300663	0.064*	0.429 (15)
H16D	0.778608	0.222487	0.388781	0.064*	0.429 (15)
C17B	0.6294 (8)	0.2691 (10)	0.3774 (10)	0.088 (4)	0.429 (15)
H17C	0.610777	0.249281	0.429818	0.105*	0.429 (15)
H17D	0.634210	0.341453	0.374449	0.105*	0.429 (15)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0345 (11)	0.0309 (10)	0.0202 (9)	0.0040 (9)	0.0040 (8)	0.0030 (8)
N2	0.0338 (11)	0.0261 (10)	0.0235 (10)	0.0025 (8)	0.0050 (8)	0.0009 (8)
O1	0.0355 (10)	0.0342 (9)	0.0209 (8)	0.0044 (7)	0.0033 (7)	0.0026 (7)
O2	0.0431 (11)	0.0363 (11)	0.0540 (13)	−0.0057 (8)	−0.0076 (10)	−0.0039 (9)
O3	0.0357 (11)	0.0657 (15)	0.0574 (14)	−0.0110 (10)	0.0096 (10)	−0.0175 (12)
C1	0.0424 (15)	0.0388 (14)	0.0355 (13)	0.0037 (12)	0.0062 (12)	−0.0026 (12)
C2	0.0465 (17)	0.0469 (17)	0.0445 (17)	−0.0021 (13)	0.0145 (14)	−0.0026 (13)
C3	0.0425 (16)	0.0437 (17)	0.063 (2)	−0.0089 (13)	0.0042 (15)	−0.0104 (15)
C4	0.0492 (18)	0.0451 (17)	0.0454 (16)	−0.0092 (14)	−0.0022 (13)	−0.0104 (13)
C5	0.0451 (16)	0.0353 (14)	0.0337 (14)	−0.0013 (12)	0.0016 (12)	−0.0016 (11)
C6	0.0337 (13)	0.0249 (11)	0.0353 (13)	0.0066 (10)	0.0010 (10)	−0.0003 (10)
C7	0.0294 (12)	0.0328 (13)	0.0360 (14)	0.0061 (10)	−0.0019 (10)	0.0012 (11)
C8	0.0277 (11)	0.0333 (12)	0.0240 (11)	0.0004 (10)	0.0008 (9)	0.0005 (9)
C9	0.0268 (11)	0.0263 (11)	0.0224 (11)	−0.0041 (9)	0.0001 (9)	−0.0019 (9)
C10	0.0250 (11)	0.0284 (11)	0.0218 (10)	−0.0018 (9)	0.0011 (9)	0.0006 (9)
C11	0.0309 (11)	0.0306 (12)	0.0210 (11)	0.0013 (10)	0.0007 (9)	−0.0018 (9)
C12	0.0396 (14)	0.0427 (15)	0.0199 (11)	0.0115 (12)	0.0000 (10)	0.0012 (10)
C13	0.0344 (13)	0.0479 (16)	0.0289 (13)	−0.0011 (12)	0.0001 (11)	0.0060 (11)
O4A	0.038 (3)	0.034 (3)	0.072 (5)	−0.003 (2)	−0.021 (3)	−0.001 (2)
C14A	0.048 (6)	0.054 (7)	0.083 (9)	0.003 (5)	−0.003 (5)	−0.012 (5)
C15A	0.037 (5)	0.059 (7)	0.043 (5)	−0.006 (4)	−0.002 (3)	−0.015 (4)
C16A	0.057 (3)	0.055 (3)	0.059 (3)	0.003 (2)	−0.009 (2)	−0.002 (2)
C17A	0.049 (3)	0.038 (2)	0.058 (3)	0.0014 (19)	0.006 (2)	0.000 (2)
O4B	0.113 (10)	0.064 (6)	0.065 (6)	0.058 (6)	−0.020 (5)	−0.008 (5)
C14B	0.040 (7)	0.047 (7)	0.042 (5)	0.024 (5)	−0.003 (4)	−0.003 (4)
C15B	0.056 (8)	0.025 (6)	0.058 (9)	0.009 (5)	0.011 (5)	0.010 (5)
C16B	0.052 (3)	0.053 (3)	0.055 (4)	0.001 (2)	−0.007 (3)	−0.003 (3)
C17B	0.088 (5)	0.087 (5)	0.089 (5)	0.009 (3)	−0.004 (3)	−0.004 (3)

Geometric parameters (Å, º)

N1—C9	1.371 (3)	C11—H11	0.9500
N1—C10	1.413 (3)	C12—C12i	1.390 (5)
N1—H1N	0.84 (4)	C12—H12	0.9500
N2—C9	1.357 (3)	O4A—C16A	1.405 (8)
N2—C8	1.441 (3)	O4A—C15A	1.430 (8)
N2—H2N	0.88 (3)	C14A—C15A	1.522 (9)
O1—C9	1.241 (3)	C14A—C17A	1.522 (10)
O2—C13	1.199 (4)	C14A—H14A	0.9900
O3—C13	1.324 (4)	C14A—H14B	0.9900
O3—H3O	0.90 (3)	C15A—H15A	0.9900
C1—C2	1.393 (5)	C15A—H15B	0.9900
C1—C6	1.395 (4)	C16A—C17A	1.515 (8)
C1—H1	0.9500	C16A—H16A	0.9900
C2—C3	1.395 (5)	C16A—H16B	0.9900
C2—H2A	0.9500	C17A—H17A	0.9900
C3—C4	1.383 (5)	C17A—H17B	0.9900
C3—H3	0.9500	O4B—C15B	1.435 (10)
C4—C5	1.387 (4)	O4B—C16B	1.460 (10)
C4—H4	0.9500	C14B—C15B	1.521 (9)
C5—C6	1.399 (4)	C14B—C17B	1.521 (11)
C5—H5	0.9500	C14B—H14C	0.9900
C6—C7	1.507 (4)	C14B—H14D	0.9900
C7—C8	1.544 (3)	C15B—H15C	0.9900
C7—H7A	0.9900	C15B—H15D	0.9900
C7—H7B	0.9900	C16B—C17B	1.560 (10)
C8—C13	1.547 (4)	C16B—H16C	0.9900
C8—H8	1.0000	C16B—H16D	0.9900
C10—C11	1.395 (3)	C17B—H17C	0.9900
C10—C12	1.402 (3)	C17B—H17D	0.9900
C11—C11i	1.390 (5)
C9—N1—C10	127.4 (2)	O3—C13—C8	111.8 (3)
C9—N1—H1N	116 (2)	C16A—O4A—C15A	111.0 (7)
C10—N1—H1N	116 (2)	C15A—C14A—C17A	101.4 (8)
C9—N2—C8	121.0 (2)	C15A—C14A—H14A	111.5
C9—N2—H2N	117 (2)	C17A—C14A—H14A	111.5
C8—N2—H2N	117 (2)	C15A—C14A—H14B	111.5
C13—O3—H3O	107 (5)	C17A—C14A—H14B	111.5
C2—C1—C6	120.8 (3)	H14A—C14A—H14B	109.3
C2—C1—H1	119.6	O4A—C15A—C14A	104.3 (7)
C6—C1—H1	119.6	O4A—C15A—H15A	110.9
C1—C2—C3	120.2 (3)	C14A—C15A—H15A	110.9
C1—C2—H2A	119.9	O4A—C15A—H15B	110.9
C3—C2—H2A	119.9	C14A—C15A—H15B	110.9
C4—C3—C2	119.4 (3)	H15A—C15A—H15B	108.9
C4—C3—H3	120.3	O4A—C16A—C17A	106.4 (6)
C2—C3—H3	120.3	O4A—C16A—H16A	110.5
C3—C4—C5	120.4 (3)	C17A—C16A—H16A	110.5
C3—C4—H4	119.8	O4A—C16A—H16B	110.5
C5—C4—H4	119.8	C17A—C16A—H16B	110.5
C4—C5—C6	121.0 (3)	H16A—C16A—H16B	108.6
C4—C5—H5	119.5	C16A—C17A—C14A	101.4 (6)
C6—C5—H5	119.5	C16A—C17A—H17A	111.5
C1—C6—C5	118.2 (3)	C14A—C17A—H17A	111.5
C1—C6—C7	121.5 (3)	C16A—C17A—H17B	111.5
C5—C6—C7	120.2 (2)	C14A—C17A—H17B	111.5
C6—C7—C8	111.9 (2)	H17A—C17A—H17B	109.3
C6—C7—H7A	109.2	C15B—O4B—C16B	107.1 (10)
C8—C7—H7A	109.2	C15B—C14B—C17B	105.2 (7)
C6—C7—H7B	109.2	C15B—C14B—H14C	110.7
C8—C7—H7B	109.2	C17B—C14B—H14C	110.7
H7A—C7—H7B	107.9	C15B—C14B—H14D	110.7
N2—C8—C7	109.0 (2)	C17B—C14B—H14D	110.7
N2—C8—C13	108.9 (2)	H14C—C14B—H14D	108.8
C7—C8—C13	112.6 (2)	O4B—C15B—C14B	104.0 (8)
N2—C8—H8	108.8	O4B—C15B—H15C	111.0
C7—C8—H8	108.8	C14B—C15B—H15C	111.0
C13—C8—H8	108.8	O4B—C15B—H15D	111.0
O1—C9—N2	123.1 (2)	C14B—C15B—H15D	111.0
O1—C9—N1	123.9 (2)	H15C—C15B—H15D	109.0
N2—C9—N1	113.0 (2)	O4B—C16B—C17B	97.6 (8)
C11—C10—C12	118.8 (2)	O4B—C16B—H16C	112.2
C11—C10—N1	124.4 (2)	C17B—C16B—H16C	112.2
C12—C10—N1	116.8 (2)	O4B—C16B—H16D	112.2
C11i—C11—C10	120.70 (14)	C17B—C16B—H16D	112.2
C11i—C11—H11	119.7	H16C—C16B—H16D	109.8
C10—C11—H11	119.7	C14B—C17B—C16B	98.8 (10)
C12i—C12—C10	120.52 (15)	C14B—C17B—H17C	112.0
C12i—C12—H12	119.7	C16B—C17B—H17C	112.0
C10—C12—H12	119.7	C14B—C17B—H17D	112.0
O2—C13—O3	124.4 (3)	C16B—C17B—H17D	112.0
O2—C13—C8	123.9 (3)	H17C—C17B—H17D	109.7
C6—C1—C2—C3	−0.1 (5)	C9—N1—C10—C12	161.9 (2)
C1—C2—C3—C4	−0.1 (5)	C12—C10—C11—C11i	−0.4 (4)
C2—C3—C4—C5	0.1 (5)	N1—C10—C11—C11i	−178.7 (3)
C3—C4—C5—C6	0.2 (5)	C11—C10—C12—C12i	−0.4 (5)
C2—C1—C6—C5	0.4 (4)	N1—C10—C12—C12i	178.1 (3)
C2—C1—C6—C7	−178.2 (3)	N2—C8—C13—O2	5.8 (4)
C4—C5—C6—C1	−0.5 (4)	C7—C8—C13—O2	126.8 (3)
C4—C5—C6—C7	178.2 (3)	N2—C8—C13—O3	−173.6 (2)
C1—C6—C7—C8	110.2 (3)	C7—C8—C13—O3	−52.6 (3)
C5—C6—C7—C8	−68.4 (3)	C16A—O4A—C15A—C14A	−16.5 (18)
C9—N2—C8—C7	167.2 (2)	C17A—C14A—C15A—O4A	34.2 (17)
C9—N2—C8—C13	−69.6 (3)	C15A—O4A—C16A—C17A	−8.6 (15)
C6—C7—C8—N2	−57.9 (3)	O4A—C16A—C17A—C14A	29.8 (13)
C6—C7—C8—C13	−178.9 (2)	C15A—C14A—C17A—C16A	−38.3 (15)
C8—N2—C9—O1	−18.6 (4)	C16B—O4B—C15B—C14B	−28 (2)
C8—N2—C9—N1	163.4 (2)	C17B—C14B—C15B—O4B	−6 (2)
C10—N1—C9—O1	−0.6 (4)	C15B—O4B—C16B—C17B	48.8 (18)
C10—N1—C9—N2	177.4 (2)	C15B—C14B—C17B—C16B	34 (2)
C9—N1—C10—C11	−19.7 (4)	O4B—C16B—C17B—C14B	−48.8 (16)

Symmetry code: (i) −x+1, −y, z.

Hydrogen-bond geometry (Å, º)

Cg is defined as the centre of gravity of the rings: Cg1 is C1···C6; Cg2 is C10/C11/C12/C10'/C11'/C12' with primed atoms generated by symmetry -x+1, -y, z.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ii	0.84 (4)	2.32 (3)	3.091 (3)	153 (3)
N2—H2N···O1ii	0.88 (3)	2.08 (4)	2.937 (3)	163 (3)
O3—H3O···O4Aiii	0.90 (3)	1.73 (3)	2.623 (7)	175 (7)
C5—H5···O2iv	0.95	2.55	3.464 (4)	161
C8—H8···O2iv	1.00	2.70	3.629 (4)	155
C11—H11···O1	0.95	2.35	2.916 (3)	118
C14A—H14B···O3v	0.99	2.78	3.581 (18)	139
C16A—H16A···Cg1vi	0.99	2.61	3.497 (8)	149
C16B—H16D···Cg1vi	0.99	2.82	3.449 (10)	122
C17A—H17B···Cg2vii	0.99	3.00	3.574 (8)	118

Symmetry codes: (ii) −y+1/2, x, z−1/4; (iii) −y, x−1/2, z+1/4; (iv) y, −x+1/2, z+1/4; (v) −x+1/2, −y+1/2, z−1/2; (vi) x, y+1, z; (vii) y+1/2, −x+1, z−1/4.

Funding Statement

Open Access Funding by the Publication Fund of the TU Bergakademie Freiberg.