Poly[[tetra­methano­lbis[4-oxo-3-(pyridin-4-yl)-1-(2,4,6-tri­chloro­phen­yl)-4,5-di­hydro-1H-pyrazolo[3,4-d]pyrimidin-6-olato]disodium]–diethyl ether–methanol (1/1/2)]

Abu Thaher, B.; Schollmeyer, D.; Laufer, S.

doi:10.1107/S2414314616010816

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161081

https://doi.org/10.1107/S2414314616010816

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Poly[[tetramethanolbis[4-oxo-3-(pyridin-4-yl)-1-(2,4,6-trichlorophenyl)-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-olato]disodium]–diethyl ether–methanol (1/1/2)]

Bassam Abu Thaher,^a Dieter Schollmeyer ^b and Stefan Laufer ^c ^*

^aFaculty of Science, Chemistry Department, Islamic University of Gaza, Gaza Strip, Palestinian Territories, ^bDepartment of Organic Chemistry, Johannes Gutenberg-University Mainz, Duesbergweg 10-14, 55099 Mainz, Germany, and ^cInstitute of Pharmacy, Department of Pharmaceutical and Medicinal Chemistry, Eberhard Karl University Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany
^*Correspondence e-mail: Stefan.laufer@uni-tuebingen.de

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 20 June 2016; accepted 4 July 2016; online 12 July 2016)

In the title compound, [Na₂(C₁₆H₇Cl₃N₅O₂)₂(CH₃OH)₄]·C₄H₁₀O·2CH₃OH, the central pyrazolo[3,4-d]pyrimidine system makes dihedral angles of 82.98 (7)° with the trichlorophenyl ring and 13.11 (15)° with the pyridine ring. The sodium ion has an octahedral environment, being coordinated by four methanol molecules and one O and one N atom of two different heterocyclic ring systems.

Keywords: crystal structure; sodium; pyridine; 2,4,6-trichlorophenyl; pyrazolo[3,4-d]pyrimidin-6-olate.

CCDC reference: 1490105

Structure description

In the framework of investigating the efficiency of 4-(4-fluorophenyl)-3-(pyridin-4-yl)-1-(aryl)-1H-pyrazol-5-amines as inhibitors for kinases relevant to cancer, many derivatives of this compound have been synthesized (Abu Thaher, Arnsmann et al., 2012 ). Recently, we have reported the crystal structures of several amino pyrazoles (Abu Thaher, Koch et al., 2012a ,b ,c ,d,e ). Finally, in our approach of synthesizing new derivatives, we managed to prepare crystals of the title compound (Fig. 1). It crystallizes with three methanol molecules which have quite different functions in the crystal structure – only two coordinate to the sodium cation and the third one does not. However, all three are involved hydrogen bonds to the pyrazolo[3,4-d]pyrimidine system (see Table 1). The sodium cation is surrounded by by four methanol O atoms and one O and one N atom of two different heterocyclic ring systems. The position of the negative charge could not be determined, and we assum that it is delocalized over the pyrazolo[3,4-d]pyrimidine system. The dihedral angle between the pyrazolo[3,4-d]pyrimidine ring system and the pyridine ring is 13.11 (15)°, smaller than that subtended to the trichlorophenyl plane [82.98 (7)°]. One diethyl ether solvent molecule is disordered about the twofold rotation axis and fills a channel parallel to the b axis.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O14ⁱ	0.81 (3)	1.99 (3)	2.771 (3)	160 (3)
C21—H21⋯O15	0.95	2.29	3.096 (3)	142
O1L—H1L⋯N2	0.86 (4)	2.21 (4)	3.062 (3)	172 (3)
O2L—H2L⋯N2	0.78 (4)	2.06 (4)	2.815 (3)	163 (4)
O3L—H3L⋯O2L	0.84 (4)	1.94 (4)	2.783 (3)	176 (4)
Symmetry code: (i) -x, -y+1, -z.

Figure 1
The molecular structure of the title compound, with the atom labelling and displacement ellipsoids drawn at the 50% probability level.

Synthesis and crystallization

2 mmol of N-(2,4,6-trichlorophenyl)-4-pyridinecarbohydrazonoyl chloride and 1.5 equiv. of ethyl (2-cyanoacetyl)carbamate were dissolved in 20 ml dry ethanol and cooled to 273 K in an ice bath. 2.0 equiv. of sodium ethoxide solution (21% ethanol) was added dropwise and the reaction was stirred overnight. The precipitate was filtered from the reaction mixture, washed with water and then with diethyl ether. Yield: 30%. Suitable crystals for X-ray analysis were obtained by slow evaporation of a methanol/diethyl ether solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. One molecule of ether is disordered about the twofold rotation axis. Consequently, the site occupation factors of all ether atoms were set to 0.5 and the displacement parameters were fixed to an isotropic behaviour. The C—C distances in the ether molecule were restrained to 1.54 (2) Å, the C—O distances to 1.46 (2) Å.

Table 2
Experimental details

Crystal data
Chemical formula	[Na₂(C₁₆H₇Cl₃N₅O₂)₂(CH₄O)₄]·C₄H₁₀O·2CH₄O
M_r	1127.58
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	173
a, b, c (Å)	11.1721 (7), 8.1249 (5), 28.8799 (18)
β (°)	100.213 (1)
V (Å³)	2580.0 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.42
Crystal size (mm)	0.56 × 0.32 × 0.19

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2000 )
T_min, T_max	0.659, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	27638, 6097, 5149
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.657

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.131, 1.15
No. of reflections	6097
No. of parameters	357
No. of restraints	34
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.40
Computer programs: APEX2 and SAINT (Bruker, 2005 ), SIR97 (Altomare et al., 1995 ), SHELXL2014 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1490105

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314616010816/bt4018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010816/bt4018Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1995); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: please specify; software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Poly[[tetramethanolbis[4-oxo-3-(pyridin-4-yl)-1-(2,4,6-trichlorophenyl)-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-olato]disodium]–diethyl ether–methanol (1/1/2)] top

Crystal data top

[Na₂(C₁₆H₇Cl₃N₅O₂)₂(CH₄O)₄]·C₄H₁₀O·2CH₄O	F(000) = 1164
M_r = 1127.58	D_x = 1.451 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.1721 (7) Å	Cell parameters from 7933 reflections
b = 8.1249 (5) Å	θ = 2.5–27.3°
c = 28.8799 (18) Å	µ = 0.42 mm⁻¹
β = 100.213 (1)°	T = 173 K
V = 2580.0 (3) Å³	Plate, colourless
Z = 2	0.56 × 0.32 × 0.19 mm

Data collection top

Bruker SMART APEXII diffractometer	6097 independent reflections
Radiation source: sealed Tube	5149 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
CCD scan	θ_max = 27.8°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→14
T_min = 0.659, T_max = 0.746	k = −10→10
27638 measured reflections	l = −37→36

Refinement top

Refinement on F²	34 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.131	w = 1/[σ²(F_o²) + (0.0325P)² + 4.0979P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max = 0.001
6097 reflections	Δρ_max = 0.43 e Å⁻³
357 parameters	Δρ_min = −0.40 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.45803 (8)	1.01629 (9)	0.10052 (3)	0.0431 (2)
Cl2	0.40976 (11)	1.11088 (12)	0.27980 (3)	0.0642 (3)
Cl3	0.37696 (9)	0.50085 (9)	0.20830 (3)	0.0475 (2)
Na1	−0.11263 (9)	0.89845 (12)	0.03200 (3)	0.0254 (2)
N1	0.42042 (17)	0.6597 (2)	0.11953 (7)	0.0220 (4)
C1A	0.3251 (2)	0.6160 (3)	0.08581 (8)	0.0191 (4)
N2	0.21387 (17)	0.6884 (2)	0.08078 (7)	0.0206 (4)
C3	0.1322 (2)	0.6233 (3)	0.04576 (8)	0.0216 (5)
N4	0.16419 (18)	0.4928 (3)	0.01943 (7)	0.0238 (4)
H4	0.109 (3)	0.463 (4)	−0.0010 (11)	0.029*
C5	0.2751 (2)	0.4123 (3)	0.02483 (8)	0.0206 (5)
C5A	0.3650 (2)	0.4882 (3)	0.06008 (8)	0.0193 (4)
C6	0.4902 (2)	0.4656 (3)	0.08111 (8)	0.0203 (5)
N7	0.52267 (18)	0.5672 (2)	0.11695 (7)	0.0230 (4)
C8	0.4183 (2)	0.7679 (3)	0.15784 (8)	0.0204 (5)
C9	0.4335 (2)	0.9364 (3)	0.15336 (8)	0.0261 (5)
C10	0.4302 (3)	1.0434 (3)	0.19022 (10)	0.0347 (6)
H10	0.4397	1.1585	0.1865	0.042*
C11	0.4126 (3)	0.9778 (4)	0.23280 (10)	0.0372 (7)
C12	0.3975 (3)	0.8119 (4)	0.23925 (9)	0.0347 (6)
H12	0.3860	0.7694	0.2688	0.042*
C13	0.3998 (2)	0.7089 (3)	0.20122 (9)	0.0271 (5)
O14	0.02442 (15)	0.6747 (2)	0.03630 (7)	0.0294 (4)
O15	0.28421 (15)	0.2879 (2)	0.00110 (6)	0.0275 (4)
C16	0.5838 (2)	0.3550 (3)	0.06783 (9)	0.0221 (5)
C17	0.6945 (2)	0.3344 (4)	0.09772 (11)	0.0374 (7)
H17	0.7116	0.3935	0.1265	0.045*
C18	0.7793 (3)	0.2279 (4)	0.08534 (12)	0.0415 (7)
H18	0.8541	0.2149	0.1066	0.050*
N19	0.7630 (2)	0.1411 (3)	0.04513 (8)	0.0315 (5)
C20	0.6562 (2)	0.1618 (3)	0.01668 (9)	0.0293 (6)
H20	0.6415	0.1018	−0.0120	0.035*
C21	0.5649 (2)	0.2660 (3)	0.02643 (9)	0.0259 (5)
H21	0.4905	0.2757	0.0048	0.031*
O1L	0.10188 (18)	1.0229 (2)	0.04918 (7)	0.0316 (4)
H1L	0.140 (3)	0.933 (5)	0.0582 (12)	0.047*
C1L	0.1214 (3)	1.1374 (4)	0.08720 (10)	0.0411 (7)
H1L1	0.2081	1.1643	0.0950	0.062*
H1L2	0.0947	1.0887	0.1147	0.062*
H1L3	0.0748	1.2380	0.0780	0.062*
O2L	0.08388 (19)	0.6785 (3)	0.15581 (7)	0.0356 (5)
H2L	0.127 (3)	0.697 (5)	0.1379 (14)	0.053*
C2L	0.0432 (4)	0.5118 (4)	0.15216 (13)	0.0524 (8)
H2L1	0.1136	0.4382	0.1550	0.079*
H2L2	−0.0095	0.4948	0.1216	0.079*
H2L3	−0.0024	0.4880	0.1774	0.079*
O3L	−0.1123 (2)	0.8688 (3)	0.11335 (8)	0.0422 (5)
H3L	−0.051 (4)	0.815 (5)	0.1263 (14)	0.063*
C3L	−0.2187 (4)	0.8095 (8)	0.1267 (2)	0.113 (2)
H3L1	−0.2072	0.8028	0.1611	0.170*
H3L2	−0.2862	0.8842	0.1151	0.170*
H3L3	−0.2371	0.6998	0.1132	0.170*
C1E	0.758 (3)	0.042 (3)	0.2224 (9)	0.216 (12)	0.5
H1E1	0.7528	−0.0644	0.2377	0.324*	0.5
H1E2	0.6874	0.0568	0.1973	0.324*	0.5
H1E3	0.8327	0.0470	0.2090	0.324*	0.5
C2E	0.760 (4)	0.180 (3)	0.2586 (10)	0.205 (14)	0.5
H2E1	0.6850	0.1772	0.2724	0.246*	0.5
H2E2	0.8311	0.1674	0.2843	0.246*	0.5
O3E	0.768 (2)	0.331 (2)	0.2334 (5)	0.185 (8)	0.5
C4E	0.762 (3)	0.459 (3)	0.2683 (7)	0.198 (13)	0.5
H4E1	0.7028	0.4289	0.2888	0.238*	0.5
H4E2	0.8426	0.4763	0.2882	0.238*	0.5
C5E	0.723 (2)	0.603 (2)	0.2411 (7)	0.159 (9)	0.5
H5E1	0.7165	0.6952	0.2623	0.239*	0.5
H5E2	0.7820	0.6289	0.2209	0.239*	0.5
H5E3	0.6432	0.5819	0.2216	0.239*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0704 (5)	0.0314 (4)	0.0307 (4)	−0.0097 (3)	0.0179 (3)	0.0028 (3)
Cl2	0.1083 (8)	0.0513 (5)	0.0354 (4)	0.0011 (5)	0.0191 (5)	−0.0229 (4)
Cl3	0.0732 (6)	0.0238 (3)	0.0498 (5)	0.0001 (3)	0.0227 (4)	0.0082 (3)
Na1	0.0244 (5)	0.0230 (5)	0.0289 (5)	0.0052 (4)	0.0045 (4)	−0.0061 (4)
N1	0.0189 (9)	0.0217 (10)	0.0251 (10)	0.0020 (8)	0.0034 (8)	−0.0043 (8)
C1A	0.0202 (11)	0.0167 (10)	0.0208 (11)	−0.0012 (8)	0.0047 (9)	−0.0015 (9)
N2	0.0189 (9)	0.0202 (9)	0.0223 (10)	0.0037 (8)	0.0026 (8)	−0.0045 (8)
C3	0.0219 (11)	0.0190 (11)	0.0236 (12)	0.0037 (9)	0.0033 (9)	−0.0032 (9)
N4	0.0196 (10)	0.0241 (10)	0.0254 (10)	0.0034 (8)	−0.0025 (8)	−0.0099 (9)
C5	0.0206 (11)	0.0180 (11)	0.0235 (11)	0.0018 (9)	0.0044 (9)	−0.0010 (9)
C5A	0.0186 (10)	0.0170 (10)	0.0226 (11)	0.0011 (8)	0.0045 (8)	−0.0014 (9)
C6	0.0193 (11)	0.0180 (11)	0.0236 (11)	0.0002 (9)	0.0042 (9)	−0.0011 (9)
N7	0.0186 (9)	0.0211 (10)	0.0289 (11)	0.0027 (8)	0.0032 (8)	−0.0048 (8)
C8	0.0187 (11)	0.0216 (11)	0.0204 (11)	0.0010 (9)	0.0023 (9)	−0.0036 (9)
C9	0.0342 (14)	0.0253 (12)	0.0191 (12)	−0.0028 (10)	0.0057 (10)	0.0002 (10)
C10	0.0518 (17)	0.0200 (12)	0.0325 (14)	−0.0027 (12)	0.0081 (13)	−0.0063 (11)
C11	0.0507 (17)	0.0351 (15)	0.0253 (13)	0.0015 (13)	0.0057 (12)	−0.0113 (12)
C12	0.0465 (16)	0.0362 (15)	0.0220 (13)	0.0052 (13)	0.0078 (12)	0.0017 (11)
C13	0.0333 (13)	0.0202 (11)	0.0281 (13)	0.0025 (10)	0.0065 (10)	0.0022 (10)
O14	0.0208 (8)	0.0265 (9)	0.0372 (10)	0.0083 (7)	−0.0047 (7)	−0.0123 (8)
O15	0.0225 (8)	0.0242 (9)	0.0352 (10)	0.0034 (7)	0.0035 (7)	−0.0120 (8)
C16	0.0192 (11)	0.0164 (10)	0.0320 (13)	0.0017 (9)	0.0084 (9)	0.0003 (9)
C17	0.0273 (13)	0.0352 (15)	0.0457 (17)	0.0082 (12)	−0.0044 (12)	−0.0184 (13)
C18	0.0261 (13)	0.0410 (16)	0.0532 (19)	0.0092 (12)	−0.0049 (13)	−0.0205 (15)
N19	0.0251 (11)	0.0292 (11)	0.0404 (13)	0.0061 (9)	0.0065 (10)	−0.0066 (10)
C20	0.0319 (13)	0.0331 (14)	0.0243 (12)	0.0083 (11)	0.0089 (10)	−0.0017 (11)
C21	0.0246 (12)	0.0322 (13)	0.0214 (12)	0.0055 (10)	0.0049 (9)	0.0019 (10)
O1L	0.0381 (11)	0.0242 (9)	0.0316 (10)	0.0037 (8)	0.0043 (8)	−0.0045 (8)
C1L	0.0551 (19)	0.0356 (16)	0.0342 (15)	−0.0047 (14)	0.0124 (14)	−0.0105 (13)
O2L	0.0424 (12)	0.0380 (11)	0.0276 (10)	0.0035 (9)	0.0094 (8)	−0.0040 (9)
C2L	0.064 (2)	0.0436 (19)	0.052 (2)	−0.0085 (17)	0.0164 (17)	−0.0005 (16)
O3L	0.0369 (11)	0.0505 (13)	0.0408 (12)	0.0119 (10)	0.0113 (9)	0.0069 (10)
C3L	0.063 (3)	0.145 (5)	0.145 (5)	0.033 (3)	0.055 (3)	0.088 (5)
C1E	0.17 (2)	0.22 (3)	0.26 (3)	0.01 (2)	0.03 (2)	−0.01 (2)
C2E	0.15 (2)	0.31 (3)	0.15 (3)	0.10 (3)	0.03 (2)	0.05 (3)
O3E	0.231 (19)	0.198 (14)	0.110 (12)	0.043 (14)	−0.016 (13)	0.000 (11)
C4E	0.19 (2)	0.29 (3)	0.136 (18)	−0.09 (2)	0.087 (19)	−0.09 (2)
C5E	0.18 (2)	0.178 (17)	0.086 (15)	0.044 (16)	−0.062 (11)	−0.011 (12)

Geometric parameters (Å, º) top

Cl1—C9	1.724 (3)	C18—N19	1.343 (4)
Cl2—C11	1.740 (3)	C18—H18	0.9500
Cl3—C13	1.727 (3)	N19—C20	1.334 (3)
Na1—O3L	2.361 (2)	N19—Na1^iv	2.479 (2)
Na1—O14	2.3660 (19)	C20—C21	1.392 (3)
Na1—O1Lⁱ	2.453 (2)	C20—H20	0.9500
Na1—N19ⁱⁱ	2.479 (2)	C21—H21	0.9500
Na1—O15ⁱⁱⁱ	2.496 (2)	O1L—C1L	1.426 (3)
Na1—O1L	2.567 (2)	O1L—Na1ⁱ	2.453 (2)
Na1—Na1ⁱ	3.758 (2)	O1L—H1L	0.86 (4)
N1—C1A	1.357 (3)	C1L—H1L1	0.9800
N1—N7	1.380 (3)	C1L—H1L2	0.9800
N1—C8	1.417 (3)	C1L—H1L3	0.9800
C1A—N2	1.359 (3)	O2L—C2L	1.426 (4)
C1A—C5A	1.396 (3)	O2L—H2L	0.78 (4)
N2—C3	1.345 (3)	C2L—H2L1	0.9800
C3—O14	1.258 (3)	C2L—H2L2	0.9800
C3—N4	1.387 (3)	C2L—H2L3	0.9800
N4—C5	1.386 (3)	O3L—C3L	1.398 (5)
N4—H4	0.81 (3)	O3L—H3L	0.84 (4)
C5—O15	1.236 (3)	C3L—H3L1	0.9800
C5—C5A	1.436 (3)	C3L—H3L2	0.9800
C5A—C6	1.434 (3)	C3L—H3L3	0.9800
C6—N7	1.323 (3)	C1E—C2E	1.525 (18)
C6—C16	1.480 (3)	C1E—H1E1	0.9800
C8—C9	1.388 (3)	C1E—H1E2	0.9800
C8—C13	1.391 (3)	C1E—H1E3	0.9800
C9—C10	1.380 (4)	C2E—O3E	1.437 (18)
C10—C11	1.386 (4)	C2E—H2E1	0.9900
C10—H10	0.9500	C2E—H2E2	0.9900
C11—C12	1.375 (4)	O3E—C4E	1.458 (15)
C12—C13	1.384 (4)	C4E—C5E	1.433 (17)
C12—H12	0.9500	C4E—H4E1	0.9900
O15—Na1ⁱⁱⁱ	2.496 (2)	C4E—H4E2	0.9900
C16—C21	1.381 (3)	C5E—H5E1	0.9800
C16—C17	1.387 (4)	C5E—H5E2	0.9800
C17—C18	1.377 (4)	C5E—H5E3	0.9800
C17—H17	0.9500

O3L—Na1—O14	89.01 (8)	C18—C17—H17	120.2
O3L—Na1—O1Lⁱ	170.31 (9)	C16—C17—H17	120.2
O14—Na1—O1Lⁱ	96.29 (7)	N19—C18—C17	124.1 (3)
O3L—Na1—N19ⁱⁱ	80.25 (8)	N19—C18—H18	118.0
O14—Na1—N19ⁱⁱ	167.94 (8)	C17—C18—H18	118.0
O1Lⁱ—Na1—N19ⁱⁱ	93.60 (8)	C20—N19—C18	115.8 (2)
O3L—Na1—O15ⁱⁱⁱ	100.64 (8)	C20—N19—Na1^iv	118.07 (17)
O14—Na1—O15ⁱⁱⁱ	89.99 (7)	C18—N19—Na1^iv	123.76 (18)
O1Lⁱ—Na1—O15ⁱⁱⁱ	87.50 (7)	N19—C20—C21	124.0 (2)
N19ⁱⁱ—Na1—O15ⁱⁱⁱ	97.33 (7)	N19—C20—H20	118.0
O3L—Na1—O1L	90.65 (8)	C21—C20—H20	118.0
O14—Na1—O1L	73.70 (7)	C16—C21—C20	119.2 (2)
O1Lⁱ—Na1—O1L	83.11 (7)	C16—C21—H21	120.4
N19ⁱⁱ—Na1—O1L	100.76 (8)	C20—C21—H21	120.4
O15ⁱⁱⁱ—Na1—O1L	160.08 (7)	C1L—O1L—Na1ⁱ	122.62 (17)
O3L—Na1—Na1ⁱ	130.64 (7)	C1L—O1L—Na1	114.57 (17)
O14—Na1—Na1ⁱ	83.09 (6)	Na1ⁱ—O1L—Na1	96.90 (7)
O1Lⁱ—Na1—Na1ⁱ	42.70 (5)	C1L—O1L—H1L	109 (2)
N19ⁱⁱ—Na1—Na1ⁱ	99.70 (7)	Na1ⁱ—O1L—H1L	114 (2)
O15ⁱⁱⁱ—Na1—Na1ⁱ	127.87 (6)	Na1—O1L—H1L	97 (2)
O1L—Na1—Na1ⁱ	40.40 (5)	O1L—C1L—H1L1	109.5
C1A—N1—N7	111.75 (19)	O1L—C1L—H1L2	109.5
C1A—N1—C8	127.10 (19)	H1L1—C1L—H1L2	109.5
N7—N1—C8	120.57 (19)	O1L—C1L—H1L3	109.5
N1—C1A—N2	123.3 (2)	H1L1—C1L—H1L3	109.5
N1—C1A—C5A	107.0 (2)	H1L2—C1L—H1L3	109.5
N2—C1A—C5A	129.6 (2)	C2L—O2L—H2L	111 (3)
C3—N2—C1A	113.27 (19)	O2L—C2L—H2L1	109.5
O14—C3—N2	121.9 (2)	O2L—C2L—H2L2	109.5
O14—C3—N4	117.6 (2)	H2L1—C2L—H2L2	109.5
N2—C3—N4	120.5 (2)	O2L—C2L—H2L3	109.5
C5—N4—C3	127.6 (2)	H2L1—C2L—H2L3	109.5
C5—N4—H4	120 (2)	H2L2—C2L—H2L3	109.5
C3—N4—H4	113 (2)	C3L—O3L—Na1	117.3 (3)
O15—C5—N4	118.9 (2)	C3L—O3L—H3L	111 (3)
O15—C5—C5A	128.9 (2)	Na1—O3L—H3L	111 (3)
N4—C5—C5A	112.1 (2)	O3L—C3L—H3L1	109.5
C1A—C5A—C6	104.4 (2)	O3L—C3L—H3L2	109.5
C1A—C5A—C5	116.6 (2)	H3L1—C3L—H3L2	109.5
C6—C5A—C5	138.8 (2)	O3L—C3L—H3L3	109.5
N7—C6—C5A	111.3 (2)	H3L1—C3L—H3L3	109.5
N7—C6—C16	118.3 (2)	H3L2—C3L—H3L3	109.5
C5A—C6—C16	130.4 (2)	C2E—C1E—H1E1	109.5
C6—N7—N1	105.50 (18)	C2E—C1E—H1E2	109.5
C9—C8—C13	117.6 (2)	H1E1—C1E—H1E2	109.5
C9—C8—N1	121.3 (2)	C2E—C1E—H1E3	109.5
C13—C8—N1	121.0 (2)	H1E1—C1E—H1E3	109.5
C10—C9—C8	121.9 (2)	H1E2—C1E—H1E3	109.5
C10—C9—Cl1	118.4 (2)	O3E—C2E—C1E	106 (2)
C8—C9—Cl1	119.67 (19)	O3E—C2E—H2E1	110.6
C9—C10—C11	118.0 (2)	C1E—C2E—H2E1	110.6
C9—C10—H10	121.0	O3E—C2E—H2E2	110.6
C11—C10—H10	121.0	C1E—C2E—H2E2	110.6
C12—C11—C10	122.5 (3)	H2E1—C2E—H2E2	108.7
C12—C11—Cl2	118.9 (2)	C2E—O3E—C4E	104.2 (16)
C10—C11—Cl2	118.6 (2)	C5E—C4E—O3E	104.5 (15)
C11—C12—C13	117.7 (3)	C5E—C4E—H4E1	110.9
C11—C12—H12	121.1	O3E—C4E—H4E1	110.9
C13—C12—H12	121.1	C5E—C4E—H4E2	110.9
C12—C13—C8	122.2 (2)	O3E—C4E—H4E2	110.9
C12—C13—Cl3	118.3 (2)	H4E1—C4E—H4E2	108.9
C8—C13—Cl3	119.51 (19)	C4E—C5E—H5E1	109.5
C3—O14—Na1	148.44 (16)	C4E—C5E—H5E2	109.5
C5—O15—Na1ⁱⁱⁱ	125.15 (15)	H5E1—C5E—H5E2	109.5
C21—C16—C17	117.3 (2)	C4E—C5E—H5E3	109.5
C21—C16—C6	122.4 (2)	H5E1—C5E—H5E3	109.5
C17—C16—C6	120.3 (2)	H5E2—C5E—H5E3	109.5
C18—C17—C16	119.5 (3)

N7—N1—C1A—N2	180.0 (2)	C13—C8—C9—Cl1	179.50 (19)
C8—N1—C1A—N2	8.7 (4)	N1—C8—C9—Cl1	−1.1 (3)
N7—N1—C1A—C5A	0.6 (3)	C8—C9—C10—C11	0.8 (4)
C8—N1—C1A—C5A	−170.6 (2)	Cl1—C9—C10—C11	−178.9 (2)
N1—C1A—N2—C3	−178.6 (2)	C9—C10—C11—C12	−0.5 (5)
C5A—C1A—N2—C3	0.6 (4)	C9—C10—C11—Cl2	179.3 (2)
C1A—N2—C3—O14	179.6 (2)	C10—C11—C12—C13	−0.4 (5)
C1A—N2—C3—N4	1.2 (3)	Cl2—C11—C12—C13	179.8 (2)
O14—C3—N4—C5	−177.1 (2)	C11—C12—C13—C8	1.0 (4)
N2—C3—N4—C5	1.3 (4)	C11—C12—C13—Cl3	−178.3 (2)
C3—N4—C5—O15	173.1 (2)	C9—C8—C13—C12	−0.7 (4)
C3—N4—C5—C5A	−5.1 (4)	N1—C8—C13—C12	179.9 (2)
N1—C1A—C5A—C6	−1.2 (2)	C9—C8—C13—Cl3	178.6 (2)
N2—C1A—C5A—C6	179.5 (2)	N1—C8—C13—Cl3	−0.9 (3)
N1—C1A—C5A—C5	174.7 (2)	N2—C3—O14—Na1	34.4 (5)
N2—C1A—C5A—C5	−4.6 (4)	N4—C3—O14—Na1	−147.2 (2)
O15—C5—C5A—C1A	−171.8 (2)	N4—C5—O15—Na1ⁱⁱⁱ	−25.5 (3)
N4—C5—C5A—C1A	6.1 (3)	C5A—C5—O15—Na1ⁱⁱⁱ	152.3 (2)
O15—C5—C5A—C6	2.1 (5)	N7—C6—C16—C21	−168.5 (2)
N4—C5—C5A—C6	−180.0 (3)	C5A—C6—C16—C21	9.0 (4)
C1A—C5A—C6—N7	1.4 (3)	N7—C6—C16—C17	12.9 (4)
C5—C5A—C6—N7	−173.0 (3)	C5A—C6—C16—C17	−169.6 (3)
C1A—C5A—C6—C16	−176.2 (2)	C21—C16—C17—C18	−0.3 (4)
C5—C5A—C6—C16	9.4 (5)	C6—C16—C17—C18	178.4 (3)
C5A—C6—N7—N1	−1.0 (3)	C16—C17—C18—N19	0.7 (5)
C16—C6—N7—N1	176.9 (2)	C17—C18—N19—C20	−0.7 (5)
C1A—N1—N7—C6	0.2 (3)	C17—C18—N19—Na1^iv	−163.0 (3)
C8—N1—N7—C6	172.1 (2)	C18—N19—C20—C21	0.3 (4)
C1A—N1—C8—C9	−87.6 (3)	Na1^iv—N19—C20—C21	163.6 (2)
N7—N1—C8—C9	101.9 (3)	C17—C16—C21—C20	−0.1 (4)
C1A—N1—C8—C13	91.8 (3)	C6—C16—C21—C20	−178.8 (2)
N7—N1—C8—C13	−78.7 (3)	N19—C20—C21—C16	0.1 (4)
C13—C8—C9—C10	−0.2 (4)	C1E—C2E—O3E—C4E	177 (2)
N1—C8—C9—C10	179.2 (2)	C2E—O3E—C4E—C5E	−159 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O14ⁱⁱⁱ	0.81 (3)	1.99 (3)	2.771 (3)	160 (3)
C21—H21···O15	0.95	2.29	3.096 (3)	142
O1L—H1L···N2	0.86 (4)	2.21 (4)	3.062 (3)	172 (3)
O2L—H2L···N2	0.78 (4)	2.06 (4)	2.815 (3)	163 (4)
O3L—H3L···O2L	0.84 (4)	1.94 (4)	2.783 (3)	176 (4)

Symmetry code: (iii) −x, −y+1, −z.

Acknowledgements

BAT thanks the Alexander von Humboldt-Foundation (AvH) for funding.

References

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