Synthesis and structure of trans-bis­(4-amino-3-nitro­benzoato-κO)bis­(4-amino-3-nitro­benzoic acid-κO)di­aqua­manganese(II) dihydrate

Narmanova, F.S.; Turaev, K.K.; Ibragimov, A.B.; Ashurov, J.M.

doi:10.1107/S2414314624000403

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 1| January 2024| x240040

https://doi.org/10.1107/S2414314624000403

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Synthesis and structure of trans-bis(4-amino-3-nitrobenzoato-κO)bis(4-amino-3-nitrobenzoic acid-κO)diaquamanganese(II) dihydrate

Feruza S. Narmanova,^a Khayit Kh. Turaev,^a Aziz B. Ibragimov ^b and Jamshid M. Ashurov ^c ^*

^aTermez State University, Barkamol Avlod Street 43, Termez city, Uzbekistan, ^bInstitute of General and Inorganic Chemistry of Uzbekistan Academy of Sciences, 100170, Mirzo Ulug'bek str., 77a, Uzbekistan, and ^cInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, 100125, M. Ulugbek Str 83, Tashkent, Uzbekistan
^*Correspondence e-mail: ashurovjamshid1@gmail.com

Edited by R. J. Butcher, Howard University, USA (Received 29 August 2023; accepted 10 January 2024; online 19 January 2024)

The manganese title complex, [Mn(C₇H₅N₂O₄)₂(C₇H₆N₂O₄)₂(H₂O)₂]·2H₂O, is one of the first 4-amino 3-nitrobenzoic acid (4 A3NBA) monoligand metal complexes to be synthesized. It crystallizes in the centrosymmetric monoclinic space group P2₁/n with the complex molecules located on inversion centers. Four 4 A3NBA ligand molecules are monodentately coordinated by the Mn²⁺ ion through the carboxylic oxygen atoms while the other two positions of the inner coordination sphere are occupied by water molecules, giving rise to a distorted octahedron, and two water molecules are in the outer coordination sphere. There are two intramolecular hydrogen bonds in the complex molecule. The first is of the common N—H⋯O=N type, while the second is a rarely occurring very strong hydrogen bond in which a common proton is shared by two uncoordinated oxygen atoms of neighboring carboxylate groups. In the crystal, an intricate system of intermolecular hydrogen bonds links the complex molecules into a three-dimensional-network.

Keywords: 4-amino 3-nitrobenzoic acid; Mn^II; crystal structure; hydrogen bond.

CCDC reference: 2324651

Structure description

The molecular structure of the title complex is shown in Fig. 1. It crystallizes in the centrosymmetric monoclinic space group P2₁/n with the complex molecules located on inversion centers. Four 4-amino 3-nitrobenzoic acid (4 A3NBA) ligands are monodentately coordinated by the Mn²⁺ ion through the oxygen atoms of carboxylic groups while two other positions of the inner coordination sphere are occupied by water molecules. The outer coordination sphere contains two water molecules, i.e. the complex is crystal hydrate. The length of the Mn—O1 bond is 2.1575 (12) Å while Mn—O5 is 2.1600 (13) Å and Mn—O1W = 2.1630 (14) Å and bond angles are in the range 84.29 (5) to 95.71 (5)°. The geometry of the manganese atom is therefore a slightly distorted octahedron. The carboxylate groups C7,O2,O1 and C14,O6,O5 are practically coplanar with the aromatic rings to which they are attached, forming dihedral angles of 4.1 (1) and 11.9 (1)°, respectively. The analogous angles for nitro groups N1,O3,O4 and N3,O7,O8 are 2.82 (9) and 8.6 (1)°. Thus in the ligand with the C8–C13 aromatic ring, the functional groups are more inclined relatively to the benzene ring.

Figure 1
The molecular structure of the title compound, showing the atom-labeling scheme and displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius and hydrogen bonds are shown as dashed lines. Symmetry code: (i) 1 − x, 1 − y, −z.

There are two intramolecular hydrogen bonds in the complex molecule (Table 1). The first bond is of the usual N—H⋯O=N type, closing a six-membered ring with an S₁¹(6) graph-set motif (Etter 1990 ; Ibragimov et al., 2017 ; Ruzmetov et al., 2022 ). The second is a rarely occurring very strong hydrogen bond closing a nine-membered ring where a common proton, H20, is shared by two uncoordinated oxygen atoms O2 and O6 of neighboring carboxylate groups. The atom H20, situated between the two oxygen atoms, is located closer to atom O2 at a distance of 1.270 (2) Å [and 1.198 (2) Å from O6]. Despite this, it is impossible to indicate which of the four carboxylic groups present are deprotonated. The total negative charge of the carboxylic groups is 2 and it compensates the +2 charge of the Mn²⁺ ion.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O3ⁱ	0.83 (2)	2.06 (2)	2.8850 (19)	176 (2)
O1W—H1WA⋯O4ⁱ	0.83 (2)	2.55 (2)	3.1418 (19)	130 (2)
O1W—H1WA⋯N1ⁱ	0.83 (2)	2.63 (2)	3.4029 (19)	157 (2)
O1W—H1WB⋯O2W	0.81 (2)	1.98 (2)	2.784 (2)	170 (2)
O2—H2O⋯O5	1.27 (4)	2.57 (4)	3.448 (2)	124 (2)
O6—H2O⋯O2	1.20 (4)	1.27 (4)	2.4541 (18)	168 (4)
N2—H2A⋯O6ⁱⁱ	0.86	2.19	3.0160 (19)	162
N2—H2B⋯O4	0.85	1.99	2.629 (2)	131
N4—H4A⋯O8	0.87	2.03	2.648 (2)	128
N4—H4B⋯O2Wⁱ	0.87	2.16	3.021 (2)	173
C5—H5⋯O2ⁱⁱ	0.93	2.57	3.489 (2)	170
C9—H9⋯N2ⁱⁱⁱ	0.93	2.66	3.544 (2)	160
C12—H12⋯O8^iv	0.93	2.42	3.178 (2)	138
O2W—H2WA⋯O7^v	0.86	2.14	2.995 (2)	173
O2W—H2WB⋯O1W^vi	0.85	2.39	3.127 (2)	145
O2W—H2WB⋯O5^vii	0.85	2.65	3.341 (2)	139
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) ; (vi) ; (vii) .

There are 17 proton-acceptor oxygen atoms, 4 proton-donor nitrogen atoms and 2 water molecules in the title complex. These atoms are involved in a complex system of intermolecular hydrogen bonds (Table 1). Moreover, three weak C—H⋯O hydrogen bonds are also observed in the structure (Table 1, Fig. 2). Together these hydrogen bonds link the complex molecules into a three-dimensional network (Fig. 2.).

Figure 2
The crystal packing viewed along [100] showing the O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds (dashed red lines) in the crystal structure.

Synthesis and crystallization

All reagents and solvents were purchased from Sigma-Aldrich (Darmstadt, Germany) and they were used as received. MnCl₂·H₂O (0.198 g, 1.0 mmol) was dissolved in a small amount of water. 4-Amino 3-nitrobenzoic acid (0.364 g, 2 mmol) was dissolved in a mixed solvent of 3 ml of absolute alcohol and 3 ml of distilled water. After dropwise addition of the 4 A3NBA solution to the manganese salt solution, the resultant solution was stirred for 2 h with a magnetic stirrer at 55°C. The solution was allowed to stand at 30°C in a beaker with small holes in the cover for evaporation. After about eight days, block-shaped single crystals ofthe title compound appeared. Analysis calculated: C₂₈H₃₀MnN₈O₂₀: C, 39.40%; H, 3.54; N, 13.13%. Found: C, 39.32%; H, 3.47%; N, 13.08%.

Refinement

Crystal data, data collection and structure refinement details for the structure of the synthesized compound are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Mn(C₇H₅MnN₂O₄)₂(C₇H₆MnN₂O₄)₂(H₂O)₂]·2H₂O
M_r	853.54
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.0419 (1), 19.2513 (3), 12.7175 (2)
β (°)	100.513 (2)
V (Å³)	1695.12 (5)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	4.08
Crystal size (mm)	0.28 × 0.22 × 0.14

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.523, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3291, 3291, 2966
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.097, 1.06
No. of reflections	3291
No. of parameters	269
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.44
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2324651

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624000403/bv4050sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624000403/bv4050Isup2.hkl

checkCIF report

Computing details top

trans-Bis(4-amino-3-nitrobenzoato-κO)bis(4-amino-3-nitrobenzoic acid-κO)diaquamanganese(II) dihydrate top

Crystal data top

[Mn(C₇H₅MnN₂O₄)₂(C₇H₆MnN₂O₄)₂(H₂O)₂]·2H₂O	F(000) = 878
M_r = 853.54	D_x = 1.672 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 7.0419 (1) Å	Cell parameters from 11377 reflections
b = 19.2513 (3) Å	θ = 2.3–71.4°
c = 12.7175 (2) Å	µ = 4.08 mm⁻¹
β = 100.513 (2)°	T = 293 K
V = 1695.12 (5) Å³	Block, light pink
Z = 2	0.28 × 0.22 × 0.14 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	3291 independent reflections
Radiation source: micro-focus sealed X-ray tube	2966 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.037
ω scans	θ_max = 71.5°, θ_min = 4.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	h = −8→8
T_min = 0.523, T_max = 1.000	k = −23→22
3291 measured reflections	l = −15→15

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)] = 0.035	Hydrogen site location: mixed
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0608P)² + 0.2227P] where P = (F_o² + 2F_c²)/3
3291 reflections	(Δ/σ)_max < 0.001
269 parameters	Δρ_max = 0.27 e Å⁻³
3 restraints	Δρ_min = −0.44 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.

Refinement. The hydrogen atoms of water molecules and amino groups were located in difference-Fourier maps and refined freely. The H atoms of the benzene ring were calculated geometrically with C—H = 0.93 A° and U_iso(H) = 1.2U_eq(C).

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

	x	y	z	U_iso*/U_eq
Mn1	0.500000	0.500000	0.000000	0.02947 (13)
O1	0.4809 (2)	0.39058 (6)	0.03322 (11)	0.0489 (4)
O1W	0.8075 (2)	0.50832 (7)	0.05836 (12)	0.0464 (3)
H1WA	0.848 (4)	0.5418 (9)	0.0964 (19)	0.070*
H1WB	0.879 (4)	0.4760 (9)	0.078 (2)	0.070*
O2	0.6022 (2)	0.36153 (7)	0.20147 (10)	0.0515 (4)
H2O	0.619 (6)	0.422 (2)	0.242 (3)	0.155 (15)*
O3	0.5562 (2)	0.13009 (7)	0.31842 (10)	0.0560 (4)
O4	0.4652 (2)	0.04466 (7)	0.21207 (11)	0.0545 (4)
O5	0.4355 (2)	0.52907 (8)	0.15374 (10)	0.0457 (3)
O6	0.6122 (2)	0.47449 (7)	0.29174 (10)	0.0483 (4)
O7	0.7667 (2)	0.59190 (8)	0.62838 (11)	0.0590 (4)
O8	0.6914 (2)	0.69874 (8)	0.65088 (11)	0.0612 (4)
N1	0.4964 (2)	0.10712 (7)	0.22733 (11)	0.0363 (3)
N2	0.3472 (2)	0.06488 (7)	0.00606 (12)	0.0431 (4)
H2A	0.302809	0.057204	−0.060340	0.052*
H2B	0.365807	0.034904	0.056060	0.052*
N3	0.6948 (2)	0.64740 (8)	0.59270 (12)	0.0410 (4)
N4	0.5654 (3)	0.77954 (8)	0.48424 (14)	0.0481 (4)
H4A	0.587279	0.778868	0.553450	0.058*
H4B	0.516269	0.814368	0.445160	0.058*
C1	0.4755 (2)	0.27328 (8)	0.08203 (13)	0.0297 (3)
C2	0.5071 (2)	0.22409 (8)	0.16193 (13)	0.0294 (3)
H2	0.557893	0.237429	0.231674	0.035*
C3	0.4636 (2)	0.15439 (8)	0.13907 (12)	0.0291 (3)
C4	0.3884 (2)	0.13131 (8)	0.03426 (12)	0.0298 (3)
C5	0.3551 (3)	0.18352 (9)	−0.04571 (13)	0.0351 (4)
H5	0.303735	0.170966	−0.115751	0.042*
C6	0.3963 (2)	0.25158 (9)	−0.02257 (13)	0.0333 (4)
H6	0.371609	0.284412	−0.076992	0.040*
C7	0.5212 (2)	0.34754 (8)	0.10562 (13)	0.0335 (4)
C8	0.5352 (2)	0.59261 (9)	0.31259 (13)	0.0330 (4)
C9	0.6043 (2)	0.59219 (9)	0.42108 (13)	0.0338 (4)
H9	0.643858	0.550494	0.455105	0.041*
C10	0.6160 (2)	0.65326 (9)	0.48065 (13)	0.0333 (4)
C11	0.5581 (2)	0.71818 (9)	0.43305 (15)	0.0358 (4)
C12	0.4899 (3)	0.71660 (9)	0.32115 (15)	0.0409 (4)
H12	0.453293	0.758055	0.285614	0.049*
C13	0.4760 (3)	0.65655 (10)	0.26390 (14)	0.0384 (4)
H13	0.426366	0.657803	0.190964	0.046*
C14	0.5253 (3)	0.52789 (9)	0.24730 (13)	0.0352 (4)
O2W	1.0872 (2)	0.40951 (8)	0.13520 (11)	0.0542 (4)
H2WA	1.119577	0.406931	0.203299	0.081*
H2WB	1.161577	0.433931	0.103999	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0436 (2)	0.02138 (19)	0.01972 (19)	−0.00214 (14)	−0.00417 (15)	0.00137 (12)
O1	0.0807 (10)	0.0235 (6)	0.0358 (7)	−0.0052 (6)	−0.0070 (6)	0.0050 (5)
O1W	0.0456 (7)	0.0419 (8)	0.0444 (8)	0.0030 (6)	−0.0114 (6)	−0.0121 (6)
O2	0.0808 (10)	0.0297 (7)	0.0340 (7)	−0.0014 (6)	−0.0157 (6)	−0.0019 (5)
O3	0.0926 (11)	0.0393 (7)	0.0283 (7)	−0.0025 (7)	−0.0099 (7)	0.0063 (5)
O4	0.0851 (10)	0.0251 (6)	0.0454 (8)	−0.0059 (6)	−0.0086 (7)	0.0091 (5)
O5	0.0584 (8)	0.0528 (8)	0.0221 (6)	0.0066 (6)	−0.0030 (5)	−0.0078 (5)
O6	0.0748 (9)	0.0322 (7)	0.0303 (7)	0.0027 (6)	−0.0106 (6)	−0.0053 (5)
O7	0.0864 (11)	0.0519 (9)	0.0318 (7)	0.0122 (8)	−0.0079 (7)	0.0002 (6)
O8	0.0824 (11)	0.0605 (9)	0.0366 (8)	0.0046 (8)	−0.0006 (7)	−0.0225 (7)
N1	0.0459 (8)	0.0285 (7)	0.0305 (7)	0.0019 (6)	−0.0038 (6)	0.0066 (5)
N2	0.0643 (10)	0.0265 (7)	0.0336 (8)	−0.0027 (7)	−0.0044 (7)	−0.0028 (6)
N3	0.0479 (9)	0.0443 (9)	0.0287 (7)	−0.0013 (7)	0.0012 (6)	−0.0084 (6)
N4	0.0589 (10)	0.0334 (8)	0.0510 (10)	0.0015 (7)	0.0072 (8)	−0.0093 (7)
C1	0.0353 (8)	0.0235 (8)	0.0280 (8)	0.0022 (6)	0.0001 (6)	0.0019 (6)
C2	0.0360 (8)	0.0249 (8)	0.0247 (7)	0.0012 (6)	−0.0010 (6)	−0.0008 (6)
C3	0.0347 (8)	0.0242 (8)	0.0267 (8)	0.0035 (6)	0.0011 (6)	0.0042 (6)
C4	0.0333 (8)	0.0243 (7)	0.0299 (8)	0.0013 (6)	0.0003 (6)	−0.0020 (6)
C5	0.0468 (9)	0.0304 (9)	0.0244 (8)	−0.0012 (7)	−0.0036 (7)	−0.0015 (6)
C6	0.0422 (9)	0.0282 (8)	0.0268 (8)	0.0010 (7)	−0.0013 (7)	0.0045 (6)
C7	0.0421 (9)	0.0248 (8)	0.0307 (8)	0.0003 (7)	−0.0012 (7)	0.0030 (6)
C8	0.0391 (9)	0.0335 (9)	0.0252 (8)	−0.0017 (7)	0.0030 (6)	−0.0033 (6)
C9	0.0394 (9)	0.0312 (8)	0.0286 (8)	0.0011 (7)	0.0004 (7)	−0.0015 (6)
C10	0.0362 (8)	0.0354 (9)	0.0264 (8)	−0.0002 (7)	0.0012 (7)	−0.0027 (6)
C11	0.0331 (8)	0.0337 (9)	0.0402 (9)	−0.0015 (7)	0.0058 (7)	−0.0043 (7)
C12	0.0484 (10)	0.0324 (9)	0.0401 (10)	0.0039 (8)	0.0032 (8)	0.0050 (7)
C13	0.0437 (9)	0.0418 (10)	0.0271 (8)	0.0016 (8)	−0.0005 (7)	0.0029 (7)
C14	0.0432 (9)	0.0372 (9)	0.0237 (8)	−0.0032 (7)	0.0021 (7)	−0.0037 (7)
O2W	0.0659 (9)	0.0496 (8)	0.0448 (8)	0.0015 (7)	0.0040 (7)	0.0036 (6)

Geometric parameters (Å, º) top

Mn1—O1ⁱ	2.1575 (12)	N4—H4A	0.8655
Mn1—O1	2.1575 (12)	N4—H4B	0.8680
Mn1—O5ⁱ	2.1600 (13)	C1—C2	1.377 (2)
Mn1—O5	2.1600 (13)	C1—C6	1.409 (2)
Mn1—O1W	2.1630 (14)	C1—C7	1.484 (2)
Mn1—O1Wⁱ	2.1630 (14)	C2—C3	1.395 (2)
O1—C7	1.233 (2)	C2—H2	0.9300
O1W—H1WA	0.827 (16)	C3—C4	1.413 (2)
O1W—H1WB	0.813 (16)	C4—C5	1.419 (2)
O2—C7	1.277 (2)	C5—C6	1.363 (2)
O2—H2O	1.27 (4)	C5—H5	0.9300
O3—N1	1.2398 (19)	C6—H6	0.9300
O4—N1	1.2314 (19)	C8—C9	1.377 (2)
O5—C14	1.242 (2)	C8—C13	1.406 (2)
O6—C14	1.275 (2)	C8—C14	1.492 (2)
O6—H2O	1.20 (4)	C9—C10	1.393 (2)
O7—N3	1.233 (2)	C9—H9	0.9300
O8—N3	1.237 (2)	C10—C11	1.416 (2)
N1—C3	1.4307 (19)	C11—C12	1.417 (3)
N2—C4	1.345 (2)	C12—C13	1.360 (3)
N2—H2A	0.8581	C12—H12	0.9300
N2—H2B	0.8510	C13—H13	0.9300
N3—C10	1.436 (2)	O2W—H2WA	0.8558
N4—C11	1.345 (2)	O2W—H2WB	0.8537

O1ⁱ—Mn1—O1	180.0	C3—C2—H2	119.7
O1ⁱ—Mn1—O5ⁱ	92.57 (6)	C2—C3—C4	121.96 (14)
O1—Mn1—O5ⁱ	87.43 (6)	C2—C3—N1	116.77 (14)
O1ⁱ—Mn1—O5	87.43 (6)	C4—C3—N1	121.27 (14)
O1—Mn1—O5	92.57 (6)	N2—C4—C3	125.16 (15)
O5ⁱ—Mn1—O5	180.0	N2—C4—C5	118.87 (14)
O1ⁱ—Mn1—O1W	84.29 (5)	C3—C4—C5	115.97 (14)
O1—Mn1—O1W	95.71 (5)	C6—C5—C4	121.70 (15)
O5ⁱ—Mn1—O1W	88.12 (5)	C6—C5—H5	119.1
O5—Mn1—O1W	91.88 (5)	C4—C5—H5	119.1
O1ⁱ—Mn1—O1Wⁱ	95.71 (5)	C5—C6—C1	121.42 (15)
O1—Mn1—O1Wⁱ	84.29 (5)	C5—C6—H6	119.3
O5ⁱ—Mn1—O1Wⁱ	91.88 (5)	C1—C6—H6	119.3
O5—Mn1—O1Wⁱ	88.12 (5)	O1—C7—O2	124.97 (16)
O1W—Mn1—O1Wⁱ	180.0	O1—C7—C1	118.99 (15)
C7—O1—Mn1	142.04 (12)	O2—C7—C1	116.03 (14)
Mn1—O1W—H1WA	118.6 (17)	C9—C8—C13	117.94 (15)
Mn1—O1W—H1WB	125.3 (18)	C9—C8—C14	121.66 (15)
H1WA—O1W—H1WB	106 (2)	C13—C8—C14	120.40 (15)
C7—O2—H2O	124.8 (18)	C8—C9—C10	121.00 (16)
C14—O5—Mn1	135.11 (13)	C8—C9—H9	119.5
C14—O6—H2O	120.4 (19)	C10—C9—H9	119.5
O4—N1—O3	121.07 (14)	C9—C10—C11	121.91 (15)
O4—N1—C3	119.93 (14)	C9—C10—N3	116.57 (15)
O3—N1—C3	119.00 (14)	C11—C10—N3	121.50 (15)
C4—N2—H2A	116.6	N4—C11—C10	125.85 (17)
C4—N2—H2B	116.7	N4—C11—C12	118.74 (17)
H2A—N2—H2B	126.7	C10—C11—C12	115.41 (15)
O7—N3—O8	121.58 (15)	C13—C12—C11	122.26 (16)
O7—N3—C10	119.44 (14)	C13—C12—H12	118.9
O8—N3—C10	118.98 (16)	C11—C12—H12	118.9
C11—N4—H4A	117.6	C12—C13—C8	121.45 (16)
C11—N4—H4B	115.2	C12—C13—H13	119.3
H4A—N4—H4B	124.9	C8—C13—H13	119.3
C2—C1—C6	118.40 (14)	O5—C14—O6	123.99 (16)
C2—C1—C7	120.90 (14)	O5—C14—C8	118.82 (16)
C6—C1—C7	120.70 (14)	O6—C14—C8	117.19 (15)
C1—C2—C3	120.53 (15)	H2WA—O2W—H2WB	115.4
C1—C2—H2	119.7

C6—C1—C2—C3	0.7 (2)	C13—C8—C9—C10	−0.2 (3)
C7—C1—C2—C3	179.94 (15)	C14—C8—C9—C10	178.81 (16)
C1—C2—C3—C4	0.8 (3)	C8—C9—C10—C11	−0.1 (3)
C1—C2—C3—N1	−178.46 (15)	C8—C9—C10—N3	−178.47 (16)
O4—N1—C3—C2	−178.27 (16)	O7—N3—C10—C9	7.9 (3)
O3—N1—C3—C2	1.7 (2)	O8—N3—C10—C9	−173.23 (17)
O4—N1—C3—C4	2.5 (2)	O7—N3—C10—C11	−170.52 (17)
O3—N1—C3—C4	−177.55 (16)	O8—N3—C10—C11	8.4 (3)
C2—C3—C4—N2	178.46 (16)	C9—C10—C11—N4	−179.64 (18)
N1—C3—C4—N2	−2.3 (3)	N3—C10—C11—N4	−1.3 (3)
C2—C3—C4—C5	−1.7 (2)	C9—C10—C11—C12	−0.6 (3)
N1—C3—C4—C5	177.57 (15)	N3—C10—C11—C12	177.70 (16)
N2—C4—C5—C6	−179.08 (17)	N4—C11—C12—C13	−179.19 (18)
C3—C4—C5—C6	1.0 (3)	C10—C11—C12—C13	1.7 (3)
C4—C5—C6—C1	0.5 (3)	C11—C12—C13—C8	−2.1 (3)
C2—C1—C6—C5	−1.4 (3)	C9—C8—C13—C12	1.3 (3)
C7—C1—C6—C5	179.42 (17)	C14—C8—C13—C12	−177.73 (17)
Mn1—O1—C7—O2	0.8 (3)	Mn1—O5—C14—O6	−51.2 (3)
Mn1—O1—C7—C1	−178.67 (15)	Mn1—O5—C14—C8	128.20 (16)
C2—C1—C7—O1	−175.97 (17)	C9—C8—C14—O5	169.25 (17)
C6—C1—C7—O1	3.2 (3)	C13—C8—C14—O5	−11.7 (3)
C2—C1—C7—O2	4.5 (3)	C9—C8—C14—O6	−11.3 (3)
C6—C1—C7—O2	−176.31 (16)	C13—C8—C14—O6	167.69 (17)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3ⁱⁱ	0.83 (2)	2.06 (2)	2.8850 (19)	176 (2)
O1W—H1WA···O4ⁱⁱ	0.83 (2)	2.55 (2)	3.1418 (19)	130 (2)
O1W—H1WA···N1ⁱⁱ	0.83 (2)	2.63 (2)	3.4029 (19)	157 (2)
O1W—H1WB···O2W	0.81 (2)	1.98 (2)	2.784 (2)	170 (2)
O2—H2O···O5	1.27 (4)	2.57 (4)	3.448 (2)	124 (2)
O6—H2O···O2	1.20 (4)	1.27 (4)	2.4541 (18)	168 (4)
N2—H2A···O6ⁱⁱⁱ	0.86	2.19	3.0160 (19)	162
N2—H2B···O4	0.85	1.99	2.629 (2)	131
N4—H4A···O8	0.87	2.03	2.648 (2)	128
N4—H4B···O2Wⁱⁱ	0.87	2.16	3.021 (2)	173
C5—H5···O2ⁱⁱⁱ	0.93	2.57	3.489 (2)	170
C9—H9···N2^iv	0.93	2.66	3.544 (2)	160
C12—H12···O8^v	0.93	2.42	3.178 (2)	138
O2W—H2WA···O7^vi	0.86	2.14	2.995 (2)	173
O2W—H2WB···O1W^vii	0.85	2.39	3.127 (2)	145
O2W—H2WB···O5^viii	0.85	2.65	3.341 (2)	139

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

Funding information

The authors gratefully acknowledge the Ministry of Higher Education, Science and Innovation for financial support (project No. F3–20200929348) and would also like to thank the Uzbekistan government for direct financial support of this research.

References

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