Crystal structure of caesium dimethyl-N-benzoyl­amido­phosphate monohydrate

Kariaka, N.S.; Dyakonenko, V.V.; Shishkina, S.V.; Sliva, T.Y.; Amirkhanov, V.M.

doi:10.1107/S2056989022012166

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ISSN: 2056-9890

Volume 79| Part 2| February 2023| Pages 70-73

https://doi.org/10.1107/S2056989022012166

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Crystal structure of caesium dimethyl-N-benzoylamidophosphate monohydrate

Nataliia S. Kariaka,^a ^* Viktoriya V. Dyakonenko,^b Svitlana V. Shishkina,^b Tatiana Yu. Sliva ^a and Vladimir M. Amirkhanov ^a

^aDepartment of Chemistry, Kyiv National Taras Shevchenko University, Volodymyrska, str. 64, 01601 Kyiv, Ukraine, and ^bSSI "Institute for Single Crystals", National Academy of Sciences of Ukraine, Nauky ave. 60, 61001 Kharkiv, Ukraine
^*Correspondence e-mail: natalia_kariaka@i.ua

Edited by J. T. Mague, Tulane University, USA (Received 22 November 2022; accepted 24 December 2022; online 6 January 2023)

The caesium salt of dimethyl-N-benzoylamidophosphate, namely, aqua[dimethyl (N-benzoylamido-κO)phosphonato-κO]caesium, [Cs(C₉H₁₁NO₄P)(H₂O)] or CsL·H₂O, is reported. The compound crystallizes in the monoclinic crystal system in the P2₁/c space group and forms a mono-periodic polymeric structure due to the bridging function of the dimethyl-N-benzoylamidophosphate anions towards the caesium cations.

Keywords: crystal structure; carbacylamidophosphate; caesium.

CCDC reference: 2232690

1. Chemical context

The carbacylamidophosphates {CAPh, compounds of general formula [RC(O)N(H)P(O)R′₂]}, first introduced by Alexandr Kirsanov in the 1960s, have now become an intensively investigated class of ligands (Amirkhanov et al., 2014 ). The structures of the alkali metal salts of CAPh anions, important starting reagents for the synthesis of their transition-metal complexes, have been poorly studied to date. The sodium and potassium salts with 2,2,2-trichloro-N-(dimorpholinophosphoryl)acetamide (HCAPh¹) contain ligated water molecules and have general formulae Na₂CAPh¹₂·2H₂O and KCAPh¹·H₂O, respectively (Litsis et al., 2010 , 2016 ). The sodium salt of dimethyl-N-benzoylamidophosphate NaCAPh² (Kariaka et al., 2019 ) and the alkali salts of dimethyl-N-trichloracetylamidophosphate NaCAPh³, RbCAPh³ (Trush et al., 2005 ) crystallize in a solvent-free form. In all of these compounds the CAPh ligands are coordinated to the metal ions in a bidentate manner (via the oxygen atoms of the phosphoryl and carbonyl groups) with the formation of six-membered chelate metallocycles. In addition, the phosphoryl or the carbonyl oxygen atom or both usually bridge the cations. Caesium salts of CAPhs have not been reported to date and are of interest as possible dopants in oxide film materials for the improvement of their electric and electron functional characteristics (Vikulova et al., 2013 ). Because of this, an actual task is the search for caesium compounds satisfying metal–organic chemical vapor deposition requirements. The combination of caesium ions with bulky organic ligands may result in compounds with molecular crystal structures that possess sufficient volatility. Thus, crystal-structure investigations of caesium salts of CAPh anions are of high interest. Herein, we present the crystal structure of the caesium salt of dimethyl-N-benzoylamidophosphate.

2. Structural commentary

Similar to the sodium salt of dimethyl-N-benzoylamidophosphate (Kariaka et al., 2019) the title compound crystallizes in the monoclinic crystal system in the P2₁/c space group and forms a 1D-polymeric structure (Fig. 1).

Figure 1
Polymeric chain of the title compound extending along the [001] crystallographic direction.

The asymmetric unit contains the Cs⁺ and CAPh⁻ ions and a water molecule (Fig. 2a). The oxygen atoms of the carbonyl and phosphoryl groups of the dimethyl-N-benzoylamidophosphate anions act as μ₂-bridges between Cs⁺ cations (Fig. 1). Additionally, both of the methoxy groups are bound to the Cs⁺ and one of them also acts as a μ₂-bridge. Thus, one CAPh⁻ anion is bound to four Cs⁺ cations (Fig. 2b), and each Cs⁺ cation links four ligand anions. Additionally, a water molecule acts as a μ₂-bridge between two Cs⁺ cations.

Figure 2
Representation of (a) the asymmetric unit of the title compound and (b) the coordination mode of L⁻.

The Cs⁺ ion contacts nine oxygen atoms. It is involved in the six-membered Cs1–O1–C1–N1–P1–O2 ring with one ligand by bonding with the oxygen atoms of the carbonyl and phosphoryl groups, in the four-membered Cs1–O2–P1–O4 ring with another CAPh ligand by bonding with the oxygen atoms of the phosphoryl and methoxy groups and in the six-membered Cs1–O1–C1–N1–P1–O3 ring with the third ligand by bonding with the μ₂-oxygen atoms of the carbonyl and methoxy groups. In addition, the Cs⁺ ion contacts with the μ₂-O3 atom of the fourth neighboring CAPh as well as with two molecules of water (Fig. 1). The six-membered chelate Cs1–O1–C1–N1–P1–O2 ring is not planar with the P1, N1 and C1 atoms deviating from the plane created through Cs1, O1 and O2 atoms by 0.471 (3), 1.403 (4) and 1.039 (4) Å, respectively. The O1—C1—N1—P1 and C1—N1—P1—O2 torsion angles are −2.4 (5) and 56.0 (3)° respectively. The six-membered Cs1–O1–C1–N1–P1–O3 ring is also not planar with the P1, N1 and C1 atoms deviating from the plane created through Cs1, O1 and O3 atoms by 0.942 (4), 0.139 (5) and 0.240 (3) Å, respectively. The C1—N1—P1—O3 torsion angle is −69.3 (3)°. The shortest Cs—O distance in the title compound (Table 1) is 3.072 (2) Å, which is comparable with the sum of the O²⁻ and Cs⁺ ionic radii (3.07 Å), so the majority of the Cs—O contacts might be considered as a mainly ionic type of bond. The Cs1—O1 distance is the longest (Table 1) and longer than the typical Cs—O bonds in crystalline solids (Leclaire et al., 2008 ).

Table 1
Selected geometric parameters (Å, °)

Cs1—O1ⁱ	3.086 (2)	Cs1—O5	3.112 (3)
Cs1—O1	3.631 (3)	Cs1—O5^iv	3.418 (4)
Cs1—O2ⁱⁱ	3.206 (3)	P1—O2	1.468 (2)
Cs1—O2	3.072 (2)	P1—N1	1.597 (3)
Cs1—O3ⁱⁱⁱ	3.431 (2)	O1—C1	1.247 (3)
Cs1—O3ⁱ	3.507 (3)	N1—C1	1.325 (4)
Cs1—O4ⁱⁱ	3.310 (2)

O2—Cs1—O1	56.40 (6)	P1—O2—Cs1	131.74 (14)
O2—P1—N1	122.26 (14)	C1—N1—P1	121.5 (2)
C1—O1—Cs1	109.9 (2)	O1—C1—N1	126.3 (3)
Symmetry codes: (i) ; (ii) ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

The average values of the C=O and P=O bond lengths in the title compound are increased as compared with HL [d(C—O)_HL = 1.219 (6) Å, d(P—O)_HL = 1.461 (4) Å] and the C—N and P—N bond lengths are decreased [d(C—N)_HL = 1.393 (7) Å, d(P—N)_HL = 1.667 (5) Å; Mizrahi & Modro, 1982 ]. Such changes are consistent with the deprotonation of HL.

3. Supramolecular features

Few intermolecular contacts are observed in the crystal structure of the title compound. There are O—H⋯O hydrogen bonds between the water molecule and the carbonyl and phosphoryl oxygen atoms of the dimethyl-N-benzoylamidophosphate anion (Table 2). In addition, the water molecule participates in a C8—H8C⋯O5 contact with the hydrogen atom of the methoxy group of the CAPh ligand. The H8C⋯O5 distance is 2.56 Å. There are no intermolecular contacts between the CAPh ligands in the crystal structure of the title compound.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O1^v	0.85 (1)	2.05 (3)	2.785 (3)	143 (4)
O5—H5B⋯O2ⁱⁱⁱ	0.86 (1)	1.87 (1)	2.721 (4)	170 (4)
Symmetry codes: (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

4. Hirshfeld surface analysis and finger print plots

For visualization of the intermolecular interactions in the crystal structure for the asymmetric unit of the title compound, the Hirshfeld surface (Fig. 3) and its corresponding two-dimensional fingerprint plots (Spackman & Jayatilaka, 2009 ) were calculated using CrystalExplorer17 (Turner et al., 2017 ).

Figure 3
The Hirshfeld surface mapped over d_norm and two-dimensional fingerprint plots for the H⋯H (42.2%), H⋯O/O⋯H (19.3%), C⋯H/H⋯C (14.3%) and Cs⋯O/O⋯Cs (12.9%) interactions for the asymmetric unit of the title compound

The dark-red spots on the surface, which correspond to the strongest contacts in the crystal structure of the title compound, are observed for the H⋯O/O⋯H hydrogen bonds between hydrogen atoms of the water molecule and the oxygen atoms of the carbonyl and phosphoryl groups of the CAPh. The lighter red spots observed near the Cs⁺ cation and the methoxy groups correspond to Cs⋯O/O⋯Cs bonds, which are involved in Cs⋯O contacts and H⋯O contacts with the water molecule. There are no red spots on the Hirshfeld surface near the phenyl ring.

The derived fingerprint plots show that H⋯H contacts make the largest contribution to the Hirshfeld surface (42.2%) and the shortest of them are at d_i = d_e = 1.2 Å. The second largest contribution (19.3%) comes from the H⋯O/O⋯H contacts, which are the shortest in the title compound (d_i + d_e = 1.75 Å). The C⋯H/H⋯C and Cs⋯O/O⋯Cs interactions make similar contributions to the surface at 14.3% and 12.9%, respectively. The shortest C⋯H/H⋯C contacts are at d_i + d_e = 2.8 Å. The shortest Cs⋯O/O⋯Cs contacts are at d_i + d_e = 3.07 Å. Among the interactions making the smallest contribution to the Hirshfeld surface of the title compound are the O⋯O, C⋯C, Cs⋯H and N⋯H interactions.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update of November 2020; Groom et al., 2016 ) for alkali metal salts of carbacylamidophosphates yielded ten hits. Six of them are sodium salts, three are potassium salts and one is a rubidium salt. No CAPh-based caesium salts have been reported to date. In all these reported salts, the carbacylamidophosphates are coordinated to the alkali metals in a bidentate chelating manner via the oxygen atoms of the phosphoryl and carbonyl groups. Additionally, in the majority of these salts, the phosphoryl or the carbonyl oxygen atom or both function as μ₂-bridges. In the alkali metal salts of CAPhs that contain methoxy groups, one of the latter is involved in contacts with the metal. In alkali metal salts of CAPhs that contain the CCl₃ group, the latter can be also involved in the metal binding. Some CAPh-based salts also contain such additional ligands as water molecules, coordinated to the metal in a μ₂-bridging manner, or crown ethers.

6. Synthesis and crystallization

CsL·H₂O was obtained by a neutralization reaction between HL (0.458 g, 2 mmol) and caesium carbonate (0.326 g, 1 mmol) solutions in aqueous 2-propanol (1:3). Yield: 0.664 g, 88%, m.p. 353 K. IR (KBr): ν_max = 3408 [ν(OH)], 1591 [ν(CC)], 1535 [ν(CO)], 1378 [ν(CN)], 1205 [ν(PO)], 1076, 1038, 928 [ν(PN)], 838, 800, 734, 710, 540, 502,466, 452 cm⁻¹. The low-frequency shift of ν(P=O) and ν(C=O) bands in the IR spectrum of CsL·H₂O with respect to HL (Δν_HL(P=O) ∼37cm⁻¹, Δν_HL(C=O) ∼147cm⁻¹] is typical for bidentate coordination of dimethyl-N-benzoylamidophosphate. ¹H NMR (DMSO-d₆): δ = 3.24 (s, H₂O), 3.54 [d, 6H, (OCH₃)₂], 7.27 (t, 3H, Ph), 8.04 (d, 2H, Ph). ³¹P NMR (acetone): δ = 15.2 (s).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. C-bound H atoms were positioned geometrically and refined as riding [C—H = 0.93–0.96 Å, U_iso(H) = 1.2–1.5U_eq(C). O-bound H atoms were refined with the restraints O5—H5A = O5—H5B = 0.84±0.01 Å and H5A⋯H5B = 1.62±0.02 Å with U_iso(H) = 1.5U_eq(O).

Table 3
Experimental details

Crystal data
Chemical formula	[Cs(C₉H₁₁NO₄P)(H₂O)]
M_r	379.08
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	14.3676 (4), 6.8089 (2), 13.7336 (3)
β (°)	90.549 (2)
V (Å³)	1343.46 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.88
Crystal size (mm)	0.5 × 0.3 × 0.2

Data collection
Diffractometer	Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.505, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13393, 3918, 3169
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.076, 1.03
No. of reflections	3918
No. of parameters	162
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)	0.52, −0.79
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT2014/4 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2232690

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989022012166/mw2194sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022012166/mw2194Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT2014/4 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

Aqua[dimethyl (N-benzoylamido-κO)phosphonato-κO]caesium top

Crystal data top

[Cs(C₉H₁₁NO₄P)(H₂O)]	F(000) = 736
M_r = 379.08	D_x = 1.874 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.3676 (4) Å	Cell parameters from 3272 reflections
b = 6.8089 (2) Å	θ = 3.6–28.2°
c = 13.7336 (3) Å	µ = 2.88 mm⁻¹
β = 90.549 (2)°	T = 294 K
V = 1343.46 (6) Å³	Block, colourless
Z = 4	0.5 × 0.3 × 0.2 mm

Data collection top

Xcalibur, Sapphire3 diffractometer	3169 reflections with I > 2σ(I)
Detector resolution: 16.1827 pixels mm^-1	R_int = 0.032
ω scans	θ_max = 30.0°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlisPro; Agilent, 2014)	h = −19→20
T_min = 0.505, T_max = 1.000	k = −9→9
13393 measured reflections	l = −18→19
3918 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0307P)² + 0.4727P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3918 reflections	Δρ_max = 0.52 e Å⁻³
162 parameters	Δρ_min = −0.79 e Å⁻³
3 restraints

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
Cs1	0.48526 (2)	0.71528 (3)	0.62552 (2)	0.04947 (8)
O5	0.4180 (2)	0.7620 (5)	0.8390 (2)	0.0816 (9)
H5A	0.371 (2)	0.806 (8)	0.869 (3)	0.122*
H5B	0.4702 (17)	0.723 (7)	0.863 (3)	0.122*
P1	0.66854 (5)	0.81111 (12)	0.39433 (6)	0.04547 (18)
O1	0.67121 (16)	0.4475 (4)	0.50718 (17)	0.0667 (7)
O2	0.57605 (15)	0.8484 (4)	0.43493 (16)	0.0618 (6)
O3	0.65141 (15)	0.6826 (4)	0.29932 (16)	0.0597 (6)
O4	0.70550 (16)	1.0147 (4)	0.3582 (2)	0.0768 (8)
N1	0.75168 (18)	0.7207 (4)	0.45799 (19)	0.0499 (6)
C1	0.74267 (19)	0.5511 (5)	0.50430 (18)	0.0438 (6)
C2	0.82889 (19)	0.4816 (4)	0.55712 (17)	0.0415 (6)
C3	0.8379 (3)	0.2855 (5)	0.5831 (2)	0.0534 (7)
H3	0.789853	0.198137	0.569188	0.064*
C4	0.9172 (3)	0.2191 (6)	0.6290 (3)	0.0668 (10)
H4	0.922916	0.087133	0.645488	0.080*
C5	0.9879 (2)	0.3473 (7)	0.6507 (3)	0.0682 (10)
H5	1.041536	0.302436	0.682000	0.082*
C6	0.9797 (2)	0.5411 (7)	0.6262 (2)	0.0607 (9)
H6	1.027423	0.628199	0.641683	0.073*
C7	0.90089 (19)	0.6085 (5)	0.5786 (2)	0.0477 (7)
H7	0.896380	0.740050	0.561044	0.057*
C8	0.7258 (3)	0.6063 (7)	0.2424 (3)	0.0770 (11)
H8A	0.772305	0.550223	0.284658	0.116*
H8B	0.752921	0.710446	0.205037	0.116*
H8C	0.702224	0.506856	0.199145	0.116*
C9	0.7984 (2)	1.0682 (6)	0.3429 (3)	0.0672 (9)
H9A	0.815023	1.038514	0.276950	0.101*
H9B	0.838067	0.996211	0.386767	0.101*
H9C	0.805753	1.206393	0.354371	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.05209 (12)	0.05443 (14)	0.04190 (11)	0.00312 (8)	0.00059 (8)	0.00041 (8)
O5	0.0608 (16)	0.129 (3)	0.0550 (15)	0.0128 (17)	0.0018 (13)	−0.0145 (15)
P1	0.0379 (4)	0.0511 (5)	0.0475 (4)	0.0007 (3)	0.0042 (3)	0.0067 (3)
O1	0.0604 (13)	0.0699 (17)	0.0694 (14)	−0.0275 (12)	−0.0167 (11)	0.0249 (12)
O2	0.0450 (11)	0.0797 (17)	0.0608 (13)	0.0057 (11)	0.0116 (10)	−0.0051 (12)
O3	0.0486 (12)	0.0814 (18)	0.0492 (12)	0.0121 (11)	0.0043 (10)	−0.0048 (11)
O4	0.0550 (13)	0.0640 (17)	0.111 (2)	−0.0022 (12)	−0.0041 (13)	0.0376 (15)
N1	0.0432 (13)	0.0525 (16)	0.0539 (14)	−0.0066 (11)	−0.0026 (11)	0.0116 (11)
C1	0.0461 (14)	0.0500 (17)	0.0353 (13)	−0.0080 (13)	0.0028 (11)	0.0029 (12)
C2	0.0455 (14)	0.0512 (17)	0.0279 (11)	−0.0044 (12)	0.0034 (10)	0.0001 (11)
C3	0.065 (2)	0.0528 (19)	0.0425 (15)	−0.0022 (15)	0.0017 (14)	0.0034 (13)
C4	0.079 (3)	0.063 (2)	0.058 (2)	0.0165 (19)	0.0020 (18)	0.0101 (17)
C5	0.057 (2)	0.096 (3)	0.0516 (18)	0.018 (2)	−0.0009 (15)	0.0060 (19)
C6	0.0455 (17)	0.087 (3)	0.0495 (17)	−0.0040 (16)	−0.0013 (13)	−0.0041 (16)
C7	0.0470 (15)	0.0526 (19)	0.0434 (14)	−0.0034 (14)	0.0025 (12)	−0.0033 (12)
C8	0.067 (2)	0.089 (3)	0.076 (2)	−0.001 (2)	0.0257 (19)	−0.020 (2)
C9	0.072 (2)	0.059 (2)	0.072 (2)	−0.0156 (18)	0.0157 (17)	0.0108 (17)

Geometric parameters (Å, º) top

Cs1—O1ⁱ	3.086 (2)	C1—C2	1.506 (4)
Cs1—O1	3.631 (3)	C2—C3	1.388 (4)
Cs1—O2ⁱⁱ	3.206 (3)	C2—C7	1.377 (4)
Cs1—O2	3.072 (2)	C3—H3	0.9300
Cs1—O3ⁱⁱⁱ	3.431 (2)	C3—C4	1.374 (5)
Cs1—O3ⁱ	3.507 (3)	C4—H4	0.9300
Cs1—O4ⁱⁱ	3.310 (2)	C4—C5	1.369 (6)
Cs1—O5	3.112 (3)	C5—H5	0.9300
Cs1—O5^iv	3.418 (4)	C5—C6	1.367 (6)
O5—H5A	0.853 (10)	C6—H6	0.9300
O5—H5B	0.856 (10)	C6—C7	1.379 (4)
P1—O2	1.468 (2)	C7—H7	0.9300
P1—O3	1.588 (2)	C8—H8A	0.9600
P1—O4	1.567 (3)	C8—H8B	0.9600
P1—N1	1.597 (3)	C8—H8C	0.9600
O1—C1	1.247 (3)	C9—H9A	0.9600
O3—C8	1.428 (4)	C9—H9B	0.9600
O4—C9	1.402 (4)	C9—H9C	0.9600
N1—C1	1.325 (4)

O1ⁱ—Cs1—O5^iv	93.03 (7)	C1—O1—Cs1ⁱ	141.26 (18)
O1ⁱ—Cs1—O5	111.22 (7)	C1—O1—Cs1	109.9 (2)
O1ⁱ—Cs1—O1	95.18 (5)	Cs1—O2—Cs1ⁱⁱ	112.10 (7)
O1ⁱ—Cs1—O2ⁱⁱ	89.03 (6)	P1—O2—Cs1	131.74 (14)
O1ⁱ—Cs1—O3ⁱⁱⁱ	169.01 (6)	P1—O2—Cs1ⁱⁱ	108.03 (13)
O1ⁱ—Cs1—O3ⁱ	59.31 (5)	Cs1^vi—O3—Cs1ⁱ	88.49 (5)
O1ⁱ—Cs1—O4ⁱⁱ	68.92 (7)	P1—O3—Cs1ⁱ	105.47 (10)
O2ⁱⁱ—Cs1—O5^iv	169.77 (6)	P1—O3—Cs1^vi	124.13 (11)
O2—Cs1—O5	155.59 (8)	C8—O3—Cs1ⁱ	107.7 (2)
O2—Cs1—O5^iv	102.27 (6)	C8—O3—Cs1^vi	102.3 (2)
O2ⁱⁱ—Cs1—O1	123.43 (5)	C8—O3—P1	122.6 (2)
O2—Cs1—O1	56.40 (6)	P1—O4—Cs1ⁱⁱ	100.77 (10)
O2—Cs1—O1ⁱ	85.16 (6)	C9—O4—Cs1ⁱⁱ	131.0 (2)
O2—Cs1—O2ⁱⁱ	67.90 (7)	C9—O4—P1	127.1 (2)
O2—Cs1—O3ⁱⁱⁱ	103.57 (6)	C1—N1—P1	121.5 (2)
O2ⁱⁱ—Cs1—O3ⁱⁱⁱ	100.36 (6)	O1—C1—N1	126.3 (3)
O2—Cs1—O3ⁱ	136.23 (6)	O1—C1—C2	118.8 (3)
O2ⁱⁱ—Cs1—O3ⁱ	129.70 (5)	N1—C1—C2	114.9 (2)
O2—Cs1—O4ⁱⁱ	104.60 (6)	C3—C2—C1	120.0 (3)
O2ⁱⁱ—Cs1—O4ⁱⁱ	43.69 (6)	C7—C2—C1	121.3 (3)
O3ⁱ—Cs1—O1	99.23 (5)	C7—C2—C3	118.7 (3)
O3ⁱⁱⁱ—Cs1—O1	84.44 (5)	C2—C3—H3	119.7
O3ⁱⁱⁱ—Cs1—O3ⁱ	109.86 (5)	C4—C3—C2	120.6 (3)
O4ⁱⁱ—Cs1—O5^iv	145.89 (7)	C4—C3—H3	119.7
O4ⁱⁱ—Cs1—O1	157.27 (6)	C3—C4—H4	120.0
O4ⁱⁱ—Cs1—O3ⁱⁱⁱ	114.31 (7)	C5—C4—C3	120.0 (4)
O4ⁱⁱ—Cs1—O3ⁱ	86.73 (6)	C5—C4—H4	120.0
O5—Cs1—O5^iv	95.01 (7)	C4—C5—H5	120.0
O5^iv—Cs1—O1	46.41 (6)	C6—C5—C4	119.9 (3)
O5—Cs1—O1	135.19 (7)	C6—C5—H5	120.0
O5—Cs1—O2ⁱⁱ	93.57 (7)	C5—C6—H6	119.8
O5^iv—Cs1—O3ⁱⁱⁱ	78.73 (7)	C5—C6—C7	120.4 (3)
O5—Cs1—O3ⁱ	67.78 (8)	C7—C6—H6	119.8
O5—Cs1—O3ⁱⁱⁱ	62.88 (7)	C2—C7—C6	120.3 (3)
O5^iv—Cs1—O3ⁱ	59.24 (6)	C2—C7—H7	119.9
O5—Cs1—O4ⁱⁱ	67.35 (7)	C6—C7—H7	119.9
Cs1—O5—Cs1^v	95.57 (9)	O3—C8—H8A	109.5
Cs1—O5—H5A	138 (3)	O3—C8—H8B	109.5
Cs1^v—O5—H5A	86 (4)	O3—C8—H8C	109.5
Cs1^v—O5—H5B	82 (4)	H8A—C8—H8B	109.5
Cs1—O5—H5B	93 (3)	H8A—C8—H8C	109.5
H5A—O5—H5B	129 (3)	H8B—C8—H8C	109.5
O2—P1—O3	105.88 (13)	O4—C9—H9A	109.5
O2—P1—O4	106.13 (15)	O4—C9—H9B	109.5
O2—P1—N1	122.26 (14)	O4—C9—H9C	109.5
O3—P1—N1	110.27 (14)	H9A—C9—H9B	109.5
O4—P1—O3	106.15 (15)	H9A—C9—H9C	109.5
O4—P1—N1	105.09 (13)	H9B—C9—H9C	109.5
Cs1ⁱ—O1—Cs1	84.82 (5)

Cs1—O1—C1—N1	−62.6 (3)	O4—P1—O3—Cs1ⁱ	−165.17 (10)
Cs1ⁱ—O1—C1—N1	44.7 (5)	O4—P1—O3—Cs1^vi	−66.28 (16)
Cs1—O1—C1—C2	117.8 (2)	O4—P1—O3—C8	71.3 (3)
Cs1ⁱ—O1—C1—C2	−135.0 (3)	O4—P1—N1—C1	176.7 (2)
P1—N1—C1—O1	−2.4 (5)	N1—P1—O2—Cs1	−13.3 (3)
P1—N1—C1—C2	177.2 (2)	N1—P1—O2—Cs1ⁱⁱ	131.82 (14)
O1—C1—C2—C3	18.9 (4)	N1—P1—O3—Cs1^vi	−179.60 (12)
O1—C1—C2—C7	−162.7 (3)	N1—P1—O3—Cs1ⁱ	81.52 (12)
O2—P1—O3—Cs1ⁱ	−52.64 (14)	N1—P1—O3—C8	−42.0 (3)
O2—P1—O3—Cs1^vi	46.24 (18)	N1—P1—O4—Cs1ⁱⁱ	−141.69 (12)
O2—P1—O3—C8	−176.2 (3)	N1—P1—O4—C9	27.5 (4)
O2—P1—O4—Cs1ⁱⁱ	−10.89 (15)	N1—C1—C2—C3	−160.8 (3)
O2—P1—O4—C9	158.3 (3)	N1—C1—C2—C7	17.7 (4)
O2—P1—N1—C1	56.0 (3)	C1—C2—C3—C4	178.3 (3)
O3—P1—O2—Cs1	113.94 (18)	C1—C2—C7—C6	−179.3 (2)
O3—P1—O2—Cs1ⁱⁱ	−100.92 (13)	C2—C3—C4—C5	0.7 (5)
O3—P1—O4—Cs1ⁱⁱ	101.47 (12)	C3—C2—C7—C6	−0.8 (4)
O3—P1—O4—C9	−89.4 (3)	C3—C4—C5—C6	−0.2 (5)
O3—P1—N1—C1	−69.3 (3)	C4—C5—C6—C7	−0.8 (5)
O4—P1—O2—Cs1ⁱⁱ	11.62 (16)	C5—C6—C7—C2	1.3 (5)
O4—P1—O2—Cs1	−133.52 (18)	C7—C2—C3—C4	−0.2 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1^v	0.85 (1)	2.05 (3)	2.785 (3)	143 (4)
O5—H5B···O2ⁱⁱⁱ	0.86 (1)	1.87 (1)	2.721 (4)	170 (4)

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

Funding information

Funding for this research was provided by: Ministry of Education and Science of Ukraine (grant No. 19BF037-05).

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