Crystal structure of caesium dimethyl-N-benzoyl­amido­phosphate monohydrate

The crystal structure of the caesium salt of dimethyl-N-benzoyl­amido­phosphate is reported and discussed.

Abstract

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.

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 Na₂CAPh¹ ₂·2H₂O 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. 2 ▸ a). 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. 2 ▸ b), 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—O5iv	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) ; (iv) .

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⋯O1v	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) ; (v) .

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-d ₆): 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[F 2 > 2σ(F 2)], wR(F 2), 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
Δρmax, Δρmin (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 ▸).

Supplementary Material

CCDC reference: 2232690

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

supplementary crystallographic information

Crystal data

[Cs(C9H11NO4P)(H2O)]	F(000) = 736
Mr = 379.08	Dx = 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

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

Refinement

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(Fo2) + (0.0307P)2 + 0.4727P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3918 reflections	Δρmax = 0.52 e Å−3
162 parameters	Δρmin = −0.79 e Å−3
3 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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—O5iv	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—O5iv	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)	Cs1vi—O3—Cs1i	88.49 (5)
O1i—Cs1—O4ii	68.92 (7)	P1—O3—Cs1i	105.47 (10)
O2ii—Cs1—O5iv	169.77 (6)	P1—O3—Cs1vi	124.13 (11)
O2—Cs1—O5	155.59 (8)	C8—O3—Cs1i	107.7 (2)
O2—Cs1—O5iv	102.27 (6)	C8—O3—Cs1vi	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—O5iv	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—O5iv	95.01 (7)	C4—C5—H5	120.0
O5iv—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
O5iv—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)
O5iv—Cs1—O3i	59.24 (6)	C2—C7—H7	119.9
O5—Cs1—O4ii	67.35 (7)	C6—C7—H7	119.9
Cs1—O5—Cs1v	95.57 (9)	O3—C8—H8A	109.5
Cs1—O5—H5A	138 (3)	O3—C8—H8B	109.5
Cs1v—O5—H5A	86 (4)	O3—C8—H8C	109.5
Cs1v—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—Cs1vi	−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—Cs1vi	−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—Cs1vi	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)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1v	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 Statement

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