Bis(tetra­phenyl­arsonium) hexa­chlorido­zirconate(IV) aceto­nitrile tetra­solvate

Borjas, R.; Mariappan Balasekaran, S.; Poineau, F.

doi:10.1107/S241431461800528X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 4| April 2018| x180528

https://doi.org/10.1107/S241431461800528X

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Bis(tetraphenylarsonium) hexachloridozirconate(IV) acetonitrile tetrasolvate

Rosendo Borjas,^a Samundeeswari Mariappan Balasekaran ^a ^* and Frederic Poineau ^a

^aDepartment of Chemistry, University of Nevada Las Vegas, 4505 South Maryland Parkway, Las Vegas, Nevada, 89154, United States
^*Correspondence e-mail: m.b.eswari@unlv.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 January 2018; accepted 3 April 2018; online 6 April 2018)

The bis(tetraphenylarsonium) hexachloridozirconate(IV) salt, (AsPh₄)₂[ZrCl₆] (Ph = C₆H₅), was prepared more than 25 years ago [Esmadi & Sutcliffe (1991 ). Indian J. Chem. 30 A, 99–101], but its crystal structure was never reported. By following a similar experimental procedure, the compound was synthesized and its crystal structure was investigated as a acetonitrile tetrasolvate, (As(C₆H₅)₄)₂[ZrCl₆]·4CH₃CN, by single-crystal X–ray diffraction. The [ZrCl₆]²⁻ anion adopts a slightly distorted octahedral coordination sphere, with Zr—Cl bond lengths of 2.4586 (6), 2.4723 (6), and 2.4818 (5) Å, and Cl—Zr—Cl angles ranging from 89.602 (19) to 90.397 (19)°.

Keywords: crystal structure; zirconium; tetraphenylarsonium; solvate.

CCDC reference: 1834601

Structure description

Zirconium tetrachloride is encountered in the nuclear fuel cycle for the recycling of zirconium from zirconium alloy cladding using a chloride volatility process (Bohe et al., 1996 ; Collins et al., 2012 ; Jeon et al., 2013 ). The ZrCl₄ produced from these alloys at temperatures above 573 K contains several impurities that are difficult to separate. It has been considered that the impurities could be present due to the formation of intermediate ternary compounds, or by the co-crystallization of various chloride species. For these reasons, investigating the chemical behavior of ZrCl₄ in the presence of other chlorides is of importance. At least ten hexachloridozirconate(IV) salts have been prepared and their structures reported. The majority of these salts were prepared using ZrCl₄ and chloride salts as starting materials (Esmadi & Sutcliffe, 1991; Ohashi et al., 1987 ). These [ZrCl₆]²⁻ salts contain single-element cations (e.g. Cs⁺, Rb⁺, Fe²⁺) or more complex cations {e.g. [P(C₆H₅)₄]⁺, [N(CH₃)₄]⁺}. On the other hand, crystal structures have not been reported for many of these hexachloridozirconates(IV) (e.g. Na₂[ZrCl₆] and K₂[ZrCl₆]; Lister, 1964 ). One of these salts, bis(tetraphenylarsonium) hexachloridozirconate(IV), was synthesized (Esmadi & Sutcliffe, 1991) but its structure never reported. Here, (AsPh₄)₂[ZrCl₆]·4(CH₃CN) (Ph = C₆H₅) was crystallized as its acetonitrile tetrasolvate (Fig. 1) and its structure investigated by single-crystal X-ray diffraction.

Figure 1
The molecular structures of the cation and anion in (AsPh₄)₂[ZrCl₆]·4CH₃CN, with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (') –x, 1 − y, 1 − z.]

The unit-cell packing of (AsPh₄)₂[ZrCl₆]·4(CH₃CN) is shown in Fig. 2. The (AsPh₄)⁺ cation adopts a distorted tetrahedral configuration in which the phenyl groups are asymmetrically attached (Fig. 1). The As—C bond lengths (Table 1) are similar to those reported for (AsPh₄)₂[TcCl₆] (Baldas et al., 1984 ) or (AsPh₄)₂[ReBr₆] (Kochel, 2007 ). The asymmetric orientation of the phenyl groups is reflected by the deviation of the C—As—C angles from those of a perfect tetrahedron (Table 1).

Table 1
Selected geometric parameters (Å, °)

Zr1—Cl2	2.4586 (6)	As1—C1	1.911 (2)
Zr1—Cl3	2.4723 (6)	As1—C13	1.911 (2)
Zr1—Cl1	2.4818 (5)	As1—C19	1.916 (2)
As1—C7	1.906 (2)

Cl2—Zr1—Cl3	90.09 (2)	C7—As1—C1	110.95 (10)
Cl2ⁱ—Zr1—Cl3	89.91 (2)	C7—As1—C13	110.73 (10)
Cl2—Zr1—Cl1ⁱ	90.398 (19)	C1—As1—C13	107.65 (10)
Cl3—Zr1—Cl1ⁱ	89.703 (19)	C7—As1—C19	107.83 (10)
Cl3ⁱ—Zr1—Cl1ⁱ	90.296 (19)	C1—As1—C19	111.76 (10)
Cl2—Zr1—Cl1	89.603 (19)	C13—As1—C19	107.89 (10)
Symmetry code: (i) -x, -y+1, -z+1.

Figure 2
Representation of the expanded unit cell of (AsPh₄)₂[ZrCl₆]·4CH₃CN. Hydrogen atoms are omitted for clarity. Color of atoms: Zr in gray, Cl in green, N in blue, As in light turquoise, C in light brown.

The [ZrCl₆]²⁻ anion, which is located on a position with site symmetry $[\overline{1}]$ (Wyckoff position 2a), adopts a slightly distorted octahedral coordination sphere (Fig. 1, Table 1), The shortest Zr ⋯ Zr distance in the structure is 9.6505 (7) Å that corresponds with the length of the a axis. The shortest As ⋯ As distance is 7.8562 (7) Å and corresponds to adjacent (AsPh₄)⁺ cations within the same unit cell.

The isolated (AsPh₄)⁺ cations and [ZrCl₆]²⁻ anions pack in alternating rows extending parallel to [100]. The two unique solvent molecules are located in the voids of this arrangement (Fig. 2). The shortest distances observed between N or Cl atoms and H atoms range between 2.61 and 2.81 Å (Table 2). These distances suggest that the components interact only weakly through hydrogen bonding and that the structural cohesion is primarily accomplished by Coulombic attraction.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3S—H3SA⋯Cl1ⁱⁱ	0.98	2.81	3.674 (3)	148
C16—H16⋯Cl1ⁱⁱⁱ	0.95	2.73	3.646 (3)	162
C18—H18⋯N1Sⁱⁱⁱ	0.95	2.61	3.483 (4)	154
Symmetry codes: (ii) x+1, y, z; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Synthesis and crystallization

All chemicals were purchased from Sigma Aldrich and used as received. The reaction used to prepare (AsPh₄)₂[ZrCl₆] (Fig. 3) is similar to that described in the literature (Esmadi & Sutcliffe, 1991): A solution of (AsPh₄)Cl (0.72 g, 1.7 mmol) in thionyl chloride (2 ml) was added dropwise to a stirring solution of ZrCl₄ (0.20 g, 0.86 mmol) in thionyl chloride (1 ml). After stirring the mixture for 20 h, ethyl acetate was added dropwise to induce precipitation. The white precipitate was washed with ethyl acetate (3 × 3 ml) and diethyl ether (3 × 3 ml), and then dried under vacuum over CaCl₂. Yield: 0.35 g (38%). Colorless block-shaped crystals were obtained by recrystallization from acetonitrile and slow evaporation at room temperature.

Figure 3
Reaction scheme.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	(C₂₄H₂₀As)₂[ZrCl₆]·4C₂H₃N
M_r	1234.77
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.6505 (7), 19.3780 (13), 15.1026 (10)
β (°)	97.849 (1)
V (Å³)	2797.8 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.70
Crystal size (mm)	0.12 × 0.10 × 0.05

Data collection
Diffractometer	Bruker SMART APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker 2015 )
T_min, T_max	0.80, 0.93
No. of measured, independent and observed [I > 2σ(I)] reflections	45888, 8589, 6236
R_int	0.079
(sin θ/λ)_max (Å⁻¹)	0.716

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.082, 1.00
No. of reflections	8589
No. of parameters	315
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.47
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2007 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1834601

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431461800528X/wm4070sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461800528X/wm4070Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431461800528X/wm4070sup3.docx

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(tetraphenylarsonium) hexachloridozirconate(IV) acetonitrile tetrasolvate top

Crystal data top

(C₂₄H₂₀As)₂[ZrCl₆]·4C₂H₃N	F(000) = 1248
M_r = 1234.77	D_x = 1.466 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.6505 (7) Å	Cell parameters from 9919 reflections
b = 19.3780 (13) Å	θ = 2.4–30.5°
c = 15.1026 (10) Å	µ = 1.70 mm⁻¹
β = 97.849 (1)°	T = 100 K
V = 2797.8 (3) Å³	Rectangular, translucent colourless
Z = 2	0.12 × 0.10 × 0.05 mm

Data collection top

Bruker SMART APEX CCD area detector diffractometer	8589 independent reflections
Radiation source: sealed tube	6236 reflections with I > 2σ(I)
Curved graphite monochromator	R_int = 0.079
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.6°, θ_min = 1.7°
ω and φ scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker 2015)	k = −27→27
T_min = 0.80, T_max = 0.93	l = −21→21
45888 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0292P)² + 0.8047P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
8589 reflections	Δρ_max = 0.59 e Å⁻³
315 parameters	Δρ_min = −0.47 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
Zr1	0	0.5	0.5	0.01200 (7)
Cl1	−0.12452 (6)	0.49192 (3)	0.63295 (4)	0.01817 (12)
Cl2	0.21611 (6)	0.46095 (3)	0.59151 (4)	0.01759 (12)
Cl3	−0.06208 (6)	0.37896 (3)	0.46088 (4)	0.01820 (12)
As1	0.33890 (2)	0.19416 (2)	0.56737 (2)	0.01347 (6)
C1	0.1981 (2)	0.20864 (12)	0.64294 (15)	0.0158 (5)
C2	0.1159 (2)	0.26745 (13)	0.63054 (15)	0.0183 (5)
H2	0.1348	0.3019	0.5891	0.022*
C3	0.0045 (3)	0.27509 (14)	0.68001 (17)	0.0233 (5)
H3	−0.053	0.315	0.6724	0.028*
C4	−0.0218 (3)	0.22430 (15)	0.74010 (17)	0.0261 (6)
H4	−0.0977	0.2297	0.7735	0.031*
C5	0.0609 (3)	0.16591 (14)	0.75216 (17)	0.0257 (6)
H5	0.0423	0.1317	0.794	0.031*
C6	0.1713 (3)	0.15734 (13)	0.70298 (16)	0.0215 (5)
H6	0.2277	0.117	0.7102	0.026*
C7	0.4895 (2)	0.14073 (12)	0.62672 (15)	0.0160 (5)
C8	0.5372 (3)	0.15342 (13)	0.71679 (16)	0.0198 (5)
H8	0.489	0.1848	0.75	0.024*
C9	0.6563 (3)	0.11940 (13)	0.75712 (17)	0.0223 (5)
H9	0.6901	0.1277	0.8182	0.027*
C10	0.7255 (3)	0.07347 (13)	0.70835 (17)	0.0232 (5)
H10	0.8069	0.0505	0.7362	0.028*
C11	0.6772 (3)	0.06076 (13)	0.61916 (17)	0.0226 (5)
H11	0.7253	0.029	0.5863	0.027*
C12	0.5584 (3)	0.09436 (12)	0.57771 (16)	0.0192 (5)
H12	0.5247	0.0857	0.5166	0.023*
C13	0.2531 (2)	0.14813 (12)	0.46202 (15)	0.0161 (5)
C14	0.1334 (3)	0.10940 (13)	0.46581 (18)	0.0232 (5)
H14	0.0967	0.104	0.5207	0.028*
C15	0.0675 (3)	0.07837 (14)	0.3877 (2)	0.0303 (6)
H15	−0.0148	0.0517	0.3891	0.036*
C16	0.1224 (3)	0.08663 (14)	0.30838 (19)	0.0319 (7)
H16	0.0763	0.0664	0.2551	0.038*
C17	0.2431 (3)	0.12383 (14)	0.30598 (18)	0.0285 (6)
H17	0.2815	0.1277	0.2515	0.034*
C18	0.3090 (3)	0.15558 (13)	0.38228 (16)	0.0220 (5)
H18	0.3913	0.1821	0.3804	0.026*
C19	0.4146 (2)	0.27956 (12)	0.53165 (15)	0.0152 (5)
C20	0.3407 (3)	0.31814 (13)	0.46303 (16)	0.0207 (5)
H20	0.2515	0.3033	0.4351	0.025*
C21	0.3994 (3)	0.37853 (14)	0.43617 (18)	0.0264 (6)
H21	0.3498	0.4055	0.3897	0.032*
C22	0.5302 (3)	0.40003 (13)	0.47654 (18)	0.0256 (6)
H22	0.5702	0.4412	0.4571	0.031*
C23	0.6021 (3)	0.36166 (14)	0.54487 (18)	0.0260 (6)
H23	0.6913	0.3767	0.5726	0.031*
C24	0.5446 (3)	0.30097 (13)	0.57344 (16)	0.0203 (5)
H24	0.5936	0.2746	0.6208	0.024*
N1S	0.6349 (3)	0.29350 (14)	0.8309 (2)	0.0488 (8)
C1S	0.8149 (3)	0.29684 (15)	0.9742 (2)	0.0354 (7)
H1SA	0.9092	0.2909	0.9581	0.053*
H1SB	0.795	0.2595	1.0144	0.053*
H1SC	0.809	0.3413	1.0043	0.053*
C2S	0.7135 (3)	0.29509 (14)	0.8939 (2)	0.0330 (7)
N2S	0.7183 (3)	0.47851 (14)	0.89707 (18)	0.0415 (7)
C3S	0.5671 (3)	0.45689 (15)	0.74402 (18)	0.0305 (6)
H3SA	0.6178	0.4728	0.6959	0.046*
H3SB	0.4785	0.4821	0.7413	0.046*
H3SC	0.548	0.4074	0.737	0.046*
C4S	0.6518 (3)	0.46939 (14)	0.8301 (2)	0.0280 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.01241 (14)	0.01349 (15)	0.01014 (14)	−0.00022 (12)	0.00168 (11)	0.00088 (11)
Cl1	0.0181 (3)	0.0237 (3)	0.0137 (3)	0.0007 (2)	0.0057 (2)	0.0023 (2)
Cl2	0.0159 (3)	0.0219 (3)	0.0144 (3)	0.0019 (2)	0.0001 (2)	0.0022 (2)
Cl3	0.0206 (3)	0.0155 (3)	0.0184 (3)	−0.0018 (2)	0.0024 (2)	−0.0012 (2)
As1	0.01339 (11)	0.01436 (12)	0.01258 (11)	−0.00053 (9)	0.00148 (8)	−0.00037 (9)
C1	0.0124 (11)	0.0194 (12)	0.0154 (11)	−0.0027 (9)	0.0017 (9)	−0.0023 (9)
C2	0.0197 (12)	0.0192 (12)	0.0162 (11)	0.0001 (10)	0.0027 (9)	0.0001 (9)
C3	0.0200 (13)	0.0240 (14)	0.0261 (14)	0.0018 (10)	0.0033 (10)	−0.0049 (11)
C4	0.0204 (13)	0.0368 (16)	0.0222 (13)	−0.0031 (11)	0.0073 (10)	−0.0072 (11)
C5	0.0269 (14)	0.0305 (15)	0.0215 (13)	−0.0052 (11)	0.0099 (11)	0.0016 (11)
C6	0.0220 (13)	0.0214 (13)	0.0216 (13)	−0.0004 (10)	0.0045 (10)	0.0028 (10)
C7	0.0148 (11)	0.0139 (11)	0.0192 (12)	0.0002 (9)	0.0020 (9)	0.0029 (9)
C8	0.0212 (12)	0.0210 (13)	0.0165 (12)	0.0000 (10)	0.0007 (10)	−0.0006 (10)
C9	0.0225 (13)	0.0231 (13)	0.0196 (12)	−0.0028 (10)	−0.0037 (10)	0.0026 (10)
C10	0.0187 (12)	0.0236 (14)	0.0266 (14)	0.0025 (10)	0.0001 (10)	0.0078 (11)
C11	0.0199 (12)	0.0193 (13)	0.0291 (14)	0.0055 (10)	0.0058 (10)	0.0041 (10)
C12	0.0225 (12)	0.0183 (12)	0.0167 (12)	0.0011 (10)	0.0017 (9)	0.0015 (9)
C13	0.0170 (11)	0.0161 (12)	0.0144 (11)	0.0038 (9)	−0.0014 (9)	−0.0030 (9)
C14	0.0195 (12)	0.0190 (13)	0.0298 (14)	0.0039 (10)	−0.0008 (10)	−0.0040 (11)
C15	0.0224 (14)	0.0228 (14)	0.0421 (17)	0.0045 (11)	−0.0087 (12)	−0.0096 (12)
C16	0.0381 (16)	0.0250 (15)	0.0280 (15)	0.0125 (12)	−0.0122 (12)	−0.0131 (11)
C17	0.0375 (16)	0.0278 (15)	0.0186 (13)	0.0133 (12)	−0.0018 (11)	−0.0057 (11)
C18	0.0273 (13)	0.0207 (13)	0.0179 (12)	0.0070 (11)	0.0030 (10)	−0.0008 (10)
C19	0.0160 (11)	0.0144 (11)	0.0165 (11)	−0.0006 (9)	0.0066 (9)	−0.0001 (9)
C20	0.0192 (12)	0.0228 (13)	0.0208 (12)	0.0021 (10)	0.0050 (10)	0.0022 (10)
C21	0.0321 (15)	0.0228 (14)	0.0271 (14)	0.0069 (11)	0.0136 (12)	0.0049 (11)
C22	0.0325 (15)	0.0152 (12)	0.0328 (15)	−0.0029 (11)	0.0179 (12)	−0.0002 (11)
C23	0.0238 (13)	0.0256 (14)	0.0309 (15)	−0.0070 (11)	0.0123 (11)	−0.0045 (11)
C24	0.0184 (12)	0.0216 (13)	0.0215 (12)	−0.0014 (10)	0.0052 (10)	−0.0021 (10)
N1S	0.0466 (17)	0.0337 (16)	0.061 (2)	0.0065 (13)	−0.0098 (15)	−0.0145 (14)
C1S	0.0304 (16)	0.0303 (16)	0.0450 (18)	−0.0015 (13)	0.0039 (13)	0.0032 (13)
C2S	0.0276 (15)	0.0175 (14)	0.054 (2)	0.0013 (11)	0.0074 (14)	−0.0045 (13)
N2S	0.0434 (16)	0.0390 (16)	0.0414 (16)	0.0038 (13)	0.0033 (13)	−0.0101 (13)
C3S	0.0279 (15)	0.0349 (16)	0.0305 (15)	0.0030 (12)	0.0096 (12)	0.0035 (12)
C4S	0.0275 (15)	0.0237 (14)	0.0354 (16)	0.0033 (11)	0.0133 (13)	−0.0013 (12)

Geometric parameters (Å, º) top

Zr1—Cl2	2.4586 (6)	C13—C14	1.385 (3)
Zr1—Cl2ⁱ	2.4587 (6)	C13—C18	1.393 (3)
Zr1—Cl3	2.4723 (6)	C14—C15	1.397 (4)
Zr1—Cl3ⁱ	2.4724 (6)	C14—H14	0.95
Zr1—Cl1ⁱ	2.4818 (6)	C15—C16	1.385 (4)
Zr1—Cl1	2.4818 (5)	C15—H15	0.95
As1—C7	1.906 (2)	C16—C17	1.374 (4)
As1—C1	1.911 (2)	C16—H16	0.95
As1—C13	1.911 (2)	C17—C18	1.382 (4)
As1—C19	1.916 (2)	C17—H17	0.95
C1—C2	1.387 (3)	C18—H18	0.95
C1—C6	1.393 (3)	C19—C24	1.389 (3)
C2—C3	1.398 (3)	C19—C20	1.393 (3)
C2—H2	0.95	C20—C21	1.385 (3)
C3—C4	1.385 (4)	C20—H20	0.95
C3—H3	0.95	C21—C22	1.388 (4)
C4—C5	1.382 (4)	C21—H21	0.95
C4—H4	0.95	C22—C23	1.380 (4)
C5—C6	1.389 (3)	C22—H22	0.95
C5—H5	0.95	C23—C24	1.394 (3)
C6—H6	0.95	C23—H23	0.95
C7—C12	1.389 (3)	C24—H24	0.95
C7—C8	1.397 (3)	N1S—C2S	1.134 (4)
C8—C9	1.391 (3)	C1S—C2S	1.451 (4)
C8—H8	0.95	C1S—H1SA	0.98
C9—C10	1.384 (4)	C1S—H1SB	0.98
C9—H9	0.95	C1S—H1SC	0.98
C10—C11	1.386 (4)	N2S—C4S	1.135 (4)
C10—H10	0.95	C3S—C4S	1.459 (4)
C11—C12	1.391 (3)	C3S—H3SA	0.98
C11—H11	0.95	C3S—H3SB	0.98
C12—H12	0.95	C3S—H3SC	0.98

Cl2—Zr1—Cl2ⁱ	180.0	C7—C12—C11	119.2 (2)
Cl2—Zr1—Cl3	90.09 (2)	C7—C12—H12	120.4
Cl2ⁱ—Zr1—Cl3	89.91 (2)	C11—C12—H12	120.4
Cl2—Zr1—Cl3ⁱ	89.91 (2)	C14—C13—C18	121.1 (2)
Cl2ⁱ—Zr1—Cl3ⁱ	90.09 (2)	C14—C13—As1	119.17 (18)
Cl3—Zr1—Cl3ⁱ	180.00 (3)	C18—C13—As1	119.75 (18)
Cl2—Zr1—Cl1ⁱ	90.398 (19)	C13—C14—C15	119.0 (3)
Cl2ⁱ—Zr1—Cl1ⁱ	89.602 (19)	C13—C14—H14	120.5
Cl3—Zr1—Cl1ⁱ	89.703 (19)	C15—C14—H14	120.5
Cl3ⁱ—Zr1—Cl1ⁱ	90.296 (19)	C16—C15—C14	119.8 (3)
Cl2—Zr1—Cl1	89.603 (19)	C16—C15—H15	120.1
Cl2ⁱ—Zr1—Cl1	90.397 (19)	C14—C15—H15	120.1
Cl3—Zr1—Cl1	90.298 (19)	C17—C16—C15	120.6 (2)
Cl3ⁱ—Zr1—Cl1	89.703 (19)	C17—C16—H16	119.7
Cl1ⁱ—Zr1—Cl1	180.0	C15—C16—H16	119.7
C7—As1—C1	110.95 (10)	C16—C17—C18	120.4 (3)
C7—As1—C13	110.73 (10)	C16—C17—H17	119.8
C1—As1—C13	107.65 (10)	C18—C17—H17	119.8
C7—As1—C19	107.83 (10)	C17—C18—C13	119.1 (3)
C1—As1—C19	111.76 (10)	C17—C18—H18	120.5
C13—As1—C19	107.89 (10)	C13—C18—H18	120.5
C2—C1—C6	121.3 (2)	C24—C19—C20	121.1 (2)
C2—C1—As1	118.72 (18)	C24—C19—As1	119.04 (18)
C6—C1—As1	119.64 (18)	C20—C19—As1	119.80 (18)
C1—C2—C3	118.9 (2)	C21—C20—C19	118.9 (2)
C1—C2—H2	120.6	C21—C20—H20	120.6
C3—C2—H2	120.6	C19—C20—H20	120.6
C4—C3—C2	119.8 (2)	C20—C21—C22	120.6 (2)
C4—C3—H3	120.1	C20—C21—H21	119.7
C2—C3—H3	120.1	C22—C21—H21	119.7
C5—C4—C3	120.9 (2)	C23—C22—C21	120.1 (2)
C5—C4—H4	119.5	C23—C22—H22	120.0
C3—C4—H4	119.5	C21—C22—H22	120.0
C4—C5—C6	119.9 (2)	C22—C23—C24	120.4 (2)
C4—C5—H5	120.1	C22—C23—H23	119.8
C6—C5—H5	120.1	C24—C23—H23	119.8
C5—C6—C1	119.1 (2)	C19—C24—C23	119.0 (2)
C5—C6—H6	120.4	C19—C24—H24	120.5
C1—C6—H6	120.4	C23—C24—H24	120.5
C12—C7—C8	121.0 (2)	C2S—C1S—H1SA	109.5
C12—C7—As1	119.35 (17)	C2S—C1S—H1SB	109.5
C8—C7—As1	119.40 (18)	H1SA—C1S—H1SB	109.5
C9—C8—C7	119.0 (2)	C2S—C1S—H1SC	109.5
C9—C8—H8	120.5	H1SA—C1S—H1SC	109.5
C7—C8—H8	120.5	H1SB—C1S—H1SC	109.5
C10—C9—C8	120.1 (2)	N1S—C2S—C1S	179.5 (4)
C10—C9—H9	119.9	C4S—C3S—H3SA	109.5
C8—C9—H9	119.9	C4S—C3S—H3SB	109.5
C9—C10—C11	120.6 (2)	H3SA—C3S—H3SB	109.5
C9—C10—H10	119.7	C4S—C3S—H3SC	109.5
C11—C10—H10	119.7	H3SA—C3S—H3SC	109.5
C10—C11—C12	120.1 (2)	H3SB—C3S—H3SC	109.5
C10—C11—H11	119.9	N2S—C4S—C3S	179.3 (3)
C12—C11—H11	119.9

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3S—H3SA···Cl1ⁱⁱ	0.98	2.81	3.674 (3)	148
C16—H16···Cl1ⁱⁱⁱ	0.95	2.73	3.646 (3)	162
C18—H18···N1Sⁱⁱⁱ	0.95	2.61	3.483 (4)	154

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

Acknowledgements

The authors thank Ms Julie Bertoia for laboratory support, Ms Wendee Johns for administrative support.

Funding information

This research was performed using funding received from the US Department of Energy, Office of Nuclear Energy's Nuclear Energy University Program (NEUP, DOE-NEUP award No. DE-NE0008449).

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