Single-crystal neutron diffraction study of β-Cs₃(HSO₄)₂[H_2−x(S_xP_1−x)O₄] (x ≃ 0.5) at 15 K

The structure of β-Cs₃(HSO₄)₂[H_2−x(S_xP_1−x)O₄] has been examined by single-crystal neutron diffraction at 15 K. The compound crystallizes in space group C2/c and contains four formula units in the unit cell, with lattice parameters a = 19.769 (9), b = 7.685 (2), c = 8.858 (3) Å and β = 100.60 (4)°. Refinement of P, S and H site occupancies indicated that the value of x (in the stoichiometry) is 0.500 (6). This, together with the unit-cell volume of 1322.8 (14) ų, implies a density of 3.463 Mg m⁻³. The structure contains zigzag rows of XO₄ anions, where X = P or S, that alternate, in a checkerboard fashion, with zigzag rows of Cs cations. Moreover, there is one proton site, H(3), with an occupancy of 0.25 and one X-atom site, X(1), that is occupied by 0.5 P and 0.5 S. These features are in general agreement with a previous X-ray structure determination carried out at 298 K. In contrast to the X-ray study, however, it was found that two different structural models adequately fit the diffraction data. In the first model, the proton vacancies and the P atoms were assumed to be randomly distributed over the H(3) and X(1) sites, respectively, and to have no impact on the local structure. In the second model, several atoms were assigned split occupancies over two neighboring sites, to reflect the presence or absence of a proton vacancy, and the presence of P or S on the X(1) site. Refinement assuming the first model, in which anisotropic displacement parameters for 12 of 14 atom sites in the asymmetric unit were employed, yielded residuals wR(F²) = 0.084 and wR(F) = 0.038. For the second model, in which anisotropic displacement parameters were utilized for only the five atoms that were not split relative to the first model, the residuals were wR(F²) = 0.081 and wR(F) = 0.036.

Computing details

For both compounds, program(s) used to solve structure: X-ray solution; program(s) used to refine structure: UPALS (Lundgren, 1982); molecular graphics: ATOMS (Dowty, 1997).

(Model1)

Crystal data

β^−Cs3(HSO4)2(H^2^−X(P^−X·SX)O4)	F(000) = 327.0304 fm
Mr = 689.9	Dx = 3.463 Mg m^−3
Monoclinic, C2/c	Neutron radiation, λ = 1.0462 (1) Å
Hall symbol: -C 2yc	Cell parameters from 32 reflections
a = 19.769 (9) Å	θ = 20–29.5°
b = 7.685 (2) Å	µ = 5.96 mm^−1
c = 8.858 (3) Å	T = 15 K
β = 100.60 (4)°	Plate-like (100) (010) (001), colorless
V = 1322.8 (14) Å^3	3.2 × 2.2 × 1.4 mm
Z = 4

Data collection

Radiation source: H6M port, High Flux Beam Reactor, Brookhaven Nat. Lab.	Rint = 0.035 (F^2)
Be (002) monochromator	θmax = 54°, θmin = 3°
ω–2θ scan (McMullan, Epstein, Ruble & Craven, 1979)	h = 0→30
Absorption correction: analytical	k = 0→11
Tmin = 0.870, Tmax = 0.925	l = −13→13
2858 (assuming C-centering) measured reflections	Standard reflections: 2 (-4, -4, -4,), (4, 0, -8);
2570 independent reflections	intensity decay: stable, no correction
1475 reflections with I > 3σ

Refinement

Refinement on F^2	104 parameters
R[F^2 > 2σ(F^2)] = 0.054F>3σ (F), 1475 reflections	w = 1/σ^2
wR(F^2) = 0.038	(Δ/σ)max < 0.1
S = 1.30	Δρmax = 4.5% of Cs (2) e Å^−3
2568 reflections	Δρmin = 3.0% of Cs (2) e Å^−3

Special details

Experimental. Crystal mounted on aluminium pin with halocarbon grease

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cs(1)	0.5	0.4015 (2)	0.25	0.0088 (7)
Cs(2)	0.3228 (1)	0.1375 (2)	0.3817 (2)	0.0065 (5)
P/S(1)	0.5	0.9050 (3)	0.25	0.0114 (9)
O(1)	0.5266 (1)	0.0191 (1)	0.1356 (1)	0.0121 (4)
O(2)	0.4423 (1)	0.7946 (2)	0.1675 (1)	0.0186 (5)
S(2)	0.1584 (1)	0.1319 (3)	0.0692 (3)	0.0087 (8)
O(3)	0.1666 (1)	0.7651 (2)	0.7203 (1)	0.0121 (5)
O(4)	0.1014 (1)	0.9845 (2)	0.5606 (1)	0.0276 (6)
O(5)	0.2226 (1)	0.9574 (2)	0.5732 (2)	0.0193 (6)
O(6)	0.1449 (1)	0.7405 (2)	0.4441 (1)	0.0505 (9)
H(1)	0.5	0	0	0.0308 (16)
H(21)	0.1199 (2)	0.7476 (5)	0.7557 (4)	0.0246 (6)	0.698 (7)
H(22)	0.0949 (5)	0.7246 (11)	0.7829 (9)	0.0246 (6)	0.302 (7)
H(3)	0.2080 (4)	0.6885 (11)	0.4516 (8)	0.022 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs(1)	0.0088 (7)	0.0076 (7)	0.0112 (7)	0	−0.0006 (5)	0
Cs(2)	0.0065 (5)	0.0110 (5)	0.0399 (8)	0.0011 (4)	−0.0009 (5)	−0.0083 (5)
P/S(1)	0.0114 (9)	0.0053 (8)	0.0030 (7)	0	0.0004 (7)	0
O(1)	0.0121 (4)	0.0095 (4)	0.0084 (4)	−0.0029 (4)	0.0006 (3)	−0.0010 (4)
O(2)	0.0186 (5)	0.0095 (5)	0.0095 (4)	−0.0052 (4)	0.0002 (4)	−0.0009 (4)
S(2)	0.0087 (8)	0.0089 (9)	0.0137 (9)	0.0035 (8)	0.0018 (7)	−0.0004 (8)
O(3)	0.0121 (5)	0.0138 (5)	0.0076 (4)	−0.0034 (4)	−0.0009 (3)	0.0024 (4)
O(4)	0.0276 (6)	0.0265 (7)	0.0129 (5)	0.0127 (6)	0.0021 (5)	0.0042 (5)
O(5)	0.0193 (6)	0.0416 (9)	0.0320 (7)	−0.0198 (6)	−0.0073 (5)	0.0221 (7)
O(6)	0.0505 (9)	0.0130 (5)	0.0095 (4)	0.0073 (6)	0.0003 (5)	−0.0022 (4)
H(1)	0.0308 (16)	0.0223 (15)	0.0418 (17)	0	0.0167 (14)	0
H(3)	0.022 (4)	0.017 (3)	0.015 (3)	−0.002 (3)	0.005 (3)	0.005 (3)

Bond lengths (Å)

Cs(1)—O(4)	2.972 (2)	Cs(2)—O(2)	3.172 (2)
Cs(1)—O(4)	3.156 (1)	Cs(2)—O(6)	3.170 (2)
Cs(1)—O(1)	3.183 (2)	Cs(2)—O(3)	3.241 (2)
Cs(1)—O(2)	3.264 (2)	Cs(2)—O(4)	3.266 (2)
Cs(1)—O(6)	3.298 (2)	Cs(2)—O(5)	3.284 (2)
Cs(2)—O(1)	3.144 (2)	Cs(2)—O(3)	3.242 (2)
Cs(2)—O(5)	3.152 (2)	Cs(2)—O(6)	3.297 (2)
Cs(2)—O(5)	3.155 (2)

(Model2)

Crystal data

β^−Cs3(HSO4)2(H^2^−X(P^−X·SX)O4)	F(000) = 327.0304 fm
Mr = 689.9	Dx = 3.463 Mg m^−3
Monoclinic, C2/c	Neutron radiation, λ = 1.0462 (1) Å
Hall symbol: -C 2yc	Cell parameters from 32 reflections
a = 19.769 (9) Å	θ = 20–29.5°
b = 7.685 (2) Å	µ = 5.96 mm^−1
c = 8.858 (3) Å	T = 15 K
β = 100.60 (4)°	Plate-like (100) (010) (001), colorless
V = 1322.8 (14) Å^3	3.2 × 2.2 × 1.4 mm
Z = 4

Data collection

Radiation source: H6M port, High Flux Beam Reactor, Brookhaven Nat. Lab.	Rint = 0.035 (F^2)
Be (002) monochromator	θmax = 54°, θmin = 3°
ω–2θ scan (McMullan, Epstein, Ruble & Craven, 1979)	h = 0→30
Absorption correction: analytical	k = 0→11
Tmin = 0.870, Tmax = 0.925	l = −13→13
2858 (assuming C-centering) measured reflections	Standard reflections: 2 (-4, -4, -4,), (4, 0, -8);
2570 independent reflections	intensity decay: stable, no correction
1475 reflections with I > 3σ

Refinement

Refinement on F^2	97 parameters
R[F^2 > 2σ(F^2)] = 0.052 [F>3σ (F), 1475 reflections]	w = 1/σ^2
wR(F^2) = 0.036	(Δ/σ)max < 0.1
S = 1.25	Δρmax = 3.7% of Cs (2) e Å^−3
2568 reflections	Δρmin = 3.4% of Cs (2) e Å^−3

Special details

Experimental. Crystal mounted on aluminium pin with halocarbon grease

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cs(1)	0.5000	0.4013 (2)	0.2500	0.0081 (7)
Cs(21)	0.3221 (1)	0.1326 (4)	0.4006 (3)	0.0093 (6)	0.5
Cs(22)	0.3233 (1)	0.1423 (3)	0.3645 (3)	0.0070 (5)	0.5
P/S(1)	0.5000	0.9051 (3)	0.2500	0.0113 (9)
O(1)	0.5266 (1)	0.0192 (1)	0.1357 (1)	0.0117 (4)
O(21)	0.4471 (2)	0.7894 (5)	0.1661 (4)	0.0078 (8)	0.5
O(22)	0.4373 (2)	0.7999 (5)	0.1690 (4)	0.0092 (9)	0.5
S(21)	0.1585 (5)	0.1328 (14)	0.0628 (11)	0.006 (3)	0.5
O(31)	0.1692 (2)	0.7559 (5)	0.7167 (4)	0.0070 (9)	0.5
O(41)	0.1069 (2)	0.9976 (4)	0.5618 (3)	0.0129 (6)	0.5
O(51)	0.2264 (1)	0.9388 (4)	0.5604 (3)	0.0121 (5)	0.5
O(61)	0.1375 (1)	0.7368 (3)	0.4449 (2)	0.0040 (4)	0.5
S(22)	0.1583 (6)	0.1306 (16)	0.0767 (12)	0.012 (3)	0.5
O(32)	0.1640 (2)	0.7747 (5)	0.7238 (4)	0.0085 (9)	0.5
O(42)	0.0956 (2)	0.9707 (4)	0.5591 (3)	0.0144 (7)	0.5
O(52)	0.2185 (1)	0.9773 (4)	0.5867 (3)	0.0130 (5)	0.5
O(62)	0.1560 (2)	0.7459 (4)	0.4432 (3)	0.0189 (6)	0.5
H(1)	0.5000	0.0000	0.0000	0.028 (2)
H(21)	0.1195 (2)	0.7474 (4)	0.7560 (3)	0.0266 (6)	0.75
H(22)	0.0936 (5)	0.7230 (11)	0.7833 (9)	0.0180 (14)	0.25
H(3)	0.2080 (4)	0.6882 (11)	0.4505 (8)	0.022 (4)	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs(1)	0.0081 (7)	0.0074 (6)	0.0114 (6)	0	−0.0009 (5)	0
P/S(1)	0.0113 (9)	0.0048 (8)	0.0024 (7)	0	0.0001 (7)	0
O(1)	0.0117 (4)	0.0097 (4)	0.0080 (4)	−0.0028 (4)	0.0004 (3)	−0.0010 (3)
H(1)	0.028 (2)	0.021 (2)	0.043 (2)	0	0.015 (1)	0
H(3)	0.022 (4)	0.018 (3)	0.014 (3)	0.004 (3)	0.003 (3)	−0.002 (3)

Bond lengths (Å)

Cs(1)—O(41)	3.023 (3)	Cs(1')—O(42)	2.928 (4)
Cs(1)—O(41)	3.239 (3)	Cs(1')—O(42)	3.074 (3)
Cs(1)—O(1b)	3.182 (2)	Cs(1')—O(1a)	3.182 (2)
Cs(1)—O(21)	3.202 (4)	Cs(1')—O(22)	3.333 (4)
Cs(1)—O(61)	3.200 (2)	Cs(1')—O(62)	3.453 (3)
Cs(22)—O(1b)	3.115 (3)	Cs(21)—O(1a)	3.187 (3)
Cs(22)—O(52)	3.052 (4)	Cs(21)—O(51)	2.965 (4)
Cs(22)—O(51)	3.466 (4)	Cs(21)—O(52)	3.111 (4)
Cs(22)—O(21)	3.317 (4)	Cs(21)—O(22)	3.019 (4)
Cs(22)—O(61)	3.070 (4)	Cs(21)—O(62)	3.216 (4)
Cs(22)—O(31)	3.153 (5)	Cs(21)—O(32)	3.346 (5)
Cs(22)—O(41)	3.108 (4)	Cs(21)—O(42)	3.443 (4)
Cs(22)—O(52)	3.352 (4)	Cs(21)—O(51)	3.296 (4)
Cs(22)—O(32)	3.230 (4)	Cs(21)—O(32)	3.464 (5)
Cs(22)—O(61)	3.385 (3)	Cs(21)—O(62)	3.272 (4)