Arsenic(III) oxide intercalate with ammonium chloride: crystal structure revision and thermal characterization

Wrześniewska, W.; Paluch, P.; Guńka, P.A.

doi:10.1107/S2052520623003086

Arsenic(III) oxide intercalate with ammonium chloride: crystal structure revision and thermal characterization

W. Wrześniewska, P. Paluch and P. A. Guńka

According to the crystal structure determination by Edstrand & Blomqvist [Ark. Kemi (1955), 8, 245–256], intercalate NH₄Cl·As₂O₃·0.5H₂O ( ${\bf Y_{{NH}_{4}Cl}}$ ) is not isostructural with compound KCl·As₂O₃·0.5H₂O. This is very unlikely because both NH₄Br·2As₂O₃ and KBr·2As₂O₃ as well as NH₄I·2As₂O₃ and KI·2As₂O₃ are isostructural. Hence, intercalate ${\bf Y_{{NH}_{4}Cl}}$ has been studied using single-crystal X-ray diffraction in addition to attenuated total reflection Fourier transform infrared (ATR-FTIR) and ¹⁵N solid-state magic-angle spinning nuclear magnetic resonance (ssNMR) spectroscopies. These techniques indicate that revising the previous crystal structure model is necessary. Compound ${\bf Y_{{NH}_{4}Cl}}$ crystallizes in space group P6/mmm with unit-cell parameters a = 5.25420 (10) Å and c = 12.6308 (3) Å and is isostructural with KCl·As₂O₃·0.5H₂O. The presence of two symmetry-independent ammonium cations in the structure has been unequivocally confirmed using ¹⁵N ssNMR spectroscopy. The ¹⁵N ssNMR spectrum of intercalate ${\bf Y_{{NH}_{4}Cl}}$ has been compared with analogous spectra of NH₄Br·2As₂O₃ and NH₄I·2As₂O₃ which allowed for a probable assignment of signals to ammonium cations occupying particular sites in the crystal structures. Thermogravimetry, differential scanning calorimetry and variable-temperature ATR-FTIR spectra have revealed that intercalate ${\bf Y_{{NH}_{4}Cl}}$ is dehydrated between 320 and 475 K. Upon cooling or standing in moist air water is re-absorbed. Dehydration leads to significant shortening of the c unit-cell parameter as revealed by powder X-ray diffraction [c = 12.1552 (7) Å at 293 K]. Compound ${\bf Y_{{NH}_{4}Cl}}$ decomposes on prolonged heating above 490 K to arsenic(III) oxide and ammonium chloride.

Keywords: arsenic(III) oxide; intercalates; solid-state NMR; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520623003086/xk5099sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520623003086/xk5099Isup2.hkl Contains datablock I
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520623003086/xk5099Isup4.rtv Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052520623003086/xk5099sup3.pdf Figs. S1, S2 and S3
	Link https://doi.org/10.5281/zenodo.7119208 raw experimental data including raw diffraction data

CCDC reference: 2202825

Computing details top

Data collection: CrysAlis PRO 1.171.42.88a (Rigaku OD, 2023); cell refinement: CrysAlis PRO 1.171.42.88a (Rigaku OD, 2023); data reduction: CrysAlis PRO 1.171.42.88a (Rigaku OD, 2023); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: SHELXL 2018/3 (Sheldrick, 2015); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

(I) top

Crystal data top

2(As₂O₃)·2(H₄N)·H₂O·2(Cl)	D_x = 2.863 Mg m⁻³
M_r = 520.68	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6/mmm	Cell parameters from 10181 reflections
a = 5.2542 (1) Å	θ = 4.5–32.3°
c = 12.6308 (3) Å	µ = 11.43 mm⁻¹
V = 301.98 (1) Å³	T = 293 K
Z = 1	Plate, colourless
F(000) = 246	0.16 × 0.13 × 0.03 mm

Data collection top

Xcalibur, Atlas, Gemini ultra diffractometer	282 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	275 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.083
Detector resolution: 10.3347 pixels mm^-1	θ_max = 32.8°, θ_min = 3.2°
ω scans	h = −7→7
Absorption correction: analytical CrysAlisPro 1.171.42.88a (Rigaku Oxford Diffraction, 2023) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)	k = −7→8
T_min = 0.258, T_max = 0.756	l = −19→18
16612 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.016	w = 1/[σ²(F_o²) + (0.0247P)² + 0.1074P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.042	(Δ/σ)_max < 0.001
S = 1.23	Δρ_max = 0.49 e Å⁻³
282 reflections	Δρ_min = −0.51 e Å⁻³
17 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.330 (12)
Primary atom site location: dual

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	Occ. (<1)
As1	0.333333	0.666667	0.21239 (2)	0.01091 (15)
O1	0.000000	0.500000	0.13663 (13)	0.0142 (3)
Cl2	0.000000	0.000000	0.32260 (11)	0.0274 (3)
N1	0.000000	0.000000	0.000000	0.0227 (11)
H1B	0.000000	0.000000	0.071341	0.034*	0.5
H1A	0.000000	0.161671	−0.023781	0.034*	0.25
O2	0.500000	0.000000	0.500000	0.089 (4)	0.3334
H2	0.351070	0.000000	0.456189	0.134*	0.1667
N2	0.500000	0.000000	0.500000	0.089 (4)	0.3334
H2A	0.359990	0.000000	0.458820	0.134*	0.1667
H2B	0.580840	0.161671	0.541181	0.134*	0.1667

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
As1	0.00866 (16)	0.00866 (16)	0.01542 (19)	0.00433 (8)	0.000	0.000
O1	0.0076 (7)	0.0138 (5)	0.0191 (7)	0.0038 (3)	0.000	0.000
Cl2	0.0251 (4)	0.0251 (4)	0.0322 (6)	0.01253 (18)	0.000	0.000
N1	0.0229 (16)	0.0229 (16)	0.022 (2)	0.0114 (8)	0.000	0.000
O2	0.147 (9)	0.056 (5)	0.034 (3)	0.028 (3)	0.000	0.000
N2	0.147 (9)	0.056 (5)	0.034 (3)	0.028 (3)	0.000	0.000

Geometric parameters (Å, º) top

As1—O1	1.7934 (9)	N1—H1A^xiii	0.9010 (1)
As1—O1ⁱ	1.7934 (9)	O2—H2	0.9584 (1)
As1—O1ⁱⁱ	1.7934 (9)	O2—H2A^xiv	0.9010 (1)
N1—H1B	0.9011 (1)	O2—H2A^xv	0.9010 (1)
N1—H1Bⁱⁱⁱ	0.9011 (1)	O2—H2A^xvi	0.9010 (1)
N1—H1A^iv	0.9010 (1)	O2—H2B^xvi	0.9010 (1)
N1—H1A^v	0.9010 (1)	O2—H2B^xiv	0.9010 (1)
N1—H1A	0.9010 (1)	O2—H2B^xv	0.9010 (1)
N1—H1A^vi	0.9010 (1)	N2—H2A^xv	0.9010 (1)
N1—H1A^vii	0.9010 (1)	N2—H2A^xiv	0.9010 (1)
N1—H1A^viii	0.9010 (1)	N2—H2A^xvi	0.9010 (1)
N1—H1A^ix	0.9010 (1)	N2—H2A	0.9010 (1)
N1—H1A^x	0.9010 (1)	N2—H2B^xiv	0.9010 (1)
N1—H1Aⁱⁱⁱ	0.9010 (1)	N2—H2B^xvi	0.9010 (1)
N1—H1A^xi	0.9010 (1)	N2—H2B	0.9010 (1)
N1—H1A^xii	0.9010 (1)	N2—H2B^xv	0.9010 (1)

O1—As1—O1ⁱⁱ	94.18 (6)	H1A^xii—N1—H1A^xi	123.8
O1ⁱⁱ—As1—O1ⁱ	94.18 (6)	H1A—N1—H1A^viii	123.750 (1)
O1—As1—O1ⁱ	94.18 (6)	H1A^ix—N1—H1A^xi	56.2
As1^xvii—O1—As1	115.50 (9)	H1Aⁱⁱⁱ—N1—H1A^viii	56.2
H1B—N1—H1Bⁱⁱⁱ	180.0	H1A^vii—N1—H1A^xi	141.051 (1)
H1Bⁱⁱⁱ—N1—H1A^viii	109.474 (1)	H1A^ix—N1—H1A^viii	141.051 (1)
H1B—N1—H1A^vi	70.526 (1)	H1A^vi—N1—H1A^xi	109.468 (1)
H1B—N1—H1A	109.474 (1)	H1A^vii—N1—H1A^viii	56.250 (1)
H1Bⁱⁱⁱ—N1—H1A^xiii	70.526 (1)	H1A^viii—N1—H1A^xi	109.468 (1)
H1Bⁱⁱⁱ—N1—H1A^x	70.526 (1)	H1A^vi—N1—H1A^viii	109.468 (1)
H1B—N1—H1A^vii	70.526 (1)	H1A^vii—N1—H1A^vi	56.250 (1)
H1B—N1—H1A^iv	109.474 (1)	H1A^xii—N1—H1A^v	109.468 (1)
H1Bⁱⁱⁱ—N1—H1A^xi	109.474 (1)	H1A^iv—N1—H1A^vi	180.0
H1B—N1—H1Aⁱⁱⁱ	70.526 (1)	H1A^ix—N1—H1A^v	70.532 (1)
H1Bⁱⁱⁱ—N1—H1A^vii	109.474 (1)	H1A^vii—N1—H1A^iv	123.750 (1)
H1Bⁱⁱⁱ—N1—H1Aⁱⁱⁱ	109.474 (1)	H1A^xii—N1—H1A^xiii	56.2
H1Bⁱⁱⁱ—N1—H1A^iv	70.526 (1)	H1A—N1—H1A^x	56.2
H1B—N1—H1A^xii	109.474 (1)	H1A^v—N1—H1A^xiii	141.051 (1)
H1B—N1—H1A^x	109.474 (1)	H1A—N1—H1A^v	109.5
H1Bⁱⁱⁱ—N1—H1A^xii	70.526 (1)	H1A^iv—N1—H1A^xiii	109.468 (1)
H1B—N1—H1A^viii	70.526 (1)	H1Aⁱⁱⁱ—N1—H1A^x	123.8
H1B—N1—H1A^ix	70.526 (1)	H1A^x—N1—H1A^xiii	109.468 (1)
H1B—N1—H1A^xiii	109.474 (1)	H1A^xii—N1—H1A^x	141.051 (1)
H1Bⁱⁱⁱ—N1—H1A^ix	109.474 (1)	H1A—N1—H1Aⁱⁱⁱ	180.0
H1B—N1—H1A^xi	70.526 (1)	H1A^ix—N1—H1A^x	38.949 (1)
H1B—N1—H1A^v	109.474 (1)	H1A—N1—H1A^vii	70.5
H1Bⁱⁱⁱ—N1—H1A^v	70.526 (1)	H1A^v—N1—H1A^x	56.250 (1)
H1Bⁱⁱⁱ—N1—H1A^vi	109.474 (1)	H1A—N1—H1A^ix	70.532 (1)
H1A—N1—H1Bⁱⁱⁱ	70.526 (1)	H1A^iv—N1—H1A^x	109.468 (1)
H1Aⁱⁱⁱ—N1—H1A^vii	109.468 (1)	H1A^v—N1—H1A^xi	38.949 (1)
H1A^vii—N1—H1A^xiii	38.949 (1)	H1Aⁱⁱⁱ—N1—H1A^vi	141.051 (1)
H1Aⁱⁱⁱ—N1—H1A^v	70.532 (1)	H1A^iv—N1—H1A^xi	70.532 (1)
H1A^xii—N1—H1A^vii	70.532 (1)	H1A^xii—N1—H1A^vi	123.8
H1A^ix—N1—H1A^vii	109.468 (1)	H1A^x—N1—H1A^xi	70.532 (1)
H1Aⁱⁱⁱ—N1—H1A^xi	56.250 (1)	H1A^ix—N1—H1A^vi	56.2
H1A^v—N1—H1A^vii	180.0	H1A^xiii—N1—H1A^xi	180.0
H1A^v—N1—H1A^viii	123.8	H1A^v—N1—H1A^vi	123.750 (1)
H1A—N1—H1A^xii	109.468 (1)	H1A^vii—N1—H1A^x	123.8
H1Aⁱⁱⁱ—N1—H1A^xiii	123.750 (1)	H2—O2—H2A^xv	180.0
H1A^x—N1—H1A^viii	180.0	H2—O2—H2A^xvi	109.468 (1)
H1A^viii—N1—H1A^xiii	70.532 (1)	H2—O2—H2A^xiv	70.532 (1)
H1Aⁱⁱⁱ—N1—H1A^ix	109.468 (1)	H2—O2—H2B^xv	70.525 (1)
H1Aⁱⁱⁱ—N1—H1A^xii	70.532 (1)	H2—O2—H2B^xiv	70.529 (1)
H1Aⁱⁱⁱ—N1—H1A^iv	38.949 (1)	H2—O2—H2B^xvi	109.471 (1)
H1A^xii—N1—H1A^viii	38.949 (1)	H2A^xv—O2—H2B^xiv	109.470 (1)
H1A^xii—N1—H1A^iv	56.2	H2A^xiv—O2—H2B^xiv	109.474 (1)
H1A^iv—N1—H1A^viii	70.532 (1)	H2A^xvi—O2—H2B^xiv	70.526 (1)
H1A^ix—N1—H1A^iv	123.8	H2B^xvi—O2—H2B^xiv	180.0
H1A—N1—H1A^iv	141.052 (1)	H2B^xv—O2—H2B^xiv	109.470 (2)
H1A^v—N1—H1A^iv	56.250 (1)	H2A—N2—H2B	109.471 (1)
H1A^ix—N1—H1A^xiii	123.8	H2A^xvi—N2—H2B^xiv	70.526 (1)
H1A—N1—H1A^xiii	56.2	H2A^xiv—N2—H2B^xiv	109.474 (1)
H1A^vi—N1—H1A^xiii	70.532 (1)	H2A—N2—H2B^xiv	70.532 (1)
H1A^xii—N1—H1A^ix	180.0	H2A^xv—N2—H2B^xiv	109.470 (1)
H1A—N1—H1A^xi	123.750 (1)	H2B^xvi—N2—H2B^xiv	180.0
H1A—N1—H1A^vi	38.948 (1)	H2B—N2—H2B^xiv	70.528 (1)
H1A^vi—N1—H1A^x	70.532 (1)	H2B^xv—N2—H2B^xiv	109.470 (2)

O1ⁱⁱ—As1—O1—As1^xvii	−132.75 (3)	O1ⁱ—As1—O1—As1^xvii	132.74 (3)

Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z; (iii) −x, −y, −z; (iv) −x, −y, z; (v) −x+y, −x, z; (vi) x, y, −z; (vii) x−y, x, −z; (viii) −y, x−y, −z; (ix) y, −x+y, −z; (x) y, −x+y, z; (xi) −x+y, −x, −z; (xii) −y, x−y, z; (xiii) x−y, x, z; (xiv) x, y, −z+1; (xv) −x+1, −y, −z+1; (xvi) −x+1, −y, z; (xvii) −x, −y+1, z.

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