Poly[bis­(O-ethyl­hydroxy­laminium) [di-μ-chlorido-di­chlorido­cadmate(II)]]

Tong, Y.-Q.; Lei, Z.-Q.; Huang, B.

doi:10.1107/S2414314623008982

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 10| October 2023| x230898

https://doi.org/10.1107/S2414314623008982

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Poly[bis(O-ethylhydroxylaminium) [di-μ-chlorido-dichloridocadmate(II)]]

Yu-Qiao Tong,^a Zi-Qiong Lei ^a and Bo Huang ^a ^*

^aFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming, 650050, People's Republic of China
^*Correspondence e-mail: huangbo@ynnu.edu.cn

Edited by M. Weil, Vienna University of Technology, Austria (Received 13 September 2023; accepted 13 October 2023; online 19 October 2023)

The title compound, {(CH₃CH₂ONH₃)₂[CdCl₄]}_n, consists of bilayers of organic CH₃CH₂ONH₃⁺ cations and infinite [CdCl₄]_n²ⁿ⁻ inorganic layers. It can be described as an organic–inorganic hybrid layered perovskite. In the crystal structure, the Cd^II cation is situated at an inversion center and is coordinated by six chloride ions, forming a slightly distorted octahedral coordination polyhedron. By corner-sharing of the [CdCl₆] octahedra, infinite [CdCl₄]_n²ⁿ⁻ inorganic layers are formed, extending parallel to (100). The inorganic layers alternate with bilayers of CH₃CH₂ONH₃⁺ cations, whereby the connection of the cationic and anionic layers is achieved through N—H⋯Cl hydrogen bonds and Coulombic interactions.

Keywords: crystal structure; O-ethylhydroxylammonium; organic-inorganic hybrid; layered perovskite.

CCDC reference: 2301057

Structure description

As a class of molecular materials with the advantages of low density, mechanical flexibility, and being easy to process into thin films, organic–inorganic hybrid layered perovskite compounds have attracted a lot of attention on account of their outstanding ferroelectric, multiferroic, and semiconducting performance (Huang et al., 2018 ). However, it is hard to predict and design advanced materials with specific performance. One reason is the lack of understanding as to why a particular crystal structure forms (Sun et al., 2020 ). In this regard, it is fundamentally important to search for and study new examples of such organic–inorganic hybrid layered perovskite compounds (Yang et al., 2022 ). Herein, we report the synthesis and crystal structure of the title compound, (CH₃CH₂ONH₃)⁺₂[CdCl₄]^2–, based on O-ethylhydroxylammonium cations and tetrachloridocadmate anions.

The asymmetric unit contains one Cd^II cation, two chloride anions and one O-ethylhydroxylammonium cation. The Cd^II cation is situated at an inversion center (Wyckoff site b) and is distorted octahedrally coordinated by six chloride anions (Fig. 1). Two medium and two long equatorial Cd—Cl1 bonds [2.6798 (5) and 2.7416 (5) Å, respectively], and two shorter axial Cd—Cl2 bonds [2.5384 (5) Å] are present.

Figure 1
A part of the crystal structure of the title compound showing the coordination around the Cd^II cation, and the N—H⋯Cl hydrogen-bonding interactions (dotted lines) between the cation and the anionic layer. Displacement ellipsoids are drawn at the 50% probability level.

The structure of the title compound can be described as an organic–inorganic hybrid layered perovskite with general formula A₂MX₄ (A = monovalent organic cation, M = divalent metal cation, X = halide anion). By corner-sharing of the [CdCl₆] octahedra, infinite inorganic [CdCl₄]_n²ⁿ⁻ layers are formed, extending parallel to (100) (Fig. 2). Neighboring inorganic layers alternate with bilayers of organic CH₃CH₂ONH₃⁺ cations along [100] (Fig. 3). The CH₃CH₂ONH₃⁺ cation is N—H⋯Cl hydrogen-bonded to three [CdCl₆] octahedra with two hydrogen bonds to the axial Cl ligand, and one hydrogen bond to an equatorial ligand (Fig. 1, Table 1). The cohesion between the inverted cations in the organic bilayer is achieved through van der Waals forces.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.89	2.38	3.259 (2)	169
N1—H1B⋯Cl2ⁱ	0.89	2.31	3.1810 (18)	167
N1—H1C⋯Cl2ⁱⁱ	0.89	2.34	3.166 (2)	155
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (ii) .

Figure 2
The organic cations and the anionic [CdCl₄]^2– layer (polyhedral representation) in the title compound, in a view along [100].

Figure 3
The stacking of (100) layers of organic cations in bilayers and anionic [CdCl₄]^2– layers (polyhedral representation) along [100], in a view along [010].

Synthesis and crystallization

An aqueous solution (15 ml) containing stoichiometric quantities of O-ethylhydroxylammonium (5 mmol), CdCl₂ (2.5 mmol), and hydrochloric acid (5 mmol) was stirred for 15 min. The clear solution was allowed to stand at room temperature for slow evaporation. About one week later, colorless, plate-shaped crystals of (CH₃CH₂ONH₃)₂[CdCl₄] were obtained in about 83% yield based on Cd.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	(C₂H₈NO)₂[CdCl₄]
M_r	378.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	11.7058 (8), 7.2365 (5), 7.6864 (5)
β (°)	96.374 (2)
V (Å³)	647.08 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	2.49
Crystal size (mm)	0.30 × 0.30 × 0.10

Data collection
Diffractometer	Oxford Diffraction, Xcalibur, Eos, Gemini CCD
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.450, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6115, 1462, 1401
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.054, 1.07
No. of reflections	1462
No. of parameters	63
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.39, −0.86
Computer programs: CrysAlis PRO (Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2301057

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314623008982/wm4199sup1.cif

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2019); cell refinement: CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[bis(O-ethylhydroxylaminium) [di-µ-chlorido-dichloridocadmate(II)]] top

Crystal data top

(C₂H₈NO)₂[CdCl₄]	F(000) = 372
M_r = 378.39	D_x = 1.942 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7058 (8) Å	Cell parameters from 6460 reflections
b = 7.2365 (5) Å	θ = 3.3–27.5°
c = 7.6864 (5) Å	µ = 2.49 mm⁻¹
β = 96.374 (2)°	T = 150 K
V = 647.08 (8) Å³	Plate, colourless
Z = 2	0.30 × 0.30 × 0.10 mm

Data collection top

Oxford Diffraction, Xcalibur, Eos, Gemini CCD diffractometer	1401 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω scans	θ_max = 27.4°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	h = −15→15
T_min = 0.450, T_max = 1.000	k = −9→9
6115 measured reflections	l = −9→9
1462 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0147P)² + 0.3935P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1462 reflections	Δρ_max = 1.39 e Å⁻³
63 parameters	Δρ_min = −0.86 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.

Refinement. All H atoms were generated by geometrical considerations and constrained to their idealized positions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.500000	0.000000	1.000000	0.01349 (9)
Cl1	0.47138 (4)	0.20056 (6)	1.29465 (6)	0.01647 (12)
Cl2	0.71450 (4)	0.05786 (7)	1.06269 (6)	0.01747 (12)
O1	0.18746 (12)	0.0684 (2)	1.49656 (18)	0.0207 (3)
N1	0.29792 (17)	−0.0137 (2)	1.5301 (3)	0.0197 (4)
H1A	0.348789	0.053052	1.479307	0.024*
H1B	0.295778	−0.127949	1.486972	0.024*
H1C	0.318415	−0.017670	1.645068	0.024*
C1	0.15465 (18)	0.0791 (3)	1.3096 (3)	0.0221 (4)
H1D	0.147058	−0.043642	1.258934	0.026*
H1E	0.211707	0.147040	1.253094	0.026*
C2	0.04102 (19)	0.1784 (4)	1.2877 (3)	0.0285 (5)
H2A	0.014672	0.189435	1.165319	0.043*
H2B	0.050075	0.299323	1.338706	0.043*
H2C	−0.014190	0.109786	1.345010	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01489 (13)	0.01250 (14)	0.01301 (13)	−0.00030 (6)	0.00125 (9)	0.00052 (6)
Cl1	0.0192 (2)	0.0145 (2)	0.0160 (2)	−0.00024 (16)	0.00327 (18)	−0.00387 (16)
Cl2	0.0156 (2)	0.0190 (3)	0.0181 (2)	−0.00023 (17)	0.00301 (18)	0.00076 (18)
O1	0.0193 (7)	0.0255 (8)	0.0173 (7)	0.0078 (6)	0.0025 (6)	0.0020 (6)
N1	0.0178 (9)	0.0196 (10)	0.0215 (10)	0.0015 (6)	0.0009 (8)	0.0016 (6)
C1	0.0234 (10)	0.0272 (12)	0.0155 (10)	−0.0014 (8)	0.0016 (8)	0.0021 (8)
C2	0.0238 (11)	0.0329 (13)	0.0279 (11)	0.0026 (9)	−0.0006 (9)	0.0074 (9)

Geometric parameters (Å, º) top

Cd1—Cl1ⁱ	2.6798 (5)	N1—H1B	0.8900
Cd1—Cl1	2.7416 (5)	N1—H1C	0.8900
Cd1—Cl1ⁱⁱ	2.7416 (5)	C1—H1D	0.9700
Cd1—Cl1ⁱⁱⁱ	2.6798 (5)	C1—H1E	0.9700
Cd1—Cl2ⁱⁱ	2.5384 (5)	C1—C2	1.505 (3)
Cd1—Cl2	2.5384 (5)	C2—H2A	0.9600
O1—N1	1.420 (2)	C2—H2B	0.9600
O1—C1	1.448 (2)	C2—H2C	0.9600
N1—H1A	0.8900

Cl1ⁱ—Cd1—Cl1ⁱⁱⁱ	180.0	O1—N1—H1B	109.5
Cl1ⁱⁱ—Cd1—Cl1	180.0	O1—N1—H1C	109.5
Cl1ⁱⁱⁱ—Cd1—Cl1	87.722 (7)	H1A—N1—H1B	109.5
Cl1ⁱⁱⁱ—Cd1—Cl1ⁱⁱ	92.278 (7)	H1A—N1—H1C	109.5
Cl1ⁱ—Cd1—Cl1	92.279 (7)	H1B—N1—H1C	109.5
Cl1ⁱ—Cd1—Cl1ⁱⁱ	87.722 (7)	O1—C1—H1D	110.6
Cl2—Cd1—Cl1ⁱⁱ	92.012 (14)	O1—C1—H1E	110.6
Cl2ⁱⁱ—Cd1—Cl1ⁱ	88.007 (15)	O1—C1—C2	105.70 (17)
Cl2ⁱⁱ—Cd1—Cl1ⁱⁱⁱ	91.993 (15)	H1D—C1—H1E	108.7
Cl2ⁱⁱ—Cd1—Cl1ⁱⁱ	87.988 (14)	C2—C1—H1D	110.6
Cl2—Cd1—Cl1ⁱⁱⁱ	88.007 (15)	C2—C1—H1E	110.6
Cl2—Cd1—Cl1ⁱ	91.993 (15)	C1—C2—H2A	109.5
Cl2—Cd1—Cl1	87.988 (15)	C1—C2—H2B	109.5
Cl2ⁱⁱ—Cd1—Cl1	92.012 (15)	C1—C2—H2C	109.5
Cl2—Cd1—Cl2ⁱⁱ	180.00 (2)	H2A—C2—H2B	109.5
Cd1^iv—Cl1—Cd1	153.62 (2)	H2A—C2—H2C	109.5
N1—O1—C1	109.78 (15)	H2B—C2—H2C	109.5
O1—N1—H1A	109.5

N1—O1—C1—C2	−176.40 (17)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y, −z+2; (iii) −x+1, y−1/2, −z+5/2; (iv) −x+1, y+1/2, −z+5/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.89	2.38	3.259 (2)	169
N1—H1B···Cl2ⁱⁱⁱ	0.89	2.31	3.1810 (18)	167
N1—H1C···Cl2^v	0.89	2.34	3.166 (2)	155

Symmetry codes: (iii) −x+1, y−1/2, −z+5/2; (v) −x+1, −y, −z+3.

Funding information

Funding for this research was provided by: Science and Technology Planning Project of Yunnan Province (grant No. 202001AU070083).

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