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Acta Crystallographica Section E: Crystallographic Communications logoLink to Acta Crystallographica Section E: Crystallographic Communications
. 2023 Jul 7;79(Pt 8):702–706. doi: 10.1107/S2056989023005753

(NH4)2[UO2Cl4]·2H2O, a new uranyl tetra­chloride with ammonium charge-balancing cations

Tsuyoshi A Kohlgruber a, Robert G Surbella III a,*
Editor: S Parkinb
PMCID: PMC10439412  PMID: 37601403

While several actinyl tetra­halides have been synthesized and their structures reported, (NH4)2(UO2Cl4)·2H2O represents a new uranyl tetra­chloride salt synthesized in a slow evaporation from a 2 M hydro­chloric acid solution. Its optical properties were measured by diffuse reflectance and luminescence spectroscopies, while powder X-ray diffraction confirmed an ammonium chloride impurity phase.

Keywords: ammonium, optical properties, uranyl tetra­chloride, X-ray diffraction, crystal structure

Abstract

A new uranyl tetra­chloride salt with chemical formula, (NH4)2[UO2Cl4]·2H2O, namely, di­ammonium uranyl tetra­chloride dihydrate, 1, was prepared and crystallized via slow evaporation from a solution of 2 M hydro­chloric acid. As confirmed by powder X-ray diffraction, the title compound crystallizes with an ammonium chloride impurity that formed as a result of the breakdown of a triazine precursor. The (UO2Cl4)2− dianion is charge balanced by ammonium cations, while an extensive hydrogen-bond network donated from structural water mol­ecules stabilize the overall assembly. Compound 1 adds to the extensive collection of actinyl tetra­chloride salts, but it represents the first without an alkali cation for purely inorganic compounds. Diffuse reflectance and luminescence spectra show typical absorption and emission behavior, respectively, of uranyl materials.

1. Chemical context

Hexavalent actinides such as uranium, neptunium, and plutonium exist in aqueous solution as the linear triatomic actinyl cation, with formula (AnO2)2+. The actinyl ion coordinates a variety of poly- and mono-atomic anions such that four to six atoms bond in the equatorial plane (Burns, 2005 ▸; Lussier et al., 2016 ▸). In part due to their ease of synthesis, structural simplicity, and high symmetry, the actinyl tetra­halide family of compounds has remained a relevant subclass of materials over several decades and has led to a deeper understanding of actinide electronic structure, bonding, and optical properties, among many others. The actinyl tetra­halides have general formula (AnO2 X 4)2− (where An = UVI, NpVI, and PuVI and X = Cl− and Br−) and have been studied to investigate periodic trends in f-element chemistry. Of the numerous compounds that include this anionic complex, the Cs+ salt with formula Cs2(AnO2Cl4) has been one of the most extensively characterized actinyl compounds. The uranyl structure was first reported in 1966 (Hall et al., 1966 ▸) with an improved model reported in 1991 (Watkin et al., 1991 ▸). In that time, it was used to qu­anti­tatively assign infrared (Ohwada, 1975 ▸) and Raman (Ohwada, 1980 ▸) active bands of the uranyl ion, which were found to be at 916 cm−1 and 831 cm−1, respectively. Improvements in analytical (i.e. X-ray absorption spectroscopies) and computational techniques (i.e. density functional theory calculations) over time have advanced our understanding in the electronic and mol­ecular orbital energies of the uranyl ion in Cs2(UO2Cl4), providing strong evidence that actinide atoms can bind with significant covalent character (Denning, 2007 ▸; Vitova et al., 2015 ▸). Luminescence spectroscopy, Raman spectroscopy, and computational works have also been used to study bond-length changes of the uranyl ion with respect to different pressures in Cs2(UO2Cl4) (Osman et al., 2016 ▸; Warzecha et al., 2019 ▸). Beyond the Cs salt, systematic studies into actinyl bond strength changes as a function of metal center (i.e. An = UVI, NpVI and PuVI) have been reported for organic-based counter-cations (Schnaars & Wilson, 2013 ▸; Surbella III et al., 2017 ▸; Schnaars & Wilson, 2018 ▸). Quite recently, focus has been placed on the cationic influence on supra­molecular assembly as well as actinyl bond-strength changes (Schnaars & Wilson, 2013 ▸; Surbella III et al., 2016 ▸; Carter et al., 2018 ▸; Pyrch et al., 2020 ▸; Augustine et al., 2023 ▸). Despite these numerous studies with actinyl tetra­halide species, we report a new inorganic uranyl tetra­chloride not charge-balanced by an alkali cation, with formula (NH4)2(UO2Cl4)·2H2O (compound 1).

2. Structural commentary

Compound 1 crystallizes in the space group P Inline graphic . The uranyl tetra­chloride dianion (UO2Cl4)2− is composed of a UVI metal center that is coordinated to two terminal, axial oxygen atoms and four equatorial chlorine atoms as shown in Fig. 1 ▸. The (UO2Cl4)2− dianion adopts a square-bipyramidal coordination geometry with D 4h point group symmetry. The UVI atom sits on a center of inversion symmetry, resulting in a linear uranyl (UO2)2+ cation with a U1—O1 bond distance of 1.7745 (14) Å and O1—U1—O1 angle of 180°. The UVI atom is also coordinated to two crystallographically unique chlorine atoms with U1—Cl1 and U1—Cl2 bond distances of 2.6752 (5) Å and 2.6623 (4) Å, respectively. The two Cl1—U1—Cl2 bond angles measure 88.855 (15)° and 91.145 (15)°, and O1—U1—Cl1, bond angles also slightly deviate from 90°. The U—O (Lussier et al., 2016 ▸) and U—Cl (Surbella III et al., 2016 ▸) bond lengths are typical for these compounds. The structure contains one crystallographically unique structural water mol­ecule (O1w) with two O—H covalent bonds with restrained bond lengths near 0.95 Å, and one crystallographically unique ammonium cation (N1) is present to provide charge balance to the overall structure. There are four N—H covalent bonds with restrained bond lengths that are approximately 0.87 Å. The extended crystal structure is shown in Fig. 2 ▸.

Figure 1.

Figure 1

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The uranyl tetra­chloride anionic unit along with a crystallographically unique water mol­ecule and ammonium cation. Displacement ellipsoids for non-hydrogen atoms are shown at 50% probability.

Figure 2.

Figure 2

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The crystal packing observed in compound 1 as viewed along the a-axis.

3. Supra­molecular features

A hydrogen-bond network consisting of seven unique inter­actions exists between ammonium cations, water mol­ecules, and uranyl tetra­chloride units as depicted in Fig. 3 ▸ and as tabulated in Table 1 ▸. Each water mol­ecule donates two hydrogen bonds via H1A and H1B donor atoms to two separate uranyl tetra­chloride complexes. On the other hand, each ammonium cation donates hydrogen bonds in three dimensions to three separate uranyl tetra­chloride units and two separate water mol­ecules, stabilizing the overall crystal structure into a complex network. Fig. 4 ▸ shows the hydrogen-bond network in the extended structure.

Figure 3.

Figure 3

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The seven unique hydrogen-bond inter­actions shown with the hydrogen-bond distances from donor hydrogen atom to acceptor atom.

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1w—H1A⋯Cl1i 0.95 (6) 2.36 (7) 3.283 (2) 165 (7)
O1w—H1B⋯Cl2ii 0.95 (5) 2.35 (5) 3.268 (2) 163 (5)
N1—H2A⋯O1w 0.87 (3) 2.02 (3) 2.843 (2) 157 (3)
N1—H2B⋯Cl1iii 0.87 (4) 2.68 (4) 3.441 (2) 148 (3)
N1—H2C⋯O1 0.87 (2) 2.32 (4) 3.014 (3) 137 (4)
N1—H2C⋯Cl1iv 0.87 (2) 2.77 (3) 3.4060 (17) 131 (4)
N1—H2D⋯O1wv 0.87 (3) 2.03 (3) 2.887 (3) 169 (3)
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Symmetry codes: (i) Inline graphic ; (ii) Inline graphic ; (iii) Inline graphic ; (iv) Inline graphic ; (v) Inline graphic .

Figure 4.

Figure 4

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The crystal packing along with the hydrogen-bond network observed in compound 1 as viewed slightly offset along the a-axis.

4. Database survey

Compound 1 is the first inorganic uranyl tetra­chloride charge-balanced with a non-alkali metal in the Inorganic Crystal Structure Database (Zagorac et al., 2019 ▸). With respect to structures in the ICSD, Cs salts of the (AnO2Cl4)2− species have been reported for U (Hall et al., 1966 ▸; Watkin et al., 1991 ▸; Tutov et al., 1991 ▸; Schnaars & Wilson, 2013 ▸), Np (Wilkerson et al., 2007 ▸), and Pu (Wilkerson & Scott, 2008 ▸; Schnaars & Wilson, 2013 ▸). Other charge-balancing cations reported in the ICSD for UVI and PuVI include Rb (Anson et al., 1996 ▸; Schnaars & Wilson, 2013 ▸) and tetra­methyl­ammonium (Schnaars & Wilson, 2013 ▸), while that of Np includes (UO2Cl4)2−-doped NpVI (Wilkerson & Berg, 2009 ▸) and a mixed NpV/VI oxidation state Cs salt (Alcock et al., 1986 ▸). Although there is a tetra­methyl­ammonium salt in the ICSD, we consider it as a better member of the Crystal Structure Database (CSD) given the presence of organic-based (i.e. C—H bonds) components in the structure (Groom et al., 2016 ▸).

With respect to the CSD, there are numerous reports with ammonium-based charge-balancing species (Di Sipio et al., 1974 a ▸,b ▸; Bois et al., 1976 a ▸,b ▸; Rogers et al., 1987 ▸; Gatto et al., 2004 ▸; Schnaars & Wilson, 2013 ▸; Biswas et al., 2017 ▸; Serezkhina et al., 2021 ▸). Compound 1 has ammonium with a water mol­ecule, while one report has ammonium with crown ethers (Rogers et al., 1987 ▸). The other ammonium-based cations include organic-functional groups (Di Sipio et al., 1974 a ▸,b ▸; Bois et al., 1976 a ▸,b ▸; Gatto et al., 2004 ▸; Schnaars & Wilson, 2013 ▸; Biswas et al., 2017 ▸; Serezkhina et al., 2021 ▸). Other types of cations that charge-balance (UO2Cl4)2− in the CSD include pyridinium-based (Graziani et al., 1975 ▸; Bombieri et al., 1978 ▸; Marsh, 1988 ▸; Pospieszna et al., 2008 ▸; Deifel & Cahill, 2009 ▸; Baker et al., 2010 ▸; Andrews & Cahill, 2012 ▸; Lhoste et al., 2013 ▸; Hashem et al., 2013 ▸; Surbella III et al., 2016 ▸, 2017 ▸; Carter et al., 2018 ▸; Mishra et al., 2019 ▸; Pyrch et al., 2020 ▸), phenanthrolinium-based (Di Sipio et al., 1981 ▸), imidazolium-based (Zalkin et al., 1983 ▸; Qu et al., 2014 ▸; Kohlgruber, 2022 ▸), and phospho­nium-based (Brown et al., 1996 ▸; Schnaars & Wilson, 2014 ▸) species. Other (UO2Cl4)2− complexes have crystallized in the presence of separate metal complexes (Moody & Ryan, 1979 ▸; Rogers et al., 1987 ▸, 1990 ▸; Pons y Moll et al., 2001 ▸; Hashem et al., 2014 ▸; Falaise et al., 2015 ▸; Zhang et al., 2017 ▸; Schöne et al., 2018 ▸), crown ethers (Wang et al., 1986 ▸; Rogers et al., 1987 ▸, 1991 ▸; Rogers & Benning, 1991 ▸; Evans et al., 2002 ▸) and porphyrins (Mishra et al., 2019 ▸). In total, there are over 60 known uranyl tetra­chloride crystal structures in the CSD. Reference codes for these compounds can be found in the supporting information.

5. Synthesis and crystallization

Concentrated hydro­chloric acid, HCl, (Sigma-Aldrich, 37%) was diluted to 2 M. Then, 0.0366 g (0.44 mmol) of 1,3,5-triazine (Sigma-Aldrich, 97.0%) was dissolved into 1 mL of 2 M HCl in a 1-dram borosilicate glass reaction vial. Uranyl acetate dihydrate (0.10216 g; 2.4 mmol) was added to this solution and allowed to dissolve completely. The vial was placed uncapped in a 20 mL centrifuge tube on a bed of desiccant. The centrifuge tube was capped, and the reaction solution was allowed to evaporate for 3 weeks until large yellow crystals formed. It was noticed that compound 1 partially dissolves in ethanol, affecting the preparation for characterization beyond single-crystal X-ray diffraction. Powder-diffraction data was collected using a Rigaku Ultima IV Diffractometer with Cu Kα radiation and a linear position-sensitive detector. The analysis revealed an ammonium chloride, NH4Cl, impurity phase along with compound 1. Diffuse reflectance and luminescence spectra were also collected for the mixed-phase material and can be found in the supporting information along with the powder-diffraction data.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 2 ▸. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were found in Fourier difference maps, and their positions refined with positional restraints.

Table 2. Experimental details.

Crystal data
Chemical formula (NH4)2[UO2Cl4]·2H2O
M r 483.95
Crystal system, space group Triclinic, P Inline graphic
Temperature (K) 100
a, b, c (Å) 6.6574 (4), 6.6954 (4), 7.4018 (4)
α, β, γ (°) 99.827 (2), 93.879 (2), 117.354 (1)
V (Å3) 284.69 (3)
Z 1
Radiation type Mo Kα
μ (mm−1) 15.17
Crystal size (mm) 0.10 × 0.03 × 0.03
 
Data collection
Diffractometer Bruker D8 Venture
Absorption correction Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max 0.460, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections 24049, 2803, 2803
R int 0.042
(sin θ/λ)max (Å−1) 0.842
 
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S 0.017, 0.041, 1.09
No. of reflections 2803
No. of parameters 76
No. of restraints 12
H-atom treatment All H-atom parameters refined
Δρmax, Δρmin (e Å−3) 2.94, −1.97
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Computer programs: APEX4 and SAINT (Bruker, 2014 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL (Sheldrick, 2015b ▸), CrystalMaker (CrystalMaker, 2014 ▸), and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023005753/pk2687sup1.cif

e-79-00702-sup1.cif (696.8KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023005753/pk2687Isup2.hkl

e-79-00702-Isup2.hkl (224.1KB, hkl)
Click here for additional data file. (327KB, docx)

Thermal Ellipsoidal plots and data, (e.g., Powder X-ray diffraction, diffuse reflectance spectroscopy, and photo luminescence spectroscopy). DOI: 10.1107/S2056989023005753/pk2687sup3.docx

CCDC reference: 2278035

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

Acknowledgments

The authors thank Dr Aaron D. Nicholas for his feedback in preparing this manuscript.

supplementary crystallographic information

Crystal data

(NH4)2[UO2Cl4]·2H2O Z = 1
Mr = 483.95 F(000) = 218
Triclinic, P1 Dx = 2.823 Mg m−3
a = 6.6574 (4) Å Mo Kα radiation, λ = 0.71073 Å
b = 6.6954 (4) Å Cell parameters from 9764 reflections
c = 7.4018 (4) Å θ = 3.5–36.7°
α = 99.827 (2)° µ = 15.17 mm−1
β = 93.879 (2)° T = 100 K
γ = 117.354 (1)° Block, yellow
V = 284.69 (3) Å3 0.10 × 0.03 × 0.03 mm
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Data collection

Bruker D8 Venture diffractometer 2803 reflections with I > 2σ(I)
Radiation source: microsource Diamond II Rint = 0.042
φ and ω scans θmax = 36.8°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015) h = −11→11
Tmin = 0.460, Tmax = 0.747 k = −11→11
24049 measured reflections l = −12→12
2803 independent reflections
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Refinement

Refinement on F2 Primary atom site location: dual
Least-squares matrix: full Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.017 Hydrogen site location: difference Fourier map
wR(F2) = 0.041 All H-atom parameters refined
S = 1.09 w = 1/[σ2(Fo2) + (0.0306P)2] where P = (Fo2 + 2Fc2)/3
2803 reflections (Δ/σ)max = 0.001
76 parameters Δρmax = 2.94 e Å−3
12 restraints Δρmin = −1.97 e Å−3
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Special details

Geometry. All estimated standard deviations (esds), except those pertaining to the dihedral angle between two least squares (ls) planes, are estimated using the full covariance matrix. 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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
U1 0.500000 0.500000 0.500000 0.00924 (3)
Cl1 0.11039 (7) 0.32334 (9) 0.63968 (6) 0.01683 (7)
Cl2 0.27372 (8) 0.27569 (9) 0.15652 (6) 0.01779 (7)
O1 0.4614 (3) 0.7395 (3) 0.4746 (2) 0.0157 (2)
O1W 0.2602 (3) 0.7346 (3) 1.0758 (2) 0.0193 (2)
H1A 0.173 (10) 0.747 (13) 1.169 (7) 0.060 (19)*
H1B 0.253 (11) 0.589 (5) 1.071 (9) 0.048 (16)*
N1 0.2678 (3) 0.9378 (3) 0.7673 (2) 0.0165 (2)
H2A 0.227 (6) 0.850 (5) 0.846 (4) 0.028 (11)*
H2B 0.186 (5) 1.008 (6) 0.765 (5) 0.042 (14)*
H2C 0.247 (7) 0.855 (6) 0.657 (2) 0.042 (14)*
H2D 0.412 (2) 1.040 (5) 0.800 (5) 0.049 (16)*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
U1 0.01069 (4) 0.01103 (4) 0.00762 (4) 0.00584 (3) 0.00291 (2) 0.00367 (2)
Cl1 0.01357 (14) 0.02264 (19) 0.01467 (15) 0.00771 (14) 0.00622 (12) 0.00655 (14)
Cl2 0.01902 (16) 0.02084 (18) 0.01029 (14) 0.00814 (14) 0.00083 (12) 0.00047 (13)
O1 0.0210 (5) 0.0150 (5) 0.0159 (5) 0.0113 (5) 0.0057 (4) 0.0067 (4)
O1W 0.0189 (6) 0.0234 (7) 0.0175 (6) 0.0096 (5) 0.0063 (5) 0.0093 (5)
N1 0.0180 (6) 0.0189 (6) 0.0126 (5) 0.0085 (5) 0.0027 (5) 0.0045 (5)
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Geometric parameters (Å, º)

U1—O1 1.7745 (14) O1W—H1A 0.948 (10)
U1—O1i 1.7745 (14) O1W—H1B 0.947 (10)
U1—Cl2 2.6623 (4) N1—H2A 0.868 (9)
U1—Cl2i 2.6623 (4) N1—H2B 0.872 (9)
U1—Cl1 2.6752 (5) N1—H2C 0.870 (9)
U1—Cl1i 2.6752 (5) N1—H2D 0.871 (9)
O1—U1—O1i 180.0 O1i—U1—Cl1i 89.87 (5)
O1—U1—Cl2 90.32 (5) Cl2—U1—Cl1i 88.855 (15)
O1i—U1—Cl2 89.68 (5) Cl2i—U1—Cl1i 91.145 (15)
O1—U1—Cl2i 89.68 (5) Cl1—U1—Cl1i 180.000 (17)
O1i—U1—Cl2i 90.32 (5) H1A—O1W—H1B 104 (6)
Cl2—U1—Cl2i 180.000 (11) H2A—N1—H2B 109.7 (14)
O1—U1—Cl1 89.86 (5) H2A—N1—H2C 109.8 (14)
O1i—U1—Cl1 90.13 (5) H2B—N1—H2C 109.1 (14)
Cl2—U1—Cl1 91.145 (15) H2A—N1—H2D 109.7 (14)
Cl2i—U1—Cl1 88.855 (15) H2B—N1—H2D 109.1 (14)
O1—U1—Cl1i 90.14 (5) H2C—N1—H2D 109.5 (14)
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Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A
O1w—H1A···Cl1ii 0.95 (6) 2.36 (7) 3.283 (2) 165 (7)
O1w—H1B···Cl2iii 0.95 (5) 2.35 (5) 3.268 (2) 163 (5)
N1—H2A···O1w 0.87 (3) 2.02 (3) 2.843 (2) 157 (3)
N1—H2B···Cl1iv 0.87 (4) 2.68 (4) 3.441 (2) 148 (3)
N1—H2C···O1 0.87 (2) 2.32 (4) 3.014 (3) 137 (4)
N1—H2C···Cl1v 0.87 (2) 2.77 (3) 3.4060 (17) 131 (4)
N1—H2D···O1wvi 0.87 (3) 2.03 (3) 2.887 (3) 169 (3)
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Symmetry codes: (ii) −x, −y+1, −z+2; (iii) x, y, z+1; (iv) x, y+1, z; (v) −x, −y+1, −z+1; (vi) −x+1, −y+2, −z+2.

Funding Statement

Funding for this research was provided by: U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Heavy Element Chemistry Program, FWP 73200 .

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023005753/pk2687sup1.cif

e-79-00702-sup1.cif (696.8KB, cif)

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989023005753/pk2687Isup2.hkl

e-79-00702-Isup2.hkl (224.1KB, hkl)
Click here for additional data file. (327KB, docx)

Thermal Ellipsoidal plots and data, (e.g., Powder X-ray diffraction, diffuse reflectance spectroscopy, and photo luminescence spectroscopy). DOI: 10.1107/S2056989023005753/pk2687sup3.docx

CCDC reference: 2278035

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

Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography

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