Isotypism and phase transitions of (NH4)M(HSO4)(SO4)(H2O)2 (M = Fe, Co and Ni) compounds

Weil, M.

doi:10.1107/S2056989025006395

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Volume 81| Part 8| August 2025| Pages 727-732

https://doi.org/10.1107/S2056989025006395

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Isotypism and phase transitions of (NH₄)M(HSO₄)(SO₄)(H₂O)₂ (M = Fe, Co and Ni) compounds

Matthias Weil ^a ^*

^aInstitute for Chemical Technologies and Analytics, Division of Applied Solid State Chemistry, TU Wien, Getreidemarkt 9/E164-05-1, A-1060 Vienna, Austria
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 10 July 2025; accepted 17 July 2025; online 23 July 2025)

A systematic crystallization study of {(NH₄)[M(HSO₄)(SO₄)(H₂O)₂]}_n compounds, catena-poly[ammonium [[diaquametal(II)]-μ-(hydrogen sulfato)-μ-sulfato]], revealed that crystals of the M = Fe, Co and Ni members could be grown by evaporation of mixed equimolar aqueous solutions of NH₄HSO₄ and the corresponding MSO₄ sulfate, whereas for M = Mn, Cu, Zn different products were obtained under these conditions. The (NH₄)M(HSO₄)(SO₄)(H₂O)₂ compounds (M = Fe, Co, Ni) show a similar behavior to the magnesium analogue, i.e. a reversible structural phase transition from an ordered triclinic crystal structure at T = 100 K (Z = 2) to a disordered triclinic structure at T = 296 K (Z = 1). The symmetry relationship between the structure at 296 K and the superstructure at 100 K is of the isomorphic type with index 2. At 100 K, the [MO₄(OH₂)₂] octahedra are linked by distinct [SO₃(OH)] and [SO₄] tetrahedra into chains. Adjacent chains are linked by very strong hydrogen bonds (O⋯O ≃ 2.5 Å) between the two types of sulfate tetrahedra into layers. These layers are held together by hydrogen-bonding interactions of medium-to-weak strength between the ammonium cations and water molecules. At 296 K, the H atoms of the ammonium tetrahedron and the H atom between two symmetry-related sulfate groups are disordered. Quantitative structural comparisons are made between the isotypic (NH₄)M(HSO₄)(SO₄)(H₂O)₂ structures (M = Mg, Fe, Co, Ni) at 296 K and 100 K, respectively.

Keywords: crystal structure; isotypism; phase transition; group–subgroup relation; sulfates; hydrogen-bonding.

CCDC references: 2473608; 2473607; 2473606; 2473605; 2473604; 2473603

1. Chemical context

In an earlier study on (NH₄)Mg(HSO₄)(SO₄)(H₂O)₂, it was found that this phase can be crystallized in high yields from equimolar aqueous solutions of NH₄HSO₄ and MgSO₄ by slow evaporation to dryness (Weil & Kolitsch, 2021 ). (NH₄)Mg(HSO₄)(SO₄)(H₂O)₂ is dimorphic and the corresponding crystal structures were determined and refined on basis of single crystal X-ray data sets recorded at 296 K and 100 K. The crystal structure of the corresponding iron compound (NH₄)Fe(HSO₄)(SO₄)(H₂O)₂ was already known previously from a 100 K data set (Heinicke et al., 2004 ) and interestingly shows isotypism with the crystal structure of the magnesium compound at 296 K.

The aim of the present study is to determine to what extent the corresponding first-row transition-metal compounds (NH₄)M(HSO₄)(SO₄)(H₂O)₂ (M^II = Mn, Fe, Co, Ni, Cu, Zn) can be crystallized from aqueous solutions in a similar way to the magnesium compound, and if so, whether they are also dimorphic.

While under these conditions other crystallization products were obtained for M = Mn, Cu and Zn, the corresponding (NH₄)M(HSO₄)(SO₄)(H₂O)₂ compounds could be crystallized for M = Fe, Co and Ni, all of which are dimorphic and crystallize isotypically with the corresponding Mg structures at 296 K and 100 K, respectively. The results of these structural investigations are reported in the present article.

2. Structural commentary

The title sulfates are new representatives of compounds with kröhnkite-type chains, which are composed of [MO₄(OH₂)₂] octahedra corner-linked by XO₄ tetrahedra (Fig. 1). The widespread occurrence of this motif is related to flexible variations of the octahedral-tetrahedral building units within a chain. Compounds comprising kröhnkite-type chains have been classified into different structure types (Fleck et al., 2002 ).

Figure 1
The kröhnkite-type chains in the crystal structures of (NH₄)M(HSO₄)(SO₄)(H₂O)₂ compounds at 296 K in polyhedral representation. The chains are composed of [MO₄(OH₂)₂] octahedra (blue) corner-linked by sulfate/hydrogen sulfate tetrahedra (red).

2.1. The disordered (NH₄)M(HSO₄)(SO₄)(H₂O)₂ crystal structure at 296 K

At 296 K, the three isotypic (NH₄)M(HSO₄)(SO₄)(H₂O)₂ (M = Fe, Co, Ni) compounds adopt a triclinic structure (space group P $[\overline{1}]$ , Z = 1) corresponding to type E in the classification of compounds with kröhnkite-type chains (Fleck et al., 2002). As explained below, it is more accurate to describe these compounds at this temperature by the general formula (NH₄)MH(SO₄)₂(H₂O)₂.

The kröhnkite-type chains run along [100] and are joined into sheets parallel to (001) by O—H⋯O hydrogen bonds involving the water molecule (O5) as the donor group. These sheets are held together along [001] through an asymmetric hydrogen bond between two SO₄ tetrahedra of two adjacent chains. This hydrogen bond involves the disordered H1O atom. The corresponding O1⋯O1ⁱ [symmetry code: (i) −x − 1, −y − 1, −x − 1] distance of about 2.48 Å indicates a very strong hydrogen bond (Jeffrey, 1997 ). The cohesion within the structure is completed by multiple N—H⋯O hydrogen bonds arising from the ammonium cations, which are located between the sheets (Fig. 2). The N atom of the ammonium cation is situated at an inversion centre and consequently its hydrogen atoms are equally disordered over two sets of sites. Numerical details of the hydrogen-bonding interactions for the 296 K structures are compiled in Tables 1–3 for the three phases.

Table 1
Hydrogen-bond geometry (Å, °) for M = Fe at 296 K

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O1ⁱ	0.80 (1)	1.70 (1)	2.4840 (13)	167 (3)
O5—H5B⋯O2ⁱⁱ	0.79 (2)	2.51 (3)	2.9951 (10)	121 (2)
O5—H5B⋯O3ⁱⁱ	0.79 (2)	2.52 (2)	3.2141 (11)	148 (2)
N1—H1A⋯O3ⁱ	0.90 (1)	2.02 (1)	2.9218 (7)	175 (6)
N1—H1B⋯O1ⁱⁱⁱ	0.90 (1)	2.29 (3)	3.1712 (8)	166 (9)
N1—H1C⋯O1	0.90 (1)	2.31 (3)	3.1222 (7)	150 (5)
N1—H1B⋯O1ⁱⁱⁱ	0.90 (1)	2.29 (3)	3.1712 (8)	166 (9)
N1—H1D⋯O4ⁱⁱⁱ	0.90 (1)	1.98 (1)	2.8736 (7)	174 (7)
Symmetry codes: (i) ; (ii) ; (iii) .

Table 2
Hydrogen-bond geometry (Å, °) for M = Co at 296 K

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O1ⁱ	0.70 (4)	1.80 (4)	2.4810 (16)	165 (5)
O5—H5A⋯O2ⁱⁱ	0.74 (3)	2.57 (3)	2.9923 (11)	118 (2)
O5—H5B⋯O3ⁱⁱ	0.77 (2)	2.51 (2)	3.2020 (13)	149 (2)
N1—H1A⋯O3ⁱ	0.98 (7)	1.96 (7)	2.9298 (8)	169 (7)
N1—H1D⋯O1ⁱⁱⁱ	0.84 (7)	2.33 (7)	3.1657 (10)	175 (7)
N1—H1C⋯O1	0.87 (6)	2.29 (6)	3.1098 (8)	158 (6)
N1—H1D⋯O1ⁱⁱⁱ	0.84 (7)	2.33 (7)	3.1657 (10)	175 (7)
N1—H1B⋯O4ⁱⁱⁱ	0.91 (9)	1.97 (9)	2.8773 (7)	176 (8)
Symmetry codes: (i) ; (ii) ; (iii) .

Table 3
Hydrogen-bond geometry (Å, °) for M = Ni at 296 K

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O1ⁱ	0.85 (1)	1.65 (2)	2.484 (3)	167 (6)
O5—H5A⋯O2ⁱⁱ	0.84 (1)	2.50 (4)	3.005 (2)	119 (3)
O5—H5B⋯O3ⁱⁱ	0.84 (1)	2.43 (2)	3.177 (3)	147 (4)
N1—H1A⋯O3ⁱ	0.90 (1)	2.05 (3)	2.9360 (17)	166 (9)
N1—H1D⋯O1ⁱⁱⁱ	0.90 (1)	2.29 (4)	3.152 (2)	159 (9)
N1—H1C⋯O1	0.90 (1)	2.23 (2)	3.0898 (18)	160 (6)
N1—H1D⋯O1ⁱⁱⁱ	0.90 (1)	2.29 (4)	3.152 (2)	159 (9)
N1—H1B⋯O4ⁱⁱⁱ	0.90 (1)	2.07 (7)	2.8761 (16)	149 (11)
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2
The crystal structure of (NH₄)M(HSO₄)(SO₄)(H₂O)₂ compounds at 296 K (data from M = Co) in a projection along [ $[\overline{1}]$ 00]. Very strong hydrogen bonds between disordered sulfate/hydrogen sulfate groups are given in red, medium-strong to weak hydrogen bonds involving the water molecules in yellow and those involving the disordered ammonium cations in green. Displacement ellipsoids are drawn at the 74% probability level; H atoms are displayed with arbitrary radius.

The [M^IIO₄(OH₂)₂] octahedra in the 296 K structures exhibit point group symmetry $[\overline{1}]$ with mean bond lengths of 2.118 Å for M = Fe, 2.091 Å for Co, and 2.059 Å for Ni, in good agreement with grand mean values of 2.147 (89), 2.108 (62) and 2.070 (54) Å, respectively, reported in literature (Gagné & Hawthorne, 2020 ). The S—O1(H10) bond (average 1.515 Å for the three structures) is the longest in the sulfate tetrahedron and is about 0.05 Å longer than the S—O bonds to the other O atoms (average 1.462 Å for the three structures). The S—O bond lengths are in good agreement with those given in a review on the sulfate group, for which the grand mean S—O distance is 1.473 Å, with minimum and maximum S—O distances of 1.430 and 1.501 Å, respectively (Hawthorne et al., 2000 ).

2.2. The ordered (NH₄)M(HSO₄)(SO₄)(H₂O)₂ crystal structure at 100 K

At 100 K, the three (NH₄)M(HSO₄)(SO₄)(H₂O)₂ compounds also adopt a triclinic structure (space group P $[\overline{1}]$ , Z = 2) corresponding to type E1 (Weil & Kolitsch, 2021) in the classification of compounds with kröhnkite-type chains. A search in the current version of the Inorganic Crystal Structure Database (ICSD, data release 2024-1; Zagorac et al., 2019 ), revealed that, apart from the Mg analogue (Weil & Kolitsch, 2021) and the title compounds, there are no other members that adopt this structure type.

The crystal structures of the (NH₄)M(HSO₄)(SO₄)(H₂O)₂ (M = Fe, Co, Ni) compounds at 100 K represent a twofold superstructure with ordered hydrogen atoms for the ammonium group and of the hydrogen sulfate group relative to the crystal structure of (NH₄)MH(SO₄)₂(H₂O)₂ at 296 K. The unit cells of the latter compounds are related to the doubled unit cells of the (NH₄)M(HSO₄)(SO₄)(H₂O)₂ superstructures at 100 K by the transformation –a–b, a–b, c. The symmetry relationship (Müller & de la Flor, 2024 ) between the substructure at 296 K and the superstructure at 100 K is of isomorphic type with index 2 (i2). All atoms in the superstructure are situated in general positions. [MO₄(OH₂)] octahedra are corner-linked by distinct [SO₃(OH)] and [SO₄] tetrahedra into chains running parallel to [ $[\overline{1}]$ 10]. Adjacent chains are joined by O—H⋯O hydrogen bonds between the hydrogen sulfate and sulfate tetrahedra into sheets extending parallel to (111). The ammonium cations, situated in-between the sheets, and water molecules are also involved in hydrogen-bonding and consolidate the crystal packing (Fig. 3). In comparison, the bond lengths of all principal building units in the ordered 100 K structure are similar to those in the disordered 296 K structure.

Figure 3
The crystal structure of (NH₄)M(HSO₄)(SO₄)(H₂O)₂ compounds at 100 K (data from M = Co) in a projection along [ $[\overline{1}]$ 10]. Color code and displacement ellipsoids are as in Fig. 2

The mean M—O bond lengths in the [MO₄(OH₂)] octahedra (2.116 Å for M = Fe, 2.087 Å for Co, and 2.053 Å for Ni) hardly differ from those of the 296 K structures. The ordering of the hydrogen atom (H1O) between two sulfate tetrahedra defines distinct S1O₄ and S2O₃(OH) groups. The longest bond in the S1O4 tetrahedron is the bond to O4 (1.491 Å on average for all three structures in contrast to 1.476 Å on average for all other S—O bonds). O4 serves as the acceptor atom for the hydrogen bond with the OH group of the hydrogen sulfate group as donor group. The corresponding [S2O₃(OH)] tetrahedron shows the typical distribution of S—O bond lengths in a hydrogen sulfate group, whereby the bond to the OH group (O8) is significantly longer by about 0.09 Å than the remaining three S—O bonds (average for all structures 1.459 Å). The hydrogen bond between the [S2O₃(OH)] and [S1O₄] tetrahedra (O8⋯O4 is on average 2.502 Å) is almost linear [178.6 (12)° for Fe, 177.4 (17)° for Co and 173 (4)° for Ni]. Like the 296 K structures, the other types of O—H⋯O hydrogen-bonding interactions are much weaker and involve the water molecules. One of them (O9) shows pairs of bifurcated (M = Co, Ni) or trifurcated (M = Fe) medium-strong to weak hydrogen bonds. The other water molecule (O10) is involved in one medium-strong and a weak bifurcated hydrogen bond. All H atoms of the ammonium cation are engaged in almost linear hydrogen-bonding interactions to the O atoms of the sulfate group as acceptor atoms. Numerical details of hydrogen-bonding interactions are compiled in Tables 4–6 for the three 100 K structures.

Table 4
Hydrogen-bond geometry (Å, °) for M = Fe at 100 K

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H1O⋯O4ⁱ	1.040 (16)	1.467 (16)	2.5067 (8)	178.6 (12)
O9—H1W⋯O1ⁱⁱ	0.816 (17)	2.030 (19)	2.7537 (7)	147.5 (18)
O9—H2W⋯O2ⁱⁱⁱ	0.875 (17)	2.447 (17)	3.0785 (7)	129.5 (13)
O9—H2W⋯O5^iv	0.875 (17)	2.599 (16)	3.3272 (8)	141.3 (13)
O9—H2W⋯O7^iv	0.875 (17)	2.439 (17)	2.9556 (7)	118.3 (14)
O10—H3W⋯O1^v	0.849 (19)	2.389 (18)	3.1467 (8)	149.0 (15)
O10—H3W⋯O2^v	0.849 (19)	2.541 (19)	3.0541 (7)	119.9 (16)
O10—H4W⋯O5^vi	0.840 (17)	1.946 (18)	2.7115 (7)	151.2 (18)
N1—H3N⋯O3ⁱ	0.873 (12)	1.967 (12)	2.8334 (7)	171.5 (11)
N1—H1N⋯O4^iv	0.871 (12)	2.138 (12)	2.9931 (7)	167.2 (11)
N1—H2N⋯O1ⁱⁱⁱ	0.857 (13)	2.040 (13)	2.8965 (7)	178.3 (12)
N1—H4N⋯O8^vii	0.890 (14)	2.266 (14)	3.0869 (8)	153.2 (11)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Table 5
Hydrogen-bond geometry (Å, °) for M = Co at 100 K

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H1O⋯O4ⁱ	0.99 (2)	1.51 (2)	2.5007 (11)	177.4 (17)
O9—H1W⋯O1ⁱⁱ	0.77 (2)	2.08 (2)	2.7566 (10)	147 (2)
O9—H2W⋯O2ⁱⁱⁱ	0.82 (2)	2.468 (19)	3.0700 (10)	130.8 (16)
O9—H2W⋯O5^iv	0.82 (2)	2.59 (2)	3.2918 (10)	144.5 (16)
O9—H1W⋯O7^iv	0.77 (2)	2.51 (2)	2.9549 (10)	118.1 (19)
O10—H3W⋯O1^v	0.79 (2)	2.42 (2)	3.1378 (10)	151.0 (18)
O10—H3W⋯O2^v	0.79 (2)	2.58 (2)	3.0492 (10)	119.8 (19)
O10—H4W⋯O5^vi	0.80 (2)	1.98 (2)	2.7127 (10)	152 (2)
N1—H3N⋯O3ⁱ	0.887 (15)	1.955 (15)	2.8328 (10)	170.1 (15)
N1—H1N⋯O4^iv	0.897 (16)	2.114 (16)	2.9890 (11)	164.7 (14)
N1—H2N⋯O1ⁱⁱⁱ	0.864 (17)	2.038 (17)	2.9017 (11)	178.9 (16)
N1—H4N⋯O8^vii	0.894 (18)	2.252 (18)	3.0777 (11)	153.4 (15)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Table 6
Hydrogen-bond geometry (Å, °) for M = Ni at 100 K

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H1O⋯O4ⁱ	0.88 (4)	1.62 (4)	2.499 (2)	173 (4)
O9—H1W⋯O1ⁱⁱ	0.80 (5)	2.08 (5)	2.747 (3)	140 (5)
O9—H2W⋯O2ⁱⁱⁱ	0.65 (4)	2.55 (4)	3.061 (3)	138 (4)
O9—H2W⋯O5^iv	0.65 (4)	2.69 (4)	3.232 (2)	143 (4)
O9—H1W⋯O7^iv	0.80 (5)	2.44 (5)	2.963 (2)	124 (5)
O10—H3W⋯O1^v	0.80 (3)	2.41 (3)	3.115 (2)	148 (3)
O10—H3W⋯O2^v	0.80 (3)	2.59 (4)	3.051 (2)	119 (3)
O10—H4W⋯O5^vi	0.78 (3)	2.00 (3)	2.719 (3)	155 (3)
N1—H3N⋯O3ⁱ	0.87 (3)	1.97 (3)	2.834 (3)	172 (3)
N1—H1N⋯O4^iv	0.93 (3)	2.07 (3)	2.980 (3)	169 (3)
N1—H2N⋯O1ⁱⁱⁱ	0.91 (3)	2.00 (3)	2.903 (3)	174 (3)
N1—H4N⋯O8^vii	0.79 (6)	2.31 (6)	3.068 (3)	159 (5)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

As already mentioned in the Introduction, the crystal structure of the Fe compound (Heinicke et al., 2004) was determined in a previous measurement at 100 K in structure type E, i.e. in the disordered variant with Z = 1, which occurs for all other (NH₄)M(HSO₄)(SO₄)(H₂O)₂ representatives at 296 K. However, the 100 K data obtained in the present study originate from a slowly cooled (NH₄)Fe(HSO₄)(SO₄)(H₂O)₂ crystal and clearly show the ordered variant with Z = 2. Whether this difference is possibly due to a different temperature treatment cannot be conclusively clarified, as no details were given in the original publication (Heinicke et al., 2004). The investigation of the exact ordering temperatures for this and all other (NH₄)M(HSO₄)(SO₄)(H₂O)₂ representatives, e.g. with temperature-dependent powder X-ray diffraction and/or differential scanning calorimetry (DSC) methods, still has to be carried out, but is outside the scope of the present structural study.

3. Structural comparison

For a quantitative structural comparison of the (NH₄)M(HSO₄)(SO₄)(H₂O)₂ (M = Mg, Fe, Co, Ni) structures at 296 K and 100 K, respectively, the program compstru (de la Flor et al., 2016 ) available at the Bilbao Crystallographic Server (Aroyo et al., 2006 ) was used. With M = Mg as the reference structure, Table 7 compiles the maximum distance (d_max) between paired atoms and numerical values regarding the arithmetic mean (d_av) of the distance between paired atoms, the degree of lattice distortion (δ), and the measure of similarity (S).

Table 7
Structural comparison of isotypic (NH₄)M(HSO₄)(SO₄)(H₂O)₂ structures with the M = Mg members as references

	Co (100 K)	Fe (100 K)	Ni (100 K)	Co (296 K)	Fe (296 K)	Ni (296 K)
S	0.0047	0.0062	0.0074	0.0055	0.0062	0.0078
d_max (atom)	0.0860 (O1)	0.0893 (O5)	0.1031 (O8)	0.0905 (O3)	0.1003 (O3)	0.0944 (O2)
d_av	0.0469	0.0485	0.0545	0.0521	0.0525	0.0574
δ	0.012	0.021	0.017	0.048	0.051	0.062
S is the degree of lattice distortion, d_max (Å) is the maximum difference between two atomic positions, d_av (Å) is the arithmetic mean of the differences between two atomic positions and δ is the measure of similarity.

As expected for isotypic structures, the comparison between the individual structures (M = Fe, Co, Ni) and the reference structure (M = Mg) shows very similar numerical values. A clearly recognizable trend cannot be identified, however it may be noted that the numerical parameters for the smallest deviations are always connected with the M = Co structure.

4. Synthesis and crystallization

Equimolar aqueous solutions of NH₄HSO₄ and the corresponding MSO₄ sulfate (M = Mn, Fe, Co, Ni, Cu, Zn) were mixed at room temperature and stirred for homogeneity. The mixed solutions were then slowly evaporated to dryness for several days at room temperature. Semi-quantitative phase analysis of the obtained bulk using the HighScorePlus program (Degen et al., 2014 ) revealed the title compounds (NH₄)M(HSO₄)(SO₄)(H₂O)₂ (M = Fe, Co, Ni) as the main products (> 90%_wt) and [(NH₄)₂M(SO₄)₂(H₂O)₆] phases as the minor products. For batches with M = Cu and Zn, (NH₄)₂M(SO₄)₂(H₂O)₆ phases were the main products and CuSO₄(H₂O)₅ and ZnSO₄(H₂O)₆ the minor products, for both with an approximate phase ratio of 3:1. For the batch with M = Mn, langbeinite-type (NH₄)₂Mn₂(SO₄)₃ was the only phase obtained.

The (NH₄)M(HSO₄)(SO₄)(H₂O)₂ single crystals (M = Fe, Co, Ni) used for the diffraction studies were broken from larger specimens.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 8. For the low-temperature measurements, the crystals were cooled from 296 K to 100 K within two h. For refinement, coordinates and labeling of atoms of all (NH₄)M(HSO₄)(SO₄)(H₂O)₂ structures were taken from the isotypic (NH₄)Mg(HSO₄)(SO₄)(H₂O)₂ structures for the 296 K and the 100 K data sets (Weil & Kolitsch, 2021). For all data (296 and 100 K), hydrogen atoms were discernible in difference-Fourier maps and were refined freely. For all 296 K structures, the four ammonium hydrogen atoms (H1A–H1D) and the H1O atom located between two symmetry-related sulfate tetrahedra are all equally disordered across a centre of symmetry and thus were refined with half-occupancy.

Table 8
Experimental details

	M = Fe at 296 K	M = Co at 296 K	M = Ni at 296 K
Crystal data
Chemical formula	(NH₄)[Fe(HSO₄)(SO₄)(H₂O)₂]	(NH₄)[Co(HSO₄)(SO₄)(H₂O)₂]	(NH₄)[Ni(HSO₄)(SO₄)(H₂O)₂]
M_r	303.05	306.13	305.91
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	296	296	296
a, b, c (Å)	4.6369 (6), 5.8481 (8), 8.4135 (11)	4.6182 (2), 5.8243 (3), 8.3576 (4)	4.5746 (16), 5.7944 (19), 8.347 (2)
α, β, γ (°)	104.010 (2), 98.145 (2), 95.077 (3)	104.2261 (11), 98.1916 (13), 94.7068 (11)	104.049 (11), 98.133 (12), 94.420 (12)
V (Å³)	217.33 (5)	214.07 (2)	211.04 (12)
Z	1	1	1
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	2.26	2.53	2.84
Crystal size (mm)	0.21 × 0.12 × 0.10	0.13 × 0.05 × 0.02	0.12 × 0.06 × 0.01

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.616, 0.748	0.677, 0.747	0.598, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	8735, 2967, 2634	4115, 1920, 1739	3532, 1591, 1307
R_int	0.028	0.016	0.027
(sin θ/λ)_max (Å⁻¹)	0.939	0.812	0.769

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.060, 1.05	0.019, 0.053, 1.05	0.031, 0.077, 1.10
No. of reflections	2967	1920	1591
No. of parameters	96	96	95
No. of restraints	7	0	7
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.45	0.43, −0.40	0.47, −0.59

	M = Fe at 100 K	M = Co at 100 K	M = Ni at 100 K
Crystal data
Chemical formula	(NH₄)[Fe(HSO₄)(SO₄)(H₂O)₂]	(NH₄)[Co(HSO₄)(SO₄)(H₂O)₂]	(NH₄)[Ni(HSO₄)(SO₄)(H₂O)₂]
M_r	303.05	306.13	305.91
Crystal system, space group	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$	Triclinic, P $[\overline{1}]$
Temperature (K)	100	100	100
a, b, c (Å)	7.0847 (6), 7.7956 (7), 8.3868 (7)	7.0775 (4), 7.7268 (4), 8.3281 (5)	7.0437 (9), 7.6405 (9), 8.3097 (10)
α, β, γ (°)	84.5953 (15), 73.2990 (15), 76.2281 (17)	84.5548 (11), 73.1705 (15), 76.3233 (11)	84.571 (3), 73.376 (3), 76.056 (3)
V (Å³)	430.74 (6)	423.40 (4)	415.73 (9)
Z	2	2	2
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	2.28	2.56	2.88
Crystal size (mm)	0.12 × 0.09 × 0.02	0.12 × 0.09 × 0.02	0.12 × 0.09 × 0.02

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015)	Multi-scan (SADABS; Krause et al., 2015)	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.619, 0.748	0.669, 0.747	0.609, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	17276, 5854, 5143	8668, 4184, 3507	7657, 3609, 2253
R_int	0.027	0.019	0.031
(sin θ/λ)_max (Å⁻¹)	0.937	0.854	0.827

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.062, 1.05	0.023, 0.062, 1.04	0.038, 0.092, 1.02
No. of reflections	5854	4184	3609
No. of parameters	164	164	163
No. of restraints	0	0	0
H-atom treatment	All H-atom parameters refined	All H-atom parameters refined	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.76	0.54, −0.53	0.86, −0.95
Computer programs: APEX4 and SAINT (Bruker, 2020 ), SHELXL (Sheldrick, 2015 ), ATOMS (Dowty, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2473608; 2473607; 2473606; 2473605; 2473604; 2473603

Crystal structure: contains datablocks Fe_296K, Co_296K, Ni_296K, Fe_100K, Co_100K, Ni_100K. DOI: https://doi.org/10.1107/S2056989025006395/hb8148sup1.cif

M = Fe at 296 K. DOI: https://doi.org/10.1107/S2056989025006395/hb8148Fe_296Ksup8.hkl

M = Co at 296 K. DOI: https://doi.org/10.1107/S2056989025006395/hb8148Co_296Ksup9.hkl

M = Ni at 296 K. DOI: https://doi.org/10.1107/S2056989025006395/hb8148Ni_296Ksup10.hkl

M = Fe at 100 K. DOI: https://doi.org/10.1107/S2056989025006395/hb8148Fe_100Ksup11.hkl

M = Co at 100 K. DOI: https://doi.org/10.1107/S2056989025006395/hb8148Co_100Ksup12.hkl

M = Ni at 100 K. DOI: https://doi.org/10.1107/S2056989025006395/hb8148Ni_100Ksup13.hkl

checkCIF report

Computing details top

catena-Poly[ammonium [[diaquairon(II)]-µ-(hydrogen sulfato)-µ-sulfato]] (Fe_296K) top

Crystal data top

(NH₄)[Fe(HSO₄)(SO₄)(H₂O)₂]	Z = 1
M_r = 303.05	F(000) = 154
Triclinic, P1	D_x = 2.315 Mg m⁻³
a = 4.6369 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.8481 (8) Å	Cell parameters from 5383 reflections
c = 8.4135 (11) Å	θ = 3.6–41.7°
α = 104.010 (2)°	µ = 2.26 mm⁻¹
β = 98.145 (2)°	T = 296 K
γ = 95.077 (3)°	Fragment, light green
V = 217.33 (5) Å³	0.21 × 0.12 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	2634 reflections with I > 2σ(I)
ω– and φ–scans	R_int = 0.028
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 41.9°, θ_min = 3.9°
T_min = 0.616, T_max = 0.748	h = −8→8
8735 measured reflections	k = −10→10
2967 independent reflections	l = −15→15

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0316P)² + 0.0223P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.060	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.53 e Å⁻³
2967 reflections	Δρ_min = −0.45 e Å⁻³
96 parameters	Extinction correction: SHELXL (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
7 restraints	Extinction coefficient: 0.216 (10)

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)
Fe1	0.000000	0.000000	0.000000	0.01282 (4)
S1	−0.59664 (3)	−0.31685 (3)	−0.23953 (2)	0.01243 (4)
O1	−0.50160 (18)	−0.30338 (11)	−0.40240 (8)	0.02469 (12)
O2	−0.33634 (14)	−0.28331 (11)	−0.11117 (8)	0.02220 (11)
O3	−0.76173 (16)	−0.54770 (11)	−0.26110 (8)	0.02589 (13)
O4	−0.77081 (14)	−0.11909 (11)	−0.19883 (7)	0.02041 (10)
O5	0.19351 (15)	−0.21979 (12)	0.14262 (9)	0.02261 (11)
H5A	0.107 (5)	−0.329 (4)	0.156 (3)	0.063 (6)*
H5B	0.338 (5)	−0.281 (5)	0.131 (3)	0.055 (6)*
N1	0.000000	0.000000	−0.500000	0.0274 (2)
H1A	−0.080 (14)	−0.134 (7)	−0.578 (6)	0.093 (18)*	0.5
H1B	−0.129 (15)	0.104 (12)	−0.510 (14)	0.12 (3)*	0.5
H1C	−0.169 (7)	−0.034 (10)	−0.463 (7)	0.071 (14)*	0.5
H1D	−0.078 (14)	0.045 (13)	−0.590 (6)	0.081 (19)*	0.5
H1O	−0.528 (7)	−0.431 (3)	−0.468 (4)	0.038 (9)*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01286 (6)	0.01288 (6)	0.01309 (6)	0.00327 (4)	0.00294 (4)	0.00303 (4)
S1	0.01381 (7)	0.01094 (6)	0.01176 (7)	0.00064 (4)	0.00384 (5)	0.00085 (4)
O1	0.0402 (4)	0.0180 (2)	0.0176 (2)	0.0022 (2)	0.0168 (2)	0.00169 (18)
O2	0.0181 (2)	0.0191 (2)	0.0269 (3)	0.00131 (18)	−0.00379 (19)	0.0059 (2)
O3	0.0308 (3)	0.0175 (2)	0.0253 (3)	−0.0097 (2)	0.0077 (2)	0.0006 (2)
O4	0.0220 (2)	0.0238 (2)	0.0188 (2)	0.0119 (2)	0.00839 (19)	0.00588 (19)
O5	0.0210 (3)	0.0206 (2)	0.0311 (3)	0.00657 (19)	0.0057 (2)	0.0139 (2)
N1	0.0354 (6)	0.0237 (4)	0.0217 (4)	0.0013 (4)	−0.0013 (4)	0.0074 (4)

Geometric parameters (Å, º) top

Fe1—O2	2.1051 (6)	O5—H5A	0.76 (2)
Fe1—O2ⁱ	2.1051 (6)	O5—H5B	0.79 (2)
Fe1—O4ⁱⁱ	2.1174 (6)	N1—H1A	0.901 (10)
Fe1—O4ⁱⁱⁱ	2.1174 (6)	N1—H1B	0.900 (10)
Fe1—O5ⁱ	2.1314 (6)	N1—H1C	0.904 (10)
Fe1—O5	2.1314 (6)	N1—H1D	0.901 (10)
S1—O3	1.4493 (6)	N1—H1A^iv	0.901 (10)
S1—O2	1.4655 (6)	N1—H1B^iv	0.900 (10)
S1—O4	1.4694 (6)	N1—H1C^iv	0.904 (10)
S1—O1	1.5151 (6)	N1—H1D^iv	0.901 (10)
O1—H1O	0.798 (6)

O2—Fe1—O2ⁱ	180.0	H1A—N1—H1C	79 (5)
O2—Fe1—O4ⁱⁱ	90.82 (3)	H1B—N1—H1C	67 (5)
O2ⁱ—Fe1—O4ⁱⁱ	89.19 (3)	H1A—N1—H1D	73 (5)
O2—Fe1—O4ⁱⁱⁱ	89.18 (3)	H1B—N1—H1D	50 (6)
O2ⁱ—Fe1—O4ⁱⁱⁱ	90.81 (3)	H1C—N1—H1D	98 (5)
O4ⁱⁱ—Fe1—O4ⁱⁱⁱ	180.0	H1A—N1—H1A^iv	180 (4)
O2—Fe1—O5ⁱ	91.74 (3)	H1B—N1—H1A^iv	76 (6)
O2ⁱ—Fe1—O5ⁱ	88.26 (3)	H1C—N1—H1A^iv	101 (5)
O4ⁱⁱ—Fe1—O5ⁱ	93.41 (3)	H1D—N1—H1A^iv	107 (5)
O4ⁱⁱⁱ—Fe1—O5ⁱ	86.59 (3)	H1A—N1—H1B^iv	76 (6)
O2—Fe1—O5	88.26 (3)	H1B—N1—H1B^iv	180.00 (5)
O2ⁱ—Fe1—O5	91.74 (3)	H1C—N1—H1B^iv	113 (5)
O4ⁱⁱ—Fe1—O5	86.59 (3)	H1D—N1—H1B^iv	130 (6)
O4ⁱⁱⁱ—Fe1—O5	93.41 (3)	H1A^iv—N1—H1B^iv	104 (6)
O5ⁱ—Fe1—O5	180.0	H1A—N1—H1C^iv	101 (5)
O3—S1—O2	109.74 (4)	H1B—N1—H1C^iv	113 (5)
O3—S1—O4	113.36 (4)	H1C—N1—H1C^iv	179.998 (15)
O2—S1—O4	110.13 (4)	H1D—N1—H1C^iv	82 (5)
O3—S1—O1	109.11 (4)	H1A^iv—N1—H1C^iv	79 (5)
O2—S1—O1	109.39 (4)	H1B^iv—N1—H1C^iv	67 (5)
O4—S1—O1	104.96 (4)	H1A—N1—H1D^iv	107 (5)
S1—O1—H1O	111 (3)	H1B—N1—H1D^iv	130 (6)
S1—O2—Fe1	133.85 (4)	H1C—N1—H1D^iv	82 (5)
S1—O4—Fe1^v	132.75 (4)	H1D—N1—H1D^iv	180 (8)
Fe1—O5—H5A	122.5 (18)	H1A^iv—N1—H1D^iv	73 (5)
Fe1—O5—H5B	127.2 (16)	H1B^iv—N1—H1D^iv	50 (6)
H5A—O5—H5B	95 (2)	H1C^iv—N1—H1D^iv	98 (5)
H1A—N1—H1B	104 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O1^vi	0.80 (1)	1.70 (1)	2.4840 (13)	167 (3)
O5—H5B···O2^vii	0.79 (2)	2.51 (3)	2.9951 (10)	121 (2)
O5—H5B···O3^vii	0.79 (2)	2.52 (2)	3.2141 (11)	148 (2)
N1—H1A···O3^vi	0.90 (1)	2.02 (1)	2.9218 (7)	175 (6)
N1—H1B···O1^viii	0.90 (1)	2.29 (3)	3.1712 (8)	166 (9)
N1—H1C···O1	0.90 (1)	2.31 (3)	3.1222 (7)	150 (5)
N1—H1B···O1^viii	0.90 (1)	2.29 (3)	3.1712 (8)	166 (9)
N1—H1D···O4^viii	0.90 (1)	1.98 (1)	2.8736 (7)	174 (7)

Symmetry codes: (vi) −x−1, −y−1, −z−1; (vii) −x, −y−1, −z; (viii) −x−1, −y, −z−1.

catena-Poly[ammonium [[diaquacobalt(II)]-µ-(hydrogen sulfato)-µ-sulfato]] (Co_296K) top

Crystal data top

(NH₄)[Co(HSO₄)(SO₄)(H₂O)₂]	Z = 1
M_r = 306.13	F(000) = 155
Triclinic, P1	D_x = 2.375 Mg m⁻³
a = 4.6182 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.8243 (3) Å	Cell parameters from 2718 reflections
c = 8.3576 (4) Å	θ = 2.5–35.3°
α = 104.2261 (11)°	µ = 2.53 mm⁻¹
β = 98.1916 (13)°	T = 296 K
γ = 94.7068 (11)°	Fragment, violet
V = 214.07 (2) Å³	0.13 × 0.05 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	1739 reflections with I > 2σ(I)
ω– and φ–scans	R_int = 0.016
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 35.3°, θ_min = 3.6°
T_min = 0.677, T_max = 0.747	h = −7→7
4115 measured reflections	k = −9→9
1920 independent reflections	l = −12→13

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.019	w = 1/[σ²(F_o²) + (0.0286P)² + 0.0382P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.053	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.43 e Å⁻³
1920 reflections	Δρ_min = −0.39 e Å⁻³
96 parameters	Extinction correction: SHELXL (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.091 (6)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.000000	0.000000	0.000000	0.01220 (6)
S1	−0.59237 (5)	−0.31481 (4)	−0.23633 (2)	0.01192 (6)
O1	−0.4974 (2)	−0.30250 (15)	−0.40060 (10)	0.02333 (16)
O2	−0.33063 (17)	−0.28375 (14)	−0.10752 (10)	0.02082 (15)
O3	−0.7600 (2)	−0.54530 (14)	−0.25781 (10)	0.02425 (16)
O4	−0.76453 (17)	−0.11339 (14)	−0.19483 (9)	0.01918 (14)
O5	0.19361 (19)	−0.21456 (15)	0.14362 (11)	0.02058 (14)
H5A	0.108 (6)	−0.320 (4)	0.157 (3)	0.056 (7)*
H5B	0.338 (5)	−0.271 (5)	0.134 (3)	0.051 (6)*
N1	0.000000	0.000000	−0.500000	0.0263 (3)
H1A	−0.103 (16)	−0.149 (12)	−0.576 (9)	0.09 (2)*	0.5
H1B	−0.07 (2)	0.041 (16)	−0.596 (10)	0.09 (3)*	0.5
H1C	−0.155 (13)	−0.046 (11)	−0.462 (8)	0.066 (16)*	0.5
H1D	−0.126 (15)	0.084 (12)	−0.530 (10)	0.064 (18)*	0.5
H1O	−0.528 (9)	−0.416 (7)	−0.456 (5)	0.033 (10)*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01195 (8)	0.01226 (8)	0.01283 (8)	0.00288 (5)	0.00301 (5)	0.00313 (6)
S1	0.01354 (10)	0.01038 (9)	0.01119 (9)	0.00054 (7)	0.00395 (7)	0.00082 (7)
O1	0.0382 (4)	0.0170 (3)	0.0162 (3)	0.0016 (3)	0.0156 (3)	0.0011 (3)
O2	0.0171 (3)	0.0176 (3)	0.0252 (3)	0.0004 (2)	−0.0035 (3)	0.0056 (3)
O3	0.0280 (4)	0.0167 (3)	0.0244 (4)	−0.0087 (3)	0.0068 (3)	0.0011 (3)
O4	0.0208 (3)	0.0216 (3)	0.0183 (3)	0.0103 (3)	0.0086 (3)	0.0058 (3)
O5	0.0198 (3)	0.0186 (3)	0.0274 (4)	0.0056 (3)	0.0058 (3)	0.0115 (3)
N1	0.0331 (8)	0.0233 (6)	0.0211 (6)	0.0014 (6)	−0.0008 (5)	0.0070 (5)

Geometric parameters (Å, º) top

Co1—O2ⁱ	2.0821 (8)	O1—H1O	0.70 (4)
Co1—O2	2.0821 (8)	O5—H5A	0.74 (3)
Co1—O4ⁱⁱ	2.0890 (7)	O5—H5B	0.77 (2)
Co1—O4ⁱⁱⁱ	2.0890 (7)	N1—H1A	0.98 (7)
Co1—O5	2.1016 (8)	N1—H1B	0.91 (9)
Co1—O5ⁱ	2.1016 (8)	N1—H1C	0.87 (6)
S1—O3	1.4508 (8)	N1—H1D	0.84 (7)
S1—O2	1.4664 (8)	N1—H1B^iv	0.91 (9)
S1—O4	1.4699 (8)	N1—H1C^iv	0.87 (6)
S1—O1	1.5155 (8)	N1—H1D^iv	0.84 (7)

O2ⁱ—Co1—O2	180.0	Co1—O5—H5A	122 (2)
O2ⁱ—Co1—O4ⁱⁱ	90.83 (3)	Co1—O5—H5B	126.8 (18)
O2—Co1—O4ⁱⁱ	89.17 (3)	H5A—O5—H5B	97 (3)
O2ⁱ—Co1—O4ⁱⁱⁱ	89.17 (3)	H1A—N1—H1B	76 (6)
O2—Co1—O4ⁱⁱⁱ	90.83 (3)	H1A—N1—H1C	70 (5)
O4ⁱⁱ—Co1—O4ⁱⁱⁱ	180.00 (3)	H1B—N1—H1C	107 (6)
O2ⁱ—Co1—O5	92.27 (3)	H1A—N1—H1D	94 (5)
O2—Co1—O5	87.73 (3)	H1B—N1—H1D	44 (6)
O4ⁱⁱ—Co1—O5	86.33 (3)	H1C—N1—H1D	77 (5)
O4ⁱⁱⁱ—Co1—O5	93.67 (3)	H1A—N1—H1B^iv	104 (6)
O2ⁱ—Co1—O5ⁱ	87.73 (3)	H1B—N1—H1B^iv	180.00 (2)
O2—Co1—O5ⁱ	92.27 (3)	H1C—N1—H1B^iv	73 (5)
O4ⁱⁱ—Co1—O5ⁱ	93.67 (3)	H1D—N1—H1B^iv	136 (6)
O4ⁱⁱⁱ—Co1—O5ⁱ	86.33 (3)	H1A—N1—H1C^iv	110 (5)
O5—Co1—O5ⁱ	180.0	H1B—N1—H1C^iv	73 (5)
O3—S1—O2	109.62 (5)	H1C—N1—H1C^iv	179.999 (15)
O3—S1—O4	113.51 (5)	H1D—N1—H1C^iv	103 (5)
O2—S1—O4	110.18 (5)	H1B^iv—N1—H1C^iv	107 (6)
O3—S1—O1	109.29 (5)	H1A—N1—H1D^iv	86 (5)
O2—S1—O1	109.38 (5)	H1B—N1—H1D^iv	136 (6)
O4—S1—O1	104.71 (5)	H1C—N1—H1D^iv	103 (5)
S1—O1—H1O	109 (3)	H1D—N1—H1D^iv	180 (7)
S1—O2—Co1	132.41 (5)	H1B^iv—N1—H1D^iv	44 (6)
S1—O4—Co1^v	132.25 (5)	H1C^iv—N1—H1D^iv	77 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O1^vi	0.70 (4)	1.80 (4)	2.4810 (16)	165 (5)
O5—H5A···O2^vii	0.74 (3)	2.57 (3)	2.9923 (11)	118 (2)
O5—H5B···O3^vii	0.77 (2)	2.51 (2)	3.2020 (13)	149 (2)
N1—H1A···O3^vi	0.98 (7)	1.96 (7)	2.9298 (8)	169 (7)
N1—H1D···O1^viii	0.84 (7)	2.33 (7)	3.1657 (10)	175 (7)
N1—H1C···O1	0.87 (6)	2.29 (6)	3.1098 (8)	158 (6)
N1—H1D···O1^viii	0.84 (7)	2.33 (7)	3.1657 (10)	175 (7)
N1—H1B···O4^viii	0.91 (9)	1.97 (9)	2.8773 (7)	176 (8)

Symmetry codes: (vi) −x−1, −y−1, −z−1; (vii) −x, −y−1, −z; (viii) −x−1, −y, −z−1.

catena-Poly[ammonium [[diaquanickel(II)]-µ-(hydrogen sulfato)-µ-sulfato]] (Ni_296K) top

Crystal data top

(NH₄)[Ni(HSO₄)(SO₄)(H₂O)₂]	Z = 1
M_r = 305.91	F(000) = 156
Triclinic, P1	D_x = 2.407 Mg m⁻³
a = 4.5746 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 5.7944 (19) Å	Cell parameters from 1458 reflections
c = 8.347 (2) Å	θ = 2.6–32.9°
α = 104.049 (11)°	µ = 2.84 mm⁻¹
β = 98.133 (12)°	T = 296 K
γ = 94.420 (12)°	Plate, green
V = 211.04 (12) Å³	0.12 × 0.06 × 0.01 mm

Data collection top

Bruker APEXII CCD diffractometer	1307 reflections with I > 2σ(I)
ω– and φ–scans	R_int = 0.027
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 33.2°, θ_min = 3.7°
T_min = 0.598, T_max = 0.747	h = −7→6
3532 measured reflections	k = −8→8
1591 independent reflections	l = −12→12

Refinement top

Refinement on F²	7 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	All H-atom parameters refined
wR(F²) = 0.077	w = 1/[σ²(F_o²) + (0.034P)² + 0.0522P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1591 reflections	Δρ_max = 0.47 e Å⁻³
95 parameters	Δρ_min = −0.59 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.000000	0.000000	0.000000	0.01194 (10)
S1	−0.58959 (10)	−0.31438 (8)	−0.23407 (5)	0.01127 (11)
O1	−0.4942 (4)	−0.3026 (3)	−0.39878 (19)	0.0221 (3)
O2	−0.3263 (3)	−0.2831 (3)	−0.1046 (2)	0.0189 (3)
O3	−0.7571 (4)	−0.5462 (3)	−0.2553 (2)	0.0221 (3)
O4	−0.7659 (3)	−0.1127 (3)	−0.19328 (18)	0.0170 (3)
O5	0.1932 (4)	−0.2084 (3)	0.1425 (2)	0.0182 (3)
H5A	0.105 (8)	−0.329 (5)	0.161 (5)	0.057 (12)*
H5B	0.352 (6)	−0.271 (7)	0.131 (5)	0.068 (14)*
N1	0.000000	0.000000	−0.500000	0.0247 (6)
H1A	−0.077 (19)	−0.149 (7)	−0.560 (11)	0.05 (2)*	0.5
H1B	−0.07 (2)	−0.02 (2)	−0.610 (3)	0.07 (3)*	0.5
H1C	−0.167 (8)	−0.054 (11)	−0.469 (8)	0.023 (15)*	0.5
H1D	−0.11 (2)	0.104 (17)	−0.540 (15)	0.09 (4)*	0.5
H1O	−0.475 (14)	−0.439 (5)	−0.459 (6)	0.020 (15)*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01190 (18)	0.01163 (16)	0.01267 (17)	0.00243 (12)	0.00245 (12)	0.00331 (12)
S1	0.0131 (2)	0.00957 (19)	0.0104 (2)	0.00016 (16)	0.00340 (16)	0.00082 (16)
O1	0.0367 (10)	0.0162 (7)	0.0149 (7)	0.0010 (7)	0.0147 (7)	0.0012 (6)
O2	0.0159 (7)	0.0152 (6)	0.0238 (7)	0.0005 (5)	−0.0023 (6)	0.0053 (6)
O3	0.0259 (9)	0.0142 (7)	0.0234 (8)	−0.0080 (6)	0.0058 (6)	0.0017 (6)
O4	0.0180 (7)	0.0195 (7)	0.0165 (6)	0.0090 (6)	0.0074 (6)	0.0057 (6)
O5	0.0179 (8)	0.0162 (7)	0.0238 (7)	0.0041 (6)	0.0042 (6)	0.0101 (6)
N1	0.0324 (17)	0.0203 (13)	0.0194 (13)	0.0000 (12)	−0.0024 (12)	0.0059 (11)

Geometric parameters (Å, º) top

Ni1—O5ⁱ	2.0539 (16)	O5—H5A	0.838 (10)
Ni1—O5	2.0539 (16)	O5—H5B	0.843 (10)
Ni1—O2ⁱ	2.0592 (16)	N1—H1A	0.901 (10)
Ni1—O2	2.0592 (16)	N1—H1B	0.898 (10)
Ni1—O4ⁱⁱ	2.0642 (15)	N1—H1C	0.899 (10)
Ni1—O4ⁱⁱⁱ	2.0642 (15)	N1—H1D	0.899 (10)
S1—O3	1.4525 (15)	N1—H1A^iv	0.901 (10)
S1—O2	1.4678 (16)	N1—H1B^iv	0.898 (10)
S1—O4	1.4703 (16)	N1—H1C^iv	0.899 (10)
S1—O1	1.5153 (16)	N1—H1D^iv	0.899 (10)
O1—H1O	0.845 (10)

O5ⁱ—Ni1—O5	180.00 (6)	H1A—N1—H1C	66 (6)
O5ⁱ—Ni1—O2ⁱ	87.64 (7)	H1B—N1—H1C	99 (7)
O5—Ni1—O2ⁱ	92.36 (7)	H1A—N1—H1D	108 (7)
O5ⁱ—Ni1—O2	92.36 (7)	H1B—N1—H1D	58 (8)
O5—Ni1—O2	87.64 (7)	H1C—N1—H1D	87 (7)
O2ⁱ—Ni1—O2	180.0	H1A—N1—H1A^iv	179.998 (12)
O5ⁱ—Ni1—O4ⁱⁱ	85.92 (7)	H1B—N1—H1A^iv	118 (7)
O5—Ni1—O4ⁱⁱ	94.08 (7)	H1C—N1—H1A^iv	114 (6)
O2ⁱ—Ni1—O4ⁱⁱ	89.36 (7)	H1D—N1—H1A^iv	72 (7)
O2—Ni1—O4ⁱⁱ	90.64 (7)	H1A—N1—H1B^iv	118 (7)
O5ⁱ—Ni1—O4ⁱⁱⁱ	94.08 (7)	H1B—N1—H1B^iv	180.00 (3)
O5—Ni1—O4ⁱⁱⁱ	85.92 (7)	H1C—N1—H1B^iv	81 (7)
O2ⁱ—Ni1—O4ⁱⁱⁱ	90.64 (7)	H1D—N1—H1B^iv	122 (8)
O2—Ni1—O4ⁱⁱⁱ	89.36 (7)	H1A^iv—N1—H1B^iv	62 (7)
O4ⁱⁱ—Ni1—O4ⁱⁱⁱ	180.00 (11)	H1A—N1—H1C^iv	114 (6)
O3—S1—O2	109.59 (10)	H1B—N1—H1C^iv	81 (7)
O3—S1—O4	113.40 (10)	H1C—N1—H1C^iv	179.999 (12)
O2—S1—O4	110.21 (9)	H1D—N1—H1C^iv	93 (7)
O3—S1—O1	109.00 (9)	H1A^iv—N1—H1C^iv	66 (6)
O2—S1—O1	109.71 (10)	H1B^iv—N1—H1C^iv	99 (7)
O4—S1—O1	104.79 (9)	H1A—N1—H1D^iv	72 (7)
S1—O1—H1O	112 (4)	H1B—N1—H1D^iv	122 (8)
S1—O2—Ni1	131.92 (10)	H1C—N1—H1D^iv	93 (7)
S1—O4—Ni1^v	132.17 (9)	H1D—N1—H1D^iv	180.00 (6)
Ni1—O5—H5A	124 (3)	H1A^iv—N1—H1D^iv	108 (7)
Ni1—O5—H5B	126 (3)	H1B^iv—N1—H1D^iv	58 (8)
H5A—O5—H5B	94 (4)	H1C^iv—N1—H1D^iv	87 (7)
H1A—N1—H1B	62 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O1^vi	0.85 (1)	1.65 (2)	2.484 (3)	167 (6)
O5—H5A···O2^vii	0.84 (1)	2.50 (4)	3.005 (2)	119 (3)
O5—H5B···O3^vii	0.84 (1)	2.43 (2)	3.177 (3)	147 (4)
N1—H1A···O3^vi	0.90 (1)	2.05 (3)	2.9360 (17)	166 (9)
N1—H1D···O1^viii	0.90 (1)	2.29 (4)	3.152 (2)	159 (9)
N1—H1C···O1	0.90 (1)	2.23 (2)	3.0898 (18)	160 (6)
N1—H1D···O1^viii	0.90 (1)	2.29 (4)	3.152 (2)	159 (9)
N1—H1B···O4^viii	0.90 (1)	2.07 (7)	2.8761 (16)	149 (11)

Symmetry codes: (vi) −x−1, −y−1, −z−1; (vii) −x, −y−1, −z; (viii) −x−1, −y, −z−1.

catena-Poly[ammonium [[diaquairon(II)]-µ-(hydrogen sulfato)-µ-sulfato]] (Fe_100K) top

Crystal data top

(NH₄)[Fe(HSO₄)(SO₄)(H₂O)₂]	Z = 2
M_r = 303.05	F(000) = 308
Triclinic, P1	D_x = 2.337 Mg m⁻³
a = 7.0847 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7956 (7) Å	Cell parameters from 8457 reflections
c = 8.3868 (7) Å	θ = 3.6–41.7°
α = 84.5953 (15)°	µ = 2.28 mm⁻¹
β = 73.2990 (15)°	T = 100 K
γ = 76.2281 (17)°	Fragment, light green
V = 430.74 (6) Å³	0.12 × 0.09 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	5143 reflections with I > 2σ(I)
ω– and φ–scans	R_int = 0.027
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 41.8°, θ_min = 3.4°
T_min = 0.619, T_max = 0.748	h = −13→13
17276 measured reflections	k = −13→14
5854 independent reflections	l = −15→15

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0297P)² + 0.0364P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.062	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.78 e Å⁻³
5854 reflections	Δρ_min = −0.76 e Å⁻³
164 parameters	Extinction correction: SHELXL (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0254 (17)

Special details top

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

	x	y	z	U_iso*/U_eq
Fe1	0.25151 (2)	0.25374 (2)	0.49272 (2)	0.00495 (3)
S1	−0.20455 (2)	0.38437 (2)	0.73962 (2)	0.00486 (3)
S2	0.71243 (2)	0.10045 (2)	0.26107 (2)	0.00509 (3)
O1	−0.40545 (7)	0.35213 (7)	0.75846 (6)	0.00970 (8)
O2	−0.05984 (7)	0.28137 (6)	0.59849 (6)	0.00805 (7)
O3	−0.20277 (8)	0.57470 (6)	0.70817 (6)	0.00806 (7)
O4	−0.14330 (7)	0.33145 (7)	0.89603 (6)	0.00878 (8)
O5	0.91507 (7)	0.12707 (7)	0.23313 (6)	0.01001 (8)
O6	0.69127 (7)	−0.08135 (6)	0.30682 (6)	0.00790 (7)
O7	0.56594 (7)	0.22548 (7)	0.38158 (6)	0.00866 (7)
O8	0.65788 (8)	0.13443 (7)	0.09282 (6)	0.00920 (8)
O9	0.26255 (8)	0.46053 (7)	0.63591 (6)	0.00918 (8)
O10	0.24415 (8)	0.04282 (7)	0.35229 (6)	0.00923 (8)
N1	0.75683 (8)	0.74104 (7)	0.00607 (6)	0.00962 (9)
H1W	0.366 (3)	0.468 (3)	0.656 (2)	0.040 (5)*
H2W	0.219 (3)	0.573 (2)	0.6169 (19)	0.034 (4)*
H3W	0.291 (3)	−0.067 (2)	0.362 (2)	0.043 (5)*
H4W	0.136 (3)	0.036 (2)	0.334 (2)	0.036 (4)*
H1O	0.741 (2)	0.217 (2)	0.0126 (16)	0.060 (6)*
H1N	0.8604 (18)	0.7089 (16)	0.0468 (14)	0.019 (3)*
H2N	0.6513 (19)	0.7147 (17)	0.0744 (15)	0.023 (3)*
H3N	0.7821 (18)	0.6913 (16)	−0.0890 (15)	0.020 (3)*
H4N	0.7343 (19)	0.8583 (19)	−0.0057 (16)	0.027 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.00537 (4)	0.00455 (4)	0.00480 (4)	−0.00135 (3)	−0.00113 (3)	0.00033 (3)
S1	0.00463 (6)	0.00543 (6)	0.00448 (5)	−0.00159 (4)	−0.00111 (4)	0.00087 (4)
S2	0.00486 (6)	0.00560 (6)	0.00485 (5)	−0.00169 (4)	−0.00126 (4)	0.00085 (4)
O1	0.00568 (17)	0.0146 (2)	0.00951 (18)	−0.00435 (15)	−0.00205 (13)	0.00177 (15)
O2	0.00666 (16)	0.00801 (17)	0.00835 (17)	−0.00108 (13)	−0.00005 (13)	−0.00243 (13)
O3	0.01220 (19)	0.00485 (16)	0.00735 (16)	−0.00189 (14)	−0.00339 (14)	0.00101 (13)
O4	0.00992 (18)	0.01136 (19)	0.00653 (16)	−0.00446 (15)	−0.00414 (13)	0.00401 (13)
O5	0.00555 (17)	0.0147 (2)	0.01045 (18)	−0.00411 (15)	−0.00241 (14)	0.00212 (15)
O6	0.01117 (18)	0.00526 (16)	0.00762 (16)	−0.00207 (14)	−0.00348 (14)	0.00165 (13)
O7	0.00748 (17)	0.00758 (17)	0.00980 (17)	−0.00150 (14)	−0.00002 (13)	−0.00261 (13)
O8	0.01154 (19)	0.01164 (19)	0.00667 (16)	−0.00573 (15)	−0.00466 (14)	0.00377 (14)
O9	0.01044 (18)	0.00697 (17)	0.01178 (18)	−0.00233 (14)	−0.00507 (15)	−0.00103 (14)
O10	0.00890 (18)	0.00700 (17)	0.01307 (19)	−0.00151 (14)	−0.00468 (15)	−0.00192 (14)
N1	0.0103 (2)	0.0110 (2)	0.0080 (2)	−0.00397 (18)	−0.00154 (17)	−0.00116 (17)

Geometric parameters (Å, º) top

Fe1—O2	2.0939 (5)	S2—O7	1.4662 (5)
Fe1—O3ⁱ	2.1063 (5)	S2—O8	1.5508 (5)
Fe1—O7	2.1192 (5)	O8—H1O	1.040 (16)
Fe1—O6ⁱⁱ	2.1222 (5)	O9—H1W	0.816 (17)
Fe1—O9	2.1273 (5)	O9—H2W	0.875 (17)
Fe1—O10	2.1294 (5)	O10—H3W	0.849 (19)
S1—O1	1.4654 (5)	O10—H4W	0.840 (17)
S1—O2	1.4786 (5)	N1—H1N	0.871 (12)
S1—O3	1.4848 (5)	N1—H2N	0.857 (13)
S1—O4	1.4897 (5)	N1—H3N	0.873 (12)
S2—O5	1.4486 (5)	N1—H4N	0.890 (14)
S2—O6	1.4642 (5)

O2—Fe1—O3ⁱ	91.39 (2)	O5—S2—O7	110.90 (3)
O2—Fe1—O7	179.016 (16)	O6—S2—O7	111.31 (3)
O3ⁱ—Fe1—O7	87.88 (2)	O5—S2—O8	107.81 (3)
O2—Fe1—O6ⁱⁱ	90.08 (2)	O6—S2—O8	103.28 (3)
O3ⁱ—Fe1—O6ⁱⁱ	178.490 (16)	O7—S2—O8	108.40 (3)
O7—Fe1—O6ⁱⁱ	90.65 (2)	S1—O2—Fe1	132.45 (3)
O2—Fe1—O9	92.376 (19)	S1—O3—Fe1ⁱ	131.15 (3)
O3ⁱ—Fe1—O9	93.37 (2)	S2—O6—Fe1ⁱⁱ	132.50 (3)
O7—Fe1—O9	88.326 (19)	S2—O7—Fe1	132.00 (3)
O6ⁱⁱ—Fe1—O9	86.24 (2)	S2—O8—H1O	112.0 (7)
O2—Fe1—O10	88.086 (19)	Fe1—O9—H1W	122.3 (13)
O3ⁱ—Fe1—O10	87.74 (2)	Fe1—O9—H2W	124.8 (10)
O7—Fe1—O10	91.225 (19)	H1W—O9—H2W	97.4 (17)
O6ⁱⁱ—Fe1—O10	92.63 (2)	Fe1—O10—H3W	129.4 (11)
O9—Fe1—O10	178.780 (17)	Fe1—O10—H4W	120.2 (12)
O1—S1—O2	108.49 (3)	H3W—O10—H4W	97.2 (17)
O1—S1—O3	111.55 (3)	H1N—N1—H2N	110.8 (12)
O2—S1—O3	109.53 (3)	H1N—N1—H3N	110.5 (12)
O1—S1—O4	110.01 (3)	H2N—N1—H3N	110.0 (12)
O2—S1—O4	110.58 (3)	H1N—N1—H4N	106.1 (12)
O3—S1—O4	106.69 (3)	H2N—N1—H4N	107.8 (13)
O5—S2—O6	114.63 (3)	H3N—N1—H4N	111.5 (13)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1O···O4ⁱⁱⁱ	1.040 (16)	1.467 (16)	2.5067 (8)	178.6 (12)
O9—H1W···O1^iv	0.816 (17)	2.030 (19)	2.7537 (7)	147.5 (18)
O9—H2W···O2ⁱ	0.875 (17)	2.447 (17)	3.0785 (7)	129.5 (13)
O9—H2W···O5^v	0.875 (17)	2.599 (16)	3.3272 (8)	141.3 (13)
O9—H2W···O7^v	0.875 (17)	2.439 (17)	2.9556 (7)	118.3 (14)
O10—H3W···O1^vi	0.849 (19)	2.389 (18)	3.1467 (8)	149.0 (15)
O10—H3W···O2^vi	0.849 (19)	2.541 (19)	3.0541 (7)	119.9 (16)
O10—H4W···O5^vii	0.840 (17)	1.946 (18)	2.7115 (7)	151.2 (18)
N1—H3N···O3ⁱⁱⁱ	0.873 (12)	1.967 (12)	2.8334 (7)	171.5 (11)
N1—H1N···O4^v	0.871 (12)	2.138 (12)	2.9931 (7)	167.2 (11)
N1—H2N···O1ⁱ	0.857 (13)	2.040 (13)	2.8965 (7)	178.3 (12)
N1—H4N···O8^viii	0.890 (14)	2.266 (14)	3.0869 (8)	153.2 (11)

Symmetry codes: (i) −x, −y+1, −z+1; (iii) x+1, y, z−1; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x, −y, −z+1; (vii) x−1, y, z; (viii) x, y+1, z.

catena-Poly[ammonium [[diaquacobalt(II)]-µ-(hydrogen sulfato)-µ-sulfato]] (Co_100K) top

Crystal data top

(NH₄)[Co(HSO₄)(SO₄)(H₂O)₂]	Z = 2
M_r = 306.13	F(000) = 310
Triclinic, P1	D_x = 2.401 Mg m⁻³
a = 7.0775 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.7268 (4) Å	Cell parameters from 3880 reflections
c = 8.3281 (5) Å	θ = 2.5–37.9°
α = 84.5548 (11)°	µ = 2.56 mm⁻¹
β = 73.1705 (15)°	T = 100 K
γ = 76.3233 (11)°	Fragment, violet
V = 423.40 (4) Å³	0.12 × 0.09 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	3507 reflections with I > 2σ(I)
ω– and φ–scans	R_int = 0.019
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 37.4°, θ_min = 2.7°
T_min = 0.669, T_max = 0.747	h = −11→11
8668 measured reflections	k = −12→13
4184 independent reflections	l = −12→14

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + (0.0279P)² + 0.0625P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.062	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.54 e Å⁻³
4184 reflections	Δρ_min = −0.53 e Å⁻³
164 parameters	Extinction correction: SHELXL (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0088 (12)

Special details top

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

	x	y	z	U_iso*/U_eq
Co1	0.25150 (2)	0.25333 (2)	0.49323 (2)	0.00461 (4)
S1	−0.20148 (3)	0.38406 (3)	0.73639 (3)	0.00453 (5)
S2	0.70903 (3)	0.10225 (3)	0.26461 (3)	0.00474 (5)
O1	−0.40347 (10)	0.35343 (10)	0.75566 (9)	0.00908 (12)
O2	−0.05715 (10)	0.27901 (9)	0.59451 (8)	0.00768 (12)
O3	−0.19659 (11)	0.57524 (9)	0.70390 (8)	0.00763 (12)
O4	−0.14110 (11)	0.33068 (9)	0.89441 (8)	0.00829 (12)
O5	0.91201 (10)	0.12872 (10)	0.23703 (9)	0.00941 (12)
O6	0.68627 (11)	−0.08057 (9)	0.31075 (8)	0.00761 (12)
O7	0.56238 (10)	0.22842 (9)	0.38606 (9)	0.00817 (12)
O8	0.65547 (11)	0.13697 (10)	0.09487 (8)	0.00857 (12)
O9	0.25915 (11)	0.45756 (10)	0.63827 (9)	0.00840 (12)
O10	0.24613 (11)	0.04547 (10)	0.35051 (9)	0.00849 (12)
N1	0.75577 (13)	0.74180 (11)	0.00616 (10)	0.00941 (14)
H1W	0.358 (3)	0.468 (3)	0.655 (3)	0.033 (5)*
H2W	0.212 (3)	0.564 (3)	0.624 (2)	0.034 (5)*
H3W	0.291 (3)	−0.058 (3)	0.359 (2)	0.037 (5)*
H4W	0.142 (3)	0.038 (3)	0.335 (2)	0.031 (5)*
H1O	0.739 (3)	0.211 (3)	0.015 (2)	0.050 (6)*
H1N	0.860 (2)	0.708 (2)	0.0516 (19)	0.021 (4)*
H2N	0.652 (3)	0.713 (2)	0.078 (2)	0.026 (4)*
H3N	0.786 (2)	0.692 (2)	−0.0922 (19)	0.018 (4)*
H4N	0.730 (3)	0.861 (2)	−0.004 (2)	0.030 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.00482 (6)	0.00409 (6)	0.00483 (6)	−0.00083 (4)	−0.00140 (4)	0.00022 (4)
S1	0.00434 (9)	0.00492 (9)	0.00429 (8)	−0.00129 (7)	−0.00126 (6)	0.00089 (6)
S2	0.00451 (9)	0.00505 (9)	0.00468 (8)	−0.00134 (7)	−0.00135 (6)	0.00081 (6)
O1	0.0053 (3)	0.0131 (3)	0.0095 (3)	−0.0040 (2)	−0.0020 (2)	0.0014 (2)
O2	0.0062 (3)	0.0077 (3)	0.0083 (3)	−0.0009 (2)	−0.0004 (2)	−0.0023 (2)
O3	0.0111 (3)	0.0044 (3)	0.0077 (3)	−0.0014 (2)	−0.0037 (2)	0.0008 (2)
O4	0.0095 (3)	0.0106 (3)	0.0063 (3)	−0.0043 (2)	−0.0041 (2)	0.0041 (2)
O5	0.0049 (3)	0.0135 (3)	0.0102 (3)	−0.0034 (2)	−0.0022 (2)	0.0018 (2)
O6	0.0106 (3)	0.0052 (3)	0.0074 (3)	−0.0019 (2)	−0.0035 (2)	0.0017 (2)
O7	0.0069 (3)	0.0071 (3)	0.0094 (3)	−0.0014 (2)	0.0001 (2)	−0.0025 (2)
O8	0.0106 (3)	0.0114 (3)	0.0059 (3)	−0.0054 (2)	−0.0045 (2)	0.0037 (2)
O9	0.0087 (3)	0.0067 (3)	0.0113 (3)	−0.0017 (2)	−0.0049 (2)	−0.0009 (2)
O10	0.0075 (3)	0.0065 (3)	0.0124 (3)	−0.0008 (2)	−0.0044 (2)	−0.0018 (2)
N1	0.0102 (4)	0.0109 (4)	0.0072 (3)	−0.0036 (3)	−0.0014 (3)	−0.0007 (3)

Geometric parameters (Å, º) top

Co1—O2	2.0695 (7)	S2—O7	1.4668 (7)
Co1—O3ⁱ	2.0771 (7)	S2—O8	1.5506 (7)
Co1—O6ⁱⁱ	2.0895 (7)	O8—H1O	0.99 (2)
Co1—O7	2.0905 (7)	O9—H1W	0.77 (2)
Co1—O9	2.0957 (7)	O9—H2W	0.82 (2)
Co1—O10	2.1003 (7)	O10—H3W	0.79 (2)
S1—O1	1.4647 (7)	O10—H4W	0.80 (2)
S1—O2	1.4797 (7)	N1—H1N	0.897 (16)
S1—O3	1.4831 (7)	N1—H2N	0.864 (17)
S1—O4	1.4912 (7)	N1—H3N	0.887 (15)
S2—O5	1.4482 (7)	N1—H4N	0.894 (18)
S2—O6	1.4621 (7)

O2—Co1—O3ⁱ	89.43 (3)	O5—S2—O7	110.82 (4)
O2—Co1—O6ⁱⁱ	91.87 (3)	O6—S2—O7	111.17 (4)
O3ⁱ—Co1—O6ⁱⁱ	178.71 (3)	O5—S2—O8	107.85 (4)
O2—Co1—O7	178.83 (2)	O6—S2—O8	103.30 (4)
O3ⁱ—Co1—O7	89.54 (3)	O7—S2—O8	108.44 (4)
O6ⁱⁱ—Co1—O7	89.16 (3)	S1—O2—Co1	131.08 (4)
O2—Co1—O9	92.65 (3)	S1—O3—Co1ⁱ	130.79 (4)
O3ⁱ—Co1—O9	93.92 (3)	S2—O6—Co1ⁱⁱ	132.17 (4)
O6ⁱⁱ—Co1—O9	85.97 (3)	S2—O7—Co1	130.91 (4)
O7—Co1—O9	87.96 (3)	S2—O8—H1O	112.7 (10)
O2—Co1—O10	87.61 (3)	Co1—O9—H1W	122.4 (15)
O3ⁱ—Co1—O10	87.02 (3)	Co1—O9—H2W	124.7 (13)
O6ⁱⁱ—Co1—O10	93.08 (3)	H1W—O9—H2W	97 (2)
O7—Co1—O10	91.79 (3)	Co1—O10—H3W	129.1 (14)
O9—Co1—O10	179.03 (3)	Co1—O10—H4W	119.8 (14)
O1—S1—O2	108.56 (4)	H3W—O10—H4W	97 (2)
O1—S1—O3	111.65 (4)	H1N—N1—H2N	106.8 (15)
O2—S1—O3	109.44 (4)	H1N—N1—H3N	110.4 (15)
O1—S1—O4	110.01 (4)	H2N—N1—H3N	112.7 (16)
O2—S1—O4	110.63 (4)	H1N—N1—H4N	107.8 (16)
O3—S1—O4	106.55 (4)	H2N—N1—H4N	107.4 (16)
O5—S2—O6	114.78 (4)	H3N—N1—H4N	111.4 (16)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1O···O4ⁱⁱⁱ	0.99 (2)	1.51 (2)	2.5007 (11)	177.4 (17)
O9—H1W···O1^iv	0.77 (2)	2.08 (2)	2.7566 (10)	147 (2)
O9—H2W···O2ⁱ	0.82 (2)	2.468 (19)	3.0700 (10)	130.8 (16)
O9—H2W···O5^v	0.82 (2)	2.59 (2)	3.2918 (10)	144.5 (16)
O9—H1W···O7^v	0.77 (2)	2.51 (2)	2.9549 (10)	118.1 (19)
O10—H3W···O1^vi	0.79 (2)	2.42 (2)	3.1378 (10)	151.0 (18)
O10—H3W···O2^vi	0.79 (2)	2.58 (2)	3.0492 (10)	119.8 (19)
O10—H4W···O5^vii	0.80 (2)	1.98 (2)	2.7127 (10)	152 (2)
N1—H3N···O3ⁱⁱⁱ	0.887 (15)	1.955 (15)	2.8328 (10)	170.1 (15)
N1—H1N···O4^v	0.897 (16)	2.114 (16)	2.9890 (11)	164.7 (14)
N1—H2N···O1ⁱ	0.864 (17)	2.038 (17)	2.9017 (11)	178.9 (16)
N1—H4N···O8^viii	0.894 (18)	2.252 (18)	3.0777 (11)	153.4 (15)

Symmetry codes: (i) −x, −y+1, −z+1; (iii) x+1, y, z−1; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x, −y, −z+1; (vii) x−1, y, z; (viii) x, y+1, z.

catena-Poly[ammonium [[diaquanickel(II)]-µ-(hydrogen sulfato)-µ-sulfato]] (Ni_100K) top

Crystal data top

(NH₄)[Ni(HSO₄)(SO₄)(H₂O)₂]	Z = 2
M_r = 305.91	F(000) = 312
Triclinic, P1	D_x = 2.444 Mg m⁻³
a = 7.0437 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6405 (9) Å	Cell parameters from 1834 reflections
c = 8.3097 (10) Å	θ = 2.6–35.4°
α = 84.571 (3)°	µ = 2.88 mm⁻¹
β = 73.376 (3)°	T = 100 K
γ = 76.056 (3)°	Plate, green
V = 415.73 (9) Å³	0.12 × 0.09 × 0.02 mm

Data collection top

Bruker APEXII CCD diffractometer	2253 reflections with I > 2σ(I)
ω– and φ–scans	R_int = 0.031
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 36.0°, θ_min = 2.8°
T_min = 0.609, T_max = 0.747	h = −11→11
7657 measured reflections	k = −12→10
3609 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.038	All H-atom parameters refined
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0362P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
3609 reflections	Δρ_max = 0.86 e Å⁻³
163 parameters	Δρ_min = −0.95 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Ni1	0.25124 (5)	0.25282 (4)	0.49418 (4)	0.00539 (7)
S1	−0.20008 (8)	0.38376 (7)	0.73454 (6)	0.00486 (11)
S2	0.70693 (8)	0.10508 (7)	0.26711 (6)	0.00487 (11)
O1	−0.4025 (3)	0.3526 (2)	0.75282 (19)	0.0092 (3)
O2	−0.0549 (2)	0.2761 (2)	0.59314 (19)	0.0075 (3)
O3	−0.1951 (3)	0.5767 (2)	0.70128 (19)	0.0071 (3)
O4	−0.1400 (3)	0.3306 (2)	0.89363 (19)	0.0083 (3)
O5	0.9098 (2)	0.1337 (2)	0.24048 (19)	0.0084 (3)
O6	0.6869 (3)	−0.0809 (2)	0.31174 (19)	0.0083 (3)
O7	0.5585 (2)	0.2307 (2)	0.39011 (19)	0.0077 (3)
O8	0.6523 (3)	0.1411 (2)	0.09759 (19)	0.0084 (3)
O9	0.2564 (3)	0.4542 (2)	0.6385 (2)	0.0078 (3)
O10	0.2491 (3)	0.0488 (2)	0.3518 (2)	0.0082 (3)
N1	0.7538 (4)	0.7431 (3)	0.0062 (3)	0.0094 (3)
H1W	0.360 (8)	0.473 (7)	0.648 (6)	0.082 (19)*
H2W	0.209 (7)	0.536 (5)	0.628 (5)	0.042 (14)*
H3W	0.294 (6)	−0.056 (5)	0.364 (4)	0.026 (10)*
H4W	0.146 (4)	0.046 (4)	0.337 (3)	0.001 (7)*
H1O	0.724 (6)	0.203 (5)	0.019 (4)	0.053 (12)*
H1N	0.864 (5)	0.713 (4)	0.051 (4)	0.017 (8)*
H2N	0.641 (6)	0.712 (4)	0.076 (4)	0.029 (9)*
H3N	0.782 (5)	0.694 (4)	−0.091 (4)	0.017 (8)*
H4N	0.730 (9)	0.850 (8)	0.004 (6)	0.10 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.00552 (12)	0.00502 (12)	0.00545 (12)	−0.00102 (9)	−0.00143 (9)	0.00004 (8)
S1	0.0051 (3)	0.0053 (2)	0.0042 (2)	−0.00159 (19)	−0.00140 (19)	0.00091 (17)
S2	0.0044 (3)	0.0058 (2)	0.0046 (2)	−0.00155 (19)	−0.00146 (18)	0.00088 (17)
O1	0.0066 (8)	0.0123 (8)	0.0092 (7)	−0.0039 (6)	−0.0021 (6)	0.0020 (6)
O2	0.0060 (8)	0.0074 (7)	0.0079 (6)	0.0005 (6)	−0.0009 (6)	−0.0023 (5)
O3	0.0098 (8)	0.0045 (7)	0.0076 (6)	−0.0008 (6)	−0.0042 (6)	0.0008 (5)
O4	0.0093 (8)	0.0118 (8)	0.0052 (6)	−0.0045 (6)	−0.0037 (6)	0.0040 (5)
O5	0.0043 (8)	0.0139 (8)	0.0089 (7)	−0.0047 (6)	−0.0034 (6)	0.0024 (6)
O6	0.0121 (9)	0.0051 (7)	0.0083 (6)	−0.0025 (6)	−0.0038 (6)	0.0022 (5)
O7	0.0067 (8)	0.0066 (7)	0.0089 (7)	−0.0007 (6)	−0.0009 (6)	−0.0021 (5)
O8	0.0113 (8)	0.0116 (8)	0.0050 (6)	−0.0059 (6)	−0.0045 (6)	0.0032 (6)
O9	0.0081 (9)	0.0067 (8)	0.0094 (7)	−0.0014 (6)	−0.0035 (6)	−0.0008 (6)
O10	0.0067 (9)	0.0077 (8)	0.0115 (7)	−0.0007 (6)	−0.0050 (6)	−0.0009 (6)
N1	0.0108 (8)	0.0107 (9)	0.0072 (8)	−0.0043 (7)	−0.0013 (7)	−0.0009 (6)

Geometric parameters (Å, º) top

Ni1—O2	2.0457 (17)	S2—O7	1.4660 (16)
Ni1—O10	2.0491 (18)	S2—O8	1.5472 (17)
Ni1—O9	2.0513 (18)	O8—H1O	0.88 (4)
Ni1—O3ⁱ	2.0519 (16)	O9—H1W	0.80 (5)
Ni1—O7	2.0594 (16)	O9—H2W	0.65 (4)
Ni1—O6ⁱⁱ	2.0595 (17)	O10—H3W	0.80 (3)
S1—O1	1.4645 (17)	O10—H4W	0.78 (3)
S1—O3	1.4806 (16)	N1—H1N	0.93 (3)
S1—O2	1.4808 (16)	N1—H2N	0.91 (3)
S1—O4	1.4924 (17)	N1—H3N	0.87 (3)
S2—O5	1.4487 (17)	N1—H4N	0.79 (6)
S2—O6	1.4639 (16)

O2—Ni1—O10	87.59 (7)	O5—S2—O7	110.67 (10)
O2—Ni1—O9	92.83 (7)	O6—S2—O7	110.96 (9)
O10—Ni1—O9	179.11 (9)	O5—S2—O8	107.92 (9)
O2—Ni1—O3ⁱ	89.49 (7)	O6—S2—O8	103.32 (10)
O10—Ni1—O3ⁱ	86.25 (7)	O7—S2—O8	108.63 (10)
O9—Ni1—O3ⁱ	94.54 (7)	S1—O2—Ni1	130.45 (10)
O2—Ni1—O7	178.91 (7)	S1—O3—Ni1ⁱ	130.68 (10)
O10—Ni1—O7	91.91 (7)	S2—O6—Ni1ⁱⁱ	131.99 (11)
O9—Ni1—O7	87.68 (7)	S2—O7—Ni1	130.71 (10)
O3ⁱ—Ni1—O7	89.52 (7)	S2—O8—H1O	117 (3)
O2—Ni1—O6ⁱⁱ	91.53 (7)	Ni1—O9—H1W	123 (4)
O10—Ni1—O6ⁱⁱ	93.68 (7)	Ni1—O9—H2W	120 (4)
O9—Ni1—O6ⁱⁱ	85.52 (7)	H1W—O9—H2W	99 (5)
O3ⁱ—Ni1—O6ⁱⁱ	178.97 (8)	Ni1—O10—H3W	127 (2)
O7—Ni1—O6ⁱⁱ	89.46 (7)	Ni1—O10—H4W	117 (2)
O1—S1—O3	111.91 (10)	H3W—O10—H4W	100 (3)
O1—S1—O2	108.25 (10)	H1N—N1—H2N	113 (3)
O3—S1—O2	109.45 (9)	H1N—N1—H3N	111 (3)
O1—S1—O4	109.98 (9)	H2N—N1—H3N	109 (3)
O3—S1—O4	106.50 (10)	H1N—N1—H4N	102 (4)
O2—S1—O4	110.77 (10)	H2N—N1—H4N	106 (4)
O5—S2—O6	114.88 (10)	H3N—N1—H4N	115 (4)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O8—H1O···O4ⁱⁱⁱ	0.88 (4)	1.62 (4)	2.499 (2)	173 (4)
O9—H1W···O1^iv	0.80 (5)	2.08 (5)	2.747 (3)	140 (5)
O9—H2W···O2ⁱ	0.65 (4)	2.55 (4)	3.061 (3)	138 (4)
O9—H2W···O5^v	0.65 (4)	2.69 (4)	3.232 (2)	143 (4)
O9—H1W···O7^v	0.80 (5)	2.44 (5)	2.963 (2)	124 (5)
O10—H3W···O1^vi	0.80 (3)	2.41 (3)	3.115 (2)	148 (3)
O10—H3W···O2^vi	0.80 (3)	2.59 (4)	3.051 (2)	119 (3)
O10—H4W···O5^vii	0.78 (3)	2.00 (3)	2.719 (3)	155 (3)
N1—H3N···O3ⁱⁱⁱ	0.87 (3)	1.97 (3)	2.834 (3)	172 (3)
N1—H1N···O4^v	0.93 (3)	2.07 (3)	2.980 (3)	169 (3)
N1—H2N···O1ⁱ	0.91 (3)	2.00 (3)	2.903 (3)	174 (3)
N1—H4N···O8^viii	0.79 (6)	2.31 (6)	3.068 (3)	159 (5)

Symmetry codes: (i) −x, −y+1, −z+1; (iii) x+1, y, z−1; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x, −y, −z+1; (vii) x−1, y, z; (viii) x, y+1, z.

Structural comparison of isotypic (NH₄)M(HSO₄)(SO₄)(H₂O)₂ structures with the M = Mg members as references top

	Co (100 K)	Fe (100 K)	Ni (100 K)	Co (296 K)	Fe (296 K)	Ni (296 K)
S	0.0047	0.0062	0.0074	0.0055	0.0062	0.0078
d_max (atom)	0.0860 (O1)	0.0893 (O5)	0.1031 (O8)	0.0905 (O3)	0.1003 (O3)	0.0944 (O2)
d_av	0.0469	0.0485	0.0545	0.0521	0.0525	0.0574
δ	0.012	0.021	0.017	0.048	0.051	0.062

S is the degree of lattice distortion, d_max Å is the maximum difference between two atomic positions, d_av Å is the arithmetic mean of the differences between two atomic positions and δ is the measure of similarity.

Acknowledgements

The X-ray Centre of TU Wien is acknowledged for providing access to the single-crystal and powder X-ray diffractometers. TU Wien Bibliothek provided financial support through its Open Access Funding Programme.

References

Aroyo, M. I., Perez-Mato, J. M., Capillas, C., Kroumova, E., Ivantchev, S., Madariaga, G., Kirov, A. & Wondratschek, H. (2006). Z. Kristallogr. 221, 15–27. Web of Science CrossRef CAS Google Scholar
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Volume 81| Part 8| August 2025| Pages 727-732

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