Synthesis, structure and characterization of five new organically templated metal sulfates with 2-amino­pyridinium

Bednarchuk, T.J.; Kinzhybalo, V.; Pietraszko, A.

doi:10.1107/S2053229616006458

Synthesis, structure and characterization of five new organically templated metal sulfates with 2-aminopyridinium

T. J. Bednarchuk, V. Kinzhybalo and A. Pietraszko

The chemistry of organically templated metal sulfates has attracted interest from the materials science community and the development of synthetic strategies for the preparation of organic-inorganic hybrid materials with novel structures and special properties is of current interest. Sulfur-oxygen-metal linkages provide the possibility of using sulfate tetrahedra as building units to form new solid-state materials. A series of novel organically templated metal sulfates of 2-aminopyridinium (2ap) with aluminium(III), cobalt(II), magnesium(II), nickel(II) and zinc(II) were obtained from the respective aqueous solutions and studied by single-crystal X-ray diffraction. The compounds crystallize in centrosymmetric triclinic unit cells in three structure types: type 1 for 2-aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate, (C₅H₇N₂)[Al(H₂O)₆](SO₄)₂·4H₂O, (I); type 2 for bis(2-aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate, (C₅H₇N₂)₂[Co(H₂O)₆]₃(SO₄)₄·2H₂O, (II), and bis(2-aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate, (C₅H₇N₂)₂[Mg(H₂O)₆]₃(SO₄)₄·2H₂O, (III); and type 3 for bis(2-aminopyridinium) hexaaquanickel(II) bis(sulfate), (C₅H₇N₂)₂[Ni(H₂O)₆](SO₄)₂, (IV), and bis(2-aminopyridinium) hexaaquazinc(II) bis(sulfate), (C₅H₇N₂)₂[Zn(H₂O)₆](SO₄)₂, (V). The templating role of the 2ap cation in all of the reported crystalline substances is governed by the formation of characteristic charge-assisted hydrogen-bonded pairs with sulfate anions and the presence of [pi]

interactions between the cations. Additionally, both coordinated and uncoordinated water molecules are involved in hydrogen-bond formation. As a consequence, extensive three-dimensional hydrogen-bonding patterns are formed in the reported crystal structures.

Keywords: charge-assisted hydrogen bonding; crystal structure; organically templated materials; 2-aminopyridinium; sulfates; Hirshfeld surface analysis; fingerprint plots.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616006458/wq3112sup1.cif Contains datablocks I, II, III, IV, V
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006458/wq3112Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006458/wq3112IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006458/wq3112IIIsup4.hkl Contains datablock III
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006458/wq3112IVsup5.hkl Contains datablock IV
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229616006458/wq3112Vsup6.hkl Contains datablock V
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616006458/wq3112sup7.pdf Selected geometry tables and fingerprint plots for salts (I)-(V)

CCDC references: 1474849; 1474848; 1474847; 1474846; 1474845

Introduction top

The chemistry of organically templated metal sulfates (OTMS) has attracted extensive interest of the materials science community. Recently, increasing attention has been paid to the development of synthetic strategies for the preparation of organic–inorganic hybrid materials with novel structures and special properties. Sulfur–oxygen–metal (S—O—M) linkages provide the possibility of using SO₄^2- tetrahedra as a building unit to form new solid-state materials with novel topological structures and interesting physical properties (Rao et al., 2006).

The 2-aminopyridinium (2ap) cation has received little attention as a template agent in OTMS. In the case of double metal and 2ap sulfates, only one representative is known up to now (Lukianova et al., 2015). The crystal structure of bis(2-aminopyridinium) sulfate has also been reported (Jebas et al., 2006a). In the literature, there are reports where simple inorganic–organic hybrids with the 2ap cation and various halogen salts characterized by interesting supramolecular networks (Luque et al., 1997; Su et al., 2002; Kumar et al., 2005; Jebas et al., 2006b; Zhang et al., 2006; Fun et al., 2008; Gelmboldt et al., 2009; Cai & Fu, 2010; Jin et al., 2011; Rao et al., 2011; Mhadhbi et al., 2016) and dielectric properties are discussed (Kulicka et al., 2004).

In general, protonated aminopyridinium cations act mainly as template agents as they directly contribute to the dimensionality of the hydrogen-bonding network in the crystal structures of hybrid organic–inorganic materials. The presence of electrostatic interactions, i.e. weak interactions such as C—H···O and π–π interactions, in these solids suggests that these weak interactions play a significant role in shaping the resultant supramolecular assemblies and stabilization of these organic–inorganic hybrid materials.

In this paper, we have directed our efforts towards the synthesis and crystal structure determination, complemented by Hirshfeld surface analysis, of five new 2-aminopyridinium metal sulfates, namely (2ap)[Al(H₂O)₆](SO₄)₂·4H₂O, (I), (2ap)₂[Co(H₂O)₆]₃(SO₄)₄·2H₂O, (II), (2ap)₂[Mg(H₂O)₆]₃(SO₄)₄·2H₂O, (III), (2ap)₂[Ni(H₂O)₆](SO₄)₂, (IV), and (2ap)₂[Zn(H₂O)₆](SO₄)₂, (V), along with the previously reported copper analogue, (VI) (Lukianova et al., 2015).

Experimental top

Synthesis and crystallization top

The title compounds were synthesized according to the previously described method of Lukianova et al. (2015). An aqueous solution (4 ml) of 2-aminopyridine (0.19 g, 2.0 mmol), the pH of which was adjusted to 2.5 by admixing 30% sulfuric acid, was added slowly to an aqueous solution (3 ml) containing the appropriate metal sulfate [2.0 mmol for (I), 3.0 mmol for (II), 3.0 mmol for (III), 1.0 mmol for (IV) and 1.0 mmol for (V)]. Single crystals of a suitable size were obtained by slow solvent evaporation under ambient conditions for a period of several weeks.

Hirshfeld surface analysis and fingerprint plots top

The three-dimensional Hirshfeld surfaces (HSs) and two-dimensional fingerprint plots of (I), (II), (IV) and the copper analogue were generated using the CrystalExplorer software (Wolff et al., 2012).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. The positions of the amine H atoms were located initially in difference Fourier maps but were subsequently allowed to ride in the refinement, with C—H = 0.96 Å and N—H = 0.91 Å. The isotropic atomic displacement parameters of the H atoms were evaluated as 1.2U_eq of the parent atom. Water H atoms were located firstly in a difference Fourier map and then fixed, with O—H = 0.840 (2) Å and U_iso(H) = 1.5U_eq(O).

Results and discussion top

\ Structure of (2ap)[Al(H\\\~2\\\Õ)\\\~6\\\~](SO\\\~4\\\~)\ \\\~2\\\~\\\\\\\·4H\\\~2\\\Õ, (I) top

Compound (I) crystallizes in the triclinic P1 space group. The asymmetric unit is composed of two halves of two crystallographically independent Al^III cations, both lying on special positions, one protonated 2-aminopyridinium cation, two isolated sulfate anions and four noncoordinated water molecules. As shown in Fig. 1, two metal ions occupy inversion centres, both of them are hexacoordinated by six water molecules, adopting a slightly distorted octahedral coordination geometry. Selected bond lengths and angles are presented below in Table S1 (see Supporting information). The lengths of the Al1—OW and Al2—OW bonds vary from 1.8739 (14) to 1.8896 (15) Å and from 1.8760 (13) to 1.8930 (14) Å, respectively. The values of cis-OW—Al—OW angles are in the range 89.07 (6)–90.93 (6)° in the Al1 octahedron and 89.63 (6)–90.37 (6)° in the Al2 octahedron. These values are comparable with those reported for Al^III complexes with a six-coordinated octahedral geometry (Bataille, 2003). Each centrosymmetric [Al(H₂O)₆]³⁺ cation donates ten hydrogen bonds to eight sulfate anions and two hydrogen bonds to two uncoordinated water molecules (Fig. 2). The first sulfate anion accepts a total of nine hydrogen bonds, i.e. five from four hexaaquaaluminium complex cations, three from three solvent water molecules and one N—H···O hydrogen bond from one 2ap cation. The second sulfate anion accepts eight hydrogen bonds, i.e. five from five [Al(H₂O)₆]³⁺ cations, one from a free water molecule and two from one 2ap cation. The 2ap cation donates three N—H···O hydrogen bonds to the O atoms of two sulfate anions. One of the carbon-bound H atoms is involved in a weak hydrogen-bond interaction with an O atom of a solvent water molecule. Four free water molecules, namely O1W, O2W, O3W and O4W, are involved in 14 multidirectional O—H···O hydrogen bonds between coordinated water molecules of the [Al(H₂O)₆]³⁺ cations, sulfate O atoms and uncoordinated water molecules, forming an inorganic network parallel to the ab plane (Fig. 3a). The O1W molecule donates one hydrogen bond to O2W and one bond to a sulfate anion, and accepts one bond from the O22W atom. O2W donates two hydrogen bonds, i.e. one to O3W and another to a sulfate anion, and accepts two bonds from two solvation water molecules (O2W and O4W). O3W donates two hydrogen bonds to two sulfate anions and accepts two hydrogen bonds from two free water molecules (O4W and O2W). O4W donates two hydrogen bonds to two uncoordinated water molecules (O3W and O2W) and accepts one bond from the O11W atom.

In the crystal structure of (I), a three-dimensional supramolecular network is built from N—H···O, O—H···O and weak C—H···O hydrogen bonds involving the inorganic and organic parts of the structure (Table 2). Organic layers are built of π–π interacting stacks of 2ap cations (Table 3) connected to inorganic layers through N—H···O and C—H···O hydrogen bonds (Table 2 and Figs. 3b/c). The planes of all the 2ap rings are perpendicular to the [100] direction.

\ Structures of (2ap)\\\~2\\\~[Co(H\\\~2\\\Õ)\\\~6\\\~]\ \\\~3\\\~(SO\\\~4\\\~)\ \\\~4\\\~\\\\\\\·2H\\\~2\\\Õ, (II), (2ap)\\\~2\\\~[Mg(H\\\~2\\\Õ)\\\~6\\\~]\ \\\~3\\\~(SO\\\~4\\\~)\ \\\~4\\\~\\\\\\\·2H\\\~2\\\Õ, (III) top

Isostructural compounds (II) and (III) (structure type 2) crystallize in the triclinic P1 space group. The asymmetric part of the unit cell contains two hexaaqua-coordinated M^II ions (one of them lies on a centre of inversion with half occupancy), one protonated amine group which is disordered over two sites, two sulfate anions and one solvent water molecule (Fig. 4). Each M^II atom is located at the centre of a distorted octahedron formed by six O atoms from six water molecules. The M—OW bond lengths are in the ranges 2.0343 (18)–2.1852 (17), 2.0513 (18)–2.1074 (17), 2.0178 (19)–2.1321 (18) and 2.0391 (17)–2.0961 (19) Å for Co1—OW, Co2—OW, Mg1—OW and Mg2—OW, respectively. The cis- and trans-OW—M—OW angles are 81.14 (7)–94.50 (7) and 172.42 (7)–178.16 (6)°, respectively, in the Co1 octahedron, 89.61 (8)–90.39 (8) and 180° in the Co2 octahedron, 85.29 (8)–98.30 (7) and 172.81 (9)–174.89 (8)° in the Mg1 octahedron, and 89.59 (8)–90.41 (8) and 180° (due to inversion symmetry) in the Mg2 octahedron Significant distortions in the coordination polyhedra of (II) and (III) are clearly evident (see Tables S2 and S3 in the Supporting information) and the most considerable distortions are observed in the case of the M1 environment, which does not lie on a centre of inversion.

The M1 octahedron donates eleven hydrogen bonds to six sulfate anions, donates one hydrogen bond to the O13W atom and accepts one hydrogen bond from the O11W water molecule (Fig. 5a), while the M2 octahedron donates eight hydrogen bonds to six sulfate anions and four hydrogen bonds to four solvent water molecules (Fig. 5b). The 2ap cations donate three N—H···O hydrogen bonds to O atoms in the main disordered part and three N—H···O hydrogen bonds in minor disordered part also. The orientationally disordered NH₂ group has the minor disordered part attached to the C6 atom, instead of to C2. Reorientation from the first to the second position appears to be impossible due to the environment of the 2ap cation, and most likely is a result of incorrect alignment during the growth of the crystal. The NH₂ groups are distributed between two positions with site occupancies equal to 0.121 (5) in the minor part of both (II) and (III).

Uncoordinated water molecule O1W donates two hydrogen bonds to two crystallographically independent sulfate anions and accepts two hydrogen bonds from two [M^II(H₂O)₆]²⁺ cations. The first sulfate anion accepts ten hydrogen bonds, i.e. seven from four hexaaqua complexes, one from a free water molecule and two N—H···O hydrogen bonds from one 2ap cation. The second sulfate anion accepts eleven hydrogen bonds, i.e. eight from five [M^II(H₂O)₆]²⁺ cations, one from a free water molecule and two from two 2ap cations. As a result, an inorganic network is formed through O—H···O hydrogen bonds between water molecules, sulfate anions and inorganic cations, and lies parallel to the ac plane (Tables 4 and 5, and Fig. 6a). Significant parallel π–π interactions between pairs of pyridinium rings (Table 3) assist in the formation of a supramolecular association along the a-axis direction and make the overall framework more stable (Fig. 6b). C—H···O hydrogen bonds are not observed in structure type 2.

\ Structures (2ap)\\\~2\\\~[Ni(H\\\~2\\\Õ)\\\~6\\\~]\ (SO\\\~4\\\~)\\\~2\\\~, (IV), and (2ap)\\\~2\\\~[Zn(H\\\~2\\\Õ)\\\~6\\\~]\ (SO\\\~4\\\~)\\\~2\\\~, (V) top

Isostructural compounds (IV) and (V) crystallize in the triclinic P1 space group. In contrast to compounds (I)–(III), type 3, is characterized by the absence of noncoordinated water molecules. One half of an [M(H₂O)₆]²⁺ cation (located on an inversion centre), one sulfate anion and one 2ap cation form the asymmetric unit (see Fig. 7). The M^II atom occupies the centre of a slightly distorted octahedron built by the coordination of six water molecules. The crystal packing reveals a layered arrangement of the inorganic and organic parts of the structure.

The M—OW bond lengths (see Tables S4 and S5 in the Supporting information) are 2.0503 (13)–2.0590 (17) and 2.0813 (19)–2.0996 (18) Å for salts (IV) and (V), respectively. The cis bond angles around the M^II centres range from 86.63 (6) to 93.37 (6)° for (IV), and from 86.88 (8) to 93.12 (8)° for (IV). The trans angles are all equal to 180°. Geometric parameters are in accord with those reported for other Ni and Zn analogs (Fleck et al., 2004).

The [M(H₂O)₆]²⁺ cation donates twelve hydrogen bonds to six sulfate anions (see Fig. 8a). The SO₄^2- anion accepts nine hydrogen bonds, i.e. six from three hexaaqua complexes and three N—H···O hydrogen bonds from two 2ap cations. The [M(H₂O)₆]²⁺ cation in salts (IV) and (V) are connected via hydrogen bonds from water molecules to sulfate anions, forming inorganic networks parallel to the ab plane (Fig. 8b). As inferred in Fig. 9, the crystal structure is represented by a series of successive layers: inorganic layers of [M(H₂O)₆]²⁺ cations connected to sulfate anions by hydrogen bonds and organic layers of 2ap cations, both being parallel to bc plane. The organic and inorganic layers are linked to each other by two types of hydrogen bonding, i.e. N—H···O and weak C—H···O, present in the crystal structure (Tables 5 and 6, and Fig. 9). This hydrogen-bonding interaction directs the infinite condensation of the respective building units. The crystal packings are further extended via π–π interactions between the 2ap rings in the a-axis direction (Table 3). Moreover, the C—H···O interactions result in the final three-dimensional supramolecular arrangement in type 3.

Hirshfeld surface analysis top

Hirshfeld surfaces (with d_norm mapped) and fingerprints (d_e versus d_i) were generated using Crystal Explorer for the 2ap cations in all of the reported structures along with the earlier studied copper-containing analog (VI) (Lukianova et al., 2015). Analysis of the Hirshfeld surfaces (Fig. 10) reveals several common features of the 2ap cations and highlights their roles in the crystal packing organization. The cation is characterized by the presence of three strong hydrogen-bond donors, while its planar structure provides the possibility for the existence of π–π interactions. The closest [immediate?] environment of the 2ap cation in all the structures is constructed in a similar manner. The cations are involved in strong double hydrogen-bond formation with the sulfate anion in order to produce a charge-assisted pair of composition [2ap···SO₄]^-. The pair is formed by two H atoms of the pyridinium ring (N1—H) and the amino group (N2—H) hydrogen bonded to two O atoms of the same sulfate anion. The fitted image reveals the distribution of sufate anions with respect to the 2ap cations (Fig. 11). It is worth noting that the remaining H atom of the amino group is hydrogen bonded to another sulfate anion in all of the reported structures. Thus, in hydrogen bonds of the N—H···O type, the role of the acceptor is played by the sulfate O atoms only. The weakest hydrogen bonds formed by the 2ap cations are of the C—H···O type, in which the acceptor O atoms belong to all possible oxygen-containing groups, viz. sulfate anions and coordinated and noncoordinated water molecules.

Another common feature of all the 2ap cations is their involvement in the formation of π–π interacting columns (Table 3) composed of antiparallel oriented cations. In all the structures, these columns propagate along the a axis. The mutual arrangement of these columns results in two different types of crystal packing. In structure types 1 [observed for Al analog (I)] and 2 [observed for Co analog (II) and Mg analog (III)], the columns are isolated and surrounded by inorganic sublattices (Figs. 3b/c and 6b). The second type of crystal packing is governed by the presence of π–π stacked columns aggregated into layers (Fig. 9) and is seen in structure types 3 [observed for Ni analog (IV) and Zn analog (V)] and 4 [observed for Cu analog (VI)]. As a result, alternating organic and inorganic layers are formed.

The fingerprint plots of the 2ap cations are all similar in shape (see Figs. S1–S4 in the Supporting information). They are characterized by the presence of spike pointing at around (d_i = 0.7, d_e = 1.1), which corresponds to hydrogen bonds of the N—H···O type. In all the plots, the contacts of inner H atoms dominate the surface area, with around 30% of the area corresponding to H···O contacts, around 40% to H···H contacts and 10–15% to π–π interactions. The strongest of the π–π interactions is illustrated by a presence of a red dot in the fingerprint plot of structure (VI) (Table 3).

Summary top

In the current work, the results of structural studies of 2-aminopyridinium-templated metal (Al, Co, Mg, Ni and Zn) sulfate hydrates are reported for the first time. The templating role of 2ap is governed by the formation of characteristic charge-assisted hydrogen-bond pairs with sulfate anions and the presence of π–π interactions between the cations. In all of the studied compounds, as well as in the previously reported Cu analog, π–π interactions between the 2ap cations lead to the formation of columns with an antiparallel orientation of the cations. Another common feature of the compounds is the presence of hexaaqua-coordinated metal centres. Sulfate anions do not coordinate to the metal centres and are incorporated in diverse three-dimentional hydrogen-bonding networks, together with hexaaquametal octahedra and uncoordinated water molecules (if present). The mutual arrangement of π–π-interacting columns results in the formation of two modes of crystal packing, i.e. the first with isolated organic columns surrounded by the inorganic counterpart (structural types 1 and 2) and the second characterized by alternate organic–inorganic layers (structural types 3 and 4).

Structure description top

Synthesis and crystallization top

Refinement details top

Computing details top

For all compounds, data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015). Program(s) used to solve structure: SHELXT (Sheldrick, 2015a) for (I), (III), (IV); SHELXS97 (Sheldrick, 2008) for (II), (V). For all compounds, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1997); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The asymmetric unit of the compound (I), showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are denoted by orange dashed lines. [Symmetry codes: (iii) -x + 1, -y, -z + 1; (iv) -x + 1, -y + 1, -z + 1.]
	Fig. 2. Sulfate ions and water molecules in the environment of (a) the first and (b) the second [Al(H₂O)₆]³⁺ cations in compound (I). [Symmetry codes: (i) x + 1, y, z; (ii) x - 1, y, z; (iv) -x + 1, -y + 1, -z + 1; (v) -x + 2, -y + 1, -z + 1.]
	Fig. 3. (a) View of inorganic network parallel to yx plane and the molecular arrangement in the compound (I) viewed along (b) [100] and (c) [010]. Dashed lines represent hydrogen bonds. C—H···O hydrogen bonds and H atoms not involved in interactions have been omitted for clarity.
	Fig. 4. The molecular entities of the compounds (II)–(III), showing the atom-numbering scheme (on the example of compound with Co). Minor part of the disordered over two sites protonated amine is shown with dashed bonds. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. Hydrogen bonds are denoted by orange dashed lines. [Symmetry code: (vii) -x + 2, -y + 1, -z].
	Fig. 5. Sulfates and water molecules in the environment of the compounds (II)–(III) of (a) the Me1 octahedron and (b) the Me2 octahedron (on the example of compound with Co). [Symmetry codes: (i) -x + 2, -y, -z + 1; (ii) x + 1, y, z; (iii) -x + 1, -y + 1, -z + 1; (iv) -x + 1, -y, -z + 1; (v) -x + 2, -y + 1, -z + 1; (vi) -x + 1, -y + 1, -z; (vii) -x + 2, -y + 1, -z.]
	Fig. 6. (a) A view of inorganic network in structure type 2 parallel to the zx plane and (b) packing diagram for (II)–(III) (on the example of compound with Co), showing the three-dimensional hydrogen-bonded network (orange dashed lines). H atoms not involved in interactions have been omitted for clarity.
	Fig. 7. The structural unit of the compounds (IV)–(V) (on the example of compound with Ni), showing the atom-numbering scheme and hydrogen-bonding interactions (dashed lines). Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (iii) -x + 1, -y + 2, -z.]
	Fig. 8. (a) Sulfates in the environment of [Me(H₂O)₆]²⁺ cation in type 3 (on the example of compound with Ni). [Symmetry codes: (i) -x + 1, -y + 1, -z; (iii) -x + 1, -y + 2, -z; (iv) -x + 2, -y + 1, -z.]. (b) View of inorganic networks in type 3 parallel to the yx plane. Dashed lines indicate the hydrogen bonds.
	Fig. 9. Crystal packing for (IV)–(V) (on the example of compound with Ni) viewed along [100]. Dashed lines indicate the hydrogen bonds. C—H···O hydrogen bonds and H atoms not involved in interactions have been omitted for clarity.
	Fig. 10. Hirshfeld surface of 2ap cation in (a) compound (I), (b) compound (II), (c) compound (IV) and (d) compound (VI).
	Fig. 11. The distribution of sufate anions in respect to the 2ap cations in four structural types.

(I) 2-Aminopyridinium hexaaquaaluminium(III) bis(sulfate) tetrahydrate top

Crystal data top

(C₅H₇N₂)[Al(H₂O)₆](SO₄)₂·4H₂O	Z = 2
M_r = 494.38	F(000) = 520
Triclinic, P1	D_x = 1.668 Mg m⁻³
a = 6.667 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.160 (4) Å	Cell parameters from 5322 reflections
c = 12.911 (4) Å	θ = 2.2–29.5°
α = 72.30 (3)°	µ = 0.41 mm⁻¹
β = 81.03 (3)°	T = 100 K
γ = 85.57 (3)°	Block, colourless
V = 984.5 (7) Å³	0.50 × 0.33 × 0.20 mm

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	4751 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3685 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 10.6249 pixels mm^-1	θ_max = 29.4°, θ_min = 2.8°
ω scans	h = −9→8
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	k = −15→15
T_min = 0.869, T_max = 0.930	l = −17→17
14826 measured reflections

Refinement top

Refinement on F²	20 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.042P)² + 0.452P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
4751 reflections	Δρ_max = 0.32 e Å⁻³
316 parameters	Δρ_min = −0.62 e Å⁻³

Crystal data top

(C₅H₇N₂)[Al(H₂O)₆](SO₄)₂·4H₂O	γ = 85.57 (3)°
M_r = 494.38	V = 984.5 (7) Å³
Triclinic, P1	Z = 2
a = 6.667 (3) Å	Mo Kα radiation
b = 12.160 (4) Å	µ = 0.41 mm⁻¹
c = 12.911 (4) Å	T = 100 K
α = 72.30 (3)°	0.50 × 0.33 × 0.20 mm
β = 81.03 (3)°

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	4751 independent reflections
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	3685 reflections with I > 2σ(I)
T_min = 0.869, T_max = 0.930	R_int = 0.027
14826 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	20 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.32 e Å⁻³
4751 reflections	Δρ_min = −0.62 e Å⁻³
316 parameters

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
Al1	0.5000	0.0000	0.5000	0.00796 (16)
O11W	0.64761 (18)	0.08727 (10)	0.36697 (11)	0.0105 (3)
H11A	0.640 (3)	0.0781 (18)	0.3073 (14)	0.016*
H11B	0.762 (2)	0.1150 (17)	0.3618 (17)	0.016*
O12W	0.38678 (18)	0.13785 (10)	0.52461 (11)	0.0105 (3)
H12A	0.284 (3)	0.1365 (18)	0.5739 (15)	0.016*
H12B	0.361 (3)	0.1918 (15)	0.4703 (15)	0.016*
O13W	0.71181 (18)	0.00732 (10)	0.57732 (11)	0.0105 (3)
H13A	0.812 (3)	−0.0391 (16)	0.5869 (17)	0.016*
H13B	0.726 (3)	0.0623 (16)	0.6018 (17)	0.016*
Al2	0.5000	0.5000	0.5000	0.00801 (16)
O21W	0.62866 (18)	0.36833 (10)	0.46954 (11)	0.0105 (3)
H21A	0.651 (3)	0.3090 (15)	0.5199 (15)	0.016*
H21B	0.729 (3)	0.3711 (18)	0.4194 (15)	0.016*
O22W	0.65215 (18)	0.59526 (11)	0.37401 (11)	0.0118 (3)
H22A	0.613 (3)	0.6341 (17)	0.3134 (14)	0.018*
H22B	0.762 (3)	0.6215 (17)	0.3759 (18)	0.018*
O23W	0.70379 (18)	0.50546 (11)	0.58517 (11)	0.0114 (3)
H23A	0.801 (3)	0.4575 (16)	0.5978 (17)	0.017*
H23B	0.718 (3)	0.5610 (16)	0.6071 (18)	0.017*
S1	0.91029 (6)	0.20997 (3)	0.68614 (4)	0.00876 (11)
O11	0.84308 (18)	0.20057 (10)	0.80334 (10)	0.0121 (3)
O12	0.98659 (18)	0.32749 (10)	0.62760 (11)	0.0129 (3)
O13	0.73407 (18)	0.19311 (10)	0.63619 (10)	0.0116 (3)
O14	1.06889 (18)	0.12046 (10)	0.67919 (11)	0.0139 (3)
S2	0.09053 (6)	0.28132 (3)	0.31390 (4)	0.00884 (11)
O21	0.00743 (17)	0.16827 (10)	0.38119 (10)	0.0124 (3)
O22	0.27136 (18)	0.30327 (10)	0.35807 (10)	0.0120 (3)
O23	−0.06040 (18)	0.37597 (10)	0.31594 (11)	0.0142 (3)
O24	0.15050 (19)	0.27888 (10)	0.19974 (10)	0.0139 (3)
N1	0.2134 (2)	0.47940 (12)	0.03559 (13)	0.0134 (3)
H1	0.1694	0.4196	0.0875	0.016*
C2	0.1898 (3)	0.58361 (15)	0.05441 (15)	0.0131 (4)
N2	0.0992 (2)	0.58848 (13)	0.15262 (13)	0.0173 (3)
H2A	0.0574	0.5264	0.2021	0.021*
H2B	0.0825	0.6537	0.1665	0.021*
C3	0.2632 (3)	0.68047 (15)	−0.03180 (16)	0.0155 (4)
H3	0.2504	0.7535	−0.0220	0.019*
C4	0.3527 (3)	0.66674 (16)	−0.12932 (17)	0.0180 (4)
H4	0.4009	0.7309	−0.1860	0.022*
C5	0.3737 (3)	0.55711 (17)	−0.14604 (16)	0.0174 (4)
H5	0.4341	0.5481	−0.2131	0.021*
C6	0.3037 (3)	0.46511 (16)	−0.06194 (16)	0.0150 (4)
H6	0.3173	0.3917	−0.0707	0.018*
O1W	0.4378 (2)	0.27903 (11)	0.81670 (11)	0.0156 (3)
H1WA	0.555 (3)	0.2484 (18)	0.8117 (19)	0.023*
H1WB	0.360 (3)	0.2229 (16)	0.8478 (18)	0.023*
O2W	0.1749 (2)	0.10078 (12)	0.92133 (12)	0.0181 (3)
H2WA	0.061 (3)	0.1135 (19)	0.9014 (19)	0.027*
H2WB	0.164 (4)	0.091 (2)	0.9861 (14)	0.027*
O3W	0.1666 (2)	0.07501 (12)	0.14593 (12)	0.0180 (3)
H3WA	0.089 (3)	0.0290 (17)	0.1929 (16)	0.027*
H3WB	0.141 (3)	0.1356 (16)	0.1639 (19)	0.027*
O4W	0.5926 (2)	0.05318 (12)	0.18214 (12)	0.0189 (3)
H4WA	0.471 (3)	0.0479 (19)	0.1738 (19)	0.028*
H4WB	0.665 (3)	0.0103 (18)	0.1544 (19)	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Al1	0.0075 (3)	0.0073 (3)	0.0095 (4)	−0.0004 (3)	−0.0019 (3)	−0.0027 (3)
O11W	0.0096 (6)	0.0129 (6)	0.0095 (7)	−0.0033 (5)	−0.0007 (5)	−0.0038 (5)
O12W	0.0113 (6)	0.0093 (6)	0.0098 (7)	0.0009 (5)	−0.0012 (5)	−0.0016 (5)
O13W	0.0103 (6)	0.0084 (6)	0.0155 (7)	0.0014 (5)	−0.0055 (5)	−0.0060 (5)
Al2	0.0078 (3)	0.0071 (3)	0.0089 (4)	−0.0005 (3)	−0.0018 (3)	−0.0017 (3)
O21W	0.0112 (6)	0.0088 (6)	0.0107 (7)	0.0010 (5)	−0.0013 (5)	−0.0019 (5)
O22W	0.0095 (6)	0.0127 (6)	0.0120 (7)	−0.0026 (5)	−0.0026 (5)	−0.0011 (5)
O23W	0.0118 (6)	0.0088 (6)	0.0159 (7)	0.0011 (5)	−0.0052 (5)	−0.0059 (5)
S1	0.0083 (2)	0.0082 (2)	0.0099 (2)	0.00001 (15)	−0.00166 (16)	−0.00276 (17)
O11	0.0130 (6)	0.0146 (6)	0.0095 (6)	0.0005 (5)	−0.0013 (5)	−0.0049 (5)
O12	0.0112 (6)	0.0090 (6)	0.0165 (7)	−0.0023 (5)	−0.0036 (5)	0.0003 (5)
O13	0.0120 (6)	0.0108 (6)	0.0134 (7)	−0.0013 (5)	−0.0039 (5)	−0.0045 (5)
O14	0.0128 (6)	0.0128 (6)	0.0141 (7)	0.0041 (5)	−0.0007 (5)	−0.0031 (5)
S2	0.0086 (2)	0.0083 (2)	0.0096 (2)	−0.00033 (15)	−0.00152 (16)	−0.00245 (17)
O21	0.0103 (6)	0.0098 (6)	0.0157 (7)	−0.0020 (5)	−0.0022 (5)	−0.0009 (5)
O22	0.0123 (6)	0.0097 (6)	0.0143 (7)	−0.0024 (5)	−0.0037 (5)	−0.0025 (5)
O23	0.0134 (6)	0.0120 (6)	0.0147 (7)	0.0029 (5)	−0.0006 (5)	−0.0018 (5)
O24	0.0187 (6)	0.0131 (6)	0.0105 (7)	−0.0003 (5)	−0.0011 (5)	−0.0048 (5)
N1	0.0142 (7)	0.0108 (7)	0.0150 (8)	−0.0015 (6)	−0.0031 (6)	−0.0025 (6)
C2	0.0100 (8)	0.0147 (9)	0.0160 (10)	−0.0004 (7)	−0.0049 (7)	−0.0050 (8)
N2	0.0261 (9)	0.0110 (7)	0.0157 (9)	−0.0030 (6)	−0.0005 (7)	−0.0059 (7)
C3	0.0156 (9)	0.0108 (8)	0.0196 (10)	−0.0002 (7)	−0.0058 (8)	−0.0024 (8)
C4	0.0142 (9)	0.0177 (9)	0.0168 (10)	−0.0016 (7)	−0.0038 (8)	0.0038 (8)
C5	0.0135 (9)	0.0252 (10)	0.0134 (10)	0.0014 (7)	−0.0036 (7)	−0.0051 (8)
C6	0.0119 (8)	0.0184 (9)	0.0178 (10)	0.0025 (7)	−0.0052 (7)	−0.0091 (8)
O1W	0.0119 (6)	0.0159 (7)	0.0168 (7)	0.0010 (5)	−0.0001 (6)	−0.0032 (6)
O2W	0.0168 (7)	0.0233 (7)	0.0145 (7)	−0.0002 (6)	−0.0040 (6)	−0.0050 (6)
O3W	0.0265 (7)	0.0128 (7)	0.0153 (8)	−0.0023 (5)	−0.0023 (6)	−0.0049 (6)
O4W	0.0195 (7)	0.0206 (7)	0.0196 (8)	0.0015 (6)	−0.0043 (6)	−0.0098 (6)

Geometric parameters (Å, º) top

Al1—O11Wⁱ	1.8896 (15)	S1—O14	1.4707 (13)
Al1—O11W	1.8896 (15)	S2—O21	1.4808 (14)
Al1—O12Wⁱ	1.8799 (13)	S2—O22	1.4855 (13)
Al1—O12W	1.8799 (13)	S2—O23	1.4728 (13)
Al1—O13Wⁱ	1.8739 (14)	S2—O24	1.4745 (14)
Al1—O13W	1.8740 (14)	N1—H1	0.8600
O11W—H11A	0.821 (15)	N1—C2	1.354 (2)
O11W—H11B	0.841 (15)	N1—C6	1.363 (2)
O12W—H12A	0.859 (15)	C2—N2	1.333 (2)
O12W—H12B	0.833 (15)	C2—C3	1.410 (3)
O13W—H13A	0.842 (15)	N2—H2A	0.8600
O13W—H13B	0.839 (15)	N2—H2B	0.8600
Al2—O21Wⁱⁱ	1.8760 (13)	C3—H3	0.9300
Al2—O21W	1.8760 (13)	C3—C4	1.359 (3)
Al2—O22Wⁱⁱ	1.8810 (16)	C4—H4	0.9300
Al2—O22W	1.8810 (16)	C4—C5	1.407 (3)
Al2—O23Wⁱⁱ	1.8930 (14)	C5—H5	0.9300
Al2—O23W	1.8930 (14)	C5—C6	1.354 (3)
O21W—H21A	0.833 (15)	C6—H6	0.9300
O21W—H21B	0.852 (15)	O1W—H1WA	0.841 (15)
O22W—H22A	0.850 (15)	O1W—H1WB	0.849 (16)
O22W—H22B	0.830 (15)	O2W—H2WA	0.825 (16)
O23W—H23A	0.837 (15)	O2W—H2WB	0.800 (16)
O23W—H23B	0.825 (15)	O3W—H3WA	0.831 (16)
S1—O11	1.4815 (14)	O3W—H3WB	0.836 (16)
S1—O12	1.4859 (14)	O4W—H4WA	0.845 (16)
S1—O13	1.4806 (13)	O4W—H4WB	0.808 (16)

O11Wⁱ—Al1—O11W	180.0	Al2—O22W—H22B	122.3 (15)
O12W—Al1—O11W	89.45 (6)	H22A—O22W—H22B	107 (2)
O12Wⁱ—Al1—O11Wⁱ	89.45 (6)	Al2—O23W—H23A	125.2 (14)
O12Wⁱ—Al1—O11W	90.54 (6)	Al2—O23W—H23B	123.8 (15)
O12W—Al1—O11Wⁱ	90.55 (6)	H23A—O23W—H23B	110 (2)
O12Wⁱ—Al1—O12W	180.0	O11—S1—O12	109.44 (8)
O13W—Al1—O11Wⁱ	89.07 (6)	O13—S1—O11	108.96 (8)
O13W—Al1—O11W	90.93 (6)	O13—S1—O12	108.18 (8)
O13Wⁱ—Al1—O11Wⁱ	90.93 (6)	O14—S1—O11	108.71 (8)
O13Wⁱ—Al1—O11W	89.07 (6)	O14—S1—O12	111.37 (8)
O13W—Al1—O12W	89.22 (6)	O14—S1—O13	110.15 (7)
O13Wⁱ—Al1—O12W	90.78 (6)	O21—S2—O22	109.45 (8)
O13W—Al1—O12Wⁱ	90.78 (6)	O23—S2—O21	111.23 (8)
O13Wⁱ—Al1—O12Wⁱ	89.22 (6)	O23—S2—O22	108.31 (7)
O13Wⁱ—Al1—O13W	180.0	O23—S2—O24	109.38 (8)
Al1—O11W—H11A	123.1 (15)	O24—S2—O21	109.05 (8)
Al1—O11W—H11B	124.4 (15)	O24—S2—O22	109.40 (8)
H11A—O11W—H11B	107 (2)	C2—N1—H1	118.5
Al1—O12W—H12A	120.6 (14)	C2—N1—C6	122.95 (16)
Al1—O12W—H12B	117.7 (14)	C6—N1—H1	118.5
H12A—O12W—H12B	105 (2)	N1—C2—C3	117.53 (16)
Al1—O13W—H13A	126.0 (14)	N2—C2—N1	118.35 (17)
Al1—O13W—H13B	123.9 (14)	N2—C2—C3	124.12 (16)
H13A—O13W—H13B	109.8 (19)	C2—N2—H2A	120.0
O21Wⁱⁱ—Al2—O21W	180.00 (4)	C2—N2—H2B	120.0
O21Wⁱⁱ—Al2—O22W	89.68 (6)	H2A—N2—H2B	120.0
O21W—Al2—O22Wⁱⁱ	89.68 (6)	C2—C3—H3	120.1
O21Wⁱⁱ—Al2—O22Wⁱⁱ	90.32 (6)	C4—C3—C2	119.75 (16)
O21W—Al2—O22W	90.32 (6)	C4—C3—H3	120.1
O21Wⁱⁱ—Al2—O23Wⁱⁱ	90.26 (6)	C3—C4—H4	119.4
O21W—Al2—O23W	90.26 (6)	C3—C4—C5	121.12 (18)
O21Wⁱⁱ—Al2—O23W	89.74 (6)	C5—C4—H4	119.4
O21W—Al2—O23Wⁱⁱ	89.74 (6)	C4—C5—H5	120.9
O22W—Al2—O22Wⁱⁱ	180.0	C6—C5—C4	118.21 (18)
O22W—Al2—O23Wⁱⁱ	89.63 (6)	C6—C5—H5	120.9
O22Wⁱⁱ—Al2—O23Wⁱⁱ	90.37 (6)	N1—C6—H6	119.8
O22W—Al2—O23W	90.37 (6)	C5—C6—N1	120.44 (16)
O22Wⁱⁱ—Al2—O23W	89.63 (6)	C5—C6—H6	119.8
O23Wⁱⁱ—Al2—O23W	180.0	H1WA—O1W—H1WB	105 (2)
Al2—O21W—H21A	121.2 (14)	H2WA—O2W—H2WB	109 (2)
Al2—O21W—H21B	123.4 (14)	H3WA—O3W—H3WB	102 (2)
H21A—O21W—H21B	105 (2)	H4WA—O4W—H4WB	109 (2)
Al2—O22W—H22A	128.9 (15)

N1—C2—C3—C4	0.3 (3)	C3—C4—C5—C6	−0.5 (3)
C2—N1—C6—C5	−0.5 (3)	C4—C5—C6—N1	0.8 (3)
C2—C3—C4—C5	0.0 (3)	C6—N1—C2—N2	179.93 (16)
N2—C2—C3—C4	−179.69 (17)	C6—N1—C2—C3	−0.1 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11W—H11A···O4W	0.82 (2)	1.81 (2)	2.626 (2)	173 (2)
O11W—H11B···O21ⁱⁱⁱ	0.84 (2)	1.89 (2)	2.715 (2)	168 (2)
O12W—H12A···O14^iv	0.86 (2)	1.79 (2)	2.648 (2)	175 (2)
O12W—H12B···O22	0.83 (2)	1.80 (2)	2.628 (2)	173 (2)
O13W—H13A···O21ⁱ	0.84 (2)	1.88 (2)	2.711 (2)	167 (2)
O13W—H13B···O13	0.84 (2)	1.78 (2)	2.6144 (18)	171 (2)
O21W—H21A···O13	0.83 (2)	1.84 (2)	2.667 (2)	170 (2)
O21W—H21B···O23ⁱⁱⁱ	0.85 (2)	1.77 (2)	2.622 (2)	180 (3)
O22W—H22A···O1Wⁱⁱ	0.85 (2)	1.76 (2)	2.606 (2)	173 (2)
O22W—H22B···O12^v	0.83 (2)	1.82 (2)	2.647 (2)	175 (2)
O23W—H23A···O12	0.84 (2)	1.91 (2)	2.740 (2)	169 (2)
O23W—H23B···O22ⁱⁱ	0.83 (2)	1.85 (2)	2.6660 (18)	172 (2)
N1—H1···O24	0.86	1.87	2.711 (2)	164
N2—H2A···O23	0.86	2.09	2.944 (2)	176
N2—H2B···O11ⁱⁱ	0.86	2.04	2.856 (2)	159
C6—H6···O1W^vi	0.93	2.30	3.127 (2)	147
O1W—H1WA···O11	0.84 (2)	1.96 (2)	2.792 (2)	170 (2)
O1W—H1WB···O2W	0.85 (2)	1.92 (2)	2.768 (2)	177 (2)
O2W—H2WA···O11^iv	0.83 (2)	2.09 (2)	2.864 (2)	156 (2)
O2W—H2WB···O3W^vii	0.80 (2)	2.02 (2)	2.812 (2)	173 (2)
O3W—H3WA···O14ⁱ	0.83 (2)	2.25 (2)	3.069 (2)	169 (2)
O3W—H3WB···O24	0.84 (2)	1.94 (2)	2.7609 (19)	166 (2)
O4W—H4WA···O3W	0.85 (2)	2.10 (2)	2.929 (2)	167 (2)
O4W—H4WB···O2Wⁱ	0.81 (2)	2.04 (2)	2.849 (2)	175 (2)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x−1, y, z; (v) −x+2, −y+1, −z+1; (vi) x, y, z−1; (vii) x, y, z+1.

(II) Bis(2-aminopyridinium) tris[hexaaquacobalt(II)] tetrakis(sulfate) dihydrate top

Crystal data top

(C₅H₇N₂)₂[Co(H₂O)₆]₃(SO₄)₄·2H₂O	Z = 1
M_r = 1111.60	F(000) = 575
Triclinic, P1	D_x = 1.812 Mg m⁻³
a = 6.640 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.710 (4) Å	Cell parameters from 5917 reflections
c = 14.294 (4) Å	θ = 3.1–29.1°
α = 67.97 (3)°	µ = 1.53 mm⁻¹
β = 81.57 (3)°	T = 100 K
γ = 85.39 (3)°	Plate, red
V = 1018.8 (7) Å³	0.42 × 0.27 × 0.08 mm

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	4878 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	4072 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 10.6249 pixels mm^-1	θ_max = 29.6°, θ_min = 2.8°
ω scans	h = −8→8
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	k = −15→15
T_min = 0.609, T_max = 0.891	l = −18→19
14070 measured reflections

Refinement top

Refinement on F²	20 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.024P)² + 0.719P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4878 reflections	Δρ_max = 0.42 e Å⁻³
321 parameters	Δρ_min = −0.44 e Å⁻³

Crystal data top

(C₅H₇N₂)₂[Co(H₂O)₆]₃(SO₄)₄·2H₂O	γ = 85.39 (3)°
M_r = 1111.60	V = 1018.8 (7) Å³
Triclinic, P1	Z = 1
a = 6.640 (3) Å	Mo Kα radiation
b = 11.710 (4) Å	µ = 1.53 mm⁻¹
c = 14.294 (4) Å	T = 100 K
α = 67.97 (3)°	0.42 × 0.27 × 0.08 mm
β = 81.57 (3)°

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	4878 independent reflections
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	4072 reflections with I > 2σ(I)
T_min = 0.609, T_max = 0.891	R_int = 0.025
14070 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	20 restraints
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.42 e Å⁻³
4878 reflections	Δρ_min = −0.44 e Å⁻³
321 parameters

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	0.81730 (4)	0.24175 (2)	0.48940 (2)	0.01270 (8)
O11W	1.0930 (2)	0.15648 (15)	0.54025 (13)	0.0193 (3)
H11A	1.117 (4)	0.0828 (16)	0.550 (2)	0.029*
H11B	1.148 (4)	0.173 (2)	0.5808 (17)	0.029*
O12W	0.5454 (2)	0.33969 (14)	0.44448 (12)	0.0163 (3)
H12A	0.482 (3)	0.327 (2)	0.4027 (16)	0.024*
H12B	0.557 (4)	0.4142 (16)	0.4194 (19)	0.024*
O13W	0.8355 (2)	0.11152 (13)	0.41171 (12)	0.0154 (3)
H13A	0.928 (3)	0.133 (2)	0.3645 (16)	0.023*
H13B	0.736 (3)	0.117 (2)	0.3823 (18)	0.023*
O14W	0.8099 (2)	0.36353 (15)	0.56340 (13)	0.0213 (4)
H14A	0.905 (3)	0.370 (2)	0.5927 (19)	0.032*
H14B	0.701 (3)	0.373 (2)	0.5938 (19)	0.032*
O15W	0.6390 (2)	0.12358 (14)	0.60913 (12)	0.0195 (3)
H15A	0.618 (4)	0.0507 (16)	0.621 (2)	0.029*
H15B	0.530 (3)	0.151 (2)	0.6307 (19)	0.029*
O16W	0.9640 (2)	0.36329 (14)	0.35903 (13)	0.0235 (4)
H16A	1.089 (3)	0.356 (3)	0.341 (2)	0.035*
H16B	0.950 (4)	0.4385 (17)	0.350 (2)	0.035*
Co2	1.0000	0.5000	0.0000	0.01264 (10)
O21W	1.0568 (2)	0.57791 (18)	0.09997 (14)	0.0279 (4)
H21A	0.968 (4)	0.614 (3)	0.126 (2)	0.042*
H21B	1.163 (3)	0.578 (3)	0.122 (2)	0.042*
O22W	0.8877 (3)	0.34331 (17)	0.12342 (14)	0.0354 (5)
H22A	0.946 (4)	0.314 (3)	0.1730 (18)	0.053*
H22B	0.766 (3)	0.322 (3)	0.139 (2)	0.053*
O23W	0.7093 (2)	0.57899 (16)	−0.00391 (12)	0.0239 (4)
H23A	0.626 (4)	0.563 (2)	0.0473 (16)	0.036*
H23B	0.661 (4)	0.625 (2)	−0.0543 (16)	0.036*
S1	0.26050 (7)	0.32185 (5)	0.71193 (4)	0.01344 (11)
O11	0.2389 (2)	0.28812 (14)	0.82416 (11)	0.0227 (4)
O12	0.4429 (2)	0.39702 (14)	0.66754 (13)	0.0240 (4)
O13	0.0779 (2)	0.39364 (13)	0.67393 (12)	0.0199 (3)
O14	0.2811 (2)	0.20808 (13)	0.68886 (11)	0.0158 (3)
S2	0.37373 (7)	0.21252 (5)	0.26165 (4)	0.01285 (11)
O21	0.3555 (2)	0.31783 (13)	0.29681 (11)	0.0160 (3)
O22	0.4874 (2)	0.11002 (13)	0.33098 (11)	0.0181 (3)
O23	0.1693 (2)	0.17496 (14)	0.25939 (11)	0.0175 (3)
O24	0.4888 (2)	0.25378 (13)	0.15788 (11)	0.0163 (3)
N1	0.2263 (3)	0.06643 (18)	0.97837 (15)	0.0226 (4)
H1	0.2200	0.1354	0.9280	0.027*
C2	0.2830 (3)	−0.0361 (2)	0.95853 (18)	0.0218 (5)
H2	0.3148	−0.0327	0.8920	0.026*	0.121 (5)
N2	0.3252 (3)	−0.0250 (2)	0.86323 (16)	0.0204 (6)	0.879 (5)
H2A	0.3163	0.0461	0.8156	0.024*	0.879 (5)
H2B	0.3618	−0.0889	0.8483	0.024*	0.879 (5)
C3	0.2927 (3)	−0.1489 (2)	1.04194 (19)	0.0251 (5)
H3	0.3328	−0.2213	1.0311	0.030*
C4	0.2426 (3)	−0.1506 (2)	1.13858 (18)	0.0261 (5)
H4	0.2474	−0.2249	1.1935	0.031*
C5	0.1840 (3)	−0.0419 (2)	1.15618 (19)	0.0284 (6)
H5	0.1498	−0.0432	1.2220	0.034*
C6	0.1785 (3)	0.0660 (2)	1.07421 (19)	0.0257 (5)
H6	0.1418	0.1394	1.0840	0.031*	0.879 (5)
O1W	0.5638 (2)	0.45007 (14)	0.83619 (11)	0.0165 (3)
H1WA	0.5340	0.4310	0.7882	0.025*
H1WB	0.5789	0.5279	0.7883	0.025*
N2A	0.1513 (18)	0.1596 (12)	1.0656 (10)	0.009 (4)*	0.121 (5)
H2AA	0.1622	0.2162	1.0058	0.011*	0.121 (5)
H2AB	0.1184	0.1789	1.1184	0.011*	0.121 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01207 (14)	0.01120 (15)	0.01479 (15)	0.00019 (10)	−0.00248 (11)	−0.00455 (11)
O11W	0.0188 (8)	0.0158 (8)	0.0283 (9)	0.0050 (6)	−0.0122 (7)	−0.0116 (7)
O12W	0.0176 (8)	0.0140 (8)	0.0189 (8)	0.0016 (6)	−0.0085 (6)	−0.0061 (7)
O13W	0.0127 (7)	0.0169 (8)	0.0162 (8)	−0.0010 (6)	−0.0018 (6)	−0.0057 (6)
O14W	0.0131 (8)	0.0274 (9)	0.0323 (10)	0.0012 (7)	−0.0052 (7)	−0.0205 (8)
O15W	0.0197 (8)	0.0128 (8)	0.0225 (8)	0.0001 (6)	0.0047 (7)	−0.0054 (7)
O16W	0.0171 (8)	0.0126 (8)	0.0342 (10)	0.0004 (6)	0.0065 (7)	−0.0048 (7)
Co2	0.00979 (18)	0.0159 (2)	0.0120 (2)	−0.00087 (14)	−0.00193 (15)	−0.00457 (16)
O21W	0.0177 (8)	0.0449 (11)	0.0370 (10)	0.0075 (8)	−0.0107 (8)	−0.0320 (9)
O22W	0.0212 (9)	0.0399 (11)	0.0271 (10)	−0.0156 (8)	−0.0124 (8)	0.0146 (8)
O23W	0.0129 (8)	0.0377 (10)	0.0156 (8)	0.0077 (7)	−0.0028 (6)	−0.0048 (8)
S1	0.0124 (2)	0.0121 (3)	0.0173 (3)	0.00063 (18)	−0.0042 (2)	−0.0064 (2)
O11	0.0365 (9)	0.0174 (8)	0.0170 (8)	0.0074 (7)	−0.0087 (7)	−0.0092 (7)
O12	0.0168 (8)	0.0189 (8)	0.0397 (10)	−0.0058 (6)	0.0030 (7)	−0.0161 (8)
O13	0.0191 (8)	0.0145 (8)	0.0290 (9)	0.0040 (6)	−0.0122 (7)	−0.0090 (7)
O14	0.0169 (7)	0.0129 (7)	0.0195 (8)	−0.0003 (6)	−0.0029 (6)	−0.0079 (6)
S2	0.0113 (2)	0.0132 (3)	0.0146 (3)	−0.00040 (18)	−0.0019 (2)	−0.0056 (2)
O21	0.0166 (7)	0.0138 (7)	0.0190 (8)	0.0005 (6)	−0.0033 (6)	−0.0075 (6)
O22	0.0195 (8)	0.0124 (7)	0.0205 (8)	0.0006 (6)	−0.0061 (6)	−0.0031 (6)
O23	0.0130 (7)	0.0229 (8)	0.0202 (8)	−0.0039 (6)	−0.0010 (6)	−0.0116 (7)
O24	0.0135 (7)	0.0191 (8)	0.0155 (8)	−0.0007 (6)	0.0007 (6)	−0.0063 (6)
N1	0.0182 (9)	0.0191 (10)	0.0247 (11)	−0.0016 (7)	−0.0063 (8)	0.0001 (8)
C2	0.0089 (10)	0.0292 (13)	0.0210 (12)	−0.0040 (9)	−0.0030 (9)	−0.0009 (10)
N2	0.0238 (12)	0.0161 (11)	0.0208 (12)	0.0019 (8)	−0.0013 (9)	−0.0073 (9)
C3	0.0165 (11)	0.0203 (12)	0.0299 (14)	−0.0002 (9)	−0.0031 (10)	0.0005 (10)
C4	0.0187 (11)	0.0288 (14)	0.0211 (12)	−0.0044 (9)	−0.0039 (10)	0.0030 (10)
C5	0.0199 (12)	0.0374 (15)	0.0231 (13)	−0.0077 (10)	−0.0056 (10)	−0.0033 (11)
C6	0.0208 (12)	0.0300 (14)	0.0268 (13)	−0.0058 (10)	−0.0065 (10)	−0.0087 (11)
O1W	0.0183 (7)	0.0168 (8)	0.0166 (8)	−0.0018 (6)	−0.0043 (6)	−0.0075 (6)

Geometric parameters (Å, º) top

Co1—O11W	2.1042 (17)	O23W—H23B	0.811 (17)
Co1—O12W	2.1074 (17)	S1—O11	1.4888 (17)
Co1—O13W	2.1852 (17)	S1—O12	1.4735 (17)
Co1—O14W	2.0640 (17)	S1—O13	1.4689 (16)
Co1—O15W	2.0343 (18)	S1—O14	1.4797 (16)
Co1—O16W	2.0368 (19)	S2—O21	1.4869 (16)
O11W—H11A	0.827 (17)	S2—O22	1.4744 (16)
O11W—H11B	0.813 (17)	S2—O23	1.4687 (16)
O12W—H12A	0.838 (16)	S2—O24	1.4855 (16)
O12W—H12B	0.815 (16)	N1—H1	0.8600
O13W—H13A	0.819 (16)	N1—C2	1.347 (3)
O13W—H13B	0.819 (16)	N1—C6	1.358 (3)
O14W—H14A	0.828 (17)	C2—H2	0.9300
O14W—H14B	0.810 (17)	C2—N2	1.309 (3)
O15W—H15A	0.824 (17)	C2—C3	1.414 (3)
O15W—H15B	0.830 (16)	N2—H2A	0.8600
O16W—H16A	0.840 (17)	N2—H2B	0.8600
O16W—H16B	0.839 (17)	C3—H3	0.9300
Co2—O21Wⁱ	2.0513 (18)	C3—C4	1.366 (4)
Co2—O21W	2.0513 (18)	C4—H4	0.9300
Co2—O22Wⁱ	2.1073 (19)	C4—C5	1.402 (4)
Co2—O22W	2.1073 (19)	C5—H5	0.9300
Co2—O23Wⁱ	2.0715 (17)	C5—C6	1.365 (3)
Co2—O23W	2.0715 (17)	C6—H6	0.9300
O21W—H21A	0.817 (17)	C6—N2A	1.060 (13)
O21W—H21B	0.818 (17)	O1W—H1WA	0.8493
O22W—H22A	0.804 (18)	O1W—H1WB	0.9143
O22W—H22B	0.837 (17)	N2A—H2AA	0.8600
O23W—H23A	0.819 (17)	N2A—H2AB	0.8600

O11W—Co1—O12W	174.53 (6)	Co2—O21W—H21B	129 (2)
O11W—Co1—O13W	84.79 (6)	H21A—O21W—H21B	109 (3)
O12W—Co1—O13W	100.63 (6)	Co2—O22W—H22A	121 (2)
O14W—Co1—O11W	93.44 (7)	Co2—O22W—H22B	126 (2)
O14W—Co1—O12W	81.14 (7)	H22A—O22W—H22B	109 (3)
O14W—Co1—O13W	178.16 (6)	Co2—O23W—H23A	121.8 (19)
O15W—Co1—O11W	94.50 (7)	Co2—O23W—H23B	126 (2)
O15W—Co1—O12W	86.37 (7)	H23A—O23W—H23B	112 (3)
O15W—Co1—O13W	89.76 (7)	O12—S1—O11	107.67 (10)
O15W—Co1—O14W	90.88 (7)	O12—S1—O14	110.99 (9)
O15W—Co1—O16W	172.42 (7)	O13—S1—O11	108.34 (10)
O16W—Co1—O11W	92.29 (7)	O13—S1—O12	110.29 (10)
O16W—Co1—O12W	87.18 (7)	O13—S1—O14	110.26 (9)
O16W—Co1—O13W	87.52 (7)	O14—S1—O11	109.22 (9)
O16W—Co1—O14W	92.06 (7)	O22—S2—O21	109.09 (9)
Co1—O11W—H11A	120.5 (18)	O22—S2—O24	109.28 (9)
Co1—O11W—H11B	123.0 (19)	O23—S2—O21	109.29 (9)
H11A—O11W—H11B	108 (3)	O23—S2—O22	110.95 (9)
Co1—O12W—H12A	121.8 (17)	O23—S2—O24	110.13 (9)
Co1—O12W—H12B	113.8 (18)	O24—S2—O21	108.03 (9)
H12A—O12W—H12B	102 (2)	C2—N1—H1	118.5
Co1—O13W—H13A	107.7 (18)	C2—N1—C6	123.1 (2)
Co1—O13W—H13B	112.8 (18)	C6—N1—H1	118.5
H13A—O13W—H13B	102 (2)	N1—C2—H2	121.0
Co1—O14W—H14A	123.3 (19)	N1—C2—C3	118.0 (2)
Co1—O14W—H14B	116 (2)	N2—C2—N1	118.0 (2)
H14A—O14W—H14B	111 (3)	N2—C2—C3	124.1 (2)
Co1—O15W—H15A	128.3 (19)	C3—C2—H2	121.0
Co1—O15W—H15B	118.3 (19)	C2—N2—H2A	120.0
H15A—O15W—H15B	105 (3)	C2—N2—H2B	120.0
Co1—O16W—H16A	122.2 (19)	H2A—N2—H2B	120.0
Co1—O16W—H16B	117.5 (19)	C2—C3—H3	120.3
H16A—O16W—H16B	102 (3)	C4—C3—C2	119.4 (2)
O21W—Co2—O21Wⁱ	180.0	C4—C3—H3	120.3
O21W—Co2—O22W	89.77 (9)	C3—C4—H4	119.5
O21Wⁱ—Co2—O22W	90.23 (9)	C3—C4—C5	121.0 (2)
O21W—Co2—O22Wⁱ	90.23 (9)	C5—C4—H4	119.5
O21Wⁱ—Co2—O22Wⁱ	89.77 (9)	C4—C5—H5	120.8
O21W—Co2—O23W	90.11 (7)	C6—C5—C4	118.3 (2)
O21W—Co2—O23Wⁱ	89.89 (7)	C6—C5—H5	120.8
O21Wⁱ—Co2—O23Wⁱ	90.11 (7)	N1—C6—C5	120.3 (2)
O21Wⁱ—Co2—O23W	89.89 (7)	N1—C6—H6	119.9
O22W—Co2—O22Wⁱ	180.00 (10)	C5—C6—H6	119.9
O23W—Co2—O22Wⁱ	90.39 (8)	N2A—C6—N1	105.6 (8)
O23Wⁱ—Co2—O22W	90.39 (8)	N2A—C6—C5	134.0 (8)
O23Wⁱ—Co2—O22Wⁱ	89.61 (8)	H1WA—O1W—H1WB	85.4
O23W—Co2—O22W	89.61 (8)	C6—N2A—H2AA	120.0
O23W—Co2—O23Wⁱ	180.0	C6—N2A—H2AB	120.0
Co2—O21W—H21A	122 (2)	H2AA—N2A—H2AB	120.0

N1—C2—C3—C4	0.8 (3)	C3—C4—C5—C6	−0.1 (3)
C2—N1—C6—C5	−0.8 (3)	C4—C5—C6—N1	0.9 (3)
C2—N1—C6—N2A	175.9 (7)	C4—C5—C6—N2A	−174.7 (10)
C2—C3—C4—C5	−0.7 (3)	C6—N1—C2—N2	179.8 (2)
N2—C2—C3—C4	−179.1 (2)	C6—N1—C2—C3	0.0 (3)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11W—H11A···O13Wⁱⁱ	0.83 (2)	2.14 (2)	2.964 (2)	175 (3)
O11W—H11B···O14ⁱⁱⁱ	0.81 (2)	2.07 (2)	2.881 (2)	178 (3)
O12W—H12A···O21	0.84 (2)	1.88 (2)	2.711 (2)	173 (3)
O12W—H12B···O12^iv	0.82 (2)	2.09 (2)	2.894 (3)	169 (3)
O13W—H13A···O23ⁱⁱⁱ	0.82 (2)	1.98 (2)	2.800 (2)	175 (2)
O13W—H13B···O22	0.82 (2)	1.92 (2)	2.735 (2)	172 (3)
O14W—H14A···O13ⁱⁱⁱ	0.83 (2)	1.85 (2)	2.671 (2)	169 (3)
O14W—H14B···O12	0.81 (2)	1.93 (2)	2.744 (2)	179 (3)
O15W—H15A···O22^v	0.82 (2)	1.90 (2)	2.706 (2)	166 (3)
O15W—H15B···O14	0.83 (2)	1.93 (2)	2.756 (2)	177 (3)
O16W—H16A···O21ⁱⁱⁱ	0.84 (2)	1.87 (2)	2.699 (2)	171 (3)
O16W—H16B···O13^iv	0.84 (2)	1.86 (2)	2.703 (2)	179 (3)
O21W—H21A···O11^iv	0.82 (2)	1.95 (2)	2.766 (2)	175 (3)
O21W—H21B···O1W^vi	0.82 (2)	1.95 (2)	2.758 (2)	168 (3)
O22W—H22A···O23ⁱⁱⁱ	0.80 (2)	2.24 (2)	2.959 (3)	150 (3)
O22W—H22B···O24	0.84 (2)	2.01 (2)	2.835 (2)	169 (3)
O23W—H23A···O1W^iv	0.82 (2)	1.90 (2)	2.714 (2)	171 (3)
O23W—H23B···O24^vii	0.81 (2)	1.96 (2)	2.759 (2)	169 (3)
N1—H1···O11	0.86	1.85	2.701 (3)	172
N2—H2A···O14	0.86	2.10	2.955 (3)	173
N2—H2B···O24^v	0.86	2.12	2.959 (3)	164
O1W—H1WA···O12	0.85	2.09	2.935 (2)	175
O1W—H1WB···O21^iv	0.91	1.80	2.711 (2)	171

Symmetry codes: (ii) −x+2, −y, −z+1; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) −x+2, −y+1, −z+1; (vii) −x+1, −y+1, −z.

(III) Bis(2-aminopyridinium) tris[hexaaquamagnesium(II)] tetrakis(sulfate) dihydrate top

Crystal data top

(C₅H₇N₂)₂[Mg(H₂O)₆]₃(SO₄)₄·2H₂O	Z = 1
M_r = 1007.74	F(000) = 530
Triclinic, P1	D_x = 1.613 Mg m⁻³
a = 6.682 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.807 (4) Å	Cell parameters from 4995 reflections
c = 14.309 (4) Å	θ = 2.8–29.2°
α = 68.23 (3)°	µ = 0.39 mm⁻¹
β = 82.13 (3)°	T = 100 K
γ = 84.76 (3)°	Block, colourless
V = 1037.5 (7) Å³	0.43 × 0.36 × 0.23 mm

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	4884 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3875 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.6249 pixels mm^-1	θ_max = 29.3°, θ_min = 1.9°
ω scans	h = −8→9
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	k = −15→14
T_min = 0.892, T_max = 0.928	l = −19→18
11467 measured reflections

Refinement top

Refinement on F²	20 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.030P)² + 0.790P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4884 reflections	Δρ_max = 0.45 e Å⁻³
324 parameters	Δρ_min = −0.40 e Å⁻³

Crystal data top

(C₅H₇N₂)₂[Mg(H₂O)₆]₃(SO₄)₄·2H₂O	γ = 84.76 (3)°
M_r = 1007.74	V = 1037.5 (7) Å³
Triclinic, P1	Z = 1
a = 6.682 (3) Å	Mo Kα radiation
b = 11.807 (4) Å	µ = 0.39 mm⁻¹
c = 14.309 (4) Å	T = 100 K
α = 68.23 (3)°	0.43 × 0.36 × 0.23 mm
β = 82.13 (3)°

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	4884 independent reflections
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	3875 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.928	R_int = 0.026
11467 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	20 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.45 e Å⁻³
4884 reflections	Δρ_min = −0.40 e Å⁻³
324 parameters

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mg1	0.81378 (10)	0.23692 (6)	0.49397 (5)	0.01481 (16)
O11W	1.0598 (2)	0.13517 (16)	0.56102 (15)	0.0275 (4)
H11A	1.101 (4)	0.0690 (19)	0.560 (2)	0.041*
H11B	1.124 (4)	0.155 (3)	0.596 (2)	0.041*
O12W	0.5724 (2)	0.35023 (14)	0.43273 (13)	0.0200 (3)
H12A	0.508 (4)	0.337 (2)	0.3931 (18)	0.030*
H12B	0.577 (4)	0.4250 (16)	0.411 (2)	0.030*
O13W	0.8425 (2)	0.12786 (14)	0.40247 (12)	0.0169 (3)
H13A	0.937 (3)	0.149 (2)	0.3562 (16)	0.025*
H13B	0.744 (3)	0.126 (2)	0.3752 (18)	0.025*
O14W	0.7913 (2)	0.32636 (17)	0.59110 (15)	0.0302 (4)
H14A	0.883 (4)	0.353 (3)	0.610 (2)	0.045*
H14B	0.681 (3)	0.350 (3)	0.615 (2)	0.045*
O15W	0.5991 (2)	0.12192 (15)	0.58580 (14)	0.0262 (4)
H15A	0.592 (4)	0.0455 (16)	0.613 (2)	0.039*
H15B	0.507 (3)	0.151 (2)	0.616 (2)	0.039*
O16W	1.0006 (3)	0.36017 (16)	0.39053 (17)	0.0397 (5)
H16A	1.113 (3)	0.346 (3)	0.361 (2)	0.060*
H16B	0.974 (5)	0.4362 (17)	0.366 (2)	0.060*
Mg2	1.0000	0.5000	0.0000	0.0143 (2)
O21W	1.0623 (2)	0.57333 (16)	0.10139 (14)	0.0261 (4)
H21A	0.982 (4)	0.613 (2)	0.128 (2)	0.039*
H21B	1.169 (3)	0.572 (3)	0.123 (2)	0.039*
O22W	0.8941 (2)	0.34472 (16)	0.12053 (14)	0.0303 (4)
H22A	0.958 (4)	0.299 (2)	0.1654 (18)	0.045*
H22B	0.775 (3)	0.321 (3)	0.137 (2)	0.045*
O23W	0.7155 (2)	0.57895 (15)	−0.00078 (12)	0.0213 (3)
H23A	0.641 (4)	0.566 (2)	0.0525 (15)	0.032*
H23B	0.661 (4)	0.623 (2)	−0.0509 (16)	0.032*
S1	0.24947 (7)	0.31939 (5)	0.71412 (4)	0.01455 (12)
O11	0.2178 (2)	0.28429 (14)	0.82576 (12)	0.0229 (4)
O12	0.4330 (2)	0.39112 (14)	0.67622 (13)	0.0221 (4)
O13	0.0741 (2)	0.39470 (13)	0.67063 (13)	0.0237 (4)
O14	0.2744 (2)	0.20773 (13)	0.68906 (11)	0.0169 (3)
S2	0.37973 (7)	0.21759 (5)	0.25672 (4)	0.01327 (12)
O21	0.3611 (2)	0.31962 (13)	0.29477 (11)	0.0165 (3)
O22	0.4965 (2)	0.11450 (13)	0.32351 (11)	0.0182 (3)
O23	0.1764 (2)	0.18145 (13)	0.25324 (11)	0.0175 (3)
O24	0.4911 (2)	0.25977 (13)	0.15362 (11)	0.0173 (3)
N1	0.2287 (3)	0.06416 (17)	0.97674 (16)	0.0236 (4)
H1	0.2199	0.1327	0.9271	0.028*
C2	0.2799 (3)	−0.0381 (2)	0.95590 (18)	0.0229 (5)
H2	0.3055	−0.0348	0.8894	0.027*	0.121 (5)
N2	0.3134 (3)	−0.0267 (2)	0.86029 (17)	0.0216 (6)	0.879 (5)
H2A	0.3024	0.0440	0.8134	0.026*	0.879 (5)
H2B	0.3462	−0.0901	0.8445	0.026*	0.879 (5)
C3	0.2935 (3)	−0.1499 (2)	1.03795 (19)	0.0268 (5)
H3	0.3296	−0.2219	1.0264	0.032*
C4	0.2530 (3)	−0.1514 (2)	1.13463 (19)	0.0284 (6)
H4	0.2599	−0.2252	1.1888	0.034*
C5	0.2012 (3)	−0.0435 (2)	1.15349 (19)	0.0292 (6)
H5	0.1747	−0.0447	1.2194	0.035*
C6	0.1906 (3)	0.0631 (2)	1.07281 (19)	0.0263 (5)
H6	0.1570	0.1359	1.0835	0.032*	0.879 (5)
N2A	0.1625 (19)	0.1588 (13)	1.0646 (11)	0.013 (4)*	0.121 (5)
H2AA	0.1679	0.2149	1.0052	0.015*	0.121 (5)
H2AB	0.1351	0.1781	1.1174	0.015*	0.121 (5)
O1W	0.5554 (2)	0.45065 (14)	0.83503 (12)	0.0176 (3)
H1WA	0.513 (4)	0.425 (2)	0.7954 (17)	0.026*
H1WB	0.570 (4)	0.5230 (16)	0.7977 (17)	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mg1	0.0141 (3)	0.0132 (4)	0.0172 (4)	0.0001 (3)	−0.0025 (3)	−0.0054 (3)
O11W	0.0259 (9)	0.0244 (10)	0.0417 (11)	0.0086 (7)	−0.0184 (8)	−0.0201 (9)
O12W	0.0231 (8)	0.0160 (8)	0.0226 (9)	0.0017 (6)	−0.0104 (7)	−0.0069 (7)
O13W	0.0153 (8)	0.0183 (8)	0.0168 (8)	−0.0017 (6)	−0.0019 (6)	−0.0059 (7)
O14W	0.0169 (8)	0.0446 (11)	0.0475 (12)	0.0042 (7)	−0.0091 (8)	−0.0373 (10)
O15W	0.0291 (9)	0.0134 (8)	0.0308 (10)	−0.0017 (7)	0.0097 (7)	−0.0063 (8)
O16W	0.0292 (10)	0.0135 (9)	0.0625 (14)	−0.0010 (7)	0.0235 (9)	−0.0075 (9)
Mg2	0.0114 (5)	0.0162 (5)	0.0142 (5)	0.0001 (4)	−0.0030 (4)	−0.0039 (4)
O21W	0.0181 (8)	0.0371 (10)	0.0341 (10)	0.0073 (7)	−0.0101 (7)	−0.0251 (9)
O22W	0.0182 (8)	0.0321 (10)	0.0269 (10)	−0.0085 (7)	−0.0083 (7)	0.0089 (8)
O23W	0.0152 (8)	0.0301 (10)	0.0141 (9)	0.0049 (6)	−0.0028 (6)	−0.0039 (7)
S1	0.0142 (2)	0.0126 (3)	0.0179 (3)	0.00057 (17)	−0.0040 (2)	−0.0063 (2)
O11	0.0326 (9)	0.0173 (8)	0.0186 (9)	0.0025 (6)	−0.0019 (7)	−0.0075 (7)
O12	0.0182 (8)	0.0182 (8)	0.0321 (10)	−0.0048 (6)	0.0013 (7)	−0.0122 (7)
O13	0.0232 (8)	0.0145 (8)	0.0379 (10)	0.0051 (6)	−0.0172 (7)	−0.0113 (7)
O14	0.0189 (7)	0.0137 (8)	0.0197 (8)	−0.0004 (5)	−0.0029 (6)	−0.0078 (6)
S2	0.0123 (2)	0.0130 (3)	0.0146 (3)	−0.00053 (17)	−0.00170 (19)	−0.0050 (2)
O21	0.0160 (7)	0.0154 (8)	0.0199 (8)	−0.0002 (5)	−0.0022 (6)	−0.0086 (7)
O22	0.0190 (8)	0.0139 (8)	0.0199 (8)	0.0008 (5)	−0.0060 (6)	−0.0032 (7)
O23	0.0137 (7)	0.0210 (8)	0.0198 (8)	−0.0036 (6)	−0.0011 (6)	−0.0093 (7)
O24	0.0149 (7)	0.0206 (8)	0.0151 (8)	−0.0007 (6)	−0.0006 (6)	−0.0053 (7)
N1	0.0199 (10)	0.0190 (10)	0.0264 (11)	−0.0028 (7)	−0.0049 (8)	−0.0006 (9)
C2	0.0113 (10)	0.0327 (14)	0.0206 (12)	−0.0045 (9)	−0.0016 (9)	−0.0042 (11)
N2	0.0266 (12)	0.0179 (12)	0.0197 (12)	0.0020 (8)	−0.0012 (9)	−0.0073 (10)
C3	0.0192 (12)	0.0244 (13)	0.0286 (14)	−0.0005 (9)	−0.0021 (10)	−0.0006 (11)
C4	0.0216 (12)	0.0312 (14)	0.0216 (13)	−0.0033 (9)	−0.0020 (10)	0.0031 (11)
C5	0.0223 (12)	0.0386 (15)	0.0218 (13)	−0.0061 (10)	−0.0026 (10)	−0.0041 (12)
C6	0.0223 (12)	0.0313 (15)	0.0257 (14)	−0.0043 (9)	−0.0049 (10)	−0.0093 (11)
O1W	0.0197 (8)	0.0169 (8)	0.0173 (9)	−0.0029 (6)	−0.0049 (6)	−0.0058 (7)

Geometric parameters (Å, º) top

Mg1—O11W	2.069 (2)	O23W—H23B	0.824 (17)
Mg1—O12W	2.0695 (19)	S1—O11	1.4836 (17)
Mg1—O13W	2.1321 (18)	S1—O12	1.4774 (16)
Mg1—O14W	2.0178 (19)	S1—O13	1.4661 (16)
Mg1—O15W	2.036 (2)	S1—O14	1.4794 (15)
Mg1—O16W	2.023 (2)	S2—O21	1.4845 (15)
O11W—H11A	0.808 (17)	S2—O22	1.4735 (16)
O11W—H11B	0.810 (17)	S2—O23	1.4733 (15)
O12W—H12A	0.821 (17)	S2—O24	1.4834 (16)
O12W—H12B	0.822 (17)	N1—H1	0.8600
O13W—H13A	0.831 (16)	N1—C2	1.352 (3)
O13W—H13B	0.815 (16)	N1—C6	1.359 (3)
O14W—H14A	0.830 (17)	C2—H2	0.9300
O14W—H14B	0.840 (17)	C2—N2	1.314 (3)
O15W—H15A	0.843 (17)	C2—C3	1.409 (3)
O15W—H15B	0.831 (17)	N2—H2A	0.8600
O16W—H16A	0.845 (18)	N2—H2B	0.8600
O16W—H16B	0.846 (18)	C3—H3	0.9300
Mg2—O21W	2.0471 (17)	C3—C4	1.367 (4)
Mg2—O21Wⁱ	2.0471 (17)	C4—H4	0.9300
Mg2—O22Wⁱ	2.0961 (19)	C4—C5	1.401 (4)
Mg2—O22W	2.0961 (19)	C5—H5	0.9300
Mg2—O23Wⁱ	2.0391 (17)	C5—C6	1.360 (4)
Mg2—O23W	2.0391 (17)	C6—H6	0.9300
O21W—H21A	0.825 (17)	C6—N2A	1.093 (14)
O21W—H21B	0.816 (17)	N2A—H2AA	0.8600
O22W—H22A	0.813 (17)	N2A—H2AB	0.8600
O22W—H22B	0.841 (17)	O1W—H1WA	0.822 (16)
O23W—H23A	0.821 (17)	O1W—H1WB	0.829 (16)

O11W—Mg1—O12W	174.72 (7)	Mg2—O21W—H21B	129 (2)
O11W—Mg1—O13W	86.78 (7)	H21A—O21W—H21B	105 (3)
O12W—Mg1—O13W	98.30 (7)	Mg2—O22W—H22A	126 (2)
O14W—Mg1—O11W	89.41 (8)	Mg2—O22W—H22B	128 (2)
O14W—Mg1—O12W	85.60 (8)	H22A—O22W—H22B	105 (3)
O14W—Mg1—O13W	174.89 (8)	Mg2—O23W—H23A	120.2 (19)
O14W—Mg1—O15W	89.96 (8)	Mg2—O23W—H23B	126.7 (19)
O14W—Mg1—O16W	92.37 (9)	H23A—O23W—H23B	113 (3)
O15W—Mg1—O11W	96.46 (9)	O12—S1—O11	107.82 (10)
O15W—Mg1—O12W	85.29 (8)	O12—S1—O14	110.69 (9)
O15W—Mg1—O13W	87.08 (7)	O13—S1—O11	108.86 (10)
O16W—Mg1—O11W	90.37 (9)	O13—S1—O12	109.67 (10)
O16W—Mg1—O12W	88.10 (8)	O13—S1—O14	110.53 (9)
O16W—Mg1—O13W	91.06 (8)	O14—S1—O11	109.20 (9)
O16W—Mg1—O15W	172.81 (9)	O22—S2—O21	109.23 (9)
Mg1—O11W—H11A	126 (2)	O22—S2—O24	108.69 (9)
Mg1—O11W—H11B	124 (2)	O23—S2—O21	109.36 (8)
H11A—O11W—H11B	110 (3)	O23—S2—O22	111.04 (9)
Mg1—O12W—H12A	122.0 (18)	O23—S2—O24	110.01 (9)
Mg1—O12W—H12B	121.8 (18)	O24—S2—O21	108.47 (9)
H12A—O12W—H12B	104 (3)	C2—N1—H1	118.6
Mg1—O13W—H13A	111.6 (17)	C2—N1—C6	122.7 (2)
Mg1—O13W—H13B	117.3 (18)	C6—N1—H1	118.6
H13A—O13W—H13B	106 (2)	N1—C2—H2	121.0
Mg1—O14W—H14A	129 (2)	N1—C2—C3	118.0 (2)
Mg1—O14W—H14B	123 (2)	N2—C2—N1	117.7 (2)
H14A—O14W—H14B	108 (3)	N2—C2—C3	124.3 (2)
Mg1—O15W—H15A	135.0 (19)	C3—C2—H2	121.0
Mg1—O15W—H15B	117 (2)	C2—N2—H2A	120.0
H15A—O15W—H15B	106 (3)	C2—N2—H2B	120.0
Mg1—O16W—H16A	127 (2)	H2A—N2—H2B	120.0
Mg1—O16W—H16B	125 (2)	C2—C3—H3	120.3
H16A—O16W—H16B	108 (3)	C4—C3—C2	119.4 (2)
O21Wⁱ—Mg2—O21W	180.0	C4—C3—H3	120.3
O21Wⁱ—Mg2—O22Wⁱ	89.74 (8)	C3—C4—H4	119.4
O21Wⁱ—Mg2—O22W	90.26 (8)	C3—C4—C5	121.1 (2)
O21W—Mg2—O22Wⁱ	90.26 (8)	C5—C4—H4	119.4
O21W—Mg2—O22W	89.73 (8)	C4—C5—H5	120.9
O22Wⁱ—Mg2—O22W	180.00 (8)	C6—C5—C4	118.2 (2)
O23Wⁱ—Mg2—O21W	90.06 (7)	C6—C5—H5	120.9
O23W—Mg2—O21Wⁱ	90.06 (7)	N1—C6—C5	120.6 (2)
O23W—Mg2—O21W	89.94 (7)	N1—C6—H6	119.7
O23Wⁱ—Mg2—O21Wⁱ	89.94 (7)	C5—C6—H6	119.7
O23W—Mg2—O22W	89.59 (8)	N2A—C6—N1	105.2 (8)
O23W—Mg2—O22Wⁱ	90.41 (8)	N2A—C6—C5	134.1 (8)
O23Wⁱ—Mg2—O22W	90.41 (8)	C6—N2A—H2AA	120.0
O23Wⁱ—Mg2—O22Wⁱ	89.59 (8)	C6—N2A—H2AB	120.0
O23W—Mg2—O23Wⁱ	180.0	H2AA—N2A—H2AB	120.0
Mg2—O21W—H21A	126 (2)	H1WA—O1W—H1WB	99 (2)

N1—C2—C3—C4	0.6 (3)	C3—C4—C5—C6	0.5 (3)
C2—N1—C6—C5	−0.6 (3)	C4—C5—C6—N1	0.2 (3)
C2—N1—C6—N2A	176.8 (7)	C4—C5—C6—N2A	−176.3 (10)
C2—C3—C4—C5	−0.9 (3)	C6—N1—C2—N2	179.9 (2)
N2—C2—C3—C4	−179.2 (2)	C6—N1—C2—C3	0.1 (3)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11W—H11A···O13Wⁱⁱ	0.81 (2)	2.19 (2)	2.977 (2)	164 (3)
O11W—H11B···O14ⁱⁱⁱ	0.81 (2)	2.06 (2)	2.873 (2)	177 (3)
O12W—H12A···O21	0.82 (2)	1.90 (2)	2.722 (2)	176 (3)
O12W—H12B···O12^iv	0.82 (2)	2.07 (2)	2.867 (2)	165 (3)
O13W—H13A···O23ⁱⁱⁱ	0.83 (2)	1.98 (2)	2.809 (2)	173 (3)
O13W—H13B···O22	0.82 (2)	1.94 (2)	2.750 (2)	174 (3)
O14W—H14A···O13ⁱⁱⁱ	0.83 (2)	1.83 (2)	2.658 (2)	172 (3)
O14W—H14B···O12	0.84 (2)	1.88 (2)	2.713 (2)	175 (3)
O15W—H15A···O22^v	0.84 (2)	1.88 (2)	2.701 (2)	165 (3)
O15W—H15B···O14	0.83 (2)	1.96 (2)	2.783 (2)	174 (3)
O16W—H16A···O21ⁱⁱⁱ	0.85 (2)	1.85 (2)	2.698 (2)	178 (3)
O16W—H16B···O13^iv	0.85 (2)	1.88 (2)	2.714 (2)	172 (3)
O21W—H21A···O11^iv	0.83 (2)	1.94 (2)	2.758 (2)	173 (3)
O21W—H21B···O1W^vi	0.82 (2)	1.98 (2)	2.783 (2)	171 (3)
O22W—H22A···O23ⁱⁱⁱ	0.81 (2)	2.12 (2)	2.912 (3)	166 (3)
O22W—H22B···O24	0.84 (2)	2.05 (2)	2.876 (2)	170 (3)
O23W—H23A···O1W^iv	0.82 (2)	1.90 (2)	2.711 (2)	173 (3)
O23W—H23B···O24^vii	0.82 (2)	1.94 (2)	2.752 (2)	170 (3)
N1—H1···O11	0.86	1.84	2.697 (3)	175
N2—H2A···O14	0.86	2.10	2.957 (3)	174
N2—H2B···O24^v	0.86	2.18	2.999 (3)	158
O1W—H1WA···O12	0.82 (2)	2.04 (2)	2.850 (2)	169 (2)
O1W—H1WB···O21^iv	0.83 (2)	1.89 (2)	2.716 (2)	172 (3)

Symmetry codes: (ii) −x+2, −y, −z+1; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) −x+2, −y+1, −z+1; (vii) −x+1, −y+1, −z.

(IV) Bis(2-aminopyridinium) hexaaquanickel(II) bis(sulfate) top

Crystal data top

(C₅H₇N₂)₂[Ni(H₂O)₆](SO₄)₂	Z = 1
M_r = 549.18	F(000) = 286
Triclinic, P1	D_x = 1.710 Mg m⁻³
a = 6.970 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.913 (3) Å	Cell parameters from 6242 reflections
c = 11.391 (4) Å	θ = 3.0–29.1°
α = 72.31 (3)°	µ = 1.18 mm⁻¹
β = 89.57 (3)°	T = 100 K
γ = 64.20 (3)°	Block, light green
V = 533.2 (4) Å³	0.15 × 0.12 × 0.1 mm

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	2662 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2341 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.6249 pixels mm^-1	θ_max = 29.6°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	k = −10→11
T_min = 0.879, T_max = 0.909	l = −15→15
11780 measured reflections

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.022P)² + 0.338P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2662 reflections	Δρ_max = 0.31 e Å⁻³
160 parameters	Δρ_min = −0.44 e Å⁻³

Crystal data top

(C₅H₇N₂)₂[Ni(H₂O)₆](SO₄)₂	γ = 64.20 (3)°
M_r = 549.18	V = 533.2 (4) Å³
Triclinic, P1	Z = 1
a = 6.970 (3) Å	Mo Kα radiation
b = 7.913 (3) Å	µ = 1.18 mm⁻¹
c = 11.391 (4) Å	T = 100 K
α = 72.31 (3)°	0.15 × 0.12 × 0.1 mm
β = 89.57 (3)°

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	2662 independent reflections
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	2341 reflections with I > 2σ(I)
T_min = 0.879, T_max = 0.909	R_int = 0.026
11780 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	6 restraints
wR(F²) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.31 e Å⁻³
2662 reflections	Δρ_min = −0.44 e Å⁻³
160 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
Ni1	0.5000	1.0000	0.0000	0.01038 (8)
O1W	0.81801 (19)	0.79924 (18)	0.06654 (11)	0.0149 (2)
H1WA	0.836 (3)	0.687 (2)	0.1100 (18)	0.022*
H1WB	0.912 (3)	0.782 (3)	0.0206 (18)	0.022*
O2W	0.40209 (19)	0.78550 (17)	0.07618 (11)	0.0143 (2)
H2WA	0.504 (3)	0.674 (2)	0.1164 (18)	0.021*
H2WB	0.323 (3)	0.769 (3)	0.0309 (18)	0.021*
O3W	0.51634 (19)	0.95526 (18)	−0.16941 (11)	0.0149 (2)
H3WA	0.448 (3)	0.903 (3)	−0.1925 (19)	0.022*
H3WB	0.639 (3)	0.908 (3)	−0.1889 (19)	0.022*
S1	0.86679 (6)	0.26220 (6)	0.19837 (3)	0.01136 (9)
O1	0.78367 (19)	0.46560 (17)	0.20867 (11)	0.0165 (2)
O2	0.84333 (19)	0.28270 (18)	0.06561 (10)	0.0171 (2)
O3	0.74195 (18)	0.16573 (17)	0.26770 (11)	0.0158 (2)
O4	1.09523 (18)	0.14692 (17)	0.25389 (10)	0.0149 (2)
N1	0.7453 (2)	0.5110 (2)	0.43941 (13)	0.0147 (3)
H1	0.7428	0.5000	0.3667	0.018*
C2	0.7799 (3)	0.3513 (2)	0.53979 (15)	0.0139 (3)
N2	0.8077 (2)	0.1831 (2)	0.52350 (13)	0.0176 (3)
H2A	0.8035	0.1768	0.4496	0.021*
H2B	0.8298	0.0806	0.5869	0.021*
C3	0.7865 (3)	0.3701 (3)	0.65929 (15)	0.0172 (3)
H3	0.8124	0.2625	0.7305	0.021*
C4	0.7541 (3)	0.5491 (3)	0.66851 (17)	0.0199 (4)
H4	0.7567	0.5630	0.7466	0.024*
C5	0.7170 (3)	0.7119 (3)	0.56133 (17)	0.0209 (4)
H5	0.6949	0.8332	0.5679	0.025*
C6	0.7140 (3)	0.6890 (3)	0.44846 (17)	0.0185 (3)
H6	0.6906	0.7950	0.3767	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01129 (15)	0.01018 (15)	0.00950 (14)	−0.00459 (12)	0.00164 (10)	−0.00349 (11)
O1W	0.0136 (6)	0.0133 (6)	0.0144 (6)	−0.0046 (5)	0.0030 (5)	−0.0027 (5)
O2W	0.0156 (6)	0.0134 (6)	0.0142 (6)	−0.0076 (5)	−0.0001 (5)	−0.0035 (5)
O3W	0.0141 (6)	0.0198 (6)	0.0151 (6)	−0.0091 (5)	0.0042 (5)	−0.0093 (5)
S1	0.01211 (19)	0.01263 (19)	0.00994 (18)	−0.00585 (16)	0.00185 (14)	−0.00423 (14)
O1	0.0198 (6)	0.0120 (6)	0.0157 (6)	−0.0053 (5)	0.0027 (5)	−0.0048 (5)
O2	0.0183 (6)	0.0259 (7)	0.0112 (5)	−0.0125 (5)	0.0032 (4)	−0.0079 (5)
O3	0.0162 (6)	0.0200 (6)	0.0149 (6)	−0.0113 (5)	0.0038 (5)	−0.0061 (5)
O4	0.0130 (6)	0.0168 (6)	0.0142 (5)	−0.0067 (5)	0.0015 (4)	−0.0043 (5)
N1	0.0153 (7)	0.0158 (7)	0.0114 (6)	−0.0058 (6)	0.0011 (5)	−0.0044 (5)
C2	0.0101 (7)	0.0165 (8)	0.0144 (7)	−0.0052 (6)	0.0024 (6)	−0.0055 (6)
N2	0.0224 (7)	0.0178 (7)	0.0129 (7)	−0.0095 (6)	0.0031 (6)	−0.0050 (6)
C3	0.0163 (8)	0.0216 (9)	0.0118 (7)	−0.0079 (7)	0.0026 (6)	−0.0043 (7)
C4	0.0153 (8)	0.0275 (10)	0.0185 (8)	−0.0075 (7)	0.0016 (7)	−0.0132 (7)
C5	0.0166 (8)	0.0183 (9)	0.0286 (9)	−0.0066 (7)	0.0000 (7)	−0.0108 (7)
C6	0.0149 (8)	0.0143 (8)	0.0224 (9)	−0.0046 (7)	−0.0005 (7)	−0.0040 (7)

Geometric parameters (Å, º) top

Ni1—O1W	2.0590 (17)	S1—O4	1.4722 (14)
Ni1—O1Wⁱ	2.0590 (17)	N1—H1	0.8600
Ni1—O2Wⁱ	2.0503 (14)	N1—C2	1.350 (2)
Ni1—O2W	2.0503 (13)	N1—C6	1.365 (2)
Ni1—O3W	2.0588 (13)	C2—N2	1.331 (2)
Ni1—O3Wⁱ	2.0588 (13)	C2—C3	1.417 (2)
O1W—H1WA	0.830 (15)	N2—H2A	0.8600
O1W—H1WB	0.825 (15)	N2—H2B	0.8600
O2W—H2WA	0.841 (15)	C3—H3	0.9300
O2W—H2WB	0.832 (15)	C3—C4	1.371 (3)
O3W—H3WA	0.839 (15)	C4—H4	0.9300
O3W—H3WB	0.829 (15)	C4—C5	1.406 (3)
S1—O1	1.4973 (13)	C5—H5	0.9300
S1—O2	1.4737 (13)	C5—C6	1.354 (3)
S1—O3	1.4714 (13)	C6—H6	0.9300

O1Wⁱ—Ni1—O1W	180.0	O3—S1—O2	111.20 (7)
O2W—Ni1—O1W	91.67 (6)	O3—S1—O4	109.79 (8)
O2Wⁱ—Ni1—O1Wⁱ	91.67 (6)	O4—S1—O1	108.40 (7)
O2Wⁱ—Ni1—O1W	88.33 (6)	O4—S1—O2	110.39 (8)
O2W—Ni1—O1Wⁱ	88.33 (6)	C2—N1—H1	118.6
O2Wⁱ—Ni1—O2W	180.0	C2—N1—C6	122.79 (15)
O2W—Ni1—O3Wⁱ	87.04 (5)	C6—N1—H1	118.6
O2Wⁱ—Ni1—O3W	87.04 (5)	N1—C2—C3	118.16 (15)
O2Wⁱ—Ni1—O3Wⁱ	92.96 (5)	N2—C2—N1	119.33 (15)
O2W—Ni1—O3W	92.96 (5)	N2—C2—C3	122.50 (15)
O3W—Ni1—O1W	93.37 (6)	C2—N2—H2A	120.0
O3Wⁱ—Ni1—O1Wⁱ	93.37 (6)	C2—N2—H2B	120.0
O3W—Ni1—O1Wⁱ	86.63 (6)	H2A—N2—H2B	120.0
O3Wⁱ—Ni1—O1W	86.63 (6)	C2—C3—H3	120.4
O3Wⁱ—Ni1—O3W	180.000 (10)	C4—C3—C2	119.10 (16)
Ni1—O1W—H1WA	113.6 (14)	C4—C3—H3	120.4
Ni1—O1W—H1WB	122.0 (15)	C3—C4—H4	119.6
H1WA—O1W—H1WB	107 (2)	C3—C4—C5	120.78 (16)
Ni1—O2W—H2WA	113.4 (14)	C5—C4—H4	119.6
Ni1—O2W—H2WB	118.8 (14)	C4—C5—H5	120.6
H2WA—O2W—H2WB	109 (2)	C6—C5—C4	118.80 (17)
Ni1—O3W—H3WA	122.5 (14)	C6—C5—H5	120.6
Ni1—O3W—H3WB	115.8 (15)	N1—C6—H6	119.8
H3WA—O3W—H3WB	108 (2)	C5—C6—N1	120.34 (16)
O2—S1—O1	108.62 (8)	C5—C6—H6	119.8
O3—S1—O1	108.37 (7)

N1—C2—C3—C4	1.1 (2)	C3—C4—C5—C6	−0.1 (3)
C2—N1—C6—C5	0.1 (2)	C4—C5—C6—N1	0.4 (3)
C2—C3—C4—C5	−0.7 (2)	C6—N1—C2—N2	179.58 (15)
N2—C2—C3—C4	−179.32 (15)	C6—N1—C2—C3	−0.8 (2)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.83 (2)	1.95 (2)	2.756 (2)	163 (2)
O1W—H1WB···O2ⁱⁱ	0.83 (2)	1.91 (2)	2.732 (2)	172 (2)
O2W—H2WA···O1	0.84 (2)	1.95 (2)	2.764 (2)	162 (2)
O2W—H2WB···O2ⁱⁱⁱ	0.83 (2)	1.85 (2)	2.6834 (18)	177 (2)
O3W—H3WA···O3ⁱⁱⁱ	0.84 (2)	1.93 (2)	2.7556 (18)	169 (2)
O3W—H3WB···O4ⁱⁱ	0.83 (2)	1.91 (2)	2.727 (2)	168 (2)
N1—H1···O1	0.86	1.90	2.755 (2)	171
N2—H2A···O3	0.86	2.15	3.006 (2)	171
N2—H2B···O4^iv	0.86	2.00	2.858 (2)	172
C6—H6···O3Wⁱ	0.93	2.51	3.363 (3)	153

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

(V) Bis(2-aminopyridinium) hexaaquazinc(II) bis(sulfate) top

Crystal data top

(C₅H₇N₂)₂[Zn(H₂O)₆](SO₄)₂	Z = 1
M_r = 555.84	F(000) = 288
Triclinic, P1	D_x = 1.715 Mg m⁻³
a = 6.977 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.929 (3) Å	Cell parameters from 3000 reflections
c = 11.441 (4) Å	θ = 3.0–28.3°
α = 72.25 (3)°	µ = 1.41 mm⁻¹
β = 89.53 (3)°	T = 100 K
γ = 64.45 (3)°	Plate, colourless
V = 538.2 (4) Å³	0.33 × 0.25 × 0.07 mm

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	2563 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2120 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 10.6249 pixels mm^-1	θ_max = 29.7°, θ_min = 3.0°
ω scans	h = −9→8
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	k = −10→10
T_min = 0.694, T_max = 0.921	l = −15→14
7323 measured reflections

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.023P)² + 0.501P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2563 reflections	Δρ_max = 0.38 e Å⁻³
160 parameters	Δρ_min = −0.56 e Å⁻³

Crystal data top

(C₅H₇N₂)₂[Zn(H₂O)₆](SO₄)₂	γ = 64.45 (3)°
M_r = 555.84	V = 538.2 (4) Å³
Triclinic, P1	Z = 1
a = 6.977 (3) Å	Mo Kα radiation
b = 7.929 (3) Å	µ = 1.41 mm⁻¹
c = 11.441 (4) Å	T = 100 K
α = 72.25 (3)°	0.33 × 0.25 × 0.07 mm
β = 89.53 (3)°

Data collection top

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	2563 independent reflections
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	2120 reflections with I > 2σ(I)
T_min = 0.694, T_max = 0.921	R_int = 0.032
7323 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	6 restraints
wR(F²) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.38 e Å⁻³
2563 reflections	Δρ_min = −0.56 e Å⁻³
160 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
Zn1	0.5000	1.0000	0.0000	0.01411 (12)
O1W	0.8228 (3)	0.7965 (3)	0.06621 (16)	0.0178 (4)
H1WA	0.840 (5)	0.684 (3)	0.108 (2)	0.027*
H1WB	0.919 (4)	0.781 (4)	0.020 (2)	0.027*
O2W	0.4015 (3)	0.7817 (3)	0.07706 (16)	0.0166 (4)
H2WA	0.508 (4)	0.678 (3)	0.114 (2)	0.025*
H2WB	0.327 (4)	0.763 (4)	0.031 (2)	0.025*
O3W	0.5158 (3)	0.9549 (3)	−0.17208 (16)	0.0181 (4)
H3WA	0.443 (4)	0.913 (4)	−0.200 (3)	0.027*
H3WB	0.636 (3)	0.915 (4)	−0.195 (3)	0.027*
S1	0.86634 (10)	0.26278 (9)	0.19970 (5)	0.01418 (15)
O1	0.7842 (3)	0.4652 (3)	0.21008 (16)	0.0189 (4)
O2	0.8423 (3)	0.2834 (3)	0.06753 (15)	0.0197 (4)
O3	0.7418 (3)	0.1661 (3)	0.26976 (15)	0.0181 (4)
O4	1.0947 (3)	0.1480 (3)	0.25429 (15)	0.0179 (4)
N1	0.7456 (3)	0.5091 (3)	0.44013 (19)	0.0169 (4)
H1	0.7426	0.4984	0.3677	0.020*
C2	0.7808 (4)	0.3492 (4)	0.5403 (2)	0.0160 (5)
N2	0.8090 (3)	0.1814 (3)	0.52404 (19)	0.0188 (5)
H2A	0.8047	0.1753	0.4504	0.023*
H2B	0.8315	0.0790	0.5872	0.023*
C3	0.7865 (4)	0.3698 (4)	0.6584 (2)	0.0187 (5)
H3	0.8115	0.2628	0.7295	0.022*
C4	0.7552 (4)	0.5472 (4)	0.6681 (2)	0.0216 (6)
H4	0.7589	0.5606	0.7459	0.026*
C5	0.7172 (4)	0.7100 (4)	0.5609 (3)	0.0229 (6)
H5	0.6944	0.8314	0.5671	0.027*
C6	0.7147 (4)	0.6865 (4)	0.4490 (2)	0.0201 (6)
H6	0.6916	0.7921	0.3775	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0148 (2)	0.0157 (2)	0.0116 (2)	−0.00715 (17)	0.00165 (15)	−0.00385 (16)
O1W	0.0166 (9)	0.0184 (10)	0.0147 (9)	−0.0068 (8)	0.0032 (7)	−0.0023 (8)
O2W	0.0166 (10)	0.0178 (10)	0.0151 (9)	−0.0089 (8)	−0.0013 (7)	−0.0030 (8)
O3W	0.0170 (10)	0.0258 (10)	0.0156 (9)	−0.0118 (8)	0.0037 (7)	−0.0093 (8)
S1	0.0151 (3)	0.0168 (3)	0.0112 (3)	−0.0079 (3)	0.0016 (2)	−0.0044 (2)
O1	0.0220 (10)	0.0168 (9)	0.0166 (9)	−0.0078 (8)	0.0026 (7)	−0.0052 (7)
O2	0.0194 (9)	0.0301 (11)	0.0132 (9)	−0.0136 (8)	0.0040 (7)	−0.0085 (8)
O3	0.0184 (9)	0.0244 (10)	0.0165 (9)	−0.0135 (8)	0.0047 (7)	−0.0077 (8)
O4	0.0160 (9)	0.0220 (10)	0.0150 (9)	−0.0091 (8)	0.0013 (7)	−0.0043 (7)
N1	0.0165 (11)	0.0220 (12)	0.0115 (10)	−0.0078 (9)	0.0015 (8)	−0.0058 (9)
C2	0.0115 (12)	0.0188 (13)	0.0162 (12)	−0.0063 (10)	0.0020 (9)	−0.0048 (10)
N2	0.0252 (12)	0.0203 (12)	0.0112 (10)	−0.0113 (10)	0.0036 (9)	−0.0045 (9)
C3	0.0152 (13)	0.0237 (14)	0.0162 (13)	−0.0085 (11)	0.0025 (10)	−0.0059 (11)
C4	0.0170 (13)	0.0308 (16)	0.0204 (13)	−0.0104 (12)	0.0029 (10)	−0.0135 (12)
C5	0.0194 (14)	0.0225 (15)	0.0274 (15)	−0.0088 (12)	0.0007 (11)	−0.0102 (12)
C6	0.0159 (13)	0.0169 (14)	0.0225 (14)	−0.0060 (11)	−0.0019 (10)	−0.0022 (11)

Geometric parameters (Å, º) top

Zn1—O1Wⁱ	2.097 (2)	S1—O4	1.475 (2)
Zn1—O1W	2.097 (2)	N1—H1	0.8600
Zn1—O2W	2.0813 (19)	N1—C2	1.353 (3)
Zn1—O2Wⁱ	2.0813 (19)	N1—C6	1.364 (3)
Zn1—O3W	2.0996 (18)	C2—N2	1.330 (3)
Zn1—O3Wⁱ	2.0996 (18)	C2—C3	1.413 (3)
O1W—H1WA	0.828 (17)	N2—H2A	0.8600
O1W—H1WB	0.844 (17)	N2—H2B	0.8600
O2W—H2WA	0.820 (17)	C3—H3	0.9300
O2W—H2WB	0.833 (17)	C3—C4	1.367 (4)
O3W—H3WA	0.823 (17)	C4—H4	0.9300
O3W—H3WB	0.828 (17)	C4—C5	1.410 (4)
S1—O1	1.4971 (18)	C5—H5	0.9300
S1—O2	1.4736 (18)	C5—C6	1.350 (4)
S1—O3	1.4744 (18)	C6—H6	0.9300

O1Wⁱ—Zn1—O1W	180.0	O2—S1—O4	110.26 (11)
O1W—Zn1—O3Wⁱ	86.88 (8)	O3—S1—O1	108.21 (10)
O1W—Zn1—O3W	93.12 (8)	O3—S1—O4	109.74 (11)
O1Wⁱ—Zn1—O3Wⁱ	93.12 (8)	O4—S1—O1	108.48 (11)
O1Wⁱ—Zn1—O3W	86.88 (8)	C2—N1—H1	118.5
O2W—Zn1—O1Wⁱ	88.54 (8)	C2—N1—C6	122.9 (2)
O2W—Zn1—O1W	91.46 (8)	C6—N1—H1	118.5
O2Wⁱ—Zn1—O1W	88.54 (8)	N1—C2—C3	117.6 (2)
O2Wⁱ—Zn1—O1Wⁱ	91.46 (8)	N2—C2—N1	119.4 (2)
O2W—Zn1—O2Wⁱ	180.0	N2—C2—C3	123.1 (2)
O2W—Zn1—O3Wⁱ	87.20 (7)	C2—N2—H2A	120.0
O2Wⁱ—Zn1—O3Wⁱ	92.80 (7)	C2—N2—H2B	120.0
O2W—Zn1—O3W	92.80 (7)	H2A—N2—H2B	120.0
O2Wⁱ—Zn1—O3W	87.20 (7)	C2—C3—H3	120.1
O3Wⁱ—Zn1—O3W	180.000 (15)	C4—C3—C2	119.9 (2)
Zn1—O1W—H1WA	113 (2)	C4—C3—H3	120.1
Zn1—O1W—H1WB	122 (2)	C3—C4—H4	119.8
H1WA—O1W—H1WB	107 (3)	C3—C4—C5	120.4 (2)
Zn1—O2W—H2WA	108 (2)	C5—C4—H4	119.8
Zn1—O2W—H2WB	118 (2)	C4—C5—H5	120.6
H2WA—O2W—H2WB	111 (3)	C6—C5—C4	118.7 (3)
Zn1—O3W—H3WA	125 (2)	C6—C5—H5	120.6
Zn1—O3W—H3WB	117 (2)	N1—C6—H6	119.7
H3WA—O3W—H3WB	110 (3)	C5—C6—N1	120.5 (2)
O2—S1—O1	108.64 (11)	C5—C6—H6	119.7
O2—S1—O3	111.43 (10)

N1—C2—C3—C4	0.5 (4)	C3—C4—C5—C6	−0.7 (4)
C2—N1—C6—C5	−0.3 (4)	C4—C5—C6—N1	0.8 (4)
C2—C3—C4—C5	0.0 (4)	C6—N1—C2—N2	179.8 (2)
N2—C2—C3—C4	−179.7 (2)	C6—N1—C2—C3	−0.4 (3)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.83 (2)	1.97 (2)	2.765 (3)	162 (3)
O1W—H1WB···O2ⁱⁱ	0.84 (2)	1.89 (2)	2.731 (3)	172 (3)
O2W—H2WA···O1	0.82 (2)	1.97 (2)	2.775 (3)	169 (3)
O2W—H2WB···O2ⁱⁱⁱ	0.83 (2)	1.85 (2)	2.687 (3)	178 (3)
O3W—H3WA···O3ⁱⁱⁱ	0.82 (2)	1.93 (2)	2.752 (3)	176 (3)
O3W—H3WB···O4ⁱⁱ	0.83 (2)	1.91 (2)	2.729 (3)	174 (3)
N1—H1···O1	0.86	1.90	2.754 (3)	171
N2—H2A···O3	0.86	2.15	2.997 (3)	171
N2—H2B···O4^iv	0.86	2.01	2.860 (3)	173
C6—H6···O3Wⁱ	0.93	2.51	3.370 (4)	153

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

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	(C₅H₇N₂)[Al(H₂O)₆](SO₄)₂·4H₂O	(C₅H₇N₂)₂[Co(H₂O)₆]₃(SO₄)₄·2H₂O	(C₅H₇N₂)₂[Mg(H₂O)₆]₃(SO₄)₄·2H₂O
M_r	494.38	1111.60	1007.74
Crystal system, space group	Triclinic, P1	Triclinic, P1	Triclinic, P1
Temperature (K)	100	100	100
a, b, c (Å)	6.667 (3), 12.160 (4), 12.911 (4)	6.640 (3), 11.710 (4), 14.294 (4)	6.682 (3), 11.807 (4), 14.309 (4)
α, β, γ (°)	72.30 (3), 81.03 (3), 85.57 (3)	67.97 (3), 81.57 (3), 85.39 (3)	68.23 (3), 82.13 (3), 84.76 (3)
V (Å³)	984.5 (7)	1018.8 (7)	1037.5 (7)
Z	2	1	1
Radiation type	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	0.41	1.53	0.39
Crystal size (mm)	0.50 × 0.33 × 0.20	0.42 × 0.27 × 0.08	0.43 × 0.36 × 0.23

Data collection
Diffractometer	Rigaku Oxford Diffraction Xcalibur Atlas	Rigaku Oxford Diffraction Xcalibur Atlas	Rigaku Oxford Diffraction Xcalibur Atlas
Absorption correction	Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.869, 0.930	0.609, 0.891	0.892, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	14826, 4751, 3685	14070, 4878, 4072	11467, 4884, 3875
R_int	0.027	0.025	0.026
(sin θ/λ)_max (Å⁻¹)	0.691	0.695	0.689

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.093, 1.02	0.031, 0.069, 1.06	0.040, 0.089, 1.03
No. of reflections	4751	4878	4884
No. of parameters	316	321	324
No. of restraints	20	20	20
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.62	0.42, −0.44	0.45, −0.40

	(IV)	(V)
Crystal data
Chemical formula	(C₅H₇N₂)₂[Ni(H₂O)₆](SO₄)₂	(C₅H₇N₂)₂[Zn(H₂O)₆](SO₄)₂
M_r	549.18	555.84
Crystal system, space group	Triclinic, P1	Triclinic, P1
Temperature (K)	100	100
a, b, c (Å)	6.970 (3), 7.913 (3), 11.391 (4)	6.977 (3), 7.929 (3), 11.441 (4)
α, β, γ (°)	72.31 (3), 89.57 (3), 64.20 (3)	72.25 (3), 89.53 (3), 64.45 (3)
V (Å³)	533.2 (4)	538.2 (4)
Z	1	1
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	1.18	1.41
Crystal size (mm)	0.15 × 0.12 × 0.1	0.33 × 0.25 × 0.07

Data collection
Diffractometer	Rigaku Oxford Diffraction Xcalibur Atlas	Rigaku Oxford Diffraction Xcalibur Atlas
Absorption correction	Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]	Analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.879, 0.909	0.694, 0.921
No. of measured, independent and observed [I > 2σ(I)] reflections	11780, 2662, 2341	7323, 2563, 2120
R_int	0.026	0.032
(sin θ/λ)_max (Å⁻¹)	0.695	0.696

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.060, 1.07	0.037, 0.078, 1.08
No. of reflections	2662	2563
No. of parameters	160	160
No. of restraints	6	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.44	0.38, −0.56

Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015), SHELXT (Sheldrick, 2015a), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg, 1997), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) for (I) top

D—H···A	D—H	H···A	D···A	D—H···A
O11W—H11A···O4W	0.821 (15)	1.810 (15)	2.626 (2)	173 (2)
O11W—H11B···O21ⁱⁱⁱ	0.841 (15)	1.885 (16)	2.715 (2)	168 (2)
O12W—H12A···O14^iv	0.859 (15)	1.791 (16)	2.648 (2)	175 (2)
O12W—H12B···O22	0.833 (15)	1.800 (16)	2.628 (2)	173 (2)
O13W—H13A···O21ⁱ	0.842 (15)	1.884 (16)	2.711 (2)	167 (2)
O13W—H13B···O13	0.839 (15)	1.783 (15)	2.6144 (18)	171 (2)
O21W—H21A···O13	0.833 (15)	1.843 (16)	2.667 (2)	170 (2)
O21W—H21B···O23ⁱⁱⁱ	0.852 (15)	1.770 (16)	2.622 (2)	180 (3)
O22W—H22A···O1Wⁱⁱ	0.850 (15)	1.760 (16)	2.606 (2)	173 (2)
O22W—H22B···O12^v	0.830 (15)	1.819 (16)	2.647 (2)	175 (2)
O23W—H23A···O12	0.837 (15)	1.913 (16)	2.740 (2)	169 (2)
O23W—H23B···O22ⁱⁱ	0.825 (15)	1.847 (16)	2.6660 (18)	172 (2)
N1—H1···O24	0.86	1.87	2.711 (2)	164
N2—H2A···O23	0.86	2.09	2.944 (2)	176
N2—H2B···O11ⁱⁱ	0.86	2.04	2.856 (2)	159
C6—H6···O1W^vi	0.93	2.30	3.127 (2)	147
O1W—H1WA···O11	0.841 (15)	1.959 (16)	2.792 (2)	170 (2)
O1W—H1WB···O2W	0.849 (16)	1.920 (16)	2.768 (2)	177 (2)
O2W—H2WA···O11^iv	0.825 (16)	2.089 (18)	2.864 (2)	156 (2)
O2W—H2WB···O3W^vii	0.800 (16)	2.016 (16)	2.812 (2)	173 (2)
O3W—H3WA···O14ⁱ	0.831 (16)	2.250 (17)	3.069 (2)	169 (2)
O3W—H3WB···O24	0.836 (16)	1.942 (16)	2.7609 (19)	166 (2)
O4W—H4WA···O3W	0.845 (16)	2.099 (17)	2.929 (2)	167 (2)
O4W—H4WB···O2Wⁱ	0.808 (16)	2.044 (16)	2.849 (2)	175 (2)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x−1, y, z; (v) −x+2, −y+1, −z+1; (vi) x, y, z−1; (vii) x, y, z+1.

π–π stacking interactions top

Compound	CgI	CgJ	Distance between ring centroids (Å)	Perpendicular distance between rings (Å)	Offset (Å)
(I)	Cg1	Cg1ⁱ	4.130 (2)	3.0792 (8)	2.753
(I)	Cg1	Cg1ⁱⁱ	3.454 (2)	3.2134 (8)	1.265
(II)	Cg1	Cg1ⁱⁱⁱ	3.634 (2)	3.2118 (8)	1.700
(II)	Cg1	Cg1^iv	3.706 (2)	3.3228 (8)	1.640
(III)	Cg1	Cg1ⁱⁱⁱ	3.677 (2)	3.2564 (8)	1.708
(III)	Cg1	Cg1^iv	3.666 (2)	3.3574 (8)	1.471
(IV)	Cg1	Cg1^v	3.955 (2)	3.3426 (9)	2.114
(IV)	Cg1	Cg1^vi	3.564 (2)	3.3101 (9)	1.321
(V)	Cg1	Cg1^v	3.950 (2)	3.3531 (12)	2.088
(V)	Cg1	Cg1^vi	3.569 (2)	3.3166 (12)	1.318
(VI)	Cg1	Cg1^vi	3.414 (3)	3.4028 (15)	0.276
(VI)	Cg1	Cg1^vii	3.958 (3)	3.4079 (15)	2.013

Symmetry codes: (i) -x, -y+1, -z; (ii) -x+1, -y+1, -z; (iii) -x, -y, -z+2; (iv) -x+1, -y, -z+2; (v) -x+1, -y+1, -z+1; (vi) -x+2, -y+1, -z+1; (vii) -x+1, -y+1, -z+2.

Hydrogen-bond geometry (Å, º) for (II) top

D—H···A	D—H	H···A	D···A	D—H···A
O11W—H11A···O13Wⁱⁱ	0.827 (17)	2.139 (17)	2.964 (2)	175 (3)
O11W—H11B···O14ⁱⁱⁱ	0.813 (17)	2.068 (17)	2.881 (2)	178 (3)
O12W—H12A···O21	0.838 (16)	1.878 (17)	2.711 (2)	173 (3)
O12W—H12B···O12^iv	0.815 (16)	2.090 (17)	2.894 (3)	169 (3)
O13W—H13A···O23ⁱⁱⁱ	0.819 (16)	1.984 (17)	2.800 (2)	175 (2)
O13W—H13B···O22	0.819 (16)	1.921 (17)	2.735 (2)	172 (3)
O14W—H14A···O13ⁱⁱⁱ	0.828 (17)	1.853 (18)	2.671 (2)	169 (3)
O14W—H14B···O12	0.810 (17)	1.934 (17)	2.744 (2)	179 (3)
O15W—H15A···O22^v	0.824 (17)	1.899 (17)	2.706 (2)	166 (3)
O15W—H15B···O14	0.830 (16)	1.928 (17)	2.756 (2)	177 (3)
O16W—H16A···O21ⁱⁱⁱ	0.840 (17)	1.867 (18)	2.699 (2)	171 (3)
O16W—H16B···O13^iv	0.839 (17)	1.864 (17)	2.703 (2)	179 (3)
O21W—H21A···O11^iv	0.817 (17)	1.951 (18)	2.766 (2)	175 (3)
O21W—H21B···O1W^vi	0.818 (17)	1.953 (18)	2.758 (2)	168 (3)
O22W—H22A···O23ⁱⁱⁱ	0.804 (18)	2.24 (2)	2.959 (3)	150 (3)
O22W—H22B···O24	0.837 (17)	2.009 (19)	2.835 (2)	169 (3)
O23W—H23A···O1W^iv	0.819 (17)	1.901 (18)	2.714 (2)	171 (3)
O23W—H23B···O24^vii	0.811 (17)	1.958 (18)	2.759 (2)	169 (3)
N1—H1···O11	0.86	1.85	2.701 (3)	172
N2—H2A···O14	0.86	2.10	2.955 (3)	173
N2—H2B···O24^v	0.86	2.12	2.959 (3)	164
O1W—H1WA···O12	0.85	2.09	2.935 (2)	175
O1W—H1WB···O21^iv	0.91	1.80	2.711 (2)	171

Symmetry codes: (ii) −x+2, −y, −z+1; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) −x+2, −y+1, −z+1; (vii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) for (III) top

D—H···A	D—H	H···A	D···A	D—H···A
O11W—H11A···O13Wⁱⁱ	0.808 (17)	2.192 (19)	2.977 (2)	164 (3)
O11W—H11B···O14ⁱⁱⁱ	0.810 (17)	2.063 (18)	2.873 (2)	177 (3)
O12W—H12A···O21	0.821 (17)	1.903 (17)	2.722 (2)	176 (3)
O12W—H12B···O12^iv	0.822 (17)	2.065 (18)	2.867 (2)	165 (3)
O13W—H13A···O23ⁱⁱⁱ	0.831 (16)	1.982 (17)	2.809 (2)	173 (3)
O13W—H13B···O22	0.815 (16)	1.938 (17)	2.750 (2)	174 (3)
O14W—H14A···O13ⁱⁱⁱ	0.830 (17)	1.834 (18)	2.658 (2)	172 (3)
O14W—H14B···O12	0.840 (17)	1.875 (18)	2.713 (2)	175 (3)
O15W—H15A···O22^v	0.843 (17)	1.877 (18)	2.701 (2)	165 (3)
O15W—H15B···O14	0.831 (17)	1.955 (17)	2.783 (2)	174 (3)
O16W—H16A···O21ⁱⁱⁱ	0.845 (18)	1.853 (18)	2.698 (2)	178 (3)
O16W—H16B···O13^iv	0.846 (18)	1.875 (19)	2.714 (2)	172 (3)
O21W—H21A···O11^iv	0.825 (17)	1.937 (18)	2.758 (2)	173 (3)
O21W—H21B···O1W^vi	0.816 (17)	1.975 (18)	2.783 (2)	171 (3)
O22W—H22A···O23ⁱⁱⁱ	0.813 (17)	2.116 (19)	2.912 (3)	166 (3)
O22W—H22B···O24	0.841 (17)	2.045 (18)	2.876 (2)	170 (3)
O23W—H23A···O1W^iv	0.821 (17)	1.895 (17)	2.711 (2)	173 (3)
O23W—H23B···O24^vii	0.824 (17)	1.936 (17)	2.752 (2)	170 (3)
N1—H1···O11	0.86	1.84	2.697 (3)	174.9
N2—H2A···O14	0.86	2.10	2.957 (3)	174.3
N2—H2B···O24^v	0.86	2.18	2.999 (3)	158.2
O1W—H1WA···O12	0.822 (16)	2.039 (17)	2.850 (2)	169 (2)
O1W—H1WB···O21^iv	0.829 (16)	1.893 (17)	2.716 (2)	172 (3)

Symmetry codes: (ii) −x+2, −y, −z+1; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) −x+2, −y+1, −z+1; (vii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) for (IV) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.830 (15)	1.953 (16)	2.756 (2)	163 (2)
O1W—H1WB···O2ⁱⁱ	0.825 (15)	1.913 (16)	2.732 (2)	172 (2)
O2W—H2WA···O1	0.841 (15)	1.951 (16)	2.764 (2)	162 (2)
O2W—H2WB···O2ⁱⁱⁱ	0.832 (15)	1.852 (16)	2.6834 (18)	177 (2)
O3W—H3WA···O3ⁱⁱⁱ	0.839 (15)	1.927 (16)	2.7556 (18)	169 (2)
O3W—H3WB···O4ⁱⁱ	0.829 (15)	1.910 (16)	2.727 (2)	168 (2)
N1—H1···O1	0.86	1.90	2.755 (2)	171.1
N2—H2A···O3	0.86	2.15	3.006 (2)	170.8
N2—H2B···O4^iv	0.86	2.00	2.858 (2)	172.3
C6—H6···O3Wⁱ	0.93	2.51	3.363 (3)	152.8

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

Hydrogen-bond geometry (Å, º) for (V) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.828 (17)	1.966 (19)	2.765 (3)	162 (3)
O1W—H1WB···O2ⁱⁱ	0.844 (17)	1.893 (18)	2.731 (3)	172 (3)
O2W—H2WA···O1	0.820 (17)	1.966 (18)	2.775 (3)	169 (3)
O2W—H2WB···O2ⁱⁱⁱ	0.833 (17)	1.854 (18)	2.687 (3)	178 (3)
O3W—H3WA···O3ⁱⁱⁱ	0.823 (17)	1.930 (18)	2.752 (3)	176 (3)
O3W—H3WB···O4ⁱⁱ	0.828 (17)	1.905 (18)	2.729 (3)	174 (3)
N1—H1···O1	0.86	1.90	2.754 (3)	171
N2—H2A···O3	0.86	2.15	2.997 (3)	171
N2—H2B···O4^iv	0.86	2.01	2.860 (3)	173
C6—H6···O3Wⁱ	0.93	2.51	3.370 (4)	153

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

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Format		BIBTeX
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		Plain Text

Synthesis, structure and characterization of five new organically templated metal sulfates with 2-amino­pyridinium

Supporting information

Synthesis, structure and characterization of five new organically templated metal sulfates with 2-aminopyridinium