Iso­propyl­ammonium halidometallates. I. [CoX4]2−·X− (X = Cl, Br), ZnCl42−, and [ZnCl3−]n salts

Birke, J.; Nguyen, T.; Bond, M.R.

doi:10.1107/S2056989025006103

research communications

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ISSN: 2056-9890

Volume 81| Part 8| August 2025| Pages 684-693

https://doi.org/10.1107/S2056989025006103

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Isopropylammonium halidometallates. I. [CoX₄]²⁻·X⁻ (X = Cl, Br), ZnCl₄²⁻, and [ZnCl₃⁻]_n salts

Josh Birke,^a Tu Nguyen ^a and Marcus R. Bond ^a ^*

^aDepartment of Chemistry and Physics, Southeast Missouri State University, Cape Girardeau, MO 63701, USA
^*Correspondence e-mail: [email protected]

Edited by K. V. Domasevitch, National Taras Shevchenko University of Kyiv, Ukraine (Received 10 June 2025; accepted 8 July 2025; online 15 July 2025)

An exploration of the isopropylammonium (IPA⁺) metal halide structural space is conducted, initially, for cobalt(II) and zinc(II) halides as a counterpart to the more extensively studied metal halide systems containing the isomeric trimethylammonium cation. For cobalt(II) halides, the only compound obtained from slow evaporation of acidic aqueous solutions of isopropylammonium halide and cobalt(II) halide is (IPA⁺)₃CoX₄·X (X = Cl, Br), namely, tris(isopropylammonium) tetrachloridocobaltate(II) chloride, (C₃H₁₀N)₃[CoCl₄]Cl, and tris(isopropylammonium) tetrabromidocobaltate(II) bromide, (C₃H₁₀N)₃[CoBr₄]Br, regardless of the starting stoichiometric ratio of (IPA⁺)X:CoX₂. These structures consist of isolated tetrahedral CoX₄²⁻ complexes and X⁻ ions separated by IPA⁺ cations. One IPA⁺ cation hydrogen bonds to two complexes and to two halide ions to produce clusters. These clusters form stacks with hydrogen bonding from the remaining IPA⁺ cations linking the stacks into a tight, three-dimensional network. A 2:1 molar ratio of (IPA⁺)Cl and ZnCl₂ under similar growth conditions readily yields crystals of bis(isopropylammonium) tetrachloridozincate(II), (C₃H₁₀N)₂[ZnCl₄] or (IPA⁺)₂ZnCl₄, consisting only of IPA⁺ cations and isolated ZnCl₄²⁻ tetrahedra. This despite the expectation of common structural chemistry for the similarly sized Co²⁺ and Zn²⁺ ions with 51 known isostructural A₂CoCl₄ and A₂ZnCl₄ compounds out of 54 for the same monopositive A cation. Growth from a 1:1 ratio of (IPA⁺)Cl:ZnCl₂ yields crystals of poly[isopropylammonium [[dichloridozincate(II)]-μ-chlorido]], {(C₃H₁₀N)[ZnCl₃]}_n or (IPA⁺)ZnCl₃, in which parallel chains of corner-sharing ZnCl₄ tetrahedra are separated by IPA⁺ cations. This unusual zinc(II) halide chain structure has previously been observed only in [YCH₂(CH₃)₃N]ZnCl₃ salts (Y = H, halogen). In contrast to these known compounds, which are found in polar orthorhombic space groups, the structure reported here is in orthorhombic Pbca.

Keywords: crystal structure; isopropylammonium; halidometallates; one-dimensional chains.

CCDC references: 2471094; 2471093; 2471092; 2471091

1. Chemical context

The isopropylammonium cation (IPA⁺) is isomeric with the trimethylammonium (TMA⁺) cation, yet is less prominent as a counter-ion in metal halide structural chemistry. A search of the Cambridge Structural Database (CSD version 5.46; Groom et al., 2016 ) yields only 28 hits with 19 different compounds for IPA⁺ metal halide salts in which at least three halide ions are bound to the metal with any type of bond and curated for strictly metal halides. A similar search for TMA⁺ salts yields 87 hits with 41 compounds. While the ions are isomeric, they can play distinctly different roles in metal halide structures. As a tertiary ammonium cation, TMA⁺ is a single hydrogen-bond donor, in contrast to the primary IPA⁺ cation. Meanwhile, the bulkiness of the isopropylammonium cation may template halidometallate structures different than those of other primary ammonium cations. For example, the A₂MX′₄ (X′ = halogen) layered perovskite structures that are commonly found with primary ammonium cations (Yu et al., 2021 ), are only reported for large metal cation (Sn²⁺ or Pb²⁺) bromides or iodides (vide infra) with IPA⁺. The bulkiness of the IPA⁺ cation also breaks the layered perovskite structure into ribbons three complexes wide in the ambient temperature structure of (IPA⁺)₂CuCl₄ (CSD refcode: IPRACU; Anderson & Willett, 1974 ). This structure transforms at higher temperature in a thermochromic (green-to-yellow) phase transition to a structure consisting of isolated flattened CuCl₄²⁻ tetrahedra. (IPRACU01; Bloomquist, Willett & Dodgen, 1981 ). Given the unique features of the IPA⁺ cation, we have initiated a more thorough exploration of the IPA⁺ halidometallate structural space. We start by reporting structures of the new compounds (IPA⁺)₃CoX₄X (X = Cl, Br, compounds I and II, respectively), (IPA⁺)₂ZnCl₄, (compound III) and (IPA⁺)ZnCl₃ (compound IV), a survey of known isopropylammonium halidometallates, and a study of IPA⁺ cation geometry (both experimental and theoretical) juxtaposed with that of TMA⁺.

2. Structural commentary

2.1. (IPA⁺)₃CoX₄·X

The structures of the chloride and bromide salts are isomorphous. Blue crystals selected from samples grown from acidic aqueous solution with starting stoichiometries of 2:1, 1:1, and 1:2 in (IPA⁺)X:CoX₂ are all found in this structure. Crystal growth from more CoX₂-rich stoichiometries yields blue crystals intermixed with an increasing larger fraction of magenta crystals of CoX₂·6H₂O.

The structures consist of isolated CoX₄²⁻ tetrahedra surrounded by isolated halide and IPA⁺ ions. The complexes exhibit minor distortions from the expected tetrahedral geometry. Co—X bond lengths are in the range 2.2561 (6)–2.2820 (6) Å for I and 2.3894 (7)–2.4110 (7) Å for II [average = 2.269 (11) Å for I and 2.410 (10) Å for II], while X—Co—X angles are in the range 104.72 (2)–112.61 (3)° for I and 105.72 (3)–112.63 (3)° for II [average = 109 (3)° for both I and II]. IPA⁺ cation #1 (N1) is ordered, while cation number #2 (N2) is slightly disordered in both structures [SOF (site occupation factor) = 0.851 (11) and 0.74 (3) for the major component in I and II, respectively]. The disorder corresponds to an ‘umbrella' inversion relationship between the two components about N2. ‘Umbrella' inversion disorder is also present for cation #3 (N3) in I only [SOF = 0.765 (5) for the major component]. Here N3 is found in different positions with two of the ammonium protons forming hydrogen bonds to the same acceptors in each component, but the third proton forming a hydrogen bond to a different acceptor. For I and II, respectively, Tables 1 and 2 contain selected geometric parameters and Figs. 1 and 2 present displacement ellipsoid plots with labels for non-H atoms of the formula units.

Table 1
Selected geometric parameters (Å, °) for I

Co1—Cl1	2.2561 (6)	Co1—Cl3	2.2820 (6)
Co1—Cl2	2.2600 (6)	Co1—Cl4	2.2762 (6)

Cl1—Co1—Cl2	112.61 (3)	Cl2—Co1—Cl3	106.68 (3)
Cl1—Co1—Cl3	111.87 (3)	Cl2—Co1—Cl4	109.22 (3)
Cl1—Co1—Cl4	111.34 (3)	Cl3—Co1—Cl4	104.72 (2)

Table 2
Selected geometric parameters (Å, °) for II

Co1—Br1	2.3939 (7)	Co1—Br3	2.4102 (7)
Co1—Br2	2.3894 (7)	Co1—Br4	2.4110 (7)

Br1—Co1—Br2	112.63 (3)	Br2—Co1—Br3	106.91 (3)
Br1—Co1—Br3	112.09 (3)	Br2—Co1—Br4	110.57 (3)
Br1—Co1—Br4	108.70 (3)	Br3—Co1—Br4	105.72 (3)

Figure 1
Displacement ellipsoid plot at the 50% level of the formula unit in (IPA⁺)₃CoCl₄·Cl (I) with labels for non-H atoms. Minor disorder components are omitted for clarity and H atoms are drawn as circles of arbitrary radii. N—H⋯Cl hydrogen-bonding interactions are drawn as dashed lines.

Figure 2
Displacement ellipsoid plot at the 50% level of the formula unit in (IPA⁺)₃CoBr₄·Br (II) with labels for non-H atoms. Minor disorder components are omitted for clarity and H atoms are drawn as circles of arbitrary radii. N—H⋯Br hydrogen-bonding interactions are drawn as dashed lines.

2.2. (IPA⁺)₂ZnCl₄

The most remarkable feature in this structure is the lack of disorder in the two symmetrically inequivalent IPA⁺ cations. The ZnCl₄²⁻ complex is approximately tetrahedral with Zn—Cl bond lengths ranging from 2.2346 (10)–2.2960 (8) Å [average = 2.27 (2) Å] and Cl—Zn—Cl angles ranging from 103.25 (4)–116.47 (4)° [average = 109 (5)°] with deviations from the ideal tetrahedral values likely arising from hydrogen bonding interactions with the organic cations. Table 3 presents selected geometric parameters and Fig. 3 presents a displacement ellipsoid plot with labels for non-H atoms of the formula unit.

Table 3
Selected geometric parameters (Å, °) for III

Zn1—Cl1	2.2960 (8)	Zn1—Cl3	2.2828 (10)
Zn1—Cl2	2.2681 (9)	Zn1—Cl4	2.2347 (10)

Cl1—Zn1—Cl2	110.35 (4)	Cl2—Zn1—Cl3	101.57 (4)
Cl1—Zn1—Cl3	103.26 (4)	Cl2—Zn1—Cl4	116.46 (4)
Cl1—Zn1—Cl4	109.44 (4)	Cl3—Zn1—Cl4	114.81 (5)

Figure 3
Displacement ellipsoid plot at the 50% level of the formula unit in (IPA⁺)₂ZnCl₄ (III) with labels for non-H atoms. H atoms are drawn as circles of arbitrary radii. N—H⋯Cl hydrogen-bonding interactions are drawn as dashed lines.

2.3. (IPA⁺)ZnCl₃

The structure consists of chains of corner-sharing ZnCl₄ tetrahedra separated by IPA⁺ ions. (ZnCl₃⁻)_n chains propagate parallel to a with neighboring Zn²⁺ centers and bridging Cl⁻ ligands staggered about the a-glide plane. Weak electrostatic attraction between a bridging Cl atom and the next nearest neighboring Zn²⁺ center [Zn1⋯Cl3ⁱⁱ = 4.1620 (7) Å; symmetry code: (ii) x − $[{1\over 2}]$ , y, −z + $[{1\over 2}]$ ] causes compression of the chain along the central axis to produce an interior Cl—Zn—Cl angle less than 109.5°. Lateral repulsion between neighboring Zn²⁺ centers [Zn1⋯Zn1ⁱ = 3.8557 (5) Å; symmetry code: (i) x + $[{1\over 2}]$ , y, −z + $[{1\over 2}]$ ) causes bulging of the chain and produces a bridging Zn—Cl—Zn angle larger than 109.5°. Bridging Zn—Cl bond lengths average 2.328 (14) Å, and are ∼0.1 Å longer than the average terminal Zn—Cl bond length [2.22 (2) Å]. The terminal Zn1—Cl1 bond is almost parallel (or antiparallel) to b. Table 4 presents selected geometric parameters while Fig. 4 presents a displacement ellipsoid plot of the organic cation and a section of the inorganic chain with labels for symmetry unique non-H atoms.

Table 4
Selected geometric parameters (Å, °) for IV

Zn1—Cl1	2.2394 (7)	Zn1—Cl3	2.3182 (7)
Zn1—Cl2	2.2089 (7)	Zn1—Cl3ⁱ	2.3387 (7)

Cl1—Zn1—Cl2	113.89 (3)	Cl3—Zn1—Cl3ⁱ	102.19 (2)
Cl1—Zn1—Cl3	106.89 (3)	Zn1—Cl3—Zn1ⁱⁱ	111.78 (3)
Cl1—Zn1—Cl3ⁱ	109.47 (3)	N1—C12—C11	108.6 (3)
Cl2—Zn1—Cl3	116.80 (3)	N1—C12—C13	110.2 (3)
Cl2—Zn1—Cl3ⁱ	106.83 (3)	C11—C12—C13	114.0 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Figure 4
Displacement ellipsoid plot at the 50% level for the IPA⁺ cation and a section of the inorganic chain in (IPA⁺)ZnCl₃ (IV) with labels for symmetry unique non-H atoms. H atoms are drawn as circles of arbitrary radii. N—H⋯Cl hydrogen-bonding interactions are drawn as dashed lines.

2.4. Isopropylammonium and trimethylammonium cation geometry

A study of bond lengths and angles for both IPA⁺ and TMA⁺ cations in the CSD (Macrae et al., 2020 ) was conducted with results summarized in the top section of Table 5. As pyramidal molecular cations, both IPA⁺ and TMA⁺ are susceptible to twofold ‘umbrella' inversion disorder. A cursory examination of disordered TMA⁺ cations indicates that twofold rotational disorder of the methyl groups about the N—H bond is another significant source of disorder not found with IPA⁺. Both cations show similar fractions of disordered structures (41/129 hits for IPA⁺, 96/318 hits for TMA⁺). The study was conducted for all structures, and for only non-disordered structures. Values for both groups were the same with minor improvements in variance about mean values for the non-disordered structures. For both cations, mean C—N bond lengths are smaller than the mean C—C length in IPA⁺, while the C—C—C angle in IPA⁺ shows the largest deviation from the ideal tetrahedral. Histograms of these geometric parameters have been placed in the supporting information.

Table 5
Database and calculated bond lengths (Å) and angles (°) for IPA⁺ and TMA⁺ cations

		C—C	C—N	C—C—C/C—N—C	C—C—N
IPA⁺
	Mean (CSD)	1.50 (5)	1.49 (5)	114 (6)	110 (5)
	Calculated (in vacuo)	1.522	1.548	114.8	108.2
	Calculated (dielectric)	1.523	1.518	114.0	108.6

TMA⁺
	Mean (CSD)		1.48 (5)	111 (5)
	Calculated (in vacuo)		1.506	111.9
	Calculated (dielectric)		1.498	111.7

For the group of structures here, bond lengths and angles of the IPA⁺ cation correlate well with mean values for IPA⁺ obtained from the CSD. C—N bonds range from 1.477 (6)–1.502 (5) Å with a mean of 1.492 (8) Å. C—C bonds range from 1.443 (7)–1.527 (4) Å with a mean value of 1.502 (9) Å. The large C—C—C angle in IPA⁺ is well represented in these structures with a range of 110.8–114.9° and a mean value of 113.1 (13)°. C—C—N angles range from 106.6 (8)–113.2 (5)° with a mean value at the tetrahedral ideal of 109.5 (14)°. (Minor components of disorder were not included in these ranges or mean values.)

DFT optimizations [B3LYP, 6311+G(d,p); GAMESS (Schmidt et al., 1993 )] of IPA⁺ and TMA⁺ cations in vacuo and in uniform dielectric (ɛ= 78.4) were performed with optimized geometric parameters presented in the lower section of Table 5. Calculated C—C and C—N bond lengths are slightly longer than experimental mean values, but could be accounted for by apparent bond-length foreshortening due to thermal motion in the database values. Calculated angles correlate well with database values, most notably in the large C—C—C angle for the IPA⁺ cation. A glaring exception is the C—N length in IPA⁺, which is ∼0.03 Å longer than the C—C distance in vacuo. However, this distance reduces substantially in dielectric where it is slightly less than the C—C distance. MOL files from the optimizations have been placed in the supporting information.

3. Supramolecular features

3.1. (IPA⁺)₃CoX₄·X

IPA⁺ cation #2 forms hydrogen bonds to two neighboring complexes and to two isolated halide ions that groups pairs of complexes and isolated halide ions into clusters about an inversion center. The cluster axis, as defined by the intracluster Co⋯Co vector, is highly canted relative to each of the unit cell axes forming angles of 43.83(<1)° with respect to a, 58.74(<1)° with respect to b, and 63.81(<1)° with respect to c for I [44.14(<1)°, 58.51(<1)°, and 64.49(<1)°, respectively, for II]. The clusters stack along a with each stack surrounded by six neighboring stacks. The other two IPA⁺ cations use one or two protons to form hydrogen-bonding contacts with halides in a given cluster while the remaining protons form contacts with clusters in neighboring stacks. In this way, the stacks are woven together with an extensive hydrogen-bonding network. Of note are methine C—H⋯X contacts from cations #1 and #3 (major component only) in the range 2.81–3.06 Å (and with C—H⋯X angles > 140°) to bound halide ions. These are significantly shorter and more direct than those found for compound III, where all contacts are greater than 3.16 Å with C—H⋯X angles < 115°. The weak C—H hydrogen-bonding interactions in I and II thus might be responsible for templating a different structure. Fig. 5 presents a plot of the cluster of hydrogen-bonded pairs in II, Fig. 6 presents a unit-cell packing diagram with organic cations absent for I and Fig. 7 presents a unit-cell packing diagram with the organic cations present that depicts the hydrogen-bonding network in II. Tables 6 and 7 present selected hydrogen-bonding parameters for I and II, respectively.

Table 6
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.89	2.43	3.321 (2)	178
N1—H1B⋯Cl3ⁱ	0.89	2.47	3.322 (2)	160
N1—H1C⋯Cl5ⁱ	0.89	2.51	3.400 (2)	173
N2—H2A⋯Cl2	0.89	2.58	3.274 (2)	136
N2—H2A⋯Cl4	0.89	2.83	3.537 (2)	137
N2—H2B⋯Cl3ⁱⁱ	0.89	2.46	3.339 (2)	169
N2—H2C⋯Cl5	0.89	2.44	3.282 (2)	157
N3—H3A⋯Cl5	0.89	2.35	3.236 (3)	173
N3—H3B⋯Cl5ⁱⁱⁱ	0.89	2.31	3.197 (3)	173
N3—H3C⋯Cl4^iv	0.89	2.75	3.374 (3)	128
C12—H12⋯Cl4^v	0.98	2.81	3.676 (2)	148
C32—H32⋯Cl2	0.98	2.88	3.732 (4)	146
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Table 7
Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Br3ⁱ	0.89	2.64	3.504 (4)	163
N1—H1B⋯Br5	0.89	2.72	3.611 (4)	175
N1—H1C⋯Br1ⁱⁱ	0.89	2.66	3.542 (4)	171
N2—H2B⋯Br3	0.89	2.65	3.499 (4)	160
N2—H2A⋯Br2ⁱ	0.89	2.70	3.445 (4)	143
N2—H2A⋯Br4ⁱ	0.89	2.99	3.607 (4)	128
N2—H2C⋯Br5	0.89	2.60	3.412 (4)	152
N3—H3A⋯Br5ⁱⁱⁱ	0.89	2.51	3.380 (4)	165
N3—H3B⋯Br5	0.89	2.49	3.368 (4)	170
N3—H3C⋯Br4ⁱⁱⁱ	0.89	3.01	3.538 (4)	119
C12—H12⋯Br4	0.98	2.85	3.751 (6)	154
C32—H32⋯Br2ⁱ	0.98	3.06	3.880 (5)	142
Symmetry codes: (i) ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 5
Plot of the hydrogen bonded cluster in (IPA⁺)₃CoBr₄·Br consisting of a pair of CoBr₄²⁻ complexes and a pair of uncoordinated Br⁻ ions. Atoms are drawn as circles of arbitrary radii, hydrogen bonds are drawn as dashed lines, and minor disorder components are omitted for clarity.

Figure 6
Packing diagram showing the clusters in (IPA⁺)₃CoCl₄·Cl stacked along a. The b axis is vertical and the c axis horizontal. Atoms are drawn as circles of arbitrary radii and organic cations are omitted for clarity.

Figure 7
Packing diagram for (IPA⁺)₃CoBr₄·Br in a similar orientation as in Fig. 6

but including the organic cations to depict the extensive hydrogen-bonding network. Atoms are drawn as circles of arbitrary radii. H atoms bound to C and minor disorder components are omitted for clarity. Hydrogen bonds are drawn as dashed lines.

3.2. (IPA⁺)₂ZnCl₄

The structure contains double layers of ZnCl₄²⁻ tetrahedra parallel to [010]. Metal complexes in a given layer are related to one another by translations along a or c. Complexes in the companion layer are offset with the two layers related by inversion. The ammonium headgroups of the IPA⁺ cations are deeply embedded within the double layer, and form multiple hydrogen bonds to chloride ligands in both layers to tie the complexes together. The methine C—H bond is approximately parallel to the layer with the methyl groups directed outward to abut the methyl groups projecting from the neighboring double layer. Symmetry-unique IPA⁺ cations are found on both sides of the double layer, but with their ammonium head groups tilted in different directions. Fig. 8 presents a unit-cell packing diagram while Table 8 presents selected hydrogen-bonding parameters.

Table 8
Hydrogen-bond geometry (Å, °) for III

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1	0.91 (6)	2.74 (6)	3.471 (4)	139 (4)
N1—H1A⋯Cl3	0.91 (6)	2.81 (6)	3.493 (4)	133 (4)
N1—H1B⋯Cl3ⁱ	0.79 (6)	2.51 (6)	3.287 (4)	166 (5)
N1—H1C⋯Cl1ⁱⁱ	0.88 (6)	2.46 (6)	3.321 (4)	167 (5)
N2—H2A⋯Cl1ⁱⁱⁱ	1.00 (6)	2.68 (6)	3.400 (4)	129 (4)
N2—H2A⋯Cl2^iv	1.00 (6)	2.53 (6)	3.346 (3)	139 (5)
N2—H2B⋯Cl2^v	0.95 (5)	2.33 (5)	3.265 (4)	169 (4)
N2—H2C⋯Cl4	0.87 (5)	2.43 (5)	3.297 (4)	169 (4)
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Figure 8
Packing diagram for (IPA⁺)₂ZnCl₄ viewed down a with the b axis horizontal and the c axis vertical. Atoms are drawn as circles of arbitrary radii, H atoms bound to C are omitted for clarity, and hydrogen bonds are drawn as dashed lines.

3.3. (IPA⁺)ZnCl₃

All protons of the ammonium headgroup are involved in hydrogen bonding to terminal chloride ligands. Two protons form hydrogen bonds (one strong and one weak) to terminal ligands (Cl1) attached to next nearest neighbor Zn²⁺ centers (on the same side of the glide plane) while the third forms the shortest hydrogen bond to a terminal ligand (Cl2) on a neighboring chain. This links chains with the same direction for their Zn1—Cl1 bonds into slabs in the ab plane. The slabs are stacked along c with neighboring slabs related by inversion symmetry to reverse the direction of the Zn1—Cl1 bond. The isopropyl groups project away from the slab to abut isopropyl groups from a neighboring slab. Of note is a direct methine C—H⋯Cl2 interaction < 3.0 Å in length. Fig. 9 presents a unit-cell packing diagram while Table 9 presents selected hydrogen-bonding parameters.

Table 9
Hydrogen-bond geometry (Å, °) for IV

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2ⁱⁱⁱ	0.84 (5)	2.47 (5)	3.292 (3)	165 (4)
N1—H1B⋯Cl1	0.88 (6)	2.81 (5)	3.317 (3)	118 (4)
N1—H1B⋯Cl1ⁱⁱ	0.88 (6)	2.74 (5)	3.356 (3)	128 (4)
N1—H1C⋯Cl1ⁱ	0.86 (5)	2.67 (5)	3.427 (3)	148 (4)
C12—H12⋯Cl2ⁱ	0.98	2.94	3.922 (4)	179
Symmetry codes: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 9
Packing diagram for (IPA⁺)ZnCl₃ viewed along a with the b axis vertical and the c axis horizontal. Atoms are drawn as circles of arbitrary radii and hydrogen bonds are drawn as dashed lines.

4. Database survey

4.1. Isopropylammonium halidometallates

The only structure containing isolated tetrahalidometallate complexes reported in the Cambridge Structural Database is the classic thermochromic compound (IPA⁺)₂CuCl₄ (vide supra). (IPA⁺)₂SbBr₅ has been reported as occurring with an isolated five-coordinate metal complex (QQQGOS), although without 3D coordinates (Jha & Rizvi, 1974 ). Crystallographic information on several other salts of IPA⁺ with isolated metal complexes have been reported. The most pertinent is the mixed valence compound (IPA⁺)₈(SbCl₆)⁻(SbCl₆)³⁻·4Cl⁻ with isolated chloride ions (IPASBC; Birke et al., 1976 ). (IPA⁺)₂ReCl₆ is known (JASHAM; Bettinelli et al., 1989 ) with reports of Pt and Sn analogs (QQQGBP and QQQGBS, respectively; Bhalla & Cross, 1974 – 3D coordinates not reported). The Re salt exhibits a layered arrangement of metal complexes sandwiched by bilayers of IPA⁺ cations.

(IPA⁺)₃SnI₅, -PbBr₅, and -PbI₅ are stoichiometrically identical to the title cobalt compounds, but these structures consist of zigzag chains of corner-sharing octahedra that result from dimensional breakdown of the 2D layered perovskite network [JANSEZ (Stoumpos et al., 2017 ), ROLWUO (Ru et al., 2023 ), and TOSSEC (Hartono et al., 2019 )]. (IPA⁺)₃Sn₂I₇ consists of a double-layered perovskite structure with one IPA⁺ cation located in the perovskite cavity and three different phases observed (JAMWIG, JAMWIG01, JAMWIG02; Stoumpos et al., 2017). The bulky IPA⁺ cation in the perovskite cavity renders this compound metastable. The mixed organic cation salts (IPA⁺)₂(Tz⁺)_n–1Pb_nBr_3n+1 (Tz = 1,2,4-triazolium) provide a range of perovskite structure types (Li et al., 2022 ) with a single layered perovskite structure for n = 1 (FIPDUH), and two- and three-layer perovskites with the planar Tz cation occupying the perovskite cavity (FINVAD and FINVEH, respectively). A subsequent study of FIPDUH (He et al., 2024 ) reveals that the ambient temperature phase in polar monoclinic Cc (FIPDUH01) transforms at 340.5 K to a phase found in centrosymmetric orthorhombic Pbca (FIPDUH02). In turn, this phase transforms at 370.5 K to a phase found in orthorhombic Cmca (FIPDUH03).

(IPA⁺)CuCl₃ (Roberts et al., 1981 ) is a thermochromic compound in which the low-temperature phase (brown) consists of stacks of Cu₂Cl₆²⁻ quasi-planar complexes (IPAMCU01). This transforms to a high-temperature phase (orange) consisting of chains of face-sharing CuCl₆ octahedra separated by disordered IPA⁺ cations (IPAMCU). The bromide analog (IPBRCU; Bloomquist & Willett, 1981 ) is isomorphous. (IPA⁺)₄Cd₃Cl₁₀ belongs to the Cs₄Mg₃F₁₀ family of layered structures consisting of trinuclear sections of face-sharing CdCl₆ octahedra linked together in a zigzag 2D network (Gagor et al., 2011 ). Here three different phases are observed with varying degrees of disorder of the IPA⁺ cation (IPEMAS, IPEMAS01, and IPEMAS02). Parallel linear chains of face-sharing CdBr₆ octahedra are found for (IPA⁺)CdBr₃ (WIZSON; Ishihara et al., 1999 ) and -PbI₃ (Fedoruk-Piskorska et al., 2024 ) in a hexagonal perovskite arrangement, and likewise for (IPA⁺)GeI₃ (YUJYUZ; Stoumpos et al., 2015 ), albeit with half the chains perpendicular to the other half. The PbI₃ salt transforms from polar monoclinic P2₁ (COYBOL) to centrosymmetric orthorhombic Cmcm (COYBOL01) above 284.1 K.

4.2. A₃(MX′₄)X′ and B(MX′₄)X′

A search of the Cambridge Structural Database yields 24 distinct compounds (from 35 hits) that fit the A₃(MX′₄)X′ stoichiometry (where A = monopositive organic cation, M = any metal, and X′ = halogen). Six are found with M = Co and one found for M = Zn. M = Mn is most numerous with nine compounds, M = Cu next with five, and one each for M = Ni, Pd, Hg. For M = Pd, the organic cation is the isomeric TMA⁺ ion with square-planar PdCl₄²⁻ (BIJNIR; Zveguintzoff et al., 1981 ). The lone reported M = Zn compound is with tert-butylammonium (WAZXEA; Ishida & Kashino, 1993 ). More numerous are B(MX′₄)X′ compounds in which B is a tripositive cation: 52 compounds from 54 hits. Compounds in which M = Zn account for 21 of these and greatly outnumber the seven compounds with M = Co. Based on reported structures to date, it appears that Co²⁺ has the greater propensity to form a tetrahedral complex with an uncoordinated halide if the cation is monopositive, whereas Zn²⁺ has the greater propensity with tripositive cations, which may account for the difference in structures here.

4.3. A₂CoCl₄ versus A₂ZnCl₄

The tetrahedral CoCl₄²⁻ and ZnCl₄²⁻ complexes are well known: a simple search in the Cambridge Structural Database yields 623 hits for CoCl₄ and 1141 hits for ZnCl₄ complexes. There are 54 instances in which both Co and Zn form an A₂MCl₄ compound with the same monopositive organic cation – including one instance of a mixed-metal structure (BICDOK; Behrens et al., 2022 ). The vast majority of Co/Zn pairs are isostructural, at least for one solid phase, with only three examples of completely dissimilar structures. This is not unexpected since the two metal ions have very similar radii [58 pm for Co²⁺ and 60 pm for Zn²⁺, Shannon effective ionic radii for tetrahedral coordination (Shannon, 1976 )]. For example, in the (1,3,4-trimethylpyridinium)₂MCl₄ series (Bond, 2009 , 2019 ) those compounds with smaller ionic radii metal ions [M = Co (COQZAM), Ni (LOHPIK), Cu (QUBHIF), Zn (COMGAP)] are isostructural (orthorhombic Fdd2) with a crossover to monoclinic C2/c structures for larger radii metal ions [M = Mn (YOKNIY), Cd (LOGRIL)]. In particular, molecular volumes for the Co and Zn members of this series agree within 0.07%. Of special note is the recently reported (2-chloro-N,N-dimethylethanaminium)₂ (Co or Zn)Cl₄ system (VOTDUH or VOTFAP, respectively; McGinness et al., 2024 ) in which the two structures are almost identical, right down to the level of disorder of the organic cation. A table containing A₂CoCl₄ and A₂ZnCl₄ compounds with common A cations is included in the supporting information.

4.4. AMX₃ structures containing chains of corner-sharing tetrahedra

Five AZnCl₃ compounds with chains of corner-sharing tetrahedra are reported in the Cambridge Structural Database among eight hits, almost all of recent origin. The earliest report is for (tetramethylammonium)ZnCl₃ (OGEYOP; Choi et al., 2009 ). The remaining compounds are found with halogeno-substituted tetramethylammonium cations (WUKROM, WUKRUS, WUKSAZ, WUKSED; Chen et al., 2020 ). In all cases these compounds are found in polar orthorhombic space groups, in contrast to the primary ammonium salt presented here. The chains in these compounds have a staggered arrangement similar to that in (IPA⁺)ZnCl₃, although without formal glide-plane symmetry. In this case, however, bridging ligands are arranged in a line parallel to the chain axis while the terminal Zn—Cl bonds (comparable to Zn1—Cl1 in this structure) are twisted inward. These terminal ligands now make the long contact to the Zn²⁺ centers with distances ∼0.15 Å less than the contact distance with the bridging ligand in the IPA⁺ salt [distances range from 3.973–4.059 Å with an average of 4.03 (3) Å]. The shorter contact distance also reduces the Zn⋯Zn distance to an average of 3.758 (14) Å (range: 3.738–3.778 Å), bridging Zn—Cl—Zn angles less than 109.5°, and more acute interior Cl—Zn—Cl angles. This reduction in angle brings the metal centers closer to the chain axis, which results in a lengthening of the chain to give an average chain repeat distance of 7.20 (3) Å compared to 6.3131 (3) Å in the IPA⁺ salt.

Similar chains with terminal ligands twisted inward are found for twelve AMX₃ systems, six of which are tetramethylammonium salts of mercury(II) halides: -HgCl₃ [BOPXIN(01, 02, 04); Rao & Rajaram, 1982 ; Sikirica et al., 1982 ; Lambarki et al., 2018 ], -HgBr₃ [TMAHGB(01); White, 1963 ; Sikirica et al., 1982], -HgI₃ (TMAIHG11; Sharutin et al., 2011 ), and mixed halide systems -HgCl_0.63Br_2.37, -HgBrI₂, HgCl_0.45I_2.55 (OSOFAG, BORYIC04, TMAIHG12 respectively; Yang et al., 2021 ). However, in these cases the long M⋯X contact to a neighboring terminal halide has become short enough to be considered a semi-coordinate bond with the structure perhaps better described as chains of asymmetrically bibridged trigonal bipyramids. Triiodocadmate(II) compounds are known with pyrrolidinium [IVIGUS(01); Rok et al., 2021 ], ethyltrimethylammonium, and TMA⁺ (KELNAS and KELNEW, respectively; Sharutin et al., 2012 ). In (pyrrolidinium)CdI₃, half the chains are perpendicular to the other half. All of these systems crystallize in polar space groups, while the remaining three chain structures are found in centrosymmetric monoclinic P2₁/c: (trimethylsulfonium)CdI₃ [NUDZAN(01); Svensson et al., 1998 ], (trimethylammonium)HgI₃ (PIJRAB; Geselle et al., 1993 ), and (4′,5′-bis(methylsulfanyl)- 4,5-(ethylenedithio)tetrathiafulvalene) HgI₃ (QOLGUU; Yang et al., 2009 ). The chains in both PIJRAB and QOLGUU contain substantially asymmetric monobridging.

(Chloro-(1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane)HgCl₃ (LUHDID; Kang et al., 2012 ) contains chains with parallel terminal Hg—Cl bonds, as in (IPA⁺)ZnCl₃, except the bridging ligands are not staggered. In (methylammonium)HgI₃ (DEBMEC; Korfer et al., 1985 ), chains arrange terminal M—Cl bonds so they are splayed uniformly about the chain axis. Spiral chains are found in (dimethylammonium)HgBr₃ (QACFIJ; Terao et al., 1998 ) and in (methylammonium)HgCl₃ (QQQBVJ21; Salah et al., 1982 ) and -HgClBr₂ (SOPDOQ; Hassen et al., 1997 ).

5. Synthesis and crystallization

1.3 mL of neat isopropylamine (d = 0.69 g mL⁻¹, 15 mmol) were neutralized by slow, dropwise addition of concentrated HCl until the solution tested acidic with litmus paper. Distilled water was added to give a total volume of 70 mL. 40 mL, 20 mL and 10 mL of this solution were placed in different beakers with addition of distilled water, as needed, to give a total volume of 40 mL of solution in each. 1.0 g of CoCl₂·6H₂O (4.2 mmol) were added to each beaker with stirring until completely dissolved to give approximately 2:1, 1:1, and 1:2 stoichiometries, respectively, of organic cation: CoCl₂. 40 mL of concentrated hydrochloric acid were then added to each beaker and crystals then grown by slow evaporation. The resulting solid mass was gently pressed between tissues to wick away mother liquor, then stored in a screw cap vial. The same procedure was used in crystallizations with CoBr₂·6H₂O and ZnCl₂·H₂O except that 1.0 mL and 2.0 mL, respectively, of neat isopropylamine were used.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 10.

Table 10
Experimental details

	I	II	III	IV
Crystal data
Chemical formula	(C₃H₁₀N)₃[CoCl₄]Cl	(C₃H₁₀N)₃[CoBr₄]Br	(C₃H₁₀N)₂[ZnCl₄]	(C₃H₁₀N)[ZnCl₃]
M_r	416.54	638.84	327.41	231.84
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Monoclinic, P2₁/n	Orthorhombic, Pbca
Temperature (K)	295	295	295	295
a, b, c (Å)	12.2051 (5), 9.5464 (4), 17.4681 (6)	12.7504 (5), 9.7339 (4), 17.8111 (7)	7.3076 (3), 20.4386 (8), 10.2616 (4)	6.3131 (3), 12.9582 (6), 21.8277 (10)
α, β, γ (°)	90, 91.360 (1), 90	90, 92.355 (2), 90	90, 107.827 (1), 90	90, 90, 90
V (Å³)	2034.72 (14)	2208.69 (15)	1459.05 (10)	1785.65 (14)
Z	4	4	4	8
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	1.49	9.81	2.38	3.56
Crystal size (mm)	0.44 × 0.31 × 0.21	0.35 × 0.30 × 0.17	0.40 × 0.31 × 0.29	0.47 × 0.22 × 0.19

Data collection
Diffractometer	Bruker D8 Quest Eco	Bruker D8 Quest Eco	Bruker D8 Quest Eco	Bruker D8 Quest Eco
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	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	0.746, 0.886	0.528, 0.746	0.639, 0.746	0.444, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	115887, 4663, 3721	88263, 5070, 3130	69211, 4105, 3568	137051, 3096, 2642
R_int	0.052	0.097	0.075	0.041
(sin θ/λ)_max (Å⁻¹)	0.650	0.650	0.696	0.746

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.076, 1.06	0.037, 0.065, 1.01	0.050, 0.105, 1.24	0.036, 0.076, 1.26
No. of reflections	4663	5070	4105	3096
No. of parameters	185	179	146	88
No. of restraints	6	3	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	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)	0.51, −0.42	0.56, −0.50	0.64, −0.50	0.58, −0.74
Computer programs: APEX3 v2017.3-0 (Bruker, 2017 ), SAINT v8.38A (Bruker, 2017), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows 2020.1 (Farrugia, 2012 ), ORTEPIII (Burnett & Johnson, 1996 ), publCIF (Westrip, 2010 ) and PARST (Nardelli, 1995 ), publCIF (Westrip, 2010).

6.1. (IPA⁺)₃CoX₄·X

Non-H atoms were identified in the initial structure solution, except those of minor disorder components. Anisotropic refinement of all atoms yielded anomalously large displacement ellipsoids for some C and N atoms with suggestions by the SHELX software to split these into disordered pairs. In addition, difference map peaks were found close to methine C atoms indicating ‘umbrella' inversion disorder. A twofold disordered model for these organic cations was pursued with each pair refined constrained so that the sum of their site occupation factors equal 1.0. H atoms were constrained to an idealized geometry and refined in a riding model with displacement parameters equal to 1.5×U_iso of the parent atom.

6.2. (IPA⁺)₂ZnCl₄ and (IPA⁺)ZnCl₃

All non-H atoms were identified from the initial structure solution and were subjected to anisotropic refinement. H atoms were visible in subsequent electron-density difference maps and were refined to reasonable geometries and displacement parameters for those bound to N. Those bound to C were constrained to an idealized geometry and refined in a riding model with displacement parameters fixed at 1.5×U_iso of the parent C-atom.

Supporting information

CCDC references: 2471094; 2471093; 2471092; 2471091

Crystal structure: contains datablocks global, I, II, III, IV. DOI: https://doi.org/10.1107/S2056989025006103/nu2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025006103/nu2010Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989025006103/nu2010IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989025006103/nu2010IIIsup4.hkl

Structure factors: contains datablock IV. DOI: https://doi.org/10.1107/S2056989025006103/nu2010IVsup5.hkl

Histograms of geometric parameters for IPA+ and TMA+ cations obtained from the Cambridge Structural Database. DOI: https://doi.org/10.1107/S2056989025006103/nu2010sup6.docx

Table of A2CoCl4 and A2ZnCl4 compounds which share a common A cation. DOI: https://doi.org/10.1107/S2056989025006103/nu2010sup7.docx

MOL file for optimized geometry of the IPA+ cation in vacuo. DOI: https://doi.org/10.1107/S2056989025006103/nu2010sup8.mol

MOL file for optimized geometry of the IPA+ cation in uniform dielectric. DOI: https://doi.org/10.1107/S2056989025006103/nu2010sup9.mol

MOL file for optimized geometry of the TMA+ cation in vacuo. DOI: https://doi.org/10.1107/S2056989025006103/nu2010sup10.mol

MOL file for optimized geometry of TMA+ cation in uniform dielectric. DOI: https://doi.org/10.1107/S2056989025006103/nu2010sup11.mol

checkCIF report

Computing details top

Tris(isopropylammonium) tetrachloridocobaltate(II) chloride (I) top

Crystal data top

(C₃H₁₀N)₃[CoCl₄]Cl	F(000) = 868
M_r = 416.54	D_x = 1.36 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9894 reflections
a = 12.2051 (5) Å	θ = 5.4–56.2°
b = 9.5464 (4) Å	µ = 1.49 mm⁻¹
c = 17.4681 (6) Å	T = 295 K
β = 91.360 (1)°	Irregular, blue
V = 2034.72 (14) Å³	0.44 × 0.31 × 0.21 mm
Z = 4

Data collection top

Bruker D8 Quest Eco diffractometer	3721 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.052
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.5°, θ_min = 3.3°
T_min = 0.746, T_max = 0.886	h = −15→15
115887 measured reflections	k = −12→12
4663 independent reflections	l = −22→22

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.028P)² + 1.2921P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.076	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.51 e Å⁻³
4663 reflections	Δρ_min = −0.42 e Å⁻³
185 parameters	Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.0154 (6)
Primary atom site location: dual

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. DFIX restraints were applied to C-C and C-N bonds of minor disorder components in order to yield more chemically reasonable geometries. Four low angle reflections with Fc >> Fo were presumed to have been blocked by the beam catcher and were omitted from the refinement. APEX3 software suggested data collection to θmax = 31.66° however data analysis showed that <I/σ(I)> is less than 1.35 beyond θ = 27.5°. Thus data with θ > 27.5° were omitted from the final refinement.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.69716 (2)	0.32140 (3)	0.58630 (2)	0.03708 (10)
Cl1	0.84051 (6)	0.17232 (7)	0.59286 (4)	0.0676 (2)
Cl2	0.57605 (5)	0.28442 (8)	0.68007 (3)	0.05848 (17)
Cl3	0.75183 (5)	0.54935 (6)	0.59658 (3)	0.05078 (15)
Cl4	0.60820 (5)	0.30846 (7)	0.47051 (3)	0.05420 (16)
Cl5	0.31607 (5)	0.51916 (6)	0.72833 (3)	0.04879 (15)
N1	0.92624 (18)	0.1541 (2)	0.77442 (12)	0.0576 (5)
H1A	0.901612	0.157398	0.726083	0.086*
H1B	0.879586	0.105505	0.802408	0.086*
H1C	0.991633	0.112882	0.776326	0.086*
C11	1.0230 (3)	0.3748 (4)	0.7629 (3)	0.0976 (12)
H11A	1.004113	0.376131	0.709216	0.146*
H11B	1.091876	0.327744	0.770645	0.146*
H11C	1.028876	0.469192	0.781518	0.146*
C12	0.9361 (2)	0.2992 (3)	0.80528 (14)	0.0527 (6)
H12	0.958964	0.293460	0.859340	0.063*
C13	0.8279 (2)	0.3728 (3)	0.80011 (17)	0.0647 (7)
H13A	0.833880	0.462314	0.824890	0.097*
H13B	0.773476	0.317389	0.824861	0.097*
H13C	0.806975	0.385861	0.747273	0.097*
N2	0.36072 (16)	0.34578 (19)	0.56983 (12)	0.0487 (5)	0.847 (9)
H2A	0.433393	0.338721	0.573053	0.073*	0.847 (9)
H2B	0.340552	0.372232	0.522713	0.073*	0.847 (9)
H2C	0.338146	0.409058	0.603386	0.073*	0.847 (9)
C21	0.1882 (2)	0.2206 (4)	0.5815 (2)	0.0825 (10)	0.847 (9)
H21A	0.154769	0.132088	0.592536	0.124*	0.847 (9)
H21B	0.164498	0.289329	0.617668	0.124*	0.847 (9)
H21C	0.167094	0.249606	0.530650	0.124*	0.847 (9)
C22	0.3102 (2)	0.2063 (3)	0.5873 (2)	0.0493 (9)	0.847 (9)
H22	0.332145	0.176822	0.639137	0.059*	0.847 (9)
C23	0.3527 (5)	0.1028 (4)	0.5296 (4)	0.0962 (19)	0.847 (9)
H23A	0.431045	0.096386	0.534981	0.144*	0.847 (9)
H23B	0.320868	0.012464	0.538435	0.144*	0.847 (9)
H23C	0.333327	0.133799	0.478798	0.144*	0.847 (9)
N2A	0.36072 (16)	0.34578 (19)	0.56983 (12)	0.0487 (5)	0.153 (9)
H2D	0.319705	0.417888	0.554243	0.073*	0.153 (9)
H2E	0.371124	0.350132	0.620374	0.073*	0.153 (9)
H2F	0.425191	0.349063	0.547137	0.073*	0.153 (9)
C21A	0.1882 (2)	0.2206 (4)	0.5815 (2)	0.0825 (10)	0.153 (9)
H21D	0.152645	0.303460	0.562131	0.124*	0.153 (9)
H21E	0.146331	0.139642	0.566456	0.124*	0.153 (9)
H21F	0.193505	0.225238	0.636376	0.124*	0.153 (9)
C22A	0.3032 (8)	0.2103 (12)	0.5490 (12)	0.054 (6)*	0.153 (9)
H22A	0.295325	0.206653	0.493049	0.064*	0.153 (9)
C23A	0.369 (2)	0.086 (2)	0.5741 (16)	0.076 (7)*	0.153 (9)
H23D	0.330711	0.001540	0.560134	0.114*	0.153 (9)
H23E	0.438843	0.087348	0.549676	0.114*	0.153 (9)
H23F	0.380523	0.088501	0.628673	0.114*	0.153 (9)
N3	0.3157 (2)	0.2693 (3)	0.85354 (17)	0.0536 (9)	0.767 (5)
H3A	0.311029	0.341121	0.821145	0.080*	0.767 (5)
H3B	0.276986	0.197557	0.834767	0.080*	0.767 (5)
H3C	0.289183	0.294581	0.898517	0.080*	0.767 (5)
C31	0.4968 (2)	0.3532 (3)	0.89475 (18)	0.0705 (8)	0.767 (5)
H31A	0.572654	0.328655	0.901980	0.106*	0.767 (5)
H31B	0.490421	0.428970	0.858792	0.106*	0.767 (5)
H31C	0.467391	0.381537	0.942811	0.106*	0.767 (5)
C32	0.4333 (2)	0.2265 (3)	0.86397 (19)	0.0436 (8)	0.767 (5)
H32	0.462624	0.197537	0.814707	0.052*	0.767 (5)
C33	0.4364 (2)	0.1053 (3)	0.91902 (17)	0.0643 (7)	0.767 (5)
H33A	0.510851	0.075157	0.927024	0.096*	0.767 (5)
H33B	0.406784	0.133995	0.966964	0.096*	0.767 (5)
H33C	0.393628	0.029341	0.898200	0.096*	0.767 (5)
N3A	0.3791 (7)	0.2390 (9)	0.8083 (4)	0.046 (2)*	0.233 (5)
H3D	0.323163	0.180367	0.800785	0.069*	0.233 (5)
H3E	0.361927	0.322420	0.788680	0.069*	0.233 (5)
H3F	0.437994	0.205562	0.785396	0.069*	0.233 (5)
C31A	0.4968 (2)	0.3532 (3)	0.89475 (18)	0.0705 (8)	0.233 (5)
H31D	0.518483	0.369427	0.947191	0.106*	0.233 (5)
H31E	0.557297	0.314157	0.867793	0.106*	0.233 (5)
H31F	0.475247	0.440206	0.871335	0.106*	0.233 (5)
C32A	0.4027 (7)	0.2533 (8)	0.8915 (5)	0.040 (3)*	0.233 (5)
H32A	0.339421	0.289118	0.918912	0.049*	0.233 (5)
C33A	0.4364 (2)	0.1053 (3)	0.91902 (17)	0.0643 (7)	0.233 (5)
H33D	0.452948	0.107515	0.973013	0.096*	0.233 (5)
H33E	0.377238	0.041121	0.908982	0.096*	0.233 (5)
H33F	0.499980	0.075242	0.892161	0.096*	0.233 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.03859 (16)	0.03711 (16)	0.03567 (16)	0.00483 (12)	0.00363 (11)	0.00090 (11)
Cl1	0.0658 (4)	0.0634 (4)	0.0741 (4)	0.0324 (3)	0.0139 (3)	0.0086 (3)
Cl2	0.0478 (3)	0.0835 (5)	0.0446 (3)	0.0001 (3)	0.0107 (2)	0.0111 (3)
Cl3	0.0607 (3)	0.0403 (3)	0.0513 (3)	−0.0041 (2)	0.0021 (3)	−0.0033 (2)
Cl4	0.0646 (4)	0.0589 (4)	0.0387 (3)	−0.0102 (3)	−0.0067 (2)	−0.0019 (2)
Cl5	0.0511 (3)	0.0439 (3)	0.0512 (3)	0.0040 (2)	−0.0027 (2)	0.0026 (2)
N1	0.0614 (13)	0.0497 (12)	0.0622 (13)	0.0076 (10)	0.0102 (10)	0.0124 (10)
C11	0.071 (2)	0.073 (2)	0.150 (4)	−0.0119 (17)	0.032 (2)	0.012 (2)
C12	0.0533 (13)	0.0557 (15)	0.0490 (13)	0.0024 (11)	−0.0033 (10)	0.0065 (11)
C13	0.0638 (16)	0.0598 (16)	0.0705 (18)	0.0155 (13)	0.0017 (13)	0.0054 (14)
N2	0.0475 (10)	0.0354 (10)	0.0629 (12)	−0.0013 (8)	−0.0048 (9)	0.0005 (9)
C21	0.0636 (18)	0.075 (2)	0.109 (3)	−0.0168 (15)	0.0059 (17)	0.0235 (19)
C22	0.0631 (18)	0.0385 (16)	0.046 (2)	−0.0051 (12)	−0.0032 (13)	0.0077 (12)
C23	0.128 (4)	0.044 (2)	0.118 (4)	−0.014 (2)	0.041 (3)	−0.024 (2)
N2A	0.0475 (10)	0.0354 (10)	0.0629 (12)	−0.0013 (8)	−0.0048 (9)	0.0005 (9)
C21A	0.0636 (18)	0.075 (2)	0.109 (3)	−0.0168 (15)	0.0059 (17)	0.0235 (19)
N3	0.0455 (15)	0.0422 (14)	0.073 (2)	−0.0085 (11)	−0.0055 (13)	0.0159 (13)
C31	0.0641 (16)	0.0670 (18)	0.0797 (19)	−0.0243 (14)	−0.0168 (14)	0.0104 (15)
C32	0.0410 (15)	0.0508 (17)	0.0394 (16)	−0.0032 (13)	0.0091 (13)	0.0010 (13)
C33	0.0663 (16)	0.0546 (15)	0.0717 (18)	0.0039 (13)	−0.0019 (13)	0.0176 (13)
C31A	0.0641 (16)	0.0670 (18)	0.0797 (19)	−0.0243 (14)	−0.0168 (14)	0.0104 (15)
C33A	0.0663 (16)	0.0546 (15)	0.0717 (18)	0.0039 (13)	−0.0019 (13)	0.0176 (13)

Geometric parameters (Å, º) top

Co1—Cl1	2.2561 (6)	C21A—H21E	0.9600
Co1—Cl2	2.2600 (6)	C21A—H21F	0.9600
Co1—Cl3	2.2820 (6)	C22A—C23A	1.496 (10)
Co1—Cl4	2.2762 (6)	C22A—H22A	0.9800
N1—H1A	0.8900	C21A—C22A	1.529 (9)
N1—H1B	0.8900	C23A—H23D	0.9600
N1—H1C	0.8900	C23A—H23E	0.9600
N1—C12	1.490 (3)	C23A—H23F	0.9600
C11—H11A	0.9600	N3—H3A	0.8900
C11—H11B	0.9600	N3—H3B	0.8900
C11—H11C	0.9600	N3—H3C	0.8900
C11—C12	1.494 (4)	N3—C32	1.499 (4)
C12—C13	1.496 (3)	C31—H31A	0.9600
C12—H12	0.9800	C31—H31B	0.9600
C13—H13A	0.9600	C31—H31C	0.9600
C13—H13B	0.9600	C31—C32	1.527 (4)
C13—H13C	0.9600	C32—C33	1.505 (4)
N2—H2A	0.8900	C32—H32	0.9800
N2—H2B	0.8900	C33—H33A	0.9600
N2—H2C	0.8900	C33—H33B	0.9600
N2—C22	1.502 (3)	C33—H33C	0.9600
C21—H21A	0.9600	N3A—H3D	0.8900
C21—H21B	0.9600	N3A—H3E	0.8900
C21—H21C	0.9600	N3A—H3F	0.8900
C21—C22	1.496 (4)	N3A—C32A	1.482 (8)
C22—C23	1.512 (5)	C31A—H31D	0.9600
C22—H22	0.9800	C31A—H31E	0.9600
C23—H23A	0.9600	C31A—H31F	0.9600
C23—H23B	0.9600	C31A—C32A	1.493 (7)
C23—H23C	0.9600	C32A—C33A	1.545 (7)
N2A—H2D	0.8900	C32A—H32A	0.9800
N2A—H2E	0.8900	C33A—H33D	0.9600
N2A—H2F	0.8900	C33A—H33E	0.9600
N2A—C22A	1.512 (9)	C33A—H33F	0.9600
C21A—H21D	0.9600

Cl1—Co1—Cl2	112.61 (3)	H21D—C21A—H21E	109.5
Cl1—Co1—Cl3	111.87 (3)	H21D—C21A—H21F	109.5
Cl1—Co1—Cl4	111.34 (3)	H21E—C21A—H21F	109.5
Cl2—Co1—Cl3	106.68 (3)	C22A—C21A—H21D	109.5
Cl2—Co1—Cl4	109.22 (3)	C22A—C21A—H21E	109.5
Cl3—Co1—Cl4	104.72 (2)	C22A—C21A—H21F	109.5
H1A—N1—H1B	109.5	C21A—C22A—H22A	107.7
C12—N1—H1A	109.5	C23A—C22A—H22A	107.7
H1A—N1—H1C	109.5	C21A—C22A—C23A	115.8 (16)
H1B—N1—H1C	109.5	C22A—C23A—H23D	109.5
C12—N1—H1B	109.5	C22A—C23A—H23E	109.5
C12—N1—H1C	109.5	C22A—C23A—H23F	109.5
N1—C12—C11	108.8 (2)	H23D—C23A—H23E	109.5
N1—C12—C13	110.6 (2)	H23D—C23A—H23F	109.5
N1—C12—H12	108.4	H23E—C23A—H23F	109.5
H11A—C11—H11B	109.5	H3A—N3—H3B	109.5
H11A—C11—H11C	109.5	H3A—N3—H3C	109.5
H11B—C11—H11C	109.5	H3B—N3—H3C	109.5
C12—C11—H11A	109.5	C32—N3—H3A	109.5
C12—C11—H11B	109.5	C32—N3—H3B	109.5
C12—C11—H11C	109.5	C32—N3—H3C	109.5
C11—C12—C13	112.3 (2)	N3—C32—C31	107.7 (3)
C11—C12—H12	108.4	N3—C32—C33	107.3 (2)
C13—C12—H12	108.4	N3—C32—H32	109.8
C12—C13—H13A	109.5	H31A—C31—H31B	109.5
C12—C13—H13B	109.5	H31A—C31—H31C	109.5
C12—C13—H13C	109.5	H31B—C31—H31C	109.5
H13A—C13—H13B	109.5	C32—C31—H31A	109.5
H13A—C13—H13C	109.5	C32—C31—H31B	109.5
H13B—C13—H13C	109.5	C32—C31—H31C	109.5
H2A—N2—H2C	109.5	C31—C32—H32	109.8
H2B—N2—H2C	109.5	C33—C32—H32	109.8
H2A—N2—H2B	109.5	C31—C32—C33	112.3 (3)
C22—N2—H2A	109.5	C32—C33—H33A	109.5
C22—N2—H2B	109.5	C32—C33—H33B	109.5
C22—N2—H2C	109.5	C32—C33—H33C	109.5
N2—C22—C21	108.5 (2)	H33A—C33—H33B	109.5
N2—C22—C23	107.2 (3)	H33A—C33—H33C	109.5
N2—C22—H22	109.7	H33B—C33—H33C	109.5
H21A—C21—H21B	109.5	H3D—N3A—H3E	109.5
H21A—C21—H21C	109.5	H3D—N3A—H3F	109.5
H21B—C21—H21C	109.5	H3E—N3A—H3F	109.5
C22—C21—H21A	109.5	C32A—N3A—H3D	109.5
C22—C21—H21B	109.5	C32A—N3A—H3E	109.5
C22—C21—H21C	109.5	C32A—N3A—H3F	109.5
C21—C22—H22	109.7	N3A—C32A—C31A	103.2 (6)
C23—C22—H22	109.7	N3A—C32A—C33A	105.3 (6)
C21—C22—C23	111.8 (4)	N3A—C32A—H32A	112.0
C22—C23—H23A	109.5	H31D—C31A—H31E	109.5
C22—C23—H23B	109.5	H31D—C31A—H31F	109.5
C22—C23—H23C	109.5	H31E—C31A—H31F	109.5
H23A—C23—H23B	109.5	C32A—C31A—H31D	109.5
H23A—C23—H23C	109.5	C32A—C31A—H31E	109.5
H23B—C23—H23C	109.5	C32A—C31A—H31F	109.5
H2D—N2A—H2E	109.5	C31A—C32A—H32A	112.0
H2D—N2A—H2F	109.5	C33A—C32A—H32A	112.0
H2E—N2A—H2F	109.5	C31A—C32A—C33A	111.9 (5)
C22A—N2A—H2D	109.5	C32A—C33A—H33D	109.5
C22A—N2A—H2E	109.5	C32A—C33A—H33E	109.5
C22A—N2A—H2F	109.5	C32A—C33A—H33F	109.5
N2A—C22A—C21A	106.3 (7)	H33D—C33A—H33E	109.5
N2A—C22A—C23A	111.4 (15)	H33D—C33A—H33F	109.5
N2A—C22A—H22A	107.7	H33E—C33A—H33F	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.89	2.43	3.321 (2)	178
N1—H1B···Cl3ⁱ	0.89	2.47	3.322 (2)	160
N1—H1C···Cl5ⁱ	0.89	2.51	3.400 (2)	173
N2—H2A···Cl2	0.89	2.58	3.274 (2)	136
N2—H2A···Cl4	0.89	2.83	3.537 (2)	137
N2—H2B···Cl3ⁱⁱ	0.89	2.46	3.339 (2)	169
N2—H2C···Cl5	0.89	2.44	3.282 (2)	157
N2A—H2D···Cl3ⁱⁱ	0.89	2.77	3.339 (2)	123
N2A—H2D···Cl4ⁱⁱ	0.89	2.79	3.3982 (19)	126
N2A—H2E···Cl5	0.89	2.58	3.282 (2)	136
N2A—H2F···Cl4	0.89	2.66	3.537 (2)	169
N3—H3A···Cl5	0.89	2.35	3.236 (3)	173
N3—H3B···Cl5ⁱⁱⁱ	0.89	2.31	3.197 (3)	173
N3—H3C···Cl4^iv	0.89	2.75	3.374 (3)	128
N3A—H3D···Cl5ⁱⁱⁱ	0.89	2.34	3.227 (8)	175
N3A—H3E···Cl5	0.89	2.22	3.106 (8)	174
N3A—H3F···Cl2	0.89	2.63	3.352 (8)	138
C12—H12···Cl4^v	0.98	2.81	3.676 (2)	148
C32—H32···Cl2	0.98	2.88	3.732 (4)	146

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

Tris(isopropylammonium) tetrabromidocobaltate(II) bromide (II) top

Crystal data top

(C₃H₁₀N)₃[CoBr₄]Br	F(000) = 1228
M_r = 638.84	D_x = 1.921 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9847 reflections
a = 12.7504 (5) Å	θ = 5.3–46.9°
b = 9.7339 (4) Å	µ = 9.81 mm⁻¹
c = 17.8111 (7) Å	T = 295 K
β = 92.355 (2)°	Irregular, blue
V = 2208.69 (15) Å³	0.35 × 0.30 × 0.17 mm
Z = 4

Data collection top

Bruker D8 Quest Eco diffractometer	3130 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.097
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.5°, θ_min = 3.1°
T_min = 0.528, T_max = 0.746	h = −16→16
88263 measured reflections	k = −12→12
5070 independent reflections	l = −23→23

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0135P)² + 4.4182P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max = 0.001
S = 1.01	Δρ_max = 0.56 e Å⁻³
5070 reflections	Δρ_min = −0.50 e Å⁻³
179 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.00346 (11)
Primary atom site location: dual

Special details top

Refinement. DFIX restraints were applied to C-C and C-N bonds of the minor disorder component in order to yield a more chemically reasonable geometry. Four low angle reflections with Fc >> Fo were presumed to have been blocked by the beam catcher and were omitted from the refinement. APEX3 software suggested data collection to θmax = 28.32° however data analysis showed that <I/σ(I)> is less than 1.03 beyond θ = 27.5°. Thus data with θ > 27.5° were omitted from the final refinement.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.69245 (4)	0.67873 (6)	0.58622 (3)	0.03968 (16)
Br1	0.83023 (4)	0.84556 (6)	0.58385 (3)	0.07107 (18)
Br2	0.57849 (4)	0.71422 (6)	0.68763 (3)	0.05936 (16)
Br3	0.75948 (4)	0.44794 (5)	0.59845 (3)	0.05384 (15)
Br4	0.59477 (4)	0.68488 (5)	0.46746 (3)	0.05525 (15)
Br5	0.68875 (4)	0.51863 (5)	0.26865 (3)	0.05417 (15)
N1	0.4261 (3)	0.6561 (4)	0.2734 (2)	0.0700 (12)
H1A	0.387031	0.612385	0.306060	0.105*
H1B	0.488965	0.616607	0.272491	0.105*
H1C	0.394878	0.651897	0.227802	0.105*
C11	0.5163 (5)	0.8676 (7)	0.2475 (5)	0.119 (3)
H11A	0.582585	0.821337	0.253886	0.178*
H11B	0.524627	0.962415	0.261344	0.178*
H11C	0.491953	0.861520	0.195882	0.178*
C12	0.4383 (4)	0.8016 (6)	0.2962 (3)	0.0760 (16)
H12	0.469908	0.801058	0.347336	0.091*
C13	0.3397 (4)	0.8734 (6)	0.3000 (4)	0.0862 (19)
H13A	0.292873	0.821329	0.329812	0.129*
H13B	0.309203	0.884725	0.250229	0.129*
H13C	0.351462	0.961995	0.322536	0.129*
N2	0.6409 (3)	0.3389 (4)	0.4281 (2)	0.0514 (10)	0.735 (18)
H2A	0.571676	0.334733	0.419948	0.077*	0.735 (18)
H2B	0.655550	0.359392	0.476060	0.077*	0.735 (18)
H2C	0.667335	0.403361	0.398883	0.077*	0.735 (18)
C21	0.8050 (4)	0.2110 (6)	0.4240 (4)	0.0846 (19)	0.735 (18)
H21A	0.836205	0.124070	0.412618	0.127*	0.735 (18)
H21B	0.833120	0.280857	0.392525	0.127*	0.735 (18)
H21C	0.820408	0.233430	0.475772	0.127*	0.735 (18)
C22	0.6886 (5)	0.2026 (7)	0.4101 (7)	0.057 (3)	0.735 (18)
H22	0.671965	0.178198	0.357558	0.068*	0.735 (18)
C23	0.6411 (9)	0.0987 (10)	0.4619 (9)	0.108 (5)	0.735 (18)
H23A	0.566526	0.094872	0.452164	0.162*	0.735 (18)
H23B	0.671012	0.009867	0.453384	0.162*	0.735 (18)
H23C	0.655539	0.125456	0.513212	0.162*	0.735 (18)
N2A	0.6409 (3)	0.3389 (4)	0.4281 (2)	0.0514 (10)	0.265 (18)
H2D	0.679737	0.408126	0.446358	0.077*	0.265 (18)
H2E	0.634447	0.345965	0.378281	0.077*	0.265 (18)
H2F	0.577688	0.341785	0.447357	0.077*	0.265 (18)
C21A	0.8050 (4)	0.2110 (6)	0.4240 (4)	0.0846 (19)	0.265 (18)
H21D	0.839173	0.290545	0.445457	0.127*	0.265 (18)
H21E	0.841824	0.129778	0.440654	0.127*	0.265 (18)
H21F	0.805155	0.216464	0.370188	0.127*	0.265 (18)
C22A	0.6932 (9)	0.2050 (13)	0.4487 (14)	0.063 (9)*	0.265 (18)
H22A	0.695959	0.198427	0.503652	0.076*	0.265 (18)
C23A	0.631 (2)	0.085 (3)	0.4190 (15)	0.067 (8)*	0.265 (18)
H23D	0.665885	0.001244	0.433085	0.101*	0.265 (18)
H23E	0.562295	0.086328	0.439779	0.101*	0.265 (18)
H23F	0.623519	0.090836	0.365270	0.101*	0.265 (18)
N3	0.6836 (3)	0.2724 (4)	0.1357 (2)	0.0678 (12)
H3A	0.724812	0.205045	0.153399	0.102*
H3B	0.689121	0.344526	0.166351	0.102*
H3C	0.703195	0.296527	0.090156	0.102*
C31	0.5040 (4)	0.3426 (6)	0.1056 (3)	0.0708 (16)
H31A	0.517748	0.365418	0.054465	0.106*
H31B	0.518158	0.420890	0.137108	0.106*
H31C	0.431723	0.316343	0.108870	0.106*
C32	0.5736 (4)	0.2247 (5)	0.1311 (3)	0.0527 (12)
H32	0.553744	0.196600	0.181377	0.063*
C33	0.5661 (4)	0.1015 (5)	0.0802 (3)	0.0687 (15)
H33A	0.584103	0.127780	0.030348	0.103*
H33B	0.495727	0.066353	0.078975	0.103*
H33C	0.613765	0.031802	0.098641	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0428 (3)	0.0400 (3)	0.0366 (3)	−0.0033 (3)	0.0061 (3)	0.0000 (3)
Br1	0.0720 (4)	0.0633 (4)	0.0790 (4)	−0.0308 (3)	0.0165 (3)	−0.0057 (3)
Br2	0.0573 (3)	0.0759 (4)	0.0460 (3)	0.0013 (3)	0.0161 (2)	−0.0079 (3)
Br3	0.0621 (3)	0.0450 (3)	0.0545 (3)	0.0077 (2)	0.0034 (2)	0.0020 (2)
Br4	0.0658 (3)	0.0610 (3)	0.0386 (3)	0.0072 (3)	−0.0031 (2)	0.0026 (2)
Br5	0.0606 (3)	0.0532 (3)	0.0487 (3)	−0.0062 (2)	0.0026 (2)	−0.0029 (2)
N1	0.084 (3)	0.053 (3)	0.075 (3)	0.006 (2)	0.020 (2)	0.013 (2)
C11	0.079 (5)	0.098 (5)	0.183 (8)	−0.010 (4)	0.047 (5)	0.031 (5)
C12	0.075 (4)	0.065 (4)	0.088 (4)	−0.003 (3)	0.000 (3)	0.008 (3)
C13	0.084 (4)	0.064 (4)	0.112 (5)	0.018 (3)	0.026 (4)	0.013 (4)
N2	0.053 (2)	0.039 (2)	0.062 (3)	0.0039 (18)	0.002 (2)	0.0024 (19)
C21	0.064 (4)	0.087 (5)	0.102 (5)	0.022 (3)	0.000 (3)	−0.025 (4)
C22	0.066 (5)	0.044 (5)	0.059 (6)	0.010 (3)	−0.007 (4)	−0.014 (4)
C23	0.132 (9)	0.052 (6)	0.142 (12)	0.018 (6)	0.033 (9)	0.029 (7)
N2A	0.053 (2)	0.039 (2)	0.062 (3)	0.0039 (18)	0.002 (2)	0.0024 (19)
C21A	0.064 (4)	0.087 (5)	0.102 (5)	0.022 (3)	0.000 (3)	−0.025 (4)
N3	0.062 (3)	0.053 (3)	0.087 (3)	0.008 (2)	−0.005 (2)	−0.017 (2)
C31	0.057 (3)	0.078 (4)	0.077 (4)	0.020 (3)	−0.007 (3)	−0.010 (3)
C32	0.045 (3)	0.056 (3)	0.057 (3)	0.006 (2)	0.010 (2)	−0.001 (2)
C33	0.074 (4)	0.056 (3)	0.076 (4)	−0.011 (3)	0.008 (3)	−0.017 (3)

Geometric parameters (Å, º) top

Co1—Br1	2.3939 (7)	C23—H23B	0.9600
Co1—Br2	2.3894 (7)	C23—H23C	0.9600
Co1—Br3	2.4102 (7)	N2A—H2D	0.8900
Co1—Br4	2.4110 (7)	N2A—H2E	0.8900
N1—H1A	0.8900	N2A—H2F	0.8900
N1—H1B	0.8900	N2A—C22A	1.502 (9)
N1—H1C	0.8900	C21A—H21D	0.9600
N1—C12	1.480 (7)	C21A—H21E	0.9600
C11—H11A	0.9600	C21A—H21F	0.9600
C11—H11B	0.9600	C21A—C22A	1.510 (9)
C11—H11C	0.9600	C22A—H22A	0.9800
C11—C12	1.492 (8)	C22A—C23A	1.498 (10)
C12—H12	0.9800	C23A—H23D	0.9600
C12—C13	1.443 (7)	C23A—H23E	0.9600
C13—H13A	0.9600	C23A—H23F	0.9600
C13—H13B	0.9600	N3—H3A	0.8900
C13—H13C	0.9600	N3—H3B	0.8900
N2—H2A	0.8900	N3—H3C	0.8900
N2—H2B	0.8900	N3—C32	1.477 (6)
N2—H2C	0.8900	C31—H31A	0.9600
N2—C22	1.499 (7)	C31—H31B	0.9600
C21—H21A	0.9600	C31—H31C	0.9600
C21—H21B	0.9600	C31—C32	1.509 (6)
C21—H21C	0.9600	C32—H32	0.9800
C21—C22	1.498 (8)	C32—C33	1.504 (6)
C22—H22	0.9800	C33—H33A	0.9600
C22—C23	1.513 (13)	C33—H33B	0.9600
C23—H23A	0.9600	C33—H33C	0.9600

Br1—Co1—Br2	112.63 (3)	H23A—C23—H23B	109.5
Br1—Co1—Br3	112.09 (3)	H23A—C23—H23C	109.5
Br1—Co1—Br4	108.70 (3)	H23B—C23—H23C	109.5
Br2—Co1—Br3	106.91 (3)	H2D—N2A—H2E	109.5
Br2—Co1—Br4	110.57 (3)	H2D—N2A—H2F	109.5
Br3—Co1—Br4	105.72 (3)	H2E—N2A—H2F	109.5
H1A—N1—H1B	109.5	C22A—N2A—H2D	109.5
H1A—N1—H1C	109.5	C22A—N2A—H2E	109.5
H1B—N1—H1C	109.5	C22A—N2A—H2F	109.5
C12—N1—H1A	109.5	N2A—C22A—C21A	108.0 (8)
C12—N1—H1B	109.5	N2A—C22A—C23A	111.4 (18)
C12—N1—H1C	109.5	N2A—C22A—H22A	107.3
N1—C12—C11	108.5 (5)	H21D—C21A—H21E	109.5
N1—C12—C13	113.2 (5)	H21D—C21A—H21F	109.5
N1—C12—H12	106.5	H21E—C21A—H21F	109.5
H11A—C11—H11B	109.5	C22A—C21A—H21D	109.5
H11A—C11—H11C	109.5	C22A—C21A—H21E	109.5
H11B—C11—H11C	109.5	C22A—C21A—H21F	109.5
C12—C11—H11A	109.5	C21A—C22A—H22A	107.3
C12—C11—H11B	109.5	C23A—C22A—H22A	107.3
C12—C11—H11C	109.5	C21A—C22A—C23A	115.0 (18)
C11—C12—H12	106.5	C22A—C23A—H23D	109.5
C13—C12—H12	106.5	C22A—C23A—H23E	109.5
C13—C12—C11	114.9 (5)	C22A—C23A—H23F	109.5
C12—C13—H13A	109.5	H23D—C23A—H23E	109.5
C12—C13—H13B	109.5	H23D—C23A—H23F	109.5
C12—C13—H13C	109.5	H23E—C23A—H23F	109.5
H13A—C13—H13B	109.5	H3A—N3—H3B	109.5
H13A—C13—H13C	109.5	H3A—N3—H3C	109.5
H13B—C13—H13C	109.5	H3B—N3—H3C	109.5
H2A—N2—H2B	109.5	C32—N3—H3A	109.5
H2A—N2—H2C	109.5	C32—N3—H3B	109.5
H2B—N2—H2C	109.5	C32—N3—H3C	109.5
C22—N2—H2A	109.5	N3—C32—C31	108.8 (4)
C22—N2—H2B	109.5	N3—C32—C33	108.7 (4)
C22—N2—H2C	109.5	N3—C32—H32	108.5
N2—C22—C21	108.9 (5)	H31A—C31—H31B	109.5
N2—C22—C23	106.6 (8)	H31A—C31—H31C	109.5
N2—C22—H22	110.2	H31B—C31—H31C	109.5
H21A—C21—H21B	109.5	C32—C31—H31A	109.5
H21A—C21—H21C	109.5	C32—C31—H31B	109.5
H21B—C21—H21C	109.5	C32—C31—H31C	109.5
C22—C21—H21A	109.5	C31—C32—H32	108.5
C22—C21—H21B	109.5	C33—C32—H32	108.5
C22—C21—H21C	109.5	C31—C32—C33	113.8 (4)
C21—C22—H22	110.2	C32—C33—H33A	109.5
C23—C22—H22	110.2	C32—C33—H33B	109.5
C21—C22—C23	110.8 (9)	C32—C33—H33C	109.5
C22—C23—H23A	109.5	H33A—C33—H33B	109.5
C22—C23—H23B	109.5	H33A—C33—H33C	109.5
C22—C23—H23C	109.5	H33B—C33—H33C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br3ⁱ	0.89	2.64	3.504 (4)	163
N1—H1B···Br5	0.89	2.72	3.611 (4)	175
N1—H1C···Br1ⁱⁱ	0.89	2.66	3.542 (4)	171
N2—H2B···Br3	0.89	2.65	3.499 (4)	160
N2—H2A···Br2ⁱ	0.89	2.70	3.445 (4)	143
N2—H2A···Br4ⁱ	0.89	2.99	3.607 (4)	128
N2—H2C···Br5	0.89	2.60	3.412 (4)	152
N2A—H2E···Br5	0.89	2.69	3.412 (4)	139
N2A—H2D···Br3	0.89	2.88	3.499 (4)	128
N2A—H2D···Br4	0.89	2.93	3.495 (3)	123
N2A—H2E···Br2ⁱ	0.89	2.97	3.445 (4)	115
N2A—H2F···Br4ⁱ	0.89	2.73	3.607 (4)	167
N3—H3A···Br5ⁱⁱⁱ	0.89	2.51	3.380 (4)	165
N3—H3B···Br5	0.89	2.49	3.368 (4)	170
N3—H3C···Br4ⁱⁱⁱ	0.89	3.01	3.538 (4)	119
C12—H12···Br4	0.98	2.85	3.751 (6)	154
C32—H32···Br2ⁱ	0.98	3.06	3.880 (5)	142

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

Bis(isopropylammonium) tetrachloridozincate(II) (III) top

Crystal data top

(C₃H₁₀N)₂[ZnCl₄]	F(000) = 672
M_r = 327.41	D_x = 1.49 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9690 reflections
a = 7.3076 (3) Å	θ = 5.8–59.0°
b = 20.4386 (8) Å	µ = 2.38 mm⁻¹
c = 10.2616 (4) Å	T = 295 K
β = 107.827 (1)°	Block, colourless
V = 1459.05 (10) Å³	0.40 × 0.31 × 0.29 mm
Z = 4

Data collection top

Bruker D8 Quest Eco diffractometer	3568 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.075
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 29.6°, θ_min = 3.0°
T_min = 0.639, T_max = 0.746	h = −10→10
69211 measured reflections	k = −28→28
4105 independent reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0206P)² + 2.6728P] where P = (F_o² + 2F_c²)/3
S = 1.24	(Δ/σ)_max = 0.001
4105 reflections	Δρ_max = 0.64 e Å⁻³
146 parameters	Δρ_min = −0.50 e Å⁻³
0 restraints

Special details top

Refinement. Two low angle reflections with Fc >> Fo were presumed to have been blocked by the beam catcher and were omitted from the refinement.

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

	x	y	z	U_iso*/U_eq
Zn1	0.87245 (5)	0.57264 (2)	0.77526 (4)	0.03468 (11)
Cl1	0.61651 (11)	0.50404 (4)	0.75532 (9)	0.03846 (18)
Cl2	1.14947 (12)	0.51445 (5)	0.82326 (11)	0.0531 (2)
Cl3	0.83177 (14)	0.60429 (6)	0.55485 (11)	0.0588 (3)
Cl4	0.86591 (15)	0.65416 (5)	0.91889 (13)	0.0632 (3)
N1	0.7569 (6)	0.43706 (17)	0.4900 (4)	0.0471 (7)
H1A	0.772 (8)	0.469 (3)	0.555 (6)	0.086 (18)*
H1B	0.852 (8)	0.432 (3)	0.469 (5)	0.072 (17)*
H1C	0.672 (8)	0.456 (3)	0.421 (6)	0.076 (16)*
C11	0.8492 (6)	0.3487 (2)	0.6582 (4)	0.0582 (10)
H11A	0.964336	0.340844	0.634118	0.087*
H11B	0.807838	0.308596	0.689201	0.087*
H11C	0.874523	0.380662	0.730045	0.087*
C12	0.6944 (5)	0.37347 (18)	0.5352 (4)	0.0419 (7)
H12	0.578190	0.381280	0.561575	0.050*
C13	0.6450 (7)	0.3269 (2)	0.4154 (5)	0.0621 (11)
H13A	0.756303	0.320013	0.386063	0.093*
H13B	0.543383	0.345116	0.341412	0.093*
H13C	0.603904	0.285848	0.442470	0.093*
N2	0.5139 (5)	0.59521 (16)	1.0224 (4)	0.0466 (7)
H2A	0.566 (9)	0.562 (3)	1.095 (7)	0.11 (2)*
H2B	0.420 (7)	0.570 (2)	0.958 (5)	0.073 (15)*
H2C	0.605 (7)	0.606 (2)	0.987 (5)	0.059 (14)*
C21	0.3642 (6)	0.7020 (2)	0.9601 (5)	0.0580 (11)
H21A	0.472466	0.716289	0.933174	0.087*
H21B	0.308334	0.738912	0.991874	0.087*
H21C	0.270247	0.682572	0.883172	0.087*
C22	0.4290 (5)	0.65261 (17)	1.0730 (4)	0.0397 (7)
H22	0.316762	0.637783	1.098095	0.048*
C23	0.5761 (7)	0.6788 (3)	1.1992 (4)	0.0663 (12)
H23A	0.690318	0.690852	1.177432	0.099*
H23B	0.606694	0.645778	1.269043	0.099*
H23C	0.524975	0.716580	1.231653	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02608 (17)	0.0375 (2)	0.0432 (2)	0.00084 (14)	0.01469 (14)	−0.00365 (16)
Cl1	0.0316 (4)	0.0402 (4)	0.0467 (4)	−0.0045 (3)	0.0168 (3)	0.0024 (3)
Cl2	0.0306 (4)	0.0554 (5)	0.0701 (6)	0.0137 (4)	0.0106 (4)	0.0022 (4)
Cl3	0.0413 (5)	0.0864 (7)	0.0550 (6)	0.0124 (5)	0.0241 (4)	0.0282 (5)
Cl4	0.0531 (6)	0.0561 (6)	0.0907 (8)	−0.0125 (4)	0.0371 (6)	−0.0363 (6)
N1	0.0476 (19)	0.0413 (17)	0.054 (2)	0.0073 (14)	0.0184 (16)	−0.0016 (15)
C11	0.055 (2)	0.071 (3)	0.051 (2)	0.013 (2)	0.0190 (19)	0.012 (2)
C12	0.0334 (16)	0.0469 (19)	0.050 (2)	0.0041 (14)	0.0190 (15)	0.0004 (15)
C13	0.065 (3)	0.049 (2)	0.067 (3)	0.005 (2)	0.010 (2)	−0.010 (2)
N2	0.0476 (18)	0.0360 (15)	0.054 (2)	0.0028 (14)	0.0120 (16)	0.0024 (14)
C21	0.053 (2)	0.045 (2)	0.072 (3)	0.0089 (17)	0.015 (2)	0.0154 (19)
C22	0.0382 (17)	0.0396 (17)	0.0452 (19)	−0.0032 (14)	0.0186 (14)	0.0025 (14)
C23	0.076 (3)	0.075 (3)	0.047 (2)	−0.018 (2)	0.017 (2)	−0.011 (2)

Geometric parameters (Å, º) top

Zn1—Cl1	2.2960 (8)	C13—H13B	0.9600
Zn1—Cl2	2.2681 (9)	C13—H13C	0.9600
Zn1—Cl3	2.2828 (10)	N2—H2A	1.00 (6)
Zn1—Cl4	2.2347 (10)	N2—H2B	0.95 (5)
N1—H1A	0.91 (6)	N2—H2C	0.87 (5)
N1—H1B	0.79 (6)	N2—C22	1.493 (5)
N1—H1C	0.88 (6)	C21—H21A	0.9600
N1—C12	1.498 (5)	C21—H21B	0.9600
C11—H11A	0.9600	C21—H21C	0.9600
C11—H11B	0.9600	C21—C22	1.500 (5)
C11—H11C	0.9600	C22—H22	0.9800
C11—C12	1.502 (5)	C22—C23	1.505 (5)
C12—H12	0.9800	C23—H23A	0.9600
C12—C13	1.509 (5)	C23—H23B	0.9600
C13—H13A	0.9600	C23—H23C	0.9600

Cl1—Zn1—Cl2	110.35 (4)	H13A—C13—H13B	109.5
Cl1—Zn1—Cl3	103.26 (4)	H13A—C13—H13C	109.5
Cl1—Zn1—Cl4	109.44 (4)	H13B—C13—H13C	109.5
Cl2—Zn1—Cl3	101.57 (4)	H2A—N2—H2B	101 (4)
Cl2—Zn1—Cl4	116.46 (4)	H2A—N2—H2C	108 (4)
Cl3—Zn1—Cl4	114.81 (5)	H2B—N2—H2C	109 (4)
H1A—N1—H1B	112 (5)	C22—N2—H2A	112 (4)
H1A—N1—H1C	100 (4)	C22—N2—H2B	112 (3)
H1B—N1—H1C	107 (5)	C22—N2—H2C	113 (3)
C12—N1—H1A	112 (3)	N2—C22—C21	109.1 (3)
C12—N1—H1B	110 (4)	N2—C22—H22	108.6
C12—N1—H1C	116 (3)	N2—C22—C23	108.4 (3)
N1—C12—C11	109.3 (3)	H21A—C21—H21B	109.5
N1—C12—H12	108.4	H21A—C21—H21C	109.5
N1—C12—C13	108.3 (3)	H21B—C21—H21C	109.5
H11A—C11—H11B	109.5	C22—C21—H21A	109.5
H11A—C11—H11C	109.5	C22—C21—H21B	109.5
H11B—C11—H11C	109.5	C22—C21—H21C	109.5
C12—C11—H11A	109.5	C21—C22—H22	108.6
C12—C11—H11B	109.5	C23—C22—H22	108.6
C12—C11—H11C	109.5	C21—C22—C23	113.4 (3)
C11—C12—C13	113.7 (3)	C22—C23—H23A	109.5
C11—C12—H12	108.4	C22—C23—H23B	109.5
C13—C12—H12	108.4	C22—C23—H23C	109.5
C12—C13—H13A	109.5	H23A—C23—H23B	109.5
C12—C13—H13B	109.5	H23A—C23—H23C	109.5
C12—C13—H13C	109.5	H23B—C23—H23C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.91 (6)	2.74 (6)	3.471 (4)	139 (4)
N1—H1A···Cl3	0.91 (6)	2.81 (6)	3.493 (4)	133 (4)
N1—H1B···Cl3ⁱ	0.79 (6)	2.51 (6)	3.287 (4)	166 (5)
N1—H1C···Cl1ⁱⁱ	0.88 (6)	2.46 (6)	3.321 (4)	167 (5)
N2—H2A···Cl1ⁱⁱⁱ	1.00 (6)	2.68 (6)	3.400 (4)	129 (4)
N2—H2A···Cl2^iv	1.00 (6)	2.53 (6)	3.346 (3)	139 (5)
N2—H2B···Cl2^v	0.95 (5)	2.33 (5)	3.265 (4)	169 (4)
N2—H2C···Cl4	0.87 (5)	2.43 (5)	3.297 (4)	169 (4)

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

Poly[isopropylammonium [dichloridozincate(II)]-µ-chlorido]] (IV) top

Crystal data top

(C₃H₁₀N)[ZnCl₃]	F(000) = 928
M_r = 231.84	D_x = 1.725 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9690 reflections
a = 6.3131 (3) Å	θ = 5.8–59.0°
b = 12.9582 (6) Å	µ = 3.56 mm⁻¹
c = 21.8277 (10) Å	T = 295 K
V = 1785.65 (14) Å³	Needle, colourless
Z = 8	0.47 × 0.22 × 0.19 mm

Data collection top

Bruker D8 Quest Eco diffractometer	2642 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.041
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 32.0°, θ_min = 3.7°
T_min = 0.444, T_max = 0.747	h = −9→9
137051 measured reflections	k = −19→19
3096 independent reflections	l = −32→32

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0106P)² + 2.9743P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.076	(Δ/σ)_max < 0.001
S = 1.25	Δρ_max = 0.58 e Å⁻³
3096 reflections	Δρ_min = −0.74 e Å⁻³
88 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b)
0 restraints	Extinction coefficient: 0.0049 (3)
Primary atom site location: dual

Special details top

Refinement. One low angle reflection with Fc>>Fo was presumed to have been blocked by the beam catcher and were omitted from the refinement. APEX3 control software suggested θmax = 37.20°, however data analysis showed that <I/σ(I)> is less than 1.64 for data beyond θ = 31.7°. Thus data with θ > 32.0° were omitted from the final refinement.

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

	x	y	z	U_iso*/U_eq
Zn1	0.71002 (4)	0.83231 (2)	0.19928 (2)	0.03189 (9)
Cl1	0.69868 (10)	0.65958 (5)	0.19958 (3)	0.03814 (14)
Cl2	0.58549 (13)	0.90289 (6)	0.11449 (3)	0.04834 (18)
Cl3	0.56133 (10)	0.88709 (6)	0.29078 (3)	0.04376 (17)
N1	0.6927 (5)	0.6086 (2)	0.34850 (11)	0.0427 (5)
H1A	0.636 (7)	0.550 (4)	0.3524 (19)	0.076 (14)*
H1B	0.622 (9)	0.655 (4)	0.327 (2)	0.105 (18)*
H1C	0.803 (7)	0.601 (3)	0.326 (2)	0.077 (14)*
C11	0.8781 (7)	0.5759 (3)	0.44385 (17)	0.0672 (10)
H11A	1.004167	0.561033	0.420867	0.101*
H11B	0.798477	0.51348	0.449539	0.101*
H11C	0.916308	0.603761	0.483068	0.101*
C12	0.7465 (6)	0.6526 (2)	0.40972 (14)	0.0516 (7)
H12	0.832846	0.714465	0.403126	0.062*
C13	0.5511 (8)	0.6841 (4)	0.44229 (17)	0.0870 (15)
H13A	0.587641	0.712362	0.481553	0.13*
H13B	0.461144	0.625124	0.447826	0.13*
H13C	0.477813	0.735335	0.418599	0.13*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02689 (14)	0.03437 (15)	0.03441 (15)	0.00108 (11)	−0.00115 (11)	0.00064 (11)
Cl1	0.0368 (3)	0.0321 (3)	0.0455 (3)	−0.0008 (2)	0.0005 (3)	−0.0010 (2)
Cl2	0.0528 (4)	0.0502 (4)	0.0420 (3)	0.0090 (3)	−0.0113 (3)	0.0061 (3)
Cl3	0.0264 (3)	0.0561 (4)	0.0488 (4)	−0.0090 (3)	0.0060 (2)	−0.0218 (3)
N1	0.0412 (13)	0.0533 (15)	0.0335 (11)	0.0061 (12)	0.0013 (10)	0.0031 (11)
C11	0.065 (2)	0.082 (3)	0.055 (2)	0.013 (2)	−0.0225 (18)	0.0027 (18)
C12	0.0607 (19)	0.0474 (16)	0.0465 (15)	0.0026 (15)	−0.0110 (15)	−0.0020 (13)
C13	0.099 (3)	0.113 (4)	0.049 (2)	0.052 (3)	−0.003 (2)	−0.020 (2)

Geometric parameters (Å, º) top

Zn1—Cl1	2.2394 (7)	C11—H11B	0.96
Zn1—Cl2	2.2089 (7)	C11—H11C	0.96
Zn1—Cl3	2.3182 (7)	C11—C12	1.495 (5)
Zn1—Cl3ⁱ	2.3387 (7)	C12—H12	0.98
N1—H1A	0.84 (5)	C12—C13	1.481 (6)
N1—H1B	0.88 (6)	C13—H13A	0.96
N1—H1C	0.86 (5)	C13—H13B	0.96
N1—C12	1.492 (4)	C13—H13C	0.96
C11—H11A	0.96

Cl1—Zn1—Cl2	113.89 (3)	H11A—C11—H11B	109.5
Cl1—Zn1—Cl3	106.89 (3)	H11A—C11—H11C	109.5
Cl1—Zn1—Cl3ⁱ	109.47 (3)	H11B—C11—H11C	109.5
Cl2—Zn1—Cl3	116.80 (3)	C12—C11—H11A	109.5
Cl2—Zn1—Cl3ⁱ	106.83 (3)	C12—C11—H11B	109.5
Cl3—Zn1—Cl3ⁱ	102.19 (2)	C12—C11—H11C	109.5
Zn1—Cl3—Zn1ⁱⁱ	111.78 (3)	C11—C12—C13	114.0 (3)
H1A—N1—H1B	116 (4)	C11—C12—H12	107.9
H1A—N1—H1C	108 (4)	C13—C12—H12	107.9
H1B—N1—H1C	100 (4)	C12—C13—H13A	109.5
C12—N1—H1A	111 (3)	C12—C13—H13B	109.5
C12—N1—H1B	110 (3)	C12—C13—H13C	109.5
C12—N1—H1C	112 (3)	H13A—C13—H13B	109.5
N1—C12—C11	108.6 (3)	H13A—C13—H13C	109.5
N1—C12—C13	110.2 (3)	H13B—C13—H13C	109.5
N1—C12—H12	107.9

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2ⁱⁱⁱ	0.84 (5)	2.47 (5)	3.292 (3)	165 (4)
N1—H1B···Cl1	0.88 (6)	2.81 (5)	3.317 (3)	118 (4)
N1—H1B···Cl1ⁱⁱ	0.88 (6)	2.74 (5)	3.356 (3)	128 (4)
N1—H1C···Cl1ⁱ	0.86 (5)	2.67 (5)	3.427 (3)	148 (4)
C12—H12···Cl2ⁱ	0.98	2.94	3.922 (4)	179

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

Database and calculated bond lengths (Å) and angles (°) for IPA⁺ and TMA⁺ cations top

		C—C	C—N	C—C—C/C—N—C	C—C—N
IPA⁺
	Mean (CSD)	1.50 (5)	1.49 (5)	114 (6)	110 (5)
	Calculated (in vacuo)	1.522	1.548	114.8	108.2
	Calculated (dielectric)	1.523	1.518	114.0	108.6

TMA⁺
	Mean (CSD)		1.48 (5)	111 (5)
	Calculated (in vacuo)		1.506	111.9
	Calculated (dielectric)		1.498	111.7

Acknowledgements

We thank Ms. Kayla Rivers for assistance in preparation of the samples.

References

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