Bis(2-chloro-N,N-di­methyl­ethan-1-aminium) tetra­chlorido­cobaltate(II) and tetra­chlorido­zincate(II)

McGinness, K.; Minton, K.; White, K.; Bond, M.R.

doi:10.1107/S2056989024003955

research communications

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ISSN: 2056-9890

Volume 80| Part 6| June 2024| Pages 577-581

https://doi.org/10.1107/S2056989024003955

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Bis(2-chloro-N,N-dimethylethan-1-aminium) tetrachloridocobaltate(II) and tetrachloridozincate(II)

Katelyn McGinness,^a Kim Minton,^a Katelyn White ^a and Marcus R. Bond ^a ^*

^aDepartment of Chemistry and Physics, Southeast Missouri State University, Cape Girardeau, MO 63701, USA
^*Correspondence e-mail: mbond@semo.edu

Edited by S. P. Kelley, University of Missouri-Columbia, USA (Received 9 April 2024; accepted 30 April 2024; online 10 May 2024)

The few examples of structures containing the 2-chloro-N,N-dimethylethan-1-aminium or 3-chloro-N,N-dimethylpropan-1-aminium cations show a competition between gauche and anti conformations for the chloroalkyl chain. To explore further the conformational landscape of these cations, and their possible use as molecular switches, the title salts, (C₄H₁₁ClN)₂[CoCl₄] and (C₄H₁₁ClN)₂[ZnCl₄], were prepared and structurally characterized. Details of both structures are in close agreement. The inorganic complex exhibits a slightly flattened tetrahedral geometry that likely arises from bifurcated N—H hydrogen bonds from the organic cations. The alkyl chain of the cation is disordered between gauche and anti conformations with the gauche conformation occupancy refined to 0.707 (2) for the cobaltate. The gauche conformation places the terminal Cl atom at a tetrahedral face of the inorganic complex with a contact distance of 3.7576 (9) Å to the Co²⁺ center. The anti conformation places the terminal Cl atom at a contact distance to a neighboring anti conformation terminal Cl atom that is ∼1 Å less than the sum of the van der Waals radii. Thus, if the anti conformation is present at a site, then the nearest neighbor must be gauche. DFT geometry optimizations indicate the gauche conformation is more stable in vacuo by 0.226 eV, which reduces to 0.0584 eV when calculated in a uniform dielectric. DFT geometry optimizations for the unprotonated molecule indicate the anti conformation is stabilized by 0.0428 eV in vacuo, with no strongly preferred conformation in uniform dielectric, to provide support to the notion that this cation could function as a molecular switch via deprotonation.

Keywords: crystal structure; gauche effect; DFT calculation; disorder; molecular switch.

CCDC references: 2352359; 2352358

1. Chemical context

The recently published structure of 3-chloro-N,N-dimethylpropan-1-aminium chloride reported the conformation of the molecular cation (henceforth 3CLPA⁺) as gauche for the terminal Cl atom (Bond & Silwal, 2023 ). DFT geometry optimizations in vacuo indicate that the gauche conformation is more stable than anti for the molecular cation, as well as for the 2-chloro-N,N-dimethylethan-1-aminium analog (henceforth 2CLEA⁺). In both cases the molecular cations appear to exhibit the gauche effect in which the bonding pair of a C—H bond β to the terminal halogen atom of the chain is donated to the antibonding orbital of the C—X bond (X = halogen) to stabilize the gauche conformation through hyperconjugation (Wolfe, 1972 ). A recent computational study of 1,2-dihaloethanes reports that this stabilization due to hyperconjugation is always present, but other energy contributions – such as steric interactions – are more important so that the gauche effect is typically observed only with fluorine (Rodrigues Silva et al., 2021 ). However, in the 3CLPA⁺ and 2CLEA⁺ cations the terminal Cl atom is closer to the formal center of positive charge when in the gauche conformation, which may provide an additional contribution to energetic stability.

We are interested in investigating the competition between gauche and anti conformations for these molecular cations in different chemical environments in order to explore their possible use as molecular switches. If the gauche conformation is stabilized by interaction with the positive charge center in the cation, then it is possible with loss of this interaction through deprotonation that the anti conformation becomes more stable and would allow for a change in conformation by altering the degree of protonation. Here we report the structures of 2CLEA⁺ with the tetrahedral complex anions CoCl₄²⁻ and ZnCl₄²⁻.

2. Structural commentary

The structures are isomorphous with unit-cell parameters in close agreement, e.g. unit-cell volumes agree within 2 s.u. Both tetrahedral complexes occupy sites of twofold rotational symmetry with a slight flattening about the twofold axis to produce some Cl—M—Cl (M = Co, Zn) angles greater than 109.5°. M—Cl bond lengths range from 2.25–2.29 Å, in good agreement with average bond lengths of 2.27 (2) Å for CoCl₄²⁻ and 2.27 (4) Å for ZnCl₄²⁻ calculated from structures in the Cambridge Structural Database [512 and 960 hits, respectively; version 5.45 (November, 2023); Groom et al. (2016 )].

Of greater interest is the organic cation, which exhibits disorder between the gauche [s.o.f = 0.707 (2) for CoCl₄²⁻ and 0.697 (2) for ZnCl₄²⁻] and anti conformations (the dimethylammonium head group is ordered). The N1—C1—C2—Cl3 torsion angles are 61.6 (7)° in the CoCl₄²⁻ and −61.3 (6)° in the ZnCl₄²⁻ salts for the gauche conformation and, likewise, −179.7 (13) and 179.3 (9)°, respectively, for the anti. Bond lengths and angles within the cation correspond to expected values, disregarding small distortions that arise due to refinement of atoms of the disordered pair in close proximity. Displacement ellipsoid plots with labels for non-H atoms are presented in Fig. 1 for the CoCl₄²⁻ salt showing only the gauche conformation of the organic cation, and in Fig. 2 for the ZnCl₄²⁻ salt showing only the anti conformation. Bond lengths and angles for non-H atoms are presented in Table 1 for the CoCl₄²⁻ salt, with only the gauche conformation values, and in Table 2 for the ZnCl₄²⁻ salt, with only the anti conformation values.

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

Co1—Cl1	2.2873 (6)	N1—C1	1.509 (5)
Co1—Cl2	2.2618 (6)	C1—C2	1.534 (6)
N1—C3	1.482 (3)	C2—Cl3	1.776 (3)
N1—C4	1.483 (3)

Cl1ⁱ—Co1—Cl1	111.86 (3)	C3—N1—C1	105.4 (3)
Cl1—Co1—Cl2	108.17 (2)	C4—N1—C1	114.8 (4)
Cl1—Co1—Cl2ⁱ	104.58 (2)	N1—C1—C2	116.2 (5)
Cl2ⁱ—Co1—Cl2	119.62 (4)	C1—C2—Cl3	111.0 (4)
C3—N1—C4	110.6 (2)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

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

Zn1—Cl2	2.2553 (5)	N1—C4	1.485 (3)
Zn1—Cl1	2.2883 (5)	N1—C1	1.515 (5)
N1—C1A	1.476 (9)	C1—C2	1.535 (5)
N1—C3	1.480 (3)	C2—Cl3	1.779 (3)

Cl2—Zn1—Cl2ⁱ	118.93 (3)	C3—N1—C4	110.5 (2)
Cl2—Zn1—Cl1ⁱ	104.94 (2)	C3—N1—C1	105.3 (2)
Cl2—Zn1—Cl1	108.36 (2)	C4—N1—C1	114.6 (3)
Cl1ⁱ—Zn1—Cl1	111.38 (3)	N1—C1—C2	116.3 (4)
C1A—N1—C3	119.8 (5)	C1—C2—Cl3	110.7 (3)
C1A—N1—C4	111.1 (8)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Figure 1
Displacement ellipsoid plot (50% level) of the organic cation and complex anion in (2CLEA⁺)₂CoCl₄ with labels for non-H atoms. The gauche conformation of the organic cation only is shown. H atoms are drawn as circles of arbitrary radii and N—H⋯Cl hydrogen bonding is represented by dashed lines.

Figure 2
Displacement ellipsoid plot (50% level) of the organic cation and complex anion in (2CLEA⁺)₂ZnCl₄ with labels for non-H atoms. The anti conformation of the organic cation only is shown. H atoms are drawn as circles of arbitrary radii and N—H⋯Cl hydrogen bonding is represented by dashed lines.

DFT geometry optimizations [B3LYP, 6311+G(d,p); GAMESS (Schmidt et al., 1993 )] in vacuo of 2CLEA⁺ yield an energy for the gauche conformation that is 0.226 eV less than the anti conformation for a 52.737° N—C—C—Cl torsion angle (0.228 eV less for a torsion angle of −52.738°). To approximate the ionic environment of the cation in the crystal, the optimizations were performed in a uniform dielectric constant of 78.4. This results in a reduction of gauche conformation stabilization to 0.0584 eV (torsion angle = 59.1°; by 0.0582 eV for torsion angle = −58.785°), but yields better agreement with observed torsion angle values. [Optimized torsion angles for the anti conformation with magnitudes of 173.858° (in vacuo) and 173.819° (dielectric) deviate slightly from observed values.] Similar optimizations for the unprotonated molecule show both gauche conformations are destabilized in vacuo (by 0.0412 eV for torsion angle = 66.377° and by 0.0428 eV for torsion angle = −64.735°). Energy differences for optimizations performed in uniform dielectric for the unprotonated molecule are not as stark: gauche conformations are slightly stabilized by 0.00792 eV (−65.149°) or 0.00624 eV (64.459°). These results show promise of a switch from gauche to anti via deprotonation. An electrostatic potential plot of the gauche conformation from the uniform dielectric calculation is presented in Fig. 3.

Figure 3
Electrostatic potential plot of the 2CLEA⁺ cation calculated in uniform dielectric for the gauche conformation with a ball-and-stick model of the optimized geometry shown within the electron density envelope. Red indicates regions of negative charge accumulation and blue regions of positive charge.

3. Supramolecular features

The dimethylammonium headgroup forms an asymmetric, bifurcated hydrogen bond to Cl1 and Cl2 resulting in the most acute Cl—M—Cl angle in the complex anion – and a likely origin for the observed tetrahedral flattening. Hydrogen-bond lengths and angles are presented in Tables 3 and 4 for the CoCl₄²⁻ and ZnCl₄²⁻ salts, respectively.

Table 3
Hydrogen-bond geometry (Å, °) for cobaltate

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.87 (3)	2.51 (3)	3.3093 (19)	152 (2)
N1—H1⋯Cl2ⁱ	0.87 (3)	3.02 (3)	3.564 (2)	122 (2)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Table 4
Hydrogen-bond geometry (Å, °) for zincate

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1ⁱ	0.87 (3)	2.51 (3)	3.3124 (18)	156 (2)
N1—H1⋯Cl2	0.87 (3)	3.03 (3)	3.5620 (19)	121 (2)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

In the gauche conformation of the molecular cation, the terminal Cl atom is placed slightly offset from the center of the tetrahedral face defined by Cl1, Cl2, and Cl2ⁱ [symmetry code: (i) 1 − x, y, $[{1\over 2}]$ − z]. This places the terminal Cl atom at a distance of 3.7576 (9) Å from the Co²⁺ center [3.7690 (10) Å for Zn²⁺] with the shortest Cl⋯Cl contact distance [Cl2⋯Cl3 = 3.4293 (11) Å for CoCl₄²⁻; 3.4237 (11) Å for ZnCl₄²⁻] slightly less than 3.50 Å – the sum of the van der Waals radii. In the anti conformation, a methylene H atom from the carbon α to the terminal Cl atom is instead directed at this face and forms contact distances of 3.2–3.3 Å to the Cl atoms. Meanwhile, the terminal Cl atom now forms a short contact [Cl3A⋯Cl3Aⁱⁱ = 2.588 (4) Å, Cl3A⋯Cl3Aⁱⁱⁱ = 2.568 (4) Å; symmetry codes: (ii) $[{3\over 2}]$ − x, $[{1\over 2}]$ − y, 1 − z, for CoCl₄²⁻; (iii) $[{1\over 2}]$ − x, $[{5\over 2}]$ − y, −z, for ZnCl₄²⁻] with a terminal anti conformation Cl atom in the nearest neighbor that is ∼1 Å less than the sum of the van der Waals radii. Hence, any anti conformation molecular cation must have a gauche conformation cation as a nearest neighbor. This provides another driver for the dominance of the gauche conformation in these structures.

The three-dimensional packing can be described starting with parallel rows of hydrogen-bonded formula units along (101) arranged into layers in the ac plane, as shown in the layer packing diagram of Fig. 4. Rows in neighboring layers nest between the rows of a given layer, with neighboring layers related by the C-centering translation, as shown in the unit-cell packing diagram of Fig. 5.

Figure 4
Layer packing diagram viewed down the b axis for (2CLEA⁺)₂CoCl₄ (gauche conformation only) that depicts portions of two rows of formula units along (101) that form a layer in the ac plane. The a axis slants down and to the right, the c axis slants up and to the right. Atoms are drawn as circles of arbitrary radii and N—H⋯Cl hydrogen bonding is represented by dashed lines

Figure 5
Unit-cell packing diagram for (2CLEA⁺)₂ZnCl₄ viewed down (101) showing the stacking of four of the layers presented in Fig. 4

with the b axis vertical. H atoms are omitted for clarity (except for N—H), atoms are drawn as circles of arbitrary radii, and N—H⋯Cl hydrogen bonding is represented by dashed lines.

4. Database survey

Structural results for 2CLEA⁺ or 3CLPA⁺ cations have been sparsely reported. A survey of the Cambridge Structural Database (version 5.45, November, 2023; Groom et al., 2016). yields only two known prior examples of structures containing 2CLEA⁺: an (Mo₂O₂Cl₈)²⁻ salt (CSD refcode POSWAX; Marchetti et al., 2015 ), in which the gauche conformation is found, and a chloride salt (CSD refcode: URORUR; Muller et al., 2021 ) where the anti conformation is found, albeit with a disordered alkyl chain. For 3CLPA⁺, besides the aforementioned chloride salt there is one other structure containing 3-chloro-N,N-propan-1-amine as a ligand in a di(μ-hydrido) dialuminium complex (CSD refcode: NIGGOZ; Andrews et al., 1997 ) where the gauche conformation is also found. No structures containing the unprotonated or uncoordinated molecules have been reported. There are also no reported structures for the longer chain chlorobutyl or chloropentyl analogs.

5. Synthesis and crystallization

Both compounds were prepared by dissolving 2-chloro-N,N-dimethylethan-1-aminium chloride with 1.00 g of CoCl₂·6H₂O or ZnCl₂ in a 2:1 molar ratio in water. The solutions were acidified with concentrated HCl(aq) to yield ∼6 M HCl and produce a definite blue color in the cobalt(II) solution. The solutions were evaporated to a syrup with the syrup redissolved in ethanol to yield crystals of the title compounds upon further evaporation.

6. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 5. For both compounds, initial structure solution identified positions of all non-H atoms except those of the anti conformation. Prominent electron density difference map peaks then identified atoms of the anti conformation. Common site occupation factors for each conformation were refined with the constraint that their sum equal 1.0. H-atom positions were visible on the electron density difference map, but were calculated and refined using a riding model for those bound to C with isotropic displacement parameters set to 1.2 or 1.5×U_iso of the parent atom for methylene or methyl H atoms, respectively. The H atom bound to N was freely refined to a reasonable N—H bond length and the N1—C1A distance was constrained to a chemically reasonable distance (1.50±0.01 Å) using the DFIX command in SHELX.

Table 5
Experimental details

	Cobaltate	Zincate
Crystal data
Chemical formula	(C₄H₁₁ClN)₂[CoCl₄]	(C₄H₁₁ClN)₂[ZnCl₄]
M_r	417.93	424.34
Crystal system, space group	Monoclinic, C2/c	Monoclinic, C2/c
Temperature (K)	295	295
a, b, c (Å)	12.7521 (6), 8.9648 (4), 16.6801 (10)	12.7297 (7), 8.9784 (5), 16.6837 (11)
β (°)	111.057 (1)	111.062 (2)
V (Å³)	1779.53 (16)	1779.43 (18)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.85	2.26
Crystal size (mm)	0.30 × 0.27 × 0.26	0.39 × 0.38 × 0.29

Data collection
Diffractometer	Bruker D8 Quest Eco	Bruker D8 Quest Eco
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.696, 0.746	0.472, 0.560
No. of measured, independent and observed [I > 2σ(I)] reflections	23748, 2041, 1676	46381, 2843, 2479
R_int	0.042	0.036
(sin θ/λ)_max (Å⁻¹)	0.650	0.725

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.064, 1.09	0.033, 0.070, 1.12
No. of reflections	2041	2843
No. of parameters	113	113
No. of restraints	1	1
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)	0.38, −0.29	0.57, −0.40
Computer programs: APEX3 and SAINT (Bruker, 2017 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick 2015b ), ORTEP-3 for Windows (Farrugia, 2012) and publCIF (Westrip, 2010 ).

Low angle reflections (four for CoCl₄²⁻ and one for ZnCl₄²⁻ salts) with F_o²<<F_c² were assumed to be blocked by the beam catcher and were omitted from the refinement. For the ZnCl₄²⁻ structure, APEX3 control software suggested a data-collection strategy to θmax = 36°. However data analysis (WinGX 2021.3; Farrugia, 2012 ) indicated <I/σ> less than 2.0 for reflections beyond θ = 30.6°. Thus reflection data beyond θ = 31° were omitted from the final refinement.

Supporting information

CCDC references: 2352359; 2352358

Crystal structure: contains datablocks global, cobaltate, zincate. DOI: https://doi.org/10.1107/S2056989024003955/ev2006sup1.cif

Structure factors: contains datablock cobaltate. DOI: https://doi.org/10.1107/S2056989024003955/ev2006cobaltatesup2.hkl

Structure factors: contains datablock zincate. DOI: https://doi.org/10.1107/S2056989024003955/ev2006zincatesup3.hkl

checkCIF report

Computing details top

Bis(2-chloro-N,N-dimethylethan-1-aminium) tetrachloridocobaltate(II) (cobaltate) top

Crystal data top

(C₄H₁₁ClN)₂[CoCl₄]	F(000) = 852
M_r = 417.93	D_x = 1.56 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9986 reflections
a = 12.7521 (6) Å	θ = 2.9–27.4°
b = 8.9648 (4) Å	µ = 1.85 mm⁻¹
c = 16.6801 (10) Å	T = 295 K
β = 111.057 (1)°	Gem, blue
V = 1779.53 (16) Å³	0.30 × 0.27 × 0.26 mm
Z = 4

Data collection top

Bruker D8 Quest Eco diffractometer	1676 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.042
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 27.5°, θ_min = 3.4°
T_min = 0.696, T_max = 0.746	h = −16→16
23748 measured reflections	k = −11→11
2041 independent reflections	l = −21→21

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)] = 0.030	w = 1/[σ²(F_o²) + (0.0202P)² + 2.2595P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.064	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 0.38 e Å⁻³
2041 reflections	Δρ_min = −0.29 e Å⁻³
113 parameters	Extinction correction: SHELXL2018/3 (Sheldrick 2015b)
1 restraint	Extinction coefficient: 0.0038 (3)
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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.5	0.77754 (4)	0.25	0.03399 (13)
Cl1	0.63314 (4)	0.92047 (6)	0.34886 (3)	0.04269 (15)
Cl2	0.40423 (5)	0.65066 (7)	0.31892 (4)	0.05376 (18)
N1	0.84438 (16)	0.6926 (2)	0.36634 (12)	0.0402 (4)
H1	0.775 (2)	0.725 (3)	0.3517 (17)	0.066 (8)*
C1	0.8515 (7)	0.5245 (5)	0.3673 (6)	0.0395 (13)	0.707 (2)
H1A	0.929586	0.496545	0.381431	0.047*	0.707 (2)
H1B	0.810217	0.488369	0.309775	0.047*	0.707 (2)
C2	0.8069 (3)	0.4440 (4)	0.4297 (2)	0.0465 (8)	0.707 (2)
H2A	0.848364	0.477204	0.487909	0.056*	0.707 (2)
H2B	0.818475	0.337488	0.427118	0.056*	0.707 (2)
Cl3	0.66156 (8)	0.48055 (11)	0.40385 (6)	0.0581 (3)	0.707 (2)
C1A	0.8273 (19)	0.5310 (12)	0.3788 (17)	0.055 (5)	0.293 (2)
H1AA	0.800336	0.479291	0.324113	0.066*	0.293 (2)
H1AB	0.897006	0.48509	0.415285	0.066*	0.293 (2)
C2A	0.7424 (9)	0.5258 (10)	0.4203 (6)	0.051 (2)	0.293 (2)
H2AA	0.672082	0.570241	0.383851	0.061*	0.293 (2)
H2AB	0.768918	0.576965	0.475201	0.061*	0.293 (2)
Cl3A	0.7270 (3)	0.3331 (3)	0.43356 (19)	0.0799 (11)	0.293 (2)
C3	0.8885 (2)	0.7413 (3)	0.29966 (17)	0.0572 (7)
H3A	0.885462	0.848115	0.295397	0.086*
H3B	0.843773	0.698591	0.245341	0.086*
H3C	0.964987	0.708767	0.315027	0.086*
C4	0.9070 (3)	0.7654 (3)	0.44973 (17)	0.0687 (8)
H4A	0.984779	0.737603	0.468255	0.103*
H4B	0.876356	0.733971	0.491816	0.103*
H4C	0.900302	0.871732	0.443083	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0301 (2)	0.0362 (2)	0.0354 (2)	0	0.01147 (16)	0
Cl1	0.0383 (3)	0.0475 (3)	0.0375 (3)	−0.0055 (2)	0.0078 (2)	−0.0033 (2)
Cl2	0.0611 (4)	0.0447 (3)	0.0666 (4)	−0.0097 (3)	0.0364 (3)	0.0013 (3)
N1	0.0339 (9)	0.0456 (11)	0.0413 (10)	0.0079 (8)	0.0137 (8)	−0.0021 (8)
C1	0.043 (4)	0.040 (2)	0.042 (3)	−0.0033 (16)	0.023 (2)	0.0027 (16)
C2	0.0492 (19)	0.0449 (19)	0.0467 (19)	0.0064 (16)	0.0188 (15)	0.0019 (16)
Cl3	0.0479 (6)	0.0665 (6)	0.0663 (6)	−0.0018 (4)	0.0280 (4)	−0.0007 (5)
C1A	0.038 (9)	0.086 (10)	0.047 (9)	−0.015 (6)	0.024 (5)	0.001 (6)
C2A	0.062 (6)	0.047 (5)	0.048 (5)	0.004 (5)	0.025 (4)	0.009 (4)
Cl3A	0.113 (2)	0.0584 (16)	0.0850 (19)	−0.0153 (14)	0.0554 (17)	0.0128 (13)
C3	0.0704 (17)	0.0520 (15)	0.0552 (15)	−0.0085 (13)	0.0297 (13)	0.0012 (12)
C4	0.081 (2)	0.0703 (19)	0.0485 (15)	0.0016 (15)	0.0150 (14)	−0.0161 (14)

Geometric parameters (Å, º) top

Co1—Cl1	2.2873 (6)	C1—H1B	0.97
Co1—Cl2	2.2618 (6)	C1—C2	1.534 (6)
N1—C3	1.482 (3)	C2—H2A	0.97
C3—H3A	0.96	C2—H2B	0.97
C3—H3B	0.96	C2—Cl3	1.776 (3)
C3—H3C	0.96	N1—C1A	1.490 (10)
N1—C4	1.483 (3)	C1A—H1AA	0.97
C4—H4A	0.96	C1A—H1AB	0.97
C4—H4B	0.96	C1A—C2A	1.480 (15)
C4—H4C	0.96	C2A—H2AA	0.97
N1—H1	0.87 (3)	C2A—H2AB	0.97
N1—C1	1.509 (5)	C2A—Cl3A	1.762 (9)
C1—H1A	0.97

Cl1ⁱ—Co1—Cl1	111.86 (3)	C2—C1—H1A	108.2
Cl1—Co1—Cl2	108.17 (2)	N1—C1—H1B	108.2
Cl1—Co1—Cl2ⁱ	104.58 (2)	C2—C1—H1B	108.2
Cl2ⁱ—Co1—Cl2	119.62 (4)	H1A—C1—H1B	107.4
C3—N1—C4	110.6 (2)	C1—C2—Cl3	111.0 (4)
N1—C3—H3A	109.5	C1—C2—H2A	109.4
N1—C3—H3B	109.5	Cl3—C2—H2A	109.4
H3A—C3—H3B	109.5	C1—C2—H2B	109.4
N1—C3—H3C	109.5	Cl3—C2—H2B	109.4
H3A—C3—H3C	109.5	H2A—C2—H2B	108
H3B—C3—H3C	109.5	C3—N1—C1A	120.4 (7)
N1—C4—H4A	109.5	C4—N1—C1A	110.7 (11)
N1—C4—H4B	109.5	C2A—C1A—N1	105.3 (9)
H4A—C4—H4B	109.5	C2A—C1A—H1AA	110.7
N1—C4—H4C	109.5	N1—C1A—H1AA	110.7
H4A—C4—H4C	109.5	C2A—C1A—H1AB	110.7
H4B—C4—H4C	109.5	N1—C1A—H1AB	110.7
C3—N1—C1	105.4 (3)	H1AA—C1A—H1AB	108.8
C4—N1—C1	114.8 (4)	C1A—C2A—Cl3A	102.9 (7)
C3—N1—H1	108.0 (18)	C1A—C2A—H2AA	111.2
C4—N1—H1	105.3 (18)	Cl3A—C2A—H2AA	111.2
C1A—N1—H1	100 (2)	C1A—C2A—H2AB	111.2
C1—N1—H1	112.6 (19)	Cl3A—C2A—H2AB	111.2
N1—C1—C2	116.2 (5)	H2AA—C2A—H2AB	109.1
N1—C1—H1A	108.2

C3—N1—C1—C2	−178.1 (5)	C3—N1—C1A—C2A	−156.9 (10)
C4—N1—C1—C2	59.9 (7)	C4—N1—C1A—C2A	71.9 (16)
N1—C1—C2—Cl3	61.6 (7)	N1—C1A—C2A—Cl3A	−179.7 (13)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.87 (3)	2.51 (3)	3.3093 (19)	152 (2)
N1—H1···Cl2ⁱ	0.87 (3)	3.02 (3)	3.564 (2)	122 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Bis(2-chloro-N,N-dimethylethan-1-aminium) tetrachloridozincate(II) (zincate) top

Crystal data top

(C₄H₁₁ClN)₂[ZnCl₄]	F(000) = 864
M_r = 424.34	D_x = 1.584 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9979 reflections
a = 12.7297 (7) Å	θ = 2.8–33.7°
b = 8.9784 (5) Å	µ = 2.26 mm⁻¹
c = 16.6837 (11) Å	T = 295 K
β = 111.062 (2)°	Irregular, colourless
V = 1779.43 (18) Å³	0.39 × 0.38 × 0.29 mm
Z = 4

Data collection top

Bruker D8 Quest Eco diffractometer	2479 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.036
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 31.0°, θ_min = 3.4°
T_min = 0.472, T_max = 0.560	h = −18→18
46381 measured reflections	k = −12→12
2843 independent reflections	l = −24→24

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)] = 0.033	w = 1/[σ²(F_o²) + (0.0155P)² + 3.2372P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.070	(Δ/σ)_max = 0.001
S = 1.12	Δρ_max = 0.57 e Å⁻³
2843 reflections	Δρ_min = −0.40 e Å⁻³
113 parameters	Extinction correction: SHELXL2018/3 (Sheldrick 2015b)
1 restraint	Extinction coefficient: 0.0035 (3)
Primary atom site location: dual

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zn1	0.5	0.72176 (4)	0.25	0.03333 (10)
Cl1	0.63307 (4)	0.57810 (6)	0.34859 (3)	0.04085 (12)
Cl2	0.40494 (5)	0.84939 (6)	0.31868 (4)	0.05219 (15)
N1	0.15576 (15)	0.8071 (2)	0.13379 (11)	0.0396 (4)
H1	0.223 (2)	0.770 (3)	0.1486 (17)	0.055 (7)*
C1	0.1482 (5)	0.9756 (5)	0.1328 (5)	0.0393 (10)	0.697 (2)
H1A	0.189643	1.011624	0.190345	0.047*	0.697 (2)
H1B	0.069934	1.003059	0.118912	0.047*	0.697 (2)
C2	0.1923 (3)	1.0567 (4)	0.0703 (2)	0.0451 (7)	0.697 (2)
H2A	0.180985	1.163084	0.073337	0.054*	0.697 (2)
H2B	0.15046	1.024182	0.012066	0.054*	0.697 (2)
Cl3	0.33801 (8)	1.01959 (11)	0.09585 (6)	0.0569 (3)	0.697 (2)
C1A	0.1726 (14)	0.9672 (11)	0.1224 (12)	0.052 (4)	0.303 (2)
H1C	0.200388	1.01761	0.177512	0.063*	0.303 (2)
H1D	0.102578	1.01361	0.086803	0.063*	0.303 (2)
C2A	0.2568 (7)	0.9742 (9)	0.0801 (5)	0.0480 (18)	0.303 (2)
H2C	0.229594	0.923437	0.025068	0.058*	0.303 (2)
H2D	0.32746	0.929578	0.115896	0.058*	0.303 (2)
Cl3A	0.2728 (3)	1.1668 (3)	0.06669 (18)	0.0773 (9)	0.303 (2)
C3	0.1113 (2)	0.7582 (3)	0.20017 (16)	0.0552 (6)
H3A	0.034943	0.791657	0.185019	0.083*
H3B	0.156482	0.799774	0.254694	0.083*
H3C	0.113532	0.65148	0.203863	0.083*
C4	0.0928 (3)	0.7347 (3)	0.05022 (17)	0.0675 (8)
H4A	0.10053	0.628507	0.056467	0.101*
H4B	0.122638	0.767543	0.007913	0.101*
H4C	0.014696	0.761126	0.032261	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02977 (15)	0.03496 (17)	0.03503 (17)	0	0.01136 (12)	0
Cl1	0.0366 (2)	0.0455 (3)	0.0358 (2)	0.00580 (19)	0.00738 (18)	0.00353 (19)
Cl2	0.0601 (3)	0.0429 (3)	0.0653 (4)	0.0098 (2)	0.0367 (3)	−0.0012 (2)
N1	0.0331 (8)	0.0453 (10)	0.0401 (9)	0.0091 (7)	0.0129 (7)	−0.0022 (7)
C1	0.042 (3)	0.0422 (18)	0.040 (2)	−0.0022 (15)	0.0234 (18)	0.0028 (14)
C2	0.0476 (16)	0.0459 (17)	0.0437 (16)	0.0085 (14)	0.0186 (13)	0.0044 (13)
Cl3	0.0477 (5)	0.0645 (6)	0.0649 (6)	−0.0009 (4)	0.0280 (4)	0.0002 (4)
C1A	0.042 (7)	0.083 (8)	0.043 (6)	−0.022 (5)	0.027 (4)	−0.003 (5)
C2A	0.055 (5)	0.052 (4)	0.042 (4)	0.001 (4)	0.023 (3)	0.008 (3)
Cl3A	0.110 (2)	0.0557 (13)	0.0823 (17)	−0.0148 (13)	0.0536 (16)	0.0132 (12)
C3	0.0694 (16)	0.0485 (13)	0.0532 (13)	−0.0096 (11)	0.0288 (12)	0.0008 (10)
C4	0.0780 (19)	0.0693 (18)	0.0481 (13)	0.0019 (15)	0.0139 (13)	−0.0172 (13)

Geometric parameters (Å, º) top

Zn1—Cl2	2.2553 (5)	C2—H2B	0.97
Zn1—Cl2ⁱ	2.2554 (5)	C1A—C2A	1.481 (12)
Zn1—Cl1ⁱ	2.2883 (5)	C1A—H1C	0.97
Zn1—Cl1	2.2883 (5)	C1A—H1D	0.97
N1—C1A	1.476 (9)	C2A—Cl3A	1.765 (8)
N1—C3	1.480 (3)	C2A—H2C	0.97
N1—C4	1.485 (3)	C2A—H2D	0.97
N1—C1	1.515 (5)	C3—H3A	0.96
N1—H1	0.87 (3)	C3—H3B	0.96
C1—C2	1.535 (5)	C3—H3C	0.96
C1—H1A	0.97	C4—H4A	0.96
C1—H1B	0.97	C4—H4B	0.96
C2—Cl3	1.779 (3)	C4—H4C	0.96
C2—H2A	0.97

Cl2—Zn1—Cl2ⁱ	118.93 (3)	H2A—C2—H2B	108.1
Cl2—Zn1—Cl1ⁱ	104.94 (2)	N1—C1A—C2A	105.4 (7)
Cl2ⁱ—Zn1—Cl1ⁱ	108.36 (2)	N1—C1A—H1C	110.7
Cl2—Zn1—Cl1	108.36 (2)	C2A—C1A—H1C	110.7
Cl2ⁱ—Zn1—Cl1	104.94 (2)	N1—C1A—H1D	110.7
Cl1ⁱ—Zn1—Cl1	111.38 (3)	C2A—C1A—H1D	110.7
C1A—N1—C3	119.8 (5)	H1C—C1A—H1D	108.8
C1A—N1—C4	111.1 (8)	C1A—C2A—Cl3A	103.8 (6)
C3—N1—C4	110.5 (2)	C1A—C2A—H2C	111
C3—N1—C1	105.3 (2)	Cl3A—C2A—H2C	111
C4—N1—C1	114.6 (3)	C1A—C2A—H2D	111
C1A—N1—H1	103.7 (19)	Cl3A—C2A—H2D	111
C3—N1—H1	106.0 (18)	H2C—C2A—H2D	109
C4—N1—H1	104.1 (18)	N1—C3—H3A	109.5
C1—N1—H1	116.1 (18)	N1—C3—H3B	109.5
N1—C1—C2	116.3 (4)	H3A—C3—H3B	109.5
N1—C1—H1A	108.2	N1—C3—H3C	109.5
C2—C1—H1A	108.2	H3A—C3—H3C	109.5
N1—C1—H1B	108.2	H3B—C3—H3C	109.5
C2—C1—H1B	108.2	N1—C4—H4A	109.5
H1A—C1—H1B	107.4	N1—C4—H4B	109.5
C1—C2—Cl3	110.7 (3)	H4A—C4—H4B	109.5
C1—C2—H2A	109.5	N1—C4—H4C	109.5
Cl3—C2—H2A	109.5	H4A—C4—H4C	109.5
C1—C2—H2B	109.5	H4B—C4—H4C	109.5
Cl3—C2—H2B	109.5

C3—N1—C1—C2	178.5 (4)	C3—N1—C1A—C2A	157.7 (7)
C4—N1—C1—C2	−59.9 (6)	C4—N1—C1A—C2A	−71.4 (12)
N1—C1—C2—Cl3	−61.3 (6)	N1—C1A—C2A—Cl3A	179.3 (9)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1ⁱ	0.87 (3)	2.51 (3)	3.3124 (18)	156 (2)
N1—H1···Cl2	0.87 (3)	3.03 (3)	3.5620 (19)	121 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Acknowledgements

The authors thank Ms Annette Drury for assistance in preparation of the ZnCl₄²⁻ salt.

References

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(2-chloro-N,N-di­methyl­ethan-1-aminium) tetra­chlorido­cobaltate(II) and tetra­chlorido­zincate(II)

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Bis(2-chloro-N,N-dimethylethan-1-aminium) tetrachloridocobaltate(II) and tetrachloridozincate(II)

3. Supramolecular features