Effect of the transition metal on the structure and order–disorder phase transition in layered hybrid metal halides (CH₃CH₂NH₃)₂[MCl₄] (M = Mn and Co)

Layered hybrid organic–inorganic metal halides (CH₃CH₂NH₃)₂[MnCl₄] and (CH₃CH₂NH₃)₂[CoCl₄] were synthesized by the slow evaporation method to understand the relationship between the crystal structure and order–disorder phase transition. Calorimetric data and crystal structure determination across the phase transition temperature establish the order–disorder phase transition. (CH₃CH₂NH₃)₂[MnCl₄] undergoes the reversible structural phase transition from tetragonal I4/mmm to orthorhombic Pbca at 212/222 K (cooling/heating), whereas (CH₃CH₂NH₃)₂CoCl₄ demonstrates the phase transition at 220/239 K from orthorhombic Pnma to orthorhombic P2₁2₁2₁. Both compounds are characterized by disordered ethyl ammonium cations in the structure above the phase transition temperature, whereas they become ordered cations at temperatures below the phase transition. Dielectric results further support the observed structural phase transitions. Additionally, magnetic measurements show canted antiferromagnetic characteristics for (CH₃CH₂NH₃)₂[MnCl₄] and paramagnetic behaviour is observed for (CH₃CH₂NH₃)₂[CoCl₄]. The structural differences, the role of intermolecular interactions and the effect of transition metals on the phase transition were evaluated using Hirshfeld surface analysis and the topological properties of electron density distributions. An accurate description of the structure and intermolecular interactions is crucial for understanding the physical properties and designing multifunctional hybrid organic–inorganic metal halide perovskites.

Computing details

(EAMn_HT)

Crystal data

Cl4Mn·2(C2H8N)	Dx = 1.564 Mg m^−3
Mr = 288.93	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4/mmm	Cell parameters from 1456 reflections
a = 5.1748 (5) Å	θ = 3.7–25.2°
c = 22.112 (3) Å	µ = 1.97 mm^−1
V = 592.12 (14) Å^3	T = 296 K
Z = 2	Block, pink
F(000) = 274	0.27 × 0.24 × 0.21 mm

Data collection

Bruker D8 Quest diffractometer	259 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.025
Absorption correction: multi-scan SADABS	θmax = 28.3°, θmin = 3.7°
Tmin = 0.619, Tmax = 0.683	h = −6→6
3486 measured reflections	k = −6→6
259 independent reflections	l = −29→29

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	All H-atom parameters refined
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0314P)^2 + 2.2579P] where P = (Fo^2 + 2Fc^2)/3
S = 1.19	(Δ/σ)max < 0.001
259 reflections	Δρmax = 0.59 e Å^−3
25 parameters	Δρmin = −0.46 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.5000	0.5000	0.5000	0.0242 (4)
Cl1	0.5000	0.0000	0.5000	0.0580 (7)
Cl2	0.5000	0.5000	0.38897 (9)	0.0837 (10)
N1	0.0000	0.0000	0.3985 (3)	0.0491 (18)
C1	0.0000	0.091 (3)	0.3371 (8)	0.059 (6)	0.25
C2	0.0000	−0.109 (5)	0.2904 (6)	0.083 (11)	0.25
H2	0.0000	0.0000	0.262 (6)	0.08 (4)*
H1	0.097 (14)	0.097 (14)	0.411 (5)	0.00 (3)*	0.25
H1A	0.08 (3)	0.23 (3)	0.338 (6)	0.00 (3)*	0.125

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0206 (5)	0.0206 (5)	0.0313 (7)	0.000	0.000	0.000
Cl1	0.0333 (10)	0.0183 (8)	0.122 (2)	0.000	0.000	0.000
Cl2	0.1108 (16)	0.1108 (16)	0.0296 (9)	0.000	0.000	0.000
N1	0.053 (3)	0.053 (3)	0.041 (4)	0.000	0.000	0.000
C1	0.081 (15)	0.040 (9)	0.057 (8)	0.000	0.000	0.010 (7)
C2	0.14 (3)	0.072 (14)	0.037 (5)	0.000	0.000	−0.004 (8)

Geometric parameters (Å, º)

Mn1—Cl1^i	2.5874 (3)	C1—C1^vi	0.67 (3)
Mn1—Cl1^ii	2.5874 (3)	C1—C2^vii	1.04 (2)
Mn1—Cl1^iii	2.5874 (3)	C1—C2^ii	1.27 (2)
Mn1—Cl1	2.5874 (3)	C1—C2	1.46 (3)
Mn1—Cl2	2.455 (2)	C1—C2^vi	1.27 (2)
Mn1—Cl2^iv	2.455 (2)	C1—H1A	0.86 (15)
Cl1—Mn1^v	2.5874 (3)	C2—C1^vi	1.27 (2)
N1—C1^ii	1.438 (18)	C2—C1^ii	1.27 (2)
N1—C1^vi	1.438 (18)	C2—C1^vii	1.04 (2)
N1—C1^vii	1.438 (18)	C2—C2^vi	0.80 (4)
N1—C1	1.438 (18)	C2—C2^vii	1.12 (5)
N1—H1	0.76 (10)	C2—C2^ii	0.80 (4)
C1—C1^vii	0.94 (4)	C2—H2	0.85 (9)
C1—C1^ii	0.67 (3)
Cl1—Mn1—Cl1^iii	180.0	C1^vi—C1—C2	60.0 (6)
Cl1^ii—Mn1—Cl1^i	180.0	C1^vii—C1—H1A	149 (8)
Cl1^iii—Mn1—Cl1^i	90.0	C1^vi—C1—H1A	104 (9)
Cl1—Mn1—Cl1^ii	90.0	C1^ii—C1—H1A	166 (8)
Cl1^iii—Mn1—Cl1^ii	90.0	C2^vi—C1—N1	130.3 (13)
Cl1—Mn1—Cl1^i	90.0	C2^ii—C1—N1	130.3 (13)
Cl2—Mn1—Cl1^ii	90.0	C2^vii—C1—N1	166 (2)
Cl2^iv—Mn1—Cl1^i	90.0	C2^ii—C1—C2	32.9 (14)
Cl2^iv—Mn1—Cl1^iii	90.0	C2^vi—C1—C2	32.9 (14)
Cl2^iv—Mn1—Cl1^ii	90.0	C2^vii—C1—C2^vi	38.8 (19)
Cl2—Mn1—Cl1^iii	90.0	C2^vii—C1—C2^ii	38.8 (19)
Cl2—Mn1—Cl1	90.0	C2^vi—C1—C2^ii	53 (2)
Cl2^iv—Mn1—Cl1	90.0	C2^vii—C1—C2	50 (2)
Cl2—Mn1—Cl1^i	90.0	C2^ii—C1—H1A	96 (9)
Cl2—Mn1—Cl2^iv	180.0	C2^vi—C1—H1A	124 (10)
Mn1^v—Cl1—Mn1	180.0	C2—C1—H1A	128 (9)
C1^ii—N1—C1^vii	26.9 (10)	C2^vii—C1—H1A	87 (9)
C1^vi—N1—C1	26.9 (10)	C1^ii—C2—C1	27.2 (10)
C1^ii—N1—C1	26.9 (10)	C1^vii—C2—C1	40.1 (17)
C1^ii—N1—C1^vi	38.4 (15)	C1^vi—C2—C1	27.2 (10)
C1^vii—N1—C1^vi	26.9 (10)	C1^vi—C2—C1^ii	43.8 (17)
C1^vii—N1—C1	38.4 (15)	C1^vii—C2—C1^ii	31.7 (13)
C1^ii—N1—H1	124 (8)	C1^vii—C2—C1^vi	31.7 (13)
C1^vi—N1—H1	98 (8)	C1^vii—C2—C2^vii	85.0 (18)
C1^vii—N1—H1	124 (8)	C1^ii—C2—H2	109 (6)
C1—N1—H1	98 (8)	C1—C2—H2	94 (7)
N1—C1—C2	115.8 (15)	C1^vii—C2—H2	134 (7)
N1—C1—H1A	105 (9)	C1^vi—C2—H2	109 (6)
C1^vii—C1—N1	70.8 (7)	C2^vi—C2—C1^ii	54.7 (10)
C1^vi—C1—N1	76.6 (5)	C2^vii—C2—C1^vi	63.7 (12)
C1^ii—C1—N1	76.6 (5)	C2^vii—C2—C1	45.0 (11)
C1^ii—C1—C1^vi	90.002 (13)	C2^vi—C2—C1^vi	87.1 (10)
C1^ii—C1—C1^vii	45.001 (7)	C2^vi—C2—C1^vii	86.5 (13)
C1^vi—C1—C1^vii	45.001 (10)	C2^ii—C2—C1^vi	54.7 (10)
C1^vii—C1—C2^vi	68.1 (8)	C2^ii—C2—C1^ii	87.1 (10)
C1^ii—C1—C2	60.0 (6)	C2^ii—C2—C1	60.0 (6)
C1^vi—C1—C2^vii	93.5 (13)	C2^vii—C2—C1^ii	63.7 (12)
C1^ii—C1—C2^ii	92.9 (10)	C2^ii—C2—C1^vii	86.5 (13)
C1^ii—C1—C2^vii	93.5 (13)	C2^vi—C2—C1	60.0 (6)
C1^vi—C1—C2^ii	54.7 (10)	C2^ii—C2—C2^vi	89.998 (11)
C1^vi—C1—C2^vi	92.9 (10)	C2^vi—C2—C2^vii	44.999 (7)
C1^vii—C1—C2^ii	68.1 (8)	C2^ii—C2—C2^vii	44.999 (7)
C1^vii—C1—C2	45.0 (11)	C2^vi—C2—H2	62 (4)
C1^vii—C1—C2^vii	95.0 (18)	C2^ii—C2—H2	62 (4)
C1^ii—C1—C2^vi	54.7 (10)	C2^vii—C2—H2	49 (6)
N1—C1—C2—C1^ii	54.8 (5)	C1^vi—C1—C2—C1^vii	54.8 (5)
N1—C1—C2—C1^vi	−54.8 (5)	C1^vii—C1—C2—C1^ii	54.8 (5)
N1—C1—C2—C1^vii	0.000 (6)	C1^ii—C1—C2—C1^vi	−109.5 (11)
N1—C1—C2—C2^vi	125.2 (5)	C1^vi—C1—C2—C2^vi	180.002 (14)
N1—C1—C2—C2^ii	−125.2 (5)	C1^vii—C1—C2—C2^ii	−125.2 (5)
N1—C1—C2—C2^vii	180.000 (5)	C1^ii—C1—C2—C2^vii	125.2 (5)
C1^vii—N1—C1—C1^ii	46.64 (13)	C1^vii—C1—C2—C2^vii	180.000 (11)
C1^ii—N1—C1—C1^vii	−46.64 (12)	C1^ii—C1—C2—C2^vi	70.5 (11)
C1^vii—N1—C1—C1^vi	−46.64 (13)	C1^ii—C1—C2—C2^ii	179.998 (4)
C1^vi—N1—C1—C1^ii	93.3 (3)	C1^vi—C1—C2—C2^ii	−70.5 (10)
C1^vi—N1—C1—C1^vii	46.64 (13)	C1^vi—C1—C2—C2^vii	−125.2 (5)
C1^ii—N1—C1—C1^vi	−93.3 (3)	C1^vii—C1—C2—C2^vi	125.2 (5)
C1^vi—N1—C1—C2	46.64 (12)	C2^vii—C1—C2—C1^vii	180.000 (13)
C1^ii—N1—C1—C2	−46.64 (13)	C2^vi—C1—C2—C1^vi	179.998 (5)
C1^vii—N1—C1—C2^vii	0.00 (3)	C2^vi—C1—C2—C1^ii	−70.5 (10)
C1^ii—N1—C1—C2^vii	−46.64 (12)	C2^vi—C1—C2—C1^vii	−125.2 (5)
C1^vii—N1—C1—C2^ii	−35.6 (17)	C2^vii—C1—C2—C1^ii	−125.2 (5)
C1^vi—N1—C1—C2^vii	46.64 (13)	C2^ii—C1—C2—C1^vii	125.2 (5)
C1^vi—N1—C1—C2^ii	11.0 (18)	C2^ii—C1—C2—C1^ii	180.002 (4)
C1^vii—N1—C1—C2^vi	35.6 (17)	C2^vii—C1—C2—C1^vi	125.2 (5)
C1^vii—N1—C1—C2	0.000 (5)	C2^ii—C1—C2—C1^vi	70.5 (10)
C1^vi—N1—C1—C2^vi	82.2 (16)	C2^vii—C1—C2—C2^ii	54.8 (5)
C1^ii—N1—C1—C2^ii	−82.2 (16)	C2^vii—C1—C2—C2^vi	−54.8 (5)
C1^ii—N1—C1—C2^vi	−11.0 (18)	C2^vi—C1—C2—C2^vii	54.8 (5)
C1^ii—C1—C2—C1^vii	−54.8 (5)	C2^vi—C1—C2—C2^ii	109.5 (10)
C1^vii—C1—C2—C1^vi	−54.8 (5)	C2^ii—C1—C2—C2^vi	−109.5 (11)
C1^vi—C1—C2—C1^ii	109.5 (10)	C2^ii—C1—C2—C2^vii	−54.8 (5)

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

(EAMn_LT)

Crystal data

Cl4Mn·2(C2H8N)	Dx = 1.657 Mg m^−3
Mr = 288.93	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 2418 reflections
a = 7.3088 (3) Å	θ = 3.3–25.2°
b = 7.1675 (3) Å	µ = 2.01 mm^−1
c = 22.1136 (10) Å	T = 150 K
V = 1158.44 (9) Å^3	Block, pink
Z = 4	0.27 × 0.24 × 0.21 mm
F(000) = 588

Data collection

Bruker D8 Quest diffractometer	1344 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.033
Absorption correction: multi-scan SADABS	θmax = 28.3°, θmin = 3.3°
Tmin = 0.613, Tmax = 0.677	h = −8→9
15025 measured reflections	k = −9→9
1423 independent reflections	l = −28→29

Refinement

Refinement on F^2	8 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	All H-atom parameters refined
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0223P)^2 + 2.3097P] where P = (Fo^2 + 2Fc^2)/3
S = 1.22	(Δ/σ)max = 0.001
1423 reflections	Δρmax = 0.48 e Å^−3
84 parameters	Δρmin = −0.44 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.0557 (3)	0.4704 (3)	0.33553 (11)	0.0249 (5)
C2	0.0525 (3)	0.5608 (3)	0.28616 (10)	0.0351 (7)
Cl1	0.45891 (8)	0.48681 (8)	0.38841 (2)	0.01737 (14)
Cl2	0.73185 (7)	0.76770 (7)	0.48886 (2)	0.01487 (14)
Mn1	0.5000	0.5000	0.5000	0.00984 (13)
N1	0.0167 (2)	0.5194 (2)	0.39633 (8)	0.0184 (4)
H1C	0.1538 (4)	0.490 (2)	0.4026 (9)	0.065 (13)*
H1D	−0.0522 (9)	0.4534 (10)	0.4311 (2)	0.057 (12)*
H1E	0.004 (4)	0.6606 (4)	0.4048 (7)	0.059 (12)*
H1A	−0.042 (4)	0.3194 (4)	0.3308 (11)	0.059 (12)*
H1B	−0.1974 (4)	0.5187 (13)	0.3348 (19)	0.064 (13)*
H2A	−0.0082 (10)	0.534 (2)	0.24360 (16)	0.036 (9)*
H2B	0.038 (4)	0.7070 (4)	0.2911 (11)	0.064 (13)*
H2C	0.1896 (4)	0.5140 (13)	0.2895 (15)	0.079 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0258 (12)	0.0326 (13)	0.0162 (12)	−0.0094 (11)	−0.0038 (9)	−0.0009 (10)
C2	0.0398 (16)	0.0517 (18)	0.0139 (12)	−0.0148 (15)	0.0000 (11)	0.0025 (12)
Cl1	0.0169 (3)	0.0237 (3)	0.0115 (3)	0.0002 (2)	−0.00029 (18)	0.0006 (2)
Cl2	0.0122 (2)	0.0122 (2)	0.0202 (3)	−0.00313 (18)	0.00037 (19)	0.00007 (19)
Mn1	0.0091 (2)	0.0097 (2)	0.0108 (2)	−0.00029 (16)	−0.00046 (15)	−0.00036 (15)
N1	0.0191 (9)	0.0223 (10)	0.0137 (9)	0.0006 (8)	0.0023 (7)	−0.0010 (8)

Geometric parameters (Å, º)

C1—N1	1.487 (3)	Cl2—Mn1^i	2.5834 (5)
C1—C2	1.496 (3)	Mn1—Cl1^ii	2.4877 (5)
C1—H1A	1.0920 (1)	Mn1—Cl2^ii	2.5717 (5)
C1—H1B	1.0920 (1)	Mn1—Cl2^iii	2.5834 (5)
C2—H2A	1.0590 (1)	Mn1—Cl2^iv	2.5834 (5)
C2—H2B	1.0590 (1)	N1—H1C	1.0330 (1)
C2—H2C	1.0590 (2)	N1—H1D	1.0330 (1)
Cl1—Mn1	2.4877 (5)	N1—H1E	1.0330 (2)
Cl2—Mn1	2.5717 (5)
N1—C1—C2	111.66 (17)	Cl1—Mn1—Cl2	90.740 (17)
N1—C1—H1A	106.8 (15)	Cl2^ii—Mn1—Cl2	180.0
C2—C1—H1A	108.1 (12)	Cl1^ii—Mn1—Cl2^iii	91.574 (17)
N1—C1—H1B	106 (2)	Cl1—Mn1—Cl2^iii	88.426 (17)
C2—C1—H1B	110.7 (17)	Cl2^ii—Mn1—Cl2^iii	91.613 (4)
H1A—C1—H1B	113.6 (15)	Cl2—Mn1—Cl2^iii	88.387 (4)
C1—C2—H2A	110.3 (5)	Cl1^ii—Mn1—Cl2^iv	88.426 (17)
C1—C2—H2B	107.6 (12)	Cl1—Mn1—Cl2^iv	91.574 (17)
H2A—C2—H2B	103.5 (18)	Cl2^ii—Mn1—Cl2^iv	88.387 (4)
C1—C2—H2C	108.2 (14)	Cl2—Mn1—Cl2^iv	91.613 (4)
H2A—C2—H2C	113.6 (19)	Cl2^iii—Mn1—Cl2^iv	180.00 (2)
H2B—C2—H2C	113.4 (16)	C1—N1—H1C	114.7 (12)
Mn1—Cl2—Mn1^i	166.31 (2)	C1—N1—H1D	113.0 (4)
Cl1^ii—Mn1—Cl1	180.0	H1C—N1—H1D	106.2 (10)
Cl1^ii—Mn1—Cl2^ii	90.741 (17)	C1—N1—H1E	111.4 (12)
Cl1—Mn1—Cl2^ii	89.260 (17)	H1C—N1—H1E	105.1 (18)
Cl1^ii—Mn1—Cl2	89.260 (17)	H1D—N1—H1E	105.8 (10)

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

(EACo_HT)

Crystal data

Cl4Co·2(C2H8N)	Dx = 1.446 Mg m^−3
Mr = 292.92	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1853 reflections
a = 10.0173 (5) Å	θ = 3.1–25.2°
b = 7.4027 (4) Å	µ = 2.09 mm^−1
c = 17.5837 (8) Å	T = 296 K
V = 1303.92 (11) Å^3	Block
Z = 4	0.24 × 0.19 × 0.18 mm
F(000) = 560

Data collection

Bruker D8 Quest diffractometer	θmax = 28.3°, θmin = 3.1°
12094 measured reflections	h = −13→10
1732 independent reflections	k = −9→9
1199 reflections with I > 2σ(I)	l = −23→18
Rint = 0.035

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.062	w = 1/[σ^2(Fo^2) + (0.1098P)^2 + 1.2926P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.208	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.56 e Å^−3
1732 reflections	Δρmin = −0.49 e Å^−3
81 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
28 restraints	Extinction coefficient: 0.019 (5)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.77171 (9)	0.7500	0.54093 (5)	0.0677 (4)
Cl1	0.9893 (2)	0.7500	0.56926 (13)	0.1121 (9)
Cl2	0.7379 (15)	0.7500	0.4153 (9)	0.097 (5)	0.5
Cl2'	0.7462 (12)	0.817 (2)	0.4122 (8)	0.068 (2)	0.25
Cl3	0.66928 (17)	0.50209 (17)	0.58768 (10)	0.1031 (6)
N1	1.0623 (7)	0.7500	0.3842 (3)	0.0928 (19)
H1A	1.1158	0.6670	0.4044	0.139*	0.5
H1B	0.9779	0.7247	0.3960	0.139*	0.5
H1C	1.0836	0.8583	0.4025	0.139*	0.5
N2	0.3728 (9)	0.7500	0.5693 (4)	0.118 (3)
C1	1.0774 (16)	0.7500	0.3046 (5)	0.226 (11)
H1D	1.0870	0.6255	0.2883	0.271*	0.5
H1E	1.1621	0.8097	0.2956	0.271*	0.5
C2	0.9746 (16)	0.830 (2)	0.2556 (7)	0.153 (8)	0.5
C3	0.3322 (16)	0.8349 (19)	0.6315 (7)	0.132 (5)	0.5
H3A	0.2530	0.9057	0.6207	0.158*	0.5
H3B	0.4029	0.9214	0.6412	0.158*	0.5
C4	0.310 (2)	0.7500	0.7080 (7)	0.172 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0707 (6)	0.0544 (6)	0.0779 (7)	0.000	0.0015 (4)	0.000
Cl1	0.0746 (12)	0.166 (2)	0.0962 (14)	0.000	−0.0201 (10)	0.000
Cl2	0.087 (5)	0.121 (14)	0.082 (4)	0.000	−0.019 (3)	0.000
Cl2'	0.069 (4)	0.059 (4)	0.077 (4)	0.005 (4)	−0.006 (3)	0.006 (4)
Cl3	0.1064 (11)	0.0557 (8)	0.1472 (14)	−0.0044 (6)	0.0223 (10)	0.0147 (8)
N1	0.075 (4)	0.137 (6)	0.066 (3)	0.000	−0.004 (3)	0.000
N2	0.127 (7)	0.144 (7)	0.084 (4)	0.000	−0.022 (4)	0.000
C1	0.170 (13)	0.42 (3)	0.086 (7)	0.000	0.005 (8)	0.000
C2	0.188 (16)	0.19 (2)	0.078 (7)	−0.051 (13)	−0.005 (9)	0.030 (8)
C3	0.119 (8)	0.123 (8)	0.152 (9)	−0.017 (7)	0.013 (7)	−0.023 (7)
C4	0.27 (2)	0.117 (9)	0.125 (9)	0.000	−0.026 (11)	0.000

Geometric parameters (Å, º)

Co1—Cl1	2.236 (2)	N2—C3	1.326 (9)
Co1—Cl2	2.234 (15)	C1—H1D	0.9700
Co1—Cl2'	2.330 (13)	C1—H1E	0.9700
Co1—Cl2'^i	2.330 (13)	C1—C2^i	1.467 (9)
Co1—Cl3^i	2.2576 (14)	C1—C2	1.467 (9)
Co1—Cl3	2.2576 (14)	C2—C2^i	1.19 (4)
Cl2'—Cl2'^i	0.99 (3)	C3—C3^i	1.26 (3)
N1—H1A	0.8900	C3—H3A	0.9700
N1—H1B	0.8900	C3—H3B	0.9700
N1—H1C	0.8900	C3—C4	1.501 (9)
N1—C1	1.408 (8)	C4—C3^i	1.501 (9)
N2—C3^i	1.326 (9)
Cl1—Co1—Cl2'^i	108.9 (3)	N1—C1—H1E	104.8
Cl1—Co1—Cl2'	108.9 (3)	N1—C1—C2	120.5 (10)
Cl1—Co1—Cl3^i	111.22 (6)	N1—C1—C2^i	120.5 (10)
Cl1—Co1—Cl3	111.22 (6)	H1D—C1—H1E	107.3
Cl2—Co1—Cl1	111.6 (4)	C2^i—C1—H1D	60.8
Cl2—Co1—Cl3	106.9 (2)	C2—C1—H1D	106.3
Cl2—Co1—Cl3^i	106.9 (2)	C2—C1—H1E	109.5
Cl2'—Co1—Cl2'^i	24.6 (8)	C2^i—C1—H1E	134.6
Cl3^i—Co1—Cl2'^i	118.5 (4)	C2^i—C1—C2	47.7 (15)
Cl3—Co1—Cl2'	118.5 (4)	C2^i—C2—C1	66.1 (7)
Cl3^i—Co1—Cl2'	97.5 (4)	N2—C3—H3A	110.2
Cl3—Co1—Cl2'^i	97.5 (4)	N2—C3—H3B	103.5
Cl3^i—Co1—Cl3	108.76 (9)	N2—C3—C4	125.9 (12)
Cl2'^i—Cl2'—Co1	77.7 (4)	C3^i—C3—N2	61.7 (6)
H1A—N1—H1B	109.5	C3^i—C3—H3A	122.7
H1A—N1—H1C	109.5	C3^i—C3—H3B	131.3
H1B—N1—H1C	109.5	C3^i—C3—C4	65.2 (6)
C1—N1—H1A	109.5	H3A—C3—H3B	106.0
C1—N1—H1B	109.5	C4—C3—H3A	106.4
C1—N1—H1C	109.5	C4—C3—H3B	103.0
C3—N2—C3^i	56.6 (13)	C3^i—C4—C3	49.5 (11)
N1—C1—H1D	107.7
N1—C1—C2—C2^i	−105.1 (9)	C3^i—N2—C3—C4	13 (2)
N2—C3—C4—C3^i	−12 (2)

Symmetry code: (i) x, −y+3/2, z.

(EACo_LT)

Crystal data

Cl4Co·2(C2H8N)	Dx = 1.554 Mg m^−3
Mr = 292.92	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 2145 reflections
a = 9.7066 (6) Å	θ = 2.5–25.5°
b = 7.6312 (5) Å	µ = 2.18 mm^−1
c = 16.9019 (11) Å	T = 150 K
V = 1251.97 (14) Å^3	Block, blue
Z = 4	0.24 × 0.19 × 0.18 mm
F(000) = 596

Data collection

Bruker D8 Quest diffractometer	2852 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.025
Absorption correction: multi-scan SADABS	θmax = 28.3°, θmin = 2.4°
Tmin = 0.623, Tmax = 0.695	h = −9→12
10145 measured reflections	k = −10→8
3035 independent reflections	l = −22→22

Refinement

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.021	w = 1/[σ^2(Fo^2) + (0.017P)^2 + 0.1464P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.043	(Δ/σ)max = 0.001
S = 1.10	Δρmax = 0.22 e Å^−3
3035 reflections	Δρmin = −0.22 e Å^−3
165 parameters	Absolute structure: Refined as an inversion twin.
16 restraints	Absolute structure parameter: 0.498 (15)

Special details

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. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9765 (3)	0.1549 (4)	0.48775 (13)	0.0413 (8)
C2	1.0414 (2)	0.3218 (4)	0.46232 (15)	0.0330 (7)
C3	0.3214 (3)	0.2678 (3)	0.04734 (15)	0.0425 (8)
C4	0.3306 (2)	0.3734 (3)	0.12179 (16)	0.0284 (6)
Cl1	0.65870 (7)	0.05516 (7)	0.16579 (4)	0.02422 (14)
Cl2	0.72884 (7)	0.34436 (7)	0.33557 (3)	0.02445 (14)
Cl3	1.00223 (7)	0.23998 (9)	0.18568 (4)	0.03137 (16)
Cl4	0.69800 (7)	0.53866 (8)	0.13878 (4)	0.02886 (15)
Co1	0.77626 (3)	0.30076 (4)	0.20517 (2)	0.01987 (9)
N1	1.0543 (2)	0.3274 (3)	0.37435 (11)	0.0262 (5)
N2	0.3638 (2)	0.2597 (2)	0.19107 (12)	0.0276 (5)
H1A	1.0332 (8)	0.0456 (7)	0.4671 (7)	0.074 (13)*
H1B	0.8746 (4)	0.137 (3)	0.4669 (7)	0.059 (10)*
H1C	0.976 (3)	0.146 (4)	0.55027 (16)	0.054 (10)*
H1D	0.9581 (5)	0.314 (4)	0.3488 (6)	0.080 (12)*
H1E	1.0846 (14)	0.4478 (6)	0.3526 (7)	0.055 (10)*
H1F	1.1222 (7)	0.2340 (8)	0.3534 (7)	0.079 (13)*
H2A	1.1483 (4)	0.333 (4)	0.4819 (7)	0.051 (10)*
H2B	0.9826 (8)	0.4382 (7)	0.4788 (9)	0.041 (9)*
H2C	0.366 (3)	0.3304 (9)	0.2432 (3)	0.048 (9)*
H2D	0.2917 (6)	0.1612 (7)	0.1974 (16)	0.071 (11)*
H2E	0.4557 (5)	0.1950 (11)	0.1812 (12)	0.050 (9)*
H3A	0.2910 (15)	0.3494 (9)	−0.0003 (3)	0.067 (11)*
H3B	0.2505 (6)	0.1629 (7)	0.0523 (16)	0.056 (10)*
H3C	0.4212 (5)	0.2251 (17)	0.0310 (9)	0.062 (11)*
H4A	0.4082 (6)	0.4768 (7)	0.1187 (17)	0.048 (9)*
H4B	0.2298 (5)	0.4308 (13)	0.1340 (11)	0.054 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.045 (2)	0.047 (2)	0.0320 (16)	0.0055 (16)	0.0096 (14)	0.0164 (14)
C2	0.0362 (17)	0.0413 (17)	0.0216 (13)	−0.0042 (15)	−0.0017 (11)	−0.0062 (13)
C3	0.066 (2)	0.0323 (16)	0.0287 (15)	−0.0035 (16)	0.0009 (15)	−0.0001 (12)
C4	0.0289 (16)	0.0212 (12)	0.0350 (15)	−0.0021 (12)	0.0024 (12)	0.0042 (11)
Cl1	0.0255 (3)	0.0195 (3)	0.0277 (3)	−0.0023 (3)	−0.0019 (3)	−0.0033 (2)
Cl2	0.0263 (3)	0.0239 (3)	0.0232 (3)	0.0018 (3)	0.0043 (3)	−0.0004 (2)
Cl3	0.0201 (3)	0.0378 (4)	0.0362 (4)	0.0003 (3)	0.0045 (3)	−0.0086 (3)
Cl4	0.0326 (4)	0.0235 (3)	0.0304 (3)	0.0000 (3)	−0.0050 (3)	0.0044 (2)
Co1	0.01954 (17)	0.01820 (15)	0.02188 (16)	−0.00018 (14)	0.00032 (13)	−0.00137 (13)
N1	0.0262 (12)	0.0271 (12)	0.0254 (11)	−0.0031 (10)	0.0015 (9)	0.0049 (10)
N2	0.0311 (13)	0.0252 (12)	0.0266 (12)	0.0008 (10)	0.0020 (10)	0.0001 (9)

Geometric parameters (Å, º)

C1—C2	1.485 (4)	C4—H4A	1.0920 (2)
C1—H1A	1.0590 (1)	C4—H4B	1.0920 (1)
C1—H1B	1.0590 (2)	Cl1—Co1	2.2929 (7)
C1—H1C	1.0590 (2)	Cl2—Co1	2.2761 (6)
C2—N1	1.493 (3)	Cl3—Co1	2.2661 (7)
C2—H2A	1.0920 (2)	Cl4—Co1	2.2654 (7)
C2—H2B	1.0920 (1)	N1—H1D	1.0330 (2)
C3—C4	1.497 (4)	N1—H1E	1.0330 (1)
C3—H3A	1.0590 (1)	N1—H1F	1.0330 (1)
C3—H3B	1.0590 (1)	N2—H2C	1.0330 (2)
C3—H3C	1.0590 (1)	N2—H2D	1.0330 (1)
C4—N2	1.492 (3)	N2—H2E	1.0330 (1)
C2—C1—H1A	111.1 (5)	N2—C4—H4B	106.1 (10)
C2—C1—H1B	114.2 (14)	C3—C4—H4B	108.7 (8)
H1A—C1—H1B	106.0 (13)	H4A—C4—H4B	109.7 (7)
C2—C1—H1C	110.3 (17)	Cl4—Co1—Cl3	114.62 (3)
H1A—C1—H1C	106.3 (18)	Cl4—Co1—Cl2	107.14 (3)
H1B—C1—H1C	108.7 (19)	Cl3—Co1—Cl2	111.50 (3)
C1—C2—N1	110.4 (2)	Cl4—Co1—Cl1	110.15 (3)
C1—C2—H2A	112.4 (15)	Cl3—Co1—Cl1	105.79 (3)
N1—C2—H2A	102.7 (7)	Cl2—Co1—Cl1	107.46 (3)
C1—C2—H2B	113.7 (5)	C2—N1—H1D	109.8 (6)
N1—C2—H2B	106.0 (8)	C2—N1—H1E	113.9 (7)
H2A—C2—H2B	110.8 (15)	H1D—N1—H1E	101.2 (18)
C4—C3—H3A	109.8 (5)	C2—N1—H1F	112.0 (7)
C4—C3—H3B	112.3 (14)	H1D—N1—H1F	111.6 (14)
H3A—C3—H3B	108.9 (14)	H1E—N1—H1F	108.0 (8)
C4—C3—H3C	109.3 (7)	C4—N2—H2C	111.7 (6)
H3A—C3—H3C	103.7 (12)	C4—N2—H2D	111.0 (13)
H3B—C3—H3C	112.5 (9)	H2C—N2—H2D	107.9 (19)
N2—C4—C3	111.08 (19)	C4—N2—H2E	109.8 (11)
N2—C4—H4A	108.0 (13)	H2C—N2—H2E	112 (2)
C3—C4—H4A	112.9 (14)	H2D—N2—H2E	104.7 (7)