Phase transition sequences in tetra­methyl­ammonium tetra­chloro­metallates by X-ray diffraction and spectroscopic measurements

The phase transition sequences of two members of the tetra­methyl­ammonium tetra­chloro­metallate(III) family of hybrid organic–inorganic salts have been determined and structurally characterized as a function of temperature for the first time. Unusually, a reduction in point-group symmetry with increasing temperature until reaching a cubic prototype phase is observed. Two additional intermediate phases are observed for Fe³⁺. First-principles calculations and the presence of short Cl...Cl contacts for Ga³⁺ suggest the [GaCl₄]⁻ anion to be conformationally hindered due to stronger lone-pair–σ-hole interactions. The conformationally more flexible Fe³⁺ structures show sublattice melting with the onset of rotational disorder in the [NMe₄]⁺ cations occurring 40 K below the corresponding onset of rotational disorder in the [FeCl₄]⁻ sublattice.

Computing details

For all structures, data collection: SuperNova, (Oxford Diffraction, 2010); cell refinement: CrysAlis, (Oxford Diffraction, 2002); data reduction: CrysAlis, (Oxford Diffraction, 2002). Program(s) used to solve structure: SHELXS 86 (Sheldrick, 1986) for TCF_oP88_220, tcf_cP22, tcg_393; SIR92 (Altomare et al., 1994) for TCF_oP88_260, TCF_oP44_295, tcf_Pm_318, TCF_mP44_365, tcg_100, tcg_180, tcg_226, tcg_248; USER DEFINED STRUCTURE SOLUTION for tcg_300. For all structures, program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Tetramethylammonium tetrachloroferrate(III) (TCF_oP88_220)

Crystal data

C4H12N·Cl4Fe	F(000) = 548
Mr = 271.80	Dx = 1.527 Mg m^−3
Orthorhombic, Pbma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ab	Cell parameters from 5660 reflections
a = 13.1442 (8) Å	θ = 3–30°
b = 13.9946 (8) Å	µ = 2.12 mm^−1
c = 6.4272 (3) Å	T = 220 K
V = 1182.27 (11) Å^3	Block, yellow
Z = 4	0.10 × 0.08 × 0.05 mm

Data collection

Oxford Diffraction SuperNova diffractometer	1007 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 25.7°, θmin = 3.1°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −16→16
Tmin = 0.84, Tmax = 0.90	k = −17→17
17459 measured reflections	l = −7→7
1169 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters not refined
wR(F^2) = 0.074	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 9.73 15.6 9.20 3.72 0.846
S = 1.00	(Δ/σ)max = 0.0001925
1162 reflections	Δρmax = 0.41 e Å^−3
51 parameters	Δρmin = −0.50 e Å^−3
22 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ### PLAT242_ALERT_2_B Low Ueq as Compared to Neighbors for ···.. N1 Check PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. Fe1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. - Fe1 is the central atom of the FeCl4- moiety, therefore it is expected that the terminal chlorine atoms will display greater thermal motion.

PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 2 Report PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 3 Report PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 22 Note - Rigid-body and rigid-bond restraints applied to NMe4 cation. - Details give in _iucr_refine_instruction_details_[constraints/restraints]

PLAT128_ALERT_4_G Alternate Setting for Input Space Group Pbma Pbcm Note - Space group has been transformed to simplify comparisons between phases.

PLAT794_ALERT_5_G Tentative Bond Valency for Fe1 (III) ···.. 3.09 Note - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - Please see: _refine_ls_weighting_details

PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 1 Report PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info

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

	x	y	z	Uiso*/Ueq
Fe1	−0.02794 (4)	0.2500	0.00577 (9)	0.0382
Cl1	0.03663 (7)	0.37950 (6)	−0.12959 (13)	0.0673
Cl2	−0.00069 (10)	0.2500	0.34100 (16)	0.0606
Cl3	−0.19273 (8)	0.2500	−0.0477 (2)	0.0723
N1	0.2500	0.0000	0.4566 (5)	0.0453
C1	0.2971 (4)	0.0734 (3)	0.5890 (8)	0.0860
C2	0.3293 (4)	−0.0447 (4)	0.3311 (9)	0.1059
H11	0.3279	0.1209	0.5036	0.1046*
H12	0.3479	0.0449	0.6745	0.1046*
H13	0.2469	0.1023	0.6745	0.1046*
H21	0.2991	−0.0918	0.2441	0.1300*
H22	0.3784	−0.0725	0.4178	0.1300*
H23	0.3600	0.0032	0.2455	0.1300*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0398 (3)	0.0374 (3)	0.0375 (3)	0.0000	−0.0012 (3)	0.0000
Cl1	0.0821 (6)	0.0556 (5)	0.0642 (5)	−0.0209 (4)	−0.0051 (4)	0.0145 (4)
Cl2	0.0734 (7)	0.0707 (7)	0.0376 (5)	0.0000	0.0007 (5)	0.0000
Cl3	0.0423 (6)	0.0798 (8)	0.0947 (10)	0.0000	−0.0110 (6)	0.0000
N1	0.0398 (15)	0.0417 (16)	0.054 (2)	−0.0021 (12)	0.0000	0.0000
C1	0.094 (3)	0.067 (2)	0.097 (3)	−0.016 (2)	−0.015 (2)	−0.023 (2)
C2	0.089 (3)	0.096 (3)	0.133 (4)	−0.005 (2)	0.050 (3)	−0.041 (3)

Geometric parameters (Å, º)

Fe1—Cl1^i	2.1821 (9)	N1—C2	1.459 (4)
Fe1—Cl1	2.1821 (9)	C1—H11	0.952
Fe1—Cl2	2.1842 (12)	C1—H12	0.952
Fe1—Cl3	2.1931 (12)	C1—H13	0.948
N1—C1^ii	1.471 (4)	C2—H21	0.950
N1—C2^ii	1.459 (4)	C2—H22	0.938
N1—C1	1.471 (4)	C2—H23	0.957
Cl1^i—Fe1—Cl1	112.31 (6)	N1—C1—H11	109.4
Cl1^i—Fe1—Cl2	109.24 (3)	N1—C1—H12	109.6
Cl1—Fe1—Cl2	109.24 (3)	H11—C1—H12	109.1
Cl1^i—Fe1—Cl3	108.77 (4)	N1—C1—H13	109.8
Cl1—Fe1—Cl3	108.77 (4)	H11—C1—H13	109.4
Cl2—Fe1—Cl3	108.45 (6)	H12—C1—H13	109.4
C1^ii—N1—C2^ii	108.6 (3)	N1—C2—H21	108.9
C1^ii—N1—C1	109.3 (4)	N1—C2—H22	109.9
C2^ii—N1—C1	108.7 (3)	H21—C2—H22	110.5
C1^ii—N1—C2	108.7 (3)	N1—C2—H23	108.5
C2^ii—N1—C2	112.8 (6)	H21—C2—H23	108.9
C1—N1—C2	108.6 (3)	H22—C2—H23	110.0

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

Tetramethylammonium tetrachloroferrate(III) (TCF_oP88_260)

Crystal data

C4H12N·Cl4Fe	F(000) = 548
Mr = 271.80	Dx = 1.512 Mg m^−3
Orthorhombic, Pbma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ab	Cell parameters from 4559 reflections
a = 13.1361 (10) Å	θ = 3–30°
b = 14.0158 (11) Å	µ = 2.10 mm^−1
c = 6.4831 (5) Å	T = 260 K
V = 1193.62 (16) Å^3	Block, yellow
Z = 4	0.10 × 0.08 × 0.05 mm

Data collection

Oxford Diffraction SuperNova diffractometer	955 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.049
ω scans	θmax = 25.7°, θmin = 3.1°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −16→16
Tmin = 0.71, Tmax = 0.90	k = −17→17
17673 measured reflections	l = −7→7
1179 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters not refined
wR(F^2) = 0.113	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 14.5 23.7 14.0 5.76 1.34
S = 1.00	(Δ/σ)max = 0.0000573
1173 reflections	Δρmax = 0.52 e Å^−3
51 parameters	Δρmin = −0.56 e Å^−3
22 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF responses ### PLAT242_ALERT_2_B Low Ueq as Compared to Neighbors for ···.. N1 Check PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. Fe1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. - Fe1 is the central atom of the FeCl4- moiety, therefore it is expected that the terminal chlorine atoms will display greater thermal motion.

PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 3 Report PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 22 Note PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - Rigid-body and rigid-bond restraints applied to NMe4 cation. - Details give in _iucr_refine_instruction_details_[constraints/restraints]

PLAT128_ALERT_4_G Alternate Setting for Input Space Group Pbma Pbcm Note - Space group has been transformed to simplify comparisons between phases.

PLAT794_ALERT_5_G Tentative Bond Valency for Fe1 (III) ···.. 3.13 Note - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - Please see: _refine_ls_weighting_details

PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 1 Report PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info

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

	x	y	z	Uiso*/Ueq
Fe1	−0.02923 (6)	0.2500	0.01513 (12)	0.0496
Cl1	0.03480 (12)	0.37878 (10)	−0.1203 (2)	0.0906
Cl2	−0.00037 (16)	0.2500	0.3467 (2)	0.0824
Cl3	−0.19389 (13)	0.2500	−0.0353 (4)	0.0969
N1	0.2500	0.0000	0.4550 (8)	0.0603
C1	0.2982 (7)	0.0705 (5)	0.5866 (13)	0.1342
C2	0.3271 (7)	−0.0449 (7)	0.3340 (16)	0.1685
H11	0.3302	0.1174	0.5011	0.1629*
H12	0.3479	0.0406	0.6697	0.1629*
H13	0.2484	0.1003	0.6697	0.1629*
H21	0.2960	−0.0912	0.2470	0.2075*
H22	0.3751	−0.0741	0.4208	0.2075*
H23	0.3592	0.0023	0.2505	0.2075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0514 (4)	0.0484 (4)	0.0490 (5)	0.0000	−0.0019 (4)	0.0000
Cl1	0.1089 (10)	0.0718 (7)	0.0909 (9)	−0.0285 (7)	−0.0095 (8)	0.0209 (7)
Cl2	0.0980 (13)	0.0995 (13)	0.0495 (9)	0.0000	−0.0007 (8)	0.0000
Cl3	0.0540 (10)	0.1083 (15)	0.1284 (18)	0.0000	−0.0145 (11)	0.0000
N1	0.051 (2)	0.057 (3)	0.073 (3)	−0.0027 (18)	0.0000	0.0000
C1	0.151 (7)	0.103 (5)	0.149 (6)	−0.027 (4)	−0.033 (5)	−0.043 (4)
C2	0.139 (6)	0.155 (7)	0.211 (9)	−0.004 (5)	0.091 (6)	−0.070 (6)

Geometric parameters (Å, º)

Fe1—Cl1^i	2.1764 (13)	N1—C2	1.427 (7)
Fe1—Cl1	2.1764 (13)	C1—H11	0.956
Fe1—Cl2	2.1826 (17)	C1—H12	0.944
Fe1—Cl3	2.1875 (19)	C1—H13	0.945
N1—C1^ii	1.452 (7)	C2—H21	0.952
N1—C2^ii	1.427 (7)	C2—H22	0.938
N1—C1	1.452 (7)	C2—H23	0.953
Cl1^i—Fe1—Cl1	112.06 (10)	N1—C1—H11	108.6
Cl1^i—Fe1—Cl2	109.29 (5)	N1—C1—H12	109.5
Cl1—Fe1—Cl2	109.29 (5)	H11—C1—H12	109.4
Cl1^i—Fe1—Cl3	108.77 (6)	N1—C1—H13	109.5
Cl1—Fe1—Cl3	108.77 (6)	H11—C1—H13	109.4
Cl2—Fe1—Cl3	108.60 (9)	H12—C1—H13	110.4
C1^ii—N1—C2^ii	108.3 (6)	N1—C2—H21	108.7
C1^ii—N1—C1	108.0 (8)	N1—C2—H22	109.8
C2^ii—N1—C1	109.4 (6)	H21—C2—H22	110.3
C1^ii—N1—C2	109.4 (6)	N1—C2—H23	108.7
C2^ii—N1—C2	113.3 (10)	H21—C2—H23	109.0
C1—N1—C2	108.3 (6)	H22—C2—H23	110.2

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

Tetramethylammonium tetrachloroferrate(III) (TCF_oP44_295)

Crystal data

C4H12N·Cl4Fe	F(000) = 274
Mr = 271.80	Dx = 1.520 Mg m^−3
Orthorhombic, Pbm2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 -2b	Cell parameters from 3355 reflections
a = 6.4471 (5) Å	θ = 3–30°
b = 14.2753 (11) Å	µ = 2.11 mm^−1
c = 6.4526 (5) Å	T = 295 K
V = 593.86 (8) Å^3	Block, yellow
Z = 2	0.10 × 0.08 × 0.05 mm

Data collection

Oxford Diffraction SuperNova diffractometer	1160 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 26.4°, θmin = 3.2°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = 0→8
Tmin = 0.73, Tmax = 0.90	k = 0→17
1248 measured reflections	l = −8→8
1248 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters not refined
wR(F^2) = 0.130	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 16.3 25.1 12.7 3.20
S = 0.96	(Δ/σ)max = 0.002
1243 reflections	Δρmax = 1.14 e Å^−3
52 parameters	Δρmin = −0.78 e Å^−3
44 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ### PLAT242_ALERT_2_B Low Ueq as Compared to Neighbors for ···.. N1 Check PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. Fe1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. - Fe1 is the central atom of the FeCl4- moiety, therefore it is expected that the terminal chlorine atoms will display greater thermal motion.

PLAT034_ALERT_1_C No Flack Parameter Given. Z > Si, NonCentro ···. Please Do ! - No Flack parameter was refined for three domain twin model.

PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 3 Note PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 3 Report PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 44 Note - Details give in _iucr_refine_instruction_details_[constraints/restraints]

PLAT128_ALERT_4_G Alternate Setting for Input Space Group Pbm2 Pma2 Note - Correct, alternative setting chosen to relate all structures by group-subgroup relationships as discussed in the text.

PLAT794_ALERT_5_G Tentative Bond Valency for Fe1 (III) ···.. 3.17 Note - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - Please see: _refine_ls_weighting_details Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982)

PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 1 Report PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info

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

	x	y	z	Uiso*/Ueq
Fe1	−0.07821 (16)	0.2500	0.0005 (3)	0.0533
Cl1	0.0424 (4)	0.12282 (13)	−0.1385 (4)	0.0895
Cl2	−0.0049 (7)	0.2500	0.3302 (4)	0.1029
Cl3	−0.4157 (4)	0.2500	−0.0342 (7)	0.1121
N1	0.5000	0.0000	0.4144 (11)	0.0781
C1	0.558 (2)	0.0776 (8)	0.5443 (16)	0.1630
C2	0.6749 (17)	−0.0264 (9)	0.2855 (16)	0.1860
H11	0.5960	0.1291	0.4597	0.1963*
H12	0.6714	0.0598	0.6289	0.1963*
H13	0.4433	0.0944	0.6289	0.1963*
H21	0.6367	−0.0777	0.2002	0.2233*
H22	0.7880	−0.0441	0.3718	0.2233*
H23	0.7142	0.0252	0.2019	0.2233*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0584 (6)	0.0424 (5)	0.0591 (5)	0.0000	−0.0005 (6)	0.0000
Cl1	0.1098 (17)	0.0554 (8)	0.1033 (14)	0.0160 (8)	−0.0075 (10)	−0.0162 (7)
Cl2	0.140 (2)	0.110 (2)	0.0591 (13)	0.0000	−0.0067 (15)	0.0000
Cl3	0.0612 (14)	0.118 (2)	0.157 (4)	0.0000	−0.0042 (19)	0.0000
N1	0.065 (4)	0.107 (5)	0.062 (4)	0.017 (4)	0.0000	0.0000
C1	0.193 (14)	0.137 (8)	0.159 (12)	−0.048 (8)	0.038 (8)	−0.052 (6)
C2	0.165 (10)	0.121 (6)	0.273 (14)	−0.012 (7)	0.140 (10)	−0.043 (9)

Geometric parameters (Å, º)

Fe1—Cl1^i	2.1694 (18)	N1—C2	1.451 (11)
Fe1—Cl1	2.1694 (18)	C1—H11	0.949
Fe1—Cl2	2.179 (3)	C1—H12	0.949
Fe1—Cl3	2.187 (3)	C1—H13	0.948
N1—C2^ii	1.451 (11)	C2—H21	0.948
N1—C1^ii	1.437 (12)	C2—H22	0.951
N1—C1	1.437 (12)	C2—H23	0.948
Cl1^i—Fe1—Cl1	113.63 (13)	N1—C1—H11	109.2
Cl1^i—Fe1—Cl2	109.02 (8)	N1—C1—H12	109.2
Cl1—Fe1—Cl2	109.02 (8)	H11—C1—H12	109.6
Cl1^i—Fe1—Cl3	108.32 (10)	N1—C1—H13	109.3
Cl1—Fe1—Cl3	108.32 (10)	H11—C1—H13	109.7
Cl2—Fe1—Cl3	108.4 (2)	H12—C1—H13	109.7
C2^ii—N1—C1^ii	109.5 (6)	N1—C2—H21	109.4
C2^ii—N1—C1	109.5 (5)	N1—C2—H22	109.2
C1^ii—N1—C1	108.7 (8)	H21—C2—H22	109.5
C2^ii—N1—C2	110.0 (9)	N1—C2—H23	109.4
C1^ii—N1—C2	109.5 (5)	H21—C2—H23	109.8
C1—N1—C2	109.5 (6)	H22—C2—H23	109.5

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

Tetramethylammonium tetrachloroferrate(III) (tcf_Pm_318)

Crystal data

C4H12N·Cl4Fe	F(000) = 125
Mr = 271.81	Dx = 1.53 Mg m^−3
Monoclinic, Pm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2y	Cell parameters from 1778 reflections
a = 6.425 (3) Å	θ = 3–29°
b = 7.1480 (16) Å	µ = 2.13 mm^−1
c = 6.4274 (18) Å	T = 318 K
β = 91.21 (3)°	Block, yellow
V = 295.10 (16) Å^3	0.10 × 0.08 × 0.05 mm
Z = 1

Data collection

Oxford Diffraction SuperNova diffractometer	1040 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.133
ω scans	θmax = 25.5°, θmin = 3.2°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −7→7
Tmin = 0.60, Tmax = 0.90	k = 0→8
1184 measured reflections	l = −7→7
1184 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.071	H-atom parameters not refined
wR(F^2) = 0.186	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 117. 186. 119. 54.7 14.0
S = 0.94	(Δ/σ)max = 0.0000109
1182 reflections	Δρmax = 0.82 e Å^−3
58 parameters	Δρmin = −0.68 e Å^−3
71 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ### PLAT043_ALERT_1_B Calculated and Reported Mol. Weight Differ by .. 12.10 Check CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01 From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_weight 271.80 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 4.00 48.04 H 1.01 0.00 0.00 N 14.01 1.00 14.01 Cl 35.45 4.00 141.81 Fe 55.85 1.00 55.85 Calculated formula weight 259.71 PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ Please Check FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C4 H12 Cl4 Fe1 N1 Atom count from the _atom_site data: C4 Cl4 Fe1 N1 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_sum C4 H12 Cl4 Fe1 N1 TEST: Compare cell contents of formula and atom_site data

atom Z*formula cif sites diff C 4.00 4.00 0.00 H 12.00 0.00 12.00 Cl 4.00 4.00 0.00 Fe 1.00 1.00 0.00 N 1.00 1.00 0.00 PLAT040_ALERT_1_G No H-atoms in this Carbon Containing Compound .. Please Check PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check - Hydrogen atoms are omitted from the model. Please disregard these warnings.

PLAT242_ALERT_2_B Low Ueq as Compared to Neighbors for ···.. Fe1 Check PLAT242_ALERT_2_B Low Ueq as Compared to Neighbors for ···.. N1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. - Fe1 is the central atom of the FeCl4- moiety, therefore it is expected that the terminal chlorine atoms will display greater thermal motion.

RINTA01_ALERT_3_C The value of Rint is greater than 0.12 Rint given 0.133 PLAT020_ALERT_3_C The value of Rint is greater than 0.12 ········· 0.133 Report PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 7 Report PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 3 Note - Due to the phase transition at 307 K, which splits the crystal into four domains, the data quality is significantly reduced leading to low theta(max), poor data to parameter ratios and high R(int) values.

PLAT034_ALERT_1_C No Flack Parameter Given. Z > Si, NonCentro ···. Please Do ! - No Flack parameter refined for 4 domain twin model. See text.

PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 4 Note PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 8 Report PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 71 Note - 1,2- 1,3- vibrational and thermal restraints as well as distance and angle restraints applied to the TMA cation.

PLAT794_ALERT_5_G Tentative Bond Valency for Fe1 (III) ···.. 3.29 Note - Correct

PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - Please see _refine_ls_weighting_details PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 1 Report PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 2 Note PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info

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

	x	y	z	Uiso*/Ueq
Fe1	−0.0885 (10)	0.5000	0.0751 (11)	0.0576
Cl1	0.0470 (15)	0.2479 (5)	−0.0435 (16)	0.0971
Cl2	−0.030 (3)	0.5000	0.406 (2)	0.1273
Cl3	−0.4263 (18)	0.5000	0.008 (2)	0.1003
N1	0.501 (2)	0.0000	0.501 (3)	0.0770
C1	0.707 (5)	0.0000	0.393 (6)	0.1510
C2	0.383 (3)	−0.164 (3)	0.443 (4)	0.1555
C3	0.537 (7)	0.0000	0.733 (6)	0.1556

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.069 (3)	0.0426 (8)	0.061 (3)	0.0000	−0.0028 (11)	0.0000
Cl1	0.108 (4)	0.0501 (11)	0.133 (5)	0.028 (3)	−0.004 (3)	−0.008 (3)
Cl2	0.219 (14)	0.093 (5)	0.069 (3)	0.0000	−0.037 (7)	0.0000
Cl3	0.063 (3)	0.097 (4)	0.141 (7)	0.0000	0.008 (5)	0.0000
N1	0.029 (8)	0.086 (9)	0.115 (13)	0.0000	−0.018 (6)	0.0000
C1	0.088 (18)	0.15 (3)	0.22 (4)	0.0000	0.06 (2)	0.0000
C2	0.112 (15)	0.123 (18)	0.23 (2)	−0.042 (12)	0.009 (15)	−0.062 (15)
C3	0.18 (4)	0.17 (4)	0.112 (13)	0.0000	−0.018 (17)	0.0000

Geometric parameters (Å, º)

Fe1—Cl1^i	2.148 (4)	N1—C2^ii	1.44 (3)
Fe1—Cl1	2.148 (4)	N1—C1	1.51 (3)
Fe1—Cl2	2.152 (13)	N1—C2	1.44 (3)
Fe1—Cl3	2.204 (13)	N1—C3	1.51 (4)
Cl1^i—Fe1—Cl1	114.0 (3)	C2^ii—N1—C1	109.9 (6)
Cl1^i—Fe1—Cl2	106.7 (5)	C2^ii—N1—C2	109.3 (9)
Cl1—Fe1—Cl2	106.7 (5)	C1—N1—C2	109.9 (6)
Cl1^i—Fe1—Cl3	109.6 (4)	C2^ii—N1—C3	109.0 (6)
Cl1—Fe1—Cl3	109.6 (4)	C1—N1—C3	109.7 (9)
Cl2—Fe1—Cl3	110.1 (4)	C2—N1—C3	109.0 (6)

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

tetramethylammonium tetrachloroferrate(III) (TCF_mP44_365)

Crystal data

C4H12N·Cl4Fe	F(000) = 250
Mr = 271.81	Dx = 1.474 Mg m^−3
Monoclinic, P121/m1	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 0 reflections
a = 6.574 (3) Å	θ = 0–0°
b = 14.156 (7) Å	µ = 2.05 mm^−1
c = 6.595 (3) Å	T = 365 K
β = 93.87 (4)°	Block, yellow
V = 612.3 (5) Å^3	0.10 × 0.05 × 0.05 mm
Z = 2

Data collection

Oxford Diffraction SuperNova diffractometer	576 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.065
ω scans	θmax = 20.9°, θmin = 3.1°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −6→6
Tmin = 0.49, Tmax = 0.90	k = −14→14
5173 measured reflections	l = −6→6
675 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.119	H-atom parameters not refined
wR(F^2) = 0.206	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 48.0 59.4 18.0
S = 1.05	(Δ/σ)max = 0.0000089
665 reflections	Δρmax = 0.59 e Å^−3
32 parameters	Δρmin = −0.62 e Å^−3
17 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ### THETM01_ALERT_3_A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5021 PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ············ 19.86 Degree RFACG01_ALERT_3_C The value of the R factor is > 0.10 R factor given 0.119 PLAT082_ALERT_2_C High R1 Value ·································. 0.12 Report PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.502 11 Report PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 3 Note PLAT918_ALERT_3_C Reflection(s) with I(obs) much smaller I(calc) . 3 Check PLAT939_ALERT_3_C Large Value of Not (SHELXL) Weight Optimized S . 32.17 - The data is of poor quality due to splitting, twinning and the high collection temperature.

PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 40 Ang3 PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) ······. 5 Report - Not correct, the volume of the spherical shell is not taken into account.

PLAT242_ALERT_2_B Low Ueq as Compared to Neighbors for ···.. Fe1 Check - Fe1 is the central atom of the FeCl4 moiety, the terminal Cl atoms would be expected to show greater thermal motion, especially at this elevated temperature.

PLAT043_ALERT_1_A Calculated and Reported Mol. Weight Differ by .. 60.14 Check CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_weight 271.80 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 4.00 48.04 H 1.01 0.00 0.00 N 14.01 1.00 14.01 Cl 35.45 4.00 141.81 Fe 55.85 1.00 55.85 Calculated formula weight 259.7 PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ Please Check PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)··· Please Check FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C4 H12 Cl4 Fe1 N1 Atom count from the _atom_site data: C4 Cl4 Fe1 N1 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C4 H12 Cl4 Fe1 N1 TEST: Compare cell contents of formula and atom_site data

atom Z*formula cif sites diff C 8.00 8.00 0.00 H 24.00 0.00 24.00 Cl 8.00 8.00 0.00 Fe 2.00 2.00 0.00 N 2.00 2.00 0.00 PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check PLAT304_ALERT_4_G Non-Integer Number of Atoms ( 0.50) in Resd. # 2 Check - CH4 groups are omitted from calculated values due to the special shape refinement. Please disregard all warnings.

PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 1 Note PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 3 Report PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 17 Note - Please see _iucr_refine_instruction_details_[constraints,restraints] - Not correct, rigid-body and rigid-bond restraints were applied to FeCl4 only

PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· m Check PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem··· b Check PLAT113_ALERT_2_G ADDSYM Suggests Possible Pseudo/New Space group. Cmcm Check - Cell restrained to primitive cell to compare with other structures in the phase sequence. Details given in text.

PLAT794_ALERT_5_G Tentative Bond Valency for Fe1 (III) ···.. 3.37 Note - Correct. PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - Please see _refine_ls_weighting_details PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 64 % PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 2 Report PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info PLAT960_ALERT_3_G Number of Intensities with I < - 2*sig(I) ··· 1 Check

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

	x	y	z	Uiso*/Ueq
Fe1	−0.0676 (10)	0.2500	0.0686 (9)	0.0980
Cl1	0.0464 (18)	0.1232 (5)	−0.0569 (15)	0.1608
Cl2	−0.032 (3)	0.2500	0.3879 (19)	0.1317
Cl3	−0.405 (3)	0.2500	−0.023 (3)	0.1727
N1	0.5000	0.0000	0.5000	0.103 (7)*
C100	0.5000	0.0000	0.5000	0.103 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.101 (7)	0.109 (3)	0.084 (5)	0.0000	0.003 (2)	0.0000
Cl1	0.226 (19)	0.096 (4)	0.158 (14)	0.067 (7)	−0.005 (5)	−0.003 (6)
Cl2	0.195 (12)	0.115 (3)	0.084 (5)	0.0000	0.004 (6)	0.0000
Cl3	0.119 (9)	0.139 (5)	0.251 (18)	0.0000	−0.056 (10)	0.0000

Geometric parameters (Å, º)

Fe1—Cl1^i	2.133 (6)	Fe1—Cl2	2.103 (13)
Fe1—Cl1	2.133 (6)	Fe1—Cl3	2.259 (17)
Cl1^i—Fe1—Cl1	114.5 (5)	Cl1^i—Fe1—Cl3	105.1 (5)
Cl1^i—Fe1—Cl2	111.7 (4)	Cl1—Fe1—Cl3	105.1 (5)
Cl1—Fe1—Cl2	111.7 (4)	Cl2—Fe1—Cl3	108.0 (5)

Symmetry code: (i) x, −y+1/2, z.

tetramethylammonium tetrachloroferrate(III) (tcf_cP22)

Crystal data

C4Cl4FeN	Dx = 1.343 Mg m^−3
Mr = 259.71	Mo Kα radiation, λ = 0.71073 Å
Cubic, Pm3m	Cell parameters from 1571 reflections
Hall symbol: -P 4 2 3	θ = 3.0–28.5°
a = 6.8470 (5) Å	µ = 1.95 mm^−1
V = 321.00 (7) Å^3	T = 365 K
Z = 1	Block, orange
F(000) = 125	0.10 × 0.05 × 0.05 mm

Data collection

SuperNova, Dual, Cu at zero, Atlas diffractometer	18 reflections with I > 2.0σ(I)
Radiation source: SuperNova (Mo) X-ray Source	Rint = 0.059
Mirror monochromator	θmax = 13.4°, θmin = 3.0°
Detector resolution: 5.1574 pixels mm^-1	h = −4→4
ω scans	k = −4→4
1895 measured reflections	l = −4→4
21 independent reflections

Refinement

Refinement on F^2	85 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.098	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 13.8 13.1 9.98
wR(F^2) = 0.138	(Δ/σ)max = 0.0000156
S = 0.99	Δρmax = 0.18 e Å^−3
18 reflections	Δρmin = −0.25 e Å^−3
14 parameters

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ###

REFNR01_ALERT_3_A Ratio of reflections to parameters is < 6 for a centrosymmetric structure sine(theta)/lambda 0.3259 Proportion of unique data used 0.8571 Ratio reflections to parameters 1.2857 THETM01_ALERT_3_A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.3259 PLAT088_ALERT_3_A Poor Data / Parameter Ratio ··················.. 1.36 Note - This is a plastic phase, as a result the diffraction limit is much reduced. Combined with the high symmetry, the data/parameter ratio is very low.

PLAT043_ALERT_1_A Calculated and Reported Mol. Weight Differ by .. 47.77 Check PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ Please Check PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)··· Please Check PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check - Calculated structure observes only 1 C atom which represents the four methyl groups refined as a spherical shell.

PLAT911_ALERT_3_B Missing # FCF Refl Between THmin & STh/L= 0.327 2 Report PLAT919_ALERT_3_B Reflection # Likely Affected by the Beamstop ··· 1 Check PLAT021_ALERT_4_C Ratio Unique / Expected Reflections too High ··· 1.050 PLAT939_ALERT_3_C Large Value of Not (SHELXL) Weight Optimized S . 63.99 - No action taken.

PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 3 Note PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 3 Report - Fe-Cl bond dinstaces were restrained.

PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - No action taken

PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 = 3 - Structure is cubic.

PLAT300_ALERT_4_G Atom Site Occupancy of <Cl2 is Constrained at 0.125 Check PLAT300_ALERT_4_G Atom Site Occupancy of <Cl3 is Constrained at 0.126 Check PLAT432_ALERT_2_G Short Inter X···Y Contact Cl2 .. Cl2 .. 2.57 Ang. PLAT432_ALERT_2_G Short Inter X···Y Contact Cl2 .. Cl2 .. 2.67 Ang. PLAT432_ALERT_2_G Short Inter X···Y Contact Cl2 .. Cl2 .. 2.67 Ang. PLAT432_ALERT_2_G Short Inter X···Y Contact Cl2 .. Cl2 .. 2.78 Ang. PLAT301_ALERT_3_G Main Residue Disorder ············ Percentage = 67 Note PLAT304_ALERT_4_G Non-Integer Number of Atoms ( 0.02) in Resd. # 2 Check - Cl sites are disordered to avoid short Cl···Cl distances. Occupancies are fixed to give correct known formula.

PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 85 Note - There are 46 applied restraints.

PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 100 % PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info PLAT961_ALERT_5_G Dataset Contains no Negative Intensities ······. Please Check PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ···. ! Info - No action taken.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.0000	0.0000	0.0000	0.2446
Cl2	0.3157 (15)	−0.0517 (19)	0.0517 (19)	0.2463	0.1250
Cl3	0.1838 (13)	0.1838 (13)	0.1838 (13)	0.2462	0.1250
N4	0.5000	0.5000	0.5000	0.2322
C100	0.5000	0.5000	0.5000	0.12 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.245 (5)	0.245 (5)	0.245 (5)	0.0000	0.0000	0.0000
Cl2	0.245 (5)	0.247 (6)	0.247 (6)	0.0005 (9)	−0.0005 (9)	0.0002 (11)
Cl3	0.246 (6)	0.246 (6)	0.246 (6)	−0.0008 (12)	−0.0008 (12)	−0.0008 (12)
N4	0.23 (2)	0.23 (2)	0.23 (2)	0.0000	0.0000	0.0000

Geometric parameters (Å, º)

Fe1—Cl2^i	2.219 (10)	Fe1—Cl2^viii	2.219 (10)
Fe1—Cl2^ii	2.219 (10)	Fe1—Cl2^ix	2.219 (10)
Fe1—Cl2^iii	2.219 (10)	Fe1—Cl2^x	2.219 (10)
Fe1—Cl2^iv	2.219 (10)	Fe1—Cl2^xi	2.219 (10)
Fe1—Cl2^v	2.219 (10)	Fe1—Cl2^xii	2.219 (10)
Fe1—Cl2^vi	2.219 (10)	Fe1—Cl2	2.219 (10)
Fe1—Cl2^vii	2.219 (10)	Fe1—Cl3	2.179 (15)
Cl2^i—Fe1—Cl2^ii	88.54 (10)	Cl2^ii—Fe1—Cl2	91.46 (10)
Cl2^i—Fe1—Cl2^iii	91.46 (10)	Cl2^iii—Fe1—Cl2	88.54 (10)
Cl2^ii—Fe1—Cl2^iii	179.995	Cl2^iv—Fe1—Cl2	91.46 (10)
Cl2^i—Fe1—Cl2^iv	88.54 (10)	Cl2^v—Fe1—Cl2	88.54 (10)
Cl2^ii—Fe1—Cl2^iv	91.46 (10)	Cl2^i—Fe1—Cl3	124.23 (7)
Cl2^iii—Fe1—Cl2^iv	88.54 (10)	Cl2^ii—Fe1—Cl3	55.77 (7)
Cl2^i—Fe1—Cl2^v	91.46 (10)	Cl2^iii—Fe1—Cl3	124.23 (7)
Cl2^ii—Fe1—Cl2^v	88.54 (10)	Cl2^iv—Fe1—Cl3	55.77 (7)
Cl2^iii—Fe1—Cl2^v	91.46 (10)	Cl2^v—Fe1—Cl3	124.23 (7)
Cl2^iv—Fe1—Cl2^v	179.995	Cl2^vi—Fe1—Cl2^vii	179.995
Cl2^i—Fe1—Cl2^vi	161.6 (7)	Cl2^vi—Fe1—Cl2^viii	91.46 (10)
Cl2^ii—Fe1—Cl2^vi	109.7 (7)	Cl2^vii—Fe1—Cl2^viii	88.54 (10)
Cl2^iii—Fe1—Cl2^vi	70.3 (7)	Cl2^vi—Fe1—Cl2^ix	88.54 (10)
Cl2^iv—Fe1—Cl2^vi	88.54 (10)	Cl2^vii—Fe1—Cl2^ix	91.46 (10)
Cl2^v—Fe1—Cl2^vi	91.46 (10)	Cl2^viii—Fe1—Cl2^ix	179.995
Cl2^i—Fe1—Cl2^vii	18.4 (7)	Cl2^vi—Fe1—Cl2^x	91.46 (10)
Cl2^ii—Fe1—Cl2^vii	70.3 (7)	Cl2^vii—Fe1—Cl2^x	88.54 (10)
Cl2^iii—Fe1—Cl2^vii	109.7 (7)	Cl2^viii—Fe1—Cl2^x	91.46 (10)
Cl2^iv—Fe1—Cl2^vii	91.46 (10)	Cl2^ix—Fe1—Cl2^x	88.54 (10)
Cl2^v—Fe1—Cl2^vii	88.54 (10)	Cl2^vi—Fe1—Cl2^xi	88.54 (10)
Cl2^i—Fe1—Cl2^viii	70.3 (7)	Cl2^vii—Fe1—Cl2^xi	91.46 (10)
Cl2^ii—Fe1—Cl2^viii	153.9 (9)	Cl2^viii—Fe1—Cl2^xi	88.54 (10)
Cl2^iii—Fe1—Cl2^viii	26.1 (9)	Cl2^ix—Fe1—Cl2^xi	91.46 (10)
Cl2^iv—Fe1—Cl2^viii	73.4 (5)	Cl2^x—Fe1—Cl2^xi	179.995
Cl2^v—Fe1—Cl2^viii	106.6 (5)	Cl2^vi—Fe1—Cl2^xii	88.54 (10)
Cl2^i—Fe1—Cl2^ix	109.7 (7)	Cl2^vii—Fe1—Cl2^xii	91.46 (10)
Cl2^ii—Fe1—Cl2^ix	26.1 (9)	Cl2^viii—Fe1—Cl2^xii	18.4 (7)
Cl2^iii—Fe1—Cl2^ix	153.9 (9)	Cl2^ix—Fe1—Cl2^xii	161.6 (7)
Cl2^iv—Fe1—Cl2^ix	106.6 (5)	Cl2^x—Fe1—Cl2^xii	109.7 (7)
Cl2^v—Fe1—Cl2^ix	73.4 (5)	Cl2^vi—Fe1—Cl2	18.4 (7)
Cl2^i—Fe1—Cl2^x	91.46 (10)	Cl2^vii—Fe1—Cl2	161.6 (7)
Cl2^ii—Fe1—Cl2^x	73.4 (5)	Cl2^viii—Fe1—Cl2	109.7 (7)
Cl2^iii—Fe1—Cl2^x	106.6 (5)	Cl2^ix—Fe1—Cl2	70.3 (7)
Cl2^iv—Fe1—Cl2^x	18.4 (7)	Cl2^x—Fe1—Cl2	88.54 (10)
Cl2^v—Fe1—Cl2^x	161.6 (7)	Cl2^vi—Fe1—Cl3	67.8 (5)
Cl2^i—Fe1—Cl2^xi	88.54 (10)	Cl2^vii—Fe1—Cl3	112.2 (5)
Cl2^ii—Fe1—Cl2^xi	106.6 (5)	Cl2^viii—Fe1—Cl3	124.23 (7)
Cl2^iii—Fe1—Cl2^xi	73.4 (5)	Cl2^ix—Fe1—Cl3	55.77 (7)
Cl2^iv—Fe1—Cl2^xi	161.6 (7)	Cl2^x—Fe1—Cl3	41.7 (5)
Cl2^v—Fe1—Cl2^xi	18.4 (7)	Cl2^xi—Fe1—Cl2^xii	70.3 (7)
Cl2^i—Fe1—Cl2^xii	73.4 (5)	Cl2^xi—Fe1—Cl2	91.46 (10)
Cl2^ii—Fe1—Cl2^xii	161.6 (7)	Cl2^xii—Fe1—Cl2	106.6 (5)
Cl2^iii—Fe1—Cl2^xii	18.4 (7)	Cl2^xi—Fe1—Cl3	138.3 (5)
Cl2^iv—Fe1—Cl2^xii	91.46 (10)	Cl2^xii—Fe1—Cl3	138.3 (5)
Cl2^v—Fe1—Cl2^xii	88.54 (10)	Cl2—Fe1—Cl3	55.77 (7)
Cl2^i—Fe1—Cl2	179.995

Symmetry codes: (i) −x, −y, −z; (ii) y, z, x; (iii) −y, −z, −x; (iv) z, x, y; (v) −z, −x, −y; (vi) x, y, −z; (vii) −x, −y, z; (viii) y, z, −x; (ix) −y, −z, x; (x) z, x, −y; (xi) −z, −x, y; (xii) y, −z, −x.

tetramethylammonium tetrachlorogallate (tcg_100)

Crystal data

C4H12N·Cl4Ga	F(000) = 568
Mr = 285.68	Dx = 1.680 Mg m^−3
Orthorhombic, Pcmb	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2c	Cell parameters from 3159 reflections
a = 6.2820 (4) Å	θ = 3–29°
b = 14.0388 (8) Å	µ = 3.32 mm^−1
c = 12.8067 (8) Å	T = 100 K
V = 1129.45 (12) Å^3	Block, colourless
Z = 4	0.15 × 0.12 × 0.10 mm

Data collection

Oxford Diffraction SuperNova diffractometer	1245 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 28.8°, θmin = 3.2°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −8→6
Tmin = 0.54, Tmax = 0.72	k = −17→17
5262 measured reflections	l = −16→16
1354 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	H-atom parameters constrained
wR(F^2) = 0.133	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 62.5 93.8 53.2 21.8 3.95
S = 1.00	(Δ/σ)max = 0.0002203
1350 reflections	Δρmax = 2.24 e Å^−3
51 parameters	Δρmin = −1.12 e Å^−3
0 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses##

PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ······. 0.950 Note - Full reflection statstics are given below:

INTENSITY STATISTICS FOR DATASET # 1 SP3085.hkl

Resolution #Data #Theory %Complete Redundancy Mean I Mean I/s R(int) Rsigma

Inf - 2.20 79 89 88.8 3.27 756.4 50.21 0.0166 0.0140 2.20 - 1.73 78 79 98.7 4.48 843.7 46.54 0.0226 0.0135 1.73 - 1.50 79 79 100.0 4.92 677.3 42.46 0.0282 0.0159 1.50 - 1.36 78 78 100.0 5.74 416.2 36.78 0.0335 0.0191 1.36 - 1.25 83 83 100.0 6.07 260.0 29.37 0.0426 0.0230 1.25 - 1.17 87 87 100.0 5.55 327.0 28.80 0.0437 0.0233 1.17 - 1.10 83 83 100.0 4.98 250.3 24.19 0.0459 0.0272 1.10 - 1.05 83 83 100.0 4.28 300.4 25.57 0.0438 0.0289 1.05 - 1.00 96 96 100.0 4.45 271.3 21.17 0.0443 0.0311 1.00 - 0.96 91 91 100.0 3.90 221.5 18.62 0.0458 0.0357 0.96 - 0.93 82 82 100.0 3.50 160.5 15.73 0.0572 0.0493 0.93 - 0.90 90 90 100.0 2.91 197.4 13.45 0.0480 0.0508 0.90 - 0.87 108 108 100.0 3.01 155.6 11.95 0.0564 0.0556 0.87 - 0.84 112 112 100.0 2.65 113.2 9.18 0.0653 0.0745 0.84 - 0.82 87 92 94.6 2.23 114.0 8.95 0.0671 0.0788 0.82 - 0.79 111 145 76.6 1.28 85.4 6.13 0.0794 0.1061 0.79 - 0.76 84 179 46.9 0.59 75.5 5.31 0.1011 0.1405 0.76 - 0.74 24 78 30.8 0.32 88.2 4.91 0.1715 0.1352 —————————————————————————— 0.84 - 0.74 345 533 64.7 1.16 90.5 6.72 0.0773 0.1050 Inf - 0.74 1535 1734 88.5 3.29 287.8 21.80 0.0362 0.0307 PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. N1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - See _iucr_refine_instruction_details_[restraints/constraints] PLAT128_ALERT_4_G Alternate Setting for Input Space Group Pcmb Pbcm Note - Correct, non-standard setting used for easy comparison to other phases. PLAT794_ALERT_5_G Tentative Bond Valency for Ga1 (III) ···.. 3.02 Note PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details for details.

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

	x	y	z	Uiso*/Ueq
Ga1	0.32407 (13)	0.2500	0.46375 (6)	0.0138
Cl2	0.4663 (2)	0.37906 (9)	0.52563 (11)	0.0197
Cl3	−0.0134 (3)	0.2500	0.50169 (17)	0.0222
Cl4	0.3614 (3)	0.2500	0.29440 (15)	0.0239
N1	−0.0467 (10)	0.5000	0.2500	0.0133
C2	−0.1858 (10)	0.4192 (4)	0.2849 (5)	0.0283
C1	0.0868 (11)	0.5318 (5)	0.3392 (5)	0.0303
H23	−0.0972	0.3654	0.3025	0.0423*
H22	−0.2672	0.4378	0.3451	0.0420*
H21	−0.2822	0.4023	0.2291	0.0421*
H13	0.1706	0.5853	0.3188	0.0449*
H12	−0.0044	0.5480	0.3970	0.0450*
H11	0.1760	0.4795	0.3595	0.0452*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ga1	0.0161 (4)	0.0091 (4)	0.0163 (4)	0.0000	0.0002 (3)	0.0000
Cl2	0.0244 (7)	0.0103 (5)	0.0245 (7)	−0.0036 (5)	−0.0002 (5)	−0.0028 (5)
Cl3	0.0161 (9)	0.0204 (9)	0.0300 (10)	0.0000	0.0025 (7)	0.0000
Cl4	0.0342 (11)	0.0209 (9)	0.0165 (9)	0.0000	0.0014 (8)	0.0000
N1	0.019 (3)	0.007 (3)	0.014 (3)	0.0000	0.0000	0.002 (2)
C2	0.030 (3)	0.026 (3)	0.029 (3)	−0.009 (3)	0.000 (3)	0.009 (2)
C1	0.032 (3)	0.027 (3)	0.032 (3)	−0.002 (3)	−0.014 (3)	−0.001 (3)

Geometric parameters (Å, º)

Ga1—Cl2^i	2.1700 (13)	N1—C1	1.486 (7)
Ga1—Cl2	2.1700 (13)	C2—H23	0.965
Ga1—Cl3	2.175 (2)	C2—H22	0.961
Ga1—Cl4	2.182 (2)	C2—H21	0.966
N1—C2^ii	1.500 (7)	C1—H13	0.953
N1—C1^ii	1.486 (7)	C1—H12	0.964
N1—C2	1.500 (7)	C1—H11	0.960
Cl2^i—Ga1—Cl2	113.21 (8)	N1—C2—H23	109.0
Cl2^i—Ga1—Cl3	108.65 (5)	N1—C2—H22	110.1
Cl2—Ga1—Cl3	108.65 (5)	H23—C2—H22	109.4
Cl2^i—Ga1—Cl4	108.59 (5)	N1—C2—H21	109.3
Cl2—Ga1—Cl4	108.59 (5)	H23—C2—H21	110.0
Cl3—Ga1—Cl4	109.08 (9)	H22—C2—H21	109.0
C2^ii—N1—C1^ii	109.1 (4)	N1—C1—H13	109.7
C2^ii—N1—C2	108.7 (6)	N1—C1—H12	109.0
C1^ii—N1—C2	109.3 (4)	H13—C1—H12	110.7
C2^ii—N1—C1	109.3 (4)	N1—C1—H11	107.9
C1^ii—N1—C1	111.3 (7)	H13—C1—H11	110.8
C2—N1—C1	109.1 (4)	H12—C1—H11	108.6

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

tetramethylammonium tetrachlorogallate (tcg_180)

Crystal data

C4H12Cl4GaN	F(000) = 568
Mr = 285.68	Dx = 1.656 Mg m^−3
Orthorhombic, Pbma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ab	Cell parameters from 3 reflections
a = 12.8303 (4) Å	θ = 29–0°
b = 14.0961 (4) Å	µ = 3.28 mm^−1
c = 6.3359 (2) Å	T = 180 K
V = 1145.89 (6) Å^3	Block, colourless
Z = 4	0.20 × 0.12 × 0.10 mm

Data collection

Oxford Diffraction SuperNova diffractometer	1019 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.041
ω/2θ scans	θmax = 25.0°, θmin = 3.2°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −15→15
Tmin = 0.58, Tmax = 0.72	k = −16→16
14938 measured reflections	l = −7→7
1058 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters constrained
wR(F^2) = 0.091	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 4.93 7.00 3.25 0.797
S = 0.98	(Δ/σ)max = 0.0001493
1053 reflections	Δρmax = 1.02 e Å^−3
51 parameters	Δρmin = −0.79 e Å^−3
22 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses### PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. Ga1 Check PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. N1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. - Ga1 is the central atom of the GaCl4- moiety, therefore it is expected that the terminal chlorine atoms will display greater thermal motion. PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.595 4 Report PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 1 Note PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 87 % PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 2 Report - Twinning and high absorption reduce the data quality significantly. Full reflection statistics are given below:

INTENSITY STATISTICS FOR DATASET # 1 SP3084_4_180_00.hkl

Resolution #Data #Theory %Complete Redundancy Mean I Mean I/s R(int) Rsigma

Inf - 2.40 63 71 88.7 9.30 73.3 95.17 0.0215 0.0072 2.40 - 1.90 62 63 98.4 13.51 71.7 95.00 0.0264 0.0076 1.90 - 1.63 63 63 100.0 15.13 85.6 77.51 0.0309 0.0078 1.63 - 1.48 63 63 100.0 15.78 47.5 68.43 0.0329 0.0090 1.48 - 1.36 67 67 100.0 18.30 32.1 59.78 0.0392 0.0112 1.36 - 1.27 62 62 100.0 18.69 19.5 45.97 0.0456 0.0146 1.27 - 1.20 69 69 100.0 19.30 18.8 42.83 0.0533 0.0153 1.20 - 1.15 64 64 100.0 16.81 19.9 40.73 0.0533 0.0160 1.15 - 1.10 64 64 100.0 15.55 17.4 34.90 0.0619 0.0189 1.10 - 1.06 64 64 100.0 13.56 21.6 36.55 0.0545 0.0201 1.06 - 1.02 78 78 100.0 13.46 17.9 30.30 0.0704 0.0229 1.02 - 0.99 68 68 100.0 12.84 13.7 25.37 0.0810 0.0243 0.99 - 0.96 63 63 100.0 12.48 15.4 27.31 0.0685 0.0239 0.96 - 0.93 81 81 100.0 11.57 9.4 20.82 0.0847 0.0345 0.93 - 0.90 95 95 100.0 9.20 10.8 17.05 0.0708 0.0380 0.90 - 0.88 72 72 100.0 8.75 10.2 14.51 0.0935 0.0460 0.88 - 0.86 75 75 100.0 8.57 5.9 12.01 0.0966 0.0575 0.86 - 0.84 39 39 100.0 8.26 6.9 11.74 0.1023 0.0542 —————————————————————————— 0.94 - 0.84 335 335 100.0 9.26 8.8 15.28 0.0855 0.0439 Inf - 0.84 1212 1221 99.3 13.29 26.7 40.91 0.0437 0.0149

PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - See _iucr_refine_instruction_details_[restraints/constraints] PLAT128_ALERT_4_G Alternate Setting for Input Space Group Pbma Pbcm Note - Correct, non-standard setting used for easy comparison to other phases. PLAT794_ALERT_5_G Tentative Bond Valency for Ga1 (III) ···.. 3.07 Note - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details for details. PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info - No action taken.

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

	x	y	z	Uiso*/Ueq
Ga1	−0.03725 (5)	0.2500	0.17000 (10)	0.0227
Cl3	0.02401 (9)	0.37808 (7)	0.02856 (18)	0.0353
Cl2	0.00132 (16)	0.2500	0.5035 (3)	0.0412
Cl1	−0.20601 (12)	0.2500	0.1351 (3)	0.0428
N1	0.2500	0.0000	0.4546 (8)	0.0254
C1	0.1608 (5)	0.0306 (4)	0.5853 (10)	0.0558
C2	0.2832 (4)	0.0810 (4)	0.3176 (9)	0.0523
H11	0.1050	0.0497	0.4963	0.0669*
H12	0.1812	0.0823	0.6719	0.0669*
H13	0.1387	−0.0207	0.6719	0.0669*
H21	0.3406	0.0620	0.2329	0.0628*
H22	0.3032	0.1331	0.4037	0.0628*
H23	0.2269	0.0993	0.2292	0.0628*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ga1	0.0260 (3)	0.0177 (3)	0.0245 (3)	0.0000	−0.0009 (3)	0.0000
Cl3	0.0436 (7)	0.0224 (5)	0.0399 (6)	−0.0064 (4)	−0.0004 (5)	0.0071 (5)
Cl2	0.0547 (9)	0.0439 (9)	0.0249 (8)	0.0000	−0.0050 (7)	0.0000
Cl1	0.0258 (7)	0.0420 (9)	0.0607 (11)	0.0000	−0.0013 (8)	0.0000
N1	0.025 (2)	0.021 (2)	0.031 (2)	−0.0020 (19)	0.0000	0.0000
C1	0.058 (3)	0.048 (3)	0.061 (3)	0.009 (2)	0.029 (3)	−0.001 (2)
C2	0.054 (3)	0.051 (3)	0.052 (3)	−0.020 (2)	−0.003 (2)	0.022 (2)

Geometric parameters (Å, º)

Ga1—Cl3^i	2.1634 (11)	N1—C2	1.496 (5)
Ga1—Cl3	2.1634 (11)	C1—H11	0.950
Ga1—Cl2	2.1700 (18)	C1—H12	0.950
Ga1—Cl1	2.1765 (17)	C1—H13	0.950
N1—C2^ii	1.496 (5)	C2—H21	0.950
N1—C1^ii	1.477 (5)	C2—H22	0.950
N1—C1	1.477 (5)	C2—H23	0.950
Cl3^i—Ga1—Cl3	113.13 (7)	N1—C1—H11	109.5
Cl3^i—Ga1—Cl2	108.69 (4)	N1—C1—H12	109.5
Cl3—Ga1—Cl2	108.69 (4)	H11—C1—H12	109.5
Cl3^i—Ga1—Cl1	108.62 (4)	N1—C1—H13	109.5
Cl3—Ga1—Cl1	108.62 (4)	H11—C1—H13	109.5
Cl2—Ga1—Cl1	109.02 (8)	H12—C1—H13	109.5
C2^ii—N1—C1^ii	108.9 (3)	N1—C2—H21	109.5
C2^ii—N1—C1	109.1 (3)	N1—C2—H22	109.5
C1^ii—N1—C1	111.8 (6)	H21—C2—H22	109.5
C2^ii—N1—C2	109.1 (5)	N1—C2—H23	109.5
C1^ii—N1—C2	109.1 (3)	H21—C2—H23	109.5
C1—N1—C2	108.9 (3)	H22—C2—H23	109.5

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

tetramethylammonium tetrachlorogallate (tcg_226)

Crystal data

C4H12N·Cl4Ga	F(000) = 568
Mr = 285.68	Dx = 1.643 Mg m^−3
Orthorhombic, Pbma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ab	Cell parameters from 7149 reflections
a = 12.8329 (7) Å	θ = 3–29°
b = 14.1248 (4) Å	µ = 3.25 mm^−1
c = 6.3718 (3) Å	T = 226 K
V = 1154.97 (9) Å^3	Block, colourless
Z = 4	0.20 × 0.12 × 0.10 mm

Data collection

Oxford Diffraction SuperNova diffractometer	994 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.044
ω scans	θmax = 24.8°, θmin = 3.2°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −15→15
Tmin = 0.53, Tmax = 0.72	k = −16→16
14843 measured reflections	l = −7→7
1032 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters not refined
wR(F^2) = 0.094	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 8.15 12.7 7.40 2.97 0.774
S = 1.00	(Δ/σ)max = 0.0000481
1028 reflections	Δρmax = 1.13 e Å^−3
51 parameters	Δρmin = −0.64 e Å^−3
22 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ###

PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. Ga1 Check PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. N1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. - Ga1 is the central atom of the GaCl4- moiety, therefore it is expected that the terminal chlorine atoms will display greater thermal motion.

PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 3 Report PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 22 Note

THETM01_ALERT_3_C The value of sine(theta_max)/wavelength is less than 0.590 Calculated sin(theta_max)/wavelength = 0.5891 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.589 6 Report PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 1 Note PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still 83 % - Reflection statistics shown below:

INTENSITY STATISTICS FOR DATASET # 1 SP3084_3_226_00.hkl

Resolution #Data #Theory %Complete Redundancy Mean I Mean I/s R(int) Rsigma

Inf - 2.23 202 219 92.2 3.81 69.5 57.85 0.0225 0.0121 2.23 - 1.81 202 202 100.0 4.70 64.1 47.10 0.0271 0.0138 1.81 - 1.58 201 201 100.0 4.78 63.5 42.05 0.0280 0.0148 1.58 - 1.43 218 218 100.0 5.24 40.3 36.90 0.0336 0.0193 1.43 - 1.33 221 221 100.0 5.76 22.9 27.49 0.0411 0.0247 1.33 - 1.25 213 213 100.0 5.72 15.0 21.66 0.0530 0.0324 1.25 - 1.18 245 245 100.0 5.56 17.6 22.10 0.0529 0.0322 1.18 - 1.13 205 205 100.0 4.78 12.4 16.35 0.0589 0.0431 1.13 - 1.09 203 203 100.0 4.48 16.6 18.29 0.0566 0.0383 1.09 - 1.05 220 220 100.0 3.95 13.3 14.78 0.0626 0.0487 1.05 - 1.02 204 204 100.0 3.88 12.2 13.72 0.0801 0.0503 1.02 - 0.99 244 244 100.0 3.78 10.3 12.35 0.0820 0.0574 0.99 - 0.96 218 218 100.0 3.56 10.4 11.83 0.0717 0.0616 0.96 - 0.94 205 205 100.0 3.26 5.9 7.93 0.0939 0.0923 0.94 - 0.91 301 301 100.0 2.90 8.4 8.55 0.0774 0.0818 0.91 - 0.89 222 222 100.0 2.59 6.2 6.62 0.0957 0.1090 0.89 - 0.87 261 262 99.6 2.46 5.0 5.44 0.1135 0.1269 0.87 - 0.85 165 165 100.0 2.38 4.7 5.39 0.1189 0.1400 —————————————————————————— 0.94 - 0.85 1045 1046 99.9 2.68 6.2 6.74 0.0940 0.1050 Inf - 0.85 3950 3968 99.5 4.07 21.4 20.38 0.0421 0.0309

PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - See _iucr_refine_instruction_details_[restraints/constraints]

PLAT128_ALERT_4_G Alternate Setting for Input Space Group Pbma Pbcm Note - Correct, see text for details.

PLAT794_ALERT_5_G Tentative Bond Valency for Ga1 (III) ···.. 3.11 Note - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details for details. PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ··· 2 Report PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info

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

	x	y	z	Uiso*/Ueq
Ga1	−0.03821 (5)	0.2500	0.16351 (11)	0.0305
Cl3	0.02266 (10)	0.37742 (8)	0.0229 (2)	0.0484
Cl2	0.00059 (19)	0.2500	0.4945 (3)	0.0562
Cl1	−0.20648 (14)	0.2500	0.1298 (4)	0.0586
N1	0.2500	0.0000	0.4559 (8)	0.0341
C1	0.1613 (6)	0.0301 (5)	0.5852 (12)	0.0828
C2	0.2824 (5)	0.0804 (5)	0.3195 (11)	0.0775
H11	0.1055	0.0489	0.4962	0.0984*
H12	0.1815	0.0818	0.6709	0.0984*
H13	0.1393	−0.0211	0.6709	0.0984*
H21	0.3398	0.0617	0.2353	0.0929*
H22	0.3019	0.1327	0.4047	0.0929*
H23	0.2258	0.0982	0.2316	0.0929*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ga1	0.0351 (4)	0.0229 (3)	0.0334 (4)	0.0000	−0.0011 (3)	0.0000
Cl3	0.0594 (8)	0.0304 (5)	0.0553 (7)	−0.0087 (5)	−0.0011 (6)	0.0099 (5)
Cl2	0.0752 (12)	0.0602 (11)	0.0331 (8)	0.0000	−0.0062 (8)	0.0000
Cl1	0.0344 (8)	0.0584 (10)	0.0829 (14)	0.0000	−0.0017 (9)	0.0000
N1	0.031 (2)	0.029 (2)	0.042 (3)	−0.002 (2)	0.0000	0.0000
C1	0.084 (4)	0.073 (4)	0.091 (4)	0.018 (3)	0.046 (3)	−0.003 (3)
C2	0.081 (4)	0.074 (4)	0.077 (4)	−0.027 (3)	−0.003 (3)	0.035 (3)

Geometric parameters (Å, º)

Ga1—Cl3^i	2.1569 (12)	N1—C2	1.490 (6)
Ga1—Cl3	2.1569 (12)	C1—H11	0.951
Ga1—Cl2	2.1668 (19)	C1—H12	0.948
Ga1—Cl1	2.1700 (18)	C1—H13	0.949
N1—C2^ii	1.490 (6)	C2—H21	0.949
N1—C1^ii	1.468 (6)	C2—H22	0.951
N1—C1	1.468 (6)	C2—H23	0.950
Cl3^i—Ga1—Cl3	113.11 (8)	N1—C1—H11	109.3
Cl3^i—Ga1—Cl2	108.73 (5)	N1—C1—H12	109.5
Cl3—Ga1—Cl2	108.73 (5)	H11—C1—H12	109.5
Cl3^i—Ga1—Cl1	108.62 (5)	N1—C1—H13	109.4
Cl3—Ga1—Cl1	108.62 (5)	H11—C1—H13	109.5
Cl2—Ga1—Cl1	108.96 (9)	H12—C1—H13	109.7
C2^ii—N1—C1^ii	108.9 (4)	N1—C2—H21	109.5
C2^ii—N1—C1	109.4 (4)	N1—C2—H22	109.4
C1^ii—N1—C1	111.7 (7)	H21—C2—H22	109.5
C2^ii—N1—C2	108.6 (6)	N1—C2—H23	109.4
C1^ii—N1—C2	109.4 (4)	H21—C2—H23	109.5
C1—N1—C2	108.9 (4)	H22—C2—H23	109.4

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

tetramethylammonium tetrachlorogallate (tcg_248)

Crystal data

C4H12N·Cl4Ga	F(000) = 568
Mr = 285.68	Dx = 1.624 Mg m^−3
Orthorhombic, Pbma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2ab	Cell parameters from 3059 reflections
a = 12.8736 (3) Å	θ = 3–29°
b = 14.1743 (3) Å	µ = 3.21 mm^−1
c = 6.4043 (2) Å	T = 249 K
V = 1168.62 (5) Å^3	Block, colourless
Z = 4	0.15 × 0.12 × 0.10 mm

Data collection

Oxford Diffraction SuperNova diffractometer	1046 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 25.3°, θmin = 3.2°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −15→15
Tmin = 0.48, Tmax = 0.73	k = −16→17
15621 measured reflections	l = −7→7
1112 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters not refined
wR(F^2) = 0.106	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)] where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2]^2 Ai are: 8.42 13.0 7.19 2.51 0.458
S = 1.00	(Δ/σ)max = 0.0000327
1108 reflections	Δρmax = 1.18 e Å^−3
1 parameters	Δρmin = −0.62 e Å^−3
0 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ### PLAT242_ALERT_2_B Low Ueq as Compared to Neighbors for ···.. N1 Check PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. Ga1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. - Ga1 is the central atom of the GaCl4- moiety, therefore it is expected that the terminal chlorine atoms will display greater thermal motion. PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - See _iucr_refine_instruction_details_[restraints/constraints] PLAT128_ALERT_4_G Alternate Setting for Input Space Group Pbma Pbcm Note - Correct, non-standard setting used for easy comparison to other phases. PLAT794_ALERT_5_G Tentative Bond Valency for Ga1 (III) ···.. 3.10 Note - Correct PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - See _refine_ls_weighting_details for details.

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

	x	y	z	Uiso*/Ueq
Ga1	−0.0388	0.2500	0.1586	0.0355
Cl3	0.0219	0.3771	0.0186	0.0565
Cl2	0.0001	0.2500	0.4884	0.0655
Cl1	−0.2067	0.2500	0.1255	0.0690
N1	0.2500	0.0000	0.4562	0.0396
C1	0.1608	0.0294	0.5842	0.1057
C2	0.2821	0.0803	0.3211	0.0961
H11	0.1052	0.0477	0.4956	0.1268*
H12	0.1803	0.0811	0.6698	0.1268*
H13	0.1393	−0.0218	0.6698	0.1268*
H21	0.3398	0.0618	0.2379	0.1154*
H22	0.3012	0.1324	0.4061	0.1154*
H23	0.2260	0.0978	0.2331	0.1154*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ga1	0.0405	0.0269	0.0389	0.0000	−0.0013	0.0000
Cl3	0.0690	0.0354	0.0650	−0.0103	−0.0020	0.0121
Cl2	0.0874	0.0708	0.0384	0.0000	−0.0071	0.0000
Cl1	0.0401	0.0693	0.0978	0.0000	−0.0021	0.0000
N1	0.0341	0.0353	0.0495	−0.0021	0.0000	0.0000
C1	0.1067	0.0918	0.1185	0.0254	0.0636	−0.0034
C2	0.0996	0.0929	0.0960	−0.0355	−0.0037	0.0454

Geometric parameters (Å, º)

Ga1—Cl3^i	2.158	N1—C2	1.488
Ga1—Cl3	2.158	C1—H11	0.950
Ga1—Cl2	2.1707 (1)	C1—H12	0.950
Ga1—Cl1	2.1716 (1)	C1—H13	0.950
N1—C2^ii	1.488	C2—H21	0.950
N1—C1^ii	1.471	C2—H22	0.950
N1—C1	1.471	C2—H23	0.950
Cl3^i—Ga1—Cl3	113.124	N1—C1—H11	109.5
Cl3^i—Ga1—Cl2	108.717	N1—C1—H12	109.5
Cl3—Ga1—Cl2	108.717	H11—C1—H12	109.5
Cl3^i—Ga1—Cl1	108.643	N1—C1—H13	109.5
Cl3—Ga1—Cl1	108.643	H11—C1—H13	109.5
Cl2—Ga1—Cl1	108.925	H12—C1—H13	109.5
C2^ii—N1—C1^ii	108.948	N1—C2—H21	109.5
C2^ii—N1—C1	108.861	N1—C2—H22	109.5
C1^ii—N1—C1	112.298	H21—C2—H22	109.5
C2^ii—N1—C2	108.870	N1—C2—H23	109.5
C1^ii—N1—C2	108.861	H21—C2—H23	109.5
C1—N1—C2	108.948	H22—C2—H23	109.5

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

Tetramethylammonium tetrachlorogallate(III) (tcg_300)

Crystal data

C4NH12·Cl4Ga	F(000) = 130
Mr = 285.68	Dx = 1.601 Mg m^−3
Monoclinic, Pm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2y	Cell parameters from 2897 reflections
a = 6.4571 (5) Å	θ = 5–29°
b = 7.1456 (5) Å	µ = 3.15 mm^−1
c = 6.4596 (6) Å	T = 300 K
β = 91.721 (8)°	Block, colourless
V = 297.91 (4) Å^3	0.20 × 0.12 × 0.10 mm
Z = 1

Data collection

Oxford Diffraction SuperNova diffractometer	1231 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 26.4°, θmin = 5.4°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −7→8
Tmin = 0.59, Tmax = 0.73	k = 0→8
1254 measured reflections	l = −8→8
1254 independent reflections

Refinement

Refinement on F^2	Primary atom site location: Other
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters not refined
wR(F^2) = 0.100	Method = Quasi-Unit weights W = 1.0 or 1./2F
S = 0.98	(Δ/σ)max = 0.0000510
1254 reflections	Δρmax = 0.77 e Å^−3
56 parameters	Δρmin = −0.44 e Å^−3
41 restraints

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ###

PLAT242_ALERT_2_B Low Ueq as Compared to Neighbors for ···.. N1 Check PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ···.. Ga1 Check - N1 is the central atom of the NC4H12+ moiety, therefore it is expected that the terminal methyl groups will display greater thermal motion. - Ga1 is the central atom of the GaCl4- moiety, therefore it is expected that the terminal chlorine atoms will display greater thermal motion.

CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01 From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_weight 285.68 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 4.00 48.04 H 1.01 0.00 0.00 N 14.01 1.00 14.01 Cl 35.45 4.00 141.81 Ga 69.72 1.00 69.72 Calculated formula weight 273.59 PLAT043_ALERT_1_B Calculated and Reported Mol. Weight Differ by .. 12.11 Check PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ Please Check FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C4 H12 Cl4 Ga1 N1 Atom count from the _atom_site data: C4 Cl4 Ga1 N1 CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected. CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional? From the CIF: _cell_formula_units_Z 1 From the CIF: _chemical_formula_sum C4 H12 Cl4 Ga1 N1 TEST: Compare cell contents of formula and atom_site data

atom Z*formula cif sites diff C 4.00 4.00 0.00 H 12.00 0.00 12.00 Cl 4.00 4.00 0.00 Ga 1.00 1.00 0.00 N 1.00 1.00 0.00 PLAT040_ALERT_1_G No H-atoms in this Carbon Containing Compound .. Please Check PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check - Hydrogen atoms are omitted from the model. Please disregard these warnings.

PLAT034_ALERT_1_C No Flack Parameter Given. Z > Si, NonCentro ···. Please Do ! PLAT910_ALERT_3_C Missing # of FCF Reflection(s) Below Th(Min) ··· 8 Report PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 5 Report PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 13 Note PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ······. 0.976 Note - Due to the phase transition which splits the crystal into at least two domains, the data quality is significantly reduced leading to low theta(max), poor data to parameter ratios and high R(int) values.

PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 4 Note PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 4 Report PLAT860_ALERT_3_G Number of Least-Squares Restraints ············. 41 Note - 1,2- 1,3- vibrational and thermal restraints as well as distance and angle restraints applied to the TMA cation.

PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! - Please see _iucr_refine_instruction_details_[restraints/constraints]

PLAT794_ALERT_5_G Tentative Bond Valency for Ga1 (III) ···.. 3.19 Note

PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found Please Check - Please see _refine_ls_weighting_details

PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 3 Note PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked ! Info

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

	x	y	z	Uiso*/Ueq
Ga1	−0.0885 (5)	0.5000	0.0772 (6)	0.0565
Cl1	0.0400 (8)	0.2487 (3)	−0.0480 (9)	0.0964
Cl2	−0.037 (2)	0.5000	0.4079 (16)	0.1315
Cl3	−0.4205 (10)	0.5000	0.0133 (14)	0.0892
N1	0.5040 (14)	0.0000	0.5026 (19)	0.0774
C1	0.703 (3)	0.0000	0.386 (4)	0.2039
C2	0.378 (2)	−0.176 (2)	0.452 (3)	0.1763
C3	0.556 (4)	0.0000	0.731 (4)	0.1770

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ga1	0.0493 (12)	0.0402 (5)	0.080 (2)	0.0000	−0.0034 (5)	0.0000
Cl1	0.089 (3)	0.0572 (12)	0.142 (5)	0.019 (3)	−0.0027 (14)	−0.014 (4)
Cl2	0.219 (13)	0.102 (9)	0.073 (6)	0.0000	−0.004 (7)	0.0000
Cl3	0.052 (3)	0.121 (9)	0.093 (6)	0.0000	−0.013 (4)	0.0000
N1	0.031 (5)	0.094 (6)	0.106 (10)	0.0000	−0.010 (4)	0.0000
C1	0.108 (16)	0.21 (3)	0.30 (3)	0.0000	0.11 (2)	0.0000
C2	0.160 (12)	0.154 (13)	0.217 (16)	−0.074 (10)	0.033 (12)	−0.078 (12)
C3	0.23 (3)	0.18 (2)	0.122 (12)	0.0000	−0.067 (14)	0.0000

Geometric parameters (Å, º)

Ga1—Cl1^i	2.146 (2)	N1—C2^ii	1.526 (17)
Ga1—Cl1	2.146 (2)	N1—C1	1.506 (18)
Ga1—Cl2	2.152 (10)	N1—C2	1.526 (17)
Ga1—Cl3	2.171 (6)	N1—C3	1.50 (3)
Cl1^i—Ga1—Cl1	113.56 (15)	C2^ii—N1—C1	110.5 (5)
Cl1^i—Ga1—Cl2	108.9 (2)	C2^ii—N1—C2	110.6 (8)
Cl1—Ga1—Cl2	108.9 (2)	C1—N1—C2	110.5 (5)
Cl1^i—Ga1—Cl3	108.60 (17)	C2^ii—N1—C3	108.2 (5)
Cl1—Ga1—Cl3	108.60 (17)	C1—N1—C3	108.7 (9)
Cl2—Ga1—Cl3	108.1 (2)	C2—N1—C3	108.2 (5)

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

Tetramethylammonium tetrachlorogallate(III) (tcg_393)

Crystal data

C4Cl4GaN	Dx = 1.413 Mg m^−3
Mr = 273.58	Mo Kα radiation, λ = 0.71073 Å
Cubic, Pm3m	Cell parameters from 0 reflections
Hall symbol: -P 4 2 3	θ = 2.8–26°
a = 6.8504 (4) Å	µ = 2.92 mm^−1
V = 321.48 (3) Å^3	T = 393 K
Z = 1	Plate, colourless
F(000) = 130	0.12 × 0.10 × 0.05 mm

Data collection

Oxford Diffraction SuperNova diffractometer	29 reflections with I > 2.0σ(I)
Graphite monochromator	Rint = 0.069
ω scans	θmax = 15.6°, θmin = 3.0°
Absorption correction: multi-scan CrysAlis, (Oxford Diffraction, 2002)	h = −5→5
Tmin = 0.57, Tmax = 0.86	k = −5→5
1506 measured reflections	l = −5→5
30 independent reflections

Refinement

Refinement on F^2	86 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.095	Method = Quasi-Unit weights W = 1.0 or 1./2F
wR(F^2) = 0.155	(Δ/σ)max = 0.0000059
S = 1.00	Δρmax = 0.48 e Å^−3
29 reflections	Δρmin = −0.36 e Å^−3
14 parameters

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems open-flow nitrogen cryostat (Cosier & Glazer, 1986) with a nominal stability of 0.1K.

Cosier, J. & Glazer, A.M., 1986. J. Appl. Cryst. 105-107.

Refinement. ### CheckCIF Responses ### Alert level A REFNR01_ALERT_3_A Ratio of reflections to parameters is < 6 for a centrosymmetric structure sine(theta)/lambda 0.3793 Proportion of unique data used 0.9667 Ratio reflections to parameters 2.0714 THETM01_ALERT_3_A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.3793 PLAT088_ALERT_3_A Poor Data / Parameter Ratio ··················.. 2.14 Note - This is a plastic phase, as a result the diffraction limit is much reduced. Combined with the high symmetry, the data/parameter ratio is very low.

PLAT043_ALERT_1_A Calculated and Reported Mol. Weight Differ by .. 48.05 Check PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ Please Check PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)··· Please Check PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings Differ Please Check PLAT301_ALERT_3_G Main Residue Disorder ············..(Resd 1).. 80 % Note - Calculated structure observes only 1 C atom which represents the four methyl groups refined as a spherical shell

PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent ········· 1 Check PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 3 Note PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ··· 3 Report - Fe-Cl bond dinstaces were restrained.

PLAT300_ALERT_4_G Atom Site Occupancy of <Cl2 is Constrained at 0.1245 Check PLAT300_ALERT_4_G Atom Site Occupancy of <Cl3 is Constrained at 0.1265 Check PLAT304_ALERT_4_G Non-Integer Number of Atoms ( 0.02) in Resd. # 2 Check PLAT432_ALERT_2_G Short Inter X···Y Contact Cl2 .. Cl2 .. 2.52 Ang. PLAT432_ALERT_2_G Short Inter X···Y Contact Cl2 .. Cl2 .. 2.60 Ang. PLAT432_ALERT_2_G Short Inter X···Y Contact Cl2 .. Cl2 .. 2.60 Ang. PLAT432_ALERT_2_G Short Inter X···Y Contact Cl2 .. Cl2 .. 2.68 Ang. - Cl sites are disordered to avoid short Cl···Cl distances. Occupancies are fixed to give correct known formula.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ga1	0.0000	0.0000	0.0000	0.2523
Cl2	0.047 (2)	0.3162 (17)	−0.047 (2)	0.2552	0.1245
Cl3	0.1812 (16)	0.1812 (16)	0.1812 (16)	0.2550	0.1265
N4	0.5000	0.5000	0.5000	0.2245
C100	0.5000	0.5000	0.5000	0.16 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ga1	0.252 (5)	0.252 (5)	0.252 (5)	0.0000	0.0000	0.0000
Cl2	0.257 (7)	0.253 (5)	0.257 (7)	−0.0007 (11)	0.0003 (13)	0.0007 (11)
Cl3	0.255 (6)	0.255 (6)	0.255 (6)	−0.0013 (15)	−0.0013 (15)	−0.0013 (15)
N4	0.22 (2)	0.22 (2)	0.22 (2)	0.0000	0.0000	0.0000

Geometric parameters (Å, º)

Ga1—Cl2^i	2.214 (13)	Ga1—Cl2^viii	2.214 (13)
Ga1—Cl2^ii	2.214 (13)	Ga1—Cl2^ix	2.214 (13)
Ga1—Cl2^iii	2.214 (13)	Ga1—Cl2^x	2.214 (13)
Ga1—Cl2^iv	2.214 (13)	Ga1—Cl2^xi	2.214 (13)
Ga1—Cl2^v	2.214 (13)	Ga1—Cl2^xii	2.214 (13)
Ga1—Cl2^vi	2.214 (13)	Ga1—Cl2	2.214 (13)
Ga1—Cl2^vii	2.214 (13)	Ga1—Cl3	2.149 (18)
Cl2^i—Ga1—Cl2^ii	88.78 (11)	Cl2^ii—Ga1—Cl2	91.22 (11)
Cl2^i—Ga1—Cl2^iii	91.22 (11)	Cl2^iii—Ga1—Cl2	88.78 (11)
Cl2^ii—Ga1—Cl2^iii	179.995	Cl2^iv—Ga1—Cl2	91.22 (11)
Cl2^i—Ga1—Cl2^iv	88.78 (11)	Cl2^v—Ga1—Cl2	88.78 (11)
Cl2^ii—Ga1—Cl2^iv	91.22 (11)	Cl2^i—Ga1—Cl3	124.39 (8)
Cl2^iii—Ga1—Cl2^iv	88.78 (11)	Cl2^ii—Ga1—Cl3	55.61 (8)
Cl2^i—Ga1—Cl2^v	91.22 (11)	Cl2^iii—Ga1—Cl3	124.39 (8)
Cl2^ii—Ga1—Cl2^v	88.78 (11)	Cl2^iv—Ga1—Cl3	55.61 (8)
Cl2^iii—Ga1—Cl2^v	91.22 (11)	Cl2^v—Ga1—Cl3	124.39 (8)
Cl2^iv—Ga1—Cl2^v	179.995	Cl2^vi—Ga1—Cl2^vii	179.995
Cl2^i—Ga1—Cl2^vi	163.2 (8)	Cl2^vi—Ga1—Cl2^viii	91.22 (11)
Cl2^ii—Ga1—Cl2^vi	88.78 (11)	Cl2^vii—Ga1—Cl2^viii	88.78 (11)
Cl2^iii—Ga1—Cl2^vi	91.22 (11)	Cl2^vi—Ga1—Cl2^ix	88.78 (11)
Cl2^iv—Ga1—Cl2^vi	74.7 (6)	Cl2^vii—Ga1—Cl2^ix	91.22 (11)
Cl2^v—Ga1—Cl2^vi	105.3 (6)	Cl2^viii—Ga1—Cl2^ix	179.995
Cl2^i—Ga1—Cl2^vii	16.8 (8)	Cl2^vi—Ga1—Cl2^x	91.22 (11)
Cl2^ii—Ga1—Cl2^vii	91.22 (11)	Cl2^vii—Ga1—Cl2^x	88.78 (11)
Cl2^iii—Ga1—Cl2^vii	88.78 (11)	Cl2^viii—Ga1—Cl2^x	91.22 (11)
Cl2^iv—Ga1—Cl2^vii	105.3 (6)	Cl2^ix—Ga1—Cl2^x	88.78 (11)
Cl2^v—Ga1—Cl2^vii	74.7 (6)	Cl2^vi—Ga1—Cl2^xi	88.78 (11)
Cl2^i—Ga1—Cl2^viii	91.22 (11)	Cl2^vii—Ga1—Cl2^xi	91.22 (11)
Cl2^ii—Ga1—Cl2^viii	16.8 (8)	Cl2^viii—Ga1—Cl2^xi	88.78 (11)
Cl2^iii—Ga1—Cl2^viii	163.2 (8)	Cl2^ix—Ga1—Cl2^xi	91.22 (11)
Cl2^iv—Ga1—Cl2^viii	107.9 (9)	Cl2^x—Ga1—Cl2^xi	179.995
Cl2^v—Ga1—Cl2^viii	72.1 (9)	Cl2^vi—Ga1—Cl2^xii	74.7 (6)
Cl2^i—Ga1—Cl2^ix	88.78 (11)	Cl2^vii—Ga1—Cl2^xii	105.3 (6)
Cl2^ii—Ga1—Cl2^ix	163.2 (8)	Cl2^viii—Ga1—Cl2^xii	16.8 (8)
Cl2^iii—Ga1—Cl2^ix	16.8 (8)	Cl2^ix—Ga1—Cl2^xii	163.2 (8)
Cl2^iv—Ga1—Cl2^ix	72.1 (9)	Cl2^x—Ga1—Cl2^xii	88.78 (11)
Cl2^v—Ga1—Cl2^ix	107.9 (9)	Cl2^vi—Ga1—Cl2	16.8 (8)
Cl2^i—Ga1—Cl2^x	105.3 (6)	Cl2^vii—Ga1—Cl2	163.2 (8)
Cl2^ii—Ga1—Cl2^x	107.9 (9)	Cl2^viii—Ga1—Cl2	88.78 (11)
Cl2^iii—Ga1—Cl2^x	72.1 (9)	Cl2^ix—Ga1—Cl2	91.22 (11)
Cl2^iv—Ga1—Cl2^x	156.1 (11)	Cl2^x—Ga1—Cl2	74.7 (6)
Cl2^v—Ga1—Cl2^x	23.9 (11)	Cl2^vi—Ga1—Cl3	42.8 (6)
Cl2^i—Ga1—Cl2^xi	74.7 (6)	Cl2^vii—Ga1—Cl3	137.2 (6)
Cl2^ii—Ga1—Cl2^xi	72.1 (9)	Cl2^viii—Ga1—Cl3	66.7 (6)
Cl2^iii—Ga1—Cl2^xi	107.9 (9)	Cl2^ix—Ga1—Cl3	113.3 (6)
Cl2^iv—Ga1—Cl2^xi	23.9 (11)	Cl2^x—Ga1—Cl3	124.39 (8)
Cl2^v—Ga1—Cl2^xi	156.1 (11)	Cl2^xi—Ga1—Cl2^xii	91.22 (11)
Cl2^i—Ga1—Cl2^xii	107.9 (9)	Cl2^xi—Ga1—Cl2	105.3 (6)
Cl2^ii—Ga1—Cl2^xii	23.9 (11)	Cl2^xii—Ga1—Cl2	72.1 (9)
Cl2^iii—Ga1—Cl2^xii	156.1 (11)	Cl2^xi—Ga1—Cl3	55.61 (8)
Cl2^iv—Ga1—Cl2^xii	105.3 (6)	Cl2^xii—Ga1—Cl3	55.61 (8)
Cl2^v—Ga1—Cl2^xii	74.7 (6)	Cl2—Ga1—Cl3	55.61 (8)
Cl2^i—Ga1—Cl2	179.995

Symmetry codes: (i) −x, −y, −z; (ii) y, z, x; (iii) −y, −z, −x; (iv) z, x, y; (v) −z, −x, −y; (vi) x, y, −z; (vii) −x, −y, z; (viii) y, z, −x; (ix) −y, −z, x; (x) z, x, −y; (xi) −z, −x, y; (xii) y, −z, −x.