Structure of [(CH₃)₂NH₂]₂CoCl₄ at elevated temperatures

The crystal structure of the title compound, dimethyl­ammonium tetrachlorocobaltate(II), has been determined at four temperatures between 297 and 366 K, in order to investigate possible phase transitions at 313 and 353 K [Kapustianik, Polovinko & Kaluza et al. (1996). Phys. Status Solidi A, 153, 117-122]. We found that there is no significant change either in the hydrogen-bonding network or in the cell parameters, apart from a linear dilatation with temperature. This study reveals that the anomalous variation in electric conductivity and some of the other physical properties of the compound cannot be explained by structural changes.

Computing details

For all compounds, data collection: Siemens SMART; cell refinement: Siemens SAINT; data reduction: Siemens SAINT & SADABS; program(s) used to solve structure: SHELXTL (Bruker AXS, 1997); program(s) used to refine structure: SHELXTL (Bruker AXS, 1997); molecular graphics: SHELXTL.

Figures

(297) Dimethylammonium tetrachlorocobaltate(II)

Crystal data

2(C2H8N)·CoCl4	F(000) = 596
Mr = 292.92	Dx = 1.498 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3419 reflections
a = 8.5313 (2) Å	θ = 1–25°
b = 11.4382 (2) Å	µ = 2.10 mm^−1
c = 13.3070 (1) Å	T = 297 K
β = 90.038 (1)°	Plate, dark-blue
V = 1298.53 (4) Å^3	0.50 × 0.35 × 0.06 mm
Z = 4

Data collection

Siemens SMART CCD diffractometer	2372 independent reflections
Radiation source: fine-focus sealed tube	1794 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: no pixels mm^-1	θmax = 25.4°, θmin = 2.4°
ω scans	h = −9→10
Absorption correction: multi-scan (blessing, 1995; Sheldrick, 1996) Blessing, Acta Cryst. (1995), A51, 33-38.	k = −13→13
Tmin = 0.420, Tmax = 0.884	l = −16→15
6987 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	See experimental
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0419P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
2372 reflections	Δρmax = 0.30 e Å^−3
121 parameters	Δρmin = −0.56 e Å^−3
0 restraints	Extinction correction: SHELXTL (Bruker AXS, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0066 (8)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Co1	0.83030 (4)	0.79927 (3)	0.58124 (3)	0.04144 (16)
Cl1	1.07371 (10)	0.73758 (7)	0.63113 (6)	0.0562 (2)
Cl2	0.80783 (11)	0.73567 (7)	0.41972 (6)	0.0568 (2)
Cl3	0.81891 (10)	0.99667 (7)	0.59011 (6)	0.0575 (2)
Cl4	0.64014 (11)	0.72083 (8)	0.67735 (7)	0.0669 (3)
N1	0.7900 (3)	0.9975 (3)	0.3351 (2)	0.0565 (7)
H1A	0.8422	1.0551	0.3668	0.112 (16)*
H1B	0.8115	0.9301	0.3672	0.121 (17)*
N2	0.7068 (3)	0.8097 (2)	0.9034 (2)	0.0591 (7)
H2A	0.6733	0.7726	0.8478	0.077 (13)*
H2B	0.6509	0.7822	0.9557	0.099 (15)*
C11	0.8467 (4)	0.9893 (3)	0.2315 (3)	0.0638 (9)
H11A	0.9583	0.9784	0.2317	0.090 (13)*
H11B	0.8213	1.0600	0.1961	0.096 (14)*
H11C	0.7976	0.9241	0.1987	0.129 (18)*
C21	0.6747 (6)	0.9348 (4)	0.8925 (4)	0.0868 (13)
H21A	0.7114	0.9756	0.9510	0.127 (19)*
H21B	0.5639	0.9468	0.8851	0.122 (18)*
H21C	0.7278	0.9641	0.8341	0.118 (18)*
C22	0.8730 (5)	0.7810 (4)	0.9196 (4)	0.0874 (14)
H22A	0.8845	0.6979	0.9263	0.14 (2)*
H22B	0.9094	0.8185	0.9798	0.14 (2)*
H22C	0.9335	0.8078	0.8634	0.128 (19)*
C12	0.6201 (4)	1.0207 (4)	0.3421 (4)	0.0838 (12)
H12A	0.5897	1.0239	0.4115	0.115 (16)*
H12B	0.5635	0.9593	0.3089	0.105 (16)*
H12C	0.5968	1.0941	0.3104	0.13 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0409 (3)	0.0424 (3)	0.0411 (2)	0.00027 (18)	0.00110 (17)	0.00023 (17)
Cl1	0.0498 (5)	0.0593 (5)	0.0596 (5)	0.0104 (4)	−0.0100 (4)	0.0019 (4)
Cl2	0.0665 (6)	0.0573 (5)	0.0466 (4)	−0.0024 (4)	−0.0060 (4)	−0.0097 (4)
Cl3	0.0636 (5)	0.0429 (4)	0.0661 (5)	0.0035 (4)	−0.0032 (4)	−0.0062 (4)
Cl4	0.0657 (6)	0.0672 (6)	0.0680 (6)	−0.0106 (4)	0.0204 (5)	0.0069 (4)
N1	0.0505 (18)	0.0633 (19)	0.0556 (17)	−0.0004 (14)	−0.0072 (14)	0.0058 (14)
N2	0.0552 (19)	0.0605 (18)	0.0615 (18)	−0.0144 (14)	0.0084 (15)	0.0033 (14)
C11	0.062 (3)	0.070 (2)	0.060 (2)	0.001 (2)	0.0008 (18)	−0.0036 (19)
C21	0.096 (4)	0.065 (3)	0.099 (4)	−0.001 (2)	0.003 (3)	0.008 (2)
C22	0.055 (3)	0.086 (3)	0.121 (4)	−0.007 (2)	0.004 (3)	0.008 (3)
C12	0.052 (2)	0.112 (4)	0.087 (3)	0.014 (2)	0.001 (2)	−0.005 (3)

Geometric parameters (Å, º)

Co1—Cl4	2.2529 (9)	C11—H11A	0.96
Co1—Cl3	2.2631 (9)	C11—H11B	0.96
Co1—Cl2	2.2770 (9)	C11—H11C	0.96
Co1—Cl1	2.2911 (9)	C21—H21A	0.96
N1—C11	1.464 (4)	C21—H21B	0.96
N1—C12	1.476 (4)	C21—H21C	0.96
N1—H1A	0.90	C22—H22A	0.96
N1—H1B	0.90	C22—H22B	0.96
N2—C21	1.464 (5)	C22—H22C	0.96
N2—C22	1.472 (5)	C12—H12A	0.96
N2—H2A	0.90	C12—H12B	0.96
N2—H2B	0.90	C12—H12C	0.96
Cl4—Co1—Cl3	109.68 (4)	N1—C11—H11C	109.5
Cl4—Co1—Cl2	110.39 (4)	H11A—C11—H11C	109.5
Cl3—Co1—Cl2	111.37 (3)	H11B—C11—H11C	109.5
Cl4—Co1—Cl1	111.45 (4)	N2—C21—H21A	109.5
Cl3—Co1—Cl1	109.34 (3)	N2—C21—H21B	109.5
Cl2—Co1—Cl1	104.53 (3)	H21A—C21—H21B	109.5
C11—N1—C12	113.3 (3)	N2—C21—H21C	109.5
C11—N1—H1A	108.9	H21A—C21—H21C	109.5
C12—N1—H1A	108.9	H21B—C21—H21C	109.5
C11—N1—H1B	108.9	N2—C22—H22A	109.5
C12—N1—H1B	108.9	N2—C22—H22B	109.5
H1A—N1—H1B	107.7	H22A—C22—H22B	109.5
C21—N2—C22	114.4 (3)	N2—C22—H22C	109.5
C21—N2—H2A	108.7	H22A—C22—H22C	109.5
C22—N2—H2A	108.7	H22B—C22—H22C	109.5
C21—N2—H2B	108.7	N1—C12—H12A	109.5
C22—N2—H2B	108.7	N1—C12—H12B	109.5
H2A—N2—H2B	107.6	H12A—C12—H12B	109.5
N1—C11—H11A	109.5	N1—C12—H12C	109.5
N1—C11—H11B	109.5	H12A—C12—H12C	109.5
H11A—C11—H11B	109.5	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl2	0.90	2.33	3.203 (3)	163
N1—H1A···Cl1^i	0.90	2.48	3.277 (3)	148
N2—H2B···Cl1^ii	0.90	2.44	3.281 (3)	156
N2—H2A···Cl4	0.90	2.36	3.226 (3)	161
C11—H11B···Cl2^iii	0.96	2.76	3.705 (4)	167
C11—H11C···Cl1^iv	0.96	2.81	3.733 (4)	163
C11—H11A···Cl4^v	0.96	2.85	3.545 (4)	130
C22—H22A···Cl3^vi	0.96	2.89	3.643 (5)	136

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

(320) Dimethylammonium tetrachlorocobaltate(II)

Crystal data

2(C2H8N)·CoCl4	F(000) = 596
Mr = 292.92	Dx = 1.490 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2719 reflections
a = 8.5513 (5) Å	θ = 1–25°
b = 11.4527 (7) Å	µ = 2.09 mm^−1
c = 13.3364 (8) Å	T = 320 K
β = 90.010 (1)°	Plate, dark-blue
V = 1306.11 (14) Å^3	0.50 × 0.35 × 0.06 mm
Z = 4

Data collection

Siemens SMART CCD diffractometer	2397 independent reflections
Radiation source: fine-focus sealed tube	1688 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Detector resolution: no pixels mm^-1	θmax = 25.4°, θmin = 2.3°
ω scans	h = −9→10
Absorption correction: multi-scan (blessing, 1995; Sheldrick, 1996) Blessing, Acta Cryst. (1995), A51, 33-38.	k = −13→13
Tmin = 0.422, Tmax = 0.885	l = −16→10
6082 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	See experimental
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0398P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
2397 reflections	Δρmax = 0.28 e Å^−3
121 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXTL (Bruker AXS, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (8)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Co1	0.83017 (5)	0.79888 (3)	0.58100 (3)	0.04526 (17)
Cl1	1.07291 (11)	0.73707 (8)	0.63069 (7)	0.0617 (3)
Cl2	0.80759 (11)	0.73592 (8)	0.41975 (7)	0.0622 (3)
Cl3	0.81906 (11)	0.99600 (7)	0.59014 (7)	0.0633 (3)
Cl4	0.64042 (13)	0.72056 (8)	0.67701 (8)	0.0738 (3)
N1	0.7898 (3)	0.9979 (3)	0.3350 (2)	0.0618 (8)
H1A	0.8114	0.9308	0.3673	0.14 (2)*
H1B	0.8418	1.0557	0.3663	0.113 (17)*
N2	0.7067 (4)	0.8094 (3)	0.9032 (3)	0.0661 (8)
H2A	0.6728	0.7726	0.8476	0.094 (16)*
H2B	0.6514	0.7817	0.9554	0.112 (17)*
C11	0.8463 (5)	0.9891 (4)	0.2317 (3)	0.0696 (10)
H11A	0.9578	0.9792	0.2320	0.108 (16)*
H11B	0.8200	1.0591	0.1959	0.101 (15)*
H11C	0.7983	0.9233	0.1996	0.118 (17)*
C21	0.6746 (6)	0.9345 (4)	0.8928 (4)	0.0971 (15)
H21A	0.7092	0.9747	0.9519	0.14 (2)*
H21B	0.5643	0.9464	0.8841	0.14 (2)*
H21C	0.7294	0.9645	0.8354	0.124 (19)*
C22	0.8724 (5)	0.7806 (5)	0.9185 (5)	0.0962 (16)
H22A	0.8835	0.6977	0.9263	0.17 (3)*
H22B	0.9099	0.8192	0.9777	0.15 (3)*
H22C	0.9319	0.8060	0.8616	0.14 (2)*
C12	0.6215 (5)	1.0208 (5)	0.3418 (4)	0.0900 (13)
H12A	0.5904	1.0219	0.4109	0.103 (16)*
H12B	0.5652	0.9606	0.3071	0.17 (3)*
H12C	0.5985	1.0951	0.3117	0.13 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0445 (3)	0.0460 (3)	0.0453 (3)	0.0004 (2)	0.00140 (19)	0.00013 (19)
Cl1	0.0537 (5)	0.0640 (5)	0.0675 (6)	0.0115 (4)	−0.0114 (4)	0.0015 (4)
Cl2	0.0724 (6)	0.0621 (5)	0.0520 (5)	−0.0018 (4)	−0.0079 (4)	−0.0106 (4)
Cl3	0.0698 (6)	0.0469 (5)	0.0732 (6)	0.0039 (4)	−0.0042 (5)	−0.0067 (4)
Cl4	0.0718 (7)	0.0734 (6)	0.0761 (7)	−0.0123 (5)	0.0236 (5)	0.0064 (5)
N1	0.0526 (19)	0.067 (2)	0.066 (2)	−0.0017 (16)	−0.0090 (16)	0.0053 (17)
N2	0.062 (2)	0.066 (2)	0.070 (2)	−0.0159 (16)	0.0087 (17)	0.0029 (17)
C11	0.070 (3)	0.074 (3)	0.065 (3)	−0.001 (2)	−0.001 (2)	−0.006 (2)
C21	0.104 (4)	0.076 (3)	0.111 (4)	0.002 (3)	0.007 (3)	0.015 (3)
C22	0.059 (3)	0.100 (4)	0.129 (5)	−0.007 (3)	0.003 (3)	0.015 (3)
C12	0.058 (3)	0.119 (4)	0.093 (4)	0.018 (3)	0.001 (2)	0.001 (3)

Geometric parameters (Å, º)

Co1—Cl4	2.2533 (10)	C11—H11A	0.96
Co1—Cl3	2.2628 (9)	C11—H11B	0.96
Co1—Cl2	2.2763 (10)	C11—H11C	0.96
Co1—Cl1	2.2910 (10)	C21—H21A	0.96
N1—C12	1.466 (5)	C21—H21B	0.96
N1—C11	1.463 (4)	C21—H21C	0.96
N1—H1A	0.90	C22—H22A	0.96
N1—H1B	0.90	C22—H22B	0.96
N2—C21	1.465 (5)	C22—H22C	0.96
N2—C22	1.469 (5)	C12—H12A	0.96
N2—H2A	0.90	C12—H12B	0.96
N2—H2B	0.90	C12—H12C	0.96
Cl4—Co1—Cl3	109.65 (4)	N1—C11—H11C	109.5
Cl4—Co1—Cl2	110.48 (4)	H11A—C11—H11C	109.5
Cl3—Co1—Cl2	111.30 (4)	H11B—C11—H11C	109.5
Cl4—Co1—Cl1	111.42 (4)	N2—C21—H21A	109.5
Cl3—Co1—Cl1	109.31 (4)	N2—C21—H21B	109.5
Cl2—Co1—Cl1	104.60 (4)	H21A—C21—H21B	109.5
C12—N1—C11	113.3 (3)	N2—C21—H21C	109.5
C12—N1—H1A	108.9	H21A—C21—H21C	109.5
C11—N1—H1A	108.9	H21B—C21—H21C	109.5
C12—N1—H1B	108.9	N2—C22—H22A	109.5
C11—N1—H1B	108.9	N2—C22—H22B	109.5
H1A—N1—H1B	107.7	H22A—C22—H22B	109.5
C21—N2—C22	114.4 (4)	N2—C22—H22C	109.5
C21—N2—H2A	108.6	H22A—C22—H22C	109.5
C22—N2—H2A	108.6	H22B—C22—H22C	109.5
C21—N2—H2B	108.6	N1—C12—H12A	109.5
C22—N2—H2B	108.6	N1—C12—H12B	109.5
H2A—N2—H2B	107.6	H12A—C12—H12B	109.5
N1—C11—H11A	109.5	N1—C12—H12C	109.5
N1—C11—H11B	109.5	H12A—C12—H12C	109.5
H11A—C11—H11B	109.5	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2	0.90	2.34	3.210 (3)	163
N1—H1B···Cl1^i	0.90	2.48	3.286 (3)	149
N2—H2B···Cl1^ii	0.90	2.44	3.287 (3)	156
N2—H2A···Cl4	0.90	2.37	3.233 (4)	161
C11—H11B···Cl2^iii	0.96	2.77	3.715 (4)	169
C11—H11C···Cl1^iv	0.96	2.82	3.741 (4)	162
C11—H11A···Cl4^v	0.96	2.87	3.553 (4)	129
C22—H22A···Cl3^vi	0.96	2.90	3.649 (5)	136

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

(343) Dimethylammonium tetrachlorocobaltate(II)

Crystal data

2(C2H8N)·CoCl4	F(000) = 596
Mr = 292.92	Dx = 1.484 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2563 reflections
a = 8.5640 (2) Å	θ = 1–25°
b = 11.4573 (3) Å	µ = 2.08 mm^−1
c = 13.3590 (3) Å	T = 343 K
β = 90.037 (1)°	Plate, dark-blue
V = 1310.79 (5) Å^3	0.50 × 0.35 × 0.06 mm
Z = 4

Data collection

Siemens SMART CCD diffractometer	2399 independent reflections
Radiation source: fine-focus sealed tube	1639 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: no pixels mm^-1	θmax = 25.3°, θmin = 2.3°
ω scans	h = −10→9
Absorption correction: multi-scan (blessing, 1995; Sheldrick, 1996) Blessing, Acta Cryst. (1995), A51, 33-38.	k = −13→13
Tmin = 0.423, Tmax = 0.885	l = −10→16
6097 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	See experimental
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0365P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
2399 reflections	Δρmax = 0.31 e Å^−3
121 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXTL (Bruker AXS, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0119 (9)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Co1	0.83009 (5)	0.79838 (4)	0.58077 (3)	0.04963 (18)
Cl1	1.07231 (12)	0.73664 (8)	0.63023 (8)	0.0682 (3)
Cl2	0.80728 (12)	0.73594 (8)	0.41986 (7)	0.0684 (3)
Cl3	0.81917 (11)	0.99526 (8)	0.59017 (8)	0.0695 (3)
Cl4	0.64056 (13)	0.72035 (9)	0.67655 (8)	0.0815 (3)
N1	0.7899 (3)	0.9989 (3)	0.3355 (2)	0.0675 (8)
H1A	0.8118	0.9323	0.3683	0.128 (19)*
H1B	0.8417	1.0573	0.3661	0.19 (3)*
N2	0.7066 (4)	0.8092 (3)	0.9022 (3)	0.0718 (9)
H2A	0.6740	0.7727	0.8463	0.13 (2)*
H2B	0.6504	0.7812	0.9538	0.116 (18)*
C11	0.8459 (5)	0.9889 (4)	0.2317 (3)	0.0781 (11)
H11A	0.9572	0.9795	0.2317	0.113 (17)*
H11B	0.8187	1.0583	0.1953	0.13 (2)*
H11C	0.7981	0.9224	0.2004	0.16 (2)*
C21	0.6749 (7)	0.9344 (4)	0.8920 (5)	0.1046 (16)
H21A	0.5649	0.9463	0.8826	0.13 (2)*
H21B	0.7306	0.9646	0.8353	0.18 (3)*
H21C	0.7083	0.9742	0.9515	0.15 (2)*
C22	0.8717 (6)	0.7807 (5)	0.9188 (5)	0.1062 (17)
H22A	0.8822	0.6984	0.9303	0.19 (3)*
H22B	0.9095	0.8227	0.9761	0.18 (3)*
H22C	0.9313	0.8024	0.8609	0.16 (3)*
C12	0.6214 (5)	1.0216 (6)	0.3421 (4)	0.1019 (15)
H12A	0.5903	1.0223	0.4111	0.115 (18)*
H12B	0.5655	0.9614	0.3073	0.17 (3)*
H12C	0.5984	1.0959	0.3123	0.15 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0490 (3)	0.0506 (3)	0.0493 (3)	0.0003 (2)	0.0011 (2)	0.0003 (2)
Cl1	0.0597 (6)	0.0704 (6)	0.0746 (6)	0.0123 (5)	−0.0128 (5)	0.0015 (5)
Cl2	0.0804 (7)	0.0684 (6)	0.0565 (6)	−0.0017 (5)	−0.0083 (5)	−0.0111 (4)
Cl3	0.0778 (7)	0.0508 (5)	0.0799 (7)	0.0040 (5)	−0.0037 (5)	−0.0075 (4)
Cl4	0.0795 (7)	0.0813 (7)	0.0836 (7)	−0.0128 (5)	0.0264 (6)	0.0085 (5)
N1	0.061 (2)	0.071 (2)	0.071 (2)	−0.0011 (17)	−0.0101 (17)	0.0094 (18)
N2	0.065 (2)	0.073 (2)	0.077 (2)	−0.0156 (18)	0.0092 (19)	0.0055 (19)
C11	0.075 (3)	0.089 (3)	0.071 (3)	−0.002 (3)	0.003 (2)	−0.009 (2)
C21	0.115 (5)	0.079 (3)	0.120 (5)	−0.001 (3)	0.001 (4)	0.010 (3)
C22	0.066 (3)	0.111 (4)	0.142 (5)	−0.007 (3)	0.004 (4)	0.014 (4)
C12	0.060 (3)	0.140 (5)	0.105 (4)	0.022 (3)	0.002 (3)	−0.001 (4)

Geometric parameters (Å, º)

Co1—Cl4	2.2525 (10)	C11—H11A	0.96
Co1—Cl3	2.2611 (10)	C11—H11B	0.96
Co1—Cl2	2.2738 (10)	C11—H11C	0.96
Co1—Cl1	2.2887 (10)	C21—H21A	0.96
N1—C12	1.469 (5)	C21—H21B	0.96
N1—C11	1.471 (5)	C21—H21C	0.96
N1—H1A	0.90	C22—H22A	0.96
N1—H1B	0.90	C22—H22B	0.96
N2—C21	1.466 (5)	C22—H22C	0.96
N2—C22	1.467 (6)	C12—H12A	0.96
N2—H2A	0.90	C12—H12B	0.96
N2—H2B	0.90	C12—H12C	0.96
Cl4—Co1—Cl3	109.54 (4)	N1—C11—H11C	109.5
Cl4—Co1—Cl2	110.53 (4)	H11A—C11—H11C	109.5
Cl3—Co1—Cl2	111.28 (4)	H11B—C11—H11C	109.5
Cl4—Co1—Cl1	111.51 (4)	N2—C21—H21A	109.5
Cl3—Co1—Cl1	109.26 (4)	N2—C21—H21B	109.5
Cl2—Co1—Cl1	104.65 (4)	H21A—C21—H21B	109.5
C12—N1—C11	113.1 (4)	N2—C21—H21C	109.5
C12—N1—H1A	109.0	H21A—C21—H21C	109.5
C11—N1—H1A	109.0	H21B—C21—H21C	109.5
C12—N1—H1B	109.0	N2—C22—H22A	109.5
C11—N1—H1B	109.0	N2—C22—H22B	109.5
H1A—N1—H1B	107.8	H22A—C22—H22B	109.5
C21—N2—C22	114.2 (4)	N2—C22—H22C	109.5
C21—N2—H2A	108.7	H22A—C22—H22C	109.5
C22—N2—H2A	108.7	H22B—C22—H22C	109.5
C21—N2—H2B	108.7	N1—C12—H12A	109.5
C22—N2—H2B	108.7	N1—C12—H12B	109.5
H2A—N2—H2B	107.6	H12A—C12—H12B	109.5
N1—C11—H11A	109.5	N1—C12—H12C	109.5
N1—C11—H11B	109.5	H12A—C12—H12C	109.5
H11A—C11—H11B	109.5	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2	0.90	2.35	3.221 (3)	162
N1—H1B···Cl1^i	0.90	2.47	3.283 (4)	150
N2—H2B···Cl1^ii	0.90	2.46	3.299 (4)	155
N2—H2A···Cl4	0.90	2.36	3.231 (4)	162
C11—H11B···Cl2^iii	0.96	2.77	3.718 (5)	170
C11—H11C···Cl1^iv	0.96	2.82	3.742 (5)	162
C11—H11A···Cl4^v	0.96	2.87	3.559 (5)	129
C22—H22A···Cl3^vi	0.96	2.91	3.658 (6)	136

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

(366) Dimethylammonium Tetrachlorocobaltate(II)

Crystal data

2(C2H8N)·CoCl4	F(000) = 596
Mr = 292.92	Dx = 1.478 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2910 reflections
a = 8.5775 (5) Å	θ = 1–25°
b = 11.4679 (6) Å	µ = 2.07 mm^−1
c = 13.3855 (6) Å	T = 366 K
β = 90.021 (1)°	Plate, dark-blue
V = 1316.68 (12) Å^3	0.50 × 0.35 × 0.06 mm
Z = 4

Data collection

Siemens SMART CCD diffractometer	2412 independent reflections
Radiation source: fine-focus sealed tube	1666 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: no pixels mm^-1	θmax = 25.4°, θmin = 2.3°
ω scans	h = −9→10
Absorption correction: multi-scan (blessing, 1995; Sheldrick, 1996) Blessing, Acta Cryst. (1995), A51, 33-38.	k = −13→13
Tmin = 0.424, Tmax = 0.886	l = −16→15
7139 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	See experimental
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0457P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
2412 reflections	Δρmax = 0.33 e Å^−3
121 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Extinction correction: SHELXTL (Bruker AXS, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0153 (11)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Co1	0.82990 (5)	0.79809 (4)	0.58059 (3)	0.0542 (2)
Cl1	1.07183 (12)	0.73627 (9)	0.62985 (8)	0.0747 (3)
Cl2	0.80737 (13)	0.73574 (9)	0.41987 (7)	0.0753 (3)
Cl3	0.81945 (11)	0.99470 (8)	0.59026 (8)	0.0763 (3)
Cl4	0.64044 (14)	0.72026 (9)	0.67605 (9)	0.0891 (4)
N1	0.7898 (4)	0.9986 (3)	0.3355 (2)	0.0742 (9)
H1A	0.8426	1.0561	0.3664	0.15 (2)*
H1B	0.8101	0.9317	0.3682	0.21 (3)*
N2	0.7066 (4)	0.8099 (3)	0.9019 (3)	0.0810 (10)
H2A	0.6741	0.7738	0.8459	0.15 (3)*
H2B	0.6502	0.7815	0.9531	0.14 (2)*
C11	0.8459 (5)	0.9883 (4)	0.2327 (3)	0.0839 (12)
H11A	0.9573	0.9800	0.2329	0.16 (2)*
H11B	0.8177	1.0570	0.1959	0.130 (19)*
H11C	0.7995	0.9212	0.2018	0.19 (3)*
C21	0.6742 (7)	0.9339 (5)	0.8924 (5)	0.1145 (17)
H21A	0.5642	0.9454	0.8836	0.14 (2)*
H21B	0.7290	0.9645	0.8356	0.17 (3)*
H21C	0.7081	0.9735	0.9517	0.19 (3)*
C22	0.8708 (6)	0.7803 (5)	0.9185 (6)	0.1146 (19)
H22A	0.8804	0.6978	0.9291	0.21 (3)*
H22B	0.9086	0.8211	0.9762	0.17 (3)*
H22C	0.9309	0.8025	0.8611	0.13 (2)*
C12	0.6220 (5)	1.0232 (6)	0.3421 (5)	0.1111 (17)
H12A	0.6005	1.0975	0.3122	0.24 (4)*
H12B	0.5909	1.0246	0.4110	0.13 (2)*
H12C	0.5650	0.9636	0.3075	0.16 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0525 (3)	0.0545 (3)	0.0554 (3)	0.0004 (2)	0.0035 (2)	0.0004 (2)
Cl1	0.0645 (6)	0.0769 (6)	0.0829 (6)	0.0135 (5)	−0.0119 (5)	0.0017 (5)
Cl2	0.0886 (7)	0.0738 (6)	0.0636 (6)	−0.0014 (5)	−0.0082 (5)	−0.0120 (5)
Cl3	0.0839 (7)	0.0546 (5)	0.0905 (7)	0.0045 (5)	−0.0021 (5)	−0.0087 (5)
Cl4	0.0862 (8)	0.0879 (8)	0.0931 (8)	−0.0149 (6)	0.0297 (6)	0.0088 (6)
N1	0.064 (2)	0.086 (2)	0.073 (2)	−0.0030 (18)	−0.0093 (17)	0.0066 (18)
N2	0.076 (2)	0.081 (2)	0.087 (2)	−0.0153 (19)	0.013 (2)	0.004 (2)
C11	0.082 (3)	0.088 (3)	0.081 (3)	−0.001 (3)	0.002 (2)	0.000 (2)
C21	0.121 (5)	0.083 (4)	0.140 (5)	0.004 (3)	0.006 (4)	0.014 (4)
C22	0.073 (3)	0.113 (5)	0.158 (6)	−0.006 (3)	0.010 (4)	0.019 (4)
C12	0.064 (3)	0.154 (5)	0.115 (4)	0.017 (3)	0.005 (3)	−0.005 (4)

Geometric parameters (Å, º)

Co1—Cl4	2.2520 (11)	C11—H11A	0.96
Co1—Cl3	2.2602 (10)	C11—H11B	0.96
Co1—Cl2	2.2752 (10)	C11—H11C	0.96
Co1—Cl1	2.2897 (10)	C21—H21A	0.96
N1—C11	1.463 (5)	C21—H21B	0.96
N1—C12	1.469 (5)	C21—H21C	0.96
N1—H1A	0.90	C22—H22A	0.96
N1—H1B	0.90	C22—H22B	0.96
N2—C21	1.455 (6)	C22—H22C	0.96
N2—C22	1.466 (6)	C12—H12A	0.96
N2—H2A	0.90	C12—H12B	0.96
N2—H2B	0.90	C12—H12C	0.96
Cl4—Co1—Cl3	109.52 (4)	N1—C11—H11C	109.5
Cl4—Co1—Cl2	110.54 (5)	H11A—C11—H11C	109.5
Cl3—Co1—Cl2	111.36 (4)	H11B—C11—H11C	109.5
Cl4—Co1—Cl1	111.59 (5)	N2—C21—H21A	109.5
Cl3—Co1—Cl1	109.17 (4)	N2—C21—H21B	109.5
Cl2—Co1—Cl1	104.57 (4)	H21A—C21—H21B	109.5
C11—N1—C12	113.2 (4)	N2—C21—H21C	109.5
C11—N1—H1A	108.9	H21A—C21—H21C	109.5
C12—N1—H1A	108.9	H21B—C21—H21C	109.5
C11—N1—H1B	108.9	N2—C22—H22A	109.5
C12—N1—H1B	108.9	N2—C22—H22B	109.5
H1A—N1—H1B	107.7	H22A—C22—H22B	109.5
C21—N2—C22	115.0 (4)	N2—C22—H22C	109.5
C21—N2—H2A	108.5	H22A—C22—H22C	109.5
C22—N2—H2A	108.5	H22B—C22—H22C	109.5
C21—N2—H2B	108.5	N1—C12—H12A	109.5
C22—N2—H2B	108.5	N1—C12—H12B	109.5
H2A—N2—H2B	107.5	H12A—C12—H12B	109.5
N1—C11—H11A	109.5	N1—C12—H12C	109.5
N1—C11—H11B	109.5	H12A—C12—H12C	109.5
H11A—C11—H11B	109.5	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl2	0.90	2.35	3.222 (4)	163
N1—H1A···Cl1^i	0.90	2.49	3.297 (4)	149
N2—H2B···Cl1^ii	0.90	2.47	3.306 (4)	155
N2—H2A···Cl4	0.90	2.37	3.243 (4)	163
C11—H11B···Cl2^iii	0.96	2.78	3.735 (5)	171
C11—H11C···Cl1^iv	0.96	2.83	3.749 (5)	161
C11—H11A···Cl4^v	0.96	2.88	3.561 (5)	128
C22—H22A···Cl3^vi	0.96	2.90	3.661 (6)	137

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