Tetra­kis(dimethyl­ammonium) hexachlorotungstate(III) chloride

The title compound, (C₂H₈N)₄[WCl₆]Cl, contains discrete [WCl₆]³⁻ and Cl⁻ anions and dimethyl­ammonium cations. Both anions lie on crystallographic twofold rotation axes. N—H...Cl hydrogen-bond inter­actions result in the formation of {[(CH₃)₂NH₂]₂(WCl₆)}⁻ anionic layers and [(CH₃)₂NH₂]₂Cl⁺ cationic units.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](W-Cl) = 0.001 Å
• R factor = 0.018
• wR factor = 0.049
• Data-to-parameter ratio = 28.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         N1

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  W1     -   Cl1     ..       5.94 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  W1     -   Cl2     ..       6.19 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  W1     -   Cl3     ..       7.48 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         W1
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1E    ..  CL1     ..       2.94 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1E    ..  CL1     ..       2.86 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.46
           From the CIF: _reflns_number_total               2674
           Count of symmetry unique reflns         1564
           Completeness (_total/calc)            170.97%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1110
           Fraction of Friedel pairs measured     0.710
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalStructure; software used to prepare material for publication: SHELXL97.

Tetrakis(dimethylammonium) hexachloridotungsten(III) chloride

Crystal data

(C2H8N)4[WCl6]Cl	F(000) = 602
Mr = 616.38	Dx = 1.741 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 11279 reflections
a = 10.297 (2) Å	θ = 3.1–27.5°
b = 13.107 (3) Å	µ = 5.70 mm^−1
c = 8.7121 (17) Å	T = 295 K
V = 1175.8 (4) Å^3	Block, colourless
Z = 2	0.24 × 0.22 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	2674 independent reflections
Radiation source: fine-focus sealed tube	2584 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
Tmin = 0.279, Tmax = 0.410	k = −16→15
11579 measured reflections	l = −11→11

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.018	w = 1/[σ^2(Fo^2) + (0.0233P)^2 + 0.3756P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.049	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.51 e Å^−3
2674 reflections	Δρmin = −0.39 e Å^−3
94 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0054 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with how many Friedel pairs?
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.179 (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
W1	0.5000	0.5000	0.429808 (18)	0.03034 (7)
Cl1	0.42517 (12)	0.37903 (9)	0.21508 (14)	0.0624 (3)
Cl2	0.27436 (9)	0.58906 (8)	0.43576 (13)	0.0472 (2)
Cl3	0.58073 (10)	0.63024 (7)	0.62699 (12)	0.0465 (2)
Cl4	0.5000	0.0000	0.0094 (2)	0.1093 (9)
N1	0.2348 (4)	0.0965 (3)	−0.0425 (4)	0.0553 (10)
H1D	0.3116	0.0643	−0.0509	0.066*
H1E	0.1848	0.0764	−0.1216	0.066*
C1	0.1728 (7)	0.0649 (6)	0.1004 (7)	0.100 (2)
H1A	0.1600	−0.0077	0.0993	0.120*
H1B	0.0904	0.0984	0.1104	0.120*
H1C	0.2273	0.0830	0.1856	0.120*
C2	0.2562 (7)	0.2037 (5)	−0.0544 (7)	0.0819 (17)
H2A	0.2961	0.2188	−0.1513	0.098*
H2B	0.3121	0.2256	0.0274	0.098*
H2C	0.1746	0.2389	−0.0472	0.098*
N2	0.8679 (5)	0.6809 (3)	0.4769 (7)	0.0797 (15)
H2D	0.7817	0.6710	0.4845	0.096*
H2E	0.8818	0.7487	0.4754	0.096*
C3	0.9301 (6)	0.6385 (5)	0.6135 (8)	0.0835 (17)
H3A	0.8942	0.6699	0.7036	0.100*
H3B	1.0218	0.6515	0.6094	0.100*
H3C	0.9152	0.5662	0.6173	0.100*
C4	0.9120 (5)	0.6383 (4)	0.3321 (7)	0.0718 (15)
H4A	0.8657	0.6699	0.2491	0.086*
H4B	0.8961	0.5661	0.3312	0.086*
H4C	1.0033	0.6507	0.3204	0.086*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.03023 (10)	0.02800 (10)	0.03279 (10)	−0.00074 (10)	0.000	0.000
Cl1	0.0607 (7)	0.0695 (7)	0.0570 (6)	−0.0060 (5)	−0.0056 (6)	−0.0254 (6)
Cl2	0.0336 (4)	0.0452 (5)	0.0628 (6)	0.0032 (4)	−0.0027 (5)	−0.0004 (5)
Cl3	0.0476 (6)	0.0430 (5)	0.0488 (5)	−0.0038 (4)	−0.0045 (4)	−0.0097 (4)
Cl4	0.0774 (14)	0.176 (3)	0.0745 (11)	0.058 (2)	0.000	0.000
N1	0.054 (2)	0.070 (3)	0.0417 (19)	−0.0052 (19)	−0.0013 (16)	−0.0047 (18)
C1	0.083 (5)	0.157 (7)	0.060 (4)	−0.018 (4)	0.018 (3)	0.014 (4)
C2	0.089 (5)	0.074 (4)	0.083 (4)	−0.008 (3)	−0.013 (3)	−0.006 (3)
N2	0.060 (3)	0.051 (2)	0.129 (5)	0.010 (2)	0.027 (3)	0.005 (3)
C3	0.065 (4)	0.087 (4)	0.099 (4)	0.001 (3)	0.007 (3)	−0.017 (4)
C4	0.061 (3)	0.062 (3)	0.092 (4)	−0.014 (2)	0.007 (3)	−0.004 (3)

Geometric parameters (Å, º)

W1—Cl1	2.5704 (11)	C2—H2A	0.9600
W1—Cl1^i	2.5704 (11)	C2—H2B	0.9600
W1—Cl2	2.6008 (10)	C2—H2C	0.9600
W1—Cl2^i	2.6008 (10)	N2—C4	1.452 (7)
W1—Cl3	2.5605 (10)	N2—C3	1.462 (9)
W1—Cl3^i	2.5605 (10)	N2—H2D	0.9000
N1—C2	1.426 (7)	N2—H2E	0.9000
N1—C1	1.459 (6)	C3—H3A	0.9600
N1—H1D	0.9000	C3—H3B	0.9600
N1—H1E	0.9000	C3—H3C	0.9600
C1—H1A	0.9600	C4—H4A	0.9600
C1—H1B	0.9600	C4—H4B	0.9600
C1—H1C	0.9600	C4—H4C	0.9600
Cl1—W1—Cl1^i	86.60 (6)	H1B—C1—H1C	109.5
Cl1—W1—Cl2	91.35 (4)	N1—C2—H2A	109.5
Cl1^i—W1—Cl2	90.31 (4)	N1—C2—H2B	109.5
Cl1—W1—Cl2^i	90.31 (4)	H2A—C2—H2B	109.5
Cl1^i—W1—Cl2^i	91.35 (4)	N1—C2—H2C	109.5
Cl2—W1—Cl2^i	177.71 (5)	H2A—C2—H2C	109.5
Cl3—W1—Cl1	175.44 (4)	H2B—C2—H2C	109.5
Cl3^i—W1—Cl1	88.84 (4)	C4—N2—C3	115.1 (4)
Cl3—W1—Cl1^i	88.84 (4)	C4—N2—H2D	108.5
Cl3—W1—Cl2	88.71 (3)	C3—N2—H2D	108.5
Cl3^i—W1—Cl2	89.76 (4)	C4—N2—H2E	108.5
Cl3—W1—Cl2^i	89.76 (4)	C3—N2—H2E	108.5
Cl3^i—W1—Cl2^i	88.71 (3)	H2D—N2—H2E	107.5
Cl3—W1—Cl3^i	95.72 (5)	N2—C3—H3A	109.5
Cl3^i—W1—Cl1^i	175.44 (4)	N2—C3—H3B	109.5
C2—N1—C1	114.2 (5)	H3A—C3—H3B	109.5
C2—N1—H1D	108.7	N2—C3—H3C	109.5
C1—N1—H1D	108.7	H3A—C3—H3C	109.5
C2—N1—H1E	108.7	H3B—C3—H3C	109.5
C1—N1—H1E	108.7	N2—C4—H4A	109.5
H1D—N1—H1E	107.6	N2—C4—H4B	109.5
N1—C1—H1A	109.5	H4A—C4—H4B	109.5
N1—C1—H1B	109.5	N2—C4—H4C	109.5
H1A—C1—H1B	109.5	H4A—C4—H4C	109.5
N1—C1—H1C	109.5	H4B—C4—H4C	109.5
H1A—C1—H1C	109.5

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Cl4	0.90	2.18	3.043 (4)	161
N1—H1E···Cl1^ii	0.90	2.94	3.619 (4)	134
N1—H1E···Cl1^iii	0.90	2.86	3.540 (4)	134
N1—H1E···Cl2^ii	0.90	2.77	3.429 (4)	131
N2—H2D···Cl3	0.90	2.47	3.301 (5)	153
N2—H2E···Cl2^iv	0.90	2.52	3.255 (4)	139
N2—H2E···Cl3^iv	0.90	2.74	3.428 (5)	134

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