Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022994/ng2267sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022994/ng2267Isup2.hkl |
CCDC reference: 650685
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (e-Cl) = 0.001 Å
- R factor = 0.034
- wR factor = 0.071
- Data-to-parameter ratio = 20.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT731_ALERT_1_C Bond Calc 0.91(3), Rep 0.907(10) ...... 3.00 su-Ra N1 -H1B 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.91(3), Rep 0.914(10) ...... 3.00 su-Ra N2 -H2B 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.91(3), Rep 0.907(10) ...... 3.00 su-Ra N1 -H1B 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.91(3), Rep 0.914(10) ...... 3.00 su-Ra N2 -H2B 1.555 1.555
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1 (2) 1.97 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 4
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
By the reaction (see Fig. 2) of the 1,4-phenylene-bridged Li scorpionate (I) (0.24 g, 0.47 mmol) with FeCl2 (0.12 g, 0.94 mmol) and [NMe2H2][Br] (ca 0.1 mmol) in 30 ml THF, [NMe2H2]2[FeCl4] was obtained. X-ray quality crystals of [NMe2H2]2[FeCl4] were grown by diffusion of hexane into a solution of [NMe2H2]2[FeCl4] in tetrahydrofuran at ambient temperature.
H atoms bonded to C were refined with fixed individual displacement parameters [Uiso(H) = 1.5Ueq(C)] using a riding model with C—H = 0.98 Å. H atoms bonded to N were freely refined with the N—H distances restrained to 0.91 (1) Å.
We report here the X-ray crystal structure analysis of [NMe2H2]2[FeCl4]. Very recently we have described the solid-state structure of the manganese complex [NMe2H2]2[MnBr4] (Morawitz et al., 2007). The synthesis protocol of [NMe2H2]2[FeCl4] was similar to that of the manganese derivative [NMe2H2]2[MnBr4]. X-ray quality crystals of [NMe2H2]2[FeCl4] were grown by diffusion of hexane into a solution of [NMe2H2]2[FeCl4] in tetrahydrofuran at ambient temperature.
The title compound is composed of discrete dimethylammonium cations and tetrachloroiron(II) anions, which are held together in the crystal by N—H···Cl hydrogen bonds. It is isostructural with dimethylammonium tetrachlorocobaltate(II) (Williams et al., 1992) and dimethylammonium tetrachloromercurate(II) (Ben Salah et al., 1982).
For the tetrachlorocobaltate, see Williams et al. (1992); for the tetrachloromercurate, see Ben Salah et al. (1982).
For related literature, see: Morawitz et al. (2007).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.
(C2H8N)2[FeCl4] | F(000) = 592 |
Mr = 289.84 | Dx = 1.496 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 10454 reflections |
a = 7.8999 (5) Å | θ = 3.4–26.0° |
b = 11.2878 (9) Å | µ = 1.96 mm−1 |
c = 14.5064 (9) Å | T = 173 K |
β = 95.828 (5)° | Block, colourless |
V = 1286.89 (15) Å3 | 0.15 × 0.13 × 0.08 mm |
Z = 4 |
Stoe IPDSII two-circle diffractometer | 2477 independent reflections |
Radiation source: fine-focus sealed tube | 2026 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ω scans | θmax = 25.9°, θmin = 3.4° |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −9→9 |
Tmin = 0.758, Tmax = 0.859 | k = −13→13 |
18093 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0296P)2] where P = (Fo2 + 2Fc2)/3 |
2477 reflections | (Δ/σ)max = 0.001 |
120 parameters | Δρmax = 0.33 e Å−3 |
4 restraints | Δρmin = −0.71 e Å−3 |
(C2H8N)2[FeCl4] | V = 1286.89 (15) Å3 |
Mr = 289.84 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.8999 (5) Å | µ = 1.96 mm−1 |
b = 11.2878 (9) Å | T = 173 K |
c = 14.5064 (9) Å | 0.15 × 0.13 × 0.08 mm |
β = 95.828 (5)° |
Stoe IPDSII two-circle diffractometer | 2477 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 2026 reflections with I > 2σ(I) |
Tmin = 0.758, Tmax = 0.859 | Rint = 0.064 |
18093 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 4 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.33 e Å−3 |
2477 reflections | Δρmin = −0.71 e Å−3 |
120 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.70968 (4) | 0.29611 (3) | 0.45336 (2) | 0.02135 (11) | |
Cl1 | 0.71106 (8) | 0.50045 (5) | 0.44186 (5) | 0.03030 (16) | |
Cl2 | 0.67392 (8) | 0.23483 (6) | 0.60487 (4) | 0.02816 (15) | |
Cl3 | 0.46470 (8) | 0.22615 (5) | 0.36767 (5) | 0.03004 (16) | |
Cl4 | 0.95767 (8) | 0.21556 (6) | 0.41103 (5) | 0.03347 (17) | |
N1 | 0.2669 (3) | 0.1914 (2) | 0.57052 (17) | 0.0304 (5) | |
H1A | 0.368 (2) | 0.227 (3) | 0.565 (2) | 0.040 (9)* | |
H1B | 0.207 (4) | 0.224 (3) | 0.5201 (16) | 0.048 (10)* | |
C1 | 0.2007 (4) | 0.2229 (3) | 0.6601 (2) | 0.0435 (7) | |
H1C | 0.0846 | 0.1925 | 0.6606 | 0.065* | |
H1D | 0.2000 | 0.3093 | 0.6671 | 0.065* | |
H1E | 0.2739 | 0.1877 | 0.7115 | 0.065* | |
C2 | 0.2777 (4) | 0.0616 (3) | 0.5549 (3) | 0.0454 (8) | |
H2C | 0.3563 | 0.0262 | 0.6038 | 0.068* | |
H2D | 0.3192 | 0.0469 | 0.4945 | 0.068* | |
H2E | 0.1646 | 0.0262 | 0.5559 | 0.068* | |
N2 | 0.3056 (3) | 0.4867 (2) | 0.32772 (16) | 0.0283 (5) | |
H2A | 0.344 (4) | 0.535 (2) | 0.3754 (16) | 0.044 (9)* | |
H2B | 0.344 (5) | 0.4129 (17) | 0.345 (3) | 0.068 (12)* | |
C3 | 0.3852 (3) | 0.5206 (3) | 0.24341 (19) | 0.0323 (6) | |
H3A | 0.3535 | 0.4631 | 0.1940 | 0.048* | |
H3B | 0.5093 | 0.5216 | 0.2572 | 0.048* | |
H3C | 0.3456 | 0.5996 | 0.2232 | 0.048* | |
C4 | 0.1171 (3) | 0.4845 (3) | 0.3142 (2) | 0.0373 (7) | |
H4A | 0.0749 | 0.5612 | 0.2900 | 0.056* | |
H4B | 0.0724 | 0.4690 | 0.3737 | 0.056* | |
H4C | 0.0793 | 0.4219 | 0.2701 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.01938 (18) | 0.02096 (19) | 0.0236 (2) | 0.00109 (13) | 0.00171 (13) | 0.00027 (14) |
Cl1 | 0.0325 (3) | 0.0207 (3) | 0.0377 (4) | −0.0013 (2) | 0.0031 (3) | 0.0037 (3) |
Cl2 | 0.0308 (3) | 0.0283 (3) | 0.0250 (3) | −0.0009 (2) | 0.0008 (2) | 0.0049 (2) |
Cl3 | 0.0281 (3) | 0.0271 (3) | 0.0330 (4) | −0.0023 (2) | −0.0066 (3) | −0.0033 (3) |
Cl4 | 0.0247 (3) | 0.0349 (4) | 0.0416 (4) | 0.0068 (2) | 0.0077 (3) | −0.0039 (3) |
N1 | 0.0281 (12) | 0.0259 (12) | 0.0373 (13) | −0.0034 (9) | 0.0039 (10) | 0.0055 (10) |
C1 | 0.0531 (19) | 0.0374 (17) | 0.0420 (18) | −0.0013 (13) | 0.0151 (15) | 0.0073 (14) |
C2 | 0.0532 (19) | 0.0236 (14) | 0.059 (2) | −0.0013 (13) | 0.0033 (16) | 0.0007 (14) |
N2 | 0.0283 (11) | 0.0287 (12) | 0.0272 (12) | 0.0016 (9) | −0.0007 (9) | 0.0012 (10) |
C3 | 0.0297 (13) | 0.0397 (16) | 0.0279 (14) | 0.0023 (11) | 0.0054 (11) | 0.0000 (12) |
C4 | 0.0271 (14) | 0.0424 (17) | 0.0422 (17) | −0.0071 (12) | 0.0025 (12) | 0.0051 (14) |
Fe1—Cl4 | 2.2992 (7) | C2—H2D | 0.9800 |
Fe1—Cl1 | 2.3128 (7) | C2—H2E | 0.9800 |
Fe1—Cl3 | 2.3293 (7) | N2—C3 | 1.482 (4) |
Fe1—Cl2 | 2.3483 (7) | N2—C4 | 1.483 (3) |
N1—C2 | 1.486 (4) | N2—H2A | 0.907 (10) |
N1—C1 | 1.493 (4) | N2—H2B | 0.914 (10) |
N1—H1A | 0.904 (10) | C3—H3A | 0.9800 |
N1—H1B | 0.907 (10) | C3—H3B | 0.9800 |
C1—H1C | 0.9800 | C3—H3C | 0.9800 |
C1—H1D | 0.9800 | C4—H4A | 0.9800 |
C1—H1E | 0.9800 | C4—H4B | 0.9800 |
C2—H2C | 0.9800 | C4—H4C | 0.9800 |
Cl4—Fe1—Cl1 | 111.39 (3) | N1—C2—H2E | 109.5 |
Cl4—Fe1—Cl3 | 114.06 (3) | H2C—C2—H2E | 109.5 |
Cl1—Fe1—Cl3 | 108.02 (3) | H2D—C2—H2E | 109.5 |
Cl4—Fe1—Cl2 | 108.68 (3) | C3—N2—C4 | 113.6 (2) |
Cl1—Fe1—Cl2 | 111.30 (3) | C3—N2—H2A | 110 (2) |
Cl3—Fe1—Cl2 | 103.14 (3) | C4—N2—H2A | 111 (2) |
C2—N1—C1 | 113.5 (2) | C3—N2—H2B | 108 (3) |
C2—N1—H1A | 111 (2) | C4—N2—H2B | 109 (3) |
C1—N1—H1A | 111 (2) | H2A—N2—H2B | 105 (3) |
C2—N1—H1B | 108 (2) | N2—C3—H3A | 109.5 |
C1—N1—H1B | 114 (2) | N2—C3—H3B | 109.5 |
H1A—N1—H1B | 98 (3) | H3A—C3—H3B | 109.5 |
N1—C1—H1C | 109.5 | N2—C3—H3C | 109.5 |
N1—C1—H1D | 109.5 | H3A—C3—H3C | 109.5 |
H1C—C1—H1D | 109.5 | H3B—C3—H3C | 109.5 |
N1—C1—H1E | 109.5 | N2—C4—H4A | 109.5 |
H1C—C1—H1E | 109.5 | N2—C4—H4B | 109.5 |
H1D—C1—H1E | 109.5 | H4A—C4—H4B | 109.5 |
N1—C2—H2C | 109.5 | N2—C4—H4C | 109.5 |
N1—C2—H2D | 109.5 | H4A—C4—H4C | 109.5 |
H2C—C2—H2D | 109.5 | H4B—C4—H4C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl2 | 0.90 (1) | 2.43 (2) | 3.240 (2) | 149 (3) |
N1—H1B···Cl4i | 0.91 (1) | 2.40 (2) | 3.201 (2) | 148 (3) |
N2—H2A···Cl2ii | 0.91 (1) | 2.62 (3) | 3.291 (2) | 131 (3) |
N2—H2A···Cl1ii | 0.91 (1) | 2.76 (3) | 3.362 (2) | 125 (3) |
N2—H2B···Cl3 | 0.91 (1) | 2.32 (1) | 3.227 (2) | 170 (4) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C2H8N)2[FeCl4] |
Mr | 289.84 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 7.8999 (5), 11.2878 (9), 14.5064 (9) |
β (°) | 95.828 (5) |
V (Å3) | 1286.89 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.96 |
Crystal size (mm) | 0.15 × 0.13 × 0.08 |
Data collection | |
Diffractometer | Stoe IPDSII two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.758, 0.859 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18093, 2477, 2026 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.614 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.071, 1.02 |
No. of reflections | 2477 |
No. of parameters | 120 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.71 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl2 | 0.904 (10) | 2.431 (19) | 3.240 (2) | 149 (3) |
N1—H1B···Cl4i | 0.907 (10) | 2.40 (2) | 3.201 (2) | 148 (3) |
N2—H2A···Cl2ii | 0.907 (10) | 2.62 (3) | 3.291 (2) | 131 (3) |
N2—H2A···Cl1ii | 0.907 (10) | 2.76 (3) | 3.362 (2) | 125 (3) |
N2—H2B···Cl3 | 0.914 (10) | 2.323 (13) | 3.227 (2) | 170 (4) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1. |
We report here the X-ray crystal structure analysis of [NMe2H2]2[FeCl4]. Very recently we have described the solid-state structure of the manganese complex [NMe2H2]2[MnBr4] (Morawitz et al., 2007). The synthesis protocol of [NMe2H2]2[FeCl4] was similar to that of the manganese derivative [NMe2H2]2[MnBr4]. X-ray quality crystals of [NMe2H2]2[FeCl4] were grown by diffusion of hexane into a solution of [NMe2H2]2[FeCl4] in tetrahydrofuran at ambient temperature.
The title compound is composed of discrete dimethylammonium cations and tetrachloroiron(II) anions, which are held together in the crystal by N—H···Cl hydrogen bonds. It is isostructural with dimethylammonium tetrachlorocobaltate(II) (Williams et al., 1992) and dimethylammonium tetrachloromercurate(II) (Ben Salah et al., 1982).