Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801012843/wn6042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801012843/wn6042Isup2.hkl |
CCDC reference: 172190
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.003 Å
- R factor = 0.048
- wR factor = 0.129
- Data-to-parameter ratio = 29.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 32.81 From the CIF: _reflns_number_total 7391 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 7848 Completeness (_total/calc) 94.18% Alert C: < 95% complete
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The synthesis and structure of (2-hydroxyethyl)diisopropylammonium chloride, (II), is described elsewhere (Mahmoudkhani & Langer, 1999c); 1HNMR (400 MHz, D2O): δ 1.33 (d, 6.4, CH3), 1.34 (d, 6.4, CH3), 3.27 (t, 5.6, CH2–N), 3.76 (m, 6.4, CH), 3.86 (t, 5.6, CH2–O). In a small round-bottomed flask with a capacity of 25 ml, 110 mmol of (II) was added to a solution of 50 mmol of CoCl2·6H2O in ethanol (15 ml). The mixture was refluxed for about 1 h. Solvents were removed by azeotropic distillation with toluene. After gently removing toluene under vacuum, a blue highly viscous oily material was obtained which was kept in a desiccator over silica gel; 1H NMR (400 MHz, CDCl3): δH 1.40 (d, 6.4), 1.52 (d, 6.4), 3.05 (s, br), 3.60 (s, br), 4.20 (s, br). Blue plate crystals of the title compound suitable for diffraction analysis were obtained after 8 months growth from the oily product (yield 20–30%).
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT and SADABS (Sheldrick, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2000).
(C16H36N2)[CoCl4] | F(000) = 964 |
Mr = 457.20 | Dx = 1.436 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1245 (3) Å | Cell parameters from 5489 reflections |
b = 17.1830 (7) Å | θ = 1–32° |
c = 17.3367 (7) Å | µ = 1.32 mm−1 |
β = 94.640 (1)° | T = 183 K |
V = 2115.41 (15) Å3 | Plate, blue |
Z = 4 | 0.60 × 0.50 × 0.04 mm |
Siemens SMART CCD diffractometer | 7391 independent reflections |
Radiation source: fine-focus sealed tube | 4998 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 32.8°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −10→10 |
Tmin = 0.505, Tmax = 0.949 | k = −26→24 |
24763 measured reflections | l = −25→25 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0728P)2P] where P = (Fo2 + 2Fc2)/3 |
7391 reflections | (Δ/σ)max = 0.001 |
252 parameters | Δρmax = 0.92 e Å−3 |
0 restraints | Δρmin = −1.08 e Å−3 |
(C16H36N2)[CoCl4] | V = 2115.41 (15) Å3 |
Mr = 457.20 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.1245 (3) Å | µ = 1.32 mm−1 |
b = 17.1830 (7) Å | T = 183 K |
c = 17.3367 (7) Å | 0.60 × 0.50 × 0.04 mm |
β = 94.640 (1)° |
Siemens SMART CCD diffractometer | 7391 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 4998 reflections with I > 2σ(I) |
Tmin = 0.505, Tmax = 0.949 | Rint = 0.052 |
24763 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.92 e Å−3 |
7391 reflections | Δρmin = −1.08 e Å−3 |
252 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 > 2σ (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 | ||
Co1 | 0.34051 (4) | 0.867580 (16) | 0.221751 (16) | 0.01777 (8) | |
Cl1 | 0.19347 (8) | 0.98156 (3) | 0.18424 (3) | 0.02645 (13) | |
Cl2 | 0.60844 (8) | 0.86655 (3) | 0.15938 (4) | 0.02959 (14) | |
Cl3 | 0.18439 (8) | 0.75342 (3) | 0.19574 (3) | 0.02979 (14) | |
Cl4 | 0.41649 (8) | 0.86937 (3) | 0.35253 (3) | 0.02717 (13) | |
N1 | 0.7340 (2) | 1.13133 (9) | 0.14845 (10) | 0.0154 (3) | |
N2 | 0.7753 (2) | 1.10352 (9) | 0.32423 (10) | 0.0150 (3) | |
C3 | 0.8255 (3) | 1.17883 (11) | 0.28536 (11) | 0.0167 (4) | |
H3A | 0.9298 | 1.2041 | 0.3172 | 0.020 (6)* | |
H3B | 0.7154 | 1.2141 | 0.2839 | 0.016 (6)* | |
C1 | 0.6866 (3) | 1.05525 (11) | 0.18729 (11) | 0.0172 (4) | |
H1A | 0.7981 | 1.0207 | 0.1888 | 0.013 (5)* | |
H1B | 0.5834 | 1.0293 | 0.1553 | 0.019 (6)* | |
C24 | 0.6724 (3) | 1.12646 (12) | 0.39734 (12) | 0.0193 (4) | |
H24 | 0.5495 | 1.1496 | 0.3769 | 0.041 (8)* | |
C13 | 0.5549 (3) | 1.18336 (12) | 0.13826 (12) | 0.0195 (4) | |
H13 | 0.4948 | 1.1791 | 0.1883 | 0.019 (6)* | |
C2 | 0.6277 (3) | 1.06464 (12) | 0.26899 (11) | 0.0162 (4) | |
H2A | 0.5106 | 1.0958 | 0.2671 | 0.020 (6)* | |
H2B | 0.5990 | 1.0126 | 0.2896 | 0.019 (6)* | |
C26 | 0.6219 (3) | 1.05716 (13) | 0.44540 (13) | 0.0239 (5) | |
H26A | 0.7363 | 1.0360 | 0.4728 | 0.021 (6)* | |
H26B | 0.5624 | 1.0171 | 0.4115 | 0.029 (7)* | |
H26C | 0.5342 | 1.0735 | 0.4830 | 0.044 (8)* | |
C21 | 0.9530 (3) | 1.05105 (12) | 0.33717 (12) | 0.0194 (4) | |
H21 | 1.0172 | 1.0544 | 0.2881 | 0.024 (6)* | |
C11 | 0.4082 (3) | 1.15292 (14) | 0.07670 (14) | 0.0273 (5) | |
H11A | 0.2890 | 1.1805 | 0.0807 | 0.050 (9)* | |
H11B | 0.3893 | 1.0971 | 0.0845 | 0.037 (8)* | |
H11C | 0.4522 | 1.1616 | 0.0253 | 0.038 (8)* | |
C14 | 0.8736 (3) | 1.17987 (14) | 0.02430 (13) | 0.0277 (5) | |
H14A | 0.9611 | 1.1649 | −0.0139 | 0.030 (7)* | |
H14B | 0.9301 | 1.2213 | 0.0574 | 0.034 (7)* | |
H14C | 0.7558 | 1.1987 | −0.0024 | 0.024 (7)* | |
C16 | 0.8329 (3) | 1.10958 (13) | 0.07380 (12) | 0.0208 (4) | |
H16 | 0.9591 | 1.0885 | 0.0928 | 0.021 (6)* | |
C23 | 1.0962 (3) | 1.08064 (15) | 0.40022 (15) | 0.0321 (5) | |
H23A | 1.0491 | 1.0714 | 0.4510 | 0.038 (8)* | |
H23B | 1.1160 | 1.1366 | 0.3932 | 0.050 (10)* | |
H23C | 1.2157 | 1.0530 | 0.3971 | 0.051 (9)* | |
C4 | 0.8837 (3) | 1.16894 (11) | 0.20386 (11) | 0.0166 (4) | |
H4A | 0.9150 | 1.2207 | 0.1833 | 0.019 (6)* | |
H4B | 0.9992 | 1.1367 | 0.2057 | 0.024 (7)* | |
C12 | 0.5921 (3) | 1.26985 (12) | 0.12786 (14) | 0.0270 (5) | |
H12A | 0.6473 | 1.2783 | 0.0785 | 0.019 (6)* | |
H12B | 0.6798 | 1.2883 | 0.1704 | 0.043 (8)* | |
H12C | 0.4734 | 1.2986 | 0.1279 | 0.045 (8)* | |
C15 | 0.7382 (4) | 1.04495 (14) | 0.02480 (13) | 0.0295 (5) | |
H15A | 0.6163 | 1.0633 | 0.0015 | 0.049 (9)* | |
H15B | 0.7189 | 0.9996 | 0.0575 | 0.042 (8)* | |
H15C | 0.8185 | 1.0303 | −0.0162 | 0.047 (9)* | |
C22 | 0.9133 (3) | 0.96463 (13) | 0.34826 (14) | 0.0267 (5) | |
H22A | 1.0326 | 0.9360 | 0.3538 | 0.041 (8)* | |
H22B | 0.8358 | 0.9450 | 0.3032 | 0.043 (9)* | |
H22C | 0.8461 | 0.9575 | 0.3949 | 0.034 (7)* | |
C25 | 0.7697 (4) | 1.18917 (14) | 0.44820 (14) | 0.0309 (5) | |
H25A | 0.6876 | 1.2048 | 0.4882 | 0.060 (10)* | |
H25B | 0.7960 | 1.2344 | 0.4163 | 0.077 (12)* | |
H25C | 0.8882 | 1.1687 | 0.4728 | 0.045 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.02212 (15) | 0.01060 (13) | 0.02071 (15) | −0.00007 (10) | 0.00251 (10) | −0.00061 (10) |
Cl1 | 0.0319 (3) | 0.0205 (3) | 0.0278 (3) | 0.0100 (2) | 0.0072 (2) | 0.0048 (2) |
Cl2 | 0.0330 (3) | 0.0123 (2) | 0.0460 (3) | 0.0011 (2) | 0.0187 (3) | 0.0005 (2) |
Cl3 | 0.0310 (3) | 0.0211 (3) | 0.0377 (3) | −0.0098 (2) | 0.0053 (2) | −0.0066 (2) |
Cl4 | 0.0338 (3) | 0.0254 (3) | 0.0218 (3) | 0.0008 (2) | −0.0011 (2) | −0.0015 (2) |
N1 | 0.0200 (8) | 0.0099 (7) | 0.0161 (8) | 0.0000 (6) | 0.0008 (6) | 0.0017 (6) |
N2 | 0.0198 (8) | 0.0084 (7) | 0.0168 (8) | −0.0013 (6) | 0.0007 (6) | 0.0001 (6) |
C3 | 0.0245 (10) | 0.0076 (8) | 0.0174 (9) | −0.0022 (7) | −0.0009 (7) | 0.0010 (7) |
C1 | 0.0243 (10) | 0.0091 (8) | 0.0178 (9) | −0.0020 (7) | −0.0004 (8) | 0.0010 (7) |
C24 | 0.0258 (10) | 0.0148 (9) | 0.0177 (9) | 0.0031 (8) | 0.0045 (8) | −0.0008 (7) |
C13 | 0.0209 (10) | 0.0145 (9) | 0.0229 (10) | 0.0013 (8) | −0.0001 (8) | 0.0024 (8) |
C2 | 0.0198 (9) | 0.0121 (9) | 0.0164 (9) | −0.0032 (7) | −0.0013 (7) | −0.0004 (7) |
C26 | 0.0317 (12) | 0.0187 (10) | 0.0225 (11) | −0.0040 (9) | 0.0089 (9) | 0.0009 (8) |
C21 | 0.0202 (10) | 0.0145 (9) | 0.0234 (10) | 0.0048 (7) | 0.0011 (8) | 0.0040 (8) |
C11 | 0.0274 (11) | 0.0222 (11) | 0.0308 (12) | −0.0010 (9) | −0.0071 (9) | 0.0058 (9) |
C14 | 0.0341 (13) | 0.0286 (12) | 0.0211 (11) | −0.0044 (10) | 0.0060 (9) | 0.0052 (9) |
C16 | 0.0265 (11) | 0.0194 (10) | 0.0170 (10) | 0.0021 (8) | 0.0051 (8) | −0.0002 (8) |
C23 | 0.0276 (12) | 0.0280 (13) | 0.0386 (14) | −0.0020 (10) | −0.0097 (10) | 0.0094 (11) |
C4 | 0.0193 (9) | 0.0124 (9) | 0.0177 (9) | −0.0026 (7) | −0.0007 (7) | 0.0014 (7) |
C12 | 0.0309 (12) | 0.0137 (10) | 0.0354 (13) | 0.0028 (9) | −0.0036 (10) | 0.0037 (9) |
C15 | 0.0438 (14) | 0.0236 (12) | 0.0216 (11) | −0.0023 (10) | 0.0055 (10) | −0.0047 (9) |
C22 | 0.0321 (12) | 0.0132 (10) | 0.0352 (13) | 0.0054 (9) | 0.0048 (10) | 0.0059 (9) |
C25 | 0.0502 (15) | 0.0189 (11) | 0.0246 (11) | −0.0088 (10) | 0.0088 (11) | −0.0063 (9) |
Co1—Cl1 | 2.2904 (6) | C21—C23 | 1.521 (3) |
Co1—Cl2 | 2.2688 (6) | C21—C22 | 1.527 (3) |
Co1—Cl3 | 2.2819 (6) | C21—H21 | 1.0000 |
Co1—Cl4 | 2.2883 (6) | C11—H11A | 0.9800 |
N1—C4 | 1.520 (3) | C11—H11B | 0.9800 |
N1—C1 | 1.521 (2) | C11—H11C | 0.9800 |
N1—C13 | 1.557 (3) | C14—C16 | 1.523 (3) |
N1—C16 | 1.568 (3) | C14—H14A | 0.9800 |
N2—C3 | 1.515 (2) | C14—H14B | 0.9800 |
N2—C2 | 1.519 (3) | C14—H14C | 0.9800 |
N2—C24 | 1.565 (3) | C16—C15 | 1.522 (3) |
N2—C21 | 1.556 (3) | C16—H16 | 1.0000 |
C3—C4 | 1.514 (3) | C23—H23A | 0.9800 |
C3—H3A | 0.9900 | C23—H23B | 0.9800 |
C3—H3B | 0.9900 | C23—H23C | 0.9800 |
C1—C2 | 1.518 (3) | C4—H4A | 0.9900 |
C1—H1A | 0.9900 | C4—H4B | 0.9900 |
C1—H1B | 0.9900 | C12—H12A | 0.9800 |
C24—C26 | 1.513 (3) | C12—H12B | 0.9800 |
C24—C25 | 1.523 (3) | C12—H12C | 0.9800 |
C24—H24 | 1.0000 | C15—H15A | 0.9800 |
C13—C12 | 1.523 (3) | C15—H15B | 0.9800 |
C13—C11 | 1.525 (3) | C15—H15C | 0.9800 |
C13—H13 | 1.0000 | C22—H22A | 0.9800 |
C2—H2A | 0.9900 | C22—H22B | 0.9800 |
C2—H2B | 0.9900 | C22—H22C | 0.9800 |
C26—H26A | 0.9800 | C25—H25A | 0.9800 |
C26—H26B | 0.9800 | C25—H25B | 0.9800 |
C26—H26C | 0.9800 | C25—H25C | 0.9800 |
Cl2—Co1—Cl1 | 104.74 (2) | C23—C21—H21 | 105.4 |
Cl2—Co1—Cl3 | 108.33 (2) | C22—C21—H21 | 105.4 |
Cl2—Co1—Cl4 | 109.37 (3) | N2—C21—H21 | 105.4 |
Cl3—Co1—Cl1 | 118.33 (3) | C13—C11—H11A | 109.5 |
Cl3—Co1—Cl4 | 106.25 (2) | C13—C11—H11B | 109.5 |
Cl4—Co1—Cl1 | 109.63 (2) | H11A—C11—H11B | 109.5 |
C4—N1—C1 | 104.79 (15) | C13—C11—H11C | 109.5 |
C4—N1—C13 | 110.74 (15) | H11A—C11—H11C | 109.5 |
C1—N1—C13 | 109.55 (15) | H11B—C11—H11C | 109.5 |
C4—N1—C16 | 106.49 (15) | C16—C14—H14A | 109.5 |
C1—N1—C16 | 106.93 (15) | C16—C14—H14B | 109.5 |
C13—N1—C16 | 117.53 (15) | H14A—C14—H14B | 109.5 |
C3—N2—C2 | 105.76 (15) | C16—C14—H14C | 109.5 |
C3—N2—C24 | 106.73 (14) | H14A—C14—H14C | 109.5 |
C2—N2—C24 | 106.01 (15) | H14B—C14—H14C | 109.5 |
C3—N2—C21 | 109.90 (15) | C14—C16—C15 | 111.10 (19) |
C2—N2—C21 | 110.48 (15) | C14—C16—N1 | 113.25 (17) |
C24—N2—C21 | 117.27 (16) | C15—C16—N1 | 115.22 (18) |
N2—C3—C4 | 114.30 (16) | C14—C16—H16 | 105.4 |
N2—C3—H3A | 108.7 | C15—C16—H16 | 105.4 |
C4—C3—H3A | 108.7 | N1—C16—H16 | 105.4 |
N2—C3—H3B | 108.7 | C21—C23—H23A | 109.5 |
C4—C3—H3B | 108.7 | C21—C23—H23B | 109.5 |
H3A—C3—H3B | 107.6 | H23A—C23—H23B | 109.5 |
N1—C1—C2 | 114.19 (16) | C21—C23—H23C | 109.5 |
N1—C1—H1A | 108.7 | H23A—C23—H23C | 109.5 |
C2—C1—H1A | 108.7 | H23B—C23—H23C | 109.5 |
N1—C1—H1B | 108.7 | N1—C4—C3 | 113.97 (16) |
C2—C1—H1B | 108.7 | N1—C4—H4A | 108.8 |
H1A—C1—H1B | 107.6 | C3—C4—H4A | 108.8 |
C26—C24—C25 | 110.81 (19) | N1—C4—H4B | 108.8 |
C26—C24—N2 | 113.30 (16) | C3—C4—H4B | 108.8 |
C25—C24—N2 | 115.20 (17) | H4A—C4—H4B | 107.7 |
C26—C24—H24 | 105.5 | C13—C12—H12A | 109.5 |
C25—C24—H24 | 105.5 | C13—C12—H12B | 109.5 |
N2—C24—H24 | 105.5 | H12A—C12—H12B | 109.5 |
C12—C13—C11 | 111.60 (18) | C13—C12—H12C | 109.5 |
C12—C13—N1 | 115.14 (17) | H12A—C12—H12C | 109.5 |
C11—C13—N1 | 113.05 (17) | H12B—C12—H12C | 109.5 |
C12—C13—H13 | 105.3 | C16—C15—H15A | 109.5 |
C11—C13—H13 | 105.3 | C16—C15—H15B | 109.5 |
N1—C13—H13 | 105.3 | H15A—C15—H15B | 109.5 |
N2—C2—C1 | 113.92 (15) | C16—C15—H15C | 109.5 |
N2—C2—H2A | 108.8 | H15A—C15—H15C | 109.5 |
C1—C2—H2A | 108.8 | H15B—C15—H15C | 109.5 |
N2—C2—H2B | 108.8 | C21—C22—H22A | 109.5 |
C1—C2—H2B | 108.8 | C21—C22—H22B | 109.5 |
H2A—C2—H2B | 107.7 | H22A—C22—H22B | 109.5 |
C24—C26—H26A | 109.5 | C21—C22—H22C | 109.5 |
C24—C26—H26B | 109.5 | H22A—C22—H22C | 109.5 |
H26A—C26—H26B | 109.5 | H22B—C22—H22C | 109.5 |
C24—C26—H26C | 109.5 | C24—C25—H25A | 109.5 |
H26A—C26—H26C | 109.5 | C24—C25—H25B | 109.5 |
H26B—C26—H26C | 109.5 | H25A—C25—H25B | 109.5 |
C23—C21—C22 | 110.79 (18) | C24—C25—H25C | 109.5 |
C23—C21—N2 | 113.61 (18) | H25A—C25—H25C | 109.5 |
C22—C21—N2 | 115.14 (17) | H25B—C25—H25C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···Cl2 | 0.99 | 2.80 | 3.319 (2) | 113 |
C13—H13···Cl3i | 1.00 | 2.78 | 3.665 (2) | 148 |
C21—H21···Cl1ii | 1.00 | 2.60 | 3.482 (2) | 147 |
C24—H24···Cl3i | 1.00 | 2.68 | 3.628 (2) | 157 |
C25—H25B···Cl2iii | 0.98 | 2.74 | 3.713 (2) | 174 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | (C16H36N2)[CoCl4] |
Mr | 457.20 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 183 |
a, b, c (Å) | 7.1245 (3), 17.1830 (7), 17.3367 (7) |
β (°) | 94.640 (1) |
V (Å3) | 2115.41 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.60 × 0.50 × 0.04 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.505, 0.949 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24763, 7391, 4998 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.762 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.129, 0.99 |
No. of reflections | 7391 |
No. of parameters | 252 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −1.08 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 2001), SHELXTL (Bruker, 2001), SHELXTL, DIAMOND (Brandenburg, 2000).
Co1—Cl1 | 2.2904 (6) | Co1—Cl3 | 2.2819 (6) |
Co1—Cl2 | 2.2688 (6) | Co1—Cl4 | 2.2883 (6) |
Cl2—Co1—Cl1 | 104.74 (2) | Cl3—Co1—Cl1 | 118.33 (3) |
Cl2—Co1—Cl3 | 108.33 (2) | Cl3—Co1—Cl4 | 106.25 (2) |
Cl2—Co1—Cl4 | 109.37 (3) | Cl4—Co1—Cl1 | 109.63 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···Cl2 | 0.99 | 2.80 | 3.319 (2) | 113.1 |
C13—H13···Cl3i | 1.00 | 2.78 | 3.665 (2) | 148.0 |
C21—H21···Cl1ii | 1.00 | 2.60 | 3.482 (2) | 147.3 |
C24—H24···Cl3i | 1.00 | 2.68 | 3.628 (2) | 157.4 |
C25—H25B···Cl2iii | 0.98 | 2.74 | 3.713 (2) | 174.0 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) −x+3/2, y+1/2, −z+1/2. |
The existence of C—H···Cl hydrogen bonds has been recently reviewed by Aakeröy et al. (1999) through a systematic data mining and statistical analysis of the Cambridge Structural Database (Allen & Kennard, 1993). It has been shown that chloride anions are better hydrogen-bond acceptors than neutral chlorine-containing molecules, however, no attention has been given to Cl(—M) groups as potential hydrogen-bond acceptors. The MX42- anions in organic–inorganic hybrid solids with the general formula A2MX4, in which A (or A2) is an organic ammonium cation (or ammonium dication), M is a divalent metal ion and X is Cl or Br, are capable of participating in C—H···Cl, as well as N—H···Cl, hydrogen bonding with organic cations. This behaviour has been reported by several groups (Barbour et al., 1996; Feist et al., 1995; Hitchcock et al., 1993; Mahmoudkhani & Langer, 1999a,b; Waśkowska, 1994). Indeed, the hydrogen bonding is of importance in assigning and describing some of the microscopic and macroscopic properties in this class of compounds (Mahmoudkhani, 1999). Gillon et al. (2000) have recently demonstrated the use of N—H···Cl—M hydrogen-bond synthons in controlling the solid-state structure of some halometallates and in the design of supramolecular aggregates. They have concluded that M—Cl moieties are much better hydrogen-bond acceptors than their organic analogues, C—Cl.
The title compound, (I), crystallizes in the monoclinic system with space group P21/n (No. 14). The asymmetric unit contains an organic dication and an inorganic dianion, as shown in Fig. 1. The coordination geometry of the CoII ion is distorted tetrahedral, with a mean Co—Cl bond distance of 2.282 (9) Å. Only three Cl atoms are involved in hydrogen bonds of the C—H···Cl type with C atoms of neighbouring organic dications, while the Cl4 atom does not act as a hydrogen-bond acceptor. However, atoms Cl3 and Cl2 are acceptors of two hydrogen bonds each from atoms C13 and C24, and atoms C25 and C1, respectively (see Table 2 for the geometry). The C—H···Cl hydrogen bonds link organic dications and inorganic dianions together to form sheets parallel to the ab plane (see Fig. 2). In each sheet, CoCl4 tetrahedra adopt alternating up and down orientations parallel to the b axis while having the same arrangement parallel to the a axis. There is no significant interaction between the sheets though the solid material exhibits a layered structure. In comparison with the crystal structure of bis[(2-chloroethyl)diisopropylammonium] tetrachlorocobaltate (Mahmoudkhani & Langer, 1999b), the title compound shows no disorder even at room temperature. This may be attributed to the relative strengths arising from the C—H···Cl hydrogen bonds.