Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017464/cf6212sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017464/cf6212Isup2.hkl |
CCDC reference: 198319
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.002 Å
- R factor = 0.023
- wR factor = 0.061
- Data-to-parameter ratio = 22.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
In a 25 ml round-bottomed flask, 100 mmol of 1,6-hexamethylenediamine was dissolved in concentrated aqueous HCl solution (10 ml). CoCl2·6H2O (100 mmol disolved in 10 ml e thanol) was added. The mixture was warmed to about 333 K and stirred for about 2 h. Slow evaporation of the solvent gave blue crystals of the product suitable for X-ray diffraction study.
The H atoms of the ammonium groups were located in a difference Fourier map and refined isotropically, whereas the C-bonded H atoms were constrained to idealized geometries using an appropriate riding model.
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); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I). Displacement ellipsoids are shown at the 50% probability level. Only the symmetry-independent atoms are labeled. | |
Fig. 2. The lamellar structure of (I). |
(C6H18N2)[CoCl4] | Z = 2 |
Mr = 318.95 | F(000) = 326 |
Triclinic, P1 | Dx = 1.518 Mg m−3 |
a = 7.2803 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.9479 (1) Å | Cell parameters from 8192 reflections |
c = 9.9572 (1) Å | θ = 1–28° |
α = 75.682 (1)° | µ = 1.96 mm−1 |
β = 87.494 (1)° | T = 183 K |
γ = 88.790 (1)° | Parallelipiped, blue |
V = 698.03 (1) Å3 | 0.40 × 0.20 × 0.15 mm |
Siemens SMART CCD diffractometer | 3458 independent reflections |
Radiation source: fine-focus sealed tube | 3135 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −9→9 |
Tmin = 0.508, Tmax = 0.758 | k = −13→13 |
9980 measured reflections | l = −13→13 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0298P)2 + 0.2211P] where P = (Fo2 + 2Fc2)/3 |
3458 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
(C6H18N2)[CoCl4] | γ = 88.790 (1)° |
Mr = 318.95 | V = 698.03 (1) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.2803 (1) Å | Mo Kα radiation |
b = 9.9479 (1) Å | µ = 1.96 mm−1 |
c = 9.9572 (1) Å | T = 183 K |
α = 75.682 (1)° | 0.40 × 0.20 × 0.15 mm |
β = 87.494 (1)° |
Siemens SMART CCD diffractometer | 3458 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 3135 reflections with I > 2σ(I) |
Tmin = 0.508, Tmax = 0.758 | Rint = 0.024 |
9980 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.061 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.48 e Å−3 |
3458 reflections | Δρmin = −0.51 e Å−3 |
154 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 | ||
Co | 0.23920 (3) | 0.55924 (2) | 0.20643 (2) | 0.02681 (7) | |
Cl1 | 0.18792 (5) | 0.32646 (4) | 0.28921 (4) | 0.02938 (8) | |
Cl2 | 0.49321 (5) | 0.62642 (4) | 0.29667 (4) | 0.03302 (9) | |
Cl3 | −0.00053 (5) | 0.67102 (4) | 0.29010 (4) | 0.03090 (9) | |
Cl4 | 0.26268 (7) | 0.61748 (4) | −0.02776 (4) | 0.04250 (11) | |
N1B | 0.77788 (19) | 0.36811 (14) | 0.41325 (16) | 0.0310 (3) | |
N1A | 0.2522 (2) | 0.28060 (14) | −0.01665 (16) | 0.0339 (3) | |
C1B | 0.6459 (2) | 0.25871 (15) | 0.40232 (15) | 0.0294 (3) | |
H1B1 | 0.6183 | 0.2695 | 0.3037 | 0.043 (5)* | |
H1B2 | 0.5294 | 0.2707 | 0.4534 | 0.047 (6)* | |
C1A | 0.3269 (2) | 0.13510 (17) | 0.0126 (2) | 0.0405 (4) | |
H1A1 | 0.4498 | 0.1322 | 0.0522 | 0.062 (7)* | |
H1A2 | 0.3415 | 0.1057 | −0.0754 | 0.054 (6)* | |
C2A | 0.2001 (3) | 0.03497 (17) | 0.11354 (19) | 0.0417 (4) | |
H2A1 | 0.1921 | 0.0626 | 0.2026 | 0.068 (7)* | |
H2A2 | 0.2562 | −0.0590 | 0.1316 | 0.048 (6)* | |
C2B | 0.7226 (2) | 0.11499 (17) | 0.4605 (2) | 0.0423 (4) | |
H2B1 | 0.7530 | 0.1051 | 0.5585 | 0.058 (7)* | |
H2B2 | 0.8376 | 0.1024 | 0.4080 | 0.053 (6)* | |
C3B | 0.5862 (2) | 0.00183 (18) | 0.4528 (2) | 0.0446 (4) | |
H3B1 | 0.5485 | 0.0170 | 0.3558 | 0.051 (6)* | |
H3B2 | 0.6492 | −0.0896 | 0.4783 | 0.069 (7)* | |
C3A | 0.0048 (2) | 0.02737 (16) | 0.06474 (17) | 0.0357 (3) | |
H3A1 | −0.0693 | −0.0333 | 0.1408 | 0.045 (5)* | |
H3A2 | −0.0514 | 0.1213 | 0.0459 | 0.041 (5)* | |
H12A | 0.802 (3) | 0.363 (2) | 0.498 (3) | 0.060 (7)* | |
H13B | 0.157 (3) | 0.290 (2) | −0.073 (2) | 0.058 (7)* | |
H12B | 0.336 (3) | 0.336 (3) | −0.066 (3) | 0.061 (7)* | |
H11B | 0.220 (3) | 0.302 (2) | 0.061 (2) | 0.046 (6)* | |
H11A | 0.880 (3) | 0.361 (2) | 0.364 (2) | 0.044 (5)* | |
H13A | 0.730 (3) | 0.455 (2) | 0.385 (2) | 0.048 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.02365 (10) | 0.02526 (11) | 0.02916 (11) | −0.00031 (7) | 0.00083 (8) | −0.00253 (8) |
Cl1 | 0.02848 (17) | 0.02551 (17) | 0.03107 (17) | −0.00012 (13) | 0.00122 (13) | −0.00156 (13) |
Cl2 | 0.02409 (17) | 0.0372 (2) | 0.03708 (19) | −0.00244 (14) | −0.00027 (14) | −0.00789 (15) |
Cl3 | 0.02417 (16) | 0.02851 (18) | 0.03859 (19) | 0.00191 (13) | 0.00055 (14) | −0.00607 (14) |
Cl4 | 0.0631 (3) | 0.0318 (2) | 0.02832 (18) | 0.00243 (18) | 0.00189 (17) | −0.00015 (15) |
N1B | 0.0274 (6) | 0.0273 (7) | 0.0353 (7) | −0.0038 (5) | 0.0027 (5) | −0.0022 (5) |
N1A | 0.0460 (8) | 0.0239 (6) | 0.0298 (7) | −0.0035 (6) | 0.0007 (6) | −0.0031 (5) |
C1B | 0.0293 (7) | 0.0284 (7) | 0.0279 (7) | −0.0055 (6) | −0.0029 (6) | −0.0011 (6) |
C1A | 0.0367 (9) | 0.0283 (8) | 0.0546 (10) | 0.0015 (6) | −0.0035 (8) | −0.0066 (7) |
C2A | 0.0504 (10) | 0.0242 (8) | 0.0461 (10) | −0.0017 (7) | −0.0077 (8) | 0.0005 (7) |
C2B | 0.0315 (8) | 0.0280 (8) | 0.0603 (11) | −0.0028 (6) | −0.0009 (8) | 0.0028 (7) |
C3B | 0.0403 (9) | 0.0281 (8) | 0.0622 (12) | −0.0058 (7) | 0.0078 (8) | −0.0065 (8) |
C3A | 0.0410 (9) | 0.0230 (7) | 0.0402 (9) | −0.0019 (6) | 0.0050 (7) | −0.0033 (6) |
Co—Cl4 | 2.2592 (4) | C1A—C2A | 1.523 (2) |
Co—Cl3 | 2.2859 (4) | C1A—H1A1 | 0.990 |
Co—Cl2 | 2.2733 (4) | C1A—H1A2 | 0.990 |
Co—Cl1 | 2.2906 (4) | C2A—C3A | 1.532 (3) |
N1B—C1B | 1.494 (2) | C2A—H2A1 | 0.990 |
N1B—H12A | 0.85 (3) | C2A—H2A2 | 0.990 |
N1B—H11A | 0.88 (2) | C2B—C3B | 1.535 (2) |
N1B—H13A | 0.91 (2) | C2B—H2B1 | 0.990 |
N1A—C1A | 1.499 (2) | C2B—H2B2 | 0.990 |
N1A—H13B | 0.90 (2) | C3B—C3Bi | 1.530 (4) |
N1A—H12B | 0.88 (3) | C3B—H3B1 | 0.990 |
N1A—H11B | 0.87 (2) | C3B—H3B2 | 0.990 |
C1B—C2B | 1.509 (2) | C3A—C3Aii | 1.523 (3) |
C1B—H1B1 | 0.990 | C3A—H3A1 | 0.990 |
C1B—H1B2 | 0.990 | C3A—H3A2 | 0.990 |
Cl4—Co—Cl1 | 110.86 (2) | N1A—C1A—H1A2 | 109.4 |
Cl4—Co—Cl2 | 110.58 (2) | C2A—C1A—H1A2 | 109.4 |
Cl4—Co—Cl3 | 112.21 (2) | H1A1—C1A—H1A2 | 108.0 |
Cl2—Co—Cl1 | 111.63 (2) | C1A—C2A—C3A | 115.10 (14) |
Cl2—Co—Cl3 | 104.87 (2) | C1A—C2A—H2A1 | 108.5 |
Cl3—Co—Cl1 | 106.50 (2) | C3A—C2A—H2A1 | 108.5 |
C1B—N1B—H12A | 111.3 (16) | C1A—C2A—H2A2 | 108.5 |
C1B—N1B—H11A | 109.9 (13) | C3A—C2A—H2A2 | 108.5 |
H12A—N1B—H11A | 110 (2) | H2A1—C2A—H2A2 | 107.5 |
C1B—N1B—H13A | 112.6 (14) | C1B—C2B—C3B | 111.94 (15) |
H12A—N1B—H13A | 103 (2) | C1B—C2B—H2B1 | 109.2 |
H11A—N1B—H13A | 109.9 (19) | C3B—C2B—H2B1 | 109.2 |
C1A—N1A—H13B | 110.2 (15) | C1B—C2B—H2B2 | 109.2 |
C1A—N1A—H12B | 107.9 (16) | C3B—C2B—H2B2 | 109.2 |
H13B—N1A—H12B | 104 (2) | H2B1—C2B—H2B2 | 107.9 |
C1A—N1A—H11B | 110.2 (14) | C3Bi—C3B—C2B | 113.8 (2) |
H13B—N1A—H11B | 112 (2) | C3Bi—C3B—H3B1 | 108.8 |
H12B—N1A—H11B | 113 (2) | C2B—C3B—H3B1 | 108.8 |
N1B—C1B—C2B | 111.55 (13) | C3Bi—C3B—H3B2 | 108.8 |
N1B—C1B—H1B1 | 109.3 | C2B—C3B—H3B2 | 108.8 |
C2B—C1B—H1B1 | 109.3 | H3B1—C3B—H3B2 | 107.7 |
N1B—C1B—H1B2 | 109.3 | C3Aii—C3A—C2A | 114.13 (18) |
C2B—C1B—H1B2 | 109.3 | C3Aii—C3A—H3A1 | 108.7 |
H1B1—C1B—H1B2 | 108.0 | C2A—C3A—H3A1 | 108.7 |
N1A—C1A—C2A | 111.28 (14) | C3Aii—C3A—H3A2 | 108.7 |
N1A—C1A—H1A1 | 109.4 | C2A—C3A—H3A2 | 108.7 |
C2A—C1A—H1A1 | 109.4 | H3A1—C3A—H3A2 | 107.6 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11B···Cl1 | 0.87 (2) | 2.35 (2) | 3.2024 (16) | 167 (2) |
N1B—H11A···Cl1iii | 0.88 (2) | 2.38 (2) | 3.2384 (15) | 165 (2) |
N1A—H12B···Cl2iv | 0.88 (3) | 2.51 (3) | 3.2267 (16) | 139 (2) |
N1B—H13A···Cl2 | 0.91 (2) | 2.43 (2) | 3.2795 (15) | 155 (2) |
N1A—H13B···Cl3v | 0.90 (2) | 2.43 (3) | 3.2791 (16) | 158 (2) |
N1B—H12A···Cl3vi | 0.85 (3) | 2.56 (3) | 3.3656 (16) | 157 (2) |
C1B—H1B1···Cl4iv | 0.99 | 2.81 | 3.6627 (15) | 145 |
Symmetry codes: (iii) x+1, y, z; (iv) −x+1, −y+1, −z; (v) −x, −y+1, −z; (vi) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C6H18N2)[CoCl4] |
Mr | 318.95 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 183 |
a, b, c (Å) | 7.2803 (1), 9.9479 (1), 9.9572 (1) |
α, β, γ (°) | 75.682 (1), 87.494 (1), 88.790 (1) |
V (Å3) | 698.03 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.96 |
Crystal size (mm) | 0.40 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.508, 0.758 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9980, 3458, 3135 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.061, 1.02 |
No. of reflections | 3458 |
No. of parameters | 154 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.51 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 2001), SHELXTL (Bruker, 2001), SHELXTL, DIAMOND (Brandenburg, 2000).
Co—Cl4 | 2.2592 (4) | Co—Cl1 | 2.2906 (4) |
Co—Cl3 | 2.2859 (4) | N1B—C1B | 1.494 (2) |
Co—Cl2 | 2.2733 (4) | N1A—C1A | 1.499 (2) |
Cl4—Co—Cl1 | 110.86 (2) | Cl2—Co—Cl1 | 111.63 (2) |
Cl4—Co—Cl2 | 110.58 (2) | Cl2—Co—Cl3 | 104.87 (2) |
Cl4—Co—Cl3 | 112.21 (2) | Cl3—Co—Cl1 | 106.50 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H11B···Cl1 | 0.87 (2) | 2.35 (2) | 3.2024 (16) | 167 (2) |
N1B—H11A···Cl1i | 0.88 (2) | 2.38 (2) | 3.2384 (15) | 165 (2) |
N1A—H12B···Cl2ii | 0.88 (3) | 2.51 (3) | 3.2267 (16) | 139 (2) |
N1B—H13A···Cl2 | 0.91 (2) | 2.43 (2) | 3.2795 (15) | 155 (2) |
N1A—H13B···Cl3iii | 0.90 (2) | 2.43 (3) | 3.2791 (16) | 158 (2) |
N1B—H12A···Cl3iv | 0.85 (3) | 2.56 (3) | 3.3656 (16) | 157 (2) |
C1B—H1B1···Cl4ii | 0.99 | 2.81 | 3.6627 (15) | 145 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+1, −z; (iv) −x+1, −y+1, −z+1. |
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A realistic goal in modern chemistry is the identification and application of reliable synthons which can control molecular aggregations and lead to crystal structures with particular patterns, creating new properties. For the construction of desirable materials, the nature and extent of weak (hydrogen bonding, van der Waals, or electrostatic) and strong (covalent or ionic) interactions between chemical components is an important issue. In the field of inorganic–organic hybrid materials, one of the most promising research areas in materials chemistry, these interactions occur within inorganic and organic components. The title compound, (I), belongs to a family of organic-inorganic hybrid solids with the general formula A2MX4, in which A (or A2) is an organic ammonium cation (or diammonium dication), M is a divalent metal ion, and X = Cl or Br. Physical and chemical properties of these materials have been widely investigated. Some of them show liquid-crystalline behavior (Bowlas et al., 1996; Kanazawa et al., 2000; Neve et al., 2001). ClO42− anions are capable of participating extensively in N—H···Cl and C—H···Cl hydrogen bonding with organic cations (Mahmoudkhani & Langer, 1999a,b; Mahmoudkhani et al., 2001).
The hexamethylenediammonium cation in (I) is centrosymmetric and the asymmetric unit contains two halves of symmetry-independent organic dications and an inorganic dianion, as shown in Fig. 1. The coordination geometry of the CoII ion is tetrahedral, with Co—Cl bond distances ranging from 2.2592 (4) to 2.2906 (4) Å. Only Cl1, Cl2 and Cl3 are involved in hydrogen bonds with the ammonium groups of surrounding organic cations, each acting as an acceptor of two hydrogen bonds (Table 2). Atom Cl4 is involved in a weak C—H···Cl hydrogen bond with C1B. This may explain a shortening of the Co—Cl4 bond compared to the other Co—Cl bonds. The N—H···Cl hydrogen bonds link organic dications and inorganic dianions together, to give layers of anions parallel to the ac plane (Fig. 2). In each layer, CoCl4 tetrahedra adopt alternating up and down orientations relative to the c axis. Adjacent layers are pillared by the alkyl chains of the organic cations, to form a three-dimensional network. In this respect, compound (I) differs from the previously known homologues [H3N–(CH2)3–NH3]ClO4 (Ning et al., 1992) and [H3N–(CH2)5–NH3]ClO4 (Criado et al., 1999). In these compounds, the organic moieties do not act as spacers between layers.