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In the title compound, (C6H18N2)[CoCl4], organic dications and inorganic dianions interact with each other through N—H...Cl hydrogen bonds, forming infinite two-dimensional sheets of anions parallel to the ac plane. Alkyl chains act as spacers between these sheets. Only three Cl atoms are involved in hydrogen bonding with ammonium groups. The asymmetric unit consists of one anion together with half of each of two cations on inversion centres.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017464/cf6212sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017464/cf6212Isup2.hkl
Contains datablock I

CCDC reference: 198319

Key indicators

  • Single-crystal X-ray study
  • T = 183 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.023
  • wR factor = 0.061
  • Data-to-parameter ratio = 22.5

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ADDSYM reports no extra symmetry








Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I). Displacement ellipsoids are shown at the 50% probability level. Only the symmetry-independent atoms are labeled.
[Figure 2] Fig. 2. The lamellar structure of (I).
1,6-hexamethylenediammonium tetrachlorocobaltate(II) top
Crystal data top
(C6H18N2)[CoCl4]Z = 2
Mr = 318.95F(000) = 326
Triclinic, P1Dx = 1.518 Mg m3
a = 7.2803 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.9479 (1) ÅCell parameters from 8192 reflections
c = 9.9572 (1) Åθ = 1–28°
α = 75.682 (1)°µ = 1.96 mm1
β = 87.494 (1)°T = 183 K
γ = 88.790 (1)°Parallelipiped, blue
V = 698.03 (1) Å30.40 × 0.20 × 0.15 mm
Data collection top
Siemens SMART CCD
diffractometer
3458 independent reflections
Radiation source: fine-focus sealed tube3135 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scansθmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
h = 99
Tmin = 0.508, Tmax = 0.758k = 1313
9980 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H 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 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
(C6H18N2)[CoCl4]γ = 88.790 (1)°
Mr = 318.95V = 698.03 (1) Å3
Triclinic, P1Z = 2
a = 7.2803 (1) ÅMo Kα radiation
b = 9.9479 (1) ŵ = 1.96 mm1
c = 9.9572 (1) ÅT = 183 K
α = 75.682 (1)°0.40 × 0.20 × 0.15 mm
β = 87.494 (1)°
Data collection top
Siemens SMART CCD
diffractometer
3458 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
3135 reflections with I > 2σ(I)
Tmin = 0.508, Tmax = 0.758Rint = 0.024
9980 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.061H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.48 e Å3
3458 reflectionsΔρmin = 0.51 e Å3
154 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Co0.23920 (3)0.55924 (2)0.20643 (2)0.02681 (7)
Cl10.18792 (5)0.32646 (4)0.28921 (4)0.02938 (8)
Cl20.49321 (5)0.62642 (4)0.29667 (4)0.03302 (9)
Cl30.00053 (5)0.67102 (4)0.29010 (4)0.03090 (9)
Cl40.26268 (7)0.61748 (4)0.02776 (4)0.04250 (11)
N1B0.77788 (19)0.36811 (14)0.41325 (16)0.0310 (3)
N1A0.2522 (2)0.28060 (14)0.01665 (16)0.0339 (3)
C1B0.6459 (2)0.25871 (15)0.40232 (15)0.0294 (3)
H1B10.61830.26950.30370.043 (5)*
H1B20.52940.27070.45340.047 (6)*
C1A0.3269 (2)0.13510 (17)0.0126 (2)0.0405 (4)
H1A10.44980.13220.05220.062 (7)*
H1A20.34150.10570.07540.054 (6)*
C2A0.2001 (3)0.03497 (17)0.11354 (19)0.0417 (4)
H2A10.19210.06260.20260.068 (7)*
H2A20.25620.05900.13160.048 (6)*
C2B0.7226 (2)0.11499 (17)0.4605 (2)0.0423 (4)
H2B10.75300.10510.55850.058 (7)*
H2B20.83760.10240.40800.053 (6)*
C3B0.5862 (2)0.00183 (18)0.4528 (2)0.0446 (4)
H3B10.54850.01700.35580.051 (6)*
H3B20.64920.08960.47830.069 (7)*
C3A0.0048 (2)0.02737 (16)0.06474 (17)0.0357 (3)
H3A10.06930.03330.14080.045 (5)*
H3A20.05140.12130.04590.041 (5)*
H12A0.802 (3)0.363 (2)0.498 (3)0.060 (7)*
H13B0.157 (3)0.290 (2)0.073 (2)0.058 (7)*
H12B0.336 (3)0.336 (3)0.066 (3)0.061 (7)*
H11B0.220 (3)0.302 (2)0.061 (2)0.046 (6)*
H11A0.880 (3)0.361 (2)0.364 (2)0.044 (5)*
H13A0.730 (3)0.455 (2)0.385 (2)0.048 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.02365 (10)0.02526 (11)0.02916 (11)0.00031 (7)0.00083 (8)0.00253 (8)
Cl10.02848 (17)0.02551 (17)0.03107 (17)0.00012 (13)0.00122 (13)0.00156 (13)
Cl20.02409 (17)0.0372 (2)0.03708 (19)0.00244 (14)0.00027 (14)0.00789 (15)
Cl30.02417 (16)0.02851 (18)0.03859 (19)0.00191 (13)0.00055 (14)0.00607 (14)
Cl40.0631 (3)0.0318 (2)0.02832 (18)0.00243 (18)0.00189 (17)0.00015 (15)
N1B0.0274 (6)0.0273 (7)0.0353 (7)0.0038 (5)0.0027 (5)0.0022 (5)
N1A0.0460 (8)0.0239 (6)0.0298 (7)0.0035 (6)0.0007 (6)0.0031 (5)
C1B0.0293 (7)0.0284 (7)0.0279 (7)0.0055 (6)0.0029 (6)0.0011 (6)
C1A0.0367 (9)0.0283 (8)0.0546 (10)0.0015 (6)0.0035 (8)0.0066 (7)
C2A0.0504 (10)0.0242 (8)0.0461 (10)0.0017 (7)0.0077 (8)0.0005 (7)
C2B0.0315 (8)0.0280 (8)0.0603 (11)0.0028 (6)0.0009 (8)0.0028 (7)
C3B0.0403 (9)0.0281 (8)0.0622 (12)0.0058 (7)0.0078 (8)0.0065 (8)
C3A0.0410 (9)0.0230 (7)0.0402 (9)0.0019 (6)0.0050 (7)0.0033 (6)
Geometric parameters (Å, º) top
Co—Cl42.2592 (4)C1A—C2A1.523 (2)
Co—Cl32.2859 (4)C1A—H1A10.990
Co—Cl22.2733 (4)C1A—H1A20.990
Co—Cl12.2906 (4)C2A—C3A1.532 (3)
N1B—C1B1.494 (2)C2A—H2A10.990
N1B—H12A0.85 (3)C2A—H2A20.990
N1B—H11A0.88 (2)C2B—C3B1.535 (2)
N1B—H13A0.91 (2)C2B—H2B10.990
N1A—C1A1.499 (2)C2B—H2B20.990
N1A—H13B0.90 (2)C3B—C3Bi1.530 (4)
N1A—H12B0.88 (3)C3B—H3B10.990
N1A—H11B0.87 (2)C3B—H3B20.990
C1B—C2B1.509 (2)C3A—C3Aii1.523 (3)
C1B—H1B10.990C3A—H3A10.990
C1B—H1B20.990C3A—H3A20.990
Cl4—Co—Cl1110.86 (2)N1A—C1A—H1A2109.4
Cl4—Co—Cl2110.58 (2)C2A—C1A—H1A2109.4
Cl4—Co—Cl3112.21 (2)H1A1—C1A—H1A2108.0
Cl2—Co—Cl1111.63 (2)C1A—C2A—C3A115.10 (14)
Cl2—Co—Cl3104.87 (2)C1A—C2A—H2A1108.5
Cl3—Co—Cl1106.50 (2)C3A—C2A—H2A1108.5
C1B—N1B—H12A111.3 (16)C1A—C2A—H2A2108.5
C1B—N1B—H11A109.9 (13)C3A—C2A—H2A2108.5
H12A—N1B—H11A110 (2)H2A1—C2A—H2A2107.5
C1B—N1B—H13A112.6 (14)C1B—C2B—C3B111.94 (15)
H12A—N1B—H13A103 (2)C1B—C2B—H2B1109.2
H11A—N1B—H13A109.9 (19)C3B—C2B—H2B1109.2
C1A—N1A—H13B110.2 (15)C1B—C2B—H2B2109.2
C1A—N1A—H12B107.9 (16)C3B—C2B—H2B2109.2
H13B—N1A—H12B104 (2)H2B1—C2B—H2B2107.9
C1A—N1A—H11B110.2 (14)C3Bi—C3B—C2B113.8 (2)
H13B—N1A—H11B112 (2)C3Bi—C3B—H3B1108.8
H12B—N1A—H11B113 (2)C2B—C3B—H3B1108.8
N1B—C1B—C2B111.55 (13)C3Bi—C3B—H3B2108.8
N1B—C1B—H1B1109.3C2B—C3B—H3B2108.8
C2B—C1B—H1B1109.3H3B1—C3B—H3B2107.7
N1B—C1B—H1B2109.3C3Aii—C3A—C2A114.13 (18)
C2B—C1B—H1B2109.3C3Aii—C3A—H3A1108.7
H1B1—C1B—H1B2108.0C2A—C3A—H3A1108.7
N1A—C1A—C2A111.28 (14)C3Aii—C3A—H3A2108.7
N1A—C1A—H1A1109.4C2A—C3A—H3A2108.7
C2A—C1A—H1A1109.4H3A1—C3A—H3A2107.6
Symmetry codes: (i) x+1, y, z+1; (ii) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11B···Cl10.87 (2)2.35 (2)3.2024 (16)167 (2)
N1B—H11A···Cl1iii0.88 (2)2.38 (2)3.2384 (15)165 (2)
N1A—H12B···Cl2iv0.88 (3)2.51 (3)3.2267 (16)139 (2)
N1B—H13A···Cl20.91 (2)2.43 (2)3.2795 (15)155 (2)
N1A—H13B···Cl3v0.90 (2)2.43 (3)3.2791 (16)158 (2)
N1B—H12A···Cl3vi0.85 (3)2.56 (3)3.3656 (16)157 (2)
C1B—H1B1···Cl4iv0.992.813.6627 (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]
Mr318.95
Crystal system, space groupTriclinic, 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)
V3)698.03 (1)
Z2
Radiation typeMo Kα
µ (mm1)1.96
Crystal size (mm)0.40 × 0.20 × 0.15
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2001)
Tmin, Tmax0.508, 0.758
No. of measured, independent and
observed [I > 2σ(I)] reflections
9980, 3458, 3135
Rint0.024
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.061, 1.02
No. of reflections3458
No. of parameters154
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.48, 0.51

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT and SADABS (Sheldrick, 2001), SHELXTL (Bruker, 2001), SHELXTL, DIAMOND (Brandenburg, 2000).

Selected geometric parameters (Å, º) top
Co—Cl42.2592 (4)Co—Cl12.2906 (4)
Co—Cl32.2859 (4)N1B—C1B1.494 (2)
Co—Cl22.2733 (4)N1A—C1A1.499 (2)
Cl4—Co—Cl1110.86 (2)Cl2—Co—Cl1111.63 (2)
Cl4—Co—Cl2110.58 (2)Cl2—Co—Cl3104.87 (2)
Cl4—Co—Cl3112.21 (2)Cl3—Co—Cl1106.50 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H11B···Cl10.87 (2)2.35 (2)3.2024 (16)167 (2)
N1B—H11A···Cl1i0.88 (2)2.38 (2)3.2384 (15)165 (2)
N1A—H12B···Cl2ii0.88 (3)2.51 (3)3.2267 (16)139 (2)
N1B—H13A···Cl20.91 (2)2.43 (2)3.2795 (15)155 (2)
N1A—H13B···Cl3iii0.90 (2)2.43 (3)3.2791 (16)158 (2)
N1B—H12A···Cl3iv0.85 (3)2.56 (3)3.3656 (16)157 (2)
C1B—H1B1···Cl4ii0.992.813.6627 (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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