(1-Butyl-1,4-diaza­bicyclo­[2.2.2]octon-1-ium-κN 4)trichloridocobalt(II)

Sanchai Luachan; Bunlawee Yotnoi; Timothy J Prior; Apinpus Rujiwatra

doi:10.1107/S1600536809005893

. 2009 Feb 25;65(Pt 3):m321–m322. doi: 10.1107/S1600536809005893

(1-Butyl-1,4-diazabicyclo[2.2.2]octon-1-ium-κN ⁴)trichloridocobalt(II)

Sanchai Luachan ^a, Bunlawee Yotnoi ^a, Timothy J Prior ^b, Apinpus Rujiwatra ^a,^*

PMCID: PMC2968682 PMID: 21582095

Abstract

The title compound, [Co(C₁₀H₂₁N₂)Cl₃], was obtained as the by-product of the attempted synthesis of a cobalt sulfate framework using 1,4-diazabicyclo[2.2.2]octane as an organic template. The asymmetric unit comprises two distinct molecules, and in each, the cobalt(II) ions are tetrahedrally coordinated by three chloride anions and one 1-butyldiazabicyclo[2.2.2]octan-1-ium cation. The organic ligands are generated in situ, and exhibit two forms differentiated by the eclipsed and staggered conformations of the butyl groups. These molecules interact by way of C—H⋯Cl hydrogen bonds, forming a three-dimensional hydrogen-bonding array.

Related literature

Examples of closely related structures are N-methyl-1,4-diazabicyclo(2.2.2) octonium trichloro-aqua-nickel(II) (Ross & Stucky, 1969 ▶) and N,N′-dimethyl-1,4-diazaniabicyclo[2.2.2]octane tetrachlorocobaltate (C₈H₁₈N₂)[CoCl₄] (Qu & Sun, 2005 ▶). The organic cation in both structures do not coordinate to the cobalt ion but, in each case, the C—H⋯Cl hydrogen-bonding interactions are similar to those in the title compound. For hydrogen bonding in related structures, see: Bremner & Harrison (2003 ▶).

Experimental

Crystal data

[Co(C₁₀H₂₁N₂)Cl₃]
M _r = 334.57
Monoclinic,
a = 8.379 (2) Å
b = 12.1090 (13) Å
c = 14.711 (4) Å
β = 91.683 (4)°
V = 1492.0 (6) Å³
Z = 4
Synchrotron radiation
λ = 0.69430 Å
μ = 1.67 mm⁻¹
T = 120 K
0.12 × 0.02 × 0.02 mm

Data collection

Bruker D8 with APEXII detector diffractometer
Absorption correction: multi-scan (TWINABS; Bruker, 2004 ▶) T _min = 0.597, T _max = 0.746 (expected range = 0.774–0.967)
12848 measured reflections
8831 independent reflections
7018 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.098
S = 1.04
8831 reflections
292 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.44 e Å⁻³
Absolute structure: Flack (1983 ▶), 3980 Friedel pairs
Flack parameter: 0.064 (17)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: TWINABS (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005893/lh2775sup1.cif

e-65-0m321-sup1.cif^{(23.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005893/lh2775Isup2.hkl

e-65-0m321-Isup2.hkl^{(423.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 5

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯Cl6ⁱ	0.99	2.66	3.567 (5)	153
C4—H4A⋯Cl1ⁱⁱ	0.99	2.66	3.511 (5)	145
C6—H6B⋯Cl3ⁱⁱ	0.99	2.69	3.606 (5)	154
C7—H7B⋯Cl3ⁱⁱⁱ	0.99	2.80	3.729 (5)	157
C12—H12B⋯Cl5^iv	0.99	2.62	3.485 (4)	146
C14—H14A⋯Cl6^iv	0.99	2.75	3.567 (5)	140
C16—H16A⋯Cl1^v	0.99	2.60	3.548 (4)	161
C16—H16B⋯Cl5^v	0.99	2.81	3.739 (4)	156

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors thank the Thailand Research Fund, Center for Innovation in Chemistry and Thailand Toray Science Foundation for financial support. BY thanks the Royal Golden Jubilee PhD program and the Graduate School of Chiang Mai University for a Graduate Scholarship.

supplementary crystallographic information

Comment

The crystals of Co(C₁₀H₂₁N₂)Cl₃ (I) were unintentionally obtained as a by-product from the hydrothermal reaction between cobalt(II) sulfate heptahydrate and 1,4-diazabicyclo[2.2.2]octane in a water/butan-1-ol mixture. The N-butyl-1,4-diazabicyclo[2.2.2]octanium ligand was presumably generated in situ under acidic conditions. The structure of I is built up from two distinct [Co(C₁₀H₂₁N₂)Cl₃] molecules as shown in Fig. 1. They are different in the spatial orientation of the butyl group of the N-butyl-1,4-diazabicyclo[2.2.2]octanium ligand, one of which is in the eclipsed conformation (A) and the other is in the staggered conformation (B). The A molecules are connected by the C—H···Cl hydrogen bonding interactions to form a two-dimensional A sheet in the ab plane (Fig. 2), whereas the B molecules form the B sheet also in theab plane using similar C—H···Cl hydrogen bonding interactions (Fig. 3). The A and B sheets are then regularly alternated in the ABAB fashion, and linked by way of also the C—H···Cl hydrogen bonding interactions along c to give the infinite three-dimensional hydrogen bonding array (Fig. 4).

The hydrogen bond geometries found in I (H···Cl, 2.62–2.81 Å; C···Cl, 3.485 (4)–3.739 (4) Å; C—H···Cl, 140.00–164.00°) are well comparable to those found in related structures, e.g. (C₆H₁₄N₂)[CoCl₄] (Bremner & Harrison, 2003) and (C₈H₁₈N₂)[CoCl₄] (Qu & Sun, 2005).

Experimental

Crystals of I were obtained as a by-product from the hydrothermal reaction of cobalt(II) sulfate heptahydrate, 1,4-diazabicyclo[2.2.2]octane and hydrochloric acid in a water/butan-1-ol mixture at 453 K for 120 h.