Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111043605/fn3091sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111043605/fn3091Isup2.hkl |
A mixture of CoCl2.6H2O (5.9 g, 0.025 mol), 1,10-phenanthroline (10.0 g, 0.05 mol), Na2CO3 (2.5 g, 0.025 mol), ethanol (72 ml) and water (6 ml) was stirred in air for 10 min and then transferred to a 110 ml PTFE-lined autoclave, which was heated to 433 K for 96 h, followed by cooling to room temperature at a rate of 5 K h-1. The resulting pink polycrystalline product was washed with large amount of ethanol/water (yield 3.0 g, 42% based on Co). Elemental analysis, calculated (found): Na 24.4 (24.8), Co 20.8 (22.3), Cl 12.4% (12.1%); Na and Co determined by ICP–OES and chloride by ion-exchange chromatography). Spectroscopic analysis: IR (KBr pellet, ν, 4000–370 cm-1): 3506 (m), 3387 (m), 2947 (w), 2854 (m), 2625 (w), 2509 (m), 1435 (s), 1414 (s), 872 (s), 708 (m).
The systematic absences in the diffraction data were consistent for the stated space group. The position of almost all atoms were found by direct methods. The remaining atoms were located in an alternating series of least-squares cycles on difference Fourier maps. All atoms were refined in a full-matrix anisotropic approximation.
Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Co(CO3)2Na3Cl | Mo Kα radiation, λ = 0.71073 Å |
Mr = 283.37 | Cell parameters from 4453 reflections |
Cubic, Fd3 | θ = 2.5–28.2° |
a = 13.9959 (5) Å | µ = 3.07 mm−1 |
V = 2741.59 (17) Å3 | T = 123 K |
Z = 16 | Plate, pink |
F(000) = 2192 | 0.14 × 0.14 × 0.08 mm |
Dx = 2.746 Mg m−3 |
Bruker SMART CCD area-detector (APEXII given in exptl_special_details) diffractometer | 294 independent reflections |
Radiation source: fine-focus sealed tube | 288 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 28.2°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→18 |
Tmin = 0.67, Tmax = 0.74 | k = −18→18 |
7452 measured reflections | l = −18→18 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.016 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.047 | w = 1/[σ2(Fo2) + (0.0207P)2 + 6.4264P] where P = (Fo2 + 2Fc2)/3 |
S = 1.30 | (Δ/σ)max < 0.001 |
294 reflections | Δρmax = 0.24 e Å−3 |
22 parameters | Δρmin = −0.67 e Å−3 |
Co(CO3)2Na3Cl | Z = 16 |
Mr = 283.37 | Mo Kα radiation |
Cubic, Fd3 | µ = 3.07 mm−1 |
a = 13.9959 (5) Å | T = 123 K |
V = 2741.59 (17) Å3 | 0.14 × 0.14 × 0.08 mm |
Bruker SMART CCD area-detector (APEXII given in exptl_special_details) diffractometer | 294 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 288 reflections with I > 2σ(I) |
Tmin = 0.67, Tmax = 0.74 | Rint = 0.022 |
7452 measured reflections |
R[F2 > 2σ(F2)] = 0.016 | 22 parameters |
wR(F2) = 0.047 | 0 restraints |
S = 1.30 | Δρmax = 0.24 e Å−3 |
294 reflections | Δρmin = −0.67 e Å−3 |
Experimental. An X-ray quality crystal was selected under ambient conditions and covered with Paratone oil. The crystal was mounted and centred in the X-ray beam using a video camera.The crystal evaluation and data collection were performed on an APEXII CCD diffractometer with a detector-to-crystal distance of 5 cm. The initial cell constants were obtained from three series of ω scans at different starting angles. Each series consisted of 30 frames collected at intervals of 0.3 in a 10 range about ω with the exposure time of 10 s per frame. The obtained reflections were successfully indexed by an automated indexing routine built into the APEX2 program package. The final cell constants were calculated from a set of strong reflections from the actual data collection. The data were collected using the full sphere routine by collecting four sets of frames with 0.3 scans in ω with an exposure time 10 s per frame. This data set was corrected for Lorentz and polarization effects. The absorption correction was based on a fit of a spherical harmonic function to the empirical transmission surface as sampled by multiple equivalent measurements using SADABS software (Sheldrick, 1996). |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.0000 | 0.5000 | 0.5000 | 0.00521 (16) | |
Na1 | 0.1250 | 0.34929 (5) | 0.6250 | 0.00880 (19) | |
O1 | −0.02419 (6) | 0.64680 (6) | 0.51647 (6) | 0.0073 (2) | |
C1 | 0.03277 (8) | 0.71723 (8) | 0.53277 (8) | 0.0058 (4) | |
Cl1 | 0.2500 | 0.2500 | 0.5000 | 0.0119 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.00521 (16) | 0.00521 (16) | 0.00521 (16) | −0.00023 (7) | −0.00023 (7) | −0.00023 (7) |
Na1 | 0.0083 (3) | 0.0088 (3) | 0.0093 (3) | 0.000 | −0.0011 (3) | 0.000 |
O1 | 0.0068 (4) | 0.0059 (4) | 0.0094 (4) | −0.0015 (3) | −0.0005 (3) | −0.0005 (3) |
C1 | 0.0058 (4) | 0.0058 (4) | 0.0058 (4) | 0.0014 (4) | −0.0014 (4) | 0.0014 (4) |
Cl1 | 0.0119 (2) | 0.0119 (2) | 0.0119 (2) | 0.00387 (15) | −0.00387 (15) | −0.00387 (15) |
Co1—O1 | 2.0950 (9) | Na1—Cl1 | 2.8377 (4) |
Co1—Na1 | 3.2512 (5) | Na1—Co1iii | 3.2512 (5) |
Na1—O1i | 2.3528 (11) | Na1—Na1iv | 3.5358 (2) |
Na1—O1ii | 2.4319 (9) | O1—C1 | 1.2882 (9) |
O1—Co1—O1v | 86.08 (3) | O1viii—Na1—Na1iv | 43.23 (2) |
O1—Co1—Na1v | 111.68 (3) | O1i—Na1—Na1iv | 125.13 (3) |
O1vi—Co1—Na1v | 46.23 (3) | O1ix—Na1—Na1iv | 60.42 (2) |
O1—Co1—Na1vi | 133.77 (3) | O1ii—Na1—Na1iv | 119.27 (3) |
O1vii—Co1—Na1vi | 48.40 (3) | Cl1iii—Na1—Na1iv | 136.27 (2) |
Na1v—Co1—Na1vi | 114.119 (8) | Cl1—Na1—Na1iv | 51.465 (8) |
O1—Co1—Na1i | 68.32 (3) | Co1iii—Na1—Na1iv | 57.060 (4) |
O1i—Co1—Na1i | 131.60 (3) | Co1—Na1—Na1iv | 114.31 (2) |
O1ii—Co1—Na1i | 111.68 (2) | O1viii—Na1—Na1x | 96.74 (2) |
Na1vi—Co1—Na1i | 65.881 (8) | O1i—Na1—Na1x | 74.30 (3) |
O1viii—Na1—O1i | 82.37 (5) | O1ix—Na1—Na1x | 41.50 (2) |
O1viii—Na1—O1ix | 73.39 (4) | O1ii—Na1—Na1x | 138.11 (3) |
O1i—Na1—O1ix | 104.60 (3) | Cl1iii—Na1—Na1x | 51.465 (8) |
O1ix—Na1—O1ii | 177.42 (6) | Cl1—Na1—Na1x | 136.27 (2) |
O1viii—Na1—Cl1iii | 147.84 (3) | Co1iii—Na1—Na1x | 57.059 (4) |
O1i—Na1—Cl1iii | 83.72 (2) | Na1iv—Na1—Na1x | 101.01 (2) |
O1ix—Na1—Cl1iii | 82.34 (2) | Na1iv—Na1—Na1vi | 77.78 (3) |
O1ii—Na1—Cl1iii | 98.93 (2) | Na1x—Na1—Na1vi | 168.32 (2) |
O1viii—Na1—Cl1 | 83.72 (2) | O1viii—Na1—Na1v | 125.13 (3) |
Cl1iii—Na1—Cl1 | 121.35 (3) | C1—O1—Co1 | 132.07 (9) |
O1viii—Na1—Co1iii | 40.01 (2) | C1—O1—Na1vii | 116.78 (5) |
O1i—Na1—Co1iii | 77.84 (3) | Co1—O1—Na1vii | 93.76 (3) |
O1ix—Na1—Co1iii | 40.10 (2) | C1—O1—Na1ii | 119.08 (10) |
O1ii—Na1—Co1iii | 137.37 (3) | Co1—O1—Na1ii | 91.50 (4) |
Cl1—Na1—Co1iii | 108.525 (4) | Na1vii—O1—Na1ii | 95.27 (3) |
O1ii—Na1—Co1 | 40.10 (2) | O1xi—C1—O1xii | 119.969 (6) |
Cl1—Na1—Co1 | 108.525 (4) | Na1—Cl1—Na1iv | 77.070 (16) |
Co1iii—Na1—Co1 | 99.10 (2) | Na1—Cl1—Na1xiii | 102.930 (16) |
Symmetry codes: (i) z−1/2, x+1/2, y; (ii) −x, −y+1, −z+1; (iii) −x+1/4, y, −z+5/4; (iv) −z+1, x+1/4, y+1/4; (v) −z+1/2, −x+1/2, −y+1; (vi) −y+1/2, −z+1, −x+1/2; (vii) y−1/2, z, x+1/2; (viii) −z+3/4, x+1/2, −y+5/4; (ix) x+1/4, −y+1, z+1/4; (x) y−1/4, −z+1, x+3/4; (xi) z−1/2, −x+3/4, −y+5/4; (xii) −y+3/4, −z+5/4, x+1/2; (xiii) z−1/2, −x+1/4, −y+3/4. |
Experimental details
Crystal data | |
Chemical formula | Co(CO3)2Na3Cl |
Mr | 283.37 |
Crystal system, space group | Cubic, Fd3 |
Temperature (K) | 123 |
a (Å) | 13.9959 (5) |
V (Å3) | 2741.59 (17) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 3.07 |
Crystal size (mm) | 0.14 × 0.14 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector (APEXII given in exptl_special_details) diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.67, 0.74 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7452, 294, 288 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.016, 0.047, 1.30 |
No. of reflections | 294 |
No. of parameters | 22 |
Δρmax, Δρmin (e Å−3) | 0.24, −0.67 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
C1—O1—Co1 | 132.07 (9) | O1i—C1—O1ii | 119.969 (6) |
Symmetry codes: (i) z−1/2, −x+3/4, −y+5/4; (ii) −y+3/4, −z+5/4, x+1/2. |
Geometrically frustrated magnetic materials continue to be a focal topic in magnetism, motivated by the multitude of magnetic phenomena they exhibit, ranging from spin-glass behaviour to phase transitions and quantum fluctuations (Ramirez, 1994; Greendan, 2001). Competing antiferromagnetic exchange interactions between localized spin centres can be realised within several classes of compound. Typically, extended (one- to three-dimensional) polymeric spin structures are at the heart of such studies, for example planar Kagomé lattices of regular triangles and hexagons (Schweika et al., 2007). Interest in spin frustration has also spawned efforts to recreate these phenomena in molecular (quasi-zerodimensional) systems (Kögerler et al., 2010). Next to spin-frustrated magnetic molecules, our interest concerns purely inorganic coordination networks that contain no hydrogen. These can thus be subjected to neutron diffraction studies, in order to study the magnetic phenomena associated with spin frustration, without the need for prior deuteration. In this context, we found that the presence of multidentate ligands can indeed induce the formation of network compounds in which magnetic transition metal cations are linked by comparatively simple and hydrogen-free inorganic bridging ligands (Fielden & Kögerler, 2009). We herein demonstrate that, under solvothermal conditions (433 K), small anions such as carbonate can compete with chelating ligands (here, 1,10-phenanthroline) to yield a three-dimensional cobalt(II) carbonate framework structure, the voids of which are filled with Na+ and Cl- ions (Fig. 1). Single crystals of the resulting compound, Co(CO3)2Na3Cl, were grown from a water–ethanol mixture and characterized at 123 K, and exhibit cubic (Fd3) symmetry.
Importantly for the magnetochemistry, the octahedrally coordinated CoII centres exhibit large single-ion magnetic anisotropy, which renders the spin centres Ising behaviour at low temperatures. The spin centres define a cubic pyrochlore lattice of corner-sharing regular Co4 tetrahedra arranged around hexagons, forming interconnected stacks of Kagome layers (Fig. 2).
The CoII centres reside in slightly distorted octahedral CoO6 coordination environments, with Co—O bond lengths of 2.0950 (9) Å, and O—Co—O bond angles alternating between 86.08 (3) and 93.92 (3)°. The nearest-neighbour Co—Co distances (i.e. the edge lengths of the Co4 tetrahedra) are 4.9483 (2) Å. Each carbonate group coordinates to, and bridges, three Co sites and the carbonate planes are coplanar with the respective faces of the Co4 tetrahedra, with an interplanar distance of 1.2256 (19) Å (Fig. 3).
Preliminary low-field magnetic susceptibility studies of Co(CO3)2Na3Cl reveal pronounced ligand-field and spin-orbit coupling effects, assessed using the simulation package CONDON 2.0 (Speldrich et al., 2011), as well as dominant antiferromagnetic coupling between the CoII spin centres. Here, nearest-neighbour antiferromagnetic coupling, mediated by bridging carbonate anions [Co—O—C bond angles 132.07 (9)°], results in a highly geometrically frustrated material (Bramwell & Harris, 1998). Preliminary susceptibility data for the title compound also indicate a gradual spin-glass transition between 3.0 and 4.5 K, where the fluctuating disorder required for the spin-glass state is supposed to stem from dynamic disorder of the Na+ and Cl- sublattice.