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Cobalt hydrogen selenite chloride dihydrate, Co(HSeO
3)Cl·2H
2O, is built up from a network of
trans CoO
4Cl
2 octahedra,
cis Co(H
2O)
4Cl
2 octahedra and HSeO
3 pyramids. These units [
dav(Co—O) = 2.075 (2) Å,
dav(Co—Cl) = 2.5370 (6) Å and
dav(Se—O) = 1.703 (2) Å] share vertices by way of Co—O—Se and Co—Cl—Co bonds to produce a three-dimensional structure. Co of the trans octahedron occupies an inversion centre; Co of the
cis octahedron and two attached water O atoms lie on a mirror plane. The hydrogen-bonding scheme has been elucidated and involves O—H
O and O—H
Cl interactions. The title compound is isostructural with Cu(HSeO
3)Cl·2H
2O, although the metal polyhedra are distinctly different in the two phases.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (Co-O) = 0.002 Å
- R factor = 0.022
- wR factor = 0.062
- Data-to-parameter ratio = 27.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level B:
CHEMS_01 Alert B The sum formula contains elements in the wrong order.
H precedes Cl
Sequence must be C, H, then alphabetical.
| Author response: Sorry, don't know what we're doing wrong!
|
General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced
by the scaled T values. Since the ratio of scaled T's is
identical to the ratio of reported T values, the scaling does
not imply a change to the absorption corrections used in the
study.
Ratio of Tmax expected/reported 0.907
Tmax scaled 0.471 Tmin scaled 0.124
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
0 Alert Level C = Please check
A mixture of 7 ml 0.5M `H2SeO3' solution (dissolved SeO2), 8 ml 1
M LiCl solution and 0.714 g (3 mmol) CoCl2·6H2O were sealed in
a 23 ml capacity Teflon-lined hydrothermal bomb, and heated to 473 K for 6 d.
After cooling over a few hours and opening the bomb, there was no solid
product. The resultant red liquor was placed in a Petri dish, and after 10 d,
purple chunky crystals of the title compound were recovered by vacuum
filtration. These were not rinsed, as the crystals redissolve very easily.
Co(HSeO3)Cl·2H2O crystals appear to be stable when stored in a dry
atmosphere.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXS97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXS97.
Crystal data top
Co(HSeO3)Cl·2H2O | F(000) = 984 |
Mr = 258.38 | Dx = 2.895 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 5736 reflections |
a = 9.3384 (4) Å | θ = 3.5–32.5° |
b = 17.3447 (7) Å | µ = 9.42 mm−1 |
c = 7.3198 (3) Å | T = 293 K |
V = 1185.60 (9) Å3 | Chunk, purple |
Z = 8 | 0.35 × 0.16 × 0.08 mm |
Data collection top
Bruker SMART1000 CCD diffractometer | 2199 independent reflections |
Radiation source: fine-focus sealed tube | 1923 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 32.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −13→14 |
Tmin = 0.137, Tmax = 0.519 | k = −22→26 |
11031 measured reflections | l = −9→11 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | H-atom parameters constrained |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0396P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
2199 reflections | Δρmax = 0.92 e Å−3 |
80 parameters | Δρmin = −0.94 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0007 (2) |
Crystal data top
Co(HSeO3)Cl·2H2O | V = 1185.60 (9) Å3 |
Mr = 258.38 | Z = 8 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 9.3384 (4) Å | µ = 9.42 mm−1 |
b = 17.3447 (7) Å | T = 293 K |
c = 7.3198 (3) Å | 0.35 × 0.16 × 0.08 mm |
Data collection top
Bruker SMART1000 CCD diffractometer | 2199 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 1923 reflections with I > 2σ(I) |
Tmin = 0.137, Tmax = 0.519 | Rint = 0.025 |
11031 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.92 e Å−3 |
2199 reflections | Δρmin = −0.94 e Å−3 |
80 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 | x | y | z | Uiso*/Ueq | |
Co1 | 0.5000 | 0.0000 | 0.5000 | 0.01431 (9) | |
Co2 | 0.34707 (4) | 0.2500 | 0.44220 (6) | 0.02110 (10) | |
Cl1 | 0.52299 (6) | 0.14898 (3) | 0.52387 (8) | 0.02438 (12) | |
Se1 | 0.185092 (19) | −0.052173 (11) | 0.34310 (2) | 0.01417 (7) | |
O1 | 0.04599 (16) | 0.00205 (9) | 0.27245 (19) | 0.0194 (3) | |
O2 | 0.28545 (15) | 0.01510 (9) | 0.4468 (2) | 0.0190 (3) | |
O3 | 0.10764 (19) | −0.09922 (10) | 0.5306 (2) | 0.0248 (3) | |
H1 | 0.0548 | −0.0635 | 0.5905 | 0.030* | |
O4 | 0.4115 (3) | 0.2500 | 0.1698 (3) | 0.0332 (6) | |
H2 | 0.4194 | 0.2907 | 0.1061 | 0.040* | |
O5 | 0.2540 (3) | 0.2500 | 0.7117 (4) | 0.0420 (7) | |
H3 | 0.2100 | 0.2097 | 0.7277 | 0.050* | |
O6 | 0.20069 (17) | 0.16398 (10) | 0.3759 (3) | 0.0289 (3) | |
H4 | 0.2298 | 0.1197 | 0.3922 | 0.035* | |
H5 | 0.1539 | 0.1618 | 0.2721 | 0.035* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.01159 (16) | 0.01917 (19) | 0.01216 (16) | 0.00094 (13) | 0.00081 (11) | 0.00035 (12) |
Co2 | 0.02045 (19) | 0.0178 (2) | 0.0250 (2) | 0.000 | 0.00051 (14) | 0.000 |
Cl1 | 0.0225 (2) | 0.0177 (2) | 0.0329 (3) | 0.00136 (18) | −0.00375 (18) | 0.00163 (19) |
Se1 | 0.01389 (10) | 0.01519 (10) | 0.01344 (10) | 0.00180 (6) | −0.00075 (6) | −0.00107 (6) |
O1 | 0.0180 (6) | 0.0260 (8) | 0.0143 (6) | 0.0075 (5) | −0.0035 (5) | −0.0022 (5) |
O2 | 0.0139 (6) | 0.0177 (7) | 0.0254 (7) | 0.0002 (5) | −0.0043 (5) | −0.0028 (5) |
O3 | 0.0299 (8) | 0.0204 (8) | 0.0241 (7) | 0.0032 (6) | 0.0086 (6) | 0.0065 (6) |
O4 | 0.0501 (16) | 0.0208 (12) | 0.0287 (12) | 0.000 | 0.0051 (11) | 0.000 |
O5 | 0.0538 (18) | 0.0298 (15) | 0.0423 (14) | 0.000 | 0.0195 (13) | 0.000 |
O6 | 0.0253 (8) | 0.0170 (8) | 0.0444 (9) | −0.0004 (6) | −0.0076 (7) | −0.0001 (7) |
Geometric parameters (Å, º) top
Co1—O1i | 2.0403 (14) | Co2—Cl1iv | 2.4751 (6) |
Co1—O1ii | 2.0403 (14) | Co2—Cl1 | 2.4751 (6) |
Co1—O2 | 2.0578 (14) | Se1—O2 | 1.6779 (15) |
Co1—O2iii | 2.0578 (14) | Se1—O1 | 1.6851 (14) |
Co1—Cl1iii | 2.5989 (6) | Se1—O3 | 1.7530 (15) |
Co1—Cl1 | 2.5989 (6) | O3—H1 | 0.9050 |
Co2—O6 | 2.0809 (17) | O4—H2 | 0.8493 |
Co2—O6iv | 2.0809 (17) | O5—H3 | 0.8200 |
Co2—O4 | 2.083 (2) | O6—H4 | 0.8227 |
Co2—O5 | 2.155 (3) | O6—H5 | 0.8776 |
| | | |
O1i—Co1—O1ii | 180.00 (9) | O6—Co2—Cl1iv | 179.19 (6) |
O1i—Co1—O2 | 91.01 (6) | O6iv—Co2—Cl1iv | 89.13 (5) |
O1ii—Co1—O2 | 88.99 (6) | O4—Co2—Cl1iv | 92.27 (6) |
O1i—Co1—O2iii | 88.99 (6) | O5—Co2—Cl1iv | 92.68 (7) |
O1ii—Co1—O2iii | 91.01 (6) | O6—Co2—Cl1 | 89.13 (5) |
O2—Co1—O2iii | 180.0 | O6iv—Co2—Cl1 | 179.19 (6) |
O1i—Co1—Cl1iii | 88.23 (5) | O4—Co2—Cl1 | 92.27 (6) |
O1ii—Co1—Cl1iii | 91.77 (5) | O5—Co2—Cl1 | 92.68 (7) |
O2—Co1—Cl1iii | 91.91 (4) | Cl1iv—Co2—Cl1 | 90.13 (3) |
O2iii—Co1—Cl1iii | 88.09 (4) | Co2—Cl1—Co1 | 129.26 (2) |
O1i—Co1—Cl1 | 91.77 (5) | O2—Se1—O1 | 100.44 (7) |
O1ii—Co1—Cl1 | 88.23 (5) | O2—Se1—O3 | 101.54 (8) |
O2—Co1—Cl1 | 88.09 (4) | O1—Se1—O3 | 100.49 (8) |
O2iii—Co1—Cl1 | 91.91 (4) | Se1—O1—Co1v | 116.90 (8) |
Cl1iii—Co1—Cl1 | 180.0 | Se1—O2—Co1 | 122.75 (8) |
O6—Co2—O6iv | 91.62 (10) | Se1—O3—H1 | 106.6 |
O6—Co2—O4 | 88.08 (8) | Co2—O4—H2 | 123.4 |
O6iv—Co2—O4 | 88.08 (8) | Co2—O5—H3 | 109.5 |
O6—Co2—O5 | 87.04 (8) | Co2—O6—H4 | 114.7 |
O6iv—Co2—O5 | 87.04 (8) | Co2—O6—H5 | 124.0 |
O4—Co2—O5 | 173.00 (12) | H4—O6—H5 | 104.5 |
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) −x+1/2, −y, z+1/2; (iii) −x+1, −y, −z+1; (iv) x, −y+1/2, z; (v) −x+1/2, −y, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O1vi | 0.90 | 1.74 | 2.641 (2) | 173 |
O4—H2···O3vii | 0.85 | 2.00 | 2.8123 (18) | 159 |
O5—H3···Cl1viii | 0.82 | 2.73 | 3.387 (2) | 138 |
O6—H4···O2 | 0.82 | 1.93 | 2.750 (2) | 175 |
O6—H5···Cl1ix | 0.88 | 2.50 | 3.3741 (18) | 177 |
Symmetry codes: (vi) −x, −y, −z+1; (vii) −x+1/2, y+1/2, z−1/2; (viii) x−1/2, y, −z+3/2; (ix) x−1/2, y, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | Co(HSeO3)Cl·2H2O |
Mr | 258.38 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 9.3384 (4), 17.3447 (7), 7.3198 (3) |
V (Å3) | 1185.60 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 9.42 |
Crystal size (mm) | 0.35 × 0.16 × 0.08 |
|
Data collection |
Diffractometer | Bruker SMART1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.137, 0.519 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11031, 2199, 1923 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.756 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.062, 1.02 |
No. of reflections | 2199 |
No. of parameters | 80 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −0.94 |
Selected geometric parameters (Å, º) topCo1—O1i | 2.0403 (14) | Co2—O5 | 2.155 (3) |
Co1—O2 | 2.0578 (14) | Co2—Cl1 | 2.4751 (6) |
Co1—Cl1 | 2.5989 (6) | Se1—O2 | 1.6779 (15) |
Co2—O6 | 2.0809 (17) | Se1—O1 | 1.6851 (14) |
Co2—O4 | 2.083 (2) | Se1—O3 | 1.7530 (15) |
| | | |
Cl1ii—Co2—Cl1 | 90.13 (3) | Se1—O1—Co1iii | 116.90 (8) |
Co2—Cl1—Co1 | 129.26 (2) | Se1—O2—Co1 | 122.75 (8) |
Symmetry codes: (i) −x+1/2, −y, z+1/2; (ii) x, −y+1/2, z; (iii) −x+1/2, −y, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O1iv | 0.90 | 1.74 | 2.641 (2) | 173 |
O4—H2···O3v | 0.85 | 2.00 | 2.8123 (18) | 159 |
O5—H3···Cl1vi | 0.82 | 2.73 | 3.387 (2) | 138 |
O6—H4···O2 | 0.82 | 1.93 | 2.750 (2) | 175 |
O6—H5···Cl1vii | 0.88 | 2.50 | 3.3741 (18) | 177 |
Symmetry codes: (iv) −x, −y, −z+1; (v) −x+1/2, y+1/2, z−1/2; (vi) x−1/2, y, −z+3/2; (vii) x−1/2, y, −z+1/2. |
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The title compound represents another example of a hydrogen selenite chloride hydrate, complementing Co(HSeO3)Cl·3H2O and Cu(HSeO3)Cl·2H2O (Johnston & Harrison, 2000). Co(HSeO3)Cl·2H2O (Figs. 1 and 2) is essentially isostructural with Cu(HSeO3)Cl·2H2O, although the metal coordinations are distinctly different in the two phases.
Co1 (site symmetry 1) has elongated octahedral coordination to four O and two Cl atoms. The cis bond angles lie between 88.09 (4) and 91.91 (4)°. The O atoms form bridges to adjacent Se atoms [θav(Co—O—Se) = 119.8 (8)°] and the Cl atoms link to Co2 cations. The average Co1—O distance of 2.049 (2) Å and the Co1—Cl separation of 2.5989 (6) Å correlate reasonably well with ionic radius (IR) sums for the species involved [dIR(Co—O) = 2.09 Å and dIR(Co—Cl) = 2.56 Å], assuming the presence of high-spin Co2+ (Shannon, 1976). In Cu(HSeO3)Cl·2H2O (Johnston & Harrison, 2000), the distinction between the equatorial Cu—O bonds [dav = 1.976 (2) Å] and apical Cu—Cl [d = 2.8066 (5) Å] bonds is more extreme, and can be ascribed to a typical Jahn–Teller distortion for the d9 Cu2+ ion.
The pyramidal geometry of the [HSeO3]- moiety and the lengthened, protonated, Se—O3H bond in the title compound are typical for the hydrogen selenite group (Verma, 1999). The unobserved SeIV lone pair of electrons is presumed to occupy the fourth vertex of a tetrahedron, and as such, is directed into empty space at an angle of about 35° with respect to a projection of the Se—E (E = lone pair) vector on to (010). These [Co(HSeO3)2Cl2]2- layers consist of polyhedral eight-rings (Fig. 3) and a pair of intra-sheet Se—O3—H1···O1 hydrogen bonds stabilizes each of these voids.
The four O and two Cl atoms around Co2 (site symmetry m) form a distorted cis Co(H2O)4Cl2 octahedron [dav(Co—O) = 2.100 (3) Å]. The cis and trans bond angles lie in the ranges 87.04 (8)–92.68 (7) and 173.00 (12)–179.19 (6)°, respectively. The [Co2(H2O)4Cl2] octahedra are isolated from each other, and bridge the (010) [Co(HSeO3)2Cl2]2- sheets via Co1—Cl1—Co2—Cl1—Co1 bonds to produce a three-dimensional structure. The hydrogen bonds (Table 2 and Fig. 4) associated with the Co2-polyhedron water molecules include O—H···O and O—H···Cl links. In Cu(HSeO3)Cl·2H2O, a Jahn-T-eller distortion led to long bonds to two of the trans water-molecule O atoms [2.229 (3) and 2.634 (5) Å], two short symmetry-equivalent Cu—OH2 links [2.0244 (16) Å] and a short Cu—Cl bond [d = 2.3127 (5) Å].