Buy article online - an online subscription or single-article purchase is required to access this article.
The structure of the one-dimensional antiferromagnet caesium diaquatrichloromanganate(II) was re-refined based on area-detector data, including the positions of H atoms. The Mn
II atom, on a twofold rotation axis, is in a distorted octahedral coordination by two bridging Cl ligands in
trans positions, two terminal Cl ligands and two aqua ligands, both in
cis positions. Hydrogen bonds of the type O—H
Cl connect octahedra along the chain and link the chains into layers which are separated by the Cs ions (also on twofold axes). The structure is discussed in comparison with non-isotypic related compounds of the morphotropic series
AMCl
3(H
2O)
2 (
A = Cs, Rb, K and
M = Mn, Fe, Co).
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (n-O) = 0.005 Å
- R factor = 0.034
- wR factor = 0.068
- Data-to-parameter ratio = 27.8
checkCIF/PLATON results
No syntax errors found
Alert level C
ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
Tmin and Tmax reported: 0.596 0.625
Tmin and Tmax expected: 0.590 0.740
RR = 1.197
Please check that your absorption correction is appropriate.
GOODF01_ALERT_2_C The least squares goodness of fit parameter lies
outside the range 0.80 <> 2.00
Goodness of fit given = 0.784
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.20
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 1.18
Alert level G
ABSTM02_ALERT_3_G 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 1.184
Tmax scaled 0.740 Tmin scaled 0.706
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
3 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: EXPOSE (Stoe & Cie, 1999); cell refinement: CELL (Stoe & Cie, 1999); data reduction: INTEGRATE (Stoe & Cie, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (version 1.0c; Westrip, 2006).
caesium diaquatrichloromanganate(II)
top
Crystal data top
Cs[MnCl3(H2O)2] | F(000) = 604 |
Mr = 330.23 | Dx = 2.925 Mg m−3 |
Orthorhombic, Pcca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2a 2ac | Cell parameters from 2772 reflections |
a = 9.0307 (12) Å | θ = 3.5–29.3° |
b = 7.2636 (8) Å | µ = 7.52 mm−1 |
c = 11.4312 (13) Å | T = 293 K |
V = 749.83 (15) Å3 | Irregular, colourless |
Z = 4 | 0.10 × 0.06 × 0.04 mm |
Data collection top
Stoe IPDS diffractometer | 1002 independent reflections |
Radiation source: fine-focus sealed tube | 529 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
Detector resolution: 6.7 pixels mm-1 | θmax = 29.0°, θmin = 3.6° |
φ scans | h = −12→12 |
Absorption correction: multi-scan (Blessing, 1995) | k = −9→9 |
Tmin = 0.596, Tmax = 0.625 | l = −15→15 |
9154 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 0.78 | w = 1/[σ2(Fo2) + (0.029P)2] where P = (Fo2 + 2Fc2)/3 |
1002 reflections | (Δ/σ)max < 0.001 |
36 parameters | Δρmax = 1.38 e Å−3 |
0 restraints | Δρmin = −0.94 e Å−3 |
Special details top
Experimental. Owing to the small and irregular size of the crystal a semiempirical absorption
correction was prefered |
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 | |
Cs1 | 0.2500 | 0.0000 | 0.14585 (5) | 0.03770 (18) | |
Mn1 | 0.0000 | 0.46686 (15) | 0.2500 | 0.0235 (3) | |
Cl1 | 0.2500 | 0.5000 | 0.14997 (18) | 0.0261 (4) | |
Cl2 | 0.08913 (17) | 0.22201 (18) | 0.39016 (16) | 0.0284 (3) | |
O1 | 0.0707 (5) | 0.6819 (6) | 0.3712 (4) | 0.0345 (12) | |
H1 | 0.0313 | 0.7029 | 0.4375 | 0.07 (2)* | |
H2 | 0.1614 | 0.7133 | 0.3725 | 0.07 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cs1 | 0.0404 (3) | 0.0344 (3) | 0.0383 (3) | 0.0127 (3) | 0.000 | 0.000 |
Mn1 | 0.0217 (6) | 0.0237 (6) | 0.0252 (7) | 0.000 | 0.0006 (5) | 0.000 |
Cl1 | 0.0205 (8) | 0.0322 (8) | 0.0256 (9) | 0.0010 (11) | 0.000 | 0.000 |
Cl2 | 0.0257 (7) | 0.0328 (8) | 0.0267 (7) | 0.0001 (6) | 0.0011 (7) | −0.0030 (6) |
O1 | 0.023 (3) | 0.045 (2) | 0.036 (4) | −0.008 (2) | −0.004 (2) | 0.016 (2) |
Geometric parameters (Å, º) top
Cs1—Cl2i | 3.4856 (15) | Mn1—O1ii | 2.183 (4) |
Cs1—Cl2ii | 3.4856 (15) | Mn1—Cl2ii | 2.5255 (18) |
Cs1—Cl2 | 3.5371 (18) | Mn1—Cl2 | 2.5255 (18) |
Cs1—Cl2iii | 3.5371 (18) | Mn1—Cl1 | 2.5422 (10) |
Cs1—Cl1 | 3.6321 (4) | Mn1—Cl1ix | 2.5422 (10) |
Cs1—Cl1iv | 3.6321 (4) | Mn1—Cs1x | 4.2443 (10) |
Cs1—Cl2v | 3.6405 (18) | Cl1—Mn1xi | 2.5422 (10) |
Cs1—Cl2vi | 3.6405 (18) | Cl1—Cs1xii | 3.6321 (4) |
Cs1—O1vii | 3.710 (5) | Cl2—Cs1x | 3.4856 (15) |
Cs1—O1viii | 3.710 (5) | Cl2—Cs1xiii | 3.6405 (18) |
Mn1—O1 | 2.183 (4) | | |
| | | |
Cl2i—Cs1—Cl2ii | 166.43 (6) | Cl2i—Cs1—O1viii | 66.18 (7) |
Cl2i—Cs1—Cl2 | 131.69 (3) | Cl2ii—Cs1—O1viii | 113.05 (7) |
Cl2ii—Cs1—Cl2 | 61.41 (5) | Cl2—Cs1—O1viii | 94.48 (7) |
Cl2i—Cs1—Cl2iii | 61.41 (5) | Cl2iii—Cs1—O1viii | 90.28 (8) |
Cl2ii—Cs1—Cl2iii | 131.69 (3) | Cl1—Cs1—O1viii | 51.53 (7) |
Cl2—Cs1—Cl2iii | 75.71 (5) | Cl1iv—Cs1—O1viii | 128.57 (7) |
Cl2i—Cs1—Cl1 | 117.65 (2) | Cl2v—Cs1—O1viii | 123.04 (8) |
Cl2ii—Cs1—Cl1 | 62.54 (2) | Cl2vi—Cs1—O1viii | 50.98 (7) |
Cl2—Cs1—Cl1 | 62.22 (4) | O1vii—Cs1—O1viii | 173.98 (15) |
Cl2iii—Cs1—Cl1 | 116.46 (4) | O1—Mn1—O1ii | 88.7 (3) |
Cl2i—Cs1—Cl1iv | 62.54 (2) | O1—Mn1—Cl2ii | 178.37 (13) |
Cl2ii—Cs1—Cl1iv | 117.65 (2) | O1ii—Mn1—Cl2ii | 90.45 (13) |
Cl2—Cs1—Cl1iv | 116.46 (4) | O1—Mn1—Cl2 | 90.45 (13) |
Cl2iii—Cs1—Cl1iv | 62.22 (4) | O1ii—Mn1—Cl2 | 178.37 (13) |
Cl1—Cs1—Cl1iv | 178.51 (7) | Cl2ii—Mn1—Cl2 | 90.47 (8) |
Cl2i—Cs1—Cl2v | 92.92 (3) | O1—Mn1—Cl1 | 87.59 (13) |
Cl2ii—Cs1—Cl2v | 76.08 (4) | O1ii—Mn1—Cl1 | 84.64 (13) |
Cl2—Cs1—Cl2v | 132.22 (5) | Cl2ii—Mn1—Cl1 | 93.69 (5) |
Cl2iii—Cs1—Cl2v | 126.57 (4) | Cl2—Mn1—Cl1 | 93.96 (5) |
Cl1—Cs1—Cl2v | 116.96 (4) | O1—Mn1—Cl1ix | 84.64 (13) |
Cl1iv—Cs1—Cl2v | 64.37 (4) | O1ii—Mn1—Cl1ix | 87.59 (13) |
Cl2i—Cs1—Cl2vi | 76.08 (4) | Cl2ii—Mn1—Cl1ix | 93.96 (5) |
Cl2ii—Cs1—Cl2vi | 92.92 (3) | Cl2—Mn1—Cl1ix | 93.69 (5) |
Cl2—Cs1—Cl2vi | 126.57 (4) | Cl1—Mn1—Cl1ix | 169.13 (5) |
Cl2iii—Cs1—Cl2vi | 132.22 (5) | Mn1xi—Cl1—Mn1 | 126.54 (8) |
Cl1—Cs1—Cl2vi | 64.37 (4) | Mn1xi—Cl1—Cs1 | 95.77 (3) |
Cl1iv—Cs1—Cl2vi | 116.96 (4) | Mn1—Cl1—Cs1 | 84.90 (3) |
Cl2v—Cs1—Cl2vi | 73.20 (5) | Mn1xi—Cl1—Cs1xii | 84.90 (3) |
Cl2i—Cs1—O1vii | 113.05 (7) | Mn1—Cl1—Cs1xii | 95.77 (3) |
Cl2ii—Cs1—O1vii | 66.18 (7) | Cs1—Cl1—Cs1xii | 178.51 (7) |
Cl2—Cs1—O1vii | 90.28 (8) | Mn1—Cl2—Cs1x | 88.33 (5) |
Cl2iii—Cs1—O1vii | 94.48 (7) | Mn1—Cl2—Cs1 | 87.19 (5) |
Cl1—Cs1—O1vii | 128.57 (7) | Cs1x—Cl2—Cs1 | 93.25 (4) |
Cl1iv—Cs1—O1vii | 51.53 (7) | Mn1—Cl2—Cs1xiii | 161.53 (6) |
Cl2v—Cs1—O1vii | 50.98 (7) | Cs1x—Cl2—Cs1xiii | 103.92 (4) |
Cl2vi—Cs1—O1vii | 123.04 (8) | Cs1—Cl2—Cs1xiii | 105.55 (4) |
Symmetry codes: (i) x+1/2, −y, −z+1/2; (ii) −x, y, −z+1/2; (iii) −x+1/2, −y, z; (iv) x, y−1, z; (v) x, −y, z−1/2; (vi) −x+1/2, y, z−1/2; (vii) −x, y−1, −z+1/2; (viii) x+1/2, −y+1, −z+1/2; (ix) x−1/2, −y+1, −z+1/2; (x) x−1/2, −y, −z+1/2; (xi) −x+1/2, −y+1, z; (xii) x, y+1, z; (xiii) −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 |
O1—H1···Cl2xiv | 0.85 | 2.32 | 3.164 (5) | 175 |
O1—H2···Cl2xi | 0.85 | 2.31 | 3.158 (5) | 175 |
Symmetry codes: (xi) −x+1/2, −y+1, z; (xiv) −x, −y+1, −z+1. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.