Cs₂K[Mn(CN)₆] at 293, 85 and 10 K

The crystal structure of dicaesium potassium hexacyanomanganese(III) has been determined by X-ray diffraction at 293, 85 and 10 K. The Mn and K atoms lie on inversion centres and the Cs atom is in a general position. The accurate and extensive data sets collected should be suitable for charge-density analysis studies.

S1. Comment

The trivalent first transition series metals from Cr to Co and some second and third series elements form complexes of formulation Cs₂M^I[M^III(CN)₆] (M^I = Li–Cs), with the elpasolite structure. They crystallize well and are of interest in inorganic chemistry as classical coordination complexes involving the most covalently bonding of ligands, the cyanide ion, and for which the physical properties are well defined. There are previous structural studies of these elpasolites by X-ray and neutron diffraction both at room and at lower temperatures, for example, Cs₂K[Cr(CN)₆] (Figgis et al., 1983; Brown et al., 1987), Cs₂K[Mn(CN)₆] (Ziegler et al., 1989; Blake et al., 1994) and Cs₂K[Fe(CN)₆] (Fletcher & Gibb, 1977; Herren et al., 1979; Figgis et al., 1990).

In particular, for M^I = K, magnetic susceptibility and polarized neutron diffraction experiments have been performed on their single crystals (Figgis et al., 1985; Brown et al., 1987; Figgis & Reynolds, 1987; Reynolds et al., 1992; Blake et al., 1994). Also, for M^I = Li, the complexities of thermal motion have received attention; see, for example, Chadwick et al. (1988) and Ryan & Swanson (1974).

We have determined by X-ray diffraction the crystal structure of Cs₂K[Mn(CN)₆] at 293, 85 and 10 K. Salts of this type are made up of Cs⁺ and K⁺ cations and [M(CN)₆]³⁻ anions, and this anion is illustrated in Fig. 1. The structural features have been described before and the present case presents no unusual results. Selected bond lengths and angles for the [Mn(CN)₆]³⁻ ion at the three temperatures are given in the Table 1. The results for the 293 K study are very similar to those of Ziegler et al. (1989) at ambient temperature, but with s.u.'s lower by a factor approaching 2.

The [Mn(CN)₆]³⁻ ion is very close to regular octahedral stereochemistry at each of the temperatures, with the bond from Mn to C3 just significantly shorter than those to C1 and C2. All the C—Mn—C angles for adjacent ligands differ from 90° by ca 0.15°, and the C—Mn—N angles are all ca 1.5° off the linear configuration. The Mn—C bond lengths are essentially independent of temperaure although the C—N bonds apparently lengthen significantly, presumably due to reduced libration, as we lower the temperature from 293 to 10 K. The mean Mn—C bond length at 85 K [1.989 (4) Å] lies between those in the [Cr(CN)₆]³⁻ ion [2.066 (4) Å; Figgis & Reynolds, 1987] and in the [Fe(CN)₆]³⁻ ion (1.932 Å; Figgis et al., 1990), while the average C—N separation of 1.159 (1) Å matches that for the Cr salt [1.160 (1) Å] and is slightly lower than for the Fe salt [1.166 (2) Å]. The Mn (d⁴) and Fe (d⁵) cases are low spin and have orbitally degenerate ground states and so are formally Jahn–Teller unstable. On the other hand, the Cr (d³) case has an orbital singlet ground state and is Jahn–Teller stable. However, the bond lengths within the respective [M(CN)₆]³⁻ ions do not show the differences which might be expected on that account. The Cs atomic displacement parameters (adp's) are quite isotropic at all temperatures. This contrasts with the results for the Cs adp's of Cs₂K[Cr(CN)₆] at 120 K and, to a lesser extent, of Cs₂K[Fe(CN)₆] at 85 K, where apparent anomalies in the thermal motion placed limitations on the interpretation of the X-ray data in terms of valence orbital parameters in a charge–density analysis. Such anomalies appear to even greater degree in the analagous Co salt (Figgis & Sobolev, 2000) and preclude its use in a charge–density study.

S2. Experimental

Cs₂K[Mn(CN)₆] was prepared by a standard procedure (Brauer, 1963). Single crystals of the complex were obtained by recrystallization from aqueous solution. Room temperature and the very low-temperature data sets were collected on a locally assembled Huber 512 goniometer equipped with a Displex 202D cryogenic refrigerator (Hendricksen et al., 1986; Larsen, 1995). The 85 K data were collected on a Syntex P21 diffractometer equipped with a locally developed nitrogen gas stream cooling device.

Computing details

Data collection: local software for I293K, I10K; P3/P4-PC Software (Siemens, 1991) for I85K. Cell refinement: local software for I293K, I10K; P3/P4-PC Software for I85K. For all compounds, data reduction: PROFIT (Streltsov & Zavodnik, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1983); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. Conventional atomic numbering of the [Mn(CN)6]^3− octahedron with 50% probability displacement ellipsoids at 85 K.

(I293K) dicesium potassium hexacyanomanganate(III)

Crystal data

Cs2K[Mn(CN)6]	Dx = 2.420 Mg m^−3
Mr = 515.98	Melting point: not measured K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.207 (2) Å	Cell parameters from 12 reflections
b = 8.210 (1) Å	θ = 15.2–16.4°
c = 7.696 (1) Å	µ = 6.28 mm^−1
β = 90.25 (1)°	T = 293 K
V = 708.1 (2) Å^3	Prism, dark red–brown
Z = 2	0.36 × 0.23 × 0.23 mm
F(000) = 464

Data collection

Huber 512 goniometer diffractometer	1217 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.025
None monochromator	θmax = 25.0°, θmin = 3.1°
ω–2θ scans	h = −13→13
Absorption correction: gaussian (Xtal3.4; Hall et al., 1994)	k = −9→9
Tmin = 0.197, Tmax = 0.268	l = −9→9
4814 measured reflections	3 standard reflections every 100 reflections
1254 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	w = 1/[σ^2(Fo^2) + (0.0311P)^2 + 0.9408P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.060	(Δ/σ)max < 0.001
S = 1.12	Δρmax = 0.48 e Å^−3
1254 reflections	Δρmin = −1.02 e Å^−3
77 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0512 (16)

Special details

Experimental. no special details

Geometry. All e.s.d.'s (except those in the dihedral angles between pairs of 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 (Ų)

	x	y	z	Uiso*/Ueq
Cs	0.25072 (2)	0.43000 (3)	−0.02177 (4)	0.05019 (17)
K	0.0000	0.5000	0.5000	0.0330 (2)
Mn	0.0000	0.0000	0.0000	0.02501 (19)
C1	0.0330 (3)	0.1298 (4)	−0.2141 (4)	0.0355 (7)
N1	0.0540 (3)	0.2043 (4)	−0.3356 (5)	0.0594 (9)
C2	0.0406 (3)	−0.2049 (4)	−0.1269 (4)	0.0356 (7)
N2	0.0658 (3)	−0.3212 (4)	−0.2003 (5)	0.0571 (9)
C3	0.1698 (3)	0.0231 (4)	0.0728 (4)	0.0364 (7)
N3	0.2671 (3)	0.0409 (5)	0.1165 (5)	0.0561 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs	0.0550 (2)	0.0424 (2)	0.0532 (2)	−0.00163 (9)	0.00202 (12)	0.00519 (9)
K	0.0347 (5)	0.0287 (5)	0.0356 (5)	−0.0005 (4)	−0.0003 (4)	0.0009 (4)
Mn	0.0263 (3)	0.0215 (3)	0.0272 (3)	0.0011 (2)	0.0015 (2)	0.0009 (2)
C1	0.0375 (16)	0.0304 (16)	0.0387 (18)	0.0048 (13)	0.0037 (13)	0.0000 (14)
N1	0.081 (2)	0.0482 (19)	0.0496 (19)	0.0127 (17)	0.0189 (17)	0.0195 (16)
C2	0.0388 (16)	0.0341 (17)	0.0340 (16)	0.0006 (13)	−0.0028 (13)	0.0021 (14)
N2	0.077 (2)	0.0406 (18)	0.053 (2)	0.0170 (16)	−0.0083 (17)	−0.0168 (16)
C3	0.0356 (18)	0.0345 (17)	0.0392 (18)	0.0001 (13)	0.0010 (14)	0.0045 (14)
N3	0.0326 (17)	0.067 (2)	0.069 (2)	−0.0023 (15)	−0.0045 (15)	0.0081 (19)

Geometric parameters (Å, º)

Cs—N1^i	3.330 (4)	Mn—C1	1.999 (3)
Cs—N1	3.753 (4)	Mn—C2	1.999 (3)
Cs—N1^ii	3.844 (4)	Mn—C3	1.991 (3)
Cs—N2^iii	3.214 (3)	Mn—C1^vii	1.999 (3)
Cs—N2^i	3.619 (4)	Mn—C2^vii	1.999 (3)
Cs—N3^iv	3.256 (4)	Mn—C3^vii	1.991 (3)
Cs—N3	3.372 (4)	Mn—Cs^vii	4.5156 (5)
Cs—C1^i	3.569 (3)	C1—N1	1.142 (5)
Cs—C1	3.766 (3)	C1—Cs^xi	3.569 (3)
Cs—C2^i	3.749 (3)	N1—K^xii	2.803 (3)
Cs—C3	3.538 (3)	N1—Cs^xi	3.330 (4)
Cs—C3^iv	3.645 (3)	N1—Cs^xiii	3.844 (4)
K—N1^v	2.803 (3)	C2—N2	1.146 (5)
K—N1^vi	2.803 (3)	C2—Cs^xi	3.749 (3)
K—N2^vii	2.829 (3)	C2—Cs^xiv	3.895 (3)
K—N2^viii	2.829 (3)	N2—K^xv	2.829 (3)
K—N3^ix	2.784 (3)	N2—Cs^xiv	3.214 (3)
K—N3^iv	2.784 (3)	N2—Cs^xi	3.619 (4)
K—Cs^iv	4.5046 (5)	C3—N3	1.149 (5)
K—Cs^ix	4.5046 (5)	C3—Cs^xvi	3.645 (3)
K—Cs^v	4.6563 (7)	N3—K^xvi	2.784 (3)
K—Cs^vi	4.6563 (7)	N3—Cs^xvi	3.256 (4)
K—Cs^x	4.9446 (7)
N2^iii—Cs—N3^iv	100.93 (9)	Cs^iv—K—Cs^v	107.739 (8)
N2^iii—Cs—N1^i	81.55 (10)	Cs^ix—K—Cs^v	72.261 (8)
N3^iv—Cs—N1^i	99.76 (9)	N3^ix—K—Cs^vi	107.09 (8)
N2^iii—Cs—N3	140.44 (9)	N3^iv—K—Cs^vi	72.91 (8)
N3^iv—Cs—N3	88.06 (6)	N1^v—K—Cs^vi	126.30 (9)
N1^i—Cs—N3	135.22 (9)	N1^vi—K—Cs^vi	53.70 (9)
N2^iii—Cs—C3	121.50 (9)	N2^vii—K—Cs^vi	137.28 (7)
N3^iv—Cs—C3	92.88 (9)	N2^viii—K—Cs^vi	42.72 (7)
N1^i—Cs—C3	151.13 (8)	Cs^iv—K—Cs^vi	72.261 (8)
N3—Cs—C3	18.94 (8)	Cs^ix—K—Cs^vi	107.739 (8)
N2^iii—Cs—C1^i	84.42 (9)	Cs^v—K—Cs^vi	180.0
N3^iv—Cs—C1^i	117.47 (8)	N3^ix—K—Cs	141.67 (8)
N1^i—Cs—C1^i	18.64 (8)	N3^iv—K—Cs	38.33 (8)
N3—Cs—C1^i	125.39 (8)	N1^v—K—Cs	81.74 (7)
C3—Cs—C1^i	136.59 (8)	N1^vi—K—Cs	98.26 (7)
N2^iii—Cs—N2^i	118.47 (5)	N2^vii—K—Cs	54.86 (8)
N3^iv—Cs—N2^i	139.72 (8)	N2^viii—K—Cs	125.14 (8)
N1^i—Cs—N2^i	79.31 (8)	Cs^iv—K—Cs	76.512 (9)
N3—Cs—N2^i	67.45 (8)	Cs^ix—K—Cs	103.488 (9)
C3—Cs—N2^i	74.35 (7)	Cs^v—K—Cs	73.473 (13)
C1^i—Cs—N2^i	62.38 (7)	Cs^vi—K—Cs	106.527 (13)
N2^iii—Cs—C3^iv	115.24 (8)	N3^ix—K—Cs^x	38.33 (8)
N3^iv—Cs—C3^iv	18.04 (8)	N3^iv—K—Cs^x	141.67 (8)
N1^i—Cs—C3^iv	90.71 (8)	N1^v—K—Cs^x	98.26 (7)
N3—Cs—C3^iv	83.49 (9)	N1^vi—K—Cs^x	81.74 (7)
C3—Cs—C3^iv	93.71 (6)	N2^vii—K—Cs^x	125.14 (8)
C1^i—Cs—C3^iv	106.24 (8)	N2^viii—K—Cs^x	54.86 (8)
N2^i—Cs—C3^iv	122.86 (8)	Cs^iv—K—Cs^x	103.488 (9)
N2^iii—Cs—C2^i	106.41 (8)	Cs^ix—K—Cs^x	76.512 (8)
N3^iv—Cs—C2^i	144.51 (7)	Cs^v—K—Cs^x	106.527 (13)
N1^i—Cs—C2^i	63.20 (8)	Cs^vi—K—Cs^x	73.473 (13)
N3—Cs—C2^i	85.11 (8)	Cs—K—Cs^x	180.0
C3—Cs—C2^i	91.76 (8)	C1—Mn—C2	90.1 (1)
C1^i—Cs—C2^i	45.41 (7)	C2—Mn—C3	89.9 (1)
N2^i—Cs—C2^i	17.77 (7)	C3—Mn—C1	90.1 (1)
C3^iv—Cs—C2^i	126.50 (7)	C3—Mn—C3^vii	180.0
N2^iii—Cs—N1	70.28 (8)	C3^vii—Mn—C2	90.11 (14)
N3^iv—Cs—N1	135.76 (8)	C3—Mn—C2^vii	90.11 (14)
N1^i—Cs—N1	120.47 (6)	C3^vii—Mn—C2^vii	89.89 (14)
N3—Cs—N1	76.48 (8)	C2—Mn—C2^vii	180.00 (18)
C3—Cs—N1	61.04 (7)	C3—Mn—C1^vii	89.93 (13)
C1^i—Cs—N1	105.01 (7)	C3^vii—Mn—C1^vii	90.07 (13)
N2^i—Cs—N1	70.85 (8)	C2—Mn—C1^vii	89.86 (13)
C3^iv—Cs—N1	148.64 (7)	C2^vii—Mn—C1^vii	90.14 (13)
C2^i—Cs—N1	75.92 (7)	C3^vii—Mn—C1	89.93 (13)
N2^iii—Cs—C1	80.34 (8)	C2^vii—Mn—C1	89.86 (13)
N3^iv—Cs—C1	121.15 (8)	C1^vii—Mn—C1	180.0 (2)
N1^i—Cs—C1	137.61 (8)	C3—Mn—Cs^vii	131.17 (10)
N3—Cs—C1	62.51 (8)	C3^vii—Mn—Cs^vii	48.83 (10)
C3—Cs—C1	45.33 (8)	C2—Mn—Cs^vii	60.22 (9)
C1^i—Cs—C1	121.15 (4)	C2^vii—Mn—Cs^vii	119.78 (9)
N2^i—Cs—C1	76.33 (7)	C1^vii—Mn—Cs^vii	55.60 (10)
C3^iv—Cs—C1	131.67 (7)	C1—Mn—Cs^vii	124.40 (10)
C2^i—Cs—C1	85.89 (7)	C3—Mn—Cs	48.83 (10)
N1—Cs—C1	17.47 (7)	C3^vii—Mn—Cs	131.17 (10)
N2^iii—Cs—N1^ii	155.38 (9)	C2—Mn—Cs	119.78 (9)
N3^iv—Cs—N1^ii	77.34 (7)	C2^vii—Mn—Cs	60.22 (9)
N1^i—Cs—N1^ii	74.66 (10)	C1^vii—Mn—Cs	124.40 (10)
N3—Cs—N1^ii	64.15 (8)	C1—Mn—Cs	55.60 (10)
C3—Cs—N1^ii	83.08 (8)	Cs^vii—Mn—Cs	180.000 (4)
C1^i—Cs—N1^ii	75.09 (8)	N1—C1—Mn	178.8 (3)
N2^i—Cs—N1^ii	63.45 (7)	N1—C1—Cs^xi	68.7 (2)
C3^iv—Cs—N1^ii	59.66 (7)	Mn—C1—Cs^xi	110.67 (12)
C2^i—Cs—N1^ii	68.34 (7)	N1—C1—Cs	80.6 (3)
N1—Cs—N1^ii	127.90 (4)	Mn—C1—Cs	98.44 (12)
C1—Cs—N1^ii	121.94 (7)	Cs^xi—C1—Cs	94.83 (7)
N3^ix—K—N3^iv	180.0	C1—N1—K^xii	142.0 (3)
N3^ix—K—N1^v	92.82 (11)	C1—N1—Cs^xi	92.6 (2)
N3^iv—K—N1^v	87.18 (11)	K^xii—N1—Cs^xi	125.30 (11)
N3^ix—K—N1^vi	87.18 (11)	C1—N1—Cs	81.9 (3)
N3^iv—K—N1^vi	92.82 (11)	K^xii—N1—Cs	89.30 (10)
N1^v—K—N1^vi	180.0	Cs^xi—N1—Cs	99.25 (10)
N3^ix—K—N2^vii	87.63 (11)	C1—N1—Cs^xiii	88.1 (3)
N3^iv—K—N2^vii	92.37 (11)	K^xii—N1—Cs^xiii	83.77 (9)
N1^v—K—N2^vii	91.51 (11)	Cs^xi—N1—Cs^xiii	105.34 (10)
N1^vi—K—N2^vii	88.49 (11)	Cs—N1—Cs^xiii	153.84 (10)
N3^ix—K—N2^viii	92.37 (11)	N2—C2—Mn	178.9 (3)
N3^iv—K—N2^viii	87.63 (11)	N2—C2—Cs^xi	74.7 (3)
N1^v—K—N2^viii	88.49 (11)	Mn—C2—Cs^xi	104.37 (12)
N1^vi—K—N2^viii	91.51 (11)	N2—C2—Cs^xiv	46.4 (2)
N2^vii—K—N2^viii	180.0	Mn—C2—Cs^xiv	133.23 (13)
N3^ix—K—Cs^iv	131.67 (8)	Cs^xi—C2—Cs^xiv	89.93 (7)
N3^iv—K—Cs^iv	48.33 (8)	C2—N2—K^xv	140.4 (3)
N1^v—K—Cs^iv	58.02 (9)	C2—N2—Cs^xiv	118.6 (3)
N1^vi—K—Cs^iv	121.98 (9)	K^xv—N2—Cs^xiv	100.61 (9)
N2^vii—K—Cs^iv	126.60 (8)	C2—N2—Cs^xi	87.5 (3)
N2^viii—K—Cs^iv	53.40 (8)	K^xv—N2—Cs^xi	87.73 (9)
N3^ix—K—Cs^ix	48.33 (8)	Cs^xiv—N2—Cs^xi	104.34 (10)
N3^iv—K—Cs^ix	131.67 (8)	N3—C3—Mn	178.0 (3)
N1^v—K—Cs^ix	121.98 (9)	N3—C3—Cs	72.3 (2)
N1^vi—K—Cs^ix	58.02 (9)	Mn—C3—Cs	106.11 (12)
N2^vii—K—Cs^ix	53.40 (8)	N3—C3—Cs^xvi	61.4 (2)
N2^viii—K—Cs^ix	126.60 (8)	Mn—C3—Cs^xvi	118.44 (13)
Cs^iv—K—Cs^ix	180.0	Cs—C3—Cs^xvi	109.34 (9)
N3^ix—K—Cs^v	72.91 (8)	C3—N3—K^xvi	141.3 (3)
N3^iv—K—Cs^v	107.09 (8)	C3—N3—Cs^xvi	100.5 (3)
N1^v—K—Cs^v	53.70 (9)	K^xvi—N3—Cs^xvi	109.64 (11)
N1^vi—K—Cs^v	126.30 (9)	C3—N3—Cs	88.8 (3)
N2^vii—K—Cs^v	42.72 (7)	K^xvi—N3—Cs	93.58 (10)
N2^viii—K—Cs^v	137.28 (7)	Cs^xvi—N3—Cs	124.33 (12)

Symmetry codes: (i) −x+1/2, y+1/2, −z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x, −y+1, −z; (vi) x, y, z+1; (vii) −x, −y, −z; (viii) x, y+1, z+1; (ix) x−1/2, −y+1/2, z+1/2; (x) −x, −y+1, −z+1; (xi) −x+1/2, y−1/2, −z−1/2; (xii) x, y, z−1; (xiii) x−1/2, −y+1/2, z−1/2; (xiv) x, y−1, z; (xv) x, y−1, z−1; (xvi) −x+1/2, y−1/2, −z+1/2.

(I85K) dicesium potassium hexacyanomanganate(III)

Crystal data

Cs2K[Mn(CN)6]	Dx = 2.472 Mg m^−3
Mr = 515.98	Melting point: not measured K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.084 (2) Å	Cell parameters from 14 reflections
b = 8.213 (1) Å	θ = 16.3–20.3°
c = 7.617 (1) Å	µ = 6.41 mm^−1
β = 90.77 (1)°	T = 85 K
V = 693.3 (2) Å^3	Prism, dark red–brown
Z = 2	0.41 × 0.27 × 0.23 mm
F(000) = 464

Data collection

Syntex P21 diffractometer	6386 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 50.2°, θmin = 3.1°
ω–2θ scans	h = −21→23
Absorption correction: gaussian (Xtal3.4; Hall et al., 1994)	k = −17→17
Tmin = 0.192, Tmax = 0.323	l = −16→16
39456 measured reflections	6 standard reflections every 100 reflections
7328 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0369P)^2 + 0.4475P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.079	(Δ/σ)max = 0.001
S = 1.09	Δρmax = 2.95 e Å^−3
7328 reflections	Δρmin = −1.63 e Å^−3
77 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0044 (4)

Special details

Experimental. no special details

Geometry. All e.s.d.'s (except those in the dihedral angles between pairs of 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 (Ų)

	x	y	z	Uiso*/Ueq
Cs	0.251911 (8)	0.423963 (10)	−0.025547 (12)	0.01871 (2)
K	0.0000	0.5000	0.5000	0.01310 (4)
Mn	0.0000	0.0000	0.0000	0.00965 (3)
C1	0.03440 (11)	0.12972 (14)	−0.21405 (16)	0.01479 (15)
N1	0.05668 (14)	0.20427 (16)	−0.33885 (19)	0.0241 (2)
C2	0.04302 (12)	−0.20430 (14)	−0.12643 (16)	0.01511 (15)
N2	0.06954 (15)	−0.32167 (15)	−0.20088 (19)	0.0237 (2)
C3	0.17029 (11)	0.02527 (15)	0.07806 (17)	0.01544 (16)
N3	0.26909 (12)	0.04408 (19)	0.1257 (2)	0.0234 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs	0.02143 (4)	0.01474 (3)	0.01999 (4)	−0.00067 (2)	0.00096 (3)	0.00118 (2)
K	0.01399 (11)	0.01182 (10)	0.01348 (10)	−0.00029 (8)	−0.00024 (8)	0.00033 (8)
Mn	0.00971 (7)	0.00861 (6)	0.01065 (7)	0.00034 (5)	0.00041 (5)	0.00042 (5)
C1	0.0169 (4)	0.0126 (3)	0.0149 (4)	0.0010 (3)	0.0018 (3)	0.0023 (3)
N1	0.0321 (6)	0.0196 (4)	0.0209 (5)	0.0046 (4)	0.0067 (4)	0.0083 (4)
C2	0.0181 (4)	0.0122 (3)	0.0150 (4)	0.0016 (3)	0.0004 (3)	−0.0012 (3)
N2	0.0329 (6)	0.0166 (4)	0.0215 (5)	0.0066 (4)	−0.0024 (4)	−0.0062 (3)
C3	0.0128 (4)	0.0152 (4)	0.0182 (4)	−0.0006 (3)	0.0001 (3)	0.0022 (3)
N3	0.0131 (4)	0.0278 (5)	0.0292 (6)	−0.0013 (4)	−0.0018 (4)	0.0047 (5)

Geometric parameters (Å, º)

Mn—C1	1.989 (1)	K—N1^vii	2.7893 (13)
Mn—C2	1.996 (1)	K—N2^i	2.8077 (13)
Mn—C3	1.982 (1)	K—N2^viii	2.8077 (13)
Mn—C1^i	1.9888 (11)	K—N3^ix	2.7684 (15)
Mn—C2^i	1.9956 (11)	K—N3^v	2.7684 (15)
Mn—C3^i	1.9822 (13)	K—Cs^v	4.4395 (5)
C1—N1	1.160 (2)	K—Cs^ix	4.4395 (5)
C2—N2	1.158 (2)	K—Cs^vi	4.5799 (6)
C3—N3	1.159 (2)	K—Cs^vii	4.5799 (6)
Mn—Cs^i	4.4691 (5)	K—Cs^x	4.9509 (7)
Cs—N1^ii	3.3056 (15)	C1—Cs^xi	3.5392 (13)
Cs—N1	3.6735 (17)	N1—K^xii	2.7893 (13)
Cs—N1^iii	3.7965 (18)	N1—Cs^xi	3.3056 (15)
Cs—N2^iv	3.1877 (14)	N1—Cs^xiii	3.7965 (18)
Cs—N2^ii	3.5269 (17)	C2—Cs^xi	3.6695 (13)
Cs—N3^v	3.2129 (16)	C2—Cs^xiv	3.9019 (12)
Cs—N3	3.3304 (16)	N2—K^xv	2.8077 (13)
Cs—C1^ii	3.5392 (13)	N2—Cs^xiv	3.1877 (14)
Cs—C1	3.6907 (13)	N2—Cs^xi	3.5269 (17)
Cs—C2^ii	3.6695 (13)	C3—Cs^xvi	3.6020 (13)
Cs—C3	3.4903 (13)	N3—K^xvi	2.7684 (15)
Cs—C3^v	3.6020 (13)	N3—Cs^xvi	3.2129 (16)
K—N1^vi	2.7893 (13)
N2^iv—Cs—N3^v	98.18 (4)	Cs^v—K—Cs^vi	72.642 (8)
N2^iv—Cs—N1^ii	79.55 (4)	Cs^ix—K—Cs^vi	107.358 (8)
N3^v—Cs—N1^ii	97.89 (4)	N3^ix—K—Cs^vii	74.58 (4)
N2^iv—Cs—N3	142.36 (4)	N3^v—K—Cs^vii	105.42 (4)
N3^v—Cs—N3	87.95 (2)	N1^vi—K—Cs^vii	126.68 (4)
N1^ii—Cs—N3	136.60 (4)	N1^vii—K—Cs^vii	53.32 (3)
N2^iv—Cs—C3	123.01 (4)	N2^i—K—Cs^vii	43.36 (3)
N3^v—Cs—C3	92.95 (4)	N2^viii—K—Cs^vii	136.64 (3)
N1^ii—Cs—C3	153.31 (3)	Cs^v—K—Cs^vii	107.358 (8)
N3—Cs—C3	19.39 (3)	Cs^ix—K—Cs^vii	72.642 (8)
N2^iv—Cs—N2^ii	119.01 (2)	Cs^vi—K—Cs^vii	180.0
N3^v—Cs—N2^ii	141.63 (3)	N3^ix—K—Cs^x	37.14 (3)
N1^ii—Cs—N2^ii	81.15 (3)	N3^v—K—Cs^x	142.86 (3)
N3—Cs—N2^ii	68.81 (3)	N1^vi—K—Cs^x	83.12 (3)
C3—Cs—N2^ii	75.30 (3)	N1^vii—K—Cs^x	96.88 (3)
N2^iv—Cs—C1^ii	82.97 (4)	N2^i—K—Cs^x	124.77 (4)
N3^v—Cs—C1^ii	116.25 (3)	N2^viii—K—Cs^x	55.23 (4)
N1^ii—Cs—C1^ii	19.12 (3)	Cs^v—K—Cs^x	102.788 (8)
N3—Cs—C1^ii	127.27 (3)	Cs^ix—K—Cs^x	77.212 (8)
C3—Cs—C1^ii	138.77 (3)	Cs^vi—K—Cs^x	73.958 (12)
N2^ii—Cs—C1^ii	63.70 (3)	Cs^vii—K—Cs^x	106.042 (12)
N2^iv—Cs—C3^v	112.80 (3)	N3^ix—K—Cs	142.86 (3)
N3^v—Cs—C3^v	18.47 (3)	N3^v—K—Cs	37.14 (3)
N1^ii—Cs—C3^v	89.33 (3)	N1^vi—K—Cs	96.88 (3)
N3—Cs—C3^v	82.95 (4)	N1^vii—K—Cs	83.12 (3)
C3—Cs—C3^v	93.57 (2)	N2^i—K—Cs	55.23 (4)
N2^ii—Cs—C3^v	124.20 (3)	N2^viii—K—Cs	124.77 (4)
C1^ii—Cs—C3^v	105.46 (3)	Cs^v—K—Cs	77.212 (8)
N2^iv—Cs—C2^ii	106.32 (3)	Cs^ix—K—Cs	102.788 (8)
N3^v—Cs—C2^ii	145.73 (3)	Cs^vi—K—Cs	106.042 (12)
N1^ii—Cs—C2^ii	64.39 (3)	Cs^vii—K—Cs	73.958 (12)
N3—Cs—C2^ii	87.01 (3)	Cs^x—K—Cs	180.0
C3—Cs—C2^ii	93.38 (3)	C1—Mn—C2	90.29 (5)
N2^ii—Cs—C2^ii	18.39 (3)	C2—Mn—C3	90.00 (5)
C1^ii—Cs—C2^ii	46.09 (3)	C3—Mn—C1	89.86 (5)
C3^v—Cs—C2^ii	127.39 (3)	C3—Mn—C3^i	180.00 (8)
N2^iv—Cs—N1	71.64 (3)	C3^i—Mn—C1	90.14 (5)
N3^v—Cs—N1	135.82 (3)	C3—Mn—C1^i	90.14 (5)
N1^ii—Cs—N1	120.93 (2)	C3^i—Mn—C1^i	89.86 (5)
N3—Cs—N1	78.17 (3)	C1—Mn—C1^i	180.00 (9)
C3—Cs—N1	62.22 (3)	C3—Mn—C2^i	90.00 (5)
N2^ii—Cs—N1	70.46 (3)	C3^i—Mn—C2^i	90.00 (5)
C1^ii—Cs—N1	105.26 (3)	C1—Mn—C2^i	89.71 (5)
C3^v—Cs—N1	149.27 (3)	C1^i—Mn—C2^i	90.29 (5)
C2^ii—Cs—N1	75.81 (3)	C3^i—Mn—C2	90.00 (5)
N2^iv—Cs—C1	81.89 (3)	C1^i—Mn—C2	89.71 (5)
N3^v—Cs—C1	120.97 (3)	C2^i—Mn—C2	180.00 (9)
N1^ii—Cs—C1	138.86 (3)	C3—Mn—Cs	48.59 (4)
N3—Cs—C1	63.59 (3)	C3^i—Mn—Cs	131.41 (4)
C3—Cs—C1	45.87 (3)	C1—Mn—Cs	54.56 (4)
N2^ii—Cs—C1	76.37 (3)	C1^i—Mn—Cs	125.44 (4)
C1^ii—Cs—C1	122.222 (18)	C2^i—Mn—Cs	61.28 (4)
C3^v—Cs—C1	131.78 (3)	C2—Mn—Cs	118.72 (4)
C2^ii—Cs—C1	86.49 (3)	C3—Mn—Cs^i	131.41 (4)
N1—Cs—C1	18.13 (3)	C3^i—Mn—Cs^i	48.59 (4)
N2^iv—Cs—N1^iii	153.48 (4)	C1—Mn—Cs^i	125.44 (4)
N3^v—Cs—N1^iii	78.79 (3)	C1^i—Mn—Cs^i	54.56 (4)
N1^ii—Cs—N1^iii	74.85 (4)	C2^i—Mn—Cs^i	118.72 (4)
N3—Cs—N1^iii	64.16 (3)	C2—Mn—Cs^i	61.28 (4)
C3—Cs—N1^iii	83.52 (3)	Cs—Mn—Cs^i	180.000 (3)
N2^ii—Cs—N1^iii	63.84 (3)	N1—C1—Mn	178.7 (1)
C1^ii—Cs—N1^iii	75.14 (3)	N1—C1—Cs^xi	68.98 (9)
C3^v—Cs—N1^iii	60.60 (3)	Mn—C1—Cs^xi	109.92 (4)
C2^ii—Cs—N1^iii	68.55 (3)	N1—C1—Cs	80.10 (10)
N1—Cs—N1^iii	128.35 (2)	Mn—C1—Cs	99.40 (5)
C1—Cs—N1^iii	122.51 (3)	Cs^xi—C1—Cs	95.28 (3)
N3^ix—K—N3^v	180.0	C1—N1—K^xii	140.45 (11)
N3^ix—K—N1^vi	86.43 (5)	C1—N1—Cs^xi	91.89 (9)
N3^v—K—N1^vi	93.57 (5)	K^xii—N1—Cs^xi	127.64 (5)
N3^ix—K—N1^vii	93.57 (5)	C1—N1—Cs	81.78 (10)
N3^v—K—N1^vii	86.43 (5)	K^xii—N1—Cs	89.16 (4)
N1^vi—K—N1^vii	180.0	Cs^xi—N1—Cs	99.79 (4)
N3^ix—K—N2^i	88.13 (5)	C1—N1—Cs^xiii	87.85 (11)
N3^v—K—N2^i	91.87 (5)	K^xii—N1—Cs^xiii	83.26 (4)
N1^vi—K—N2^i	87.74 (4)	Cs^xi—N1—Cs^xiii	105.15 (4)
N1^vii—K—N2^i	92.26 (4)	Cs—N1—Cs^xiii	153.25 (4)
N3^ix—K—N2^viii	91.87 (5)	N2—C2—Mn	178.9 (1)
N3^v—K—N2^viii	88.13 (5)	N2—C2—Cs^xi	73.83 (10)
N1^vi—K—N2^viii	92.26 (4)	Mn—C2—Cs^xi	105.16 (4)
N1^vii—K—N2^viii	87.74 (4)	N2—C2—Cs^xiv	44.88 (9)
N2^i—K—N2^viii	180.0	Mn—C2—Cs^xiv	135.06 (5)
N3^ix—K—Cs^v	131.48 (3)	Cs^xi—C2—Cs^xiv	89.73 (3)
N3^v—K—Cs^v	48.52 (3)	C2—N2—K^xv	139.70 (12)
N1^vi—K—Cs^v	121.87 (4)	C2—N2—Cs^xiv	120.26 (11)
N1^vii—K—Cs^v	58.13 (4)	K^xv—N2—Cs^xiv	99.42 (4)
N2^i—K—Cs^v	127.43 (3)	C2—N2—Cs^xi	87.78 (10)
N2^viii—K—Cs^v	52.57 (3)	K^xv—N2—Cs^xi	88.23 (4)
N3^ix—K—Cs^ix	48.52 (3)	Cs^xiv—N2—Cs^xi	105.35 (5)
N3^v—K—Cs^ix	131.48 (3)	N3—C3—Mn	178.2 (1)
N1^vi—K—Cs^ix	58.13 (4)	N3—C3—Cs	72.49 (9)
N1^vii—K—Cs^ix	121.87 (4)	Mn—C3—Cs	106.21 (4)
N2^i—K—Cs^ix	52.57 (3)	N3—C3—Cs^xvi	61.42 (10)
N2^viii—K—Cs^ix	127.43 (3)	Mn—C3—Cs^xvi	118.33 (5)
Cs^v—K—Cs^ix	180.000 (2)	Cs—C3—Cs^xvi	111.79 (3)
N3^ix—K—Cs^vi	105.42 (4)	C3—N3—K^xvi	138.43 (13)
N3^v—K—Cs^vi	74.58 (4)	C3—N3—Cs^xvi	100.11 (10)
N1^vi—K—Cs^vi	53.32 (4)	K^xvi—N3—Cs^xvi	111.52 (5)
N1^vii—K—Cs^vi	126.68 (3)	C3—N3—Cs	88.12 (10)
N2^i—K—Cs^vi	136.64 (3)	K^xvi—N3—Cs	92.96 (4)
N2^viii—K—Cs^vi	43.36 (3)	Cs^xvi—N3—Cs	127.66 (5)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y+1/2, −z−1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) x, y+1, z; (v) −x+1/2, y+1/2, −z+1/2; (vi) x, y, z+1; (vii) −x, −y+1, −z; (viii) x, y+1, z+1; (ix) x−1/2, −y+1/2, z+1/2; (x) −x, −y+1, −z+1; (xi) −x+1/2, y−1/2, −z−1/2; (xii) x, y, z−1; (xiii) x−1/2, −y+1/2, z−1/2; (xiv) x, y−1, z; (xv) x, y−1, z−1; (xvi) −x+1/2, y−1/2, −z+1/2.

(I10K) dicesium potassium hexacyanomanganate(III)

Crystal data

Cs2K[Mn(CN)6]	Dx = 2.471 Mg m^−3
Mr = 515.98	Melting point: not measured K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.074 (7) Å	Cell parameters from 16 reflections
b = 8.227 (2) Å	θ = 37.4–42.7°
c = 7.6135 (5) Å	µ = 6.41 mm^−1
β = 90.95 (4)°	T = 10 K
V = 693.5 (5) Å^3	Prism, dark red-brown
Z = 2	0.36 × 0.23 × 0.23 mm
F(000) = 464

Data collection

Huber 512 goniometer diffractometer	7143 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.039
None monochromator	θmax = 50.2°, θmin = 3.1°
ω–2θ scans	h = −23→23
Absorption correction: gaussian (PROFIT; Streltsov & Zavodnik, 1989)	k = −17→17
Tmin = 0.192, Tmax = 0.291	l = −16→16
28154 measured reflections	3 standard reflections every 100 reflections
7317 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0341P)^2 + 0.778P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.077	(Δ/σ)max = 0.001
S = 1.22	Δρmax = 2.18 e Å^−3
7317 reflections	Δρmin = −3.75 e Å^−3
77 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0535 (12)

Special details

Experimental. The correction for the absorption by the beryllium shield was performed by PROFIT (Streltsov & Zavodnik, 1989) program.

Geometry. All e.s.d.'s (except those in the dihedral angles between pairs of 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 (Ų)

	x	y	z	Uiso*/Ueq
Cs	0.252711 (6)	0.421945 (8)	−0.026975 (9)	0.00883 (2)
K	0.0000	0.5000	0.5000	0.00896 (5)
Mn	0.0000	0.0000	0.0000	0.00650 (3)
C1	0.03499 (12)	0.12958 (15)	−0.21408 (16)	0.01033 (14)
N1	0.05787 (13)	0.20445 (16)	−0.33885 (17)	0.01469 (17)
C2	0.04456 (12)	−0.20376 (15)	−0.12616 (16)	0.01046 (14)
N2	0.07206 (13)	−0.32080 (15)	−0.20091 (17)	0.01414 (16)
C3	0.17055 (11)	0.02607 (15)	0.08083 (17)	0.01070 (15)
N3	0.26977 (11)	0.04553 (17)	0.12979 (18)	0.01415 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs	0.00929 (4)	0.00759 (3)	0.00964 (3)	−0.00016 (1)	0.00060 (2)	0.00016 (1)
K	0.00900 (11)	0.00869 (10)	0.00918 (10)	−0.00023 (8)	0.00009 (8)	0.00019 (8)
Mn	0.00633 (7)	0.00632 (7)	0.00685 (7)	0.00007 (5)	0.00042 (5)	0.00014 (5)
C1	0.0114 (4)	0.0097 (3)	0.0100 (3)	0.0002 (3)	0.0013 (3)	0.0012 (3)
N1	0.0183 (5)	0.0128 (4)	0.0131 (4)	0.0014 (3)	0.0033 (3)	0.0043 (3)
C2	0.0119 (4)	0.0092 (3)	0.0103 (3)	0.0005 (3)	0.0008 (3)	−0.0007 (3)
N2	0.0182 (5)	0.0110 (3)	0.0133 (4)	0.0028 (3)	−0.0003 (3)	−0.0027 (3)
C3	0.0089 (3)	0.0110 (4)	0.0122 (4)	−0.0004 (3)	−0.0007 (3)	0.0012 (3)
N3	0.0096 (4)	0.0167 (4)	0.0162 (4)	−0.0012 (3)	−0.0011 (3)	0.0012 (3)

Geometric parameters (Å, º)

Cs—N1^i	3.3040 (17)	Mn—C1	1.991 (1)
Cs—N1	3.650 (2)	Mn—C2	1.998 (1)
Cs—N1^ii	3.794 (3)	Mn—C3	1.988 (2)
Cs—N2^iii	3.1855 (17)	Mn—C1^vii	1.9910 (12)
Cs—N2^i	3.4898 (18)	Mn—C2^vii	1.9980 (12)
Cs—N3^iv	3.2039 (14)	Mn—C3^vii	1.9883 (17)
Cs—N3	3.3230 (16)	Mn—Cs^vii	4.4658 (13)
Cs—C1^i	3.5335 (18)	C1—N1	1.164 (2)
Cs—C1	3.6762 (18)	C1—Cs^xi	3.5335 (18)
Cs—C2^i	3.6442 (19)	N1—K^xii	2.7932 (13)
Cs—C3	3.4833 (15)	N1—Cs^xi	3.3040 (17)
Cs—C3^iv	3.5914 (14)	N1—Cs^xiii	3.794 (3)
K—N1^v	2.7932 (13)	C2—N2	1.162 (2)
K—N1^vi	2.7932 (13)	C2—Cs^xi	3.6442 (19)
K—N2^vii	2.8170 (14)	C2—Cs^xiv	3.9126 (17)
K—N2^viii	2.8170 (14)	N2—K^xv	2.8170 (14)
K—N3^ix	2.775 (2)	N2—Cs^xiv	3.1855 (17)
K—N3^iv	2.775 (2)	N2—Cs^xi	3.4898 (18)
K—Cs^ix	4.4241 (13)	C3—N3	1.165 (2)
K—Cs^iv	4.4241 (13)	C3—Cs^xvi	3.5914 (14)
K—Cs^v	4.5694 (19)	N3—K^xvi	2.775 (2)
K—Cs^vi	4.5694 (19)	N3—Cs^xvi	3.2039 (14)
K—Cs^x	4.9713 (19)
N2^iii—Cs—N3^iv	97.09 (4)	Cs^ix—K—Cs^v	72.73 (3)
N2^iii—Cs—N1^i	78.56 (5)	Cs^iv—K—Cs^v	107.27 (3)
N3^iv—Cs—N1^i	97.37 (4)	N3^ix—K—Cs^vi	104.75 (5)
N2^iii—Cs—N3	143.13 (4)	N3^iv—K—Cs^vi	75.25 (5)
N3^iv—Cs—N3	87.80 (2)	N1^v—K—Cs^vi	126.98 (3)
N1^i—Cs—N3	137.22 (4)	N1^vi—K—Cs^vi	53.02 (3)
N2^iii—Cs—C3	123.68 (4)	N2^vii—K—Cs^vi	136.48 (3)
N3^iv—Cs—C3	92.85 (4)	N2^viii—K—Cs^vi	43.52 (3)
N1^i—Cs—C3	154.19 (3)	Cs^ix—K—Cs^vi	107.27 (3)
N3—Cs—C3	19.53 (3)	Cs^iv—K—Cs^vi	72.73 (3)
N2^iii—Cs—N2^i	119.01 (2)	Cs^v—K—Cs^vi	180.000 (2)
N3^iv—Cs—N2^i	142.61 (4)	N3^ix—K—Cs	143.40 (4)
N1^i—Cs—N2^i	81.77 (4)	N3^iv—K—Cs	36.60 (4)
N3—Cs—N2^i	69.58 (3)	N1^v—K—Cs	83.46 (3)
C3—Cs—N2^i	75.81 (4)	N1^vi—K—Cs	96.54 (3)
N2^iii—Cs—C1^i	82.30 (5)	N2^vii—K—Cs	55.65 (4)
N3^iv—Cs—C1^i	115.85 (4)	N2^viii—K—Cs	124.35 (4)
N1^i—Cs—C1^i	19.22 (3)	Cs^ix—K—Cs	102.56 (3)
N3—Cs—C1^i	128.06 (3)	Cs^iv—K—Cs	77.44 (3)
C3—Cs—C1^i	139.66 (3)	Cs^v—K—Cs	74.20 (3)
N2^i—Cs—C1^i	64.14 (4)	Cs^vi—K—Cs	105.80 (3)
N2^iii—Cs—C3^iv	111.83 (4)	N3^ix—K—Cs^x	36.60 (4)
N3^iv—Cs—C3^iv	18.65 (3)	N3^iv—K—Cs^x	143.40 (4)
N1^i—Cs—C3^iv	89.04 (4)	N1^v—K—Cs^x	96.54 (3)
N3—Cs—C3^iv	82.61 (3)	N1^vi—K—Cs^x	83.46 (3)
C3—Cs—C3^iv	93.37 (2)	N2^vii—K—Cs^x	124.35 (4)
N2^i—Cs—C3^iv	124.94 (4)	N2^viii—K—Cs^x	55.65 (4)
C1^i—Cs—C3^iv	105.26 (4)	Cs^ix—K—Cs^x	77.44 (3)
N2^iii—Cs—C2^i	106.11 (4)	Cs^iv—K—Cs^x	102.56 (3)
N3^iv—Cs—C2^i	146.35 (4)	Cs^v—K—Cs^x	105.80 (3)
N1^i—Cs—C2^i	64.76 (4)	Cs^vi—K—Cs^x	74.20 (3)
N3—Cs—C2^i	87.93 (3)	Cs—K—Cs^x	180.000 (2)
C3—Cs—C2^i	94.12 (3)	C1—Mn—C2	90.15 (5)
N2^i—Cs—C2^i	18.58 (3)	C2—Mn—C3	89.91 (6)
C1^i—Cs—C2^i	46.31 (3)	C3—Mn—C1	89.94 (6)
C3^iv—Cs—C2^i	127.89 (4)	C3—Mn—C3^vii	180.00 (8)
N2^iii—Cs—N1	72.24 (4)	C3^vii—Mn—C1	90.06 (6)
N3^iv—Cs—N1	135.66 (4)	C3—Mn—C1^vii	90.06 (6)
N1^i—Cs—N1	121.01 (3)	C3^vii—Mn—C1^vii	89.94 (6)
N3—Cs—N1	78.83 (3)	C1—Mn—C1^vii	180.00 (6)
C3—Cs—N1	62.68 (3)	C3^vii—Mn—C2	90.09 (6)
N2^i—Cs—N1	70.24 (5)	C1^vii—Mn—C2	89.85 (5)
C1^i—Cs—N1	105.40 (4)	C3—Mn—C2^vii	90.09 (6)
C3^iv—Cs—N1	149.33 (3)	C3^vii—Mn—C2^vii	89.91 (6)
C2^i—Cs—N1	75.77 (4)	C1—Mn—C2^vii	89.85 (5)
N2^iii—Cs—C1	82.55 (5)	C1^vii—Mn—C2^vii	90.15 (5)
N3^iv—Cs—C1	120.84 (4)	C2—Mn—C2^vii	180.00 (7)
N1^i—Cs—C1	139.12 (3)	C3—Mn—Cs	48.52 (4)
N3—Cs—C1	64.05 (4)	C3^vii—Mn—Cs	131.48 (4)
C3—Cs—C1	46.16 (3)	C1—Mn—Cs	54.24 (4)
N2^i—Cs—C1	76.30 (5)	C1^vii—Mn—Cs	125.76 (4)
C1^i—Cs—C1	122.57 (2)	C2—Mn—Cs	118.04 (5)
C3^iv—Cs—C1	131.76 (3)	C2^vii—Mn—Cs	61.96 (5)
C2^i—Cs—C1	86.64 (4)	C3—Mn—Cs^vii	131.48 (4)
N1—Cs—C1	18.27 (3)	C3^vii—Mn—Cs^vii	48.52 (4)
N2^iii—Cs—N1^ii	152.67 (3)	C1—Mn—Cs^vii	125.76 (4)
N3^iv—Cs—N1^ii	79.24 (4)	C1^vii—Mn—Cs^vii	54.24 (4)
N1^i—Cs—N1^ii	75.13 (5)	C2—Mn—Cs^vii	61.96 (5)
N3—Cs—N1^ii	64.15 (3)	C2^vii—Mn—Cs^vii	118.04 (5)
C3—Cs—N1^ii	83.64 (4)	Cs—Mn—Cs^vii	180.000 (1)
N2^i—Cs—N1^ii	64.32 (4)	N1—C1—Mn	178.6 (1)
C1^i—Cs—N1^ii	75.31 (5)	N1—C1—Cs^xi	69.18 (9)
C3^iv—Cs—N1^ii	60.85 (4)	Mn—C1—Cs^xi	109.77 (5)
C2^i—Cs—N1^ii	68.91 (4)	N1—C1—Cs	79.61 (10)
N1—Cs—N1^ii	128.64 (3)	Mn—C1—Cs	99.69 (5)
C1—Cs—N1^ii	122.78 (4)	Cs^xi—C1—Cs	95.41 (5)
N3^ix—K—N3^iv	180.0	C1—N1—K^xii	140.17 (11)
N3^ix—K—N1^v	93.93 (5)	C1—N1—Cs^xi	91.60 (10)
N3^iv—K—N1^v	86.07 (5)	K^xii—N1—Cs^xi	128.22 (4)
N3^ix—K—N1^vi	86.07 (5)	C1—N1—Cs	82.12 (10)
N3^iv—K—N1^vi	93.93 (5)	K^xii—N1—Cs	89.30 (4)
N1^v—K—N1^vi	180.0	Cs^xi—N1—Cs	100.05 (5)
N3^ix—K—N2^vii	88.14 (5)	C1—N1—Cs^xiii	87.62 (10)
N3^iv—K—N2^vii	91.86 (5)	K^xii—N1—Cs^xiii	82.90 (4)
N1^v—K—N2^vii	92.33 (4)	Cs^xi—N1—Cs^xiii	104.87 (5)
N1^vi—K—N2^vii	87.67 (4)	Cs—N1—Cs^xiii	153.27 (4)
N3^ix—K—N2^viii	91.86 (5)	N2—C2—Mn	178.8 (1)
N3^iv—K—N2^viii	88.14 (5)	N2—C2—Cs^xi	73.18 (9)
N1^v—K—N2^viii	87.67 (4)	Mn—C2—Cs^xi	105.69 (5)
N1^vi—K—N2^viii	92.33 (4)	N2—C2—Cs^xiv	44.26 (9)
N2^vii—K—N2^viii	180.0	Mn—C2—Cs^xiv	135.80 (5)
N3^ix—K—Cs^ix	48.62 (3)	Cs^xi—C2—Cs^xiv	89.72 (4)
N3^iv—K—Cs^ix	131.38 (3)	C2—N2—K^xv	139.18 (11)
N1^v—K—Cs^ix	121.69 (4)	C2—N2—Cs^xiv	121.00 (10)
N1^vi—K—Cs^ix	58.31 (4)	K^xv—N2—Cs^xiv	98.97 (4)
N2^vii—K—Cs^ix	52.05 (3)	C2—N2—Cs^xi	88.24 (10)
N2^viii—K—Cs^ix	127.95 (3)	K^xv—N2—Cs^xi	88.42 (4)
N3^ix—K—Cs^iv	131.38 (3)	Cs^xiv—N2—Cs^xi	105.99 (5)
N3^iv—K—Cs^iv	48.62 (3)	N3—C3—Mn	178.2 (1)
N1^v—K—Cs^iv	58.31 (4)	N3—C3—Cs	72.44 (9)
N1^vi—K—Cs^iv	121.69 (4)	Mn—C3—Cs	106.17 (5)
N2^vii—K—Cs^iv	127.95 (3)	N3—C3—Cs^xvi	61.52 (9)
N2^viii—K—Cs^iv	52.05 (3)	Mn—C3—Cs^xvi	118.40 (6)
Cs^ix—K—Cs^iv	180.0	Cs—C3—Cs^xvi	112.78 (4)
N3^ix—K—Cs^v	75.25 (5)	C3—N3—K^xvi	137.26 (12)
N3^iv—K—Cs^v	104.75 (5)	C3—N3—Cs^xvi	99.83 (10)
N1^v—K—Cs^v	53.02 (3)	K^xvi—N3—Cs^xvi	112.30 (5)
N1^vi—K—Cs^v	126.98 (3)	C3—N3—Cs	88.02 (10)
N2^vii—K—Cs^v	43.52 (3)	K^xvi—N3—Cs	92.58 (4)
N2^viii—K—Cs^v	136.48 (3)	Cs^xvi—N3—Cs	129.04 (5)

Symmetry codes: (i) −x+1/2, y+1/2, −z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y+1, z; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x, −y+1, −z; (vi) x, y, z+1; (vii) −x, −y, −z; (viii) x, y+1, z+1; (ix) x−1/2, −y+1/2, z+1/2; (x) −x, −y+1, −z+1; (xi) −x+1/2, y−1/2, −z−1/2; (xii) x, y, z−1; (xiii) x−1/2, −y+1/2, z−1/2; (xiv) x, y−1, z; (xv) x, y−1, z−1; (xvi) −x+1/2, y−1/2, −z+1/2.