Tetra­potassium hepta­cyanido­molybdate(III) dihydrate

Nakabayashi, K.; Tomono, K.; Tsunobuchi, Y.; Kosaka, W.; Ohkoshi, S.

doi:10.1107/S1600536809039336

inorganic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages i79-i80

https://doi.org/10.1107/S1600536809039336

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Tetrapotassium heptacyanidomolybdate(III) dihydrate

Koji Nakabayashi,^a Keisuke Tomono,^a Yoshihide Tsunobuchi,^a Wataru Kosaka ^a and Shin-ichi Ohkoshi ^a ^*

^aDepartment of Chemistry, School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-Ku, Tokyo 113-0033, Japan
^*Correspondence e-mail: ohkoshi@chem.s.u-tokyo.ac.jp

(Received 8 July 2009; accepted 28 September 2009; online 17 October 2009)

The asymmetric unit of the title compound, K^I₄[Mo^III(CN)₇]·2H₂O, consists of one [Mo(CN)₇]⁴⁻ anion, four K⁺ cations, and two water molecules. The [Mo^III(CN)₇]⁴⁻ anion has a seven-coordinated capped-trigonal-prismatic coordination geometry. The site-occupancy factors of the disordered water molecules were set at 0.90, 0.60 and 0.50. The H-atom positions could not be determined for two of the water molecules. The H atoms of the water with a site-occupancy factor of 0.90 were refined using O—H and H⋯H distance restraints.

Related literature

For the synthesis and spectroscopic information for the title compound, see: Young (1932 ); Rossman et al. (1973 ). For octacyanidometalate-based materials with photomagnetic and magnetic properties, see: Arimoto et al. (2003 ); Catala et al. (2005 ); Ohkoshi et al. (2007 , 2008 ). For the related heptacyanido molybdate(III) crystal structure with D_5h and C_2v symmetry, see: Hursthouse et al. (1980 )); Larionova et al. (2004 ); For a heptacyanido molybdate(II) crystal structure with C_s symmetry, see: Drew et al. (1977 ).

Experimental

Crystal data

K₄[Mo(CN)₇]·2H₂O
M_r = 468.29
Triclinic, $[P \overline 1]$
a = 8.8813 (5) Å
b = 9.2896 (4) Å
c = 9.7221 (4) Å
α = 86.6480 (13)°
β = 82.2150 (19)°
γ = 71.2570 (17)°
V = 752.48 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.99 mm⁻¹
T = 90 K
0.10 × 0.05 × 0.02 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1999 ) T_min = 0.826, T_max = 0.961
7367 measured reflections
3421 independent reflections
2893 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.153
S = 1.25
3421 reflections
210 parameters
3 restraints
H-atom parameters not defined
Δρ_max = 2.85 e Å⁻³
Δρ_min = −1.08 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2007); software used to prepare material for publication: ORTEP-3 (Farrugia, 1997 ) and PyMOLWin (DeLano, 2007 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039336/si2189sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039336/si2189Isup2.hkl

checkCIF report

Comment top

In the field of molecule-based magnets, cyano-bridged metal assemblies have been much studied to demonstrate novel functionalities. Octacyanometalate-based materials show interesting functionalities such as photomagnetism (Arimoto et al., 2003; Catala et al., 2005; Ohkoshi et al., 2008) and chemically sensitive magnetism (Ohkoshi et al., 2007). As a versatile class of building blocks, a heptacyanomolybdate ion [Mo^III(CN)₇]^4- is also attractive because this metal complex can adopt various spatial configurations, depending on the chemical environment, pentagonal bipyramid (D_{5 h}) and capped trigonal prism (C_2v) (Rossman et al., 1973; Larionova et al., 2004). Although the coordination geometry of pentagonal bipyramid (D_{5 h}) has been observed with the mixed salt Na^IK^I ₃[Mo(CN)₇]2H₂O, that of capped trigonal prism (C_{2 v}) has not been reported (Hursthouse et al., 1980, Drew et al., 1977). In this paper, we report the crystal structure of K^I₄[Mo^III(CN)₇]2H₂O with capped trigonal prism (C_2v) symmetry, which has the asymmetric unit of one [Mo^III(CN)₇]^4- anion, four K⁺ cations, and two water molecules distributed over three sites with site occupation factors (s.o.f's) of 0.90, 0.60 and 0.50. (Fig. 1). The synthesis and the spectral information of the title compound as been reported by Young (1932) and Rossman et al., (1973).

Related literature top

For the synthesis and spectroscopic information for the title compound, see: Young (1932); Rossman et al. (1973). For octacyanometalate-based materials with photomagnetic and magnetic properties, see: Arimoto et al. (2003); Catala et al. (2005); Ohkoshi et al. (2007, 2008). For the related heptacyano molybdate(III) crystal structure with D_5h and C_2v symmetry, see: Hursthouse et al. (1980)); Larionova et al. (2004); For a heptacyano molybdate(II) crystal structure with C_s symmetry, see: Drew et al. (1977).

Experimental top

The title compound was prepared by reacting (NH₄)₂[MoCl₅(H₂O)] (1.81 g) with KCN (4 g) in H₂O (23 ml) at room temperature. The prepared compound was a green plate-type crystal. Elemental analyses: calcd for K^I₄[Mo^III(CN)₇]2.75H₂O, Calculated: Mo, 19.82%; C, 17.37%; H, 1.15%; N, 20.26%. Found: Mo, 19.44%; C, 17.65%; H, 1.13%; N, 20.01%. In the Infrared (IR) spectra, cyano stretching peaks were observed at 2114 and 2069 cm^-1.

Structure description top

Mo1 K2 4.0798 (8) . ? Mo1 K3 4.1049 (8) . ?

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2007); software used to prepare material for publication: ORTEP-3 (Farrugia, 1997) and PyMOLWin (DeLano, 2007).

Figures top

Fig. 1. Thermal ellipsoid plots (50% probability level) of independent atoms of K^I₄[Mo^III(CN)₇]2H₂O. Positions of hydrogen atoms of the disordered water molecules could not be determined.

Tetrapotassium heptacyanidomolybdate(III) dihydrate top

Crystal data top

K₄[Mo(CN)₇]·2H₂O	Z = 2
M_r = 468.29	F(000) = 454
Triclinic, P1	D_x = 2.067 Mg m⁻³
a = 8.8813 (5) Å	Mo Kα radiation, λ = 0.71075 Å
b = 9.2896 (4) Å	Cell parameters from 6568 reflections
c = 9.7221 (4) Å	θ = 3.0–27.5°
α = 86.6480 (13)°	µ = 1.99 mm⁻¹
β = 82.2150 (19)°	T = 90 K
γ = 71.2570 (17)°	Platelet, green
V = 752.48 (6) Å³	0.10 × 0.05 × 0.02 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	3421 independent reflections
Radiation source: fine-focus sealed tube	2893 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1999)	h = −11→11
T_min = 0.826, T_max = 0.961	k = −12→11
7367 measured reflections	l = −12→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	H-atom parameters not defined
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.0908P)²] where P = (F_o² + 2F_c²)/3
S = 1.25	(Δ/σ)_max < 0.001
3421 reflections	Δρ_max = 2.85 e Å⁻³
210 parameters	Δρ_min = −1.08 e Å⁻³
3 restraints

Crystal data top

K₄[Mo(CN)₇]·2H₂O	γ = 71.2570 (17)°
M_r = 468.29	V = 752.48 (6) Å³
Triclinic, P1	Z = 2
a = 8.8813 (5) Å	Mo Kα radiation
b = 9.2896 (4) Å	µ = 1.99 mm⁻¹
c = 9.7221 (4) Å	T = 90 K
α = 86.6480 (13)°	0.10 × 0.05 × 0.02 mm
β = 82.2150 (19)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3421 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1999)	2893 reflections with I > 2σ(I)
T_min = 0.826, T_max = 0.961	R_int = 0.025
7367 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	3 restraints
wR(F²) = 0.153	H-atom parameters not defined
S = 1.25	Δρ_max = 2.85 e Å⁻³
3421 reflections	Δρ_min = −1.08 e Å⁻³
210 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. Some weak peaks appeared around all O atoms (O1, O2, and O3). Although we could assign the H atoms of O1 with restraints of DFIX (O—H 0.85 0.02 Å and H···H distances about 1.38 0.02 Å), the H atoms of O2 and O3 could not be placed using restraints of DFIX.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mo1	−0.28013 (4)	0.18814 (3)	0.22632 (3)	0.00989 (16)
K4	0.28925 (10)	0.01355 (9)	0.17415 (9)	0.0124 (2)
K1	0.27995 (11)	−0.37242 (10)	0.36699 (9)	0.0146 (2)
K2	−0.28226 (10)	0.58985 (9)	0.03172 (9)	0.0129 (2)
K3	−0.27856 (10)	−0.21632 (9)	0.42126 (9)	0.0133 (2)
N3	−0.3585 (4)	−0.1085 (4)	0.1198 (4)	0.0150 (7)
N4	−0.3673 (5)	0.3229 (4)	−0.0868 (4)	0.0182 (8)
N1	−0.3641 (5)	0.0960 (4)	0.5568 (4)	0.0157 (7)
N2	0.0322 (5)	−0.0987 (5)	0.2950 (5)	0.0298 (10)
N5	0.0203 (5)	0.3068 (5)	0.0908 (5)	0.0336 (11)
C6	−0.3280 (5)	0.4105 (4)	0.3111 (4)	0.0144 (8)
C4	−0.3348 (5)	0.2756 (4)	0.0224 (4)	0.0127 (7)
C5	−0.0799 (5)	0.2568 (5)	0.1380 (5)	0.0219 (9)
C1	−0.3329 (5)	0.1282 (4)	0.4402 (4)	0.0125 (7)
C3	−0.3286 (5)	−0.0076 (4)	0.1562 (4)	0.0136 (8)
C2	−0.0739 (5)	0.0069 (5)	0.2682 (5)	0.0206 (9)
N6	−0.3562 (5)	0.5301 (4)	0.3555 (4)	0.0174 (8)
C7	−0.5434 (6)	0.2691 (4)	0.2568 (4)	0.0166 (8)
N7	−0.6817 (5)	0.3103 (4)	0.2748 (4)	0.0209 (8)
O1	−0.0067 (7)	−0.3954 (6)	0.2344 (7)	0.0609 (15)	0.90
O2	−0.0141 (11)	−0.2434 (11)	0.5544 (12)	0.075 (3)	0.60
O3	−0.0025 (13)	−0.4462 (11)	0.4867 (14)	0.070 (3)	0.50
H1	0.019 (9)	−0.488 (3)	0.199 (6)	0.05 (2)*	0.90
H2	0.007 (9)	−0.343 (6)	0.157 (4)	0.05 (2)*	0.90

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mo1	0.0125 (2)	0.0083 (2)	0.0092 (2)	−0.00373 (15)	−0.00109 (14)	−0.00049 (14)
K4	0.0150 (5)	0.0119 (5)	0.0117 (5)	−0.0060 (4)	−0.0028 (4)	0.0013 (4)
K1	0.0201 (5)	0.0125 (4)	0.0116 (5)	−0.0058 (4)	−0.0027 (4)	0.0011 (3)
K2	0.0167 (5)	0.0075 (4)	0.0163 (5)	−0.0065 (4)	−0.0022 (4)	0.0014 (4)
K3	0.0172 (5)	0.0080 (4)	0.0156 (5)	−0.0044 (4)	−0.0034 (4)	−0.0020 (4)
N3	0.0166 (18)	0.0182 (17)	0.0096 (16)	−0.0053 (14)	−0.0019 (13)	0.0032 (13)
N4	0.0192 (19)	0.0188 (18)	0.0187 (19)	−0.0099 (15)	0.0020 (15)	−0.0051 (14)
N1	0.0215 (19)	0.0164 (17)	0.0104 (17)	−0.0066 (14)	−0.0051 (14)	0.0010 (13)
N2	0.020 (2)	0.030 (2)	0.037 (3)	−0.0057 (17)	−0.0057 (18)	0.006 (2)
N5	0.018 (2)	0.036 (3)	0.045 (3)	−0.0082 (19)	−0.004 (2)	0.012 (2)
C6	0.018 (2)	0.0144 (18)	0.0123 (19)	−0.0064 (15)	−0.0022 (15)	−0.0001 (14)
C4	0.019 (2)	0.0074 (16)	0.0137 (19)	−0.0076 (14)	−0.0029 (15)	0.0011 (14)
C5	0.016 (2)	0.016 (2)	0.033 (3)	−0.0037 (16)	−0.0025 (18)	0.0030 (17)
C1	0.0159 (19)	0.0104 (17)	0.0136 (19)	−0.0065 (14)	−0.0026 (15)	−0.0040 (14)
C3	0.0150 (19)	0.0171 (19)	0.0077 (17)	−0.0042 (15)	−0.0020 (14)	0.0036 (14)
C2	0.018 (2)	0.023 (2)	0.023 (2)	−0.0085 (17)	−0.0036 (17)	0.0039 (17)
N6	0.024 (2)	0.0174 (18)	0.0123 (18)	−0.0094 (15)	−0.0003 (14)	0.0027 (13)
C7	0.027 (2)	0.0129 (18)	0.0099 (18)	−0.0064 (16)	−0.0014 (16)	−0.0054 (14)
N7	0.019 (2)	0.0197 (19)	0.026 (2)	−0.0070 (15)	−0.0041 (16)	−0.0097 (16)
O1	0.056 (4)	0.035 (3)	0.090 (4)	−0.013 (3)	−0.004 (3)	−0.006 (3)
O2	0.058 (6)	0.070 (6)	0.088 (7)	−0.008 (5)	−0.014 (5)	0.015 (5)
O3	0.052 (6)	0.054 (6)	0.105 (9)	−0.024 (6)	−0.009 (6)	0.022 (6)

Geometric parameters (Å, º) top

Mo1—C2	2.120 (4)	K2—N4^vii	2.934 (4)
Mo1—C5	2.135 (4)	K2—N7^vii	3.096 (4)
Mo1—C1	2.150 (4)	K2—C4	3.109 (4)
Mo1—C4	2.156 (4)	K2—N4	3.134 (4)
Mo1—C6	2.160 (4)	K2—C6	3.150 (4)
Mo1—C3	2.164 (4)	K2—N6	3.181 (4)
Mo1—C7	2.198 (5)	K2—N5	3.188 (4)
K4—N1ⁱ	2.836 (4)	K2—C5	3.229 (4)
K4—N2	2.888 (5)	K2—C4^vii	3.329 (4)
K4—N3ⁱⁱ	2.948 (4)	K2—C7^vii	3.380 (4)
K4—N3ⁱⁱⁱ	2.983 (4)	K3—O2	2.767 (10)
K4—N7ⁱⁱ	3.076 (4)	K3—N6^viii	2.788 (4)
K4—N4ⁱⁱⁱ	3.119 (4)	K3—O3	2.806 (11)
K4—N5	3.141 (4)	K3—O1	2.912 (6)
K4—C3ⁱⁱⁱ	3.185 (4)	K3—N1^ix	2.989 (4)
K4—C2	3.250 (4)	K3—N7^ix	3.039 (4)
K4—C4ⁱⁱⁱ	3.274 (4)	K3—N1	3.081 (4)
K4—C3ⁱⁱ	3.317 (4)	K3—C1	3.093 (4)
K4—C7ⁱⁱ	3.362 (4)	K3—C3	3.125 (4)
K1—N4ⁱⁱⁱ	2.783 (4)	K3—N3	3.140 (4)
K1—O3	2.888 (10)	K3—C2	3.339 (4)
K1—N2	2.900 (4)	K3—N2	3.344 (5)
K1—O2	2.921 (10)	N3—C3	1.140 (6)
K1—N7^iv	3.031 (4)	N4—C4	1.161 (6)
K1—N6ⁱ	3.046 (4)	N1—C1	1.174 (5)
K1—N1ⁱ	3.051 (4)	N2—C2	1.167 (6)
K1—N6^iv	3.051 (4)	N5—C5	1.161 (6)
K1—O1	3.075 (6)	C6—N6	1.154 (5)
K1—C6ⁱ	3.200 (4)	C7—N7	1.154 (6)
K1—C1ⁱ	3.210 (4)	O1—K2^viii	3.383 (6)
K1—C7^iv	3.362 (4)	O1—H1	0.89 (2)
K2—N3^v	2.819 (4)	O1—H2	0.89 (2)
K2—N5^vi	2.882 (5)	O3—O3^x	1.005 (18)

C2—Mo1—C5	74.20 (16)	C5—K2—C4^vii	129.62 (10)
C2—Mo1—C1	75.73 (16)	N3^v—K2—C7^vii	88.06 (10)
C5—Mo1—C1	126.45 (17)	N5^vi—K2—C7^vii	86.38 (12)
C2—Mo1—C4	125.11 (16)	N4^vii—K2—C7^vii	68.44 (11)
C5—Mo1—C4	75.08 (17)	N7^vii—K2—C7^vii	19.92 (11)
C1—Mo1—C4	155.91 (15)	C4—K2—C7^vii	95.04 (10)
C2—Mo1—C6	120.52 (17)	N4—K2—C7^vii	74.03 (10)
C5—Mo1—C6	75.93 (16)	C6—K2—C7^vii	142.50 (11)
C1—Mo1—C6	82.82 (14)	N6—K2—C7^vii	143.29 (11)
C4—Mo1—C6	93.98 (14)	N5—K2—C7^vii	133.68 (11)
C2—Mo1—C3	77.55 (16)	C5—K2—C7^vii	135.26 (11)
C5—Mo1—C3	122.98 (16)	C4^vii—K2—C7^vii	48.32 (10)
C1—Mo1—C3	91.60 (14)	O2—K3—N6^viii	121.8 (2)
C4—Mo1—C3	82.69 (14)	O2—K3—O3	42.0 (3)
C6—Mo1—C3	158.53 (16)	N6^viii—K3—O3	80.6 (2)
C2—Mo1—C7	144.39 (15)	O2—K3—O1	75.4 (3)
C5—Mo1—C7	141.38 (15)	N6^viii—K3—O1	74.07 (13)
C1—Mo1—C7	77.75 (15)	O3—K3—O1	51.2 (3)
C4—Mo1—C7	78.21 (15)	O2—K3—N1^ix	144.9 (2)
C6—Mo1—C7	78.68 (15)	N6^viii—K3—N1^ix	77.83 (11)
C3—Mo1—C7	79.88 (14)	O3—K3—N1^ix	148.6 (2)
C2—Mo1—K2	125.94 (11)	O1—K3—N1^ix	139.68 (15)
C5—Mo1—K2	51.79 (11)	O2—K3—N7^ix	66.5 (2)
C1—Mo1—K2	132.54 (9)	N6^viii—K3—N7^ix	88.30 (11)
C4—Mo1—K2	48.64 (10)	O3—K3—N7^ix	69.5 (3)
C6—Mo1—K2	49.76 (10)	O1—K3—N7^ix	119.81 (15)
C3—Mo1—K2	131.31 (10)	N1^ix—K3—N7^ix	87.22 (11)
C7—Mo1—K2	89.59 (10)	O2—K3—N1	76.9 (2)
C2—Mo1—K3	54.13 (11)	N6^viii—K3—N1	151.78 (12)
C5—Mo1—K3	128.27 (11)	O3—K3—N1	118.3 (3)
C1—Mo1—K3	47.57 (9)	O1—K3—N1	133.85 (13)
C4—Mo1—K3	131.21 (10)	N1^ix—K3—N1	75.93 (11)
C6—Mo1—K3	130.36 (11)	N7^ix—K3—N1	80.28 (9)
C3—Mo1—K3	48.53 (10)	O2—K3—C1	83.5 (2)
C7—Mo1—K3	90.34 (10)	N6^viii—K3—C1	154.61 (11)
K2—Mo1—K3	179.844 (19)	O3—K3—C1	124.7 (2)
N1ⁱ—K4—N2	74.36 (12)	O1—K3—C1	118.24 (13)
N1ⁱ—K4—N3ⁱⁱ	79.64 (10)	N1^ix—K3—C1	79.58 (10)
N2—K4—N3ⁱⁱ	136.55 (11)	N7^ix—K3—C1	102.07 (10)
N1ⁱ—K4—N3ⁱⁱⁱ	155.68 (12)	N1—K3—C1	21.93 (10)
N2—K4—N3ⁱⁱⁱ	128.12 (12)	O2—K3—C3	118.1 (2)
N3ⁱⁱ—K4—N3ⁱⁱⁱ	76.83 (11)	N6^viii—K3—C3	104.25 (11)
N1ⁱ—K4—N7ⁱⁱ	83.60 (11)	O3—K3—C3	129.1 (3)
N2—K4—N7ⁱⁱ	120.85 (12)	O1—K3—C3	80.92 (15)
N3ⁱⁱ—K4—N7ⁱⁱ	89.44 (11)	N1^ix—K3—C3	78.63 (10)
N3ⁱⁱⁱ—K4—N7ⁱⁱ	90.10 (11)	N7^ix—K3—C3	158.45 (10)
N1ⁱ—K4—N4ⁱⁱⁱ	88.28 (10)	N1—K3—C3	80.57 (10)
N2—K4—N4ⁱⁱⁱ	70.89 (11)	C1—K3—C3	59.65 (10)
N3ⁱⁱ—K4—N4ⁱⁱⁱ	74.16 (11)	O2—K3—N3	132.2 (2)
N3ⁱⁱⁱ—K4—N4ⁱⁱⁱ	91.13 (11)	N6^viii—K3—N3	83.31 (10)
N7ⁱⁱ—K4—N4ⁱⁱⁱ	162.80 (11)	O3—K3—N3	125.4 (3)
N1ⁱ—K4—N5	128.70 (12)	O1—K3—N3	74.17 (15)
N2—K4—N5	86.40 (12)	N1^ix—K3—N3	74.35 (10)
N3ⁱⁱ—K4—N5	136.58 (11)	N7^ix—K3—N3	160.97 (11)
N3ⁱⁱⁱ—K4—N5	68.27 (11)	N1—K3—N3	99.33 (10)
N7ⁱⁱ—K4—N5	66.26 (12)	C1—K3—N3	79.57 (10)
N4ⁱⁱⁱ—K4—N5	129.74 (12)	C3—K3—N3	20.96 (10)
N1ⁱ—K4—C3ⁱⁱⁱ	155.52 (11)	O2—K3—C2	69.3 (2)
N2—K4—C3ⁱⁱⁱ	111.36 (12)	N6^viii—K3—C2	137.97 (11)
N3ⁱⁱ—K4—C3ⁱⁱⁱ	80.82 (10)	O3—K3—C2	93.7 (2)
N3ⁱⁱⁱ—K4—C3ⁱⁱⁱ	20.96 (10)	O1—K3—C2	70.34 (13)
N7ⁱⁱ—K4—C3ⁱⁱⁱ	110.84 (11)	N1^ix—K3—C2	117.51 (11)
N4ⁱⁱⁱ—K4—C3ⁱⁱⁱ	72.25 (10)	N7^ix—K3—C2	128.83 (11)
N5—K4—C3ⁱⁱⁱ	75.78 (11)	N1—K3—C2	65.60 (11)
N1ⁱ—K4—C2	88.58 (11)	C1—K3—C2	47.92 (11)
N2—K4—C2	20.85 (11)	C3—K3—C2	48.92 (11)
N3ⁱⁱ—K4—C2	157.13 (11)	N3—K3—C2	66.16 (10)
N3ⁱⁱⁱ—K4—C2	115.65 (11)	O2—K3—N2	54.2 (2)
N7ⁱⁱ—K4—C2	108.80 (11)	N6^viii—K3—N2	130.22 (11)
N4ⁱⁱⁱ—K4—C2	86.05 (11)	O3—K3—N2	73.6 (2)
N5—K4—C2	65.55 (11)	O1—K3—N2	56.52 (13)
C3ⁱⁱⁱ—K4—C2	104.29 (11)	N1^ix—K3—N2	137.62 (10)
N1ⁱ—K4—C4ⁱⁱⁱ	109.02 (10)	N7^ix—K3—N2	119.73 (11)
N2—K4—C4ⁱⁱⁱ	77.45 (11)	N1—K3—N2	77.35 (10)
N3ⁱⁱ—K4—C4ⁱⁱⁱ	78.98 (10)	C1—K3—N2	63.97 (10)
N3ⁱⁱⁱ—K4—C4ⁱⁱⁱ	72.38 (10)	C3—K3—N2	64.95 (10)
N7ⁱⁱ—K4—C4ⁱⁱⁱ	160.72 (11)	N3—K3—N2	78.27 (10)
N4ⁱⁱⁱ—K4—C4ⁱⁱⁱ	20.75 (10)	C2—K3—N2	20.11 (10)
N5—K4—C4ⁱⁱⁱ	112.42 (12)	C3—N3—K2^viii	154.0 (3)
C3ⁱⁱⁱ—K4—C4ⁱⁱⁱ	52.41 (10)	C3—N3—K4^xi	98.7 (3)
C2—K4—C4ⁱⁱⁱ	86.57 (11)	K2^viii—N3—K4^xi	106.90 (12)
N1ⁱ—K4—C3ⁱⁱ	77.63 (10)	C3—N3—K4ⁱⁱⁱ	89.6 (3)
N2—K4—C3ⁱⁱ	148.30 (11)	K2^viii—N3—K4ⁱⁱⁱ	89.18 (11)
N3ⁱⁱ—K4—C3ⁱⁱ	19.86 (10)	K4^xi—N3—K4ⁱⁱⁱ	103.17 (11)
N3ⁱⁱⁱ—K4—C3ⁱⁱ	78.16 (9)	C3—N3—K3	78.8 (3)
N7ⁱⁱ—K4—C3ⁱⁱ	69.59 (10)	K2^viii—N3—K3	92.09 (10)
N4ⁱⁱⁱ—K4—C3ⁱⁱ	93.89 (10)	K4^xi—N3—K3	99.76 (11)
N5—K4—C3ⁱⁱ	123.26 (11)	K4ⁱⁱⁱ—N3—K3	155.59 (14)
C3ⁱⁱⁱ—K4—C3ⁱⁱ	88.77 (10)	C4—N4—K1ⁱⁱⁱ	151.2 (3)
C2—K4—C3ⁱⁱ	166.20 (10)	C4—N4—K2^vii	99.5 (3)
C4ⁱⁱⁱ—K4—C3ⁱⁱ	98.25 (10)	K1ⁱⁱⁱ—N4—K2^vii	109.07 (13)
N1ⁱ—K4—C7ⁱⁱ	80.29 (10)	C4—N4—K4ⁱⁱⁱ	87.2 (3)
N2—K4—C7ⁱⁱ	136.66 (12)	K1ⁱⁱⁱ—N4—K4ⁱⁱⁱ	84.27 (10)
N3ⁱⁱ—K4—C7ⁱⁱ	69.42 (10)	K2^vii—N4—K4ⁱⁱⁱ	99.88 (11)
N3ⁱⁱⁱ—K4—C7ⁱⁱ	85.77 (10)	C4—N4—K2	78.1 (3)
N7ⁱⁱ—K4—C7ⁱⁱ	20.02 (10)	K1ⁱⁱⁱ—N4—K2	97.92 (11)
N4ⁱⁱⁱ—K4—C7ⁱⁱ	143.19 (10)	K2^vii—N4—K2	104.52 (11)
N5—K4—C7ⁱⁱ	82.72 (12)	K4ⁱⁱⁱ—N4—K2	153.20 (14)
C3ⁱⁱⁱ—K4—C7ⁱⁱ	106.31 (10)	C1—N1—K4ⁱ	154.3 (3)
C2—K4—C7ⁱⁱ	128.06 (11)	C1—N1—K3^ix	99.3 (3)
C4ⁱⁱⁱ—K4—C7ⁱⁱ	144.98 (11)	K4ⁱ—N1—K3^ix	106.16 (12)
C3ⁱⁱ—K4—C7ⁱⁱ	49.57 (10)	C1—N1—K1ⁱ	86.9 (3)
N4ⁱⁱⁱ—K1—O3	126.5 (3)	K4ⁱ—N1—K1ⁱ	84.65 (10)
N4ⁱⁱⁱ—K1—N2	75.70 (12)	K3^ix—N1—K1ⁱ	102.10 (11)
O3—K1—N2	79.8 (2)	C1—N1—K3	79.6 (3)
N4ⁱⁱⁱ—K1—O2	132.7 (2)	K4ⁱ—N1—K3	97.05 (11)
O3—K1—O2	40.3 (3)	K3^ix—N1—K3	104.07 (11)
N2—K1—O2	58.2 (2)	K1ⁱ—N1—K3	152.14 (14)
N4ⁱⁱⁱ—K1—N7^iv	83.94 (11)	C2—N2—K4	97.4 (3)
O3—K1—N7^iv	72.6 (3)	C2—N2—K1	176.0 (4)
N2—K1—N7^iv	124.93 (12)	K4—N2—K1	86.55 (12)
O2—K1—N7^iv	112.8 (2)	C2—N2—K3	79.7 (3)
N4ⁱⁱⁱ—K1—N6ⁱ	151.13 (12)	K4—N2—K3	176.65 (16)
O3—K1—N6ⁱ	73.8 (3)	K1—N2—K3	96.37 (12)
N2—K1—N6ⁱ	132.09 (12)	C5—N5—K2^vi	176.1 (4)
O2—K1—N6ⁱ	76.2 (2)	C5—N5—K4	91.7 (3)
N7^iv—K1—N6ⁱ	83.89 (11)	K2^vi—N5—K4	85.04 (11)
N4ⁱⁱⁱ—K1—N1ⁱ	90.63 (10)	C5—N5—K2	81.6 (3)
O3—K1—N1ⁱ	124.6 (3)	K2^vi—N5—K2	101.74 (12)
N2—K1—N1ⁱ	71.04 (12)	K4—N5—K2	173.03 (16)
O2—K1—N1ⁱ	84.5 (2)	N6—C6—Mo1	178.8 (4)
N7^iv—K1—N1ⁱ	160.62 (11)	N6—C6—K2	81.0 (3)
N6ⁱ—K1—N1ⁱ	92.27 (10)	Mo1—C6—K2	98.68 (14)
N4ⁱⁱⁱ—K1—N6^iv	79.25 (11)	N6—C6—K1ⁱ	71.9 (3)
O3—K1—N6^iv	143.8 (2)	Mo1—C6—K1ⁱ	108.80 (14)
N2—K1—N6^iv	135.46 (11)	K2—C6—K1ⁱ	146.00 (14)
O2—K1—N6^iv	141.7 (2)	N6—C6—K1^xii	62.6 (3)
N7^iv—K1—N6^iv	87.65 (11)	Mo1—C6—K1^xii	116.23 (15)
N6ⁱ—K1—N6^iv	74.18 (11)	K2—C6—K1^xii	90.47 (10)
N1ⁱ—K1—N6^iv	73.05 (10)	K1ⁱ—C6—K1^xii	94.81 (10)
N4ⁱⁱⁱ—K1—O1	77.78 (15)	N4—C4—Mo1	178.7 (4)
O3—K1—O1	48.9 (3)	N4—C4—K2	80.5 (3)
N2—K1—O1	59.89 (13)	Mo1—C4—K2	100.01 (13)
O2—K1—O1	70.8 (3)	N4—C4—K4ⁱⁱⁱ	72.1 (3)
N7^iv—K1—O1	66.03 (12)	Mo1—C4—K4ⁱⁱⁱ	107.93 (13)
N6ⁱ—K1—O1	120.18 (14)	K2—C4—K4ⁱⁱⁱ	144.67 (13)
N1ⁱ—K1—O1	130.92 (12)	N4—C4—K2^vii	60.4 (3)
N6^iv—K1—O1	146.53 (13)	Mo1—C4—K2^vii	118.33 (15)
N4ⁱⁱⁱ—K1—C6ⁱ	155.00 (11)	K2—C4—K2^vii	96.36 (10)
O3—K1—C6ⁱ	78.4 (3)	K4ⁱⁱⁱ—C4—K2^vii	89.15 (10)
N2—K1—C6ⁱ	115.01 (12)	N5—C5—Mo1	174.1 (4)
O2—K1—C6ⁱ	66.0 (2)	N5—C5—K2	77.6 (3)
N7^iv—K1—C6ⁱ	104.87 (11)	Mo1—C5—K2	96.91 (15)
N6ⁱ—K1—C6ⁱ	21.12 (10)	N5—C5—K4	68.2 (3)
N1ⁱ—K1—C6ⁱ	73.26 (10)	Mo1—C5—K4	117.19 (16)
N6^iv—K1—C6ⁱ	77.82 (10)	K2—C5—K4	145.76 (14)
O1—K1—C6ⁱ	127.22 (14)	N1—C1—Mo1	179.0 (3)
N4ⁱⁱⁱ—K1—C1ⁱ	112.02 (11)	N1—C1—K3	78.5 (3)
O3—K1—C1ⁱ	108.7 (3)	Mo1—C1—K3	101.55 (13)
N2—K1—C1ⁱ	78.95 (12)	N1—C1—K1ⁱ	71.7 (3)
O2—K1—C1ⁱ	71.3 (2)	Mo1—C1—K1ⁱ	108.74 (13)
N7^iv—K1—C1ⁱ	154.97 (11)	K3—C1—K1ⁱ	141.57 (14)
N6ⁱ—K1—C1ⁱ	72.96 (10)	N1—C1—K3^ix	60.7 (3)
N1ⁱ—K1—C1ⁱ	21.43 (10)	Mo1—C1—K3^ix	118.36 (15)
N6^iv—K1—C1ⁱ	77.16 (10)	K3—C1—K3^ix	95.18 (10)
O1—K1—C1ⁱ	134.42 (12)	K1ⁱ—C1—K3^ix	90.83 (9)
C6ⁱ—K1—C1ⁱ	52.82 (10)	N3—C3—Mo1	178.1 (4)
N4ⁱⁱⁱ—K1—C7^iv	78.81 (10)	N3—C3—K3	80.3 (3)
O3—K1—C7^iv	90.8 (2)	Mo1—C3—K3	100.21 (13)
N2—K1—C7^iv	139.24 (12)	N3—C3—K4ⁱⁱⁱ	69.5 (3)
O2—K1—C7^iv	129.9 (2)	Mo1—C3—K4ⁱⁱⁱ	110.74 (14)
N7^iv—K1—C7^iv	19.95 (11)	K3—C3—K4ⁱⁱⁱ	143.04 (14)
N6ⁱ—K1—C7^iv	80.85 (10)	N3—C3—K4^xi	61.5 (3)
N1ⁱ—K1—C7^iv	140.67 (11)	Mo1—C3—K4^xi	116.62 (15)
N6^iv—K1—C7^iv	67.80 (10)	K3—C3—K4^xi	92.56 (10)
O1—K1—C7^iv	84.04 (12)	K4ⁱⁱⁱ—C3—K4^xi	91.23 (10)
C6ⁱ—K1—C7^iv	101.40 (10)	N2—C2—Mo1	175.1 (4)
C1ⁱ—K1—C7^iv	140.79 (11)	N2—C2—K4	61.8 (3)
N3^v—K2—N5^vi	74.20 (12)	Mo1—C2—K4	123.11 (17)
N3^v—K2—N4^vii	79.00 (11)	N2—C2—K3	80.2 (3)
N5^vi—K2—N4^vii	143.65 (11)	Mo1—C2—K3	94.90 (14)
N3^v—K2—N7^vii	92.82 (10)	K4—C2—K3	141.94 (14)
N5^vi—K2—N7^vii	69.19 (12)	C6—N6—K3^v	154.2 (3)
N4^vii—K2—N7^vii	88.33 (11)	C6—N6—K1ⁱ	87.0 (3)
N3^v—K2—C4	154.84 (11)	K3^v—N6—K1ⁱ	93.00 (11)
N5^vi—K2—C4	130.86 (12)	C6—N6—K1^xii	97.7 (3)
N4^vii—K2—C4	78.98 (11)	K3^v—N6—K1^xii	107.02 (12)
N7^vii—K2—C4	98.55 (10)	K1ⁱ—N6—K1^xii	105.82 (11)
N3^v—K2—N4	152.82 (11)	C6—N6—K2	78.0 (3)
N5^vi—K2—N4	123.51 (12)	K3^v—N6—K2	91.82 (10)
N4^vii—K2—N4	75.48 (11)	K1ⁱ—N6—K2	154.44 (14)
N7^vii—K2—N4	77.34 (10)	K1^xii—N6—K2	96.69 (11)
C4—K2—N4	21.43 (10)	N7—C7—Mo1	178.9 (4)
N3^v—K2—C6	103.06 (11)	N7—C7—K1^xii	63.6 (2)
N5^vi—K2—C6	131.04 (12)	Mo1—C7—K1^xii	116.63 (15)
N4^vii—K2—C6	78.58 (11)	N7—C7—K4^xi	65.9 (3)
N7^vii—K2—C6	156.93 (10)	Mo1—C7—K4^xi	113.90 (14)
C4—K2—C6	60.55 (10)	K1^xii—C7—K4^xi	129.43 (15)
N4—K2—C6	81.01 (10)	N7—C7—K2^vii	66.0 (3)
N3^v—K2—N6	82.07 (9)	Mo1—C7—K2^vii	115.03 (15)
N5^vi—K2—N6	123.91 (12)	K1^xii—C7—K2^vii	83.05 (10)
N4^vii—K2—N6	74.98 (11)	K4^xi—C7—K2^vii	74.38 (9)
N7^vii—K2—N6	163.17 (11)	N7—C7—K3^ix	62.5 (3)
C4—K2—N6	80.61 (10)	Mo1—C7—K3^ix	116.39 (16)
N4—K2—N6	100.02 (10)	K1^xii—C7—K3^ix	77.65 (9)
C6—K2—N6	21.00 (10)	K4^xi—C7—K3^ix	82.09 (10)
N3^v—K2—N5	127.59 (12)	K2^vii—C7—K3^ix	128.45 (14)
N5^vi—K2—N5	78.26 (12)	C7—N7—K1^xii	96.4 (3)
N4^vii—K2—N5	138.08 (11)	C7—N7—K3^ix	97.8 (3)
N7^vii—K2—N5	117.52 (11)	K1^xii—N7—K3^ix	88.49 (10)
C4—K2—N5	65.63 (11)	C7—N7—K4^xi	94.1 (3)
N4—K2—N5	78.79 (11)	K1^xii—N7—K4^xi	169.07 (15)
C6—K2—N5	65.05 (11)	K3^ix—N7—K4^xi	93.01 (11)
N6—K2—N5	77.64 (11)	C7—N7—K2^vii	94.0 (3)
N3^v—K2—C5	136.31 (12)	K1^xii—N7—K2^vii	93.66 (11)
N5^vi—K2—C5	99.08 (12)	K3^ix—N7—K2^vii	167.66 (15)
N4^vii—K2—C5	117.27 (11)	K4^xi—N7—K2^vii	82.64 (10)
N7^vii—K2—C5	125.79 (11)	K3—O1—K1	102.27 (19)
C4—K2—C5	48.67 (11)	K3—O1—K2^viii	85.71 (15)
N4—K2—C5	66.00 (11)	K1—O1—K2^viii	169.2 (2)
C6—K2—C5	48.91 (11)	K3—O1—H1	133 (5)
N6—K2—C5	65.90 (11)	K1—O1—H1	109 (5)
N5—K2—C5	20.83 (10)	K2^viii—O1—H1	70 (5)
N3^v—K2—C4^vii	79.86 (10)	K3—O1—H2	110 (4)
N5^vi—K2—C4^vii	128.22 (11)	K1—O1—H2	97 (5)
N4^vii—K2—C4^vii	20.13 (10)	K2^viii—O1—H2	73 (5)
N7^vii—K2—C4^vii	68.23 (10)	H1—O1—H2	100 (3)
C4—K2—C4^vii	83.64 (10)	K3—O2—K1	110.1 (4)
N4—K2—C4^vii	72.96 (10)	O3^x—O3—K3	124.8 (14)
C6—K2—C4^vii	97.92 (10)	O3^x—O3—K1	121.3 (14)
N6—K2—C4^vii	95.04 (10)	K3—O3—K1	109.9 (3)
N5—K2—C4^vii	149.11 (11)

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

Experimental details

Crystal data
Chemical formula	K₄[Mo(CN)₇]·2H₂O
M_r	468.29
Crystal system, space group	Triclinic, P1
Temperature (K)	90
a, b, c (Å)	8.8813 (5), 9.2896 (4), 9.7221 (4)
α, β, γ (°)	86.6480 (13), 82.2150 (19), 71.2570 (17)
V (Å³)	752.48 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.99
Crystal size (mm)	0.10 × 0.05 × 0.02

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1999)
T_min, T_max	0.826, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	7367, 3421, 2893
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.153, 1.25
No. of reflections	3421
No. of parameters	210
No. of restraints	3
H-atom treatment	H-atom parameters not defined
Δρ_max, Δρ_min (e Å⁻³)	2.85, −1.08

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PyMOLWin (DeLano, 2007).

Acknowledgements

The present research was supported in part by a Grant-in-Aid for Young Scientists (S) from JSPS, a grant for the Global COE Program, Chemistry Innovation through Cooperation of Science and Engineering, the Photon Frontier Network Program from MEXT, Japan, the Kurata Memorial Hitachi Science and Technology Foundation, and the Inamori Foundation. YT is grateful to JSPS Research Fellowships for Young Scientists. A part of this work was conducted at the Center for Nano Lithography & Analysis at the University of Tokyo, supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.

References

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