Tetra-aqua-tetra-kis-(4,4'-bipyridine dioxide-κO)terbium(III) octa-cyanido-molybdate(V).

In the title compound, [Tb(C(10)H(8)N(2)O(2))(4)(H(2)O)(4)][Mo(CN)(8)], both metal atoms are eight-coordinated. The Tb(III) atom displays a dodecahedral geometry, while the Mo(V) ion exhibits a distorted square-anti-prismatic geometry. The Tb atoms are located on a special position of site symmetry [Formula: see text], whereas the Mo atoms are located on a twofold rotation axis. The cations are linked by O-H⋯O hydrogen bonds.

Related literature

For general background to octa­cyanidometallate-based complexes involving lanthanide ions, see: Chelebaeva et al. (2009 ▶); Ma et al. (2009 ▶); Qian et al. (2010 ▶); Wang et al. (2006 ▶); Zhou et al. (2010 ▶). For the preparation of the title compound, see: Bok et al. (1975 ▶). For related structures, see: Kozieł et al. (2010 ▶); Przychodzeń et al. (2007 ▶).

Experimental

Crystal data

[Tb(C10H8N2O2)4(H2O)4][Mo(CN)8]

M = 1287.72

Tetragonal,

a = 17.9226 (7) Å

c = 7.8877 (6) Å

V = 2533.7 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.71 mm−1

T = 291 K

0.22 × 0.21 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.693, T max = 0.843

21243 measured reflections

2921 independent reflections

2730 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.016

wR(F 2) = 0.043

S = 1.08

2921 reflections

177 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811020022/bt5505sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020022/bt5505Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Tb(C10H8N2O2)4(H2O)4][Mo(CN)8]	Dx = 1.688 Mg m−3
Mr = 1287.72	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 9881 reflections
Hall symbol: -P 4a	θ = 2.3–27.5°
a = 17.9226 (7) Å	µ = 1.71 mm−1
c = 7.8877 (6) Å	T = 291 K
V = 2533.7 (2) Å3	Block, yellow
Z = 2	0.22 × 0.21 × 0.12 mm
F(000) = 1286

Bruker SMART APEX CCD diffractometer	2730 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −23→23
Tmin = 0.693, Tmax = 0.843	k = −23→23
21243 measured reflections	l = −10→10
2921 independent reflections

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)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.043	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0183P)2 + 1.8165P] where P = (Fo2 + 2Fc2)/3
2921 reflections	(Δ/σ)max = 0.001
177 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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.

	x	y	z	Uiso*/Ueq
Tb1	0.7500	0.2500	0.0000	0.01136 (5)
Mo1	0.7500	0.7500	−0.24987 (4)	0.02019 (7)
O1	0.64962 (6)	0.17736 (7)	0.10113 (14)	0.0251 (3)
O2	0.27973 (7)	−0.11246 (7)	−0.50459 (14)	0.0223 (2)
O3	0.70614 (6)	0.31664 (6)	0.24591 (13)	0.0183 (2)
N1	0.60473 (10)	0.81932 (10)	−0.4592 (3)	0.0422 (4)
N2	0.59644 (10)	0.70470 (10)	−0.0373 (3)	0.0393 (4)
N3	0.60104 (8)	0.13848 (8)	0.00837 (16)	0.0201 (3)
N4	0.33441 (7)	−0.07064 (7)	−0.44088 (17)	0.0176 (2)
C1	0.65693 (10)	0.79577 (9)	−0.3922 (3)	0.0300 (4)
C2	0.65123 (10)	0.71973 (9)	−0.1057 (3)	0.0293 (4)
C3	0.62224 (9)	0.07458 (9)	−0.0674 (2)	0.0234 (3)
H3	0.6709	0.0575	−0.0537	0.028*
C4	0.57297 (9)	0.03404 (9)	−0.1648 (2)	0.0215 (3)
H4	0.5888	−0.0098	−0.2166	0.026*
C5	0.49930 (8)	0.05822 (8)	−0.1867 (2)	0.0175 (3)
C6	0.47918 (9)	0.12409 (9)	−0.1031 (2)	0.0248 (3)
H6	0.4306	0.1419	−0.1129	0.030*
C7	0.53013 (10)	0.16301 (10)	−0.0063 (2)	0.0257 (4)
H7	0.5155	0.2064	0.0491	0.031*
C8	0.44383 (8)	0.01450 (8)	−0.28394 (19)	0.0168 (3)
C9	0.45913 (8)	−0.05724 (8)	−0.3460 (2)	0.0182 (3)
H9	0.5070	−0.0768	−0.3356	0.022*
C10	0.40389 (8)	−0.09908 (8)	−0.4224 (2)	0.0189 (3)
H10	0.4144	−0.1469	−0.4613	0.023*
C12	0.37208 (9)	0.04249 (8)	−0.3126 (2)	0.0209 (3)
H12	0.3604	0.0907	−0.2780	0.025*
C13	0.31847 (9)	−0.00028 (9)	−0.3913 (2)	0.0217 (3)
H13	0.2712	0.0193	−0.4103	0.026*
H3WA	0.6727	0.3040	0.3134	0.033*
H3WB	0.7363	0.3368	0.3136	0.033*

	U11	U22	U33	U12	U13	U23
Tb1	0.01183 (5)	0.01183 (5)	0.01043 (7)	0.000	0.000	0.000
Mo1	0.01407 (8)	0.01407 (8)	0.03243 (15)	0.000	0.000	0.000
O1	0.0234 (6)	0.0348 (6)	0.0171 (5)	−0.0157 (5)	−0.0019 (5)	−0.0008 (5)
O2	0.0190 (5)	0.0247 (6)	0.0231 (6)	−0.0067 (4)	−0.0023 (4)	−0.0059 (4)
O3	0.0179 (5)	0.0232 (5)	0.0139 (5)	−0.0007 (4)	0.0019 (4)	−0.0032 (4)
N1	0.0310 (9)	0.0290 (8)	0.0666 (12)	−0.0020 (7)	−0.0123 (9)	0.0126 (8)
N2	0.0297 (8)	0.0313 (8)	0.0569 (11)	0.0000 (7)	0.0099 (8)	0.0101 (8)
N3	0.0188 (6)	0.0246 (7)	0.0170 (6)	−0.0095 (5)	−0.0005 (5)	0.0018 (5)
N4	0.0183 (6)	0.0198 (6)	0.0146 (6)	−0.0043 (5)	−0.0004 (5)	−0.0006 (5)
C1	0.0243 (8)	0.0195 (8)	0.0462 (11)	−0.0031 (6)	−0.0026 (8)	0.0050 (7)
C2	0.0241 (8)	0.0201 (8)	0.0438 (11)	0.0008 (6)	0.0020 (8)	0.0045 (7)
C3	0.0166 (7)	0.0280 (8)	0.0257 (8)	−0.0021 (6)	−0.0004 (6)	0.0010 (7)
C4	0.0189 (7)	0.0217 (7)	0.0239 (8)	−0.0016 (6)	0.0000 (6)	−0.0011 (6)
C5	0.0177 (7)	0.0172 (7)	0.0176 (7)	−0.0041 (5)	0.0004 (6)	0.0026 (6)
C6	0.0186 (7)	0.0210 (8)	0.0349 (9)	−0.0013 (6)	−0.0035 (7)	−0.0042 (7)
C7	0.0230 (8)	0.0215 (8)	0.0328 (9)	−0.0044 (6)	0.0002 (7)	−0.0052 (7)
C8	0.0173 (7)	0.0163 (7)	0.0168 (7)	−0.0037 (5)	0.0011 (5)	0.0019 (5)
C9	0.0162 (7)	0.0188 (7)	0.0198 (7)	−0.0004 (5)	0.0022 (6)	0.0009 (6)
C10	0.0203 (7)	0.0171 (7)	0.0191 (7)	−0.0006 (5)	0.0030 (6)	−0.0018 (6)
C12	0.0222 (7)	0.0166 (7)	0.0241 (8)	0.0009 (6)	−0.0023 (6)	−0.0016 (6)
C13	0.0192 (7)	0.0213 (7)	0.0246 (8)	0.0022 (6)	−0.0034 (6)	−0.0026 (6)

Tb1—O1i	2.3596 (11)	N3—C3	1.346 (2)
Tb1—O1ii	2.3596 (11)	N3—C7	1.350 (2)
Tb1—O1	2.3596 (11)	N4—C13	1.351 (2)
Tb1—O1iii	2.3596 (11)	N4—C10	1.3533 (19)
Tb1—O3i	2.4097 (10)	C3—C4	1.378 (2)
Tb1—O3ii	2.4097 (10)	C3—H3	0.9300
Tb1—O3	2.4097 (10)	C4—C5	1.400 (2)
Tb1—O3iii	2.4097 (10)	C4—H4	0.9300
Mo1—C1iv	2.1715 (18)	C5—C6	1.400 (2)
Mo1—C1	2.1715 (18)	C5—C8	1.480 (2)
Mo1—C1v	2.1715 (18)	C6—C7	1.379 (2)
Mo1—C1vi	2.1715 (18)	C6—H6	0.9300
Mo1—C2iv	2.1731 (18)	C7—H7	0.9300
Mo1—C2	2.1731 (18)	C8—C12	1.399 (2)
Mo1—C2vi	2.1731 (18)	C8—C9	1.403 (2)
Mo1—C2v	2.1731 (18)	C9—C10	1.380 (2)
O1—N3	1.3338 (17)	C9—H9	0.9300
O2—N4	1.3323 (16)	C10—H10	0.9300
O3—H3WA	0.8326	C12—C13	1.377 (2)
O3—H3WB	0.8422	C12—H12	0.9300
N1—C1	1.155 (2)	C13—H13	0.9300
N2—C2	1.152 (2)
O1i—Tb1—O1ii	96.562 (17)	C1iv—Mo1—C2v	143.33 (6)
O1i—Tb1—O1	96.562 (17)	C1—Mo1—C2v	76.77 (7)
O1ii—Tb1—O1	140.48 (5)	C1v—Mo1—C2v	74.88 (7)
O1i—Tb1—O1iii	140.48 (5)	C1vi—Mo1—C2v	140.36 (6)
O1ii—Tb1—O1iii	96.562 (17)	C2iv—Mo1—C2v	116.87 (11)
O1—Tb1—O1iii	96.562 (17)	C2—Mo1—C2v	74.10 (5)
O1i—Tb1—O3i	75.68 (4)	C2vi—Mo1—C2v	74.10 (5)
O1ii—Tb1—O3i	146.10 (4)	N3—O1—Tb1	126.90 (9)
O1—Tb1—O3i	73.39 (4)	Tb1—O3—H3WA	128.0
O1iii—Tb1—O3i	72.73 (4)	Tb1—O3—H3WB	120.9
O1i—Tb1—O3ii	73.39 (4)	H3WA—O3—H3WB	100.0
O1ii—Tb1—O3ii	75.68 (4)	O1—N3—C3	120.24 (14)
O1—Tb1—O3ii	72.73 (4)	O1—N3—C7	119.45 (14)
O1iii—Tb1—O3ii	146.10 (4)	C3—N3—C7	120.30 (14)
O3i—Tb1—O3ii	130.38 (3)	O2—N4—C13	118.60 (13)
O1i—Tb1—O3	146.10 (4)	O2—N4—C10	120.38 (13)
O1ii—Tb1—O3	72.73 (4)	C13—N4—C10	121.00 (13)
O1—Tb1—O3	75.68 (4)	N1—C1—Mo1	175.79 (19)
O1iii—Tb1—O3	73.39 (4)	N2—C2—Mo1	176.07 (18)
O3i—Tb1—O3	130.38 (3)	N3—C3—C4	121.02 (15)
O3ii—Tb1—O3	72.79 (5)	N3—C3—H3	119.5
O1i—Tb1—O3iii	72.73 (4)	C4—C3—H3	119.5
O1ii—Tb1—O3iii	73.39 (4)	C3—C4—C5	120.65 (15)
O1—Tb1—O3iii	146.10 (4)	C3—C4—H4	119.7
O1iii—Tb1—O3iii	75.68 (4)	C5—C4—H4	119.7
O3i—Tb1—O3iii	72.79 (5)	C6—C5—C4	116.49 (14)
O3ii—Tb1—O3iii	130.38 (3)	C6—C5—C8	121.17 (14)
O3—Tb1—O3iii	130.38 (3)	C4—C5—C8	122.23 (14)
C1iv—Mo1—C1	74.50 (5)	C7—C6—C5	121.10 (15)
C1iv—Mo1—C1v	117.74 (11)	C7—C6—H6	119.4
C1—Mo1—C1v	74.50 (5)	C5—C6—H6	119.4
C1iv—Mo1—C1vi	74.50 (5)	N3—C7—C6	120.42 (16)
C1—Mo1—C1vi	117.74 (11)	N3—C7—H7	119.8
C1v—Mo1—C1vi	74.50 (5)	C6—C7—H7	119.8
C1iv—Mo1—C2iv	74.88 (7)	C12—C8—C9	116.87 (14)
C1—Mo1—C2iv	140.36 (6)	C12—C8—C5	120.77 (13)
C1v—Mo1—C2iv	143.33 (6)	C9—C8—C5	122.32 (13)
C1vi—Mo1—C2iv	76.77 (7)	C10—C9—C8	120.66 (14)
C1iv—Mo1—C2	76.77 (7)	C10—C9—H9	119.7
C1—Mo1—C2	74.88 (7)	C8—C9—H9	119.7
C1v—Mo1—C2	140.36 (6)	N4—C10—C9	120.16 (14)
C1vi—Mo1—C2	143.33 (6)	N4—C10—H10	119.9
C2iv—Mo1—C2	74.10 (5)	C9—C10—H10	119.9
C1iv—Mo1—C2vi	140.36 (6)	C13—C12—C8	120.98 (14)
C1—Mo1—C2vi	143.33 (6)	C13—C12—H12	119.5
C1v—Mo1—C2vi	76.77 (7)	C8—C12—H12	119.5
C1vi—Mo1—C2vi	74.88 (7)	N4—C13—C12	120.17 (14)
C2iv—Mo1—C2vi	74.10 (5)	N4—C13—H13	119.9
C2—Mo1—C2vi	116.87 (11)	C12—C13—H13	119.9

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3WA···O2vii	0.83	1.85	2.6702 (15)	169
O3—H3WB···O2viii	0.84	1.92	2.7417 (16)	164
O3—H3WB···N4viii	0.84	2.62	3.4251 (16)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3WA⋯O2i	0.83	1.85	2.6702 (15)	169
O3—H3WB⋯O2ii	0.84	1.92	2.7417 (16)	164

Symmetry codes: (i) ; (ii) .