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

In the title compound, [Tb(C(10)H(8)N(2)O(2))(4)(H(2)O)(4)][W(CN)(8)], both metal atoms are eight-coordinated. The Tb(III) ion displays a dodeca-hedral geometry, while the W(v) ion exhibits a distorted square-anti-prismatic geometry. The Tb atoms are located on a special position of site symmetry -4, whereas the W atoms are located on a twofold rotation axis. The cations are linked by O-H⋯O hydrogen bonds. The title compound is isotypic with the corresponding and previously described Mo compound [Qian & Yuan (2011 ▶). Acta Cryst. E67, m845].

Related literature

For general background to octa­cyano­metallate-based compounds, see: Sieklucka et al. (2011 ▶); Zhou et al. (2010 ▶). For related structures, see: Qian & Yuan (2011 ▶). For the preparation of the title compound, see: Bok et al. (1975 ▶).

Experimental

Crystal data

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

M = 1375.73

Tetragonal,

a = 17.9222 (7) Å

c = 7.8915 (6) Å

V = 2534.8 (2) Å3

Z = 2

Mo Kα radiation

μ = 3.73 mm−1

T = 291 K

0.26 × 0.23 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.444, T max = 0.522

19073 measured reflections

2498 independent reflections

2299 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.014

wR(F 2) = 0.037

S = 1.07

2498 reflections

177 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.64 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/S1600536812005004/bx2386sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005004/bx2386Isup2.hkl

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

[Tb(C10H8N2O2)4(H2O)4][W(CN)8]	Dx = 1.802 Mg m−3
Mr = 1375.73	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 9955 reflections
Hall symbol: -P 4a	θ = 2.3–27.5°
a = 17.9222 (7) Å	µ = 3.73 mm−1
c = 7.8915 (6) Å	T = 291 K
V = 2534.8 (2) Å3	Block, yellow
Z = 2	0.26 × 0.23 × 0.20 mm
F(000) = 1350

Bruker SMART APEX CCD diffractometer	2498 independent reflections
Radiation source: fine-focus sealed tube	2299 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 26.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −22→22
Tmin = 0.444, Tmax = 0.522	k = −22→22
19073 measured reflections	l = −9→9

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)] = 0.014	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.037	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0164P)2 + 1.703P] where P = (Fo2 + 2Fc2)/3
2498 reflections	(Δ/σ)max = 0.001
177 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.64 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
W1	0.7500	0.7500	0.24882 (2)	0.01913 (5)
Tb1	0.2500	0.7500	0.5000	0.01051 (5)
O1	0.29389 (7)	0.81662 (7)	0.25409 (15)	0.0171 (3)
H1B	0.3287	0.8015	0.1848	0.021*
H1A	0.2637	0.8394	0.1839	0.021*
N1	0.68065 (11)	0.89541 (11)	0.0386 (3)	0.0393 (5)
C1	0.70418 (11)	0.84317 (11)	0.1061 (3)	0.0284 (5)
O2	0.35045 (7)	0.67744 (8)	0.39890 (16)	0.0239 (3)
N2	0.59625 (11)	0.79552 (11)	0.4621 (3)	0.0374 (5)
C2	0.65117 (11)	0.78032 (11)	0.3929 (3)	0.0278 (4)
O3	0.72018 (7)	0.38740 (8)	1.00441 (16)	0.0212 (3)
N3	0.39907 (9)	0.63844 (9)	0.49170 (19)	0.0194 (3)
C7	0.46983 (11)	0.66305 (11)	0.5066 (3)	0.0248 (4)
H7	0.4843	0.7066	0.4515	0.030*
C6	0.52093 (11)	0.62425 (11)	0.6029 (3)	0.0234 (4)
H6	0.5695	0.6420	0.6125	0.028*
C5	0.50060 (10)	0.55836 (10)	0.6866 (2)	0.0171 (4)
C4	0.42720 (10)	0.53429 (11)	0.6643 (2)	0.0200 (4)
H4	0.4114	0.4903	0.7157	0.024*
C3	0.37781 (11)	0.57476 (11)	0.5672 (2)	0.0226 (4)
H3	0.3291	0.5578	0.5538	0.027*
C8	0.55622 (10)	0.51442 (10)	0.7837 (2)	0.0158 (4)
C12	0.62818 (10)	0.54238 (10)	0.8120 (2)	0.0194 (4)
H12	0.6399	0.5906	0.7774	0.023*
C11	0.68155 (10)	0.49949 (10)	0.8903 (2)	0.0202 (4)
H11	0.7290	0.5189	0.9089	0.024*
N4	0.66553 (8)	0.42914 (8)	0.94064 (19)	0.0163 (3)
C10	0.59602 (10)	0.40097 (10)	0.9223 (2)	0.0178 (4)
H10	0.5854	0.3532	0.9613	0.021*
C9	0.54087 (10)	0.44284 (10)	0.8461 (2)	0.0171 (4)
H9	0.4930	0.4234	0.8360	0.021*

	U11	U22	U33	U12	U13	U23
W1	0.01293 (6)	0.01293 (6)	0.03153 (10)	0.000	0.000	0.000
Tb1	0.01091 (6)	0.01091 (6)	0.00970 (8)	0.000	0.000	0.000
O1	0.0165 (6)	0.0216 (7)	0.0134 (6)	0.0015 (5)	0.0022 (5)	0.0030 (5)
N1	0.0269 (10)	0.0294 (10)	0.0617 (14)	−0.0036 (8)	−0.0126 (9)	0.0106 (10)
C1	0.0180 (10)	0.0236 (10)	0.0435 (12)	−0.0035 (8)	−0.0054 (9)	0.0016 (10)
O2	0.0219 (7)	0.0334 (8)	0.0165 (6)	0.0156 (6)	−0.0023 (5)	0.0007 (6)
N2	0.0276 (10)	0.0317 (10)	0.0528 (12)	−0.0001 (8)	0.0092 (9)	−0.0084 (9)
C2	0.0233 (10)	0.0178 (9)	0.0422 (12)	−0.0016 (8)	0.0001 (9)	−0.0039 (9)
O3	0.0184 (7)	0.0235 (7)	0.0217 (7)	0.0064 (5)	−0.0021 (5)	0.0064 (5)
N3	0.0183 (8)	0.0235 (8)	0.0163 (8)	0.0101 (7)	−0.0004 (6)	−0.0014 (6)
C7	0.0223 (10)	0.0201 (10)	0.0322 (11)	0.0039 (8)	0.0008 (8)	0.0060 (8)
C6	0.0164 (9)	0.0200 (9)	0.0337 (11)	0.0009 (7)	−0.0031 (8)	0.0037 (8)
C5	0.0190 (9)	0.0165 (9)	0.0159 (8)	0.0048 (7)	0.0009 (7)	−0.0032 (7)
C4	0.0186 (9)	0.0199 (9)	0.0216 (9)	0.0009 (7)	−0.0002 (8)	0.0014 (8)
C3	0.0171 (9)	0.0268 (10)	0.0238 (10)	0.0021 (8)	−0.0004 (8)	−0.0016 (8)
C8	0.0170 (9)	0.0166 (9)	0.0137 (8)	0.0032 (7)	0.0022 (7)	−0.0039 (7)
C12	0.0218 (9)	0.0144 (9)	0.0220 (9)	−0.0014 (7)	−0.0017 (8)	0.0015 (7)
C11	0.0182 (9)	0.0201 (9)	0.0222 (9)	−0.0031 (7)	−0.0024 (8)	0.0019 (8)
N4	0.0167 (7)	0.0188 (8)	0.0133 (7)	0.0048 (6)	−0.0001 (6)	0.0008 (6)
C10	0.0202 (9)	0.0163 (9)	0.0169 (9)	0.0004 (7)	0.0037 (7)	0.0008 (7)
C9	0.0164 (9)	0.0180 (9)	0.0170 (9)	0.0005 (7)	0.0027 (7)	−0.0013 (7)

W1—C2i	2.174 (2)	N3—C3	1.343 (3)
W1—C2ii	2.174 (2)	N3—C7	1.348 (3)
W1—C2iii	2.174 (2)	C7—C6	1.378 (3)
W1—C2	2.174 (2)	C7—H7	0.9300
W1—C1i	2.175 (2)	C6—C5	1.401 (3)
W1—C1ii	2.175 (2)	C6—H6	0.9300
W1—C1	2.175 (2)	C5—C4	1.396 (3)
W1—C1iii	2.175 (2)	C5—C8	1.484 (3)
Tb1—O2iv	2.3598 (13)	C4—C3	1.377 (3)
Tb1—O2v	2.3598 (13)	C4—H4	0.9300
Tb1—O2	2.3598 (13)	C3—H3	0.9300
Tb1—O2vi	2.3598 (13)	C8—C9	1.401 (3)
Tb1—O1vi	2.4104 (12)	C8—C12	1.402 (3)
Tb1—O1iv	2.4104 (12)	C12—C11	1.374 (3)
Tb1—O1	2.4104 (12)	C12—H12	0.9300
Tb1—O1v	2.4104 (12)	C11—N4	1.353 (2)
O1—H1B	0.8724	C11—H11	0.9300
O1—H1A	0.8755	N4—C10	1.352 (2)
N1—C1	1.157 (3)	C10—C9	1.379 (3)
O2—N3	1.336 (2)	C10—H10	0.9300
N2—C2	1.158 (3)	C9—H9	0.9300
O3—N4	1.3312 (19)
C2i—W1—C2ii	74.13 (6)	O2iv—Tb1—O1v	72.77 (5)
C2i—W1—C2iii	116.94 (12)	O2v—Tb1—O1v	75.63 (5)
C2ii—W1—C2iii	74.13 (6)	O2—Tb1—O1v	146.09 (4)
C2i—W1—C2	74.13 (6)	O2vi—Tb1—O1v	73.41 (4)
C2ii—W1—C2	116.94 (12)	O1vi—Tb1—O1v	130.40 (4)
C2iii—W1—C2	74.13 (6)	O1iv—Tb1—O1v	72.76 (6)
C2i—W1—C1i	76.77 (8)	O1—Tb1—O1v	130.40 (4)
C2ii—W1—C1i	143.32 (7)	Tb1—O1—H1B	125.7
C2iii—W1—C1i	140.38 (7)	Tb1—O1—H1A	122.6
C2—W1—C1i	74.90 (8)	H1B—O1—H1A	101.0
C2i—W1—C1ii	74.90 (8)	N1—C1—W1	175.9 (2)
C2ii—W1—C1ii	76.77 (8)	N3—O2—Tb1	126.92 (10)
C2iii—W1—C1ii	143.32 (7)	N2—C2—W1	176.3 (2)
C2—W1—C1ii	140.38 (7)	O2—N3—C3	120.20 (16)
C1i—W1—C1ii	74.45 (6)	O2—N3—C7	119.38 (16)
C2i—W1—C1	143.32 (7)	C3—N3—C7	120.42 (16)
C2ii—W1—C1	140.38 (7)	N3—C7—C6	120.54 (18)
C2iii—W1—C1	74.90 (8)	N3—C7—H7	119.7
C2—W1—C1	76.77 (8)	C6—C7—H7	119.7
C1i—W1—C1	74.45 (6)	C7—C6—C5	120.81 (18)
C1ii—W1—C1	117.63 (12)	C7—C6—H6	119.6
C2i—W1—C1iii	140.38 (7)	C5—C6—H6	119.6
C2ii—W1—C1iii	74.90 (8)	C4—C5—C6	116.52 (17)
C2iii—W1—C1iii	76.77 (8)	C4—C5—C8	122.29 (17)
C2—W1—C1iii	143.32 (7)	C6—C5—C8	121.07 (17)
C1i—W1—C1iii	117.63 (12)	C3—C4—C5	120.87 (18)
C1ii—W1—C1iii	74.45 (6)	C3—C4—H4	119.6
C1—W1—C1iii	74.45 (6)	C5—C4—H4	119.6
O2iv—Tb1—O2v	140.48 (6)	N3—C3—C4	120.81 (18)
O2iv—Tb1—O2	96.56 (2)	N3—C3—H3	119.6
O2v—Tb1—O2	96.56 (2)	C4—C3—H3	119.6
O2iv—Tb1—O2vi	96.56 (2)	C9—C8—C12	116.87 (17)
O2v—Tb1—O2vi	96.56 (2)	C9—C8—C5	122.38 (17)
O2—Tb1—O2vi	140.48 (6)	C12—C8—C5	120.72 (17)
O2iv—Tb1—O1vi	73.41 (4)	C11—C12—C8	120.82 (17)
O2v—Tb1—O1vi	146.09 (4)	C11—C12—H12	119.6
O2—Tb1—O1vi	72.77 (5)	C8—C12—H12	119.6
O2vi—Tb1—O1vi	75.63 (5)	N4—C11—C12	120.38 (17)
O2iv—Tb1—O1iv	75.63 (5)	N4—C11—H11	119.8
O2v—Tb1—O1iv	72.77 (5)	C12—C11—H11	119.8
O2—Tb1—O1iv	73.41 (4)	O3—N4—C10	120.56 (15)
O2vi—Tb1—O1iv	146.09 (4)	O3—N4—C11	118.59 (15)
O1vi—Tb1—O1iv	130.40 (4)	C10—N4—C11	120.83 (16)
O2iv—Tb1—O1	146.09 (4)	N4—C10—C9	120.25 (17)
O2v—Tb1—O1	73.41 (4)	N4—C10—H10	119.9
O2—Tb1—O1	75.63 (5)	C9—C10—H10	119.9
O2vi—Tb1—O1	72.77 (5)	C10—C9—C8	120.71 (17)
O1vi—Tb1—O1	72.76 (6)	C10—C9—H9	119.6
O1iv—Tb1—O1	130.40 (4)	C8—C9—H9	119.6

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O3vii	0.87	1.81	2.6695 (18)	167
O1—H1A···O3viii	0.88	1.89	2.7415 (18)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O3i	0.87	1.81	2.6695 (18)	167
O1—H1A⋯O3ii	0.88	1.89	2.7415 (18)	165

Symmetry codes: (i) ; (ii) .