Double complexes [Co(NH3)5(H2O)]2[Zr3F18]·6H2O and [Co(NH3)6]2[Zr3F18]·6H2O

Gubanov, A.I.; Kuratieva, N.V.

doi:10.1107/S010827010704108X

Double complexes [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O and [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O

The structures of orthorhombic bis[pentaammineaquacobalt(III)] tetra-μ₂-fluorido-tetradecafluoridotrizirconium(IV) hexahydrate (space group Ibam), [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O, (I), and bis[hexaamminecobalt(III)] tetra-μ₂-fluorido-tetradecafluoridotrizirconium(IV) hexahydrate (space group Pnna), [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), consist of complex [Co(NH₃)_x(H₂O)_y]³⁺ cations with either m [in (I)] or $\overline{1}$ and 2 [in (II)] symmetry, [Zr₃F₁₈]⁶⁻ anionic chains located on sites with 222 [in (I)] or 2 [in (II)] symmetry, and water molecules.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010704108X/bc3047sup1.cif Contains datablocks I, II, global
	Structure factor file (CIF format) https://doi.org/10.1107/S010827010704108X/bc3047Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S010827010704108X/bc3047IIsup3.hkl Contains datablock II

Comment top

Double salts built from both cationic and anionic metal complexes represent an intensively studied field of modern chemistry [Du et al., 2005; Gubanov et al., 2003; Korenev et al., 1996; Korolkov et al., 2005]. Special attention has been paid to the unique products of their thermal decomposition which, in many cases, yields nano-particles of metal solid solutions. The latter can be used in many areas of applied chemistry, such as powder metallurgy and catalysis. The decomposition of double complexes in an oxygen atmosphere may afford complex ceramics with unusual properties. The title double complexes, [Co(NH₃)₅H₂O]₂[Zr₃F₁₈]·6H₂O, (I), and [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), are expected to yield nanosized ceramic powders.

The two title compounds have isotypic structures. The octahedral coordination of the Co^III cation is similar in both cases, the only difference being the presence of a water molecule instead of ammonia in (I) (Figs. 1 and 2). Both structures include an analogous [Zr₃F₁₈]⁶⁻ anion with a trimeric chain structure. The terminal Zr atoms have a coordination number of seven with a distorted pentagonal–bipyramidal geometry. The central Zr atoms are coordinated by eight F atoms forming a distorted square antiprism. The average Zr—F distance of 2.08 (9) Å is the same in both compounds.

The chain defined by the Zr atoms of the trimeric anion is parallel to the crystallographic a axis in both cases (Figs. 3 and 4). In spite of similar unit-cell dimensions, the two compounds have different local symmetries. In (I), the anion has point symmetry 222 and the Co atom is located on a mirror plane. In (II), the anion occupies a position of symmetry 2 and the two unique Co1 and Co2 atoms are located on an inversion centre and a twofold axis, respectively.

Both compounds contain several solvent water molecules that form a hydrogen-bond network with the NH₃ ligands and the F atoms of the anions, with average distances of 2.67 Å for (I) and 2.79 Å for (II). Differential thermal analysis and thermogravimetric analysis data (Derivatograf NETZCH STA 409) show that (II) loses about 5.5 water molecules over the 333–373 K range, whereas (I) loses water in three stages, at 333–393 K (two H₂O), 393–443 K (four H₂O) and 443–513 K (two H₂O). These data confirm the presence of three types of water molecules in (I): the first stage of weight loss corresponds to water molecules with contacts to hydrogen-bond acceptor atoms of more than 3 Å, the second stage corresponds to the loss of all hydrogen-bonded water molecules with an average distance of 2.66 Å, and the last stage represents the loss of coordinated water molecules.

Experimental top

Crystals of (I) were grown from an aqueous solution prepared at room temperature by the reaction of 0.001 M solutions of [Co(NH₃)₅Cl]Cl₂ (100 ml) and K₂[ZrF₆] (150 ml). After one week, deep-purple crystals were collected by filtration and dried in air. Crystals of (II) were grown from the reaction of aqueous 0.001 M solutions of [Co(NH₃)₆]Cl₃ (100 ml) and K₂[ZrF₆] (150 ml). After 4 d, fine yellow crystals were collected and dried in air. The crystal size was 2–3 mm for both (I) and (II).

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2004); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The structure fragment of compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The structure fragment of compound (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A packing diagram for (I), viewed along the a axis. The [Zr₃F₁₈]⁶⁻ anions have a chain structure aligned long the a axis.
	Fig. 4. A packing diagram for (II), viewed along the a axis. The structure of the [Zr₃F₁₈]⁶⁻ anion differs from that in (I).

(I) tetra-µ₂-fluorido-tetradecafluoridotrizirconium(IV) hexahydrate top

Crystal data top

[Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O	F(000) = 2064
M_r = 1047.99	D_x = 2.308 Mg m⁻³
Orthorhombic, Ibam	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2 2c	Cell parameters from 4145 reflections
a = 16.1440 (4) Å	θ = 3.2–30.4°
b = 12.7191 (3) Å	µ = 2.23 mm⁻¹
c = 14.6859 (3) Å	T = 293 K
V = 3015.56 (12) Å³	Prism, purple
Z = 4	0.17 × 0.12 × 0.12 mm

Data collection top

Bruker Nonius X8 APEX CCD area-detector diffractometer	1614 independent reflections
Radiation source: fine-focus sealed tube	1460 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 25 pixels mm^-1	θ_max = 26.4°, θ_min = 2.0°
ϕ scans	h = −20→18
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −15→15
T_min = 0.703, T_max = 0.775	l = −18→15
10490 measured reflections

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0395P)² + 40.5555P] where P = (F_o² + 2F_c²)/3
1614 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 1.52 e Å⁻³
6 restraints	Δρ_min = −2.37 e Å⁻³

Crystal data top

[Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O	V = 3015.56 (12) Å³
M_r = 1047.99	Z = 4
Orthorhombic, Ibam	Mo Kα radiation
a = 16.1440 (4) Å	µ = 2.23 mm⁻¹
b = 12.7191 (3) Å	T = 293 K
c = 14.6859 (3) Å	0.17 × 0.12 × 0.12 mm

Data collection top

Bruker Nonius X8 APEX CCD area-detector diffractometer	1614 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1460 reflections with I > 2σ(I)
T_min = 0.703, T_max = 0.775	R_int = 0.033
10490 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	6 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0395P)² + 40.5555P] where P = (F_o² + 2F_c²)/3
1614 reflections	Δρ_max = 1.52 e Å⁻³
113 parameters	Δρ_min = −2.37 e Å⁻³

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zr1	0.22644 (4)	0.0000	0.2500	0.0240 (2)
Zr2	0.0000	0.0000	0.2500	0.0141 (2)
F1	0.3523 (4)	0.0000	0.2500	0.081 (2)
F2	0.2598 (3)	0.0840 (4)	0.3629 (3)	0.0582 (12)
F3	0.2278 (2)	0.1295 (3)	0.1733 (3)	0.0533 (11)
F4	0.11569 (18)	0.0662 (3)	0.3054 (2)	0.0301 (8)
F5	0.0336 (2)	0.1056 (3)	0.1546 (3)	0.0485 (11)
Co1	0.38985 (6)	0.21269 (8)	0.0000	0.0169 (2)
O1	0.5048 (4)	0.1662 (6)	0.0000	0.0411 (16)
N1	0.4227 (5)	0.3602 (6)	0.0000	0.0375 (18)
H11	0.3845	0.3981	−0.0287	0.056*	0.50
H12	0.4711	0.3670	−0.0284	0.056*	0.50
H13	0.4276	0.3827	0.0571	0.056*	0.50
N2	0.3916 (3)	0.2137 (4)	0.1332 (3)	0.0282 (10)
H21	0.3941	0.2797	0.1530	0.042*
H22	0.4356	0.1783	0.1529	0.042*
H23	0.3457	0.1834	0.1542	0.042*
N3	0.3588 (5)	0.0630 (6)	0.0000	0.0395 (18)
H31	0.3152	0.0534	0.0362	0.059*	0.50
H32	0.4011	0.0247	0.0202	0.059*	0.50
H33	0.3460	0.0432	−0.0564	0.059*	0.50
N4	0.2759 (4)	0.2536 (7)	0.0000	0.0377 (18)
H41	0.2637	0.2845	0.0527	0.057*	0.50
H42	0.2442	0.1970	−0.0072	0.057*	0.50
H43	0.2668	0.2984	−0.0455	0.057*	0.50
O1W	0.0949 (3)	0.3024 (4)	0.1454 (4)	0.0521 (13)
O3W	0.1502 (7)	0.0831 (10)	0.0000	0.035 (3)	0.50
O2W	0.0000	0.5000	0.1695 (10)	0.053 (4)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.0129 (3)	0.0226 (4)	0.0365 (5)	0.000	0.000	−0.0070 (3)
Zr2	0.0135 (4)	0.0158 (4)	0.0132 (4)	0.000	0.000	0.000
F1	0.039 (3)	0.088 (4)	0.115 (4)	0.000	0.000	−0.032 (4)
F2	0.041 (2)	0.070 (3)	0.063 (3)	0.002 (2)	−0.025 (2)	−0.027 (2)
F3	0.047 (2)	0.042 (2)	0.071 (3)	−0.0114 (18)	0.017 (2)	0.018 (2)
F4	0.0182 (15)	0.0365 (18)	0.0356 (18)	0.0023 (13)	−0.0026 (13)	−0.0180 (15)
F5	0.0219 (17)	0.065 (3)	0.059 (2)	−0.0110 (17)	−0.0049 (17)	0.046 (2)
Co1	0.0187 (5)	0.0186 (5)	0.0134 (5)	−0.0021 (4)	0.000	0.000
O1	0.029 (3)	0.064 (4)	0.031 (3)	0.017 (3)	0.000	0.000
N1	0.058 (5)	0.031 (4)	0.024 (4)	−0.022 (4)	0.000	0.000
N2	0.034 (3)	0.030 (2)	0.020 (2)	−0.002 (2)	0.001 (2)	0.005 (2)
N3	0.061 (5)	0.025 (4)	0.032 (4)	−0.010 (4)	0.000	0.000
N4	0.029 (4)	0.057 (5)	0.028 (4)	0.007 (4)	0.000	0.000
O1W	0.047 (3)	0.051 (3)	0.057 (3)	−0.013 (2)	−0.022 (2)	0.003 (3)
O3W	0.030 (6)	0.056 (8)	0.017 (5)	−0.021 (6)	0.000	0.000
O2W	0.049 (8)	0.056 (9)	0.054 (9)	0.013 (7)	0.000	0.000

Geometric parameters (Å, º) top

Co1—O1	1.947 (6)	Zr2—F5ⁱⁱⁱ	2.014 (3)
Co1—N1	1.949 (7)	Zr2—F5^iv	2.014 (3)
Co1—N2	1.956 (5)	Zr2—F5ⁱⁱ	2.014 (3)
Co1—N3	1.969 (7)	Zr2—F5	2.015 (3)
Co1—N4	1.911 (7)	Zr2—Zr1ⁱⁱⁱ	3.6556 (7)
Co1—N2ⁱ	1.956 (5)	N1—H11	0.89
Zr1—F1	2.032 (7)	N1—H12	0.89
Zr1—F2	2.045 (4)	N1—H13	0.89
Zr1—F3	1.995 (4)	N2—H21	0.89
Zr1—F3ⁱⁱ	1.995 (4)	N2—H22	0.89
Zr1—F4	2.137 (3)	N2—H23	0.89
Zr1—F4ⁱⁱ	2.137 (3)	N3—H31	0.89
Zr1—F2ⁱⁱ	2.045 (4)	N3—H32	0.89
Zr1—Zr2	3.6556 (7)	N3—H33	0.89
Zr2—F4	2.205 (3)	N4—H41	0.89
Zr2—F4ⁱⁱⁱ	2.205 (3)	N4—H42	0.89
Zr2—F4^iv	2.205 (3)	N4—H43	0.89
Zr2—F4ⁱⁱ	2.205 (3)

F3ⁱⁱ—Zr1—F3	178.7 (2)	F5^iv—Zr2—Zr1	105.61 (10)
F3ⁱⁱ—Zr1—F1	89.36 (11)	F5ⁱⁱ—Zr2—Zr1	74.39 (10)
F3—Zr1—F1	89.36 (11)	F5—Zr2—Zr1	74.39 (10)
F3ⁱⁱ—Zr1—F2	88.32 (19)	F4—Zr2—Zr1	32.09 (8)
F3—Zr1—F2	91.34 (19)	F4ⁱⁱⁱ—Zr2—Zr1	147.91 (8)
F1—Zr1—F2	74.74 (12)	F4^iv—Zr2—Zr1	147.91 (8)
F3ⁱⁱ—Zr1—F2ⁱⁱ	91.35 (19)	F4ⁱⁱ—Zr2—Zr1	32.09 (8)
F3—Zr1—F2ⁱⁱ	88.32 (19)	F5ⁱⁱⁱ—Zr2—Zr1ⁱⁱⁱ	74.39 (10)
F1—Zr1—F2ⁱⁱ	74.74 (12)	F5^iv—Zr2—Zr1ⁱⁱⁱ	74.39 (10)
F2—Zr1—F2ⁱⁱ	149.5 (2)	F5ⁱⁱ—Zr2—Zr1ⁱⁱⁱ	105.61 (10)
F3ⁱⁱ—Zr1—F4ⁱⁱ	84.22 (15)	F5—Zr2—Zr1ⁱⁱⁱ	105.61 (10)
F3—Zr1—F4ⁱⁱ	96.87 (16)	F4—Zr2—Zr1ⁱⁱⁱ	147.91 (8)
F1—Zr1—F4ⁱⁱ	146.77 (8)	F4ⁱⁱⁱ—Zr2—Zr1ⁱⁱⁱ	32.09 (8)
F2—Zr1—F4ⁱⁱ	137.29 (15)	F4^iv—Zr2—Zr1ⁱⁱⁱ	32.09 (8)
F2ⁱⁱ—Zr1—F4ⁱⁱ	72.87 (14)	F4ⁱⁱ—Zr2—Zr1ⁱⁱⁱ	147.91 (8)
F3ⁱⁱ—Zr1—F4	96.87 (16)	Zr1—Zr2—Zr1ⁱⁱⁱ	180.0
F3—Zr1—F4	84.22 (15)	Zr1—F4—Zr2	114.69 (13)
F1—Zr1—F4	146.78 (8)	N4—Co1—O1	178.1 (3)
F2—Zr1—F4	72.87 (14)	N4—Co1—N1	90.0 (4)
F2ⁱⁱ—Zr1—F4	137.29 (15)	O1—Co1—N1	91.9 (3)
F4ⁱⁱ—Zr1—F4	66.45 (16)	N4—Co1—N2	90.68 (14)
F3ⁱⁱ—Zr1—Zr2	90.64 (11)	O1—Co1—N2	89.34 (14)
F3—Zr1—Zr2	90.64 (11)	N1—Co1—N2	89.42 (14)
F1—Zr1—Zr2	180.0	N4—Co1—N2ⁱ	90.68 (14)
F2—Zr1—Zr2	105.26 (12)	O1—Co1—N2ⁱ	89.34 (14)
F2ⁱⁱ—Zr1—Zr2	105.26 (12)	N1—Co1—N2ⁱ	89.43 (14)
F4ⁱⁱ—Zr1—Zr2	33.23 (8)	N2—Co1—N2ⁱ	178.2 (3)
F4—Zr1—Zr2	33.22 (8)	N4—Co1—N3	91.1 (4)
F5ⁱⁱⁱ—Zr2—F5^iv	148.78 (19)	O1—Co1—N3	87.1 (3)
F5ⁱⁱⁱ—Zr2—F5ⁱⁱ	96.4 (3)	N1—Co1—N3	179.0 (4)
F5^iv—Zr2—F5ⁱⁱ	91.9 (3)	N2—Co1—N3	90.56 (14)
F5ⁱⁱⁱ—Zr2—F5	91.9 (3)	N2ⁱ—Co1—N3	90.56 (14)
F5^iv—Zr2—F5	96.4 (3)	Co1—N1—H11	109.5
F5ⁱⁱ—Zr2—F5	148.78 (19)	Co1—N1—H12	109.5
F5ⁱⁱⁱ—Zr2—F4	137.66 (12)	H11—N1—H12	109.5
F5^iv—Zr2—F4	73.54 (12)	Co1—N1—H13	109.5
F5ⁱⁱ—Zr2—F4	76.69 (15)	H11—N1—H13	109.5
F5—Zr2—F4	76.95 (14)	H12—N1—H13	109.5
F5ⁱⁱⁱ—Zr2—F4ⁱⁱⁱ	76.95 (14)	Co1—N2—H21	109.5
F5^iv—Zr2—F4ⁱⁱⁱ	76.70 (15)	Co1—N2—H22	109.5
F5ⁱⁱ—Zr2—F4ⁱⁱⁱ	73.54 (12)	H21—N2—H22	109.5
F5—Zr2—F4ⁱⁱⁱ	137.66 (12)	Co1—N2—H23	109.5
F4—Zr2—F4ⁱⁱⁱ	136.67 (18)	H21—N2—H23	109.5
F5ⁱⁱⁱ—Zr2—F4^iv	76.70 (15)	H22—N2—H23	109.5
F5^iv—Zr2—F4^iv	76.95 (14)	Co1—N3—H31	109.5
F5ⁱⁱ—Zr2—F4^iv	137.66 (12)	Co1—N3—H32	109.5
F5—Zr2—F4^iv	73.55 (12)	H31—N3—H32	109.5
F4—Zr2—F4^iv	135.10 (17)	Co1—N3—H33	109.5
F4ⁱⁱⁱ—Zr2—F4^iv	64.17 (15)	H31—N3—H33	109.5
F5ⁱⁱⁱ—Zr2—F4ⁱⁱ	73.54 (12)	H32—N3—H33	109.5
F5^iv—Zr2—F4ⁱⁱ	137.66 (12)	Co1—N4—H41	109.5
F5ⁱⁱ—Zr2—F4ⁱⁱ	76.95 (14)	Co1—N4—H42	109.5
F5—Zr2—F4ⁱⁱ	76.69 (15)	H41—N4—H42	109.5
F4—Zr2—F4ⁱⁱ	64.17 (15)	Co1—N4—H43	109.5
F4ⁱⁱⁱ—Zr2—F4ⁱⁱ	135.10 (17)	H41—N4—H43	109.5
F4^iv—Zr2—F4ⁱⁱ	136.67 (18)	H42—N4—H43	109.5
F5ⁱⁱⁱ—Zr2—Zr1	105.61 (10)

Symmetry codes: (i) x, y, −z; (ii) x, −y, −z+1/2; (iii) −x, −y, z; (iv) −x, y, −z+1/2.

(II) bis[hexaamminecobalt(III)] tetra-µ₂-fluorido-tetradecafluoridotrizirconium(IV) hexahydrate top

Crystal data top

[Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O	F(000) = 2064
M_r = 1046.02	D_x = 2.269 Mg m⁻³
Orthorhombic, Pnna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2bc	Cell parameters from 8258 reflections
a = 16.0370 (3) Å	θ = 2.5–32.6°
b = 14.6920 (2) Å	µ = 2.20 mm⁻¹
c = 12.9942 (2) Å	T = 293 K
V = 3061.64 (9) Å³	Prism, yellow
Z = 4	0.26 × 0.20 × 0.16 mm

Data collection top

Bruker Nonius X8 APEX CCD area-detector diffractometer	3136 independent reflections
Radiation source: fine-focus sealed tube	2608 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 25 pixels mm^-1	θ_max = 26.4°, θ_min = 2.0°
ϕ scans	h = −20→20
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −14→18
T_min = 0.599, T_max = 0.720	l = −16→14
20871 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.110	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.0489P)² + 15.8103P] where P = (F_o² + 2F_c²)/3
3136 reflections	(Δ/σ)_max = 0.002
211 parameters	Δρ_max = 1.24 e Å⁻³
0 restraints	Δρ_min = −2.23 e Å⁻³

Crystal data top

[Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O	V = 3061.64 (9) Å³
M_r = 1046.02	Z = 4
Orthorhombic, Pnna	Mo Kα radiation
a = 16.0370 (3) Å	µ = 2.20 mm⁻¹
b = 14.6920 (2) Å	T = 293 K
c = 12.9942 (2) Å	0.26 × 0.20 × 0.16 mm

Data collection top

Bruker Nonius X8 APEX CCD area-detector diffractometer	3136 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2608 reflections with I > 2σ(I)
T_min = 0.599, T_max = 0.720	R_int = 0.031
20871 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.0489P)² + 15.8103P] where P = (F_o² + 2F_c²)/3
3136 reflections	Δρ_max = 1.24 e Å⁻³
211 parameters	Δρ_min = −2.23 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Zr1	0.13816 (3)	0.2500	0.7500	0.01921 (16)
Co1	0.0000	0.0000	0.0000	0.01850 (19)
Zr2	0.36785 (3)	0.2500	0.7500	0.01612 (15)
Co2	0.2500	0.0000	0.47050 (6)	0.0191 (2)
Zr3	0.59825 (4)	0.2500	0.7500	0.01999 (16)
F11	0.0108 (3)	0.2633 (9)	0.7306 (8)	0.036 (2)	0.50
N11	0.1134 (3)	0.0292 (3)	0.0437 (3)	0.0334 (10)
H11A	0.1435	−0.0216	0.0468	0.050*
H11B	0.1120	0.0553	0.1054	0.050*
H11C	0.1365	0.0673	−0.0014	0.050*
F12	0.25049 (16)	0.18864 (19)	0.6937 (2)	0.0312 (6)
N12	−0.0203 (3)	0.1300 (3)	−0.0211 (3)	0.0300 (9)
H12A	−0.0589	0.1373	−0.0697	0.045*
H12B	0.0268	0.1570	−0.0408	0.045*
H12C	−0.0380	0.1548	0.0374	0.045*
F13	0.1390 (2)	0.1615 (2)	0.8662 (3)	0.0536 (9)
N13	−0.0376 (3)	0.0085 (3)	0.1438 (3)	0.0303 (9)
H13A	−0.0648	−0.0421	0.1609	0.045*
H13B	−0.0714	0.0562	0.1508	0.045*
H13C	0.0064	0.0154	0.1848	0.045*
F14	0.1052 (2)	0.1457 (2)	0.6532 (3)	0.0559 (10)
F21	0.33673 (19)	0.1700 (3)	0.8697 (3)	0.0554 (11)
N21	0.1308 (3)	0.0272 (3)	0.4704 (4)	0.0361 (10)
H21A	0.1185	0.0611	0.4157	0.054*
H21B	0.1177	0.0574	0.5275	0.054*
H21C	0.1020	−0.0245	0.4679	0.054*
F22	0.40106 (19)	0.1412 (2)	0.6659 (3)	0.0501 (9)
N22	0.2500	0.0000	0.3209 (4)	0.0326 (13)
H22A	0.2523	0.0571	0.2980	0.049*	0.50
H22B	0.2036	−0.0264	0.2980	0.049*	0.50
H22C	0.2941	−0.0307	0.2980	0.049*	0.50
F23	0.48665 (15)	0.2071 (2)	0.8248 (2)	0.0334 (7)
N23	0.2716 (3)	0.1312 (3)	0.4704 (3)	0.0302 (9)
H23A	0.3209	0.1421	0.4413	0.045*
H23B	0.2721	0.1517	0.5349	0.045*
H23C	0.2318	0.1595	0.4351	0.045*
N24	0.2500	0.0000	0.6213 (5)	0.0438 (17)
H24A	0.2341	0.0544	0.6442	0.066*	0.50
H24B	0.3011	−0.0121	0.6442	0.066*	0.50
H24C	0.2148	−0.0423	0.6442	0.066*	0.50
F31	0.7251 (4)	0.2678 (10)	0.7648 (13)	0.055 (3)	0.50
F32	0.6244 (2)	0.2539 (3)	0.9015 (3)	0.0647 (12)
F33	0.6093 (2)	0.1131 (2)	0.7434 (3)	0.0532 (9)
O1W	0.2823 (4)	0.1483 (4)	0.0647 (5)	0.0770 (16)
O2W	0.3836 (4)	0.1253 (5)	0.2389 (5)	0.068 (2)	0.75
O3W	0.4607 (3)	0.1485 (3)	0.4634 (4)	0.0581 (12)
O4W	0.2500	0.0000	0.8746 (8)	0.041 (3)	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.0136 (3)	0.0195 (3)	0.0245 (3)	0.000	0.000	−0.0064 (2)
Co1	0.0211 (4)	0.0172 (4)	0.0172 (4)	−0.0043 (3)	0.0032 (3)	−0.0053 (3)
Zr2	0.0143 (3)	0.0171 (3)	0.0170 (3)	0.000	0.000	0.0034 (2)
Co2	0.0219 (4)	0.0170 (4)	0.0184 (4)	0.0036 (3)	0.000	0.000
Zr3	0.0140 (3)	0.0245 (3)	0.0215 (3)	0.000	0.000	0.0073 (2)
F11	0.016 (2)	0.047 (7)	0.045 (8)	0.008 (3)	−0.004 (3)	−0.007 (4)
N11	0.026 (2)	0.042 (3)	0.032 (2)	−0.0076 (19)	0.0021 (17)	−0.0070 (19)
F12	0.0190 (12)	0.0305 (15)	0.0441 (17)	0.0001 (11)	−0.0001 (12)	−0.0188 (13)
N12	0.040 (2)	0.025 (2)	0.025 (2)	0.0023 (18)	0.0039 (17)	−0.0022 (16)
F13	0.058 (2)	0.056 (2)	0.046 (2)	−0.0208 (17)	0.0136 (17)	0.0168 (17)
N13	0.035 (2)	0.024 (2)	0.031 (2)	−0.0057 (17)	0.0078 (18)	−0.0066 (16)
F14	0.0311 (16)	0.058 (2)	0.078 (3)	−0.0022 (16)	−0.0084 (17)	−0.044 (2)
F21	0.0236 (15)	0.084 (3)	0.059 (2)	0.0006 (16)	0.0049 (15)	0.050 (2)
N21	0.030 (2)	0.031 (2)	0.047 (3)	0.0065 (18)	0.0072 (19)	−0.001 (2)
F22	0.0289 (16)	0.049 (2)	0.072 (2)	0.0061 (15)	0.0026 (16)	−0.0304 (18)
N22	0.038 (3)	0.034 (3)	0.026 (3)	0.009 (3)	0.000	0.000
F23	0.0167 (13)	0.0507 (18)	0.0327 (15)	0.0026 (12)	0.0005 (11)	0.0264 (14)
N23	0.034 (2)	0.023 (2)	0.034 (2)	0.0010 (17)	−0.0032 (18)	0.0032 (16)
N24	0.078 (5)	0.024 (3)	0.029 (3)	0.005 (3)	0.000	0.000
F31	0.022 (3)	0.072 (11)	0.069 (10)	−0.001 (4)	−0.005 (4)	−0.008 (6)
F32	0.065 (2)	0.099 (3)	0.0302 (18)	−0.037 (2)	−0.0203 (16)	0.0142 (18)
F33	0.068 (2)	0.0320 (17)	0.059 (2)	0.0201 (17)	0.0247 (18)	0.0060 (15)
O1W	0.076 (4)	0.068 (3)	0.087 (4)	0.009 (3)	0.019 (3)	−0.002 (3)
O2W	0.081 (5)	0.063 (4)	0.062 (4)	−0.040 (4)	0.022 (4)	−0.008 (3)
O3W	0.044 (2)	0.058 (3)	0.072 (3)	−0.013 (2)	0.012 (2)	−0.001 (2)
O4W	0.071 (8)	0.018 (5)	0.035 (6)	0.010 (5)	0.000	0.000

Geometric parameters (Å, º) top

Co1—N11	1.953 (4)	Zr3—F23ⁱⁱⁱ	2.132 (3)
Co1—N11ⁱ	1.953 (4)	Zr3—F31	2.061 (6)
Co1—N12	1.957 (4)	Zr3—F31ⁱⁱⁱ	2.061 (6)
Co1—N12ⁱ	1.957 (4)	Zr3—F32	2.013 (4)
Co1—N13	1.967 (4)	Zr3—F32ⁱⁱⁱ	2.014 (4)
Co1—N13ⁱ	1.967 (4)	Zr3—F33	2.021 (3)
Co2—N21	1.953 (4)	Zr3—F33ⁱⁱⁱ	2.021 (3)
Co2—N21ⁱⁱ	1.953 (4)	F11—F11ⁱⁱⁱ	0.638 (13)
Co2—N22	1.944 (6)	N11—H11A	0.89
Co2—N23	1.959 (4)	N11—H11B	0.89
Co2—N23ⁱⁱ	1.959 (4)	N11—H11C	0.89
Co2—N24	1.960 (6)	N12—H12A	0.89
Zr1—F11	2.067 (5)	N12—H12B	0.89
Zr1—F11ⁱⁱⁱ	2.067 (5)	N12—H12C	0.89
Zr1—F12	2.143 (3)	N13—H13A	0.89
Zr1—F12ⁱⁱⁱ	2.143 (3)	N13—H13B	0.89
Zr1—F13	1.993 (3)	N13—H13C	0.89
Zr1—F13ⁱⁱⁱ	1.993 (3)	N21—H21A	0.89
Zr1—F14	2.051 (3)	N21—H21B	0.89
Zr1—F14ⁱⁱⁱ	2.051 (3)	N21—H21C	0.89
Zr2—F12	2.211 (3)	N22—H22A	0.89
Zr2—F12ⁱⁱⁱ	2.211 (3)	N22—H22B	0.89
Zr2—F21	2.013 (3)	N22—H22C	0.89
Zr2—F21ⁱⁱⁱ	2.013 (3)	N23—H23A	0.89
Zr2—F22	2.008 (3)	N23—H23B	0.89
Zr2—F22ⁱⁱⁱ	2.008 (3)	N23—H23C	0.89
Zr2—F23	2.230 (3)	N24—H24A	0.89
Zr2—F23ⁱⁱⁱ	2.230 (3)	N24—H24B	0.89
Zr3—F23	2.132 (3)	N24—H24C	0.89

F13—Zr1—F13ⁱⁱⁱ	179.2 (2)	N23ⁱⁱ—Co2—N23	179.9 (3)
F13—Zr1—F14ⁱⁱⁱ	91.40 (17)	N22—Co2—N24	180.000 (1)
F13ⁱⁱⁱ—Zr1—F14ⁱⁱⁱ	88.81 (17)	N21ⁱⁱ—Co2—N24	90.04 (15)
F13—Zr1—F14	88.81 (17)	N21—Co2—N24	90.04 (15)
F13ⁱⁱⁱ—Zr1—F14	91.40 (17)	N23ⁱⁱ—Co2—N24	90.03 (13)
F14ⁱⁱⁱ—Zr1—F14	150.10 (18)	N23—Co2—N24	90.03 (13)
F13—Zr1—F11	99.3 (2)	F32—Zr3—F32ⁱⁱⁱ	156.0 (2)
F13ⁱⁱⁱ—Zr1—F11	81.5 (2)	F32—Zr3—F33ⁱⁱⁱ	84.92 (15)
F14ⁱⁱⁱ—Zr1—F11	75.5 (4)	F32ⁱⁱⁱ—Zr3—F33ⁱⁱⁱ	92.98 (16)
F14—Zr1—F11	75.0 (4)	F32—Zr3—F33	92.99 (16)
F13—Zr1—F11ⁱⁱⁱ	81.5 (2)	F32ⁱⁱⁱ—Zr3—F33	84.92 (15)
F13ⁱⁱⁱ—Zr1—F11ⁱⁱⁱ	99.3 (2)	F33ⁱⁱⁱ—Zr3—F33	170.0 (2)
F14ⁱⁱⁱ—Zr1—F11ⁱⁱⁱ	75.0 (4)	F32—Zr3—F31	72.5 (5)
F14—Zr1—F11ⁱⁱⁱ	75.5 (4)	F32ⁱⁱⁱ—Zr3—F31	83.6 (5)
F11—Zr1—F11ⁱⁱⁱ	17.8 (4)	F33ⁱⁱⁱ—Zr3—F31	77.5 (4)
F13—Zr1—F12ⁱⁱⁱ	90.57 (13)	F33—Zr3—F31	92.5 (4)
F13ⁱⁱⁱ—Zr1—F12ⁱⁱⁱ	88.76 (14)	F32—Zr3—F31ⁱⁱⁱ	83.6 (5)
F14ⁱⁱⁱ—Zr1—F12ⁱⁱⁱ	72.15 (11)	F32ⁱⁱⁱ—Zr3—F31ⁱⁱⁱ	72.5 (5)
F14—Zr1—F12ⁱⁱⁱ	137.75 (11)	F33ⁱⁱⁱ—Zr3—F31ⁱⁱⁱ	92.5 (4)
F11—Zr1—F12ⁱⁱⁱ	146.3 (4)	F33—Zr3—F31ⁱⁱⁱ	77.5 (4)
F11ⁱⁱⁱ—Zr1—F12ⁱⁱⁱ	146.0 (4)	F31—Zr3—F31ⁱⁱⁱ	18.1 (4)
F13—Zr1—F12	88.76 (14)	F32—Zr3—F23	74.79 (13)
F13ⁱⁱⁱ—Zr1—F12	90.57 (13)	F32ⁱⁱⁱ—Zr3—F23	127.75 (15)
F14ⁱⁱⁱ—Zr1—F12	137.75 (12)	F33ⁱⁱⁱ—Zr3—F23	110.39 (15)
F14—Zr1—F12	72.15 (11)	F33—Zr3—F23	78.38 (13)
F11—Zr1—F12	146.0 (4)	F31—Zr3—F23	145.5 (6)
F11ⁱⁱⁱ—Zr1—F12	146.3 (4)	F31ⁱⁱⁱ—Zr3—F23	146.5 (6)
F12ⁱⁱⁱ—Zr1—F12	65.60 (14)	F32—Zr3—F23ⁱⁱⁱ	127.75 (15)
N11—Co1—N11ⁱ	180.0	F32ⁱⁱⁱ—Zr3—F23ⁱⁱⁱ	74.79 (13)
N11—Co1—N12	88.93 (19)	F33ⁱⁱⁱ—Zr3—F23ⁱⁱⁱ	78.38 (13)
N11ⁱ—Co1—N12	91.07 (19)	F33—Zr3—F23ⁱⁱⁱ	110.39 (15)
N11—Co1—N12ⁱ	91.07 (19)	F31—Zr3—F23ⁱⁱⁱ	146.5 (6)
N11ⁱ—Co1—N12ⁱ	88.93 (19)	F31ⁱⁱⁱ—Zr3—F23ⁱⁱⁱ	145.5 (6)
N12—Co1—N12ⁱ	180.0	F23—Zr3—F23ⁱⁱⁱ	65.84 (13)
N11—Co1—N13	89.74 (18)	F11ⁱⁱⁱ—F11—Zr1	81.12 (18)
N11ⁱ—Co1—N13	90.25 (18)	Co1—N11—H11A	109.5
N12—Co1—N13	91.16 (17)	Co1—N11—H11B	109.5
N12ⁱ—Co1—N13	88.85 (17)	H11A—N11—H11B	109.5
N11—Co1—N13ⁱ	90.26 (18)	Co1—N11—H11C	109.5
N11ⁱ—Co1—N13ⁱ	89.75 (18)	H11A—N11—H11C	109.5
N12—Co1—N13ⁱ	88.84 (17)	H11B—N11—H11C	109.5
N12ⁱ—Co1—N13ⁱ	91.16 (17)	Zr1—F12—Zr2	115.53 (11)
N13—Co1—N13ⁱ	180.0	Co1—N12—H12A	109.5
F22—Zr2—F22ⁱⁱⁱ	149.23 (18)	Co1—N12—H12B	109.5
F22—Zr2—F21ⁱⁱⁱ	96.34 (17)	H12A—N12—H12B	109.5
F22ⁱⁱⁱ—Zr2—F21ⁱⁱⁱ	91.21 (17)	Co1—N12—H12C	109.5
F22—Zr2—F21	91.21 (17)	H12A—N12—H12C	109.5
F22ⁱⁱⁱ—Zr2—F21	96.34 (17)	H12B—N12—H12C	109.5
F21ⁱⁱⁱ—Zr2—F21	151.29 (17)	Co1—N13—H13A	109.5
F22—Zr2—F12	73.82 (11)	Co1—N13—H13B	109.5
F22ⁱⁱⁱ—Zr2—F12	136.91 (11)	H13A—N13—H13B	109.5
F21ⁱⁱⁱ—Zr2—F12	76.79 (13)	Co1—N13—H13C	109.5
F21—Zr2—F12	78.84 (13)	H13A—N13—H13C	109.5
F22—Zr2—F12ⁱⁱⁱ	136.91 (11)	H13B—N13—H13C	109.5
F22ⁱⁱⁱ—Zr2—F12ⁱⁱⁱ	73.82 (11)	Co2—N21—H21A	109.5
F21ⁱⁱⁱ—Zr2—F12ⁱⁱⁱ	78.84 (13)	Co2—N21—H21B	109.5
F21—Zr2—F12ⁱⁱⁱ	76.79 (13)	H21A—N21—H21B	109.5
F12—Zr2—F12ⁱⁱⁱ	63.33 (13)	Co2—N21—H21C	109.5
F22—Zr2—F23	77.61 (13)	H21A—N21—H21C	109.5
F22ⁱⁱⁱ—Zr2—F23	76.19 (13)	H21B—N21—H21C	109.5
F21ⁱⁱⁱ—Zr2—F23	135.56 (11)	Co2—N22—H22A	109.5
F21—Zr2—F23	73.12 (11)	Co2—N22—H22B	109.5
F12—Zr2—F23	139.12 (11)	H22A—N22—H22B	109.5
F12ⁱⁱⁱ—Zr2—F23	134.29 (11)	Co2—N22—H22C	109.5
F22—Zr2—F23ⁱⁱⁱ	76.19 (13)	H22A—N22—H22C	109.5
F22ⁱⁱⁱ—Zr2—F23ⁱⁱⁱ	77.61 (13)	H22B—N22—H22C	109.5
F21ⁱⁱⁱ—Zr2—F23ⁱⁱⁱ	73.12 (11)	Zr3—F23—Zr2	115.77 (11)
F21—Zr2—F23ⁱⁱⁱ	135.56 (11)	Co2—N23—H23A	109.5
F12—Zr2—F23ⁱⁱⁱ	134.29 (11)	Co2—N23—H23B	109.5
F12ⁱⁱⁱ—Zr2—F23ⁱⁱⁱ	139.12 (11)	H23A—N23—H23B	109.5
F23—Zr2—F23ⁱⁱⁱ	62.62 (13)	Co2—N23—H23C	109.5
N22—Co2—N21ⁱⁱ	89.96 (15)	H23A—N23—H23C	109.5
N22—Co2—N21	89.96 (15)	H23B—N23—H23C	109.5
N21ⁱⁱ—Co2—N21	179.9 (3)	Co2—N24—H24A	109.5
N22—Co2—N23ⁱⁱ	89.97 (13)	Co2—N24—H24B	109.5
N21ⁱⁱ—Co2—N23ⁱⁱ	88.39 (18)	H24A—N24—H24B	109.5
N21—Co2—N23ⁱⁱ	91.61 (18)	Co2—N24—H24C	109.5
N22—Co2—N23	89.97 (13)	H24A—N24—H24C	109.5
N21ⁱⁱ—Co2—N23	91.61 (18)	H24B—N24—H24C	109.5
N21—Co2—N23	88.39 (18)	F31ⁱⁱⁱ—F31—Zr3	81.0 (2)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, −y, z; (iii) x, −y+1/2, −z+3/2.

Experimental details

	(I)	(II)
Crystal data
Chemical formula	[Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O	[Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O
M_r	1047.99	1046.02
Crystal system, space group	Orthorhombic, Ibam	Orthorhombic, Pnna
Temperature (K)	293	293
a, b, c (Å)	16.1440 (4), 12.7191 (3), 14.6859 (3)	16.0370 (3), 14.6920 (2), 12.9942 (2)
V (Å³)	3015.56 (12)	3061.64 (9)
Z	4	4
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	2.23	2.20
Crystal size (mm)	0.17 × 0.12 × 0.12	0.26 × 0.20 × 0.16

Data collection
Diffractometer	Bruker Nonius X8 APEX CCD area-detector diffractometer	Bruker Nonius X8 APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.703, 0.775	0.599, 0.720
No. of measured, independent and observed [I > 2σ(I)] reflections	10490, 1614, 1460	20871, 3136, 2608
R_int	0.033	0.031
(sin θ/λ)_max (Å⁻¹)	0.625	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.109, 1.11	0.041, 0.110, 1.19
No. of reflections	1614	3136
No. of parameters	113	211
No. of restraints	6	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0395P)² + 40.5555P] where P = (F_o² + 2F_c²)/3	w = 1/[σ²(F_o²) + (0.0489P)² + 15.8103P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.52, −2.37	1.24, −2.23

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXTL (Bruker, 2004), SHELXTL.

Selected bond lengths (Å) for (I) top

Co1—O1	1.947 (6)	Zr1—F2	2.045 (4)
Co1—N1	1.949 (7)	Zr1—F3	1.995 (4)
Co1—N2	1.956 (5)	Zr1—F4	2.137 (3)
Co1—N3	1.969 (7)	Zr2—F4	2.205 (3)
Co1—N4	1.911 (7)	Zr2—F5	2.015 (3)
Zr1—F1	2.032 (7)

Selected bond lengths (Å) for (II) top

Co1—N11	1.953 (4)	Zr1—F14	2.051 (3)
Co1—N12	1.957 (4)	Zr2—F12	2.211 (3)
Co1—N13	1.967 (4)	Zr2—F21	2.013 (3)
Co2—N21	1.953 (4)	Zr2—F22	2.008 (3)
Co2—N22	1.944 (6)	Zr2—F23	2.230 (3)
Co2—N23	1.959 (4)	Zr3—F23	2.132 (3)
Co2—N24	1.960 (6)	Zr3—F31	2.061 (6)
Zr1—F11	2.067 (5)	Zr3—F32	2.013 (4)
Zr1—F12	2.143 (3)	Zr3—F33	2.021 (3)
Zr1—F13	1.993 (3)

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