5,6-Dihydro-1,10-phenanthroline-1,10-diium μ-oxido-bis­[penta­fluoridotantalate(V)]

Meng, Z.-H.; Feng, Y.-Q.; Chen, X.-F.

doi:10.1107/S1600536812014742

metal-organic compounds

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5,6-Dihydro-1,10-phenanthroline-1,10-diium μ-oxido-bis[pentafluoridotantalate(V)]

Zhao-Hui Meng,^a ^* Yu-Quan Feng ^a and Xin-Feng Chen ^a

^aCollege of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang 473061, People's Republic of China
^*Correspondence e-mail: nysymzh@126.com

(Received 8 March 2012; accepted 4 April 2012; online 13 April 2012)

In the title compound, (C₁₂H₁₂N₂)[Ta₂F₁₀O], the doubly protonated 5,6-dihydro-1,10-phenantroline-1,10-diium cation is located on a twofold rotation axis, whereas the isolated [Ta₂OF₁₀]²⁻ dianion has -1 symmetry. In the so far unknown dianion, the symmetry-related Ta^V atoms are octahedrally coordinated by five F atoms and a bridging O atom, the latter being located on an inversion centre. The two pyridine rings in the cation make a dihedral angle of 22.8 (4)°. The cations and dianions are arranged in layers parallel to (100) and are connected through N—H⋯F and C—H⋯F hydrogen-bonding interactions into a three-dimensional structure.

Related literature

For structure–property relations of metal oxyfluorides, see: Hagerman & Poeppelmeier (1995 ); Halasyamani & Poeppelmeier (1998 ); Welk et al. (2002 ).

Experimental

Crystal data

(C₁₂H₁₂N₂)[Ta₂F₁₀O]
M_r = 752.14
Monoclinic, C 2/c
a = 13.536 (2) Å
b = 11.3031 (17) Å
c = 11.5316 (17) Å
β = 90.093 (2)°
V = 1764.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 12.50 mm⁻¹
T = 296 K
0.21 × 0.20 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.179, T_max = 0.225
4738 measured reflections
1725 independent reflections
1573 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.072
S = 1.05
1725 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 1.96 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Table 1
Selected bond lengths (Å)

Ta1—F4	1.877 (5)
Ta1—F5	1.886 (5)
Ta1—F1	1.886 (5)
Ta1—O1	1.8924 (3)
Ta1—F3	1.895 (4)
Ta1—F2	1.905 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯F4ⁱ	0.86	2.45	3.114 (10)	135
C4—H4A⋯F1ⁱⁱ	0.93	2.26	3.066 (9)	145
C6—H6A⋯F3ⁱⁱⁱ	0.97	2.28	3.219 (8)	163
C6—H6B⋯F5^iv	0.97	2.45	3.268 (9)	142
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+1]$ ; (iii) -x+1, -y, -z+1; (iv) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812014742/wm2602sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812014742/wm2602Isup2.hkl

checkCIF report

Comment top

Metal oxyfluorides have received considerable attention in recent years due to their structure-related properties such as ferroelectricity, piezoelectricity and second-order nonlinear optical activity (Hagerman & Poeppelmeier, 1995; Halasyamani & Poeppelmeier, 1998; Welk et al., 2002). In this article, we report on a new oxidofluoridotantalate with composition [C₁₂H₁₂N₂][Ta₂OF₁₀] that was obtained by means of a two-step hydrothermal method.

The title compound (Fig. 1) contains one diprotonated 5,6-dihydro-1,10-phenantroline-1,10-diium cation (symmetry 2) and one [Ta₂OF₁₀]^2- dianion (symmetry 1). In the latter, the Ta^V ion is coordinated by five fluorine atoms and one oxygen atom, forming an octahedral coordination geometry. It is noteworthy that the title compound features the first oxidofluoridotantalate with composition [Ta₂OF₁₀]^2-. The cation is not flat, as can be expected from the 5,6-dihydro bridging sp³ carbon atoms, with a dihedral angle of of 22.8 (4)° between the two pyridine rings. The cations and dianions are arranged in layers parallel to (100) and are connected through N—H···F and C—H···F hydrogen bonding interactions into a three-dimensional structure (Fig. 2).

It should be noted that the hydrothermal conditions make it possible that parts of the fluorine atoms are replaced by OH^- ions. To exclude the presence of the latter, additional characterisation methods were employed (see details in the experimental part). Moreover, IR spectroscopy revealed no inclusion of OH^- in the compound (Fig. 3).

Related literature top

For structure–property relations of metal oxyfluorides, see: Hagerman & Poeppelmeier (1995); Halasyamani & Poeppelmeier (1998); Welk et al. (2002).

Experimental top

All chemicals were of reagent grade quality obtained from commercial sources and were used without further purification. The title compound was obtained by using a two-step hydrothermal method in a 50 mL Teflon-lined autoclave. Firstly, 0.66 g Ta₂O₅ (1.5 mmol) was dissolved in 1.11 g HF (40_wt%) (7.4 mmol) and heated to 453 K for 4 hours. After it was cooled, the solution was added into 0.90 mL H₃PO₄ (85_wt%), 0.24 g 2,2'-bipyridine (1.5 mmol), 2.0 mL ethylene glycol and 1.0 mL H₂O. Then the mixture was stirred for half an hour, and transferred into a Teflon-lined stainless steel autoclave (50 mL) and treated at 453 K for 7 days. After the mixture was slowly cooled to room temperature, yellow block-like crystals suitable for X-ray structure determination were obtained. It worth noting that the reaction of 2,2'-bipyridine and ethylene glycol produced the 5,6-dihydro-1,10-phenantroline ligand. The chemical composition of the title compound was confirmed by EDS and elemental analysis. The results of EDS indicate the presence of the elements Ta, F, O, C and N. The Ta composition was quantified by ICP-OES: Anal./Calcd (%): Ta: 48.59/48.12. C, H, and N analysis was performed on a PerkinElmer 2400II elemental analyzer. Anal./Calcd (%): C, 19.16; H, 1.61; N,3.72 %. Found: C, 19.63; H, 1.94; N, 3.17 %. IR (KBr, cm^-1) (Fig. 3): 3110, 3057, 2920, 2861, 1621,1584,1494, 1457, 1431, 1367, 1330, 1282, 1234, 1181, 1149, 1033, 869, 784, 715, 593 and 535.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title molecule with displacement ellipsoids drawn at the 30% probability level [symmetry code A: -x+2, y, -z+3/2].
	Fig. 2. Crystal packing viewed along the c axis. Hydrogen bonding interactions are shown as dashed lines.
	Fig. 3. IR spectrum of the title compound.

5,6-Dihydro-1,10-phenanthroline-1,10-diium µ-oxido-bis[pentafluoridotantalate(V)] top

Crystal data top

(C₁₂H₁₂N₂)[Ta₂F₁₀O]	F(000) = 1368
M_r = 752.14	D_x = 2.831 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3156 reflections
a = 13.536 (2) Å	θ = 2.4–28.3°
b = 11.3031 (17) Å	µ = 12.50 mm⁻¹
c = 11.5316 (17) Å	T = 296 K
β = 90.093 (2)°	Block, yellow
V = 1764.4 (5) Å³	0.21 × 0.20 × 0.17 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1725 independent reflections
Radiation source: fine-focus sealed tube	1573 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→16
T_min = 0.179, T_max = 0.225	k = −13→13
4738 measured reflections	l = −14→12

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0278P)² + 20.5568P] where P = (F_o² + 2F_c²)/3
1725 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 1.96 e Å⁻³
0 restraints	Δρ_min = −1.14 e Å⁻³

Crystal data top

(C₁₂H₁₂N₂)[Ta₂F₁₀O]	V = 1764.4 (5) Å³
M_r = 752.14	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.536 (2) Å	µ = 12.50 mm⁻¹
b = 11.3031 (17) Å	T = 296 K
c = 11.5316 (17) Å	0.21 × 0.20 × 0.17 mm
β = 90.093 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1725 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1573 reflections with I > 2σ(I)
T_min = 0.179, T_max = 0.225	R_int = 0.029
4738 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0278P)² + 20.5568P] where P = (F_o² + 2F_c²)/3
1725 reflections	Δρ_max = 1.96 e Å⁻³
124 parameters	Δρ_min = −1.14 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Ta1	0.193168 (19)	0.18732 (2)	0.13666 (2)	0.03630 (12)
C2	0.9169 (6)	0.2166 (8)	0.9660 (7)	0.0499 (19)
H2A	0.9123	0.1448	1.0050	0.060*
C1	0.9649 (4)	0.2220 (5)	0.8646 (5)	0.0210 (10)
C5	0.9738 (5)	0.3254 (5)	0.8051 (5)	0.0332 (13)
N1	0.9318 (6)	0.4270 (7)	0.8502 (7)	0.069 (2)
H1A	0.9361	0.4931	0.8136	0.083*
C4	0.8832 (7)	0.4207 (9)	0.9546 (7)	0.062 (2)
H4A	0.8558	0.4890	0.9858	0.075*
C3	0.8742 (7)	0.3164 (9)	1.0135 (7)	0.060 (2)
H3A	0.8403	0.3127	1.0834	0.072*
F1	0.2944 (5)	0.0732 (6)	0.1479 (5)	0.093 (2)
F2	0.1355 (4)	0.1192 (5)	0.2716 (4)	0.0684 (14)
F3	0.1159 (4)	0.0811 (4)	0.0475 (4)	0.0692 (15)
F4	0.0908 (5)	0.2992 (5)	0.1343 (7)	0.0867 (19)
F5	0.2665 (4)	0.2877 (5)	0.2351 (5)	0.0720 (15)
O1	0.2500	0.2500	0.0000	0.082 (3)
C6	1.0104 (5)	0.1139 (6)	0.8134 (6)	0.0408 (15)
H6A	0.9827	0.0436	0.8490	0.049*
H6B	1.0811	0.1141	0.8270	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ta1	0.03744 (18)	0.03940 (18)	0.03206 (18)	−0.00695 (11)	0.00427 (11)	−0.00056 (11)
C2	0.047 (4)	0.069 (5)	0.033 (4)	−0.008 (4)	0.001 (3)	0.012 (4)
C1	0.023 (3)	0.023 (2)	0.016 (2)	−0.001 (2)	0.004 (2)	0.002 (2)
C5	0.039 (3)	0.032 (3)	0.028 (3)	0.000 (3)	0.001 (3)	−0.004 (2)
N1	0.087 (5)	0.062 (5)	0.059 (4)	0.015 (4)	0.000 (4)	−0.007 (4)
C4	0.069 (6)	0.076 (6)	0.042 (4)	0.016 (5)	0.015 (4)	−0.022 (4)
C3	0.056 (5)	0.099 (7)	0.025 (4)	0.003 (4)	0.013 (3)	−0.012 (4)
F1	0.094 (4)	0.117 (5)	0.066 (3)	0.058 (4)	−0.006 (3)	−0.024 (3)
F2	0.097 (4)	0.066 (3)	0.042 (3)	−0.019 (3)	0.024 (3)	0.005 (2)
F3	0.095 (4)	0.065 (3)	0.048 (3)	−0.038 (3)	−0.010 (3)	0.002 (2)
F4	0.070 (4)	0.061 (3)	0.128 (6)	0.017 (3)	−0.009 (4)	0.007 (3)
F5	0.071 (3)	0.082 (4)	0.063 (3)	−0.031 (3)	0.001 (3)	−0.023 (3)
O1	0.106 (8)	0.095 (7)	0.045 (5)	−0.054 (6)	0.018 (5)	0.008 (5)
C6	0.043 (4)	0.031 (3)	0.048 (4)	0.002 (3)	0.005 (3)	0.004 (3)

Geometric parameters (Å, º) top

Ta1—F4	1.877 (5)	C5—N1	1.384 (9)
Ta1—F5	1.886 (5)	C5—C5ⁱ	1.455 (13)
Ta1—F1	1.886 (5)	N1—C4	1.374 (11)
Ta1—O1	1.8924 (3)	N1—H1A	0.8600
Ta1—F3	1.895 (4)	C4—C3	1.366 (13)
Ta1—F2	1.905 (4)	C4—H4A	0.9300
C2—C1	1.340 (9)	C3—H3A	0.9300
C2—C3	1.381 (12)	O1—Ta1ⁱⁱ	1.8924 (3)
C2—H2A	0.9300	C6—C6ⁱ	1.488 (14)
C1—C5	1.361 (8)	C6—H6A	0.9700
C1—C6	1.490 (8)	C6—H6B	0.9700

F4—Ta1—F5	89.5 (3)	C5—C1—C6	117.8 (5)
F4—Ta1—F1	176.8 (3)	C1—C5—N1	119.1 (6)
F5—Ta1—F1	89.3 (3)	C1—C5—C5ⁱ	119.0 (4)
F4—Ta1—O1	92.1 (2)	N1—C5—C5ⁱ	122.0 (5)
F5—Ta1—O1	93.55 (17)	C4—N1—C5	118.9 (8)
F1—Ta1—O1	91.0 (2)	C4—N1—H1A	120.5
F4—Ta1—F3	90.7 (3)	C5—N1—H1A	120.5
F5—Ta1—F3	175.8 (2)	C3—C4—N1	121.6 (8)
F1—Ta1—F3	90.2 (3)	C3—C4—H4A	119.2
O1—Ta1—F3	90.60 (15)	N1—C4—H4A	119.2
F4—Ta1—F2	88.9 (3)	C4—C3—C2	118.1 (7)
F5—Ta1—F2	88.1 (2)	C4—C3—H3A	121.0
F1—Ta1—F2	88.1 (3)	C2—C3—H3A	121.0
O1—Ta1—F2	178.07 (15)	Ta1ⁱⁱ—O1—Ta1	180.00 (2)
F3—Ta1—F2	87.7 (2)	C1—C6—C6ⁱ	108.2 (5)
C1—C2—C3	120.8 (7)	C1—C6—H6A	110.1
C1—C2—H2A	119.6	C6ⁱ—C6—H6A	110.1
C3—C2—H2A	119.6	C1—C6—H6B	110.1
C2—C1—C5	121.5 (6)	C6ⁱ—C6—H6B	110.1
C2—C1—C6	120.7 (6)	H6A—C6—H6B	108.4

C3—C2—C1—C5	0.4 (11)	C5ⁱ—C5—N1—C4	179.8 (8)
C3—C2—C1—C6	−179.6 (7)	C5—N1—C4—C3	−1.0 (13)
C2—C1—C5—N1	−0.4 (10)	N1—C4—C3—C2	1.0 (14)
C6—C1—C5—N1	179.6 (6)	C1—C2—C3—C4	−0.7 (13)
C2—C1—C5—C5ⁱ	−179.6 (8)	C2—C1—C6—C6ⁱ	138.0 (7)
C6—C1—C5—C5ⁱ	0.4 (10)	C5—C1—C6—C6ⁱ	−42.0 (9)
C1—C5—N1—C4	0.7 (11)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F4ⁱⁱⁱ	0.86	2.45	3.114 (10)	135
C4—H4A···F1^iv	0.93	2.26	3.066 (9)	145
C6—H6A···F3^v	0.97	2.28	3.219 (8)	163
C6—H6B···F5^vi	0.97	2.45	3.268 (9)	142

Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x+1/2, y+1/2, z+1; (v) −x+1, −y, −z+1; (vi) −x+3/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₂N₂)[Ta₂F₁₀O]
M_r	752.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	13.536 (2), 11.3031 (17), 11.5316 (17)
β (°)	90.093 (2)
V (Å³)	1764.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	12.50
Crystal size (mm)	0.21 × 0.20 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.179, 0.225
No. of measured, independent and observed [I > 2σ(I)] reflections	4738, 1725, 1573
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.072, 1.05
No. of reflections	1725
No. of parameters	124
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0278P)² + 20.5568P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.96, −1.14

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ta1—F4	1.877 (5)	Ta1—O1	1.8924 (3)
Ta1—F5	1.886 (5)	Ta1—F3	1.895 (4)
Ta1—F1	1.886 (5)	Ta1—F2	1.905 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F4ⁱ	0.86	2.45	3.114 (10)	134.5
C4—H4A···F1ⁱⁱ	0.93	2.26	3.066 (9)	145.0
C6—H6A···F3ⁱⁱⁱ	0.97	2.28	3.219 (8)	162.8
C6—H6B···F5^iv	0.97	2.45	3.268 (9)	141.7

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

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hagerman, M. E. & Poeppelmeier, K. R. (1995). Chem. Mater. 7, 602–621. CrossRef CAS Web of Science Google Scholar
Halasyamani, P. S. & Poeppelmeier, K. R. (1998). Chem. Mater. 10, 2753–2769. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Welk, M. E., Norquist, A. J., Arnold, F. P., Stern, C. L. & Poeppelmeier, K. R. (2002). Inorg. Chem. 41, 5119–5125. Web of Science CSD CrossRef PubMed CAS Google Scholar

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5,6-Di­hydro-1,10-phenanthroline-1,10-diium μ-oxido-bis­­[penta­fluoridotantalate(V)]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

5,6-Dihydro-1,10-phenanthroline-1,10-diium μ-oxido-bis[pentafluoridotantalate(V)]