metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 TaV 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[Hagerman, M. E. & Poeppelmeier, K. R. (1995). Chem. Mater. 7, 602-621.]); Halasyamani & Poeppelmeier (1998[Halasyamani, P. S. & Poeppelmeier, K. R. (1998). Chem. Mater. 10, 2753-2769.]); Welk et al. (2002[Welk, M. E., Norquist, A. J., Arnold, F. P., Stern, C. L. & Poeppelmeier, K. R. (2002). Inorg. Chem. 41, 5119-5125.]).

[Scheme 1]

Experimental

Crystal data
  • (C12H12N2)[Ta2F10O]

  • Mr = 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[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.179, Tmax = 0.225

  • 4738 measured reflections

  • 1725 independent reflections

  • 1573 reflections with I > 2σ(I)

  • Rint = 0.029

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.072

  • S = 1.05

  • 1725 reflections

  • 124 parameters

  • H-atom parameters constrained

  • Δρmax = 1.96 e Å−3

  • Δρmin = −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 DA 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⋯F5iv 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[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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 TaV 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 (40wt%) (7.4 mmol) and heated to 453 K for 4 hours. After it was cooled, the solution was added into 0.90 mL H3PO4 (85wt%), 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.

Refinement top

The H atoms bonded to C and N were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for H atoms bound to sp2 C atoms, and 0.97 Å for H atoms bound to sp3 C atoms, and with N—H = 0.86 Å, and with Uiso(H) = 1.2 (1.5) times Ueq(C), and Uiso(H) = 1.2 times Ueq(N), respectively. The highest and lowest remaining electron density was located 0.84 Å and 0.72 Å from atom Ta1.

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
[Figure 1] 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].
[Figure 2] Fig. 2. Crystal packing viewed along the c axis. Hydrogen bonding interactions are shown as dashed lines.
[Figure 3] 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
Mr = 752.14Dx = 2.831 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3156 reflections
a = 13.536 (2) Åθ = 2.4–28.3°
b = 11.3031 (17) ŵ = 12.50 mm1
c = 11.5316 (17) ÅT = 296 K
β = 90.093 (2)°Block, yellow
V = 1764.4 (5) Å30.21 × 0.20 × 0.17 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
1725 independent reflections
Radiation source: fine-focus sealed tube1573 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ϕ and ω scansθmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1316
Tmin = 0.179, Tmax = 0.225k = 1313
4738 measured reflectionsl = 1412
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0278P)2 + 20.5568P]
where P = (Fo2 + 2Fc2)/3
1725 reflections(Δ/σ)max < 0.001
124 parametersΔρmax = 1.96 e Å3
0 restraintsΔρmin = 1.14 e Å3
Crystal data top
(C12H12N2)[Ta2F10O]V = 1764.4 (5) Å3
Mr = 752.14Z = 4
Monoclinic, C2/cMo Kα radiation
a = 13.536 (2) ŵ = 12.50 mm1
b = 11.3031 (17) ÅT = 296 K
c = 11.5316 (17) Å0.21 × 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)
Tmin = 0.179, Tmax = 0.225Rint = 0.029
4738 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0278P)2 + 20.5568P]
where P = (Fo2 + 2Fc2)/3
1725 reflectionsΔρmax = 1.96 e Å3
124 parametersΔρmin = 1.14 e Å3
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
xyzUiso*/Ueq
Ta10.193168 (19)0.18732 (2)0.13666 (2)0.03630 (12)
C20.9169 (6)0.2166 (8)0.9660 (7)0.0499 (19)
H2A0.91230.14481.00500.060*
C10.9649 (4)0.2220 (5)0.8646 (5)0.0210 (10)
C50.9738 (5)0.3254 (5)0.8051 (5)0.0332 (13)
N10.9318 (6)0.4270 (7)0.8502 (7)0.069 (2)
H1A0.93610.49310.81360.083*
C40.8832 (7)0.4207 (9)0.9546 (7)0.062 (2)
H4A0.85580.48900.98580.075*
C30.8742 (7)0.3164 (9)1.0135 (7)0.060 (2)
H3A0.84030.31271.08340.072*
F10.2944 (5)0.0732 (6)0.1479 (5)0.093 (2)
F20.1355 (4)0.1192 (5)0.2716 (4)0.0684 (14)
F30.1159 (4)0.0811 (4)0.0475 (4)0.0692 (15)
F40.0908 (5)0.2992 (5)0.1343 (7)0.0867 (19)
F50.2665 (4)0.2877 (5)0.2351 (5)0.0720 (15)
O10.25000.25000.00000.082 (3)
C61.0104 (5)0.1139 (6)0.8134 (6)0.0408 (15)
H6A0.98270.04360.84900.049*
H6B1.08110.11410.82700.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ta10.03744 (18)0.03940 (18)0.03206 (18)0.00695 (11)0.00427 (11)0.00056 (11)
C20.047 (4)0.069 (5)0.033 (4)0.008 (4)0.001 (3)0.012 (4)
C10.023 (3)0.023 (2)0.016 (2)0.001 (2)0.004 (2)0.002 (2)
C50.039 (3)0.032 (3)0.028 (3)0.000 (3)0.001 (3)0.004 (2)
N10.087 (5)0.062 (5)0.059 (4)0.015 (4)0.000 (4)0.007 (4)
C40.069 (6)0.076 (6)0.042 (4)0.016 (5)0.015 (4)0.022 (4)
C30.056 (5)0.099 (7)0.025 (4)0.003 (4)0.013 (3)0.012 (4)
F10.094 (4)0.117 (5)0.066 (3)0.058 (4)0.006 (3)0.024 (3)
F20.097 (4)0.066 (3)0.042 (3)0.019 (3)0.024 (3)0.005 (2)
F30.095 (4)0.065 (3)0.048 (3)0.038 (3)0.010 (3)0.002 (2)
F40.070 (4)0.061 (3)0.128 (6)0.017 (3)0.009 (4)0.007 (3)
F50.071 (3)0.082 (4)0.063 (3)0.031 (3)0.001 (3)0.023 (3)
O10.106 (8)0.095 (7)0.045 (5)0.054 (6)0.018 (5)0.008 (5)
C60.043 (4)0.031 (3)0.048 (4)0.002 (3)0.005 (3)0.004 (3)
Geometric parameters (Å, º) top
Ta1—F41.877 (5)C5—N11.384 (9)
Ta1—F51.886 (5)C5—C5i1.455 (13)
Ta1—F11.886 (5)N1—C41.374 (11)
Ta1—O11.8924 (3)N1—H1A0.8600
Ta1—F31.895 (4)C4—C31.366 (13)
Ta1—F21.905 (4)C4—H4A0.9300
C2—C11.340 (9)C3—H3A0.9300
C2—C31.381 (12)O1—Ta1ii1.8924 (3)
C2—H2A0.9300C6—C6i1.488 (14)
C1—C51.361 (8)C6—H6A0.9700
C1—C61.490 (8)C6—H6B0.9700
F4—Ta1—F589.5 (3)C5—C1—C6117.8 (5)
F4—Ta1—F1176.8 (3)C1—C5—N1119.1 (6)
F5—Ta1—F189.3 (3)C1—C5—C5i119.0 (4)
F4—Ta1—O192.1 (2)N1—C5—C5i122.0 (5)
F5—Ta1—O193.55 (17)C4—N1—C5118.9 (8)
F1—Ta1—O191.0 (2)C4—N1—H1A120.5
F4—Ta1—F390.7 (3)C5—N1—H1A120.5
F5—Ta1—F3175.8 (2)C3—C4—N1121.6 (8)
F1—Ta1—F390.2 (3)C3—C4—H4A119.2
O1—Ta1—F390.60 (15)N1—C4—H4A119.2
F4—Ta1—F288.9 (3)C4—C3—C2118.1 (7)
F5—Ta1—F288.1 (2)C4—C3—H3A121.0
F1—Ta1—F288.1 (3)C2—C3—H3A121.0
O1—Ta1—F2178.07 (15)Ta1ii—O1—Ta1180.00 (2)
F3—Ta1—F287.7 (2)C1—C6—C6i108.2 (5)
C1—C2—C3120.8 (7)C1—C6—H6A110.1
C1—C2—H2A119.6C6i—C6—H6A110.1
C3—C2—H2A119.6C1—C6—H6B110.1
C2—C1—C5121.5 (6)C6i—C6—H6B110.1
C2—C1—C6120.7 (6)H6A—C6—H6B108.4
C3—C2—C1—C50.4 (11)C5i—C5—N1—C4179.8 (8)
C3—C2—C1—C6179.6 (7)C5—N1—C4—C31.0 (13)
C2—C1—C5—N10.4 (10)N1—C4—C3—C21.0 (14)
C6—C1—C5—N1179.6 (6)C1—C2—C3—C40.7 (13)
C2—C1—C5—C5i179.6 (8)C2—C1—C6—C6i138.0 (7)
C6—C1—C5—C5i0.4 (10)C5—C1—C6—C6i42.0 (9)
C1—C5—N1—C40.7 (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···AD—HH···AD···AD—H···A
N1—H1A···F4iii0.862.453.114 (10)135
C4—H4A···F1iv0.932.263.066 (9)145
C6—H6A···F3v0.972.283.219 (8)163
C6—H6B···F5vi0.972.453.268 (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]
Mr752.14
Crystal system, space groupMonoclinic, C2/c
Temperature (K)296
a, b, c (Å)13.536 (2), 11.3031 (17), 11.5316 (17)
β (°) 90.093 (2)
V3)1764.4 (5)
Z4
Radiation typeMo Kα
µ (mm1)12.50
Crystal size (mm)0.21 × 0.20 × 0.17
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.179, 0.225
No. of measured, independent and
observed [I > 2σ(I)] reflections
4738, 1725, 1573
Rint0.029
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.072, 1.05
No. of reflections1725
No. of parameters124
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0278P)2 + 20.5568P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)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—F41.877 (5)Ta1—O11.8924 (3)
Ta1—F51.886 (5)Ta1—F31.895 (4)
Ta1—F11.886 (5)Ta1—F21.905 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···F4i0.862.453.114 (10)134.5
C4—H4A···F1ii0.932.263.066 (9)145.0
C6—H6A···F3iii0.972.283.219 (8)162.8
C6—H6B···F5iv0.972.453.268 (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

First citationBruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationHagerman, M. E. & Poeppelmeier, K. R. (1995). Chem. Mater. 7, 602–621.  CrossRef CAS Web of Science
First citationHalasyamani, P. S. & Poeppelmeier, K. R. (1998). Chem. Mater. 10, 2753–2769.  Web of Science CrossRef CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWelk, 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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds