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ISSN: 2056-9890

Crystal structure and electrochemical properties of [Ni(bztmpen)(CH3CN)](BF4)2 {bztmpen is N-benzyl-N,N′,N′-tris­­[(6-methyl­pyridin-2-yl)meth­yl]ethane-1,2-di­amine}

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aScience and Technology on Surface Physics and Chemistry Laboratory, Jiangyou 621908, People's Republic of China, and bInstitute of Materials, China Academy of Engineering Physics, Jiangyou 621908, People's Republic of China
*Correspondence e-mail: chenlin101101@aliyun.com

Edited by A. Van der Lee, Université de Montpellier II, France (Received 20 April 2017; accepted 5 May 2017; online 9 May 2017)

The mononuclear nickel title complex (acetonitrile-κN){N-benzyl-N,N′,N′-tris­[(6-methyl­pyridin-2-yl)meth­yl]ethane-1,2-di­amine}­nickel(II) bis­(tetra­fluor­ido­borate), [Ni(C30H35N5)(CH3CN)](BF4)2, was prepared from the reaction of Ni(BF4)2·6H2O with N-benzyl-N,N′,N′-tris­[(6-methyl­pyridin-2-yl)meth­yl]ethane-1,2-di­amine (bztmpen) in aceto­nitrile at room temperature. With an open site occupied by the aceto­nitrile mol­ecule, the nickel(II) atom is chelated by five N-atom sites from the ligand and one N atom from the ligand, showing an overall octa­hedral coordination environment. Compared with analogues where the 6–methyl substituent is absent, the bond length around the Ni2+ cation are evidently longer. Upon reductive dissociation of the acetro­nitrile mol­ecule, the title complex has an open site for a catalytic reaction. The title complex has two redox couples at −1.50 and −1.80 V (versus Fc+/0) based on nickel. The F atoms of the two BF4 counter-anions are split into two groups and the occupancy ratios refined to 0.611 (18):0.389 (18) and 0.71 (2):0.29 (2).

1. Chemical context

Nickel complexes with polypyridine–amine ligands are of great inter­est in catalytic reactions. For example, nickel complexes containing N5-penta­dentate ligands with different amine-to-pyridine ratios have been studied for electrochemical H2 production in water at pH = 7 and the complex with a di­amine–tri­pyridine ligand displays a TON (turn-over number) of up to 308000 over 60 h electrolysis at −1.25 V vs the standard hydrogen electrode (SHE), with a Faradaic efficiency of 91% (Zhang et al., 2014[Zhang, P.-L., Wang, M., Yang, Y., Zheng, D. H., Han, K. & Sun, L.-C. (2014). Chem. Commun. 50, 14153-14156.]). The nickel-based complex Ni–PY5 {PY5 = 2,6-bis­[1,1-bis­(2-pyrid­yl)eth­yl]pyridine} has been found to act as an electro-catalyst for oxidizing water to di­oxy­gen in aqueous phosphate buffer solutions (Wang et al., 2016[Wang, L., Duan, L. L., Ambre, R. B., Daniel, Q., Chen, H., Sun, J. L., Das, B., Thapper, A., Uhlig, J., Dinér, P. & Sun, L. C. (2016). J. Catal. 335, 72-78.]). The rate of water oxidation catalyzed by the Ni–PY5 complex is enhanced remarkably by the proton-acceptor base HPO42−, with a rate constant of 1820 M−1 s−1. A stable configuration is important for the stability of a catalyst. In the title complex, the Ni2+ cation is chelated by five N-atom sites, so the configuration is stable. With the reductive dissociation of aceto­nitrile, the title complex would give an open site for a catalytic reaction. Herein, we describe the crystal structure and electrochemical properties of the title complex.

[Scheme 1]

2. Structural commentary

In the title complex (Fig. 1[link]), the coordination sphere of the nickel(II) atom adopts a normal octa­hedral geometry. The Ni2+ cation lies almost in the equatorial plane. One pyridine nitro­gen atom (N1) and two amino nitro­gen atoms (N2, N3) as well as the nitrogen atom of an acetonitrile ligand (N4) form the equatorial plane. The latter can easily be dissociated from nickel. The axial positions are occupied by two pyridine nitro­gen atoms (N5, N6). The Ni—N bond lengths for the two axial pyridine–nitro­gen atoms [Ni—N5 = 2.209 (3) and Ni—N6 = 2.187 (3) Å] are significantly longer than that for the other four nitro­gen atoms [Ni—N1 = 2.151 (3), Ni—N2 = 2.082 (3), Ni—N3 = 2.188 (2), Ni—N4 = 2.061 (3) Å]. The presence of the 6-methyl substit­uent hinders the approach of the pyridine group to the Ni2+ core. A a result of the steric hindrance from the methyl substituent, the three atoms N5, Ni1 and N6 are not completely linear in the axial direction, with a contact angle of 170.89 (9)°. Two intra­molecular C—H⋯N contacts occur (Table 1[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1C⋯N4 0.96 2.94 3.251 (6) 100
C3—H3A⋯F8i 0.93 2.57 3.457 (14) 159
C8—H8B⋯F7 0.97 2.57 3.371 (13) 140
C8—H8B⋯F5A 0.97 2.42 3.36 (4) 163
C9—H9B⋯F4ii 0.97 2.61 3.291 (16) 128
C10—H10A⋯N6 0.97 2.67 3.273 (5) 1213
C12—H12A⋯F8Aiii 0.93 2.53 3.35 (2) 146
C17—H17B⋯N1 0.96 2.64 3.071 (7) 108
C21—H21A⋯F3ii 0.93 2.62 3.122 (10) 114
C23—H23B⋯F6Aiii 0.97 2.33 3.241 (16) 157
C24—H24A⋯F7 0.97 2.53 3.443 (15) 156
C24—H24B⋯F3iv 0.97 2.32 3.179 (13) 148
C24—H24B⋯F1Aiv 0.97 2.54 3.43 (3) 153
C28—H28A⋯F4iii 0.93 2.59 3.345 (19) 138
C30—H30A⋯F4iii 0.96 2.60 3.390 (17) 140
C30—H30A⋯F4Aiii 0.96 2.50 3.26 (3) 136
C30—H30B⋯N4 0.96 2.85 3.126 (6) 98
C32—H32A⋯F6iii 0.96 2.40 3.196 (14) 140
C32—H32A⋯F7Aiii 0.96 2.33 3.19 (3) 150
C32—H32B⋯F3v 0.96 2.55 3.145 (15) 121
C32—H32B⋯F3Av 0.96 2.32 3.11 (4) 140
Symmetry codes: (i) [x+{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) [x+1, -y, z+{\script{1\over 2}}]; (iii) x+1, y, z; (iv) [x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]; (v) [x+{\script{3\over 2}}, y-{\script{1\over 2}}, z].
[Figure 1]
Figure 1
The structures of the molecular components in the title compound, showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity.

3. Electrochemical commentary

Generally, the reduction of a metal complex is accompanied by the dissociation of the ligand, or the weakest ligand if more than one ligand is present, which could induce the appearance of an open site for a catalytic reaction (Knoll et al., 2014[Knoll, J.-D., Albani, B. A., Durr, C. B. & Turro, C. (2014). J. Phys. Chem. A, 118, 10603-10610.]; Johnson et al., 2016[Johnson, B. A., Maji, S., Agarwala, H., White, T. A., Mijangos, E. & Ott, S. (2016). Angew. Chem. Int. Ed. 55, 1825-1829.]). The introduction of o-methyl in the title complex is in favor of the dissociation of aceto­nitrile. On the cathodic scan under Ar, the title complex features one reversible couple at −1.50 V and one half-reversible couple at −1.80 V (vs Fc+/0) based on nickel, assigned to NiII/I and NiI/0 respectively (Fig. 2[link]). The third couple at −2.15 V could be assigned to the reduction of pyridine. The free ligand bztmpen itself is electrochemically silent in the potential range (Fig. 3[link]). The coordination with nickel leads to a positive shift of the reduction on pyridine. The good reversibility of the couple indicates a negligible change in the configuration of the title complex after one electron reduction. The second reduction might result in a change of the configuration. Analogues in the absence of o-methyl show only one redox couple more negative than −1.50 V (vs Fc+/0; Zhang et al., 2014[Zhang, P.-L., Wang, M., Yang, Y., Zheng, D. H., Han, K. & Sun, L.-C. (2014). Chem. Commun. 50, 14153-14156.]). The positive shift of the first redox couple for the title complex results from the weaker electron-donating ability of the pyridine ligands, which are farther from the nickel core. The electrochemical properties of these analogues are consistent with the differences shown in the structure.

[Figure 2]
Figure 2
Cyclic voltammograms of the title complex (1 mM) with a varied scan range under Ar in CH3CN with 0.1 M nBu4NBF4 as the supporting electrolyte.
[Figure 3]
Figure 3
Cyclic voltammograms of ligand bztmpen (1 mM) under Ar in CH3CN with 0.1 M nBu4NBF4 as the supporting electrolyte.

4. Supra­molecular features

In the title crystal, no classical hydrogen bonds have been found. Weak C—H⋯F contacts (Table 1[link]) link the components into a three-dimensional network. The crytal paacking is illustrated in Fig. 4[link].

[Figure 4]
Figure 4
Packing plot of the mol­ecular components in the title compound viewed down the a axis. C—H⋯F weak bonds are shown as dotted lines.

5. Database survey

There are three published nickel complexes with poly-pyridine groups (Shi et al., 2015[Shi, W. D., Zheng, D. H. & Wang, M. (2015). Chin. J. Inorg. Chem. 31, 2205-2212.]; Zhang et al., 2014[Zhang, P.-L., Wang, M., Yang, Y., Zheng, D. H., Han, K. & Sun, L.-C. (2014). Chem. Commun. 50, 14153-14156.]; Wang et al., 2016[Wang, L., Duan, L. L., Ambre, R. B., Daniel, Q., Chen, H., Sun, J. L., Das, B., Thapper, A., Uhlig, J., Dinér, P. & Sun, L. C. (2016). J. Catal. 335, 72-78.]), but to the best of our knowledge, the title compound has not been reported previously. The nickel complex with N,N,N′,N′-tetra­(2-pyridyl­meth­yl)ethyl­enedi­amine (tpen) adopts a normal octa­hedral geometry (Shi et al., 2015[Shi, W. D., Zheng, D. H. & Wang, M. (2015). Chin. J. Inorg. Chem. 31, 2205-2212.]). In the Ni2+(tpen) complex, the Ni—N1, Ni—N2, Ni—N3, Ni—N4, Ni—N5 and Ni—N6 bonds [2.106 (3), 2.099 (3), 2.114 (3), 2.086 (3), 2.094 (3) and 2.120 (2) Å, respectively] are shorter than the corresponding bond lengths in the title complex. Among the earliest reports, the nickel complex with N-benzyl-N,N′,N′-tris­(2-pyridyl­meth­yl)ethyl­enedi­amine (bztpen) ligand is most similar to the title complex (Zhang et al., 2014[Zhang, P.-L., Wang, M., Yang, Y., Zheng, D. H., Han, K. & Sun, L.-C. (2014). Chem. Commun. 50, 14153-14156.]). Under reductive conditions, Ni2+(bztpen) displays a high activity on electro-catalytic water reduction. The title complex possesses a higher steric hindrance than Ni2+(bztpen), which affects evidently the bond lengths, especially in the axial direction. The bonds lengths in the title complex [Ni—N5 = 2.209 (3), Ni—N6 = 2.187 (3) Å] are longer than those in Ni2+(bztpen) [Ni—N5 = 2.149 (3), Ni—N6 = 2.096 (3) Å]. The nickel complex with a PY5 ligand {PY5 = 2,6-bis­[1,1-bis­(2-pyrid­yl)eth­yl]pyridine} displays a similar configuration to the title complex, but the labile ligand is at the axial site (Wang et al., 2016[Wang, L., Duan, L. L., Ambre, R. B., Daniel, Q., Chen, H., Sun, J. L., Das, B., Thapper, A., Uhlig, J., Dinér, P. & Sun, L. C. (2016). J. Catal. 335, 72-78.]). Ni2+(PY5) has been found to act as an electro-catalyst for oxidizing water to di­oxy­gen in an aqueous phosphate buffer solution.

6. Synthesis and crystallization

The tri­pyridine-di­amine ligand N-benzyl-N,N′,N′-tris­[(6-methyl­pyridin-2-yl)meth­yl]ethane-1,2-di­amine (bztmpen) was prepared according to literature procedures (Zhang et al., 2013[Zhang, P.-L., Wang, M., Gloaguen, F., Chen, L., Quentel, F. & Sun, L.-C. (2013). Chem. Commun. 49, 9455-9457.]), 1H NMR (CDCl3, 600 MHz): δ 7.44 (m, 4H), 7.25 (m, 6H), 6.96 (m, 4H), 3.74 (s, 6H), 3.58 (s, 2H), 2.75 (d, 4H), 2.49 (s, 9H). ESI–MS: calculated for [M + H]+: m/z 466.63; found: 466.27.

Preparation of [Ni(bztmpen)(CH3CN)](BF4)2. Compound Ni(BF4)2·6H2O (0.16 g, 0.5 mmol) was added to an aceto­nitrile solution (5 mL) of bztmpen (0.2 g, 0.5 mmol). The mixture was stirred at room temperature for 6 h. The purple solution was then transferred to tubes, which were placed in a flask containing ether. Block-shaped blue crystals were obtained in a yield of 85% (0.25 g). Analysis calculated for C32H38B2F8N6Ni (%): C, 50.01; H, 5.18; N, 11.37; found: 50.01; H, 5.19; N, 11.36; MS (TOF–ES): m/z = 282.6341 {[M−2BF4]/2}+, 599.3015 [M – 2BF4 + Cl]+.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. The F atoms of the two BF4 counter-anions were split into two groups and the occupancies refined to 0.611 (18)/0.389 (18) and 0.71 (2)/0.29 (2). The hydrogen atoms were refined in a riding mode with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(C).

Table 2
Experimental details

Crystal data
Chemical formula [Ni(C30H35N5)(C2H3N)](BF4)2
Mr 739.01
Crystal system, space group Monoclinic, Cc
Temperature (K) 298
a, b, c (Å) 11.230 (3), 17.204 (5), 18.110 (6)
β (°) 103.248 (7)
V3) 3405.7 (18)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.65
Crystal size (mm) 0.30 × 0.20 × 0.10
 
Data collection
Diffractometer Bruker SMART CCD area detector
Absorption correction Multi-scan (SADABS; Bruker, 2016[Bruker (2016). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.847, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections 14710, 6476, 6304
Rint 0.032
(sin θ/λ)max−1) 0.668
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.092, 1.03
No. of reflections 6476
No. of parameters 520
No. of restraints 2
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.29, −0.25
Absolute structure Classical Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) method preferred over Parsons because s.u. lower.
Absolute structure parameter −0.017 (12)
Computer programs: SMART and SAINT (Bruker, 2016[Bruker (2016). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and SHELXL2016 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

Supporting information


Computing details top

Data collection: SMART (Bruker, 2016); cell refinement: SMART (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(Acetonitrile-κN){N-benzyl-N,N',N'-Tris[(6-methylpyridin-2-yl)methyl]ethane-1,2-diamine}nickel(II) bis(tetrafluoridoborate) top
Crystal data top
[Ni(C30H35N5)(C2H3N)](BF4)2F(000) = 1528
Mr = 739.01Dx = 1.441 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
a = 11.230 (3) ÅCell parameters from 8509 reflections
b = 17.204 (5) Åθ = 2.3–28.4°
c = 18.110 (6) ŵ = 0.65 mm1
β = 103.248 (7)°T = 298 K
V = 3405.7 (18) Å3Block, blue
Z = 40.30 × 0.20 × 0.10 mm
Data collection top
Bruker SMART CCD area detector
diffractometer
6304 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.032
phi and ω scansθmax = 28.4°, θmin = 3.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2016)
h = 1411
Tmin = 0.847, Tmax = 0.955k = 2222
14710 measured reflectionsl = 2424
6476 independent reflections
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.060P)2 + 1.7104P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.035(Δ/σ)max = 0.001
wR(F2) = 0.092Δρmax = 0.29 e Å3
S = 1.03Δρmin = 0.25 e Å3
6476 reflectionsExtinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
520 parametersExtinction coefficient: 0.0091 (17)
2 restraintsAbsolute structure: Classical Flack method preferred over Parsons because s.u. lower.
Hydrogen site location: mixedAbsolute structure parameter: 0.017 (12)
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*/UeqOcc. (<1)
Ni10.73459 (2)0.19011 (2)0.24468 (2)0.02752 (12)
N10.6542 (3)0.29110 (15)0.18272 (14)0.0333 (5)
N20.5812 (3)0.20749 (17)0.28899 (14)0.0331 (5)
N30.7742 (3)0.09858 (14)0.33073 (13)0.0325 (5)
N40.8969 (3)0.17465 (19)0.21169 (18)0.0395 (6)
N50.8531 (3)0.25827 (15)0.33616 (14)0.0361 (5)
N60.6119 (2)0.11087 (13)0.16863 (13)0.0303 (5)
C10.7455 (4)0.2798 (2)0.0724 (2)0.0515 (9)
H1A0.7279640.2990780.0213140.077*
H1B0.8306870.2871600.0952480.077*
H1C0.7261210.2254250.0720110.077*
C20.6698 (3)0.32319 (17)0.11726 (17)0.0354 (6)
C30.6181 (4)0.3937 (2)0.0906 (2)0.0460 (8)
H3A0.6318920.4147160.0459750.055*
C40.5459 (4)0.4324 (2)0.1306 (3)0.0599 (10)
H4A0.5103110.4798250.1132950.072*
C50.5270 (5)0.3999 (2)0.1971 (3)0.0569 (10)
H5A0.4783340.4250110.2249610.068*
C60.5816 (3)0.32968 (18)0.22115 (19)0.0382 (6)
C70.5658 (4)0.29254 (19)0.29387 (19)0.0421 (7)
H7A0.4850060.3041990.3016340.051*
H7B0.6260110.3131710.3365240.051*
C80.6011 (3)0.1684 (2)0.36392 (17)0.0405 (7)
H8A0.6538120.2000030.4023420.049*
H8B0.5235440.1616370.3781520.049*
C90.6601 (3)0.08985 (19)0.35846 (17)0.0379 (6)
H9A0.6031900.0566300.3240160.046*
H9B0.6789160.0652850.4079930.046*
C100.8122 (4)0.02283 (16)0.30210 (16)0.0376 (6)
H10A0.7478530.0065130.2594920.045*
H10B0.8846500.0323040.2827920.045*
C110.8397 (3)0.04463 (17)0.35776 (17)0.0387 (6)
C120.9533 (4)0.0523 (2)0.4080 (2)0.0506 (8)
H12A1.0118550.0135460.4106910.061*
C130.9795 (5)0.1177 (3)0.4540 (2)0.0639 (12)
H13A1.0558170.1221760.4871390.077*
C140.8960 (6)0.1749 (3)0.4515 (3)0.0665 (15)
H14A0.9150010.2183240.4825370.080*
C150.7850 (7)0.1685 (3)0.4038 (4)0.0741 (17)
H15A0.7273250.2075990.4023220.089*
C160.7555 (5)0.1034 (2)0.3562 (3)0.0588 (10)
H16A0.6786910.0999060.3234330.071*
C170.8769 (5)0.3819 (2)0.2717 (2)0.0618 (11)
H17A0.9473320.4152220.2794140.093*
H17B0.8770060.3475130.2299950.093*
H17C0.8039890.4129990.2606170.093*
C180.8809 (4)0.3350 (2)0.3424 (2)0.0462 (7)
C190.9179 (5)0.3706 (2)0.4121 (3)0.0648 (12)
H19A0.9359340.4234350.4149150.078*
C200.9283 (6)0.3275 (3)0.4778 (3)0.0703 (14)
H20A0.9465990.3516250.5250120.084*
C210.9112 (4)0.2481 (2)0.4721 (2)0.0530 (9)
H21A0.9231360.2171950.5152920.064*
C220.8758 (3)0.21540 (18)0.40064 (17)0.0374 (6)
C230.8742 (3)0.12851 (18)0.39211 (17)0.0391 (6)
H23A0.8669180.1052720.4396830.047*
H23B0.9517440.1119910.3823790.047*
C240.4730 (3)0.1755 (2)0.23570 (19)0.0376 (6)
H24A0.4160270.1563550.2644460.045*
H24B0.4327390.2170510.2031760.045*
C250.5017 (3)0.11045 (16)0.18656 (15)0.0328 (5)
C260.4120 (4)0.0560 (2)0.1587 (2)0.0485 (8)
H26A0.3385110.0560830.1740920.058*
C270.4340 (4)0.0012 (2)0.1072 (3)0.0581 (10)
H27A0.3749680.0357660.0871760.070*
C280.5429 (4)0.00225 (18)0.0866 (2)0.0481 (8)
H28A0.5578830.0336260.0513380.058*
C290.6327 (3)0.05676 (16)0.11773 (16)0.0356 (6)
C300.7518 (4)0.0552 (2)0.0947 (2)0.0522 (9)
H30A0.7494430.0157460.0568180.078*
H30B0.7662660.1048500.0742270.078*
H30C0.8164920.0438360.1380650.078*
C310.9942 (4)0.1705 (3)0.2068 (2)0.0524 (9)
C321.1190 (6)0.1620 (6)0.1991 (5)0.116 (3)
H32A1.1511320.1126480.2190800.139*
H32B1.1211020.1652180.1464500.139*
H32C1.1676030.2030080.2266700.139*
B10.2984 (7)0.1828 (4)0.0952 (4)0.0668 (16)
B20.2397 (7)0.0699 (4)0.3807 (4)0.0734 (15)
F10.2730 (12)0.1428 (8)0.1633 (4)0.118 (4)0.71 (2)
F20.4166 (9)0.1922 (5)0.0757 (8)0.124 (5)0.71 (2)
F30.2264 (10)0.2458 (7)0.1037 (7)0.111 (4)0.71 (2)
F40.275 (2)0.1337 (9)0.0395 (8)0.093 (5)0.71 (2)
F1A0.233 (2)0.181 (2)0.1638 (17)0.138 (11)0.29 (2)
F2A0.411 (3)0.185 (2)0.111 (3)0.21 (2)0.29 (2)
F3A0.287 (4)0.2622 (10)0.067 (2)0.127 (12)0.29 (2)
F4A0.251 (6)0.1297 (18)0.054 (2)0.098 (10)0.29 (2)
F50.205 (2)0.1435 (7)0.3810 (10)0.208 (10)0.611 (18)
F60.1540 (9)0.0300 (7)0.3264 (5)0.122 (4)0.611 (18)
F70.3403 (11)0.0688 (7)0.3563 (10)0.135 (5)0.611 (18)
F80.2472 (17)0.0380 (11)0.4477 (6)0.137 (6)0.611 (18)
F5A0.348 (2)0.105 (3)0.414 (4)0.30 (2)0.389 (18)
F6A0.1583 (13)0.1213 (13)0.3817 (13)0.125 (8)0.389 (18)
F7A0.246 (7)0.0368 (13)0.3222 (13)0.30 (3)0.389 (18)
F8A0.2379 (16)0.0186 (17)0.4387 (13)0.126 (8)0.389 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02251 (17)0.03240 (16)0.02857 (16)0.00093 (15)0.00773 (11)0.00228 (14)
N10.0299 (13)0.0365 (11)0.0343 (11)0.0040 (11)0.0090 (10)0.0032 (9)
N20.0284 (14)0.0418 (11)0.0315 (11)0.0022 (12)0.0119 (10)0.0037 (10)
N30.0326 (14)0.0335 (10)0.0312 (10)0.0008 (10)0.0068 (10)0.0013 (9)
N40.0288 (15)0.0488 (13)0.0434 (14)0.0049 (13)0.0132 (12)0.0014 (12)
N50.0320 (13)0.0372 (12)0.0362 (11)0.0008 (11)0.0021 (10)0.0009 (10)
N60.0281 (12)0.0332 (10)0.0294 (10)0.0016 (9)0.0065 (9)0.0017 (8)
C10.066 (3)0.0537 (18)0.0417 (15)0.0160 (18)0.0256 (17)0.0068 (14)
C20.0337 (16)0.0370 (12)0.0347 (13)0.0021 (12)0.0060 (12)0.0009 (11)
C30.044 (2)0.0420 (15)0.0517 (18)0.0067 (15)0.0094 (16)0.0100 (14)
C40.056 (3)0.0379 (16)0.088 (3)0.0169 (17)0.022 (2)0.0129 (17)
C50.059 (3)0.0411 (16)0.078 (3)0.0205 (17)0.031 (2)0.0019 (17)
C60.0331 (16)0.0349 (13)0.0491 (16)0.0040 (12)0.0147 (13)0.0065 (12)
C70.0426 (19)0.0430 (14)0.0469 (16)0.0064 (14)0.0229 (15)0.0086 (13)
C80.0397 (17)0.0529 (16)0.0331 (13)0.0016 (15)0.0171 (13)0.0012 (12)
C90.0375 (16)0.0451 (14)0.0323 (12)0.0035 (13)0.0104 (12)0.0047 (11)
C100.0492 (19)0.0302 (12)0.0334 (12)0.0008 (12)0.0092 (12)0.0013 (10)
C110.0458 (19)0.0350 (12)0.0376 (13)0.0027 (13)0.0143 (13)0.0011 (11)
C120.055 (2)0.0464 (17)0.0496 (17)0.0074 (17)0.0103 (17)0.0017 (14)
C130.076 (3)0.069 (2)0.0478 (18)0.029 (2)0.016 (2)0.0131 (17)
C140.093 (4)0.057 (2)0.060 (2)0.020 (2)0.038 (3)0.0246 (19)
C150.088 (5)0.053 (2)0.091 (4)0.008 (3)0.041 (4)0.021 (3)
C160.059 (3)0.0444 (17)0.074 (2)0.0061 (18)0.016 (2)0.0109 (17)
C170.067 (3)0.0478 (19)0.062 (2)0.025 (2)0.003 (2)0.0082 (16)
C180.0418 (19)0.0396 (14)0.0519 (18)0.0044 (15)0.0004 (15)0.0004 (14)
C190.077 (3)0.0410 (18)0.065 (2)0.011 (2)0.006 (2)0.0104 (17)
C200.094 (4)0.057 (2)0.048 (2)0.011 (3)0.008 (2)0.0191 (17)
C210.062 (3)0.0508 (18)0.0377 (15)0.0027 (18)0.0049 (16)0.0066 (13)
C220.0342 (16)0.0367 (13)0.0366 (13)0.0000 (13)0.0017 (12)0.0033 (11)
C230.0385 (17)0.0373 (13)0.0358 (13)0.0018 (13)0.0031 (12)0.0006 (11)
C240.0218 (14)0.0504 (15)0.0420 (15)0.0030 (12)0.0104 (12)0.0007 (12)
C250.0257 (14)0.0377 (13)0.0330 (12)0.0018 (11)0.0025 (10)0.0031 (10)
C260.0308 (17)0.0517 (17)0.0593 (19)0.0097 (15)0.0027 (15)0.0021 (15)
C270.048 (2)0.0453 (17)0.071 (2)0.0153 (17)0.0058 (18)0.0078 (16)
C280.060 (2)0.0326 (13)0.0449 (16)0.0005 (15)0.0022 (16)0.0093 (12)
C290.0428 (18)0.0313 (12)0.0300 (11)0.0028 (12)0.0030 (12)0.0020 (10)
C300.055 (2)0.0528 (18)0.0553 (19)0.0033 (17)0.0252 (18)0.0177 (16)
C310.038 (2)0.066 (2)0.059 (2)0.0107 (18)0.0219 (17)0.0207 (18)
C320.047 (3)0.176 (7)0.139 (6)0.035 (4)0.050 (4)0.083 (6)
B10.062 (4)0.071 (3)0.062 (3)0.015 (3)0.004 (3)0.014 (2)
B20.081 (4)0.073 (3)0.072 (3)0.004 (3)0.029 (3)0.004 (3)
F10.127 (8)0.174 (9)0.049 (3)0.013 (6)0.014 (3)0.000 (4)
F20.066 (5)0.090 (5)0.181 (10)0.003 (4)0.044 (6)0.009 (5)
F30.106 (6)0.105 (6)0.136 (7)0.057 (5)0.055 (5)0.073 (6)
F40.157 (13)0.077 (5)0.052 (3)0.032 (6)0.036 (6)0.014 (3)
F1A0.069 (12)0.17 (3)0.15 (2)0.006 (12)0.033 (12)0.037 (17)
F2A0.14 (2)0.20 (3)0.34 (5)0.10 (2)0.18 (3)0.16 (3)
F3A0.20 (3)0.060 (6)0.17 (2)0.013 (11)0.14 (2)0.025 (10)
F4A0.135 (19)0.047 (8)0.11 (2)0.006 (9)0.017 (18)0.020 (10)
F50.35 (3)0.080 (6)0.159 (11)0.074 (10)0.018 (14)0.039 (6)
F60.125 (7)0.170 (9)0.071 (4)0.085 (7)0.020 (4)0.029 (4)
F70.098 (7)0.134 (8)0.207 (13)0.026 (5)0.105 (9)0.001 (7)
F80.174 (13)0.183 (13)0.053 (4)0.015 (9)0.025 (5)0.006 (6)
F5A0.087 (14)0.37 (5)0.44 (6)0.09 (2)0.06 (3)0.03 (5)
F6A0.056 (6)0.179 (19)0.151 (13)0.046 (8)0.047 (8)0.033 (12)
F7A0.73 (8)0.102 (13)0.113 (13)0.14 (3)0.18 (3)0.021 (10)
F8A0.061 (7)0.163 (15)0.155 (17)0.008 (8)0.029 (9)0.090 (13)
Geometric parameters (Å, º) top
Ni1—N42.061 (3)C15—H15A0.9300
Ni1—N22.082 (3)C16—H16A0.9300
Ni1—N12.151 (3)C17—C181.505 (5)
Ni1—N62.187 (3)C17—H17A0.9600
Ni1—N32.188 (2)C17—H17B0.9600
Ni1—N52.209 (3)C17—H17C0.9600
N1—C21.355 (4)C18—C191.378 (6)
N1—C61.361 (4)C19—C201.385 (7)
N2—C241.475 (5)C19—H19A0.9300
N2—C71.479 (4)C20—C211.381 (6)
N2—C81.485 (4)C20—H20A0.9300
N3—C231.480 (4)C21—C221.382 (4)
N3—C91.488 (4)C21—H21A0.9300
N3—C101.500 (4)C22—C231.503 (4)
N4—C311.119 (5)C23—H23A0.9700
N5—C221.355 (4)C23—H23B0.9700
N5—C181.356 (4)C24—C251.509 (4)
N6—C251.350 (4)C24—H24A0.9700
N6—C291.367 (3)C24—H24B0.9700
C1—C21.502 (4)C25—C261.384 (5)
C1—H1A0.9600C26—C271.386 (6)
C1—H1B0.9600C26—H26A0.9300
C1—H1C0.9600C27—C281.360 (7)
C2—C31.383 (4)C27—H27A0.9300
C3—C41.377 (5)C28—C291.398 (5)
C3—H3A0.9300C28—H28A0.9300
C4—C51.388 (6)C29—C301.490 (5)
C4—H4A0.9300C30—H30A0.9600
C5—C61.380 (5)C30—H30B0.9600
C5—H5A0.9300C30—H30C0.9600
C6—C71.510 (4)C31—C321.448 (6)
C7—H7A0.9700C32—H32A0.9600
C7—H7B0.9700C32—H32B0.9600
C8—C91.519 (5)C32—H32C0.9598
C8—H8A0.9700B1—F1A1.29 (3)
C8—H8B0.9700B1—F21.303 (12)
C9—H9A0.9700B1—F31.339 (10)
C9—H9B0.9700B1—F4A1.36 (4)
C10—C111.522 (4)B1—F2A1.36 (2)
C10—H10A0.9700B1—F11.384 (11)
C10—H10B0.9700B1—F41.385 (14)
C11—C161.380 (5)B1—F3A1.470 (16)
C11—C121.392 (6)B2—F7A1.219 (16)
C12—C131.391 (5)B2—F6A1.276 (17)
C12—H12A0.9300B2—F71.305 (10)
C13—C141.352 (8)B2—F81.317 (14)
C13—H13A0.9300B2—F51.324 (12)
C14—C151.349 (9)B2—F5A1.36 (3)
C14—H14A0.9300B2—F8A1.38 (2)
C15—C161.405 (7)B2—F61.389 (10)
N4—Ni1—N2174.24 (13)C13—C14—H14A120.2
N4—Ni1—N1104.24 (12)C14—C15—C16120.7 (5)
N2—Ni1—N178.45 (10)C14—C15—H15A119.6
N4—Ni1—N6102.02 (11)C16—C15—H15A119.6
N2—Ni1—N682.81 (10)C11—C16—C15120.5 (5)
N1—Ni1—N692.67 (10)C11—C16—H16A119.8
N4—Ni1—N393.70 (11)C15—C16—H16A119.8
N2—Ni1—N383.11 (10)C18—C17—H17A109.5
N1—Ni1—N3160.94 (9)C18—C17—H17B109.5
N6—Ni1—N389.77 (9)H17A—C17—H17B109.5
N4—Ni1—N582.24 (12)C18—C17—H17C109.5
N2—Ni1—N592.54 (11)H17A—C17—H17C109.5
N1—Ni1—N594.07 (11)H17B—C17—H17C109.5
N6—Ni1—N5170.89 (9)N5—C18—C19121.6 (3)
N3—Ni1—N581.87 (10)N5—C18—C17119.3 (3)
C2—N1—C6117.5 (3)C19—C18—C17119.0 (4)
C2—N1—Ni1131.5 (2)C18—C19—C20119.8 (4)
C6—N1—Ni1110.9 (2)C18—C19—H19A120.1
C24—N2—C7108.6 (3)C20—C19—H19A120.1
C24—N2—C8111.0 (3)C21—C20—C19118.8 (4)
C7—N2—C8112.9 (2)C21—C20—H20A120.6
C24—N2—Ni1108.95 (18)C19—C20—H20A120.6
C7—N2—Ni1106.5 (2)C20—C21—C22118.6 (4)
C8—N2—Ni1108.8 (2)C20—C21—H21A120.7
C23—N3—C9110.2 (2)C22—C21—H21A120.7
C23—N3—C10109.6 (3)N5—C22—C21122.8 (3)
C9—N3—C10111.4 (2)N5—C22—C23117.2 (3)
C23—N3—Ni1106.27 (18)C21—C22—C23119.7 (3)
C9—N3—Ni1105.24 (19)N3—C23—C22114.4 (3)
C10—N3—Ni1113.98 (16)N3—C23—H23A108.7
C31—N4—Ni1167.3 (4)C22—C23—H23A108.7
C22—N5—C18117.7 (3)N3—C23—H23B108.7
C22—N5—Ni1108.6 (2)C22—C23—H23B108.7
C18—N5—Ni1131.8 (2)H23A—C23—H23B107.6
C25—N6—C29117.8 (3)N2—C24—C25114.0 (3)
C25—N6—Ni1109.39 (18)N2—C24—H24A108.7
C29—N6—Ni1131.9 (2)C25—C24—H24A108.7
C2—C1—H1A109.5N2—C24—H24B108.7
C2—C1—H1B109.5C25—C24—H24B108.7
H1A—C1—H1B109.5H24A—C24—H24B107.6
C2—C1—H1C109.5N6—C25—C26123.1 (3)
H1A—C1—H1C109.5N6—C25—C24118.0 (3)
H1B—C1—H1C109.5C26—C25—C24118.8 (3)
N1—C2—C3122.3 (3)C25—C26—C27118.6 (4)
N1—C2—C1118.2 (3)C25—C26—H26A120.7
C3—C2—C1119.4 (3)C27—C26—H26A120.7
C4—C3—C2119.4 (3)C28—C27—C26119.1 (3)
C4—C3—H3A120.3C28—C27—H27A120.5
C2—C3—H3A120.3C26—C27—H27A120.5
C3—C4—C5119.2 (3)C27—C28—C29120.6 (3)
C3—C4—H4A120.4C27—C28—H28A119.7
C5—C4—H4A120.4C29—C28—H28A119.7
C6—C5—C4118.8 (3)N6—C29—C28120.7 (3)
C6—C5—H5A120.6N6—C29—C30120.3 (3)
C4—C5—H5A120.6C28—C29—C30119.0 (3)
N1—C6—C5122.8 (3)C29—C30—H30A109.5
N1—C6—C7116.3 (3)C29—C30—H30B109.5
C5—C6—C7120.9 (3)H30A—C30—H30B109.5
N2—C7—C6109.1 (2)C29—C30—H30C109.5
N2—C7—H7A109.9H30A—C30—H30C109.5
C6—C7—H7A109.9H30B—C30—H30C109.5
N2—C7—H7B109.9N4—C31—C32177.5 (7)
C6—C7—H7B109.9C31—C32—H32A110.0
H7A—C7—H7B108.3C31—C32—H32B109.6
N2—C8—C9108.6 (2)H32A—C32—H32B109.5
N2—C8—H8A110.0C31—C32—H32C108.8
C9—C8—H8A110.0H32A—C32—H32C109.5
N2—C8—H8B110.0H32B—C32—H32C109.5
C9—C8—H8B110.0F2—B1—F3118.9 (9)
H8A—C8—H8B108.3F1A—B1—F4A107 (3)
N3—C9—C8110.8 (2)F1A—B1—F2A99 (2)
N3—C9—H9A109.5F4A—B1—F2A129 (3)
C8—C9—H9A109.5F2—B1—F1107.0 (9)
N3—C9—H9B109.5F3—B1—F1107.7 (8)
C8—C9—H9B109.5F2—B1—F4103.1 (13)
H9A—C9—H9B108.1F3—B1—F4111.7 (10)
N3—C10—C11117.7 (2)F1—B1—F4108.1 (9)
N3—C10—H10A107.9F1A—B1—F3A106.1 (18)
C11—C10—H10A107.9F4A—B1—F3A111.3 (18)
N3—C10—H10B107.9F2A—B1—F3A102 (2)
C11—C10—H10B107.9F7A—B2—F6A122 (3)
H10A—C10—H10B107.2F7—B2—F8115.4 (12)
C16—C11—C12117.7 (3)F7—B2—F5106.9 (13)
C16—C11—C10120.7 (4)F8—B2—F5110.6 (12)
C12—C11—C10121.4 (3)F7A—B2—F5A111 (3)
C13—C12—C11120.3 (4)F6A—B2—F5A105 (2)
C13—C12—H12A119.9F7A—B2—F8A112.3 (16)
C11—C12—H12A119.9F6A—B2—F8A107.4 (13)
C14—C13—C12121.2 (5)F5A—B2—F8A97 (2)
C14—C13—H13A119.4F7—B2—F6105.5 (9)
C12—C13—H13A119.4F8—B2—F6109.6 (10)
C15—C14—C13119.6 (4)F5—B2—F6108.6 (12)
C15—C14—H14A120.2
C6—N1—C2—C32.1 (5)C22—N5—C18—C197.0 (6)
Ni1—N1—C2—C3173.2 (3)Ni1—N5—C18—C19155.3 (4)
C6—N1—C2—C1177.5 (3)C22—N5—C18—C17170.0 (4)
Ni1—N1—C2—C17.2 (5)Ni1—N5—C18—C1727.7 (6)
N1—C2—C3—C41.4 (6)N5—C18—C19—C200.4 (8)
C1—C2—C3—C4178.2 (4)C17—C18—C19—C20176.6 (5)
C2—C3—C4—C50.2 (7)C18—C19—C20—C215.4 (9)
C3—C4—C5—C60.2 (7)C19—C20—C21—C224.5 (8)
C2—N1—C6—C51.7 (5)C18—N5—C22—C218.1 (6)
Ni1—N1—C6—C5174.5 (3)Ni1—N5—C22—C21158.1 (3)
C2—N1—C6—C7179.9 (3)C18—N5—C22—C23165.5 (3)
Ni1—N1—C6—C73.8 (4)Ni1—N5—C22—C2328.3 (4)
C4—C5—C6—N10.6 (7)C20—C21—C22—N52.3 (7)
C4—C5—C6—C7178.9 (4)C20—C21—C22—C23171.1 (4)
C24—N2—C7—C672.3 (3)C9—N3—C23—C2284.2 (3)
C8—N2—C7—C6164.3 (3)C10—N3—C23—C22152.9 (3)
Ni1—N2—C7—C644.9 (3)Ni1—N3—C23—C2229.3 (3)
N1—C6—C7—N227.5 (4)N5—C22—C23—N341.5 (4)
C5—C6—C7—N2154.1 (4)C21—C22—C23—N3144.7 (4)
C24—N2—C8—C978.0 (3)C7—N2—C24—C25142.1 (3)
C7—N2—C8—C9159.8 (3)C8—N2—C24—C2593.4 (3)
Ni1—N2—C8—C941.8 (3)Ni1—N2—C24—C2526.5 (3)
C23—N3—C9—C875.9 (3)C29—N6—C25—C263.1 (4)
C10—N3—C9—C8162.3 (3)Ni1—N6—C25—C26167.6 (3)
Ni1—N3—C9—C838.3 (3)C29—N6—C25—C24173.2 (3)
N2—C8—C9—N355.1 (4)Ni1—N6—C25—C2416.2 (3)
C23—N3—C10—C1162.0 (4)N2—C24—C25—N629.8 (4)
C9—N3—C10—C1160.2 (4)N2—C24—C25—C26153.7 (3)
Ni1—N3—C10—C11179.1 (3)N6—C25—C26—C272.9 (5)
N3—C10—C11—C16102.0 (4)C24—C25—C26—C27173.3 (3)
N3—C10—C11—C1282.8 (4)C25—C26—C27—C280.7 (6)
C16—C11—C12—C130.5 (5)C26—C27—C28—C291.3 (6)
C10—C11—C12—C13174.8 (3)C25—N6—C29—C281.0 (4)
C11—C12—C13—C140.3 (6)Ni1—N6—C29—C28167.1 (2)
C12—C13—C14—C150.2 (7)C25—N6—C29—C30179.0 (3)
C13—C14—C15—C160.5 (8)Ni1—N6—C29—C3013.0 (4)
C12—C11—C16—C150.2 (6)C27—C28—C29—N61.1 (5)
C10—C11—C16—C15175.1 (4)C27—C28—C29—C30178.9 (4)
C14—C15—C16—C110.2 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1C···N40.962.943.251 (6)100
C3—H3A···F8i0.932.573.457 (14)159
C8—H8B···F70.972.573.371 (13)140
C8—H8B···F5A0.972.423.36 (4)163
C9—H9B···F4ii0.972.613.291 (16)128
C10—H10A···N60.972.673.273 (5)1213
C12—H12A···F8Aiii0.932.533.35 (2)146
C17—H17B···N10.962.643.071 (7)108
C21—H21A···F3ii0.932.623.122 (10)114
C23—H23B···F6Aiii0.972.333.241 (16)157
C24—H24A···F70.972.533.443 (15)156
C24—H24B···F3iv0.972.323.179 (13)148
C24—H24B···F1Aiv0.972.543.43 (3)153
C28—H28A···F4iii0.932.593.345 (19)138
C30—H30A···F4iii0.962.603.390 (17)140
C30—H30A···F4Aiii0.962.503.26 (3)136
C30—H30B···N40.962.853.126 (6)98
C32—H32A···F6iii0.962.403.196 (14)140
C32—H32A···F7Aiii0.962.333.19 (3)150
C32—H32B···F3v0.962.553.145 (15)121
C32—H32B···F3Av0.962.323.11 (4)140
Symmetry codes: (i) x+1/2, y1/2, z1/2; (ii) x+1, y, z+1/2; (iii) x+1, y, z; (iv) x+1/2, y1/2, z; (v) x+3/2, y1/2, z.
 

Funding information

Funding for this research was provided by: China Postdoctoral Science Foundation (award Nos. 2015M582573, Chinese National Natural Science Foundation, 21601164, 21573200, 21573223).

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