Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615019002/yp3107sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615019002/yp3107Isup2.hkl |
CCDC reference: 1430361
Crystal engineering deals with competition, co-operation and balance between different intermolecular forces in extended crystal structures (Aakeroy, 1997; Steiner, 2002; Desiraju, 2014; Deringer et al., 2014; Thakur et al., 2015).
Hydrogen bonds are considered a powerful organizing force in designing supramolecular architectures because they are directional, selective and reversible at room temperature.
Halogen bonding implies a directional interaction between an electron-density donor (a neutral or anionic Lewis base with an N, O, S, P or halogen functionality) and a (usually heavy) halogen atom as electrophile. Halogen bonds have been defined by Mate Erdélyi in his tutorial review (Erdélyi, 2012) as `the cement to assemble molecules into supramolecular architectures' (Metrangolo & Resnati, 2001; Metrangolo et al., 2008; Wang et al., 2012, 2013; Erdélyi, 2012; Pan et al., 2015). Halogen bonds in which an S atom is the formal acceptor, i.e. it acts as a lone-pair donor towards the σ hole of a heavy halide, are quite rare. For S···I contacts, the Camdridge Structural Database (CSD, Version 5.36, including updates of November 2014, 717876 entries; Groom & Allen, 2014) lists only 17 occurrences for C—S···I—C with S···I < 3.4 Å. It goes without explicit literature citation that this infrequency is in marked contrast with the many examples of short N···X or O···X (X = Cl, Br or I) contacts.
We expected to design a representative for such a rare S···I halogen bond by combining two particularly suitable constituents in a cocrystal. For the sulfur halogen-bond acceptor group, we chose dithiocyanatotetrakis(4-vinylpyridine)nickel(II). This NiII complex is suitable for cocrystal formation; according to Moore and co-workers, the reason is the remarkable rotational freedom of the pyridine rings about their Ni—N bonds, which allows the molecule to adjust its shape to accommodate various guest molecules of different shape, size and polarity. Moreover, the isothiocyanate group allows a secondary interaction between the S atom and the nonmetallic elements of the guest molecules (Moore et al., 1987; Nassimbeni et al., 1989).
This pseudo-octahedral complex was originally described by Lipkowski et al. (1984) and Nassimbeni & coworkers (Moore et al.,1986); the latter group used it as host to accomodate a variety of small guest molecules, such as: (i) p-xylene, m-xylene and o-xylene (Moore et al.,1986; CSD refcodes FINCOU, FINCUA and FINDAH, respectively) or chloroform (Moore et al., 1987; refcode FOCDEG); (ii) cyclohexane and tetrahydrofuran; 1,3-cyclohexadiene and tetrahydrofuran; 1,4-cyclohexadiene and tetrahydrofuran; benzene and tetrahydrofuran, benzene or tetrahydrofuran (Lavelle & Nassimbeni, 1993; CSD refcodes PIZLOZ, PIZMAM, PIZMIU, PIZMOA, PIZMUG and PIZNAN, respectively); (iii) tetrachloromethane or triiodomethane (Nassimbeni et al., 1989; CSD refcodes VAXVAR, VAXVEV and VAXVIZ, respectively).
Tetrafluorodiiodobenzene (TFDIB) meets the requirements for a good halogen-bond donor through its iodo substituents towards nucleophiles such as the S atom from the isothiocyanate ligand. Our group has used TFDIB for the construction of cocrystals in which hydrogen and halogen bonds of different strengths co-exist with coordinative bonds (Merkens et al., 2013).
The present contribution deals with the successful cocrystallization of dithiocyanatotetrakis(4-vinylpyridine)nickel(II), [Ni(NCS)2(4ViPy)4], and TFDIB. In the resulting adduct, (1) (see scheme), the isothiocyanate S atom acts as electron-density donor or halogen-bond acceptor.
Chemicals were used as supplied without further purification. The powder X-ray diffraction (PXRD) pattern was recorded at the Institute of Inorganic Chemistry, RWTH Aachen University, using a Stoe IP-PSD imaging-plate detector. A flat sample was measured in transmission using Cu Kα1 radiation at ambient temperature. Nickel(II) thiocyanate was prepared according to the procedure described by Sarma & Poddar (1984). Dithiocyanatotetrakis(4-vinylpyridine)nickel(II), [Ni(NCS)2(4ViPy)4], was prepared following the procedure of Moore et al. (1986).
For the preparation of (1), [Ni(NCS)2(4ViPy)4] (0.1 mmol, 59.5 mg) and 2,3,5,6-tetrafluoro-1,4-diiodobenzene (0.1 mmol, 40.18 mg) were dissolved in ethanol (6 ml) at room temperature. Blue crystals of (1) were obtained from the resulting solution by partial evaporation at room temperature overnight. The phase purity of the product was confirmed by powder X-ray diffraction (see Fig. 1).
Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C atoms were calculated, introduced in their idealized positions and treated as riding, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).
The title compound, (1), crystallizes in the centrosymmetric tetragonal space group I41/a with half a molecule of dithiocyanatotetrakis(4-vinylpyridine)nickel(II), [Ni(NCS)2(4ViPy)4], and half a molecule of 2,3,5,6-tetrafluoro-1,4-diiodobenzene (TFDIB) in the asymmetric unit. The larger coordination compound can be perceived as host; it is situated on a twofold crystallographic axis, with the Ni atom on Wyckoff position 8e, whereas the centre of gravity of the perhalogenated guest coincides with a centre of inversion.
The NiII cation is coordinated by six N atoms, four from the 4-vinylpyridine (4ViPy) ligands in equatorial positions and two from the isothiocyanate (NCS) ligands in axial positions (Fig. 2). The Ni—N distances range from 2.084 (3) to 2.118 (3) Å (Table 2). The Ni—N bonds to the isothiocyanate ligands are shorter than those to the pyridine ligands, as reported previously for this type of compound (Roy et al., 2007; Lavelle & Nassimbeni, 1993; Moore et al., 1987; Miklovic et al., 2004).
The complex molecule adopts a four-blade propeller geometry. The four torsion angles of the 4-vinylpyridine ligands (N1—Ni1—Nx1—Cx2) differ only slightly from each other and adopt the following values: N1—Ni1—N2—C5 = -139.8 (3)°, N1—Ni1—N2i—C5i = 41.5 (3)°, N1—Ni1—N3—C8 = -134.1 (3)° and N1—Ni1—N3i—C8i = 44.7 (3)° [symmetry code: (i) -x, -y + 1/2, z].
The isothioyanate ligand is significantly bent at the N-atom position, with an Ni—N—C angle of 157.1 (3)°. The two NCS ligands in a trans geometry are not coplanar but subtend a C—N···N—C angle of 9.9 (2)°.
The iodine substituents in the TFDIB residue are suitable halogen-bond donors towards nucleophiles such as the terminal S atom from the isothiocyanate ligands. TFDIB has been used successfully as an electrophilic component in short halogen bonds with pyridine derivatives (Roper et al., 2010; Sgarbossa et al., 2012; Merkens et al., 2013).
According to Desiraju and co-workers (Thalladi et al., 1998; Thakur et al., 2015), in the absence of strong hydrogen bonds, weak intermolecular interactions are very important for the overall crystal packing. This is true in the crystal structure of (1), which is stabilized through very short S···I halogen bonds of 3.2891 (12) Å, considerably shorter than the sum of the common van der Waals radii, i.e. I 1.98 Å and S 1.80 Å (Batsanov, 2001). Hirshfeld surfaces (Hirshfeld, 1977; Wolff et al., 2010) allow the visualization of the relevant intermolecular contacts. They are presented in Figs. 3(a) and 3(b) for both residues of (1); the short S···I interaction corresponds to the pronounced red spot on the surface.
A histogram of S···I contacts allows the classification of the halogen bond in (1) as unusually short. Fig. 4 shows that the vast majority of intermolecular S···I contacts retrieved from the CSD are associated with distances longer than 3.4 Å.
Interatomic distances do not represent the only criteria for halogen bonds: Nassimbeni and co-workers (Nassimbeni et al., 1989; Lavelle & Nassimbeni, 1993) have already described two alternative geometries in which `secondary bonding' between an isothiocyanate S atom and an I atom of the guest can occur. Either the (NiNC)—S···I or the S···I—C angle should be approximately linear. In the case of (1), the latter amounts to 164.20 (13)° and thus matches the expected geometry for a halogen bond, with the S atom approaching the σ hole at the I atom opposite the aryl C—I bond.
Space-filling in cocrystal (1) is efficient: its density of 1.758 Mg m-3 is significantly higher than that for unsolvated α-[Ni(NCS)2(4ViPy)4] with a density of 1.3 Mg m-3 (Lipkowski et al., 1984). The packing for (1) does not show any relevant voids: the cocrystal is associated with a packing index of 68.9%, whereas a hypothetical unsolvated guest structure (Fig. 5) would correspond to a much more close-packed solid with 53.1% space filling.
Alternatively, the packing density can be expressed as the ratio (volume of the unit cell):(number of non-H atoms in the unit cell). When such a comparison is made for (1) with clathrates reported by Moore et al. (1986) or Lavelle & Nassimbeni (1993), it confirms that our compound is more efficiently packed than the clathrates reported earlier [Is it worth giving the specific numbers here?].
A coordination complex prone to encapsulating small guest molecules and tetrafluorodiiodobenzene, a well-established halogen-bond donor, have been cocrystallized. These particularly well suited residues subtend an unusually short S···I contact. Future work will focus on aspects beyond molecular geometry. We will attempt to grow crystals suitable for high-resolution diffraction experiments, perform multipole refinements and analyze the resulting experimental electron density in terms of Bader's AIM (atoms in molecules) theory (Bader, 1990). Very short intermolecular contacts can be associated with significant electron density in the bond critical point (Wang et al., 2013).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Ni(NCS)2(C7H7N)4]·C6F4I2 | Dx = 1.758 Mg m−3 |
Mr = 997.27 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | θ = 2.5–20.0° |
a = 16.2034 (14) Å | µ = 2.32 mm−1 |
c = 28.698 (2) Å | T = 100 K |
V = 7534.6 (14) Å3 | Block, blue |
Z = 8 | 0.13 × 0.12 × 0.10 mm |
F(000) = 3904 |
Bruker SMART CCD area-detector diffractometer | 2947 reflections with I > 2σ(I) |
Radiation source: Incoatec microsource | Rint = 0.065 |
ω scans | θmax = 26.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −18→20 |
Tmin = 0.622, Tmax = 0.745 | k = −20→20 |
22801 measured reflections | l = −26→35 |
3877 independent reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0276P)2] where P = (Fo2 + 2Fc2)/3 |
3877 reflections | (Δ/σ)max = 0.006 |
231 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −1.00 e Å−3 |
[Ni(NCS)2(C7H7N)4]·C6F4I2 | Z = 8 |
Mr = 997.27 | Mo Kα radiation |
Tetragonal, I41/a | µ = 2.32 mm−1 |
a = 16.2034 (14) Å | T = 100 K |
c = 28.698 (2) Å | 0.13 × 0.12 × 0.10 mm |
V = 7534.6 (14) Å3 |
Bruker SMART CCD area-detector diffractometer | 3877 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2947 reflections with I > 2σ(I) |
Tmin = 0.622, Tmax = 0.745 | Rint = 0.065 |
22801 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.79 e Å−3 |
3877 reflections | Δρmin = −1.00 e Å−3 |
231 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.2500 | 0.78471 (2) | 0.01796 (15) | |
S1 | −0.11466 (6) | −0.02162 (6) | 0.77532 (4) | 0.0328 (3) | |
N1 | −0.07587 (17) | 0.14614 (18) | 0.78356 (10) | 0.0202 (7) | |
N2 | 0.07433 (17) | 0.19832 (17) | 0.83794 (10) | 0.0178 (6) | |
N3 | −0.07086 (17) | 0.30733 (17) | 0.73194 (10) | 0.0191 (7) | |
C1 | 0.0871 (2) | 0.1165 (2) | 0.84181 (13) | 0.0217 (8) | |
H1 | 0.0689 | 0.0814 | 0.8173 | 0.026* | |
C2 | 0.1256 (2) | 0.0816 (2) | 0.88005 (13) | 0.0232 (8) | |
H2 | 0.1339 | 0.0236 | 0.8812 | 0.028* | |
C3 | 0.1522 (2) | 0.1308 (2) | 0.91691 (12) | 0.0214 (8) | |
C4 | 0.1408 (2) | 0.2151 (2) | 0.91201 (12) | 0.0211 (8) | |
H4 | 0.1597 | 0.2516 | 0.9356 | 0.025* | |
C5 | 0.1020 (2) | 0.2462 (2) | 0.87280 (12) | 0.0209 (8) | |
H5 | 0.0947 | 0.3042 | 0.8704 | 0.025* | |
C6 | 0.1881 (2) | 0.0927 (2) | 0.95838 (13) | 0.0269 (9) | |
H6 | 0.2041 | 0.0365 | 0.9559 | 0.032* | |
C7 | 0.2004 (2) | 0.1291 (3) | 0.99889 (14) | 0.0350 (10) | |
H7A | 0.1854 | 0.1853 | 1.0030 | 0.042* | |
H7B | 0.2242 | 0.0991 | 1.0240 | 0.042* | |
C8 | −0.0340 (2) | 0.3445 (2) | 0.69534 (12) | 0.0222 (8) | |
H8 | 0.0245 | 0.3487 | 0.6954 | 0.027* | |
C9 | −0.0764 (2) | 0.3768 (2) | 0.65782 (13) | 0.0242 (9) | |
H9 | −0.0472 | 0.4015 | 0.6327 | 0.029* | |
C10 | −0.1621 (2) | 0.3729 (2) | 0.65694 (13) | 0.0240 (8) | |
C11 | −0.1999 (2) | 0.3365 (2) | 0.69524 (14) | 0.0266 (9) | |
H11 | −0.2584 | 0.3333 | 0.6967 | 0.032* | |
C12 | −0.1529 (2) | 0.3049 (2) | 0.73121 (13) | 0.0251 (9) | |
H12 | −0.1807 | 0.2801 | 0.7568 | 0.030* | |
C13 | −0.2112 (3) | 0.4051 (2) | 0.61799 (15) | 0.0368 (11) | |
H13 | −0.2695 | 0.4006 | 0.6205 | 0.044* | |
C14 | −0.1824 (3) | 0.4394 (3) | 0.58024 (15) | 0.0462 (12) | |
H14A | −0.1245 | 0.4454 | 0.5761 | 0.055* | |
H14B | −0.2192 | 0.4585 | 0.5569 | 0.055* | |
C15 | −0.0925 (2) | 0.0770 (2) | 0.78008 (12) | 0.0220 (8) | |
I1 | 0.06962 (2) | 0.03854 (2) | 1.11334 (2) | 0.03788 (11) | |
F1 | −0.06105 (14) | 0.12477 (14) | 0.94756 (8) | 0.0441 (7) | |
F2 | −0.00803 (16) | 0.15593 (15) | 1.03344 (9) | 0.0478 (7) | |
C16 | −0.0313 (2) | 0.0619 (3) | 0.97335 (15) | 0.0336 (10) | |
C17 | 0.0285 (2) | 0.0164 (3) | 1.04525 (14) | 0.0333 (10) | |
C18 | −0.0037 (2) | 0.0788 (3) | 1.01741 (16) | 0.0347 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0152 (3) | 0.0198 (3) | 0.0189 (4) | 0.0001 (3) | 0.000 | 0.000 |
S1 | 0.0331 (6) | 0.0248 (5) | 0.0404 (7) | −0.0060 (4) | −0.0020 (5) | −0.0011 (5) |
N1 | 0.0175 (15) | 0.0241 (17) | 0.0190 (18) | 0.0004 (12) | −0.0003 (13) | −0.0001 (13) |
N2 | 0.0164 (15) | 0.0168 (15) | 0.0203 (18) | 0.0013 (12) | 0.0014 (12) | −0.0028 (13) |
N3 | 0.0170 (15) | 0.0226 (16) | 0.0178 (18) | −0.0005 (12) | −0.0003 (13) | −0.0007 (13) |
C1 | 0.0191 (18) | 0.0201 (18) | 0.026 (2) | −0.0005 (15) | −0.0011 (16) | −0.0043 (16) |
C2 | 0.0186 (18) | 0.0188 (18) | 0.032 (2) | 0.0044 (14) | 0.0021 (16) | 0.0011 (16) |
C3 | 0.0151 (17) | 0.0239 (19) | 0.025 (2) | 0.0014 (15) | 0.0008 (15) | 0.0050 (16) |
C4 | 0.0204 (19) | 0.0240 (19) | 0.019 (2) | 0.0011 (15) | −0.0009 (15) | −0.0042 (15) |
C5 | 0.0247 (19) | 0.0180 (18) | 0.020 (2) | 0.0017 (15) | 0.0019 (16) | −0.0004 (15) |
C6 | 0.0205 (19) | 0.028 (2) | 0.032 (3) | 0.0029 (16) | −0.0036 (17) | 0.0113 (18) |
C7 | 0.032 (2) | 0.037 (2) | 0.035 (3) | −0.0012 (19) | −0.009 (2) | 0.010 (2) |
C8 | 0.0168 (18) | 0.026 (2) | 0.024 (2) | 0.0001 (15) | 0.0017 (15) | −0.0009 (16) |
C9 | 0.031 (2) | 0.0215 (19) | 0.020 (2) | 0.0017 (16) | 0.0036 (17) | 0.0009 (16) |
C10 | 0.029 (2) | 0.0189 (19) | 0.024 (2) | 0.0052 (16) | −0.0103 (17) | −0.0042 (16) |
C11 | 0.0189 (19) | 0.022 (2) | 0.039 (3) | 0.0003 (15) | −0.0050 (17) | 0.0007 (17) |
C12 | 0.0175 (18) | 0.028 (2) | 0.030 (2) | −0.0020 (15) | 0.0003 (16) | 0.0005 (17) |
C13 | 0.044 (3) | 0.024 (2) | 0.042 (3) | −0.0025 (18) | −0.021 (2) | 0.003 (2) |
C14 | 0.073 (4) | 0.033 (3) | 0.033 (3) | 0.016 (2) | −0.020 (2) | −0.005 (2) |
C15 | 0.0154 (18) | 0.033 (2) | 0.017 (2) | 0.0035 (16) | −0.0006 (15) | 0.0003 (17) |
I1 | 0.02717 (15) | 0.04786 (19) | 0.0386 (2) | −0.00369 (12) | −0.00040 (12) | 0.01396 (14) |
F1 | 0.0450 (15) | 0.0412 (15) | 0.0461 (16) | 0.0175 (12) | 0.0013 (12) | 0.0217 (12) |
F2 | 0.0542 (17) | 0.0403 (15) | 0.0488 (17) | 0.0080 (12) | −0.0012 (13) | 0.0109 (12) |
C16 | 0.023 (2) | 0.042 (3) | 0.036 (3) | 0.0099 (18) | 0.0029 (18) | 0.022 (2) |
C17 | 0.024 (2) | 0.044 (3) | 0.032 (3) | 0.0037 (18) | 0.0043 (18) | 0.018 (2) |
C18 | 0.026 (2) | 0.032 (2) | 0.046 (3) | 0.0025 (18) | 0.004 (2) | 0.012 (2) |
Ni1—N1 | 2.084 (3) | C7—H7A | 0.9500 |
Ni1—N1i | 2.084 (3) | C7—H7B | 0.9500 |
Ni1—N3i | 2.115 (3) | C8—C9 | 1.380 (5) |
Ni1—N2 | 2.118 (3) | C8—H8 | 0.9500 |
Ni1—N3 | 2.115 (3) | C9—C10 | 1.391 (5) |
Ni1—N2i | 2.118 (3) | C9—H9 | 0.9500 |
S1—C15 | 1.643 (4) | C10—C11 | 1.389 (5) |
N1—C15 | 1.157 (4) | C10—C13 | 1.468 (5) |
N2—C5 | 1.343 (4) | C11—C12 | 1.381 (5) |
N2—C1 | 1.346 (4) | C11—H11 | 0.9500 |
N3—C12 | 1.331 (4) | C12—H12 | 0.9500 |
N3—C8 | 1.350 (4) | C13—C14 | 1.304 (6) |
C1—C2 | 1.384 (5) | C13—H13 | 0.9500 |
C1—H1 | 0.9500 | C14—H14A | 0.9500 |
C2—C3 | 1.393 (5) | C14—H14B | 0.9500 |
C2—H2 | 0.9500 | I1—C17 | 2.096 (4) |
C3—C4 | 1.385 (5) | F1—C16 | 1.349 (4) |
C3—C6 | 1.461 (5) | F2—C18 | 1.334 (5) |
C4—C5 | 1.384 (5) | C16—C18 | 1.369 (6) |
C4—H4 | 0.9500 | C16—C17ii | 1.377 (6) |
C5—H5 | 0.9500 | C17—C16ii | 1.377 (6) |
C6—C7 | 1.319 (5) | C17—C18 | 1.390 (5) |
C6—H6 | 0.9500 | ||
N1—Ni1—N1i | 178.17 (16) | C7—C6—C3 | 126.1 (4) |
N1—Ni1—N3i | 87.37 (11) | C7—C6—H6 | 116.9 |
N1i—Ni1—N3i | 91.32 (11) | C3—C6—H6 | 116.9 |
N1—Ni1—N3 | 91.32 (11) | C6—C7—H7A | 120.0 |
N1i—Ni1—N3 | 87.37 (11) | C6—C7—H7B | 120.0 |
N3i—Ni1—N3 | 88.56 (15) | H7A—C7—H7B | 120.0 |
N1—Ni1—N2 | 91.59 (11) | N3—C8—C9 | 123.8 (3) |
N1i—Ni1—N2 | 89.73 (11) | N3—C8—H8 | 118.1 |
N3i—Ni1—N2 | 91.95 (10) | C9—C8—H8 | 118.1 |
N3—Ni1—N2 | 177.07 (11) | C8—C9—C10 | 119.6 (3) |
N1—Ni1—N2i | 89.73 (11) | C8—C9—H9 | 120.2 |
N1i—Ni1—N2i | 91.59 (11) | C10—C9—H9 | 120.2 |
N3i—Ni1—N2i | 177.07 (11) | C11—C10—C9 | 116.4 (3) |
N3—Ni1—N2i | 91.95 (10) | C11—C10—C13 | 121.0 (4) |
N2—Ni1—N2i | 87.69 (15) | C9—C10—C13 | 122.6 (4) |
C15—N1—Ni1 | 157.0 (3) | C12—C11—C10 | 120.4 (3) |
C5—N2—C1 | 117.1 (3) | C12—C11—H11 | 119.8 |
C5—N2—Ni1 | 119.9 (2) | C10—C11—H11 | 119.8 |
C1—N2—Ni1 | 122.4 (2) | N3—C12—C11 | 123.5 (4) |
C12—N3—C8 | 116.3 (3) | N3—C12—H12 | 118.3 |
C12—N3—Ni1 | 122.7 (2) | C11—C12—H12 | 118.3 |
C8—N3—Ni1 | 120.9 (2) | C14—C13—C10 | 126.1 (4) |
N2—C1—C2 | 122.5 (3) | C14—C13—H13 | 116.9 |
N2—C1—H1 | 118.7 | C10—C13—H13 | 116.9 |
C2—C1—H1 | 118.7 | C13—C14—H14A | 120.0 |
C1—C2—C3 | 120.5 (3) | C13—C14—H14B | 120.0 |
C1—C2—H2 | 119.7 | H14A—C14—H14B | 120.0 |
C3—C2—H2 | 119.7 | N1—C15—S1 | 179.2 (4) |
C4—C3—C2 | 116.5 (3) | F1—C16—C18 | 118.2 (4) |
C4—C3—C6 | 123.5 (3) | F1—C16—C17ii | 119.7 (4) |
C2—C3—C6 | 120.0 (3) | C18—C16—C17ii | 122.1 (4) |
C5—C4—C3 | 120.2 (3) | C16ii—C17—C18 | 117.4 (4) |
C5—C4—H4 | 119.9 | C16ii—C17—I1 | 120.6 (3) |
C3—C4—H4 | 119.9 | C18—C17—I1 | 122.1 (3) |
N2—C5—C4 | 123.2 (3) | F2—C18—C16 | 119.3 (4) |
N2—C5—H5 | 118.4 | F2—C18—C17 | 120.2 (4) |
C4—C5—H5 | 118.4 | C16—C18—C17 | 120.5 (4) |
Symmetry codes: (i) −x, −y+1/2, z; (ii) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(NCS)2(C7H7N)4]·C6F4I2 |
Mr | 997.27 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 100 |
a, c (Å) | 16.2034 (14), 28.698 (2) |
V (Å3) | 7534.6 (14) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.32 |
Crystal size (mm) | 0.13 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.622, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22801, 3877, 2947 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.077, 1.03 |
No. of reflections | 3877 |
No. of parameters | 231 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.79, −1.00 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008).
Ni1—N1 | 2.084 (3) | Ni1—N3 | 2.115 (3) |
Ni1—N2 | 2.118 (3) | ||
N1—Ni1—N1i | 178.17 (16) | N3—Ni1—N2 | 177.07 (11) |
N1—Ni1—N3 | 91.32 (11) | N1—Ni1—N2i | 89.73 (11) |
N3i—Ni1—N3 | 88.56 (15) |
Symmetry code: (i) −x, −y+1/2, z. |
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