Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104007796/fg1744sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007796/fg1744Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007796/fg1744IIsup3.hkl |
CCDC references: 241219; 241220
The organic ligands were prepared according the literature procedures of Eloy & Deryckere (1971) (fupy) and Bobošík et al. (1995) (Me2fupy). To NiCl2·6H2O (0.04 mol) in ethanol (60 ml) was added finely divided KSCN powder (0.08 mol). The KCl which precipitated was filtered off and fupy (0.16 mol) or Me2fupy (0.16 mol) in ethanol (60 ml) was added to the pure solution. At room temperature, small crystals were formed within 2–3 d. Crystals suitable for X-ray diffraction study were obtained after the slow diffusion of diethyl ether into a tetrahydrofuran solution of (I) or a wet dichloromethane solution of (II).
All H atoms were positioned geometrically and treated as riding, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) = 1.2 or 1.5Ueq(C). In (I), the tetrahydrofuran molecule in the asymmetric unit is equally disordered over two interpenetrating orientations. This was allowed for in the refinement by use of appropriate DFIX restraints on the C—C and C—O distances. There is a solvent-containing volume (ca 250 Å3) in the lattice of (II) centred at (0,1/2,1/2). The electron-density peaks corresponding to disordered partial-occupancy water molecules were not well defined. The SQUEEZE option in PLATON (Spek, 2003) identified a density of approximately 66 electrons, corresponding to a disordered solvent of 6.6 water molecules per unit cell. The presence of water as the only solvent in lattice was confirmed by IR measurement. Refinement was then concluded with a `dry' data set.
For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I); SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003) for (II). For both compounds, molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
[Ni(NCS)2(C7H5NO)4]·C4H8O | Z = 2 |
Mr = 723.45 | F(000) = 748 |
Triclinic, P1 | Dx = 1.425 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4916 (10) Å | Cell parameters from 983 reflections |
b = 10.7191 (11) Å | θ = 2.5–27.7° |
c = 17.8360 (19) Å | µ = 0.75 mm−1 |
α = 99.580 (2)° | T = 300 K |
β = 92.278 (2)° | Prism, blue |
γ = 108.726 (2)° | 0.50 × 0.36 × 0.30 mm |
V = 1686.2 (3) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 7414 independent reflections |
Radiation source: fine-focus sealed tube | 6280 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 512 pixels mm-1 | θmax = 28.0°, θmin = 2.0° |
ϕ and ω scans | h = −12→11 |
Absorption correction: multi-scan (XPREP; Sheldrick, 1990) | k = −13→11 |
Tmin = 0.829, Tmax = 0.936 | l = −22→23 |
10159 measured 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) = 0.109 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0644P)2 + 0.5868P] where P = (Fo2 + 2Fc2)/3 |
7414 reflections | (Δ/σ)max < 0.001 |
448 parameters | Δρmax = 0.56 e Å−3 |
10 restraints | Δρmin = −0.54 e Å−3 |
[Ni(NCS)2(C7H5NO)4]·C4H8O | γ = 108.726 (2)° |
Mr = 723.45 | V = 1686.2 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.4916 (10) Å | Mo Kα radiation |
b = 10.7191 (11) Å | µ = 0.75 mm−1 |
c = 17.8360 (19) Å | T = 300 K |
α = 99.580 (2)° | 0.50 × 0.36 × 0.30 mm |
β = 92.278 (2)° |
Bruker SMART 1K CCD area-detector diffractometer | 7414 independent reflections |
Absorption correction: multi-scan (XPREP; Sheldrick, 1990) | 6280 reflections with I > 2σ(I) |
Tmin = 0.829, Tmax = 0.936 | Rint = 0.018 |
10159 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 10 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.56 e Å−3 |
7414 reflections | Δρmin = −0.54 e Å−3 |
448 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. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.85956 (3) | 0.03466 (2) | 0.236853 (13) | 0.03752 (9) | |
S1 | 1.20529 (9) | 0.25490 (9) | 0.08049 (5) | 0.0781 (2) | |
S2 | 0.36033 (7) | −0.14529 (9) | 0.31014 (4) | 0.0748 (2) | |
O3 | 1.25975 (19) | −0.01982 (17) | 0.50419 (9) | 0.0592 (4) | |
O4 | 0.8585 (2) | 0.56168 (16) | 0.44489 (12) | 0.0767 (6) | |
O5 | 0.5799 (2) | 0.18986 (18) | −0.03845 (10) | 0.0660 (5) | |
O6 | 0.8166 (3) | −0.53342 (17) | 0.06670 (12) | 0.0783 (6) | |
N1 | 1.0572 (2) | 0.12562 (18) | 0.19190 (10) | 0.0472 (4) | |
N2 | 0.6564 (2) | −0.05484 (18) | 0.27681 (10) | 0.0469 (4) | |
N3 | 0.98511 (18) | 0.01051 (16) | 0.33150 (9) | 0.0397 (3) | |
N4 | 0.86889 (19) | 0.22411 (16) | 0.30434 (9) | 0.0422 (4) | |
N5 | 0.74534 (18) | 0.07314 (17) | 0.14247 (9) | 0.0418 (3) | |
N6 | 0.84588 (19) | −0.15872 (17) | 0.17597 (9) | 0.0430 (4) | |
C1 | 1.1208 (2) | 0.1807 (2) | 0.14669 (12) | 0.0458 (4) | |
C2 | 0.5340 (2) | −0.0923 (2) | 0.29049 (11) | 0.0430 (4) | |
C31 | 0.9421 (2) | −0.10016 (19) | 0.36316 (11) | 0.0438 (4) | |
H31 | 0.8504 | −0.1653 | 0.3446 | 0.053* | |
C32 | 1.0255 (3) | −0.1226 (2) | 0.42123 (12) | 0.0484 (5) | |
H32 | 0.9939 | −0.2008 | 0.4412 | 0.058* | |
C33 | 1.1578 (2) | −0.0226 (2) | 0.44763 (11) | 0.0433 (4) | |
C34 | 1.3726 (3) | 0.1022 (3) | 0.51058 (14) | 0.0654 (7) | |
H34 | 1.4572 | 0.1306 | 0.5455 | 0.078* | |
C35 | 1.3464 (3) | 0.1746 (2) | 0.46110 (13) | 0.0571 (6) | |
H35 | 1.4067 | 0.2594 | 0.4554 | 0.069* | |
C36 | 1.2054 (2) | 0.0947 (2) | 0.41833 (11) | 0.0421 (4) | |
C37 | 1.1150 (2) | 0.10681 (19) | 0.35885 (11) | 0.0412 (4) | |
H37 | 1.1453 | 0.1835 | 0.3375 | 0.049* | |
C41 | 0.9241 (3) | 0.3425 (2) | 0.28128 (13) | 0.0513 (5) | |
H41 | 0.9615 | 0.3425 | 0.2339 | 0.062* | |
C42 | 0.9283 (3) | 0.4633 (2) | 0.32372 (15) | 0.0622 (6) | |
H42 | 0.9678 | 0.5436 | 0.3065 | 0.075* | |
C43 | 0.8707 (3) | 0.4582 (2) | 0.39304 (14) | 0.0541 (5) | |
C44 | 0.7934 (3) | 0.5050 (3) | 0.50449 (16) | 0.0723 (7) | |
H44 | 0.7721 | 0.5538 | 0.5481 | 0.087* | |
C45 | 0.7648 (3) | 0.3738 (2) | 0.49274 (13) | 0.0574 (6) | |
H45 | 0.7217 | 0.3159 | 0.5253 | 0.069* | |
C46 | 0.8138 (2) | 0.3386 (2) | 0.41915 (11) | 0.0450 (4) | |
C47 | 0.8150 (2) | 0.2226 (2) | 0.37228 (11) | 0.0438 (4) | |
H47 | 0.7771 | 0.1413 | 0.3885 | 0.053* | |
C51 | 0.6373 (2) | 0.1288 (2) | 0.15318 (12) | 0.0471 (4) | |
H51 | 0.6047 | 0.1386 | 0.2016 | 0.057* | |
C52 | 0.5718 (2) | 0.1722 (2) | 0.09653 (13) | 0.0517 (5) | |
H52 | 0.4974 | 0.2104 | 0.1055 | 0.062* | |
C53 | 0.6239 (2) | 0.1550 (2) | 0.02637 (13) | 0.0491 (5) | |
C54 | 0.6655 (3) | 0.1516 (3) | −0.09330 (15) | 0.0703 (7) | |
H54 | 0.6588 | 0.1641 | −0.1435 | 0.084* | |
C55 | 0.7575 (3) | 0.0957 (3) | −0.06672 (13) | 0.0610 (6) | |
H55 | 0.8238 | 0.0624 | −0.0936 | 0.073* | |
C56 | 0.7336 (2) | 0.0972 (2) | 0.01274 (11) | 0.0456 (4) | |
C57 | 0.7917 (2) | 0.0561 (2) | 0.07309 (11) | 0.0437 (4) | |
H57 | 0.8646 | 0.0158 | 0.0650 | 0.052* | |
C61 | 0.7178 (3) | −0.2369 (2) | 0.13330 (12) | 0.0507 (5) | |
H61 | 0.6401 | −0.2022 | 0.1306 | 0.061* | |
C62 | 0.6945 (3) | −0.3645 (2) | 0.09355 (13) | 0.0600 (6) | |
H62 | 0.6051 | −0.4153 | 0.0641 | 0.072* | |
C63 | 0.8112 (3) | −0.4117 (2) | 0.10019 (13) | 0.0559 (6) | |
C64 | 0.9569 (4) | −0.5339 (3) | 0.09094 (19) | 0.0815 (9) | |
H64 | 0.9907 | −0.6061 | 0.0768 | 0.098* | |
C65 | 1.0378 (3) | −0.4197 (3) | 0.13661 (16) | 0.0674 (7) | |
H65 | 1.1347 | −0.3983 | 0.1592 | 0.081* | |
C66 | 0.9454 (3) | −0.3358 (2) | 0.14416 (12) | 0.0501 (5) | |
C67 | 0.9586 (2) | −0.2073 (2) | 0.18107 (12) | 0.0454 (4) | |
H67 | 1.0477 | −0.1538 | 0.2100 | 0.054* | |
O711 | 0.619 (5) | 0.593 (2) | 0.657 (3) | 0.1166 (18) | 0.50 |
C741 | 0.541 (5) | 0.650 (5) | 0.711 (3) | 0.099 (4) | 0.50 |
H74A | 0.4798 | 0.6903 | 0.6851 | 0.119* | 0.50 |
H74B | 0.6112 | 0.7193 | 0.7489 | 0.119* | 0.50 |
C751 | 0.442 (2) | 0.5431 (18) | 0.7495 (17) | 0.109 (3) | 0.50 |
H75A | 0.4324 | 0.5782 | 0.8021 | 0.131* | 0.50 |
H75B | 0.3433 | 0.4996 | 0.7218 | 0.131* | 0.50 |
C761 | 0.5331 (9) | 0.4531 (7) | 0.7438 (5) | 0.0942 (17) | 0.50 |
H76A | 0.5812 | 0.4587 | 0.7938 | 0.113* | 0.50 |
H76B | 0.4694 | 0.3610 | 0.7254 | 0.113* | 0.50 |
C771 | 0.6470 (14) | 0.4931 (12) | 0.6909 (7) | 0.138 (4) | 0.50 |
H77A | 0.7461 | 0.5272 | 0.7183 | 0.165* | 0.50 |
H77B | 0.6418 | 0.4165 | 0.6519 | 0.165* | 0.50 |
O712 | 0.614 (5) | 0.597 (2) | 0.651 (3) | 0.1166 (18) | 0.50 |
C742 | 0.538 (5) | 0.665 (6) | 0.699 (3) | 0.099 (4) | 0.50 |
H74C | 0.4593 | 0.6823 | 0.6709 | 0.119* | 0.50 |
H74D | 0.6061 | 0.7497 | 0.7280 | 0.119* | 0.50 |
C752 | 0.474 (2) | 0.5682 (17) | 0.7517 (16) | 0.109 (3) | 0.50 |
H75C | 0.5487 | 0.5776 | 0.7931 | 0.131* | 0.50 |
H75D | 0.3880 | 0.5839 | 0.7732 | 0.131* | 0.50 |
C762 | 0.4312 (10) | 0.4326 (7) | 0.7027 (5) | 0.0942 (17) | 0.50 |
H76C | 0.4422 | 0.3661 | 0.7312 | 0.113* | 0.50 |
H76D | 0.3297 | 0.4041 | 0.6787 | 0.113* | 0.50 |
C772 | 0.5426 (13) | 0.4597 (11) | 0.6465 (7) | 0.138 (4) | 0.50 |
H77C | 0.6168 | 0.4180 | 0.6558 | 0.165* | 0.50 |
H77D | 0.4931 | 0.4199 | 0.5954 | 0.165* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.03978 (14) | 0.03955 (14) | 0.03418 (13) | 0.01439 (10) | 0.00266 (9) | 0.00745 (9) |
S1 | 0.0694 (4) | 0.1076 (6) | 0.0804 (5) | 0.0395 (4) | 0.0319 (4) | 0.0551 (4) |
S2 | 0.0447 (3) | 0.1199 (6) | 0.0624 (4) | 0.0288 (4) | 0.0117 (3) | 0.0195 (4) |
O3 | 0.0650 (10) | 0.0690 (10) | 0.0494 (8) | 0.0231 (8) | −0.0032 (7) | 0.0278 (8) |
O4 | 0.1005 (15) | 0.0391 (9) | 0.0841 (13) | 0.0180 (9) | 0.0302 (11) | −0.0001 (8) |
O5 | 0.0595 (10) | 0.0737 (11) | 0.0646 (11) | 0.0162 (8) | −0.0152 (8) | 0.0293 (9) |
O6 | 0.1084 (16) | 0.0414 (9) | 0.0789 (13) | 0.0211 (10) | 0.0172 (12) | 0.0000 (8) |
N1 | 0.0461 (9) | 0.0554 (10) | 0.0417 (9) | 0.0178 (8) | 0.0044 (7) | 0.0116 (8) |
N2 | 0.0462 (9) | 0.0477 (9) | 0.0454 (9) | 0.0141 (8) | 0.0052 (7) | 0.0080 (7) |
N3 | 0.0440 (8) | 0.0366 (8) | 0.0381 (8) | 0.0118 (7) | 0.0024 (6) | 0.0092 (6) |
N4 | 0.0516 (9) | 0.0400 (8) | 0.0374 (8) | 0.0169 (7) | 0.0042 (7) | 0.0105 (6) |
N5 | 0.0420 (8) | 0.0460 (9) | 0.0392 (8) | 0.0173 (7) | 0.0005 (6) | 0.0086 (7) |
N6 | 0.0467 (9) | 0.0427 (9) | 0.0398 (8) | 0.0160 (7) | 0.0037 (7) | 0.0061 (7) |
C1 | 0.0415 (10) | 0.0562 (12) | 0.0468 (11) | 0.0245 (9) | 0.0050 (8) | 0.0123 (9) |
C2 | 0.0484 (11) | 0.0488 (11) | 0.0336 (9) | 0.0205 (9) | 0.0025 (8) | 0.0045 (8) |
C31 | 0.0477 (10) | 0.0362 (9) | 0.0440 (10) | 0.0082 (8) | 0.0046 (8) | 0.0089 (8) |
C32 | 0.0610 (13) | 0.0400 (10) | 0.0479 (11) | 0.0161 (9) | 0.0109 (9) | 0.0185 (8) |
C33 | 0.0519 (11) | 0.0479 (11) | 0.0363 (9) | 0.0214 (9) | 0.0057 (8) | 0.0147 (8) |
C34 | 0.0570 (14) | 0.0781 (17) | 0.0556 (14) | 0.0132 (12) | −0.0126 (11) | 0.0206 (12) |
C35 | 0.0522 (12) | 0.0584 (13) | 0.0522 (12) | 0.0057 (10) | −0.0092 (10) | 0.0157 (10) |
C36 | 0.0466 (10) | 0.0417 (10) | 0.0373 (9) | 0.0124 (8) | 0.0022 (8) | 0.0110 (8) |
C37 | 0.0472 (10) | 0.0353 (9) | 0.0407 (10) | 0.0108 (8) | 0.0015 (8) | 0.0125 (7) |
C41 | 0.0604 (13) | 0.0491 (12) | 0.0486 (11) | 0.0186 (10) | 0.0143 (10) | 0.0174 (9) |
C42 | 0.0782 (17) | 0.0410 (11) | 0.0689 (15) | 0.0158 (11) | 0.0223 (13) | 0.0188 (10) |
C43 | 0.0598 (13) | 0.0381 (10) | 0.0611 (13) | 0.0129 (9) | 0.0109 (10) | 0.0054 (9) |
C44 | 0.0851 (19) | 0.0595 (15) | 0.0651 (16) | 0.0212 (14) | 0.0217 (14) | −0.0055 (12) |
C45 | 0.0655 (14) | 0.0534 (13) | 0.0475 (12) | 0.0157 (11) | 0.0117 (10) | 0.0007 (10) |
C46 | 0.0477 (11) | 0.0421 (10) | 0.0426 (10) | 0.0133 (9) | 0.0034 (8) | 0.0047 (8) |
C47 | 0.0536 (11) | 0.0387 (10) | 0.0394 (10) | 0.0145 (8) | 0.0044 (8) | 0.0097 (8) |
C51 | 0.0451 (11) | 0.0527 (12) | 0.0454 (11) | 0.0202 (9) | 0.0037 (8) | 0.0069 (9) |
C52 | 0.0433 (11) | 0.0536 (12) | 0.0614 (13) | 0.0215 (9) | −0.0034 (9) | 0.0106 (10) |
C53 | 0.0435 (10) | 0.0464 (11) | 0.0522 (12) | 0.0063 (9) | −0.0102 (9) | 0.0158 (9) |
C54 | 0.0672 (16) | 0.0839 (18) | 0.0488 (13) | 0.0042 (13) | −0.0069 (12) | 0.0274 (13) |
C55 | 0.0599 (14) | 0.0718 (16) | 0.0431 (12) | 0.0086 (12) | 0.0024 (10) | 0.0157 (11) |
C56 | 0.0424 (10) | 0.0460 (11) | 0.0415 (10) | 0.0055 (8) | −0.0021 (8) | 0.0096 (8) |
C57 | 0.0416 (10) | 0.0486 (11) | 0.0414 (10) | 0.0162 (8) | 0.0017 (8) | 0.0075 (8) |
C61 | 0.0513 (12) | 0.0523 (12) | 0.0455 (11) | 0.0158 (10) | −0.0009 (9) | 0.0054 (9) |
C62 | 0.0643 (14) | 0.0516 (13) | 0.0500 (12) | 0.0059 (11) | −0.0036 (10) | 0.0005 (10) |
C63 | 0.0765 (16) | 0.0396 (11) | 0.0483 (12) | 0.0146 (11) | 0.0140 (11) | 0.0068 (9) |
C64 | 0.121 (3) | 0.0515 (15) | 0.088 (2) | 0.0437 (17) | 0.0379 (19) | 0.0194 (14) |
C65 | 0.0810 (18) | 0.0599 (15) | 0.0773 (17) | 0.0375 (14) | 0.0258 (14) | 0.0243 (13) |
C66 | 0.0630 (13) | 0.0450 (11) | 0.0491 (11) | 0.0221 (10) | 0.0190 (10) | 0.0158 (9) |
C67 | 0.0469 (11) | 0.0470 (11) | 0.0438 (10) | 0.0176 (9) | 0.0073 (8) | 0.0081 (8) |
O711 | 0.166 (3) | 0.085 (2) | 0.106 (7) | 0.038 (2) | 0.070 (3) | 0.0345 (17) |
C741 | 0.104 (3) | 0.098 (9) | 0.111 (12) | 0.040 (5) | 0.026 (6) | 0.044 (5) |
C751 | 0.097 (9) | 0.105 (7) | 0.126 (4) | 0.023 (7) | 0.053 (5) | 0.037 (5) |
C761 | 0.107 (5) | 0.069 (3) | 0.116 (5) | 0.030 (3) | 0.046 (3) | 0.035 (3) |
C771 | 0.188 (11) | 0.089 (5) | 0.153 (9) | 0.053 (7) | 0.103 (8) | 0.034 (6) |
O712 | 0.166 (3) | 0.085 (2) | 0.106 (7) | 0.038 (2) | 0.070 (3) | 0.0345 (17) |
C742 | 0.104 (3) | 0.098 (9) | 0.111 (12) | 0.040 (5) | 0.026 (6) | 0.044 (5) |
C752 | 0.097 (9) | 0.105 (7) | 0.126 (4) | 0.023 (7) | 0.053 (5) | 0.037 (5) |
C762 | 0.107 (5) | 0.069 (3) | 0.116 (5) | 0.030 (3) | 0.046 (3) | 0.035 (3) |
C772 | 0.188 (11) | 0.089 (5) | 0.153 (9) | 0.053 (7) | 0.103 (8) | 0.034 (6) |
Ni1—N2 | 2.0730 (18) | C51—C52 | 1.384 (3) |
Ni1—N1 | 2.0781 (18) | C51—H51 | 0.9300 |
Ni1—N3 | 2.1262 (16) | C52—C53 | 1.369 (3) |
Ni1—N5 | 2.1336 (16) | C52—H52 | 0.9300 |
Ni1—N6 | 2.1354 (17) | C53—C56 | 1.383 (3) |
Ni1—N4 | 2.1547 (17) | C54—C55 | 1.320 (4) |
S1—C1 | 1.627 (2) | C54—H54 | 0.9300 |
S2—C2 | 1.635 (2) | C55—C56 | 1.442 (3) |
O3—C33 | 1.359 (2) | C55—H55 | 0.9300 |
O3—C34 | 1.383 (3) | C56—C57 | 1.387 (3) |
O4—C43 | 1.359 (3) | C57—H57 | 0.9300 |
O4—C44 | 1.381 (3) | C61—C62 | 1.376 (3) |
O5—C53 | 1.362 (2) | C61—H61 | 0.9300 |
O5—C54 | 1.389 (3) | C62—C63 | 1.367 (4) |
O6—C63 | 1.359 (3) | C62—H62 | 0.9300 |
O6—C64 | 1.386 (4) | C63—C66 | 1.393 (3) |
N1—C1 | 1.154 (3) | C64—C65 | 1.329 (4) |
N2—C2 | 1.151 (3) | C64—H64 | 0.9300 |
N3—C37 | 1.338 (2) | C65—C66 | 1.440 (3) |
N3—C31 | 1.350 (2) | C65—H65 | 0.9300 |
N4—C47 | 1.335 (2) | C66—C67 | 1.389 (3) |
N4—C41 | 1.349 (3) | C67—H67 | 0.9300 |
N5—C57 | 1.334 (3) | O711—C771 | 1.400 (10) |
N5—C51 | 1.347 (3) | O711—C741 | 1.407 (9) |
N6—C67 | 1.338 (3) | C741—C751 | 1.512 (9) |
N6—C61 | 1.349 (3) | C741—H74A | 0.9700 |
C31—C32 | 1.378 (3) | C741—H74B | 0.9700 |
C31—H31 | 0.9300 | C751—C761 | 1.484 (10) |
C32—C33 | 1.367 (3) | C751—H75A | 0.9700 |
C32—H32 | 0.9300 | C751—H75B | 0.9700 |
C33—C36 | 1.390 (3) | C761—C771 | 1.470 (8) |
C34—C35 | 1.333 (3) | C761—H76A | 0.9700 |
C34—H34 | 0.9300 | C761—H76B | 0.9700 |
C35—C36 | 1.439 (3) | C771—H77A | 0.9700 |
C35—H35 | 0.9300 | C771—H77B | 0.9700 |
C36—C37 | 1.387 (3) | O712—C772 | 1.401 (10) |
C37—H37 | 0.9300 | O712—C742 | 1.407 (8) |
C41—C42 | 1.374 (3) | C742—C752 | 1.510 (9) |
C41—H41 | 0.9300 | C742—H74C | 0.9700 |
C42—C43 | 1.374 (3) | C742—H74D | 0.9700 |
C42—H42 | 0.9300 | C752—C762 | 1.486 (10) |
C43—C46 | 1.388 (3) | C752—H75C | 0.9700 |
C44—C45 | 1.322 (4) | C752—H75D | 0.9700 |
C44—H44 | 0.9300 | C762—C772 | 1.480 (8) |
C45—C46 | 1.441 (3) | C762—H76C | 0.9700 |
C45—H45 | 0.9300 | C762—H76D | 0.9700 |
C46—C47 | 1.381 (3) | C772—H77C | 0.9700 |
C47—H47 | 0.9300 | C772—H77D | 0.9700 |
N2—Ni1—N1 | 177.03 (7) | C52—C53—C56 | 122.34 (19) |
N2—Ni1—N3 | 93.18 (7) | C55—C54—O5 | 113.0 (2) |
N1—Ni1—N3 | 89.79 (6) | C55—C54—H54 | 123.5 |
N2—Ni1—N5 | 89.99 (7) | O5—C54—H54 | 123.5 |
N1—Ni1—N5 | 87.05 (7) | C54—C55—C56 | 105.6 (2) |
N3—Ni1—N5 | 175.81 (6) | C54—C55—H55 | 127.2 |
N2—Ni1—N6 | 88.26 (7) | C56—C55—H55 | 127.2 |
N1—Ni1—N6 | 91.66 (7) | C53—C56—C57 | 117.88 (19) |
N3—Ni1—N6 | 90.92 (6) | C53—C56—C55 | 106.2 (2) |
N5—Ni1—N6 | 91.91 (6) | C57—C56—C55 | 136.0 (2) |
N2—Ni1—N4 | 89.17 (7) | N5—C57—C56 | 121.39 (19) |
N1—Ni1—N4 | 91.04 (7) | N5—C57—H57 | 119.3 |
N3—Ni1—N4 | 86.74 (6) | C56—C57—H57 | 119.3 |
N5—Ni1—N4 | 90.57 (6) | N6—C61—C62 | 124.4 (2) |
N6—Ni1—N4 | 176.43 (6) | N6—C61—H61 | 117.8 |
C33—O3—C34 | 105.63 (16) | C62—C61—H61 | 117.8 |
C43—O4—C44 | 105.54 (19) | C63—C62—C61 | 115.6 (2) |
C53—O5—C54 | 104.98 (19) | C63—C62—H62 | 122.2 |
C63—O6—C64 | 105.3 (2) | C61—C62—H62 | 122.2 |
C1—N1—Ni1 | 151.07 (16) | O6—C63—C62 | 127.1 (2) |
C2—N2—Ni1 | 167.61 (18) | O6—C63—C66 | 110.6 (2) |
C37—N3—C31 | 118.71 (17) | C62—C63—C66 | 122.4 (2) |
C37—N3—Ni1 | 118.51 (12) | C65—C64—O6 | 112.4 (2) |
C31—N3—Ni1 | 122.74 (13) | C65—C64—H64 | 123.8 |
C47—N4—C41 | 118.77 (18) | O6—C64—H64 | 123.8 |
C47—N4—Ni1 | 117.53 (13) | C64—C65—C66 | 106.2 (3) |
C41—N4—Ni1 | 123.70 (14) | C64—C65—H65 | 126.9 |
C57—N5—C51 | 118.86 (17) | C66—C65—H65 | 126.9 |
C57—N5—Ni1 | 119.90 (13) | C67—C66—C63 | 117.6 (2) |
C51—N5—Ni1 | 120.83 (13) | C67—C66—C65 | 137.0 (2) |
C67—N6—C61 | 118.65 (18) | C63—C66—C65 | 105.4 (2) |
C67—N6—Ni1 | 122.04 (14) | N6—C67—C66 | 121.4 (2) |
C61—N6—Ni1 | 119.26 (14) | N6—C67—H67 | 119.3 |
N1—C1—S1 | 177.8 (2) | C66—C67—H67 | 119.3 |
N2—C2—S2 | 179.8 (2) | C771—O711—C741 | 104 (4) |
N3—C31—C32 | 124.14 (19) | O711—C741—C751 | 110 (4) |
N3—C31—H31 | 117.9 | O711—C741—H74A | 109.6 |
C32—C31—H31 | 117.9 | C751—C741—H74A | 109.6 |
C33—C32—C31 | 115.67 (18) | O711—C741—H74B | 109.6 |
C33—C32—H32 | 122.2 | C751—C741—H74B | 109.6 |
C31—C32—H32 | 122.2 | H74A—C741—H74B | 108.1 |
O3—C33—C32 | 127.32 (18) | C761—C751—C741 | 98 (3) |
O3—C33—C36 | 110.25 (18) | C761—C751—H75A | 112.2 |
C32—C33—C36 | 122.44 (18) | C741—C751—H75A | 112.2 |
C35—C34—O3 | 112.4 (2) | C761—C751—H75B | 112.2 |
C35—C34—H34 | 123.8 | C741—C751—H75B | 112.2 |
O3—C34—H34 | 123.8 | H75A—C751—H75B | 109.8 |
C34—C35—C36 | 105.9 (2) | C771—C761—C751 | 109.5 (15) |
C34—C35—H35 | 127.1 | C771—C761—H76A | 109.8 |
C36—C35—H35 | 127.1 | C751—C761—H76A | 109.8 |
C37—C36—C33 | 117.58 (18) | C771—C761—H76B | 109.8 |
C37—C36—C35 | 136.53 (19) | C751—C761—H76B | 109.8 |
C33—C36—C35 | 105.89 (18) | H76A—C761—H76B | 108.2 |
N3—C37—C36 | 121.44 (17) | O711—C771—C761 | 108 (3) |
N3—C37—H37 | 119.3 | O711—C771—H77A | 110.2 |
C36—C37—H37 | 119.3 | C761—C771—H77A | 110.2 |
N4—C41—C42 | 123.8 (2) | O711—C771—H77B | 110.2 |
N4—C41—H41 | 118.1 | C761—C771—H77B | 110.2 |
C42—C41—H41 | 118.1 | H77A—C771—H77B | 108.5 |
C43—C42—C41 | 116.0 (2) | C772—O712—C742 | 107 (5) |
C43—C42—H42 | 122.0 | O712—C742—C752 | 103 (4) |
C41—C42—H42 | 122.0 | O712—C742—H74C | 111.2 |
O4—C43—C42 | 127.8 (2) | C752—C742—H74C | 111.2 |
O4—C43—C46 | 110.2 (2) | O712—C742—H74D | 111.2 |
C42—C43—C46 | 122.0 (2) | C752—C742—H74D | 111.2 |
C45—C44—O4 | 112.6 (2) | H74C—C742—H74D | 109.1 |
C45—C44—H44 | 123.7 | C762—C752—C742 | 105 (3) |
O4—C44—H44 | 123.7 | C762—C752—H75C | 110.7 |
C44—C45—C46 | 106.0 (2) | C742—C752—H75C | 110.7 |
C44—C45—H45 | 127.0 | C762—C752—H75D | 110.7 |
C46—C45—H45 | 127.0 | C742—C752—H75D | 110.7 |
C47—C46—C43 | 117.57 (19) | H75C—C752—H75D | 108.8 |
C47—C46—C45 | 136.7 (2) | C772—C762—C752 | 99.7 (14) |
C43—C46—C45 | 105.68 (19) | C772—C762—H76C | 111.8 |
N4—C47—C46 | 121.83 (18) | C752—C762—H76C | 111.8 |
N4—C47—H47 | 119.1 | C772—C762—H76D | 111.8 |
C46—C47—H47 | 119.1 | C752—C762—H76D | 111.8 |
N5—C51—C52 | 124.0 (2) | H76C—C762—H76D | 109.5 |
N5—C51—H51 | 118.0 | O712—C772—C762 | 112 (3) |
C52—C51—H51 | 118.0 | O712—C772—H77C | 109.2 |
C53—C52—C51 | 115.50 (19) | C762—C772—H77C | 109.2 |
C53—C52—H52 | 122.2 | O712—C772—H77D | 109.2 |
C51—C52—H52 | 122.2 | C762—C772—H77D | 109.2 |
O5—C53—C52 | 127.4 (2) | H77C—C772—H77D | 107.9 |
O5—C53—C56 | 110.3 (2) |
[Ni(NCS)2(C9H8NO)4]·6.6H2O | Z = 1 |
Mr = 882.46 | F(000) = 464 |
Triclinic, P1 | Dx = 1.326 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1663 (10) Å | Cell parameters from 801 reflections |
b = 10.5562 (11) Å | θ = 3.4–27.9° |
c = 12.1745 (13) Å | µ = 0.59 mm−1 |
α = 79.863 (2)° | T = 299 K |
β = 79.030 (2)° | Prism, blue |
γ = 74.521 (2)° | 0.18 × 0.18 × 0.13 mm |
V = 1104.7 (2) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 4782 independent reflections |
Radiation source: fine-focus sealed tube | 3571 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
Detector resolution: 512 pixels mm-1 | θmax = 29.0°, θmin = 1.7° |
ϕ and ω scans | h = −11→12 |
Absorption correction: multi-scan (XPREP; Sheldrick, 1990) | k = −13→14 |
Tmin = 0.793, Tmax = 0.984 | l = 0→16 |
4782 measured 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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.069P)2 + 0.6061P] where P = (Fo2 + 2Fc2)/3 |
4782 reflections | (Δ/σ)max < 0.001 |
236 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −1.52 e Å−3 |
[Ni(NCS)2(C9H8NO)4]·6.6H2O | γ = 74.521 (2)° |
Mr = 882.46 | V = 1104.7 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.1663 (10) Å | Mo Kα radiation |
b = 10.5562 (11) Å | µ = 0.59 mm−1 |
c = 12.1745 (13) Å | T = 299 K |
α = 79.863 (2)° | 0.18 × 0.18 × 0.13 mm |
β = 79.030 (2)° |
Bruker SMART 1K CCD area-detector diffractometer | 4782 independent reflections |
Absorption correction: multi-scan (XPREP; Sheldrick, 1990) | 3571 reflections with I > 2σ(I) |
Tmin = 0.793, Tmax = 0.984 | Rint = 0.000 |
4782 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.54 e Å−3 |
4782 reflections | Δρmin = −1.52 e Å−3 |
236 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. |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 1.0000 | 1.0000 | 0.03847 (17) | |
S1 | 0.50386 (10) | 1.00781 (12) | 0.81429 (10) | 0.0841 (4) | |
O1 | 0.0147 (3) | 0.7790 (2) | 0.5499 (2) | 0.0652 (6) | |
O2 | 0.3516 (3) | 0.4267 (2) | 1.1722 (3) | 0.0790 (8) | |
N1 | 0.2085 (2) | 1.0390 (2) | 0.93194 (19) | 0.0430 (5) | |
N2 | −0.0087 (2) | 0.9288 (2) | 0.84305 (19) | 0.0416 (5) | |
N3 | 0.1160 (3) | 0.8012 (2) | 1.0660 (2) | 0.0455 (6) | |
C1 | 0.3319 (3) | 1.0277 (3) | 0.8838 (2) | 0.0421 (6) | |
C2 | −0.1111 (3) | 0.8601 (3) | 0.8371 (3) | 0.0526 (7) | |
H2 | −0.1838 | 0.8496 | 0.9005 | 0.063* | |
C3 | −0.1160 (4) | 0.8044 (4) | 0.7443 (3) | 0.0596 (8) | |
H3 | −0.1881 | 0.7570 | 0.7437 | 0.072* | |
C4 | −0.0070 (4) | 0.8236 (3) | 0.6523 (3) | 0.0525 (7) | |
C5 | 0.1399 (4) | 0.8238 (4) | 0.4867 (3) | 0.0599 (8) | |
C6 | 0.1879 (5) | 0.7824 (5) | 0.3717 (3) | 0.0828 (12) | |
H6A | 0.2538 | 0.8353 | 0.3270 | 0.124* | |
H6B | 0.0990 | 0.7946 | 0.3365 | 0.124* | |
H6C | 0.2418 | 0.6906 | 0.3775 | 0.124* | |
C7 | 0.1929 (4) | 0.8943 (3) | 0.5436 (3) | 0.0558 (8) | |
C8 | 0.3228 (5) | 0.9600 (5) | 0.5065 (3) | 0.0856 (13) | |
H8A | 0.3789 | 0.9322 | 0.4363 | 0.128* | |
H8B | 0.3895 | 0.9356 | 0.5627 | 0.128* | |
H8C | 0.2835 | 1.0545 | 0.4966 | 0.128* | |
C9 | 0.0973 (3) | 0.8961 (3) | 0.6534 (2) | 0.0452 (6) | |
C10 | 0.0927 (3) | 0.9475 (3) | 0.7506 (2) | 0.0456 (6) | |
H10 | 0.1623 | 0.9969 | 0.7521 | 0.055* | |
C11 | 0.0421 (4) | 0.7033 (3) | 1.0912 (4) | 0.0673 (10) | |
H11 | −0.0611 | 0.7250 | 1.0840 | 0.081* | |
C12 | 0.1079 (4) | 0.5740 (4) | 1.1269 (4) | 0.0847 (14) | |
H12 | 0.0528 | 0.5090 | 1.1429 | 0.102* | |
C13 | 0.2603 (4) | 0.5455 (3) | 1.1377 (3) | 0.0625 (9) | |
C14 | 0.4958 (4) | 0.4496 (3) | 1.1674 (3) | 0.0598 (8) | |
C15 | 0.6159 (5) | 0.3301 (4) | 1.2015 (4) | 0.0793 (11) | |
H15A | 0.7154 | 0.3458 | 1.1723 | 0.119* | |
H15B | 0.6050 | 0.2552 | 1.1718 | 0.119* | |
H15C | 0.6046 | 0.3123 | 1.2824 | 0.119* | |
C16 | 0.4961 (3) | 0.5768 (3) | 1.1316 (3) | 0.0522 (7) | |
C17 | 0.6288 (4) | 0.6386 (4) | 1.1112 (5) | 0.0865 (13) | |
H17A | 0.6113 | 0.7027 | 1.1622 | 0.130* | |
H17B | 0.6405 | 0.6816 | 1.0348 | 0.130* | |
H17C | 0.7202 | 0.5712 | 1.1234 | 0.130* | |
C18 | 0.3412 (3) | 0.6428 (3) | 1.1125 (2) | 0.0452 (6) | |
C19 | 0.2646 (3) | 0.7700 (3) | 1.0776 (2) | 0.0441 (6) | |
H19 | 0.3174 | 0.8367 | 1.0616 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0287 (3) | 0.0409 (3) | 0.0444 (3) | −0.00923 (19) | 0.00484 (18) | −0.0118 (2) |
S1 | 0.0462 (5) | 0.1084 (8) | 0.0993 (8) | −0.0304 (5) | 0.0302 (5) | −0.0441 (7) |
O1 | 0.0730 (15) | 0.0724 (16) | 0.0567 (14) | −0.0208 (12) | −0.0024 (11) | −0.0291 (12) |
O2 | 0.0632 (15) | 0.0387 (13) | 0.131 (2) | −0.0093 (11) | −0.0247 (15) | 0.0068 (13) |
N1 | 0.0352 (11) | 0.0490 (13) | 0.0436 (12) | −0.0119 (10) | 0.0031 (9) | −0.0096 (10) |
N2 | 0.0345 (11) | 0.0422 (12) | 0.0461 (12) | −0.0082 (9) | 0.0007 (9) | −0.0099 (10) |
N3 | 0.0380 (12) | 0.0404 (13) | 0.0566 (14) | −0.0094 (10) | 0.0002 (10) | −0.0106 (10) |
C1 | 0.0411 (14) | 0.0447 (15) | 0.0429 (14) | −0.0150 (12) | −0.0011 (11) | −0.0109 (11) |
C2 | 0.0449 (16) | 0.0621 (19) | 0.0538 (17) | −0.0224 (14) | 0.0071 (13) | −0.0170 (14) |
C3 | 0.0571 (19) | 0.071 (2) | 0.0599 (19) | −0.0306 (17) | 0.0019 (15) | −0.0212 (16) |
C4 | 0.0529 (17) | 0.0543 (18) | 0.0522 (17) | −0.0109 (14) | −0.0039 (13) | −0.0201 (14) |
C5 | 0.061 (2) | 0.072 (2) | 0.0413 (16) | −0.0065 (16) | 0.0003 (14) | −0.0155 (15) |
C6 | 0.094 (3) | 0.098 (3) | 0.051 (2) | −0.008 (2) | −0.0024 (19) | −0.029 (2) |
C7 | 0.0467 (17) | 0.071 (2) | 0.0452 (16) | −0.0093 (15) | 0.0004 (13) | −0.0123 (15) |
C8 | 0.068 (2) | 0.144 (4) | 0.050 (2) | −0.045 (3) | 0.0102 (17) | −0.015 (2) |
C9 | 0.0371 (14) | 0.0510 (17) | 0.0448 (15) | −0.0057 (12) | −0.0038 (11) | −0.0094 (12) |
C10 | 0.0374 (14) | 0.0537 (17) | 0.0472 (15) | −0.0143 (12) | −0.0017 (11) | −0.0102 (12) |
C11 | 0.0415 (17) | 0.0454 (18) | 0.111 (3) | −0.0115 (14) | −0.0139 (18) | 0.0036 (18) |
C12 | 0.054 (2) | 0.048 (2) | 0.151 (4) | −0.0216 (17) | −0.026 (2) | 0.012 (2) |
C13 | 0.0528 (19) | 0.0390 (17) | 0.092 (3) | −0.0096 (14) | −0.0128 (17) | −0.0005 (16) |
C14 | 0.0561 (19) | 0.0490 (19) | 0.072 (2) | −0.0024 (15) | −0.0171 (16) | −0.0106 (15) |
C15 | 0.073 (2) | 0.055 (2) | 0.102 (3) | 0.0087 (18) | −0.029 (2) | −0.009 (2) |
C16 | 0.0467 (16) | 0.0446 (17) | 0.0644 (19) | −0.0030 (13) | −0.0116 (14) | −0.0136 (14) |
C17 | 0.054 (2) | 0.062 (2) | 0.144 (4) | −0.0086 (18) | −0.032 (2) | −0.006 (2) |
C18 | 0.0455 (15) | 0.0399 (15) | 0.0501 (16) | −0.0086 (12) | −0.0044 (12) | −0.0113 (12) |
C19 | 0.0435 (15) | 0.0439 (16) | 0.0468 (15) | −0.0130 (12) | −0.0021 (12) | −0.0124 (12) |
Ni1—N1 | 2.051 (2) | C6—H6C | 0.9600 |
Ni1—N1i | 2.051 (2) | C7—C9 | 1.452 (4) |
Ni1—N3i | 2.172 (2) | C7—C8 | 1.493 (5) |
Ni1—N3 | 2.172 (2) | C8—H8A | 0.9600 |
Ni1—N2i | 2.195 (2) | C8—H8B | 0.9600 |
Ni1—N2 | 2.195 (2) | C8—H8C | 0.9600 |
S1—C1 | 1.620 (3) | C9—C10 | 1.375 (4) |
O1—C4 | 1.371 (4) | C10—H10 | 0.9300 |
O1—C5 | 1.399 (4) | C11—C12 | 1.366 (5) |
O2—C13 | 1.356 (4) | C11—H11 | 0.9300 |
O2—C14 | 1.395 (4) | C12—C13 | 1.375 (5) |
N1—C1 | 1.156 (3) | C12—H12 | 0.9300 |
N2—C10 | 1.338 (3) | C13—C18 | 1.381 (4) |
N2—C2 | 1.350 (4) | C14—C16 | 1.338 (5) |
N3—C19 | 1.343 (4) | C14—C15 | 1.491 (5) |
N3—C11 | 1.343 (4) | C15—H15A | 0.9600 |
C2—C3 | 1.376 (4) | C15—H15B | 0.9600 |
C2—H2 | 0.9300 | C15—H15C | 0.9600 |
C3—C4 | 1.377 (4) | C16—C18 | 1.447 (4) |
C3—H3 | 0.9300 | C16—C17 | 1.489 (5) |
C4—C9 | 1.378 (4) | C17—H17A | 0.9600 |
C5—C7 | 1.332 (5) | C17—H17B | 0.9600 |
C5—C6 | 1.491 (4) | C17—H17C | 0.9600 |
C6—H6A | 0.9600 | C18—C19 | 1.374 (4) |
C6—H6B | 0.9600 | C19—H19 | 0.9300 |
N1—Ni1—N1i | 180.000 (1) | C7—C8—H8A | 109.5 |
N1—Ni1—N3i | 90.48 (9) | C7—C8—H8B | 109.5 |
N1i—Ni1—N3i | 89.52 (9) | H8A—C8—H8B | 109.5 |
N1—Ni1—N3 | 89.52 (9) | C7—C8—H8C | 109.5 |
N1i—Ni1—N3 | 90.48 (9) | H8A—C8—H8C | 109.5 |
N3i—Ni1—N3 | 180.000 (1) | H8B—C8—H8C | 109.5 |
N1—Ni1—N2i | 90.24 (9) | C10—C9—C4 | 118.2 (3) |
N1i—Ni1—N2i | 89.76 (9) | C10—C9—C7 | 135.6 (3) |
N3i—Ni1—N2i | 90.12 (9) | C4—C9—C7 | 106.2 (3) |
N3—Ni1—N2i | 89.88 (9) | N2—C10—C9 | 122.2 (3) |
N1—Ni1—N2 | 89.76 (9) | N2—C10—H10 | 118.9 |
N1i—Ni1—N2 | 90.24 (9) | C9—C10—H10 | 118.9 |
N3i—Ni1—N2 | 89.88 (9) | N3—C11—C12 | 124.6 (3) |
N3—Ni1—N2 | 90.12 (9) | N3—C11—H11 | 117.7 |
N2i—Ni1—N2 | 180.000 (1) | C12—C11—H11 | 117.7 |
C4—O1—C5 | 105.3 (2) | C11—C12—C13 | 116.2 (3) |
C13—O2—C14 | 105.9 (3) | C11—C12—H12 | 121.9 |
C1—N1—Ni1 | 161.2 (2) | C13—C12—H12 | 121.9 |
C10—N2—C2 | 117.5 (2) | O2—C13—C12 | 128.0 (3) |
C10—N2—Ni1 | 120.71 (19) | O2—C13—C18 | 110.6 (3) |
C2—N2—Ni1 | 121.74 (18) | C12—C13—C18 | 121.4 (3) |
C19—N3—C11 | 117.7 (3) | C16—C14—O2 | 111.6 (3) |
C19—N3—Ni1 | 121.74 (18) | C16—C14—C15 | 133.6 (3) |
C11—N3—Ni1 | 120.5 (2) | O2—C14—C15 | 114.9 (3) |
N1—C1—S1 | 178.0 (3) | C14—C15—H15A | 109.5 |
N2—C2—C3 | 124.8 (3) | C14—C15—H15B | 109.5 |
N2—C2—H2 | 117.6 | H15A—C15—H15B | 109.5 |
C3—C2—H2 | 117.6 | C14—C15—H15C | 109.5 |
C2—C3—C4 | 115.4 (3) | H15A—C15—H15C | 109.5 |
C2—C3—H3 | 122.3 | H15B—C15—H15C | 109.5 |
C4—C3—H3 | 122.3 | C14—C16—C18 | 106.0 (3) |
O1—C4—C3 | 127.7 (3) | C14—C16—C17 | 127.5 (3) |
O1—C4—C9 | 110.5 (3) | C18—C16—C17 | 126.4 (3) |
C3—C4—C9 | 121.8 (3) | C16—C17—H17A | 109.5 |
C7—C5—O1 | 112.2 (3) | C16—C17—H17B | 109.5 |
C7—C5—C6 | 133.2 (3) | H17A—C17—H17B | 109.5 |
O1—C5—C6 | 114.6 (3) | C16—C17—H17C | 109.5 |
C5—C6—H6A | 109.5 | H17A—C17—H17C | 109.5 |
C5—C6—H6B | 109.5 | H17B—C17—H17C | 109.5 |
H6A—C6—H6B | 109.5 | C19—C18—C13 | 118.1 (3) |
C5—C6—H6C | 109.5 | C19—C18—C16 | 136.0 (3) |
H6A—C6—H6C | 109.5 | C13—C18—C16 | 105.9 (3) |
H6B—C6—H6C | 109.5 | N3—C19—C18 | 122.1 (3) |
C5—C7—C9 | 105.8 (3) | N3—C19—H19 | 119.0 |
C5—C7—C8 | 128.9 (3) | C18—C19—H19 | 119.0 |
C9—C7—C8 | 125.2 (3) |
Symmetry code: (i) −x, −y+2, −z+2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Ni(NCS)2(C7H5NO)4]·C4H8O | [Ni(NCS)2(C9H8NO)4]·6.6H2O |
Mr | 723.45 | 882.46 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 300 | 299 |
a, b, c (Å) | 9.4916 (10), 10.7191 (11), 17.8360 (19) | 9.1663 (10), 10.5562 (11), 12.1745 (13) |
α, β, γ (°) | 99.580 (2), 92.278 (2), 108.726 (2) | 79.863 (2), 79.030 (2), 74.521 (2) |
V (Å3) | 1686.2 (3) | 1104.7 (2) |
Z | 2 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.75 | 0.59 |
Crystal size (mm) | 0.50 × 0.36 × 0.30 | 0.18 × 0.18 × 0.13 |
Data collection | ||
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (XPREP; Sheldrick, 1990) | Multi-scan (XPREP; Sheldrick, 1990) |
Tmin, Tmax | 0.829, 0.936 | 0.793, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10159, 7414, 6280 | 4782, 4782, 3571 |
Rint | 0.018 | 0.000 |
(sin θ/λ)max (Å−1) | 0.661 | 0.682 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.109, 1.05 | 0.052, 0.152, 1.06 |
No. of reflections | 7414 | 4782 |
No. of parameters | 448 | 236 |
No. of restraints | 10 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −0.54 | 0.54, −1.52 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003), SHELXTL (Bruker, 1999), SHELXTL.
Ni1—N2 | 2.0730 (18) | Ni1—N4 | 2.1547 (17) |
Ni1—N1 | 2.0781 (18) | S1—C1 | 1.627 (2) |
Ni1—N3 | 2.1262 (16) | S2—C2 | 1.635 (2) |
Ni1—N5 | 2.1336 (16) | N1—C1 | 1.154 (3) |
Ni1—N6 | 2.1354 (17) | N2—C2 | 1.151 (3) |
N2—Ni1—N1 | 177.03 (7) | N2—Ni1—N4 | 89.17 (7) |
N2—Ni1—N3 | 93.18 (7) | N1—Ni1—N4 | 91.04 (7) |
N1—Ni1—N3 | 89.79 (6) | N3—Ni1—N4 | 86.74 (6) |
N2—Ni1—N5 | 89.99 (7) | N5—Ni1—N4 | 90.57 (6) |
N1—Ni1—N5 | 87.05 (7) | N6—Ni1—N4 | 176.43 (6) |
N3—Ni1—N5 | 175.81 (6) | C1—N1—Ni1 | 151.07 (16) |
N2—Ni1—N6 | 88.26 (7) | C2—N2—Ni1 | 167.61 (18) |
N1—Ni1—N6 | 91.66 (7) | N1—C1—S1 | 177.8 (2) |
N3—Ni1—N6 | 90.92 (6) | N2—C2—S2 | 179.8 (2) |
N5—Ni1—N6 | 91.91 (6) |
Ni1—N1 | 2.051 (2) | S1—C1 | 1.620 (3) |
Ni1—N3 | 2.172 (2) | N1—C1 | 1.156 (3) |
Ni1—N2 | 2.195 (2) | ||
N1—Ni1—N3 | 89.52 (9) | C1—N1—Ni1 | 161.2 (2) |
N1—Ni1—N2 | 89.76 (9) | N1—C1—S1 | 178.0 (3) |
N3—Ni1—N2 | 90.12 (9) |
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Pyridine and its derivatives are common organic ligands in transition metal coordination compounds. Interest in nickel complexes with pyridines increased after 1957, when it was demonstrated (Schaeffer et al., 1957) that some Werner complexes are able to absorb organic compounds in a reversible manner. Recently, the syntheses of furo[3,2-c]pyridines and pyrrolo[2',3':4,5]furo[3,2-c]pyridines have been reported (New et al., 1989; Bencková & Krutošíková, 1995; Krutošíková & Dandárová, 1994; Krutošíková & Sleziak, 1996). To the best of our knowledge, until our recent synthesis of a series of Ni(fupy*)4(NCS)2 complexes, with fupy* being differently substituted furopyridines (Miklovič et al., 2003), these compounds had not been used in complexation reactions. This paper describes the molecular and crystal structures of the first two members of this family, namely [Ni(fupy)4(NCS)2]·THF, (I) (where fupy is furo[3,2-c]pyridine and THF is tetrahydrofuran), and [Ni(Me2fupy)4(NCS)2]·6.6H2O, (II), (where Me2fupy is 2,3-dimethylfuro[3,2-c]pyridine). \sch
In complexes (I) (Fig. 1) and (II) (Fig. 2), the central Ni atom is in a tetragonally distorted bipyramidal environment. Four N atoms from monodentate furopyridine ligands form the tetragonal base, with atom Ni1 sitting in the idealized plane. Two N atoms from isothiocyanato anions occupy the apical positions, at Ni—N distances [2.0730 (18) and 2.0781 (18) Å for (I), and 2.051 (2) Å for (II)] considerably shorter than the equatorial ones [2.1262 (16)–2.1547 (17) Å for (I), and 2.172 (2) and 2.195 (2) Å for (II)]. Both compounds contain interstitial solvent molecules in the crystal structure and can be considered as Werner clathrates (Lipkowski, 1996). Indeed, their molecular structures possess all the characteristics of Werner host complexes.
A Cambridge Structural Database (CSD; Allen, 2002) search for mononuclear complexes with four monodentate pyridine-type ligands coordinated to NiII revealed 110 structures, all of them containing Ni in a trans-octahedral coordination, with a high preference (84 compounds) for species with NCS− as the two trans anionic ligands. These 84 structures represent 91 hits (more than one symmetry-independent molecule present in multiple cases), from which only 79 were used for comparison with (I) and (II) for the following reasons. Eight hits were omitted (CSD refcodes CULLOK10, CULLUQ10, GAJXOE, GAJXUK, SABHAE10 Please provide all references for these), since their structural parameters were of poor quality and the geometrical data for their [NiN6] polyhedra were out of the range of the other 79 species. Another four hits, all describing complexes with 4-vinylpyridine, were omitted from the pool because of anomalous rhombohedral distortion of their [NiN6] polyhedra (CSD refcodes DOJXOP, DOJXOP01, VAXVEV, VAXVIZ Please provide all references for these). In addition to 79 hits with differently substituted pyridines, one NiII complex was found with quinoline as an equatorial ligand (Soldatov & Lipkovski, 1997). This means that the title compounds, (I) and (II), represent only the second and third examples of [Ni(L)4(NCS)2] complexes, with L being a monodentate ligand in which pyridine is part of a condensed ring system.
As was elegantly described by Lipkowski (1996), the most common structure for [Ni(L)4(NCS)2] complexes is a `four-blade propeller' arrangement of ligands around the central Ni atom, which minimizes the energy of the non-bonded interactions within the molecule. Compound (I) adopts the `propeller' structure, while (II) represents an alternative centrosymmetric arrangement of the Me2fupy ligands. It is believed (Lipkowski, 1996) that the preference for the alternative arrangement is probably affected by the presence of interstitial molecules; in the case of the title compounds, these are THF in (I) and H2O in (II). The differences in molecular conformation between (I) (Fig. 1) and (II) (Fig. 2) are worth discussing in detail and comparing with compounds from the CSD.
The axial-equatorial effect in NiII complexes is known as a version of the `cis effect' (Gažo et al., 1982). The ranges for Ni—Nax and Ni—Neq distances for the above-mentioned 79 hits from the CSD were 2.01–2.10 and 2.11–2.17 Å, respectively. The calculated mean difference between the averaged Ni—Nax and Ni—Neq distances was 0.07 Å for the database data, 0.06 Å for (I), and noticeably higher (0.13 Å) for (II), but still within the range of the CSD data (0.03–0.15 Å). A more extreme compression of the tetragonal bipyramid (0.22 Å) was observed for the quinoline complex (Soldatov & Lipkovski, 1997). Because (II) has a centrosymmetric arrangement of ligands, the three angles in the Ni coordination polyhedron are 180°, while they are 176.43 (6), 175.81 (6) and 177.03 (7)° in (I).
The `propeller' arrangement of four equatorial ligands is a preferred environment for the central Ni atom and is observed in (I), while the Me2fupy ligands in (II) are not far from being perpendicular to the basal octahedron plane formed by four N donor atoms. However, the propeller arrangement of the fupy ligands in (I) is not very regular, as seen from the conformational angles between the normals of the calculated fupy planes and the octahedron basal plane [38.70 (7), 47.02 (6), 51.98 (5) and 55.28 (4)°]. Much higher conformational angles are observed for the Me2fupy ligands in (II) [69.97 (9) and 78.86 (8)°]. The calculated best-fit planes for the ligands, which are mutually trans, are almost perpendicular to each other [81.44 (5) and 86.12 (5)°] in (I), while being coplanar in (II). It seems to be a general trend that, when equatorial ligands are coplanar or almost coplanar, their conformational angles are higher. Lower conformational angles (ideally 45°) minimize steric hindrance between equatorial ligands and axial NCS− anions. This is why the plane in which lie two NCS− anions in (II) is almost diagonal to the [N4] square (which forms a base of the Ni octahedron), while in (I), the same plane collides with the Ni1 → N5 vector (Fig. 3).
The reasons for propeller versus centrosymmetric arrangements seem to be well understood (Lipkowski, 1981; Nassimbeni et al., 1986), but to the best of our knowledge, nobody has previously discussed the orientation of NCS− ligands with respect to the arrangement of four equatorial ligands, nor the mutual conformation of two NCS− ligands. Linear NCS groups are attached to Ni atoms, forming Ni—N—C angles of 151.07 (16) and 167.61 (18)° in (I) and two angles of 161.2 (2)° in (II). Trans NCS ligands are not necessarily coplanar. They form a C—N···N—C dihedral angle of −13.9 (8)° in (I) and of 180° in (II), as depicted in Fig. 3. The observed centrosymmetric `trans-NCS' conformation in (II) is by far the most preferable arrangement of NCS− anions in NiII Werner complexes (Fig. 4), while the `cis' conformation found in (I) is relatively rare. Since it is believed that the propeller arrangement of four equatorial pyridine-type ligands is adopted in order to minimize intramolecular interactions, the apical NCS− anions could be liberated to afford any orientation with respect to the basal plane. Indeed, the angle between a plane in which both NCS and Ni lie and a vector Ni → N (N from pyridine) is typically in the range 42–45°, which not inevitably further minimizes the steric hindrance between equatorial and axial ligands. Such behaviour would be rather expected for centrosymmetric complexes in which the 45° angle (as defined above) was the only means of minimizing intramolecular interactions, but angles close to 0 or 31° were observed for centrosymmetric complexes in the CSD search.
In contrast with the database statistical results, (I) possesses the `cis' mutual conformation of NCS groups, and forming angles of 3.2 and 21.3° with the Ni1 → N5 vector. This angle is 41.6° in (II), the highest value among the centrosymmetric database complexes. It seems to us that other factors (probably intermolecular host–guest or host-host interactions) might significantly influence the fine-tuning of the molecular structure of Werner clathrates.
In (I), a THF molecule is trapped in the intermolecular cavity between four complex molecules, with closest H···H or O1···H intermolecular contacts of 2.5 Å and above. In (II), the water molecules which were present were disordered (see Experimental). Two mutually almost perpendicular [86.7 (1)°] π–π stacking interactions between coplanar aromatic furan rings, which are held 3.52 (2) and 3.61 (4) Å apart, seem to be the driving packing forces. The energetic contribution to the packing from the aromatic ring interactions and a lack of dominant determining host–guest interactions might explain the centrosymmetric arrangement in (II). Since the involvement of more extended aromatic molecules, such as fupy and Me2fupy, as equatorial ligands does not have (beside quinoline) an analogy in the family of [Ni(L)4(NCS)2] complexes, more structures with extended aromatic monodentate ligands will have to be studied to draw statistically more relevant and precise conclusions about the molecular structure.