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Three cis nickel-dithiocyanate (SCN) complexes with different N,N'-bidentate bases have been prepared and their crystal structures determined: bis(2,2'-bipyridine-N,N')bis(thiocyan-ato-N)nickel(II), [Ni(SCN)2(C10H8N2)2], bis(1,10-phenanthroline-N,N')bis(thiocyanato-N)nickel(II), [Ni(SCN)2(C12H8N2)2], and bis(2,9-dimethyl-1,10-phenanthroline-N,N')bis(thiocyanato-N)nickel(II) monohydrate, [Ni(SCN)2(C12H8N2)2]·H2O. Distortions due to ligand size are discussed.
Supporting information
CCDC references: 170170; 170171; 170172
Single crystals of the three compounds were obtained from diffusion in an
undisturbed liquid setup containing below a mixture of aqueous solutions of
nickel nitrate and potassium thiocyanate and above a methanolic solution of
the corresponding base. In all cases the reactants were present in a 1:1:1
molar ratio. All the specimens appeared at the interface, those corresponding
to (I) and (II) as small thin violet plates, while those for (III) consisting
of slightly thicker tablets of a turquoise color. Bulk material in the form of
crystalline powder and used for the different analyses performed was easily
obtained by direct mixing of the above mentioned solutions. All starting
materials were purchased from Aldrich and used without further purification.
Elemental Analyses (C, H, N) were performed on a Carlo Erba EA 1108
instrument. Nickel was determined on a Shimadzu AA6501 spectrophotometer.
In all cases the structure solution was achieved routinely by direct methods and
difference Fourier. The structures were refined by least squares on F2, with
anisotropic displacement parameters for non-H atoms. Hydrogen atoms
unambiguously defined by the stereochemistry (C—H's) were placed at their
calculated positions and allowed to ride into their host carbons both in
coordinates as well as in thermal parameter; methyl H atoms were further
allowed to rotate around the C—C bond. In compound (3), the hydration water
molecule site appeared disordered and slightly depleted (overall SOf ca
0.88) for what the corresponding H atoms could not be found nand were
accordingly disregarded. The molecule in compound (II) is positioned on a
twofold symmetry axis, for what only half of the monomer is independent.
Crystals of (I) did not diffract adequately and accordingly the data set
gathered was of a poor quality. This was evidenced in the rather large
Rint (0.061) and R (0.063) factors attained, as well as in the
residual peaks in the final Difference Fourier (1.12/-1.15 Å-3). The
latter were scattered around the cation position, at about 0.90 Å from its
center.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (I), (II); SMART (Bruker, for (III). Cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (I); MSC/AFC Diffractometer Control Software for (II); SAINT for (III). Data reduction: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (I); MSC/AFC Diffractometer Control Software for (II); SAINT for (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (I), (II); SHELXS97 (Sheldrick, 1997) for (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1994); software used to prepare material for publication: PARST (Nardelli, 1983) and CSD (Allen & Kennard, 1993).
(I) bis(Isothiocyanato-(2,2'-Bipyridine))-nickel(ii)
top
Crystal data top
[Ni(CNS)2(C10H8N2)2] | F(000) = 1000 |
Mr = 487.24 | Dx = 1.488 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.647 (3) Å | Cell parameters from 30 reflections |
b = 16.385 (3) Å | θ = 7.5–15° |
c = 8.0530 (16) Å | µ = 1.11 mm−1 |
β = 98.08 (3)° | T = 293 K |
V = 2174.7 (8) Å3 | Plates, violet |
Z = 4 | 0.24 × 0.18 × 0.08 mm |
Data collection top
Rigaku AFC7S Difractometer diffractometer | 3122 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.061 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω/2θ scans | h = −21→21 |
Absorption correction: ψ scan (MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988) | k = −21→0 |
Tmin = 0.84, Tmax = 0.92 | l = −1→10 |
6054 measured reflections | 3 standard reflections every 150 reflections |
5008 independent reflections | intensity decay: <3% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.205 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.134P)2] where P = (Fo2 + 2Fc2)/3 |
5008 reflections | (Δ/σ)max < 0.01 |
280 parameters | Δρmax = 1.12 e Å−3 |
0 restraints | Δρmin = −1.15 e Å−3 |
Crystal data top
[Ni(CNS)2(C10H8N2)2] | V = 2174.7 (8) Å3 |
Mr = 487.24 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.647 (3) Å | µ = 1.11 mm−1 |
b = 16.385 (3) Å | T = 293 K |
c = 8.0530 (16) Å | 0.24 × 0.18 × 0.08 mm |
β = 98.08 (3)° | |
Data collection top
Rigaku AFC7S Difractometer diffractometer | 3122 reflections with I > 2σ(I) |
Absorption correction: ψ scan (MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988) | Rint = 0.061 |
Tmin = 0.84, Tmax = 0.92 | 3 standard reflections every 150 reflections |
6054 measured reflections | intensity decay: <3% |
5008 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.205 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.12 e Å−3 |
5008 reflections | Δρmin = −1.15 e Å−3 |
280 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni | 0.24795 (3) | 0.51414 (3) | 0.79095 (6) | 0.0310 (2) | |
S1C | 0.40415 (11) | 0.65712 (15) | 0.4367 (3) | 0.1013 (7) | |
C1C | 0.3570 (2) | 0.6179 (3) | 0.5821 (6) | 0.0445 (10) | |
N1C | 0.3231 (2) | 0.5927 (2) | 0.6842 (5) | 0.0420 (8) | |
S1D | 0.00070 (7) | 0.62619 (9) | 0.49934 (16) | 0.0568 (4) | |
C1D | 0.0861 (2) | 0.5869 (2) | 0.5844 (5) | 0.0355 (9) | |
N1D | 0.1480 (2) | 0.5589 (2) | 0.6433 (5) | 0.0437 (9) | |
N1A | 0.22107 (19) | 0.5897 (2) | 0.9797 (4) | 0.0349 (7) | |
N2A | 0.1713 (2) | 0.4403 (2) | 0.9119 (4) | 0.0368 (8) | |
C1A | 0.2476 (3) | 0.6667 (3) | 1.0078 (6) | 0.0466 (10) | |
H1AA | 0.2900 | 0.6851 | 0.9539 | 0.056* | |
C2A | 0.2150 (3) | 0.7187 (3) | 1.1118 (7) | 0.0587 (13) | |
H2AA | 0.2343 | 0.7718 | 1.1261 | 0.070* | |
C3A | 0.1533 (3) | 0.6924 (3) | 1.1955 (7) | 0.0635 (15) | |
H3AA | 0.1298 | 0.7275 | 1.2656 | 0.076* | |
C4A | 0.1271 (3) | 0.6126 (3) | 1.1730 (6) | 0.0530 (12) | |
H4AA | 0.0865 | 0.5926 | 1.2304 | 0.064* | |
C5A | 0.1617 (2) | 0.5630 (3) | 1.0651 (5) | 0.0362 (9) | |
C6A | 0.1352 (2) | 0.4777 (3) | 1.0271 (5) | 0.0376 (9) | |
C7A | 0.0772 (3) | 0.4388 (3) | 1.1087 (6) | 0.0497 (11) | |
H7AA | 0.0526 | 0.4658 | 1.1898 | 0.060* | |
C8A | 0.0572 (3) | 0.3587 (4) | 1.0655 (7) | 0.0634 (15) | |
H8AA | 0.0185 | 0.3314 | 1.1171 | 0.076* | |
C9A | 0.0941 (3) | 0.3203 (3) | 0.9484 (7) | 0.0607 (14) | |
H9AA | 0.0815 | 0.2663 | 0.9200 | 0.073* | |
C10A | 0.1511 (3) | 0.3623 (3) | 0.8708 (6) | 0.0498 (11) | |
H10A | 0.1759 | 0.3362 | 0.7889 | 0.060* | |
N1B | 0.27418 (19) | 0.4260 (2) | 0.6214 (4) | 0.0359 (7) | |
N2B | 0.35100 (19) | 0.4580 (2) | 0.9244 (4) | 0.0357 (7) | |
C1B | 0.2318 (3) | 0.4123 (3) | 0.4724 (6) | 0.0484 (11) | |
H1BA | 0.1822 | 0.4388 | 0.4455 | 0.058* | |
C2B | 0.2575 (3) | 0.3604 (3) | 0.3539 (6) | 0.0574 (13) | |
H2BA | 0.2269 | 0.3527 | 0.2493 | 0.069* | |
C3B | 0.3304 (3) | 0.3209 (3) | 0.3985 (7) | 0.0613 (14) | |
H3BA | 0.3496 | 0.2850 | 0.3237 | 0.074* | |
C4B | 0.3742 (3) | 0.3342 (3) | 0.5507 (6) | 0.0507 (11) | |
H4BA | 0.4239 | 0.3082 | 0.5792 | 0.061* | |
C5B | 0.3454 (2) | 0.3865 (2) | 0.6649 (5) | 0.0354 (9) | |
C6B | 0.3866 (2) | 0.4020 (2) | 0.8344 (5) | 0.0369 (9) | |
C7B | 0.4572 (2) | 0.3620 (3) | 0.9048 (6) | 0.0475 (11) | |
H7BA | 0.4816 | 0.3239 | 0.8424 | 0.057* | |
C8B | 0.4908 (3) | 0.3795 (3) | 1.0686 (7) | 0.0533 (12) | |
H8BA | 0.5374 | 0.3528 | 1.1177 | 0.064* | |
C9B | 0.4542 (3) | 0.4363 (3) | 1.1564 (7) | 0.0558 (13) | |
H9BA | 0.4756 | 0.4494 | 1.2661 | 0.067* | |
C10B | 0.3848 (3) | 0.4742 (3) | 1.0792 (6) | 0.0461 (10) | |
H10B | 0.3604 | 0.5132 | 1.1396 | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0264 (3) | 0.0308 (3) | 0.0356 (3) | 0.00053 (18) | 0.0039 (2) | 0.0015 (2) |
S1C | 0.0690 (10) | 0.1496 (19) | 0.0935 (13) | −0.0046 (11) | 0.0406 (10) | 0.0465 (13) |
C1C | 0.031 (2) | 0.049 (3) | 0.052 (3) | 0.0022 (18) | 0.003 (2) | 0.003 (2) |
N1C | 0.0361 (18) | 0.046 (2) | 0.045 (2) | −0.0009 (15) | 0.0103 (17) | 0.0098 (17) |
S1D | 0.0398 (6) | 0.0691 (8) | 0.0622 (8) | 0.0254 (5) | 0.0096 (6) | 0.0114 (6) |
C1D | 0.035 (2) | 0.036 (2) | 0.038 (2) | 0.0031 (16) | 0.0109 (17) | 0.0006 (17) |
N1D | 0.0361 (18) | 0.046 (2) | 0.048 (2) | 0.0056 (16) | 0.0026 (16) | 0.0024 (17) |
N1A | 0.0306 (16) | 0.0359 (17) | 0.0385 (18) | −0.0004 (13) | 0.0059 (14) | −0.0026 (14) |
N2A | 0.0324 (16) | 0.0340 (18) | 0.0437 (19) | −0.0057 (13) | 0.0041 (15) | 0.0029 (15) |
C1A | 0.046 (2) | 0.040 (2) | 0.053 (3) | −0.0088 (19) | 0.005 (2) | −0.005 (2) |
C2A | 0.067 (3) | 0.043 (3) | 0.065 (3) | −0.006 (2) | 0.005 (3) | −0.018 (2) |
C3A | 0.062 (3) | 0.067 (3) | 0.062 (3) | 0.009 (3) | 0.009 (3) | −0.026 (3) |
C4A | 0.046 (3) | 0.064 (3) | 0.051 (3) | 0.000 (2) | 0.014 (2) | −0.004 (2) |
C5A | 0.0319 (19) | 0.044 (2) | 0.0321 (19) | 0.0022 (16) | 0.0026 (16) | 0.0019 (17) |
C6A | 0.0281 (18) | 0.045 (2) | 0.038 (2) | −0.0018 (17) | −0.0007 (17) | 0.0100 (18) |
C7A | 0.035 (2) | 0.064 (3) | 0.050 (3) | −0.004 (2) | 0.008 (2) | 0.014 (2) |
C8A | 0.044 (3) | 0.072 (4) | 0.072 (4) | −0.019 (3) | 0.002 (3) | 0.032 (3) |
C9A | 0.063 (3) | 0.052 (3) | 0.064 (3) | −0.028 (2) | −0.001 (3) | 0.014 (3) |
C10A | 0.054 (3) | 0.039 (2) | 0.056 (3) | −0.012 (2) | 0.007 (2) | 0.000 (2) |
N1B | 0.0288 (16) | 0.0407 (18) | 0.0378 (18) | 0.0046 (13) | 0.0033 (14) | −0.0017 (14) |
N2B | 0.0302 (16) | 0.0347 (16) | 0.0408 (18) | −0.0032 (13) | −0.0003 (14) | 0.0065 (15) |
C1B | 0.043 (2) | 0.056 (3) | 0.044 (2) | 0.012 (2) | −0.001 (2) | −0.002 (2) |
C2B | 0.060 (3) | 0.058 (3) | 0.050 (3) | 0.011 (2) | −0.007 (2) | −0.008 (2) |
C3B | 0.066 (3) | 0.054 (3) | 0.065 (3) | 0.012 (2) | 0.013 (3) | −0.013 (3) |
C4B | 0.040 (2) | 0.047 (3) | 0.065 (3) | 0.013 (2) | 0.012 (2) | −0.002 (2) |
C5B | 0.0296 (18) | 0.032 (2) | 0.045 (2) | 0.0005 (15) | 0.0062 (17) | 0.0062 (17) |
C6B | 0.0279 (18) | 0.0317 (19) | 0.051 (2) | −0.0017 (15) | 0.0046 (17) | 0.0098 (18) |
C7B | 0.035 (2) | 0.042 (2) | 0.062 (3) | 0.0018 (18) | −0.003 (2) | 0.010 (2) |
C8B | 0.033 (2) | 0.058 (3) | 0.065 (3) | 0.001 (2) | −0.008 (2) | 0.014 (3) |
C9B | 0.050 (3) | 0.063 (3) | 0.049 (3) | −0.009 (2) | −0.011 (2) | 0.007 (2) |
C10B | 0.043 (2) | 0.049 (3) | 0.044 (2) | −0.004 (2) | −0.001 (2) | 0.005 (2) |
Geometric parameters (Å, º) top
Ni—N1D | 2.040 (4) | C5A—C6A | 1.484 (6) |
Ni—N1A | 2.057 (3) | C6A—C7A | 1.396 (6) |
Ni—N1C | 2.065 (4) | C7A—C8A | 1.386 (8) |
Ni—N1B | 2.076 (3) | C8A—C9A | 1.351 (8) |
Ni—N2A | 2.096 (3) | C9A—C10A | 1.390 (7) |
Ni—N2B | 2.104 (3) | N1B—C1B | 1.323 (5) |
S1C—C1C | 1.631 (5) | N1B—C5B | 1.352 (5) |
C1C—N1C | 1.138 (6) | N2B—C10B | 1.321 (6) |
S1D—C1D | 1.622 (4) | N2B—C6B | 1.356 (6) |
C1D—N1D | 1.166 (5) | C1B—C2B | 1.390 (7) |
N1A—C1A | 1.345 (5) | C2B—C3B | 1.378 (7) |
N1A—C5A | 1.354 (5) | C3B—C4B | 1.353 (7) |
N2A—C6A | 1.324 (6) | C4B—C5B | 1.391 (6) |
N2A—C10A | 1.350 (6) | C5B—C6B | 1.462 (6) |
C1A—C2A | 1.359 (7) | C6B—C7B | 1.395 (5) |
C2A—C3A | 1.374 (8) | C7B—C8B | 1.388 (7) |
C3A—C4A | 1.383 (8) | C8B—C9B | 1.364 (7) |
C4A—C5A | 1.373 (6) | C9B—C10B | 1.380 (7) |
| | | |
N1D—Ni—N1A | 88.29 (14) | N1A—C5A—C6A | 114.6 (4) |
N1D—Ni—N1C | 91.45 (14) | C4A—C5A—C6A | 123.3 (4) |
N1A—Ni—N1C | 98.04 (14) | N2A—C6A—C7A | 122.0 (4) |
N1D—Ni—N1B | 95.53 (14) | N2A—C6A—C5A | 115.5 (3) |
N1A—Ni—N1B | 172.83 (13) | C7A—C6A—C5A | 122.6 (4) |
N1C—Ni—N1B | 87.96 (15) | C8A—C7A—C6A | 118.2 (5) |
N1D—Ni—N2A | 88.75 (14) | C9A—C8A—C7A | 120.0 (4) |
N1A—Ni—N2A | 78.11 (14) | C8A—C9A—C10A | 119.3 (5) |
N1C—Ni—N2A | 176.13 (14) | N2A—C10A—C9A | 121.3 (5) |
N1B—Ni—N2A | 95.87 (14) | C1B—N1B—C5B | 119.4 (4) |
N1D—Ni—N2B | 173.92 (14) | C1B—N1B—Ni | 125.4 (3) |
N1A—Ni—N2B | 97.60 (14) | C5B—N1B—Ni | 114.9 (3) |
N1C—Ni—N2B | 89.26 (13) | C10B—N2B—C6B | 118.7 (4) |
N1B—Ni—N2B | 78.46 (13) | C10B—N2B—Ni | 127.1 (3) |
N2A—Ni—N2B | 90.94 (13) | C6B—N2B—Ni | 114.2 (3) |
N1C—C1C—S1C | 178.0 (4) | N1B—C1B—C2B | 123.3 (4) |
C1C—N1C—Ni | 156.6 (4) | C3B—C2B—C1B | 117.0 (5) |
N1D—C1D—S1D | 179.0 (4) | C4B—C3B—C2B | 120.2 (5) |
C1D—N1D—Ni | 168.5 (4) | C3B—C4B—C5B | 120.4 (4) |
C1A—N1A—C5A | 117.5 (4) | N1B—C5B—C4B | 119.7 (4) |
C1A—N1A—Ni | 126.1 (3) | N1B—C5B—C6B | 116.0 (4) |
C5A—N1A—Ni | 115.6 (3) | C4B—C5B—C6B | 124.3 (4) |
C6A—N2A—C10A | 119.3 (4) | N2B—C6B—C7B | 120.5 (4) |
C6A—N2A—Ni | 115.1 (3) | N2B—C6B—C5B | 115.7 (3) |
C10A—N2A—Ni | 125.3 (3) | C7B—C6B—C5B | 123.8 (4) |
N1A—C1A—C2A | 122.8 (5) | C8B—C7B—C6B | 119.5 (5) |
C1A—C2A—C3A | 119.8 (5) | C9B—C8B—C7B | 119.0 (4) |
C2A—C3A—C4A | 118.4 (5) | C8B—C9B—C10B | 118.7 (5) |
C5A—C4A—C3A | 119.3 (4) | N2B—C10B—C9B | 123.6 (5) |
N1A—C5A—C4A | 122.1 (4) | | |
| | | |
N1A—C5A—C6A—N2A | −1.9 (5) | N1B—C5B—C6B—N2B | −3.8 (5) |
(II) bis(Isothiocyanato-(1,10-Phenanthroline))-nickel(ii)
top
Crystal data top
[Ni(CNS)2(C12H8N2)2] | F(000) = 1096 |
Mr = 535.28 | Dx = 1.540 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 30 reflections |
a = 13.018 (3) Å | θ = 7.5–15° |
b = 10.116 (2) Å | µ = 1.05 mm−1 |
c = 17.536 (4) Å | T = 293 K |
V = 2309.3 (8) Å3 | Plates, violet |
Z = 4 | 0.20 × 0.20 × 0.14 mm |
Data collection top
Rigaku AFC7S Difractometer diffractometer | 1410 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
ω/2θ scans | h = −1→16 |
Absorption correction: ψ scan (MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988) | k = −1→13 |
Tmin = 0.77, Tmax = 0.85 | l = −22→1 |
3409 measured reflections | 3 standard reflections every 150 reflections |
2663 independent reflections | intensity decay: <3% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0534P)2] where P = (Fo2 + 2Fc2)/3 |
2663 reflections | (Δ/σ)max < 0.01 |
159 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
[Ni(CNS)2(C12H8N2)2] | V = 2309.3 (8) Å3 |
Mr = 535.28 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 13.018 (3) Å | µ = 1.05 mm−1 |
b = 10.116 (2) Å | T = 293 K |
c = 17.536 (4) Å | 0.20 × 0.20 × 0.14 mm |
Data collection top
Rigaku AFC7S Difractometer diffractometer | 1410 reflections with I > 2σ(I) |
Absorption correction: ψ scan (MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988) | Rint = 0.032 |
Tmin = 0.77, Tmax = 0.85 | 3 standard reflections every 150 reflections |
3409 measured reflections | intensity decay: <3% |
2663 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.28 e Å−3 |
2663 reflections | Δρmin = −0.25 e Å−3 |
159 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni | 0.5000 | 0.14932 (4) | 0.7500 | 0.04498 (14) | |
S1C | 0.36738 (6) | 0.47038 (8) | 0.92184 (4) | 0.0775 (2) | |
C1C | 0.42580 (17) | 0.3644 (2) | 0.86805 (14) | 0.0502 (6) | |
N1C | 0.46872 (16) | 0.2886 (2) | 0.83068 (13) | 0.0610 (6) | |
N1A | 0.34410 (14) | 0.12650 (19) | 0.72242 (11) | 0.0459 (5) | |
N2A | 0.50816 (14) | 0.00397 (19) | 0.66427 (10) | 0.0479 (4) | |
C1A | 0.26146 (19) | 0.1865 (3) | 0.75271 (16) | 0.0591 (6) | |
H1AA | 0.2720 | 0.2523 | 0.7890 | 0.071* | |
C2A | 0.1616 (2) | 0.1555 (3) | 0.73267 (17) | 0.0680 (8) | |
H2AA | 0.1069 | 0.1988 | 0.7558 | 0.082* | |
C3A | 0.14416 (19) | 0.0620 (3) | 0.67928 (17) | 0.0682 (8) | |
H3AA | 0.0771 | 0.0415 | 0.6652 | 0.082* | |
C4A | 0.22676 (18) | −0.0044 (3) | 0.64487 (14) | 0.0557 (6) | |
C5A | 0.32699 (17) | 0.0324 (2) | 0.66914 (13) | 0.0478 (6) | |
C6A | 0.41377 (17) | −0.0325 (2) | 0.63694 (13) | 0.0475 (6) | |
C7A | 0.40052 (19) | −0.1279 (3) | 0.57973 (15) | 0.0603 (7) | |
C8A | 0.4900 (2) | −0.1845 (3) | 0.54941 (18) | 0.0813 (9) | |
H8AA | 0.4851 | −0.2490 | 0.5118 | 0.098* | |
C9A | 0.5845 (2) | −0.1449 (3) | 0.5752 (2) | 0.0804 (9) | |
H9AA | 0.6441 | −0.1812 | 0.5548 | 0.096* | |
C10A | 0.5903 (2) | −0.0497 (3) | 0.63239 (16) | 0.0664 (7) | |
H10A | 0.6548 | −0.0225 | 0.6489 | 0.080* | |
C12A | 0.2997 (2) | −0.1616 (3) | 0.55696 (17) | 0.0711 (8) | |
H12A | 0.2904 | −0.2247 | 0.5190 | 0.085* | |
C11A | 0.2173 (2) | −0.1048 (3) | 0.58879 (17) | 0.0705 (8) | |
H11A | 0.1521 | −0.1318 | 0.5737 | 0.085* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0372 (2) | 0.0441 (2) | 0.0537 (2) | 0.000 | −0.0061 (2) | 0.000 |
S1C | 0.0795 (5) | 0.0761 (5) | 0.0770 (5) | 0.0113 (4) | 0.0084 (4) | −0.0117 (4) |
C1C | 0.0439 (12) | 0.0519 (14) | 0.0549 (14) | −0.0121 (12) | −0.0039 (11) | 0.0006 (13) |
N1C | 0.0526 (11) | 0.0566 (13) | 0.0739 (15) | −0.0014 (11) | 0.0023 (11) | −0.0081 (12) |
N1A | 0.0417 (10) | 0.0424 (11) | 0.0535 (11) | −0.0021 (8) | −0.0048 (9) | 0.0018 (9) |
N2A | 0.0374 (9) | 0.0498 (10) | 0.0564 (11) | 0.0038 (10) | −0.0047 (10) | −0.0066 (9) |
C1A | 0.0466 (13) | 0.0634 (15) | 0.0673 (15) | 0.0078 (11) | −0.0043 (14) | −0.0010 (14) |
C2A | 0.0430 (13) | 0.0744 (19) | 0.086 (2) | 0.0032 (14) | 0.0012 (13) | 0.0006 (17) |
C3A | 0.0382 (13) | 0.0716 (19) | 0.095 (2) | −0.0101 (13) | −0.0146 (14) | 0.0086 (18) |
C4A | 0.0519 (13) | 0.0563 (15) | 0.0589 (14) | −0.0069 (12) | −0.0102 (12) | 0.0089 (13) |
C5A | 0.0432 (12) | 0.0423 (13) | 0.0578 (14) | −0.0032 (11) | −0.0083 (11) | 0.0110 (12) |
C6A | 0.0493 (13) | 0.0447 (13) | 0.0485 (13) | −0.0066 (11) | −0.0063 (11) | 0.0061 (12) |
C7A | 0.0626 (16) | 0.0587 (16) | 0.0596 (16) | 0.0006 (13) | −0.0114 (13) | −0.0090 (15) |
C8A | 0.083 (2) | 0.082 (2) | 0.0797 (19) | 0.0047 (19) | −0.0042 (18) | −0.0315 (16) |
C9A | 0.0607 (17) | 0.083 (2) | 0.098 (2) | 0.0154 (17) | 0.0033 (16) | −0.024 (2) |
C10A | 0.0544 (16) | 0.0669 (18) | 0.0778 (18) | −0.0004 (14) | −0.0065 (14) | −0.0154 (17) |
C12A | 0.0767 (18) | 0.0705 (19) | 0.0661 (18) | −0.0072 (17) | −0.0161 (15) | −0.0122 (15) |
C11A | 0.0575 (16) | 0.0748 (18) | 0.0791 (19) | −0.0145 (15) | −0.0224 (15) | −0.0003 (16) |
Geometric parameters (Å, º) top
Ni—N1C | 2.038 (2) | C1A—C2A | 1.382 (4) |
Ni—N1Ci | 2.038 (2) | C2A—C3A | 1.351 (4) |
Ni—N1A | 2.0990 (19) | C3A—C4A | 1.404 (4) |
Ni—N1Ai | 2.0990 (19) | C4A—C11A | 1.419 (4) |
Ni—N2A | 2.1056 (19) | C4A—C5A | 1.422 (3) |
Ni—N2Ai | 2.1056 (19) | C5A—C6A | 1.424 (3) |
S1C—C1C | 1.618 (3) | C6A—C7A | 1.402 (3) |
C1C—N1C | 1.153 (3) | C7A—C8A | 1.402 (4) |
N1A—C1A | 1.345 (3) | C7A—C12A | 1.414 (3) |
N1A—C5A | 1.352 (3) | C8A—C9A | 1.372 (3) |
N2A—C10A | 1.323 (3) | C9A—C10A | 1.393 (4) |
N2A—C6A | 1.370 (3) | C12A—C11A | 1.339 (4) |
| | | |
N1C—Ni—N1Ci | 92.51 (13) | C6A—N2A—Ni | 113.13 (15) |
N1C—Ni—N1A | 92.45 (8) | N1A—C1A—C2A | 123.3 (3) |
N1Ci—Ni—N1A | 96.27 (8) | C3A—C2A—C1A | 119.6 (3) |
N1C—Ni—N1Ai | 96.27 (8) | C2A—C3A—C4A | 120.3 (2) |
N1Ci—Ni—N1Ai | 92.45 (8) | C3A—C4A—C11A | 125.0 (2) |
N1A—Ni—N1Ai | 167.37 (10) | C3A—C4A—C5A | 116.7 (2) |
N1C—Ni—N2A | 171.35 (8) | C11A—C4A—C5A | 118.3 (2) |
N1Ci—Ni—N2A | 88.68 (9) | N1A—C5A—C4A | 122.8 (2) |
N1A—Ni—N2A | 78.90 (7) | N1A—C5A—C6A | 117.9 (2) |
N1Ai—Ni—N2A | 92.23 (7) | C4A—C5A—C6A | 119.2 (2) |
N1C—Ni—N2Ai | 88.68 (9) | N2A—C6A—C7A | 123.1 (2) |
N1Ci—Ni—N2Ai | 171.35 (8) | N2A—C6A—C5A | 116.7 (2) |
N1A—Ni—N2Ai | 92.23 (7) | C7A—C6A—C5A | 120.2 (2) |
N1Ai—Ni—N2Ai | 78.90 (7) | C8A—C7A—C6A | 116.8 (2) |
N2A—Ni—N2Ai | 91.42 (11) | C8A—C7A—C12A | 124.4 (3) |
N1C—C1C—S1C | 178.8 (2) | C6A—C7A—C12A | 118.8 (2) |
C1C—N1C—Ni | 162.0 (2) | C9A—C8A—C7A | 120.1 (3) |
C1A—N1A—C5A | 117.3 (2) | C8A—C9A—C10A | 119.2 (3) |
C1A—N1A—Ni | 129.26 (16) | N2A—C10A—C9A | 123.0 (2) |
C5A—N1A—Ni | 113.32 (15) | C11A—C12A—C7A | 121.5 (3) |
C10A—N2A—C6A | 117.83 (19) | C12A—C11A—C4A | 121.8 (2) |
C10A—N2A—Ni | 128.96 (16) | | |
| | | |
N1A—C5A—C6A—N2A | 1.6 (5) | | |
Symmetry code: (i) −x+1, y, −z+3/2. |
(III) bis(Isothiocyanato-(2,9-dimethyl-1,10-phenanthroline))-nickel(ii) hydrate
top
Crystal data top
[Ni(CNS)2(C14H12N2)2]·H2O | Z = 2 |
Mr = 609.40 | F(000) = 6132 |
Triclinic, P1 | Dx = 1.445 Mg m−3 |
a = 9.689 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.757 (1) Å | Cell parameters from 10054 reflections |
c = 14.754 (1) Å | θ = 3.5–27.5° |
α = 77.71 (1)° | µ = 0.88 mm−1 |
β = 79.00 (1)° | T = 293 K |
γ = 70.07 (1)° | Plates, turquoise |
V = 1400.8 (2) Å3 | 0.23 × 0.22 × 0.16 mm |
Data collection top
Bruker SMART 6000 diffractometer | 3612 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.031 |
Mirrors monochromator | θmax = 27.5°, θmin = 2.0° |
Detector resolution: 4.923 pixels mm-1 | h = −12→12 |
ω scans | k = −13→13 |
10079 measured reflections | l = −19→18 |
6316 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full with fixed elements per cycle | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
6316 reflections | (Δ/σ)max < 0.01 |
366 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
[Ni(CNS)2(C14H12N2)2]·H2O | γ = 70.07 (1)° |
Mr = 609.40 | V = 1400.8 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.689 (1) Å | Mo Kα radiation |
b = 10.757 (1) Å | µ = 0.88 mm−1 |
c = 14.754 (1) Å | T = 293 K |
α = 77.71 (1)° | 0.23 × 0.22 × 0.16 mm |
β = 79.00 (1)° | |
Data collection top
Bruker SMART 6000 diffractometer | 3612 reflections with I > 2σ(I) |
10079 measured reflections | Rint = 0.031 |
6316 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.40 e Å−3 |
6316 reflections | Δρmin = −0.27 e Å−3 |
366 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ni | 0.82294 (4) | 0.27321 (3) | 0.25293 (2) | 0.04137 (11) | |
S1C | 0.70021 (9) | −0.11960 (7) | 0.25321 (6) | 0.0675 (2) | |
C1C | 0.7278 (3) | 0.0229 (3) | 0.24860 (17) | 0.0457 (6) | |
N1C | 0.7458 (2) | 0.1251 (2) | 0.24459 (15) | 0.0567 (6) | |
S1D | 0.45217 (8) | 0.68917 (7) | 0.18791 (5) | 0.0607 (2) | |
C1D | 0.5617 (3) | 0.5375 (3) | 0.21096 (16) | 0.0403 (6) | |
N1D | 0.6381 (2) | 0.4286 (2) | 0.22766 (15) | 0.0554 (6) | |
N1A | 0.9236 (2) | 0.31038 (19) | 0.11203 (13) | 0.0446 (5) | |
N2A | 0.9381 (2) | 0.41592 (17) | 0.25843 (13) | 0.0365 (5) | |
C1A | 0.9023 (3) | 0.2813 (3) | 0.0338 (2) | 0.0571 (8) | |
C2A | 1.0101 (4) | 0.2774 (3) | −0.0468 (2) | 0.0686 (9) | |
H2AA | 0.9933 | 0.2572 | −0.1011 | 0.082* | |
C3A | 1.1365 (4) | 0.3027 (3) | −0.0450 (2) | 0.0714 (9) | |
H3AA | 1.2083 | 0.2963 | −0.0971 | 0.086* | |
C4A | 1.1594 (3) | 0.3386 (3) | 0.03490 (18) | 0.0539 (7) | |
C5A | 1.0468 (3) | 0.3456 (2) | 0.11103 (17) | 0.0434 (6) | |
C6A | 1.0578 (3) | 0.3959 (2) | 0.19040 (16) | 0.0394 (6) | |
C7A | 1.1839 (3) | 0.4314 (3) | 0.19346 (19) | 0.0487 (7) | |
C8A | 1.1833 (3) | 0.4878 (3) | 0.2698 (2) | 0.0592 (8) | |
H8AA | 1.2674 | 0.5055 | 0.2778 | 0.071* | |
C9A | 1.0596 (3) | 0.5171 (3) | 0.33280 (19) | 0.0579 (8) | |
H9AA | 1.0570 | 0.5602 | 0.3818 | 0.069* | |
C10A | 0.9363 (3) | 0.4832 (2) | 0.32459 (17) | 0.0425 (6) | |
C11A | 1.2891 (3) | 0.3689 (3) | 0.0425 (2) | 0.0690 (9) | |
H11A | 1.3659 | 0.3600 | −0.0068 | 0.083* | |
C12A | 1.3019 (3) | 0.4101 (3) | 0.1193 (2) | 0.0659 (8) | |
H12A | 1.3893 | 0.4249 | 0.1239 | 0.079* | |
C13A | 0.7642 (4) | 0.2495 (3) | 0.0321 (2) | 0.0785 (10) | |
H13D | 0.6877 | 0.2916 | 0.0779 | 0.118* | |
H13E | 0.7834 | 0.1543 | 0.0461 | 0.118* | |
H13F | 0.7328 | 0.2823 | −0.0289 | 0.118* | |
C14A | 0.7957 (3) | 0.5283 (2) | 0.38971 (17) | 0.0536 (7) | |
H14A | 0.7180 | 0.5079 | 0.3701 | 0.080* | |
H14B | 0.7686 | 0.6232 | 0.3884 | 0.080* | |
H14C | 0.8109 | 0.4826 | 0.4522 | 0.080* | |
N1B | 0.7828 (2) | 0.23593 (18) | 0.40256 (13) | 0.0410 (5) | |
N2B | 1.0319 (2) | 0.12763 (18) | 0.29239 (13) | 0.0398 (5) | |
C1B | 0.6569 (3) | 0.2669 (2) | 0.46061 (19) | 0.0511 (7) | |
C2B | 0.6573 (3) | 0.2699 (3) | 0.55492 (19) | 0.0611 (8) | |
H2BA | 0.5681 | 0.2927 | 0.5940 | 0.073* | |
C3B | 0.7867 (4) | 0.2399 (3) | 0.58968 (19) | 0.0583 (8) | |
H3BA | 0.7858 | 0.2457 | 0.6518 | 0.070* | |
C4B | 0.9219 (3) | 0.2002 (2) | 0.53210 (17) | 0.0484 (7) | |
C5B | 0.9136 (3) | 0.1962 (2) | 0.43871 (16) | 0.0392 (6) | |
C6B | 1.0467 (3) | 0.1447 (2) | 0.37892 (16) | 0.0397 (6) | |
C7B | 1.1835 (3) | 0.1071 (2) | 0.41210 (18) | 0.0462 (7) | |
C8B | 1.3095 (3) | 0.0537 (3) | 0.3503 (2) | 0.0571 (8) | |
H8BA | 1.4035 | 0.0359 | 0.3661 | 0.069* | |
C9B | 1.2935 (3) | 0.0281 (3) | 0.2673 (2) | 0.0569 (8) | |
H9BA | 1.3767 | −0.0117 | 0.2277 | 0.068* | |
C10B | 1.1522 (3) | 0.0612 (2) | 0.24103 (18) | 0.0458 (6) | |
C11B | 1.0621 (4) | 0.1616 (3) | 0.56350 (19) | 0.0583 (8) | |
H11B | 1.0675 | 0.1654 | 0.6251 | 0.070* | |
C12B | 1.1872 (3) | 0.1195 (3) | 0.5056 (2) | 0.0573 (8) | |
H12B | 1.2781 | 0.0980 | 0.5271 | 0.069* | |
C13B | 0.5130 (3) | 0.2994 (3) | 0.4232 (2) | 0.0746 (9) | |
H13A | 0.5308 | 0.2642 | 0.3660 | 0.112* | |
H13B | 0.4680 | 0.3948 | 0.4115 | 0.112* | |
H13C | 0.4479 | 0.2600 | 0.4683 | 0.112* | |
C14B | 1.1335 (3) | 0.0152 (3) | 0.15603 (18) | 0.0619 (8) | |
H14F | 1.0305 | 0.0457 | 0.1480 | 0.093* | |
H14G | 1.1695 | −0.0809 | 0.1640 | 0.093* | |
H14D | 1.1884 | 0.0514 | 0.1018 | 0.093* | |
O1WA | 0.506 (3) | 0.0266 (19) | 0.0222 (11) | 0.170 (7)* | 0.264 (9) |
O1WB | 0.379 (3) | 0.022 (3) | −0.0311 (15) | 0.134 (8)* | 0.140 (9) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0439 (2) | 0.03700 (19) | 0.0439 (2) | −0.01291 (15) | −0.00792 (15) | −0.00539 (13) |
S1C | 0.0765 (6) | 0.0493 (5) | 0.0867 (6) | −0.0250 (4) | −0.0174 (5) | −0.0168 (4) |
C1C | 0.0422 (16) | 0.0519 (17) | 0.0430 (15) | −0.0104 (14) | −0.0094 (12) | −0.0113 (12) |
N1C | 0.0631 (16) | 0.0514 (15) | 0.0621 (15) | −0.0228 (13) | −0.0136 (12) | −0.0101 (12) |
S1D | 0.0607 (5) | 0.0467 (4) | 0.0608 (5) | −0.0077 (4) | 0.0036 (4) | −0.0046 (3) |
C1D | 0.0349 (15) | 0.0542 (17) | 0.0367 (14) | −0.0185 (13) | −0.0005 (11) | −0.0136 (11) |
N1D | 0.0470 (14) | 0.0560 (15) | 0.0613 (15) | −0.0133 (12) | −0.0087 (12) | −0.0086 (11) |
N1A | 0.0565 (14) | 0.0405 (12) | 0.0362 (12) | −0.0114 (11) | −0.0119 (11) | −0.0061 (9) |
N2A | 0.0407 (12) | 0.0297 (11) | 0.0367 (11) | −0.0097 (9) | −0.0033 (10) | −0.0041 (8) |
C1A | 0.075 (2) | 0.0462 (17) | 0.0507 (18) | −0.0144 (15) | −0.0213 (16) | −0.0041 (13) |
C2A | 0.101 (3) | 0.066 (2) | 0.0390 (17) | −0.021 (2) | −0.0140 (18) | −0.0136 (14) |
C3A | 0.088 (3) | 0.071 (2) | 0.0453 (19) | −0.021 (2) | 0.0075 (17) | −0.0081 (14) |
C4A | 0.068 (2) | 0.0492 (17) | 0.0379 (16) | −0.0124 (15) | 0.0017 (15) | −0.0094 (12) |
C5A | 0.0488 (17) | 0.0389 (14) | 0.0378 (15) | −0.0124 (13) | −0.0036 (13) | 0.0001 (11) |
C6A | 0.0447 (16) | 0.0326 (13) | 0.0378 (14) | −0.0118 (12) | −0.0024 (12) | −0.0021 (10) |
C7A | 0.0464 (17) | 0.0485 (16) | 0.0525 (17) | −0.0213 (14) | 0.0020 (14) | −0.0072 (12) |
C8A | 0.0580 (19) | 0.0635 (19) | 0.068 (2) | −0.0320 (16) | −0.0092 (17) | −0.0124 (15) |
C9A | 0.072 (2) | 0.0613 (19) | 0.0536 (18) | −0.0346 (17) | −0.0045 (16) | −0.0174 (14) |
C10A | 0.0520 (17) | 0.0306 (13) | 0.0439 (15) | −0.0150 (12) | −0.0037 (13) | −0.0029 (11) |
C11A | 0.064 (2) | 0.080 (2) | 0.059 (2) | −0.0306 (18) | 0.0186 (17) | −0.0122 (16) |
C12A | 0.060 (2) | 0.076 (2) | 0.066 (2) | −0.0338 (17) | 0.0059 (17) | −0.0113 (16) |
C13A | 0.101 (3) | 0.085 (2) | 0.063 (2) | −0.035 (2) | −0.0305 (19) | −0.0126 (17) |
C14A | 0.0668 (19) | 0.0412 (15) | 0.0521 (17) | −0.0193 (14) | 0.0056 (14) | −0.0139 (12) |
N1B | 0.0449 (13) | 0.0340 (11) | 0.0437 (12) | −0.0153 (10) | −0.0007 (11) | −0.0048 (9) |
N2B | 0.0459 (13) | 0.0312 (11) | 0.0403 (12) | −0.0108 (10) | −0.0031 (10) | −0.0057 (9) |
C1B | 0.0545 (19) | 0.0437 (16) | 0.0555 (18) | −0.0226 (14) | 0.0017 (15) | −0.0048 (12) |
C2B | 0.068 (2) | 0.0589 (19) | 0.0515 (19) | −0.0265 (17) | 0.0166 (16) | −0.0103 (14) |
C3B | 0.084 (2) | 0.0545 (18) | 0.0381 (16) | −0.0311 (17) | 0.0042 (16) | −0.0063 (12) |
C4B | 0.069 (2) | 0.0383 (15) | 0.0400 (15) | −0.0229 (14) | −0.0063 (15) | −0.0016 (11) |
C5B | 0.0494 (16) | 0.0308 (13) | 0.0398 (14) | −0.0181 (12) | −0.0043 (13) | −0.0026 (10) |
C6B | 0.0489 (16) | 0.0273 (13) | 0.0425 (15) | −0.0136 (12) | −0.0054 (13) | −0.0022 (10) |
C7B | 0.0508 (18) | 0.0344 (14) | 0.0542 (17) | −0.0128 (13) | −0.0155 (14) | −0.0019 (12) |
C8B | 0.0465 (18) | 0.0472 (17) | 0.077 (2) | −0.0120 (14) | −0.0160 (16) | −0.0052 (14) |
C9B | 0.0478 (18) | 0.0436 (16) | 0.069 (2) | −0.0034 (14) | 0.0004 (15) | −0.0116 (14) |
C10B | 0.0522 (18) | 0.0317 (14) | 0.0489 (16) | −0.0096 (13) | −0.0061 (14) | −0.0033 (11) |
C11B | 0.084 (2) | 0.0494 (17) | 0.0466 (17) | −0.0236 (17) | −0.0224 (17) | −0.0024 (13) |
C12B | 0.065 (2) | 0.0469 (17) | 0.067 (2) | −0.0189 (15) | −0.0306 (17) | −0.0021 (14) |
C13B | 0.052 (2) | 0.093 (3) | 0.078 (2) | −0.0308 (18) | 0.0095 (17) | −0.0165 (18) |
C14B | 0.075 (2) | 0.0485 (17) | 0.0544 (18) | −0.0052 (15) | −0.0061 (15) | −0.0172 (13) |
Geometric parameters (Å, º) top
Ni—N1C | 2.011 (2) | C7A—C12A | 1.417 (4) |
Ni—N1D | 2.022 (2) | C8A—C9A | 1.357 (4) |
Ni—N1A | 2.138 (2) | C9A—C10A | 1.396 (3) |
Ni—N1B | 2.1419 (19) | C10A—C14A | 1.504 (3) |
Ni—N2B | 2.1886 (19) | C11A—C12A | 1.343 (4) |
Ni—N2A | 2.2054 (19) | N1B—C1B | 1.333 (3) |
S1C—C1C | 1.629 (3) | N1B—C5B | 1.365 (3) |
C1C—N1C | 1.158 (3) | N2B—C10B | 1.330 (3) |
S1D—C1D | 1.620 (3) | N2B—C6B | 1.368 (3) |
C1D—N1D | 1.157 (3) | C1B—C2B | 1.399 (4) |
N1A—C1A | 1.328 (3) | C1B—C13B | 1.500 (4) |
N1A—C5A | 1.366 (3) | C2B—C3B | 1.356 (4) |
N2A—C10A | 1.328 (3) | C3B—C4B | 1.403 (4) |
N2A—C6A | 1.370 (3) | C4B—C5B | 1.406 (3) |
C1A—C2A | 1.423 (4) | C4B—C11B | 1.417 (4) |
C1A—C13A | 1.495 (4) | C5B—C6B | 1.426 (3) |
C2A—C3A | 1.348 (4) | C6B—C7B | 1.399 (3) |
C3A—C4A | 1.393 (4) | C7B—C8B | 1.405 (4) |
C4A—C5A | 1.404 (3) | C7B—C12B | 1.423 (4) |
C4A—C11A | 1.431 (4) | C8B—C9B | 1.359 (4) |
C5A—C6A | 1.425 (3) | C9B—C10B | 1.401 (4) |
C6A—C7A | 1.409 (3) | C10B—C14B | 1.504 (3) |
C7A—C8A | 1.387 (4) | C11B—C12B | 1.341 (4) |
| | | |
N1C—Ni—N1D | 97.81 (9) | C8A—C7A—C12A | 123.7 (3) |
N1C—Ni—N1A | 100.37 (9) | C6A—C7A—C12A | 119.3 (3) |
N1D—Ni—N1A | 91.63 (8) | C9A—C8A—C7A | 119.7 (3) |
N1C—Ni—N1B | 90.97 (8) | C8A—C9A—C10A | 120.5 (3) |
N1D—Ni—N1B | 99.07 (8) | N2A—C10A—C9A | 121.6 (2) |
N1A—Ni—N1B | 163.24 (8) | N2A—C10A—C14A | 118.9 (2) |
N1C—Ni—N2B | 91.01 (8) | C9A—C10A—C14A | 119.4 (2) |
N1D—Ni—N2B | 170.31 (8) | C12A—C11A—C4A | 121.2 (3) |
N1A—Ni—N2B | 90.71 (7) | C11A—C12A—C7A | 120.8 (3) |
N1B—Ni—N2B | 76.67 (7) | C1B—N1B—C5B | 118.4 (2) |
N1C—Ni—N2A | 172.14 (8) | C1B—N1B—Ni | 130.65 (17) |
N1D—Ni—N2A | 89.55 (8) | C5B—N1B—Ni | 109.74 (15) |
N1A—Ni—N2A | 76.56 (8) | C10B—N2B—C6B | 118.0 (2) |
N1B—Ni—N2A | 90.58 (7) | C10B—N2B—Ni | 131.34 (16) |
N2B—Ni—N2A | 81.85 (7) | C6B—N2B—Ni | 107.53 (15) |
N1C—C1C—S1C | 179.0 (2) | N1B—C1B—C2B | 121.2 (3) |
C1C—N1C—Ni | 165.4 (2) | N1B—C1B—C13B | 118.9 (2) |
N1D—C1D—S1D | 178.9 (2) | C2B—C1B—C13B | 119.9 (3) |
C1D—N1D—Ni | 159.8 (2) | C3B—C2B—C1B | 120.5 (3) |
C1A—N1A—C5A | 118.2 (2) | C2B—C3B—C4B | 120.1 (3) |
C1A—N1A—Ni | 130.6 (2) | C3B—C4B—C5B | 116.4 (3) |
C5A—N1A—Ni | 109.80 (16) | C3B—C4B—C11B | 123.9 (3) |
C10A—N2A—C6A | 117.8 (2) | C5B—C4B—C11B | 119.6 (3) |
C10A—N2A—Ni | 132.44 (16) | N1B—C5B—C4B | 123.0 (2) |
C6A—N2A—Ni | 106.91 (15) | N1B—C5B—C6B | 117.8 (2) |
N1A—C1A—C2A | 120.8 (3) | C4B—C5B—C6B | 119.2 (2) |
N1A—C1A—C13A | 119.0 (3) | N2B—C6B—C7B | 123.2 (2) |
C2A—C1A—C13A | 120.3 (3) | N2B—C6B—C5B | 117.0 (2) |
C3A—C2A—C1A | 120.6 (3) | C7B—C6B—C5B | 119.7 (2) |
C2A—C3A—C4A | 119.9 (3) | C6B—C7B—C8B | 116.5 (2) |
C3A—C4A—C5A | 117.0 (3) | C6B—C7B—C12B | 119.2 (3) |
C3A—C4A—C11A | 123.7 (3) | C8B—C7B—C12B | 124.1 (3) |
C5A—C4A—C11A | 119.4 (3) | C9B—C8B—C7B | 119.7 (3) |
N1A—C5A—C4A | 123.2 (3) | C8B—C9B—C10B | 120.3 (3) |
N1A—C5A—C6A | 117.8 (2) | N2B—C10B—C9B | 121.3 (2) |
C4A—C5A—C6A | 118.9 (3) | N2B—C10B—C14B | 118.6 (2) |
N2A—C6A—C7A | 122.7 (2) | C9B—C10B—C14B | 120.0 (3) |
N2A—C6A—C5A | 117.2 (2) | C12B—C11B—C4B | 120.9 (3) |
C7A—C6A—C5A | 120.0 (2) | C11B—C12B—C7B | 121.2 (3) |
C8A—C7A—C6A | 117.0 (3) | | |
| | | |
N1A—C5A—C6A—N2A | −5.6 (3) | N1B—C5B—C6B—N2B | −5.6 (3) |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | [Ni(CNS)2(C10H8N2)2] | [Ni(CNS)2(C12H8N2)2] | [Ni(CNS)2(C14H12N2)2]·H2O |
Mr | 487.24 | 535.28 | 609.40 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, Pbcn | Triclinic, P1 |
Temperature (K) | 293 | 293 | 293 |
a, b, c (Å) | 16.647 (3), 16.385 (3), 8.0530 (16) | 13.018 (3), 10.116 (2), 17.536 (4) | 9.689 (1), 10.757 (1), 14.754 (1) |
α, β, γ (°) | 90, 98.08 (3), 90 | 90, 90, 90 | 77.71 (1), 79.00 (1), 70.07 (1) |
V (Å3) | 2174.7 (8) | 2309.3 (8) | 1400.8 (2) |
Z | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.11 | 1.05 | 0.88 |
Crystal size (mm) | 0.24 × 0.18 × 0.08 | 0.20 × 0.20 × 0.14 | 0.23 × 0.22 × 0.16 |
|
Data collection |
Diffractometer | Rigaku AFC7S Difractometer diffractometer | Rigaku AFC7S Difractometer diffractometer | Bruker SMART 6000 diffractometer |
Absorption correction | ψ scan (MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988) | ψ scan (MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988) | – |
Tmin, Tmax | 0.84, 0.92 | 0.77, 0.85 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6054, 5008, 3122 | 3409, 2663, 1410 | 10079, 6316, 3612 |
Rint | 0.061 | 0.032 | 0.031 |
(sin θ/λ)max (Å−1) | 0.651 | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.205, 1.04 | 0.029, 0.091, 0.97 | 0.040, 0.081, 0.97 |
No. of reflections | 5008 | 2663 | 6316 |
No. of parameters | 280 | 159 | 366 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.12, −1.15 | 0.28, −0.25 | 0.40, −0.27 |
Selected geometric parameters (Å, º) for (I) topNi—N1D | 2.040 (4) | Ni—N2B | 2.104 (3) |
Ni—N1A | 2.057 (3) | S1C—C1C | 1.631 (5) |
Ni—N1C | 2.065 (4) | C1C—N1C | 1.138 (6) |
Ni—N1B | 2.076 (3) | S1D—C1D | 1.622 (4) |
Ni—N2A | 2.096 (3) | C1D—N1D | 1.166 (5) |
| | | |
N1D—Ni—N1A | 88.29 (14) | N1B—Ni—N2A | 95.87 (14) |
N1D—Ni—N1C | 91.45 (14) | N1D—Ni—N2B | 173.92 (14) |
N1A—Ni—N1C | 98.04 (14) | N1A—Ni—N2B | 97.60 (14) |
N1D—Ni—N1B | 95.53 (14) | N1C—Ni—N2B | 89.26 (13) |
N1A—Ni—N1B | 172.83 (13) | N1B—Ni—N2B | 78.46 (13) |
N1C—Ni—N1B | 87.96 (15) | N2A—Ni—N2B | 90.94 (13) |
N1D—Ni—N2A | 88.75 (14) | N1C—C1C—S1C | 178.0 (4) |
N1A—Ni—N2A | 78.11 (14) | N1D—C1D—S1D | 179.0 (4) |
N1C—Ni—N2A | 176.13 (14) | | |
| | | |
N1A—C5A—C6A—N2A | −1.9 (5) | N1B—C5B—C6B—N2B | −3.8 (5) |
Selected geometric parameters (Å, º) for (II) topNi—N1C | 2.038 (2) | Ni—N2A | 2.1056 (19) |
Ni—N1Ci | 2.038 (2) | Ni—N2Ai | 2.1056 (19) |
Ni—N1A | 2.0990 (19) | S1C—C1C | 1.618 (3) |
Ni—N1Ai | 2.0990 (19) | C1C—N1C | 1.153 (3) |
| | | |
N1C—Ni—N1Ci | 92.51 (13) | N1Ai—Ni—N2A | 92.23 (7) |
N1C—Ni—N1A | 92.45 (8) | N1C—Ni—N2Ai | 88.68 (9) |
N1Ci—Ni—N1A | 96.27 (8) | N1Ci—Ni—N2Ai | 171.35 (8) |
N1C—Ni—N1Ai | 96.27 (8) | N1A—Ni—N2Ai | 92.23 (7) |
N1Ci—Ni—N1Ai | 92.45 (8) | N1Ai—Ni—N2Ai | 78.90 (7) |
N1A—Ni—N1Ai | 167.37 (10) | N2A—Ni—N2Ai | 91.42 (11) |
N1C—Ni—N2A | 171.35 (8) | N1C—C1C—S1C | 178.8 (2) |
N1Ci—Ni—N2A | 88.68 (9) | C1C—N1C—Ni | 162.0 (2) |
N1A—Ni—N2A | 78.90 (7) | | |
| | | |
N1A—C5A—C6A—N2A | 1.6 (5) | | |
Symmetry code: (i) −x+1, y, −z+3/2. |
Selected geometric parameters (Å, º) for (III) topNi—N1C | 2.011 (2) | Ni—N2A | 2.2054 (19) |
Ni—N1D | 2.022 (2) | S1C—C1C | 1.629 (3) |
Ni—N1A | 2.138 (2) | C1C—N1C | 1.158 (3) |
Ni—N1B | 2.1419 (19) | S1D—C1D | 1.620 (3) |
Ni—N2B | 2.1886 (19) | C1D—N1D | 1.157 (3) |
| | | |
N1C—Ni—N1D | 97.81 (9) | N1B—Ni—N2B | 76.67 (7) |
N1C—Ni—N1A | 100.37 (9) | N1C—Ni—N2A | 172.14 (8) |
N1D—Ni—N1A | 91.63 (8) | N1D—Ni—N2A | 89.55 (8) |
N1C—Ni—N1B | 90.97 (8) | N1A—Ni—N2A | 76.56 (8) |
N1D—Ni—N1B | 99.07 (8) | N1B—Ni—N2A | 90.58 (7) |
N1A—Ni—N1B | 163.24 (8) | N2B—Ni—N2A | 81.85 (7) |
N1C—Ni—N2B | 91.01 (8) | N1C—C1C—S1C | 179.0 (2) |
N1D—Ni—N2B | 170.31 (8) | N1D—C1D—S1D | 178.9 (2) |
N1A—Ni—N2B | 90.71 (7) | | |
| | | |
N1A—C5A—C6A—N2A | −5.6 (3) | N1B—C5B—C6B—N2B | −5.6 (3) |
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In the last few years we have developed a sustained interest in the study of complexes with sulfur-containing ambidentate anionic ligands (those with a capability to coordinate through more than one, non-equivalent, sites) like thiosulfate, sulfite, etc., and mainly focused in the effects introduced in the structure by the change of similar but differently sized N-bidentate organic ligands (Freire et al., 1999; Freire, Baggio, Mombru & Baggio et al., 2000; Freire, Baggio, Mariezcurrena & Baggio et al., 2000; Freire et al., 2001). Nickel(II) is a quite interesting probe for this purpose because when coordinating to non-interacting monodentate ligands (Sotofte et al., 1976; Leban et al., 1888; Vicente et al., 1996; Kruger & McKee, 1996), or when the steric hindrances eventually arising among them can be satisfactorily solved by a spatial re-arrangement of the latter (Perec et al., 1999; Povse et al., 1998) the resulting chromophore is absolutely regular. In this line of thought we tried to look at the distortions which would arise from this ideal octahedral configuration when these non-interacting conditions were set aside in a somehow "continuous" way, for example by the inclusion of bidentate ligands of increasing size and, concomitantly, disturbing effect. We have thus prepared a series of three Ni2+ complexes containing both small monodentate ligands (SCN: thiocyanate) as well as larger N-bidentate bases (bpy: 1,10-bipyridine, phen: 1,10-phenanthroline, dmph: 2,9-dimethyl-1,10-phenanthroline), namely Ni(bpy)2(SCN)2, (I), Ni (phen)2(SCN)2, (II) and Ni (dmph)2(SCN)2·(H2O), (III), in order to compare the differences appearing in their coordination geometry. \sch
There are in the literature examples of structures which are similar to the ones herein presented [structure (2) has already been reported, though with a larger R factor (Travnicek et al., 1998) at the same time that it is isostructural to the analogous Cu, Fe and Mn compounds (Parker et al., 1996; Gallois et al., 1990; Holleman et al., 1994, respectively); structure (III) is isostructural to Fe(SCN)2(dmph)2 (Figg et al., 1992); structure (I) displays a similar coordination, though with a different crystal structure, to Ru(SCN)2(bipy)2 (Herber et al., 1989)). However, this is the first complete series with a unique cation to be presented, thus making it suitable for comparison purposes.
The three compounds are monomeric. Compounds (I) and (III) have one independent monomer per asymmetric unit. The one in (II), instead, is positioned on a twofold axis through the cation thus rendering only half of it independent. In all three structures the Ni2+ cation appears surrounded by very similar hexacoordinated octahedral environments (Figures 1–3) achieved through two SCN molecules binding through N, as expected, and completed by two dinitrogenated bidentate ligands almost at right angles to each other (however, see discussion below). Tables 1, 2 and 3 allow an easy comparison of the coordination bond distances and angles in all three structures. Inspection of the values therein shows both the similarity among the nickel environments as well as the fact that the main departures from regularity are due to the bidentate character of the bases, with their small bite angle of ca 80° promoting the major distortions.
For bipy and phen the analogies go even further on, to the way in which the ligands attach to the core, the planar ligands being almost parallel to the coordination plane defined by their bites, with deviations of 8.5 (1) and 4.7 (1)° for bipy and 7.6 (1)° for phen, and the linear thiocyanates being almost parallel to the Ni—NSCN coordination direction and nearly normal to each other: 93.6 (2)° for bipy, 96.6 (1)° for phen. The situation is quite different for dmph, where to overcome the important steric hindrance introduced by the bulky methyl groups the planar ligands depart sensibly from the plane of coordination [36.7 (2) and 36.2 (2)°, respectively], and SCN groups span a large 131.9 (2)° apart. This situation can be clearly seen in Figure 4, where a comparative sketch of the three coordination cores is presented. Steric effects are such that the two dmph molecules in (III) are forced to move towards each other in order to make room to the protruding methyl groups, and this leads to a surprising small dihedral angle of 29.7 (2)° between dmph groups, as compared with 95.6 (2)° for bipy and 90.8 (1)° for phen.
The whole situation sensibly jeopardizes the ability of the dmph nitrogen atoms to make full overlap of their free sp2 orbitals with those of the cation; the result is a clear weakening of the Ni—Ndmph bond, as well as a shortening of the Ni—NSCN bond length in order to provide for valence bond conservation.
The stresses arising from coordination are also revealed in the deformation of the dmph ligand, which deviates sensibly from planarity. As a measure we compare the dihedral angles between lateral loops in all three cases: 4.1 (2)° / 5.3 (2)° for bipy (mainly the result of the unhindered rotation around the C5—C6 bond), 2.2 (1)° for phen and 13.7 (2)° / 12.2 (2)° for dmph. Fig. 4 shows that the dmph distortion has also an important component of twisting around the C5A—C6A bond, as evidenced by the N1—C5—C6—N2 torsion angles presented in Table 3.
As expected there are no unusually short intermolecular contacts in the structures, packing interactions being mainly van der Waals.