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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101008460/bk1604sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101008460/bk1604Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101008460/bk1604IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101008460/bk1604IIIsup4.hkl
Contains datablock III

CCDC references: 170170; 170171; 170172

Comment top

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.

Related literature top

For related literature, see: Figg et al. (1992); Freire et al. (1999); Freire, Baggio, Mariezcurrena & Baggio (2000); Freire, Baggio, Mombru & Baggio (2000); Gallois et al. (1990); Herber et al. (1989); Kruger & McKee (1996); Perec et al. (1999); Povse et al. (1998); Sotofte et al. (1976); Travnicek et al. (1998); Vicente et al. (1996).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Molecular drawing of the monomer in (I) showing atom labeling. Displacement ellipsoids are drawn at the 50% level.
[Figure 2] Fig. 2. Molecular drawing of the monomer in (II) showing atom labeling. Note that only half of the unit is independent, the rest being generated by symmetry. Displacement ellipsoids are drawn at 50% level.
[Figure 3] Fig. 3. Molecular drawing of the monomer in (III) showing atom labeling. Displacement ellipsoids are drawn at 50% level.
[Figure 4] Fig. 4. Schematic superposition of the cores of the three coordination polyhedra, showing different degrees of deformation. Hard full line: bipy, thin broken: phen, hard broken: dmph.
(I) bis(Isothiocyanato-(2,2'-Bipyridine))-nickel(ii) top
Crystal data top
[Ni(CNS)2(C10H8N2)2]F(000) = 1000
Mr = 487.24Dx = 1.488 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 16.647 (3) ÅCell parameters from 30 reflections
b = 16.385 (3) Åθ = 7.5–15°
c = 8.0530 (16) ŵ = 1.11 mm1
β = 98.08 (3)°T = 293 K
V = 2174.7 (8) Å3Plates, violet
Z = 40.24 × 0.18 × 0.08 mm
Data collection top
Rigaku AFC7S Difractometer
diffractometer
3122 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.061
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
ω/2θ scansh = 2121
Absorption correction: ψ scan
(MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988)
k = 210
Tmin = 0.84, Tmax = 0.92l = 110
6054 measured reflections3 standard reflections every 150 reflections
5008 independent reflections intensity decay: <3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.205H-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 parametersΔρmax = 1.12 e Å3
0 restraintsΔρmin = 1.15 e Å3
Crystal data top
[Ni(CNS)2(C10H8N2)2]V = 2174.7 (8) Å3
Mr = 487.24Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.647 (3) ŵ = 1.11 mm1
b = 16.385 (3) ÅT = 293 K
c = 8.0530 (16) Å0.24 × 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 = 0.923 standard reflections every 150 reflections
6054 measured reflections intensity decay: <3%
5008 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.205H-atom parameters constrained
S = 1.04Δρmax = 1.12 e Å3
5008 reflectionsΔρmin = 1.15 e Å3
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
xyzUiso*/Ueq
Ni0.24795 (3)0.51414 (3)0.79095 (6)0.0310 (2)
S1C0.40415 (11)0.65712 (15)0.4367 (3)0.1013 (7)
C1C0.3570 (2)0.6179 (3)0.5821 (6)0.0445 (10)
N1C0.3231 (2)0.5927 (2)0.6842 (5)0.0420 (8)
S1D0.00070 (7)0.62619 (9)0.49934 (16)0.0568 (4)
C1D0.0861 (2)0.5869 (2)0.5844 (5)0.0355 (9)
N1D0.1480 (2)0.5589 (2)0.6433 (5)0.0437 (9)
N1A0.22107 (19)0.5897 (2)0.9797 (4)0.0349 (7)
N2A0.1713 (2)0.4403 (2)0.9119 (4)0.0368 (8)
C1A0.2476 (3)0.6667 (3)1.0078 (6)0.0466 (10)
H1AA0.29000.68510.95390.056*
C2A0.2150 (3)0.7187 (3)1.1118 (7)0.0587 (13)
H2AA0.23430.77181.12610.070*
C3A0.1533 (3)0.6924 (3)1.1955 (7)0.0635 (15)
H3AA0.12980.72751.26560.076*
C4A0.1271 (3)0.6126 (3)1.1730 (6)0.0530 (12)
H4AA0.08650.59261.23040.064*
C5A0.1617 (2)0.5630 (3)1.0651 (5)0.0362 (9)
C6A0.1352 (2)0.4777 (3)1.0271 (5)0.0376 (9)
C7A0.0772 (3)0.4388 (3)1.1087 (6)0.0497 (11)
H7AA0.05260.46581.18980.060*
C8A0.0572 (3)0.3587 (4)1.0655 (7)0.0634 (15)
H8AA0.01850.33141.11710.076*
C9A0.0941 (3)0.3203 (3)0.9484 (7)0.0607 (14)
H9AA0.08150.26630.92000.073*
C10A0.1511 (3)0.3623 (3)0.8708 (6)0.0498 (11)
H10A0.17590.33620.78890.060*
N1B0.27418 (19)0.4260 (2)0.6214 (4)0.0359 (7)
N2B0.35100 (19)0.4580 (2)0.9244 (4)0.0357 (7)
C1B0.2318 (3)0.4123 (3)0.4724 (6)0.0484 (11)
H1BA0.18220.43880.44550.058*
C2B0.2575 (3)0.3604 (3)0.3539 (6)0.0574 (13)
H2BA0.22690.35270.24930.069*
C3B0.3304 (3)0.3209 (3)0.3985 (7)0.0613 (14)
H3BA0.34960.28500.32370.074*
C4B0.3742 (3)0.3342 (3)0.5507 (6)0.0507 (11)
H4BA0.42390.30820.57920.061*
C5B0.3454 (2)0.3865 (2)0.6649 (5)0.0354 (9)
C6B0.3866 (2)0.4020 (2)0.8344 (5)0.0369 (9)
C7B0.4572 (2)0.3620 (3)0.9048 (6)0.0475 (11)
H7BA0.48160.32390.84240.057*
C8B0.4908 (3)0.3795 (3)1.0686 (7)0.0533 (12)
H8BA0.53740.35281.11770.064*
C9B0.4542 (3)0.4363 (3)1.1564 (7)0.0558 (13)
H9BA0.47560.44941.26610.067*
C10B0.3848 (3)0.4742 (3)1.0792 (6)0.0461 (10)
H10B0.36040.51321.13960.055*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0264 (3)0.0308 (3)0.0356 (3)0.00053 (18)0.0039 (2)0.0015 (2)
S1C0.0690 (10)0.1496 (19)0.0935 (13)0.0046 (11)0.0406 (10)0.0465 (13)
C1C0.031 (2)0.049 (3)0.052 (3)0.0022 (18)0.003 (2)0.003 (2)
N1C0.0361 (18)0.046 (2)0.045 (2)0.0009 (15)0.0103 (17)0.0098 (17)
S1D0.0398 (6)0.0691 (8)0.0622 (8)0.0254 (5)0.0096 (6)0.0114 (6)
C1D0.035 (2)0.036 (2)0.038 (2)0.0031 (16)0.0109 (17)0.0006 (17)
N1D0.0361 (18)0.046 (2)0.048 (2)0.0056 (16)0.0026 (16)0.0024 (17)
N1A0.0306 (16)0.0359 (17)0.0385 (18)0.0004 (13)0.0059 (14)0.0026 (14)
N2A0.0324 (16)0.0340 (18)0.0437 (19)0.0057 (13)0.0041 (15)0.0029 (15)
C1A0.046 (2)0.040 (2)0.053 (3)0.0088 (19)0.005 (2)0.005 (2)
C2A0.067 (3)0.043 (3)0.065 (3)0.006 (2)0.005 (3)0.018 (2)
C3A0.062 (3)0.067 (3)0.062 (3)0.009 (3)0.009 (3)0.026 (3)
C4A0.046 (3)0.064 (3)0.051 (3)0.000 (2)0.014 (2)0.004 (2)
C5A0.0319 (19)0.044 (2)0.0321 (19)0.0022 (16)0.0026 (16)0.0019 (17)
C6A0.0281 (18)0.045 (2)0.038 (2)0.0018 (17)0.0007 (17)0.0100 (18)
C7A0.035 (2)0.064 (3)0.050 (3)0.004 (2)0.008 (2)0.014 (2)
C8A0.044 (3)0.072 (4)0.072 (4)0.019 (3)0.002 (3)0.032 (3)
C9A0.063 (3)0.052 (3)0.064 (3)0.028 (2)0.001 (3)0.014 (3)
C10A0.054 (3)0.039 (2)0.056 (3)0.012 (2)0.007 (2)0.000 (2)
N1B0.0288 (16)0.0407 (18)0.0378 (18)0.0046 (13)0.0033 (14)0.0017 (14)
N2B0.0302 (16)0.0347 (16)0.0408 (18)0.0032 (13)0.0003 (14)0.0065 (15)
C1B0.043 (2)0.056 (3)0.044 (2)0.012 (2)0.001 (2)0.002 (2)
C2B0.060 (3)0.058 (3)0.050 (3)0.011 (2)0.007 (2)0.008 (2)
C3B0.066 (3)0.054 (3)0.065 (3)0.012 (2)0.013 (3)0.013 (3)
C4B0.040 (2)0.047 (3)0.065 (3)0.013 (2)0.012 (2)0.002 (2)
C5B0.0296 (18)0.032 (2)0.045 (2)0.0005 (15)0.0062 (17)0.0062 (17)
C6B0.0279 (18)0.0317 (19)0.051 (2)0.0017 (15)0.0046 (17)0.0098 (18)
C7B0.035 (2)0.042 (2)0.062 (3)0.0018 (18)0.003 (2)0.010 (2)
C8B0.033 (2)0.058 (3)0.065 (3)0.001 (2)0.008 (2)0.014 (3)
C9B0.050 (3)0.063 (3)0.049 (3)0.009 (2)0.011 (2)0.007 (2)
C10B0.043 (2)0.049 (3)0.044 (2)0.004 (2)0.001 (2)0.005 (2)
Geometric parameters (Å, º) top
Ni—N1D2.040 (4)C5A—C6A1.484 (6)
Ni—N1A2.057 (3)C6A—C7A1.396 (6)
Ni—N1C2.065 (4)C7A—C8A1.386 (8)
Ni—N1B2.076 (3)C8A—C9A1.351 (8)
Ni—N2A2.096 (3)C9A—C10A1.390 (7)
Ni—N2B2.104 (3)N1B—C1B1.323 (5)
S1C—C1C1.631 (5)N1B—C5B1.352 (5)
C1C—N1C1.138 (6)N2B—C10B1.321 (6)
S1D—C1D1.622 (4)N2B—C6B1.356 (6)
C1D—N1D1.166 (5)C1B—C2B1.390 (7)
N1A—C1A1.345 (5)C2B—C3B1.378 (7)
N1A—C5A1.354 (5)C3B—C4B1.353 (7)
N2A—C6A1.324 (6)C4B—C5B1.391 (6)
N2A—C10A1.350 (6)C5B—C6B1.462 (6)
C1A—C2A1.359 (7)C6B—C7B1.395 (5)
C2A—C3A1.374 (8)C7B—C8B1.388 (7)
C3A—C4A1.383 (8)C8B—C9B1.364 (7)
C4A—C5A1.373 (6)C9B—C10B1.380 (7)
N1D—Ni—N1A88.29 (14)N1A—C5A—C6A114.6 (4)
N1D—Ni—N1C91.45 (14)C4A—C5A—C6A123.3 (4)
N1A—Ni—N1C98.04 (14)N2A—C6A—C7A122.0 (4)
N1D—Ni—N1B95.53 (14)N2A—C6A—C5A115.5 (3)
N1A—Ni—N1B172.83 (13)C7A—C6A—C5A122.6 (4)
N1C—Ni—N1B87.96 (15)C8A—C7A—C6A118.2 (5)
N1D—Ni—N2A88.75 (14)C9A—C8A—C7A120.0 (4)
N1A—Ni—N2A78.11 (14)C8A—C9A—C10A119.3 (5)
N1C—Ni—N2A176.13 (14)N2A—C10A—C9A121.3 (5)
N1B—Ni—N2A95.87 (14)C1B—N1B—C5B119.4 (4)
N1D—Ni—N2B173.92 (14)C1B—N1B—Ni125.4 (3)
N1A—Ni—N2B97.60 (14)C5B—N1B—Ni114.9 (3)
N1C—Ni—N2B89.26 (13)C10B—N2B—C6B118.7 (4)
N1B—Ni—N2B78.46 (13)C10B—N2B—Ni127.1 (3)
N2A—Ni—N2B90.94 (13)C6B—N2B—Ni114.2 (3)
N1C—C1C—S1C178.0 (4)N1B—C1B—C2B123.3 (4)
C1C—N1C—Ni156.6 (4)C3B—C2B—C1B117.0 (5)
N1D—C1D—S1D179.0 (4)C4B—C3B—C2B120.2 (5)
C1D—N1D—Ni168.5 (4)C3B—C4B—C5B120.4 (4)
C1A—N1A—C5A117.5 (4)N1B—C5B—C4B119.7 (4)
C1A—N1A—Ni126.1 (3)N1B—C5B—C6B116.0 (4)
C5A—N1A—Ni115.6 (3)C4B—C5B—C6B124.3 (4)
C6A—N2A—C10A119.3 (4)N2B—C6B—C7B120.5 (4)
C6A—N2A—Ni115.1 (3)N2B—C6B—C5B115.7 (3)
C10A—N2A—Ni125.3 (3)C7B—C6B—C5B123.8 (4)
N1A—C1A—C2A122.8 (5)C8B—C7B—C6B119.5 (5)
C1A—C2A—C3A119.8 (5)C9B—C8B—C7B119.0 (4)
C2A—C3A—C4A118.4 (5)C8B—C9B—C10B118.7 (5)
C5A—C4A—C3A119.3 (4)N2B—C10B—C9B123.6 (5)
N1A—C5A—C4A122.1 (4)
N1A—C5A—C6A—N2A1.9 (5)N1B—C5B—C6B—N2B3.8 (5)
(II) bis(Isothiocyanato-(1,10-Phenanthroline))-nickel(ii) top
Crystal data top
[Ni(CNS)2(C12H8N2)2]F(000) = 1096
Mr = 535.28Dx = 1.540 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 30 reflections
a = 13.018 (3) Åθ = 7.5–15°
b = 10.116 (2) ŵ = 1.05 mm1
c = 17.536 (4) ÅT = 293 K
V = 2309.3 (8) Å3Plates, violet
Z = 40.20 × 0.20 × 0.14 mm
Data collection top
Rigaku AFC7S Difractometer
diffractometer
1410 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
Graphite monochromatorθmax = 27.5°, θmin = 2.3°
ω/2θ scansh = 116
Absorption correction: ψ scan
(MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988)
k = 113
Tmin = 0.77, Tmax = 0.85l = 221
3409 measured reflections3 standard reflections every 150 reflections
2663 independent reflections intensity decay: <3%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-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 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
[Ni(CNS)2(C12H8N2)2]V = 2309.3 (8) Å3
Mr = 535.28Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 13.018 (3) ŵ = 1.05 mm1
b = 10.116 (2) ÅT = 293 K
c = 17.536 (4) Å0.20 × 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 = 0.853 standard reflections every 150 reflections
3409 measured reflections intensity decay: <3%
2663 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.091H-atom parameters constrained
S = 0.97Δρmax = 0.28 e Å3
2663 reflectionsΔρmin = 0.25 e Å3
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
xyzUiso*/Ueq
Ni0.50000.14932 (4)0.75000.04498 (14)
S1C0.36738 (6)0.47038 (8)0.92184 (4)0.0775 (2)
C1C0.42580 (17)0.3644 (2)0.86805 (14)0.0502 (6)
N1C0.46872 (16)0.2886 (2)0.83068 (13)0.0610 (6)
N1A0.34410 (14)0.12650 (19)0.72242 (11)0.0459 (5)
N2A0.50816 (14)0.00397 (19)0.66427 (10)0.0479 (4)
C1A0.26146 (19)0.1865 (3)0.75271 (16)0.0591 (6)
H1AA0.27200.25230.78900.071*
C2A0.1616 (2)0.1555 (3)0.73267 (17)0.0680 (8)
H2AA0.10690.19880.75580.082*
C3A0.14416 (19)0.0620 (3)0.67928 (17)0.0682 (8)
H3AA0.07710.04150.66520.082*
C4A0.22676 (18)0.0044 (3)0.64487 (14)0.0557 (6)
C5A0.32699 (17)0.0324 (2)0.66914 (13)0.0478 (6)
C6A0.41377 (17)0.0325 (2)0.63694 (13)0.0475 (6)
C7A0.40052 (19)0.1279 (3)0.57973 (15)0.0603 (7)
C8A0.4900 (2)0.1845 (3)0.54941 (18)0.0813 (9)
H8AA0.48510.24900.51180.098*
C9A0.5845 (2)0.1449 (3)0.5752 (2)0.0804 (9)
H9AA0.64410.18120.55480.096*
C10A0.5903 (2)0.0497 (3)0.63239 (16)0.0664 (7)
H10A0.65480.02250.64890.080*
C12A0.2997 (2)0.1616 (3)0.55696 (17)0.0711 (8)
H12A0.29040.22470.51900.085*
C11A0.2173 (2)0.1048 (3)0.58879 (17)0.0705 (8)
H11A0.15210.13180.57370.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0372 (2)0.0441 (2)0.0537 (2)0.0000.0061 (2)0.000
S1C0.0795 (5)0.0761 (5)0.0770 (5)0.0113 (4)0.0084 (4)0.0117 (4)
C1C0.0439 (12)0.0519 (14)0.0549 (14)0.0121 (12)0.0039 (11)0.0006 (13)
N1C0.0526 (11)0.0566 (13)0.0739 (15)0.0014 (11)0.0023 (11)0.0081 (12)
N1A0.0417 (10)0.0424 (11)0.0535 (11)0.0021 (8)0.0048 (9)0.0018 (9)
N2A0.0374 (9)0.0498 (10)0.0564 (11)0.0038 (10)0.0047 (10)0.0066 (9)
C1A0.0466 (13)0.0634 (15)0.0673 (15)0.0078 (11)0.0043 (14)0.0010 (14)
C2A0.0430 (13)0.0744 (19)0.086 (2)0.0032 (14)0.0012 (13)0.0006 (17)
C3A0.0382 (13)0.0716 (19)0.095 (2)0.0101 (13)0.0146 (14)0.0086 (18)
C4A0.0519 (13)0.0563 (15)0.0589 (14)0.0069 (12)0.0102 (12)0.0089 (13)
C5A0.0432 (12)0.0423 (13)0.0578 (14)0.0032 (11)0.0083 (11)0.0110 (12)
C6A0.0493 (13)0.0447 (13)0.0485 (13)0.0066 (11)0.0063 (11)0.0061 (12)
C7A0.0626 (16)0.0587 (16)0.0596 (16)0.0006 (13)0.0114 (13)0.0090 (15)
C8A0.083 (2)0.082 (2)0.0797 (19)0.0047 (19)0.0042 (18)0.0315 (16)
C9A0.0607 (17)0.083 (2)0.098 (2)0.0154 (17)0.0033 (16)0.024 (2)
C10A0.0544 (16)0.0669 (18)0.0778 (18)0.0004 (14)0.0065 (14)0.0154 (17)
C12A0.0767 (18)0.0705 (19)0.0661 (18)0.0072 (17)0.0161 (15)0.0122 (15)
C11A0.0575 (16)0.0748 (18)0.0791 (19)0.0145 (15)0.0224 (15)0.0003 (16)
Geometric parameters (Å, º) top
Ni—N1C2.038 (2)C1A—C2A1.382 (4)
Ni—N1Ci2.038 (2)C2A—C3A1.351 (4)
Ni—N1A2.0990 (19)C3A—C4A1.404 (4)
Ni—N1Ai2.0990 (19)C4A—C11A1.419 (4)
Ni—N2A2.1056 (19)C4A—C5A1.422 (3)
Ni—N2Ai2.1056 (19)C5A—C6A1.424 (3)
S1C—C1C1.618 (3)C6A—C7A1.402 (3)
C1C—N1C1.153 (3)C7A—C8A1.402 (4)
N1A—C1A1.345 (3)C7A—C12A1.414 (3)
N1A—C5A1.352 (3)C8A—C9A1.372 (3)
N2A—C10A1.323 (3)C9A—C10A1.393 (4)
N2A—C6A1.370 (3)C12A—C11A1.339 (4)
N1C—Ni—N1Ci92.51 (13)C6A—N2A—Ni113.13 (15)
N1C—Ni—N1A92.45 (8)N1A—C1A—C2A123.3 (3)
N1Ci—Ni—N1A96.27 (8)C3A—C2A—C1A119.6 (3)
N1C—Ni—N1Ai96.27 (8)C2A—C3A—C4A120.3 (2)
N1Ci—Ni—N1Ai92.45 (8)C3A—C4A—C11A125.0 (2)
N1A—Ni—N1Ai167.37 (10)C3A—C4A—C5A116.7 (2)
N1C—Ni—N2A171.35 (8)C11A—C4A—C5A118.3 (2)
N1Ci—Ni—N2A88.68 (9)N1A—C5A—C4A122.8 (2)
N1A—Ni—N2A78.90 (7)N1A—C5A—C6A117.9 (2)
N1Ai—Ni—N2A92.23 (7)C4A—C5A—C6A119.2 (2)
N1C—Ni—N2Ai88.68 (9)N2A—C6A—C7A123.1 (2)
N1Ci—Ni—N2Ai171.35 (8)N2A—C6A—C5A116.7 (2)
N1A—Ni—N2Ai92.23 (7)C7A—C6A—C5A120.2 (2)
N1Ai—Ni—N2Ai78.90 (7)C8A—C7A—C6A116.8 (2)
N2A—Ni—N2Ai91.42 (11)C8A—C7A—C12A124.4 (3)
N1C—C1C—S1C178.8 (2)C6A—C7A—C12A118.8 (2)
C1C—N1C—Ni162.0 (2)C9A—C8A—C7A120.1 (3)
C1A—N1A—C5A117.3 (2)C8A—C9A—C10A119.2 (3)
C1A—N1A—Ni129.26 (16)N2A—C10A—C9A123.0 (2)
C5A—N1A—Ni113.32 (15)C11A—C12A—C7A121.5 (3)
C10A—N2A—C6A117.83 (19)C12A—C11A—C4A121.8 (2)
C10A—N2A—Ni128.96 (16)
N1A—C5A—C6A—N2A1.6 (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]·H2OZ = 2
Mr = 609.40F(000) = 6132
Triclinic, P1Dx = 1.445 Mg m3
a = 9.689 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.757 (1) ÅCell parameters from 10054 reflections
c = 14.754 (1) Åθ = 3.5–27.5°
α = 77.71 (1)°µ = 0.88 mm1
β = 79.00 (1)°T = 293 K
γ = 70.07 (1)°Plates, turquoise
V = 1400.8 (2) Å30.23 × 0.22 × 0.16 mm
Data collection top
Bruker SMART 6000
diffractometer
3612 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.031
Mirrors monochromatorθmax = 27.5°, θmin = 2.0°
Detector resolution: 4.923 pixels mm-1h = 1212
ω scansk = 1313
10079 measured reflectionsl = 1918
6316 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: full with fixed elements per cycleSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-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 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
[Ni(CNS)2(C14H12N2)2]·H2Oγ = 70.07 (1)°
Mr = 609.40V = 1400.8 (2) Å3
Triclinic, P1Z = 2
a = 9.689 (1) ÅMo Kα radiation
b = 10.757 (1) ŵ = 0.88 mm1
c = 14.754 (1) ÅT = 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 reflectionsRint = 0.031
6316 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 0.97Δρmax = 0.40 e Å3
6316 reflectionsΔρmin = 0.27 e Å3
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
xyzUiso*/UeqOcc. (<1)
Ni0.82294 (4)0.27321 (3)0.25293 (2)0.04137 (11)
S1C0.70021 (9)0.11960 (7)0.25321 (6)0.0675 (2)
C1C0.7278 (3)0.0229 (3)0.24860 (17)0.0457 (6)
N1C0.7458 (2)0.1251 (2)0.24459 (15)0.0567 (6)
S1D0.45217 (8)0.68917 (7)0.18791 (5)0.0607 (2)
C1D0.5617 (3)0.5375 (3)0.21096 (16)0.0403 (6)
N1D0.6381 (2)0.4286 (2)0.22766 (15)0.0554 (6)
N1A0.9236 (2)0.31038 (19)0.11203 (13)0.0446 (5)
N2A0.9381 (2)0.41592 (17)0.25843 (13)0.0365 (5)
C1A0.9023 (3)0.2813 (3)0.0338 (2)0.0571 (8)
C2A1.0101 (4)0.2774 (3)0.0468 (2)0.0686 (9)
H2AA0.99330.25720.10110.082*
C3A1.1365 (4)0.3027 (3)0.0450 (2)0.0714 (9)
H3AA1.20830.29630.09710.086*
C4A1.1594 (3)0.3386 (3)0.03490 (18)0.0539 (7)
C5A1.0468 (3)0.3456 (2)0.11103 (17)0.0434 (6)
C6A1.0578 (3)0.3959 (2)0.19040 (16)0.0394 (6)
C7A1.1839 (3)0.4314 (3)0.19346 (19)0.0487 (7)
C8A1.1833 (3)0.4878 (3)0.2698 (2)0.0592 (8)
H8AA1.26740.50550.27780.071*
C9A1.0596 (3)0.5171 (3)0.33280 (19)0.0579 (8)
H9AA1.05700.56020.38180.069*
C10A0.9363 (3)0.4832 (2)0.32459 (17)0.0425 (6)
C11A1.2891 (3)0.3689 (3)0.0425 (2)0.0690 (9)
H11A1.36590.36000.00680.083*
C12A1.3019 (3)0.4101 (3)0.1193 (2)0.0659 (8)
H12A1.38930.42490.12390.079*
C13A0.7642 (4)0.2495 (3)0.0321 (2)0.0785 (10)
H13D0.68770.29160.07790.118*
H13E0.78340.15430.04610.118*
H13F0.73280.28230.02890.118*
C14A0.7957 (3)0.5283 (2)0.38971 (17)0.0536 (7)
H14A0.71800.50790.37010.080*
H14B0.76860.62320.38840.080*
H14C0.81090.48260.45220.080*
N1B0.7828 (2)0.23593 (18)0.40256 (13)0.0410 (5)
N2B1.0319 (2)0.12763 (18)0.29239 (13)0.0398 (5)
C1B0.6569 (3)0.2669 (2)0.46061 (19)0.0511 (7)
C2B0.6573 (3)0.2699 (3)0.55492 (19)0.0611 (8)
H2BA0.56810.29270.59400.073*
C3B0.7867 (4)0.2399 (3)0.58968 (19)0.0583 (8)
H3BA0.78580.24570.65180.070*
C4B0.9219 (3)0.2002 (2)0.53210 (17)0.0484 (7)
C5B0.9136 (3)0.1962 (2)0.43871 (16)0.0392 (6)
C6B1.0467 (3)0.1447 (2)0.37892 (16)0.0397 (6)
C7B1.1835 (3)0.1071 (2)0.41210 (18)0.0462 (7)
C8B1.3095 (3)0.0537 (3)0.3503 (2)0.0571 (8)
H8BA1.40350.03590.36610.069*
C9B1.2935 (3)0.0281 (3)0.2673 (2)0.0569 (8)
H9BA1.37670.01170.22770.068*
C10B1.1522 (3)0.0612 (2)0.24103 (18)0.0458 (6)
C11B1.0621 (4)0.1616 (3)0.56350 (19)0.0583 (8)
H11B1.06750.16540.62510.070*
C12B1.1872 (3)0.1195 (3)0.5056 (2)0.0573 (8)
H12B1.27810.09800.52710.069*
C13B0.5130 (3)0.2994 (3)0.4232 (2)0.0746 (9)
H13A0.53080.26420.36600.112*
H13B0.46800.39480.41150.112*
H13C0.44790.26000.46830.112*
C14B1.1335 (3)0.0152 (3)0.15603 (18)0.0619 (8)
H14F1.03050.04570.14800.093*
H14G1.16950.08090.16400.093*
H14D1.18840.05140.10180.093*
O1WA0.506 (3)0.0266 (19)0.0222 (11)0.170 (7)*0.264 (9)
O1WB0.379 (3)0.022 (3)0.0311 (15)0.134 (8)*0.140 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0439 (2)0.03700 (19)0.0439 (2)0.01291 (15)0.00792 (15)0.00539 (13)
S1C0.0765 (6)0.0493 (5)0.0867 (6)0.0250 (4)0.0174 (5)0.0168 (4)
C1C0.0422 (16)0.0519 (17)0.0430 (15)0.0104 (14)0.0094 (12)0.0113 (12)
N1C0.0631 (16)0.0514 (15)0.0621 (15)0.0228 (13)0.0136 (12)0.0101 (12)
S1D0.0607 (5)0.0467 (4)0.0608 (5)0.0077 (4)0.0036 (4)0.0046 (3)
C1D0.0349 (15)0.0542 (17)0.0367 (14)0.0185 (13)0.0005 (11)0.0136 (11)
N1D0.0470 (14)0.0560 (15)0.0613 (15)0.0133 (12)0.0087 (12)0.0086 (11)
N1A0.0565 (14)0.0405 (12)0.0362 (12)0.0114 (11)0.0119 (11)0.0061 (9)
N2A0.0407 (12)0.0297 (11)0.0367 (11)0.0097 (9)0.0033 (10)0.0041 (8)
C1A0.075 (2)0.0462 (17)0.0507 (18)0.0144 (15)0.0213 (16)0.0041 (13)
C2A0.101 (3)0.066 (2)0.0390 (17)0.021 (2)0.0140 (18)0.0136 (14)
C3A0.088 (3)0.071 (2)0.0453 (19)0.021 (2)0.0075 (17)0.0081 (14)
C4A0.068 (2)0.0492 (17)0.0379 (16)0.0124 (15)0.0017 (15)0.0094 (12)
C5A0.0488 (17)0.0389 (14)0.0378 (15)0.0124 (13)0.0036 (13)0.0001 (11)
C6A0.0447 (16)0.0326 (13)0.0378 (14)0.0118 (12)0.0024 (12)0.0021 (10)
C7A0.0464 (17)0.0485 (16)0.0525 (17)0.0213 (14)0.0020 (14)0.0072 (12)
C8A0.0580 (19)0.0635 (19)0.068 (2)0.0320 (16)0.0092 (17)0.0124 (15)
C9A0.072 (2)0.0613 (19)0.0536 (18)0.0346 (17)0.0045 (16)0.0174 (14)
C10A0.0520 (17)0.0306 (13)0.0439 (15)0.0150 (12)0.0037 (13)0.0029 (11)
C11A0.064 (2)0.080 (2)0.059 (2)0.0306 (18)0.0186 (17)0.0122 (16)
C12A0.060 (2)0.076 (2)0.066 (2)0.0338 (17)0.0059 (17)0.0113 (16)
C13A0.101 (3)0.085 (2)0.063 (2)0.035 (2)0.0305 (19)0.0126 (17)
C14A0.0668 (19)0.0412 (15)0.0521 (17)0.0193 (14)0.0056 (14)0.0139 (12)
N1B0.0449 (13)0.0340 (11)0.0437 (12)0.0153 (10)0.0007 (11)0.0048 (9)
N2B0.0459 (13)0.0312 (11)0.0403 (12)0.0108 (10)0.0031 (10)0.0057 (9)
C1B0.0545 (19)0.0437 (16)0.0555 (18)0.0226 (14)0.0017 (15)0.0048 (12)
C2B0.068 (2)0.0589 (19)0.0515 (19)0.0265 (17)0.0166 (16)0.0103 (14)
C3B0.084 (2)0.0545 (18)0.0381 (16)0.0311 (17)0.0042 (16)0.0063 (12)
C4B0.069 (2)0.0383 (15)0.0400 (15)0.0229 (14)0.0063 (15)0.0016 (11)
C5B0.0494 (16)0.0308 (13)0.0398 (14)0.0181 (12)0.0043 (13)0.0026 (10)
C6B0.0489 (16)0.0273 (13)0.0425 (15)0.0136 (12)0.0054 (13)0.0022 (10)
C7B0.0508 (18)0.0344 (14)0.0542 (17)0.0128 (13)0.0155 (14)0.0019 (12)
C8B0.0465 (18)0.0472 (17)0.077 (2)0.0120 (14)0.0160 (16)0.0052 (14)
C9B0.0478 (18)0.0436 (16)0.069 (2)0.0034 (14)0.0004 (15)0.0116 (14)
C10B0.0522 (18)0.0317 (14)0.0489 (16)0.0096 (13)0.0061 (14)0.0033 (11)
C11B0.084 (2)0.0494 (17)0.0466 (17)0.0236 (17)0.0224 (17)0.0024 (13)
C12B0.065 (2)0.0469 (17)0.067 (2)0.0189 (15)0.0306 (17)0.0021 (14)
C13B0.052 (2)0.093 (3)0.078 (2)0.0308 (18)0.0095 (17)0.0165 (18)
C14B0.075 (2)0.0485 (17)0.0544 (18)0.0052 (15)0.0061 (15)0.0172 (13)
Geometric parameters (Å, º) top
Ni—N1C2.011 (2)C7A—C12A1.417 (4)
Ni—N1D2.022 (2)C8A—C9A1.357 (4)
Ni—N1A2.138 (2)C9A—C10A1.396 (3)
Ni—N1B2.1419 (19)C10A—C14A1.504 (3)
Ni—N2B2.1886 (19)C11A—C12A1.343 (4)
Ni—N2A2.2054 (19)N1B—C1B1.333 (3)
S1C—C1C1.629 (3)N1B—C5B1.365 (3)
C1C—N1C1.158 (3)N2B—C10B1.330 (3)
S1D—C1D1.620 (3)N2B—C6B1.368 (3)
C1D—N1D1.157 (3)C1B—C2B1.399 (4)
N1A—C1A1.328 (3)C1B—C13B1.500 (4)
N1A—C5A1.366 (3)C2B—C3B1.356 (4)
N2A—C10A1.328 (3)C3B—C4B1.403 (4)
N2A—C6A1.370 (3)C4B—C5B1.406 (3)
C1A—C2A1.423 (4)C4B—C11B1.417 (4)
C1A—C13A1.495 (4)C5B—C6B1.426 (3)
C2A—C3A1.348 (4)C6B—C7B1.399 (3)
C3A—C4A1.393 (4)C7B—C8B1.405 (4)
C4A—C5A1.404 (3)C7B—C12B1.423 (4)
C4A—C11A1.431 (4)C8B—C9B1.359 (4)
C5A—C6A1.425 (3)C9B—C10B1.401 (4)
C6A—C7A1.409 (3)C10B—C14B1.504 (3)
C7A—C8A1.387 (4)C11B—C12B1.341 (4)
N1C—Ni—N1D97.81 (9)C8A—C7A—C12A123.7 (3)
N1C—Ni—N1A100.37 (9)C6A—C7A—C12A119.3 (3)
N1D—Ni—N1A91.63 (8)C9A—C8A—C7A119.7 (3)
N1C—Ni—N1B90.97 (8)C8A—C9A—C10A120.5 (3)
N1D—Ni—N1B99.07 (8)N2A—C10A—C9A121.6 (2)
N1A—Ni—N1B163.24 (8)N2A—C10A—C14A118.9 (2)
N1C—Ni—N2B91.01 (8)C9A—C10A—C14A119.4 (2)
N1D—Ni—N2B170.31 (8)C12A—C11A—C4A121.2 (3)
N1A—Ni—N2B90.71 (7)C11A—C12A—C7A120.8 (3)
N1B—Ni—N2B76.67 (7)C1B—N1B—C5B118.4 (2)
N1C—Ni—N2A172.14 (8)C1B—N1B—Ni130.65 (17)
N1D—Ni—N2A89.55 (8)C5B—N1B—Ni109.74 (15)
N1A—Ni—N2A76.56 (8)C10B—N2B—C6B118.0 (2)
N1B—Ni—N2A90.58 (7)C10B—N2B—Ni131.34 (16)
N2B—Ni—N2A81.85 (7)C6B—N2B—Ni107.53 (15)
N1C—C1C—S1C179.0 (2)N1B—C1B—C2B121.2 (3)
C1C—N1C—Ni165.4 (2)N1B—C1B—C13B118.9 (2)
N1D—C1D—S1D178.9 (2)C2B—C1B—C13B119.9 (3)
C1D—N1D—Ni159.8 (2)C3B—C2B—C1B120.5 (3)
C1A—N1A—C5A118.2 (2)C2B—C3B—C4B120.1 (3)
C1A—N1A—Ni130.6 (2)C3B—C4B—C5B116.4 (3)
C5A—N1A—Ni109.80 (16)C3B—C4B—C11B123.9 (3)
C10A—N2A—C6A117.8 (2)C5B—C4B—C11B119.6 (3)
C10A—N2A—Ni132.44 (16)N1B—C5B—C4B123.0 (2)
C6A—N2A—Ni106.91 (15)N1B—C5B—C6B117.8 (2)
N1A—C1A—C2A120.8 (3)C4B—C5B—C6B119.2 (2)
N1A—C1A—C13A119.0 (3)N2B—C6B—C7B123.2 (2)
C2A—C1A—C13A120.3 (3)N2B—C6B—C5B117.0 (2)
C3A—C2A—C1A120.6 (3)C7B—C6B—C5B119.7 (2)
C2A—C3A—C4A119.9 (3)C6B—C7B—C8B116.5 (2)
C3A—C4A—C5A117.0 (3)C6B—C7B—C12B119.2 (3)
C3A—C4A—C11A123.7 (3)C8B—C7B—C12B124.1 (3)
C5A—C4A—C11A119.4 (3)C9B—C8B—C7B119.7 (3)
N1A—C5A—C4A123.2 (3)C8B—C9B—C10B120.3 (3)
N1A—C5A—C6A117.8 (2)N2B—C10B—C9B121.3 (2)
C4A—C5A—C6A118.9 (3)N2B—C10B—C14B118.6 (2)
N2A—C6A—C7A122.7 (2)C9B—C10B—C14B120.0 (3)
N2A—C6A—C5A117.2 (2)C12B—C11B—C4B120.9 (3)
C7A—C6A—C5A120.0 (2)C11B—C12B—C7B121.2 (3)
C8A—C7A—C6A117.0 (3)
N1A—C5A—C6A—N2A5.6 (3)N1B—C5B—C6B—N2B5.6 (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
Mr487.24535.28609.40
Crystal system, space groupMonoclinic, P21/cOrthorhombic, PbcnTriclinic, P1
Temperature (K)293293293
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), 9090, 90, 9077.71 (1), 79.00 (1), 70.07 (1)
V3)2174.7 (8)2309.3 (8)1400.8 (2)
Z442
Radiation typeMo KαMo KαMo Kα
µ (mm1)1.111.050.88
Crystal size (mm)0.24 × 0.18 × 0.080.20 × 0.20 × 0.140.23 × 0.22 × 0.16
Data collection
DiffractometerRigaku AFC7S Difractometer
diffractometer
Rigaku AFC7S Difractometer
diffractometer
Bruker SMART 6000
diffractometer
Absorption correctionψ scan
(MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988)
ψ scan
(MSC/AFC Diffractometer Software; Molecular Structure Corporation, 1988)
Tmin, Tmax0.84, 0.920.77, 0.85
No. of measured, independent and
observed [I > 2σ(I)] reflections
6054, 5008, 3122 3409, 2663, 1410 10079, 6316, 3612
Rint0.0610.0320.031
(sin θ/λ)max1)0.6510.6500.650
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 reflections500826636316
No. of parameters280159366
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.12, 1.150.28, 0.250.40, 0.27

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), SMART (Bruker,, MSC/AFC Diffractometer Control Software, SAINT, SHELXS97 (Sheldrick, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL/PC (Sheldrick, 1994), PARST (Nardelli, 1983) and CSD (Allen & Kennard, 1993).

Selected geometric parameters (Å, º) for (I) top
Ni—N1D2.040 (4)Ni—N2B2.104 (3)
Ni—N1A2.057 (3)S1C—C1C1.631 (5)
Ni—N1C2.065 (4)C1C—N1C1.138 (6)
Ni—N1B2.076 (3)S1D—C1D1.622 (4)
Ni—N2A2.096 (3)C1D—N1D1.166 (5)
N1D—Ni—N1A88.29 (14)N1B—Ni—N2A95.87 (14)
N1D—Ni—N1C91.45 (14)N1D—Ni—N2B173.92 (14)
N1A—Ni—N1C98.04 (14)N1A—Ni—N2B97.60 (14)
N1D—Ni—N1B95.53 (14)N1C—Ni—N2B89.26 (13)
N1A—Ni—N1B172.83 (13)N1B—Ni—N2B78.46 (13)
N1C—Ni—N1B87.96 (15)N2A—Ni—N2B90.94 (13)
N1D—Ni—N2A88.75 (14)N1C—C1C—S1C178.0 (4)
N1A—Ni—N2A78.11 (14)N1D—C1D—S1D179.0 (4)
N1C—Ni—N2A176.13 (14)
N1A—C5A—C6A—N2A1.9 (5)N1B—C5B—C6B—N2B3.8 (5)
Selected geometric parameters (Å, º) for (II) top
Ni—N1C2.038 (2)Ni—N2A2.1056 (19)
Ni—N1Ci2.038 (2)Ni—N2Ai2.1056 (19)
Ni—N1A2.0990 (19)S1C—C1C1.618 (3)
Ni—N1Ai2.0990 (19)C1C—N1C1.153 (3)
N1C—Ni—N1Ci92.51 (13)N1Ai—Ni—N2A92.23 (7)
N1C—Ni—N1A92.45 (8)N1C—Ni—N2Ai88.68 (9)
N1Ci—Ni—N1A96.27 (8)N1Ci—Ni—N2Ai171.35 (8)
N1C—Ni—N1Ai96.27 (8)N1A—Ni—N2Ai92.23 (7)
N1Ci—Ni—N1Ai92.45 (8)N1Ai—Ni—N2Ai78.90 (7)
N1A—Ni—N1Ai167.37 (10)N2A—Ni—N2Ai91.42 (11)
N1C—Ni—N2A171.35 (8)N1C—C1C—S1C178.8 (2)
N1Ci—Ni—N2A88.68 (9)C1C—N1C—Ni162.0 (2)
N1A—Ni—N2A78.90 (7)
N1A—C5A—C6A—N2A1.6 (5)
Symmetry code: (i) x+1, y, z+3/2.
Selected geometric parameters (Å, º) for (III) top
Ni—N1C2.011 (2)Ni—N2A2.2054 (19)
Ni—N1D2.022 (2)S1C—C1C1.629 (3)
Ni—N1A2.138 (2)C1C—N1C1.158 (3)
Ni—N1B2.1419 (19)S1D—C1D1.620 (3)
Ni—N2B2.1886 (19)C1D—N1D1.157 (3)
N1C—Ni—N1D97.81 (9)N1B—Ni—N2B76.67 (7)
N1C—Ni—N1A100.37 (9)N1C—Ni—N2A172.14 (8)
N1D—Ni—N1A91.63 (8)N1D—Ni—N2A89.55 (8)
N1C—Ni—N1B90.97 (8)N1A—Ni—N2A76.56 (8)
N1D—Ni—N1B99.07 (8)N1B—Ni—N2A90.58 (7)
N1A—Ni—N1B163.24 (8)N2B—Ni—N2A81.85 (7)
N1C—Ni—N2B91.01 (8)N1C—C1C—S1C179.0 (2)
N1D—Ni—N2B170.31 (8)N1D—C1D—S1D178.9 (2)
N1A—Ni—N2B90.71 (7)
N1A—C5A—C6A—N2A5.6 (3)N1B—C5B—C6B—N2B5.6 (3)
 

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