The crystal structures of dicaesium nickel disilver hexathiocyanate dihydrate, Cs2NiAg2(SCN)6·2H2O, (I), and caesium nickel trithiocyanate, CsNi(SCN)3, (II), have been determined by single-crystal X-ray diffraction at 273 K. Compounds (I) and (II) are monoclinic, with P21/c and P21/n symmetry, respectively. In (I), the Ni atom lies on an inversion centre; in (II), there are two independent Ni atoms, each of which lies on an inversion centre. The coordination polyhedra and the bonding schemes in the structures are discussed.
Supporting information
For compound (I), stoichiometric quantities of Cs2CO3 (1680 mg), NiCl2·6H2O (1089 mg), AgSCN (821 mg) and NH4SCN (392 mg) were dissolved in approximately 150 ml of distilled water. For compound (II), stoichiometric quantities of Cs2CO3 (1702 mg), NiCl2·6H2O (1065 mg) and NH4SCN (402 mg) and approximately 120 ml distilled water were used. The solutions were heated to a temperature of 353 K until the material was completely dissolved, and subsequently cooled to 293 K over a period of 14 d. The syntheses yielded small (up to 0.5 mm) blue [for (I)] or green [for (II)] crystals. In both cases, the products were accompanied by large, colourless crystals of NH4Cl. The products were picked manually from the supernatant liquors and carefully washed with distilled water.
The H atoms in (I) were refined freely. After the refinement, the residual electron-density maxima and minima were 2.18 (0.79 Å from Ag) and −1.59 e Å−3 (0.76 Å from Ag), respectively, for (I), and 1.40 (0.76 Å from Cs) and −1.28 e Å−3 (0.65 Å from Cs), respectively, for (II).
For both compounds, data collection: COLLECT (Nonius, 2003); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff et al., 1996) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(I) dicaesium disilver nickel hexathiocyanate dihydrate
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Crystal data top
Cs2NiAg2(SCN)6·2H2O | F(000) = 852 |
Mr = 924.82 | Dx = 2.824 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3260 reflections |
a = 7.503 (2) Å | θ = 4.1–30.0° |
b = 18.766 (4) Å | µ = 6.53 mm−1 |
c = 7.733 (2) Å | T = 293 K |
β = 92.59 (3)° | Prism, blue |
V = 1087.7 (5) Å3 | 0.17 × 0.10 × 0.08 mm |
Z = 2 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3167 independent reflections |
Radiation source: fine-focus sealed tube | 2538 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 9 pixels mm-1 | θmax = 30.0°, θmin = 4.2° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | k = −26→26 |
Tmin = 0.403, Tmax = 0.623 | l = −10→10 |
6227 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | All H-atom parameters refined |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0279P)2 + 2.7068P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3167 reflections | Δρmax = 2.18 e Å−3 |
124 parameters | Δρmin = −1.59 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0024 (2) |
Crystal data top
Cs2NiAg2(SCN)6·2H2O | V = 1087.7 (5) Å3 |
Mr = 924.82 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.503 (2) Å | µ = 6.53 mm−1 |
b = 18.766 (4) Å | T = 293 K |
c = 7.733 (2) Å | 0.17 × 0.10 × 0.08 mm |
β = 92.59 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 3167 independent reflections |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | 2538 reflections with I > 2σ(I) |
Tmin = 0.403, Tmax = 0.623 | Rint = 0.017 |
6227 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.077 | All H-atom parameters refined |
S = 1.05 | Δρmax = 2.18 e Å−3 |
3167 reflections | Δρmin = −1.59 e Å−3 |
124 parameters | |
Special details top
Experimental. The single-crystal data were collected on a Nonius Kappa CCD four-circle diffractometer using 595 frames with phi and omega-increments of 1 degree and a counting time of 60 s per frame. The crystal to detector distance was 30 mm. The whole Ewald sphere was measured. |
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. Single-crystal X-ray intensity data were collected at 293 K on a Nonius Kappa diffractometer with CCD area detector, using Mo—Kα radiation. The reflection data were processed with the Nonius program suite DENZO-SMN and corrected for Lorentz, polarization, background and absorption effects (Otwinowski and Minor, 1997). The crystal structure was determined by either automatic Patterson or direct methods (SHELXS97 - Sheldrick, 1997) and subsequent Fourier and difference Fourier syntheses, followed by full-matrix least-squares refinements on F2 (SHELXL97 - Sheldrick, 1997). 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ag | 0.76600 (5) | −0.286655 (18) | 0.50326 (5) | 0.05315 (12) | |
Ni | 0.5000 | 0.0000 | 0.5000 | 0.03128 (15) | |
Cs | 0.73749 (4) | 0.117368 (15) | 0.97081 (4) | 0.04816 (11) | |
S1 | 0.53818 (15) | −0.24142 (5) | 0.71930 (13) | 0.0386 (2) | |
C1 | 0.5165 (5) | −0.16058 (19) | 0.6369 (5) | 0.0320 (7) | |
N1 | 0.5001 (5) | −0.10316 (18) | 0.5855 (5) | 0.0423 (8) | |
S2 | 0.79442 (15) | −0.07904 (5) | 0.99078 (13) | 0.0382 (2) | |
C2 | 0.6886 (5) | −0.05434 (18) | 1.1626 (5) | 0.0301 (7) | |
N2 | 0.6098 (5) | −0.0340 (2) | 1.2769 (5) | 0.0464 (9) | |
S3 | 1.02943 (16) | −0.21508 (6) | 0.40624 (15) | 0.0465 (3) | |
C3 | 1.0220 (5) | −0.1503 (2) | 0.5490 (6) | 0.0395 (9) | |
N3 | 1.0205 (6) | −0.1031 (2) | 0.6453 (6) | 0.0588 (11) | |
OW | 0.7605 (4) | 0.01837 (18) | 0.6107 (4) | 0.0421 (7) | |
H1W | 0.810 (10) | −0.013 (4) | 0.624 (10) | 0.09 (3)* | |
H2W | 0.787 (6) | 0.042 (3) | 0.519 (7) | 0.043 (13)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ag | 0.0518 (2) | 0.03179 (17) | 0.0766 (3) | −0.00260 (13) | 0.01119 (18) | −0.00135 (15) |
Ni | 0.0360 (3) | 0.0249 (3) | 0.0336 (3) | 0.0035 (2) | 0.0083 (3) | −0.0006 (2) |
Cs | 0.04069 (15) | 0.03630 (15) | 0.0670 (2) | −0.00005 (10) | −0.00311 (12) | 0.00055 (12) |
S1 | 0.0539 (6) | 0.0267 (4) | 0.0352 (5) | −0.0041 (4) | 0.0017 (4) | 0.0020 (4) |
C1 | 0.0315 (17) | 0.0322 (18) | 0.0325 (18) | 0.0006 (14) | 0.0031 (14) | −0.0004 (14) |
N1 | 0.0447 (19) | 0.0347 (17) | 0.048 (2) | 0.0058 (14) | 0.0035 (15) | 0.0045 (15) |
S2 | 0.0510 (6) | 0.0275 (4) | 0.0372 (5) | 0.0028 (4) | 0.0149 (4) | 0.0000 (4) |
C2 | 0.0314 (17) | 0.0248 (16) | 0.0339 (18) | 0.0007 (13) | 0.0007 (14) | −0.0016 (13) |
N2 | 0.050 (2) | 0.0428 (19) | 0.048 (2) | 0.0041 (16) | 0.0158 (17) | −0.0076 (16) |
S3 | 0.0525 (6) | 0.0391 (5) | 0.0487 (6) | −0.0060 (4) | 0.0113 (5) | −0.0005 (4) |
C3 | 0.039 (2) | 0.034 (2) | 0.046 (2) | −0.0060 (16) | 0.0089 (17) | 0.0053 (17) |
N3 | 0.065 (3) | 0.049 (2) | 0.064 (3) | −0.005 (2) | 0.019 (2) | −0.005 (2) |
OW | 0.0433 (17) | 0.0369 (16) | 0.0462 (17) | −0.0002 (13) | 0.0042 (13) | 0.0069 (14) |
Geometric parameters (Å, º) top
Ag—S3 | 2.5314 (13) | Cs—C2iii | 3.520 (4) |
Ag—S2i | 2.5316 (11) | Cs—N2iii | 3.530 (4) |
Ag—S1 | 2.5868 (13) | Cs—C2 | 3.573 (4) |
Ag—S1i | 2.7716 (14) | Cs—S2v | 3.5841 (15) |
Ni—N1 | 2.046 (3) | Cs—S1vi | 3.6315 (12) |
Ni—N1ii | 2.046 (3) | S1—C1 | 1.651 (4) |
Ni—N2iii | 2.047 (3) | C1—N1 | 1.153 (5) |
Ni—N2iv | 2.047 (3) | S2—C2 | 1.645 (4) |
Ni—OW | 2.126 (3) | C2—N2 | 1.151 (5) |
Ni—OWii | 2.126 (3) | S3—C3 | 1.645 (4) |
Cs—OW | 3.359 (3) | C3—N3 | 1.157 (6) |
Cs—N3v | 3.420 (5) | | |
| | | |
S3—Ag—S2i | 116.66 (4) | S3ix—Cs—C1iii | 81.94 (6) |
S3—Ag—S1 | 124.39 (4) | S2—Cs—C1iii | 104.07 (6) |
S2i—Ag—S1 | 114.24 (3) | OW—Cs—N2 | 97.21 (8) |
S3—Ag—S1i | 97.25 (4) | N3v—Cs—N2 | 62.93 (9) |
S2i—Ag—S1i | 102.06 (3) | C2iii—Cs—N2 | 71.59 (9) |
S1—Ag—S1i | 92.72 (4) | N2iii—Cs—N2 | 78.95 (10) |
S3—Ag—Csvii | 62.07 (3) | C2—Cs—N2 | 17.35 (8) |
S2i—Ag—Csvii | 59.40 (3) | S2v—Cs—N2 | 94.08 (6) |
S1—Ag—Csvii | 137.04 (3) | S1vi—Cs—N2 | 129.41 (6) |
S1i—Ag—Csvii | 130.04 (3) | S3ix—Cs—N2 | 126.66 (6) |
S3—Ag—Csviii | 163.37 (3) | S2—Cs—N2 | 43.35 (5) |
S2i—Ag—Csviii | 69.65 (3) | C1iii—Cs—N2 | 60.73 (8) |
S1—Ag—Csviii | 59.18 (3) | OW—Cs—S3x | 66.47 (6) |
S1i—Ag—Csviii | 66.13 (3) | N3v—Cs—S3x | 116.42 (7) |
Csvii—Ag—Csviii | 128.430 (19) | C2iii—Cs—S3x | 111.64 (7) |
N1—Ni—N1ii | 180.00 (6) | N2iii—Cs—S3x | 98.44 (7) |
N1—Ni—N2iii | 90.94 (15) | C2—Cs—S3x | 141.98 (6) |
N1ii—Ni—N2iii | 89.06 (15) | S2v—Cs—S3x | 71.78 (3) |
N1—Ni—N2iv | 89.06 (15) | S1vi—Cs—S3x | 67.84 (3) |
N1ii—Ni—N2iv | 90.94 (15) | S3ix—Cs—S3x | 64.69 (2) |
N2iii—Ni—N2iv | 180.00 (11) | S2—Cs—S3x | 116.15 (3) |
N1—Ni—OW | 92.09 (14) | C1iii—Cs—S3x | 139.60 (6) |
N1ii—Ni—OW | 87.91 (14) | N2—Cs—S3x | 159.17 (5) |
N2iii—Ni—OW | 90.46 (15) | C1—S1—Ag | 96.23 (13) |
N2iv—Ni—OW | 89.54 (15) | C1—S1—Agxi | 100.23 (14) |
N1—Ni—OWii | 87.91 (14) | Ag—S1—Agxi | 99.92 (4) |
N1ii—Ni—OWii | 92.09 (14) | C1—S1—Csviii | 118.04 (14) |
N2iii—Ni—OWii | 89.54 (15) | Ag—S1—Csviii | 83.10 (3) |
N2iv—Ni—OWii | 90.46 (15) | Agxi—S1—Csviii | 141.17 (3) |
OW—Ni—OWii | 180.00 (8) | C1—S1—Csiii | 69.56 (13) |
OW—Cs—N3v | 129.14 (10) | Ag—S1—Csiii | 162.93 (4) |
OW—Cs—C2iii | 69.58 (8) | Agxi—S1—Csiii | 74.39 (3) |
N3v—Cs—C2iii | 131.90 (9) | Csviii—S1—Csiii | 111.59 (3) |
OW—Cs—N2iii | 50.88 (8) | N1—C1—S1 | 177.4 (4) |
N3v—Cs—N2iii | 141.85 (10) | N1—C1—Csiii | 91.5 (3) |
C2iii—Cs—N2iii | 18.79 (8) | S1—C1—Csiii | 86.04 (14) |
OW—Cs—C2 | 81.69 (9) | C1—N1—Ni | 173.8 (3) |
N3v—Cs—C2 | 68.23 (9) | C2—S2—Agxi | 101.84 (13) |
C2iii—Cs—C2 | 73.13 (9) | C2—S2—Csv | 119.75 (14) |
N2iii—Cs—C2 | 74.84 (9) | Agxi—S2—Csv | 83.16 (3) |
OW—Cs—S2v | 82.57 (6) | C2—S2—Cs | 72.25 (12) |
N3v—Cs—S2v | 55.42 (8) | Agxi—S2—Cs | 168.57 (4) |
C2iii—Cs—S2v | 146.16 (6) | Csv—S2—Cs | 108.25 (3) |
N2iii—Cs—S2v | 130.74 (6) | C2—S2—Csiii | 58.77 (13) |
C2—Cs—S2v | 84.44 (6) | Agxi—S2—Csiii | 74.77 (3) |
OW—Cs—S1vi | 96.76 (7) | Csv—S2—Csiii | 156.47 (3) |
N3v—Cs—S1vi | 132.77 (7) | Cs—S2—Csiii | 93.84 (2) |
C2iii—Cs—S1vi | 68.49 (6) | N2—C2—S2 | 175.9 (4) |
N2iii—Cs—S1vi | 73.19 (7) | N2—C2—Csiii | 81.1 (3) |
C2—Cs—S1vi | 139.37 (6) | S2—C2—Csiii | 97.67 (15) |
S2v—Cs—S1vi | 135.89 (3) | N2—C2—Cs | 94.9 (3) |
OW—Cs—S3ix | 129.90 (6) | S2—C2—Cs | 81.74 (13) |
N3v—Cs—S3ix | 67.51 (7) | Csiii—C2—Cs | 106.87 (9) |
C2iii—Cs—S3ix | 140.64 (6) | C2—N2—Nixii | 172.4 (4) |
N2iii—Cs—S3ix | 147.65 (7) | C2—N2—Csiii | 80.1 (3) |
C2—Cs—S3ix | 135.69 (6) | Nixii—N2—Csiii | 106.27 (14) |
S2v—Cs—S3ix | 72.50 (3) | C2—N2—Cs | 67.8 (2) |
S1vi—Cs—S3ix | 74.81 (3) | Nixii—N2—Cs | 114.19 (14) |
OW—Cs—S2 | 58.35 (6) | Csiii—N2—Cs | 101.05 (10) |
N3v—Cs—S2 | 80.24 (7) | C3—S3—Ag | 98.20 (14) |
C2iii—Cs—S2 | 77.28 (6) | C3—S3—Csvii | 119.05 (16) |
N2iii—Cs—S2 | 70.31 (7) | Ag—S3—Csvii | 80.75 (3) |
C2—Cs—S2 | 26.01 (6) | C3—S3—Csx | 100.55 (14) |
S2v—Cs—S2 | 71.75 (3) | Ag—S3—Csx | 148.08 (5) |
S1vi—Cs—S2 | 143.48 (3) | Csvii—S3—Csx | 111.52 (3) |
S3ix—Cs—S2 | 141.31 (3) | N3—C3—S3 | 177.4 (4) |
OW—Cs—C1iii | 147.02 (8) | C3—N3—Csv | 118.5 (4) |
N3v—Cs—C1iii | 65.38 (9) | Ni—OW—Cs | 110.04 (12) |
C2iii—Cs—C1iii | 79.71 (8) | Ni—OW—H1W | 113 (6) |
N2iii—Cs—C1iii | 98.37 (8) | Cs—OW—H1W | 113 (6) |
C2—Cs—C1iii | 78.08 (8) | Ni—OW—H2W | 90 (3) |
S2v—Cs—C1iii | 120.61 (6) | Cs—OW—H2W | 114 (3) |
S1vi—Cs—C1iii | 82.44 (6) | H1W—OW—H2W | 114 (7) |
Symmetry codes: (i) x, −y−1/2, z−1/2; (ii) −x+1, −y, −z+1; (iii) −x+1, −y, −z+2; (iv) x, y, z−1; (v) −x+2, −y, −z+2; (vi) −x+1, y+1/2, −z+3/2; (vii) −x+2, y−1/2, −z+3/2; (viii) −x+1, y−1/2, −z+3/2; (ix) −x+2, y+1/2, −z+3/2; (x) −x+2, −y, −z+1; (xi) x, −y−1/2, z+1/2; (xii) x, y, z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW—H1W···N3 | 0.71 (8) | 2.31 (8) | 3.004 (6) | 168 (8) |
OW—H2W···N3x | 0.87 (5) | 2.27 (5) | 3.072 (5) | 153 (4) |
Symmetry code: (x) −x+2, −y, −z+1. |
(II) caesium nickel trithiocyanate
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Crystal data top
CsNi(SCN)3 | F(000) = 680 |
Mr = 365.86 | Dx = 2.633 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2800 reflections |
a = 5.554 (1) Å | θ = 4.1–30.0° |
b = 13.294 (3) Å | µ = 6.61 mm−1 |
c = 12.589 (3) Å | T = 293 K |
β = 96.87 (3)° | Fragment, green |
V = 922.8 (3) Å3 | 0.15 × 0.08 × 0.05 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2695 independent reflections |
Radiation source: fine-focus sealed tube | 2441 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
Detector resolution: 9 pixels mm-1 | θmax = 30.0°, θmin = 4.2° |
ϕ and ω scans | h = −7→7 |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | k = −18→17 |
Tmin = 0.437, Tmax = 0.734 | l = −17→17 |
5137 measured reflections | |
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)] = 0.022 | w = 1/[σ2(Fo2) + (0.0231P)2 + 1.4456P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.057 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 1.40 e Å−3 |
2695 reflections | Δρmin = −1.28 e Å−3 |
104 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0042 (4) |
Crystal data top
CsNi(SCN)3 | V = 922.8 (3) Å3 |
Mr = 365.86 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.554 (1) Å | µ = 6.61 mm−1 |
b = 13.294 (3) Å | T = 293 K |
c = 12.589 (3) Å | 0.15 × 0.08 × 0.05 mm |
β = 96.87 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2695 independent reflections |
Absorption correction: multi-scan (Otwinowski & Minor, 1997) | 2441 reflections with I > 2σ(I) |
Tmin = 0.437, Tmax = 0.734 | Rint = 0.014 |
5137 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | 104 parameters |
wR(F2) = 0.057 | 0 restraints |
S = 1.05 | Δρmax = 1.40 e Å−3 |
2695 reflections | Δρmin = −1.28 e Å−3 |
Special details top
Experimental. The single-crystal data were collected on a Nonius Kappa CCD four-circle diffractometer using 534 frames with phi and omega-increments of 1 degrees and a counting time of 300 s per frame. The crystal to detector distance was 30 mm. The whole ewald sphere was measured. |
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. Single-crystal X-ray intensity data were collected at 293 K on a Nonius Kappa diffractometer with CCD area detector, using Mo—Kα radiation. The reflection data were processed with the Nonius program suite DENZO-SMN and corrected for Lorentz, polarization, background and absorption effects (Otwinowski and Minor, 1997). The crystal structure was determined by either automatic Patterson or direct methods (SHELXS97 - Sheldrick, 1997) and subsequent Fourier and difference Fourier syntheses, followed by full-matrix least-squares refinements on F2 (SHELXL97 - Sheldrick, 1997). 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cs | 0.84679 (3) | 0.770463 (15) | 0.782236 (14) | 0.03794 (8) | |
Ni1 | 1.0000 | 1.0000 | 1.0000 | 0.01849 (9) | |
Ni2 | 1.0000 | 1.0000 | 0.5000 | 0.01929 (10) | |
S1 | 0.73286 (11) | 1.14465 (5) | 0.42234 (6) | 0.03133 (15) | |
C1 | 0.4635 (4) | 1.09370 (18) | 0.42543 (18) | 0.0212 (4) | |
N1 | 0.2735 (3) | 1.05985 (16) | 0.42909 (16) | 0.0239 (4) | |
S2 | 0.75413 (10) | 1.16164 (5) | 0.98419 (5) | 0.02523 (13) | |
C2 | 1.4903 (4) | 1.11767 (18) | 1.01032 (18) | 0.0216 (4) | |
N2 | 1.3046 (4) | 1.08680 (16) | 1.02800 (18) | 0.0264 (4) | |
S3 | 1.14552 (14) | 1.10980 (5) | 0.65465 (5) | 0.03376 (15) | |
C3 | 1.0811 (4) | 1.04944 (19) | 0.76231 (19) | 0.0252 (5) | |
N3 | 1.0350 (4) | 1.01092 (18) | 0.83928 (17) | 0.0311 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cs | 0.04006 (12) | 0.04138 (12) | 0.03114 (10) | 0.00496 (7) | −0.00081 (7) | −0.00430 (7) |
Ni1 | 0.01560 (18) | 0.0232 (2) | 0.01736 (18) | −0.00227 (14) | 0.00478 (13) | 0.00133 (14) |
Ni2 | 0.01391 (17) | 0.0246 (2) | 0.01988 (19) | −0.00270 (14) | 0.00413 (14) | 0.00280 (14) |
S1 | 0.0172 (3) | 0.0292 (3) | 0.0479 (4) | −0.0036 (2) | 0.0053 (2) | 0.0109 (3) |
C1 | 0.0184 (9) | 0.0234 (10) | 0.0218 (10) | 0.0023 (8) | 0.0034 (8) | 0.0048 (8) |
N1 | 0.0172 (8) | 0.0283 (10) | 0.0267 (9) | −0.0004 (7) | 0.0050 (7) | 0.0051 (8) |
S2 | 0.0180 (2) | 0.0243 (3) | 0.0339 (3) | −0.0026 (2) | 0.0051 (2) | 0.0048 (2) |
C2 | 0.0203 (10) | 0.0201 (10) | 0.0243 (10) | 0.0027 (8) | 0.0028 (8) | −0.0007 (8) |
N2 | 0.0180 (9) | 0.0241 (10) | 0.0377 (11) | −0.0003 (8) | 0.0060 (8) | −0.0018 (8) |
S3 | 0.0473 (4) | 0.0331 (3) | 0.0214 (3) | −0.0161 (3) | 0.0064 (2) | 0.0007 (2) |
C3 | 0.0260 (11) | 0.0276 (12) | 0.0224 (10) | −0.0022 (9) | 0.0043 (9) | −0.0023 (9) |
N3 | 0.0365 (12) | 0.0372 (12) | 0.0205 (9) | −0.0015 (10) | 0.0075 (8) | 0.0013 (8) |
Geometric parameters (Å, º) top
Cs—N2i | 3.240 (2) | Ni1—N3 | 2.061 (2) |
Cs—N3 | 3.413 (3) | Ni1—S2 | 2.5411 (8) |
Cs—C1ii | 3.462 (2) | Ni1—S2i | 2.5411 (8) |
Cs—N1ii | 3.491 (2) | Ni2—N1ii | 2.015 (2) |
Cs—S3iii | 3.5508 (9) | Ni2—N1vi | 2.015 (2) |
Cs—S2i | 3.5798 (13) | Ni2—S3v | 2.4896 (8) |
Cs—S3iv | 3.6317 (10) | Ni2—S3 | 2.4896 (8) |
Cs—S2iv | 3.6341 (10) | Ni2—S1v | 2.5511 (8) |
Cs—C2i | 3.702 (2) | Ni2—S1 | 2.5511 (8) |
Cs—C3iv | 3.778 (3) | S1—C1 | 1.647 (2) |
Cs—S1v | 3.8464 (12) | C1—N1 | 1.154 (3) |
Cs—S1ii | 4.0357 (14) | S2—C2vii | 1.647 (2) |
Ni1—N2i | 2.043 (2) | C2—N2 | 1.156 (3) |
Ni1—N2 | 2.043 (2) | S3—C3 | 1.651 (3) |
Ni1—N3i | 2.061 (2) | C3—N3 | 1.152 (3) |
| | | |
N2i—Cs—N3 | 52.85 (5) | N3—Ni1—S2 | 88.65 (7) |
N2i—Cs—C1ii | 95.83 (6) | N2i—Ni1—S2i | 87.82 (6) |
N3—Cs—C1ii | 77.44 (6) | N2—Ni1—S2i | 92.18 (6) |
N2i—Cs—N1ii | 98.08 (6) | N3i—Ni1—S2i | 88.65 (7) |
N3—Cs—N1ii | 65.23 (5) | N3—Ni1—S2i | 91.35 (7) |
C1ii—Cs—N1ii | 19.09 (5) | S2—Ni1—S2i | 180.0 |
N2i—Cs—S3iii | 117.16 (4) | N2i—Ni1—Csi | 129.31 (6) |
N3—Cs—S3iii | 107.54 (5) | N2—Ni1—Csi | 50.69 (6) |
C1ii—Cs—S3iii | 142.46 (4) | N3i—Ni1—Csi | 55.62 (7) |
N1ii—Cs—S3iii | 129.32 (4) | N3—Ni1—Csi | 124.38 (7) |
N2i—Cs—S2i | 55.69 (4) | S2—Ni1—Csi | 59.49 (2) |
N3—Cs—S2i | 56.43 (4) | S2i—Ni1—Csi | 120.51 (2) |
C1ii—Cs—S2i | 133.80 (4) | N2i—Ni1—Cs | 50.69 (6) |
N1ii—Cs—S2i | 120.41 (4) | N2—Ni1—Cs | 129.31 (6) |
S3iii—Cs—S2i | 64.58 (2) | N3i—Ni1—Cs | 124.38 (7) |
N2i—Cs—S3iv | 85.10 (4) | N3—Ni1—Cs | 55.62 (7) |
N3—Cs—S3iv | 136.42 (4) | S2—Ni1—Cs | 120.51 (2) |
C1ii—Cs—S3iv | 98.75 (4) | S2i—Ni1—Cs | 59.49 (2) |
N1ii—Cs—S3iv | 117.80 (4) | Csi—Ni1—Cs | 180.0 |
S3iii—Cs—S3iv | 101.29 (2) | N1ii—Ni2—N1vi | 180.00 (11) |
S2i—Cs—S3iv | 112.15 (2) | N1ii—Ni2—S3v | 85.62 (7) |
N2i—Cs—S2iv | 152.72 (4) | N1vi—Ni2—S3v | 94.38 (7) |
N3—Cs—S2iv | 125.21 (4) | N1ii—Ni2—S3 | 94.38 (7) |
C1ii—Cs—S2iv | 60.19 (4) | N1vi—Ni2—S3 | 85.62 (7) |
N1ii—Cs—S2iv | 63.87 (4) | S3v—Ni2—S3 | 180.0 |
S3iii—Cs—S2iv | 89.87 (3) | N1ii—Ni2—S1v | 88.12 (6) |
S2i—Cs—S2iv | 150.51 (2) | N1vi—Ni2—S1v | 91.88 (6) |
S3iv—Cs—S2iv | 86.03 (3) | S3v—Ni2—S1v | 88.70 (3) |
N2i—Cs—C2i | 17.60 (5) | S3—Ni2—S1v | 91.30 (3) |
N3—Cs—C2i | 69.10 (5) | N1ii—Ni2—S1 | 91.88 (6) |
C1ii—Cs—C2i | 94.31 (5) | N1vi—Ni2—S1 | 88.12 (6) |
N1ii—Cs—C2i | 102.19 (5) | S3v—Ni2—S1 | 91.30 (3) |
S3iii—Cs—C2i | 122.60 (4) | S3—Ni2—S1 | 88.70 (3) |
S2i—Cs—C2i | 68.59 (4) | S1v—Ni2—S1 | 180.0 |
S3iv—Cs—C2i | 67.94 (4) | C1—S1—Ni2 | 99.74 (8) |
S2iv—Cs—C2i | 140.87 (4) | C1—S1—Csv | 139.67 (9) |
N2i—Cs—C3iv | 110.54 (5) | Ni2—S1—Csv | 96.08 (2) |
N3—Cs—C3iv | 158.59 (6) | C1—S1—Csii | 58.17 (8) |
C1ii—Cs—C3iv | 92.64 (6) | Ni2—S1—Csii | 146.96 (3) |
N1ii—Cs—C3iv | 109.26 (5) | Csv—S1—Csii | 89.57 (2) |
S3iii—Cs—C3iv | 91.95 (4) | C1—S1—Csviii | 87.14 (9) |
S2i—Cs—C3iv | 129.39 (4) | Ni2—S1—Csviii | 94.58 (3) |
S3iv—Cs—C3iv | 25.64 (4) | Csv—S1—Csviii | 128.33 (2) |
S2iv—Cs—C3iv | 61.88 (4) | Csii—S1—Csviii | 107.27 (3) |
C2i—Cs—C3iv | 93.15 (5) | N1—C1—S1 | 178.4 (2) |
N2i—Cs—S1v | 123.62 (4) | N1—C1—Csii | 81.86 (15) |
N3—Cs—S1v | 70.79 (4) | S1—C1—Csii | 98.00 (9) |
C1ii—Cs—S1v | 68.20 (4) | C1—N1—Ni2vii | 156.00 (19) |
N1ii—Cs—S1v | 51.41 (4) | C1—N1—Csii | 79.05 (15) |
S3iii—Cs—S1v | 78.28 (2) | Ni2vii—N1—Csii | 120.47 (8) |
S2i—Cs—S1v | 96.33 (2) | C2vii—S2—Ni1 | 99.61 (8) |
S3iv—Cs—S1v | 148.450 (18) | C2vii—S2—Csi | 113.81 (9) |
S2iv—Cs—S1v | 62.47 (2) | Ni1—S2—Csi | 82.80 (2) |
C2i—Cs—S1v | 138.86 (4) | C2vii—S2—Csviii | 106.44 (9) |
C3iv—Cs—S1v | 123.38 (4) | Ni1—S2—Csviii | 115.53 (3) |
N2i—Cs—S1ii | 92.82 (4) | Csi—S2—Csviii | 132.05 (2) |
N3—Cs—S1ii | 94.20 (4) | N2—C2—S2vi | 179.6 (2) |
C1ii—Cs—S1ii | 23.83 (4) | N2—C2—Csi | 57.91 (15) |
N1ii—Cs—S1ii | 42.92 (4) | S2vi—C2—Csi | 122.37 (11) |
S3iii—Cs—S1ii | 149.599 (18) | C2—N2—Ni1 | 155.0 (2) |
S2i—Cs—S1ii | 145.28 (2) | C2—N2—Csi | 104.49 (17) |
S3iv—Cs—S1ii | 74.93 (2) | Ni1—N2—Csi | 100.11 (8) |
S2iv—Cs—S1ii | 59.94 (2) | C3—S3—Ni2 | 105.97 (9) |
C2i—Cs—S1ii | 84.59 (4) | C3—S3—Csix | 110.67 (9) |
C3iv—Cs—S1ii | 71.53 (4) | Ni2—S3—Csix | 134.63 (3) |
S1v—Cs—S1ii | 89.57 (2) | C3—S3—Csviii | 82.15 (9) |
N2i—Ni1—N2 | 180.00 (10) | Ni2—S3—Csviii | 109.48 (3) |
N2i—Ni1—N3i | 87.50 (10) | Csix—S3—Csviii | 101.29 (2) |
N2—Ni1—N3i | 92.50 (10) | N3—C3—S3 | 177.3 (2) |
N2i—Ni1—N3 | 92.50 (10) | N3—C3—Csviii | 105.75 (19) |
N2—Ni1—N3 | 87.50 (10) | S3—C3—Csviii | 72.21 (9) |
N3i—Ni1—N3 | 180.000 (1) | C3—N3—Ni1 | 156.1 (2) |
N2i—Ni1—S2 | 92.18 (6) | C3—N3—Cs | 109.44 (18) |
N2—Ni1—S2 | 87.82 (6) | Ni1—N3—Cs | 94.48 (8) |
N3i—Ni1—S2 | 91.35 (7) | | |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+2, −z+1; (iii) −x+5/2, y−1/2, −z+3/2; (iv) −x+3/2, y−1/2, −z+3/2; (v) −x+2, −y+2, −z+1; (vi) x+1, y, z; (vii) x−1, y, z; (viii) −x+3/2, y+1/2, −z+3/2; (ix) −x+5/2, y+1/2, −z+3/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | Cs2NiAg2(SCN)6·2H2O | CsNi(SCN)3 |
Mr | 924.82 | 365.86 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.503 (2), 18.766 (4), 7.733 (2) | 5.554 (1), 13.294 (3), 12.589 (3) |
β (°) | 92.59 (3) | 96.87 (3) |
V (Å3) | 1087.7 (5) | 922.8 (3) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 6.53 | 6.61 |
Crystal size (mm) | 0.17 × 0.10 × 0.08 | 0.15 × 0.08 × 0.05 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (Otwinowski & Minor, 1997) | Multi-scan (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.403, 0.623 | 0.437, 0.734 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6227, 3167, 2538 | 5137, 2695, 2441 |
Rint | 0.017 | 0.014 |
(sin θ/λ)max (Å−1) | 0.703 | 0.704 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.077, 1.05 | 0.022, 0.057, 1.05 |
No. of reflections | 3167 | 2695 |
No. of parameters | 124 | 104 |
H-atom treatment | All H-atom parameters refined | – |
Δρmax, Δρmin (e Å−3) | 2.18, −1.59 | 1.40, −1.28 |
Selected geometric parameters (Å, º) for (I) topAg—S3 | 2.5314 (13) | Cs—C2 | 3.573 (4) |
Ag—S1 | 2.5868 (13) | Cs—S2iii | 3.5841 (15) |
Ag—S1i | 2.7716 (14) | Cs—S1v | 3.6315 (12) |
Ni—N1 | 2.046 (3) | S1—C1 | 1.651 (4) |
Ni—N2ii | 2.047 (3) | C1—N1 | 1.153 (5) |
Ni—OW | 2.126 (3) | S2—C2 | 1.645 (4) |
Cs—OW | 3.359 (3) | C2—N2 | 1.151 (5) |
Cs—N3iii | 3.420 (5) | S3—C3 | 1.645 (4) |
Cs—C2iv | 3.520 (4) | C3—N3 | 1.157 (6) |
Cs—N2iv | 3.530 (4) | | |
| | | |
N1—C1—S1 | 177.4 (4) | N3—C3—S3 | 177.4 (4) |
N2—C2—S2 | 175.9 (4) | | |
Symmetry codes: (i) x, −y−1/2, z−1/2; (ii) x, y, z−1; (iii) −x+2, −y, −z+2; (iv) −x+1, −y, −z+2; (v) −x+1, y+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW—H1W···N3 | 0.71 (8) | 2.31 (8) | 3.004 (6) | 168 (8) |
OW—H2W···N3vi | 0.87 (5) | 2.27 (5) | 3.072 (5) | 153 (4) |
Symmetry code: (vi) −x+2, −y, −z+1. |
Selected geometric parameters (Å, º) for (II) topCs—N2i | 3.240 (2) | Ni1—S2 | 2.5411 (8) |
Cs—N3 | 3.413 (3) | Ni2—N1v | 2.015 (2) |
Cs—C1ii | 3.462 (2) | Ni2—S3 | 2.4896 (8) |
Cs—N1ii | 3.491 (2) | Ni2—S1 | 2.5511 (8) |
Cs—S3iii | 3.5508 (9) | S1—C1 | 1.647 (2) |
Cs—S2i | 3.5798 (13) | C1—N1 | 1.154 (3) |
Cs—S3iv | 3.6317 (10) | S2—C2vi | 1.647 (2) |
Cs—S2iv | 3.6341 (10) | C2—N2 | 1.156 (3) |
Cs—C2i | 3.702 (2) | S3—C3 | 1.651 (3) |
Ni1—N2 | 2.043 (2) | C3—N3 | 1.152 (3) |
Ni1—N3 | 2.061 (2) | | |
| | | |
N1—C1—S1 | 178.4 (2) | N3—C3—S3 | 177.3 (2) |
N2—C2—S2v | 179.6 (2) | | |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+1, −y+2, −z+1; (iii) −x+5/2, y−1/2, −z+3/2; (iv) −x+3/2, y−1/2, −z+3/2; (v) x+1, y, z; (vi) x−1, y, z. |
A detailed search through the literature revealed that more than 80 inorganic thiocyanates are known. They include two compounds containing nickel (Kuo Chan & Porai-Koshits, 1960) and 13 containing caesium (Bohatý & Fröhlich, 1992), but none that contain both. The NCS− anion can interact with metal atoms in various ways, whereby both the N and S atoms can act as ligands forming covalent or ionic bonds, or by simple van der Waals interactions. In the present structures, the Ni—N and Ag—S bonds are covalent, whereas the Ni—S bonds and all bonds to Cs are ionic. \sch
The structure of compound (I) (Fig. 1) is characterized by corner-linked irregular [AgS4] tetrahedra forming chains along [001] (Fig. 3). The length of the Ag—S1 bond [2.7716 (14) Å] indicates an ionic rather than covalent interaction, as estimated from the sums of the covalent and ionic radii of 2.55 and 2.84 Å, respectively (Sanderson, 1962; Sutton, 1965; Shannon, 1976). These polyhedral chains are interconnected by octahedral [Ni(H2O)2(SCN)4] groups, in which the central Ni atom forms four equatorial covalent Ni—N bonds and two apical Ni—O bonds. The Ag-(SCN)-Ni framework forms slightly puckered sheets parallel to (100). Cs atoms are located between these sheets and link them into a three-dimensional structure by forming ionic bonds with the thiocyanate groups (Fig. 2). In addition, hydrogen bonds are formed between the H atoms of the water molecules and the N atoms of adjacent sheets.
The structure of compound (II) (Fig. 3) is altogether different. The prominent features are the coordination polyhedra of the Ni atoms, which are of two different types. Atom Ni1 is [4 + 2]-coordinated, with four covalent Ni—N bonds [mean distance 2.052 (2) Å; calculated sum of covalent radii 1.96 Å] and two ionic Ni—S bonds [distances 2.5411 (8) Å; calculated sum of ionic radii 2.53 Å]. The coordination polyhedron of atom Ni2 can be described as a [2 + 4] coordination, with two covalent Ni—N bonds [distances 2.015 (2) Å] and four ionic Ni—S bonds [mean distance 2.5204 (8) Å]. It is remarkable that the Ni atoms in the unit cell form a pseudo-tetragonal F-centred lattice. However, the irregularity of the polyhedra and the positions of the other atoms clearly show that the symmetry is monoclinic·The thiocyanate groups are all approximately parallel to the (010) plane, connecting the Ni polyhedra into sheets parallel to (010) (Fig. 4). The Cs atoms are located between these sheets and are connected to the thiocyanate groups by ionic bonds.
X-ray powder diffraction data have been collected for both compounds and the resulting data have been submitted to the powder diffraction file of the International Centre for Diffraction Data (JCPDS-ICDD).