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The crystal and molecular structure of green [Cu(NCS)2(C11H10N2O2)]·2(CH3)2SO, which forms a distinct dimer in the crystalline state, was determined. The stereochemistry of the monomer is a distorted five-coordinate square pyramidal arrangement of four N atoms and a displaced fifth ligand position occupied by an oxy­gen of a hydroxy group of the gem-diol ligand. Two of the nitro­gen ligands are N-bonded thio­cyanates and the other two N atoms are furnished by the di(2-pyridyl)­methanediol ligand. The copper to nitro­gen distances are 1.935 (4), 1.942 (4) Å for the two thio­cyanates and 2.025 (3), 2.032 (3) Å for the di(2-pyridyl)­methanediol ligand. The copper to oxy­gen distance is 2.475 (3) Å and the copper to sulfur distance in the dimer is 3.1394 (17) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008534/om6029sup1.cif
Contains datablocks [Cu(NCS)~2~(dpydiol)], I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008534/om6029Isup2.hkl
Contains datablock I

CCDC reference: 143378

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.007 Å
  • Disorder in solvent or counterion
  • R factor = 0.057
  • wR factor = 0.152
  • Data-to-parameter ratio = 11.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Amber Alert Alert Level B:
THETM_01 Alert B The value of sine(theta_max)/wavelength is less than 0.575 Calculated sin(theta_max)/wavelength = 0.5513
Author response: ......Data collected some time ago by a student. Original crystal is gone.

Yellow Alert Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 11.00 Perc.
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The isolation of the normally labile hydrate of a ketone by complexing a ketone containing ligand with a transition metal has been demostrated by several different authors (Parker et al., 2000; Deveson et al., 1996; Wang et al., 1986; Sommerer et al., 1993; Papadopoulos et al., 1996; Tangoulis et al., 1997; Breeze et al., 1996; Yang et al., 1998). The title compound, [Cu(NCS)2(dpydiol)]·2(CH3)2SO, (I), where dpydiol = di(2-pyridyl)methanediol, contains one gem-diol ligand with the two hydroxy groups each hydrogen bonded to a solvent dimethylsulfoxide molecule. The two hydroxy groups on a gem-diol ligand have a strong tendency to hydrogen bond to the solvent and one of the hydroxy groups has an oxygen atom occupying a fifth ligand position. The thiocyanate complex with only one gem-diol ligand is uniquely different because the sixth ligand position about the copper atom is occupied by a sulfur atom from a neighboring molecule which produces a distinct dimer in the crystalline state.

A drawing of the structure showing thermal ellipsoids and the atom labeling scheme is shown in Fig. 1. Selected bond distances and angles are given in Table 1.

The X-ray structure of the complex (Fig. 1) contains a copper atom positioned at the center of a distorted octahedron. The N atoms from the di(2-pyridyl)methanediol ligand and the two thiocyanate ions surround the copper atom in a square planar arrangement. The thiocyanate ligand distances and angles are: Cu—N1, Cu—N2, 1.935 (4) Å, 1.942 (4) Å, and N1—Cu—N2 angle of 91.77 (17)°. The di(2-pyridyl)methanediol ligand distances and angles are: Cu—N3, Cu—N4, 2.032 (3) Å, 2.025 (3) Å, and N3—Cu—N4 87.43 (13)°. The fifth ligand position is occupied by an oxygen atom of the di(2-pyridyl)methanediol ligand with a Cu—O1 distance of 2.475 (3) Å with O1—Cu—N1 and O1—Cu—N2 angles of 110.15 (16) and 100.91 (13)° respectively. These results are very close to the observed distances in [Cu(dpydiol)2]Br2·4H2O which had a Cu—O distance of 2.464 (3) Å for the two di(2-pyridyl)methanediol ligands (Parker et al., 2000).

Two diisothiocyanato copper(II) complexes, [Cu(NCS)2(bipy)] and [Cu(NCS)2(phen)] where bipy is 2,2'-bipyridine and phen is 1,10-phenanthroline, crystallize as infinite linear polymers (Breneman & Parker, 1993; Parker et al., 1994). The ability of the ketone ligand to hydrate and then bond to the central copper as the fifth ligand is the preferred crystalline state in the case of [Cu(NCS)2(dpydiol)]. The resulting Cu—O bond distance of 2.475 (3) Å is shorter than what would be expected if an infinite polymer rather than a dimer with a Cu—S bond distance of 3.1394 (17) Å were formed.

Experimental top

A 15 ml solution of di-2-pyridyl ketone (0.737 g, 4.0 mmol) dissolved in ethanol was added to a 15 ml solution of Cu(NO3)2.3 H2O (0.483 g, 2.0 mmol) in water. Mixing of these two solutions produced a exothermic reaction and a brilliant purple solution. A 15 ml solution of NH4NCS (0.304 g, 4.0 mmol) in water was slowly added with continuous stirring to the purple solution. The reaction with ammonium thiocyanate produced a blue-purple solution which contained a dark green precipitate. The green solid was filtered and air-dried. This green solid was dissolved in dimethylsulfoxide and allowed to crystallize by solvent evaporation for several days. A single crop of bright green crystals was obtained for the X-ray structure determination.

Refinement top

H atoms were set to ride on respective C atoms. Ideal positions were determined with C—H bond lengths = 0.96 Å, O—H bond lengths = 0.85 Å and Uiso = 0.08 Å2 The sulfur atom on one of the DMSO molecules is disordered with two refined occupancy factors of 0.776 and 0.224 for S4 and S5. H atoms were omitted on this disordered DMSO and S5 was refined isotropically.

Computing details top

Data collection: CAD4 Version 5.0 (Schagen et al. 1989); cell refinement: CAD4 Version 5.0 (Schagen et al. 1989); data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXTL/PC (Siemens, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid (50% probability) plot of [Cu(NCS)2(dpydiol)] showing the atom-numbering scheme. H atoms have been omitted.
(I) top
Crystal data top
C17H16CuN4O4S4Z = 2
Mr = 532.12Dx = 1.484 Mg m3
Triclinic, P1Mo Kα radiation, λ = 0.71073 Å
a = 9.317 (4) ÅCell parameters from 25 reflections
b = 10.713 (5) Åθ = 20.0–22.9°
c = 12.797 (6) ŵ = 1.30 mm1
α = 104.99 (2)°T = 295 K
β = 93.03 (3)°Prism, green
γ = 103.46 (2)°0.50 × 0.30 × 0.30 mm
V = 1191 (1) Å3
Data collection top
Enraf Nonius CAD4
diffractometer
Rint = 0.019
θ/2θ scansθmax = 23.1°
Absorption correction: psi scan
MolEN (Fair,1990)
h = 1010
Tmin = 0.613, Tmax = 0.677k = 1111
3354 measured reflectionsl = 014
3185 independent reflections1 standard reflections every 167 min
3090 reflections with I > 2σ(I) intensity decay: 3.8%
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.057 w = 1/(σ2(Fo2) + (0.1156P)2 + 0.9807)
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.152(Δ/σ)max = 0.001
S = 1.07Δρmax = 1.01 e Å3
3185 reflectionsΔρmin = 0.88 e Å3
281 parameters
Crystal data top
C17H16CuN4O4S4γ = 103.46 (2)°
Mr = 532.12V = 1191 (1) Å3
Triclinic, P1Z = 2
a = 9.317 (4) ÅMo Kα radiation
b = 10.713 (5) ŵ = 1.30 mm1
c = 12.797 (6) ÅT = 295 K
α = 104.99 (2)°0.50 × 0.30 × 0.30 mm
β = 93.03 (3)°
Data collection top
Enraf Nonius CAD4
diffractometer
3090 reflections with I > 2σ(I)
Absorption correction: psi scan
MolEN (Fair,1990)
Rint = 0.019
Tmin = 0.613, Tmax = 0.677θmax = 23.1°
3354 measured reflections1 standard reflections every 167 min
3185 independent reflections intensity decay: 3.8%
Refinement top
R[F2 > 2σ(F2)] = 0.057281 parameters
wR(F2) = 0.152H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 1.01 e Å3
3185 reflectionsΔρmin = 0.88 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu0.33274 (5)0.07023 (4)0.35941 (4)0.0421 (3)
S10.00034 (17)0.35298 (12)0.29304 (14)0.0762 (5)
S20.71608 (14)0.14112 (14)0.39346 (12)0.0638 (4)
S30.15773 (14)0.01354 (14)0.08643 (9)0.0629 (4)
S40.6755 (3)0.4085 (2)0.00869 (19)0.0955 (12)0.776 (9)
S50.666 (3)0.297 (3)0.033 (2)0.237 (12)*0.224 (9)
O10.3696 (3)0.1373 (3)0.1896 (2)0.0443 (7)
H1A0.29910.09440.13900.080*
O20.3541 (4)0.3429 (3)0.1641 (2)0.0549 (8)
H2A0.42830.33830.12880.080*
O30.1627 (4)0.0071 (3)0.0331 (3)0.0611 (8)
O40.5849 (8)0.3281 (8)0.0562 (6)0.149 (3)
N10.1842 (5)0.0984 (4)0.3291 (4)0.0682 (12)
N20.4932 (4)0.0160 (4)0.3672 (3)0.0532 (9)
N30.4839 (3)0.2506 (3)0.3972 (3)0.0390 (7)
N40.1747 (3)0.1673 (3)0.3417 (3)0.0391 (7)
C10.1074 (5)0.2046 (4)0.3143 (4)0.0502 (11)
C20.5865 (5)0.0671 (4)0.3789 (3)0.0428 (9)
C30.5929 (4)0.2929 (4)0.4807 (3)0.0449 (10)
H3B0.59950.23670.52740.080*
C40.6958 (5)0.4138 (5)0.5013 (4)0.0533 (11)
H4A0.77390.44170.56090.080*
C50.6842 (5)0.4947 (4)0.4345 (4)0.0555 (12)
H5A0.75350.58050.44830.080*
C60.5735 (5)0.4521 (4)0.3480 (4)0.0482 (10)
H6A0.56410.50720.30080.080*
C70.4751 (4)0.3270 (4)0.3311 (3)0.0386 (9)
C80.3503 (4)0.2665 (4)0.2369 (3)0.0401 (9)
C90.2010 (4)0.2543 (4)0.2823 (3)0.0378 (9)
C100.1027 (5)0.3270 (4)0.2667 (4)0.0482 (10)
H10A0.12440.38980.22450.080*
C110.0278 (5)0.3080 (5)0.3128 (4)0.0557 (12)
H11A0.09830.35810.30350.080*
C120.0565 (5)0.2169 (5)0.3724 (4)0.0550 (11)
H12A0.14740.20220.40470.080*
C130.0464 (5)0.1476 (4)0.3854 (4)0.0484 (10)
H13A0.02620.08330.42640.080*
C140.3400 (7)0.0155 (8)0.1191 (6)0.094 (2)
H14A0.35910.09910.11690.080*
H14B0.34880.00480.19090.080*
H14C0.41090.05640.06730.080*
C150.1555 (7)0.1467 (6)0.0973 (5)0.0843 (17)
H15A0.06120.16380.08140.080*
H15B0.23330.21250.04630.080*
H15C0.17110.15130.16990.080*
C160.8390 (13)0.3523 (14)0.0068 (10)0.165 (4)
C170.6052 (10)0.3311 (9)0.1486 (6)0.114 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0380 (4)0.0253 (3)0.0602 (4)0.0022 (2)0.0016 (2)0.0130 (2)
S10.0754 (9)0.0335 (7)0.1101 (11)0.0064 (6)0.0195 (8)0.0198 (7)
S20.0545 (7)0.0673 (8)0.0854 (9)0.0258 (6)0.0126 (6)0.0387 (7)
S30.0547 (7)0.0684 (8)0.0490 (7)0.0037 (6)0.0023 (5)0.0058 (6)
S40.134 (2)0.0658 (16)0.0812 (15)0.0153 (12)0.0435 (13)0.0143 (10)
O10.0439 (15)0.0337 (15)0.0482 (15)0.0076 (12)0.0035 (12)0.0016 (12)
O20.0602 (19)0.0496 (17)0.0580 (17)0.0079 (14)0.0095 (14)0.0256 (14)
O30.0536 (18)0.063 (2)0.0529 (18)0.0054 (15)0.0011 (14)0.0123 (15)
O40.151 (5)0.184 (7)0.146 (5)0.054 (5)0.102 (5)0.076 (5)
N10.060 (2)0.031 (2)0.106 (4)0.001 (2)0.004 (2)0.018 (2)
N20.058 (2)0.0382 (19)0.066 (2)0.0147 (18)0.0052 (18)0.0163 (17)
N30.0350 (17)0.0287 (16)0.0472 (18)0.0016 (13)0.0040 (14)0.0062 (14)
N40.0356 (17)0.0266 (16)0.0513 (18)0.0028 (13)0.0036 (14)0.0091 (14)
C10.048 (2)0.034 (3)0.070 (3)0.011 (2)0.010 (2)0.015 (2)
C20.047 (2)0.032 (2)0.049 (2)0.0041 (19)0.0078 (18)0.0160 (17)
C30.037 (2)0.039 (2)0.051 (2)0.0046 (18)0.0021 (18)0.0035 (18)
C40.040 (2)0.048 (3)0.057 (3)0.001 (2)0.0027 (19)0.002 (2)
C50.042 (2)0.034 (2)0.073 (3)0.0076 (18)0.010 (2)0.001 (2)
C60.042 (2)0.031 (2)0.064 (3)0.0007 (18)0.013 (2)0.0101 (19)
C70.038 (2)0.0259 (19)0.047 (2)0.0037 (16)0.0110 (16)0.0047 (16)
C80.043 (2)0.030 (2)0.044 (2)0.0033 (16)0.0045 (17)0.0103 (16)
C90.038 (2)0.0242 (18)0.043 (2)0.0003 (15)0.0024 (16)0.0045 (15)
C100.048 (2)0.030 (2)0.061 (3)0.0056 (18)0.0011 (19)0.0078 (18)
C110.044 (2)0.043 (2)0.077 (3)0.016 (2)0.002 (2)0.007 (2)
C120.038 (2)0.044 (2)0.074 (3)0.0055 (19)0.013 (2)0.005 (2)
C130.038 (2)0.042 (2)0.062 (3)0.0014 (18)0.0078 (19)0.0164 (19)
C140.072 (4)0.126 (6)0.090 (4)0.025 (4)0.031 (3)0.035 (4)
C150.080 (4)0.095 (5)0.083 (4)0.014 (3)0.010 (3)0.042 (3)
C160.127 (8)0.192 (12)0.167 (10)0.012 (8)0.020 (7)0.069 (9)
C170.123 (6)0.110 (6)0.093 (5)0.000 (5)0.017 (4)0.025 (4)
Geometric parameters (Å, º) top
Cu—N11.935 (4)N4—C91.336 (5)
Cu—N21.942 (4)C3—C41.373 (6)
Cu—N42.025 (3)C3—H3B0.9600
Cu—N32.032 (3)C4—C51.382 (7)
Cu—O12.477 (3)C4—H4A0.9600
S1—C11.614 (5)C5—C61.378 (7)
S2—C21.619 (5)C5—H5A0.9600
S3—O31.511 (3)C6—C71.393 (6)
S3—C151.763 (6)C6—H6A0.9600
S3—C141.774 (6)C7—C81.524 (6)
S4—S51.13 (3)C8—C91.526 (5)
S4—O41.500 (6)C9—C101.371 (6)
S4—C171.782 (8)C10—C111.375 (7)
S4—C161.764 (13)C10—H10A0.9600
S5—O41.41 (3)C11—C121.375 (7)
S5—C161.56 (3)C11—H11A0.9600
S5—C171.71 (3)C12—C131.370 (6)
O1—C81.417 (5)C12—H12A0.9600
O1—H1A0.8500C13—H13A0.9600
O2—C81.387 (5)C14—H14A0.9600
O2—H2A0.8500C14—H14B0.9600
N1—C11.156 (6)C14—H14C0.9600
N2—C21.153 (6)C15—H15A0.9600
N3—C71.332 (5)C15—H15B0.9600
N3—C31.342 (5)C15—H15C0.9600
N4—C131.342 (5)
N1—Cu—N291.77 (17)C6—C5—C4120.1 (4)
N1—Cu—N491.24 (16)C6—C5—H5A119.9
N2—Cu—N4174.98 (14)C4—C5—H5A120.0
N1—Cu—N3177.36 (16)C5—C6—C7118.0 (4)
N2—Cu—N389.71 (15)C5—C6—H6A121.0
N4—Cu—N387.43 (13)C7—C6—H6A121.0
O1—Cu—N1110.0 (1)N3—C7—C6121.9 (4)
O1—Cu—N2100.9 (1)N3—C7—C8114.7 (3)
O1—Cu—N371.7 (1)C6—C7—C8123.4 (4)
O1—Cu—N474.3 (1)O2—C8—O1113.4 (3)
O3—S3—C15107.2 (3)O2—C8—C7112.9 (3)
O3—S3—C14105.4 (3)O1—C8—C7103.7 (3)
C15—S3—C1499.1 (3)O2—C8—C9108.0 (3)
S5—S4—O463.2 (14)O1—C8—C9109.6 (3)
S5—S4—C1767.7 (14)C7—C8—C9109.1 (3)
O4—S4—C17107.1 (4)N4—C9—C10122.1 (4)
S5—S4—C1660.8 (15)N4—C9—C8113.8 (3)
O4—S4—C16100.7 (5)C10—C9—C8124.0 (4)
C17—S4—C1698.6 (5)C9—C10—C11118.6 (4)
S4—S5—O471.2 (17)C9—C10—H10A120.8
S4—S5—C1680 (2)C11—C10—H10A120.6
O4—S5—C16115 (2)C12—C11—C10119.5 (4)
S4—S5—C1774.6 (16)C12—C11—H11A120.3
O4—S5—C17115.3 (19)C10—C11—H11A120.2
C16—S5—C17110.3 (18)C13—C12—C11119.2 (4)
C8—O1—H1A109.4C13—C12—H12A120.4
C8—O2—H2A109.5C11—C12—H12A120.4
S5—O4—S445.6 (14)N4—C13—C12121.4 (4)
C1—N1—Cu172.8 (4)N4—C13—H13A119.3
C2—N2—Cu175.4 (4)C12—C13—H13A119.3
C7—N3—C3119.4 (3)S3—C14—H14A109.5
C7—N3—Cu116.6 (3)S3—C14—H14B109.4
C3—N3—Cu123.9 (3)H14A—C14—H14B109.5
C13—N4—C9119.2 (3)S3—C14—H14C109.5
C13—N4—Cu123.4 (3)H14A—C14—H14C109.5
C9—N4—Cu117.3 (3)H14B—C14—H14C109.5
N1—C1—S1179.8 (5)S3—C15—H15A109.6
N2—C2—S2179.0 (4)S3—C15—H15B109.3
N3—C3—C4122.1 (4)H15A—C15—H15B109.5
N3—C3—H3B119.0S3—C15—H15C109.6
C4—C3—H3B118.9H15A—C15—H15C109.5
C3—C4—C5118.5 (4)H15B—C15—H15C109.5
C3—C4—H4A120.8S5—C16—S439.2 (13)
C5—C4—H4A120.7S4—C17—S537.7 (11)

Experimental details

Crystal data
Chemical formulaC17H16CuN4O4S4
Mr532.12
Crystal system, space groupTriclinic, P1
Temperature (K)295
a, b, c (Å)9.317 (4), 10.713 (5), 12.797 (6)
α, β, γ (°)104.99 (2), 93.03 (3), 103.46 (2)
V3)1191 (1)
Z2
Radiation typeMo Kα
µ (mm1)1.30
Crystal size (mm)0.50 × 0.30 × 0.30
Data collection
DiffractometerEnraf Nonius CAD4
diffractometer
Absorption correctionPsi scan
MolEN (Fair,1990)
Tmin, Tmax0.613, 0.677
No. of measured, independent and
observed [I > 2σ(I)] reflections
3354, 3185, 3090
Rint0.019
θmax (°)23.1
(sin θ/λ)max1)0.551
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.152, 1.07
No. of reflections3185
No. of parameters281
No. of restraints?
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.01, 0.88

Computer programs: CAD4 Version 5.0 (Schagen et al. 1989), MolEN (Fair, 1990), SHELXTL/PC (Siemens, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL/PC.

Selected geometric parameters (Å, º) top
Cu—N11.935 (4)Cu—N32.032 (3)
Cu—N21.942 (4)Cu—O12.477 (3)
Cu—N42.025 (3)
N1—Cu—N291.77 (17)N4—Cu—N387.43 (13)
N1—Cu—N491.24 (16)O1—Cu—N1110.0 (1)
N2—Cu—N4174.98 (14)O1—Cu—N2100.9 (1)
N1—Cu—N3177.36 (16)O1—Cu—N371.7 (1)
N2—Cu—N389.71 (15)O1—Cu—N474.3 (1)
 

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