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In the title compound, (C16H36N)2[Co(C4N2S2)2]2, pairs of [Co(C4N2S2)2]- anions combine to form discrete crystallographically centrosymmetric dimers, which stack along the c axis, surrounded by the counter-cations. The metal atom in the anion has a five-coordinate distorted square-pyramidal geometry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102010430/ta1380sup1.cif
Contains datablocks General, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102010430/ta1380Isup2.hkl
Contains datablock I

CCDC reference: 193398

Comment top

1,3-Dithiolato complexes of transition metals are planar electron acceptors, which have received attention in connection with their magnetic and electrical conducting properties. Molecular conductors based on extended 1,3-dithiolato complexes have received special attention recently (Kobayashi et al., 1999, 2001; Moriyama et al., 2001). Further, the discovery of ferromagnetic ordering in (NH4)[Ni(mnt)2]·H2O below 4.5 K (Coomber et al., 1996) has especially stimulated interest in [M(mnt)2]-based compounds (mnt is S2C4N22-, dimercaptomaleodinitrilato). In addition, [M(mnt)2]n- anions have been used as motifs for supramolecular assembly, taking advantage of their variation in molecular stereochemistry and formal charges (Lewis & Dance, 2000). Among the [M(mnt)2] salts, however, examples of Co complexes are fewer than those incorporating Ni, Pd or Pt ions. We report here the crystal structure of the title compound, (nBu4N)[Co(mnt)2], (I), at 90 K. \sch

Several examples of [Co(mnt)2]n- salts have been reported, involving the [Co(mnt)2]- monoanion (Fettouchi et al., 1995; Rodrigues et al., 1994; Zürcher et al., 1998), the [Co(mnt)2]2- dianion (Fallon et al., 1997; Fettouchi et al., 1995), and the mixed-valence [Co(mnt)2]3- anion (Gama et al., 1993; Lam et al., 1995). The monoanion tends to afford an antiferromagnetically interacting dimer, while the dianion often exists in the form of a monomer, showing alternate stacking with counter-cations. The structure of a 1:2 salt, (nBu4N)2[Co(mnt)2], has also been reported (Forrester et al., 1964).

Fig. 1 shows the molecular structre of (I). The [Co(mnt)2] units form discrete dimers and the components of the dimer are related to each other by a centre of symmetry located between the two metal centres. The metal atom has a distorted square-pyramidal coordination geometry and is displaced by 0.231 (1) Å from the least-squares plane defined by the four S atoms of the basal ligand. The dihedral angle between the Co/S1/S2 and Co/S3/S4 planes is ca 19.9°. Factors affecting the displacement of the metal atom from the ligand plane in [M(mnt)2]n- anions have been discussed by Alvarez et al. (1985).

The important intramolecular and intradimer distances and angles in the anion are listed in Table 1. The coordination distances are virtually identical to those of other [Co(mnt)2]- salts (Fettouchi et al., 1995). The long molecular axes of the anions are parallel, being in a slipped configuration such that the central metal atom is coordinated by the S atom of the adjacent anion, with a Co···S distance of 2.3916 (8) Å, which is somewhat longer than the four basal Co—S distances. The intradimer Co···Co distance is 3.1150 (8) Å. In contrast with the square-pyramidal [CoIII(mnt)2]- anion of (I), the dianion of [CoII(mnt)2]2- is planar, showing D2 h geometry (Forrester et al., 1964). The intramolecular distances show significant differences, depending on the formal charges on the anion.

The packing in (I) is illustrated in Fig. 2. The [Co(mnt)2]22- dimers are stacked in a columnar fashion along the c axis. The dimer units are stacked such that the long axes of adjacent dimers make an angle of ca 71° with each other. The metal atom of one dimer unit sits 3.923 (1) Å above atom S3i of the adjacent dimer unit [symmetry code: (i) -x, 1 - y, 1 - z]. There is also an S3···S3i contact distance of 3.734 (1) Å between the dimers. The interdimer Co···Co distance is 5.063 (1) Å.

The anion columns in (I) are surrounded by the tetrabutylammonium cations. Three of the nBu groups in the cation adopt the all-trans conformation, but one terminal group, C19—C20, adopts a gauche conformation. Presumably, this occurs to reduce steric hindrance between adjacent counter-cations, which have mutual contacts at these ends along the b direction.

The corresponding NiIII complex (Mochida et al., 2000) crystallizes in the same space group (C2/c), and shows similar cell parameters to those of (I). In the NiIII complex, the anions are arranged in the form of a weakly interacting dimer, and the cell volume is larger than that for the CoIII complex, by 6.5%.

Experimental top

Compound (I) was synthesized according to the literature method of Davison & Holm (1967). Single crystals of (I) suitable for X-ray analysis were grown by vapour diffusion of pentane into a dichloromethane solution of the compound.

Refinement top

H atoms were treated as riding, with C—H = 0.95 Å. Is this added text correct?

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku Corporation, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku Corporation, 2001; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure.

Figures top
[Figure 1] Fig. 1. The cation and anion of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 70% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (I). Atoms other than C atoms are represented by shaded circles and H atoms have been omitted for clarity.
(I) top
Crystal data top
(C16H36N)2[Co(C4N2S2)2]2F(000) = 2448
Mr = 1163.52Dx = 1.374 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.7107 Å
a = 29.457 (4) ÅCell parameters from 7543 reflections
b = 14.060 (2) Åθ = 1.6–13.7°
c = 14.703 (2) ŵ = 0.93 mm1
β = 112.518 (5)°T = 90 K
V = 5625.2 (14) Å3Prism, black
Z = 40.3 × 0.3 × 0.2 mm
Data collection top
Rigaku Mercury CCD area-detector
diffractometer
4718 reflections with F2 > 2σ(F2)
Detector resolution: 14.62 pixels mm-1Rint = 0.050
ω scansθmax = 27.5°
Absorption correction: analytical
(de Meulenaer & Tompa, 1965)
h = 3738
Tmin = 0.827, Tmax = 0.830k = 1813
21339 measured reflectionsl = 1919
6176 independent reflections
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045Weighting scheme based on measured s.u.'s w = 1/σ2(Fo2)
wR(F2) = 0.067(Δ/σ)max < 0.001
S = 1.44Δρmax = 0.48 e Å3
4749 reflectionsΔρmin = 0.52 e Å3
343 parameters
Crystal data top
(C16H36N)2[Co(C4N2S2)2]2V = 5625.2 (14) Å3
Mr = 1163.52Z = 4
Monoclinic, C2/cMo Kα radiation
a = 29.457 (4) ŵ = 0.93 mm1
b = 14.060 (2) ÅT = 90 K
c = 14.703 (2) Å0.3 × 0.3 × 0.2 mm
β = 112.518 (5)°
Data collection top
Rigaku Mercury CCD area-detector
diffractometer
6176 independent reflections
Absorption correction: analytical
(de Meulenaer & Tompa, 1965)
4718 reflections with F2 > 2σ(F2)
Tmin = 0.827, Tmax = 0.830Rint = 0.050
21339 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045343 parameters
wR(F2) = 0.067H-atom parameters constrained
S = 1.44Δρmax = 0.48 e Å3
4749 reflectionsΔρmin = 0.52 e Å3
Special details top

Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co0.013000 (10)0.43129 (3)0.43045 (3)0.01125 (9)
S10.02318 (2)0.58522 (5)0.44991 (5)0.0120 (2)
S20.08942 (2)0.40651 (5)0.53106 (5)0.0137 (2)
S30.05077 (2)0.46157 (5)0.29644 (5)0.0128 (2)
S40.00555 (2)0.27876 (5)0.40032 (5)0.0143 (2)
N50.15918 (7)0.9093 (2)0.0802 (2)0.0108 (5)
N30.16020 (9)0.3463 (2)0.1147 (2)0.0229 (7)
N40.08676 (8)0.1012 (2)0.2597 (2)0.0178 (6)
N10.12491 (8)0.7651 (2)0.5526 (2)0.0193 (6)
N20.20616 (9)0.5364 (2)0.6644 (2)0.0234 (7)
C130.18286 (9)0.8190 (2)0.0630 (2)0.0118 (7)
C220.08261 (9)1.0102 (2)0.0132 (2)0.0150 (7)
C140.23019 (9)0.7904 (2)0.1460 (2)0.0157 (7)
C230.03346 (9)1.0057 (2)0.1007 (2)0.0180 (7)
C150.24573 (11)0.6925 (2)0.1266 (2)0.0204 (8)
C170.19216 (10)0.9950 (2)0.0892 (2)0.0142 (7)
C210.11087 (9)0.9194 (2)0.0084 (2)0.0124 (6)
C180.20605 (10)1.0141 (2)0.0018 (2)0.0175 (7)
C10.08605 (9)0.5979 (2)0.5176 (2)0.0126 (7)
C100.12307 (10)0.8145 (2)0.1852 (2)0.0146 (7)
C20.11360 (9)0.5183 (2)0.5530 (2)0.0125 (7)
C60.16541 (10)0.5279 (2)0.6149 (2)0.0156 (7)
C30.07578 (10)0.3508 (2)0.2605 (2)0.0140 (7)
C70.12267 (10)0.3468 (2)0.1792 (2)0.0152 (7)
C40.05140 (9)0.2703 (2)0.3055 (2)0.0132 (7)
C80.07137 (9)0.1767 (2)0.2785 (2)0.0135 (7)
C190.23540 (10)1.1065 (2)0.0157 (2)0.0206 (8)
C90.15048 (9)0.9029 (2)0.1758 (2)0.0135 (7)
C110.11506 (10)0.8122 (2)0.2813 (2)0.0155 (7)
C50.10706 (9)0.6909 (2)0.5372 (2)0.0139 (7)
C120.08396 (10)0.7266 (2)0.2842 (2)0.0202 (8)
C240.00476 (10)1.0968 (2)0.1133 (2)0.0224 (8)
C160.29103 (10)0.6559 (2)0.2093 (2)0.0225 (8)
C200.28614 (11)1.1013 (2)0.0977 (3)0.0339 (9)
H10.023051.14770.12480.0258*
H20.025701.09080.16770.0258*
H30.001161.10920.05520.0259*
H40.284710.65140.26790.0263*
H50.299260.59480.19250.0261*
H60.317600.69840.21960.0263*
H70.282951.08720.15820.039*
H80.304771.05270.08330.039*
H90.302381.16060.10300.039*
H100.079070.72660.34440.0245*
H110.053050.72990.23060.0242*
H120.100370.66980.27940.0241*
H130.159970.76860.05270.0140*
H140.189670.82770.00550.0140*
H150.255200.83500.15050.0182*
H160.225260.78960.20620.0182*
H170.219470.64940.11750.0236*
H180.252310.69500.06830.0235*
H190.117940.91590.06610.0138*
H200.090360.86760.00740.0136*
H210.076981.01750.04590.0169*
H220.101071.06280.02090.0171*
H230.039420.99420.15880.0204*
H240.014590.95500.09060.0203*
H250.175611.04970.09900.0160*
H260.221640.98560.14520.0164*
H270.225450.96270.00520.0212*
H280.176961.01900.05590.0212*
H290.239191.12070.04420.0252*
H300.217441.15600.03060.0252*
H310.181530.90360.22910.0159*
H320.131980.95690.17970.0155*
H330.091980.81300.13200.0180*
H340.141550.76000.18220.0179*
H350.146010.80840.33470.0175*
H360.098710.86880.28700.0173*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0102 (2)0.0101 (2)0.0141 (2)0.0004 (2)0.0054 (2)0.0002 (2)
S10.0106 (3)0.0108 (3)0.0149 (3)0.0001 (3)0.0050 (3)0.0011 (3)
S20.0110 (3)0.0108 (3)0.0184 (4)0.0016 (3)0.0048 (3)0.0004 (3)
S30.0133 (3)0.0123 (3)0.0135 (3)0.0005 (3)0.0058 (3)0.0011 (3)
S40.0131 (3)0.0115 (3)0.0174 (4)0.0013 (3)0.0050 (3)0.0012 (3)
N50.0098 (11)0.0111 (11)0.0091 (11)0.0001 (9)0.0010 (9)0.0020 (9)
N30.022 (1)0.024 (1)0.0173 (13)0.0020 (11)0.0024 (12)0.0013 (11)
N40.0150 (12)0.0188 (13)0.0189 (13)0.0004 (10)0.0057 (10)0.0013 (10)
N10.0181 (13)0.0168 (13)0.0209 (13)0.0011 (11)0.0051 (11)0.0017 (10)
N20.016 (1)0.021 (1)0.027 (1)0.0022 (11)0.0018 (12)0.0021 (11)
C130.0111 (13)0.0098 (13)0.0140 (13)0.0012 (11)0.0041 (11)0.0011 (11)
C220.013 (1)0.013 (1)0.016 (1)0.0033 (11)0.0026 (11)0.0003 (11)
C140.0122 (13)0.015 (1)0.018 (1)0.0004 (11)0.0038 (11)0.0023 (11)
C230.015 (1)0.020 (2)0.016 (1)0.0040 (12)0.0022 (12)0.0003 (12)
C150.023 (2)0.016 (2)0.019 (2)0.0062 (13)0.0050 (13)0.0007 (12)
C170.0130 (13)0.0103 (13)0.018 (1)0.0007 (11)0.0040 (11)0.0004 (11)
C210.0126 (13)0.013 (1)0.0091 (12)0.0025 (11)0.0008 (11)0.0008 (11)
C180.018 (1)0.017 (2)0.018 (2)0.0019 (12)0.0078 (12)0.0012 (12)
C10.0132 (13)0.0146 (13)0.0099 (13)0.0007 (11)0.0044 (11)0.0015 (11)
C100.015 (1)0.014 (1)0.016 (1)0.0009 (11)0.0071 (12)0.0029 (11)
C20.0108 (13)0.016 (1)0.0133 (13)0.0015 (11)0.0072 (11)0.0016 (11)
C60.017 (2)0.013 (1)0.017 (1)0.0017 (12)0.0073 (13)0.0007 (11)
C30.017 (1)0.016 (1)0.012 (1)0.0008 (12)0.0086 (12)0.0019 (11)
C70.019 (2)0.013 (1)0.017 (2)0.0004 (12)0.0106 (13)0.0010 (11)
C40.0138 (13)0.014 (1)0.0137 (13)0.0002 (11)0.0076 (11)0.0020 (11)
C80.0117 (13)0.016 (1)0.013 (1)0.0030 (11)0.0056 (11)0.0010 (11)
C190.019 (2)0.017 (1)0.027 (2)0.0014 (12)0.0100 (13)0.0043 (13)
C90.0141 (13)0.014 (1)0.0113 (13)0.0017 (11)0.0039 (11)0.0013 (11)
C110.017 (1)0.017 (1)0.0104 (13)0.0034 (12)0.0019 (11)0.0015 (11)
C50.0121 (13)0.017 (1)0.012 (1)0.0029 (12)0.0040 (11)0.0027 (11)
C120.023 (2)0.023 (2)0.014 (1)0.0010 (13)0.0071 (12)0.0027 (12)
C240.018 (2)0.026 (2)0.020 (2)0.0081 (13)0.0041 (13)0.0039 (13)
C160.017 (1)0.022 (2)0.026 (2)0.0068 (13)0.0050 (13)0.0068 (13)
C200.022 (2)0.033 (2)0.041 (2)0.013 (2)0.006 (2)0.006 (2)
Geometric parameters (Å, º) top
Co—S12.1886 (8)C15—H170.950
Co—S22.1969 (8)C15—H180.950
Co—S32.1812 (8)C17—H250.950
Co—S42.1839 (8)C17—H260.950
S1—C11.744 (3)C21—H190.950
S2—C21.705 (3)C21—H200.950
S3—C31.718 (3)C18—H270.950
S4—C41.727 (3)C18—H280.950
N3—C71.148 (3)C10—H330.950
N4—C81.147 (3)C10—H340.950
N1—C51.151 (3)C19—H290.950
N2—C61.147 (3)C19—H300.950
C1—C21.363 (4)C9—H310.950
C1—C51.427 (4)C9—H320.950
C2—C61.453 (4)C11—H350.950
C3—C71.440 (4)C11—H360.950
C3—C41.367 (4)C12—H100.950
C4—C81.434 (4)C12—H110.950
Co—Coi3.1150 (8)C12—H120.950
Co—S1i2.3916 (8)C24—H10.950
C13—H130.950C24—H20.950
C13—H140.950C24—H30.950
C22—H210.950C16—H40.950
C22—H220.950C16—H50.950
C14—H150.950C16—H60.950
C14—H160.950C20—H70.950
C23—H230.950C20—H80.950
C23—H240.950C20—H90.950
S1—Co—S290.87 (3)C22—C21—H19107.86
S1—Co—S387.28 (3)N5—C21—H20107.86
S2—Co—S3160.94 (3)C22—C21—H20107.84
S1—Co—S4174.69 (3)C17—C18—H27109.08
S2—Co—S488.76 (3)C19—C18—H27109.06
S3—Co—S491.35 (3)C17—C18—H28109.07
Co—S1—C1103.79 (9)C19—C18—H28109.08
Co—S2—C2103.14 (9)C9—C10—H33108.76
Co—S3—C3102.74 (9)C11—C10—H33108.76
Co—S4—C4102.84 (9)C9—C10—H34108.77
N5—C13—H13107.96C11—C10—H34108.75
C14—C13—H13107.97C18—C19—H29108.48
N5—C13—H14107.96C20—C19—H29108.46
C14—C13—H14107.97C18—C19—H30108.47
C23—C22—H21109.50C20—C19—H30108.47
C21—C22—H21109.50N5—C9—H31108.17
C23—C22—H22109.50C10—C9—H31108.18
C21—C22—H22109.48N5—C9—H32108.18
C13—C14—H15109.34C10—C9—H32108.18
C15—C14—H15109.34C10—C11—H35109.19
C13—C14—H16109.33C12—C11—H35109.20
C15—C14—H16109.33C10—C11—H36109.19
C22—C23—H23108.85C12—C11—H36109.19
C24—C23—H23108.83C11—C12—H10109.47
C22—C23—H24108.83C11—C12—H11109.47
C24—C23—H24108.84C11—C12—H12109.47
C14—C15—H17108.50C23—C24—H1109.46
C16—C15—H17108.50C23—C24—H2109.47
C14—C15—H18108.49C23—C24—H3109.46
C16—C15—H18108.50C15—C16—H4109.46
N5—C17—H25107.83C15—C16—H5109.46
C18—C17—H25107.84C15—C16—H6109.47
N5—C17—H26107.84C19—C20—H7109.46
C18—C17—H26107.84C19—C20—H8109.47
N5—C21—H19107.87C19—C20—H9109.47
Symmetry code: (i) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula(C16H36N)2[Co(C4N2S2)2]2
Mr1163.52
Crystal system, space groupMonoclinic, C2/c
Temperature (K)90
a, b, c (Å)29.457 (4), 14.060 (2), 14.703 (2)
β (°) 112.518 (5)
V3)5625.2 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.93
Crystal size (mm)0.3 × 0.3 × 0.2
Data collection
DiffractometerRigaku Mercury CCD area-detector
diffractometer
Absorption correctionAnalytical
(de Meulenaer & Tompa, 1965)
Tmin, Tmax0.827, 0.830
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
21339, 6176, 4718
Rint0.050
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.067, 1.44
No. of reflections4749
No. of parameters343
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.48, 0.52

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku Corporation, 2001), CrystalClear, CrystalStructure (Molecular Structure Corporation & Rigaku Corporation, 2001, SHELXS97 (Sheldrick, 1997), CRYSTALS (Watkin et al., 1996), ORTEP-3 (Farrugia, 1997), CrystalStructure.

Selected geometric parameters (Å, º) top
Co—S12.1886 (8)N1—C51.151 (3)
Co—S22.1969 (8)N2—C61.147 (3)
Co—S32.1812 (8)C1—C21.363 (4)
Co—S42.1839 (8)C1—C51.427 (4)
S1—C11.744 (3)C2—C61.453 (4)
S2—C21.705 (3)C3—C71.440 (4)
S3—C31.718 (3)C3—C41.367 (4)
S4—C41.727 (3)C4—C81.434 (4)
N3—C71.148 (3)Co—Coi3.1150 (8)
N4—C81.147 (3)Co—S1i2.3916 (8)
S1—Co—S290.87 (3)S3—Co—S491.35 (3)
S1—Co—S387.28 (3)Co—S1—C1103.79 (9)
S2—Co—S3160.94 (3)Co—S2—C2103.14 (9)
S1—Co—S4174.69 (3)Co—S3—C3102.74 (9)
S2—Co—S488.76 (3)Co—S4—C4102.84 (9)
Symmetry code: (i) x, y+1, z+1.
 

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