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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 8| August 2014| Pages 48-50
doi:10.1107/S1600536814009532

Crystal structure of [NiHg(SCN)4(CH3OH)2]n

Matthias Weila* and Thomas Häuslera

aInstitute for Chemical Technologies and Analytics, Division of Structural Chemistry, Vienna University of Technology, Getreidemarkt 9/164-SC, A-1060 Vienna, Austria
*Correspondence e-mail: mweil@mail.zserv.tuwien.ac.at

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 16 April 2014; accepted 28 April 2014; online 19 July 2014)

The title compound, catena-poly[[bis­(methanol-κO)nickel(II)]-di-μ-thio­cyanato-κ4N:S-mercurate(II)-di-μ-thio­cyanato-κ4N:S], was obtained from a gel-growth method using tetra­meth­oxy­silane as gelling agent. The crystal structure is composed of rather regular HgS4 tetra­hedra (point group symmetry .2.) and trans-NiN4O2 octa­hedra (point group symmetry 2..) that are linked through thio­cyanato bridges into a three-dimensional framework. The methanol mol­ecules coordinate via the O atom to the Ni2+ cations and point into the voids of this arrangement while a weak O—H⋯S hydrogen bond to an adjacent S atom stabilizes it.

CCDC reference: 1004260

1. Chemical context

Compounds of the type MHg(SCN)4 (M is a divalent trans­ition metal) exhibit inter­esting physical properties. For example, CoHg(SCN)4 is a calibrant for magnetic susceptibility measurements using the Faraday method (Brown et al., 1977[Brown, D. B., Crawford, V. H., Hall, J. W. & Hatfield, W. E. (1977). J. Phys. Chem. 81, 1303-1306.]), and representatives with M = Fe, Mn, Zn and Cd show second-order non-linear optical (NLO) properties (Bergman et al., 1970[Bergman, J. G. Jr, McFee, J. H. & Crane, G. R. (1970). Mater. Res. Bull. 5, 913-917.]; Yan et al., 1999[Yan, Y.-X., Fang, Q., Yu, W.-T., Yuan, D.-R., Tian, Y.-P. & Williams, I. D. (1999). Acta Chim. Sin. 57, 1257-1261.]).

[Scheme 1]

Most of the MHg(SCN)4 compounds have been structurally characterized, including MnHg(SCN)4, FeHg(SCN)4 (Yan et al., 1999[Yan, Y.-X., Fang, Q., Yu, W.-T., Yuan, D.-R., Tian, Y.-P. & Williams, I. D. (1999). Acta Chim. Sin. 57, 1257-1261.]), CoHg(SCN)4 (Jeffery & Rose, 1968[Jeffery, J. W. & Rose, K. M. (1968). Acta Cryst. B24, 653-662.]), CuHg(SCN)4 (Porai Koshits, 1963[Porai Koshits, M. A. (1963). Zh. Strukt. Khim. 4, 584-593.]; Khandar et al., 2011[Khandar, A. A., Klein, A., Bakhtiari, A., Mahjoub, A. R. & Pohl, R. W. H. (2011). J. Solid State Chem. 184, 379-386.]), ZnHg(SCN)4 (Xu et al., 1999[Xu, D., Yu, W.-T., Wang, X.-Q., Yuan, D.-R., Lu, M.-K., Yang, P., Guo, S.-Y., Meng, F.-Q. & Jiang, M.-H. (1999). Acta Cryst. C55, 1203-1205.]) and CdHg(SCN)4 (Iizuka & Sudo, 1968[Iizuka, M. & Sudo, T. (1968). Z. Kristallogr. 126, 376-378.]). The crystal structure of NiHg(SCN)4 has not been reported up to now, and only the structures of the related hydrous phase [NiHg(SCN)4(H2O)2]n (Porai Koshits, 1960[Porai Koshits, M. A. (1960). Kristallografiya, 5, 462-463.]) and of the mercury-richer phase NiHg2(SCN)6 (Iizuka, 1978[Iizuka, M. (1978). Annual Report of Bunkyo University, March issue, pp. 65-68.]) have been determined.

In an attempt to grow crystals of the desired compound NiHg(SCN)4 using a gel-growth method (Henisch, 1996[Henisch, H. K. (1996). In Crystal Growth in Gels. New York: Dover Publications.]), starting from TMOS (tetra­meth­oxy­silane) as gelling agent, we obtained the title compound, [NiHg(SCN)4(CH3OH)2]n viz. a methanol-containing phase, instead. Methanol is generated during the gelling process of the silicate-based material according to the idealized reaction (H3CO)4Si + 4 H2O → 4 H4SiO4 + 4 H3COH and then becomes part of the crystal structure.

2. Structural commentary

The basic structure units of [NiHg(SCN)4(CH3OH)2]n are HgS4 tetra­hedra (point group symmetry .2.) and trans-NiN4O2 octa­hedra (point group symmetry 2..) that are linked through the bridging thio­cyanate anions into a three-dimensional framework structure (Fig. 1[link]). The Hg—S bond lengths [mean 2.552 (3) Å; Table 1[link]] are in very good agreement compared with those of HgS4 tetra­hedra in the above-mentioned solvent-free MHg(SCN)4 structures, which have a mean of 2.57 (5) Å. The trans-NiN4O2 octa­hedra are defined by four N atoms belonging to four bridging thio­cyanate anions and by two O atoms of isolated methanol mol­ecules. The displacement parameters of the methanol mol­ecule are rather high. The methanol mol­ecule has relatively much space for libration, because it is not part of the framework structure and points into the remaining free space. Thus the displacement ellipsoids of the methanol O and especially of the C atom are enlarged (Fig. 1[link]). Moreover, there is only a weak hydrogen-bonding inter­action to an adjacent S atom that stabilizes this arrangement (Table 2[link]).

Table 1
Selected bond lengths (Å)

Hg1—S1i 2.5499 (7) Ni1—N2iii 2.041 (2)
Hg1—S1 2.5499 (7) Ni1—N1iv 2.045 (2)
Hg1—S2 2.5546 (7) Ni1—N1 2.045 (2)
Hg1—S2i 2.5546 (7) Ni1—O1 2.066 (2)
Ni1—N2ii 2.041 (2) Ni1—O1iv 2.066 (2)
Symmetry codes: (i) [-x+{\script{1\over 2}}, y, -z+{\script{7\over 4}}]; (ii) [y-1, x+{\script{1\over 2}}, z+{\script{1\over 4}}]; (iii) [-y+1, -x+{\script{1\over 2}}, z+{\script{1\over 4}}]; (iv) -x, -y+1, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1⋯S1v 0.90 (1) 2.40 (2) 3.262 (2) 160 (4)
Symmetry code: (v) -y, x, -z+2.
[Figure 1]
Figure 1
The crystal structure of [NiHg(SCN)4(CH3OH)2] in a projection along [010]. Displacement ellipsoids are drawn at the 90% probability level. H atoms are omitted for clarity. [Symmetry code: (iv) −x, −y + 1, z.]

[NiHg(SCN)4(CH3OH)2]n and [NiHg(SCN)4(H2O)2]n have a similar composition. Although the basic structure units (HgS4 tetra­hedra and trans-NiN4O2 octa­hedra linked by thio­cyanate bridges) are the same, the corresponding crystal structures are markedly different. The methanol-containing structure has tetra­gonal symmetry and is non-centrosymmetric, the water-containing structure has monoclinic symmetry and is centrosymmetric (space group C2/c). Whereas in the water-containing structure the HgS4 and NiN4O2 polyhedra are alternately arranged in layers parallel to (001) (Fig. 2[link]), the arrangement in the methanol-containing compound is markedly different (Fig. 1[link]).

[Figure 2]
Figure 2
The crystal structure of [NiHg(SCN)4(H2O)2] (Porai Koshits, 1960[Porai Koshits, M. A. (1960). Kristallografiya, 5, 462-463.]) in a projection along [010]. Colour code as in Fig. 1[link].

The common structural motif in the above-mentioned MHg(SCN)4 compounds is the linkage of MN4 units (planar configuration for Cu and tetrahedral for all other M members) and tetra­hedral HgS4 units through thio­cyanate bridges. It seems that a coordination number of four is not favoured for structures with M = Ni. In the structures of [NiHg(SCN)4(CH3OH)2]n, [NiHg(SCN)4(H2O)2]n and NiHg2(SCN)6, the Ni2+ ions all have coordination numbers of six, which is probably the reason why a compound with composition NiHg(SCN)4 (most probably requiring a [4]-coordination for Ni2+) has not yet been isolated.

3. Synthesis and crystallization

Hg(SCN)2 was prepared by adding stoichiometric amounts of KSCN to a slightly acidified aqueous solution of Hg(NO3)2. The colourless precipitate was filtered off, washed with water and dried.

For the gel-growth experiment, 1.2 g Ni(NO3)2·6H2O and 1.2 g NH4SCN were dissolved in 20 ml water. To this solution, 0.5 g freshly prepared Hg(SCN)2 was slowly added until complete dissolution. Then 2 ml TMOS was added dropwise under stirring. Gelling time was about 3 h. After one week, blue single crystals of the title compound up to 5 mm in length had formed in the gel matrix.

4. Refinement

The H atom of the methanol hy­droxy group was located from a difference map and was refined with a distance restraint of 0.90 (1) Å. The H atoms associated with the methyl group of the methanol mol­ecule could not be located from difference Fourier maps. As a result of the high libration of this mol­ecule, it seems probable that the methyl H atoms are disordered and were therefore refined with two positions with half-occupancy and rotated by 60 degrees. Ueq of these H atoms were set 1.5Uiso of the parent C atom. The remaining maximum and minimum electron densities are found 0.36 and 0.06 Å, respectively, from atom O1. Reflection (011) was affected by the beamstop and was discarded from the refinement. Experimental details are given in Table 3[link].

Table 3
Experimental details

Crystal data
Chemical formula [NiHg(NCS)4(CH4O)2]
Mr 555.70
Crystal system, space group Tetragonal, I[\overline{4}]2d
Temperature (K) 100
a, c (Å) 10.1746 (3), 29.5107 (11)
V (Å3) 3055.02 (17)
Z 8
Radiation type Mo Kα
μ (mm−1) 11.81
Crystal size (mm) 0.18 × 0.18 × 0.18
 
Data collection
Diffractometer Bruker APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.567, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections 17699, 4684, 4214
Rint 0.028
(sin θ/λ)max (Å−1) 0.904
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.051, 0.96
No. of reflections 4684
No. of parameters 87
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 1.63, −1.46
Absolute structure Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 2098 Friedel pairs
Absolute structure parameter 0.011 (4)
Computer programs: APEX2 and SAINT (Bruker, 2008[Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and ATOMS for Windows (Dowty, 2006[Dowty, E. (2006). ATOMS for Windows. Shape Software, Kingsport, Tennessee, USA.]).

Supporting information

CCDC reference: 1004260

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814009532/hb0003sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009532/hb0003Isup2.hkl

checkCIF report


Chemical context top

Compounds of the type MHg(SCN)4 (M is a divalent transition metal) exhibit inter­esting physical properties. For example, CoHg(SCN)4 is a calibrant for magnetic susceptibility measurements using the Faraday method (Brown et al., 1977), and representatives with M = Fe, Mn, Zn and Cd show second-order non-linear optical (NLO) properties (Bergman et al., 1970; Yan et al., 1999).

Most of the MHg(SCN)4 compounds have been structurally characterized, including MnHg(SCN)4, FeHg(SCN)4 (Yan et al., 1999), CoHg(SCN)4 (Jeffery & Rose, 1968), CuHg(SCN)4 (Porai Koshits, 1963; Khandar et al., 2011), ZnHg(SCN)4 (Xu et al., 1999) and CdHg(SCN)4 (Iizuka & Sudo, 1968). The crystal structure of NiHg(SCN)4 has not been reported up to now, and only the structures of the related hydrous phase [NiHg(SCN)4(H2O)2]n (Porai Koshits, 1960) and of the mercury-richer phase NiHg2(SCN)6 (Iizuka, 1978) have been determined.

In an attempt to grow crystals of the desired compound NiHg(SCN)4 using a gel-growth method (Henisch, 1996), starting from TMOS (tetra­meth­oxy­silane) as gelling agent, we obtained the title compound, [NiHg(SCN)4(CH3OH)2]n viz. a methanol-containing phase, instead. Methanol is generated during the gelling process of the silicate-based material according to the idealized reaction (H3CO)4Si + 4 H2O → 4 H4SiO4 + 4 H3COH and then becomes part of the crystal structure.

Structural commentary top

The basic structure units of [NiHg(SCN)4(CH3OH)2]n are HgS4 tetra­hedra (point group symmetry .2.) and trans-NiN4O2 o­cta­hedra (point group symmetry 2..) that are linked through the bridging thio­cyanate anions into a three-dimensional framework structure (Fig. 1). The Hg—S bond lengths [mean 2.552 (3) Å] are in very good agreement compared with those of HgS4 tetra­hedra in the above-mentioned solvent-free MHg(SCN)4 structures, which have a mean of 2.57 (5) Å. The trans-NiN4O2 o­cta­hedra are defined by four N atoms belonging to four bridging thio­cyanate anions and by two O atoms of isolated methanol molecules. The displacement parameters of the methanol molecule are rather high. The methanol molecule has relatively much space for libration, because it is not part of the framework structure and points into the remaining free space. Thus the displacement ellipsoids of the methanol O and especially of the C atom are enlarged (Fig. 1). Moreover, there is only a weak hydrogen-bonding inter­action to an adjacent S atom that stabilizes this arrangement (Table 2).

[NiHg(SCN)4(CH3OH)2]n and [NiHg(SCN)4(H2O)2]n have a similar composition. Although the basic structure units (HgS4 tetra­hedra and trans-NiN4O2 o­cta­hedra linked by thio­cyanate bridges) are the same, the corresponding crystal structures are markedly different. The methanol-containing structure has tetra­gonal symmetry and is non-centrosymmetric, the water-containing structure has monoclinic symmetry and is centrosymmetric (space group C2/c). Whereas in the water-containing structure the HgS4 and NiN4O2 polyhedra are alternately arranged in layers parallel to (001) (Fig. 2), the arrangement in the methanol-containing compound is markedly different (Fig. 1).

The common structural motif in the above-mentioned MHg(SCN)4 compounds is the linkage of MN4 units (planar configuration for Cu and tetahedral for all other M members) and tetra­hedral HgS4 units through thio­cyanate bridges. It seems that a coordination number of four is not favoured for structures with M = Ni. In the structures of [NiHg(SCN)4(CH3OH)2]n, [NiHg(SCN)4(H2O)2]n and NiHg2(SCN)6, the Ni2+ ions all have coordination numbers of six, which probably is the reason why a compound with composition NiHg(SCN)4 (most probably requiring a [4]-coordination for Ni2+) has not yet been isolated.

Synthesis and crystallization top

Hg(SCN)2 was prepared by adding stoichiometric amounts of KSCN to a slightly acidified aqueous solution of Hg(NO3)2. The colourless precipitate was filtered off, washed with water and dried.

For the gel-growth experiment, 1.2 g Ni(NO3)2.6H2O and 1.2 g NH4SCN were dissolved in 20 ml water. To this solution, 0.5 g freshly prepared Hg(SCN)2 was slowly added until complete dissolution. Then 2 ml TMOS was added dropwise under stirring. Gelling time was about 3 hours. After one week, blue single crystals of the title compound up to 5 mm in length had formed in the gel matrix.

Refinement top

The H atom of the methanol hy­droxy group was located from a difference map and was refined with a distance restraint of 0.90 (1) Å. The H atoms associated with the methyl group of the methanol molecule could not be located from difference Fourier maps. As a result of the high libration of this molecule, it seems probable that the methyl H atoms are disordered and were therefore refined with two positions with half-occupancy and rotated by 60 degrees. Ueq of these H atoms were set 1.5Uiso of the parent C atom. The remaining maximum and minimum electron densities are found 0.36 and 0.06 Å, respectively, from atom O1. Reflection (011) was affected by the beamstop and was discarded from the refinement.

Related literature top

For related literature, see: Bergman, McFee & Crane (1970); Brown et al. (1977); Henisch (1996); Iizuka (1978); Iizuka & Sudo (1968); Jeffery & Rose (1968); Khandar et al. (2011); Porai (1960, 1963); Xu et al. (1999); Yan et al. (1999).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS for Windows (Dowty, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The crystal structure of [NiHg(SCN)4(CH3OH)2] in a projection along [010]. Displacement ellipsoids are drawn at the 90% probability level. H atoms are omitted for clarity. [Symmetry code: iv) -x, -y + 1, z.]
[Figure 2] Fig. 2. The crystal structure of [NiHg(SCN)4(H2O)2] (Porai Koshits, 1960) in a projection along [010]. Colour code as in Fig. 1.
catena-Poly[[bis(methanol-κO)nickel(II)]-di-µ-thiocyanato-κ4N:S-mercurate(II)-di-µ-thiocyanato-κ4N:S] top
Crystal data top
[NiHg(NCS)4(CH4O)2]Dx = 2.416 Mg m−3
Mr = 555.70Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42dCell parameters from 9082 reflections
Hall symbol: I -4 2bwθ = 2.9–40.0°
a = 10.1746 (3) ŵ = 11.81 mm−1
c = 29.5107 (11) ÅT = 100 K
V = 3055.02 (17) Å3Spherical, blue
Z = 80.18 × 0.18 × 0.18 mm
F(000) = 2080
Data collection top
Bruker APEXII CCD
diffractometer		4684 independent reflections
Radiation source: fine-focus sealed tube4214 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
ω and ϕ scansθmax = 40.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −17→17
Tmin = 0.567, Tmax = 0.748k = −18→12
17699 measured reflectionsl = −41→53
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.051 w = 1/[σ2(Fo2) + (0.P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.004
4684 reflectionsΔρmax = 1.63 e Å−3
87 parametersΔρmin = −1.46 e Å−3
0 restraintsAbsolute structure: Flack (1983), 2098 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.011 (4)
Crystal data top
[NiHg(NCS)4(CH4O)2]Z = 8
Mr = 555.70Mo Kα radiation
Tetragonal, I42dµ = 11.81 mm−1
a = 10.1746 (3) ÅT = 100 K
c = 29.5107 (11) Å0.18 × 0.18 × 0.18 mm
V = 3055.02 (17) Å3
Data collection top
Bruker APEXII CCD
diffractometer		4684 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		4214 reflections with I > 2σ(I)
Tmin = 0.567, Tmax = 0.748Rint = 0.028
17699 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.051Δρmax = 1.63 e Å−3
S = 0.96Δρmin = −1.46 e Å−3
4684 reflectionsAbsolute structure: Flack (1983), 2098 Friedel pairs
87 parametersAbsolute structure parameter: 0.011 (4)
0 restraints
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.

Refinement. 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
xyzUiso*/UeqOcc. (<1)
Hg10.25000.529525 (12)0.87500.01652 (3)
Ni10.00000.50001.050596 (14)0.01130 (8)
S10.34284 (7)0.39974 (6)0.94163 (2)0.01777 (12)
S20.07460 (8)0.66758 (7)0.91464 (2)0.02210 (14)
C10.0628 (3)0.7838 (2)0.87530 (12)0.0204 (4)
C20.2196 (2)0.4289 (2)0.97739 (8)0.0141 (4)
N10.1356 (2)0.4484 (2)1.00263 (8)0.0177 (4)
N20.0514 (3)0.8668 (2)0.84917 (8)0.0256 (5)
O1−0.0812 (2)0.3139 (2)1.05077 (16)0.0593 (11)
C3−0.0338 (4)0.1958 (4)1.0511 (3)0.075 (2)
H2A−0.10610.13221.05110.112*0.50
H2B0.01980.18341.07830.112*0.50
H2C0.02070.18251.02410.112*0.50
H2D0.06240.19991.05130.112*0.50
H2E−0.06350.14871.02400.112*0.50
H2F−0.06440.14951.07820.112*0.50
H1−0.164 (2)0.331 (5)1.0596 (16)0.061 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.02513 (7)0.01081 (5)0.01362 (5)0.0000.00653 (5)0.000
Ni10.00883 (17)0.01668 (19)0.00839 (15)0.00111 (13)0.0000.000
S10.0170 (3)0.0176 (3)0.0187 (3)0.0054 (2)0.0082 (2)0.0037 (2)
S20.0323 (4)0.0168 (3)0.0173 (3)0.0118 (3)0.0094 (3)0.0071 (2)
C10.0318 (12)0.0153 (10)0.0141 (9)0.0070 (9)0.0014 (11)−0.0010 (10)
C20.0144 (10)0.0145 (9)0.0133 (10)0.0015 (8)−0.0006 (8)0.0005 (8)
N10.0153 (9)0.0255 (11)0.0121 (8)0.0009 (8)−0.0008 (7)−0.0011 (8)
N20.0478 (16)0.0150 (10)0.0141 (9)0.0107 (10)−0.0019 (10)−0.0006 (8)
O10.0126 (10)0.0178 (11)0.147 (4)0.0008 (8)0.0117 (16)0.0146 (16)
C30.030 (2)0.0187 (16)0.176 (7)0.0003 (15)−0.011 (3)−0.011 (3)
Geometric parameters (Å, º) top
Hg1—S1i2.5499 (7)C1—N21.149 (4)
Hg1—S12.5499 (7)C2—N11.151 (3)
Hg1—S22.5546 (7)N2—Ni1v2.041 (2)
Hg1—S2i2.5546 (7)O1—C31.295 (4)
Ni1—N2ii2.041 (2)O1—H10.897 (10)
Ni1—N2iii2.041 (2)C3—H2A0.9800
Ni1—N1iv2.045 (2)C3—H2B0.9800
Ni1—N12.045 (2)C3—H2C0.9800
Ni1—O12.066 (2)C3—H2D0.9800
Ni1—O1iv2.066 (2)C3—H2E0.9800
S1—C21.666 (2)C3—H2F0.9800
S2—C11.661 (3)
S1i—Hg1—S1117.62 (3)C1—N2—Ni1v170.1 (3)
S1i—Hg1—S2112.27 (2)C3—O1—Ni1134.5 (2)
S1—Hg1—S2100.98 (2)C3—O1—H1122 (3)
S1i—Hg1—S2i100.98 (2)Ni1—O1—H1101 (3)
S1—Hg1—S2i112.27 (2)O1—C3—H2A109.5
S2—Hg1—S2i113.29 (3)O1—C3—H2B109.5
N2ii—Ni1—N2iii90.77 (13)H2A—C3—H2B109.5
N2ii—Ni1—N1iv88.42 (9)O1—C3—H2C109.5
N2iii—Ni1—N1iv179.17 (9)H2A—C3—H2C109.5
N2ii—Ni1—N1179.17 (9)H2B—C3—H2C109.5
N2iii—Ni1—N188.42 (9)O1—C3—H2D109.5
N1iv—Ni1—N192.40 (12)H2A—C3—H2D141.1
N2ii—Ni1—O188.12 (13)H2B—C3—H2D56.3
N2iii—Ni1—O191.68 (14)H2C—C3—H2D56.3
N1iv—Ni1—O188.11 (13)O1—C3—H2E109.5
N1—Ni1—O192.08 (13)H2A—C3—H2E56.3
N2ii—Ni1—O1iv91.68 (14)H2B—C3—H2E141.1
N2iii—Ni1—O1iv88.12 (13)H2C—C3—H2E56.3
N1iv—Ni1—O1iv92.08 (13)H2D—C3—H2E109.5
N1—Ni1—O1iv88.11 (13)O1—C3—H2F109.5
O1—Ni1—O1iv179.7 (3)H2A—C3—H2F56.3
C2—S1—Hg196.75 (9)H2B—C3—H2F56.3
C1—S2—Hg197.01 (10)H2C—C3—H2F141.1
N2—C1—S2177.4 (3)H2D—C3—H2F109.5
N1—C2—S1179.0 (2)H2E—C3—H2F109.5
C2—N1—Ni1173.3 (2)
Symmetry codes: (i) −x+1/2, y, −z+7/4; (ii) y−1, x+1/2, z+1/4; (iii) −y+1, −x+1/2, z+1/4; (iv) −x, −y+1, z; (v) −y+1/2, −x+1, z−1/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···S1vi0.90 (1)2.40 (2)3.262 (2)160 (4)
Symmetry code: (vi) −y, x, −z+2.

Experimental details

Crystal data
Chemical formula[NiHg(NCS)4(CH4O)2]
Mr555.70
Crystal system, space groupTetragonal, I42d
Temperature (K)100
a, c (Å)10.1746 (3), 29.5107 (11)
V (Å3)3055.02 (17)
Z8
Radiation typeMo Kα
µ (mm−1)11.81
Crystal size (mm)0.18 × 0.18 × 0.18
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.567, 0.748
No. of measured, independent and
observed [I > 2σ(I)] reflections		17699, 4684, 4214
Rint0.028
(sin θ/λ)max (Å−1)0.904
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.051, 0.96
No. of reflections4684
No. of parameters87
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)1.63, −1.46
Absolute structureFlack (1983), 2098 Friedel pairs
Absolute structure parameter0.011 (4)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ATOMS for Windows (Dowty, 2006).

Selected bond lengths (Å) top
Hg1—S1i2.5499 (7)Ni1—N2iii2.041 (2)
Hg1—S12.5499 (7)Ni1—N1iv2.045 (2)
Hg1—S22.5546 (7)Ni1—N12.045 (2)
Hg1—S2i2.5546 (7)Ni1—O12.066 (2)
Ni1—N2ii2.041 (2)Ni1—O1iv2.066 (2)
Symmetry codes: (i) −x+1/2, y, −z+7/4; (ii) y−1, x+1/2, z+1/4; (iii) −y+1, −x+1/2, z+1/4; (iv) −x, −y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···S1v0.897 (10)2.40 (2)3.262 (2)160 (4)
Symmetry code: (v) −y, x, −z+2.
 

Acknowledgements

The X-ray centre of the Vienna University of Technology is acknowledged for providing access to the single-crystal diffractometer.

References

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ISSN: 2056-9890
Volume 70| Part 8| August 2014| Pages 48-50
doi:10.1107/S1600536814009532
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