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In the title complex, [MnHg(SCN)4(C2H6SO)2]n, each Hg atom is tetrahedrally coordinated to four S atoms of the SCN ions, while each Mn atom is octahedrally coordinated to four N atoms of the SCN ions and two O atoms of the di­methyl sulfoxide mol­ecules which occupy the trans positions. Each pair of Hg and Mn atoms is bridged by one SCN ion. Two Mn atoms, two Hg atoms and four SCN ions make a 16-membered ring which organises into a two-dimensional network. The di­methyl sulfoxide ligands are extended perpendicular to the plane on both sides.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016765/sk1349sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016765/sk1349Isup2.hkl
Contains datablock I

CCDC reference: 144611

Comment top

There is considerable interest in the synthesis of new materials with excellent second-order optical nonlinearities. During the last few years, organometallic and coordination complexes have been a very active field in the search for useful nonlinear optical (NLO) materials, because such materials have the potential to combine the high optical nonlinearity and chemical flexibility of organics with the physical ruggedness of inorganics (Long, 1995). Many new metal-organic NLO crystals have been successfully found on the basis of molecular engineering and the double-ligand model (Xu et al., 1987, 1994, 1999; Tao et al., 1987; Zhang et al., 1989; Yuan et al., 1990, 1997; Yu et al., 1991; Hou et al., 1993; Wang, 1996; Tian et al., 1997). The compound manganese mercury tetrathiocyanate, MnHg(SCN)4 (MMTC), was reported by Yan et al. (1999), and the crystal shows a 532 nm second harmonic intensity 18 times that of the crystal urea. The title compound, MMTD, is the dimethyl sulfoxide (DMSO) adduct of MMTC and is a new NLO crystal. It exhibits a strong NLO effect and is easy to grow into large crystals. \scheme

The concept of hard and soft acids and bases tells us that hard cations such as Mn2+ and Co2+ show a pronounced affinity for coordination with the harder ligands, while soft cations such as Cd2+ and Hg2+ prefer coordination with softer ligands (Pearson, 1963, 1966; Balarew & Duhlew, 1984; Yamaguchi et al., 1985; Ozutsmi et al., 1989). In the structure of MMTD, the hard Mn2+ are coordinated with the harder N (SCN) and O (DMSO) ligands, while the soft Hg2+ is coordinated with the softer S (SCN) ligands.

The Hg2+ is coordinated with four SCN S atoms and is in a tetrahedral geometry. The Mn2+ is six-coordinate and is in an octahedral geometry: both of the O atoms of the DMSO molecules are coordinated axially, while four SCN N atoms are coordinated equatorially. The average Hg—S length is 2.545 Å and the average bond angle around the Hg atoms is 109.48° (range 105.97 to 113.84°), which is slightly different from typical tetrahedral angles.

The average Mn—N and Mn—O bond lengths are 2.222 Å and 2.156 Å, respectively. These values are about the same as the lengths in common octahedral managanese(II) complexes. The average bond angles for N—Mn—O and N—Mn—N (between vicinal N atoms) are 90.0 and 90.2°, respectively. The O—Mn—O angle is little distorted from 180, at 177.8 (3)°.

Overall, the tetrahedral geometry of the Hg core and the octahedral geometry of the Mn core are both sightly deformed from the ideal forms. The most striking features are the —SCN— bridges which connect Mn and Hg, forming an infinite two-dimensional network. The macroscopic non-linear susceptibility may be related to the microscopic hyperpolarizabilities of the dipolar SCN ions, just as in MMTC, and to the distorted HgS4 tetrahedra and MnN4O2 octahedra (Zyss, 1991). What is more, the average Mn—N—C bond angle is 156.1°, which is significantly different from 180° (such large distortions of these angles are probably due to steric hindrance to form the planar complex networks in the crystal). Also, the DMSO ligands coordinated to Mn2+ are extended approximately perpendicular to the complex layer. The interaction of the DMSO adduct base renders this new crystal structure much more distorted than that of the original crystal, MMTC. The novel infinite two-dimensional network confers larger polarization, which in turn, we believe, induces greater macroscopic non-linearity than MMTC. The second harmonic generation (SHG) of the crystals was studied by the power SHG method (Kurtz & Perry, 1968). It was found that MMTD crystals are superior to those of MMTC, and one order of magnitude higher than urea in their SHG effect. Query.

Experimental top

A crystalline powder of MMTC was added to a mixed solvent of DMSO and water. This mixture was heated and stirred until the MMTC was dissolved. The colourless solution was left at room temperature until crystals of MMTD were formed.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of MMTD showing 50% probability displacement ellipsoids. H atoms are omitted for clarity.
[Figure 2] Fig. 2. Packing diagram for MMTD showing the two-dimensional network.
Poly[[bis(dimethyl sulfoxide-κO)tris(thiocyanato-κN)manganese(II)]-µ- thiocyanato-κ2N:S-mercury(II)] top
Crystal data top
[MnHg(SCN)4(C2H6SO)2]nDx = 2.120 Mg m3
Mr = 644.11Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 35 reflections
a = 8.4937 (6) Åθ = 5.7–13.0°
b = 8.5226 (4) ŵ = 8.85 mm1
c = 27.884 (4) ÅT = 293 K
V = 2018.5 (3) Å3Orthorhombic, colourless
Z = 40.25 × 0.22 × 0.20 mm
F(000) = 1220
Data collection top
Bruker P4
diffractometer
2310 reflections with I > 2s(I)
Radiation source: fine-focus sealed tubeRint = 0.035
Graphite monochromatorθmax = 27.5°, θmin = 2.5°
ω/2θ scansh = 111
Absorption correction: ψ-scan
(XSCANS; Siemens, 1996)
k = 111
Tmin = 0.119, Tmax = 0.165l = 136
3460 measured reflections3 standard reflections every 97 reflections
3231 independent reflections intensity decay: none
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043 w = 1/[σ2(Fo2) + (0.0513P)2 + 2.4486P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.112(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.96 e Å3
3231 reflectionsΔρmin = 1.40 e Å3
200 parametersExtinction correction: SHELXTL (Bruker, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0045 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.004 (12)
Crystal data top
[MnHg(SCN)4(C2H6SO)2]nV = 2018.5 (3) Å3
Mr = 644.11Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.4937 (6) ŵ = 8.85 mm1
b = 8.5226 (4) ÅT = 293 K
c = 27.884 (4) Å0.25 × 0.22 × 0.20 mm
Data collection top
Bruker P4
diffractometer
2310 reflections with I > 2s(I)
Absorption correction: ψ-scan
(XSCANS; Siemens, 1996)
Rint = 0.035
Tmin = 0.119, Tmax = 0.1653 standard reflections every 97 reflections
3460 measured reflections intensity decay: none
3231 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.96 e Å3
S = 1.03Δρmin = 1.40 e Å3
3231 reflectionsAbsolute structure: Flack (1983)
200 parametersAbsolute structure parameter: 0.004 (12)
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*/Ueq
Hg10.50115 (4)0.76042 (4)0.124232 (15)0.04915 (17)
Mn10.01478 (16)0.26376 (13)0.12569 (4)0.0303 (3)
S10.2443 (3)0.7718 (4)0.07682 (12)0.0597 (9)
S20.7461 (4)0.7898 (5)0.07283 (13)0.0655 (10)
S30.4929 (5)0.9918 (3)0.18212 (11)0.0709 (10)
S40.5085 (4)0.4984 (3)0.16740 (11)0.0557 (7)
S50.0055 (4)0.1553 (3)0.23607 (9)0.0514 (6)
S60.1016 (3)0.2368 (3)0.01571 (10)0.0490 (6)
O10.0013 (9)0.2962 (7)0.2023 (2)0.0477 (15)
O20.0396 (7)0.2355 (8)0.0493 (2)0.0482 (17)
N10.1125 (11)0.5007 (11)0.1165 (3)0.049 (2)
N20.2450 (11)0.1529 (11)0.1375 (4)0.050 (2)
N30.1050 (11)0.0286 (10)0.1251 (4)0.054 (2)
N40.2267 (10)0.3699 (11)0.1219 (4)0.051 (2)
C10.1666 (12)0.6107 (12)0.1005 (4)0.038 (2)
C20.3472 (12)0.0847 (11)0.1557 (4)0.039 (2)
C30.1679 (12)0.0692 (12)0.1044 (4)0.041 (3)
C40.3338 (13)0.4239 (11)0.1403 (4)0.039 (2)
C50.1219 (16)0.2015 (17)0.2829 (4)0.083 (4)
H5A0.22860.19880.27160.124*
H5B0.10920.12660.30830.124*
H5C0.09820.30470.29470.124*
C60.1808 (13)0.171 (2)0.2673 (5)0.097 (6)
H6A0.26720.14970.24620.145*
H6B0.19090.27580.27980.145*
H6C0.18140.09750.29330.145*
C70.0473 (18)0.1048 (18)0.0300 (5)0.103 (6)
H7A0.05030.00050.01780.154*
H7B0.05740.12860.04070.154*
H7C0.11940.11430.05630.154*
C80.088 (2)0.4156 (16)0.0161 (6)0.114 (6)
H8A0.11340.50110.00490.171*
H8B0.15980.41430.04260.171*
H8C0.01770.42860.02780.171*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.03086 (19)0.03146 (19)0.0851 (3)0.0001 (3)0.0003 (3)0.00503 (18)
Mn10.0271 (6)0.0287 (5)0.0351 (6)0.0004 (8)0.0012 (7)0.0006 (5)
S10.0491 (14)0.0420 (18)0.088 (2)0.0149 (16)0.0207 (17)0.0249 (18)
S20.0510 (15)0.061 (2)0.084 (2)0.0208 (18)0.0165 (17)0.028 (2)
S30.064 (2)0.0596 (15)0.089 (2)0.028 (2)0.034 (2)0.0259 (16)
S40.0425 (15)0.0443 (12)0.0803 (18)0.0128 (19)0.019 (2)0.0106 (13)
S50.0681 (17)0.0423 (11)0.0436 (13)0.003 (2)0.001 (2)0.0025 (10)
S60.0445 (13)0.0566 (16)0.0459 (14)0.0045 (15)0.0050 (12)0.0024 (14)
O10.065 (4)0.038 (3)0.039 (3)0.004 (6)0.004 (4)0.004 (3)
O20.039 (3)0.068 (4)0.037 (3)0.005 (4)0.001 (3)0.003 (4)
N10.038 (5)0.041 (5)0.069 (6)0.009 (4)0.001 (5)0.008 (5)
N20.041 (5)0.039 (5)0.071 (6)0.015 (4)0.000 (5)0.007 (5)
N30.045 (5)0.035 (4)0.082 (7)0.006 (4)0.001 (6)0.006 (5)
N40.030 (4)0.044 (5)0.081 (7)0.008 (4)0.001 (5)0.005 (5)
C10.032 (5)0.040 (5)0.042 (6)0.002 (5)0.008 (5)0.002 (5)
C20.039 (6)0.027 (5)0.050 (6)0.001 (5)0.004 (5)0.014 (5)
C30.030 (5)0.039 (6)0.053 (7)0.000 (5)0.010 (5)0.017 (5)
C40.042 (6)0.029 (5)0.046 (6)0.002 (5)0.010 (5)0.004 (5)
C50.086 (9)0.084 (10)0.078 (9)0.020 (10)0.032 (8)0.030 (8)
C60.051 (7)0.157 (17)0.082 (10)0.003 (10)0.027 (8)0.055 (12)
C70.084 (11)0.114 (12)0.110 (12)0.022 (10)0.007 (9)0.069 (10)
C80.132 (15)0.074 (9)0.136 (13)0.002 (10)0.067 (13)0.049 (10)
Geometric parameters (Å, º) top
Hg1—S42.538 (3)S5—O11.526 (6)
Hg1—S22.539 (3)S5—C61.730 (11)
Hg1—S32.549 (3)S5—C51.742 (12)
Hg1—S12.552 (3)S6—O21.523 (7)
Mn1—O22.153 (6)S6—C71.761 (12)
Mn1—O12.158 (6)S6—C81.766 (12)
Mn1—N22.196 (9)N1—C11.134 (13)
Mn1—N12.199 (9)N2—C21.162 (13)
Mn1—N42.244 (9)N3—C31.147 (13)
Mn1—N32.248 (9)N4—C41.141 (13)
S1—C11.660 (11)C2—S3iv1.643 (11)
S2—C3i1.659 (12)C3—S2v1.659 (12)
S3—C2ii1.643 (11)C4—S4vi1.664 (11)
S4—C4iii1.664 (11)
S4—Hg1—S2109.54 (12)C1—S1—Hg195.9 (4)
S4—Hg1—S3112.40 (11)C3i—S2—Hg197.7 (4)
S2—Hg1—S3107.68 (13)C2ii—S3—Hg196.3 (3)
S4—Hg1—S1107.46 (11)C4iii—S4—Hg198.0 (4)
S2—Hg1—S1113.84 (11)O1—S5—C6105.6 (6)
S3—Hg1—S1105.97 (12)O1—S5—C5105.7 (5)
O2—Mn1—O1177.8 (3)C6—S5—C598.0 (7)
O2—Mn1—N290.7 (3)O2—S6—C7103.6 (6)
O1—Mn1—N287.9 (3)O2—S6—C8105.2 (6)
O2—Mn1—N187.1 (3)C7—S6—C899.8 (8)
O1—Mn1—N191.3 (3)S5—O1—Mn1120.8 (3)
N2—Mn1—N194.4 (3)S6—O2—Mn1122.1 (4)
O2—Mn1—N495.1 (3)C1—N1—Mn1163.3 (9)
O1—Mn1—N486.4 (3)C2—N2—Mn1161.1 (9)
N2—Mn1—N4173.8 (4)C3—N3—Mn1149.6 (9)
N1—Mn1—N488.2 (3)C4—N4—Mn1150.5 (9)
O2—Mn1—N386.4 (3)N1—C1—S1179.4 (11)
O1—Mn1—N395.3 (3)N2—C2—S3iv178.7 (10)
N2—Mn1—N391.2 (3)N3—C3—S2v177.9 (10)
N1—Mn1—N3171.5 (4)N4—C4—S4vi178.6 (10)
N4—Mn1—N386.9 (3)
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x, y1, z; (v) x1, y1, z; (vi) x1, y, z.

Experimental details

Crystal data
Chemical formula[MnHg(SCN)4(C2H6SO)2]n
Mr644.11
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)8.4937 (6), 8.5226 (4), 27.884 (4)
V3)2018.5 (3)
Z4
Radiation typeMo Kα
µ (mm1)8.85
Crystal size (mm)0.25 × 0.22 × 0.20
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionψ-scan
(XSCANS; Siemens, 1996)
Tmin, Tmax0.119, 0.165
No. of measured, independent and
observed [I > 2s(I)] reflections
3460, 3231, 2310
Rint0.035
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.112, 1.03
No. of reflections3231
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.96, 1.40
Absolute structureFlack (1983)
Absolute structure parameter0.004 (12)

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Hg1—S42.538 (3)Mn1—O12.158 (6)
Hg1—S22.539 (3)Mn1—N22.196 (9)
Hg1—S32.549 (3)Mn1—N12.199 (9)
Hg1—S12.552 (3)Mn1—N42.244 (9)
Mn1—O22.153 (6)Mn1—N32.248 (9)
S4—Hg1—S2109.54 (12)N1—Mn1—N488.2 (3)
S4—Hg1—S3112.40 (11)O2—Mn1—N386.4 (3)
S2—Hg1—S3107.68 (13)O1—Mn1—N395.3 (3)
S4—Hg1—S1107.46 (11)N2—Mn1—N391.2 (3)
S2—Hg1—S1113.84 (11)N4—Mn1—N386.9 (3)
S3—Hg1—S1105.97 (12)C1—N1—Mn1163.3 (9)
O2—Mn1—O1177.8 (3)C2—N2—Mn1161.1 (9)
O2—Mn1—N290.7 (3)C3—N3—Mn1149.6 (9)
O1—Mn1—N287.9 (3)C4—N4—Mn1150.5 (9)
O2—Mn1—N187.1 (3)N1—C1—S1179.4 (11)
O1—Mn1—N191.3 (3)N2—C2—S3i178.7 (10)
N2—Mn1—N194.4 (3)N3—C3—S2ii177.9 (10)
O2—Mn1—N495.1 (3)N4—C4—S4iii178.6 (10)
O1—Mn1—N486.4 (3)
Symmetry codes: (i) x, y1, z; (ii) x1, y1, z; (iii) x1, y, z.
 

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