Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199016765/sk1349sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199016765/sk1349Isup2.hkl |
CCDC reference: 144611
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.
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.
Fig. 1. The molecular structure of MMTD showing 50% probability displacement ellipsoids. H atoms are omitted for clarity. | |
Fig. 2. Packing diagram for MMTD showing the two-dimensional network. |
[MnHg(SCN)4(C2H6SO)2]n | Dx = 2.120 Mg m−3 |
Mr = 644.11 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 35 reflections |
a = 8.4937 (6) Å | θ = 5.7–13.0° |
b = 8.5226 (4) Å | µ = 8.85 mm−1 |
c = 27.884 (4) Å | T = 293 K |
V = 2018.5 (3) Å3 | Orthorhombic, colourless |
Z = 4 | 0.25 × 0.22 × 0.20 mm |
F(000) = 1220 |
Bruker P4 diffractometer | 2310 reflections with I > 2s(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω/2θ scans | h = −1→11 |
Absorption correction: ψ-scan (XSCANS; Siemens, 1996) | k = −1→11 |
Tmin = 0.119, Tmax = 0.165 | l = −1→36 |
3460 measured reflections | 3 standard reflections every 97 reflections |
3231 independent reflections | intensity decay: none |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-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 = 1.03 | Δρmax = 0.96 e Å−3 |
3231 reflections | Δρmin = −1.40 e Å−3 |
200 parameters | Extinction correction: SHELXTL (Bruker, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0045 (2) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.004 (12) |
[MnHg(SCN)4(C2H6SO)2]n | V = 2018.5 (3) Å3 |
Mr = 644.11 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.4937 (6) Å | µ = 8.85 mm−1 |
b = 8.5226 (4) Å | T = 293 K |
c = 27.884 (4) Å | 0.25 × 0.22 × 0.20 mm |
Bruker P4 diffractometer | 2310 reflections with I > 2s(I) |
Absorption correction: ψ-scan (XSCANS; Siemens, 1996) | Rint = 0.035 |
Tmin = 0.119, Tmax = 0.165 | 3 standard reflections every 97 reflections |
3460 measured reflections | intensity decay: none |
3231 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.112 | Δρmax = 0.96 e Å−3 |
S = 1.03 | Δρmin = −1.40 e Å−3 |
3231 reflections | Absolute structure: Flack (1983) |
200 parameters | Absolute structure parameter: 0.004 (12) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Hg1 | 0.50115 (4) | 0.76042 (4) | 0.124232 (15) | 0.04915 (17) | |
Mn1 | 0.01478 (16) | 0.26376 (13) | 0.12569 (4) | 0.0303 (3) | |
S1 | 0.2443 (3) | 0.7718 (4) | 0.07682 (12) | 0.0597 (9) | |
S2 | 0.7461 (4) | 0.7898 (5) | 0.07283 (13) | 0.0655 (10) | |
S3 | 0.4929 (5) | 0.9918 (3) | 0.18212 (11) | 0.0709 (10) | |
S4 | 0.5085 (4) | 0.4984 (3) | 0.16740 (11) | 0.0557 (7) | |
S5 | −0.0055 (4) | 0.1553 (3) | 0.23607 (9) | 0.0514 (6) | |
S6 | −0.1016 (3) | 0.2368 (3) | 0.01571 (10) | 0.0490 (6) | |
O1 | −0.0013 (9) | 0.2962 (7) | 0.2023 (2) | 0.0477 (15) | |
O2 | 0.0396 (7) | 0.2355 (8) | 0.0493 (2) | 0.0482 (17) | |
N1 | 0.1125 (11) | 0.5007 (11) | 0.1165 (3) | 0.049 (2) | |
N2 | 0.2450 (11) | 0.1529 (11) | 0.1375 (4) | 0.050 (2) | |
N3 | −0.1050 (11) | 0.0286 (10) | 0.1251 (4) | 0.054 (2) | |
N4 | −0.2267 (10) | 0.3699 (11) | 0.1219 (4) | 0.051 (2) | |
C1 | 0.1666 (12) | 0.6107 (12) | 0.1005 (4) | 0.038 (2) | |
C2 | 0.3472 (12) | 0.0847 (11) | 0.1557 (4) | 0.039 (2) | |
C3 | −0.1679 (12) | −0.0692 (12) | 0.1044 (4) | 0.041 (3) | |
C4 | −0.3338 (13) | 0.4239 (11) | 0.1403 (4) | 0.039 (2) | |
C5 | 0.1219 (16) | 0.2015 (17) | 0.2829 (4) | 0.083 (4) | |
H5A | 0.2286 | 0.1988 | 0.2716 | 0.124* | |
H5B | 0.1092 | 0.1266 | 0.3083 | 0.124* | |
H5C | 0.0982 | 0.3047 | 0.2947 | 0.124* | |
C6 | −0.1808 (13) | 0.171 (2) | 0.2673 (5) | 0.097 (6) | |
H6A | −0.2672 | 0.1497 | 0.2462 | 0.145* | |
H6B | −0.1909 | 0.2758 | 0.2798 | 0.145* | |
H6C | −0.1814 | 0.0975 | 0.2933 | 0.145* | |
C7 | −0.0473 (18) | 0.1048 (18) | −0.0300 (5) | 0.103 (6) | |
H7A | −0.0503 | −0.0005 | −0.0178 | 0.154* | |
H7B | 0.0574 | 0.1286 | −0.0407 | 0.154* | |
H7C | −0.1194 | 0.1143 | −0.0563 | 0.154* | |
C8 | −0.088 (2) | 0.4156 (16) | −0.0161 (6) | 0.114 (6) | |
H8A | −0.1134 | 0.5011 | 0.0049 | 0.171* | |
H8B | −0.1598 | 0.4143 | −0.0426 | 0.171* | |
H8C | 0.0177 | 0.4286 | −0.0278 | 0.171* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.03086 (19) | 0.03146 (19) | 0.0851 (3) | 0.0001 (3) | −0.0003 (3) | −0.00503 (18) |
Mn1 | 0.0271 (6) | 0.0287 (5) | 0.0351 (6) | 0.0004 (8) | 0.0012 (7) | 0.0006 (5) |
S1 | 0.0491 (14) | 0.0420 (18) | 0.088 (2) | −0.0149 (16) | −0.0207 (17) | 0.0249 (18) |
S2 | 0.0510 (15) | 0.061 (2) | 0.084 (2) | −0.0208 (18) | 0.0165 (17) | −0.028 (2) |
S3 | 0.064 (2) | 0.0596 (15) | 0.089 (2) | 0.028 (2) | −0.034 (2) | −0.0259 (16) |
S4 | 0.0425 (15) | 0.0443 (12) | 0.0803 (18) | 0.0128 (19) | 0.019 (2) | 0.0106 (13) |
S5 | 0.0681 (17) | 0.0423 (11) | 0.0436 (13) | −0.003 (2) | 0.001 (2) | 0.0025 (10) |
S6 | 0.0445 (13) | 0.0566 (16) | 0.0459 (14) | −0.0045 (15) | −0.0050 (12) | −0.0024 (14) |
O1 | 0.065 (4) | 0.038 (3) | 0.039 (3) | 0.004 (6) | 0.004 (4) | 0.004 (3) |
O2 | 0.039 (3) | 0.068 (4) | 0.037 (3) | 0.005 (4) | −0.001 (3) | −0.003 (4) |
N1 | 0.038 (5) | 0.041 (5) | 0.069 (6) | −0.009 (4) | −0.001 (5) | 0.008 (5) |
N2 | 0.041 (5) | 0.039 (5) | 0.071 (6) | 0.015 (4) | 0.000 (5) | −0.007 (5) |
N3 | 0.045 (5) | 0.035 (4) | 0.082 (7) | −0.006 (4) | −0.001 (6) | −0.006 (5) |
N4 | 0.030 (4) | 0.044 (5) | 0.081 (7) | 0.008 (4) | 0.001 (5) | −0.005 (5) |
C1 | 0.032 (5) | 0.040 (5) | 0.042 (6) | −0.002 (5) | −0.008 (5) | −0.002 (5) |
C2 | 0.039 (6) | 0.027 (5) | 0.050 (6) | 0.001 (5) | 0.004 (5) | −0.014 (5) |
C3 | 0.030 (5) | 0.039 (6) | 0.053 (7) | 0.000 (5) | 0.010 (5) | 0.017 (5) |
C4 | 0.042 (6) | 0.029 (5) | 0.046 (6) | 0.002 (5) | −0.010 (5) | 0.004 (5) |
C5 | 0.086 (9) | 0.084 (10) | 0.078 (9) | −0.020 (10) | −0.032 (8) | 0.030 (8) |
C6 | 0.051 (7) | 0.157 (17) | 0.082 (10) | 0.003 (10) | 0.027 (8) | 0.055 (12) |
C7 | 0.084 (11) | 0.114 (12) | 0.110 (12) | −0.022 (10) | −0.007 (9) | −0.069 (10) |
C8 | 0.132 (15) | 0.074 (9) | 0.136 (13) | 0.002 (10) | −0.067 (13) | 0.049 (10) |
Hg1—S4 | 2.538 (3) | S5—O1 | 1.526 (6) |
Hg1—S2 | 2.539 (3) | S5—C6 | 1.730 (11) |
Hg1—S3 | 2.549 (3) | S5—C5 | 1.742 (12) |
Hg1—S1 | 2.552 (3) | S6—O2 | 1.523 (7) |
Mn1—O2 | 2.153 (6) | S6—C7 | 1.761 (12) |
Mn1—O1 | 2.158 (6) | S6—C8 | 1.766 (12) |
Mn1—N2 | 2.196 (9) | N1—C1 | 1.134 (13) |
Mn1—N1 | 2.199 (9) | N2—C2 | 1.162 (13) |
Mn1—N4 | 2.244 (9) | N3—C3 | 1.147 (13) |
Mn1—N3 | 2.248 (9) | N4—C4 | 1.141 (13) |
S1—C1 | 1.660 (11) | C2—S3iv | 1.643 (11) |
S2—C3i | 1.659 (12) | C3—S2v | 1.659 (12) |
S3—C2ii | 1.643 (11) | C4—S4vi | 1.664 (11) |
S4—C4iii | 1.664 (11) | ||
S4—Hg1—S2 | 109.54 (12) | C1—S1—Hg1 | 95.9 (4) |
S4—Hg1—S3 | 112.40 (11) | C3i—S2—Hg1 | 97.7 (4) |
S2—Hg1—S3 | 107.68 (13) | C2ii—S3—Hg1 | 96.3 (3) |
S4—Hg1—S1 | 107.46 (11) | C4iii—S4—Hg1 | 98.0 (4) |
S2—Hg1—S1 | 113.84 (11) | O1—S5—C6 | 105.6 (6) |
S3—Hg1—S1 | 105.97 (12) | O1—S5—C5 | 105.7 (5) |
O2—Mn1—O1 | 177.8 (3) | C6—S5—C5 | 98.0 (7) |
O2—Mn1—N2 | 90.7 (3) | O2—S6—C7 | 103.6 (6) |
O1—Mn1—N2 | 87.9 (3) | O2—S6—C8 | 105.2 (6) |
O2—Mn1—N1 | 87.1 (3) | C7—S6—C8 | 99.8 (8) |
O1—Mn1—N1 | 91.3 (3) | S5—O1—Mn1 | 120.8 (3) |
N2—Mn1—N1 | 94.4 (3) | S6—O2—Mn1 | 122.1 (4) |
O2—Mn1—N4 | 95.1 (3) | C1—N1—Mn1 | 163.3 (9) |
O1—Mn1—N4 | 86.4 (3) | C2—N2—Mn1 | 161.1 (9) |
N2—Mn1—N4 | 173.8 (4) | C3—N3—Mn1 | 149.6 (9) |
N1—Mn1—N4 | 88.2 (3) | C4—N4—Mn1 | 150.5 (9) |
O2—Mn1—N3 | 86.4 (3) | N1—C1—S1 | 179.4 (11) |
O1—Mn1—N3 | 95.3 (3) | N2—C2—S3iv | 178.7 (10) |
N2—Mn1—N3 | 91.2 (3) | N3—C3—S2v | 177.9 (10) |
N1—Mn1—N3 | 171.5 (4) | N4—C4—S4vi | 178.6 (10) |
N4—Mn1—N3 | 86.9 (3) |
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x, y−1, z; (v) x−1, y−1, z; (vi) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [MnHg(SCN)4(C2H6SO)2]n |
Mr | 644.11 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 8.4937 (6), 8.5226 (4), 27.884 (4) |
V (Å3) | 2018.5 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 8.85 |
Crystal size (mm) | 0.25 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ-scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.119, 0.165 |
No. of measured, independent and observed [I > 2s(I)] reflections | 3460, 3231, 2310 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.112, 1.03 |
No. of reflections | 3231 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.96, −1.40 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.004 (12) |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Bruker, 1997), SHELXTL.
Hg1—S4 | 2.538 (3) | Mn1—O1 | 2.158 (6) |
Hg1—S2 | 2.539 (3) | Mn1—N2 | 2.196 (9) |
Hg1—S3 | 2.549 (3) | Mn1—N1 | 2.199 (9) |
Hg1—S1 | 2.552 (3) | Mn1—N4 | 2.244 (9) |
Mn1—O2 | 2.153 (6) | Mn1—N3 | 2.248 (9) |
S4—Hg1—S2 | 109.54 (12) | N1—Mn1—N4 | 88.2 (3) |
S4—Hg1—S3 | 112.40 (11) | O2—Mn1—N3 | 86.4 (3) |
S2—Hg1—S3 | 107.68 (13) | O1—Mn1—N3 | 95.3 (3) |
S4—Hg1—S1 | 107.46 (11) | N2—Mn1—N3 | 91.2 (3) |
S2—Hg1—S1 | 113.84 (11) | N4—Mn1—N3 | 86.9 (3) |
S3—Hg1—S1 | 105.97 (12) | C1—N1—Mn1 | 163.3 (9) |
O2—Mn1—O1 | 177.8 (3) | C2—N2—Mn1 | 161.1 (9) |
O2—Mn1—N2 | 90.7 (3) | C3—N3—Mn1 | 149.6 (9) |
O1—Mn1—N2 | 87.9 (3) | C4—N4—Mn1 | 150.5 (9) |
O2—Mn1—N1 | 87.1 (3) | N1—C1—S1 | 179.4 (11) |
O1—Mn1—N1 | 91.3 (3) | N2—C2—S3i | 178.7 (10) |
N2—Mn1—N1 | 94.4 (3) | N3—C3—S2ii | 177.9 (10) |
O2—Mn1—N4 | 95.1 (3) | N4—C4—S4iii | 178.6 (10) |
O1—Mn1—N4 | 86.4 (3) |
Symmetry codes: (i) x, y−1, z; (ii) x−1, y−1, z; (iii) x−1, y, z. |
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 —S═C═N— 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.