



Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810030424/wm2389sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810030424/wm2389Isup2.hkl |
CCDC reference: 792246
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean
(N-C) = 0.008 Å
- R factor = 0.017
- wR factor = 0.036
- Data-to-parameter ratio = 16.5
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Hg1 -- S1 .. 5.32 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Hg1 -- C4 .. 6.15 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
To 0.25 g (1.0 mmol) mercury(II) cyanide in 10 ml methanol was added 2 equivalents of N,N'-dimethylthiourea in methanol. On mixing, a clear solution was obtained. It was then stirred for 30 minutes after which it was filtered and the filtrate kept at RT for crystallization by slow evaporation of the solvent. As a result, colourless block-like crystals, suitable for X-ray diffraction analysis, were obtained.
The NH H-atoms were located in difference electron-density maps and were freely refined: N—H = 0.80 (6) & 0.79 (5) Å. The C-bound H-atoms were included in calculated positions and treated as riding atoms: C—H = 0.98 Å, with Uiso(H) = 1.5Ueq(parent C-atom).
The structural characterization of mercury(II) complexes of thioamides is an important aspect of inorganic chemistry because such complexes can be used as models for metal-sulfur interactions in biological systems (Akrivos, 2001; Bell et al., 2001; Popovic et al., 2000). Several crystallographic reports about mercury(II) complexes of the type, L2HgX2 (L = thiourea or its derivatives) reveal that these complexes usually consist of discrete monomeric molecules with tetrahedral (somewhat distorted) coordination environments around mercury(II) (Ahmad et al., 2009; Bell et al., 2001; Jiang et al., 2001; Lobana et al., 2008; Mufakkar et al., 2010; Nawaz et al., 2010; Popovic et al., 2000; Wu et al., 2004). Recently, we have reported the crystal structures of a number of cyanido complexes of d10 metal ions with L-type ligands, including the crystal structure of a trinuclear complex, [{(tmtu)2Hg(CN)2}2.Hg(CN)2] (tmtu = tetramethylthiourea), which presents a unique example of a Hg(CN)2 bridged mercury(II)-thione complex (Ahmad et al., 2009; Altaf et al., 2010; Fettouhi et al. 2010; Hanif et al., 2007). Herein, we report on the crystal structure of the title mercury cyanide complex of N,N'-dimethylthiourea, [Hg(dmtu)2(CN)2].
The title monomeric complex is composed of an Hg(CN)2 unit with two N,N'-dimethylthiourea (dmtu) ligands coordinated to the Hg atom via the S atom (Fig. 1). The four-coordinate mercury atom is located on a two-fold rotation axis and adopts a severely distorted tetrahedral geometry, the bond angles being in the range of 94.31 (3) - 148.83 (13)°. The molecular structure is stabilized by intramolecular N-H···S interactions involving dmtu units related by the two-fold symmetry (Fig. 1, Table 1). The bond distances and bond angles are in agreement with those reported for related compounds (Ahmad et al., 2009; Altaf et al., 2010; Jiang et al., 2001; Lobana et al., 2008; Mufakkar et al., 2010; Nawaz et al., 2010; Popovic et al., 2000; Wu et al., 2004). The SCN2 moiety of dmtu is planar [to within 0.002 (1) Å] with the C—N and C—S bond lengths corresponding to the values intermediate between single and double bonds. The Hg-C≡N unit is nearly linear with a bond angle of 175.3 (3)°. The compound is closely related with [Hg(N,N'-dibutylthiourea)2(CN)2] (Ahmad et al., 2009).
In the crystal packing of the title complex, symmetry-related molecules are connected via intermolecular N—H···N hydrogen bonds, involving the thiourea NH atoms and the N atom of the CN- anions (Fig. 2, Table 1). This gives rise to the formation of a two-dimensional network in (110). This is the same arrangement as observed previously for the dibutylthiourea compound mentioned above.
For biological applications of mercury(II) complexes of thiones, see: Akrivos (2001); Bell et al. (2001); Popovic et al. (2000). For background to mercury(II) complexes of thiourea and its derivatives, see: Ahmad et al. (2009); Jiang et al. (2001); Lobana et al. (2008); Mufakkar et al. (2010); Nawaz et al. (2010); Popovic et al. (2000); Wu et al. (2004). For the crystal structures of cyanide complexes of d10 metals, see: Ahmad et al. (2009); Altaf et al. (2010); Fettouhi et al. (2010); Hanif et al. (2007).
Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
[Hg(CN)2(C3H8N2S)2] | F(000) = 872 |
Mr = 460.98 | Dx = 1.983 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 12331 reflections |
a = 18.1161 (11) Å | θ = 1.9–26.1° |
b = 7.7533 (5) Å | µ = 10.23 mm−1 |
c = 14.0553 (8) Å | T = 173 K |
β = 128.533 (3)° | Block, colourless |
V = 1544.32 (16) Å3 | 0.40 × 0.31 × 0.25 mm |
Z = 4 |
Stoe IPDS 2 diffractometer | 1451 independent reflections |
Radiation source: fine-focus sealed tube | 1411 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
φ– + ω– scans | θmax = 25.6°, θmin = 2.9° |
Absorption correction: multi-scan (MULscanABS embedded in PLATON; Spek, 2009) | h = −21→21 |
Tmin = 0.270, Tmax = 1.000 | k = −9→9 |
8116 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.017 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0129P)2 + 2.6833P] where P = (Fo2 + 2Fc2)/3 |
1451 reflections | (Δ/σ)max < 0.001 |
88 parameters | Δρmax = 0.68 e Å−3 |
0 restraints | Δρmin = −1.97 e Å−3 |
[Hg(CN)2(C3H8N2S)2] | V = 1544.32 (16) Å3 |
Mr = 460.98 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.1161 (11) Å | µ = 10.23 mm−1 |
b = 7.7533 (5) Å | T = 173 K |
c = 14.0553 (8) Å | 0.40 × 0.31 × 0.25 mm |
β = 128.533 (3)° |
Stoe IPDS 2 diffractometer | 1451 independent reflections |
Absorption correction: multi-scan (MULscanABS embedded in PLATON; Spek, 2009) | 1411 reflections with I > 2σ(I) |
Tmin = 0.270, Tmax = 1.000 | Rint = 0.049 |
8116 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | 0 restraints |
wR(F2) = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.68 e Å−3 |
1451 reflections | Δρmin = −1.97 e Å−3 |
88 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | 0.50000 | −0.21587 (2) | 0.25000 | 0.0231 (1) | |
S1 | 0.37952 (6) | 0.02195 (11) | 0.08082 (7) | 0.0255 (3) | |
N1 | 0.3941 (2) | 0.1650 (4) | 0.2640 (3) | 0.0277 (9) | |
N2 | 0.2450 (2) | 0.0856 (4) | 0.1004 (2) | 0.0241 (8) | |
N3 | 0.3776 (3) | −0.3173 (4) | 0.3370 (3) | 0.0441 (12) | |
C1 | 0.3355 (2) | 0.0948 (4) | 0.1535 (3) | 0.0210 (9) | |
C2 | 0.3657 (3) | 0.2174 (5) | 0.3367 (3) | 0.0386 (13) | |
C3 | 0.1748 (2) | 0.0052 (5) | −0.0168 (3) | 0.0306 (11) | |
C4 | 0.4229 (3) | −0.2883 (4) | 0.3084 (3) | 0.0295 (10) | |
H1N | 0.449 (3) | 0.161 (5) | 0.296 (3) | 0.024 (10)* | |
H2A | 0.31970 | 0.31150 | 0.29540 | 0.0580* | |
H2B | 0.42120 | 0.25690 | 0.41680 | 0.0580* | |
H2C | 0.33710 | 0.11910 | 0.34680 | 0.0580* | |
H2N | 0.227 (3) | 0.128 (5) | 0.134 (3) | 0.030 (10)* | |
H3A | 0.17870 | 0.05510 | −0.07770 | 0.0460* | |
H3B | 0.11180 | 0.02530 | −0.04110 | 0.0460* | |
H3C | 0.18680 | −0.11920 | −0.01060 | 0.0460* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0209 (1) | 0.0274 (1) | 0.0294 (1) | 0.0000 | 0.0197 (1) | 0.0000 |
S1 | 0.0249 (5) | 0.0344 (4) | 0.0242 (4) | 0.0067 (3) | 0.0188 (4) | 0.0020 (3) |
N1 | 0.0244 (18) | 0.0359 (17) | 0.0275 (13) | 0.0008 (14) | 0.0185 (14) | −0.0045 (12) |
N2 | 0.0225 (16) | 0.0279 (15) | 0.0273 (13) | 0.0015 (11) | 0.0181 (12) | −0.0035 (11) |
N3 | 0.040 (2) | 0.058 (2) | 0.054 (2) | −0.0070 (17) | 0.0389 (19) | 0.0028 (16) |
C1 | 0.0236 (18) | 0.0192 (15) | 0.0255 (14) | 0.0042 (12) | 0.0179 (14) | 0.0031 (11) |
C2 | 0.041 (3) | 0.050 (2) | 0.0352 (18) | −0.0019 (18) | 0.0288 (19) | −0.0128 (16) |
C3 | 0.022 (2) | 0.0341 (19) | 0.0336 (16) | −0.0025 (15) | 0.0163 (16) | −0.0047 (14) |
C4 | 0.028 (2) | 0.0288 (17) | 0.0344 (16) | −0.0018 (15) | 0.0207 (16) | 0.0009 (14) |
Hg1—S1 | 2.7114 (9) | N3—C4 | 1.139 (8) |
Hg1—C4 | 2.090 (6) | N1—H1N | 0.80 (6) |
Hg1—S1i | 2.7114 (9) | N2—H2N | 0.79 (5) |
Hg1—C4i | 2.090 (6) | C2—H2A | 0.9800 |
S1—C1 | 1.736 (4) | C2—H2B | 0.9800 |
N1—C1 | 1.335 (5) | C2—H2C | 0.9800 |
N1—C2 | 1.459 (7) | C3—H3A | 0.9800 |
N2—C1 | 1.314 (6) | C3—H3B | 0.9800 |
N2—C3 | 1.452 (4) | C3—H3C | 0.9800 |
S1—Hg1—C4 | 99.05 (11) | S1—C1—N1 | 119.6 (3) |
S1—Hg1—S1i | 94.31 (3) | Hg1—C4—N3 | 175.3 (3) |
S1—Hg1—C4i | 102.01 (9) | N1—C2—H2A | 109.00 |
S1i—Hg1—C4 | 102.01 (9) | N1—C2—H2B | 110.00 |
C4—Hg1—C4i | 148.83 (13) | N1—C2—H2C | 109.00 |
S1i—Hg1—C4i | 99.05 (11) | H2A—C2—H2B | 109.00 |
Hg1—S1—C1 | 96.84 (11) | H2A—C2—H2C | 109.00 |
C1—N1—C2 | 123.8 (4) | H2B—C2—H2C | 109.00 |
C1—N2—C3 | 124.7 (3) | N2—C3—H3A | 109.00 |
C1—N1—H1N | 117 (3) | N2—C3—H3B | 110.00 |
C2—N1—H1N | 118 (3) | N2—C3—H3C | 109.00 |
C3—N2—H2N | 117 (3) | H3A—C3—H3B | 110.00 |
C1—N2—H2N | 118 (3) | H3A—C3—H3C | 109.00 |
S1—C1—N2 | 121.1 (3) | H3B—C3—H3C | 109.00 |
N1—C1—N2 | 119.3 (4) | ||
C4—Hg1—S1—C1 | 32.52 (15) | C2—N1—C1—S1 | −174.9 (3) |
S1i—Hg1—S1—C1 | −70.39 (13) | C2—N1—C1—N2 | 6.6 (5) |
C4i—Hg1—S1—C1 | −170.60 (16) | C3—N2—C1—S1 | 4.6 (5) |
Hg1—S1—C1—N1 | 60.6 (3) | C3—N2—C1—N1 | −177.0 (3) |
Hg1—S1—C1—N2 | −121.0 (3) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···S1i | 0.80 (6) | 2.67 (5) | 3.415 (4) | 157 (4) |
N2—H2N···N3ii | 0.79 (5) | 2.21 (6) | 2.951 (7) | 155 (4) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Hg(CN)2(C3H8N2S)2] |
Mr | 460.98 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 18.1161 (11), 7.7533 (5), 14.0553 (8) |
β (°) | 128.533 (3) |
V (Å3) | 1544.32 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.23 |
Crystal size (mm) | 0.40 × 0.31 × 0.25 |
Data collection | |
Diffractometer | Stoe IPDS 2 |
Absorption correction | Multi-scan (MULscanABS embedded in PLATON; Spek, 2009) |
Tmin, Tmax | 0.270, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8116, 1451, 1411 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.036, 1.14 |
No. of reflections | 1451 |
No. of parameters | 88 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.68, −1.97 |
Computer programs: X-AREA (Stoe & Cie, 2009), X-RED32 (Stoe & Cie, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXL97 and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···S1i | 0.80 (6) | 2.67 (5) | 3.415 (4) | 157 (4) |
N2—H2N···N3ii | 0.79 (5) | 2.21 (6) | 2.951 (7) | 155 (4) |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2. |
The structural characterization of mercury(II) complexes of thioamides is an important aspect of inorganic chemistry because such complexes can be used as models for metal-sulfur interactions in biological systems (Akrivos, 2001; Bell et al., 2001; Popovic et al., 2000). Several crystallographic reports about mercury(II) complexes of the type, L2HgX2 (L = thiourea or its derivatives) reveal that these complexes usually consist of discrete monomeric molecules with tetrahedral (somewhat distorted) coordination environments around mercury(II) (Ahmad et al., 2009; Bell et al., 2001; Jiang et al., 2001; Lobana et al., 2008; Mufakkar et al., 2010; Nawaz et al., 2010; Popovic et al., 2000; Wu et al., 2004). Recently, we have reported the crystal structures of a number of cyanido complexes of d10 metal ions with L-type ligands, including the crystal structure of a trinuclear complex, [{(tmtu)2Hg(CN)2}2.Hg(CN)2] (tmtu = tetramethylthiourea), which presents a unique example of a Hg(CN)2 bridged mercury(II)-thione complex (Ahmad et al., 2009; Altaf et al., 2010; Fettouhi et al. 2010; Hanif et al., 2007). Herein, we report on the crystal structure of the title mercury cyanide complex of N,N'-dimethylthiourea, [Hg(dmtu)2(CN)2].
The title monomeric complex is composed of an Hg(CN)2 unit with two N,N'-dimethylthiourea (dmtu) ligands coordinated to the Hg atom via the S atom (Fig. 1). The four-coordinate mercury atom is located on a two-fold rotation axis and adopts a severely distorted tetrahedral geometry, the bond angles being in the range of 94.31 (3) - 148.83 (13)°. The molecular structure is stabilized by intramolecular N-H···S interactions involving dmtu units related by the two-fold symmetry (Fig. 1, Table 1). The bond distances and bond angles are in agreement with those reported for related compounds (Ahmad et al., 2009; Altaf et al., 2010; Jiang et al., 2001; Lobana et al., 2008; Mufakkar et al., 2010; Nawaz et al., 2010; Popovic et al., 2000; Wu et al., 2004). The SCN2 moiety of dmtu is planar [to within 0.002 (1) Å] with the C—N and C—S bond lengths corresponding to the values intermediate between single and double bonds. The Hg-C≡N unit is nearly linear with a bond angle of 175.3 (3)°. The compound is closely related with [Hg(N,N'-dibutylthiourea)2(CN)2] (Ahmad et al., 2009).
In the crystal packing of the title complex, symmetry-related molecules are connected via intermolecular N—H···N hydrogen bonds, involving the thiourea NH atoms and the N atom of the CN- anions (Fig. 2, Table 1). This gives rise to the formation of a two-dimensional network in (110). This is the same arrangement as observed previously for the dibutylthiourea compound mentioned above.