The title compound, [Hg2(C14H13N4S)2I2], is a dimeric complex of mercury(II) with the N,N,S-tridentate electron-donor Schiff base ligand and lies on a crystallographic twofold axis. The two Hg atoms are linked by two bridging S atoms, forming a rectangular base with Hg—S bond lengths of 2.6490 (12) and 2.6173 (11) Å. The two tridentate ligands are almost perpendicular to the base, resulting in an open box-like structure. The geometry of the Hg atoms is between trigonal bipyramidal and square pyramidal, but closer to the latter.
Supporting information
CCDC reference: 269365
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.026
- wR factor = 0.068
- Data-to-parameter ratio = 20.4
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Hg1 - S1 .. 33.30 su
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Hg1 - S1_a .. 24.79 su
Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.26
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 32.00 A 3
0 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
3 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
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
Bis[µ-1-(2-pyridyl-
κN)ethanone
4-phenylthiosemicarbazonato-
κ2N1,
S]bis[iodomercury(II)]
top
Crystal data top
[Hg2(C14H13N4S)2I2] | F(000) = 2192 |
Mr = 1193.67 | Dx = 2.377 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 8944 reflections |
a = 18.466 (3) Å | θ = 1.8–27.6° |
b = 16.745 (2) Å | µ = 11.20 mm−1 |
c = 13.9140 (19) Å | T = 293 K |
β = 129.174 (2)° | Block, colourless |
V = 3335.3 (8) Å3 | 0.38 × 0.18 × 0.13 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3875 independent reflections |
Radiation source: fine-focus sealed tube | 3277 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 83.66 pixels mm-1 | θmax = 27.6°, θmin = 1.8° |
ω scans | h = −24→24 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −21→21 |
Tmin = 0.072, Tmax = 0.233 | l = −18→18 |
21199 measured reflections | |
Refinement top
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0336P)2 + 5.0737P] where P = (Fo2 + 2Fc2)/3 |
3875 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 1.31 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Hg1 | 0.57060 (1) | 0.17471 (2) | 0.41619 (2) | 0.05013 (8) | |
I1 | 0.60536 (2) | 0.30807 (2) | 0.54338 (4) | 0.07217 (13) | |
S1 | 0.60992 (7) | 0.16663 (6) | 0.26337 (11) | 0.0418 (2) | |
N1 | 0.7105 (2) | 0.0386 (2) | 0.3607 (3) | 0.0439 (8) | |
H1A | 0.7477 | 0.0775 | 0.4050 | 0.053* | |
N2 | 0.4387 (2) | 0.0090 (2) | 0.3086 (3) | 0.0413 (7) | |
N3 | 0.5270 (2) | 0.03771 (19) | 0.4022 (3) | 0.0385 (7) | |
N4 | 0.6987 (3) | 0.0940 (2) | 0.5749 (3) | 0.0492 (9) | |
C1 | 0.8462 (4) | −0.0377 (3) | 0.5053 (5) | 0.0585 (12) | |
H1B | 0.8765 | 0.0101 | 0.5443 | 0.070* | |
C2 | 0.8935 (5) | −0.1084 (4) | 0.5512 (6) | 0.0776 (17) | |
H2C | 0.9562 | −0.1085 | 0.6213 | 0.093* | |
C3 | 0.8497 (6) | −0.1787 (4) | 0.4952 (8) | 0.096 (2) | |
H3A | 0.8815 | −0.2268 | 0.5280 | 0.115* | |
C4 | 0.7582 (5) | −0.1776 (3) | 0.3902 (7) | 0.089 (2) | |
H4A | 0.7289 | −0.2255 | 0.3503 | 0.107* | |
C5 | 0.7085 (4) | −0.1075 (3) | 0.3418 (5) | 0.0643 (13) | |
H5A | 0.6461 | −0.1077 | 0.2709 | 0.077* | |
C6 | 0.7533 (3) | −0.0373 (3) | 0.4010 (4) | 0.0465 (10) | |
C7 | 0.6228 (3) | 0.0618 (2) | 0.2664 (4) | 0.0388 (9) | |
C8 | 0.5898 (3) | −0.0146 (2) | 0.4739 (4) | 0.0405 (9) | |
C9 | 0.5720 (4) | −0.1017 (3) | 0.4602 (5) | 0.0621 (13) | |
H9A | 0.5077 | −0.1117 | 0.3908 | 0.093* | |
H9B | 0.5855 | −0.1226 | 0.5342 | 0.093* | |
H9C | 0.6113 | −0.1274 | 0.4465 | 0.093* | |
C10 | 0.6841 (3) | 0.0156 (3) | 0.5742 (4) | 0.0418 (9) | |
C11 | 0.7824 (4) | 0.1238 (3) | 0.6622 (5) | 0.0618 (13) | |
H11A | 0.7911 | 0.1784 | 0.6615 | 0.074* | |
C12 | 0.8568 (4) | 0.0790 (4) | 0.7534 (5) | 0.0661 (14) | |
H12A | 0.9151 | 0.1020 | 0.8122 | 0.079* | |
C13 | 0.8424 (4) | −0.0015 (4) | 0.7553 (5) | 0.0659 (14) | |
H13A | 0.8908 | −0.0339 | 0.8174 | 0.079* | |
C14 | 0.7561 (3) | −0.0332 (3) | 0.6646 (4) | 0.0548 (12) | |
H14A | 0.7459 | −0.0876 | 0.6639 | 0.066* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Hg1 | 0.05786 (13) | 0.02722 (10) | 0.05052 (11) | −0.00165 (7) | 0.02720 (9) | −0.00433 (6) |
I1 | 0.0549 (2) | 0.04750 (19) | 0.0834 (3) | −0.00232 (15) | 0.02905 (19) | −0.02969 (17) |
S1 | 0.0399 (5) | 0.0300 (5) | 0.0548 (6) | 0.0008 (4) | 0.0296 (5) | 0.0045 (4) |
N1 | 0.0431 (19) | 0.0367 (18) | 0.051 (2) | 0.0068 (15) | 0.0292 (17) | 0.0000 (15) |
N2 | 0.0462 (19) | 0.0324 (17) | 0.051 (2) | −0.0051 (15) | 0.0331 (17) | −0.0025 (15) |
N3 | 0.0459 (19) | 0.0316 (17) | 0.0463 (18) | −0.0010 (14) | 0.0331 (17) | 0.0003 (14) |
N4 | 0.052 (2) | 0.041 (2) | 0.047 (2) | −0.0019 (16) | 0.0271 (18) | −0.0013 (16) |
C1 | 0.059 (3) | 0.053 (3) | 0.060 (3) | 0.016 (2) | 0.036 (3) | 0.013 (2) |
C2 | 0.071 (4) | 0.069 (4) | 0.080 (4) | 0.029 (3) | 0.042 (3) | 0.025 (3) |
C3 | 0.102 (5) | 0.049 (4) | 0.116 (6) | 0.036 (3) | 0.059 (5) | 0.032 (3) |
C4 | 0.087 (5) | 0.044 (3) | 0.110 (5) | 0.018 (3) | 0.050 (4) | 0.011 (3) |
C5 | 0.071 (3) | 0.039 (3) | 0.079 (4) | 0.014 (2) | 0.045 (3) | 0.011 (2) |
C6 | 0.059 (3) | 0.043 (2) | 0.053 (3) | 0.016 (2) | 0.043 (2) | 0.0128 (19) |
C7 | 0.049 (2) | 0.032 (2) | 0.049 (2) | 0.0100 (17) | 0.037 (2) | 0.0069 (17) |
C8 | 0.053 (2) | 0.0300 (19) | 0.048 (2) | 0.0032 (17) | 0.037 (2) | 0.0034 (17) |
C9 | 0.082 (4) | 0.032 (2) | 0.074 (3) | 0.002 (2) | 0.049 (3) | 0.004 (2) |
C10 | 0.054 (2) | 0.040 (2) | 0.041 (2) | 0.0072 (19) | 0.035 (2) | 0.0053 (17) |
C11 | 0.066 (3) | 0.048 (3) | 0.056 (3) | −0.008 (2) | 0.031 (3) | −0.003 (2) |
C12 | 0.047 (3) | 0.085 (4) | 0.053 (3) | −0.006 (3) | 0.026 (2) | 0.003 (3) |
C13 | 0.051 (3) | 0.085 (4) | 0.057 (3) | 0.016 (3) | 0.032 (3) | 0.022 (3) |
C14 | 0.063 (3) | 0.050 (3) | 0.061 (3) | 0.013 (2) | 0.044 (3) | 0.018 (2) |
Geometric parameters (Å, º) top
Hg1—N4 | 2.387 (4) | C3—C4 | 1.367 (10) |
Hg1—N3 | 2.398 (3) | C3—H3A | 0.9300 |
Hg1—S1i | 2.6173 (11) | C4—C5 | 1.376 (7) |
Hg1—S1 | 2.6490 (12) | C4—H4A | 0.9300 |
Hg1—I1 | 2.6635 (4) | C5—C6 | 1.372 (7) |
S1—C7 | 1.768 (4) | C5—H5A | 0.9300 |
S1—Hg1i | 2.6173 (11) | C7—N2i | 1.290 (5) |
N1—C7 | 1.346 (5) | C8—C10 | 1.472 (6) |
N1—C6 | 1.413 (5) | C8—C9 | 1.481 (6) |
N1—H1A | 0.8600 | C9—H9A | 0.9600 |
N2—C7i | 1.290 (5) | C9—H9B | 0.9600 |
N2—N3 | 1.379 (5) | C9—H9C | 0.9600 |
N3—C8 | 1.283 (5) | C10—C14 | 1.379 (6) |
N4—C11 | 1.319 (6) | C11—C12 | 1.362 (7) |
N4—C10 | 1.339 (5) | C11—H11A | 0.9300 |
C1—C2 | 1.368 (7) | C12—C13 | 1.378 (8) |
C1—C6 | 1.380 (7) | C12—H12A | 0.9300 |
C1—H1B | 0.9300 | C13—C14 | 1.369 (7) |
C2—C3 | 1.359 (9) | C13—H13A | 0.9300 |
C2—H2C | 0.9300 | C14—H14A | 0.9300 |
| | | |
N4—Hg1—N3 | 67.63 (12) | C5—C4—H4A | 119.1 |
N4—Hg1—S1i | 140.71 (9) | C6—C5—C4 | 118.3 (6) |
N3—Hg1—S1i | 73.32 (9) | C6—C5—H5A | 120.9 |
N4—Hg1—S1 | 95.73 (9) | C4—C5—H5A | 120.9 |
N3—Hg1—S1 | 97.71 (8) | C5—C6—C1 | 120.4 (4) |
S1i—Hg1—S1 | 93.48 (3) | C5—C6—N1 | 124.0 (4) |
N4—Hg1—I1 | 100.24 (9) | C1—C6—N1 | 115.6 (4) |
N3—Hg1—I1 | 141.58 (8) | N2i—C7—N1 | 119.6 (4) |
S1i—Hg1—I1 | 107.74 (2) | N2i—C7—S1 | 128.6 (3) |
S1—Hg1—I1 | 120.20 (2) | N1—C7—S1 | 111.8 (3) |
C7—S1—Hg1i | 98.36 (15) | N3—C8—C10 | 116.8 (4) |
C7—S1—Hg1 | 97.64 (13) | N3—C8—C9 | 123.6 (4) |
Hg1i—S1—Hg1 | 86.22 (3) | C10—C8—C9 | 119.6 (4) |
C7—N1—C6 | 132.3 (4) | C8—C9—H9A | 109.5 |
C7—N1—H1A | 113.8 | C8—C9—H9B | 109.5 |
C6—N1—H1A | 113.8 | H9A—C9—H9B | 109.5 |
C7i—N2—N3 | 115.9 (3) | C8—C9—H9C | 109.5 |
C8—N3—N2 | 116.5 (3) | H9A—C9—H9C | 109.5 |
C8—N3—Hg1 | 119.8 (3) | H9B—C9—H9C | 109.5 |
N2—N3—Hg1 | 123.1 (2) | N4—C10—C14 | 120.0 (4) |
C11—N4—C10 | 119.4 (4) | N4—C10—C8 | 117.1 (4) |
C11—N4—Hg1 | 122.5 (3) | C14—C10—C8 | 122.9 (4) |
C10—N4—Hg1 | 118.1 (3) | N4—C11—C12 | 123.7 (5) |
C2—C1—C6 | 119.9 (5) | N4—C11—H11A | 118.1 |
C2—C1—H1B | 120.1 | C12—C11—H11A | 118.1 |
C6—C1—H1B | 120.1 | C11—C12—C13 | 117.6 (5) |
C3—C2—C1 | 120.6 (6) | C11—C12—H12A | 121.2 |
C3—C2—H2C | 119.7 | C13—C12—H12A | 121.2 |
C1—C2—H2C | 119.7 | C14—C13—C12 | 119.2 (5) |
C2—C3—C4 | 119.2 (5) | C14—C13—H13A | 120.4 |
C2—C3—H3A | 120.4 | C12—C13—H13A | 120.4 |
C4—C3—H3A | 120.4 | C13—C14—C10 | 120.1 (5) |
C3—C4—C5 | 121.7 (6) | C13—C14—H14A | 120.0 |
C3—C4—H4A | 119.1 | C10—C14—H14A | 120.0 |
| | | |
N4—Hg1—S1—C7 | 49.76 (17) | C4—C5—C6—N1 | 179.6 (5) |
N3—Hg1—S1—C7 | −18.37 (17) | C2—C1—C6—C5 | −1.1 (7) |
S1i—Hg1—S1—C7 | −92.00 (15) | C2—C1—C6—N1 | −180.0 (5) |
I1—Hg1—S1—C7 | 155.13 (14) | C7—N1—C6—C5 | 2.5 (7) |
N4—Hg1—S1—Hg1i | 147.70 (9) | C7—N1—C6—C1 | −178.6 (4) |
N3—Hg1—S1—Hg1i | 79.56 (9) | C6—N1—C7—N2i | −1.8 (7) |
S1i—Hg1—S1—Hg1i | 5.94 (4) | C6—N1—C7—S1 | 179.1 (4) |
I1—Hg1—S1—Hg1i | −106.93 (2) | Hg1i—S1—C7—N2i | 6.6 (4) |
C7i—N2—N3—C8 | −177.0 (4) | Hg1—S1—C7—N2i | 93.9 (4) |
C7i—N2—N3—Hg1 | −6.1 (5) | Hg1i—S1—C7—N1 | −174.4 (3) |
N4—Hg1—N3—C8 | −6.3 (3) | Hg1—S1—C7—N1 | −87.1 (3) |
S1i—Hg1—N3—C8 | 178.1 (3) | N2—N3—C8—C10 | −179.9 (3) |
S1—Hg1—N3—C8 | 86.8 (3) | Hg1—N3—C8—C10 | 8.9 (5) |
I1—Hg1—N3—C8 | −84.2 (3) | N2—N3—C8—C9 | 0.4 (6) |
N4—Hg1—N3—N2 | −176.8 (3) | Hg1—N3—C8—C9 | −170.8 (3) |
S1i—Hg1—N3—N2 | 7.5 (3) | C11—N4—C10—C14 | 0.4 (6) |
S1—Hg1—N3—N2 | −83.8 (3) | Hg1—N4—C10—C14 | −179.6 (3) |
I1—Hg1—N3—N2 | 105.3 (3) | C11—N4—C10—C8 | −179.3 (4) |
N3—Hg1—N4—C11 | −177.5 (4) | Hg1—N4—C10—C8 | 0.6 (5) |
S1i—Hg1—N4—C11 | −170.8 (3) | N3—C8—C10—N4 | −6.3 (5) |
S1—Hg1—N4—C11 | 86.5 (4) | C9—C8—C10—N4 | 173.4 (4) |
I1—Hg1—N4—C11 | −35.6 (4) | N3—C8—C10—C14 | 174.0 (4) |
N3—Hg1—N4—C10 | 2.6 (3) | C9—C8—C10—C14 | −6.3 (6) |
S1i—Hg1—N4—C10 | 9.2 (4) | C10—N4—C11—C12 | 0.4 (8) |
S1—Hg1—N4—C10 | −93.4 (3) | Hg1—N4—C11—C12 | −179.6 (4) |
I1—Hg1—N4—C10 | 144.5 (3) | N4—C11—C12—C13 | −1.6 (8) |
C6—C1—C2—C3 | −0.3 (9) | C11—C12—C13—C14 | 2.0 (8) |
C1—C2—C3—C4 | 1.9 (11) | C12—C13—C14—C10 | −1.3 (8) |
C2—C3—C4—C5 | −2.2 (13) | N4—C10—C14—C13 | 0.1 (7) |
C3—C4—C5—C6 | 0.8 (11) | C8—C10—C14—C13 | 179.8 (4) |
C4—C5—C6—C1 | 0.8 (8) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···N2 | 0.96 | 2.27 | 2.718 (7) | 107 |
C5—H5A···N2i | 0.93 | 2.30 | 2.896 (7) | 121 |
N1—H1A···I1ii | 0.86 | 3.01 | 3.769 (4) | 147 |
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+3/2, −y+1/2, −z+1. |