Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030060/hb6265sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030060/hb6265Isup2.hkl |
CCDC reference: 287567
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.005 Å
- R factor = 0.020
- wR factor = 0.056
- Data-to-parameter ratio = 17.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.41 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C5 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N4 PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ? PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.19 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 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 3 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 2 ALERT type 4 Improvement, methodology, query or suggestion
IM-thz was synthesized using a method in the literature (Ullman et al., 1972 or ??1970). Diethyl ether vapor was diffused into acetonitrile solution (6 ml) containing Hg(NO3)2 (0.25 mmol) and IM-thz (0.5 mmol) in a closed vessel in the dark for two weeks, affording red blocks of (I) suitable for X-ray analysis. Analysis calculated for C20H30HgS2N8O8: C 30.98, H 3.90, N 14.46%; found: C 31.03, H 3.81, N 14.37%.
The H atoms were located geometrically and refined using the riding-model approximation, with C—H = 0.93 or 0.96 Å and O—H = 0.82 Å and Uiso(H) = 1.2Ueq(carrier) or Uiso(H) = 1.5Ueq(methyl carrier).
Data collection: APEX II (Bruker, 2004); cell refinement: APEX II; data reduction: SAINT (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 2004); software used to prepare material for publication: SHELXTL.
[Hg(C10H15N3OS)2(NO3)2] | F(000) = 1528 |
Mr = 775.22 | Dx = 1.839 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6354 reflections |
a = 19.758 (4) Å | θ = 2.3–28.7° |
b = 13.580 (3) Å | µ = 5.70 mm−1 |
c = 11.587 (3) Å | T = 295 K |
β = 115.739 (3)° | Block, red |
V = 2800.3 (11) Å3 | 0.36 × 0.24 × 0.15 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 3212 independent reflections |
Radiation source: fine-focus sealed tube | 2498 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −25→25 |
Tmin = 0.202, Tmax = 0.425 | k = −17→17 |
11946 measured reflections | l = −15→14 |
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)] = 0.020 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0288P)2 + 3.1412P] where P = (Fo2 + 2Fc2)/3 |
3212 reflections | (Δ/σ)max < 0.001 |
183 parameters | Δρmax = 0.96 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Hg(C10H15N3OS)2(NO3)2] | V = 2800.3 (11) Å3 |
Mr = 775.22 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.758 (4) Å | µ = 5.70 mm−1 |
b = 13.580 (3) Å | T = 295 K |
c = 11.587 (3) Å | 0.36 × 0.24 × 0.15 mm |
β = 115.739 (3)° |
Bruker SMART APEX CCD diffractometer | 3212 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2498 reflections with I > 2σ(I) |
Tmin = 0.202, Tmax = 0.425 | Rint = 0.016 |
11946 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.96 e Å−3 |
3212 reflections | Δρmin = −0.40 e Å−3 |
183 parameters |
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 | 0.2500 | 0.2500 | 0.5000 | 0.04859 (6) | |
S1 | 0.43205 (5) | 0.48240 (6) | 0.82883 (8) | 0.0656 (2) | |
O1 | 0.45347 (14) | 0.31673 (16) | 0.9825 (2) | 0.0702 (6) | |
H1 | 0.4980 | 0.3012 | 1.0159 | 0.105* | |
O2 | 0.4047 (2) | 0.2581 (2) | 0.4725 (4) | 0.1045 (12) | |
O3 | 0.4007 (2) | 0.2036 (3) | 0.2983 (3) | 0.1112 (10) | |
O4 | 0.32587 (17) | 0.1501 (2) | 0.3728 (4) | 0.1127 (11) | |
N1 | 0.33715 (14) | 0.42170 (17) | 0.6085 (2) | 0.0523 (6) | |
N2 | 0.32075 (15) | 0.22847 (17) | 0.6903 (2) | 0.0473 (5) | |
N3 | 0.41408 (16) | 0.25380 (14) | 0.8804 (3) | 0.0523 (6) | |
N4 | 0.37707 (17) | 0.2034 (2) | 0.3807 (3) | 0.0674 (7) | |
C1 | 0.40165 (18) | 0.5627 (2) | 0.7046 (3) | 0.0643 (8) | |
H1A | 0.4167 | 0.6281 | 0.7102 | 0.077* | |
C2 | 0.35261 (18) | 0.5186 (2) | 0.5967 (3) | 0.0572 (7) | |
H2 | 0.3306 | 0.5517 | 0.5188 | 0.069* | |
C3 | 0.37655 (16) | 0.3925 (2) | 0.7267 (3) | 0.0461 (6) | |
C4 | 0.37006 (15) | 0.2924 (2) | 0.7654 (3) | 0.0426 (5) | |
C5 | 0.33397 (17) | 0.1318 (2) | 0.7599 (3) | 0.0510 (6) | |
C6 | 0.37633 (16) | 0.1656 (2) | 0.9020 (3) | 0.0506 (6) | |
C7 | 0.3818 (3) | 0.0700 (3) | 0.7140 (4) | 0.0885 (13) | |
H7A | 0.3559 | 0.0619 | 0.6228 | 0.133* | |
H7B | 0.3908 | 0.0067 | 0.7547 | 0.133* | |
H7C | 0.4289 | 0.1027 | 0.7356 | 0.133* | |
C8 | 0.2598 (2) | 0.0810 (3) | 0.7286 (3) | 0.0826 (12) | |
H8A | 0.2275 | 0.1245 | 0.7472 | 0.124* | |
H8B | 0.2685 | 0.0224 | 0.7794 | 0.124* | |
H8C | 0.2363 | 0.0639 | 0.6394 | 0.124* | |
C9 | 0.4339 (2) | 0.0927 (3) | 0.9906 (3) | 0.0790 (11) | |
H9A | 0.4724 | 0.0826 | 0.9622 | 0.119* | |
H9B | 0.4096 | 0.0312 | 0.9892 | 0.119* | |
H9C | 0.4560 | 0.1183 | 1.0763 | 0.119* | |
C10 | 0.3241 (2) | 0.1990 (3) | 0.9601 (3) | 0.0788 (10) | |
H10A | 0.3530 | 0.2306 | 1.0409 | 0.118* | |
H10B | 0.2986 | 0.1429 | 0.9728 | 0.118* | |
H10C | 0.2879 | 0.2446 | 0.9030 | 0.118* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.05756 (10) | 0.04837 (9) | 0.03641 (8) | −0.00462 (7) | 0.01720 (7) | −0.00048 (6) |
S1 | 0.0729 (5) | 0.0483 (4) | 0.0584 (4) | −0.0122 (4) | 0.0124 (4) | −0.0021 (3) |
O1 | 0.0802 (16) | 0.0499 (12) | 0.0503 (12) | 0.0002 (11) | 0.0000 (11) | −0.0045 (10) |
O2 | 0.093 (2) | 0.118 (3) | 0.102 (3) | −0.0023 (16) | 0.043 (2) | −0.0382 (18) |
O3 | 0.137 (3) | 0.129 (3) | 0.091 (2) | 0.023 (2) | 0.072 (2) | 0.017 (2) |
O4 | 0.087 (2) | 0.099 (2) | 0.161 (3) | −0.0109 (18) | 0.062 (2) | −0.017 (2) |
N1 | 0.0614 (14) | 0.0444 (12) | 0.0481 (13) | 0.0018 (11) | 0.0209 (11) | 0.0033 (10) |
N2 | 0.0561 (14) | 0.0448 (12) | 0.0390 (12) | −0.0033 (10) | 0.0186 (11) | 0.0017 (9) |
N3 | 0.0574 (14) | 0.0415 (12) | 0.0448 (13) | −0.0010 (10) | 0.0099 (11) | −0.0008 (9) |
N4 | 0.0658 (18) | 0.0631 (18) | 0.076 (2) | 0.0176 (15) | 0.0333 (16) | 0.0088 (16) |
C1 | 0.073 (2) | 0.0433 (16) | 0.073 (2) | −0.0063 (14) | 0.0286 (17) | 0.0038 (14) |
C2 | 0.0701 (19) | 0.0437 (14) | 0.0585 (17) | 0.0042 (13) | 0.0285 (15) | 0.0100 (13) |
C3 | 0.0490 (15) | 0.0413 (14) | 0.0482 (15) | 0.0000 (11) | 0.0214 (12) | −0.0024 (11) |
C4 | 0.0463 (14) | 0.0383 (13) | 0.0423 (14) | 0.0055 (11) | 0.0184 (12) | −0.0001 (11) |
C5 | 0.0664 (18) | 0.0409 (14) | 0.0477 (15) | −0.0040 (13) | 0.0265 (14) | 0.0031 (11) |
C6 | 0.0560 (16) | 0.0449 (15) | 0.0443 (14) | 0.0006 (12) | 0.0158 (13) | 0.0041 (11) |
C7 | 0.147 (4) | 0.051 (2) | 0.090 (3) | 0.020 (2) | 0.072 (3) | 0.0025 (19) |
C8 | 0.091 (3) | 0.081 (2) | 0.058 (2) | −0.034 (2) | 0.0160 (19) | 0.0144 (18) |
C9 | 0.081 (2) | 0.0545 (19) | 0.074 (2) | 0.0032 (17) | 0.0088 (19) | 0.0239 (17) |
C10 | 0.102 (3) | 0.087 (3) | 0.060 (2) | 0.001 (2) | 0.047 (2) | −0.0018 (19) |
Hg1—N2 | 2.055 (2) | C1—H1A | 0.9300 |
Hg1—N1 | 2.846 (2) | C2—H2 | 0.9300 |
Hg1—O4 | 2.859 (3) | C3—C4 | 1.455 (4) |
Hg1—N2i | 2.055 (2) | C5—C8 | 1.515 (4) |
Hg1—N1i | 2.846 (2) | C5—C7 | 1.522 (4) |
Hg1—O4i | 2.859 (3) | C5—C6 | 1.558 (4) |
S1—C1 | 1.695 (3) | C6—C9 | 1.521 (4) |
S1—C3 | 1.722 (3) | C6—C10 | 1.524 (4) |
N3—O1 | 1.391 (3) | C7—H7A | 0.9600 |
O1—H1 | 0.8200 | C7—H7B | 0.9600 |
O2—N4 | 1.214 (5) | C7—H7C | 0.9600 |
O3—N4 | 1.231 (4) | C8—H8A | 0.9600 |
O4—N4 | 1.215 (4) | C8—H8B | 0.9600 |
N1—C3 | 1.309 (4) | C8—H8C | 0.9600 |
N1—C2 | 1.371 (4) | C9—H9A | 0.9600 |
C4—N2 | 1.313 (4) | C9—H9B | 0.9600 |
N2—C5 | 1.503 (3) | C9—H9C | 0.9600 |
C4—N3 | 1.342 (4) | C10—H10A | 0.9600 |
N3—C6 | 1.488 (4) | C10—H10B | 0.9600 |
C1—C2 | 1.345 (4) | C10—H10C | 0.9600 |
N2i—Hg1—N1 | 110.89 (8) | N2—C4—C3 | 123.6 (3) |
N2—Hg1—N1 | 69.11 (8) | N3—C4—C3 | 124.4 (3) |
N2i—Hg1—O4 | 77.24 (10) | N2—C5—C8 | 110.2 (3) |
N2—Hg1—O4 | 102.76 (10) | N2—C5—C7 | 106.4 (2) |
N1—Hg1—O4 | 105.32 (8) | C8—C5—C7 | 110.4 (3) |
N1i—Hg1—O4 | 74.68 (10) | N2—C5—C6 | 101.4 (2) |
N2—Hg1—N1i | 110.89 (8) | C8—C5—C6 | 114.0 (3) |
N2i—Hg1—N1i | 69.11 (8) | C7—C5—C6 | 113.7 (3) |
N2—Hg1—O4i | 77.24 (10) | N3—C6—C9 | 110.8 (3) |
N2i—Hg1—O4i | 102.76 (10) | N3—C6—C10 | 108.6 (3) |
N1i—Hg1—O4i | 105.32 (8) | C9—C6—C10 | 110.3 (3) |
N1—Hg1—O4i | 74.68 (10) | N3—C6—C5 | 97.9 (2) |
N2i—Hg1—N2 | 180.0 | C9—C6—C5 | 115.0 (3) |
O4—Hg1—O4i | 180.0 | C10—C6—C5 | 113.5 (3) |
N1—Hg1—N1i | 180.0 | C5—C7—H7A | 109.5 |
N4—O4—Hg1 | 106.5 (2) | C5—C7—H7B | 109.5 |
C1—S1—C3 | 89.29 (15) | H7A—C7—H7B | 109.5 |
N3—O1—H1 | 109.5 | C5—C7—H7C | 109.5 |
C3—N1—C2 | 109.8 (2) | H7A—C7—H7C | 109.5 |
C4—N2—C5 | 108.4 (2) | H7B—C7—H7C | 109.5 |
C4—N2—Hg1 | 125.50 (19) | C5—C8—H8A | 109.5 |
C5—N2—Hg1 | 125.36 (18) | C5—C8—H8B | 109.5 |
C4—N3—O1 | 119.1 (2) | H8A—C8—H8B | 109.5 |
C4—N3—C6 | 109.0 (2) | C5—C8—H8C | 109.5 |
O1—N3—C6 | 119.2 (3) | H8A—C8—H8C | 109.5 |
O2—N4—O4 | 118.2 (4) | H8B—C8—H8C | 109.5 |
O2—N4—O3 | 120.0 (4) | C6—C9—H9A | 109.5 |
O4—N4—O3 | 121.7 (4) | C6—C9—H9B | 109.5 |
C2—C1—S1 | 110.4 (2) | H9A—C9—H9B | 109.5 |
C2—C1—H1A | 124.8 | C6—C9—H9C | 109.5 |
S1—C1—H1A | 124.8 | H9A—C9—H9C | 109.5 |
C1—C2—N1 | 115.9 (3) | H9B—C9—H9C | 109.5 |
C1—C2—H2 | 122.1 | C6—C10—H10A | 109.5 |
N1—C2—H2 | 122.1 | C6—C10—H10B | 109.5 |
N1—C3—C4 | 120.9 (2) | H10A—C10—H10B | 109.5 |
N1—C3—S1 | 114.6 (2) | C6—C10—H10C | 109.5 |
C4—C3—S1 | 124.5 (2) | H10A—C10—H10C | 109.5 |
N2—C4—N3 | 112.0 (2) | H10B—C10—H10C | 109.5 |
C3—S1—C1—C2 | 0.3 (3) | Hg1—N2—C5—C8 | −46.4 (3) |
S1—C1—C2—N1 | 0.5 (4) | C4—N2—C5—C7 | −97.1 (3) |
C3—N1—C2—C1 | −1.4 (4) | Hg1—N2—C5—C7 | 73.4 (3) |
C2—N1—C3—C4 | 179.4 (3) | C4—N2—C5—C6 | 22.1 (3) |
C2—N1—C3—S1 | 1.6 (3) | Hg1—N2—C5—C6 | −167.48 (19) |
C1—S1—C3—N1 | −1.1 (2) | C4—N3—C6—C9 | 152.1 (3) |
C1—S1—C3—C4 | −178.9 (3) | O1—N3—C6—C9 | −66.6 (3) |
C5—N2—C4—N3 | −2.4 (3) | C4—N3—C6—C10 | −86.6 (3) |
Hg1—N2—C4—N3 | −172.9 (2) | O1—N3—C6—C10 | 54.8 (3) |
C5—N2—C4—C3 | 176.6 (2) | C4—N3—C6—C5 | 31.5 (3) |
Hg1—N2—C4—C3 | 6.1 (4) | O1—N3—C6—C5 | 172.9 (2) |
O1—N3—C4—N2 | −161.4 (3) | N2—C5—C6—N3 | −30.4 (3) |
C6—N3—C4—N2 | −20.0 (3) | C8—C5—C6—N3 | −148.8 (3) |
O1—N3—C4—C3 | 19.6 (4) | C7—C5—C6—N3 | 83.4 (3) |
C6—N3—C4—C3 | 161.0 (3) | N2—C5—C6—C9 | −147.8 (3) |
N1—C3—C4—N2 | −6.4 (4) | C8—C5—C6—C9 | 93.8 (3) |
S1—C3—C4—N2 | 171.3 (2) | C7—C5—C6—C9 | −34.0 (4) |
N1—C3—C4—N3 | 172.5 (3) | N2—C5—C6—C10 | 83.9 (3) |
S1—C3—C4—N3 | −9.8 (4) | C8—C5—C6—C10 | −34.5 (4) |
C4—N2—C5—C8 | 143.2 (3) | C7—C5—C6—C10 | −162.2 (3) |
Symmetry code: (i) −x+1/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2ii | 0.82 | 1.96 | 2.737 (5) | 158 |
Symmetry code: (ii) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Hg(C10H15N3OS)2(NO3)2] |
Mr | 775.22 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 19.758 (4), 13.580 (3), 11.587 (3) |
β (°) | 115.739 (3) |
V (Å3) | 2800.3 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.70 |
Crystal size (mm) | 0.36 × 0.24 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.202, 0.425 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11946, 3212, 2498 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.056, 1.03 |
No. of reflections | 3212 |
No. of parameters | 183 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.96, −0.40 |
Computer programs: APEX II (Bruker, 2004), APEX II, SAINT (Bruker 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker 2004), SHELXTL.
Hg1—N2 | 2.055 (2) | N3—O1 | 1.391 (3) |
Hg1—N1 | 2.846 (2) | C4—N2 | 1.313 (4) |
Hg1—O4 | 2.859 (3) | C4—N3 | 1.342 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.82 | 1.96 | 2.737 (5) | 158 |
Symmetry code: (i) −x+1, y, −z+3/2. |
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The engineering of molecular magnets constitutes a major contemporary research aim and has spawned interest in organic radicals as building blocks for the construction of such materials (Yamamoto et al., 2001; Aoki et al., 2003; Iino et al., 2003; Pillet et al., 2001). In the past two decades, there have been a large number of investigations on magneto/structural chemistry of transition metal complexes containing nitronyl and imino nitroxide radicals (Taylor et al., 2003; Zhou et al., 2004; Wang et al., 2003; Ruiz et al., 2000). However, nitroxide radicals can undergo redox reactions with transition metal ions and the mechanistic details of the reduction of the imino radicals are not completely clear. It is likely that the imino radicals are reduced by acidic impurities or other experimental conditions during the reaction process (Jiang et al., 1998; Li et al., 2001). In this paper, we report the synthesis and crystal structure of the title compound, (I) (Fig. 1), Hg(Him-thz)2(NO3)2, where Him-thz = 2-(2'-thiazole)-4,4,5,5-tetramethyldihydro-1H-imidazolyl-1-hydroxy), i.e. the reduced IM-thz radical.
The mercury(II) ion (site symmetry 1) in (I) is six-coordinated in a grossly distorted octahedral HgN4O2 environment. Two Him-thz molecules acting as bidentate chelating ligands, coordinate the mercury(II) ion through a very long (Table 1) Hg—N bond to the N atom of the thiazole ring and a short Hg—N bond to the N atom of the imidazole ring leading to a five-membered chelate rings. The mercury coordination is completed by long Hg—O bonds to nearby monodentate nitrate anions. Similar Hg—N and Hg—O bond lengths have been seen in other complexes (Lee et al., 1998; Kim et al., 1998).
Molecules of (I) are linked into chains by way of an O—H···O hydrogen bond (Fig. 2 and Table 2) involving a reduced N—OH group as donor and a nitrate O atom as acceptor.