Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112017659/wq3013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112017659/wq3013Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112017659/wq3013IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112017659/wq3013IIIsup4.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270112017659/wq3013IIsup5.pdf | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270112017659/wq3013IIIsup6.pdf |
CCDC references: 889364; 889365; 889366
For related literature, see: Dong et al. (2003); Du et al. (2006); Morsali & Masoomi (2009); Mu et al. (2008); Liu et al. (2009); Long & Yaghi (2009); Park, et al. (2009); Song et al. (2010); Spokoyny et al. (2009); Tang et al. (2011).
For the preparation of 4-amino-5-(3-bromophenyl)-3-(pyridin-3-yl)-4H-1,2,4-triazole, a mixture of hydrazine hydrate (6.90 g, 110 mmol), 3-bromobenzonitrile (5.00 g, 27.5 mmol) and pyridine-3-carbonitrile (2.86 g, 27.5 mmol) in ethanediol (10 ml) was stirred at 413 K for 12 h. The reaction was monitored by thin layer chromatography (TLC). Sufficient water was added to the mixture to cause precipitation. The precipitate was purified by silica-gel column chromatography using dichloromethane (DCM) and MeOH (30:1 v/v) as eluent to afford 4-amino-5-(3-bromophenyl)-3-(pyridin-3-yl)-4H-1,2,4-triazole as a white crystalline solid (yield 2.40 g, 7.6 mmol, 27.6%). 1H NMR (300 MHz, DMSO, 298 K, TMS): δ 9.18 (s, 1H, –C5H4N), 8.73 (d, 1H, –C5H4N), 8.39 (d, 1H, –C5H4N), 8.27 (s, 1H), 8.06 (d, 1H,–C6H4–), 7.75 (d, 1H, –C6H4–), 7.61 (m, 1H, –C6H4–), 7.54 (t, 1H, –C6H4–), 6.42 (s, 2H, –NH2); IR (KBr pellet, cm-1): 3417 (s), 3355 (s), 1623 (m), 1598 (m), 1567 (m), 1515 (w), 1477 (s), 1447 (m), 1399 (vs), 1331 (w), 1192 (w), 1070 (m), 1030 (w), 1015 (m), 997 (w), 976 (w), 892 (m), 815 (m), 794 (m), 766 (m), 690 (w). Analysis calculated for C12H12BrN5: C 22.45, H 1.54, N 8.96%; found: C 22.48, H 1.51, N 9.01%.
For the preparation of 4-amino-3-[4-(pyridin-4-yl)phenyl]-5-(pyridin-3-yl)-4H-1,2,4-triazole (L), a mixture of 4-amino-5-(3-bromophenyl)-3-(pyridin-3-yl)-4H-1,2,4-triazole (2.0 mmol) and pyridine-4-boronic acid (2.4 mmol), Pd(PPh3)4 (0.048 mmol), K2CO3 (6 mmol) in an EtOH–H2O system was stirred at 348–353 K for 48 h. After removal of the solvent under vacuum, the residue was purified by silica-gel column chromatography using DCM–MeOH (10:1 v/v) as eluent to afford L as a white crystalline solid (yield 2.40 g, 7.6 mmol, 90.2%). 1H NMR (300 MHz, DMSO, 298 K, TMS): δ 9.22 (s, 1H, –C5H4N), 8.73 (d, 3H, –C5H4N), 8.44 (d, 2H, –C5H4N), 8.13 (d, 1H, –C5H4N), 8.01 (d, 1H, –C5H4N), 7.90 (d, 2H, –C6H4–), 7.75 (t, 1H, –C6H4–), 7.63 (m, 1H, –C6H4–), 6.47 (s, 2H, –NH2); IR (KBr pellet, cm-1): 3406 (s), 3355 (s), 1637 (m), 1593 (m), 1509 (w), 1463 (m), 1400 (vs), 1264 (w), 1193 (w), 1070 (m), 1026 (w), 970 (w), 919 (w), 901 (m), 814 (w), 795 (m), 713 (m), 692 (m), 610 (m). Analysis calculated for C18H14N6: C 68.78, H 4.49, N 24.73%; found: C 68.80, H 4.47, N 24.73%.
For the preparation of (I), a solution of HgCl2 (10.86 mg, 0.04 mmol) in CH3CN (7 ml) was layered onto a solution of L (6.28 mg, 0.02 mmol) in CH2Cl2 (7 ml). The solution was left for about 5 d at room temperature and colorless crystals of (I) were obtained (yield 80%). IR (KBr pellet, cm-1): 3417 (s), 3330 (s), 2170 (w), 1607 (s), 1518 (w), 1459 (m), 1400 (vs), 1231 (m), 1192 (m), 1122 (m), 1076 (m), 1015 (m), 987 (m), 794 (s), 686 (m), 641 (m), 574 (m). Analysis calculated for C38H31Cl6Hg3N13: C 30.75, H 2.11, N 12.27%; found: C 30.78, H 2.06, N 12.28%.
For the preparation of (II), a solution of HgBr2 (14.42 mg, 0.04 mmol) in CH3CN (7 ml) was layered onto a solution of L (6.28 mg, 0.02 mmol) in CH2Cl2 (7 ml). The solution was left for about 5 d at room temperature and colorless crystals of (II) were obtained (yield 78%). IR (KBr pellet, cm-1): 3417 (s), 3330 (s), 2170 (w), 1607 (s), 1518 (w), 1459 (m), 1400 (vs), 1231 (m), 1192 (m), 1122 (m), 1076 (m), 1015 (m), 987 (m), 794 (s), 686 (m), 641 (m), 574 (m). Analysis calculated for C38H31Br6Hg3N13: C 26.07, H 1.78, N 10.40%; found: C 26.09, H 1.76, N 10.41%.
For the preparation of (III), a solution of HgI2 (18.18 mg, 0.04 mmol) in CH3CN (7 ml) was layered onto a solution of L (6.28 mg, 0.02 mmol) in CH2Cl2 (7 ml). The solution was left for about 5 d at room temperature and colorless crystals (III) were obtained (yield 80%). IR (KBr pellet, cm-1): 3417 (s), 3332 (s), 2170 (w), 1607 (s), 1515 (m), 1458 (m), 1400 (vs), 1230 (m), 1191 (m), 1121 (m), 1074 (m), 1013 (m), 986 (m), 796 (s), 687 (m), 640 (m), 573(m). Analysis calculated for C38H31Hg3I6N13: C 22.45, H 1.54, N 8.96%; found: C 22.46, H 1.52, N 8.98%.
For (I), H atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) (aromatic) and C—H = 0.96 Å and Uiso(H) = 1.2Ueq(C) (acetonitrile). The NH2 group was assumed to be NH3 and three H atoms were added in geometrically idealized positions. One H atom without an acceptor was then deleted and refined as riding model, with N—H = 0.89 Å and Uiso(H) = 1.2Ueq(N). Half of one Cl atom (Cl4) is disordered over two orientations in the refined ratio 0.64 (8):0.36 (8), and the anisotropic displacement parameters (ADPs) of atoms Cl4 and Cl4' were restrained to be isotropic within a standard uncertainty of 0.01 Å2. The acetonitrile solvent molecule lies on a mirror position and was refined as partially occupied, using a total of 12 restraints. The highest peak of residual electron density was located at (0.0982, 0.7500, 0.0785), 1.00 Å from atom Hg2.
For (II), H atoms on C and N atoms were treated as for (I). The acetonitrile solvent molecule lies on a mirror position and wasrefined as partially occupied. The highest peak of residual electron density was located at (0.0488, 0.7500, 0.9981), 0.99 Å from atom Hg2.
For (III), H atoms on C and N atoms were treated as for (I). The acetonitrile solvent molecule lies on a mirror position and was refined as partially occupied; the ADPs of atoms C19, C20 and N7 was restrained to be isotropic within a standard uncertainty of 0.01 Å2, using a total of 18 restraints. The highest peak of residual electron density was located at (0.1152, 0.7500, 0.2023), 0.99 Å from atom I4.
For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SMART (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Hg3Cl6(C18H14N6)2]·C2H3N | Dx = 2.187 Mg m−3 |
Mr = 1484.23 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 4616 reflections |
a = 12.773 (2) Å | θ = 2.4–24.4° |
b = 27.267 (5) Å | µ = 10.60 mm−1 |
c = 12.941 (2) Å | T = 298 K |
V = 4506.9 (14) Å3 | Plan, colourless |
Z = 4 | 0.32 × 0.18 × 0.05 mm |
F(000) = 2768 |
Bruker SMART CCD area-detector diffractometer | 4277 independent reflections |
Radiation source: fine-focus sealed tube | 3278 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.077 |
ϕ and ω scans | θmax = 25.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −15→15 |
Tmin = 0.133, Tmax = 0.619 | k = −33→17 |
22532 measured reflections | l = −15→15 |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.188 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1128P)2 + 27.9072P] where P = (Fo2 + 2Fc2)/3 |
4277 reflections | (Δ/σ)max = 0.001 |
287 parameters | Δρmax = 2.67 e Å−3 |
12 restraints | Δρmin = −1.89 e Å−3 |
[Hg3Cl6(C18H14N6)2]·C2H3N | V = 4506.9 (14) Å3 |
Mr = 1484.23 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.773 (2) Å | µ = 10.60 mm−1 |
b = 27.267 (5) Å | T = 298 K |
c = 12.941 (2) Å | 0.32 × 0.18 × 0.05 mm |
Bruker SMART CCD area-detector diffractometer | 4277 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3278 reflections with I > 2σ(I) |
Tmin = 0.133, Tmax = 0.619 | Rint = 0.077 |
22532 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 12 restraints |
wR(F2) = 0.188 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1128P)2 + 27.9072P] where P = (Fo2 + 2Fc2)/3 |
4277 reflections | Δρmax = 2.67 e Å−3 |
287 parameters | Δρmin = −1.89 e Å−3 |
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 | Occ. (<1) | |
C1 | 0.2512 (11) | 0.5128 (6) | 0.3878 (12) | 0.064 (4) | |
H1 | 0.2145 | 0.5071 | 0.3269 | 0.077* | |
C2 | 0.3371 (12) | 0.5424 (6) | 0.3839 (11) | 0.062 (4) | |
H2 | 0.3551 | 0.5581 | 0.3226 | 0.074* | |
C3 | 0.3977 (9) | 0.5490 (5) | 0.4722 (9) | 0.037 (2) | |
C4 | 0.3600 (9) | 0.5277 (5) | 0.5608 (9) | 0.044 (3) | |
H4 | 0.3942 | 0.5326 | 0.6234 | 0.053* | |
C5 | 0.2722 (10) | 0.4992 (6) | 0.5568 (9) | 0.052 (3) | |
H5 | 0.2510 | 0.4842 | 0.6179 | 0.062* | |
C6 | 0.4950 (9) | 0.5790 (4) | 0.4695 (8) | 0.036 (2) | |
C7 | 0.5323 (10) | 0.5987 (5) | 0.3788 (9) | 0.050 (3) | |
H7 | 0.4939 | 0.5944 | 0.3184 | 0.060* | |
C8 | 0.6262 (12) | 0.6251 (6) | 0.3744 (9) | 0.063 (4) | |
H8 | 0.6516 | 0.6365 | 0.3115 | 0.075* | |
C9 | 0.6799 (10) | 0.6337 (5) | 0.4639 (9) | 0.048 (3) | |
H9 | 0.7410 | 0.6522 | 0.4616 | 0.057* | |
C10 | 0.6455 (8) | 0.6156 (4) | 0.5576 (8) | 0.034 (2) | |
C11 | 0.5513 (9) | 0.5883 (5) | 0.5610 (8) | 0.040 (3) | |
H11 | 0.5265 | 0.5764 | 0.6238 | 0.048* | |
C12 | 0.7090 (7) | 0.6225 (4) | 0.6489 (8) | 0.031 (2) | |
C13 | 0.7644 (8) | 0.6399 (4) | 0.8043 (8) | 0.035 (2) | |
C14 | 0.7714 (8) | 0.6557 (4) | 0.9109 (7) | 0.033 (2) | |
C15 | 0.8593 (8) | 0.6798 (4) | 0.9434 (8) | 0.036 (2) | |
H15 | 0.9108 | 0.6865 | 0.8947 | 0.043* | |
C16 | 0.8017 (11) | 0.6836 (6) | 1.1088 (10) | 0.058 (4) | |
H16 | 0.8135 | 0.6919 | 1.1776 | 0.069* | |
C17 | 0.7105 (12) | 0.6617 (6) | 1.0845 (10) | 0.063 (4) | |
H17 | 0.6595 | 0.6567 | 1.1347 | 0.075* | |
C18 | 0.6942 (10) | 0.6468 (6) | 0.9846 (9) | 0.055 (4) | |
H18 | 0.6324 | 0.6310 | 0.9663 | 0.066* | |
C19 | 0.905 (3) | 0.7500 | 0.638 (3) | 0.090 (8) | |
C20 | 0.926 (5) | 0.7500 | 0.525 (4) | 0.21 (3) | |
H20A | 0.9369 | 0.7169 | 0.5013 | 0.320* | 0.50 |
H20B | 0.9882 | 0.7690 | 0.5105 | 0.320* | 0.50 |
H20C | 0.8679 | 0.7641 | 0.4888 | 0.320* | 0.50 |
Cl1 | 0.9409 (2) | 0.61459 (14) | 0.3833 (2) | 0.0510 (8) | |
Cl2 | 1.0295 (2) | 0.52970 (12) | 0.6709 (2) | 0.0447 (7) | |
Cl3 | 1.1093 (4) | 0.7500 | 0.9121 (4) | 0.0573 (12) | |
Cl4 | 1.066 (4) | 0.7500 | 1.253 (2) | 0.029 (6) | 0.36 (8) |
Cl4' | 1.024 (3) | 0.7500 | 1.2638 (8) | 0.039 (4) | 0.64 (8) |
Hg1 | 0.92151 (4) | 0.56482 (2) | 0.53538 (4) | 0.0524 (2) | |
Hg2 | 1.02020 (6) | 0.7500 | 1.07687 (5) | 0.0520 (3) | |
N1 | 0.2163 (8) | 0.4912 (4) | 0.4757 (8) | 0.045 (3) | |
N2 | 0.8105 (7) | 0.6135 (4) | 0.6523 (7) | 0.037 (2) | |
N3 | 0.8451 (6) | 0.6237 (4) | 0.7500 (7) | 0.039 (2) | |
N4 | 0.6777 (6) | 0.6387 (4) | 0.7429 (6) | 0.033 (2) | |
N5 | 0.5797 (6) | 0.6573 (4) | 0.7741 (7) | 0.045 (3) | |
H5A | 0.5660 | 0.6847 | 0.7392 | 0.067* | |
H5B | 0.5303 | 0.6352 | 0.7610 | 0.067* | |
N6 | 0.8757 (8) | 0.6942 (4) | 1.0405 (7) | 0.044 (2) | |
N7 | 0.880 (3) | 0.7500 | 0.713 (3) | 0.129 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.059 (8) | 0.073 (11) | 0.059 (8) | −0.028 (8) | −0.016 (7) | −0.002 (8) |
C2 | 0.079 (10) | 0.060 (9) | 0.047 (7) | −0.031 (8) | −0.016 (7) | 0.011 (7) |
C3 | 0.034 (5) | 0.033 (6) | 0.044 (6) | −0.002 (5) | −0.005 (5) | −0.008 (5) |
C4 | 0.044 (7) | 0.053 (8) | 0.037 (6) | −0.008 (6) | −0.009 (5) | −0.003 (6) |
C5 | 0.048 (7) | 0.068 (10) | 0.040 (6) | −0.006 (7) | 0.004 (5) | −0.007 (6) |
C6 | 0.038 (6) | 0.038 (7) | 0.031 (5) | 0.001 (5) | −0.006 (4) | −0.003 (5) |
C7 | 0.047 (7) | 0.067 (9) | 0.037 (6) | −0.013 (6) | −0.013 (5) | 0.005 (6) |
C8 | 0.072 (9) | 0.088 (12) | 0.028 (6) | −0.024 (8) | −0.004 (6) | 0.016 (7) |
C9 | 0.039 (6) | 0.058 (9) | 0.046 (6) | −0.011 (6) | −0.008 (5) | 0.000 (6) |
C10 | 0.032 (5) | 0.039 (6) | 0.030 (5) | 0.004 (4) | 0.001 (4) | −0.006 (5) |
C11 | 0.037 (6) | 0.053 (8) | 0.031 (5) | −0.005 (5) | 0.002 (5) | −0.008 (5) |
C12 | 0.026 (5) | 0.035 (6) | 0.033 (5) | −0.005 (4) | 0.006 (4) | −0.003 (5) |
C13 | 0.026 (5) | 0.037 (7) | 0.041 (6) | −0.006 (4) | 0.000 (4) | −0.003 (5) |
C14 | 0.025 (5) | 0.043 (7) | 0.032 (5) | −0.001 (4) | −0.001 (4) | 0.003 (5) |
C15 | 0.028 (5) | 0.041 (7) | 0.039 (6) | −0.002 (5) | 0.001 (4) | −0.005 (5) |
C16 | 0.069 (9) | 0.072 (10) | 0.032 (6) | −0.011 (7) | −0.007 (6) | −0.012 (6) |
C17 | 0.065 (9) | 0.082 (11) | 0.041 (7) | −0.022 (8) | 0.018 (6) | −0.005 (7) |
C18 | 0.041 (7) | 0.082 (11) | 0.043 (7) | −0.014 (7) | 0.004 (5) | 0.000 (7) |
C19 | 0.12 (2) | 0.069 (19) | 0.076 (18) | 0.000 | 0.010 (17) | 0.000 |
C20 | 0.34 (9) | 0.09 (4) | 0.20 (6) | 0.000 | 0.04 (6) | 0.000 |
Cl1 | 0.0514 (16) | 0.073 (2) | 0.0286 (13) | −0.0121 (15) | 0.0170 (12) | −0.0064 (14) |
Cl2 | 0.0352 (14) | 0.0536 (18) | 0.0452 (15) | 0.0143 (12) | −0.0051 (11) | −0.0117 (14) |
Cl3 | 0.063 (3) | 0.048 (3) | 0.062 (3) | 0.000 | 0.005 (2) | 0.000 |
Cl4 | 0.036 (11) | 0.030 (7) | 0.021 (6) | 0.000 | −0.021 (6) | 0.000 |
Cl4' | 0.054 (10) | 0.048 (4) | 0.016 (3) | 0.000 | −0.017 (4) | 0.000 |
Hg1 | 0.0437 (3) | 0.0625 (4) | 0.0512 (4) | −0.0099 (2) | 0.0037 (2) | −0.0105 (2) |
Hg2 | 0.0537 (4) | 0.0539 (5) | 0.0484 (4) | 0.000 | −0.0190 (3) | 0.000 |
N1 | 0.041 (5) | 0.045 (6) | 0.050 (6) | −0.010 (4) | −0.010 (5) | −0.011 (5) |
N2 | 0.033 (5) | 0.042 (6) | 0.035 (4) | −0.004 (4) | 0.003 (4) | −0.010 (4) |
N3 | 0.025 (4) | 0.052 (6) | 0.041 (5) | −0.002 (4) | −0.005 (4) | −0.015 (5) |
N4 | 0.016 (4) | 0.045 (6) | 0.038 (5) | −0.004 (3) | 0.000 (3) | −0.006 (4) |
N5 | 0.024 (4) | 0.072 (8) | 0.038 (5) | 0.004 (4) | −0.007 (4) | −0.013 (5) |
N6 | 0.052 (6) | 0.046 (6) | 0.034 (5) | −0.007 (5) | −0.010 (4) | −0.013 (4) |
N7 | 0.18 (3) | 0.10 (2) | 0.11 (2) | 0.000 | −0.02 (2) | 0.000 |
C1—N1 | 1.356 (18) | C14—C18 | 1.393 (16) |
C1—C2 | 1.363 (19) | C15—N6 | 1.333 (13) |
C1—H1 | 0.9300 | C15—H15 | 0.9300 |
C2—C3 | 1.392 (17) | C16—N6 | 1.326 (17) |
C2—H2 | 0.9300 | C16—C17 | 1.35 (2) |
C3—C4 | 1.374 (17) | C16—H16 | 0.9300 |
C3—C6 | 1.487 (16) | C17—C18 | 1.372 (18) |
C4—C5 | 1.365 (18) | C17—H17 | 0.9300 |
C4—H4 | 0.9300 | C18—H18 | 0.9300 |
C5—N1 | 1.288 (15) | C19—N7 | 1.03 (4) |
C5—H5 | 0.9300 | C19—C20 | 1.49 (6) |
C6—C7 | 1.377 (17) | C20—H20A | 0.9600 |
C6—C11 | 1.407 (15) | C20—H20B | 0.9600 |
C7—C8 | 1.398 (18) | C20—H20C | 0.9600 |
C7—H7 | 0.9300 | Cl1—Hg1 | 2.403 (3) |
C8—C9 | 1.366 (17) | Cl2—Hg1 | 2.428 (3) |
C8—H8 | 0.9300 | Cl3—Hg2 | 2.418 (5) |
C9—C10 | 1.382 (16) | Cl4—Hg2 | 2.353 (19) |
C9—H9 | 0.9300 | Hg1—N1i | 2.336 (10) |
C10—C11 | 1.416 (16) | Hg1—N2 | 2.462 (9) |
C10—C12 | 1.445 (14) | Hg2—N6 | 2.438 (10) |
C11—H11 | 0.9300 | Hg2—N6ii | 2.438 (10) |
C12—N2 | 1.319 (13) | N1—Hg1i | 2.336 (10) |
C12—N4 | 1.355 (13) | N2—N3 | 1.369 (12) |
C13—N3 | 1.323 (14) | N4—N5 | 1.410 (12) |
C13—N4 | 1.364 (13) | N5—H5A | 0.8900 |
C13—C14 | 1.447 (14) | N5—H5B | 0.8900 |
C14—C15 | 1.367 (15) | ||
N1—C1—C2 | 123.5 (12) | N6—C16—C17 | 123.8 (11) |
N1—C1—H1 | 118.2 | N6—C16—H16 | 118.1 |
C2—C1—H1 | 118.2 | C17—C16—H16 | 118.1 |
C1—C2—C3 | 119.7 (13) | C16—C17—C18 | 118.9 (12) |
C1—C2—H2 | 120.2 | C16—C17—H17 | 120.5 |
C3—C2—H2 | 120.2 | C18—C17—H17 | 120.5 |
C4—C3—C2 | 115.8 (11) | C17—C18—C14 | 119.1 (12) |
C4—C3—C6 | 123.0 (10) | C17—C18—H18 | 120.5 |
C2—C3—C6 | 121.2 (11) | C14—C18—H18 | 120.5 |
C5—C4—C3 | 119.9 (11) | N7—C19—C20 | 172 (5) |
C5—C4—H4 | 120.1 | C19—C20—H20A | 109.5 |
C3—C4—H4 | 120.1 | C19—C20—H20B | 109.5 |
N1—C5—C4 | 125.6 (12) | H20A—C20—H20B | 109.5 |
N1—C5—H5 | 117.2 | C19—C20—H20C | 109.5 |
C4—C5—H5 | 117.2 | H20A—C20—H20C | 109.5 |
C7—C6—C11 | 118.0 (11) | H20B—C20—H20C | 109.5 |
C7—C6—C3 | 121.6 (10) | N1i—Hg1—Cl1 | 113.4 (3) |
C11—C6—C3 | 120.4 (10) | N1i—Hg1—Cl2 | 102.4 (3) |
C6—C7—C8 | 122.2 (11) | Cl1—Hg1—Cl2 | 139.08 (11) |
C6—C7—H7 | 118.9 | N1i—Hg1—N2 | 87.5 (3) |
C8—C7—H7 | 118.9 | Cl1—Hg1—N2 | 105.0 (2) |
C9—C8—C7 | 119.0 (11) | Cl2—Hg1—N2 | 95.5 (2) |
C9—C8—H8 | 120.5 | Cl4—Hg2—Cl3 | 137.4 (12) |
C7—C8—H8 | 120.5 | Cl4—Hg2—N6 | 112.1 (9) |
C8—C9—C10 | 121.6 (12) | Cl3—Hg2—N6 | 100.7 (2) |
C8—C9—H9 | 119.2 | Cl4—Hg2—N6ii | 112.1 (9) |
C10—C9—H9 | 119.2 | Cl3—Hg2—N6ii | 100.7 (2) |
C9—C10—C11 | 119.0 (10) | N6—Hg2—N6ii | 77.3 (5) |
C9—C10—C12 | 119.5 (10) | C5—N1—C1 | 115.4 (11) |
C11—C10—C12 | 121.4 (10) | C5—N1—Hg1i | 125.3 (9) |
C6—C11—C10 | 120.2 (10) | C1—N1—Hg1i | 118.7 (8) |
C6—C11—H11 | 119.9 | C12—N2—N3 | 108.0 (8) |
C10—C11—H11 | 119.9 | C12—N2—Hg1 | 130.2 (7) |
N2—C12—N4 | 108.7 (8) | N3—N2—Hg1 | 119.5 (6) |
N2—C12—C10 | 123.7 (9) | C13—N3—N2 | 107.9 (8) |
N4—C12—C10 | 127.6 (9) | C12—N4—C13 | 106.9 (8) |
N3—C13—N4 | 108.4 (9) | C12—N4—N5 | 129.6 (8) |
N3—C13—C14 | 123.9 (9) | C13—N4—N5 | 123.0 (8) |
N4—C13—C14 | 127.8 (9) | N4—N5—H5A | 109.4 |
C15—C14—C18 | 117.0 (10) | N4—N5—H5B | 109.3 |
C15—C14—C13 | 119.2 (9) | H5A—N5—H5B | 109.5 |
C18—C14—C13 | 123.8 (10) | C16—N6—C15 | 116.9 (10) |
N6—C15—C14 | 124.2 (10) | C16—N6—Hg2 | 123.1 (8) |
N6—C15—H15 | 117.9 | C15—N6—Hg2 | 119.1 (8) |
C14—C15—H15 | 117.9 | ||
N1—C1—C2—C3 | 4 (3) | C4—C5—N1—Hg1i | 172.2 (11) |
C1—C2—C3—C4 | −5 (2) | C2—C1—N1—C5 | −2 (2) |
C1—C2—C3—C6 | 176.8 (14) | C2—C1—N1—Hg1i | −173.7 (13) |
C2—C3—C4—C5 | 4 (2) | N4—C12—N2—N3 | 0.2 (13) |
C6—C3—C4—C5 | −177.6 (12) | C10—C12—N2—N3 | −179.7 (10) |
C3—C4—C5—N1 | −3 (2) | N4—C12—N2—Hg1 | 162.7 (7) |
C4—C3—C6—C7 | 178.1 (13) | C10—C12—N2—Hg1 | −17.2 (16) |
C2—C3—C6—C7 | −4 (2) | N1i—Hg1—N2—C12 | −39.2 (10) |
C4—C3—C6—C11 | −2.5 (19) | Cl1—Hg1—N2—C12 | 74.4 (10) |
C2—C3—C6—C11 | 175.3 (13) | Cl2—Hg1—N2—C12 | −141.4 (10) |
C11—C6—C7—C8 | 4 (2) | N1i—Hg1—N2—N3 | 121.6 (8) |
C3—C6—C7—C8 | −177.1 (14) | Cl1—Hg1—N2—N3 | −124.9 (7) |
C6—C7—C8—C9 | −3 (2) | Cl2—Hg1—N2—N3 | 19.4 (8) |
C7—C8—C9—C10 | 2 (2) | N4—C13—N3—N2 | 1.7 (12) |
C8—C9—C10—C11 | −1 (2) | C14—C13—N3—N2 | −178.3 (10) |
C8—C9—C10—C12 | 175.3 (13) | C12—N2—N3—C13 | −1.2 (13) |
C7—C6—C11—C10 | −2.4 (19) | Hg1—N2—N3—C13 | −165.9 (7) |
C3—C6—C11—C10 | 178.2 (11) | N2—C12—N4—C13 | 0.8 (12) |
C9—C10—C11—C6 | 1.3 (18) | C10—C12—N4—C13 | −179.3 (11) |
C12—C10—C11—C6 | −175.2 (11) | N2—C12—N4—N5 | 173.2 (11) |
C9—C10—C12—N2 | −47.6 (17) | C10—C12—N4—N5 | −7.0 (19) |
C11—C10—C12—N2 | 128.9 (12) | N3—C13—N4—C12 | −1.5 (12) |
C9—C10—C12—N4 | 132.6 (13) | C14—C13—N4—C12 | 178.5 (11) |
C11—C10—C12—N4 | −51.0 (18) | N3—C13—N4—N5 | −174.5 (10) |
N3—C13—C14—C15 | 35.9 (18) | C14—C13—N4—N5 | 5.5 (18) |
N4—C13—C14—C15 | −144.1 (12) | C17—C16—N6—C15 | −3 (2) |
N3—C13—C14—C18 | −142.5 (13) | C17—C16—N6—Hg2 | 165.3 (13) |
N4—C13—C14—C18 | 37 (2) | C14—C15—N6—C16 | 0.8 (19) |
C18—C14—C15—N6 | 1.3 (19) | C14—C15—N6—Hg2 | −168.3 (9) |
C13—C14—C15—N6 | −177.2 (11) | Cl4—Hg2—N6—C16 | 29.8 (14) |
N6—C16—C17—C18 | 4 (3) | Cl3—Hg2—N6—C16 | −177.8 (11) |
C16—C17—C18—C14 | −1 (3) | N6ii—Hg2—N6—C16 | −79.1 (11) |
C15—C14—C18—C17 | −1 (2) | Cl4—Hg2—N6—C15 | −161.8 (12) |
C13—C14—C18—C17 | 177.4 (14) | Cl3—Hg2—N6—C15 | −9.4 (9) |
C4—C5—N1—C1 | 1 (2) | N6ii—Hg2—N6—C15 | 89.3 (9) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···Cl1iii | 0.93 | 2.75 | 3.613 (12) | 154 |
N5—H5A···Cl3iv | 0.89 | 2.70 | 3.512 (12) | 152 |
N5—H5B···N3iv | 0.89 | 2.39 | 3.149 (12) | 143 |
Symmetry codes: (iii) x−1/2, y, −z+1/2; (iv) x−1/2, y, −z+3/2. |
[Hg3Br6(C18H14N6)2]·C2H3N | Dx = 2.501 Mg m−3 |
Mr = 1750.99 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 4737 reflections |
a = 12.8037 (16) Å | θ = 2.2–24.2° |
b = 27.890 (4) Å | µ = 15.08 mm−1 |
c = 13.0245 (17) Å | T = 298 K |
V = 4651.0 (10) Å3 | Plan, colourless |
Z = 4 | 0.25 × 0.20 × 0.03 mm |
F(000) = 3200 |
Bruker SMART CCD area-detector diffractometer | 4422 independent reflections |
Radiation source: fine-focus sealed tube | 3338 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
ϕ and ω scans | θmax = 25.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −10→15 |
Tmin = 0.117, Tmax = 0.661 | k = −30→33 |
23320 measured reflections | l = −15→15 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0646P)2 + 19.0915P] where P = (Fo2 + 2Fc2)/3 |
4422 reflections | (Δ/σ)max = 0.001 |
281 parameters | Δρmax = 2.17 e Å−3 |
0 restraints | Δρmin = −2.04 e Å−3 |
[Hg3Br6(C18H14N6)2]·C2H3N | V = 4651.0 (10) Å3 |
Mr = 1750.99 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.8037 (16) Å | µ = 15.08 mm−1 |
b = 27.890 (4) Å | T = 298 K |
c = 13.0245 (17) Å | 0.25 × 0.20 × 0.03 mm |
Bruker SMART CCD area-detector diffractometer | 4422 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3338 reflections with I > 2σ(I) |
Tmin = 0.117, Tmax = 0.661 | Rint = 0.075 |
23320 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0646P)2 + 19.0915P] where P = (Fo2 + 2Fc2)/3 |
4422 reflections | Δρmax = 2.17 e Å−3 |
281 parameters | Δρmin = −2.04 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | Occ. (<1) | |
C1 | 0.2547 (9) | 0.5098 (5) | 0.3954 (8) | 0.063 (4) | |
H1 | 0.2159 | 0.5054 | 0.3358 | 0.076* | |
C2 | 0.3395 (9) | 0.5395 (4) | 0.3905 (8) | 0.058 (3) | |
H2 | 0.3574 | 0.5545 | 0.3291 | 0.069* | |
C3 | 0.3995 (7) | 0.5473 (4) | 0.4794 (7) | 0.038 (2) | |
C4 | 0.3639 (8) | 0.5246 (4) | 0.5667 (7) | 0.046 (3) | |
H4 | 0.3976 | 0.5296 | 0.6291 | 0.055* | |
C5 | 0.2781 (7) | 0.4944 (4) | 0.5621 (7) | 0.046 (3) | |
H5 | 0.2579 | 0.4785 | 0.6217 | 0.055* | |
C6 | 0.4918 (7) | 0.5790 (4) | 0.4759 (6) | 0.039 (2) | |
C7 | 0.5274 (8) | 0.5985 (4) | 0.3854 (7) | 0.050 (3) | |
H7 | 0.4907 | 0.5924 | 0.3252 | 0.061* | |
C8 | 0.6158 (9) | 0.6267 (4) | 0.3814 (7) | 0.053 (3) | |
H8 | 0.6370 | 0.6401 | 0.3194 | 0.063* | |
C9 | 0.6721 (7) | 0.6348 (4) | 0.4684 (7) | 0.042 (2) | |
H9 | 0.7324 | 0.6532 | 0.4654 | 0.050* | |
C10 | 0.6395 (7) | 0.6154 (4) | 0.5627 (6) | 0.034 (2) | |
C11 | 0.5495 (7) | 0.5878 (4) | 0.5656 (7) | 0.035 (2) | |
H11 | 0.5270 | 0.5750 | 0.6276 | 0.042* | |
C12 | 0.7065 (7) | 0.6219 (4) | 0.6518 (6) | 0.034 (2) | |
C13 | 0.7665 (7) | 0.6386 (4) | 0.8048 (6) | 0.035 (2) | |
C14 | 0.7750 (7) | 0.6544 (4) | 0.9115 (6) | 0.037 (2) | |
C15 | 0.8625 (7) | 0.6803 (4) | 0.9401 (7) | 0.039 (2) | |
H15 | 0.9106 | 0.6886 | 0.8896 | 0.047* | |
C16 | 0.8097 (9) | 0.6841 (5) | 1.1072 (8) | 0.060 (3) | |
H16 | 0.8212 | 0.6944 | 1.1742 | 0.072* | |
C17 | 0.7212 (9) | 0.6592 (6) | 1.0851 (8) | 0.069 (4) | |
H17 | 0.6739 | 0.6523 | 1.1372 | 0.083* | |
C18 | 0.7007 (8) | 0.6442 (4) | 0.9860 (8) | 0.050 (3) | |
H18 | 0.6396 | 0.6278 | 0.9699 | 0.061* | |
C19 | 0.9133 (18) | 0.7500 | 0.638 (2) | 0.088 (7) | |
C20 | 0.943 (3) | 0.7500 | 0.531 (2) | 0.175 (17) | |
H20A | 0.9534 | 0.7176 | 0.5080 | 0.263* | 0.50 |
H20B | 1.0071 | 0.7677 | 0.5224 | 0.263* | 0.50 |
H20C | 0.8891 | 0.7647 | 0.4906 | 0.263* | 0.50 |
Br1 | 0.93810 (11) | 0.61893 (6) | 0.37937 (9) | 0.0699 (4) | |
Br2 | 1.02939 (9) | 0.52835 (5) | 0.66479 (9) | 0.0633 (4) | |
Br3 | 1.11989 (15) | 0.7500 | 0.90326 (14) | 0.0651 (5) | |
Br4 | 1.0444 (2) | 0.7500 | 1.25598 (15) | 0.0980 (8) | |
Hg1 | 0.91579 (3) | 0.566873 (18) | 0.53097 (3) | 0.05143 (17) | |
Hg2 | 1.02217 (5) | 0.7500 | 1.06911 (4) | 0.0520 (2) | |
N1 | 0.2243 (6) | 0.4871 (3) | 0.4787 (6) | 0.042 (2) | |
N2 | 0.8075 (6) | 0.6138 (3) | 0.6533 (5) | 0.0393 (19) | |
N3 | 0.8451 (6) | 0.6236 (3) | 0.7500 (5) | 0.0398 (19) | |
N4 | 0.6770 (5) | 0.6370 (3) | 0.7464 (5) | 0.0337 (18) | |
N5 | 0.5794 (6) | 0.6554 (4) | 0.7804 (6) | 0.046 (2) | |
H5A | 0.5657 | 0.6828 | 0.7455 | 0.069* | |
H5B | 0.5300 | 0.6332 | 0.7673 | 0.069* | |
N6 | 0.8809 (7) | 0.6939 (3) | 1.0349 (6) | 0.043 (2) | |
N7 | 0.890 (2) | 0.7500 | 0.7162 (17) | 0.120 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.057 (7) | 0.098 (11) | 0.035 (5) | −0.031 (7) | −0.013 (5) | 0.001 (6) |
C2 | 0.075 (8) | 0.064 (9) | 0.034 (5) | −0.028 (6) | −0.016 (5) | 0.001 (5) |
C3 | 0.037 (5) | 0.032 (6) | 0.045 (6) | 0.003 (4) | −0.003 (4) | −0.008 (4) |
C4 | 0.051 (6) | 0.060 (8) | 0.027 (4) | 0.002 (5) | 0.000 (4) | −0.005 (5) |
C5 | 0.039 (5) | 0.061 (8) | 0.037 (5) | −0.009 (5) | 0.000 (4) | −0.004 (5) |
C6 | 0.038 (5) | 0.050 (7) | 0.028 (5) | 0.001 (4) | −0.005 (4) | −0.006 (4) |
C7 | 0.050 (6) | 0.074 (9) | 0.027 (5) | −0.009 (6) | −0.009 (4) | 0.001 (5) |
C8 | 0.068 (7) | 0.061 (8) | 0.029 (5) | −0.013 (6) | −0.008 (5) | 0.009 (5) |
C9 | 0.039 (5) | 0.049 (7) | 0.037 (5) | −0.004 (5) | 0.005 (4) | 0.002 (4) |
C10 | 0.037 (5) | 0.037 (6) | 0.029 (4) | 0.005 (4) | 0.002 (4) | −0.008 (4) |
C11 | 0.033 (5) | 0.040 (6) | 0.032 (5) | −0.004 (4) | 0.002 (4) | −0.005 (4) |
C12 | 0.036 (5) | 0.040 (6) | 0.025 (4) | −0.002 (4) | −0.001 (4) | −0.007 (4) |
C13 | 0.031 (4) | 0.044 (6) | 0.031 (4) | −0.007 (4) | 0.000 (4) | −0.004 (4) |
C14 | 0.038 (5) | 0.047 (7) | 0.027 (4) | 0.000 (4) | 0.001 (4) | −0.001 (4) |
C15 | 0.039 (5) | 0.038 (6) | 0.041 (5) | −0.002 (4) | −0.001 (4) | −0.001 (4) |
C16 | 0.072 (8) | 0.080 (9) | 0.027 (5) | −0.003 (7) | −0.014 (5) | −0.002 (5) |
C17 | 0.063 (7) | 0.113 (12) | 0.031 (5) | −0.025 (7) | 0.008 (5) | 0.002 (6) |
C18 | 0.046 (6) | 0.063 (8) | 0.043 (6) | −0.016 (5) | 0.003 (5) | −0.001 (5) |
C19 | 0.083 (15) | 0.073 (17) | 0.107 (18) | 0.000 | −0.012 (14) | 0.000 |
C20 | 0.29 (5) | 0.15 (4) | 0.09 (2) | 0.000 | 0.05 (2) | 0.000 |
Br1 | 0.0775 (8) | 0.0880 (11) | 0.0441 (6) | −0.0077 (7) | 0.0171 (6) | 0.0010 (6) |
Br2 | 0.0578 (7) | 0.0794 (10) | 0.0529 (7) | 0.0176 (6) | −0.0055 (5) | −0.0120 (6) |
Br3 | 0.0744 (11) | 0.0568 (12) | 0.0640 (10) | 0.000 | 0.0057 (9) | 0.000 |
Br4 | 0.171 (2) | 0.0764 (16) | 0.0471 (10) | 0.000 | −0.0423 (12) | 0.000 |
Hg1 | 0.0461 (3) | 0.0649 (4) | 0.0433 (3) | −0.0102 (2) | 0.00130 (17) | −0.0057 (2) |
Hg2 | 0.0564 (4) | 0.0571 (4) | 0.0426 (3) | 0.000 | −0.0175 (3) | 0.000 |
N1 | 0.041 (4) | 0.037 (5) | 0.047 (5) | −0.011 (4) | 0.003 (4) | −0.010 (4) |
N2 | 0.037 (4) | 0.052 (6) | 0.030 (4) | −0.002 (4) | 0.003 (3) | −0.006 (3) |
N3 | 0.035 (4) | 0.052 (6) | 0.033 (4) | −0.002 (4) | −0.004 (3) | −0.007 (4) |
N4 | 0.026 (4) | 0.044 (5) | 0.031 (4) | −0.001 (3) | −0.003 (3) | −0.006 (3) |
N5 | 0.028 (4) | 0.070 (7) | 0.041 (4) | 0.003 (4) | 0.000 (3) | −0.004 (4) |
N6 | 0.047 (5) | 0.048 (6) | 0.033 (4) | −0.003 (4) | −0.008 (4) | −0.005 (4) |
N7 | 0.14 (2) | 0.13 (2) | 0.083 (14) | 0.000 | −0.011 (15) | 0.000 |
C1—N1 | 1.315 (13) | C14—C18 | 1.389 (13) |
C1—C2 | 1.368 (15) | C15—N6 | 1.314 (11) |
C1—H1 | 0.9300 | C15—H15 | 0.9300 |
C2—C3 | 1.406 (13) | C16—N6 | 1.339 (14) |
C2—H2 | 0.9300 | C16—C17 | 1.359 (17) |
C3—C4 | 1.379 (14) | C16—H16 | 0.9300 |
C3—C6 | 1.478 (14) | C17—C18 | 1.383 (15) |
C4—C5 | 1.386 (14) | C17—H17 | 0.9300 |
C4—H4 | 0.9300 | C18—H18 | 0.9300 |
C5—N1 | 1.303 (12) | C19—N7 | 1.06 (3) |
C5—H5 | 0.9300 | C19—C20 | 1.45 (4) |
C6—C7 | 1.375 (13) | C20—H20A | 0.9600 |
C6—C11 | 1.403 (12) | C20—H20B | 0.9600 |
C7—C8 | 1.381 (15) | C20—H20C | 0.9600 |
C7—H7 | 0.9300 | Br1—Hg1 | 2.4674 (14) |
C8—C9 | 1.361 (13) | Br2—Hg1 | 2.5115 (13) |
C8—H8 | 0.9300 | Br3—Hg2 | 2.4963 (19) |
C9—C10 | 1.406 (12) | Br4—Hg2 | 2.4505 (19) |
C9—H9 | 0.9300 | Hg1—N1i | 2.345 (8) |
C10—C11 | 1.386 (13) | Hg1—N2 | 2.484 (8) |
C10—C12 | 1.455 (12) | Hg2—N6 | 2.432 (8) |
C11—H11 | 0.9300 | Hg2—N6ii | 2.432 (8) |
C12—N2 | 1.313 (11) | N1—Hg1i | 2.345 (8) |
C12—N4 | 1.356 (10) | N2—N3 | 1.376 (10) |
C13—N3 | 1.302 (11) | N4—N5 | 1.422 (10) |
C13—N4 | 1.375 (11) | N5—H5A | 0.9059 |
C13—C14 | 1.462 (12) | N5—H5B | 0.9007 |
C14—C15 | 1.384 (13) | ||
N1—C1—C2 | 124.4 (10) | N6—C16—C17 | 121.5 (10) |
N1—C1—H1 | 117.8 | N6—C16—H16 | 119.2 |
C2—C1—H1 | 117.8 | C17—C16—H16 | 119.2 |
C1—C2—C3 | 119.2 (10) | C16—C17—C18 | 120.7 (10) |
C1—C2—H2 | 120.4 | C16—C17—H17 | 119.6 |
C3—C2—H2 | 120.4 | C18—C17—H17 | 119.6 |
C4—C3—C2 | 115.4 (9) | C17—C18—C14 | 117.4 (10) |
C4—C3—C6 | 124.4 (9) | C17—C18—H18 | 121.3 |
C2—C3—C6 | 120.2 (9) | C14—C18—H18 | 121.3 |
C3—C4—C5 | 120.4 (9) | N7—C19—C20 | 179 (3) |
C3—C4—H4 | 119.8 | C19—C20—H20A | 109.5 |
C5—C4—H4 | 119.8 | C19—C20—H20B | 109.5 |
N1—C5—C4 | 123.4 (10) | H20A—C20—H20B | 109.5 |
N1—C5—H5 | 118.3 | C19—C20—H20C | 109.5 |
C4—C5—H5 | 118.3 | H20A—C20—H20C | 109.5 |
C7—C6—C11 | 118.1 (9) | H20B—C20—H20C | 109.5 |
C7—C6—C3 | 121.8 (8) | N1i—Hg1—Br1 | 115.0 (2) |
C11—C6—C3 | 120.0 (8) | N1i—Hg1—N2 | 86.9 (3) |
C6—C7—C8 | 121.9 (9) | Br1—Hg1—N2 | 105.5 (2) |
C6—C7—H7 | 119.0 | N1i—Hg1—Br2 | 101.9 (2) |
C8—C7—H7 | 119.0 | Br1—Hg1—Br2 | 137.73 (5) |
C9—C8—C7 | 119.8 (9) | N2—Hg1—Br2 | 95.95 (18) |
C9—C8—H8 | 120.1 | N6—Hg2—N6ii | 80.0 (4) |
C7—C8—H8 | 120.1 | N6—Hg2—Br4 | 105.57 (18) |
C8—C9—C10 | 120.5 (10) | N6ii—Hg2—Br4 | 105.57 (18) |
C8—C9—H9 | 119.8 | N6—Hg2—Br3 | 102.38 (18) |
C10—C9—H9 | 119.8 | N6ii—Hg2—Br3 | 102.38 (18) |
C11—C10—C9 | 118.9 (8) | Br4—Hg2—Br3 | 143.24 (9) |
C11—C10—C12 | 122.6 (8) | C5—N1—C1 | 117.2 (9) |
C9—C10—C12 | 118.3 (9) | C5—N1—Hg1i | 123.3 (7) |
C10—C11—C6 | 120.8 (9) | C1—N1—Hg1i | 119.5 (7) |
C10—C11—H11 | 119.6 | C12—N2—N3 | 108.9 (7) |
C6—C11—H11 | 119.6 | C12—N2—Hg1 | 129.1 (6) |
N2—C12—N4 | 108.3 (7) | N3—N2—Hg1 | 119.8 (5) |
N2—C12—C10 | 124.8 (8) | C13—N3—N2 | 107.1 (7) |
N4—C12—C10 | 126.9 (8) | C12—N4—C13 | 106.3 (7) |
N3—C13—N4 | 109.3 (7) | C12—N4—N5 | 129.8 (7) |
N3—C13—C14 | 124.0 (8) | C13—N4—N5 | 123.3 (7) |
N4—C13—C14 | 126.6 (8) | N4—N5—H5A | 108.6 |
C15—C14—C18 | 118.2 (9) | N4—N5—H5B | 108.1 |
C15—C14—C13 | 118.3 (8) | H5A—N5—H5B | 110.3 |
C18—C14—C13 | 123.5 (9) | C15—N6—C16 | 118.7 (9) |
N6—C15—C14 | 123.3 (9) | C15—N6—Hg2 | 119.4 (7) |
N6—C15—H15 | 118.3 | C16—N6—Hg2 | 120.6 (7) |
C14—C15—H15 | 118.3 | ||
N1—C1—C2—C3 | 0 (2) | C4—C5—N1—Hg1i | 176.9 (8) |
C1—C2—C3—C4 | −2.1 (17) | C2—C1—N1—C5 | 1.4 (19) |
C1—C2—C3—C6 | 179.7 (11) | C2—C1—N1—Hg1i | −175.4 (11) |
C2—C3—C4—C5 | 3.6 (16) | N4—C12—N2—N3 | 0.1 (11) |
C6—C3—C4—C5 | −178.3 (10) | C10—C12—N2—N3 | −179.8 (9) |
C3—C4—C5—N1 | −2.9 (17) | N4—C12—N2—Hg1 | 162.7 (6) |
C4—C3—C6—C7 | 176.1 (11) | C10—C12—N2—Hg1 | −17.2 (15) |
C2—C3—C6—C7 | −5.9 (16) | N1i—Hg1—N2—C12 | −38.1 (9) |
C4—C3—C6—C11 | 0.0 (16) | Br1—Hg1—N2—C12 | 77.1 (9) |
C2—C3—C6—C11 | 178.0 (10) | Br2—Hg1—N2—C12 | −139.7 (8) |
C11—C6—C7—C8 | −1.3 (17) | N1i—Hg1—N2—N3 | 122.9 (7) |
C3—C6—C7—C8 | −177.5 (11) | Br1—Hg1—N2—N3 | −122.0 (6) |
C6—C7—C8—C9 | 1.9 (19) | Br2—Hg1—N2—N3 | 21.3 (7) |
C7—C8—C9—C10 | −1.3 (18) | N4—C13—N3—N2 | 2.3 (11) |
C8—C9—C10—C11 | 0.2 (16) | C14—C13—N3—N2 | −177.6 (9) |
C8—C9—C10—C12 | 175.3 (10) | C12—N2—N3—C13 | −1.5 (11) |
C9—C10—C11—C6 | 0.4 (15) | Hg1—N2—N3—C13 | −166.0 (6) |
C12—C10—C11—C6 | −174.5 (9) | N2—C12—N4—C13 | 1.2 (11) |
C7—C6—C11—C10 | 0.2 (15) | C10—C12—N4—C13 | −178.9 (10) |
C3—C6—C11—C10 | 176.4 (9) | N2—C12—N4—N5 | 171.9 (9) |
C11—C10—C12—N2 | 127.0 (11) | C10—C12—N4—N5 | −8.2 (17) |
C9—C10—C12—N2 | −48.0 (15) | N3—C13—N4—C12 | −2.2 (11) |
C11—C10—C12—N4 | −52.9 (15) | C14—C13—N4—C12 | 177.7 (10) |
C9—C10—C12—N4 | 132.2 (11) | N3—C13—N4—N5 | −173.7 (9) |
N3—C13—C14—C15 | 38.0 (15) | C14—C13—N4—N5 | 6.2 (15) |
N4—C13—C14—C15 | −141.9 (10) | C14—C15—N6—C16 | −2.9 (16) |
N3—C13—C14—C18 | −141.0 (11) | C14—C15—N6—Hg2 | −170.2 (8) |
N4—C13—C14—C18 | 39.1 (17) | C17—C16—N6—C15 | 2.0 (18) |
C18—C14—C15—N6 | 3.1 (16) | C17—C16—N6—Hg2 | 169.1 (11) |
C13—C14—C15—N6 | −176.0 (10) | N6ii—Hg2—N6—C15 | 87.7 (8) |
N6—C16—C17—C18 | −1 (2) | Br4—Hg2—N6—C15 | −168.8 (7) |
C16—C17—C18—C14 | 2 (2) | Br3—Hg2—N6—C15 | −12.9 (8) |
C15—C14—C18—C17 | −2.3 (17) | N6ii—Hg2—N6—C16 | −79.4 (9) |
C13—C14—C18—C17 | 176.7 (11) | Br4—Hg2—N6—C16 | 24.2 (9) |
C4—C5—N1—C1 | 0.3 (16) | Br3—Hg2—N6—C16 | −180.0 (8) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···Br1iii | 0.93 | 2.85 | 3.678 (9) | 150 |
N5—H5A···Br3iv | 0.91 | 2.78 | 3.599 (10) | 150 |
N5—H5B···N3iv | 0.90 | 2.39 | 3.153 (10) | 142 |
Symmetry codes: (iii) x−1/2, y, −z+1/2; (iv) x−1/2, y, −z+3/2. |
[Hg3I6(C18H14N6)2]·C2H3N | Dx = 2.731 Mg m−3 |
Mr = 2032.93 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 7784 reflections |
a = 12.822 (3) Å | θ = 2.3–27.5° |
b = 28.976 (7) Å | µ = 13.08 mm−1 |
c = 13.309 (3) Å | T = 298 K |
V = 4945 (2) Å3 | Plan, colourless |
Z = 4 | 0.50 × 0.20 × 0.04 mm |
F(000) = 3632 |
Bruker SMART CCD area-detector diffractometer | 4701 independent reflections |
Radiation source: fine-focus sealed tube | 3888 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.060 |
ϕ and ω scans | θmax = 25.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −15→15 |
Tmin = 0.059, Tmax = 0.623 | k = −35→32 |
24554 measured reflections | l = −15→16 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0671P)2 + 52.8532P] where P = (Fo2 + 2Fc2)/3 |
4701 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 2.60 e Å−3 |
18 restraints | Δρmin = −1.85 e Å−3 |
[Hg3I6(C18H14N6)2]·C2H3N | V = 4945 (2) Å3 |
Mr = 2032.93 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.822 (3) Å | µ = 13.08 mm−1 |
b = 28.976 (7) Å | T = 298 K |
c = 13.309 (3) Å | 0.50 × 0.20 × 0.04 mm |
Bruker SMART CCD area-detector diffractometer | 4701 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3888 reflections with I > 2σ(I) |
Tmin = 0.059, Tmax = 0.623 | Rint = 0.060 |
24554 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 18 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0671P)2 + 52.8532P] where P = (Fo2 + 2Fc2)/3 |
4701 reflections | Δρmax = 2.60 e Å−3 |
280 parameters | Δρmin = −1.85 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | Occ. (<1) | |
C1 | 0.2600 (10) | 0.5064 (5) | 0.4001 (9) | 0.057 (4) | |
H1 | 0.2219 | 0.5022 | 0.3413 | 0.069* | |
C2 | 0.3397 (11) | 0.5365 (5) | 0.3982 (8) | 0.054 (3) | |
H2 | 0.3564 | 0.5518 | 0.3389 | 0.065* | |
C3 | 0.3971 (8) | 0.5448 (4) | 0.4850 (7) | 0.030 (2) | |
C4 | 0.3663 (9) | 0.5214 (4) | 0.5691 (8) | 0.042 (3) | |
H4 | 0.3994 | 0.5271 | 0.6300 | 0.051* | |
C5 | 0.2876 (9) | 0.4899 (4) | 0.5644 (8) | 0.042 (3) | |
H5 | 0.2715 | 0.4730 | 0.6218 | 0.051* | |
C6 | 0.4870 (7) | 0.5782 (3) | 0.4854 (7) | 0.027 (2) | |
C7 | 0.5198 (8) | 0.5989 (4) | 0.3964 (7) | 0.036 (2) | |
H7 | 0.4834 | 0.5931 | 0.3373 | 0.044* | |
C8 | 0.6039 (9) | 0.6274 (4) | 0.3944 (8) | 0.045 (3) | |
H8 | 0.6225 | 0.6417 | 0.3344 | 0.054* | |
C9 | 0.6614 (8) | 0.6354 (4) | 0.4782 (7) | 0.035 (2) | |
H9 | 0.7201 | 0.6542 | 0.4758 | 0.042* | |
C10 | 0.6301 (8) | 0.6146 (3) | 0.5691 (7) | 0.028 (2) | |
C11 | 0.5450 (7) | 0.5865 (4) | 0.5712 (7) | 0.028 (2) | |
H11 | 0.5255 | 0.5727 | 0.6314 | 0.034* | |
C12 | 0.7022 (8) | 0.6202 (3) | 0.6574 (7) | 0.029 (2) | |
C13 | 0.7647 (7) | 0.6366 (3) | 0.8038 (7) | 0.028 (2) | |
C14 | 0.7755 (8) | 0.6525 (4) | 0.9088 (7) | 0.033 (2) | |
C15 | 0.8606 (8) | 0.6801 (4) | 0.9316 (7) | 0.034 (2) | |
H15 | 0.9057 | 0.6886 | 0.8801 | 0.041* | |
C16 | 0.8154 (10) | 0.6831 (4) | 1.0988 (8) | 0.046 (3) | |
H16 | 0.8285 | 0.6936 | 1.1636 | 0.055* | |
C17 | 0.7288 (11) | 0.6557 (5) | 1.0810 (9) | 0.059 (4) | |
H17 | 0.6846 | 0.6474 | 1.1335 | 0.071* | |
C18 | 0.7089 (9) | 0.6407 (5) | 0.9837 (8) | 0.049 (3) | |
H18 | 0.6505 | 0.6227 | 0.9700 | 0.059* | |
C19 | 0.922 (2) | 0.7500 | 0.638 (2) | 0.097 (8) | |
C20 | 0.967 (4) | 0.7500 | 0.536 (3) | 0.169 (17) | |
H20A | 0.9771 | 0.7188 | 0.5134 | 0.253* | 0.50 |
H20B | 1.0335 | 0.7656 | 0.5366 | 0.253* | 0.50 |
H20C | 0.9210 | 0.7657 | 0.4905 | 0.253* | 0.50 |
I1 | 0.93194 (8) | 0.62394 (4) | 0.37414 (6) | 0.0631 (3) | |
I2 | 1.03030 (7) | 0.52660 (3) | 0.66052 (6) | 0.0599 (3) | |
I3 | 1.12891 (13) | 0.7500 | 0.88685 (11) | 0.0707 (4) | |
I4 | 1.05389 (15) | 0.7500 | 1.24935 (10) | 0.0764 (5) | |
Hg1 | 0.90889 (4) | 0.569653 (17) | 0.53010 (3) | 0.04264 (16) | |
Hg2 | 1.02075 (5) | 0.7500 | 1.05464 (4) | 0.04159 (19) | |
N1 | 0.2324 (7) | 0.4823 (3) | 0.4806 (6) | 0.040 (2) | |
N2 | 0.8025 (6) | 0.6127 (3) | 0.6544 (6) | 0.0317 (19) | |
N3 | 0.8420 (7) | 0.6234 (3) | 0.7481 (6) | 0.036 (2) | |
N4 | 0.6741 (6) | 0.6355 (3) | 0.7499 (5) | 0.0287 (17) | |
N5 | 0.5783 (6) | 0.6520 (4) | 0.7853 (6) | 0.040 (2) | |
H5A | 0.5646 | 0.6794 | 0.7504 | 0.060* | |
H5B | 0.5289 | 0.6298 | 0.7721 | 0.060* | |
N6 | 0.8802 (7) | 0.6948 (3) | 1.0249 (6) | 0.035 (2) | |
N7 | 0.902 (2) | 0.7500 | 0.711 (2) | 0.129 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.062 (8) | 0.072 (10) | 0.037 (6) | −0.038 (7) | −0.015 (6) | 0.004 (6) |
C2 | 0.071 (9) | 0.058 (8) | 0.033 (5) | −0.029 (7) | −0.010 (5) | 0.004 (5) |
C3 | 0.030 (5) | 0.025 (5) | 0.034 (5) | −0.004 (4) | −0.003 (4) | 0.002 (4) |
C4 | 0.038 (6) | 0.052 (7) | 0.037 (5) | −0.009 (5) | −0.005 (5) | 0.001 (5) |
C5 | 0.036 (6) | 0.052 (7) | 0.039 (6) | −0.011 (5) | 0.002 (5) | −0.001 (5) |
C6 | 0.027 (5) | 0.026 (5) | 0.027 (4) | −0.002 (4) | −0.001 (4) | −0.004 (4) |
C7 | 0.040 (6) | 0.041 (6) | 0.028 (5) | −0.008 (5) | −0.008 (4) | 0.002 (4) |
C8 | 0.052 (7) | 0.044 (7) | 0.038 (6) | −0.003 (6) | 0.002 (5) | 0.011 (5) |
C9 | 0.034 (6) | 0.027 (6) | 0.044 (6) | −0.001 (4) | 0.000 (4) | 0.001 (4) |
C10 | 0.037 (5) | 0.015 (5) | 0.033 (5) | −0.003 (4) | −0.006 (4) | −0.005 (4) |
C11 | 0.023 (5) | 0.035 (6) | 0.027 (4) | 0.000 (4) | −0.001 (4) | −0.006 (4) |
C12 | 0.033 (5) | 0.026 (5) | 0.029 (5) | −0.010 (4) | 0.000 (4) | −0.002 (4) |
C13 | 0.030 (5) | 0.025 (5) | 0.030 (5) | −0.006 (4) | −0.002 (4) | −0.005 (4) |
C14 | 0.038 (6) | 0.029 (6) | 0.032 (5) | −0.002 (4) | −0.002 (4) | 0.002 (4) |
C15 | 0.038 (6) | 0.036 (6) | 0.028 (5) | −0.010 (5) | −0.005 (4) | −0.004 (4) |
C16 | 0.052 (7) | 0.055 (8) | 0.032 (5) | −0.001 (6) | −0.010 (5) | −0.009 (5) |
C17 | 0.058 (8) | 0.085 (11) | 0.035 (6) | −0.014 (7) | 0.009 (6) | −0.003 (6) |
C18 | 0.034 (6) | 0.066 (9) | 0.048 (6) | −0.019 (6) | 0.005 (5) | −0.011 (6) |
C19 | 0.095 (11) | 0.096 (12) | 0.099 (11) | 0.000 | 0.006 (9) | 0.000 |
C20 | 0.177 (19) | 0.168 (19) | 0.162 (19) | 0.000 | 0.004 (10) | 0.000 |
I1 | 0.0694 (6) | 0.0741 (7) | 0.0458 (5) | −0.0059 (5) | 0.0160 (4) | 0.0063 (4) |
I2 | 0.0613 (6) | 0.0665 (6) | 0.0520 (5) | 0.0142 (4) | −0.0041 (4) | −0.0122 (4) |
I3 | 0.0941 (11) | 0.0454 (8) | 0.0725 (8) | 0.000 | 0.0119 (8) | 0.000 |
I4 | 0.1369 (14) | 0.0489 (8) | 0.0433 (6) | 0.000 | −0.0357 (7) | 0.000 |
Hg1 | 0.0415 (3) | 0.0468 (3) | 0.0396 (2) | −0.0112 (2) | −0.00049 (18) | −0.00256 (19) |
Hg2 | 0.0483 (4) | 0.0382 (4) | 0.0383 (3) | 0.000 | −0.0146 (3) | 0.000 |
N1 | 0.041 (5) | 0.040 (5) | 0.039 (5) | −0.005 (4) | −0.001 (4) | −0.014 (4) |
N2 | 0.022 (4) | 0.038 (5) | 0.035 (4) | −0.002 (4) | −0.005 (3) | −0.010 (4) |
N3 | 0.030 (5) | 0.047 (6) | 0.031 (4) | −0.002 (4) | 0.001 (4) | −0.009 (4) |
N4 | 0.024 (4) | 0.035 (5) | 0.028 (4) | −0.004 (3) | 0.003 (3) | −0.003 (3) |
N5 | 0.019 (4) | 0.063 (7) | 0.038 (4) | −0.002 (4) | −0.001 (3) | −0.008 (4) |
N6 | 0.044 (5) | 0.028 (5) | 0.034 (4) | −0.006 (4) | −0.012 (4) | −0.004 (4) |
N7 | 0.129 (13) | 0.133 (13) | 0.127 (12) | 0.000 | −0.005 (9) | 0.000 |
C1—N1 | 1.327 (15) | C14—C15 | 1.386 (14) |
C1—C2 | 1.344 (16) | C15—N6 | 1.337 (12) |
C1—H1 | 0.9300 | C15—H15 | 0.9300 |
C2—C3 | 1.390 (14) | C16—N6 | 1.331 (15) |
C2—H2 | 0.9300 | C16—C17 | 1.386 (18) |
C3—C4 | 1.366 (15) | C16—H16 | 0.9300 |
C3—C6 | 1.506 (13) | C17—C18 | 1.391 (16) |
C4—C5 | 1.363 (15) | C17—H17 | 0.9300 |
C4—H4 | 0.9300 | C18—H18 | 0.9300 |
C5—N1 | 1.340 (14) | C19—N7 | 1.00 (4) |
C5—H5 | 0.9300 | C19—C20 | 1.47 (4) |
C6—C11 | 1.385 (13) | C20—H20A | 0.9600 |
C6—C7 | 1.392 (14) | C20—H20B | 0.9600 |
C7—C8 | 1.358 (16) | C20—H20C | 0.9600 |
C7—H7 | 0.9300 | I1—Hg1 | 2.6211 (11) |
C8—C9 | 1.357 (15) | I2—Hg1 | 2.6444 (11) |
C8—H8 | 0.9300 | I3—Hg2 | 2.6287 (17) |
C9—C10 | 1.410 (14) | I4—Hg2 | 2.6258 (14) |
C9—H9 | 0.9300 | Hg1—N1i | 2.359 (9) |
C10—C11 | 1.361 (14) | Hg1—N2 | 2.481 (8) |
C10—C12 | 1.504 (13) | Hg2—N6 | 2.442 (9) |
C11—H11 | 0.9300 | Hg2—N6ii | 2.442 (9) |
C12—N2 | 1.305 (13) | N1—Hg1i | 2.359 (9) |
C12—N4 | 1.356 (12) | N2—N3 | 1.381 (11) |
C13—N3 | 1.296 (12) | N4—N5 | 1.400 (11) |
C13—N4 | 1.366 (12) | N5—H5A | 0.9360 |
C13—C14 | 1.477 (13) | N5—H5B | 0.9187 |
C14—C18 | 1.356 (15) | ||
N1—C1—C2 | 124.0 (11) | N6—C16—C17 | 121.3 (10) |
N1—C1—H1 | 118.0 | N6—C16—H16 | 119.3 |
C2—C1—H1 | 118.0 | C17—C16—H16 | 119.3 |
C1—C2—C3 | 119.9 (11) | C16—C17—C18 | 119.1 (11) |
C1—C2—H2 | 120.0 | C16—C17—H17 | 120.5 |
C3—C2—H2 | 120.0 | C18—C17—H17 | 120.5 |
C4—C3—C2 | 116.3 (10) | C14—C18—C17 | 119.3 (11) |
C4—C3—C6 | 122.5 (9) | C14—C18—H18 | 120.4 |
C2—C3—C6 | 121.3 (9) | C17—C18—H18 | 120.4 |
C5—C4—C3 | 120.5 (10) | N7—C19—C20 | 172 (4) |
C5—C4—H4 | 119.7 | C19—C20—H20A | 109.5 |
C3—C4—H4 | 119.7 | C19—C20—H20B | 109.5 |
N1—C5—C4 | 122.7 (10) | H20A—C20—H20B | 109.5 |
N1—C5—H5 | 118.7 | C19—C20—H20C | 109.5 |
C4—C5—H5 | 118.7 | H20A—C20—H20C | 109.5 |
C11—C6—C7 | 117.7 (9) | H20B—C20—H20C | 109.5 |
C11—C6—C3 | 121.8 (9) | N1i—Hg1—N2 | 86.5 (3) |
C7—C6—C3 | 120.4 (8) | N1i—Hg1—I1 | 114.9 (2) |
C8—C7—C6 | 121.2 (9) | N2—Hg1—I1 | 106.8 (2) |
C8—C7—H7 | 119.4 | N1i—Hg1—I2 | 101.0 (2) |
C6—C7—H7 | 119.4 | N2—Hg1—I2 | 97.08 (19) |
C9—C8—C7 | 121.3 (10) | I1—Hg1—I2 | 137.44 (4) |
C9—C8—H8 | 119.4 | N6—Hg2—N6ii | 81.9 (4) |
C7—C8—H8 | 119.4 | N6—Hg2—I4 | 106.2 (2) |
C8—C9—C10 | 118.5 (10) | N6ii—Hg2—I4 | 106.2 (2) |
C8—C9—H9 | 120.7 | N6—Hg2—I3 | 104.6 (2) |
C10—C9—H9 | 120.7 | N6ii—Hg2—I3 | 104.6 (2) |
C11—C10—C9 | 120.1 (9) | I4—Hg2—I3 | 138.85 (7) |
C11—C10—C12 | 122.8 (9) | C1—N1—C5 | 116.4 (10) |
C9—C10—C12 | 116.7 (9) | C1—N1—Hg1i | 119.5 (7) |
C10—C11—C6 | 121.2 (9) | C5—N1—Hg1i | 124.1 (7) |
C10—C11—H11 | 119.4 | C12—N2—N3 | 107.3 (8) |
C6—C11—H11 | 119.4 | C12—N2—Hg1 | 130.2 (6) |
N2—C12—N4 | 110.0 (8) | N3—N2—Hg1 | 120.9 (6) |
N2—C12—C10 | 124.3 (9) | C13—N3—N2 | 107.6 (8) |
N4—C12—C10 | 125.6 (9) | C12—N4—C13 | 105.1 (8) |
N3—C13—N4 | 110.0 (8) | C12—N4—N5 | 130.5 (8) |
N3—C13—C14 | 124.1 (9) | C13—N4—N5 | 124.1 (7) |
N4—C13—C14 | 125.8 (9) | N4—N5—H5A | 106.7 |
C18—C14—C15 | 118.8 (9) | N4—N5—H5B | 107.6 |
C18—C14—C13 | 123.9 (10) | H5A—N5—H5B | 111.6 |
C15—C14—C13 | 117.4 (9) | C16—N6—C15 | 119.2 (9) |
N6—C15—C14 | 122.4 (10) | C16—N6—Hg2 | 120.5 (7) |
N6—C15—H15 | 118.8 | C15—N6—Hg2 | 119.9 (7) |
C14—C15—H15 | 118.8 | ||
N1—C1—C2—C3 | −2 (2) | C2—C1—N1—Hg1i | −179.5 (12) |
C1—C2—C3—C4 | −1.0 (19) | C4—C5—N1—C1 | 1.6 (18) |
C1—C2—C3—C6 | 179.8 (12) | C4—C5—N1—Hg1i | −177.5 (9) |
C2—C3—C4—C5 | 3.8 (18) | N4—C12—N2—N3 | −0.1 (11) |
C6—C3—C4—C5 | −177.0 (10) | C10—C12—N2—N3 | 177.6 (9) |
C3—C4—C5—N1 | −4.3 (19) | N4—C12—N2—Hg1 | 165.1 (6) |
C4—C3—C6—C11 | 1.2 (16) | C10—C12—N2—Hg1 | −17.2 (15) |
C2—C3—C6—C11 | −179.6 (11) | N1i—Hg1—N2—C12 | −36.9 (9) |
C4—C3—C6—C7 | 175.8 (11) | I1—Hg1—N2—C12 | 78.1 (9) |
C2—C3—C6—C7 | −5.1 (16) | I2—Hg1—N2—C12 | −137.6 (9) |
C11—C6—C7—C8 | −1.9 (16) | N1i—Hg1—N2—N3 | 126.5 (8) |
C3—C6—C7—C8 | −176.7 (10) | I1—Hg1—N2—N3 | −118.4 (7) |
C6—C7—C8—C9 | 2.4 (19) | I2—Hg1—N2—N3 | 25.9 (7) |
C7—C8—C9—C10 | −2.0 (17) | N4—C13—N3—N2 | −0.4 (11) |
C8—C9—C10—C11 | 1.1 (16) | C14—C13—N3—N2 | −178.0 (9) |
C8—C9—C10—C12 | 173.7 (10) | C12—N2—N3—C13 | 0.3 (11) |
C9—C10—C11—C6 | −0.7 (15) | Hg1—N2—N3—C13 | −166.6 (7) |
C12—C10—C11—C6 | −172.8 (9) | N2—C12—N4—C13 | −0.2 (11) |
C7—C6—C11—C10 | 1.1 (15) | C10—C12—N4—C13 | −177.8 (9) |
C3—C6—C11—C10 | 175.8 (9) | N2—C12—N4—N5 | 173.1 (10) |
C11—C10—C12—N2 | 123.8 (11) | C10—C12—N4—N5 | −4.5 (16) |
C9—C10—C12—N2 | −48.6 (14) | N3—C13—N4—C12 | 0.3 (11) |
C11—C10—C12—N4 | −59.0 (14) | C14—C13—N4—C12 | 177.9 (9) |
C9—C10—C12—N4 | 128.7 (11) | N3—C13—N4—N5 | −173.4 (9) |
N3—C13—C14—C18 | −138.5 (12) | C14—C13—N4—N5 | 4.1 (15) |
N4—C13—C14—C18 | 44.3 (17) | C17—C16—N6—C15 | 0.7 (18) |
N3—C13—C14—C15 | 39.9 (15) | C17—C16—N6—Hg2 | 173.1 (10) |
N4—C13—C14—C15 | −137.4 (11) | C14—C15—N6—C16 | −0.9 (17) |
C18—C14—C15—N6 | 1.2 (17) | C14—C15—N6—Hg2 | −173.3 (8) |
C13—C14—C15—N6 | −177.3 (10) | N6ii—Hg2—N6—C16 | −83.0 (9) |
N6—C16—C17—C18 | −1 (2) | I4—Hg2—N6—C16 | 21.6 (9) |
C15—C14—C18—C17 | −1.3 (19) | I3—Hg2—N6—C16 | 173.9 (8) |
C13—C14—C18—C17 | 177.0 (12) | N6ii—Hg2—N6—C15 | 89.3 (8) |
C16—C17—C18—C14 | 1 (2) | I4—Hg2—N6—C15 | −166.1 (8) |
C2—C1—N1—C5 | 1 (2) | I3—Hg2—N6—C15 | −13.7 (8) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5B···N3iii | 0.92 | 2.42 | 3.173 (12) | 139 |
N5—H5A···I3iii | 0.94 | 2.86 | 3.706 (10) | 150 |
C7—H7···I1iv | 0.93 | 3.02 | 3.842 (10) | 148 |
Symmetry codes: (iii) x−1/2, y, −z+3/2; (iv) x−1/2, y, −z+1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | [Hg3Cl6(C18H14N6)2]·C2H3N | [Hg3Br6(C18H14N6)2]·C2H3N | [Hg3I6(C18H14N6)2]·C2H3N |
Mr | 1484.23 | 1750.99 | 2032.93 |
Crystal system, space group | Orthorhombic, Pnma | Orthorhombic, Pnma | Orthorhombic, Pnma |
Temperature (K) | 298 | 298 | 298 |
a, b, c (Å) | 12.773 (2), 27.267 (5), 12.941 (2) | 12.8037 (16), 27.890 (4), 13.0245 (17) | 12.822 (3), 28.976 (7), 13.309 (3) |
V (Å3) | 4506.9 (14) | 4651.0 (10) | 4945 (2) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 10.60 | 15.08 | 13.08 |
Crystal size (mm) | 0.32 × 0.18 × 0.05 | 0.25 × 0.20 × 0.03 | 0.50 × 0.20 × 0.04 |
Data collection | |||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) | Multi-scan (SADABS; Bruker, 2003) | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.133, 0.619 | 0.117, 0.661 | 0.059, 0.623 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22532, 4277, 3278 | 23320, 4422, 3338 | 24554, 4701, 3888 |
Rint | 0.077 | 0.075 | 0.060 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 | 0.606 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.188, 1.02 | 0.049, 0.133, 1.03 | 0.050, 0.138, 1.04 |
No. of reflections | 4277 | 4422 | 4701 |
No. of parameters | 287 | 281 | 280 |
No. of restraints | 12 | 0 | 18 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.1128P)2 + 27.9072P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0646P)2 + 19.0915P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0671P)2 + 52.8532P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.67, −1.89 | 2.17, −2.04 | 2.60, −1.85 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···Cl1i | 0.93 | 2.75 | 3.613 (12) | 154.3 |
N5—H5A···Cl3ii | 0.89 | 2.70 | 3.512 (12) | 151.6 |
N5—H5B···N3ii | 0.89 | 2.39 | 3.149 (12) | 143.3 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x−1/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···Br1i | 0.93 | 2.85 | 3.678 (9) | 149.6 |
N5—H5A···Br3ii | 0.91 | 2.78 | 3.599 (10) | 150.3 |
N5—H5B···N3ii | 0.90 | 2.39 | 3.153 (10) | 142.2 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x−1/2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5B···N3i | 0.92 | 2.42 | 3.173 (12) | 139.3 |
N5—H5A···I3i | 0.94 | 2.86 | 3.706 (10) | 150.2 |
C7—H7···I1ii | 0.93 | 3.02 | 3.842 (10) | 147.5 |
Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x−1/2, y, −z+1/2. |
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Coordination polymers containing metal nodes and organic ligands have attracted tremendous attention over the past 30 years because of their wide application as functional materials (Long & Yaghi, 2009; Spokoyny et al., 2009). The syntheses of coordination polymers by judicious choice of organic spacers and metal centers can be an efficient method for obtaining new types of luminescent materials, especially for d10 or d10–d10 systems of metal centers (Morsali & Masoomi, 2009; Tang et al., 2011). The design and construction of coordination polymers based on rigid and bent organic ligands bridged by 4-amino-4H-1,2,4-triazole have been pursued because of their specific geometry (Liu et al., 2009; Du et al., 2006). In addition, hydrogen bonds play an important role in constructing high-dimensional supramolecular compounds (Mu et al., 2008).
The study of the asymmetric oxadiazole ligand with d10 metal centers has been previously carried out by our group (Song et al., 2010), but the coordination polymers generated by asymmetric 4-amino-4H-1,2,4-triazole-based organic ligands are extremely rare. As part of our systematic studies into self-assembly based on asymmetric ligands, we have synthesized a novel asymmetric rigid ligand, viz. 4-amino-3-[4-(pyridin-4-yl)phenyl]-5-(pyridin-3-yl)-4H-1,2,4-triazole (L), which has a short (pyridin-3-yl) and a long arm [4-(pyridin-4-yl)phenyl]. Three novel isomorphous coordination complexes, viz. {[Hg3X6(L)2].CH3CN}n, with X = Cl, (I), Br, (II), and I, (III), based on L were obtained and their structures explored.
The isomorphous compounds (I), (II) and (III) were crystallized in the orthorhombic space group Pnma, with one and a half HgII centers, one L ligand, three halide atoms and half an acetonitrile solvent molecule in the asymmetric unit. Single-crystal structural analysis revealed that complex (I) contains two crystallographically independent HgII centers, as shown in Fig. 1(a). The Hg1 center is coordinated by one pyridine N atom in the long arm of the ligand, one N atom of the triazole group and two halide atoms. The Hg2 center is coordinated by two pyridine N atoms in the short arm of the ligand in addition to two halide atoms. The intrachain Hg···Hg distance is 8.729 (1) Å, which is similar to our previous report on diiodido[2,5-bis(3-pyridyl)-1,3,4-oxadiazole]mercury (Dong et al., 2003). As shown in Fig. 1(b), two ligands, two Hg1 centers and four halide atoms form rectangular units. In these structural units, the long arms of two ligands and part of the triazole ring with two Hg1 centers form a rectangular 20-membered macrocycle. The pyridine and benzene rings of the long arms of the ligand are almost coplanar, with a dihedral angle of 4.158 (4)° between the planes. In the `rectangle', there are π–π interactions (π–π = 3.800 Å) between the aromatic groups (Fig. 3), while the two pyridine rings and the two benzene rings in the macrocycle are parallel. As shown in Fig. 2, the nearby Hg2 centers are coordinated to form one-dimensional zigzag chains along the [110] direction through Hg—N bonds involving the terminal pyridin-3-yl N atom of the short arm on the ligands. The Hg2 center is located in a distorted tetrahedral environment consisting of two pyridine N-atom donors and two coordinated halide counter-ions, which is similar to our previously reported complex diiodido[2,5-bis(3-pyridyl)-1,3,4-oxadiazole]mercury (Dong et al., 2003).
As shown in Figs. 4(a) and 4(b), the chains are linked by two types of hydrogen-bonding interactions {N—H···N [N5···N3 = 3.15 (1) Å] and N—H···Cl [N5···Cl3 = 3.51 (1) Å]} into three-dimensional networks. Weaker hydrogen-bonding interactions C—H···Cl [C7···Cl1 3.61 (1) Å] extended along the a axis (Fig. 4c). In the three-dimensional network, there are ellipsoidal grids, within which the the acetonitrile solvent molecules are arranged regularly (Fig. 5).
The luminescent properties of these three new coordination polymers were investigated in the solid state at room temperature. Upon excitation at λ = 395 nm, compounds (I)–(III) showed emission maxima at 469, 474 and 474 nm, respectively. Notably, in the cases of (I), (II) and (III), almost identical emission bands were observed with the different intensities (Fig. 6); thus, the different emission luminescent intensities of (I)–(III) might be attributed to the halide-to-ligand charge transfer (XLCT) (Park et al., 2009).
In summary, the asymmetric rigid ligand L can be used as a tridentate ligand to coordinate transition metal ions. Three novel one-dimensional coordination polymers have been synthesized based on L and HgX2 (X = Cl, Br and I), and their luminescent properties investigated in the solid state at room temperature.