Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112019233/ov3013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112019233/ov3013Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112019233/ov3013IIsup3.hkl |
CCDC references: 889367; 889368
For related literature, see: Cui et al. (2012); Eddaoudi et al. (2002); Kim et al. (2010); Liu et al. (2008, 2009, 2010); Müller et al. (2006); Ma & Zhou (2010); Wang et al. (2007, 2009); Yoshizawa et al. (2006); Zachara et al. (2004).
For the preparation of (I), 80% hydrazine hydrate (2.8 g, 45 mmol) was added with stirring to a solution of 3,5-bis{4-[(benzimidazol-1-yl)methyl]phenyl}-1,3,4-oxadiazole (1.49 g, 3.0 mmol) in N,N-dimethylformamide (DMF; 20 ml). The mixture was stirred for 4 h at 423 K, then cooled to room temperature and poured into water (100 ml). The product was obtained as a white solid and purified on a silica-gel column using tetrahydrofuran as the eluent to afford L, (I), as a white crystalline solid (yield 1.00 g, 67%). A solution of L (5.00 mg, 0.010 mmol) in CH2Cl2 (10 ml) was left for about 2 d at room temperature, after which time colourless crystals were obtained (yield 3.24 mg, 65%). IR (KBr pellet, ν, cm-): 3442 (s), 1633 (s), 1496 (s), 1385 (s), 1295 (m), 1200 (w), 1123 (w), 974 (w), 765 (s), 619 (m); 1H NMR (300 MHz, DMSO, 298 K, TMS, δ, p.p.m.): 8.44 (s, 2H, –C3H2N2–), 7.96–7.94, 7.47–7.44 (aabb, 8H, –C6H4–), 7.67–7.64 (d, 2H, –C3H2N2–, 7.56–7.53 (d, 2H, –C6H3–), 7.23–7.18 (m, 4H, –C6H3–), 6.17 (s, 2H, –NH2), 5.57 (s, 4H, –CH2–). Elemental analysis, calculated for C30H24N8: C 72.32, H 4.91, N 22.77%; found: C 72.56, H 4.87, N 22.57%.
For the synthesis of (II), a solution of HgCl2 (5.42 mg, 0.020 mmol) in CH3OH (5 ml) was layered on to a solution of (I) (9.93 mg, 0.020 mmol) in CH2Cl2 (8 ml). The mixture was left for about a week at room temperature and colourless crystals of (II) were obtained (yield 8.64 mg, 62%). IR (KBr pellet, ν, cm-): 3447 (w), 1636 (s), 1509 (w), 1459 (m), 1384 (w), 1266 (m), 1193 (m), 740 (s). Elemental analysis, calculated for C61H50Cl6Hg2N16: C 45.34, H 3.23, N 13.66%; found: C 45.20, H 3.11, N 13.82%.
The H atoms on N4 were located in a difference map and their positions were initially refined subject to an N—H distance restraint of 0.89 Å. Subsequently, these H atoms were treated in fixed positions, with Uiso(H) = 1.2Ueq(N). The remaining 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) or C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) (methylene).
In noncentrosymmetric (I), Friedel pairs were merged in the final refinement. In (II), Cl atoms bonded to C33 were located in a difference Fourier map and were subsequently restrained to a C—Cl distance of 1.78 (1) Å and a Cl···Cl distance of 2.80 (2) Å to retain a tetrahedral geometry. The main directions of movement of covalently bonded atoms C29, C30 and C31 were likewise restrained with an s.u. value of 0.005 Å2 (Müller et al., 2006).
For both 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).
C30H24N8 | F(000) = 1040 |
Mr = 496.57 | Dx = 1.364 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 815 reflections |
a = 6.141 (2) Å | θ = 2.3–19.6° |
b = 19.914 (6) Å | µ = 0.09 mm−1 |
c = 19.910 (6) Å | T = 298 K |
β = 96.537 (6)° | Plate, colourless |
V = 2418.8 (13) Å3 | 0.17 × 0.11 × 0.09 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2748 independent reflections |
Radiation source: fine-focus sealed tube | 2008 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.6°, θmin = 2.1° |
ϕ and ω scans | h = −6→7 |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | k = −22→23 |
Tmin = 0.986, Tmax = 0.992 | l = −20→24 |
5790 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0369P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2748 reflections | Δρmax = 0.14 e Å−3 |
343 parameters | Δρmin = −0.15 e Å−3 |
2 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 6 (3) |
C30H24N8 | V = 2418.8 (13) Å3 |
Mr = 496.57 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 6.141 (2) Å | µ = 0.09 mm−1 |
b = 19.914 (6) Å | T = 298 K |
c = 19.910 (6) Å | 0.17 × 0.11 × 0.09 mm |
β = 96.537 (6)° |
Bruker SMART CCD area-detector diffractometer | 2748 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2008 reflections with I > 2σ(I) |
Tmin = 0.986, Tmax = 0.992 | Rint = 0.063 |
5790 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.116 | Δρmax = 0.14 e Å−3 |
S = 1.00 | Δρmin = −0.15 e Å−3 |
2748 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
343 parameters | Absolute structure parameter: 6 (3) |
2 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0844 (9) | 0.7758 (3) | −0.1891 (3) | 0.0642 (15) | |
H1 | −0.0197 | 0.8099 | −0.1919 | 0.077* | |
C2 | 0.2671 (8) | 0.7767 (2) | −0.1404 (2) | 0.0449 (12) | |
C3 | 0.4198 (8) | 0.7254 (2) | −0.1388 (2) | 0.0427 (11) | |
C4 | 0.4001 (9) | 0.6719 (2) | −0.1827 (2) | 0.0635 (15) | |
H4 | 0.5048 | 0.6380 | −0.1806 | 0.076* | |
C5 | 0.2176 (10) | 0.6709 (3) | −0.2299 (3) | 0.0694 (17) | |
H5 | 0.1970 | 0.6353 | −0.2602 | 0.083* | |
C6 | 0.0656 (10) | 0.7218 (3) | −0.2329 (3) | 0.0703 (16) | |
H6 | −0.0546 | 0.7199 | −0.2658 | 0.084* | |
C7 | 0.5107 (11) | 0.8003 (2) | −0.0606 (2) | 0.0574 (15) | |
H7 | 0.5907 | 0.8226 | −0.0249 | 0.069* | |
C8 | 0.7913 (9) | 0.7097 (3) | −0.0689 (3) | 0.0701 (15) | |
H8A | 0.8766 | 0.7368 | −0.0349 | 0.084* | |
H8B | 0.8670 | 0.7101 | −0.1090 | 0.084* | |
C9 | 0.7883 (8) | 0.6390 (2) | −0.0433 (2) | 0.0471 (11) | |
C10 | 0.9736 (8) | 0.5995 (3) | −0.0493 (2) | 0.0556 (13) | |
H10 | 1.0876 | 0.6166 | −0.0711 | 0.067* | |
C11 | 0.9893 (8) | 0.5349 (2) | −0.0229 (2) | 0.0530 (12) | |
H11 | 1.1146 | 0.5095 | −0.0264 | 0.064* | |
C12 | 0.8171 (7) | 0.5080 (2) | 0.00876 (19) | 0.0404 (11) | |
C13 | 0.6322 (8) | 0.5467 (2) | 0.0121 (2) | 0.0451 (11) | |
H13 | 0.5149 | 0.5291 | 0.0321 | 0.054* | |
C14 | 0.6186 (8) | 0.6113 (2) | −0.0138 (2) | 0.0472 (12) | |
H14 | 0.4920 | 0.6363 | −0.0110 | 0.057* | |
C15 | 0.8474 (7) | 0.4422 (2) | 0.03978 (19) | 0.0386 (10) | |
C16 | 0.7993 (7) | 0.3416 (2) | 0.08063 (19) | 0.0403 (11) | |
C17 | 0.7076 (7) | 0.2776 (2) | 0.0998 (2) | 0.0407 (11) | |
C18 | 0.8355 (8) | 0.2208 (2) | 0.0985 (2) | 0.0505 (12) | |
H18 | 0.9689 | 0.2232 | 0.0807 | 0.061* | |
C19 | 0.7687 (9) | 0.1605 (2) | 0.1232 (2) | 0.0542 (13) | |
H19 | 0.8580 | 0.1230 | 0.1216 | 0.065* | |
C20 | 0.5727 (8) | 0.1546 (2) | 0.1501 (2) | 0.0466 (12) | |
C21 | 0.4440 (9) | 0.2110 (3) | 0.1501 (3) | 0.0624 (14) | |
H21 | 0.3109 | 0.2083 | 0.1680 | 0.075* | |
C22 | 0.5062 (8) | 0.2719 (3) | 0.1243 (2) | 0.0536 (13) | |
H22 | 0.4130 | 0.3088 | 0.1234 | 0.064* | |
C23 | 0.5040 (8) | 0.0895 (2) | 0.1806 (2) | 0.0563 (13) | |
H23A | 0.3560 | 0.0942 | 0.1925 | 0.068* | |
H23B | 0.5035 | 0.0540 | 0.1472 | 0.068* | |
C24 | 0.6435 (9) | 0.0920 (2) | 0.3054 (2) | 0.0563 (13) | |
H24 | 0.5298 | 0.1183 | 0.3179 | 0.068* | |
C25 | 0.9393 (8) | 0.0366 (2) | 0.3092 (2) | 0.0457 (11) | |
C26 | 1.1378 (9) | 0.0054 (2) | 0.3271 (3) | 0.0591 (14) | |
H26 | 1.2057 | 0.0081 | 0.3712 | 0.071* | |
C27 | 1.2336 (9) | −0.0297 (2) | 0.2792 (3) | 0.0617 (14) | |
H27 | 1.3692 | −0.0499 | 0.2908 | 0.074* | |
C28 | 1.1312 (9) | −0.0358 (2) | 0.2129 (3) | 0.0598 (14) | |
H28 | 1.1966 | −0.0616 | 0.1818 | 0.072* | |
C29 | 0.9361 (9) | −0.0044 (2) | 0.1935 (2) | 0.0554 (14) | |
H29 | 0.8688 | −0.0076 | 0.1494 | 0.066* | |
C30 | 0.8420 (8) | 0.0325 (2) | 0.2417 (2) | 0.0415 (11) | |
N1 | 1.0373 (6) | 0.42256 (18) | 0.07188 (18) | 0.0493 (10) | |
N2 | 1.0063 (6) | 0.35886 (18) | 0.09779 (18) | 0.0485 (10) | |
N3 | 0.6930 (5) | 0.39314 (17) | 0.04478 (16) | 0.0393 (9) | |
N4 | 0.4818 (6) | 0.38538 (18) | 0.00842 (19) | 0.0480 (10) | |
H4A | 0.4807 | 0.3928 | −0.0355 | 0.058* | |
H4B | 0.4034 | 0.4155 | 0.0287 | 0.058* | |
N5 | 0.5785 (7) | 0.74170 (19) | −0.08529 (18) | 0.0506 (10) | |
N6 | 0.3272 (8) | 0.8236 (2) | −0.0900 (2) | 0.0618 (12) | |
N7 | 0.6508 (7) | 0.07047 (18) | 0.24115 (18) | 0.0485 (10) | |
N8 | 0.8080 (7) | 0.0730 (2) | 0.34802 (19) | 0.0585 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.058 (4) | 0.064 (3) | 0.070 (3) | 0.016 (3) | 0.006 (3) | 0.019 (3) |
C2 | 0.053 (3) | 0.037 (3) | 0.045 (3) | 0.005 (2) | 0.008 (2) | 0.003 (2) |
C3 | 0.054 (3) | 0.041 (2) | 0.032 (2) | −0.006 (2) | 0.006 (2) | 0.001 (2) |
C4 | 0.079 (4) | 0.056 (3) | 0.055 (3) | 0.005 (3) | 0.004 (3) | −0.007 (3) |
C5 | 0.091 (5) | 0.068 (4) | 0.046 (3) | −0.012 (3) | −0.004 (3) | −0.013 (3) |
C6 | 0.073 (4) | 0.087 (4) | 0.047 (3) | −0.007 (4) | −0.014 (3) | 0.006 (3) |
C7 | 0.086 (5) | 0.049 (3) | 0.038 (3) | −0.022 (3) | 0.011 (3) | −0.008 (2) |
C8 | 0.048 (3) | 0.077 (4) | 0.084 (4) | −0.010 (3) | 0.001 (3) | 0.022 (3) |
C9 | 0.038 (3) | 0.060 (3) | 0.041 (3) | −0.007 (3) | −0.006 (2) | 0.007 (2) |
C10 | 0.039 (3) | 0.079 (4) | 0.048 (3) | −0.008 (3) | 0.002 (2) | 0.016 (3) |
C11 | 0.026 (3) | 0.074 (3) | 0.056 (3) | 0.003 (3) | −0.003 (2) | 0.008 (3) |
C12 | 0.035 (3) | 0.052 (3) | 0.032 (2) | 0.003 (2) | −0.0059 (19) | −0.008 (2) |
C13 | 0.040 (3) | 0.053 (3) | 0.043 (2) | −0.002 (2) | 0.005 (2) | 0.001 (2) |
C14 | 0.042 (3) | 0.052 (3) | 0.048 (3) | 0.006 (2) | 0.006 (2) | 0.004 (2) |
C15 | 0.036 (3) | 0.048 (3) | 0.030 (2) | 0.006 (2) | −0.0047 (19) | −0.005 (2) |
C16 | 0.033 (3) | 0.053 (3) | 0.034 (2) | 0.007 (2) | −0.0041 (19) | −0.005 (2) |
C17 | 0.031 (3) | 0.051 (3) | 0.038 (2) | 0.003 (2) | −0.0043 (19) | 0.001 (2) |
C18 | 0.040 (3) | 0.059 (3) | 0.053 (3) | 0.005 (3) | 0.011 (2) | −0.003 (2) |
C19 | 0.052 (3) | 0.045 (3) | 0.066 (3) | 0.010 (2) | 0.010 (3) | −0.005 (2) |
C20 | 0.035 (3) | 0.055 (3) | 0.048 (3) | −0.004 (2) | −0.004 (2) | −0.001 (2) |
C21 | 0.040 (3) | 0.082 (4) | 0.065 (3) | −0.003 (3) | 0.004 (2) | 0.017 (3) |
C22 | 0.032 (3) | 0.067 (3) | 0.062 (3) | 0.013 (3) | 0.003 (2) | 0.004 (3) |
C23 | 0.041 (3) | 0.067 (3) | 0.059 (3) | −0.013 (3) | 0.000 (2) | 0.003 (3) |
C24 | 0.054 (4) | 0.065 (3) | 0.053 (3) | −0.005 (3) | 0.016 (3) | −0.008 (3) |
C25 | 0.056 (3) | 0.046 (3) | 0.036 (2) | −0.009 (2) | 0.006 (2) | −0.001 (2) |
C26 | 0.066 (4) | 0.060 (3) | 0.049 (3) | −0.007 (3) | −0.006 (3) | 0.008 (3) |
C27 | 0.062 (4) | 0.055 (3) | 0.067 (4) | 0.002 (3) | 0.003 (3) | 0.010 (3) |
C28 | 0.068 (4) | 0.050 (3) | 0.064 (3) | −0.001 (3) | 0.018 (3) | −0.004 (3) |
C29 | 0.072 (4) | 0.051 (3) | 0.042 (3) | −0.020 (3) | 0.007 (2) | −0.005 (2) |
C30 | 0.053 (3) | 0.040 (2) | 0.032 (2) | −0.009 (2) | 0.006 (2) | 0.000 (2) |
N1 | 0.037 (2) | 0.058 (2) | 0.050 (2) | 0.010 (2) | −0.0060 (19) | −0.0017 (19) |
N2 | 0.034 (2) | 0.057 (2) | 0.051 (2) | 0.007 (2) | −0.0096 (18) | 0.0021 (19) |
N3 | 0.022 (2) | 0.054 (2) | 0.041 (2) | 0.0055 (18) | −0.0060 (16) | −0.0020 (18) |
N4 | 0.030 (2) | 0.065 (3) | 0.045 (2) | −0.0010 (19) | −0.0121 (17) | 0.0018 (18) |
N5 | 0.052 (3) | 0.049 (2) | 0.049 (2) | −0.002 (2) | −0.002 (2) | 0.0064 (19) |
N6 | 0.077 (3) | 0.047 (2) | 0.062 (3) | 0.003 (2) | 0.014 (2) | −0.005 (2) |
N7 | 0.050 (3) | 0.058 (2) | 0.037 (2) | −0.008 (2) | −0.0005 (19) | 0.0016 (19) |
N8 | 0.068 (3) | 0.065 (3) | 0.042 (2) | −0.008 (2) | 0.005 (2) | −0.007 (2) |
C1—C6 | 1.381 (7) | C16—C17 | 1.463 (6) |
C1—C2 | 1.398 (7) | C17—C18 | 1.379 (6) |
C1—H1 | 0.9300 | C17—C22 | 1.385 (6) |
C2—C3 | 1.385 (6) | C18—C19 | 1.377 (6) |
C2—N6 | 1.388 (6) | C18—H18 | 0.9300 |
C3—C4 | 1.374 (6) | C19—C20 | 1.377 (6) |
C3—N5 | 1.398 (6) | C19—H19 | 0.9300 |
C4—C5 | 1.379 (7) | C20—C21 | 1.374 (7) |
C4—H4 | 0.9300 | C20—C23 | 1.512 (6) |
C5—C6 | 1.375 (7) | C21—C22 | 1.387 (7) |
C5—H5 | 0.9300 | C21—H21 | 0.9300 |
C6—H6 | 0.9300 | C22—H22 | 0.9300 |
C7—N6 | 1.295 (7) | C23—N7 | 1.470 (5) |
C7—N5 | 1.351 (6) | C23—H23A | 0.9700 |
C7—H7 | 0.9300 | C23—H23B | 0.9700 |
C8—N5 | 1.457 (6) | C24—N8 | 1.300 (6) |
C8—C9 | 1.498 (6) | C24—N7 | 1.354 (5) |
C8—H8A | 0.9700 | C24—H24 | 0.9300 |
C8—H8B | 0.9700 | C25—C26 | 1.379 (7) |
C9—C14 | 1.370 (6) | C25—N8 | 1.384 (6) |
C9—C10 | 1.400 (7) | C25—C30 | 1.408 (6) |
C10—C11 | 1.387 (6) | C26—C27 | 1.368 (7) |
C10—H10 | 0.9300 | C26—H26 | 0.9300 |
C11—C12 | 1.398 (6) | C27—C28 | 1.401 (7) |
C11—H11 | 0.9300 | C27—H27 | 0.9300 |
C12—C13 | 1.380 (6) | C28—C29 | 1.368 (7) |
C12—C15 | 1.452 (6) | C28—H28 | 0.9300 |
C13—C14 | 1.384 (6) | C29—C30 | 1.386 (6) |
C13—H13 | 0.9300 | C29—H29 | 0.9300 |
C14—H14 | 0.9300 | C30—N7 | 1.395 (5) |
C15—N1 | 1.323 (5) | N1—N2 | 1.390 (5) |
C15—N3 | 1.373 (5) | N3—N4 | 1.420 (4) |
C16—N2 | 1.323 (5) | N4—H4A | 0.8859 |
C16—N3 | 1.371 (5) | N4—H4B | 0.8947 |
C6—C1—C2 | 116.9 (5) | C17—C18—H18 | 119.5 |
C6—C1—H1 | 121.6 | C20—C19—C18 | 121.5 (5) |
C2—C1—H1 | 121.6 | C20—C19—H19 | 119.2 |
C3—C2—N6 | 110.9 (4) | C18—C19—H19 | 119.2 |
C3—C2—C1 | 119.6 (4) | C21—C20—C19 | 117.3 (5) |
N6—C2—C1 | 129.5 (5) | C21—C20—C23 | 121.0 (5) |
C4—C3—C2 | 123.2 (4) | C19—C20—C23 | 121.7 (5) |
C4—C3—N5 | 131.9 (5) | C20—C21—C22 | 122.1 (5) |
C2—C3—N5 | 104.9 (4) | C20—C21—H21 | 118.9 |
C3—C4—C5 | 116.8 (5) | C22—C21—H21 | 118.9 |
C3—C4—H4 | 121.6 | C17—C22—C21 | 119.8 (5) |
C5—C4—H4 | 121.6 | C17—C22—H22 | 120.1 |
C6—C5—C4 | 120.9 (5) | C21—C22—H22 | 120.1 |
C6—C5—H5 | 119.6 | N7—C23—C20 | 112.2 (4) |
C4—C5—H5 | 119.6 | N7—C23—H23A | 109.2 |
C5—C6—C1 | 122.6 (5) | C20—C23—H23A | 109.2 |
C5—C6—H6 | 118.7 | N7—C23—H23B | 109.2 |
C1—C6—H6 | 118.7 | C20—C23—H23B | 109.2 |
N6—C7—N5 | 115.7 (5) | H23A—C23—H23B | 107.9 |
N6—C7—H7 | 122.2 | N8—C24—N7 | 114.7 (5) |
N5—C7—H7 | 122.2 | N8—C24—H24 | 122.6 |
N5—C8—C9 | 116.3 (4) | N7—C24—H24 | 122.6 |
N5—C8—H8A | 108.2 | C26—C25—N8 | 130.2 (4) |
C9—C8—H8A | 108.2 | C26—C25—C30 | 119.2 (4) |
N5—C8—H8B | 108.2 | N8—C25—C30 | 110.6 (4) |
C9—C8—H8B | 108.2 | C27—C26—C25 | 119.1 (5) |
H8A—C8—H8B | 107.4 | C27—C26—H26 | 120.4 |
C14—C9—C10 | 118.4 (4) | C25—C26—H26 | 120.4 |
C14—C9—C8 | 124.3 (4) | C26—C27—C28 | 121.3 (5) |
C10—C9—C8 | 117.3 (5) | C26—C27—H27 | 119.4 |
C11—C10—C9 | 120.8 (5) | C28—C27—H27 | 119.4 |
C11—C10—H10 | 119.6 | C29—C28—C27 | 120.7 (5) |
C9—C10—H10 | 119.6 | C29—C28—H28 | 119.6 |
C10—C11—C12 | 120.1 (5) | C27—C28—H28 | 119.6 |
C10—C11—H11 | 119.9 | C28—C29—C30 | 117.9 (4) |
C12—C11—H11 | 119.9 | C28—C29—H29 | 121.1 |
C13—C12—C11 | 118.5 (4) | C30—C29—H29 | 121.1 |
C13—C12—C15 | 123.4 (4) | C29—C30—N7 | 134.3 (4) |
C11—C12—C15 | 118.1 (4) | C29—C30—C25 | 121.7 (5) |
C12—C13—C14 | 121.0 (4) | N7—C30—C25 | 104.0 (4) |
C12—C13—H13 | 119.5 | C15—N1—N2 | 107.4 (4) |
C14—C13—H13 | 119.5 | C16—N2—N1 | 108.0 (3) |
C9—C14—C13 | 121.2 (4) | C16—N3—C15 | 106.2 (3) |
C9—C14—H14 | 119.4 | C16—N3—N4 | 122.5 (3) |
C13—C14—H14 | 119.4 | C15—N3—N4 | 129.7 (3) |
N1—C15—N3 | 109.4 (4) | N3—N4—H4A | 112.9 |
N1—C15—C12 | 122.4 (4) | N3—N4—H4B | 101.7 |
N3—C15—C12 | 128.1 (4) | H4A—N4—H4B | 113.0 |
N2—C16—N3 | 109.1 (4) | C7—N5—C3 | 105.1 (4) |
N2—C16—C17 | 123.1 (4) | C7—N5—C8 | 127.0 (5) |
N3—C16—C17 | 127.8 (4) | C3—N5—C8 | 126.8 (4) |
C18—C17—C22 | 118.3 (5) | C7—N6—C2 | 103.4 (4) |
C18—C17—C16 | 118.2 (4) | C24—N7—C30 | 106.4 (4) |
C22—C17—C16 | 123.3 (4) | C24—N7—C23 | 127.5 (4) |
C19—C18—C17 | 120.9 (5) | C30—N7—C23 | 125.7 (4) |
C19—C18—H18 | 119.5 | C24—N8—C25 | 104.2 (4) |
C6—C1—C2—C3 | 1.1 (7) | C25—C26—C27—C28 | −1.6 (7) |
C6—C1—C2—N6 | −179.5 (5) | C26—C27—C28—C29 | 2.8 (8) |
N6—C2—C3—C4 | 179.4 (5) | C27—C28—C29—C30 | −1.2 (7) |
C1—C2—C3—C4 | −1.0 (7) | C28—C29—C30—N7 | 179.7 (4) |
N6—C2—C3—N5 | 0.1 (5) | C28—C29—C30—C25 | −1.5 (7) |
C1—C2—C3—N5 | 179.7 (4) | C26—C25—C30—C29 | 2.6 (7) |
C2—C3—C4—C5 | 0.1 (7) | N8—C25—C30—C29 | −176.6 (4) |
N5—C3—C4—C5 | 179.1 (5) | C26—C25—C30—N7 | −178.3 (4) |
C3—C4—C5—C6 | 0.9 (8) | N8—C25—C30—N7 | 2.5 (5) |
C4—C5—C6—C1 | −0.8 (9) | N3—C15—N1—N2 | 0.6 (5) |
C2—C1—C6—C5 | −0.2 (8) | C12—C15—N1—N2 | 177.3 (4) |
N5—C8—C9—C14 | −22.8 (7) | N3—C16—N2—N1 | −0.8 (4) |
N5—C8—C9—C10 | 158.4 (4) | C17—C16—N2—N1 | −179.6 (4) |
C14—C9—C10—C11 | −3.0 (7) | C15—N1—N2—C16 | 0.1 (5) |
C8—C9—C10—C11 | 175.8 (4) | N2—C16—N3—C15 | 1.2 (4) |
C9—C10—C11—C12 | 1.3 (7) | C17—C16—N3—C15 | 179.9 (4) |
C10—C11—C12—C13 | 1.0 (6) | N2—C16—N3—N4 | 167.7 (4) |
C10—C11—C12—C15 | −175.7 (4) | C17—C16—N3—N4 | −13.5 (6) |
C11—C12—C13—C14 | −1.5 (6) | N1—C15—N3—C16 | −1.1 (4) |
C15—C12—C13—C14 | 174.9 (4) | C12—C15—N3—C16 | −177.6 (4) |
C10—C9—C14—C13 | 2.5 (6) | N1—C15—N3—N4 | −166.3 (4) |
C8—C9—C14—C13 | −176.3 (4) | C12—C15—N3—N4 | 17.2 (7) |
C12—C13—C14—C9 | −0.2 (6) | N6—C7—N5—C3 | 1.4 (6) |
C13—C12—C15—N1 | −138.9 (4) | N6—C7—N5—C8 | 170.2 (5) |
C11—C12—C15—N1 | 37.5 (6) | C4—C3—N5—C7 | −180.0 (5) |
C13—C12—C15—N3 | 37.1 (6) | C2—C3—N5—C7 | −0.8 (5) |
C11—C12—C15—N3 | −146.5 (4) | C4—C3—N5—C8 | 11.2 (8) |
N2—C16—C17—C18 | −39.0 (6) | C2—C3—N5—C8 | −169.7 (4) |
N3—C16—C17—C18 | 142.4 (4) | C9—C8—N5—C7 | 124.6 (5) |
N2—C16—C17—C22 | 135.6 (5) | C9—C8—N5—C3 | −68.8 (6) |
N3—C16—C17—C22 | −42.9 (6) | N5—C7—N6—C2 | −1.2 (6) |
C22—C17—C18—C19 | −2.3 (7) | C3—C2—N6—C7 | 0.6 (5) |
C16—C17—C18—C19 | 172.6 (4) | C1—C2—N6—C7 | −178.9 (5) |
C17—C18—C19—C20 | −0.1 (7) | N8—C24—N7—C30 | 0.4 (5) |
C18—C19—C20—C21 | 1.3 (7) | N8—C24—N7—C23 | −172.6 (4) |
C18—C19—C20—C23 | −176.7 (4) | C29—C30—N7—C24 | 177.2 (5) |
C19—C20—C21—C22 | 0.0 (7) | C25—C30—N7—C24 | −1.7 (4) |
C23—C20—C21—C22 | 178.1 (4) | C29—C30—N7—C23 | −9.6 (7) |
C18—C17—C22—C21 | 3.6 (7) | C25—C30—N7—C23 | 171.5 (4) |
C16—C17—C22—C21 | −171.0 (4) | C20—C23—N7—C24 | 83.6 (6) |
C20—C21—C22—C17 | −2.5 (8) | C20—C23—N7—C30 | −88.2 (5) |
C21—C20—C23—N7 | −113.4 (5) | N7—C24—N8—C25 | 1.1 (6) |
C19—C20—C23—N7 | 64.5 (6) | C26—C25—N8—C24 | 178.6 (5) |
N8—C25—C26—C27 | 178.1 (4) | C30—C25—N8—C24 | −2.2 (5) |
C30—C25—C26—C27 | −1.0 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···N8i | 0.89 | 2.53 | 3.354 (5) | 155 |
N4—H4B···N1ii | 0.89 | 2.50 | 3.222 (6) | 138 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1, y, z. |
[HgCl2(C30H24N8)]·0.5CH2Cl2 | F(000) = 1580 |
Mr = 810.53 | Dx = 1.657 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5424 reflections |
a = 16.627 (3) Å | θ = 2.2–24.9° |
b = 10.6199 (18) Å | µ = 5.02 mm−1 |
c = 20.082 (3) Å | T = 298 K |
β = 113.586 (2)° | Block, colourless |
V = 3249.9 (10) Å3 | 0.40 × 0.38 × 0.34 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 6097 independent reflections |
Radiation source: fine-focus sealed tube | 4599 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.6°, θmin = 2.1° |
ϕ and ω scans | h = −20→20 |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | k = −11→12 |
Tmin = 0.239, Tmax = 0.280 | l = −24→21 |
16724 measured reflections |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.050P)2 + 0.9206P] where P = (Fo2 + 2Fc2)/3 |
6097 reflections | (Δ/σ)max = 0.002 |
397 parameters | Δρmax = 1.22 e Å−3 |
6 restraints | Δρmin = −0.64 e Å−3 |
[HgCl2(C30H24N8)]·0.5CH2Cl2 | V = 3249.9 (10) Å3 |
Mr = 810.53 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.627 (3) Å | µ = 5.02 mm−1 |
b = 10.6199 (18) Å | T = 298 K |
c = 20.082 (3) Å | 0.40 × 0.38 × 0.34 mm |
β = 113.586 (2)° |
Bruker SMART CCD area-detector diffractometer | 6097 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 4599 reflections with I > 2σ(I) |
Tmin = 0.239, Tmax = 0.280 | Rint = 0.040 |
16724 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 6 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.22 e Å−3 |
6097 reflections | Δρmin = −0.64 e Å−3 |
397 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 | Occ. (<1) | |
C1 | 0.2929 (4) | 0.1686 (6) | 0.7716 (3) | 0.0679 (17) | |
H1 | 0.2704 | 0.1287 | 0.8017 | 0.081* | |
C2 | 0.3518 (4) | 0.2680 (5) | 0.7960 (3) | 0.0473 (13) | |
C3 | 0.3825 (3) | 0.3279 (6) | 0.7500 (3) | 0.0495 (13) | |
C4 | 0.3583 (4) | 0.2890 (6) | 0.6783 (3) | 0.0646 (17) | |
H4 | 0.3803 | 0.3284 | 0.6478 | 0.078* | |
C5 | 0.3018 (5) | 0.1923 (7) | 0.6551 (4) | 0.082 (2) | |
H5 | 0.2839 | 0.1649 | 0.6073 | 0.098* | |
C6 | 0.2694 (5) | 0.1321 (7) | 0.7008 (4) | 0.083 (2) | |
H6 | 0.2307 | 0.0652 | 0.6827 | 0.099* | |
C7 | 0.4375 (4) | 0.4134 (5) | 0.8577 (3) | 0.0505 (13) | |
H7 | 0.4696 | 0.4671 | 0.8956 | 0.061* | |
C8 | 0.4972 (4) | 0.4987 (6) | 0.7699 (3) | 0.0666 (17) | |
H8A | 0.5362 | 0.4447 | 0.7575 | 0.080* | |
H8B | 0.5330 | 0.5495 | 0.8113 | 0.080* | |
C9 | 0.4485 (3) | 0.5848 (6) | 0.7062 (3) | 0.0544 (15) | |
C10 | 0.3975 (4) | 0.6818 (6) | 0.7121 (3) | 0.0542 (14) | |
H10 | 0.3889 | 0.6921 | 0.7548 | 0.065* | |
C11 | 0.3583 (4) | 0.7649 (5) | 0.6546 (3) | 0.0522 (14) | |
H11 | 0.3237 | 0.8306 | 0.6590 | 0.063* | |
C12 | 0.3706 (4) | 0.7502 (5) | 0.5915 (3) | 0.0457 (13) | |
C13 | 0.4207 (4) | 0.6519 (6) | 0.5858 (3) | 0.0579 (15) | |
H13 | 0.4284 | 0.6410 | 0.5428 | 0.069* | |
C14 | 0.4596 (4) | 0.5695 (6) | 0.6417 (3) | 0.0594 (15) | |
H14 | 0.4934 | 0.5034 | 0.6366 | 0.071* | |
C15 | 0.3380 (3) | 0.8477 (5) | 0.5345 (3) | 0.0455 (12) | |
C16 | 0.2797 (3) | 0.9393 (5) | 0.4296 (2) | 0.0428 (12) | |
C17 | 0.2339 (3) | 0.9643 (5) | 0.3522 (2) | 0.0439 (12) | |
C18 | 0.1805 (4) | 1.0706 (5) | 0.3297 (3) | 0.0582 (15) | |
H18 | 0.1724 | 1.1222 | 0.3639 | 0.070* | |
C19 | 0.1394 (4) | 1.0992 (5) | 0.2559 (3) | 0.0605 (15) | |
H19 | 0.1048 | 1.1711 | 0.2410 | 0.073* | |
C20 | 0.1498 (3) | 1.0212 (5) | 0.2048 (3) | 0.0494 (13) | |
C21 | 0.2011 (4) | 0.9170 (5) | 0.2269 (3) | 0.0596 (15) | |
H21 | 0.2078 | 0.8644 | 0.1924 | 0.072* | |
C22 | 0.2446 (4) | 0.8873 (5) | 0.3013 (3) | 0.0528 (14) | |
H22 | 0.2801 | 0.8163 | 0.3159 | 0.063* | |
C23 | 0.1038 (5) | 1.0571 (6) | 0.1257 (3) | 0.0731 (19) | |
H23A | 0.0433 | 1.0780 | 0.1156 | 0.088* | |
H23B | 0.1315 | 1.1319 | 0.1168 | 0.088* | |
C24 | 0.1647 (4) | 0.9441 (7) | 0.0470 (3) | 0.0694 (17) | |
H24 | 0.2110 | 0.9997 | 0.0557 | 0.083* | |
C25 | 0.0777 (5) | 0.7911 (6) | 0.0073 (4) | 0.0733 (18) | |
C26 | 0.0486 (4) | 0.8590 (6) | 0.0517 (3) | 0.0634 (17) | |
C27 | −0.0272 (5) | 0.8288 (9) | 0.0619 (4) | 0.088 (2) | |
H27 | −0.0466 | 0.8767 | 0.0914 | 0.106* | |
C28 | −0.0717 (7) | 0.7234 (11) | 0.0254 (7) | 0.119 (4) | |
H28 | −0.1226 | 0.6992 | 0.0307 | 0.143* | |
C29 | −0.0438 (7) | 0.6535 (9) | −0.0182 (6) | 0.120 (4) | |
H29 | −0.0757 | 0.5831 | −0.0419 | 0.144* | |
C30 | 0.0314 (7) | 0.6859 (8) | −0.0277 (5) | 0.102 (3) | |
H30 | 0.0505 | 0.6376 | −0.0572 | 0.122* | |
C31 | 0.0981 (11) | 0.9236 (17) | 0.7769 (8) | 0.145 (10) | 0.50 |
H31A | 0.1551 | 0.9285 | 0.8171 | 0.174* | 0.50 |
H31B | 0.0610 | 0.8651 | 0.7888 | 0.174* | 0.50 |
Cl1 | 0.51584 (11) | 1.22810 (16) | 0.56785 (9) | 0.0722 (4) | |
Cl2 | 0.26955 (13) | 1.38869 (17) | 0.45231 (11) | 0.0874 (5) | |
Cl3 | 0.0483 (6) | 1.0747 (10) | 0.7525 (6) | 0.265 (5) | 0.50 |
Cl4 | 0.1068 (10) | 0.8832 (9) | 0.6947 (7) | 0.358 (9) | 0.50 |
Hg1 | 0.371973 (15) | 1.22327 (2) | 0.467698 (11) | 0.05320 (11) | |
N1 | 0.3515 (3) | 0.9673 (4) | 0.5471 (2) | 0.0507 (11) | |
N2 | 0.3141 (3) | 1.0265 (4) | 0.4796 (2) | 0.0504 (11) | |
N3 | 0.2942 (3) | 0.8264 (4) | 0.4617 (2) | 0.0431 (10) | |
N4 | 0.2625 (3) | 0.7124 (4) | 0.4262 (2) | 0.0561 (13) | |
H4B | 0.2237 | 0.6805 | 0.4419 | 0.084* | |
H4A | 0.3070 | 0.6590 | 0.4361 | 0.084* | |
N5 | 0.4387 (3) | 0.4201 (4) | 0.7905 (2) | 0.0494 (11) | |
N6 | 0.3877 (3) | 0.3256 (4) | 0.8638 (2) | 0.0452 (10) | |
N7 | 0.1055 (3) | 0.9591 (5) | 0.0766 (2) | 0.0597 (13) | |
N8 | 0.1522 (4) | 0.8465 (6) | 0.0057 (3) | 0.0791 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.073 (4) | 0.070 (4) | 0.062 (4) | −0.014 (4) | 0.028 (3) | −0.013 (3) |
C2 | 0.053 (3) | 0.049 (3) | 0.041 (3) | 0.000 (3) | 0.019 (3) | −0.002 (2) |
C3 | 0.045 (3) | 0.064 (3) | 0.037 (3) | 0.010 (3) | 0.014 (2) | 0.007 (3) |
C4 | 0.067 (4) | 0.088 (5) | 0.044 (4) | 0.008 (4) | 0.028 (3) | 0.003 (3) |
C5 | 0.086 (5) | 0.097 (6) | 0.059 (4) | 0.005 (4) | 0.026 (4) | −0.023 (4) |
C6 | 0.085 (5) | 0.082 (5) | 0.075 (5) | −0.017 (4) | 0.027 (4) | −0.035 (4) |
C7 | 0.054 (3) | 0.059 (3) | 0.032 (3) | 0.002 (3) | 0.009 (3) | 0.005 (2) |
C8 | 0.047 (3) | 0.089 (4) | 0.053 (3) | −0.011 (3) | 0.010 (3) | 0.030 (3) |
C9 | 0.039 (3) | 0.074 (4) | 0.044 (3) | −0.006 (3) | 0.011 (3) | 0.020 (3) |
C10 | 0.053 (3) | 0.075 (4) | 0.032 (3) | −0.007 (3) | 0.015 (3) | 0.008 (3) |
C11 | 0.056 (3) | 0.057 (3) | 0.038 (3) | −0.007 (3) | 0.015 (3) | 0.002 (2) |
C12 | 0.055 (3) | 0.046 (3) | 0.032 (3) | −0.007 (2) | 0.012 (2) | 0.004 (2) |
C13 | 0.069 (4) | 0.064 (4) | 0.040 (3) | −0.002 (3) | 0.022 (3) | 0.009 (3) |
C14 | 0.069 (4) | 0.061 (4) | 0.052 (3) | 0.008 (3) | 0.028 (3) | 0.015 (3) |
C15 | 0.052 (3) | 0.052 (3) | 0.028 (3) | −0.004 (3) | 0.012 (2) | 0.004 (2) |
C16 | 0.048 (3) | 0.045 (3) | 0.034 (3) | −0.001 (2) | 0.015 (2) | 0.004 (2) |
C17 | 0.042 (3) | 0.053 (3) | 0.031 (3) | −0.005 (2) | 0.009 (2) | 0.004 (2) |
C18 | 0.070 (4) | 0.054 (3) | 0.043 (3) | 0.008 (3) | 0.015 (3) | −0.001 (3) |
C19 | 0.065 (4) | 0.052 (3) | 0.050 (3) | 0.018 (3) | 0.009 (3) | 0.012 (3) |
C20 | 0.046 (3) | 0.062 (3) | 0.035 (3) | 0.010 (3) | 0.011 (2) | 0.013 (3) |
C21 | 0.078 (4) | 0.060 (4) | 0.043 (3) | 0.020 (3) | 0.027 (3) | 0.006 (3) |
C22 | 0.058 (3) | 0.060 (3) | 0.032 (3) | 0.014 (3) | 0.009 (3) | 0.009 (2) |
C23 | 0.093 (5) | 0.076 (4) | 0.038 (3) | 0.021 (4) | 0.014 (3) | 0.014 (3) |
C24 | 0.062 (4) | 0.092 (5) | 0.052 (4) | 0.005 (4) | 0.021 (3) | 0.017 (4) |
C25 | 0.080 (5) | 0.075 (4) | 0.049 (4) | 0.022 (3) | 0.008 (4) | 0.015 (3) |
C26 | 0.058 (4) | 0.080 (5) | 0.043 (3) | 0.016 (3) | 0.010 (3) | 0.027 (3) |
C27 | 0.076 (5) | 0.110 (6) | 0.074 (5) | 0.016 (5) | 0.025 (4) | 0.035 (5) |
C28 | 0.091 (7) | 0.120 (9) | 0.120 (9) | −0.016 (6) | 0.017 (6) | 0.052 (7) |
C29 | 0.115 (7) | 0.075 (6) | 0.123 (8) | −0.002 (5) | −0.003 (6) | 0.030 (5) |
C30 | 0.117 (6) | 0.074 (4) | 0.081 (5) | 0.028 (4) | 0.004 (5) | 0.004 (4) |
C31 | 0.061 (10) | 0.21 (3) | 0.136 (17) | −0.012 (13) | 0.012 (11) | 0.086 (18) |
Cl1 | 0.0664 (10) | 0.0896 (11) | 0.0531 (9) | −0.0014 (8) | 0.0162 (8) | 0.0094 (8) |
Cl2 | 0.1004 (14) | 0.0686 (10) | 0.1054 (14) | 0.0271 (10) | 0.0540 (12) | −0.0017 (10) |
Cl3 | 0.220 (9) | 0.299 (12) | 0.321 (12) | −0.151 (9) | 0.155 (9) | −0.056 (10) |
Cl4 | 0.50 (2) | 0.145 (8) | 0.298 (14) | −0.040 (11) | 0.021 (14) | −0.026 (9) |
Hg1 | 0.06895 (18) | 0.04852 (15) | 0.04283 (15) | 0.00558 (10) | 0.02311 (12) | −0.00091 (9) |
N1 | 0.064 (3) | 0.053 (3) | 0.029 (2) | −0.006 (2) | 0.012 (2) | −0.0017 (19) |
N2 | 0.067 (3) | 0.047 (2) | 0.031 (2) | −0.002 (2) | 0.014 (2) | 0.0024 (19) |
N3 | 0.049 (2) | 0.046 (2) | 0.031 (2) | −0.005 (2) | 0.0129 (19) | 0.0003 (19) |
N4 | 0.074 (3) | 0.047 (3) | 0.040 (3) | −0.017 (2) | 0.015 (2) | −0.003 (2) |
N5 | 0.045 (3) | 0.063 (3) | 0.036 (2) | −0.003 (2) | 0.010 (2) | 0.013 (2) |
N6 | 0.052 (3) | 0.051 (2) | 0.035 (2) | −0.008 (2) | 0.020 (2) | 0.002 (2) |
N7 | 0.066 (3) | 0.074 (3) | 0.031 (2) | 0.008 (3) | 0.010 (2) | 0.013 (2) |
N8 | 0.082 (4) | 0.095 (5) | 0.060 (4) | 0.023 (4) | 0.028 (3) | 0.007 (3) |
C1—C6 | 1.371 (8) | C19—C20 | 1.382 (7) |
C1—C2 | 1.390 (8) | C19—H19 | 0.9300 |
C1—H1 | 0.9300 | C20—C21 | 1.359 (8) |
C2—C3 | 1.376 (8) | C20—C23 | 1.510 (7) |
C2—N6 | 1.390 (7) | C21—C22 | 1.411 (7) |
C3—N5 | 1.373 (7) | C21—H21 | 0.9300 |
C3—C4 | 1.394 (8) | C22—H22 | 0.9300 |
C4—C5 | 1.344 (10) | C23—N7 | 1.442 (7) |
C4—H4 | 0.9300 | C23—H23A | 0.9700 |
C5—C6 | 1.390 (10) | C23—H23B | 0.9700 |
C5—H5 | 0.9300 | C24—N8 | 1.292 (9) |
C6—H6 | 0.9300 | C24—N7 | 1.348 (8) |
C7—N6 | 1.284 (7) | C24—H24 | 0.9300 |
C7—N5 | 1.360 (6) | C25—C26 | 1.377 (9) |
C7—H7 | 0.9300 | C25—C30 | 1.379 (11) |
C8—N5 | 1.462 (7) | C25—N8 | 1.383 (10) |
C8—C9 | 1.517 (7) | C26—N7 | 1.376 (8) |
C8—H8A | 0.9700 | C26—C27 | 1.393 (9) |
C8—H8B | 0.9700 | C27—C28 | 1.380 (13) |
C9—C10 | 1.369 (8) | C27—H27 | 0.9300 |
C9—C14 | 1.389 (7) | C28—C29 | 1.363 (14) |
C10—C11 | 1.391 (8) | C28—H28 | 0.9300 |
C10—H10 | 0.9300 | C29—C30 | 1.382 (13) |
C11—C12 | 1.371 (8) | C29—H29 | 0.9300 |
C11—H11 | 0.9300 | C30—H30 | 0.9300 |
C12—C13 | 1.368 (8) | C31—Cl4 | 1.766 (9) |
C12—C15 | 1.477 (7) | C31—Cl3 | 1.782 (9) |
C13—C14 | 1.364 (7) | C31—H31A | 0.9700 |
C13—H13 | 0.9300 | C31—H31B | 0.9700 |
C14—H14 | 0.9300 | Cl1—Hg1 | 2.4331 (17) |
C15—N1 | 1.297 (7) | Cl2—Hg1 | 2.3793 (17) |
C15—N3 | 1.367 (6) | Hg1—N6i | 2.265 (4) |
C16—N2 | 1.316 (6) | Hg1—N2 | 2.353 (4) |
C16—N3 | 1.337 (6) | N1—N2 | 1.395 (5) |
C16—C17 | 1.455 (6) | N3—N4 | 1.397 (6) |
C17—C22 | 1.374 (7) | N4—H4B | 0.8900 |
C17—C18 | 1.394 (8) | N4—H4A | 0.8900 |
C18—C19 | 1.396 (7) | N6—Hg1ii | 2.265 (4) |
C18—H18 | 0.9300 | ||
C6—C1—C2 | 116.6 (6) | C20—C21—H21 | 119.5 |
C6—C1—H1 | 121.7 | C22—C21—H21 | 119.5 |
C2—C1—H1 | 121.7 | C17—C22—C21 | 119.4 (5) |
C3—C2—N6 | 108.9 (5) | C17—C22—H22 | 120.3 |
C3—C2—C1 | 120.8 (5) | C21—C22—H22 | 120.3 |
N6—C2—C1 | 130.3 (5) | N7—C23—C20 | 113.4 (5) |
N5—C3—C2 | 106.2 (4) | N7—C23—H23A | 108.9 |
N5—C3—C4 | 132.0 (5) | C20—C23—H23A | 108.9 |
C2—C3—C4 | 121.7 (6) | N7—C23—H23B | 108.9 |
C5—C4—C3 | 117.2 (6) | C20—C23—H23B | 108.9 |
C5—C4—H4 | 121.4 | H23A—C23—H23B | 107.7 |
C3—C4—H4 | 121.4 | N8—C24—N7 | 114.8 (7) |
C4—C5—C6 | 121.6 (6) | N8—C24—H24 | 122.6 |
C4—C5—H5 | 119.2 | N7—C24—H24 | 122.6 |
C6—C5—H5 | 119.2 | C26—C25—C30 | 119.0 (8) |
C1—C6—C5 | 122.0 (7) | C26—C25—N8 | 110.0 (6) |
C1—C6—H6 | 119.0 | C30—C25—N8 | 130.9 (8) |
C5—C6—H6 | 119.0 | N7—C26—C25 | 105.8 (6) |
N6—C7—N5 | 113.5 (5) | N7—C26—C27 | 130.9 (7) |
N6—C7—H7 | 123.3 | C25—C26—C27 | 123.2 (8) |
N5—C7—H7 | 123.3 | C28—C27—C26 | 115.7 (9) |
N5—C8—C9 | 113.0 (4) | C28—C27—H27 | 122.2 |
N5—C8—H8A | 109.0 | C26—C27—H27 | 122.2 |
C9—C8—H8A | 109.0 | C29—C28—C27 | 122.3 (10) |
N5—C8—H8B | 109.0 | C29—C28—H28 | 118.8 |
C9—C8—H8B | 109.0 | C27—C28—H28 | 118.8 |
H8A—C8—H8B | 107.8 | C28—C29—C30 | 120.9 (10) |
C10—C9—C14 | 119.1 (5) | C28—C29—H29 | 119.6 |
C10—C9—C8 | 121.4 (5) | C30—C29—H29 | 119.6 |
C14—C9—C8 | 119.4 (6) | C25—C30—C29 | 118.8 (9) |
C9—C10—C11 | 120.4 (5) | C25—C30—H30 | 120.6 |
C9—C10—H10 | 119.8 | C29—C30—H30 | 120.6 |
C11—C10—H10 | 119.8 | Cl4—C31—Cl3 | 99.5 (6) |
C12—C11—C10 | 120.1 (6) | Cl4—C31—H31A | 111.9 |
C12—C11—H11 | 120.0 | Cl3—C31—H31A | 111.9 |
C10—C11—H11 | 120.0 | Cl4—C31—H31B | 111.9 |
C13—C12—C11 | 119.1 (5) | Cl3—C31—H31B | 111.9 |
C13—C12—C15 | 121.1 (5) | H31A—C31—H31B | 109.6 |
C11—C12—C15 | 119.5 (5) | N6i—Hg1—N2 | 95.32 (15) |
C14—C13—C12 | 121.6 (5) | N6i—Hg1—Cl2 | 112.97 (12) |
C14—C13—H13 | 119.2 | N2—Hg1—Cl2 | 111.62 (13) |
C12—C13—H13 | 119.2 | N6i—Hg1—Cl1 | 109.17 (12) |
C13—C14—C9 | 119.7 (6) | N2—Hg1—Cl1 | 103.99 (11) |
C13—C14—H14 | 120.1 | Cl2—Hg1—Cl1 | 120.51 (7) |
C9—C14—H14 | 120.1 | C15—N1—N2 | 106.1 (4) |
N1—C15—N3 | 110.3 (4) | C16—N2—N1 | 108.3 (4) |
N1—C15—C12 | 123.7 (5) | C16—N2—Hg1 | 128.2 (3) |
N3—C15—C12 | 126.0 (5) | N1—N2—Hg1 | 117.2 (3) |
N2—C16—N3 | 108.9 (4) | C16—N3—C15 | 106.5 (4) |
N2—C16—C17 | 124.6 (4) | C16—N3—N4 | 125.0 (4) |
N3—C16—C17 | 126.5 (4) | C15—N3—N4 | 128.3 (4) |
C22—C17—C18 | 119.8 (5) | N3—N4—H4B | 109.2 |
C22—C17—C16 | 121.1 (5) | N3—N4—H4A | 109.1 |
C18—C17—C16 | 119.1 (5) | H4B—N4—H4A | 109.5 |
C17—C18—C19 | 119.9 (5) | C7—N5—C3 | 105.9 (4) |
C17—C18—H18 | 120.1 | C7—N5—C8 | 125.9 (5) |
C19—C18—H18 | 120.1 | C3—N5—C8 | 127.8 (5) |
C20—C19—C18 | 120.3 (5) | C7—N6—C2 | 105.5 (4) |
C20—C19—H19 | 119.9 | C7—N6—Hg1ii | 124.8 (3) |
C18—C19—H19 | 119.9 | C2—N6—Hg1ii | 129.7 (3) |
C21—C20—C19 | 119.6 (5) | C24—N7—C26 | 105.4 (6) |
C21—C20—C23 | 122.4 (5) | C24—N7—C23 | 127.1 (6) |
C19—C20—C23 | 117.9 (5) | C26—N7—C23 | 127.5 (6) |
C20—C21—C22 | 121.1 (5) | C24—N8—C25 | 104.0 (6) |
C6—C1—C2—C3 | 1.7 (10) | C26—C25—C30—C29 | 1.4 (11) |
C6—C1—C2—N6 | −179.9 (6) | N8—C25—C30—C29 | −177.7 (7) |
N6—C2—C3—N5 | 1.4 (6) | C28—C29—C30—C25 | −0.5 (13) |
C1—C2—C3—N5 | −179.9 (5) | N3—C15—N1—N2 | 0.6 (6) |
N6—C2—C3—C4 | 179.1 (5) | C12—C15—N1—N2 | 177.3 (5) |
C1—C2—C3—C4 | −2.2 (9) | N3—C16—N2—N1 | −0.9 (6) |
N5—C3—C4—C5 | 178.7 (6) | C17—C16—N2—N1 | 179.4 (5) |
C2—C3—C4—C5 | 1.6 (9) | N3—C16—N2—Hg1 | 149.8 (4) |
C3—C4—C5—C6 | −0.8 (11) | C17—C16—N2—Hg1 | −29.9 (8) |
C2—C1—C6—C5 | −0.9 (11) | C15—N1—N2—C16 | 0.2 (6) |
C4—C5—C6—C1 | 0.4 (12) | C15—N1—N2—Hg1 | −154.2 (4) |
N5—C8—C9—C10 | 67.2 (8) | N6i—Hg1—N2—C16 | −17.7 (5) |
N5—C8—C9—C14 | −116.4 (6) | Cl2—Hg1—N2—C16 | 99.6 (5) |
C14—C9—C10—C11 | −0.9 (9) | Cl1—Hg1—N2—C16 | −128.9 (4) |
C8—C9—C10—C11 | 175.5 (5) | N6i—Hg1—N2—N1 | 130.9 (3) |
C9—C10—C11—C12 | 0.0 (9) | Cl2—Hg1—N2—N1 | −111.9 (3) |
C10—C11—C12—C13 | 0.9 (9) | Cl1—Hg1—N2—N1 | 19.6 (4) |
C10—C11—C12—C15 | −172.5 (5) | N2—C16—N3—C15 | 1.2 (6) |
C11—C12—C13—C14 | −1.0 (9) | C17—C16—N3—C15 | −179.1 (5) |
C15—C12—C13—C14 | 172.3 (5) | N2—C16—N3—N4 | 175.9 (5) |
C12—C13—C14—C9 | 0.0 (9) | C17—C16—N3—N4 | −4.4 (8) |
C10—C9—C14—C13 | 0.9 (9) | N1—C15—N3—C16 | −1.1 (6) |
C8—C9—C14—C13 | −175.6 (5) | C12—C15—N3—C16 | −177.8 (5) |
C13—C12—C15—N1 | −125.5 (6) | N1—C15—N3—N4 | −175.5 (5) |
C11—C12—C15—N1 | 47.8 (8) | C12—C15—N3—N4 | 7.8 (9) |
C13—C12—C15—N3 | 50.8 (8) | N6—C7—N5—C3 | 1.1 (6) |
C11—C12—C15—N3 | −136.0 (6) | N6—C7—N5—C8 | −171.6 (5) |
N2—C16—C17—C22 | 140.7 (6) | C2—C3—N5—C7 | −1.4 (6) |
N3—C16—C17—C22 | −38.9 (8) | C4—C3—N5—C7 | −178.9 (6) |
N2—C16—C17—C18 | −37.2 (8) | C2—C3—N5—C8 | 171.0 (5) |
N3—C16—C17—C18 | 143.1 (6) | C4—C3—N5—C8 | −6.4 (10) |
C22—C17—C18—C19 | −1.0 (9) | C9—C8—N5—C7 | −124.7 (6) |
C16—C17—C18—C19 | 177.0 (5) | C9—C8—N5—C3 | 64.2 (8) |
C17—C18—C19—C20 | 1.4 (9) | N5—C7—N6—C2 | −0.2 (6) |
C18—C19—C20—C21 | −0.7 (9) | N5—C7—N6—Hg1ii | 177.1 (3) |
C18—C19—C20—C23 | −179.9 (6) | C3—C2—N6—C7 | −0.7 (6) |
C19—C20—C21—C22 | −0.4 (9) | C1—C2—N6—C7 | −179.3 (6) |
C23—C20—C21—C22 | 178.8 (6) | C3—C2—N6—Hg1ii | −177.9 (4) |
C18—C17—C22—C21 | −0.1 (8) | C1—C2—N6—Hg1ii | 3.6 (9) |
C16—C17—C22—C21 | −178.0 (5) | N8—C24—N7—C26 | 0.4 (7) |
C20—C21—C22—C17 | 0.8 (9) | N8—C24—N7—C23 | 178.7 (5) |
C21—C20—C23—N7 | 11.6 (9) | C25—C26—N7—C24 | −0.9 (6) |
C19—C20—C23—N7 | −169.2 (6) | C27—C26—N7—C24 | −176.9 (6) |
C30—C25—C26—N7 | −178.1 (6) | C25—C26—N7—C23 | −179.2 (5) |
N8—C25—C26—N7 | 1.1 (6) | C27—C26—N7—C23 | 4.9 (9) |
C30—C25—C26—C27 | −1.8 (9) | C20—C23—N7—C24 | −93.4 (7) |
N8—C25—C26—C27 | 177.5 (6) | C20—C23—N7—C26 | 84.6 (7) |
N7—C26—C27—C28 | 176.6 (7) | N7—C24—N8—C25 | 0.3 (7) |
C25—C26—C27—C28 | 1.3 (10) | C26—C25—N8—C24 | −0.9 (7) |
C26—C27—C28—C29 | −0.4 (13) | C30—C25—N8—C24 | 178.3 (7) |
C27—C28—C29—C30 | 0.0 (15) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) x, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···N8ii | 0.89 | 2.09 | 2.940 (8) | 160 |
N4—H4A···Cl2iii | 0.89 | 2.98 | 3.473 (5) | 117 |
Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) x, y−1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C30H24N8 | [HgCl2(C30H24N8)]·0.5CH2Cl2 |
Mr | 496.57 | 810.53 |
Crystal system, space group | Monoclinic, Cc | Monoclinic, P21/c |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 6.141 (2), 19.914 (6), 19.910 (6) | 16.627 (3), 10.6199 (18), 20.082 (3) |
β (°) | 96.537 (6) | 113.586 (2) |
V (Å3) | 2418.8 (13) | 3249.9 (10) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 5.02 |
Crystal size (mm) | 0.17 × 0.11 × 0.09 | 0.40 × 0.38 × 0.34 |
Data collection | ||
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) |
Tmin, Tmax | 0.986, 0.992 | 0.239, 0.280 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5790, 2748, 2008 | 16724, 6097, 4599 |
Rint | 0.063 | 0.040 |
(sin θ/λ)max (Å−1) | 0.608 | 0.608 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.116, 1.00 | 0.038, 0.102, 1.04 |
No. of reflections | 2748 | 6097 |
No. of parameters | 343 | 397 |
No. of restraints | 2 | 6 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.15 | 1.22, −0.64 |
Absolute structure | Flack (1983), with how many Friedel pairs? | ? |
Absolute structure parameter | 6 (3) | ? |
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 |
N4—H4A···N8i | 0.89 | 2.53 | 3.354 (5) | 154.7 |
N4—H4B···N1ii | 0.89 | 2.50 | 3.222 (6) | 138.1 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1, y, z. |
Cl1—Hg1 | 2.4331 (17) | Hg1—N6i | 2.265 (4) |
Cl2—Hg1 | 2.3793 (17) | Hg1—N2 | 2.353 (4) |
N6i—Hg1—N2 | 95.32 (15) | N6i—Hg1—Cl1 | 109.17 (12) |
N6i—Hg1—Cl2 | 112.97 (12) | N2—Hg1—Cl1 | 103.99 (11) |
N2—Hg1—Cl2 | 111.62 (13) | Cl2—Hg1—Cl1 | 120.51 (7) |
Symmetry code: (i) x, −y+3/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4B···N8ii | 0.89 | 2.09 | 2.940 (8) | 160.2 |
N4—H4A···Cl2iii | 0.89 | 2.98 | 3.473 (5) | 116.5 |
Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) x, y−1, z. |
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Organometallic complexes have attracted considerable attention because of their fascinating topological structures (Eddaoudi et al., 2002) and potential applications as functional materials in gas storage (Ma & Zhou, 2010), host–guest chemistry (Yoshizawa et al., 2006), catalysis (Kim et al., 2010) and luminescence (Cui et al., 2012). Over the past decade, the design and construction of rigid organic ligands bridged by 1,2,4-triazol-4-amine has been pursued, due to their diversity in coordination chemistry and model applications in functional materials (Wang et al., 2007, 2009; Liu et al., 2009, 2010).
To date, various organic ligands have been used as molecular building blocks, but the use of 1,2,4-triazol-4-amine-based bent organic ligands as semi-rigid components has remained rare until recently. In order to investigate how the semi-rigid organic ligands bridged by 1,2,4-triazol-4-amine affect the arrangement of molecular complexes in self-assembled aggregates, we synthesized a new 1,2,4-triazol-4-amine bridging ligand, namely 3,5-bis{4-[(benzimidazol-1-yl)methyl]phenyl}-4H-1,2,4-triazol-4-amine, denoted L or (I). This compound introduces two large aromatic benzimidazole groups to the ligand. The combination of (I) with HgCl2 afforded {[HgCl2L].CH2Cl2}n, (II), which features hydrogen-bonded stacking-driven two-dimensional networks.
Within the free ligand, (I) (Fig. 1), the terminal benzimidazole groups adopt a trans conformation with respect to the central bridging 1,2,4-triazol-4-amine group. The dihedral angles between the planes of the benzimidazole and triazole rings are 58.328 (2) and 89.328 (2)° [For which sides of the molecule?], and the dihedral angles between the benzimidazole and adjacent benzene rings are 78.663 (1) and 78.934 (2)° [For which sides of the molecule?]. The two benzene rings of (I) are almost coplanar, with a dihedral angle of 7.288 (1)°.
In the crystal structure, molecules of (I) are arranged in chains via N4—H4A···N8i hydrogen bonds along the crystallographic a axis (Table 1; symmetry codes given in Table 1). The chains stack via a second hydrogen-bond interaction (N4—H4B···N1ii) to form a two-dimensional network (Fig. 2). This is in contrast with 3,5-bis(2-chlorophenyl)-1H-1,2,4-triazol-4-amine (Zachara et al., 2004), the molecules of which are linked by hydrogen bonds to form a one-dimensional chain.
Compound (II) crystallizes with one unique four-coordinated HgII centre in a distorted tetrahedral {HgCl2N2} environment involving two Cl atoms (Cl1 and Cl2) and two N atoms [N1 and N6i; symmetry code: (i) x, -y + 3/2, z - 1/2] from two different ligands (Fig. 3). Neighbouring HgII cations are bound together by triazole atom N1 and the terminal benzimidazole N atoms of the L ligands to form an {HgCl2L} one-dimensional zigzag chain. The coordination behaviour of the HgII cation is similar to that observed in Hg[1-(pyridin-2-ylmethyl)-1H-benzotriazole]Cl2 (Liu et al., 2008), where the 1-(pyridin-2-ylmethyl)-1H-benzotriazole ligand (L2) is also coordinated to an HgII centre to form a single chain. Similarly, in Hg(L2)Cl2 there are no bonding interactions observed between adjacent chains.
The ligand L adopts different conformations under different conditions. In the solid state, the benzimidazole moieties adopt a trans geometry about the triazole core in the free ligand, whereas after coordination to HgII the benzimidazole groups adopt a cis conformation. Compared with those given above for (I), the dihedral angles in (II) between the planes of the benzimidazole groups and the adjacent benzene rings change to 89.328 (2) and 75.986 (2)° [For which sides of the molecule?]. These are nearly perpendicular, clearly as a result of coordination to HgII. Additionally, the dihedral angle formed by the two benzene rings changes from 7.288 (1)° in the free ligand, (I), to 18.829 (2)° in (II).
In the solid state, the zigzag chains in (II) are arranged along the a axis, where they interact via N4—H4A···Cl2iii hydrogen-bond interactions, as shown in Fig. 4 (details in Table 2; symmetry code given in Table 2). The result is that a two-dimensional sheet is generated in the bc plane. The dichloromethane solvent molecules are located within the cavities formed by the layered stacking of (II) (Fig. 5).
In summary, a new compound with a common zigzag chain motif has been successfully obtained based on a new 1,2,4-triazol-4-amine bridging bent organic ligand, (I), and HgCl2. The chains assemble through hydrogen bonds to form a two-dimensional network. The hydrogen-bond interactions play an important role in constructing high-dimensional supramolecular compounds.