Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113006471/eg3111sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113006471/eg3111Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113006471/eg3111IIsup3.hkl |
CCDC references: 950349; 950350
4-(Pyridin-3-yl)benzoic acid was obtained according to the method of Gong & Pauls (2000).
For the preparation of 2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole, polyphosphoric acid (30.0 g) was added to a mixture of 4-(pyridin-3-yl)benzoic acid (2.60 g, 13.07 mmol) and o-phenylenediamine (1.41 g, 13.07 mmol). The reaction mixture was stirred for 5 h at 453 K, and then water was poured into the cooled beaker. After adjusting the pH to 9 with aqueous ammonia, the precipitate was filtered off, washed with water, dried and purified by column chromatography on silica gel with dichloromethane and methanol (15:1 v/v) as the eluent to afford 2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole as a white solid (yield 2.67 g, 75.4%). Spectroscopic analysis: 1H NMR (300 MHz, DMSO, 298 K, TMS, δ, p.p.m.): 13.00 (s, 1H, –NH), 9.00 (s, 1H, –C5H4N), 8.61–8.59 (d, 1H, –C5H4N), 8.32–8.29 (d, 2H, –C5H4N), 8.19–8.16 (d, 1H, –C6H4), 7.95–7.93 (d, 2H, –C6H4), 7.53 (m, 1H, –C6H4), 7.51 (t, 2H, –C6H4), 7.23–7.21 (s, 2H, –C6H4); IR (KBr pellet, ν, cm-1): 3054 (m), 1621 (w), 1592 (w), 1550 (m), 1501 (s), 1473 (s), 1449 (s), 1417 (s),1316 (s), 1280 (s), 1230 (m), 1187 (w), 1103 (m), 1058 (m), 1027 (s), 1005 (m), 950 (w), 858 (w), 814 (s), 766 (s), 710 (m), 671 (w), 630 (m), 562 (m), 538 (m), 504 (w), 455 (w). Elemental analysis, calculated for C18H18N3: C 78.23, H 6.57, N 15.21%; found: C 78.25, H 6.55, N 15.20%.
For the preparation of (L), anhydrous dimethylformamide (10 ml) was added with stirring to a mixture of 2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole (0.90 g, 3.33 mmol), 3-chloromethylpyridine hydrochloride (0.55 g, 3.33 mmol), anhydrous potassium carbonate (4.60 g, 33.3 mmol) and potassium iodide (0.06 g). Stirring was continued for 24 h at 341 K, and the reaction was monitored by thin-layer chromatography (TLC). The resulting mixture was poured into water and the precipitate was filtered off, washed with water, dried and purified by column chromatography on silica gel with dichloromethane and tetrahydrofuran (2:1 v/v) as the eluent to afford L as a white solid (yield 0.82 g, 68.3%). Spectroscopic analysis: 1H NMR (300 MHz, CDCl3, 298 K, TMS, δ, p.p.m.): 8.89 (s, 1H, –C5H4N), 8.65–8.64 (d, 1H, –C5H4N), 8.59 (d, 1H, –C5H4N), 8.53 (s, 1H, –C5H4N), 7.96–7.94 (d, 2H, –C6H4), 7.84–7.83 (d, 2H, –C5H4N), 7.74–7.71 (d, 2H, –C5H4N), 7.46–7.44 (d, 2H, –C6H4), 7.38–7.36 (d, 2H, –C6H4), 7.33–7.32 (m, 2H, –C6H4); IR (KBr pellet, ν, cm-1): 3324 (s), 1637 (s), 1457 (s), 1396 (s), 1329 (m), 1283 (m), 1249 (m), 1162 (m), 1124 (w), 1024 (m), 989 (w), 942 (w), 852 (s), 809 (m), 765 (m), 746 (s), 711 (s), 594 (w). Elemental analysis, calculated for C16H11N3O4: C 79.54, H 5.01, N 15.46%; found: C79.58, H 4.96, N 15.49%.
For the preparation of (I), a mixture of L (3.62 mg, 0.01 mmol), CdBr2 (13.8 mg, 0.04 mmol) and water (2 ml) was sealed in a 5 ml test tube, heated to 423 K for 38 h and cooled slowly to room temperature over a period of 50 h. Colourless crystals of (I) were obtained (yield 5.43 mg, 75%). Spectroscopic analysis: IR (KBr pellet, ν, cm-1): 3485 (s), 1626 (s), 1461 (s), 1440 (m), 1407 (s), 1291 (w), 1257 (w), 1131 (m), 1031 (w), 1008 (w), 989 (w), 856 (m), 816 (m), 752 (s), 701 (s), 491 (w).
For the preparation of (II), a mixture of L (3.62 mg, 0.01 mmol), CdI2 (14.7 mg, 0.04 mmol) and water (2 ml) was sealed in a 5 ml test tube, heated to 423 K for 38 h and cooled slowly to room temperature over a period of 50 h. Colourless [Yellow in CIF tables - please clarify] crystals of compound (II) were obtained (yield 5.82 mg, 80%). Spectroscopic analysis: IR (KBr pellet, ν, cm-1): 3439 (s), 1661 (s), 1614 (s), 1509 (w), 1456 (m), 1402 (s), 1293 (w), 1131 (m), 1030 (w), 1007 (w), 989 (w), 854 (m), 807 (w), 749 (m), 699 (s), 528 (w).
H atoms attached to C atoms were placed in geometrically idealized positions and included as riding, with C—H = 0.93 (aromatic) or 0.97 Å (methylene). Water H atoms were located in difference maps and constrained to an O—H distance of 0.85 Å. All H atoms were refined with Uiso(H) = 1.2Ueq(parent atom).
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).
[CdBr2(C24H18N4)]·H2O | Z = 2 |
Mr = 652.66 | F(000) = 636 |
Triclinic, P1 | Dx = 1.845 Mg m−3 |
Hall symbol: -P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.379 (2) Å | Cell parameters from 3305 reflections |
b = 10.023 (2) Å | θ = 2.3–28.1° |
c = 13.773 (3) Å | µ = 4.36 mm−1 |
α = 101.504 (3)° | T = 298 K |
β = 107.424 (3)° | Bar, colourless |
γ = 99.561 (3)° | 0.28 × 0.16 × 0.12 mm |
V = 1174.7 (5) Å3 |
Bruker SMART CCD area-detector diffractometer | 4256 independent reflections |
Radiation source: fine-focus sealed tube | 3348 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 25.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −11→10 |
Tmin = 0.375, Tmax = 0.623 | k = −10→12 |
6132 measured reflections | l = −14→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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0941P)2 + 1.6163P] where P = (Fo2 + 2Fc2)/3 |
4256 reflections | (Δ/σ)max < 0.001 |
289 parameters | Δρmax = 2.03 e Å−3 |
0 restraints | Δρmin = −1.63 e Å−3 |
[CdBr2(C24H18N4)]·H2O | γ = 99.561 (3)° |
Mr = 652.66 | V = 1174.7 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.379 (2) Å | Mo Kα radiation |
b = 10.023 (2) Å | µ = 4.36 mm−1 |
c = 13.773 (3) Å | T = 298 K |
α = 101.504 (3)° | 0.28 × 0.16 × 0.12 mm |
β = 107.424 (3)° |
Bruker SMART CCD area-detector diffractometer | 4256 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3348 reflections with I > 2σ(I) |
Tmin = 0.375, Tmax = 0.623 | Rint = 0.031 |
6132 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.178 | H-atom parameters constrained |
S = 1.10 | Δρmax = 2.03 e Å−3 |
4256 reflections | Δρmin = −1.63 e Å−3 |
289 parameters |
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 | ||
Br1 | 0.72809 (12) | 0.13263 (12) | 0.08554 (8) | 0.0669 (3) | |
Br2 | 0.50224 (10) | −0.02270 (10) | 0.31475 (8) | 0.0564 (3) | |
C1 | 0.7284 (9) | 0.8361 (9) | −0.1574 (6) | 0.0447 (19) | |
H1 | 0.7302 | 0.8830 | −0.2090 | 0.054* | |
C2 | 0.8654 (10) | 0.8238 (11) | −0.0919 (7) | 0.054 (2) | |
H2 | 0.9577 | 0.8601 | −0.1000 | 0.064* | |
C3 | 0.8640 (10) | 0.7573 (10) | −0.0145 (7) | 0.051 (2) | |
H3 | 0.9556 | 0.7473 | 0.0303 | 0.061* | |
C4 | 0.7246 (8) | 0.7048 (8) | −0.0032 (6) | 0.0348 (16) | |
C5 | 0.5922 (8) | 0.7210 (8) | −0.0741 (6) | 0.0364 (17) | |
H5 | 0.4980 | 0.6861 | −0.0677 | 0.044* | |
C6 | 0.7147 (8) | 0.6424 (8) | 0.0847 (6) | 0.0361 (17) | |
C7 | 0.6005 (8) | 0.6606 (8) | 0.1269 (6) | 0.0348 (16) | |
H7 | 0.5261 | 0.7048 | 0.0961 | 0.042* | |
C8 | 0.5952 (8) | 0.6144 (8) | 0.2135 (6) | 0.0357 (16) | |
H8 | 0.5169 | 0.6271 | 0.2403 | 0.043* | |
C9 | 0.7062 (8) | 0.5486 (7) | 0.2616 (6) | 0.0345 (16) | |
C10 | 0.8169 (9) | 0.5250 (8) | 0.2178 (6) | 0.0431 (19) | |
H10 | 0.8881 | 0.4767 | 0.2468 | 0.052* | |
C11 | 0.8230 (9) | 0.5726 (8) | 0.1305 (6) | 0.0427 (18) | |
H11 | 0.8996 | 0.5578 | 0.1025 | 0.051* | |
C12 | 0.7061 (8) | 0.5069 (8) | 0.3580 (5) | 0.0333 (16) | |
C13 | 0.7188 (8) | 0.3921 (8) | 0.4776 (6) | 0.0352 (16) | |
C14 | 0.7294 (10) | 0.2935 (9) | 0.5360 (6) | 0.047 (2) | |
H14 | 0.7313 | 0.2021 | 0.5066 | 0.057* | |
C15 | 0.7368 (10) | 0.3366 (10) | 0.6388 (7) | 0.053 (2) | |
H15 | 0.7453 | 0.2728 | 0.6796 | 0.064* | |
C16 | 0.7322 (10) | 0.4709 (10) | 0.6838 (7) | 0.053 (2) | |
H16 | 0.7396 | 0.4957 | 0.7542 | 0.064* | |
C17 | 0.7169 (9) | 0.5691 (9) | 0.6268 (6) | 0.047 (2) | |
H17 | 0.7104 | 0.6590 | 0.6560 | 0.057* | |
C18 | 0.7115 (8) | 0.5260 (8) | 0.5227 (6) | 0.0380 (17) | |
C19 | 0.7062 (9) | 0.7475 (8) | 0.4641 (7) | 0.0453 (19) | |
H19A | 0.6173 | 0.7624 | 0.4829 | 0.054* | |
H19B | 0.6970 | 0.7741 | 0.3989 | 0.054* | |
C20 | 0.8490 (8) | 0.8410 (7) | 0.5493 (6) | 0.0340 (16) | |
C21 | 0.8425 (9) | 0.9734 (8) | 0.5980 (7) | 0.046 (2) | |
H21 | 0.7514 | 1.0026 | 0.5790 | 0.056* | |
C22 | 0.9733 (11) | 1.0613 (10) | 0.6751 (9) | 0.074 (3) | |
H22 | 0.9718 | 1.1506 | 0.7094 | 0.089* | |
C23 | 1.1053 (11) | 1.0151 (9) | 0.7002 (9) | 0.068 (3) | |
H23 | 1.1935 | 1.0765 | 0.7509 | 0.081* | |
C24 | 0.9868 (8) | 0.8034 (8) | 0.5820 (6) | 0.0384 (17) | |
H24 | 0.9911 | 0.7138 | 0.5503 | 0.046* | |
Cd1 | 0.64339 (6) | 0.16969 (6) | 0.24849 (4) | 0.0364 (2) | |
N1 | 0.5924 (7) | 0.7835 (7) | −0.1503 (5) | 0.0393 (15) | |
N2 | 0.7140 (7) | 0.3821 (6) | 0.3747 (5) | 0.0363 (14) | |
N3 | 0.7043 (7) | 0.5982 (6) | 0.4458 (5) | 0.0350 (14) | |
N4 | 1.1153 (7) | 0.8880 (7) | 0.6567 (6) | 0.0488 (17) | |
O1 | 0.7725 (9) | 0.2847 (11) | −0.1092 (7) | 0.104 (3) | |
H1A | 0.7634 | 0.2575 | −0.0559 | 0.125* | |
H1B | 0.7134 | 0.2208 | −0.1642 | 0.125* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0616 (6) | 0.0932 (8) | 0.0639 (6) | 0.0345 (5) | 0.0373 (5) | 0.0227 (6) |
Br2 | 0.0507 (5) | 0.0512 (6) | 0.0753 (7) | 0.0100 (4) | 0.0215 (4) | 0.0361 (5) |
C1 | 0.048 (5) | 0.048 (5) | 0.049 (5) | 0.013 (4) | 0.026 (4) | 0.022 (4) |
C2 | 0.040 (4) | 0.075 (6) | 0.059 (5) | 0.016 (4) | 0.027 (4) | 0.029 (5) |
C3 | 0.041 (4) | 0.066 (6) | 0.055 (5) | 0.020 (4) | 0.018 (4) | 0.026 (5) |
C4 | 0.032 (4) | 0.038 (4) | 0.035 (4) | 0.010 (3) | 0.013 (3) | 0.010 (3) |
C5 | 0.032 (4) | 0.042 (4) | 0.037 (4) | 0.008 (3) | 0.013 (3) | 0.013 (3) |
C6 | 0.033 (4) | 0.034 (4) | 0.037 (4) | 0.008 (3) | 0.005 (3) | 0.011 (3) |
C7 | 0.034 (4) | 0.037 (4) | 0.038 (4) | 0.013 (3) | 0.012 (3) | 0.015 (3) |
C8 | 0.031 (4) | 0.040 (4) | 0.038 (4) | 0.012 (3) | 0.009 (3) | 0.016 (3) |
C9 | 0.036 (4) | 0.029 (4) | 0.035 (4) | 0.005 (3) | 0.008 (3) | 0.009 (3) |
C10 | 0.040 (4) | 0.041 (4) | 0.046 (5) | 0.014 (3) | 0.006 (3) | 0.016 (4) |
C11 | 0.044 (4) | 0.043 (4) | 0.051 (5) | 0.020 (4) | 0.020 (4) | 0.021 (4) |
C12 | 0.029 (3) | 0.034 (4) | 0.029 (4) | 0.006 (3) | 0.003 (3) | 0.003 (3) |
C13 | 0.033 (4) | 0.032 (4) | 0.041 (4) | 0.007 (3) | 0.012 (3) | 0.012 (3) |
C14 | 0.059 (5) | 0.041 (5) | 0.046 (5) | 0.014 (4) | 0.018 (4) | 0.019 (4) |
C15 | 0.055 (5) | 0.051 (5) | 0.055 (5) | 0.003 (4) | 0.018 (4) | 0.027 (5) |
C16 | 0.055 (5) | 0.063 (6) | 0.039 (5) | 0.003 (4) | 0.019 (4) | 0.012 (4) |
C17 | 0.055 (5) | 0.044 (5) | 0.038 (4) | 0.005 (4) | 0.019 (4) | 0.003 (4) |
C18 | 0.035 (4) | 0.037 (4) | 0.038 (4) | 0.004 (3) | 0.009 (3) | 0.011 (3) |
C19 | 0.042 (4) | 0.035 (4) | 0.050 (5) | 0.016 (3) | 0.003 (4) | 0.009 (4) |
C20 | 0.037 (4) | 0.026 (4) | 0.040 (4) | 0.009 (3) | 0.011 (3) | 0.012 (3) |
C21 | 0.044 (4) | 0.040 (4) | 0.053 (5) | 0.019 (4) | 0.010 (4) | 0.010 (4) |
C22 | 0.064 (6) | 0.036 (5) | 0.095 (8) | 0.018 (4) | −0.002 (6) | −0.004 (5) |
C23 | 0.048 (5) | 0.034 (5) | 0.091 (7) | 0.011 (4) | −0.006 (5) | −0.003 (5) |
C24 | 0.036 (4) | 0.032 (4) | 0.045 (4) | 0.012 (3) | 0.013 (3) | 0.004 (3) |
Cd1 | 0.0355 (3) | 0.0342 (3) | 0.0396 (3) | 0.0091 (2) | 0.0113 (2) | 0.0123 (2) |
N1 | 0.040 (3) | 0.044 (4) | 0.038 (3) | 0.010 (3) | 0.015 (3) | 0.017 (3) |
N2 | 0.041 (3) | 0.033 (3) | 0.036 (3) | 0.011 (3) | 0.010 (3) | 0.012 (3) |
N3 | 0.032 (3) | 0.036 (3) | 0.034 (3) | 0.009 (3) | 0.007 (2) | 0.008 (3) |
N4 | 0.040 (4) | 0.033 (4) | 0.066 (5) | 0.009 (3) | 0.007 (3) | 0.015 (3) |
O1 | 0.075 (5) | 0.151 (9) | 0.082 (6) | 0.016 (5) | 0.021 (4) | 0.039 (6) |
Cd1—Br1 | 2.5766 (12) | C14—H14 | 0.9300 |
Cd1—Br2 | 2.6233 (10) | C15—C16 | 1.379 (13) |
C1—N1 | 1.336 (10) | C15—H15 | 0.9300 |
C1—C2 | 1.373 (12) | C16—C17 | 1.376 (12) |
C1—H1 | 0.9300 | C16—H16 | 0.9300 |
C2—C3 | 1.367 (12) | C17—C18 | 1.396 (11) |
C2—H2 | 0.9300 | C17—H17 | 0.9300 |
C3—C4 | 1.392 (11) | C18—N3 | 1.389 (9) |
C3—H3 | 0.9300 | C19—N3 | 1.463 (9) |
C4—C5 | 1.388 (10) | C19—C20 | 1.500 (10) |
C4—C6 | 1.488 (10) | C19—H19A | 0.9700 |
C5—N1 | 1.326 (9) | C19—H19B | 0.9700 |
C5—H5 | 0.9300 | C20—C24 | 1.377 (10) |
C6—C7 | 1.383 (11) | C20—C21 | 1.382 (11) |
C6—C11 | 1.396 (10) | C21—C22 | 1.377 (12) |
C7—C8 | 1.374 (10) | C21—H21 | 0.9300 |
C7—H7 | 0.9300 | C22—C23 | 1.365 (13) |
C8—C9 | 1.396 (10) | C22—H22 | 0.9300 |
C8—H8 | 0.9300 | C23—N4 | 1.327 (11) |
C9—C10 | 1.378 (11) | C23—H23 | 0.9300 |
C9—C12 | 1.470 (10) | C24—N4 | 1.342 (10) |
C10—C11 | 1.392 (11) | C24—H24 | 0.9300 |
C10—H10 | 0.9300 | Cd1—N2 | 2.315 (6) |
C11—H11 | 0.9300 | Cd1—N1i | 2.397 (6) |
C12—N2 | 1.327 (9) | Cd1—N4ii | 2.475 (7) |
C12—N3 | 1.368 (9) | N1—Cd1i | 2.397 (6) |
C13—C18 | 1.384 (10) | N4—Cd1ii | 2.475 (7) |
C13—N2 | 1.387 (9) | O1—H1A | 0.8549 |
C13—C14 | 1.392 (10) | O1—H1B | 0.8530 |
C14—C15 | 1.372 (12) | ||
Cd1—Br1—H1A | 140.3 | C16—C17—H17 | 122.0 |
N1—C1—C2 | 122.9 (7) | C18—C17—H17 | 122.0 |
N1—C1—H1 | 118.6 | C13—C18—N3 | 105.8 (7) |
C2—C1—H1 | 118.6 | C13—C18—C17 | 122.8 (7) |
C3—C2—C1 | 119.0 (8) | N3—C18—C17 | 131.4 (7) |
C3—C2—H2 | 120.5 | N3—C19—C20 | 113.7 (6) |
C1—C2—H2 | 120.5 | N3—C19—H19A | 108.8 |
C2—C3—C4 | 119.6 (8) | C20—C19—H19A | 108.8 |
C2—C3—H3 | 120.2 | N3—C19—H19B | 108.8 |
C4—C3—H3 | 120.2 | C20—C19—H19B | 108.8 |
C5—C4—C3 | 117.1 (7) | H19A—C19—H19B | 107.7 |
C5—C4—C6 | 120.0 (6) | C24—C20—C21 | 117.7 (7) |
C3—C4—C6 | 122.8 (7) | C24—C20—C19 | 124.1 (7) |
N1—C5—C4 | 123.6 (7) | C21—C20—C19 | 118.2 (7) |
N1—C5—H5 | 118.2 | C22—C21—C20 | 118.9 (8) |
C4—C5—H5 | 118.2 | C22—C21—H21 | 120.6 |
C7—C6—C11 | 118.5 (7) | C20—C21—H21 | 120.6 |
C7—C6—C4 | 119.5 (6) | C23—C22—C21 | 118.9 (9) |
C11—C6—C4 | 121.9 (7) | C23—C22—H22 | 120.6 |
C8—C7—C6 | 121.2 (7) | C21—C22—H22 | 120.6 |
C8—C7—H7 | 119.4 | N4—C23—C22 | 124.0 (8) |
C6—C7—H7 | 119.4 | N4—C23—H23 | 118.0 |
C7—C8—C9 | 120.5 (7) | C22—C23—H23 | 118.0 |
C7—C8—H8 | 119.7 | N4—C24—C20 | 124.1 (7) |
C9—C8—H8 | 119.7 | N4—C24—H24 | 117.9 |
C10—C9—C8 | 118.8 (7) | C20—C24—H24 | 117.9 |
C10—C9—C12 | 120.7 (7) | N2—Cd1—N1i | 92.7 (2) |
C8—C9—C12 | 120.5 (7) | N2—Cd1—N4ii | 89.9 (2) |
C9—C10—C11 | 120.6 (7) | N1i—Cd1—N4ii | 177.4 (2) |
C9—C10—H10 | 119.7 | N2—Cd1—Br1 | 123.50 (15) |
C11—C10—H10 | 119.7 | N1i—Cd1—Br1 | 91.39 (15) |
C10—C11—C6 | 120.3 (8) | N4ii—Cd1—Br1 | 86.88 (18) |
C10—C11—H11 | 119.9 | N2—Cd1—Br2 | 108.50 (15) |
C6—C11—H11 | 119.9 | N1i—Cd1—Br2 | 93.21 (15) |
N2—C12—N3 | 111.0 (6) | N4ii—Cd1—Br2 | 86.34 (16) |
N2—C12—C9 | 126.3 (7) | Br1—Cd1—Br2 | 127.48 (4) |
N3—C12—C9 | 122.7 (7) | C5—N1—C1 | 117.8 (7) |
C18—C13—N2 | 109.3 (6) | C5—N1—Cd1i | 118.4 (5) |
C18—C13—C14 | 119.9 (7) | C1—N1—Cd1i | 123.0 (5) |
N2—C13—C14 | 130.8 (7) | C12—N2—C13 | 106.6 (6) |
C15—C14—C13 | 117.3 (8) | C12—N2—Cd1 | 127.1 (5) |
C15—C14—H14 | 121.4 | C13—N2—Cd1 | 122.8 (5) |
C13—C14—H14 | 121.4 | C12—N3—C18 | 107.3 (6) |
C14—C15—C16 | 122.5 (8) | C12—N3—C19 | 129.1 (6) |
C14—C15—H15 | 118.8 | C18—N3—C19 | 123.4 (6) |
C16—C15—H15 | 118.8 | C23—N4—C24 | 116.4 (7) |
C17—C16—C15 | 121.4 (8) | C23—N4—Cd1ii | 113.1 (5) |
C17—C16—H16 | 119.3 | C24—N4—Cd1ii | 129.4 (5) |
C15—C16—H16 | 119.3 | H1A—O1—H1B | 107.0 |
C16—C17—C18 | 116.1 (8) | ||
N1—C1—C2—C3 | −1.3 (14) | C21—C20—C24—N4 | −1.1 (12) |
C1—C2—C3—C4 | −0.5 (14) | C19—C20—C24—N4 | 178.6 (8) |
C2—C3—C4—C5 | 1.3 (13) | H1A—Br1—Cd1—N2 | −41.4 |
C2—C3—C4—C6 | −174.5 (8) | H1A—Br1—Cd1—N1i | 52.7 |
C3—C4—C5—N1 | −0.3 (12) | H1A—Br1—Cd1—N4ii | −129.2 |
C6—C4—C5—N1 | 175.6 (7) | H1A—Br1—Cd1—Br2 | 147.8 |
C5—C4—C6—C7 | −30.2 (10) | C4—C5—N1—C1 | −1.4 (12) |
C3—C4—C6—C7 | 145.5 (8) | C4—C5—N1—Cd1i | −171.4 (6) |
C5—C4—C6—C11 | 153.6 (8) | C2—C1—N1—C5 | 2.2 (13) |
C3—C4—C6—C11 | −30.7 (11) | C2—C1—N1—Cd1i | 171.7 (7) |
C11—C6—C7—C8 | 1.6 (11) | N3—C12—N2—C13 | −0.4 (8) |
C4—C6—C7—C8 | −174.7 (7) | C9—C12—N2—C13 | 176.8 (7) |
C6—C7—C8—C9 | 0.5 (11) | N3—C12—N2—Cd1 | 158.6 (5) |
C7—C8—C9—C10 | −3.0 (11) | C9—C12—N2—Cd1 | −24.1 (10) |
C7—C8—C9—C12 | 176.3 (7) | C18—C13—N2—C12 | 0.8 (8) |
C8—C9—C10—C11 | 3.5 (11) | C14—C13—N2—C12 | −179.1 (8) |
C12—C9—C10—C11 | −175.8 (7) | C18—C13—N2—Cd1 | −159.4 (5) |
C9—C10—C11—C6 | −1.4 (12) | C14—C13—N2—Cd1 | 20.7 (11) |
C7—C6—C11—C10 | −1.1 (11) | N1i—Cd1—N2—C12 | −44.9 (6) |
C4—C6—C11—C10 | 175.1 (7) | N4ii—Cd1—N2—C12 | 134.7 (6) |
C10—C9—C12—N2 | −50.4 (10) | Br1—Cd1—N2—C12 | 48.5 (6) |
C8—C9—C12—N2 | 130.3 (8) | Br2—Cd1—N2—C12 | −139.2 (5) |
C10—C9—C12—N3 | 126.6 (8) | N1i—Cd1—N2—C13 | 111.0 (5) |
C8—C9—C12—N3 | −52.7 (10) | N4ii—Cd1—N2—C13 | −69.4 (5) |
C18—C13—C14—C15 | −2.0 (11) | Br1—Cd1—N2—C13 | −155.6 (5) |
N2—C13—C14—C15 | 177.9 (8) | Br2—Cd1—N2—C13 | 16.7 (6) |
C13—C14—C15—C16 | 0.8 (13) | N2—C12—N3—C18 | 0.0 (8) |
C14—C15—C16—C17 | 1.2 (14) | C9—C12—N3—C18 | −177.5 (6) |
C15—C16—C17—C18 | −2.1 (12) | N2—C12—N3—C19 | 175.7 (6) |
N2—C13—C18—N3 | −0.8 (8) | C9—C12—N3—C19 | −1.7 (11) |
C14—C13—C18—N3 | 179.1 (7) | C13—C18—N3—C12 | 0.5 (8) |
N2—C13—C18—C17 | −178.8 (7) | C17—C18—N3—C12 | 178.3 (8) |
C14—C13—C18—C17 | 1.1 (11) | C13—C18—N3—C19 | −175.5 (6) |
C16—C17—C18—C13 | 0.9 (11) | C17—C18—N3—C19 | 2.2 (12) |
C16—C17—C18—N3 | −176.5 (8) | C20—C19—N3—C12 | −114.9 (8) |
N3—C19—C20—C24 | 22.1 (12) | C20—C19—N3—C18 | 60.3 (10) |
N3—C19—C20—C21 | −158.2 (7) | C22—C23—N4—C24 | 1.6 (17) |
C24—C20—C21—C22 | 0.9 (13) | C22—C23—N4—Cd1ii | −167.4 (10) |
C19—C20—C21—C22 | −178.9 (9) | C20—C24—N4—C23 | −0.1 (13) |
C20—C21—C22—C23 | 0.5 (16) | C20—C24—N4—Cd1ii | 166.8 (6) |
C21—C22—C23—N4 | −1.8 (19) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···Br2iii | 0.85 | 2.62 | 3.459 (9) | 170 |
O1—H1A···Br1 | 0.85 | 2.59 | 3.433 (9) | 170 |
Symmetry code: (iii) −x+1, −y, −z. |
[CdI2(C24H18N4)] | Z = 2 |
Mr = 728.62 | F(000) = 688 |
Triclinic, P1 | Dx = 2.096 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.128 (2) Å | Cell parameters from 3305 reflections |
b = 10.254 (3) Å | θ = 2.3–28.0° |
c = 13.429 (4) Å | µ = 3.64 mm−1 |
α = 70.065 (3)° | T = 298 K |
β = 77.717 (4)° | Bar, yellow |
γ = 86.952 (3)° | 0.28 × 0.16 × 0.12 mm |
V = 1154.4 (5) Å3 |
Bruker SMART CCD area-detector diffractometer | 4424 independent reflections |
Radiation source: fine-focus sealed tube | 3863 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −11→11 |
Tmin = 0.502, Tmax = 0.646 | k = −10→12 |
6318 measured reflections | l = −11→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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0387P)2 + 0.214P] where P = (Fo2 + 2Fc2)/3 |
4424 reflections | (Δ/σ)max = 0.001 |
280 parameters | Δρmax = 0.84 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
[CdI2(C24H18N4)] | γ = 86.952 (3)° |
Mr = 728.62 | V = 1154.4 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.128 (2) Å | Mo Kα radiation |
b = 10.254 (3) Å | µ = 3.64 mm−1 |
c = 13.429 (4) Å | T = 298 K |
α = 70.065 (3)° | 0.28 × 0.16 × 0.12 mm |
β = 77.717 (4)° |
Bruker SMART CCD area-detector diffractometer | 4424 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 3863 reflections with I > 2σ(I) |
Tmin = 0.502, Tmax = 0.646 | Rint = 0.017 |
6318 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.84 e Å−3 |
4424 reflections | Δρmin = −0.55 e Å−3 |
280 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 | ||
Cd1 | 0.36190 (3) | 1.32721 (3) | 0.23763 (2) | 0.02950 (9) | |
I1 | 0.64498 (4) | 1.37177 (4) | 0.10783 (3) | 0.05443 (11) | |
I2 | 0.13184 (3) | 1.50971 (3) | 0.27458 (2) | 0.04140 (10) | |
N1 | 0.7491 (4) | 0.7373 (3) | −0.1127 (3) | 0.0330 (8) | |
N2 | 0.3074 (4) | 1.1119 (3) | 0.3762 (2) | 0.0272 (7) | |
N3 | 0.2289 (4) | 0.8917 (3) | 0.4570 (3) | 0.0268 (7) | |
N4 | 0.5115 (4) | 0.6109 (3) | 0.6357 (3) | 0.0354 (8) | |
C1 | 0.8846 (5) | 0.6977 (5) | −0.0930 (3) | 0.0393 (10) | |
H1 | 0.9473 | 0.6579 | −0.1386 | 0.047* | |
C2 | 0.9356 (5) | 0.7129 (6) | −0.0089 (4) | 0.0508 (13) | |
H2 | 1.0314 | 0.6851 | 0.0017 | 0.061* | |
C3 | 0.8426 (5) | 0.7702 (5) | 0.0600 (4) | 0.0446 (11) | |
H3 | 0.8747 | 0.7793 | 0.1187 | 0.053* | |
C4 | 0.7029 (5) | 0.8138 (4) | 0.0419 (3) | 0.0318 (9) | |
C5 | 0.6607 (5) | 0.7932 (4) | −0.0451 (3) | 0.0312 (9) | |
H5 | 0.5653 | 0.8198 | −0.0573 | 0.037* | |
C6 | 0.5966 (5) | 0.8703 (4) | 0.1159 (3) | 0.0307 (9) | |
C7 | 0.6494 (5) | 0.9482 (4) | 0.1686 (3) | 0.0351 (9) | |
H7 | 0.7503 | 0.9741 | 0.1502 | 0.042* | |
C8 | 0.5542 (5) | 0.9875 (4) | 0.2477 (3) | 0.0328 (9) | |
H8 | 0.5920 | 1.0385 | 0.2825 | 0.039* | |
C9 | 0.4032 (4) | 0.9520 (4) | 0.2757 (3) | 0.0274 (8) | |
C10 | 0.3474 (5) | 0.8807 (4) | 0.2189 (3) | 0.0313 (9) | |
H10 | 0.2453 | 0.8601 | 0.2339 | 0.038* | |
C11 | 0.4436 (5) | 0.8408 (4) | 0.1405 (3) | 0.0317 (9) | |
H11 | 0.4053 | 0.7933 | 0.1035 | 0.038* | |
C12 | 0.3096 (4) | 0.9876 (4) | 0.3660 (3) | 0.0267 (8) | |
C13 | 0.2237 (4) | 1.0964 (4) | 0.4795 (3) | 0.0253 (8) | |
C14 | 0.1860 (4) | 1.1918 (4) | 0.5325 (3) | 0.0306 (9) | |
H14 | 0.2162 | 1.2845 | 0.4990 | 0.037* | |
C15 | 0.1027 (5) | 1.1447 (4) | 0.6358 (3) | 0.0347 (9) | |
H15 | 0.0773 | 1.2070 | 0.6731 | 0.042* | |
C16 | 0.0539 (5) | 1.0056 (5) | 0.6879 (3) | 0.0386 (10) | |
H16 | −0.0027 | 0.9778 | 0.7582 | 0.046* | |
C17 | 0.0893 (5) | 0.9100 (4) | 0.6354 (3) | 0.0355 (9) | |
H17 | 0.0582 | 0.8175 | 0.6686 | 0.043* | |
C18 | 0.1736 (4) | 0.9588 (4) | 0.5304 (3) | 0.0272 (8) | |
C19 | 0.2048 (4) | 0.7445 (4) | 0.4788 (3) | 0.0311 (9) | |
H19A | 0.2187 | 0.7284 | 0.4103 | 0.037* | |
H19B | 0.1016 | 0.7197 | 0.5162 | 0.037* | |
C20 | 0.3062 (4) | 0.6507 (4) | 0.5452 (3) | 0.0259 (8) | |
C21 | 0.4219 (4) | 0.6962 (4) | 0.5774 (3) | 0.0306 (9) | |
H21 | 0.4382 | 0.7913 | 0.5573 | 0.037* | |
C22 | 0.4864 (5) | 0.4756 (4) | 0.6638 (4) | 0.0391 (10) | |
H22 | 0.5486 | 0.4150 | 0.7041 | 0.047* | |
C23 | 0.3738 (5) | 0.4208 (4) | 0.6364 (4) | 0.0392 (10) | |
H23 | 0.3602 | 0.3252 | 0.6580 | 0.047* | |
C24 | 0.2816 (5) | 0.5083 (4) | 0.5770 (3) | 0.0338 (9) | |
H24 | 0.2037 | 0.4732 | 0.5581 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03043 (16) | 0.02622 (16) | 0.03053 (17) | 0.00191 (12) | −0.00370 (12) | −0.00968 (12) |
I1 | 0.03719 (18) | 0.0559 (2) | 0.0597 (2) | −0.00668 (15) | 0.00824 (15) | −0.01606 (17) |
I2 | 0.03625 (17) | 0.03927 (17) | 0.0528 (2) | 0.01083 (12) | −0.00949 (14) | −0.02213 (14) |
N1 | 0.0385 (19) | 0.0304 (18) | 0.0294 (18) | 0.0044 (15) | −0.0058 (15) | −0.0105 (14) |
N2 | 0.0313 (17) | 0.0228 (16) | 0.0280 (17) | 0.0005 (13) | −0.0044 (14) | −0.0104 (13) |
N3 | 0.0323 (17) | 0.0197 (15) | 0.0282 (17) | 0.0012 (13) | −0.0093 (14) | −0.0060 (13) |
N4 | 0.0380 (19) | 0.0253 (18) | 0.046 (2) | 0.0016 (15) | −0.0164 (17) | −0.0110 (16) |
C1 | 0.037 (2) | 0.044 (3) | 0.035 (2) | 0.001 (2) | 0.0017 (19) | −0.017 (2) |
C2 | 0.036 (2) | 0.073 (4) | 0.049 (3) | 0.018 (2) | −0.010 (2) | −0.030 (3) |
C3 | 0.045 (3) | 0.060 (3) | 0.039 (3) | 0.008 (2) | −0.015 (2) | −0.028 (2) |
C4 | 0.034 (2) | 0.031 (2) | 0.028 (2) | 0.0038 (17) | −0.0037 (17) | −0.0108 (17) |
C5 | 0.036 (2) | 0.029 (2) | 0.028 (2) | 0.0028 (17) | −0.0064 (17) | −0.0088 (17) |
C6 | 0.040 (2) | 0.026 (2) | 0.026 (2) | 0.0064 (17) | −0.0100 (17) | −0.0074 (16) |
C7 | 0.032 (2) | 0.035 (2) | 0.038 (2) | 0.0030 (18) | −0.0060 (18) | −0.0131 (19) |
C8 | 0.038 (2) | 0.030 (2) | 0.032 (2) | 0.0006 (18) | −0.0092 (18) | −0.0124 (18) |
C9 | 0.036 (2) | 0.0180 (18) | 0.0260 (19) | 0.0034 (16) | −0.0074 (17) | −0.0045 (15) |
C10 | 0.031 (2) | 0.030 (2) | 0.033 (2) | 0.0023 (17) | −0.0063 (17) | −0.0104 (17) |
C11 | 0.039 (2) | 0.028 (2) | 0.033 (2) | 0.0051 (17) | −0.0128 (19) | −0.0136 (17) |
C12 | 0.0280 (19) | 0.0243 (19) | 0.029 (2) | 0.0045 (15) | −0.0108 (16) | −0.0080 (16) |
C13 | 0.0262 (19) | 0.0231 (19) | 0.0259 (19) | 0.0011 (15) | −0.0069 (16) | −0.0066 (15) |
C14 | 0.033 (2) | 0.026 (2) | 0.034 (2) | 0.0016 (16) | −0.0080 (18) | −0.0117 (17) |
C15 | 0.036 (2) | 0.036 (2) | 0.036 (2) | 0.0065 (18) | −0.0097 (19) | −0.0178 (19) |
C16 | 0.034 (2) | 0.050 (3) | 0.027 (2) | 0.000 (2) | −0.0009 (18) | −0.012 (2) |
C17 | 0.038 (2) | 0.032 (2) | 0.034 (2) | 0.0013 (18) | −0.0076 (19) | −0.0072 (18) |
C18 | 0.0242 (19) | 0.0263 (19) | 0.031 (2) | 0.0026 (15) | −0.0084 (16) | −0.0087 (16) |
C19 | 0.035 (2) | 0.0228 (19) | 0.036 (2) | −0.0019 (16) | −0.0112 (18) | −0.0076 (17) |
C20 | 0.032 (2) | 0.0208 (18) | 0.0246 (19) | −0.0002 (15) | −0.0037 (16) | −0.0085 (15) |
C21 | 0.035 (2) | 0.0202 (19) | 0.039 (2) | 0.0000 (16) | −0.0107 (18) | −0.0116 (17) |
C22 | 0.040 (2) | 0.029 (2) | 0.048 (3) | 0.0063 (19) | −0.015 (2) | −0.0108 (19) |
C23 | 0.048 (3) | 0.020 (2) | 0.050 (3) | 0.0006 (18) | −0.015 (2) | −0.0090 (18) |
C24 | 0.034 (2) | 0.026 (2) | 0.044 (2) | 0.0008 (17) | −0.0084 (19) | −0.0149 (18) |
Cd1—N2 | 2.346 (3) | C8—C9 | 1.383 (5) |
Cd1—N1i | 2.415 (3) | C8—H8 | 0.9300 |
Cd1—N4ii | 2.507 (3) | C9—C10 | 1.401 (5) |
Cd1—I1 | 2.7551 (7) | C9—C12 | 1.470 (5) |
Cd1—I2 | 2.8161 (7) | C10—C11 | 1.382 (6) |
N1—C1 | 1.334 (5) | C10—H10 | 0.9300 |
N1—C5 | 1.340 (5) | C11—H11 | 0.9300 |
N1—Cd1i | 2.415 (3) | C13—C14 | 1.384 (5) |
N2—C12 | 1.326 (5) | C13—C18 | 1.394 (5) |
N2—C13 | 1.395 (5) | C14—C15 | 1.368 (6) |
N3—C12 | 1.370 (5) | C14—H14 | 0.9300 |
N3—C18 | 1.384 (5) | C15—C16 | 1.406 (6) |
N3—C19 | 1.456 (5) | C15—H15 | 0.9300 |
N4—C22 | 1.326 (5) | C16—C17 | 1.379 (6) |
N4—C21 | 1.333 (5) | C16—H16 | 0.9300 |
N4—Cd1ii | 2.507 (3) | C17—C18 | 1.389 (6) |
C1—C2 | 1.367 (6) | C17—H17 | 0.9300 |
C1—H1 | 0.9300 | C19—C20 | 1.500 (5) |
C2—C3 | 1.381 (6) | C19—H19A | 0.9700 |
C2—H2 | 0.9300 | C19—H19B | 0.9700 |
C3—C4 | 1.372 (6) | C20—C21 | 1.380 (5) |
C3—H3 | 0.9300 | C20—C24 | 1.390 (5) |
C4—C5 | 1.389 (5) | C21—H21 | 0.9300 |
C4—C6 | 1.479 (5) | C22—C23 | 1.368 (6) |
C5—H5 | 0.9300 | C22—H22 | 0.9300 |
C6—C11 | 1.390 (6) | C23—C24 | 1.367 (6) |
C6—C7 | 1.393 (6) | C23—H23 | 0.9300 |
C7—C8 | 1.382 (6) | C24—H24 | 0.9300 |
C7—H7 | 0.9300 | ||
N2—Cd1—N1i | 94.05 (11) | C11—C10—C9 | 120.1 (4) |
N2—Cd1—N4ii | 85.75 (11) | C11—C10—H10 | 119.9 |
N1i—Cd1—N4ii | 177.27 (11) | C9—C10—H10 | 119.9 |
N2—Cd1—I1 | 118.09 (8) | C10—C11—C6 | 121.3 (4) |
N1i—Cd1—I1 | 94.54 (9) | C10—C11—H11 | 119.4 |
N4ii—Cd1—I1 | 83.17 (9) | C6—C11—H11 | 119.4 |
N2—Cd1—I2 | 107.95 (8) | N2—C12—N3 | 111.4 (3) |
N1i—Cd1—I2 | 94.30 (8) | N2—C12—C9 | 124.5 (3) |
N4ii—Cd1—I2 | 88.35 (8) | N3—C12—C9 | 123.6 (3) |
I1—Cd1—I2 | 132.223 (19) | C14—C13—C18 | 120.1 (4) |
C1—N1—C5 | 117.2 (4) | C14—C13—N2 | 130.9 (3) |
C1—N1—Cd1i | 123.5 (3) | C18—C13—N2 | 109.0 (3) |
C5—N1—Cd1i | 118.2 (3) | C15—C14—C13 | 117.5 (4) |
C12—N2—C13 | 106.3 (3) | C15—C14—H14 | 121.2 |
C12—N2—Cd1 | 127.6 (3) | C13—C14—H14 | 121.2 |
C13—N2—Cd1 | 123.6 (2) | C14—C15—C16 | 122.5 (4) |
C12—N3—C18 | 107.5 (3) | C14—C15—H15 | 118.8 |
C12—N3—C19 | 128.6 (3) | C16—C15—H15 | 118.8 |
C18—N3—C19 | 123.9 (3) | C17—C16—C15 | 120.5 (4) |
C22—N4—C21 | 117.5 (4) | C17—C16—H16 | 119.7 |
C22—N4—Cd1ii | 113.2 (3) | C15—C16—H16 | 119.7 |
C21—N4—Cd1ii | 123.6 (3) | C16—C17—C18 | 116.6 (4) |
N1—C1—C2 | 123.0 (4) | C16—C17—H17 | 121.7 |
N1—C1—H1 | 118.5 | C18—C17—H17 | 121.7 |
C2—C1—H1 | 118.5 | N3—C18—C17 | 131.3 (4) |
C1—C2—C3 | 118.9 (4) | N3—C18—C13 | 105.9 (3) |
C1—C2—H2 | 120.5 | C17—C18—C13 | 122.8 (4) |
C3—C2—H2 | 120.5 | N3—C19—C20 | 114.5 (3) |
C4—C3—C2 | 119.9 (4) | N3—C19—H19A | 108.6 |
C4—C3—H3 | 120.0 | C20—C19—H19A | 108.6 |
C2—C3—H3 | 120.0 | N3—C19—H19B | 108.6 |
C3—C4—C5 | 116.9 (4) | C20—C19—H19B | 108.6 |
C3—C4—C6 | 122.0 (4) | H19A—C19—H19B | 107.6 |
C5—C4—C6 | 120.9 (4) | C21—C20—C24 | 117.8 (4) |
N1—C5—C4 | 124.0 (4) | C21—C20—C19 | 124.4 (3) |
N1—C5—H5 | 118.0 | C24—C20—C19 | 117.8 (3) |
C4—C5—H5 | 118.0 | N4—C21—C20 | 123.4 (4) |
C11—C6—C7 | 118.0 (4) | N4—C21—H21 | 118.3 |
C11—C6—C4 | 121.7 (4) | C20—C21—H21 | 118.3 |
C7—C6—C4 | 120.2 (4) | N4—C22—C23 | 123.3 (4) |
C8—C7—C6 | 121.1 (4) | N4—C22—H22 | 118.3 |
C8—C7—H7 | 119.5 | C23—C22—H22 | 118.3 |
C6—C7—H7 | 119.5 | C22—C23—C24 | 119.2 (4) |
C7—C8—C9 | 120.7 (4) | C22—C23—H23 | 120.4 |
C7—C8—H8 | 119.6 | C24—C23—H23 | 120.4 |
C9—C8—H8 | 119.6 | C23—C24—C20 | 118.8 (4) |
C8—C9—C10 | 118.6 (4) | C23—C24—H24 | 120.6 |
C8—C9—C12 | 118.3 (4) | C20—C24—H24 | 120.6 |
C10—C9—C12 | 123.1 (4) | ||
N1i—Cd1—N2—C12 | 36.3 (3) | C19—N3—C12—C9 | −7.4 (6) |
N4ii—Cd1—N2—C12 | −141.0 (3) | C8—C9—C12—N2 | 49.5 (5) |
I1—Cd1—N2—C12 | −61.0 (3) | C10—C9—C12—N2 | −132.3 (4) |
I2—Cd1—N2—C12 | 132.1 (3) | C8—C9—C12—N3 | −121.6 (4) |
N1i—Cd1—N2—C13 | −123.2 (3) | C10—C9—C12—N3 | 56.7 (5) |
N4ii—Cd1—N2—C13 | 59.6 (3) | C12—N2—C13—C14 | 179.9 (4) |
I1—Cd1—N2—C13 | 139.5 (3) | Cd1—N2—C13—C14 | −17.0 (6) |
I2—Cd1—N2—C13 | −27.3 (3) | C12—N2—C13—C18 | −0.9 (4) |
C5—N1—C1—C2 | −0.6 (6) | Cd1—N2—C13—C18 | 162.2 (2) |
Cd1i—N1—C1—C2 | −167.8 (4) | C18—C13—C14—C15 | 1.7 (6) |
N1—C1—C2—C3 | 0.8 (8) | N2—C13—C14—C15 | −179.2 (4) |
C1—C2—C3—C4 | −1.5 (8) | C13—C14—C15—C16 | −0.8 (6) |
C2—C3—C4—C5 | 1.9 (7) | C14—C15—C16—C17 | 0.1 (7) |
C2—C3—C4—C6 | 177.4 (4) | C15—C16—C17—C18 | −0.2 (6) |
C1—N1—C5—C4 | 1.1 (6) | C12—N3—C18—C17 | −177.9 (4) |
Cd1i—N1—C5—C4 | 169.0 (3) | C19—N3—C18—C17 | 0.7 (6) |
C3—C4—C5—N1 | −1.7 (6) | C12—N3—C18—C13 | 0.3 (4) |
C6—C4—C5—N1 | −177.3 (4) | C19—N3—C18—C13 | 178.9 (3) |
C3—C4—C6—C11 | −141.7 (4) | C16—C17—C18—N3 | 179.0 (4) |
C5—C4—C6—C11 | 33.6 (6) | C16—C17—C18—C13 | 1.1 (6) |
C3—C4—C6—C7 | 34.1 (6) | C14—C13—C18—N3 | 179.7 (3) |
C5—C4—C6—C7 | −150.6 (4) | N2—C13—C18—N3 | 0.4 (4) |
C11—C6—C7—C8 | 3.9 (6) | C14—C13—C18—C17 | −1.9 (6) |
C4—C6—C7—C8 | −172.0 (4) | N2—C13—C18—C17 | 178.8 (3) |
C6—C7—C8—C9 | −0.8 (6) | C12—N3—C19—C20 | 98.4 (5) |
C7—C8—C9—C10 | −2.9 (6) | C18—N3—C19—C20 | −79.9 (5) |
C7—C8—C9—C12 | 175.5 (3) | N3—C19—C20—C21 | −5.0 (6) |
C8—C9—C10—C11 | 3.4 (6) | N3—C19—C20—C24 | 174.8 (4) |
C12—C9—C10—C11 | −174.9 (3) | C22—N4—C21—C20 | −0.1 (6) |
C9—C10—C11—C6 | −0.2 (6) | Cd1ii—N4—C21—C20 | −151.6 (3) |
C7—C6—C11—C10 | −3.4 (6) | C24—C20—C21—N4 | 0.9 (6) |
C4—C6—C11—C10 | 172.5 (4) | C19—C20—C21—N4 | −179.4 (4) |
C13—N2—C12—N3 | 1.1 (4) | C21—N4—C22—C23 | −0.4 (7) |
Cd1—N2—C12—N3 | −161.1 (2) | Cd1ii—N4—C22—C23 | 153.9 (4) |
C13—N2—C12—C9 | −170.8 (3) | N4—C22—C23—C24 | 0.1 (7) |
Cd1—N2—C12—C9 | 26.9 (5) | C22—C23—C24—C20 | 0.6 (6) |
C18—N3—C12—N2 | −0.9 (4) | C21—C20—C24—C23 | −1.1 (6) |
C19—N3—C12—N2 | −179.4 (3) | C19—C20—C24—C23 | 179.2 (4) |
C18—N3—C12—C9 | 171.1 (3) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [CdBr2(C24H18N4)]·H2O | [CdI2(C24H18N4)] |
Mr | 652.66 | 728.62 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 9.379 (2), 10.023 (2), 13.773 (3) | 9.128 (2), 10.254 (3), 13.429 (4) |
α, β, γ (°) | 101.504 (3), 107.424 (3), 99.561 (3) | 70.065 (3), 77.717 (4), 86.952 (3) |
V (Å3) | 1174.7 (5) | 1154.4 (5) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 4.36 | 3.64 |
Crystal size (mm) | 0.28 × 0.16 × 0.12 | 0.28 × 0.16 × 0.12 |
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 | 0.375, 0.623 | 0.502, 0.646 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6132, 4256, 3348 | 6318, 4424, 3863 |
Rint | 0.031 | 0.017 |
(sin θ/λ)max (Å−1) | 0.606 | 0.617 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.178, 1.10 | 0.030, 0.077, 1.04 |
No. of reflections | 4256 | 4424 |
No. of parameters | 289 | 280 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.03, −1.63 | 0.84, −0.55 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Cd1—Br1 | 2.5766 (12) | Cd1—N1i | 2.397 (6) |
Cd1—Br2 | 2.6233 (10) | Cd1—N4ii | 2.475 (7) |
Cd1—N2 | 2.315 (6) | ||
N2—Cd1—N1i | 92.7 (2) | N4ii—Cd1—Br1 | 86.88 (18) |
N2—Cd1—N4ii | 89.9 (2) | N2—Cd1—Br2 | 108.50 (15) |
N1i—Cd1—N4ii | 177.4 (2) | N1i—Cd1—Br2 | 93.21 (15) |
N2—Cd1—Br1 | 123.50 (15) | N4ii—Cd1—Br2 | 86.34 (16) |
N1i—Cd1—Br1 | 91.39 (15) | Br1—Cd1—Br2 | 127.48 (4) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···Br2iii | 0.85 | 2.62 | 3.459 (9) | 169.9 |
O1—H1A···Br1 | 0.85 | 2.59 | 3.433 (9) | 170.2 |
Symmetry code: (iii) −x+1, −y, −z. |
Cd1—N2 | 2.346 (3) | Cd1—I1 | 2.7551 (7) |
Cd1—N1i | 2.415 (3) | Cd1—I2 | 2.8161 (7) |
Cd1—N4ii | 2.507 (3) | ||
N2—Cd1—N1i | 94.05 (11) | N4ii—Cd1—I1 | 83.17 (9) |
N2—Cd1—N4ii | 85.75 (11) | N2—Cd1—I2 | 107.95 (8) |
N1i—Cd1—N4ii | 177.27 (11) | N1i—Cd1—I2 | 94.30 (8) |
N2—Cd1—I1 | 118.09 (8) | N4ii—Cd1—I2 | 88.35 (8) |
N1i—Cd1—I1 | 94.54 (9) | I1—Cd1—I2 | 132.223 (19) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
Coordination polymers assembled from metal nodes and organic ligands have attracted considerable interest over recent decades. Due to their often porous structures and special properties, they may have potential applications in, for example, absorption and separation processes (Gu et al., 2010), gas storage (Stavila et al., 2012) or drug delivery (Horcajada et al., 2008), or as functional materials (Wang et al., 2011), for photophysical applications (Yanai et al., 2012) or as catalysts (Li et al., 2012).
Appropriate ligands doubtless play an important role as building blocks to construct supramolecular complexes. Among the numerous reports concerned with benzimidazole ligands (Kundu et al., 2010; Li et al., 2010; Xiao et al., 2011), no coordination compound generated from 1-[(pyridin-3-yl)methyl]-2-[4-(pyridin-3-yl)phenyl]-1H-benzimidazole (L) has yet been reported. In order to investigate its self-assembly reactions, we have synthesized this novel ligand. The combination of L with CdBr2 and CdI2 afforded two one-dimensional coordination complexes, {[CdBr2(L)].H2O}n, (I) (Fig. 1), and [CdI2(L)]n, (II) (Fig. 2).
The compounds crystallize in the triclinic system; the asymmetric unit comprises one CdII centre, one L ligand and two halide anions in both cases and, only for (I), a solvent water molecule. As a consequence of this solvent content, the unit cell of (I) has a larger volume [1174.7 (5) Å3] than that of (II) [1154.4 (5) Å3], despite the sterically less demanding halide in the former. The chains in (I) extend in the [101] direction, with the length of this diagonal being 14.153 (3) Å, whereas (II) forms chains along the [001] direction, the lattice parameter c being 13.429 (4) Å.
In (I), each CdII centre is five-coordinated by two Br and three N atoms; one N atom belongs to the benzimidazole ring, and the other two originate from the pyridine rings of two different ligands. The distortion parameter τ(I) (Addison et al., 1984) of 0.83 indicates that the coordination environment corresponds to a slightly distorted trigonal bipyramid; expected values are τ = 0 for a square pyramid and τ = 1 for an ideal trigonal bipyramid, with τ = (β - α)/60°, α and β being the two largest angles around the central atom (Addison et al., 1984).
The tridentate ligands and the coordinated CdII cations subtend two kinds of macrocycles. In the 20-membered macrocycle of (I) (Fig. 3a), the distance between atoms Cd1 and N1i is 2.397 (6) Å [symmetry code: (i) -x + 1, -y + 1, -z], similar to the Cd—N distance reported by Ding et al. (2012). Moreover, the dihedral angle between the benzene rings and the neighbouring imidazole rings is 52.0 (2)°, and the dihedral angle between the benzene rings and the neighbouring pyridine rings is 32.1 (3)°. The 16-membered macrocycle is also centrosymmetric (Fig. 3b), with Cd1—N2 = 2.315 (6) Å and Cd1—N4ii = 2.475 (7) Å [symmetry code: (ii) -x + 2, -y + 1, -z + 1], similar to published values (Xu et al., 2011; Lan et al., 2009). The overall chain in (I) extends in the [101] direction and is shown in Fig. 3(c). Adjacent chains are linked to form two-dimensional sheets by hydrogen bonds (Table 1 and Fig. 4). Water molecules are arranged regularly in the voids and play an important role in connecting the chains via O—H···Br interactions.
The CdII centre in (II) has a similar coordination environment to that in polymer (I), with two iodide ligands and τ(II) = 0.75. Chains extend along the c axis, with an intrachain geometry similar to that depicted for (I) in Fig. 3. The Cd—N bonds (Table 3) are slightly longer than in the bromide derivative, (I). In the 20-membered macrocycle, the dihedral angle between the benzene rings and the neighbouring imidazole rings is 54.3 (2)°, and the interplanar angle between the benzene ring and the neighbouring pyridine ring is 34.7 (2)°.
Fig. 5 shows, in the direction of the a axis, how neighbouring chains in (II) are linked by π–π interactions between two parallel pyridine rings and by C—H···π interactions C23—H23···Cgi, where Cgi denotes the centroid of the C6—C11 ring at the symmetry-related position (-x + 1, -y + 1, -z + 1). The π–π interactions in (II) are associated with a centroid-to-centroid distance of 3.612 (2) Å; in contrast, the analogous contacts in (I) amount to 4.117 (2) Å and are not relevant. The C—H···π angle of 133° and the H···π distance of 3.00 Å are in close agreement with values reported previously (Goswami et al., 2007) and lead to the formation of two-dimensional sheets in the bc plane. A second kind of π–π interaction between the imidazole rings and benzene rings of the benzimidazoles from adjacent chains, with a centroid-to-centroid distance of 3.723 (2) Å, is shown in Fig. 6 and results in a three-dimensional network. No water molecules reside in the crystal structure of (II), presumably due to the larger ionic radius of the iodide anion. If the water molecule is not taken into account, the `cavity' in (I), with a Br1···Br2i [symmetry code: (i) -x + 1, -y, -z] distance of 5.092 (2) Å, is much larger than that in (II), where the corresponding distance between two iodides amounts to 4.853 (2) Å.
In summary, a novel asymmetric bridging benzimidazole ligand has been successfully synthesized and used as a tridentate ligand to construct two coordination polymers. In (I), hydrogen bonds between water molecules and bromide anions play an important role in linking the chains to form a two-dimensional motif; in (II), weak π–π interactions generate a three-dimensional framework.