Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107063718/ln3071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107063718/ln3071Isup2.hkl |
CCDC reference: 677203
For related literature, see: Liu et al. (2004); Mizobe et al. (2006); Zhang et al. (2006); Zheng et al. (2003).
Cd(ClO4)2·6H2O (0.2727 g, 0.65 mmol) was dissolved in 10 ml of methanol and then mixed with 10 ml of a methanol solution of PP (0.1774 g, 0.65 mmol), and the mixed solution was stirred for a few minutes. Yellow single crystals were obtained after allowing the mixed solution to stand at room temperature for two weeks (m.p. 367 K). The IR spectrum displays a strong and sharp peak at 1661 cm-1 corresponding to the vibration of the C═O group, and strong peaks at 1145, 1115 and 1085 cm-1 can be attributed to vibrations of the perchlorate ion.
The H atoms of the water ligand were located in a difference map and the other H atoms were placed in calculated positions. All H atoms were refined using a riding model [O—H = 0.897–0.898 Å, C—H = 0.93 Å, and Uiso(H) = 1.5Ueq(O) and 1.2Ueq(C)].
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Cd2(C17H11N3O)4(H2O)2](ClO4)4 | Z = 1 |
Mr = 1751.78 | F(000) = 880 |
Triclinic, P1 | Dx = 1.734 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 11.681 (2) Å | Cell parameters from 2995 reflections |
b = 12.437 (2) Å | θ = 2.0–24.0° |
c = 12.709 (2) Å | µ = 0.88 mm−1 |
α = 107.317 (2)° | T = 298 K |
β = 106.340 (2)° | Block, pale yellow |
γ = 91.838 (2)° | 0.24 × 0.16 × 0.10 mm |
V = 1677.9 (5) Å3 |
Bruker SMART APEX CCD diffractometer | 6304 independent reflections |
Radiation source: fine-focus sealed tube | 5004 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 25.8°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→12 |
Tmin = 0.816, Tmax = 0.917 | k = −12→15 |
9002 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0572P)2] where P = (Fo2 + 2Fc2)/3 |
6304 reflections | (Δ/σ)max = 0.001 |
488 parameters | Δρmax = 0.81 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
[Cd2(C17H11N3O)4(H2O)2](ClO4)4 | γ = 91.838 (2)° |
Mr = 1751.78 | V = 1677.9 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.681 (2) Å | Mo Kα radiation |
b = 12.437 (2) Å | µ = 0.88 mm−1 |
c = 12.709 (2) Å | T = 298 K |
α = 107.317 (2)° | 0.24 × 0.16 × 0.10 mm |
β = 106.340 (2)° |
Bruker SMART APEX CCD diffractometer | 6304 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5004 reflections with I > 2σ(I) |
Tmin = 0.816, Tmax = 0.917 | Rint = 0.023 |
9002 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.81 e Å−3 |
6304 reflections | Δρmin = −0.35 e Å−3 |
488 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 | ||
C1 | 0.8506 (4) | 0.8888 (3) | 0.5029 (4) | 0.0530 (11) | |
H1 | 0.7921 | 0.8944 | 0.4385 | 0.064* | |
C2 | 0.8858 (5) | 0.9779 (4) | 0.5998 (5) | 0.0644 (13) | |
H2 | 0.8497 | 1.0440 | 0.6042 | 0.077* | |
C3 | 0.9768 (5) | 0.9703 (4) | 0.6936 (4) | 0.0639 (13) | |
H3 | 1.0032 | 1.0325 | 0.7607 | 0.077* | |
C4 | 1.0272 (4) | 0.8747 (4) | 0.6889 (4) | 0.0586 (11) | |
H4 | 1.0880 | 0.8721 | 0.7533 | 0.070* | |
C5 | 0.9912 (4) | 0.7767 (3) | 0.5887 (3) | 0.0463 (10) | |
C6 | 0.8662 (3) | 0.7014 (3) | 0.3873 (3) | 0.0397 (9) | |
C7 | 0.8905 (4) | 0.7242 (3) | 0.2956 (4) | 0.0494 (10) | |
H7 | 0.9267 | 0.7955 | 0.3047 | 0.059* | |
C8 | 0.8606 (4) | 0.6405 (4) | 0.1914 (4) | 0.0547 (11) | |
H8 | 0.8752 | 0.6543 | 0.1280 | 0.066* | |
C9 | 0.8080 (4) | 0.5342 (3) | 0.1803 (3) | 0.0432 (9) | |
C10 | 0.7843 (3) | 0.5188 (3) | 0.2779 (3) | 0.0351 (8) | |
C11 | 0.7265 (3) | 0.4107 (3) | 0.2678 (3) | 0.0356 (8) | |
C12 | 0.6981 (4) | 0.3224 (3) | 0.1624 (3) | 0.0436 (9) | |
C13 | 0.7223 (4) | 0.3414 (4) | 0.0657 (3) | 0.0538 (11) | |
H13 | 0.7013 | 0.2828 | −0.0044 | 0.065* | |
C14 | 0.7745 (4) | 0.4417 (4) | 0.0732 (3) | 0.0520 (11) | |
H14 | 0.7893 | 0.4518 | 0.0084 | 0.062* | |
C15 | 0.6471 (4) | 0.2182 (4) | 0.1583 (4) | 0.0602 (12) | |
H15 | 0.6272 | 0.1573 | 0.0901 | 0.072* | |
C16 | 0.6265 (5) | 0.2054 (3) | 0.2532 (4) | 0.0680 (14) | |
H16 | 0.5942 | 0.1353 | 0.2514 | 0.082* | |
C17 | 0.6540 (4) | 0.2978 (3) | 0.3538 (4) | 0.0593 (12) | |
H17 | 0.6388 | 0.2883 | 0.4188 | 0.071* | |
C18 | 0.9210 (4) | 0.6649 (4) | 0.7921 (4) | 0.0576 (12) | |
H18 | 0.9608 | 0.6017 | 0.7735 | 0.069* | |
C19 | 0.9582 (5) | 0.7387 (5) | 0.9046 (4) | 0.0739 (15) | |
H19 | 1.0202 | 0.7237 | 0.9608 | 0.089* | |
C20 | 0.9037 (5) | 0.8323 (4) | 0.9318 (4) | 0.0714 (14) | |
H20 | 0.9283 | 0.8824 | 1.0071 | 0.086* | |
C21 | 0.8103 (4) | 0.8546 (3) | 0.8475 (3) | 0.0490 (10) | |
C22 | 0.7752 (3) | 0.7741 (3) | 0.7361 (3) | 0.0372 (8) | |
C23 | 0.7503 (5) | 0.9532 (4) | 0.8696 (4) | 0.0648 (13) | |
H23 | 0.7736 | 1.0059 | 0.9435 | 0.078* | |
C24 | 0.6615 (4) | 0.9714 (3) | 0.7865 (4) | 0.0581 (12) | |
H24 | 0.6253 | 1.0374 | 0.8030 | 0.070* | |
C25 | 0.6212 (4) | 0.8905 (3) | 0.6723 (3) | 0.0429 (9) | |
C26 | 0.6765 (3) | 0.7912 (3) | 0.6476 (3) | 0.0343 (8) | |
C27 | 0.5267 (4) | 0.9037 (3) | 0.5840 (4) | 0.0499 (10) | |
H27 | 0.4895 | 0.9692 | 0.5970 | 0.060* | |
C28 | 0.4880 (4) | 0.8217 (3) | 0.4786 (3) | 0.0451 (9) | |
H28 | 0.4248 | 0.8297 | 0.4189 | 0.054* | |
C29 | 0.5470 (3) | 0.7250 (3) | 0.4640 (3) | 0.0344 (8) | |
C30 | 0.4280 (3) | 0.5434 (3) | 0.3450 (3) | 0.0371 (8) | |
C31 | 0.3986 (4) | 0.4551 (3) | 0.2356 (3) | 0.0466 (10) | |
H31 | 0.3527 | 0.3881 | 0.2252 | 0.056* | |
C32 | 0.4347 (4) | 0.4660 (4) | 0.1483 (3) | 0.0494 (10) | |
H32 | 0.4138 | 0.4069 | 0.0785 | 0.059* | |
C33 | 0.5039 (4) | 0.5654 (3) | 0.1608 (3) | 0.0455 (10) | |
H33 | 0.5259 | 0.5739 | 0.0986 | 0.055* | |
C34 | 0.5382 (3) | 0.6478 (3) | 0.2622 (3) | 0.0407 (9) | |
H34 | 0.5838 | 0.7143 | 0.2708 | 0.049* | |
Cd1 | 0.75342 (2) | 0.55115 (2) | 0.52738 (2) | 0.03562 (11) | |
Cl1 | 0.81961 (10) | 0.28114 (9) | 0.77260 (8) | 0.0493 (3) | |
Cl2 | 0.64738 (10) | 0.87777 (8) | 0.14325 (9) | 0.0550 (3) | |
N1 | 0.8136 (3) | 0.6030 (2) | 0.3815 (2) | 0.0334 (7) | |
N2 | 0.7009 (3) | 0.3984 (2) | 0.3606 (3) | 0.0411 (8) | |
N3 | 0.6377 (3) | 0.7092 (2) | 0.5427 (2) | 0.0313 (6) | |
N4 | 0.8310 (3) | 0.6810 (3) | 0.7099 (3) | 0.0393 (7) | |
N5 | 0.8994 (3) | 0.7893 (2) | 0.4972 (3) | 0.0421 (7) | |
N6 | 0.5061 (3) | 0.6348 (2) | 0.3543 (2) | 0.0328 (6) | |
O1 | 0.8961 (3) | 0.4436 (2) | 0.5954 (2) | 0.0522 (7) | |
H10 | 0.8597 | 0.3878 | 0.6106 | 0.078* | |
H9 | 0.9262 | 0.4042 | 0.5401 | 0.078* | |
O2 | 1.0333 (3) | 0.6864 (2) | 0.5789 (2) | 0.0625 (8) | |
O3 | 0.3926 (2) | 0.5445 (2) | 0.4279 (2) | 0.0456 (7) | |
O4 | 0.6224 (5) | 0.7621 (3) | 0.0875 (4) | 0.1285 (18) | |
O5 | 0.7559 (5) | 0.9176 (5) | 0.1408 (5) | 0.163 (2) | |
O6 | 0.6520 (5) | 0.9025 (3) | 0.2605 (3) | 0.1084 (15) | |
O7 | 0.5617 (5) | 0.9343 (4) | 0.0901 (4) | 0.137 (2) | |
O8 | 0.8088 (3) | 0.2512 (3) | 0.6516 (2) | 0.0645 (8) | |
O9 | 0.7059 (3) | 0.2557 (3) | 0.7859 (3) | 0.0801 (10) | |
O10 | 0.9035 (3) | 0.2190 (3) | 0.8237 (3) | 0.0699 (9) | |
O11 | 0.8608 (4) | 0.3994 (3) | 0.8252 (4) | 0.0981 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.054 (3) | 0.037 (2) | 0.067 (3) | 0.0078 (19) | 0.019 (2) | 0.015 (2) |
C2 | 0.074 (3) | 0.036 (2) | 0.079 (4) | 0.008 (2) | 0.029 (3) | 0.006 (2) |
C3 | 0.078 (4) | 0.043 (2) | 0.059 (3) | −0.005 (2) | 0.025 (3) | −0.004 (2) |
C4 | 0.065 (3) | 0.057 (3) | 0.041 (2) | 0.002 (2) | 0.010 (2) | 0.004 (2) |
C5 | 0.051 (3) | 0.047 (2) | 0.039 (2) | 0.007 (2) | 0.017 (2) | 0.0093 (18) |
C6 | 0.039 (2) | 0.039 (2) | 0.043 (2) | 0.0108 (17) | 0.0151 (18) | 0.0124 (17) |
C7 | 0.058 (3) | 0.043 (2) | 0.054 (3) | 0.005 (2) | 0.023 (2) | 0.021 (2) |
C8 | 0.066 (3) | 0.068 (3) | 0.046 (3) | 0.016 (2) | 0.028 (2) | 0.029 (2) |
C9 | 0.045 (2) | 0.055 (2) | 0.034 (2) | 0.0170 (19) | 0.0157 (18) | 0.0161 (18) |
C10 | 0.036 (2) | 0.041 (2) | 0.0272 (18) | 0.0125 (16) | 0.0096 (16) | 0.0085 (15) |
C11 | 0.037 (2) | 0.0379 (19) | 0.0294 (19) | 0.0110 (16) | 0.0109 (16) | 0.0058 (15) |
C12 | 0.047 (2) | 0.043 (2) | 0.034 (2) | 0.0077 (18) | 0.0137 (18) | 0.0006 (16) |
C13 | 0.062 (3) | 0.060 (3) | 0.027 (2) | 0.011 (2) | 0.012 (2) | −0.0028 (18) |
C14 | 0.059 (3) | 0.070 (3) | 0.027 (2) | 0.020 (2) | 0.017 (2) | 0.0121 (19) |
C15 | 0.068 (3) | 0.045 (2) | 0.049 (3) | −0.001 (2) | 0.018 (2) | −0.012 (2) |
C16 | 0.096 (4) | 0.035 (2) | 0.069 (3) | −0.010 (2) | 0.044 (3) | −0.005 (2) |
C17 | 0.089 (4) | 0.036 (2) | 0.055 (3) | 0.000 (2) | 0.044 (3) | −0.0010 (19) |
C18 | 0.060 (3) | 0.067 (3) | 0.039 (2) | 0.022 (2) | 0.009 (2) | 0.012 (2) |
C19 | 0.075 (3) | 0.095 (4) | 0.031 (2) | 0.023 (3) | −0.003 (2) | 0.007 (2) |
C20 | 0.077 (3) | 0.085 (4) | 0.028 (2) | 0.011 (3) | 0.004 (2) | −0.006 (2) |
C21 | 0.057 (3) | 0.051 (2) | 0.029 (2) | 0.004 (2) | 0.0118 (19) | −0.0013 (17) |
C22 | 0.046 (2) | 0.0371 (19) | 0.0246 (18) | 0.0031 (17) | 0.0117 (17) | 0.0033 (15) |
C23 | 0.077 (3) | 0.054 (3) | 0.040 (3) | 0.007 (2) | 0.016 (2) | −0.018 (2) |
C24 | 0.075 (3) | 0.036 (2) | 0.053 (3) | 0.010 (2) | 0.025 (3) | −0.0065 (19) |
C25 | 0.053 (3) | 0.0312 (19) | 0.042 (2) | 0.0036 (17) | 0.016 (2) | 0.0063 (16) |
C26 | 0.044 (2) | 0.0277 (17) | 0.0317 (19) | 0.0026 (15) | 0.0178 (17) | 0.0053 (14) |
C27 | 0.061 (3) | 0.031 (2) | 0.058 (3) | 0.0138 (19) | 0.022 (2) | 0.0102 (18) |
C28 | 0.053 (3) | 0.039 (2) | 0.044 (2) | 0.0145 (18) | 0.012 (2) | 0.0144 (17) |
C29 | 0.042 (2) | 0.0306 (18) | 0.0306 (19) | 0.0030 (16) | 0.0123 (17) | 0.0084 (15) |
C30 | 0.046 (2) | 0.0323 (19) | 0.033 (2) | 0.0074 (17) | 0.0136 (18) | 0.0098 (15) |
C31 | 0.060 (3) | 0.037 (2) | 0.036 (2) | −0.0012 (19) | 0.016 (2) | 0.0017 (16) |
C32 | 0.054 (3) | 0.055 (2) | 0.033 (2) | 0.006 (2) | 0.017 (2) | 0.0007 (18) |
C33 | 0.047 (2) | 0.062 (3) | 0.031 (2) | 0.010 (2) | 0.0160 (18) | 0.0157 (18) |
C34 | 0.042 (2) | 0.049 (2) | 0.037 (2) | 0.0086 (18) | 0.0151 (18) | 0.0183 (18) |
Cd1 | 0.05008 (19) | 0.02992 (15) | 0.02490 (15) | 0.00881 (11) | 0.01215 (12) | 0.00486 (10) |
Cl1 | 0.0582 (7) | 0.0550 (6) | 0.0368 (5) | 0.0177 (5) | 0.0169 (5) | 0.0142 (4) |
Cl2 | 0.0636 (7) | 0.0419 (5) | 0.0497 (6) | 0.0063 (5) | 0.0076 (5) | 0.0094 (5) |
N1 | 0.0366 (17) | 0.0345 (16) | 0.0281 (16) | 0.0076 (13) | 0.0111 (13) | 0.0072 (12) |
N2 | 0.055 (2) | 0.0335 (16) | 0.0340 (17) | 0.0042 (15) | 0.0203 (16) | 0.0027 (13) |
N3 | 0.0415 (17) | 0.0271 (14) | 0.0266 (15) | 0.0061 (13) | 0.0149 (14) | 0.0060 (12) |
N4 | 0.0449 (19) | 0.0428 (18) | 0.0278 (16) | 0.0090 (15) | 0.0094 (14) | 0.0088 (13) |
N5 | 0.0460 (19) | 0.0307 (16) | 0.047 (2) | 0.0048 (14) | 0.0155 (16) | 0.0074 (14) |
N6 | 0.0383 (17) | 0.0327 (15) | 0.0264 (15) | 0.0068 (13) | 0.0089 (13) | 0.0085 (12) |
O1 | 0.068 (2) | 0.0493 (16) | 0.0460 (17) | 0.0224 (14) | 0.0218 (15) | 0.0200 (13) |
O2 | 0.081 (2) | 0.0566 (19) | 0.0446 (18) | 0.0319 (17) | 0.0157 (16) | 0.0101 (14) |
O3 | 0.0583 (18) | 0.0405 (14) | 0.0376 (15) | −0.0028 (13) | 0.0221 (14) | 0.0058 (12) |
O4 | 0.227 (6) | 0.044 (2) | 0.093 (3) | 0.006 (3) | 0.041 (4) | 0.001 (2) |
O5 | 0.113 (4) | 0.211 (6) | 0.155 (5) | −0.050 (4) | 0.061 (4) | 0.033 (4) |
O6 | 0.175 (5) | 0.086 (3) | 0.054 (2) | 0.017 (3) | 0.025 (3) | 0.016 (2) |
O7 | 0.161 (5) | 0.113 (4) | 0.092 (3) | 0.068 (3) | −0.017 (3) | 0.016 (3) |
O8 | 0.081 (2) | 0.079 (2) | 0.0379 (17) | 0.0209 (18) | 0.0220 (16) | 0.0211 (15) |
O9 | 0.057 (2) | 0.130 (3) | 0.061 (2) | 0.015 (2) | 0.0264 (18) | 0.034 (2) |
O10 | 0.068 (2) | 0.086 (2) | 0.057 (2) | 0.0250 (18) | 0.0089 (17) | 0.0318 (18) |
O11 | 0.144 (4) | 0.050 (2) | 0.096 (3) | 0.011 (2) | 0.052 (3) | 0.0015 (19) |
C2—C1 | 1.337 (6) | C21—C23 | 1.425 (6) |
C2—C3 | 1.387 (7) | C22—N4 | 1.348 (4) |
C2—H2 | 0.9300 | C22—C26 | 1.438 (5) |
C1—N5 | 1.370 (5) | C23—C24 | 1.336 (7) |
C1—H1 | 0.9300 | C23—H23 | 0.9300 |
C3—C4 | 1.336 (6) | C24—C25 | 1.435 (5) |
C3—H3 | 0.9300 | C24—H24 | 0.9300 |
C4—C5 | 1.423 (6) | C25—C27 | 1.389 (6) |
C4—H4 | 0.9300 | C25—C26 | 1.405 (5) |
C5—O2 | 1.228 (5) | C26—N3 | 1.357 (4) |
C5—N5 | 1.394 (5) | C27—C28 | 1.362 (5) |
C7—C8 | 1.363 (6) | C27—H27 | 0.9300 |
C7—C6 | 1.377 (5) | C28—C29 | 1.396 (5) |
C7—H7 | 0.9300 | C28—H28 | 0.9300 |
C6—N1 | 1.323 (4) | C29—N3 | 1.302 (4) |
C6—N5 | 1.434 (5) | C29—N6 | 1.446 (4) |
C8—C9 | 1.390 (6) | C30—O3 | 1.233 (4) |
C8—H8 | 0.9300 | C30—N6 | 1.389 (4) |
C9—C10 | 1.408 (5) | C30—C31 | 1.433 (5) |
C9—C14 | 1.439 (5) | C31—C32 | 1.333 (5) |
C10—N1 | 1.360 (4) | C31—H31 | 0.9300 |
C10—C11 | 1.439 (5) | C32—C33 | 1.398 (6) |
C11—N2 | 1.344 (4) | C32—H32 | 0.9300 |
C11—C12 | 1.400 (5) | C33—C34 | 1.330 (5) |
C12—C15 | 1.390 (6) | C33—H33 | 0.9300 |
C12—C13 | 1.418 (5) | C34—N6 | 1.376 (4) |
C13—C14 | 1.335 (6) | C34—H34 | 0.9300 |
C13—H13 | 0.9300 | Cd1—N2 | 2.296 (3) |
C14—H14 | 0.9300 | Cd1—N4 | 2.303 (3) |
C15—C16 | 1.346 (6) | Cd1—O1 | 2.309 (3) |
C15—H15 | 0.9300 | Cd1—O3i | 2.337 (2) |
C16—C17 | 1.389 (6) | Cd1—N1 | 2.402 (3) |
C16—H16 | 0.9300 | Cd1—N3 | 2.412 (3) |
C17—N2 | 1.319 (5) | Cl1—O10 | 1.403 (3) |
C17—H17 | 0.9300 | Cl1—O9 | 1.423 (3) |
C18—N4 | 1.325 (5) | Cl1—O11 | 1.424 (4) |
C18—C19 | 1.386 (6) | Cl1—O8 | 1.437 (3) |
C18—H18 | 0.9300 | Cl2—O5 | 1.358 (5) |
C19—C20 | 1.347 (6) | Cl2—O7 | 1.379 (4) |
C19—H19 | 0.9300 | Cl2—O4 | 1.381 (4) |
C20—C21 | 1.398 (6) | Cl2—O6 | 1.414 (4) |
C20—H20 | 0.9300 | O1—H10 | 0.8983 |
C21—C22 | 1.407 (5) | O1—H9 | 0.8965 |
C1—C2—C3 | 119.0 (4) | N3—C26—C22 | 118.7 (3) |
C1—C2—H2 | 120.5 | C25—C26—C22 | 119.5 (3) |
C3—C2—H2 | 120.5 | C28—C27—C25 | 120.8 (4) |
C2—C1—N5 | 121.0 (4) | C28—C27—H27 | 119.6 |
C2—C1—H1 | 119.5 | C25—C27—H27 | 119.6 |
N5—C1—H1 | 119.5 | C27—C28—C29 | 117.2 (4) |
C4—C3—C2 | 120.9 (4) | C27—C28—H28 | 121.4 |
C4—C3—H3 | 119.6 | C29—C28—H28 | 121.4 |
C2—C3—H3 | 119.6 | N3—C29—C28 | 124.7 (3) |
C3—C4—C5 | 122.2 (4) | N3—C29—N6 | 116.6 (3) |
C3—C4—H4 | 118.9 | C28—C29—N6 | 118.7 (3) |
C5—C4—H4 | 118.9 | O3—C30—N6 | 119.3 (3) |
O2—C5—N5 | 120.2 (4) | O3—C30—C31 | 126.9 (3) |
O2—C5—C4 | 125.5 (4) | N6—C30—C31 | 113.8 (3) |
N5—C5—C4 | 114.4 (4) | C32—C31—C30 | 122.1 (4) |
C8—C7—C6 | 118.7 (4) | C32—C31—H31 | 118.9 |
C8—C7—H7 | 120.6 | C30—C31—H31 | 118.9 |
C6—C7—H7 | 120.6 | C31—C32—C33 | 120.6 (4) |
N1—C6—C7 | 124.5 (4) | C31—C32—H32 | 119.7 |
N1—C6—N5 | 117.0 (3) | C33—C32—H32 | 119.7 |
C7—C6—N5 | 118.5 (3) | C34—C33—C32 | 119.6 (4) |
C7—C8—C9 | 119.6 (4) | C34—C33—H33 | 120.2 |
C7—C8—H8 | 120.2 | C32—C33—H33 | 120.2 |
C9—C8—H8 | 120.2 | C33—C34—N6 | 120.0 (4) |
C8—C9—C10 | 117.9 (4) | C33—C34—H34 | 120.0 |
C8—C9—C14 | 122.6 (4) | N6—C34—H34 | 120.0 |
C10—C9—C14 | 119.4 (4) | N2—Cd1—N4 | 168.48 (11) |
N1—C10—C9 | 122.2 (3) | N2—Cd1—O1 | 84.05 (11) |
N1—C10—C11 | 118.8 (3) | N4—Cd1—O1 | 84.52 (10) |
C9—C10—C11 | 119.1 (3) | N2—Cd1—O3i | 83.31 (10) |
N2—C11—C12 | 122.2 (3) | N4—Cd1—O3i | 95.45 (10) |
N2—C11—C10 | 118.3 (3) | O1—Cd1—O3i | 90.95 (10) |
C12—C11—C10 | 119.4 (3) | N2—Cd1—N1 | 71.08 (10) |
C15—C12—C11 | 117.3 (4) | N4—Cd1—N1 | 113.63 (10) |
C15—C12—C13 | 122.8 (4) | O1—Cd1—N1 | 105.73 (9) |
C11—C12—C13 | 119.9 (4) | O3i—Cd1—N1 | 147.35 (10) |
C14—C13—C12 | 121.4 (4) | N2—Cd1—N3 | 120.17 (11) |
C14—C13—H13 | 119.3 | N4—Cd1—N3 | 71.13 (10) |
C12—C13—H13 | 119.3 | O1—Cd1—N3 | 155.43 (10) |
C13—C14—C9 | 120.8 (4) | O3i—Cd1—N3 | 88.18 (9) |
C13—C14—H14 | 119.6 | N1—Cd1—N3 | 87.58 (9) |
C9—C14—H14 | 119.6 | O10—Cl1—O9 | 109.8 (2) |
C16—C15—C12 | 120.0 (4) | O10—Cl1—O11 | 109.5 (3) |
C16—C15—H15 | 120.0 | O9—Cl1—O11 | 110.4 (2) |
C12—C15—H15 | 120.0 | O10—Cl1—O8 | 109.11 (19) |
C15—C16—C17 | 119.4 (4) | O9—Cl1—O8 | 109.6 (2) |
C15—C16—H16 | 120.3 | O11—Cl1—O8 | 108.4 (2) |
C17—C16—H16 | 120.3 | O5—Cl2—O7 | 107.8 (4) |
N2—C17—C16 | 122.4 (4) | O5—Cl2—O4 | 110.5 (4) |
N2—C17—H17 | 118.8 | O7—Cl2—O4 | 110.8 (3) |
C16—C17—H17 | 118.8 | O5—Cl2—O6 | 107.8 (3) |
N4—C18—C19 | 122.6 (4) | O7—Cl2—O6 | 109.7 (3) |
N4—C18—H18 | 118.7 | O4—Cl2—O6 | 110.1 (3) |
C19—C18—H18 | 118.7 | C6—N1—C10 | 117.1 (3) |
C20—C19—C18 | 119.3 (4) | C6—N1—Cd1 | 129.2 (2) |
C20—C19—H19 | 120.4 | C10—N1—Cd1 | 113.7 (2) |
C18—C19—H19 | 120.4 | C17—N2—C11 | 118.6 (3) |
C19—C20—C21 | 120.3 (4) | C17—N2—Cd1 | 123.2 (3) |
C19—C20—H20 | 119.8 | C11—N2—Cd1 | 118.1 (2) |
C21—C20—H20 | 119.8 | C29—N3—C26 | 118.0 (3) |
C20—C21—C22 | 117.1 (4) | C29—N3—Cd1 | 128.4 (2) |
C20—C21—C23 | 123.4 (4) | C26—N3—Cd1 | 113.6 (2) |
C22—C21—C23 | 119.6 (4) | C18—N4—C22 | 118.8 (3) |
N4—C22—C21 | 122.0 (3) | C18—N4—Cd1 | 123.6 (3) |
N4—C22—C26 | 118.9 (3) | C22—N4—Cd1 | 117.5 (2) |
C21—C22—C26 | 119.1 (3) | C34—N6—C30 | 123.2 (3) |
C24—C23—C21 | 121.5 (4) | C34—N6—C29 | 118.6 (3) |
C24—C23—H23 | 119.2 | C30—N6—C29 | 118.0 (3) |
C21—C23—H23 | 119.2 | C1—N5—C5 | 122.5 (3) |
C23—C24—C25 | 120.7 (4) | C1—N5—C6 | 117.8 (3) |
C23—C24—H24 | 119.6 | C5—N5—C6 | 119.1 (3) |
C25—C24—H24 | 119.6 | Cd1—O1—H10 | 108.9 |
C27—C25—C26 | 117.5 (3) | Cd1—O1—H9 | 111.8 |
C27—C25—C24 | 123.0 (4) | H10—O1—H9 | 101.8 |
C26—C25—C24 | 119.5 (4) | C30—O3—Cd1i | 140.3 (2) |
N3—C26—C25 | 121.8 (3) | ||
C3—C2—C1—N5 | 2.8 (7) | N4—Cd1—N1—C10 | 170.0 (2) |
C1—C2—C3—C4 | −1.5 (7) | O1—Cd1—N1—C10 | 79.2 (2) |
C2—C3—C4—C5 | 0.2 (7) | O3i—Cd1—N1—C10 | −39.0 (3) |
C3—C4—C5—O2 | −179.7 (4) | N3—Cd1—N1—C10 | −121.8 (2) |
C3—C4—C5—N5 | −0.2 (6) | C16—C17—N2—C11 | −2.2 (7) |
C8—C7—C6—N1 | −0.9 (6) | C16—C17—N2—Cd1 | −177.8 (4) |
C8—C7—C6—N5 | 179.2 (4) | C12—C11—N2—C17 | 4.2 (6) |
C6—C7—C8—C9 | −0.9 (6) | C10—C11—N2—C17 | −176.3 (4) |
C7—C8—C9—C10 | 2.0 (6) | C12—C11—N2—Cd1 | 180.0 (3) |
C7—C8—C9—C14 | −179.7 (4) | C10—C11—N2—Cd1 | −0.5 (4) |
C8—C9—C10—N1 | −1.6 (5) | N4—Cd1—N2—C17 | 59.1 (7) |
C14—C9—C10—N1 | −179.9 (3) | O1—Cd1—N2—C17 | 66.3 (4) |
C8—C9—C10—C11 | 178.1 (4) | O3i—Cd1—N2—C17 | −25.4 (3) |
C14—C9—C10—C11 | −0.2 (5) | N1—Cd1—N2—C17 | 175.2 (4) |
N1—C10—C11—N2 | 1.8 (5) | N3—Cd1—N2—C17 | −109.3 (3) |
C9—C10—C11—N2 | −177.9 (3) | N4—Cd1—N2—C11 | −116.5 (5) |
N1—C10—C11—C12 | −178.6 (3) | O1—Cd1—N2—C11 | −109.3 (3) |
C9—C10—C11—C12 | 1.6 (5) | O3i—Cd1—N2—C11 | 159.0 (3) |
N2—C11—C12—C15 | −3.2 (6) | N1—Cd1—N2—C11 | −0.4 (3) |
C10—C11—C12—C15 | 177.3 (4) | N3—Cd1—N2—C11 | 75.1 (3) |
N2—C11—C12—C13 | 177.2 (4) | C28—C29—N3—C26 | 1.5 (5) |
C10—C11—C12—C13 | −2.3 (6) | N6—C29—N3—C26 | −178.5 (3) |
C15—C12—C13—C14 | −178.1 (4) | C28—C29—N3—Cd1 | −177.2 (3) |
C11—C12—C13—C14 | 1.5 (6) | N6—C29—N3—Cd1 | 2.8 (4) |
C12—C13—C14—C9 | 0.0 (7) | C25—C26—N3—C29 | 0.3 (5) |
C8—C9—C14—C13 | −178.8 (4) | C22—C26—N3—C29 | 178.9 (3) |
C10—C9—C14—C13 | −0.6 (6) | C25—C26—N3—Cd1 | 179.2 (3) |
C11—C12—C15—C16 | 0.3 (7) | C22—C26—N3—Cd1 | −2.3 (4) |
C13—C12—C15—C16 | 179.9 (4) | N2—Cd1—N3—C29 | −3.6 (3) |
C12—C15—C16—C17 | 1.5 (8) | N4—Cd1—N3—C29 | 178.9 (3) |
C15—C16—C17—N2 | −0.6 (8) | O1—Cd1—N3—C29 | −173.1 (3) |
N4—C18—C19—C20 | −1.9 (8) | O3i—Cd1—N3—C29 | −84.8 (3) |
C18—C19—C20—C21 | 0.2 (8) | N1—Cd1—N3—C29 | 62.9 (3) |
C19—C20—C21—C22 | 1.6 (7) | N2—Cd1—N3—C26 | 177.7 (2) |
C19—C20—C21—C23 | −178.6 (5) | N4—Cd1—N3—C26 | 0.1 (2) |
C20—C21—C22—N4 | −2.0 (6) | O1—Cd1—N3—C26 | 8.2 (4) |
C23—C21—C22—N4 | 178.2 (4) | O3i—Cd1—N3—C26 | 96.5 (2) |
C20—C21—C22—C26 | 177.7 (4) | N1—Cd1—N3—C26 | −115.9 (2) |
C23—C21—C22—C26 | −2.1 (6) | C19—C18—N4—C22 | 1.5 (7) |
C20—C21—C23—C24 | 179.9 (5) | C19—C18—N4—Cd1 | −173.2 (4) |
C22—C21—C23—C24 | −0.3 (7) | C21—C22—N4—C18 | 0.5 (6) |
C21—C23—C24—C25 | 1.5 (8) | C26—C22—N4—C18 | −179.2 (4) |
C23—C24—C25—C27 | 177.9 (4) | C21—C22—N4—Cd1 | 175.6 (3) |
C23—C24—C25—C26 | −0.4 (7) | C26—C22—N4—Cd1 | −4.2 (4) |
C27—C25—C26—N3 | −1.8 (5) | N2—Cd1—N4—C18 | 7.5 (7) |
C24—C25—C26—N3 | 176.5 (4) | O1—Cd1—N4—C18 | 0.3 (3) |
C27—C25—C26—C22 | 179.7 (3) | O3i—Cd1—N4—C18 | 90.7 (3) |
C24—C25—C26—C22 | −2.0 (5) | N1—Cd1—N4—C18 | −104.5 (3) |
N4—C22—C26—N3 | 4.4 (5) | N3—Cd1—N4—C18 | 176.9 (3) |
C21—C22—C26—N3 | −175.4 (3) | N2—Cd1—N4—C22 | −167.3 (5) |
N4—C22—C26—C25 | −177.0 (3) | O1—Cd1—N4—C22 | −174.5 (3) |
C21—C22—C26—C25 | 3.2 (5) | O3i—Cd1—N4—C22 | −84.1 (3) |
C26—C25—C27—C28 | 1.5 (6) | N1—Cd1—N4—C22 | 80.7 (3) |
C24—C25—C27—C28 | −176.7 (4) | N3—Cd1—N4—C22 | 2.1 (2) |
C25—C27—C28—C29 | 0.1 (6) | C33—C34—N6—C30 | −6.9 (5) |
C27—C28—C29—N3 | −1.7 (6) | C33—C34—N6—C29 | 178.6 (3) |
C27—C28—C29—N6 | 178.3 (3) | O3—C30—N6—C34 | −171.5 (3) |
O3—C30—C31—C32 | 175.0 (4) | C31—C30—N6—C34 | 9.2 (5) |
N6—C30—C31—C32 | −5.8 (6) | O3—C30—N6—C29 | 3.0 (5) |
C30—C31—C32—C33 | 0.1 (7) | C31—C30—N6—C29 | −176.2 (3) |
C31—C32—C33—C34 | 2.8 (6) | N3—C29—N6—C34 | −102.2 (4) |
C32—C33—C34—N6 | 0.4 (6) | C28—C29—N6—C34 | 77.8 (4) |
C7—C6—N1—C10 | 1.3 (5) | N3—C29—N6—C30 | 83.0 (4) |
N5—C6—N1—C10 | −178.7 (3) | C28—C29—N6—C30 | −97.0 (4) |
C7—C6—N1—Cd1 | −175.9 (3) | C2—C1—N5—C5 | −2.9 (6) |
N5—C6—N1—Cd1 | 4.1 (5) | C2—C1—N5—C6 | −173.9 (4) |
C9—C10—N1—C6 | 0.0 (5) | O2—C5—N5—C1 | −179.0 (4) |
C11—C10—N1—C6 | −179.8 (3) | C4—C5—N5—C1 | 1.5 (6) |
C9—C10—N1—Cd1 | 177.6 (3) | O2—C5—N5—C6 | −8.1 (6) |
C11—C10—N1—Cd1 | −2.1 (4) | C4—C5—N5—C6 | 172.4 (3) |
N2—Cd1—N1—C6 | 178.6 (3) | N1—C6—N5—C1 | −120.6 (4) |
N4—Cd1—N1—C6 | −12.7 (3) | C7—C6—N5—C1 | 59.3 (5) |
O1—Cd1—N1—C6 | −103.5 (3) | N1—C6—N5—C5 | 68.1 (5) |
O3i—Cd1—N1—C6 | 138.3 (3) | C7—C6—N5—C5 | −112.0 (4) |
N3—Cd1—N1—C6 | 55.5 (3) | N6—C30—O3—Cd1i | 166.7 (2) |
N2—Cd1—N1—C10 | 1.3 (2) | C31—C30—O3—Cd1i | −14.1 (7) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H9···O2ii | 0.90 | 1.79 | 2.680 (4) | 172 |
O1—H10···O8 | 0.90 | 2.04 | 2.924 (5) | 169 |
C2—H2···O8iii | 0.93 | 2.56 | 3.463 (5) | 164 |
C17—H17···O3i | 0.93 | 2.51 | 3.085 (5) | 120 |
C19—H19···O10iv | 0.93 | 2.50 | 3.246 (5) | 138 |
C28—H28···O9i | 0.93 | 2.50 | 3.318 (5) | 147 |
C32—H32···O4v | 0.93 | 2.42 | 3.342 (5) | 172 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+2, −y+1, −z+2; (v) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cd2(C17H11N3O)4(H2O)2](ClO4)4 |
Mr | 1751.78 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 11.681 (2), 12.437 (2), 12.709 (2) |
α, β, γ (°) | 107.317 (2), 106.340 (2), 91.838 (2) |
V (Å3) | 1677.9 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.24 × 0.16 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.816, 0.917 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9002, 6304, 5004 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.612 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.103, 0.99 |
No. of reflections | 6304 |
No. of parameters | 488 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.81, −0.35 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Bruker, 2001).
Cd1—N2 | 2.296 (3) | Cd1—O3i | 2.337 (2) |
Cd1—N4 | 2.303 (3) | Cd1—N1 | 2.402 (3) |
Cd1—O1 | 2.309 (3) | Cd1—N3 | 2.412 (3) |
N2—Cd1—N4 | 168.48 (11) | O1—Cd1—N1 | 105.73 (9) |
N2—Cd1—O1 | 84.05 (11) | O3i—Cd1—N1 | 147.35 (10) |
N4—Cd1—O1 | 84.52 (10) | N2—Cd1—N3 | 120.17 (11) |
N2—Cd1—O3i | 83.31 (10) | N4—Cd1—N3 | 71.13 (10) |
N4—Cd1—O3i | 95.45 (10) | O1—Cd1—N3 | 155.43 (10) |
O1—Cd1—O3i | 90.95 (10) | O3i—Cd1—N3 | 88.18 (9) |
N2—Cd1—N1 | 71.08 (10) | N1—Cd1—N3 | 87.58 (9) |
N4—Cd1—N1 | 113.63 (10) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H9···O2ii | 0.90 | 1.79 | 2.680 (4) | 172 |
O1—H10···O8 | 0.90 | 2.04 | 2.924 (5) | 169 |
C2—H2···O8iii | 0.93 | 2.56 | 3.463 (5) | 164 |
C17—H17···O3i | 0.93 | 2.51 | 3.085 (5) | 120 |
C19—H19···O10iv | 0.93 | 2.50 | 3.246 (5) | 138 |
C28—H28···O9i | 0.93 | 2.50 | 3.318 (5) | 147 |
C32—H32···O4v | 0.93 | 2.42 | 3.342 (5) | 172 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+2, −y+1, −z+2; (v) −x+1, −y+1, −z. |
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Derivatives of 1,10-phenanthroline play a pivotal role in modern coordination chemistry and a number of complexes with these ligands have been synthesized. Some of them exhibit interesting properties as molecular electrical conductors (Zheng et al. 2003), as photolumisescent materials (Zhang et al., 2006) and for cancer therapy (Liu et al., 2004). Complexes with 2-(2-keto-pyridin-1-yl)-1,10-phenanthroline (PP) as a ligand have not been reported to our knowledge to date. Our interest in synthesizing new complexes with derivatives of 1,10-phenanthroline as ligand resulted in the title binuclear complex, (I). We report here the structure and fluorescence properties of (I).
Fig. 1 shows the dinuclear cation, which sits about a crystallographic centre of inversion. The CdII ion assumes a distorted octahdral CdN4O2 coordination geometry (Table 1). Each CdII ion is coordinated in a bidentate fashion by the N atoms of two PP ligands. One of the PP ligands also bridges via keto atom O3 to the other CdII ion in the cation. The two CdII ions are separated by 5.8159 (11) Å. The other PP ligand only functions as a terminal bidentate ligand, but its keto atom O2 is a hydrogen-bond acceptor (Table 2). This interaction is with a water ligand of an adjacent cation and leads to the formation of a supramolecular one-dimensional chain which runs parallel to the [100] direction (Fig. 2). Table 2 and Fig. 2 also depict the hydrogen bonds and weaker C—H···O interactions between the complex cations and surrounding perchlorate anions.
The dihedral angles between the pyridine and 1,10-phenanthroline ring system planes are 64.44 (18)° for PP as a terminal ligand and 80.15 (15)° for PP as a bridging ligand. These differences can be expected in terms of steric relief. There are π–π stacking interactions between the pyridine and 1,10-phenanthroline ring systems of adjacent ligands at the same CdII center [Cg1···Cg2 = 3.439 (2) Å, Cg1···Cg2perp = 3.333 Å, α = 8.05° and Cg3···Cg4 = 3.426 (3) Å, Cg3···Cg4perp = 3.238°, α = 9.23°; Cg1, Cg2, Cg3 and Cg4 are the centroids of the Cd1/N1/C10/C11/N2, N5/C31–C34, Cd1/N3/C26/C22N/4 and N6/C1–C5 rings, respectively; CgI···Jperp is the perpendicular distance from CgI to the plane containing ring J; α is the dihedral angle between planes I and J].
The fluorescence spectra for complex (I) and native PP were measured at room temperature in the solid state, and the excitation wavelengths are at 395 nm for the complex and 467 nm for PP. The emission peak positions are at 444 and 473 nm for the complex and at 529 nm for PP. The appearance of the two emission peaks for the complex implys that there may be two different structures for the PP ligand in complex (I), which is consistent with the crystal structure. The peak at 444 nm may be attributed to the PP bridging ligand because of the larger dihedral angle between the pyridine and 1,10-phenanthroline ring planes and, consequently, the lower degree of conjugation. Compared with the fluorescence spectrum of the complex, the bathochromic shift of the maximum emission peak of uncoordinated PP may imply that there should be a larger degree of conjugation and a smaller dihedral angle between the pyridine and 1,10-phenanthroline ring planes, although the crystal data for the PP ligand are not available as yet. At the same time, the emission intensity of complex (I) is stronger than that of the PP ligand, which may imply the existance of a strong π–π stacking interaction between PP molecules (Mizobe et al., 2006).