Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027055/hb2432sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027055/hb2432Isup2.hkl |
CCDC reference: 654716
5 mmol of calcium perchlorate was added to a solution of 1,10-phenanthroline (10 mmol) and 4-(dimethylamino)benzaldehyde (5 mmol) in in 10 ml of methanol. The mixture was continuously stirred for 3 h at refluxing temperature, then filtered, Brown blocks of (I) were obtained by evaporation the filtrate after two weeks.
The H atoms were geometrically placed (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
Phenanthroline and its derivatives and their complexes with metal ions have received considerable attention over the past three decades (Summers, 1978). This may be attributed to unusual structural features in the resultant metal complexes and their biological activities. The chemical and pharmacological properties of the complexes on phenanthroline have been investigated extensively, owing to their chelating ability with metal ions and to their potentially beneficial activities, such as catalytic, antitumor, antineoplastic and antibacterial (Guo et al., 2004). As part of our onging studies of metal coordination complexes (Tai et al., 2005), the synthesis and structure of the title compound, (I), is reported.
Four N,N-bidentate ligands are attached to the calcium ion (site symmetry 2) resulting in a CaN8 unit (Table 1).
Various π-π stacking interactions of the 1,10-phenanthroline rings help to consolidate the crystal packing.
For background, see: Summers (1978); Guo et al. (2004); Tai et al. (2005).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
[Ca(C12H8N2)4](ClO4)2·2C9H11NO | Dx = 1.408 Mg m−3 |
Mr = 1258.17 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 2661 reflections |
Hall symbol: -I 4ad | θ = 2.7–20.5° |
a = 17.455 (3) Å | µ = 0.27 mm−1 |
c = 38.952 (3) Å | T = 298 K |
V = 11868 (3) Å3 | Block, brown |
Z = 8 | 0.45 × 0.42 × 0.40 mm |
F(000) = 5232 |
Bruker SMART CCD diffractometer | 5234 independent reflections |
Radiation source: fine-focus sealed tube | 1808 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.103 |
ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −20→20 |
Tmin = 0.889, Tmax = 0.900 | k = −20→20 |
29937 measured reflections | l = −46→30 |
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)] = 0.079 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.388 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.1079P)2 + 113.9196P] where P = (Fo2 + 2Fc2)/3 |
5234 reflections | (Δ/σ)max = 0.001 |
433 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
[Ca(C12H8N2)4](ClO4)2·2C9H11NO | Z = 8 |
Mr = 1258.17 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.27 mm−1 |
a = 17.455 (3) Å | T = 298 K |
c = 38.952 (3) Å | 0.45 × 0.42 × 0.40 mm |
V = 11868 (3) Å3 |
Bruker SMART CCD diffractometer | 5234 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1808 reflections with I > 2σ(I) |
Tmin = 0.889, Tmax = 0.900 | Rint = 0.103 |
29937 measured reflections |
R[F2 > 2σ(F2)] = 0.079 | 0 restraints |
wR(F2) = 0.388 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.1079P)2 + 113.9196P] where P = (Fo2 + 2Fc2)/3 |
5234 reflections | Δρmax = 0.41 e Å−3 |
433 parameters | Δρmin = −0.56 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ca1 | 0.0000 | 0.7500 | 0.12539 (6) | 0.0351 (6) | |
Cl1 | 0.5000 | 0.7500 | 0.02830 (9) | 0.0715 (11) | |
Cl2 | 0.0000 | 0.2500 | 0.02789 (8) | 0.0603 (10) | |
N1 | −0.0545 (4) | 0.8700 (4) | 0.15864 (19) | 0.0474 (19) | |
N2 | 0.0017 (4) | 0.8820 (4) | 0.09279 (19) | 0.0452 (19) | |
N3 | 0.1283 (4) | 0.7490 (4) | 0.09188 (19) | 0.0452 (19) | |
N4 | 0.1188 (4) | 0.8022 (4) | 0.15835 (19) | 0.0462 (19) | |
N5 | 0.2086 (6) | 0.0408 (6) | 0.1909 (3) | 0.086 (3) | |
O1 | 0.2703 (8) | −0.0671 (6) | 0.0342 (3) | 0.153 (5) | |
O2 | 0.5000 | 0.7500 | 0.0637 (3) | 0.114 (4) | |
O3 | 0.5413 (15) | 0.8168 (15) | 0.0180 (6) | 0.107 (7) | 0.50 |
O4 | 0.4339 (13) | 0.741 (2) | 0.0105 (5) | 0.103 (7) | 0.50 |
O5 | 0.5532 (14) | 0.6898 (15) | 0.0198 (5) | 0.110 (7) | 0.50 |
O6 | 0.0000 | 0.2500 | 0.0636 (3) | 0.094 (4) | |
O7 | 0.0611 (13) | 0.2976 (13) | 0.0161 (5) | 0.092 (6) | 0.50 |
O8 | −0.0639 (12) | 0.3007 (11) | 0.0189 (4) | 0.091 (5) | 0.50 |
O9 | −0.0071 (17) | 0.1840 (12) | 0.0108 (5) | 0.089 (6) | 0.50 |
C1 | −0.0806 (6) | 0.8672 (6) | 0.1906 (3) | 0.060 (3) | |
H1 | −0.0858 | 0.8191 | 0.2006 | 0.072* | |
C2 | −0.1006 (6) | 0.9302 (7) | 0.2101 (3) | 0.068 (3) | |
H2 | −0.1174 | 0.9248 | 0.2326 | 0.082* | |
C3 | −0.0950 (6) | 1.0007 (7) | 0.1951 (3) | 0.071 (3) | |
H3 | −0.1092 | 1.0441 | 0.2074 | 0.085* | |
C4 | −0.0685 (6) | 1.0082 (6) | 0.1618 (3) | 0.055 (3) | |
C5 | −0.0482 (5) | 0.9408 (5) | 0.1440 (3) | 0.044 (2) | |
C6 | −0.0206 (5) | 0.9465 (5) | 0.1093 (3) | 0.044 (2) | |
C7 | −0.0164 (5) | 1.0191 (6) | 0.0936 (3) | 0.055 (3) | |
C8 | 0.0096 (6) | 1.0232 (7) | 0.0594 (3) | 0.067 (3) | |
H8 | 0.0132 | 1.0702 | 0.0483 | 0.080* | |
C9 | 0.0293 (6) | 0.9581 (7) | 0.0431 (3) | 0.065 (3) | |
H9 | 0.0455 | 0.9595 | 0.0203 | 0.078* | |
C10 | 0.0251 (5) | 0.8889 (6) | 0.0604 (2) | 0.052 (2) | |
H10 | 0.0394 | 0.8447 | 0.0488 | 0.062* | |
C11 | −0.0615 (6) | 1.0812 (6) | 0.1450 (4) | 0.069 (3) | |
H11 | −0.0741 | 1.1257 | 0.1569 | 0.083* | |
C12 | −0.0371 (6) | 1.0860 (6) | 0.1124 (3) | 0.068 (3) | |
H12 | −0.0335 | 1.1337 | 0.1019 | 0.082* | |
C13 | 0.1337 (6) | 0.7300 (6) | 0.0587 (2) | 0.055 (3) | |
H13 | 0.0893 | 0.7150 | 0.0473 | 0.066* | |
C14 | 0.2021 (7) | 0.7315 (6) | 0.0403 (3) | 0.065 (3) | |
H14 | 0.2027 | 0.7218 | 0.0168 | 0.078* | |
C15 | 0.2674 (7) | 0.7476 (6) | 0.0573 (3) | 0.067 (3) | |
H15 | 0.3139 | 0.7458 | 0.0458 | 0.080* | |
C16 | 0.2660 (6) | 0.7666 (6) | 0.0918 (3) | 0.060 (3) | |
C17 | 0.1935 (5) | 0.7696 (5) | 0.1083 (3) | 0.044 (2) | |
C18 | 0.1890 (5) | 0.7927 (5) | 0.1433 (3) | 0.048 (2) | |
C19 | 0.2581 (6) | 0.8087 (6) | 0.1616 (3) | 0.062 (3) | |
C20 | 0.2527 (7) | 0.8315 (7) | 0.1959 (3) | 0.080 (4) | |
H20 | 0.2968 | 0.8404 | 0.2087 | 0.096* | |
C21 | 0.1828 (7) | 0.8407 (6) | 0.2104 (3) | 0.072 (3) | |
H21 | 0.1783 | 0.8566 | 0.2331 | 0.087* | |
C22 | 0.1170 (6) | 0.8257 (6) | 0.1907 (3) | 0.060 (3) | |
H22 | 0.0694 | 0.8326 | 0.2010 | 0.072* | |
C23 | 0.3336 (6) | 0.7822 (6) | 0.1108 (4) | 0.070 (3) | |
H23 | 0.3811 | 0.7797 | 0.1000 | 0.084* | |
C24 | 0.3295 (6) | 0.8005 (7) | 0.1442 (4) | 0.076 (3) | |
H24 | 0.3746 | 0.8081 | 0.1564 | 0.091* | |
C25 | 0.3071 (10) | −0.0484 (7) | 0.0583 (4) | 0.112 (6) | |
H25 | 0.3600 | −0.0476 | 0.0555 | 0.135* | |
C26 | 0.2777 (10) | −0.0262 (7) | 0.0920 (4) | 0.093 (5) | |
C27 | 0.2001 (9) | −0.0254 (7) | 0.1016 (5) | 0.104 (6) | |
H27 | 0.1632 | −0.0407 | 0.0858 | 0.124* | |
C28 | 0.1778 (8) | −0.0032 (8) | 0.1332 (4) | 0.092 (5) | |
H28 | 0.1258 | −0.0030 | 0.1383 | 0.110* | |
C29 | 0.2297 (7) | 0.0196 (6) | 0.1587 (4) | 0.069 (3) | |
C30 | 0.3079 (7) | 0.0191 (6) | 0.1488 (3) | 0.073 (3) | |
H30 | 0.3448 | 0.0349 | 0.1645 | 0.087* | |
C31 | 0.3309 (7) | −0.0042 (7) | 0.1166 (3) | 0.081 (4) | |
H31 | 0.3828 | −0.0052 | 0.1112 | 0.097* | |
C32 | 0.1287 (8) | 0.0439 (9) | 0.2004 (4) | 0.130 (6) | |
H32A | 0.1014 | 0.0753 | 0.1843 | 0.196* | |
H32B | 0.1239 | 0.0653 | 0.2230 | 0.196* | |
H32C | 0.1076 | −0.0069 | 0.2002 | 0.196* | |
C33 | 0.2644 (8) | 0.0570 (8) | 0.2170 (4) | 0.103 (4) | |
H33A | 0.2985 | 0.0141 | 0.2193 | 0.154* | |
H33B | 0.2388 | 0.0659 | 0.2384 | 0.154* | |
H33C | 0.2931 | 0.1017 | 0.2107 | 0.154* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ca1 | 0.0386 (13) | 0.0338 (13) | 0.0330 (12) | 0.0015 (10) | 0.000 | 0.000 |
Cl1 | 0.061 (3) | 0.107 (4) | 0.046 (2) | −0.007 (3) | 0.000 | 0.000 |
Cl2 | 0.083 (3) | 0.060 (3) | 0.0385 (19) | −0.006 (3) | 0.000 | 0.000 |
N1 | 0.051 (5) | 0.048 (5) | 0.043 (5) | 0.004 (4) | −0.002 (4) | −0.002 (4) |
N2 | 0.049 (5) | 0.039 (5) | 0.048 (5) | 0.000 (4) | −0.007 (4) | 0.007 (4) |
N3 | 0.045 (5) | 0.041 (4) | 0.050 (5) | −0.001 (3) | 0.005 (4) | 0.002 (4) |
N4 | 0.047 (5) | 0.044 (5) | 0.047 (5) | 0.000 (4) | −0.005 (4) | 0.001 (4) |
N5 | 0.077 (8) | 0.077 (7) | 0.103 (9) | 0.000 (6) | 0.011 (7) | 0.009 (6) |
O1 | 0.234 (14) | 0.111 (9) | 0.114 (9) | 0.002 (9) | −0.064 (9) | −0.002 (7) |
O2 | 0.120 (11) | 0.152 (13) | 0.069 (8) | −0.018 (9) | 0.000 | 0.000 |
O3 | 0.106 (19) | 0.128 (19) | 0.088 (15) | −0.017 (16) | 0.004 (12) | 0.004 (15) |
O4 | 0.092 (16) | 0.13 (2) | 0.083 (15) | −0.012 (16) | −0.017 (12) | −0.007 (16) |
O5 | 0.106 (18) | 0.131 (19) | 0.094 (15) | 0.004 (16) | −0.002 (12) | −0.012 (15) |
O6 | 0.126 (11) | 0.099 (9) | 0.058 (7) | 0.005 (8) | 0.000 | 0.000 |
O7 | 0.100 (16) | 0.100 (17) | 0.074 (13) | −0.009 (14) | 0.004 (13) | 0.005 (11) |
O8 | 0.101 (15) | 0.101 (15) | 0.070 (12) | 0.007 (12) | −0.007 (11) | −0.001 (10) |
O9 | 0.11 (2) | 0.086 (15) | 0.068 (13) | 0.001 (14) | 0.003 (14) | −0.010 (10) |
C1 | 0.070 (7) | 0.054 (7) | 0.055 (7) | 0.001 (5) | 0.006 (6) | −0.003 (5) |
C2 | 0.075 (8) | 0.078 (8) | 0.051 (7) | 0.011 (6) | −0.002 (6) | −0.014 (6) |
C3 | 0.073 (8) | 0.064 (8) | 0.075 (8) | 0.019 (6) | −0.015 (6) | −0.028 (6) |
C4 | 0.052 (6) | 0.052 (6) | 0.060 (7) | 0.006 (5) | −0.008 (5) | −0.006 (5) |
C5 | 0.040 (5) | 0.040 (6) | 0.053 (6) | 0.006 (4) | −0.015 (5) | −0.006 (5) |
C6 | 0.040 (5) | 0.042 (6) | 0.049 (6) | −0.005 (4) | −0.013 (4) | 0.008 (5) |
C7 | 0.042 (6) | 0.044 (6) | 0.077 (8) | −0.003 (4) | −0.020 (5) | 0.010 (5) |
C8 | 0.063 (7) | 0.061 (7) | 0.076 (8) | −0.006 (6) | −0.013 (6) | 0.032 (6) |
C9 | 0.061 (7) | 0.074 (8) | 0.058 (7) | 0.004 (6) | −0.002 (5) | 0.028 (6) |
C10 | 0.055 (6) | 0.053 (6) | 0.048 (6) | 0.004 (5) | −0.001 (5) | 0.007 (5) |
C11 | 0.068 (8) | 0.035 (6) | 0.105 (10) | 0.007 (5) | −0.013 (7) | −0.013 (6) |
C12 | 0.070 (8) | 0.040 (7) | 0.095 (9) | −0.003 (5) | −0.010 (7) | 0.008 (6) |
C13 | 0.059 (7) | 0.064 (7) | 0.042 (6) | 0.007 (5) | 0.002 (5) | 0.001 (5) |
C14 | 0.079 (8) | 0.060 (7) | 0.057 (7) | 0.008 (6) | 0.024 (6) | 0.002 (5) |
C15 | 0.060 (7) | 0.058 (7) | 0.082 (9) | 0.000 (5) | 0.028 (7) | 0.005 (6) |
C16 | 0.049 (7) | 0.050 (6) | 0.079 (8) | 0.003 (5) | 0.009 (6) | 0.012 (6) |
C17 | 0.038 (6) | 0.039 (5) | 0.057 (6) | 0.001 (4) | 0.006 (5) | 0.005 (5) |
C18 | 0.041 (6) | 0.039 (6) | 0.063 (7) | −0.002 (4) | −0.007 (5) | 0.002 (5) |
C19 | 0.054 (7) | 0.052 (6) | 0.080 (8) | −0.004 (5) | −0.014 (6) | −0.001 (6) |
C20 | 0.075 (9) | 0.081 (9) | 0.083 (9) | −0.009 (7) | −0.029 (7) | −0.009 (7) |
C21 | 0.085 (9) | 0.075 (8) | 0.057 (7) | −0.010 (7) | −0.024 (7) | −0.012 (6) |
C22 | 0.065 (7) | 0.058 (7) | 0.056 (7) | 0.000 (5) | −0.010 (5) | −0.009 (5) |
C23 | 0.040 (7) | 0.068 (8) | 0.102 (10) | 0.001 (5) | 0.007 (6) | 0.001 (7) |
C24 | 0.040 (7) | 0.081 (9) | 0.106 (10) | −0.006 (6) | −0.017 (7) | 0.009 (8) |
C25 | 0.171 (16) | 0.071 (9) | 0.094 (11) | −0.008 (9) | −0.063 (11) | 0.004 (8) |
C26 | 0.147 (15) | 0.053 (8) | 0.078 (10) | −0.014 (8) | −0.055 (10) | 0.008 (7) |
C27 | 0.086 (11) | 0.064 (9) | 0.161 (17) | −0.023 (8) | −0.074 (12) | 0.022 (10) |
C28 | 0.072 (9) | 0.078 (9) | 0.125 (13) | −0.020 (7) | −0.039 (9) | 0.026 (9) |
C29 | 0.059 (8) | 0.046 (6) | 0.103 (10) | −0.006 (5) | −0.019 (7) | 0.018 (6) |
C30 | 0.063 (8) | 0.060 (7) | 0.096 (10) | −0.007 (6) | −0.019 (7) | −0.002 (7) |
C31 | 0.073 (8) | 0.067 (8) | 0.103 (11) | −0.004 (6) | −0.015 (7) | 0.002 (7) |
C32 | 0.094 (12) | 0.124 (13) | 0.174 (17) | 0.009 (10) | 0.039 (11) | 0.033 (12) |
C33 | 0.115 (12) | 0.100 (11) | 0.094 (10) | −0.016 (9) | −0.009 (9) | −0.002 (9) |
Ca1—N3i | 2.593 (7) | C4—C5 | 1.410 (12) |
Ca1—N3 | 2.593 (7) | C4—C11 | 1.437 (14) |
Ca1—N4 | 2.604 (7) | C5—C6 | 1.438 (13) |
Ca1—N4i | 2.604 (7) | C6—C7 | 1.409 (12) |
Ca1—N2i | 2.631 (7) | C7—C8 | 1.407 (14) |
Ca1—N2 | 2.631 (7) | C7—C12 | 1.426 (14) |
Ca1—N1 | 2.641 (7) | C8—C9 | 1.348 (14) |
Ca1—N1i | 2.641 (7) | C8—H8 | 0.9300 |
Cl1—O4 | 1.36 (2) | C9—C10 | 1.385 (13) |
Cl1—O4ii | 1.36 (2) | C9—H9 | 0.9300 |
Cl1—O2 | 1.377 (13) | C10—H10 | 0.9300 |
Cl1—O3ii | 1.43 (2) | C11—C12 | 1.341 (15) |
Cl1—O3 | 1.43 (2) | C11—H11 | 0.9300 |
Cl1—O5 | 1.44 (2) | C12—H12 | 0.9300 |
Cl1—O5ii | 1.44 (2) | C13—C14 | 1.393 (13) |
Cl2—O9 | 1.34 (2) | C13—H13 | 0.9300 |
Cl2—O9iii | 1.34 (2) | C14—C15 | 1.349 (15) |
Cl2—O6 | 1.389 (11) | C14—H14 | 0.9300 |
Cl2—O7iii | 1.43 (2) | C15—C16 | 1.382 (14) |
Cl2—O7 | 1.43 (2) | C15—H15 | 0.9300 |
Cl2—O8iii | 1.466 (19) | C16—C23 | 1.418 (15) |
Cl2—O8 | 1.466 (19) | C16—C17 | 1.422 (13) |
N1—C1 | 1.325 (11) | C17—C18 | 1.421 (13) |
N1—C5 | 1.366 (11) | C18—C19 | 1.432 (13) |
N2—C10 | 1.331 (11) | C19—C20 | 1.396 (15) |
N2—C6 | 1.353 (11) | C19—C24 | 1.425 (15) |
N3—C13 | 1.338 (11) | C20—C21 | 1.354 (15) |
N3—C17 | 1.354 (11) | C20—H20 | 0.9300 |
N4—C22 | 1.326 (11) | C21—C22 | 1.405 (14) |
N4—C18 | 1.368 (11) | C21—H21 | 0.9300 |
N5—C29 | 1.356 (16) | C22—H22 | 0.9300 |
N5—C33 | 1.436 (15) | C23—C24 | 1.343 (16) |
N5—C32 | 1.445 (15) | C23—H23 | 0.9300 |
O1—C25 | 1.183 (15) | C24—H24 | 0.9300 |
O3—O4ii | 1.14 (3) | C25—C26 | 1.46 (2) |
O3—O5ii | 1.66 (3) | C25—H25 | 0.9300 |
O4—O3ii | 1.14 (3) | C26—C31 | 1.386 (16) |
O4—O5ii | 1.28 (3) | C26—C27 | 1.41 (2) |
O5—O4ii | 1.28 (3) | C27—C28 | 1.35 (2) |
O5—O3ii | 1.66 (3) | C27—H27 | 0.9300 |
O7—O9iii | 1.02 (2) | C28—C29 | 1.403 (16) |
O7—O8iii | 1.72 (3) | C28—H28 | 0.9300 |
O8—O9iii | 1.31 (3) | C29—C30 | 1.419 (15) |
O8—O7iii | 1.72 (3) | C30—C31 | 1.380 (16) |
O9—O7iii | 1.02 (2) | C30—H30 | 0.9300 |
O9—O8iii | 1.31 (3) | C31—H31 | 0.9300 |
C1—C2 | 1.382 (13) | C32—H32A | 0.9600 |
C1—H1 | 0.9300 | C32—H32B | 0.9600 |
C2—C3 | 1.365 (15) | C32—H32C | 0.9600 |
C2—H2 | 0.9300 | C33—H33A | 0.9600 |
C3—C4 | 1.385 (14) | C33—H33B | 0.9600 |
C3—H3 | 0.9300 | C33—H33C | 0.9600 |
N3i—Ca1—N3 | 119.5 (3) | N1—C1—H1 | 117.5 |
N3i—Ca1—N4 | 159.1 (2) | C2—C1—H1 | 117.5 |
N3—Ca1—N4 | 64.0 (2) | C3—C2—C1 | 117.7 (11) |
N3i—Ca1—N4i | 64.0 (2) | C3—C2—H2 | 121.2 |
N3—Ca1—N4i | 159.1 (2) | C1—C2—H2 | 121.2 |
N4—Ca1—N4i | 120.9 (3) | C2—C3—C4 | 120.6 (10) |
N3i—Ca1—N2i | 75.7 (2) | C2—C3—H3 | 119.7 |
N3—Ca1—N2i | 76.2 (2) | C4—C3—H3 | 119.7 |
N4—Ca1—N2i | 123.6 (2) | C3—C4—C5 | 117.7 (10) |
N4i—Ca1—N2i | 85.5 (2) | C3—C4—C11 | 122.6 (10) |
N3i—Ca1—N2 | 76.2 (2) | C5—C4—C11 | 119.7 (10) |
N3—Ca1—N2 | 75.7 (2) | N1—C5—C4 | 122.0 (9) |
N4—Ca1—N2 | 85.5 (2) | N1—C5—C6 | 118.8 (8) |
N4i—Ca1—N2 | 123.6 (2) | C4—C5—C6 | 119.2 (9) |
N2i—Ca1—N2 | 122.3 (3) | N2—C6—C7 | 121.7 (9) |
N3i—Ca1—N1 | 86.0 (2) | N2—C6—C5 | 119.1 (8) |
N3—Ca1—N1 | 124.3 (2) | C7—C6—C5 | 119.2 (9) |
N4—Ca1—N1 | 76.6 (2) | C8—C7—C6 | 118.3 (10) |
N4i—Ca1—N1 | 75.5 (2) | C8—C7—C12 | 121.7 (10) |
N2i—Ca1—N1 | 158.0 (2) | C6—C7—C12 | 120.0 (11) |
N2—Ca1—N1 | 63.0 (2) | C9—C8—C7 | 119.1 (10) |
N3i—Ca1—N1i | 124.3 (2) | C9—C8—H8 | 120.5 |
N3—Ca1—N1i | 86.0 (2) | C7—C8—H8 | 120.5 |
N4—Ca1—N1i | 75.5 (2) | C8—C9—C10 | 119.4 (10) |
N4i—Ca1—N1i | 76.6 (2) | C8—C9—H9 | 120.3 |
N2i—Ca1—N1i | 63.0 (2) | C10—C9—H9 | 120.3 |
N2—Ca1—N1i | 158.0 (2) | N2—C10—C9 | 123.9 (10) |
N1—Ca1—N1i | 121.3 (3) | N2—C10—H10 | 118.0 |
O4—Cl1—O4ii | 118.4 (19) | C9—C10—H10 | 118.0 |
O4—Cl1—O2 | 120.8 (9) | C12—C11—C4 | 120.8 (10) |
O4ii—Cl1—O2 | 120.8 (9) | C12—C11—H11 | 119.6 |
O4—Cl1—O3ii | 48.1 (11) | C4—C11—H11 | 119.6 |
O4ii—Cl1—O3ii | 112.3 (13) | C11—C12—C7 | 121.1 (10) |
O2—Cl1—O3ii | 106.3 (9) | C11—C12—H12 | 119.4 |
O4—Cl1—O3 | 112.3 (13) | C7—C12—H12 | 119.4 |
O4ii—Cl1—O3 | 48.1 (11) | N3—C13—C14 | 123.6 (10) |
O2—Cl1—O3 | 106.3 (9) | N3—C13—H13 | 118.2 |
O3ii—Cl1—O3 | 147.3 (18) | C14—C13—H13 | 118.2 |
O4—Cl1—O5 | 110.4 (13) | C15—C14—C13 | 118.3 (10) |
O4ii—Cl1—O5 | 54.4 (12) | C15—C14—H14 | 120.8 |
O2—Cl1—O5 | 103.2 (9) | C13—C14—H14 | 120.8 |
O3ii—Cl1—O5 | 70.5 (12) | C14—C15—C16 | 120.9 (10) |
O3—Cl1—O5 | 101.9 (13) | C14—C15—H15 | 119.5 |
O4—Cl1—O5ii | 54.4 (12) | C16—C15—H15 | 119.5 |
O4ii—Cl1—O5ii | 110.4 (13) | C15—C16—C23 | 122.6 (11) |
O2—Cl1—O5ii | 103.2 (9) | C15—C16—C17 | 117.7 (10) |
O3ii—Cl1—O5ii | 101.9 (13) | C23—C16—C17 | 119.7 (11) |
O3—Cl1—O5ii | 70.5 (12) | N3—C17—C18 | 118.8 (8) |
O5—Cl1—O5ii | 153.6 (17) | N3—C17—C16 | 121.5 (9) |
O9—Cl2—O9iii | 120.2 (17) | C18—C17—C16 | 119.6 (9) |
O9—Cl2—O6 | 119.9 (9) | N4—C18—C17 | 119.7 (8) |
O9iii—Cl2—O6 | 119.9 (9) | N4—C18—C19 | 121.1 (10) |
O9—Cl2—O7iii | 43.0 (10) | C17—C18—C19 | 119.2 (10) |
O9iii—Cl2—O7iii | 114.3 (11) | C20—C19—C24 | 122.9 (11) |
O6—Cl2—O7iii | 108.7 (8) | C20—C19—C18 | 118.5 (11) |
O9—Cl2—O7 | 114.3 (11) | C24—C19—C18 | 118.6 (11) |
O9iii—Cl2—O7 | 43.0 (10) | C21—C20—C19 | 119.5 (11) |
O6—Cl2—O7 | 108.7 (8) | C21—C20—H20 | 120.2 |
O7iii—Cl2—O7 | 142.6 (17) | C19—C20—H20 | 120.2 |
O9—Cl2—O8iii | 55.4 (11) | C20—C21—C22 | 119.2 (11) |
O9iii—Cl2—O8iii | 109.4 (12) | C20—C21—H21 | 120.4 |
O6—Cl2—O8iii | 103.8 (7) | C22—C21—H21 | 120.4 |
O7iii—Cl2—O8iii | 98.1 (11) | N4—C22—C21 | 123.7 (10) |
O7—Cl2—O8iii | 73.0 (11) | N4—C22—H22 | 118.1 |
O9—Cl2—O8 | 109.4 (12) | C21—C22—H22 | 118.1 |
O9iii—Cl2—O8 | 55.4 (11) | C24—C23—C16 | 120.5 (11) |
O6—Cl2—O8 | 103.8 (7) | C24—C23—H23 | 119.7 |
O7iii—Cl2—O8 | 73.0 (11) | C16—C23—H23 | 119.7 |
O7—Cl2—O8 | 98.1 (11) | C23—C24—C19 | 122.2 (11) |
O8iii—Cl2—O8 | 152.5 (14) | C23—C24—H24 | 118.9 |
C1—N1—C5 | 117.0 (8) | C19—C24—H24 | 118.9 |
C1—N1—Ca1 | 123.7 (6) | O1—C25—C26 | 126.6 (18) |
C5—N1—Ca1 | 118.9 (6) | O1—C25—H25 | 116.7 |
C10—N2—C6 | 117.6 (8) | C26—C25—H25 | 116.7 |
C10—N2—Ca1 | 122.7 (6) | C31—C26—C27 | 117.4 (14) |
C6—N2—Ca1 | 119.7 (6) | C31—C26—C25 | 117.2 (16) |
C13—N3—C17 | 117.7 (8) | C27—C26—C25 | 125.4 (14) |
C13—N3—Ca1 | 123.3 (6) | C28—C27—C26 | 121.6 (13) |
C17—N3—Ca1 | 119.0 (6) | C28—C27—H27 | 119.2 |
C22—N4—C18 | 117.9 (8) | C26—C27—H27 | 119.2 |
C22—N4—Ca1 | 123.9 (6) | C27—C28—C29 | 122.8 (14) |
C18—N4—Ca1 | 117.3 (6) | C27—C28—H28 | 118.6 |
C29—N5—C33 | 121.6 (11) | C29—C28—H28 | 118.6 |
C29—N5—C32 | 120.6 (12) | N5—C29—C28 | 123.8 (12) |
C33—N5—C32 | 117.8 (13) | N5—C29—C30 | 121.0 (11) |
O4ii—O3—Cl1 | 62.5 (17) | C28—C29—C30 | 115.2 (13) |
O4ii—O3—O5ii | 109 (2) | C31—C30—C29 | 122.0 (12) |
Cl1—O3—O5ii | 55.1 (11) | C31—C30—H30 | 119.0 |
O3ii—O4—O5ii | 134 (3) | C29—C30—H30 | 119.0 |
O3ii—O4—Cl1 | 69.3 (18) | C30—C31—C26 | 120.9 (13) |
O5ii—O4—Cl1 | 66.2 (15) | C30—C31—H31 | 119.5 |
O4ii—O5—Cl1 | 59.4 (14) | C26—C31—H31 | 119.5 |
O4ii—O5—O3ii | 103 (2) | N5—C32—H32A | 109.5 |
Cl1—O5—O3ii | 54.4 (11) | N5—C32—H32B | 109.5 |
O9iii—O7—Cl2 | 63.7 (19) | H32A—C32—H32B | 109.5 |
O9iii—O7—O8iii | 111 (3) | N5—C32—H32C | 109.5 |
Cl2—O7—O8iii | 54.5 (10) | H32A—C32—H32C | 109.5 |
O9iii—O8—Cl2 | 57.3 (12) | H32B—C32—H32C | 109.5 |
O9iii—O8—O7iii | 99.3 (15) | N5—C33—H33A | 109.5 |
Cl2—O8—O7iii | 52.5 (9) | N5—C33—H33B | 109.5 |
O7iii—O9—O8iii | 140 (3) | H33A—C33—H33B | 109.5 |
O7iii—O9—Cl2 | 73 (2) | N5—C33—H33C | 109.5 |
O8iii—O9—Cl2 | 67.4 (14) | H33A—C33—H33C | 109.5 |
N1—C1—C2 | 125.0 (10) | H33B—C33—H33C | 109.5 |
N3i—Ca1—N1—C1 | 105.0 (8) | O6—Cl2—O8—O7iii | −105.7 (9) |
N3—Ca1—N1—C1 | −131.6 (7) | O7—Cl2—O8—O7iii | 142.7 (17) |
N4—Ca1—N1—C1 | −86.6 (8) | O8iii—Cl2—O8—O7iii | 74.3 (9) |
N4i—Ca1—N1—C1 | 40.8 (7) | O9iii—Cl2—O9—O7iii | −94.2 (19) |
N2i—Ca1—N1—C1 | 71.7 (10) | O6—Cl2—O9—O7iii | 85.8 (19) |
N2—Ca1—N1—C1 | −178.5 (8) | O7—Cl2—O9—O7iii | −142.5 (19) |
N1i—Ca1—N1—C1 | −23.2 (7) | O8iii—Cl2—O9—O7iii | 172 (2) |
N3i—Ca1—N1—C5 | −82.6 (6) | O8—Cl2—O9—O7iii | −34 (2) |
N3—Ca1—N1—C5 | 40.8 (7) | O9iii—Cl2—O9—O8iii | 93.7 (12) |
N4—Ca1—N1—C5 | 85.8 (6) | O6—Cl2—O9—O8iii | −86.3 (12) |
N4i—Ca1—N1—C5 | −146.8 (7) | O7iii—Cl2—O9—O8iii | −172 (2) |
N2i—Ca1—N1—C5 | −115.9 (8) | O7—Cl2—O9—O8iii | 45.4 (14) |
N2—Ca1—N1—C5 | −6.1 (6) | O8—Cl2—O9—O8iii | 154.1 (13) |
N1i—Ca1—N1—C5 | 149.2 (7) | C5—N1—C1—C2 | −0.9 (15) |
N3i—Ca1—N2—C10 | −84.1 (7) | Ca1—N1—C1—C2 | 171.6 (8) |
N3—Ca1—N2—C10 | 41.8 (7) | N1—C1—C2—C3 | 1.7 (17) |
N4—Ca1—N2—C10 | 106.2 (7) | C1—C2—C3—C4 | −1.4 (16) |
N4i—Ca1—N2—C10 | −129.3 (7) | C2—C3—C4—C5 | 0.4 (15) |
N2i—Ca1—N2—C10 | −21.3 (6) | C2—C3—C4—C11 | −179.9 (10) |
N1—Ca1—N2—C10 | −176.7 (8) | C1—N1—C5—C4 | −0.2 (13) |
N1i—Ca1—N2—C10 | 76.3 (10) | Ca1—N1—C5—C4 | −173.1 (6) |
N3i—Ca1—N2—C6 | 97.0 (6) | C1—N1—C5—C6 | −179.7 (8) |
N3—Ca1—N2—C6 | −137.0 (6) | Ca1—N1—C5—C6 | 7.4 (10) |
N4—Ca1—N2—C6 | −72.7 (6) | C3—C4—C5—N1 | 0.4 (14) |
N4i—Ca1—N2—C6 | 51.9 (7) | C11—C4—C5—N1 | −179.3 (9) |
N2i—Ca1—N2—C6 | 159.9 (7) | C3—C4—C5—C6 | 179.9 (9) |
N1—Ca1—N2—C6 | 4.5 (6) | C11—C4—C5—C6 | 0.2 (13) |
N1i—Ca1—N2—C6 | −102.6 (8) | C10—N2—C6—C7 | −2.7 (12) |
N3i—Ca1—N3—C13 | −17.2 (6) | Ca1—N2—C6—C7 | 176.2 (6) |
N4—Ca1—N3—C13 | −173.8 (8) | C10—N2—C6—C5 | 178.3 (8) |
N4i—Ca1—N3—C13 | 77.0 (10) | Ca1—N2—C6—C5 | −2.8 (10) |
N2i—Ca1—N3—C13 | 47.2 (7) | N1—C5—C6—N2 | −3.1 (12) |
N2—Ca1—N3—C13 | −81.9 (7) | C4—C5—C6—N2 | 177.4 (8) |
N1—Ca1—N3—C13 | −124.0 (7) | N1—C5—C6—C7 | 177.8 (8) |
N1i—Ca1—N3—C13 | 110.4 (7) | C4—C5—C6—C7 | −1.7 (12) |
N3i—Ca1—N3—C17 | 161.9 (7) | N2—C6—C7—C8 | 2.0 (13) |
N4—Ca1—N3—C17 | 5.2 (6) | C5—C6—C7—C8 | −179.0 (8) |
N4i—Ca1—N3—C17 | −103.9 (9) | N2—C6—C7—C12 | −177.0 (8) |
N2i—Ca1—N3—C17 | −133.7 (6) | C5—C6—C7—C12 | 2.0 (13) |
N2—Ca1—N3—C17 | 97.2 (6) | C6—C7—C8—C9 | 0.1 (14) |
N1—Ca1—N3—C17 | 55.0 (7) | C12—C7—C8—C9 | 179.2 (10) |
N1i—Ca1—N3—C17 | −70.6 (6) | C7—C8—C9—C10 | −1.4 (15) |
N3i—Ca1—N4—C22 | 77.3 (10) | C6—N2—C10—C9 | 1.4 (14) |
N3—Ca1—N4—C22 | −177.5 (8) | Ca1—N2—C10—C9 | −177.5 (7) |
N4i—Ca1—N4—C22 | −20.6 (7) | C8—C9—C10—N2 | 0.7 (16) |
N2i—Ca1—N4—C22 | −127.4 (7) | C3—C4—C11—C12 | −178.6 (11) |
N2—Ca1—N4—C22 | 106.3 (7) | C5—C4—C11—C12 | 1.1 (16) |
N1—Ca1—N4—C22 | 43.0 (7) | C4—C11—C12—C7 | −0.8 (17) |
N1i—Ca1—N4—C22 | −84.8 (7) | C8—C7—C12—C11 | −179.8 (10) |
N3i—Ca1—N4—C18 | −114.1 (8) | C6—C7—C12—C11 | −0.8 (15) |
N3—Ca1—N4—C18 | −8.9 (6) | C17—N3—C13—C14 | −1.0 (14) |
N4i—Ca1—N4—C18 | 148.0 (7) | Ca1—N3—C13—C14 | 178.0 (7) |
N2i—Ca1—N4—C18 | 41.1 (7) | N3—C13—C14—C15 | 5.0 (15) |
N2—Ca1—N4—C18 | −85.1 (6) | C13—C14—C15—C16 | −3.9 (16) |
N1—Ca1—N4—C18 | −148.4 (6) | C14—C15—C16—C23 | 178.6 (10) |
N1i—Ca1—N4—C18 | 83.8 (6) | C14—C15—C16—C17 | −0.9 (15) |
O4—Cl1—O3—O4ii | −109 (3) | C13—N3—C17—C18 | 177.8 (8) |
O2—Cl1—O3—O4ii | 117.0 (16) | Ca1—N3—C17—C18 | −1.3 (10) |
O3ii—Cl1—O3—O4ii | −63.0 (16) | C13—N3—C17—C16 | −4.0 (13) |
O5—Cl1—O3—O4ii | 9 (2) | Ca1—N3—C17—C16 | 176.9 (6) |
O5ii—Cl1—O3—O4ii | −144 (2) | C15—C16—C17—N3 | 5.0 (14) |
O4—Cl1—O3—O5ii | 35.6 (13) | C23—C16—C17—N3 | −174.5 (9) |
O4ii—Cl1—O3—O5ii | 144 (2) | C15—C16—C17—C18 | −176.8 (9) |
O2—Cl1—O3—O5ii | −98.6 (10) | C23—C16—C17—C18 | 3.7 (14) |
O3ii—Cl1—O3—O5ii | 81.4 (10) | C22—N4—C18—C17 | −178.3 (8) |
O5—Cl1—O3—O5ii | 153.7 (17) | Ca1—N4—C18—C17 | 12.4 (10) |
O4ii—Cl1—O4—O3ii | 95.4 (19) | C22—N4—C18—C19 | −1.0 (13) |
O2—Cl1—O4—O3ii | −84.6 (19) | Ca1—N4—C18—C19 | −170.3 (7) |
O3—Cl1—O4—O3ii | 148.7 (19) | N3—C17—C18—N4 | −7.5 (13) |
O5—Cl1—O4—O3ii | 36 (2) | C16—C17—C18—N4 | 174.2 (8) |
O5ii—Cl1—O4—O3ii | −169 (2) | N3—C17—C18—C19 | 175.0 (8) |
O4ii—Cl1—O4—O5ii | −95.7 (16) | C16—C17—C18—C19 | −3.2 (13) |
O2—Cl1—O4—O5ii | 84.3 (16) | N4—C18—C19—C20 | 2.4 (14) |
O3ii—Cl1—O4—O5ii | 169 (2) | C17—C18—C19—C20 | 179.8 (9) |
O3—Cl1—O4—O5ii | −42.4 (17) | N4—C18—C19—C24 | −177.7 (9) |
O5—Cl1—O4—O5ii | −155.4 (17) | C17—C18—C19—C24 | −0.3 (14) |
O4—Cl1—O5—O4ii | 111 (2) | C24—C19—C20—C21 | 177.7 (11) |
O2—Cl1—O5—O4ii | −118.6 (13) | C18—C19—C20—C21 | −2.4 (17) |
O3ii—Cl1—O5—O4ii | 138.5 (18) | C19—C20—C21—C22 | 1.0 (18) |
O3—Cl1—O5—O4ii | −8.4 (18) | C18—N4—C22—C21 | −0.5 (14) |
O5ii—Cl1—O5—O4ii | 61.4 (13) | Ca1—N4—C22—C21 | 168.0 (8) |
O4—Cl1—O5—O3ii | −27.5 (14) | C20—C21—C22—N4 | 0.5 (17) |
O4ii—Cl1—O5—O3ii | −138.5 (18) | C15—C16—C23—C24 | 179.9 (11) |
O2—Cl1—O5—O3ii | 102.9 (10) | C17—C16—C23—C24 | −0.7 (16) |
O3—Cl1—O5—O3ii | −146.9 (19) | C16—C23—C24—C19 | −3.0 (18) |
O5ii—Cl1—O5—O3ii | −77.1 (10) | C20—C19—C24—C23 | −176.6 (12) |
O9—Cl2—O7—O9iii | 109 (3) | C18—C19—C24—C23 | 3.5 (17) |
O6—Cl2—O7—O9iii | −114.1 (17) | O1—C25—C26—C31 | −178.4 (13) |
O7iii—Cl2—O7—O9iii | 65.9 (17) | O1—C25—C26—C27 | 2 (2) |
O8iii—Cl2—O7—O9iii | 147 (2) | C31—C26—C27—C28 | 1.0 (19) |
O8—Cl2—O7—O9iii | −7 (2) | C25—C26—C27—C28 | −179.1 (13) |
O9—Cl2—O7—O8iii | −37.8 (11) | C26—C27—C28—C29 | −1 (2) |
O9iii—Cl2—O7—O8iii | −147 (2) | C33—N5—C29—C28 | 174.2 (11) |
O6—Cl2—O7—O8iii | 99.1 (8) | C32—N5—C29—C28 | −2.5 (18) |
O7iii—Cl2—O7—O8iii | −80.9 (8) | C33—N5—C29—C30 | −5.5 (17) |
O8—Cl2—O7—O8iii | −153.3 (14) | C32—N5—C29—C30 | 177.7 (11) |
O9—Cl2—O8—O9iii | −114 (2) | C27—C28—C29—N5 | −178.7 (12) |
O6—Cl2—O8—O9iii | 117.0 (11) | C27—C28—C29—C30 | 1.1 (18) |
O7iii—Cl2—O8—O9iii | −137.3 (14) | N5—C29—C30—C31 | 178.2 (11) |
O7—Cl2—O8—O9iii | 5.4 (16) | C28—C29—C30—C31 | −1.6 (16) |
O8iii—Cl2—O8—O9iii | −63.0 (11) | C29—C30—C31—C26 | 1.8 (18) |
O9—Cl2—O8—O7iii | 23.3 (13) | C27—C26—C31—C30 | −1.4 (17) |
O9iii—Cl2—O8—O7iii | 137.3 (14) | C25—C26—C31—C30 | 178.7 (11) |
Symmetry codes: (i) −x, −y+3/2, z; (ii) −x+1, −y+3/2, z; (iii) −x, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Ca(C12H8N2)4](ClO4)2·2C9H11NO |
Mr | 1258.17 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 298 |
a, c (Å) | 17.455 (3), 38.952 (3) |
V (Å3) | 11868 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.45 × 0.42 × 0.40 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.889, 0.900 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29937, 5234, 1808 |
Rint | 0.103 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.079, 0.388, 1.13 |
No. of reflections | 5234 |
No. of parameters | 433 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.1079P)2 + 113.9196P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.41, −0.56 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
Phenanthroline and its derivatives and their complexes with metal ions have received considerable attention over the past three decades (Summers, 1978). This may be attributed to unusual structural features in the resultant metal complexes and their biological activities. The chemical and pharmacological properties of the complexes on phenanthroline have been investigated extensively, owing to their chelating ability with metal ions and to their potentially beneficial activities, such as catalytic, antitumor, antineoplastic and antibacterial (Guo et al., 2004). As part of our onging studies of metal coordination complexes (Tai et al., 2005), the synthesis and structure of the title compound, (I), is reported.
Four N,N-bidentate ligands are attached to the calcium ion (site symmetry 2) resulting in a CaN8 unit (Table 1).
Various π-π stacking interactions of the 1,10-phenanthroline rings help to consolidate the crystal packing.