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Acta Cryst. (2007). E63, m1827    [ doi:10.1107/S1600536807027055 ]

Tetrakis(1,10-phenanthroline)calcium(II) bis(perchlorate) 4-(dimethylamino)benzaldehyde disolvate

X.-S. Tai, J. Yin and M.-Y. Hao

Abstract top

In the title compound, [Ca(C12H8N2)4](ClO4)2·2C9H11NO, the Ca2+ cation (site symmetry 2) is coordinated by four bidentate 1,10-phenanthroline (phen) molecules, resulting in a square-antiprismatic CaN8 polyhedron for the metal ion. Two disordered perchlorate ions (Cl site symmetry 2 in both cases) and a 4-(dimethylamino)benzaldehyde molecule complete the structure. A large number of [pi]-[pi] stacking interactions involving the phen aromatic rings [centroid separations are in the range 3.667 (6)-3.907 (7) Å] help to stabilize the structure. The O atoms of the perchlorate anions are disordered equally over two sites each.

Comment top

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.

Related literature top

For background, see: Summers (1978); Guo et al. (2004); Tai et al. (2005).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 30% displacement ellipsoids. H atoms omitted for clarity. The unlabelled atoms in the cation, the Cl1 and Cl2 perchlorate ions are generated by the symmetry operations (−x, 3/2 − y, z), (1 − x, 3/2 − y, z) and (−x, 1/2 − y, z), respectively.
Tetrakis(1,10-phenanthroline)calcium(II) bis(perchlorate) 4-(dimethylamino)benzaldehyde disolvate top
Crystal data top
[Ca(C12H8N2)4](ClO4)2·2C9H11NOZ = 8
Mr = 1258.17F000 = 5232
Tetragonal, I41/aDx = 1.408 Mg m−3
Hall symbol: -I 4adMo Kα radiation
λ = 0.71073 Å
a = 17.455 (3) ÅCell parameters from 2661 reflections
b = 17.455 (3) Åθ = 2.7–20.5º
c = 38.952 (3) ŵ = 0.27 mm−1
α = 90ºT = 298 (2) K
β = 90ºBlock, brown
γ = 90º0.45 × 0.42 × 0.40 mm
V = 11868 (3) Å3
Data collection top
Bruker SMART CCD
diffractometer		5234 independent reflections
Radiation source: fine-focus sealed tube1808 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.103
T = 298(2) Kθmax = 25.0º
ω scansθmin = 1.3º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −20→20
Tmin = 0.889, Tmax = 0.900k = −20→20
29937 measured reflectionsl = −46→30
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.1079P)2 + 113.9196P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.079(Δ/σ)max = 0.001
wR(F2) = 0.388Δρmax = 0.41 e Å−3
S = 1.13Δρmin = −0.56 e Å−3
5234 reflectionsExtinction correction: none
433 parameters
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
Crystal data top
[Ca(C12H8N2)4](ClO4)2·2C9H11NOγ = 90º
Mr = 1258.17V = 11868 (3) Å3
Tetragonal, I41/aZ = 8
a = 17.455 (3) ÅMo Kα
b = 17.455 (3) ŵ = 0.27 mm−1
c = 38.952 (3) ÅT = 298 (2) K
α = 90º0.45 × 0.42 × 0.40 mm
β = 90º
Data collection top
Bruker SMART CCD
diffractometer		5234 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1808 reflections with I > 2σ(I)
Tmin = 0.889, Tmax = 0.900Rint = 0.103
29937 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.079  w = 1/[σ2(Fo2) + (0.1079P)2 + 113.9196P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.388Δρmax = 0.41 e Å−3
S = 1.13Δρmin = −0.56 e Å−3
5234 reflectionsAbsolute structure: ?
433 parametersFlack parameter: ?
H-atom parameters constrainedRogers parameter: ?
Special details top

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ca10.00000.75000.12539 (6)0.0351 (6)
Cl10.50000.75000.02830 (9)0.0715 (11)
Cl20.00000.25000.02789 (8)0.0603 (10)
N1−0.0545 (4)0.8700 (4)0.15864 (19)0.0474 (19)
N20.0017 (4)0.8820 (4)0.09279 (19)0.0452 (19)
N30.1283 (4)0.7490 (4)0.09188 (19)0.0452 (19)
N40.1188 (4)0.8022 (4)0.15835 (19)0.0462 (19)
N50.2086 (6)0.0408 (6)0.1909 (3)0.086 (3)
O10.2703 (8)−0.0671 (6)0.0342 (3)0.153 (5)
O20.50000.75000.0637 (3)0.114 (4)
O30.5413 (15)0.8168 (15)0.0180 (6)0.107 (7)0.50
O40.4339 (13)0.741 (2)0.0105 (5)0.103 (7)0.50
O50.5532 (14)0.6898 (15)0.0198 (5)0.110 (7)0.50
O60.00000.25000.0636 (3)0.094 (4)
O70.0611 (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)
H1−0.08580.81910.20060.072*
C2−0.1006 (6)0.9302 (7)0.2101 (3)0.068 (3)
H2−0.11740.92480.23260.082*
C3−0.0950 (6)1.0007 (7)0.1951 (3)0.071 (3)
H3−0.10921.04410.20740.085*
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)
C80.0096 (6)1.0232 (7)0.0594 (3)0.067 (3)
H80.01321.07020.04830.080*
C90.0293 (6)0.9581 (7)0.0431 (3)0.065 (3)
H90.04550.95950.02030.078*
C100.0251 (5)0.8889 (6)0.0604 (2)0.052 (2)
H100.03940.84470.04880.062*
C11−0.0615 (6)1.0812 (6)0.1450 (4)0.069 (3)
H11−0.07411.12570.15690.083*
C12−0.0371 (6)1.0860 (6)0.1124 (3)0.068 (3)
H12−0.03351.13370.10190.082*
C130.1337 (6)0.7300 (6)0.0587 (2)0.055 (3)
H130.08930.71500.04730.066*
C140.2021 (7)0.7315 (6)0.0403 (3)0.065 (3)
H140.20270.72180.01680.078*
C150.2674 (7)0.7476 (6)0.0573 (3)0.067 (3)
H150.31390.74580.04580.080*
C160.2660 (6)0.7666 (6)0.0918 (3)0.060 (3)
C170.1935 (5)0.7696 (5)0.1083 (3)0.044 (2)
C180.1890 (5)0.7927 (5)0.1433 (3)0.048 (2)
C190.2581 (6)0.8087 (6)0.1616 (3)0.062 (3)
C200.2527 (7)0.8315 (7)0.1959 (3)0.080 (4)
H200.29680.84040.20870.096*
C210.1828 (7)0.8407 (6)0.2104 (3)0.072 (3)
H210.17830.85660.23310.087*
C220.1170 (6)0.8257 (6)0.1907 (3)0.060 (3)
H220.06940.83260.20100.072*
C230.3336 (6)0.7822 (6)0.1108 (4)0.070 (3)
H230.38110.77970.10000.084*
C240.3295 (6)0.8005 (7)0.1442 (4)0.076 (3)
H240.37460.80810.15640.091*
C250.3071 (10)−0.0484 (7)0.0583 (4)0.112 (6)
H250.3600−0.04760.05550.135*
C260.2777 (10)−0.0262 (7)0.0920 (4)0.093 (5)
C270.2001 (9)−0.0254 (7)0.1016 (5)0.104 (6)
H270.1632−0.04070.08580.124*
C280.1778 (8)−0.0032 (8)0.1332 (4)0.092 (5)
H280.1258−0.00300.13830.110*
C290.2297 (7)0.0196 (6)0.1587 (4)0.069 (3)
C300.3079 (7)0.0191 (6)0.1488 (3)0.073 (3)
H300.34480.03490.16450.087*
C310.3309 (7)−0.0042 (7)0.1166 (3)0.081 (4)
H310.3828−0.00520.11120.097*
C320.1287 (8)0.0439 (9)0.2004 (4)0.130 (6)
H32A0.10140.07530.18430.196*
H32B0.12390.06530.22300.196*
H32C0.1076−0.00690.20020.196*
C330.2644 (8)0.0570 (8)0.2170 (4)0.103 (4)
H33A0.29850.01410.21930.154*
H33B0.23880.06590.23840.154*
H33C0.29310.10170.21070.154*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ca10.0386 (13)0.0338 (13)0.0330 (12)0.0015 (10)0.0000.000
Cl10.061 (3)0.107 (4)0.046 (2)−0.007 (3)0.0000.000
Cl20.083 (3)0.060 (3)0.0385 (19)−0.006 (3)0.0000.000
N10.051 (5)0.048 (5)0.043 (5)0.004 (4)−0.002 (4)−0.002 (4)
N20.049 (5)0.039 (5)0.048 (5)0.000 (4)−0.007 (4)0.007 (4)
N30.045 (5)0.041 (4)0.050 (5)−0.001 (3)0.005 (4)0.002 (4)
N40.047 (5)0.044 (5)0.047 (5)0.000 (4)−0.005 (4)0.001 (4)
N50.077 (8)0.077 (7)0.103 (9)0.000 (6)0.011 (7)0.009 (6)
O10.234 (14)0.111 (9)0.114 (9)0.002 (9)−0.064 (9)−0.002 (7)
O20.120 (11)0.152 (13)0.069 (8)−0.018 (9)0.0000.000
O30.106 (19)0.128 (19)0.088 (15)−0.017 (16)0.004 (12)0.004 (15)
O40.092 (16)0.13 (2)0.083 (15)−0.012 (16)−0.017 (12)−0.007 (16)
O50.106 (18)0.131 (19)0.094 (15)0.004 (16)−0.002 (12)−0.012 (15)
O60.126 (11)0.099 (9)0.058 (7)0.005 (8)0.0000.000
O70.100 (16)0.100 (17)0.074 (13)−0.009 (14)0.004 (13)0.005 (11)
O80.101 (15)0.101 (15)0.070 (12)0.007 (12)−0.007 (11)−0.001 (10)
O90.11 (2)0.086 (15)0.068 (13)0.001 (14)0.003 (14)−0.010 (10)
C10.070 (7)0.054 (7)0.055 (7)0.001 (5)0.006 (6)−0.003 (5)
C20.075 (8)0.078 (8)0.051 (7)0.011 (6)−0.002 (6)−0.014 (6)
C30.073 (8)0.064 (8)0.075 (8)0.019 (6)−0.015 (6)−0.028 (6)
C40.052 (6)0.052 (6)0.060 (7)0.006 (5)−0.008 (5)−0.006 (5)
C50.040 (5)0.040 (6)0.053 (6)0.006 (4)−0.015 (5)−0.006 (5)
C60.040 (5)0.042 (6)0.049 (6)−0.005 (4)−0.013 (4)0.008 (5)
C70.042 (6)0.044 (6)0.077 (8)−0.003 (4)−0.020 (5)0.010 (5)
C80.063 (7)0.061 (7)0.076 (8)−0.006 (6)−0.013 (6)0.032 (6)
C90.061 (7)0.074 (8)0.058 (7)0.004 (6)−0.002 (5)0.028 (6)
C100.055 (6)0.053 (6)0.048 (6)0.004 (5)−0.001 (5)0.007 (5)
C110.068 (8)0.035 (6)0.105 (10)0.007 (5)−0.013 (7)−0.013 (6)
C120.070 (8)0.040 (7)0.095 (9)−0.003 (5)−0.010 (7)0.008 (6)
C130.059 (7)0.064 (7)0.042 (6)0.007 (5)0.002 (5)0.001 (5)
C140.079 (8)0.060 (7)0.057 (7)0.008 (6)0.024 (6)0.002 (5)
C150.060 (7)0.058 (7)0.082 (9)0.000 (5)0.028 (7)0.005 (6)
C160.049 (7)0.050 (6)0.079 (8)0.003 (5)0.009 (6)0.012 (6)
C170.038 (6)0.039 (5)0.057 (6)0.001 (4)0.006 (5)0.005 (5)
C180.041 (6)0.039 (6)0.063 (7)−0.002 (4)−0.007 (5)0.002 (5)
C190.054 (7)0.052 (6)0.080 (8)−0.004 (5)−0.014 (6)−0.001 (6)
C200.075 (9)0.081 (9)0.083 (9)−0.009 (7)−0.029 (7)−0.009 (7)
C210.085 (9)0.075 (8)0.057 (7)−0.010 (7)−0.024 (7)−0.012 (6)
C220.065 (7)0.058 (7)0.056 (7)0.000 (5)−0.010 (5)−0.009 (5)
C230.040 (7)0.068 (8)0.102 (10)0.001 (5)0.007 (6)0.001 (7)
C240.040 (7)0.081 (9)0.106 (10)−0.006 (6)−0.017 (7)0.009 (8)
C250.171 (16)0.071 (9)0.094 (11)−0.008 (9)−0.063 (11)0.004 (8)
C260.147 (15)0.053 (8)0.078 (10)−0.014 (8)−0.055 (10)0.008 (7)
C270.086 (11)0.064 (9)0.161 (17)−0.023 (8)−0.074 (12)0.022 (10)
C280.072 (9)0.078 (9)0.125 (13)−0.020 (7)−0.039 (9)0.026 (9)
C290.059 (8)0.046 (6)0.103 (10)−0.006 (5)−0.019 (7)0.018 (6)
C300.063 (8)0.060 (7)0.096 (10)−0.007 (6)−0.019 (7)−0.002 (7)
C310.073 (8)0.067 (8)0.103 (11)−0.004 (6)−0.015 (7)0.002 (7)
C320.094 (12)0.124 (13)0.174 (17)0.009 (10)0.039 (11)0.033 (12)
C330.115 (12)0.100 (11)0.094 (10)−0.016 (9)−0.009 (9)−0.002 (9)
Geometric parameters (Å, °) top
Ca1—N3i2.593 (7)C4—C51.410 (12)
Ca1—N32.593 (7)C4—C111.437 (14)
Ca1—N42.604 (7)C5—C61.438 (13)
Ca1—N4i2.604 (7)C6—C71.409 (12)
Ca1—N2i2.631 (7)C7—C81.407 (14)
Ca1—N22.631 (7)C7—C121.426 (14)
Ca1—N12.641 (7)C8—C91.348 (14)
Ca1—N1i2.641 (7)C8—H80.9300
Cl1—O41.36 (2)C9—C101.385 (13)
Cl1—O4ii1.36 (2)C9—H90.9300
Cl1—O21.377 (13)C10—H100.9300
Cl1—O3ii1.43 (2)C11—C121.341 (15)
Cl1—O31.43 (2)C11—H110.9300
Cl1—O51.44 (2)C12—H120.9300
Cl1—O5ii1.44 (2)C13—C141.393 (13)
Cl2—O91.34 (2)C13—H130.9300
Cl2—O9iii1.34 (2)C14—C151.349 (15)
Cl2—O61.389 (11)C14—H140.9300
Cl2—O7iii1.43 (2)C15—C161.382 (14)
Cl2—O71.43 (2)C15—H150.9300
Cl2—O8iii1.466 (19)C16—C231.418 (15)
Cl2—O81.466 (19)C16—C171.422 (13)
N1—C11.325 (11)C17—C181.421 (13)
N1—C51.366 (11)C18—C191.432 (13)
N2—C101.331 (11)C19—C201.396 (15)
N2—C61.353 (11)C19—C241.425 (15)
N3—C131.338 (11)C20—C211.354 (15)
N3—C171.354 (11)C20—H200.9300
N4—C221.326 (11)C21—C221.405 (14)
N4—C181.368 (11)C21—H210.9300
N5—C291.356 (16)C22—H220.9300
N5—C331.436 (15)C23—C241.343 (16)
N5—C321.445 (15)C23—H230.9300
O1—C251.183 (15)C24—H240.9300
O3—O4ii1.14 (3)C25—C261.46 (2)
O3—O5ii1.66 (3)C25—H250.9300
O4—O3ii1.14 (3)C26—C311.386 (16)
O4—O5ii1.28 (3)C26—C271.41 (2)
O5—O4ii1.28 (3)C27—C281.35 (2)
O5—O3ii1.66 (3)C27—H270.9300
O7—O9iii1.02 (2)C28—C291.403 (16)
O7—O8iii1.72 (3)C28—H280.9300
O8—O9iii1.31 (3)C29—C301.419 (15)
O8—O7iii1.72 (3)C30—C311.380 (16)
O9—O7iii1.02 (2)C30—H300.9300
O9—O8iii1.31 (3)C31—H310.9300
C1—C21.382 (13)C32—H32A0.9600
C1—H10.9300C32—H32B0.9600
C2—C31.365 (15)C32—H32C0.9600
C2—H20.9300C33—H33A0.9600
C3—C41.385 (14)C33—H33B0.9600
C3—H30.9300C33—H33C0.9600
N3i—Ca1—N3119.5 (3)N1—C1—H1117.5
N3i—Ca1—N4159.1 (2)C2—C1—H1117.5
N3—Ca1—N464.0 (2)C3—C2—C1117.7 (11)
N3i—Ca1—N4i64.0 (2)C3—C2—H2121.2
N3—Ca1—N4i159.1 (2)C1—C2—H2121.2
N4—Ca1—N4i120.9 (3)C2—C3—C4120.6 (10)
N3i—Ca1—N2i75.7 (2)C2—C3—H3119.7
N3—Ca1—N2i76.2 (2)C4—C3—H3119.7
N4—Ca1—N2i123.6 (2)C3—C4—C5117.7 (10)
N4i—Ca1—N2i85.5 (2)C3—C4—C11122.6 (10)
N3i—Ca1—N276.2 (2)C5—C4—C11119.7 (10)
N3—Ca1—N275.7 (2)N1—C5—C4122.0 (9)
N4—Ca1—N285.5 (2)N1—C5—C6118.8 (8)
N4i—Ca1—N2123.6 (2)C4—C5—C6119.2 (9)
N2i—Ca1—N2122.3 (3)N2—C6—C7121.7 (9)
N3i—Ca1—N186.0 (2)N2—C6—C5119.1 (8)
N3—Ca1—N1124.3 (2)C7—C6—C5119.2 (9)
N4—Ca1—N176.6 (2)C8—C7—C6118.3 (10)
N4i—Ca1—N175.5 (2)C8—C7—C12121.7 (10)
N2i—Ca1—N1158.0 (2)C6—C7—C12120.0 (11)
N2—Ca1—N163.0 (2)C9—C8—C7119.1 (10)
N3i—Ca1—N1i124.3 (2)C9—C8—H8120.5
N3—Ca1—N1i86.0 (2)C7—C8—H8120.5
N4—Ca1—N1i75.5 (2)C8—C9—C10119.4 (10)
N4i—Ca1—N1i76.6 (2)C8—C9—H9120.3
N2i—Ca1—N1i63.0 (2)C10—C9—H9120.3
N2—Ca1—N1i158.0 (2)N2—C10—C9123.9 (10)
N1—Ca1—N1i121.3 (3)N2—C10—H10118.0
O4—Cl1—O4ii118.4 (19)C9—C10—H10118.0
O4—Cl1—O2120.8 (9)C12—C11—C4120.8 (10)
O4ii—Cl1—O2120.8 (9)C12—C11—H11119.6
O4—Cl1—O3ii48.1 (11)C4—C11—H11119.6
O4ii—Cl1—O3ii112.3 (13)C11—C12—C7121.1 (10)
O2—Cl1—O3ii106.3 (9)C11—C12—H12119.4
O4—Cl1—O3112.3 (13)C7—C12—H12119.4
O4ii—Cl1—O348.1 (11)N3—C13—C14123.6 (10)
O2—Cl1—O3106.3 (9)N3—C13—H13118.2
O3ii—Cl1—O3147.3 (18)C14—C13—H13118.2
O4—Cl1—O5110.4 (13)C15—C14—C13118.3 (10)
O4ii—Cl1—O554.4 (12)C15—C14—H14120.8
O2—Cl1—O5103.2 (9)C13—C14—H14120.8
O3ii—Cl1—O570.5 (12)C14—C15—C16120.9 (10)
O3—Cl1—O5101.9 (13)C14—C15—H15119.5
O4—Cl1—O5ii54.4 (12)C16—C15—H15119.5
O4ii—Cl1—O5ii110.4 (13)C15—C16—C23122.6 (11)
O2—Cl1—O5ii103.2 (9)C15—C16—C17117.7 (10)
O3ii—Cl1—O5ii101.9 (13)C23—C16—C17119.7 (11)
O3—Cl1—O5ii70.5 (12)N3—C17—C18118.8 (8)
O5—Cl1—O5ii153.6 (17)N3—C17—C16121.5 (9)
O9—Cl2—O9iii120.2 (17)C18—C17—C16119.6 (9)
O9—Cl2—O6119.9 (9)N4—C18—C17119.7 (8)
O9iii—Cl2—O6119.9 (9)N4—C18—C19121.1 (10)
O9—Cl2—O7iii43.0 (10)C17—C18—C19119.2 (10)
O9iii—Cl2—O7iii114.3 (11)C20—C19—C24122.9 (11)
O6—Cl2—O7iii108.7 (8)C20—C19—C18118.5 (11)
O9—Cl2—O7114.3 (11)C24—C19—C18118.6 (11)
O9iii—Cl2—O743.0 (10)C21—C20—C19119.5 (11)
O6—Cl2—O7108.7 (8)C21—C20—H20120.2
O7iii—Cl2—O7142.6 (17)C19—C20—H20120.2
O9—Cl2—O8iii55.4 (11)C20—C21—C22119.2 (11)
O9iii—Cl2—O8iii109.4 (12)C20—C21—H21120.4
O6—Cl2—O8iii103.8 (7)C22—C21—H21120.4
O7iii—Cl2—O8iii98.1 (11)N4—C22—C21123.7 (10)
O7—Cl2—O8iii73.0 (11)N4—C22—H22118.1
O9—Cl2—O8109.4 (12)C21—C22—H22118.1
O9iii—Cl2—O855.4 (11)C24—C23—C16120.5 (11)
O6—Cl2—O8103.8 (7)C24—C23—H23119.7
O7iii—Cl2—O873.0 (11)C16—C23—H23119.7
O7—Cl2—O898.1 (11)C23—C24—C19122.2 (11)
O8iii—Cl2—O8152.5 (14)C23—C24—H24118.9
C1—N1—C5117.0 (8)C19—C24—H24118.9
C1—N1—Ca1123.7 (6)O1—C25—C26126.6 (18)
C5—N1—Ca1118.9 (6)O1—C25—H25116.7
C10—N2—C6117.6 (8)C26—C25—H25116.7
C10—N2—Ca1122.7 (6)C31—C26—C27117.4 (14)
C6—N2—Ca1119.7 (6)C31—C26—C25117.2 (16)
C13—N3—C17117.7 (8)C27—C26—C25125.4 (14)
C13—N3—Ca1123.3 (6)C28—C27—C26121.6 (13)
C17—N3—Ca1119.0 (6)C28—C27—H27119.2
C22—N4—C18117.9 (8)C26—C27—H27119.2
C22—N4—Ca1123.9 (6)C27—C28—C29122.8 (14)
C18—N4—Ca1117.3 (6)C27—C28—H28118.6
C29—N5—C33121.6 (11)C29—C28—H28118.6
C29—N5—C32120.6 (12)N5—C29—C28123.8 (12)
C33—N5—C32117.8 (13)N5—C29—C30121.0 (11)
O4ii—O3—Cl162.5 (17)C28—C29—C30115.2 (13)
O4ii—O3—O5ii109 (2)C31—C30—C29122.0 (12)
Cl1—O3—O5ii55.1 (11)C31—C30—H30119.0
O3ii—O4—O5ii134 (3)C29—C30—H30119.0
O3ii—O4—Cl169.3 (18)C30—C31—C26120.9 (13)
O5ii—O4—Cl166.2 (15)C30—C31—H31119.5
O4ii—O5—Cl159.4 (14)C26—C31—H31119.5
O4ii—O5—O3ii103 (2)N5—C32—H32A109.5
Cl1—O5—O3ii54.4 (11)N5—C32—H32B109.5
O9iii—O7—Cl263.7 (19)H32A—C32—H32B109.5
O9iii—O7—O8iii111 (3)N5—C32—H32C109.5
Cl2—O7—O8iii54.5 (10)H32A—C32—H32C109.5
O9iii—O8—Cl257.3 (12)H32B—C32—H32C109.5
O9iii—O8—O7iii99.3 (15)N5—C33—H33A109.5
Cl2—O8—O7iii52.5 (9)N5—C33—H33B109.5
O7iii—O9—O8iii140 (3)H33A—C33—H33B109.5
O7iii—O9—Cl273 (2)N5—C33—H33C109.5
O8iii—O9—Cl267.4 (14)H33A—C33—H33C109.5
N1—C1—C2125.0 (10)H33B—C33—H33C109.5
N3i—Ca1—N1—C1105.0 (8)O6—Cl2—O8—O7iii−105.7 (9)
N3—Ca1—N1—C1−131.6 (7)O7—Cl2—O8—O7iii142.7 (17)
N4—Ca1—N1—C1−86.6 (8)O8iii—Cl2—O8—O7iii74.3 (9)
N4i—Ca1—N1—C140.8 (7)O9iii—Cl2—O9—O7iii−94.2 (19)
N2i—Ca1—N1—C171.7 (10)O6—Cl2—O9—O7iii85.8 (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—O7iii172 (2)
N3i—Ca1—N1—C5−82.6 (6)O8—Cl2—O9—O7iii−34 (2)
N3—Ca1—N1—C540.8 (7)O9iii—Cl2—O9—O8iii93.7 (12)
N4—Ca1—N1—C585.8 (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—O8iii45.4 (14)
N2—Ca1—N1—C5−6.1 (6)O8—Cl2—O9—O8iii154.1 (13)
N1i—Ca1—N1—C5149.2 (7)C5—N1—C1—C2−0.9 (15)
N3i—Ca1—N2—C10−84.1 (7)Ca1—N1—C1—C2171.6 (8)
N3—Ca1—N2—C1041.8 (7)N1—C1—C2—C31.7 (17)
N4—Ca1—N2—C10106.2 (7)C1—C2—C3—C4−1.4 (16)
N4i—Ca1—N2—C10−129.3 (7)C2—C3—C4—C50.4 (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—C1076.3 (10)Ca1—N1—C5—C4−173.1 (6)
N3i—Ca1—N2—C697.0 (6)C1—N1—C5—C6−179.7 (8)
N3—Ca1—N2—C6−137.0 (6)Ca1—N1—C5—C67.4 (10)
N4—Ca1—N2—C6−72.7 (6)C3—C4—C5—N10.4 (14)
N4i—Ca1—N2—C651.9 (7)C11—C4—C5—N1−179.3 (9)
N2i—Ca1—N2—C6159.9 (7)C3—C4—C5—C6179.9 (9)
N1—Ca1—N2—C64.5 (6)C11—C4—C5—C60.2 (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—C7176.2 (6)
N4—Ca1—N3—C13−173.8 (8)C10—N2—C6—C5178.3 (8)
N4i—Ca1—N3—C1377.0 (10)Ca1—N2—C6—C5−2.8 (10)
N2i—Ca1—N3—C1347.2 (7)N1—C5—C6—N2−3.1 (12)
N2—Ca1—N3—C13−81.9 (7)C4—C5—C6—N2177.4 (8)
N1—Ca1—N3—C13−124.0 (7)N1—C5—C6—C7177.8 (8)
N1i—Ca1—N3—C13110.4 (7)C4—C5—C6—C7−1.7 (12)
N3i—Ca1—N3—C17161.9 (7)N2—C6—C7—C82.0 (13)
N4—Ca1—N3—C175.2 (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—C122.0 (13)
N2—Ca1—N3—C1797.2 (6)C6—C7—C8—C90.1 (14)
N1—Ca1—N3—C1755.0 (7)C12—C7—C8—C9179.2 (10)
N1i—Ca1—N3—C17−70.6 (6)C7—C8—C9—C10−1.4 (15)
N3i—Ca1—N4—C2277.3 (10)C6—N2—C10—C91.4 (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—N20.7 (16)
N2i—Ca1—N4—C22−127.4 (7)C3—C4—C11—C12−178.6 (11)
N2—Ca1—N4—C22106.3 (7)C5—C4—C11—C121.1 (16)
N1—Ca1—N4—C2243.0 (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—C18148.0 (7)Ca1—N3—C13—C14178.0 (7)
N2i—Ca1—N4—C1841.1 (7)N3—C13—C14—C155.0 (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—C23178.6 (10)
N1i—Ca1—N4—C1883.8 (6)C14—C15—C16—C17−0.9 (15)
O4—Cl1—O3—O4ii−109 (3)C13—N3—C17—C18177.8 (8)
O2—Cl1—O3—O4ii117.0 (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—O4ii9(2)Ca1—N3—C17—C16176.9 (6)
O5ii—Cl1—O3—O4ii−144 (2)C15—C16—C17—N35.0 (14)
O4—Cl1—O3—O5ii35.6 (13)C23—C16—C17—N3−174.5 (9)
O4ii—Cl1—O3—O5ii144 (2)C15—C16—C17—C18−176.8 (9)
O2—Cl1—O3—O5ii−98.6 (10)C23—C16—C17—C183.7 (14)
O3ii—Cl1—O3—O5ii81.4 (10)C22—N4—C18—C17−178.3 (8)
O5—Cl1—O3—O5ii153.7 (17)Ca1—N4—C18—C1712.4 (10)
O4ii—Cl1—O4—O3ii95.4 (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—O3ii148.7 (19)N3—C17—C18—N4−7.5 (13)
O5—Cl1—O4—O3ii36 (2)C16—C17—C18—N4174.2 (8)
O5ii—Cl1—O4—O3ii−169 (2)N3—C17—C18—C19175.0 (8)
O4ii—Cl1—O4—O5ii−95.7 (16)C16—C17—C18—C19−3.2 (13)
O2—Cl1—O4—O5ii84.3 (16)N4—C18—C19—C202.4 (14)
O3ii—Cl1—O4—O5ii169 (2)C17—C18—C19—C20179.8 (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—O4ii111 (2)C24—C19—C20—C21177.7 (11)
O2—Cl1—O5—O4ii−118.6 (13)C18—C19—C20—C21−2.4 (17)
O3ii—Cl1—O5—O4ii138.5 (18)C19—C20—C21—C221.0 (18)
O3—Cl1—O5—O4ii−8.4 (18)C18—N4—C22—C21−0.5 (14)
O5ii—Cl1—O5—O4ii61.4 (13)Ca1—N4—C22—C21168.0 (8)
O4—Cl1—O5—O3ii−27.5 (14)C20—C21—C22—N40.5 (17)
O4ii—Cl1—O5—O3ii−138.5 (18)C15—C16—C23—C24179.9 (11)
O2—Cl1—O5—O3ii102.9 (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—O9iii109 (3)C18—C19—C24—C233.5 (17)
O6—Cl2—O7—O9iii−114.1 (17)O1—C25—C26—C31−178.4 (13)
O7iii—Cl2—O7—O9iii65.9 (17)O1—C25—C26—C272(2)
O8iii—Cl2—O7—O9iii147 (2)C31—C26—C27—C281.0 (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—C28174.2 (11)
O6—Cl2—O7—O8iii99.1 (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—C30177.7 (11)
O9—Cl2—O8—O9iii−114 (2)C27—C28—C29—N5−178.7 (12)
O6—Cl2—O8—O9iii117.0 (11)C27—C28—C29—C301.1 (18)
O7iii—Cl2—O8—O9iii−137.3 (14)N5—C29—C30—C31178.2 (11)
O7—Cl2—O8—O9iii5.4 (16)C28—C29—C30—C31−1.6 (16)
O8iii—Cl2—O8—O9iii−63.0 (11)C29—C30—C31—C261.8 (18)
O9—Cl2—O8—O7iii23.3 (13)C27—C26—C31—C30−1.4 (17)
O9iii—Cl2—O8—O7iii137.3 (14)C25—C26—C31—C30178.7 (11)
Symmetry codes: (i) −x, −y+3/2, z; (ii) −x+1, −y+3/2, z; (iii) −x, −y+1/2, z.
Selected geometric parameters (Å) top
Ca1—N32.593 (7)Ca1—N22.631 (7)
Ca1—N42.604 (7)Ca1—N12.641 (7)
Acknowledgements top

The authors thank the National Natural Science Foundation of China (20671073), NingXia Natural Gas Transfering Key Laboratory (2004007), the Science and Technology Foundation of Weifang, and Weifang University for research grants.

references
References top

Bruker (2000). SMART, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Guo, D. F., He, J. & Zeng, Z. Z. (2004). J. Chin. Rare Earth Soc. 22, 55–60.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Summers, L. A. (1978). Advances in Hetrocyclic Chemistry, Vol. 22, pp. 1–69. New York: Academic Press.

Tai et al. (2005). Please provide full reference.