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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 π–π 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027055/hb2432sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027055/hb2432Isup2.hkl
Contains datablock I

CCDC reference: 654716

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.017 Å
  • Disorder in solvent or counterion
  • R factor = 0.079
  • wR factor = 0.388
  • Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Alert level B RFACR01_ALERT_3_B The value of the weighted R factor is > 0.35 Weighted R factor given 0.388 PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 35 Perc. PLAT084_ALERT_2_B High R2 Value .................................. 0.39 PLAT341_ALERT_3_B Low Bond Precision on C-C Bonds (x 1000) Ang ... 17
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.103 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.10 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 38.00 Perc. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.18 Ratio PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 43.00 Deg. O9 -CL2 -O7 1.555 1.555 6.454 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 43.00 Deg. O9 -CL2 -O7 6.454 1.555 1.555
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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).

Structure description 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.

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

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)2·2C9H11NODx = 1.408 Mg m3
Mr = 1258.17Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 2661 reflections
Hall symbol: -I 4adθ = 2.7–20.5°
a = 17.455 (3) ŵ = 0.27 mm1
c = 38.952 (3) ÅT = 298 K
V = 11868 (3) Å3Block, brown
Z = 80.45 × 0.42 × 0.40 mm
F(000) = 5232
Data collection top
Bruker SMART CCD
diffractometer
5234 independent reflections
Radiation source: fine-focus sealed tube1808 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.103
ω scansθmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 2020
Tmin = 0.889, Tmax = 0.900k = 2020
29937 measured reflectionsl = 4630
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.079Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.388H-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 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.56 e Å3
Crystal data top
[Ca(C12H8N2)4](ClO4)2·2C9H11NOZ = 8
Mr = 1258.17Mo Kα radiation
Tetragonal, I41/aµ = 0.27 mm1
a = 17.455 (3) ÅT = 298 K
c = 38.952 (3) Å0.45 × 0.42 × 0.40 mm
V = 11868 (3) Å3
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)] = 0.0790 restraints
wR(F2) = 0.388H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.1079P)2 + 113.9196P]
where P = (Fo2 + 2Fc2)/3
5234 reflectionsΔρmax = 0.41 e Å3
433 parametersΔρmin = 0.56 e Å3
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 > 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.

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)
N10.0545 (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
O80.0639 (12)0.3007 (11)0.0189 (4)0.091 (5)0.50
O90.0071 (17)0.1840 (12)0.0108 (5)0.089 (6)0.50
C10.0806 (6)0.8672 (6)0.1906 (3)0.060 (3)
H10.08580.81910.20060.072*
C20.1006 (6)0.9302 (7)0.2101 (3)0.068 (3)
H20.11740.92480.23260.082*
C30.0950 (6)1.0007 (7)0.1951 (3)0.071 (3)
H30.10921.04410.20740.085*
C40.0685 (6)1.0082 (6)0.1618 (3)0.055 (3)
C50.0482 (5)0.9408 (5)0.1440 (3)0.044 (2)
C60.0206 (5)0.9465 (5)0.1093 (3)0.044 (2)
C70.0164 (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*
C110.0615 (6)1.0812 (6)0.1450 (4)0.069 (3)
H110.07411.12570.15690.083*
C120.0371 (6)1.0860 (6)0.1124 (3)0.068 (3)
H120.03351.13370.10190.082*
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)
H250.36000.04760.05550.135*
C260.2777 (10)0.0262 (7)0.0920 (4)0.093 (5)
C270.2001 (9)0.0254 (7)0.1016 (5)0.104 (6)
H270.16320.04070.08580.124*
C280.1778 (8)0.0032 (8)0.1332 (4)0.092 (5)
H280.12580.00300.13830.110*
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)
H310.38280.00520.11120.097*
C320.1287 (8)0.0439 (9)0.2004 (4)0.130 (6)
H32A0.10140.07530.18430.196*
H32B0.12390.06530.22300.196*
H32C0.10760.00690.20020.196*
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, º) 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—O7iii105.7 (9)
N3—Ca1—N1—C1131.6 (7)O7—Cl2—O8—O7iii142.7 (17)
N4—Ca1—N1—C186.6 (8)O8iii—Cl2—O8—O7iii74.3 (9)
N4i—Ca1—N1—C140.8 (7)O9iii—Cl2—O9—O7iii94.2 (19)
N2i—Ca1—N1—C171.7 (10)O6—Cl2—O9—O7iii85.8 (19)
N2—Ca1—N1—C1178.5 (8)O7—Cl2—O9—O7iii142.5 (19)
N1i—Ca1—N1—C123.2 (7)O8iii—Cl2—O9—O7iii172 (2)
N3i—Ca1—N1—C582.6 (6)O8—Cl2—O9—O7iii34 (2)
N3—Ca1—N1—C540.8 (7)O9iii—Cl2—O9—O8iii93.7 (12)
N4—Ca1—N1—C585.8 (6)O6—Cl2—O9—O8iii86.3 (12)
N4i—Ca1—N1—C5146.8 (7)O7iii—Cl2—O9—O8iii172 (2)
N2i—Ca1—N1—C5115.9 (8)O7—Cl2—O9—O8iii45.4 (14)
N2—Ca1—N1—C56.1 (6)O8—Cl2—O9—O8iii154.1 (13)
N1i—Ca1—N1—C5149.2 (7)C5—N1—C1—C20.9 (15)
N3i—Ca1—N2—C1084.1 (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—C41.4 (16)
N4i—Ca1—N2—C10129.3 (7)C2—C3—C4—C50.4 (15)
N2i—Ca1—N2—C1021.3 (6)C2—C3—C4—C11179.9 (10)
N1—Ca1—N2—C10176.7 (8)C1—N1—C5—C40.2 (13)
N1i—Ca1—N2—C1076.3 (10)Ca1—N1—C5—C4173.1 (6)
N3i—Ca1—N2—C697.0 (6)C1—N1—C5—C6179.7 (8)
N3—Ca1—N2—C6137.0 (6)Ca1—N1—C5—C67.4 (10)
N4—Ca1—N2—C672.7 (6)C3—C4—C5—N10.4 (14)
N4i—Ca1—N2—C651.9 (7)C11—C4—C5—N1179.3 (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—C6102.6 (8)C10—N2—C6—C72.7 (12)
N3i—Ca1—N3—C1317.2 (6)Ca1—N2—C6—C7176.2 (6)
N4—Ca1—N3—C13173.8 (8)C10—N2—C6—C5178.3 (8)
N4i—Ca1—N3—C1377.0 (10)Ca1—N2—C6—C52.8 (10)
N2i—Ca1—N3—C1347.2 (7)N1—C5—C6—N23.1 (12)
N2—Ca1—N3—C1381.9 (7)C4—C5—C6—N2177.4 (8)
N1—Ca1—N3—C13124.0 (7)N1—C5—C6—C7177.8 (8)
N1i—Ca1—N3—C13110.4 (7)C4—C5—C6—C71.7 (12)
N3i—Ca1—N3—C17161.9 (7)N2—C6—C7—C82.0 (13)
N4—Ca1—N3—C175.2 (6)C5—C6—C7—C8179.0 (8)
N4i—Ca1—N3—C17103.9 (9)N2—C6—C7—C12177.0 (8)
N2i—Ca1—N3—C17133.7 (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—C1770.6 (6)C7—C8—C9—C101.4 (15)
N3i—Ca1—N4—C2277.3 (10)C6—N2—C10—C91.4 (14)
N3—Ca1—N4—C22177.5 (8)Ca1—N2—C10—C9177.5 (7)
N4i—Ca1—N4—C2220.6 (7)C8—C9—C10—N20.7 (16)
N2i—Ca1—N4—C22127.4 (7)C3—C4—C11—C12178.6 (11)
N2—Ca1—N4—C22106.3 (7)C5—C4—C11—C121.1 (16)
N1—Ca1—N4—C2243.0 (7)C4—C11—C12—C70.8 (17)
N1i—Ca1—N4—C2284.8 (7)C8—C7—C12—C11179.8 (10)
N3i—Ca1—N4—C18114.1 (8)C6—C7—C12—C110.8 (15)
N3—Ca1—N4—C188.9 (6)C17—N3—C13—C141.0 (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—C1885.1 (6)C13—C14—C15—C163.9 (16)
N1—Ca1—N4—C18148.4 (6)C14—C15—C16—C23178.6 (10)
N1i—Ca1—N4—C1883.8 (6)C14—C15—C16—C170.9 (15)
O4—Cl1—O3—O4ii109 (3)C13—N3—C17—C18177.8 (8)
O2—Cl1—O3—O4ii117.0 (16)Ca1—N3—C17—C181.3 (10)
O3ii—Cl1—O3—O4ii63.0 (16)C13—N3—C17—C164.0 (13)
O5—Cl1—O3—O4ii9 (2)Ca1—N3—C17—C16176.9 (6)
O5ii—Cl1—O3—O4ii144 (2)C15—C16—C17—N35.0 (14)
O4—Cl1—O3—O5ii35.6 (13)C23—C16—C17—N3174.5 (9)
O4ii—Cl1—O3—O5ii144 (2)C15—C16—C17—C18176.8 (9)
O2—Cl1—O3—O5ii98.6 (10)C23—C16—C17—C183.7 (14)
O3ii—Cl1—O3—O5ii81.4 (10)C22—N4—C18—C17178.3 (8)
O5—Cl1—O3—O5ii153.7 (17)Ca1—N4—C18—C1712.4 (10)
O4ii—Cl1—O4—O3ii95.4 (19)C22—N4—C18—C191.0 (13)
O2—Cl1—O4—O3ii84.6 (19)Ca1—N4—C18—C19170.3 (7)
O3—Cl1—O4—O3ii148.7 (19)N3—C17—C18—N47.5 (13)
O5—Cl1—O4—O3ii36 (2)C16—C17—C18—N4174.2 (8)
O5ii—Cl1—O4—O3ii169 (2)N3—C17—C18—C19175.0 (8)
O4ii—Cl1—O4—O5ii95.7 (16)C16—C17—C18—C193.2 (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—O5ii42.4 (17)N4—C18—C19—C24177.7 (9)
O5—Cl1—O4—O5ii155.4 (17)C17—C18—C19—C240.3 (14)
O4—Cl1—O5—O4ii111 (2)C24—C19—C20—C21177.7 (11)
O2—Cl1—O5—O4ii118.6 (13)C18—C19—C20—C212.4 (17)
O3ii—Cl1—O5—O4ii138.5 (18)C19—C20—C21—C221.0 (18)
O3—Cl1—O5—O4ii8.4 (18)C18—N4—C22—C210.5 (14)
O5ii—Cl1—O5—O4ii61.4 (13)Ca1—N4—C22—C21168.0 (8)
O4—Cl1—O5—O3ii27.5 (14)C20—C21—C22—N40.5 (17)
O4ii—Cl1—O5—O3ii138.5 (18)C15—C16—C23—C24179.9 (11)
O2—Cl1—O5—O3ii102.9 (10)C17—C16—C23—C240.7 (16)
O3—Cl1—O5—O3ii146.9 (19)C16—C23—C24—C193.0 (18)
O5ii—Cl1—O5—O3ii77.1 (10)C20—C19—C24—C23176.6 (12)
O9—Cl2—O7—O9iii109 (3)C18—C19—C24—C233.5 (17)
O6—Cl2—O7—O9iii114.1 (17)O1—C25—C26—C31178.4 (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—O9iii7 (2)C25—C26—C27—C28179.1 (13)
O9—Cl2—O7—O8iii37.8 (11)C26—C27—C28—C291 (2)
O9iii—Cl2—O7—O8iii147 (2)C33—N5—C29—C28174.2 (11)
O6—Cl2—O7—O8iii99.1 (8)C32—N5—C29—C282.5 (18)
O7iii—Cl2—O7—O8iii80.9 (8)C33—N5—C29—C305.5 (17)
O8—Cl2—O7—O8iii153.3 (14)C32—N5—C29—C30177.7 (11)
O9—Cl2—O8—O9iii114 (2)C27—C28—C29—N5178.7 (12)
O6—Cl2—O8—O9iii117.0 (11)C27—C28—C29—C301.1 (18)
O7iii—Cl2—O8—O9iii137.3 (14)N5—C29—C30—C31178.2 (11)
O7—Cl2—O8—O9iii5.4 (16)C28—C29—C30—C311.6 (16)
O8iii—Cl2—O8—O9iii63.0 (11)C29—C30—C31—C261.8 (18)
O9—Cl2—O8—O7iii23.3 (13)C27—C26—C31—C301.4 (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.

Experimental details

Crystal data
Chemical formula[Ca(C12H8N2)4](ClO4)2·2C9H11NO
Mr1258.17
Crystal system, space groupTetragonal, I41/a
Temperature (K)298
a, c (Å)17.455 (3), 38.952 (3)
V3)11868 (3)
Z8
Radiation typeMo Kα
µ (mm1)0.27
Crystal size (mm)0.45 × 0.42 × 0.40
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.889, 0.900
No. of measured, independent and
observed [I > 2σ(I)] reflections
29937, 5234, 1808
Rint0.103
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.079, 0.388, 1.13
No. of reflections5234
No. of parameters433
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.1079P)2 + 113.9196P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.41, 0.56

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.

Selected bond lengths (Å) top
Ca1—N32.593 (7)Ca1—N22.631 (7)
Ca1—N42.604 (7)Ca1—N12.641 (7)
 

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