supplementary materials


ng5303 scheme

Acta Cryst. (2012). E68, m1557-m1558    [ doi:10.1107/S1600536812048052 ]

Di-[mu]-azido-bis([mu]-1,4,7,10,13,16-hexaoxacyclooctadecane)bis(5,10,15,20-tetraphenylporphyrinato)dicadmiumdisodium

H. Toumi, N. Amiri, M. S. Belkhiria, J.-C. Daran and H. Nasri

Abstract top

The asymmetric unit of the title compound, [Cd2Na2(N3)2(C44H28N4)2(C12H24O6)2], consists of one half of the dimeric complex; the tetranuclear molecule lies about an inversion centre. The CdII atom is coordinated by the four pyrrole N atoms of the 5,10,15,20-tetraphenylporphyrinate ligand and one N atom of the axial azide ligand in a square-pyramidal geometry. The azide group is also linked to the NaI atom, which is surrounded by one 18-crown-6 molecule and additionally bonded to a second 18-crown-6 molecule trans to the azide group. The porphyrin core exhibits a major doming distortion (~40%) and the crystal structure is stabilized by weak C-H...[pi] interactions. The molecular structure features weak intramolecular hydrogen bonds: two O-H...O interactions within the 18-crown-6 molecule and one C-H(18-crown-6)...N(azido) contact.

Comment top

As part of a systematic investigation of metalloporphyrins used as biomimetic models for hemoproteines and in several other domains (e.g. catalysis, medicine, electronic) several metalloporphyrin complexes has been characterized by our group (Mansour et al., 2010).

We report herein on the molecular structure of the title compound. The Cd atom is five-coordinated bound to the four porphyrin N atoms and to the nitrogen N5 atom of the azido ligand (Fig. 1). The Cd__N(azido) bond length [2.238 (2) Å] is in the range [2.250 (4) - 2.417 (6) Å] found for bridging µ2 (Cd-azido-M) moiety in non-porphyrin complexes where M is a metal atom (i.e., Liu et al. 2009).

The most interesting features of the structure of (I) are: (i) each [Cd(TPP)(N3)]- complex ion is strongly linked to the sodium atom of the counterion [Na(18-crown-6)]+ through the nitrogen N7 of the azido ligand where the Na__N(azido) distance is 2.492 (2) Å, (ii) the sodium atoms of two symmetry related [Na(18—C-6)]+ counterions are linked by two strong Na—O distances where the Na+ belongs to one 18-crown-6 molecule and the oxygen atom belong to the symmetry related adjacent ether crown molecule. The value of this distance [2.540 (1) Å] is shorter than the average Na—O(18-crown-6) which is 2.703 (2) Å.

The average equatorial cadmium-pyrrole N bond length (Cd—Np) [2.2148 (13) Å] is in the range [2.126 (9), 2.3167 (3) Å] for Cd porphyrin complexes (i.e., Byrn et al., 1991). The porphyrin core is not very distorted but present a major doming deformation as confirmed by the Normal Structural Decomposition (NSD) calculations (Jentzen, et al.,1997) with a value of 42%.

The molecular structure of (I) shows the presence of weak intramoleculair hydrogen bonds: two O—H···O bonds within the 18-crown-6 molecule and one CH(18-crown-6)···N6(azido) bond. The crystal packing of the title compound is stabilized by C—H······π intermolecular interactions involving Cg pyrrole and phenyl centroids rings (Table 1 and Fig. 2).

Related literature top

For the synthesis of [Cd(TPP)] (TPP = [please define]), see: Rodesiler et al. (1985). For related structures, see: Byrn et al. (1991); Mansour et al. (2010); Liu et al. (2009). For further details of geometric distortions in related compounds, see: Jentzen et al. (1997).

Experimental top

The [Cd(TPP)] complex (Rodesiler et al. 1985) (20 mg, 0.027 mmol) with an excess of sodium azide NaN3 (100 mg, 1.5 mmol) and 18-crown-6 (52 mg, 0.19 mmol) in chlorobenzene (10 ml) were stirred overnight at room temperature under air to yield a dark-purple solution. Crystals of the title complex were obtained by diffusion of hexanes through the chlorobenzene solution.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.99 Å (methylene) and 0.95 Å (aromatic) with Uiso(H) = 1.2Ueq(Caromatic, methylene).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title molecule with the atom-numbering. Displacement ellipsoids are drawn at 50% and H atoms have been omitted.
[Figure 2] Fig. 2. The crystal structure of the title compound plotted in projection along [100]. H atoms have been omitted.
[(5,10,15,20-Retraphenylporphyrinato)cadmium]-µ-azido-sodium-bis(µ- 1,4,7,10,13,16-hexaoxacyclooctadecane)-sodium-µ-azido-[(5,10,15,20- tetraphenylporphyrinato)cadmium] top
Crystal data top
[Cd2Na2(N3)2(C44H28N4)2(C12H24O6)2]F(000) = 2176.0
Mr = 2108.90Dx = 1.424 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 23347 reflections
a = 11.4175 (3) Åθ = 3.0–32.2°
b = 19.5363 (4) ŵ = 0.51 mm1
c = 22.6086 (6) ÅT = 180 K
β = 102.683 (2)°Prism, dark purple
V = 4919.9 (2) Å30.48 × 0.42 × 0.28 mm
Z = 2
Data collection top
Oxford Diffraction Xcalibur (Sapphire1)
diffractometer
12338 independent reflections
Radiation source: fine-focus sealed tube9493 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 8.2632 pixels mm-1θmax = 28.4°, θmin = 3.1°
ω scansh = 1515
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
k = 2626
Tmin = 0.791, Tmax = 0.870l = 3026
44385 measured reflections
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.041P)2]
where P = (Fo2 + 2Fc2)/3
12338 reflections(Δ/σ)max = 0.002
640 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
[Cd2Na2(N3)2(C44H28N4)2(C12H24O6)2]V = 4919.9 (2) Å3
Mr = 2108.90Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.4175 (3) ŵ = 0.51 mm1
b = 19.5363 (4) ÅT = 180 K
c = 22.6086 (6) Å0.48 × 0.42 × 0.28 mm
β = 102.683 (2)°
Data collection top
Oxford Diffraction Xcalibur (Sapphire1)
diffractometer
12338 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2009)
9493 reflections with I > 2σ(I)
Tmin = 0.791, Tmax = 0.870Rint = 0.030
44385 measured reflectionsθmax = 28.4°
Refinement top
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.071Δρmax = 0.54 e Å3
S = 1.02Δρmin = 0.39 e Å3
12338 reflectionsAbsolute structure: ?
640 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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*/Ueq
Cd0.955191 (10)0.298901 (6)0.222285 (5)0.01846 (4)
C110.79257 (14)0.16615 (8)0.18211 (7)0.0200 (3)
C120.75768 (15)0.12022 (8)0.13139 (7)0.0228 (3)
H120.68980.09080.12360.027*
C130.84030 (15)0.12703 (9)0.09686 (8)0.0250 (4)
H130.84090.10340.06020.030*
C140.92715 (14)0.17697 (8)0.12627 (7)0.0210 (3)
C150.73057 (14)0.17493 (8)0.22913 (7)0.0196 (3)
C210.76402 (14)0.21780 (8)0.27977 (7)0.0198 (3)
C220.70306 (15)0.22250 (9)0.32908 (7)0.0235 (3)
H220.63310.19810.33270.028*
C230.76396 (14)0.26804 (9)0.36900 (7)0.0233 (3)
H230.74480.28160.40610.028*
C240.86392 (14)0.29252 (8)0.34505 (7)0.0192 (3)
C250.95047 (14)0.33965 (8)0.37323 (7)0.0193 (3)
C311.05490 (14)0.36012 (8)0.35404 (7)0.0187 (3)
C321.15390 (14)0.39757 (8)0.39028 (7)0.0221 (3)
H321.15750.41630.42940.026*
C331.24091 (14)0.40109 (8)0.35806 (7)0.0213 (3)
H331.31720.42230.37060.026*
C341.19591 (13)0.36672 (8)0.30123 (7)0.0185 (3)
C351.25978 (14)0.35663 (8)0.25478 (7)0.0191 (3)
C411.22266 (14)0.31638 (8)0.20222 (7)0.0199 (3)
C421.28971 (14)0.30580 (8)0.15556 (7)0.0221 (3)
H421.36520.32550.15430.027*
C431.22553 (15)0.26289 (9)0.11422 (7)0.0239 (3)
H431.24720.24690.07840.029*
C441.11770 (14)0.24567 (8)0.13440 (7)0.0210 (3)
C451.02922 (14)0.19925 (8)0.10574 (7)0.0220 (3)
C610.57959 (19)0.32908 (10)0.09250 (9)0.0379 (5)
H61A0.49700.31320.07480.046*
H61B0.59760.31890.13650.046*
C620.6662 (2)0.29300 (10)0.06335 (10)0.0400 (5)
H62A0.74920.30680.08260.048*
H62B0.65910.24290.06810.048*
C630.51419 (17)0.43920 (10)0.11408 (8)0.0329 (4)
H63A0.51620.41910.15450.039*
H63B0.43010.43880.09060.039*
C640.56024 (19)0.51090 (10)0.12088 (8)0.0372 (5)
H64A0.51720.53730.14690.045*
H64B0.64680.51090.14030.045*
C650.60174 (17)0.60662 (10)0.06432 (10)0.0363 (4)
H65A0.59690.63060.10230.044*
H65B0.55940.63500.02990.044*
C660.73074 (18)0.60012 (11)0.06112 (9)0.0392 (5)
H66A0.76900.64590.06490.047*
H66B0.77380.57120.09490.047*
C670.85595 (17)0.57584 (10)0.00566 (11)0.0420 (5)
H67A0.91290.54900.02500.050*
H67B0.88200.62430.00250.050*
C680.85524 (19)0.54956 (10)0.06700 (11)0.0439 (5)
H68A0.79500.57460.09750.053*
H68B0.93510.55620.07650.053*
C690.8252 (2)0.44956 (13)0.12541 (11)0.0554 (6)
H69A0.90250.45840.13700.066*
H69B0.76000.47000.15660.066*
C700.8059 (3)0.37510 (13)0.12149 (12)0.0630 (7)
H70A0.80780.35300.16070.076*
H70B0.87020.35480.08980.076*
C710.6697 (2)0.29346 (12)0.09761 (12)0.0543 (7)
H71A0.71170.26490.12260.065*
H71B0.58250.28460.11100.065*
C720.7101 (2)0.27356 (12)0.03293 (11)0.0491 (6)
H72A0.69930.22370.02820.059*
H72B0.79620.28460.01820.059*
C1510.61833 (14)0.13391 (8)0.22497 (7)0.0205 (3)
C1520.50758 (15)0.16382 (9)0.20413 (8)0.0283 (4)
H1520.50280.21070.19280.034*
C1530.40297 (18)0.12598 (12)0.19951 (10)0.0415 (5)
H1530.32700.14720.18580.050*
C1540.4095 (2)0.05846 (12)0.21466 (10)0.0476 (6)
H1540.33790.03230.21010.057*
C1560.62280 (18)0.06554 (9)0.24185 (9)0.0346 (4)
H1560.69820.04440.25730.042*
C1550.5182 (2)0.02790 (10)0.23634 (11)0.0475 (6)
H1550.52190.01900.24760.057*
C2510.93115 (14)0.37047 (9)0.43087 (7)0.0217 (3)
C2520.89204 (19)0.43716 (10)0.43156 (9)0.0361 (4)
H2520.87920.46370.39550.043*
C2530.8714 (2)0.46554 (12)0.48412 (10)0.0491 (6)
H2530.84480.51160.48400.059*
C2540.8890 (2)0.42795 (11)0.53662 (9)0.0426 (5)
H2540.87400.44770.57260.051*
C2550.92830 (18)0.36194 (11)0.53656 (8)0.0357 (4)
H2550.94170.33580.57290.043*
C2560.94880 (17)0.33272 (10)0.48362 (8)0.0315 (4)
H2560.97510.28660.48380.038*
C3511.37943 (14)0.39124 (9)0.26353 (7)0.0213 (3)
C3521.48392 (15)0.35385 (10)0.26812 (8)0.0266 (4)
H3521.48000.30530.26550.032*
C3531.59456 (16)0.38634 (11)0.27650 (8)0.0368 (5)
H3531.66540.36010.27850.044*
C3541.60158 (18)0.45626 (12)0.28195 (9)0.0429 (5)
H3541.67760.47830.28870.051*
C3551.4996 (2)0.49444 (11)0.27768 (9)0.0397 (5)
H3551.50450.54280.28140.048*
C3561.38891 (16)0.46187 (9)0.26790 (8)0.0302 (4)
H3561.31810.48860.26410.036*
C4511.04429 (15)0.16895 (10)0.04724 (8)0.0280 (4)
C4521.0733 (2)0.10085 (11)0.04350 (10)0.0447 (5)
H4521.08720.07280.07870.054*
C4531.0821 (2)0.07327 (14)0.01290 (14)0.0646 (8)
H4531.10200.02640.01580.078*
C4541.0622 (2)0.11344 (18)0.06310 (12)0.0666 (9)
H4541.06860.09450.10100.080*
C4551.0333 (2)0.18053 (17)0.05956 (10)0.0575 (7)
H4551.01880.20810.09500.069*
C4561.02489 (17)0.20883 (12)0.00495 (9)0.0390 (5)
H4561.00570.25600.00290.047*
N10.89440 (12)0.19971 (7)0.17725 (6)0.0217 (3)
N20.86096 (12)0.26054 (7)0.29118 (6)0.0203 (3)
N31.08356 (11)0.34256 (7)0.30064 (6)0.0187 (3)
N41.11881 (12)0.27945 (7)0.18739 (6)0.0217 (3)
N50.85120 (16)0.38938 (9)0.17817 (8)0.0395 (4)
N60.85280 (14)0.41290 (8)0.13048 (8)0.0376 (4)
N70.85002 (16)0.43766 (11)0.08343 (10)0.0583 (6)
Na0.67309 (6)0.44498 (4)0.00329 (3)0.03434 (17)
O10.58802 (11)0.40026 (6)0.08330 (6)0.0298 (3)
O20.54207 (11)0.54180 (6)0.06255 (6)0.0310 (3)
O60.63991 (12)0.31060 (6)0.00076 (6)0.0360 (3)
O30.73794 (11)0.57028 (6)0.00506 (6)0.0334 (3)
O40.82635 (13)0.47896 (7)0.06839 (6)0.0410 (3)
O50.69298 (14)0.36427 (8)0.10704 (7)0.0518 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd0.01716 (6)0.02225 (6)0.01685 (6)0.00263 (5)0.00563 (4)0.00278 (5)
C110.0196 (8)0.0186 (8)0.0216 (8)0.0015 (6)0.0044 (6)0.0016 (6)
C120.0237 (8)0.0204 (8)0.0245 (8)0.0039 (6)0.0053 (7)0.0040 (7)
C130.0267 (9)0.0252 (9)0.0235 (9)0.0032 (7)0.0068 (7)0.0083 (7)
C140.0210 (8)0.0226 (8)0.0205 (8)0.0024 (6)0.0068 (7)0.0049 (6)
C150.0188 (8)0.0193 (7)0.0214 (8)0.0026 (6)0.0061 (6)0.0000 (6)
C210.0182 (8)0.0215 (8)0.0208 (8)0.0029 (6)0.0065 (6)0.0004 (6)
C220.0207 (8)0.0281 (9)0.0236 (8)0.0038 (6)0.0093 (7)0.0003 (7)
C230.0206 (8)0.0309 (9)0.0202 (8)0.0019 (7)0.0086 (7)0.0013 (7)
C240.0175 (7)0.0240 (8)0.0171 (7)0.0012 (6)0.0063 (6)0.0020 (6)
C250.0199 (8)0.0209 (8)0.0181 (8)0.0018 (6)0.0060 (6)0.0022 (6)
C310.0189 (8)0.0199 (8)0.0177 (7)0.0008 (6)0.0049 (6)0.0025 (6)
C320.0245 (8)0.0230 (8)0.0190 (8)0.0022 (7)0.0056 (6)0.0051 (7)
C330.0186 (8)0.0235 (8)0.0216 (8)0.0040 (6)0.0036 (6)0.0040 (7)
C340.0169 (7)0.0192 (8)0.0196 (8)0.0004 (6)0.0043 (6)0.0009 (6)
C350.0162 (7)0.0208 (8)0.0210 (8)0.0006 (6)0.0057 (6)0.0013 (6)
C410.0165 (8)0.0235 (8)0.0207 (8)0.0013 (6)0.0065 (6)0.0002 (6)
C420.0202 (8)0.0261 (9)0.0222 (8)0.0016 (6)0.0093 (6)0.0005 (7)
C430.0230 (8)0.0303 (9)0.0209 (8)0.0003 (7)0.0103 (7)0.0016 (7)
C440.0208 (8)0.0244 (8)0.0197 (8)0.0007 (6)0.0085 (6)0.0034 (6)
C450.0216 (8)0.0264 (8)0.0196 (8)0.0008 (7)0.0081 (6)0.0046 (7)
C610.0470 (12)0.0309 (10)0.0344 (11)0.0095 (9)0.0059 (9)0.0088 (9)
C620.0441 (12)0.0273 (10)0.0433 (12)0.0012 (8)0.0017 (9)0.0067 (9)
C630.0348 (10)0.0419 (11)0.0237 (9)0.0026 (8)0.0100 (8)0.0030 (8)
C640.0427 (12)0.0448 (12)0.0235 (9)0.0007 (9)0.0055 (8)0.0022 (8)
C650.0359 (11)0.0258 (10)0.0456 (12)0.0008 (8)0.0058 (9)0.0055 (9)
C660.0362 (11)0.0347 (11)0.0441 (12)0.0065 (8)0.0030 (9)0.0082 (9)
C670.0265 (10)0.0329 (11)0.0671 (15)0.0077 (8)0.0113 (10)0.0014 (10)
C680.0361 (11)0.0372 (11)0.0645 (15)0.0014 (9)0.0241 (11)0.0149 (11)
C690.0664 (17)0.0668 (17)0.0399 (13)0.0115 (13)0.0267 (12)0.0002 (12)
C700.0738 (18)0.0661 (17)0.0622 (17)0.0110 (14)0.0436 (15)0.0202 (13)
C710.0617 (16)0.0451 (14)0.0637 (16)0.0151 (11)0.0307 (13)0.0267 (12)
C720.0434 (13)0.0357 (11)0.0723 (17)0.0059 (9)0.0213 (12)0.0117 (11)
C1510.0223 (8)0.0207 (8)0.0202 (8)0.0047 (6)0.0081 (6)0.0027 (6)
C1520.0246 (9)0.0295 (10)0.0299 (9)0.0050 (7)0.0043 (7)0.0027 (7)
C1530.0232 (10)0.0557 (14)0.0441 (12)0.0090 (9)0.0042 (9)0.0019 (10)
C1540.0401 (12)0.0531 (14)0.0526 (14)0.0289 (11)0.0170 (10)0.0047 (11)
C1560.0374 (11)0.0237 (9)0.0446 (12)0.0001 (8)0.0131 (9)0.0022 (8)
C1550.0630 (16)0.0250 (10)0.0608 (15)0.0171 (10)0.0273 (12)0.0012 (10)
C2510.0180 (8)0.0285 (9)0.0198 (8)0.0035 (6)0.0068 (6)0.0064 (7)
C2520.0494 (12)0.0324 (10)0.0289 (10)0.0084 (9)0.0140 (9)0.0026 (8)
C2530.0714 (16)0.0392 (12)0.0405 (12)0.0149 (11)0.0205 (11)0.0108 (10)
C2540.0523 (13)0.0511 (13)0.0305 (11)0.0047 (10)0.0220 (10)0.0164 (10)
C2550.0409 (11)0.0474 (12)0.0213 (9)0.0065 (9)0.0120 (8)0.0019 (8)
C2560.0366 (10)0.0334 (10)0.0259 (9)0.0001 (8)0.0101 (8)0.0015 (8)
C3510.0186 (8)0.0284 (9)0.0176 (8)0.0038 (6)0.0055 (6)0.0003 (7)
C3520.0209 (9)0.0368 (10)0.0220 (8)0.0010 (7)0.0042 (7)0.0051 (7)
C3530.0185 (9)0.0617 (14)0.0291 (10)0.0010 (9)0.0030 (7)0.0131 (9)
C3540.0273 (11)0.0715 (16)0.0281 (10)0.0240 (10)0.0023 (8)0.0087 (10)
C3550.0465 (12)0.0388 (11)0.0359 (11)0.0222 (10)0.0132 (9)0.0037 (9)
C3560.0300 (10)0.0295 (10)0.0332 (10)0.0056 (7)0.0115 (8)0.0027 (8)
C4510.0220 (9)0.0395 (10)0.0254 (9)0.0098 (7)0.0115 (7)0.0130 (8)
C4520.0498 (13)0.0425 (12)0.0495 (13)0.0070 (10)0.0272 (11)0.0187 (10)
C4530.0583 (16)0.0649 (17)0.082 (2)0.0199 (13)0.0394 (15)0.0508 (16)
C4540.0459 (14)0.121 (3)0.0415 (14)0.0345 (15)0.0288 (11)0.0446 (16)
C4550.0363 (13)0.113 (2)0.0262 (11)0.0203 (13)0.0136 (9)0.0123 (13)
C4560.0271 (10)0.0663 (15)0.0259 (10)0.0075 (9)0.0105 (8)0.0044 (9)
N10.0209 (7)0.0252 (7)0.0210 (7)0.0036 (6)0.0088 (5)0.0059 (6)
N20.0191 (7)0.0246 (7)0.0188 (7)0.0038 (5)0.0074 (5)0.0039 (6)
N30.0168 (6)0.0221 (7)0.0179 (7)0.0004 (5)0.0057 (5)0.0008 (5)
N40.0203 (7)0.0258 (7)0.0207 (7)0.0036 (5)0.0080 (6)0.0055 (6)
N50.0441 (10)0.0371 (10)0.0324 (9)0.0111 (8)0.0021 (7)0.0051 (8)
N60.0250 (8)0.0361 (9)0.0477 (11)0.0010 (7)0.0008 (7)0.0112 (8)
N70.0320 (10)0.0777 (15)0.0622 (13)0.0044 (9)0.0041 (9)0.0414 (12)
Na0.0301 (4)0.0364 (4)0.0349 (4)0.0041 (3)0.0035 (3)0.0096 (3)
O10.0304 (7)0.0290 (7)0.0316 (7)0.0025 (5)0.0100 (5)0.0066 (5)
O20.0317 (7)0.0307 (7)0.0285 (7)0.0027 (5)0.0018 (5)0.0008 (5)
O60.0353 (8)0.0314 (7)0.0405 (8)0.0058 (5)0.0068 (6)0.0025 (6)
O30.0248 (7)0.0324 (7)0.0421 (8)0.0053 (5)0.0057 (6)0.0019 (6)
O40.0522 (9)0.0348 (8)0.0409 (8)0.0053 (6)0.0209 (7)0.0043 (6)
O50.0538 (10)0.0521 (10)0.0553 (10)0.0120 (8)0.0244 (8)0.0128 (8)
Geometric parameters (Å, º) top
Cd—N32.2076 (13)C68—H68A0.9900
Cd—N22.2093 (13)C68—H68B0.9900
Cd—N42.2145 (13)C69—O41.409 (3)
Cd—N12.2278 (13)C69—C701.477 (3)
Cd—N52.2380 (16)C69—H69A0.9900
C11—N11.360 (2)C69—H69B0.9900
C11—C151.411 (2)C70—O51.413 (3)
C11—C121.442 (2)C70—H70A0.9900
C12—C131.356 (2)C70—H70B0.9900
C12—H120.9500C71—O51.433 (3)
C13—C141.445 (2)C71—C721.485 (3)
C13—H130.9500C71—H71A0.9900
C14—N11.362 (2)C71—H71B0.9900
C14—C451.414 (2)C72—O61.419 (2)
C15—C211.402 (2)C72—H72A0.9900
C15—C1511.497 (2)C72—H72B0.9900
C21—N21.365 (2)C151—C1521.379 (2)
C21—C221.441 (2)C151—C1561.387 (2)
C22—C231.347 (2)C152—C1531.389 (2)
C22—H220.9500C152—H1520.9500
C23—C241.448 (2)C153—C1541.361 (3)
C23—H230.9500C153—H1530.9500
C24—N21.3626 (19)C154—C1551.367 (3)
C24—C251.398 (2)C154—H1540.9500
C25—C311.413 (2)C156—C1551.385 (3)
C25—C2511.495 (2)C156—H1560.9500
C31—N31.3623 (19)C155—H1550.9500
C31—C321.441 (2)C251—C2521.379 (2)
C32—C331.356 (2)C251—C2561.379 (2)
C32—H320.9500C252—C2531.378 (3)
C33—C341.441 (2)C252—H2520.9500
C33—H330.9500C253—C2541.372 (3)
C34—N31.3641 (19)C253—H2530.9500
C34—C351.418 (2)C254—C2551.365 (3)
C35—C411.410 (2)C254—H2540.9500
C35—C3511.498 (2)C255—C2561.392 (2)
C41—N41.365 (2)C255—H2550.9500
C41—C421.448 (2)C256—H2560.9500
C42—C431.346 (2)C351—C3521.383 (2)
C42—H420.9500C351—C3561.386 (2)
C43—C441.444 (2)C352—C3531.389 (2)
C43—H430.9500C352—H3520.9500
C44—N41.365 (2)C353—C3541.372 (3)
C44—C451.405 (2)C353—H3530.9500
C45—C4511.493 (2)C354—C3551.368 (3)
C61—O11.412 (2)C354—H3540.9500
C61—C621.482 (3)C355—C3561.389 (3)
C61—H61A0.9900C355—H3550.9500
C61—H61B0.9900C356—H3560.9500
C62—O61.423 (2)C451—C4521.378 (3)
C62—H62A0.9900C451—C4561.390 (3)
C62—H62B0.9900C452—C4531.408 (3)
C63—O11.425 (2)C452—H4520.9500
C63—C641.492 (3)C453—C4541.357 (4)
C63—H63A0.9900C453—H4530.9500
C63—H63B0.9900C454—C4551.358 (4)
C64—O21.424 (2)C454—H4540.9500
C64—H64A0.9900C455—C4561.375 (3)
C64—H64B0.9900C455—H4550.9500
C65—O21.434 (2)C456—H4560.9500
C65—C661.496 (3)N5—N61.176 (2)
C65—H65A0.9900N6—N71.163 (2)
C65—H65B0.9900N7—Na2.491 (2)
C66—O31.414 (2)Na—O12.5248 (14)
C66—H66A0.9900Na—O2i2.5400 (14)
C66—H66B0.9900Na—O32.5523 (14)
C67—O31.425 (2)Na—O42.6076 (15)
C67—C681.477 (3)Na—O62.6570 (15)
C67—H67A0.9900Na—O52.8765 (17)
C67—H67B0.9900Na—O23.0015 (15)
C68—O41.417 (2)O2—Nai2.5400 (14)
N3—Cd—N284.58 (5)O6—C72—H72B110.2
N3—Cd—N483.62 (5)C71—C72—H72B110.2
N2—Cd—N4140.58 (5)H72A—C72—H72B108.5
N3—Cd—N1142.01 (5)C152—C151—C156118.53 (16)
N2—Cd—N182.88 (5)C152—C151—C15120.20 (15)
N4—Cd—N183.71 (5)C156—C151—C15121.27 (15)
N3—Cd—N5104.25 (6)C151—C152—C153120.61 (18)
N2—Cd—N5106.81 (6)C151—C152—H152119.7
N4—Cd—N5112.54 (6)C153—C152—H152119.7
N1—Cd—N5113.69 (6)C154—C153—C152119.9 (2)
N1—C11—C15125.56 (14)C154—C153—H153120.0
N1—C11—C12109.12 (14)C152—C153—H153120.0
C15—C11—C12125.33 (14)C153—C154—C155120.55 (19)
C13—C12—C11106.93 (14)C153—C154—H154119.7
C13—C12—H12126.5C155—C154—H154119.7
C11—C12—H12126.5C155—C156—C151120.50 (19)
C12—C13—C14107.16 (14)C155—C156—H156119.7
C12—C13—H13126.4C151—C156—H156119.7
C14—C13—H13126.4C154—C155—C156119.85 (19)
N1—C14—C45125.20 (15)C154—C155—H155120.1
N1—C14—C13108.75 (14)C156—C155—H155120.1
C45—C14—C13126.05 (15)C252—C251—C256118.81 (16)
C21—C15—C11126.58 (14)C252—C251—C25120.04 (15)
C21—C15—C151116.55 (13)C256—C251—C25121.13 (15)
C11—C15—C151116.86 (14)C253—C252—C251120.48 (19)
N2—C21—C15125.71 (14)C253—C252—H252119.8
N2—C21—C22108.92 (14)C251—C252—H252119.8
C15—C21—C22125.35 (14)C254—C253—C252120.7 (2)
C23—C22—C21107.13 (14)C254—C253—H253119.7
C23—C22—H22126.4C252—C253—H253119.7
C21—C22—H22126.4C255—C254—C253119.36 (18)
C22—C23—C24107.51 (14)C255—C254—H254120.3
C22—C23—H23126.2C253—C254—H254120.3
C24—C23—H23126.2C254—C255—C256120.36 (18)
N2—C24—C25125.85 (14)C254—C255—H255119.8
N2—C24—C23108.43 (14)C256—C255—H255119.8
C25—C24—C23125.70 (14)C251—C256—C255120.29 (18)
C24—C25—C31127.32 (14)C251—C256—H256119.9
C24—C25—C251115.96 (13)C255—C256—H256119.9
C31—C25—C251116.71 (14)C352—C351—C356117.90 (15)
N3—C31—C25125.72 (14)C352—C351—C35121.20 (15)
N3—C31—C32108.70 (13)C356—C351—C35120.90 (15)
C25—C31—C32125.33 (14)C351—C352—C353120.83 (18)
C33—C32—C31107.21 (14)C351—C352—H352119.6
C33—C32—H32126.4C353—C352—H352119.6
C31—C32—H32126.4C354—C353—C352120.04 (19)
C32—C33—C34107.18 (14)C354—C353—H353120.0
C32—C33—H33126.4C352—C353—H353120.0
C34—C33—H33126.4C355—C354—C353120.28 (18)
N3—C34—C35125.46 (14)C355—C354—H354119.9
N3—C34—C33108.69 (13)C353—C354—H354119.9
C35—C34—C33125.78 (14)C354—C355—C356119.5 (2)
C41—C35—C34126.39 (14)C354—C355—H355120.3
C41—C35—C351117.37 (13)C356—C355—H355120.3
C34—C35—C351116.22 (14)C351—C356—C355121.45 (18)
N4—C41—C35125.85 (14)C351—C356—H356119.3
N4—C41—C42108.38 (14)C355—C356—H356119.3
C35—C41—C42125.75 (14)C452—C451—C456118.98 (18)
C43—C42—C41107.49 (14)C452—C451—C45120.86 (18)
C43—C42—H42126.3C456—C451—C45120.12 (18)
C41—C42—H42126.3C451—C452—C453119.4 (2)
C42—C43—C44107.31 (14)C451—C452—H452120.3
C42—C43—H43126.3C453—C452—H452120.3
C44—C43—H43126.3C454—C453—C452120.3 (2)
N4—C44—C45125.71 (14)C454—C453—H453119.9
N4—C44—C43108.69 (14)C452—C453—H453119.9
C45—C44—C43125.54 (14)C453—C454—C455120.5 (2)
C44—C45—C14127.44 (15)C453—C454—H454119.8
C44—C45—C451116.95 (14)C455—C454—H454119.8
C14—C45—C451115.61 (14)C454—C455—C456120.4 (2)
O1—C61—C62109.22 (16)C454—C455—H455119.8
O1—C61—H61A109.8C456—C455—H455119.8
C62—C61—H61A109.8C455—C456—C451120.5 (2)
O1—C61—H61B109.8C455—C456—H456119.8
C62—C61—H61B109.8C451—C456—H456119.8
H61A—C61—H61B108.3C11—N1—C14108.04 (13)
O6—C62—C61108.16 (16)C11—N1—Cd124.64 (10)
O6—C62—H62A110.1C14—N1—Cd123.68 (11)
C61—C62—H62A110.1C24—N2—C21108.01 (13)
O6—C62—H62B110.1C24—N2—Cd123.66 (10)
C61—C62—H62B110.1C21—N2—Cd125.06 (10)
H62A—C62—H62B108.4C31—N3—C34108.21 (13)
O1—C63—C64108.58 (15)C31—N3—Cd124.20 (10)
O1—C63—H63A110.0C34—N3—Cd126.78 (10)
C64—C63—H63A110.0C41—N4—C44108.13 (13)
O1—C63—H63B110.0C41—N4—Cd125.23 (11)
C64—C63—H63B110.0C44—N4—Cd123.33 (11)
H63A—C63—H63B108.4N6—N5—Cd127.13 (14)
O2—C64—C63109.03 (15)N7—N6—N5177.1 (2)
O2—C64—H64A109.9N6—N7—Na126.76 (14)
C63—C64—H64A109.9N7—Na—O175.73 (6)
O2—C64—H64B109.9N7—Na—O2i160.77 (7)
C63—C64—H64B109.9O1—Na—O2i87.25 (5)
H64A—C64—H64B108.3N7—Na—O379.92 (6)
O2—C65—C66112.97 (16)O1—Na—O3115.42 (5)
O2—C65—H65A109.0O2i—Na—O399.95 (5)
C66—C65—H65A109.0N7—Na—O485.99 (6)
O2—C65—H65B109.0O1—Na—O4161.06 (5)
C66—C65—H65B109.0O2i—Na—O4111.57 (5)
H65A—C65—H65B107.8O3—Na—O465.03 (5)
O3—C66—C65109.27 (16)N7—Na—O690.76 (6)
O3—C66—H66A109.8O1—Na—O663.21 (4)
C65—C66—H66A109.8O2i—Na—O689.42 (5)
O3—C66—H66B109.8O3—Na—O6170.52 (5)
C65—C66—H66B109.8O4—Na—O6112.92 (5)
H66A—C66—H66B108.3N7—Na—O5114.50 (7)
O3—C67—C68108.84 (17)O1—Na—O5123.73 (5)
O3—C67—H67A109.9O2i—Na—O582.30 (5)
C68—C67—H67A109.9O3—Na—O5120.83 (5)
O3—C67—H67B109.9O4—Na—O559.76 (5)
C68—C67—H67B109.9O6—Na—O561.56 (5)
H67A—C67—H67B108.3N7—Na—O292.99 (6)
O4—C68—C67108.21 (16)O1—Na—O260.99 (4)
O4—C68—H68A110.1O2i—Na—O270.60 (5)
C67—C68—H68A110.1O3—Na—O261.77 (4)
O4—C68—H68B110.1O4—Na—O2126.07 (5)
C67—C68—H68B110.1O6—Na—O2121.01 (4)
H68A—C68—H68B108.4O5—Na—O2152.50 (5)
O4—C69—C70108.55 (18)C61—O1—C63112.76 (14)
O4—C69—H69A110.0C61—O1—Na120.34 (11)
C70—C69—H69A110.0C63—O1—Na124.29 (10)
O4—C69—H69B110.0C64—O2—C65112.14 (14)
C70—C69—H69B110.0C64—O2—Nai117.33 (11)
H69A—C69—H69B108.4C65—O2—Nai108.86 (11)
O5—C70—C69108.5 (2)C64—O2—Na101.84 (10)
O5—C70—H70A110.0C65—O2—Na106.55 (10)
C69—C70—H70A110.0Nai—O2—Na109.40 (5)
O5—C70—H70B110.0C72—O6—C62112.94 (16)
C69—C70—H70B110.0C72—O6—Na112.55 (13)
H70A—C70—H70B108.4C62—O6—Na105.81 (10)
O5—C71—C72111.80 (19)C66—O3—C67111.37 (15)
O5—C71—H71A109.3C66—O3—Na112.88 (11)
C72—C71—H71A109.3C67—O3—Na109.29 (11)
O5—C71—H71B109.3C69—O4—C68111.87 (16)
C72—C71—H71B109.3C69—O4—Na122.69 (13)
H71A—C71—H71B107.9C68—O4—Na114.65 (11)
O6—C72—C71107.75 (18)C70—O5—C71112.78 (18)
O6—C72—H72A110.2C70—O5—Na110.22 (13)
C71—C72—H72A110.2C71—O5—Na110.93 (12)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
Cg1, Cg2, Cg3 and Cg11 are the centroids of the N1/C11–C14, N2/C21–C24, N3/C31–C34 and C351–C356 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C62—H62A···N60.992.513.303 (3)137
C63—H63B···O3i0.992.563.489 (2)156
C65—H65B···O6i0.992.473.257 (2)136
C62—H62B···Cg10.992.903.555 (2)124
C63—H63A···Cg11ii0.992.753.662 (2)154
C71—H71A···Cg3iii0.992.883.535 (2)124
C353—H353···Cg2iv0.952.623.459 (2)147
C454—H454···Cg11iii0.952.823.697 (3)153
Symmetry codes: (i) x+1, y+1, z; (ii) x1, y, z; (iii) x3/2, y1/2, z3/2; (iv) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
Cg1, Cg2, Cg3 and Cg11 are the centroids of the N1/C11–C14, N2/C21–C24, N3/C31–C34 and C351–C356 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C62—H62A···N60.992.513.303 (3)137.0
C63—H63B···O3i0.992.563.489 (2)156.0
C65—H65B···O6i0.992.473.257 (2)136.0
C62—H62B···Cg10.992.903.555 (2)124.0
C63—H63A···Cg11ii0.992.753.662 (2)154.0
C71—H71A···Cg3iii0.992.883.535 (2)124.0
C353—H353···Cg2iv0.952.623.459 (2)147.0
C454—H454···Cg11iii0.952.823.697 (3)153.0
Symmetry codes: (i) x+1, y+1, z; (ii) x1, y, z; (iii) x3/2, y1/2, z3/2; (iv) x+1, y, z.
Acknowledgements top

The authors gratefully acknowledge financial support from the Ministry of Higher Education and Scientific Research of Tunisia.

references
References top

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388.

Burnett, M. N. & Johnson, C. K. (1996). ORTEPII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Byrn, M. P., Curtis, C. J., Goldberg, I., Hsiou, Y., Khan, S. I., Sawin, P. A., Tendick, S. K. & Strouse, C. E. (1991). J. Am. Chem. Soc. 113, 6549–6557.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Jentzen, W., Song, X. & Shelnutt, J. A. (1997). J. Phys. Chem. B, 101, 1684–1699.

Liu, J.-J., He, X., Shao, M. & Li, M.-X. (2009). Inorg. Chem. Commun. 12, 972–974.

Mansour, A., Belkhiria, M. S., Daran, J.-C. & Nasri, H. (2010). Acta Cryst. E66, m509–m510.

Oxford Diffraction (2009). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.

Rodesiler, P. F., Griffith, E. A. H., Charles, N. G., Lebioda, L. & Amma, E. L. (1985). Inorg. Chem. 24, 4595-4600.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.