Di-μ-chromato-κ4O:O′-bis­[bis­(phenan­throline-κ2N,N′)cadmium(II)] dihydrate

Liu, H.-X.; Jian, F.-F.; Wang, J.

doi:10.1107/S160053680900823X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages m392-m393

doi:10.1107/S160053680900823X

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Di-μ-chromato-κ⁴O:O′-bis[bis(phenanthroline-κ²N,N′)cadmium(II)] dihydrate

Hai-Xing Liu,^a Fang-Fang Jian ^a ^* and Jing Wang ^b

^aMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China, and ^bNew Materials and Function Coordination Chemistry Laboratory, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: ffj2003@163169.net

(Received 12 February 2009; accepted 6 March 2009; online 14 March 2009)

In the title compound, [Cd₂Cr₂O₈(C₁₂H₈N₂)₄]·2H₂O, which was obtained by hydrothermal reaction of CdCO₃ and phenanthroline with K₂CrO₄ at 393 K, two distorted Cd(N₄O₂) octahedra are linked through μ₂-bridging chromate anions, forming a centrosymmetric tetranuclear eight-membered ring complex. The water molecules link the chromate O atoms via intermolecular O—H⋯O hydrogen bonds. These aggregates pack to a three-dimensional network through weak intermolecular C—H⋯O and C—H⋯π hydrogen-bonding contacts.

Related literature

For the properties of multimetallic complexes, see: Costisor et al. (2001 ). For the structures of heterometallic macrocyclic rings, see: Larsen et al. (2003 ); Timco et al. (2005 ). For related structures, see: Dai et al. (2002 ); Chaudhuri et al. (1988 ); Yoshikawa et al. (2002 ).

Experimental

Crystal data

[Cd₂Cr₂O₈(C₁₂H₈N₂)₄]·2H₂O
M_r = 1213.65
Monoclinic, P 2₁ /n
a = 11.2303 (13) Å
b = 13.6892 (16) Å
c = 14.5352 (19) Å
β = 91.928 (1)°
V = 2233.3 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 298 K
0.13 × 0.08 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.830, T_max = 0.930
11590 measured reflections
3922 independent reflections
2145 reflections with I > 2σ(I)
R_int = 0.096

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.065
S = 0.86
3922 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cd1—O2	2.215 (4)
Cd1—O1	2.226 (4)
Cd1—N2	2.370 (5)
Cd1—N1	2.376 (5)
Cd1—N4	2.394 (5)
Cd1—N3	2.397 (5)
O1—Cr1	1.660 (4)
O2—Cr1ⁱ	1.683 (4)
O3—Cr1	1.638 (4)
O4—Cr1	1.619 (4)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O2ⁱⁱ	0.85	2.13	2.849 (6)	142
O5—H5B⋯O4ⁱⁱⁱ	0.85	2.40	3.122 (6)	144
C2—H2⋯O3^iv	0.93	2.49	3.274 (7)	142
C3—H3⋯O3ⁱⁱⁱ	0.93	2.50	3.352 (8)	153
C9—H9⋯O3^v	0.93	2.48	3.391 (7)	168
C10—H10⋯O3	0.93	2.55	3.478 (7)	175
C12—H12⋯O4ⁱⁱ	0.93	2.58	3.423 (7)	151
C20—H20⋯O5^vi	0.93	2.49	3.344 (8)	152
C23—H23⋯Cg1^vii	0.93	2.61	3.509 (7)	164
Symmetry codes: (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (v) -x+2, -y+1, -z+1; (vi) x-1, y, z-1; (vii) -x+1, -y+2, -z+1. Cg1 is the centroid of atoms N1,C1–C5.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680900823X/si2157sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680900823X/si2157Isup2.hkl

checkCIF report

Comment top

In recent decades, research on multimetallic complexes has grown in modern inorganic chemistry, because of searching for new materials, exhibiting exciting magnetic properties, electrical and optical properties (Costisor et al., 2001). But the heterometallic systems are rare because of the difficult synthesis. In contrast to the heterometallic macrocylic ring structures reported (Larsen et al., 2003 & Timco et al., 2005), we describe the synthesis and structure of the title compound, which represents a centrosymmetric heterobinuclear eight-membered ring system.

The title structure (Fig. 1) has a centrosymmetric eight-membered ring, build up of [Cd(phenanthroline)₂]²⁺, [CrO₄]^2- units and two free water molecules. Each Cd atom is coordinated with four N atoms from phenanthroline ligands and two O atoms, presenting a distorted octahedral geometry. The Cr atoms are tetrahedrally coordinated. Two distorted Cd(N₄O₂) octahedra are linked through bridging chromate anions to form the centrosymmetric tetranuclear eight-membered ring complex. The mean Cd—O, Cr—O and Cd—N bond lengths are similar to the values reported (Dai et al., 2002, Chaudhuri et al., 1988, Yoshikawa et al., 2002). The Cr1ⁱ—O2—Cd1, O1—Cr1—O2, O2—Cd1—O1 angles are 133.1 (2)°, 109.40 (18)°, and 97.47 (13)°, respectively. Other selected geometrical parameters are given in Table 1. The dihedral angle between the phenanthroline ligands is 89.00 (1)°. The free water molecules link the chromate oxygen atoms via intermolecular O—H···O hydrogen bonds. The intermolecular C—H···O hydrogen bonds and the C—H···π interactions (Table 2) cause the crystal packing to be energetically preferable and generate a three-dimensional network as shown in Fig. 2.

Related literature top

For the properties of multimetallic complexes, see: Costisor et al. (2001). For the structures of heterometallic macrocyclic rings, see: Larsen et al. (2003); Timco et al. (2005). For related structures, see: Dai et al. (2002); Chaudhuri et al. (1988); Yoshikawa et al. (2002). Cg1 is the centroid of atoms N1,C1–C5.

Experimental top

All commercially obtained reagent-grade chemicals were used without further purication. CdCO₃ (3.40 g, 2.00 mmol) was dissolved in water and methanol (2:1 v/v, 30 ml), mixed with phenanthroline (6.00 g, 3.00 mmol). After stirring for 0.5 h, K₂CrO₄ (1.94 g, 1.00 mmol) was added to the mixture. The hydrothermal reaction was conducted at 393 K for 4 h. The yellow prism crystals were collected, after cooling and filtering (yield 1.20 g). Analysis calculated for C₄₈H₃₆Cd₂Cr₂N₈O₁₀: C 47.46, H 2.97, N 9.22%; found: C 47.44, H 3.03, N 9.20%.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The packing view of the molecules of (I) along the crystallographic a direction.

Di-µ-chromato-κ⁴O:O'-bis[bis(phenanthroline- κ²N,N')cadmium(II)] dihydrate top

Crystal data top

[Cd₂Cr₂O₈(C₁₂H₈N₂)₄]·2H₂O	F(000) = 1208
M_r = 1213.65	D_x = 1.805 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.2303 (13) Å	Cell parameters from 1518 reflections
b = 13.6892 (16) Å	θ = 2.3–25.0°
c = 14.5352 (19) Å	µ = 1.48 mm⁻¹
β = 91.928 (1)°	T = 298 K
V = 2233.3 (5) Å³	Prism, yellow
Z = 2	0.13 × 0.08 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3922 independent reflections
Radiation source: fine-focus sealed tube	2145 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.096
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −13→9
T_min = 0.830, T_max = 0.930	k = −16→14
11590 measured reflections	l = −17→17

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 0.86	w = 1/[σ²(F_o²) + (0.0001P)²] where P = (F_o² + 2F_c²)/3
3922 reflections	(Δ/σ)_max = 0.001
316 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

[Cd₂Cr₂O₈(C₁₂H₈N₂)₄]·2H₂O	V = 2233.3 (5) Å³
M_r = 1213.65	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.2303 (13) Å	µ = 1.48 mm⁻¹
b = 13.6892 (16) Å	T = 298 K
c = 14.5352 (19) Å	0.13 × 0.08 × 0.05 mm
β = 91.928 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3922 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2145 reflections with I > 2σ(I)
T_min = 0.830, T_max = 0.930	R_int = 0.096
11590 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 0.86	Δρ_max = 0.50 e Å⁻³
3922 reflections	Δρ_min = −0.52 e Å⁻³
316 parameters

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

	x	y	z	U_iso*/U_eq
Cd1	0.54305 (4)	0.67292 (3)	0.58619 (3)	0.03350 (14)
N1	0.5517 (4)	0.7535 (3)	0.7310 (3)	0.0336 (13)
N2	0.7407 (4)	0.6723 (3)	0.6487 (3)	0.0345 (12)
N3	0.6012 (5)	0.8015 (3)	0.4851 (4)	0.0439 (15)
N4	0.3768 (4)	0.7747 (3)	0.5434 (3)	0.0359 (13)
O1	0.6078 (4)	0.5715 (3)	0.4790 (3)	0.0484 (13)
O2	0.4197 (3)	0.5701 (3)	0.6521 (3)	0.0407 (12)
O3	0.7995 (3)	0.4755 (3)	0.4225 (3)	0.0453 (12)
O4	0.6869 (3)	0.5992 (3)	0.3082 (3)	0.0482 (12)
O5	0.9994 (4)	1.0021 (3)	1.3274 (3)	0.0759 (16)
H5A	0.9990	0.9605	1.2840	0.091*
H5B	0.9505	1.0471	1.3117	0.091*
Cr1	0.66961 (8)	0.51967 (7)	0.38910 (7)	0.0325 (3)
C1	0.4611 (5)	0.7872 (4)	0.7770 (4)	0.0391 (17)
H1	0.3848	0.7689	0.7570	0.047*
C2	0.4718 (6)	0.8482 (4)	0.8532 (4)	0.0436 (18)
H2	0.4043	0.8706	0.8819	0.052*
C3	0.5821 (6)	0.8746 (4)	0.8852 (4)	0.0431 (18)
H3	0.5907	0.9143	0.9368	0.052*
C4	0.6834 (5)	0.8415 (4)	0.8399 (4)	0.0341 (15)
C5	0.6630 (5)	0.7787 (4)	0.7641 (4)	0.0276 (15)
C6	0.7639 (5)	0.7354 (4)	0.7186 (4)	0.0276 (15)
C7	0.8814 (6)	0.7601 (4)	0.7509 (4)	0.0346 (16)
C8	0.9753 (6)	0.7126 (4)	0.7098 (4)	0.0429 (18)
H8	1.0533	0.7264	0.7289	0.051*
C9	0.9533 (6)	0.6458 (4)	0.6413 (5)	0.049 (2)
H9	1.0154	0.6119	0.6152	0.059*
C10	0.8346 (6)	0.6298 (4)	0.6116 (4)	0.0391 (17)
H10	0.8206	0.5869	0.5629	0.047*
C11	0.8043 (6)	0.8687 (4)	0.8675 (4)	0.0435 (18)
H11	0.8177	0.9134	0.9149	0.052*
C12	0.8964 (5)	0.8294 (5)	0.8249 (4)	0.0423 (16)
H12	0.9732	0.8475	0.8437	0.051*
C13	0.7115 (6)	0.8143 (5)	0.4542 (4)	0.053 (2)
H13	0.7723	0.7738	0.4766	0.063*
C14	0.7391 (7)	0.8865 (5)	0.3892 (5)	0.060 (2)
H14	0.8168	0.8932	0.3700	0.072*
C15	0.6527 (6)	0.9458 (5)	0.3549 (5)	0.052 (2)
H15	0.6705	0.9934	0.3119	0.063*
C16	0.5359 (6)	0.9354 (5)	0.3845 (4)	0.0423 (18)
C17	0.5154 (6)	0.8613 (4)	0.4499 (4)	0.0380 (17)
C18	0.3954 (5)	0.8468 (4)	0.4803 (4)	0.0306 (15)
C19	0.3029 (6)	0.9051 (4)	0.4452 (4)	0.0396 (18)
C20	0.1869 (6)	0.8889 (5)	0.4757 (4)	0.050 (2)
H20	0.1234	0.9270	0.4540	0.060*
C21	0.1692 (5)	0.8152 (5)	0.5387 (5)	0.0480 (18)
H21	0.0935	0.8025	0.5598	0.058*
C22	0.2666 (6)	0.7604 (5)	0.5700 (4)	0.0460 (19)
H22	0.2535	0.7107	0.6122	0.055*
C23	0.4397 (7)	0.9928 (5)	0.3503 (5)	0.054 (2)
H23	0.4540	1.0412	0.3071	0.065*
C24	0.3285 (6)	0.9795 (5)	0.3783 (4)	0.053 (2)
H24	0.2671	1.0185	0.3544	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0289 (2)	0.0347 (3)	0.0369 (3)	0.0001 (3)	0.0019 (2)	−0.0027 (3)
N1	0.021 (3)	0.046 (3)	0.034 (3)	0.003 (3)	0.003 (3)	−0.002 (3)
N2	0.037 (3)	0.032 (3)	0.034 (3)	0.011 (3)	0.002 (3)	−0.008 (3)
N3	0.039 (3)	0.041 (4)	0.053 (4)	0.005 (3)	0.011 (3)	−0.003 (3)
N4	0.035 (3)	0.034 (3)	0.039 (4)	0.002 (3)	0.000 (3)	0.008 (3)
O1	0.044 (3)	0.051 (3)	0.050 (3)	−0.002 (2)	0.007 (2)	−0.018 (2)
O2	0.043 (3)	0.037 (3)	0.043 (3)	−0.015 (2)	0.003 (2)	−0.005 (2)
O3	0.027 (3)	0.052 (3)	0.057 (3)	0.010 (2)	0.003 (2)	0.004 (2)
O4	0.042 (3)	0.049 (3)	0.054 (3)	−0.004 (2)	0.003 (2)	0.019 (2)
O5	0.079 (4)	0.088 (4)	0.059 (4)	0.000 (3)	−0.019 (3)	0.011 (3)
Cr1	0.0274 (6)	0.0340 (6)	0.0361 (7)	−0.0011 (5)	0.0021 (5)	0.0003 (5)
C1	0.030 (4)	0.039 (4)	0.048 (5)	0.000 (3)	0.005 (4)	0.005 (3)
C2	0.044 (4)	0.042 (5)	0.046 (5)	0.009 (4)	0.006 (4)	−0.008 (3)
C3	0.059 (5)	0.037 (4)	0.033 (4)	0.008 (4)	0.001 (4)	−0.012 (3)
C4	0.044 (4)	0.025 (4)	0.033 (4)	0.002 (3)	−0.001 (3)	0.002 (3)
C5	0.034 (4)	0.021 (3)	0.028 (4)	0.002 (3)	−0.002 (3)	0.002 (3)
C6	0.026 (4)	0.030 (4)	0.027 (4)	−0.008 (3)	0.002 (3)	−0.004 (3)
C7	0.032 (4)	0.039 (4)	0.033 (4)	0.001 (3)	−0.002 (3)	0.002 (3)
C8	0.029 (4)	0.053 (5)	0.047 (5)	−0.005 (4)	−0.001 (4)	0.012 (4)
C9	0.035 (4)	0.052 (5)	0.061 (5)	0.007 (4)	0.017 (4)	0.009 (4)
C10	0.041 (4)	0.044 (4)	0.033 (4)	−0.001 (4)	0.009 (4)	−0.001 (3)
C11	0.050 (5)	0.043 (4)	0.037 (4)	−0.017 (4)	−0.009 (4)	−0.008 (3)
C12	0.033 (4)	0.051 (4)	0.042 (4)	−0.008 (4)	−0.010 (3)	0.011 (4)
C13	0.048 (5)	0.045 (5)	0.067 (5)	0.003 (4)	0.017 (4)	−0.004 (4)
C14	0.051 (5)	0.064 (6)	0.067 (6)	−0.017 (5)	0.023 (5)	0.009 (4)
C15	0.063 (5)	0.039 (5)	0.055 (5)	0.003 (4)	0.014 (5)	0.004 (4)
C16	0.057 (5)	0.038 (4)	0.033 (4)	−0.008 (4)	0.009 (4)	0.001 (3)
C17	0.038 (4)	0.036 (4)	0.039 (4)	0.003 (4)	0.005 (4)	−0.006 (3)
C18	0.037 (4)	0.022 (4)	0.033 (4)	−0.004 (3)	0.001 (3)	−0.003 (3)
C19	0.048 (5)	0.032 (4)	0.039 (5)	−0.003 (4)	0.000 (4)	−0.001 (3)
C20	0.048 (5)	0.049 (5)	0.053 (5)	0.018 (4)	−0.004 (4)	−0.005 (4)
C21	0.032 (4)	0.049 (5)	0.063 (5)	0.002 (4)	−0.005 (4)	0.007 (4)
C22	0.046 (5)	0.052 (5)	0.040 (5)	−0.004 (4)	0.008 (4)	0.003 (4)
C23	0.075 (6)	0.040 (5)	0.049 (5)	−0.005 (5)	0.008 (5)	0.015 (4)
C24	0.060 (5)	0.050 (5)	0.048 (5)	0.004 (4)	−0.006 (4)	0.009 (4)

Geometric parameters (Å, º) top

Cd1—O2	2.215 (4)	C7—C8	1.390 (7)
Cd1—O1	2.226 (4)	C7—C12	1.440 (8)
Cd1—N2	2.370 (5)	C8—C9	1.367 (8)
Cd1—N1	2.376 (5)	C8—H8	0.9300
Cd1—N4	2.394 (5)	C9—C10	1.405 (8)
Cd1—N3	2.397 (5)	C9—H9	0.9300
N1—C1	1.319 (6)	C10—H10	0.9300
N1—C5	1.369 (7)	C11—C12	1.336 (7)
N2—C10	1.334 (6)	C11—H11	0.9300
N2—C6	1.353 (6)	C12—H12	0.9300
N3—C13	1.344 (7)	C13—C14	1.408 (8)
N3—C17	1.352 (7)	C13—H13	0.9300
N4—C22	1.324 (7)	C14—C15	1.348 (8)
N4—C18	1.369 (6)	C14—H14	0.9300
O1—Cr1	1.660 (4)	C15—C16	1.401 (8)
O2—Cr1ⁱ	1.683 (4)	C15—H15	0.9300
O3—Cr1	1.638 (4)	C16—C23	1.412 (9)
O4—Cr1	1.619 (4)	C16—C17	1.415 (8)
O5—H5A	0.8501	C17—C18	1.445 (7)
O5—H5B	0.8500	C18—C19	1.394 (8)
Cr1—O2ⁱ	1.683 (4)	C19—C20	1.408 (8)
C1—C2	1.388 (7)	C19—C24	1.442 (8)
C1—H1	0.9300	C20—C21	1.381 (7)
C2—C3	1.357 (8)	C20—H20	0.9300
C2—H2	0.9300	C21—C22	1.390 (8)
C3—C4	1.408 (7)	C21—H21	0.9300
C3—H3	0.9300	C22—H22	0.9300
C4—C5	1.410 (7)	C23—C24	1.339 (8)
C4—C11	1.452 (8)	C23—H23	0.9300
C5—C6	1.456 (7)	C24—H24	0.9300
C6—C7	1.426 (8)

O2—Cd1—O1	97.47 (13)	C8—C7—C6	117.1 (6)
O2—Cd1—N2	115.01 (15)	C8—C7—C12	123.9 (6)
O1—Cd1—N2	86.70 (15)	C6—C7—C12	119.0 (5)
O2—Cd1—N1	85.37 (15)	C9—C8—C7	120.3 (6)
O1—Cd1—N1	154.79 (16)	C9—C8—H8	119.9
N2—Cd1—N1	69.64 (15)	C7—C8—H8	119.9
O2—Cd1—N4	89.34 (15)	C8—C9—C10	118.3 (6)
O1—Cd1—N4	116.81 (16)	C8—C9—H9	120.9
N2—Cd1—N4	144.46 (17)	C10—C9—H9	120.9
N1—Cd1—N4	88.19 (16)	N2—C10—C9	124.3 (6)
O2—Cd1—N3	156.75 (17)	N2—C10—H10	117.9
O1—Cd1—N3	85.81 (15)	C9—C10—H10	117.9
N2—Cd1—N3	88.10 (17)	C12—C11—C4	120.0 (6)
N1—Cd1—N3	101.44 (17)	C12—C11—H11	120.0
N4—Cd1—N3	68.90 (17)	C4—C11—H11	120.0
C1—N1—C5	116.4 (5)	C11—C12—C7	122.6 (6)
C1—N1—Cd1	127.0 (4)	C11—C12—H12	118.7
C5—N1—Cd1	116.0 (4)	C7—C12—H12	118.7
C10—N2—C6	116.6 (5)	N3—C13—C14	122.8 (6)
C10—N2—Cd1	126.1 (4)	N3—C13—H13	118.6
C6—N2—Cd1	116.1 (4)	C14—C13—H13	118.6
C13—N3—C17	116.6 (5)	C15—C14—C13	119.9 (7)
C13—N3—Cd1	125.1 (5)	C15—C14—H14	120.0
C17—N3—Cd1	118.1 (4)	C13—C14—H14	120.0
C22—N4—C18	117.9 (5)	C14—C15—C16	119.7 (7)
C22—N4—Cd1	124.5 (4)	C14—C15—H15	120.2
C18—N4—Cd1	117.3 (4)	C16—C15—H15	120.2
Cr1—O1—Cd1	166.5 (2)	C15—C16—C23	123.3 (6)
Cr1ⁱ—O2—Cd1	133.1 (2)	C15—C16—C17	117.0 (7)
H5A—O5—H5B	107.4	C23—C16—C17	119.7 (6)
O4—Cr1—O3	109.6 (2)	N3—C17—C16	124.0 (6)
O4—Cr1—O1	110.4 (2)	N3—C17—C18	117.5 (6)
O3—Cr1—O1	108.4 (2)	C16—C17—C18	118.5 (6)
O4—Cr1—O2ⁱ	108.5 (2)	N4—C18—C19	122.0 (5)
O3—Cr1—O2ⁱ	110.5 (2)	N4—C18—C17	117.9 (6)
O1—Cr1—O2ⁱ	109.40 (18)	C19—C18—C17	120.1 (6)
N1—C1—C2	124.5 (6)	C18—C19—C20	118.7 (6)
N1—C1—H1	117.7	C18—C19—C24	119.2 (6)
C2—C1—H1	117.7	C20—C19—C24	122.1 (7)
C3—C2—C1	119.1 (6)	C21—C20—C19	118.6 (6)
C3—C2—H2	120.4	C21—C20—H20	120.7
C1—C2—H2	120.4	C19—C20—H20	120.7
C2—C3—C4	119.7 (6)	C20—C21—C22	118.9 (6)
C2—C3—H3	120.1	C20—C21—H21	120.6
C4—C3—H3	120.1	C22—C21—H21	120.6
C3—C4—C5	116.7 (6)	N4—C22—C21	123.9 (6)
C3—C4—C11	123.4 (6)	N4—C22—H22	118.1
C5—C4—C11	119.9 (5)	C21—C22—H22	118.1
N1—C5—C4	123.4 (5)	C24—C23—C16	121.8 (6)
N1—C5—C6	117.0 (5)	C24—C23—H23	119.1
C4—C5—C6	119.6 (6)	C16—C23—H23	119.1
N2—C6—C7	123.4 (5)	C23—C24—C19	120.7 (7)
N2—C6—C5	117.9 (5)	C23—C24—H24	119.7
C7—C6—C5	118.7 (5)	C19—C24—H24	119.7

O2—Cd1—N1—C1	−55.4 (5)	C11—C4—C5—N1	−176.7 (5)
O1—Cd1—N1—C1	−153.1 (4)	C3—C4—C5—C6	−175.1 (5)
N2—Cd1—N1—C1	−174.2 (5)	C11—C4—C5—C6	4.8 (9)
N4—Cd1—N1—C1	34.1 (5)	C10—N2—C6—C7	2.1 (8)
N3—Cd1—N1—C1	102.1 (5)	Cd1—N2—C6—C7	−166.0 (5)
O2—Cd1—N1—C5	133.8 (4)	C10—N2—C6—C5	−176.5 (5)
O1—Cd1—N1—C5	36.1 (6)	Cd1—N2—C6—C5	15.3 (6)
N2—Cd1—N1—C5	15.0 (4)	N1—C5—C6—N2	−1.5 (8)
N4—Cd1—N1—C5	−136.7 (4)	C4—C5—C6—N2	177.2 (5)
N3—Cd1—N1—C5	−68.6 (4)	N1—C5—C6—C7	179.8 (5)
O2—Cd1—N2—C10	102.9 (4)	C4—C5—C6—C7	−1.5 (8)
O1—Cd1—N2—C10	6.2 (5)	N2—C6—C7—C8	−2.7 (9)
N1—Cd1—N2—C10	177.3 (5)	C5—C6—C7—C8	175.9 (5)
N4—Cd1—N2—C10	−127.9 (4)	N2—C6—C7—C12	179.1 (5)
N3—Cd1—N2—C10	−79.7 (5)	C5—C6—C7—C12	−2.3 (9)
O2—Cd1—N2—C6	−90.2 (4)	C6—C7—C8—C9	0.2 (9)
O1—Cd1—N2—C6	173.1 (4)	C12—C7—C8—C9	178.3 (6)
N1—Cd1—N2—C6	−15.8 (4)	C7—C8—C9—C10	2.6 (9)
N4—Cd1—N2—C6	38.9 (5)	C6—N2—C10—C9	0.9 (9)
N3—Cd1—N2—C6	87.2 (4)	Cd1—N2—C10—C9	167.7 (5)
O2—Cd1—N3—C13	−156.8 (4)	C8—C9—C10—N2	−3.3 (10)
O1—Cd1—N3—C13	−57.6 (5)	C3—C4—C11—C12	175.7 (6)
N2—Cd1—N3—C13	29.2 (5)	C5—C4—C11—C12	−4.2 (9)
N1—Cd1—N3—C13	98.0 (5)	C4—C11—C12—C7	0.3 (10)
N4—Cd1—N3—C13	−178.5 (5)	C8—C7—C12—C11	−175.1 (6)
O2—Cd1—N3—C17	17.3 (7)	C6—C7—C12—C11	3.0 (10)
O1—Cd1—N3—C17	116.5 (5)	C17—N3—C13—C14	0.7 (10)
N2—Cd1—N3—C17	−156.7 (5)	Cd1—N3—C13—C14	174.9 (5)
N1—Cd1—N3—C17	−87.9 (5)	N3—C13—C14—C15	−0.5 (11)
N4—Cd1—N3—C17	−4.4 (4)	C13—C14—C15—C16	0.2 (11)
O2—Cd1—N4—C22	6.7 (5)	C14—C15—C16—C23	−178.3 (7)
O1—Cd1—N4—C22	104.8 (5)	C14—C15—C16—C17	−0.2 (10)
N2—Cd1—N4—C22	−128.6 (5)	C13—N3—C17—C16	−0.7 (9)
N1—Cd1—N4—C22	−78.7 (5)	Cd1—N3—C17—C16	−175.3 (5)
N3—Cd1—N4—C22	178.3 (5)	C13—N3—C17—C18	178.2 (5)
O2—Cd1—N4—C18	−166.9 (4)	Cd1—N3—C17—C18	3.6 (7)
O1—Cd1—N4—C18	−68.8 (4)	C15—C16—C17—N3	0.4 (10)
N2—Cd1—N4—C18	57.8 (5)	C23—C16—C17—N3	178.6 (6)
N1—Cd1—N4—C18	107.8 (4)	C15—C16—C17—C18	−178.5 (6)
N3—Cd1—N4—C18	4.8 (4)	C23—C16—C17—C18	−0.3 (9)
O2—Cd1—O1—Cr1	168.8 (11)	C22—N4—C18—C19	0.9 (9)
N2—Cd1—O1—Cr1	−76.4 (11)	Cd1—N4—C18—C19	174.9 (4)
N1—Cd1—O1—Cr1	−96.2 (12)	C22—N4—C18—C17	−178.9 (5)
N4—Cd1—O1—Cr1	75.7 (11)	Cd1—N4—C18—C17	−4.9 (7)
N3—Cd1—O1—Cr1	11.9 (11)	N3—C17—C18—N4	0.8 (8)
O1—Cd1—O2—Cr1ⁱ	−35.6 (3)	C16—C17—C18—N4	179.8 (5)
N2—Cd1—O2—Cr1ⁱ	−125.5 (3)	N3—C17—C18—C19	−178.9 (6)
N1—Cd1—O2—Cr1ⁱ	169.6 (3)	C16—C17—C18—C19	0.1 (9)
N4—Cd1—O2—Cr1ⁱ	81.3 (3)	N4—C18—C19—C20	−0.1 (9)
N3—Cd1—O2—Cr1ⁱ	61.2 (5)	C17—C18—C19—C20	179.7 (5)
Cd1—O1—Cr1—O4	−24.0 (12)	N4—C18—C19—C24	−179.6 (5)
Cd1—O1—Cr1—O3	96.1 (11)	C17—C18—C19—C24	0.2 (9)
Cd1—O1—Cr1—O2ⁱ	−143.3 (11)	C18—C19—C20—C21	−0.6 (9)
C5—N1—C1—C2	2.4 (9)	C24—C19—C20—C21	178.9 (6)
Cd1—N1—C1—C2	−168.3 (4)	C19—C20—C21—C22	0.4 (10)
N1—C1—C2—C3	−1.4 (10)	C18—N4—C22—C21	−1.0 (10)
C1—C2—C3—C4	1.2 (10)	Cd1—N4—C22—C21	−174.6 (5)
C2—C3—C4—C5	−2.2 (9)	C20—C21—C22—N4	0.4 (11)
C2—C3—C4—C11	177.9 (6)	C15—C16—C23—C24	178.3 (7)
C1—N1—C5—C4	−3.5 (8)	C17—C16—C23—C24	0.2 (11)
Cd1—N1—C5—C4	168.3 (4)	C16—C23—C24—C19	0.0 (11)
C1—N1—C5—C6	175.1 (5)	C18—C19—C24—C23	−0.2 (10)
Cd1—N1—C5—C6	−13.1 (6)	C20—C19—C24—C23	−179.7 (6)
C3—C4—C5—N1	3.4 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2ⁱⁱ	0.85	2.13	2.849 (6)	142
O5—H5B···O4ⁱⁱⁱ	0.85	2.40	3.122 (6)	144
C2—H2···O3^iv	0.93	2.49	3.274 (7)	142
C3—H3···O3ⁱⁱⁱ	0.93	2.50	3.352 (8)	153
C9—H9···O3^v	0.93	2.48	3.391 (7)	168
C10—H10···O3	0.93	2.55	3.478 (7)	175
C12—H12···O4ⁱⁱ	0.93	2.58	3.423 (7)	151
C20—H20···O5^vi	0.93	2.49	3.344 (8)	152
C8—H8···Cg2ⁱⁱ	0.93	3.07	3.638 (7)	113
C12—H12···Cg3ⁱⁱ	0.93	3.03	3.277 (7)	95
C23—H23···Cg1^vii	0.93	2.61	3.509 (7)	164

Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x−1/2, −y+3/2, z+1/2; (v) −x+2, −y+1, −z+1; (vi) x−1, y, z−1; (vii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cd₂Cr₂O₈(C₁₂H₈N₂)₄]·2H₂O
M_r	1213.65
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	11.2303 (13), 13.6892 (16), 14.5352 (19)
β (°)	91.928 (1)
V (Å³)	2233.3 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.48
Crystal size (mm)	0.13 × 0.08 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.830, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	11590, 3922, 2145
R_int	0.096
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.065, 0.86
No. of reflections	3922
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.52

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cd1—O2	2.215 (4)	Cd1—N3	2.397 (5)
Cd1—O1	2.226 (4)	O1—Cr1	1.660 (4)
Cd1—N2	2.370 (5)	O2—Cr1ⁱ	1.683 (4)
Cd1—N1	2.376 (5)	O3—Cr1	1.638 (4)
Cd1—N4	2.394 (5)	O4—Cr1	1.619 (4)

Cr1—O1—Cd1	166.5 (2)	Cr1ⁱ—O2—Cd1	133.1 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2ⁱⁱ	0.85	2.13	2.849 (6)	142.3
O5—H5B···O4ⁱⁱⁱ	0.85	2.40	3.122 (6)	143.5
C2—H2···O3^iv	0.93	2.49	3.274 (7)	141.6
C3—H3···O3ⁱⁱⁱ	0.93	2.50	3.352 (8)	153.2
C9—H9···O3^v	0.93	2.48	3.391 (7)	168.2
C10—H10···O3	0.93	2.55	3.478 (7)	174.7
C12—H12···O4ⁱⁱ	0.93	2.58	3.423 (7)	151.3
C20—H20···O5^vi	0.93	2.49	3.344 (8)	152.3
C23—H23···Cg1^vii	0.93	2.61	3.509 (7)	164.0

Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x−1/2, −y+3/2, z+1/2; (v) −x+2, −y+1, −z+1; (vi) x−1, y, z−1; (vii) −x+1, −y+2, −z+1.

References

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Volume 65| Part 4| April 2009| Pages m392-m393

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