Diiodidobis(1,10-phenanthroline-κ²N,N′)cadmium(II)

The title compound, [CdI₂(C₁₂H₈N₂)₂], consists of two 1,10-phenanthroline (phen) ligands, two I atoms and one Cd atom. The coordination geometry around the Cd atom, which lies on a twofold rotation axis, is slightly distorted octa­hedral. In the crystal structure, the dihedral angle between the two phen ligands is 89.03 (5)°. The crystal packing is stabilized by inter­molecular π–π inter­actions of phen rings, with a parallel distance of 3.362 Å, a centroid–centroid distance of 3.903 Å and a slip distance of 1.983 Å, and C—H...I hydrogen bonding [I...H = 3.091 and 2.990 Å].

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.014 Å
• R factor = 0.045
• wR factor = 0.144
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found





Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.664     1.000
            Tmin(prime) and Tmax expected:      0.734     0.963
            RR(prime) =      0.872
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.86
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         14

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1         (2)       2.09

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

The title compound, (I), is a complex with organic and inorganic ligands, which can be used as a catalyst in chemical and biochemical reactions (Boys et al. 1988).

The molecular structure of (I) is shown in Fig. 1. Four N atoms from phen and two I atoms form a distorted octahedron arrangement around the Cd atom. The dihedral angle between the two phen rings of one molecule is 89.03 (5)°. The angles of the axial and equatorial I—Cd—N bonds are different at 161.72 (17) and 90.13 (17), respectively.

In the crystal structure of (I), the crystal packing is stabilized by intermolecular \p-\p stacking interactions, with the distances between phen rings centroids of 3.362\%A, 3.903\%A, and a slip distance of 1.983\%A. There are also weak I–H secondary interactions with distances of 3.091\%A for I(1)–H(16 A) and 2.990\%A for I(1)–H(9 A).

Related literature

For related literature, see: Bowmaker et al. (1973); Boys (1988); Boys et al. (1981); Healy et al. (1985); Pallenberg et al. (1995); Wicholas & Wolford (1974); Yang et al. (2004).

S2. Experimental

The title compound was prepared by the slow addition of CdI~2~ (0.0183 g, 0.05 mmol) and phen (0.018 g, 0.1 mmol) to 10 ml DMF, stirred for 30 min. The solution was filtered, after the solvent was slowly evaporated at room temperature, colorless crystals was obtained.

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1996); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the molecular structure of (I), with displacement ellipsoids drawn at the 50% probabilty level for non-H atoms.

Diiodidobis(1,10-phenanthroline-κ²N,N')cadmium(II)

Crystal data

[CdI2(C12H8N2)2]	F(000) = 1368
Mr = 726.61	Dx = 2.168 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P2n2ab	Cell parameters from 12645 reflections
a = 13.4833 (5) Å	θ = 6.0–55.0°
b = 9.5244 (3) Å	µ = 3.77 mm^−1
c = 17.3385 (5) Å	T = 173 K
V = 2226.41 (13) Å^3	Block, colorless
Z = 4	0.08 × 0.07 × 0.01 mm

Data collection

Rigaku R-AXIS SPIDER diffractometer	2554 independent reflections
Radiation source: fine-focus sealed tube	1786 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
Detector resolution: 10 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω oscillation scans	h = −17→17
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→12
Tmin = 0.664, Tmax = 1.000	l = −22→22
20141 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	Only H-atom displacement parameters refined
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.0462P)^2 + 27.7932P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max = 0.001
2554 reflections	Δρmax = 1.84 e Å^−3
149 parameters	Δρmin = −2.73 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.58713 (4)	0.08128 (7)	0.85926 (4)	0.0384 (2)
Cd1	0.5000	0.27221 (10)	0.7500	0.0314 (3)
N1	0.6549 (5)	0.3396 (8)	0.6981 (4)	0.0325 (16)
N2	0.4792 (5)	0.4653 (8)	0.6587 (4)	0.0314 (16)
C4	0.7434 (7)	0.4817 (10)	0.6051 (5)	0.037 (2)
C5	0.6541 (6)	0.4377 (10)	0.6418 (5)	0.035 (2)
C6	0.7409 (7)	0.2878 (11)	0.7207 (5)	0.039 (2)
H6A	0.7406	0.2197	0.7591	0.050*
C7	0.8321 (7)	0.3292 (12)	0.6905 (6)	0.045 (3)
H7A	0.8913	0.2940	0.7101	0.04 (3)*
C8	0.7383 (8)	0.5822 (11)	0.5438 (6)	0.047 (3)
H8A	0.7956	0.6042	0.5165	0.06 (4)*
C9	0.8314 (7)	0.4227 (11)	0.6314 (6)	0.045 (3)
H9A	0.8909	0.4477	0.6081	0.04 (3)*
C11	0.5627 (7)	0.6104 (10)	0.5635 (5)	0.037 (2)
C13	0.3902 (8)	0.6415 (11)	0.5886 (6)	0.043 (2)
H13A	0.3304	0.6874	0.5799	0.06 (3)*
C14	0.3957 (7)	0.5325 (12)	0.6420 (6)	0.041 (2)
H14A	0.3379	0.5055	0.6672	0.05 (3)*
C15	0.5633 (6)	0.5036 (11)	0.6210 (5)	0.034 (2)
C16	0.6540 (8)	0.6442 (11)	0.5252 (6)	0.048 (3)
H16A	0.6538	0.7115	0.4863	0.06 (4)*
C17	0.4733 (8)	0.6804 (11)	0.5493 (6)	0.045 (2)
H17A	0.4705	0.7527	0.5133	0.06 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0315 (3)	0.0445 (4)	0.0391 (4)	−0.0002 (3)	−0.0038 (3)	0.0038 (3)
Cd1	0.0224 (4)	0.0394 (5)	0.0323 (5)	0.000	0.0013 (4)	0.000
N1	0.025 (4)	0.044 (4)	0.028 (4)	0.001 (3)	0.003 (3)	0.002 (3)
N2	0.030 (4)	0.034 (4)	0.030 (4)	0.007 (3)	−0.002 (3)	0.001 (3)
C4	0.028 (4)	0.041 (5)	0.041 (5)	−0.012 (4)	0.012 (4)	−0.012 (4)
C5	0.027 (4)	0.043 (5)	0.033 (5)	−0.006 (4)	0.001 (4)	−0.008 (4)
C6	0.030 (4)	0.049 (6)	0.037 (5)	0.003 (4)	0.002 (4)	−0.004 (4)
C7	0.023 (4)	0.065 (7)	0.047 (6)	0.008 (4)	−0.001 (4)	−0.021 (5)
C8	0.043 (6)	0.051 (6)	0.046 (6)	−0.013 (5)	0.018 (5)	−0.003 (5)
C9	0.028 (5)	0.060 (7)	0.049 (6)	−0.017 (5)	0.008 (4)	−0.019 (5)
C11	0.041 (5)	0.041 (5)	0.028 (5)	−0.004 (4)	0.003 (4)	0.002 (4)
C13	0.045 (6)	0.040 (5)	0.044 (6)	0.009 (4)	−0.004 (5)	0.015 (5)
C14	0.028 (4)	0.061 (6)	0.036 (5)	−0.008 (4)	0.001 (4)	0.000 (5)
C15	0.028 (4)	0.046 (5)	0.029 (5)	−0.017 (4)	0.002 (3)	−0.007 (4)
C16	0.058 (7)	0.045 (6)	0.041 (6)	−0.005 (5)	0.011 (5)	0.001 (5)
C17	0.051 (6)	0.044 (6)	0.041 (6)	−0.007 (5)	−0.005 (5)	0.007 (5)

Geometric parameters (Å, º)

I1—Cd1	2.8766 (9)	C6—H6A	0.9300
Cd1—N1	2.362 (7)	C7—C9	1.357 (15)
Cd1—N1^i	2.362 (7)	C7—H7A	0.9300
Cd1—N2^i	2.442 (7)	C8—C16	1.321 (15)
Cd1—N2	2.442 (7)	C8—H8A	0.9300
Cd1—I1^i	2.8766 (9)	C9—H9A	0.9300
N1—C6	1.319 (12)	C11—C17	1.400 (14)
N1—C5	1.351 (12)	C11—C15	1.425 (13)
N2—C14	1.327 (12)	C11—C16	1.435 (14)
N2—C15	1.358 (11)	C13—C17	1.362 (14)
C4—C9	1.390 (15)	C13—C14	1.393 (14)
C4—C5	1.424 (12)	C13—H13A	0.9300
C4—C8	1.432 (14)	C14—H14A	0.9300
C5—C15	1.423 (13)	C16—H16A	0.9300
C6—C7	1.394 (14)	C17—H17A	0.9300
N1—Cd1—N1^i	148.5 (4)	C7—C6—H6A	118.0
N1—Cd1—N2^i	86.6 (3)	C9—C7—C6	117.6 (9)
N1^i—Cd1—N2^i	69.5 (3)	C9—C7—H7A	121.2
N1—Cd1—N2	69.5 (2)	C6—C7—H7A	121.2
N1^i—Cd1—N2	86.6 (3)	C16—C8—C4	121.5 (9)
N2^i—Cd1—N2	82.3 (3)	C16—C8—H8A	119.3
N1—Cd1—I1^i	106.37 (18)	C4—C8—H8A	119.3
N1^i—Cd1—I1^i	93.52 (18)	C7—C9—C4	121.2 (9)
N2^i—Cd1—I1^i	161.72 (17)	C7—C9—H9A	119.4
N2—Cd1—I1^i	90.13 (17)	C4—C9—H9A	119.4
N1—Cd1—I1	93.52 (18)	C17—C11—C15	117.9 (9)
N1^i—Cd1—I1	106.37 (18)	C17—C11—C16	123.4 (9)
N2^i—Cd1—I1	90.13 (17)	C15—C11—C16	118.7 (9)
N2—Cd1—I1	161.72 (17)	C17—C13—C14	119.4 (9)
I1^i—Cd1—I1	101.59 (4)	C17—C13—H13A	120.3
C6—N1—C5	118.6 (8)	C14—C13—H13A	120.3
C6—N1—Cd1	124.2 (6)	N2—C14—C13	123.4 (9)
C5—N1—Cd1	117.1 (6)	N2—C14—H14A	118.3
C14—N2—C15	118.2 (8)	C13—C14—H14A	118.3
C14—N2—Cd1	127.0 (6)	N2—C15—C5	118.5 (8)
C15—N2—Cd1	114.7 (6)	N2—C15—C11	121.6 (9)
C9—C4—C5	117.1 (9)	C5—C15—C11	119.8 (8)
C9—C4—C8	123.7 (9)	C8—C16—C11	121.6 (10)
C5—C4—C8	119.2 (9)	C8—C16—H16A	119.2
N1—C5—C15	119.6 (8)	C11—C16—H16A	119.2
N1—C5—C4	121.3 (9)	C13—C17—C11	119.4 (9)
C15—C5—C4	119.0 (9)	C13—C17—H17A	120.3
N1—C6—C7	124.0 (10)	C11—C17—H17A	120.3
N1—C6—H6A	118.0

Symmetry code: (i) −x+1, y, −z+3/2.