Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807022921/lh2387sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807022921/lh2387Isup2.hkl |
CCDC reference: 651157
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.030
- wR factor = 0.070
- Data-to-parameter ratio = 21.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.95 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.15 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1 (2) 2.21
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 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 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
In most reported crystal structures the CdII ion has coordination number six (Shi et al., 2006), while those with coordination number five are rarer (Reger et al., 2002). The title structure is similar to that of {[Cd(µ-I)(µ-ONC5H5)]I}n (where ONC5H5 is pyridine N-oxide) (Sawitzki & Schnering, 1974).
For related literature, see: Pecaut et al. (1993); Selvasekarapandian et al. (1997).
Cd(ClO4)2.6H2O (0.2724 g, 0.649 mmol), 4-methylpyridine N-oxide (0.0793 g, 0.727 mmol) and NaI (0.2417 g, 1.61 mmol) were dissolved in 10 ml H2O, respectively, and then the three solutions were mixed together. The colorless single crystals (I) were obtained after allowing the mixed solution to stand at room temperature for two weeks.
The H atoms were placed in calculated positions and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2eq(C) for pyridine ring; C—H = 0.96 Å, Uiso(H) = 1.5eq(C) for the methyl group.
Complexes containing Cd(II) are very common and useful, and they have played an important role in functional materials, especially in the area of optics (Pecaut et al., 1993; Selvasekarapandian et al., 1997). In published work most CdII ions assume octahedron geometry with six coordinated atoms (Shi et al., 2006), and Cd(II) complexes with coordination number five are limited (Reger et al., 2002). We report here a novel one-dimensional Cd(II) complex (I) with five coordinated atoms.
The asymmetric unit and symmetry-related fragments of (I) are shown in Fig. 1. Atom Cd1 is in a distorted trigonal-bipyramidal CdO2I3 coordination geometry (Table 1). Atom I1 acts as a bridging ligand coordinated two CdII ions with a separation of 3.9511 (11) Å, which creates a four-membered ring with the four atoms strictly coplanar by virtue of the crystallographic inversion center which is in the middle of the four-membered ring. A neutral 4-methylpyridine N-oxide group also acts as bridging ligand with a pair of CdII ions having a separation of 3.8705 (11) Å also leading to the formation of a four-membered ring with the four atoms strictly coplanar by virtue of the crystallographic inversion center which is also at the middle of this four-membered ring. The dihedral angle of the two planes is 56.99 °. The two kinds of four-membered rings connect alternately, leading to the formation of a one-dimensional zigzag chain along the a axis as shown in Fig. 2. There is one weak interchain C—H···I interaction [H6A···I1(x, -1 + y, -1 + z) = 3.24 Å; C6—H6A···I1(x, -1 + y, -1 + z) = 160°. The chain structure in (I) is very similar to that of the complex {[Cd(µ-I)(µ-ONC5H5)]I}n (where ONC5H5 is pyridine N-oxide) (Sawitzki & Schnering, 1974), but the crystal system and space groups of the two crystals are different and probably attributed to the minor difference of the methyl substitution.
In most reported crystal structures the CdII ion has coordination number six (Shi et al., 2006), while those with coordination number five are rarer (Reger et al., 2002). The title structure is similar to that of {[Cd(µ-I)(µ-ONC5H5)]I}n (where ONC5H5 is pyridine N-oxide) (Sawitzki & Schnering, 1974).
For related literature, see: Pecaut et al. (1993); Selvasekarapandian et al. (1997).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[CdI2(C6H7NO)] | Z = 2 |
Mr = 475.33 | F(000) = 424 |
Triclinic, P1 | Dx = 2.880 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0584 (16) Å | Cell parameters from 1365 reflections |
b = 8.4025 (19) Å | θ = 2.6–26.8° |
c = 9.875 (2) Å | µ = 7.58 mm−1 |
α = 102.633 (3)° | T = 293 K |
β = 96.050 (3)° | Block, colorless |
γ = 103.510 (3)° | 0.09 × 0.08 × 0.07 mm |
V = 548.1 (2) Å3 |
Bruker SMART APEX CCD diffractometer | 2147 independent reflections |
Radiation source: fine-focus sealed tube | 1839 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 26.2°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.549, Tmax = 0.619 | k = −8→10 |
3046 measured reflections | l = −12→10 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0308P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.037 |
2147 reflections | Δρmax = 0.85 e Å−3 |
102 parameters | Δρmin = −0.89 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0063 (5) |
[CdI2(C6H7NO)] | γ = 103.510 (3)° |
Mr = 475.33 | V = 548.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.0584 (16) Å | Mo Kα radiation |
b = 8.4025 (19) Å | µ = 7.58 mm−1 |
c = 9.875 (2) Å | T = 293 K |
α = 102.633 (3)° | 0.09 × 0.08 × 0.07 mm |
β = 96.050 (3)° |
Bruker SMART APEX CCD diffractometer | 2147 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1839 reflections with I > 2σ(I) |
Tmin = 0.549, Tmax = 0.619 | Rint = 0.017 |
3046 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.070 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.85 e Å−3 |
2147 reflections | Δρmin = −0.89 e Å−3 |
102 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.25296 (6) | 0.96122 (5) | 1.07178 (4) | 0.03312 (14) | |
I1 | 0.12264 (5) | 1.25617 (5) | 1.10555 (4) | 0.03973 (14) | |
I2 | 0.31135 (7) | 0.81337 (6) | 1.28439 (4) | 0.05230 (16) | |
C6 | 0.1724 (11) | 0.2298 (9) | 0.5226 (7) | 0.0588 (19) | |
H6A | 0.1267 | 0.2389 | 0.4302 | 0.088* | |
H6B | 0.0671 | 0.1605 | 0.5548 | 0.088* | |
H6C | 0.2813 | 0.1795 | 0.5192 | 0.088* | |
N1 | 0.3549 (6) | 0.7153 (6) | 0.8070 (5) | 0.0322 (10) | |
C4 | 0.2630 (9) | 0.4203 (8) | 0.7651 (6) | 0.0419 (14) | |
H4 | 0.2387 | 0.3249 | 0.8005 | 0.050* | |
O1 | 0.4163 (6) | 0.8687 (5) | 0.8971 (4) | 0.0409 (10) | |
C1 | 0.3308 (9) | 0.7026 (8) | 0.6688 (6) | 0.0438 (14) | |
H1 | 0.3538 | 0.7997 | 0.6357 | 0.053* | |
C5 | 0.3229 (9) | 0.5765 (8) | 0.8557 (6) | 0.0419 (14) | |
H5 | 0.3418 | 0.5869 | 0.9522 | 0.050* | |
C2 | 0.2719 (9) | 0.5459 (9) | 0.5757 (6) | 0.0475 (16) | |
H2 | 0.2549 | 0.5384 | 0.4796 | 0.057* | |
C3 | 0.2378 (9) | 0.4012 (8) | 0.6209 (6) | 0.0397 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0310 (2) | 0.0323 (2) | 0.0372 (2) | 0.01002 (18) | 0.00636 (17) | 0.00883 (17) |
I1 | 0.0335 (2) | 0.0305 (2) | 0.0513 (3) | 0.00987 (16) | −0.00021 (17) | 0.00418 (17) |
I2 | 0.0631 (3) | 0.0504 (3) | 0.0487 (3) | 0.0166 (2) | 0.0047 (2) | 0.0239 (2) |
C6 | 0.070 (5) | 0.042 (4) | 0.051 (4) | 0.004 (4) | 0.014 (4) | −0.005 (3) |
N1 | 0.030 (2) | 0.025 (2) | 0.037 (3) | 0.0046 (19) | 0.0080 (19) | 0.001 (2) |
C4 | 0.050 (4) | 0.029 (3) | 0.050 (4) | 0.013 (3) | 0.011 (3) | 0.011 (3) |
O1 | 0.035 (2) | 0.033 (2) | 0.047 (2) | 0.0046 (17) | 0.0123 (18) | −0.0046 (18) |
C1 | 0.053 (4) | 0.038 (4) | 0.041 (3) | 0.010 (3) | 0.008 (3) | 0.013 (3) |
C5 | 0.046 (4) | 0.043 (4) | 0.037 (3) | 0.012 (3) | 0.006 (3) | 0.010 (3) |
C2 | 0.052 (4) | 0.049 (4) | 0.038 (3) | 0.010 (3) | 0.005 (3) | 0.010 (3) |
C3 | 0.039 (3) | 0.039 (4) | 0.037 (3) | 0.007 (3) | 0.011 (3) | 0.005 (3) |
Cd1—O1 | 2.272 (4) | N1—C5 | 1.337 (8) |
Cd1—O1i | 2.384 (4) | N1—O1 | 1.340 (5) |
Cd1—I2 | 2.7054 (7) | C4—C5 | 1.360 (8) |
Cd1—I1 | 2.8049 (8) | C4—C3 | 1.385 (8) |
Cd1—I1ii | 2.9650 (7) | C4—H4 | 0.9300 |
I1—Cd1ii | 2.9650 (7) | O1—Cd1i | 2.384 (4) |
C6—C3 | 1.487 (8) | C1—C2 | 1.374 (9) |
C6—H6A | 0.9600 | C1—H1 | 0.9300 |
C6—H6B | 0.9600 | C5—H5 | 0.9300 |
C6—H6C | 0.9600 | C2—C3 | 1.364 (9) |
N1—C1 | 1.335 (7) | C2—H2 | 0.9300 |
O1—Cd1—O1i | 67.55 (15) | C5—N1—O1 | 120.0 (5) |
O1—Cd1—I2 | 109.61 (11) | C5—C4—C3 | 121.0 (6) |
O1i—Cd1—I2 | 96.51 (11) | C5—C4—H4 | 119.5 |
O1—Cd1—I1 | 124.55 (11) | C3—C4—H4 | 119.5 |
O1i—Cd1—I1 | 88.89 (10) | N1—O1—Cd1 | 123.9 (3) |
I2—Cd1—I1 | 122.90 (2) | N1—O1—Cd1i | 121.8 (3) |
O1—Cd1—I1ii | 88.83 (10) | Cd1—O1—Cd1i | 112.45 (15) |
O1i—Cd1—I1ii | 152.48 (9) | N1—C1—C2 | 119.9 (6) |
I2—Cd1—I1ii | 104.94 (2) | N1—C1—H1 | 120.1 |
I1—Cd1—I1ii | 93.61 (2) | C2—C1—H1 | 120.1 |
Cd1—I1—Cd1ii | 86.39 (2) | N1—C5—C4 | 120.5 (5) |
C3—C6—H6A | 109.5 | N1—C5—H5 | 119.8 |
C3—C6—H6B | 109.5 | C4—C5—H5 | 119.8 |
H6A—C6—H6B | 109.5 | C3—C2—C1 | 121.5 (6) |
C3—C6—H6C | 109.5 | C3—C2—H2 | 119.3 |
H6A—C6—H6C | 109.5 | C1—C2—H2 | 119.3 |
H6B—C6—H6C | 109.5 | C2—C3—C4 | 116.7 (6) |
C1—N1—C5 | 120.5 (5) | C2—C3—C6 | 122.7 (6) |
C1—N1—O1 | 119.4 (5) | C4—C3—C6 | 120.6 (6) |
O1—Cd1—I1—Cd1ii | 91.06 (12) | I2—Cd1—O1—Cd1i | −89.03 (17) |
O1i—Cd1—I1—Cd1ii | 152.57 (10) | I1—Cd1—O1—Cd1i | 71.94 (19) |
I2—Cd1—I1—Cd1ii | −110.39 (3) | I1ii—Cd1—O1—Cd1i | 165.52 (16) |
I1ii—Cd1—I1—Cd1ii | 0.0 | C5—N1—C1—C2 | 0.3 (9) |
C1—N1—O1—Cd1 | 125.4 (5) | O1—N1—C1—C2 | 178.6 (5) |
C5—N1—O1—Cd1 | −56.2 (6) | C1—N1—C5—C4 | −0.8 (9) |
C1—N1—O1—Cd1i | −71.6 (6) | O1—N1—C5—C4 | −179.2 (5) |
C5—N1—O1—Cd1i | 106.8 (5) | C3—C4—C5—N1 | 1.3 (10) |
O1i—Cd1—O1—N1 | 164.4 (5) | N1—C1—C2—C3 | −0.3 (10) |
I2—Cd1—O1—N1 | 75.4 (4) | C1—C2—C3—C4 | 0.8 (10) |
I1—Cd1—O1—N1 | −123.6 (4) | C1—C2—C3—C6 | 179.5 (6) |
I1ii—Cd1—O1—N1 | −30.1 (4) | C5—C4—C3—C2 | −1.3 (9) |
O1i—Cd1—O1—Cd1i | 0.0 | C5—C4—C3—C6 | 179.9 (6) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [CdI2(C6H7NO)] |
Mr | 475.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.0584 (16), 8.4025 (19), 9.875 (2) |
α, β, γ (°) | 102.633 (3), 96.050 (3), 103.510 (3) |
V (Å3) | 548.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 7.58 |
Crystal size (mm) | 0.09 × 0.08 × 0.07 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.549, 0.619 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3046, 2147, 1839 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.621 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.070, 1.02 |
No. of reflections | 2147 |
No. of parameters | 102 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.89 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.
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Complexes containing Cd(II) are very common and useful, and they have played an important role in functional materials, especially in the area of optics (Pecaut et al., 1993; Selvasekarapandian et al., 1997). In published work most CdII ions assume octahedron geometry with six coordinated atoms (Shi et al., 2006), and Cd(II) complexes with coordination number five are limited (Reger et al., 2002). We report here a novel one-dimensional Cd(II) complex (I) with five coordinated atoms.
The asymmetric unit and symmetry-related fragments of (I) are shown in Fig. 1. Atom Cd1 is in a distorted trigonal-bipyramidal CdO2I3 coordination geometry (Table 1). Atom I1 acts as a bridging ligand coordinated two CdII ions with a separation of 3.9511 (11) Å, which creates a four-membered ring with the four atoms strictly coplanar by virtue of the crystallographic inversion center which is in the middle of the four-membered ring. A neutral 4-methylpyridine N-oxide group also acts as bridging ligand with a pair of CdII ions having a separation of 3.8705 (11) Å also leading to the formation of a four-membered ring with the four atoms strictly coplanar by virtue of the crystallographic inversion center which is also at the middle of this four-membered ring. The dihedral angle of the two planes is 56.99 °. The two kinds of four-membered rings connect alternately, leading to the formation of a one-dimensional zigzag chain along the a axis as shown in Fig. 2. There is one weak interchain C—H···I interaction [H6A···I1(x, -1 + y, -1 + z) = 3.24 Å; C6—H6A···I1(x, -1 + y, -1 + z) = 160°. The chain structure in (I) is very similar to that of the complex {[Cd(µ-I)(µ-ONC5H5)]I}n (where ONC5H5 is pyridine N-oxide) (Sawitzki & Schnering, 1974), but the crystal system and space groups of the two crystals are different and probably attributed to the minor difference of the methyl substitution.