Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042717/cv2294sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042717/cv2294Isup2.hkl |
CCDC reference: 663562
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.033
- wR factor = 0.080
- Data-to-parameter ratio = 17.8
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT420_ALERT_2_B D-H Without Acceptor O5 - H5 ... ?
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.744 0.989 Tmin(prime) and Tmax expected: 0.657 0.689 RR(prime) = 0.790 Please check that your absorption correction is appropriate. PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.77 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.70 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cd1 - Cl2_a .. 8.53 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cd2 - Cl3 .. 5.39 su PLAT417_ALERT_2_C Short Inter D-H..H-D H3A .. H7C .. 2.12 Ang. PLAT417_ALERT_2_C Short Inter D-H..H-D H4B .. H5 .. 2.12 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.697 Tmax scaled 0.689 Tmin scaled 0.519 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT793_ALERT_1_G Check the Absolute Configuration of C17 = ... R PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd1 (2) 1.98 PLAT794_ALERT_5_G Check Predicted Bond Valency for Cd2 (2) 2.00 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 7 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 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 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
One similar dinuclear Cd complex with Br has been reported by Zhu et al. (2000).
The title compound was synthesized by refluxing a 20 ml EtOH/H2O solution (3:1, v/v) of CdCl2.2.5H2O (0.458 g, 2 mmol), di-2-pyridylketone (0.185 g, 1 mmol) for 1 h with stirring. After cooling, the solution was filtered. Colourless prism crystals of (I) were obtained by slow evaporation of the colourless filtrate for several days. Yield: 60.6% based on di-2-pyridylketone (0.250 g). (Anal. Calcd. for C22H26Cd2Cl4N4O7: C, 32.03; H, 3.18; N 6.79. Found: C, 31.89; H, 3.23; N 6.65%). IR (KBr pellet, cm-1): v(OH) 3430, v(C–O) 1600, v(C?N, C?C) 1467, 1441, 1384.
The C-bound H-atoms were positioned geometrically (C—H 0.93 Å), and treated as riding with Uiso(H) = 1.2 Ueq(C). H atoms of the water molecules were located in a difference Fourier map and isotropically refined with the O—H distance restrained to 0.85 (4) Å. The hydroxy H atoms were positioned geometrically (O—H 0.82 Å), and treated as riding with Uiso(H) = 1.5 Ueq(O).
The coordination behavior of di-2-pyridylketone [(C5H4N)2CO, dpk] and its hydrolyzed derivative, di-2-pyridylmethanediol [(C5H4N)2C(OH)2, dpd], have attracted much attention. Based on dpd, one dinuclear cadmium complex with Br has been reported (Zhu et al., 2000). Herein we present the similar dinuclear cadmium compoud with Cl - the title compound, (I).
The structure of (I) contains two kinds of neutral conformational isomers, α-Cd2(C11H10N2O2)2Cl4 and β-Cd2(C11H10N2O2)2Cl4, and crystalline water molecules (Fig. 1). Each isomer is centrosymmetric. Both of them contain di-2-chloro bridging between the two metal atoms, and each metal atom is also bonded to a terminal chloro ligand and capped by the organic dpd ligand in an N,N',O -tridentate mode, resulting in a distorted octahedral coordination environment. In α isomer, the terminal chloro atom is trans oriented to the oxygen atom of dpd with respect to the bridge plane and the Cl1—Cd1—O1 angle is 160.09 (5) ° (Table 1), while the Cl3—Cd2—O4 angle is 88.84 (6) ° in β isomer. The Cd···Cd distances are 3.8048 (7) and 3.7281 (7) Å, respectively, in α- and β-isomers.
The crystal structure is stabilized by O—H···O and O—H···Cl hydrogen bonds (Table 2, Fig. 2) involving the hydroxyl groups, crystalline water molecules and terminal Cl ligands.
One similar dinuclear Cd complex with Br has been reported by Zhu et al. (2000).
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).
[Cd2Cl4(C11H10N2O2)2]·3H2O | Z = 2 |
Mr = 825.07 | F(000) = 812 |
Triclinic, P1 | Dx = 1.868 Mg m−3 |
a = 8.1634 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7180 (1) Å | Cell parameters from 3698 reflections |
c = 19.6761 (2) Å | θ = 3.2–27.5° |
α = 100.453 (7)° | µ = 1.86 mm−1 |
β = 92.230 (11)° | T = 293 K |
γ = 106.272 (8)° | Prism, colourless |
V = 1466.87 (8) Å3 | 0.22 × 0.20 × 0.20 mm |
Rigaku Mercury CCD diffractometer | 6631 independent reflections |
Radiation source: fine-focus sealed tube | 5655 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | h = −10→7 |
Tmin = 0.744, Tmax = 0.989 | k = −11→12 |
11364 measured reflections | l = −25→25 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0361P)2 + 0.9676P] where P = (Fo2 + 2Fc2)/3 |
6631 reflections | (Δ/σ)max = 0.004 |
373 parameters | Δρmax = 0.78 e Å−3 |
6 restraints | Δρmin = −0.80 e Å−3 |
[Cd2Cl4(C11H10N2O2)2]·3H2O | γ = 106.272 (8)° |
Mr = 825.07 | V = 1466.87 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1634 (1) Å | Mo Kα radiation |
b = 9.7180 (1) Å | µ = 1.86 mm−1 |
c = 19.6761 (2) Å | T = 293 K |
α = 100.453 (7)° | 0.22 × 0.20 × 0.20 mm |
β = 92.230 (11)° |
Rigaku Mercury CCD diffractometer | 6631 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 5655 reflections with I > 2σ(I) |
Tmin = 0.744, Tmax = 0.989 | Rint = 0.017 |
11364 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 6 restraints |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.78 e Å−3 |
6631 reflections | Δρmin = −0.80 e Å−3 |
373 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 | 0.12516 (3) | 0.16234 (2) | 0.069775 (11) | 0.03408 (7) | |
Cd2 | 0.88520 (3) | 0.34097 (3) | 0.537679 (12) | 0.04439 (8) | |
Cl1 | 0.34946 (12) | 0.07703 (10) | 0.12495 (5) | 0.0496 (2) | |
Cl2 | 0.12820 (12) | 0.08617 (8) | −0.06028 (4) | 0.0454 (2) | |
Cl3 | 0.90828 (13) | 0.13407 (11) | 0.44696 (5) | 0.0555 (2) | |
Cl4 | 1.19742 (11) | 0.50737 (11) | 0.55079 (4) | 0.0497 (2) | |
C1 | 0.4615 (4) | 0.4596 (4) | 0.09048 (18) | 0.0413 (7) | |
H9A | 0.5216 | 0.3906 | 0.0833 | 0.050* | |
C2 | 0.5530 (4) | 0.6055 (4) | 0.10414 (19) | 0.0462 (8) | |
H11A | 0.6720 | 0.6344 | 0.1059 | 0.055* | |
C3 | 0.4642 (4) | 0.7079 (4) | 0.11517 (18) | 0.0423 (7) | |
H16A | 0.5227 | 0.8073 | 0.1245 | 0.051* | |
C4 | 0.2877 (4) | 0.6612 (3) | 0.11222 (16) | 0.0344 (6) | |
H17A | 0.2258 | 0.7288 | 0.1199 | 0.041* | |
C5 | 0.2041 (3) | 0.5132 (3) | 0.09775 (13) | 0.0261 (5) | |
C6 | 0.0099 (3) | 0.4529 (3) | 0.09272 (14) | 0.0258 (5) | |
C7 | −0.0475 (4) | 0.3887 (3) | 0.15610 (14) | 0.0278 (6) | |
C8 | −0.1184 (4) | 0.4594 (4) | 0.20905 (16) | 0.0383 (7) | |
H12A | −0.1306 | 0.5513 | 0.2079 | 0.046* | |
C9 | −0.1709 (5) | 0.3918 (4) | 0.26377 (17) | 0.0493 (9) | |
H10A | −0.2176 | 0.4379 | 0.3004 | 0.059* | |
C10 | −0.1529 (5) | 0.2552 (5) | 0.26312 (19) | 0.0571 (10) | |
H6A | −0.1893 | 0.2063 | 0.2988 | 0.068* | |
C11 | −0.0806 (6) | 0.1923 (4) | 0.20897 (19) | 0.0555 (10) | |
H2B | −0.0692 | 0.0996 | 0.2087 | 0.067* | |
C12 | 1.0703 (4) | 0.2108 (4) | 0.65684 (18) | 0.0434 (7) | |
H7A | 1.1651 | 0.2332 | 0.6317 | 0.052* | |
C13 | 1.0857 (5) | 0.1573 (4) | 0.71639 (18) | 0.0474 (8) | |
H13A | 1.1885 | 0.1435 | 0.7312 | 0.057* | |
C14 | 0.9443 (5) | 0.1247 (4) | 0.75334 (18) | 0.0476 (8) | |
H8A | 0.9519 | 0.0919 | 0.7946 | 0.057* | |
C15 | 0.7918 (5) | 0.1410 (4) | 0.72893 (17) | 0.0439 (8) | |
H15A | 0.6946 | 0.1165 | 0.7525 | 0.053* | |
C16 | 0.7863 (4) | 0.1945 (3) | 0.66889 (15) | 0.0360 (7) | |
C17 | 0.6250 (4) | 0.2239 (4) | 0.64035 (16) | 0.0403 (7) | |
C18 | 0.6458 (4) | 0.3874 (4) | 0.65905 (16) | 0.0376 (7) | |
C19 | 0.5705 (5) | 0.4500 (4) | 0.71349 (18) | 0.0491 (8) | |
H5A | 0.5014 | 0.3921 | 0.7403 | 0.059* | |
C20 | 0.5994 (5) | 0.5989 (5) | 0.7273 (2) | 0.0571 (10) | |
H4A | 0.5507 | 0.6435 | 0.7637 | 0.069* | |
C21 | 0.7017 (6) | 0.6814 (5) | 0.6863 (2) | 0.0626 (11) | |
H1A | 0.7212 | 0.7823 | 0.6940 | 0.075* | |
C22 | 0.7744 (6) | 0.6122 (5) | 0.6337 (2) | 0.0588 (10) | |
H3B | 0.8445 | 0.6683 | 0.6066 | 0.071* | |
N1 | 0.2894 (3) | 0.4120 (3) | 0.08710 (13) | 0.0313 (5) | |
N2 | −0.0253 (4) | 0.2578 (3) | 0.15643 (13) | 0.0371 (6) | |
N3 | 0.9250 (4) | 0.2317 (3) | 0.63383 (13) | 0.0392 (6) | |
N4 | 0.7482 (4) | 0.4674 (3) | 0.62011 (15) | 0.0461 (7) | |
O1 | −0.0368 (3) | 0.3405 (2) | 0.03214 (10) | 0.0312 (4) | |
H1B | −0.1361 | 0.2908 | 0.0325 | 0.047* | |
O2 | −0.0707 (3) | 0.5609 (2) | 0.08952 (11) | 0.0346 (5) | |
H2A | −0.0454 | 0.5959 | 0.0551 | 0.052* | |
O3 | 0.4792 (3) | 0.1514 (3) | 0.66786 (13) | 0.0513 (6) | |
H3A | 0.4639 | 0.0629 | 0.6571 | 0.077* | |
O4 | 0.6143 (3) | 0.1775 (3) | 0.56695 (11) | 0.0463 (6) | |
H4B | 0.5195 | 0.1736 | 0.5499 | 0.069* | |
O5 | 0.3165 (5) | 0.1509 (6) | 0.4914 (2) | 0.0882 (11) | |
H5 | 0.323 (9) | 0.241 (2) | 0.504 (3) | 0.12 (3)* | |
H5B | 0.219 (3) | 0.094 (5) | 0.494 (3) | 0.10 (3)* | |
O6 | 0.6482 (4) | 0.1664 (3) | 0.02199 (17) | 0.0596 (7) | |
H6 | 0.612 (7) | 0.137 (6) | 0.0581 (18) | 0.11 (3)* | |
H6B | 0.646 (7) | 0.096 (4) | −0.011 (2) | 0.11 (2)* | |
O7 | 0.4677 (5) | 0.8691 (4) | 0.62350 (19) | 0.0735 (9) | |
H7C | 0.369 (4) | 0.844 (8) | 0.601 (3) | 0.14 (3)* | |
H7B | 0.530 (10) | 0.855 (10) | 0.591 (3) | 0.17 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.03876 (13) | 0.02852 (11) | 0.03738 (12) | 0.01258 (9) | 0.00889 (9) | 0.00729 (9) |
Cd2 | 0.04591 (15) | 0.05942 (17) | 0.03354 (13) | 0.01892 (12) | 0.01373 (10) | 0.01615 (11) |
Cl1 | 0.0498 (5) | 0.0502 (5) | 0.0578 (5) | 0.0239 (4) | 0.0051 (4) | 0.0190 (4) |
Cl2 | 0.0534 (5) | 0.0352 (4) | 0.0396 (4) | −0.0006 (3) | 0.0168 (4) | 0.0065 (3) |
Cl3 | 0.0609 (6) | 0.0567 (5) | 0.0496 (5) | 0.0190 (4) | 0.0167 (4) | 0.0072 (4) |
Cl4 | 0.0445 (5) | 0.0677 (6) | 0.0401 (4) | 0.0151 (4) | 0.0053 (3) | 0.0207 (4) |
C1 | 0.0272 (15) | 0.0465 (18) | 0.057 (2) | 0.0179 (14) | 0.0084 (14) | 0.0147 (15) |
C2 | 0.0229 (15) | 0.052 (2) | 0.061 (2) | 0.0038 (14) | 0.0080 (14) | 0.0173 (17) |
C3 | 0.0339 (17) | 0.0360 (17) | 0.054 (2) | 0.0022 (13) | 0.0032 (14) | 0.0130 (14) |
C4 | 0.0340 (15) | 0.0299 (14) | 0.0400 (16) | 0.0105 (12) | 0.0053 (13) | 0.0061 (12) |
C5 | 0.0243 (13) | 0.0295 (13) | 0.0259 (13) | 0.0084 (11) | 0.0041 (10) | 0.0081 (10) |
C6 | 0.0267 (13) | 0.0261 (13) | 0.0270 (13) | 0.0109 (11) | 0.0043 (10) | 0.0061 (10) |
C7 | 0.0248 (13) | 0.0312 (14) | 0.0273 (13) | 0.0068 (11) | 0.0037 (11) | 0.0074 (11) |
C8 | 0.0411 (17) | 0.0418 (17) | 0.0362 (16) | 0.0185 (14) | 0.0108 (13) | 0.0067 (13) |
C9 | 0.053 (2) | 0.066 (2) | 0.0335 (17) | 0.0239 (18) | 0.0173 (15) | 0.0089 (16) |
C10 | 0.071 (3) | 0.071 (3) | 0.0400 (19) | 0.025 (2) | 0.0247 (18) | 0.0274 (18) |
C11 | 0.081 (3) | 0.051 (2) | 0.049 (2) | 0.029 (2) | 0.023 (2) | 0.0278 (17) |
C12 | 0.0378 (18) | 0.0492 (19) | 0.0459 (18) | 0.0172 (15) | 0.0091 (14) | 0.0083 (15) |
C13 | 0.053 (2) | 0.050 (2) | 0.049 (2) | 0.0278 (17) | 0.0050 (16) | 0.0127 (16) |
C14 | 0.065 (2) | 0.0461 (19) | 0.0416 (18) | 0.0259 (17) | 0.0062 (17) | 0.0171 (15) |
C15 | 0.052 (2) | 0.0460 (19) | 0.0406 (17) | 0.0201 (16) | 0.0167 (15) | 0.0148 (14) |
C16 | 0.0388 (17) | 0.0394 (16) | 0.0323 (15) | 0.0141 (14) | 0.0103 (13) | 0.0080 (12) |
C17 | 0.0359 (17) | 0.0533 (19) | 0.0336 (15) | 0.0144 (15) | 0.0119 (13) | 0.0096 (14) |
C18 | 0.0332 (16) | 0.0513 (19) | 0.0330 (15) | 0.0178 (14) | 0.0051 (12) | 0.0114 (13) |
C19 | 0.045 (2) | 0.064 (2) | 0.0419 (18) | 0.0218 (18) | 0.0113 (15) | 0.0092 (16) |
C20 | 0.056 (2) | 0.070 (3) | 0.050 (2) | 0.031 (2) | 0.0089 (18) | 0.0038 (19) |
C21 | 0.070 (3) | 0.055 (2) | 0.068 (3) | 0.029 (2) | 0.004 (2) | 0.010 (2) |
C22 | 0.068 (3) | 0.059 (2) | 0.059 (2) | 0.025 (2) | 0.016 (2) | 0.0250 (19) |
N1 | 0.0268 (12) | 0.0321 (12) | 0.0392 (13) | 0.0140 (10) | 0.0066 (10) | 0.0084 (10) |
N2 | 0.0449 (15) | 0.0359 (13) | 0.0357 (13) | 0.0155 (12) | 0.0121 (11) | 0.0132 (11) |
N3 | 0.0405 (15) | 0.0449 (15) | 0.0354 (13) | 0.0156 (12) | 0.0108 (11) | 0.0100 (11) |
N4 | 0.0534 (18) | 0.0530 (17) | 0.0403 (15) | 0.0225 (14) | 0.0147 (13) | 0.0177 (13) |
O1 | 0.0290 (10) | 0.0350 (10) | 0.0278 (10) | 0.0071 (8) | 0.0040 (8) | 0.0048 (8) |
O2 | 0.0330 (11) | 0.0394 (11) | 0.0423 (12) | 0.0212 (9) | 0.0114 (9) | 0.0174 (9) |
O3 | 0.0374 (13) | 0.0594 (15) | 0.0582 (15) | 0.0116 (11) | 0.0201 (11) | 0.0154 (12) |
O4 | 0.0367 (13) | 0.0643 (16) | 0.0358 (12) | 0.0143 (11) | 0.0071 (10) | 0.0045 (11) |
O5 | 0.0504 (19) | 0.134 (4) | 0.094 (3) | 0.031 (2) | 0.0098 (19) | 0.049 (3) |
O6 | 0.0455 (15) | 0.0456 (15) | 0.076 (2) | 0.0007 (12) | 0.0092 (14) | 0.0007 (14) |
O7 | 0.073 (2) | 0.069 (2) | 0.068 (2) | 0.0071 (18) | −0.0006 (18) | 0.0113 (16) |
Cd1—N2 | 2.346 (3) | C11—N2 | 1.339 (4) |
Cd1—N1 | 2.375 (2) | C11—H2B | 0.9300 |
Cd1—Cl1 | 2.4983 (9) | C12—N3 | 1.334 (4) |
Cd1—O1 | 2.639 (2) | C12—C13 | 1.380 (5) |
Cd1—Cl2 | 2.5348 (8) | C12—H7A | 0.9300 |
Cd1—Cl2i | 2.6744 (8) | C13—C14 | 1.381 (5) |
Cd2—N4 | 2.362 (3) | C13—H13A | 0.9300 |
Cd2—N3 | 2.385 (3) | C14—C15 | 1.377 (5) |
Cd2—Cl3 | 2.4902 (10) | C14—H8A | 0.9300 |
Cd2—O4 | 2.491 (2) | C15—C16 | 1.378 (4) |
Cd2—Cl4 | 2.5818 (10) | C15—H15A | 0.9300 |
Cd2—Cl4ii | 2.6560 (9) | C16—N3 | 1.346 (4) |
Cl2—Cd1i | 2.6744 (8) | C16—C17 | 1.531 (5) |
Cl4—Cd2ii | 2.6560 (9) | C17—O3 | 1.387 (4) |
C1—N1 | 1.345 (4) | C17—O4 | 1.424 (4) |
C1—C2 | 1.376 (5) | C17—C18 | 1.523 (5) |
C1—H9A | 0.9300 | C18—N4 | 1.339 (4) |
C2—C3 | 1.378 (5) | C18—C19 | 1.386 (5) |
C2—H11A | 0.9300 | C19—C20 | 1.373 (6) |
C3—C4 | 1.380 (4) | C19—H5A | 0.9300 |
C3—H16A | 0.9300 | C20—C21 | 1.380 (6) |
C4—C5 | 1.379 (4) | C20—H4A | 0.9300 |
C4—H17A | 0.9300 | C21—C22 | 1.376 (6) |
C5—N1 | 1.348 (3) | C21—H1A | 0.9300 |
C5—C6 | 1.521 (4) | C22—N4 | 1.337 (5) |
C6—O2 | 1.396 (3) | C22—H3B | 0.9300 |
C6—O1 | 1.420 (3) | O1—H1B | 0.8200 |
C6—C7 | 1.526 (4) | O2—H2A | 0.8200 |
C7—N2 | 1.336 (4) | O3—H3A | 0.8200 |
C7—C8 | 1.379 (4) | O4—H4B | 0.8200 |
C8—C9 | 1.382 (5) | O5—H5 | 0.85 (4) |
C8—H12A | 0.9300 | O5—H5B | 0.84 (3) |
C9—C10 | 1.374 (5) | O6—H6 | 0.85 (4) |
C9—H10A | 0.9300 | O6—H6B | 0.85 (4) |
C10—C11 | 1.369 (5) | O7—H7C | 0.85 (4) |
C10—H6A | 0.9300 | O7—H7B | 0.85 (5) |
N2—Cd1—N1 | 81.85 (8) | C9—C10—H6A | 120.6 |
N2—Cd1—Cl1 | 109.16 (7) | N2—C11—C10 | 123.1 (3) |
N1—Cd1—Cl1 | 96.06 (6) | N2—C11—H2B | 118.4 |
N2—Cd1—Cl2 | 143.92 (7) | C10—C11—H2B | 118.4 |
N1—Cd1—Cl2 | 100.22 (6) | N3—C12—C13 | 122.7 (3) |
Cl1—Cd1—Cl2 | 106.43 (3) | N3—C12—H7A | 118.6 |
N2—Cd1—O1 | 65.70 (7) | C13—C12—H7A | 118.6 |
N1—Cd1—O1 | 64.51 (7) | C12—C13—C14 | 118.1 (3) |
Cl1—Cd1—O1 | 160.09 (5) | C12—C13—H13A | 120.9 |
Cl2—Cd1—O1 | 82.55 (5) | C14—C13—H13A | 120.9 |
N2—Cd1—Cl2i | 84.56 (7) | C15—C14—C13 | 119.8 (3) |
N1—Cd1—Cl2i | 164.27 (6) | C15—C14—H8A | 120.1 |
Cl1—Cd1—Cl2i | 95.85 (3) | C13—C14—H8A | 120.1 |
Cl2—Cd1—Cl2i | 86.19 (3) | C14—C15—C16 | 118.7 (3) |
O1—Cd1—Cl2i | 102.56 (5) | C14—C15—H15A | 120.7 |
N4—Cd2—N3 | 80.74 (9) | C16—C15—H15A | 120.7 |
N4—Cd2—Cl3 | 155.96 (8) | N3—C16—C15 | 122.1 (3) |
N3—Cd2—Cl3 | 95.66 (7) | N3—C16—C17 | 115.8 (3) |
N4—Cd2—O4 | 67.82 (9) | C15—C16—C17 | 122.1 (3) |
N3—Cd2—O4 | 66.64 (9) | O3—C17—O4 | 111.8 (3) |
Cl3—Cd2—O4 | 88.84 (6) | O3—C17—C18 | 108.1 (3) |
N4—Cd2—Cl4 | 104.22 (8) | O4—C17—C18 | 110.1 (3) |
N3—Cd2—Cl4 | 94.53 (7) | O3—C17—C16 | 112.1 (3) |
Cl3—Cd2—Cl4 | 99.75 (3) | O4—C17—C16 | 105.7 (2) |
O4—Cd2—Cl4 | 160.13 (6) | C18—C17—C16 | 109.1 (3) |
N4—Cd2—Cl4ii | 86.73 (7) | N4—C18—C19 | 122.3 (3) |
N3—Cd2—Cl4ii | 167.44 (7) | N4—C18—C17 | 114.6 (3) |
Cl3—Cd2—Cl4ii | 95.49 (3) | C19—C18—C17 | 123.1 (3) |
O4—Cd2—Cl4ii | 107.86 (6) | C20—C19—C18 | 118.9 (3) |
Cl4—Cd2—Cl4ii | 89.25 (3) | C20—C19—H5A | 120.5 |
Cd1—Cl2—Cd1i | 93.81 (3) | C18—C19—H5A | 120.5 |
Cd2—Cl4—Cd2ii | 90.75 (3) | C19—C20—C21 | 119.0 (4) |
N1—C1—C2 | 123.1 (3) | C19—C20—H4A | 120.5 |
N1—C1—H9A | 118.4 | C21—C20—H4A | 120.5 |
C2—C1—H9A | 118.4 | C22—C21—C20 | 118.9 (4) |
C1—C2—C3 | 118.5 (3) | C22—C21—H1A | 120.5 |
C1—C2—H11A | 120.7 | C20—C21—H1A | 120.5 |
C3—C2—H11A | 120.7 | N4—C22—C21 | 122.6 (4) |
C2—C3—C4 | 119.3 (3) | N4—C22—H3B | 118.7 |
C2—C3—H16A | 120.4 | C21—C22—H3B | 118.7 |
C4—C3—H16A | 120.4 | C1—N1—C5 | 117.8 (3) |
C5—C4—C3 | 119.2 (3) | C1—N1—Cd1 | 124.7 (2) |
C5—C4—H17A | 120.4 | C5—N1—Cd1 | 117.38 (18) |
C3—C4—H17A | 120.4 | C7—N2—C11 | 118.0 (3) |
N1—C5—C4 | 122.1 (3) | C7—N2—Cd1 | 118.51 (18) |
N1—C5—C6 | 115.4 (2) | C11—N2—Cd1 | 123.4 (2) |
C4—C5—C6 | 122.5 (2) | C12—N3—C16 | 118.6 (3) |
O2—C6—O1 | 111.5 (2) | C12—N3—Cd2 | 126.5 (2) |
O2—C6—C5 | 112.1 (2) | C16—N3—Cd2 | 114.8 (2) |
O1—C6—C5 | 105.9 (2) | C22—N4—C18 | 118.3 (3) |
O2—C6—C7 | 106.8 (2) | C22—N4—Cd2 | 125.1 (2) |
O1—C6—C7 | 109.6 (2) | C18—N4—Cd2 | 116.5 (2) |
C5—C6—C7 | 110.9 (2) | C6—O1—Cd1 | 98.73 (14) |
N2—C7—C8 | 122.2 (3) | C6—O1—H1B | 109.5 |
N2—C7—C6 | 115.0 (2) | Cd1—O1—H1B | 99.5 |
C8—C7—C6 | 122.8 (3) | C6—O2—H2A | 109.5 |
C7—C8—C9 | 119.1 (3) | C17—O3—H3A | 109.5 |
C7—C8—H12A | 120.5 | C17—O4—Cd2 | 101.91 (18) |
C9—C8—H12A | 120.5 | C17—O4—H4B | 109.5 |
C10—C9—C8 | 118.8 (3) | Cd2—O4—H4B | 122.8 |
C10—C9—H10A | 120.6 | H5—O5—H5B | 113 (6) |
C8—C9—H10A | 120.6 | H6—O6—H6B | 112 (5) |
C11—C10—C9 | 118.8 (3) | H7C—O7—H7B | 101 (7) |
C11—C10—H6A | 120.6 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O6iii | 0.82 | 1.82 | 2.630 (3) | 172 |
O2—H2A···O1iv | 0.82 | 2.01 | 2.818 (3) | 171 |
O3—H3A···O7v | 0.82 | 1.89 | 2.698 (5) | 169 |
O4—H4B···O5 | 0.82 | 1.92 | 2.720 (4) | 168 |
O5—H5B···Cl3vi | 0.84 (4) | 2.66 (5) | 3.324 (5) | 137 (4) |
O6—H6···Cl1 | 0.85 (4) | 2.54 (5) | 3.262 (3) | 144 (5) |
O6—H6B···Cl1vii | 0.85 (4) | 2.56 (4) | 3.392 (3) | 169 (4) |
O7—H7C···Cl3viii | 0.85 (4) | 2.50 (4) | 3.308 (4) | 159 (6) |
O7—H7B···O5viii | 0.85 (5) | 2.09 (5) | 2.932 (6) | 172 (6) |
Symmetry codes: (iii) x−1, y, z; (iv) −x, −y+1, −z; (v) x, y−1, z; (vi) −x+1, −y, −z+1; (vii) −x+1, −y, −z; (viii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cd2Cl4(C11H10N2O2)2]·3H2O |
Mr | 825.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.1634 (1), 9.7180 (1), 19.6761 (2) |
α, β, γ (°) | 100.453 (7), 92.230 (11), 106.272 (8) |
V (Å3) | 1466.87 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.86 |
Crystal size (mm) | 0.22 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2000) |
Tmin, Tmax | 0.744, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11364, 6631, 5655 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.080, 1.06 |
No. of reflections | 6631 |
No. of parameters | 373 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.78, −0.80 |
Computer programs: CrystalClear (Rigaku, 2000), SHELXTL (Sheldrick, 1997).
Cd1—Cl1 | 2.4983 (9) | Cd2—Cl3 | 2.4902 (10) |
Cd1—O1 | 2.639 (2) | Cd2—O4 | 2.491 (2) |
N2—Cd1—Cl1 | 109.16 (7) | N4—Cd2—Cl3 | 155.96 (8) |
Cl1—Cd1—O1 | 160.09 (5) | Cl3—Cd2—O4 | 88.84 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O6i | 0.82 | 1.82 | 2.630 (3) | 172.2 |
O2—H2A···O1ii | 0.82 | 2.01 | 2.818 (3) | 171.3 |
O3—H3A···O7iii | 0.82 | 1.89 | 2.698 (5) | 168.9 |
O4—H4B···O5 | 0.82 | 1.92 | 2.720 (4) | 167.6 |
O5—H5B···Cl3iv | 0.84 (4) | 2.66 (5) | 3.324 (5) | 137 (4) |
O6—H6···Cl1 | 0.85 (4) | 2.54 (5) | 3.262 (3) | 144 (5) |
O6—H6B···Cl1v | 0.85 (4) | 2.56 (4) | 3.392 (3) | 169 (4) |
O7—H7C···Cl3vi | 0.85 (4) | 2.50 (4) | 3.308 (4) | 159 (6) |
O7—H7B···O5vi | 0.85 (5) | 2.09 (5) | 2.932 (6) | 172 (6) |
Symmetry codes: (i) x−1, y, z; (ii) −x, −y+1, −z; (iii) x, y−1, z; (iv) −x+1, −y, −z+1; (v) −x+1, −y, −z; (vi) −x+1, −y+1, −z+1. |
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The coordination behavior of di-2-pyridylketone [(C5H4N)2CO, dpk] and its hydrolyzed derivative, di-2-pyridylmethanediol [(C5H4N)2C(OH)2, dpd], have attracted much attention. Based on dpd, one dinuclear cadmium complex with Br has been reported (Zhu et al., 2000). Herein we present the similar dinuclear cadmium compoud with Cl - the title compound, (I).
The structure of (I) contains two kinds of neutral conformational isomers, α-Cd2(C11H10N2O2)2Cl4 and β-Cd2(C11H10N2O2)2Cl4, and crystalline water molecules (Fig. 1). Each isomer is centrosymmetric. Both of them contain di-2-chloro bridging between the two metal atoms, and each metal atom is also bonded to a terminal chloro ligand and capped by the organic dpd ligand in an N,N',O -tridentate mode, resulting in a distorted octahedral coordination environment. In α isomer, the terminal chloro atom is trans oriented to the oxygen atom of dpd with respect to the bridge plane and the Cl1—Cd1—O1 angle is 160.09 (5) ° (Table 1), while the Cl3—Cd2—O4 angle is 88.84 (6) ° in β isomer. The Cd···Cd distances are 3.8048 (7) and 3.7281 (7) Å, respectively, in α- and β-isomers.
The crystal structure is stabilized by O—H···O and O—H···Cl hydrogen bonds (Table 2, Fig. 2) involving the hydroxyl groups, crystalline water molecules and terminal Cl ligands.