Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020442/ng2256sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020442/ng2256Isup2.hkl |
CCDC reference: 650619
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.006 Å
- Disorder in solvent or counterion
- R factor = 0.023
- wR factor = 0.060
- Data-to-parameter ratio = 7.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) ..... 7.29 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 200 Ang. PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for O7 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for O9 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for O12 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for O13 PLAT243_ALERT_4_C High 'Solvent' Ueq as Compared to Neighbors for O14 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for O8 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for O10 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 40.00 Perc. PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........ O10 PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........ O12 PLAT432_ALERT_2_C Short Inter X...Y Contact O3 .. C6 .. 2.97 Ang.
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 2346 Count of symmetry unique reflns 2346 Completeness (_total/calc) 100.00% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present yes PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 = . R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 13
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 17 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 3 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 12 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Treatment of ΛL-[Co(L-Hcys-N,S)(en)2](ClO4)2 with a mixture of 0.5 molar equiv. of AgClO4 and 0.5 equiv. of NaOH in water at room temperature gave a red solution, from which red crystals (I) were isolated by adding an aqueous solution of NaClO4.
H atoms bonded to C and N atoms were placed at calculated positions [C—H = 0.97 (methylene) and 0.98 (methine) Å, and N—H = 0.90 Å] and refined as riding with Uiso(H) = 1.2Ueq (C,N). H atoms of water molecules were found in a difference Fourier map and were refined with restrained geometrical parameters [O—H = 0.85 (2) Å, H···H = 1.38 (2) Å, and Uiso = 1.5Ueq(O)]. One H atom of one water molecule is disordered over two positions (H23/H24), which were refined with site occupancies of 0.5. Atom H26 of a water molecule was refined with a restrained geometrical parameter to form an ideal hydrogen bond [H26···O2v = 2.00 (5) Å; symmetry code: (v) -x + 1/2, y + 1/2, -z + 1]. One perchrolate anion is disordered over two positions (O7—O10 and O11—O14), which were refined with site occupancies of 0.5. Atoms O7, O8, O9 and O10, disordered on a twofold axis of the Cl2, were refined with site occupancies of 0.5.
Thiolato groups coordinated to a metal center possess relatively strong Lewis basicity, which allows them to bind with a second metal center (Konno, 2004). Previously, Konno et al. (2001) reported ΛL-[Co(L-cys-N,S)(en)2]+ (L-cys = L-cysteinate, en = ethylenediamine) reacts with AgNO3 to give an S-bridged (CoIIIAgI)n coordination polymer, {ΛL-[Ag{Co(L-cys-N,S)(en)2}](NO3)2}n.H2O (II). In this compound, the ΛL-[Co(L-cys-N,S)(en)2]+ unit binds with two AgI atoms through sulfur and with another AgI atom through a carboxylate group, to give a sheet-like structure. In this paper, we report on the structure of ΛLΛL-[Ag{Co(L-cys-N,S)(en)2}2](ClO4)3.5H2O (I), which was obtained by the 2:1 reaction of ΛL-[Co(L-cys-N,S)(en)2]+ with AgClO4.
The cation is composed of two octahedral [Co(L-cys-N,S)(en)2]+ units that are linked by an AgI atom through the S atoms to form a linear-type S-bridged CoIIIAgICoIII trinuclear structure in [Ag{Co(L-cys-N,S)(en)2}2]3+ (Fig. 1). The AgI atom, which is locate on a twofold axis, adopts an almost linear coordination geometry, unlike an angular geometry found in (II) (S—Ag—S = 149.62 (7) °). Furthermore, the Ag—S bonds in (I) are appreciably shorter than those in (II) (Ag—S = 2.501 (3), 2.511 (3) Å). These differences are ascribed to the fact that the AgI center in (II) is coordinated by a carboxylate group (Ag—O = 2.598 (1), 2.490 (8) Å), besides two thiolato groups. Other bond distances and angles in (I) are similar to those in (II) (Table 1). The two [Co(L-cys-N,S)(en)2]+ units in (I) have an Λ configuration because of the configuration of the mononuclear ΛL-[Co(L-cys-N,S)(en)2]+ reactant. The L-cys N,S-chelate ring adopts a λ conformation; the two en N,N-chelate rings adopt δ and λ conformations.
The cation is connected with to four adjacent cations through N–H···O hydrogen bonds between coordinated amine groups and non-coordinated carboxylate groups to give a sheet-like structure (Fig. 2). The sheets are further linked through the perchlorate anions and water molecules through hydrogen bonds.
For related literature, see: Konno (2004); Konno et al. (2001).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[AgCo2(C3H5NO2S)2(C2H8N2)4](ClO4)3·5H2O | F(000) = 1116 |
Mr = 1092.86 | Dx = 1.898 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: C 2y | Cell parameters from 25 reflections |
a = 16.542 (2) Å | θ = 14.6–15.0° |
b = 9.050 (2) Å | µ = 1.77 mm−1 |
c = 13.728 (2) Å | T = 296 K |
β = 111.507 (10)° | Rod, dark red |
V = 1912.0 (6) Å3 | 0.40 × 0.18 × 0.18 mm |
Z = 2 |
Rigaku AFC-7S diffractometer | 2219 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω–2θ scans | h = 0→21 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→11 |
Tmin = 0.537, Tmax = 0.741 | l = −17→16 |
2426 measured reflections | 3 standard reflections every 150 reflections |
2346 independent reflections | intensity decay: 14.4% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0348P)2 + 0.6577P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.060 | (Δ/σ)max < 0.001 |
S = 1.05 | Δρmax = 0.37 e Å−3 |
2346 reflections | Δρmin = −0.25 e Å−3 |
322 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
13 restraints | Extinction coefficient: 0.0150 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.001 (18) |
[AgCo2(C3H5NO2S)2(C2H8N2)4](ClO4)3·5H2O | V = 1912.0 (6) Å3 |
Mr = 1092.86 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 16.542 (2) Å | µ = 1.77 mm−1 |
b = 9.050 (2) Å | T = 296 K |
c = 13.728 (2) Å | 0.40 × 0.18 × 0.18 mm |
β = 111.507 (10)° |
Rigaku AFC-7S diffractometer | 2219 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.015 |
Tmin = 0.537, Tmax = 0.741 | 3 standard reflections every 150 reflections |
2426 measured reflections | intensity decay: 14.4% |
2346 independent reflections |
R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.060 | Δρmax = 0.37 e Å−3 |
S = 1.05 | Δρmin = −0.25 e Å−3 |
2346 reflections | Absolute structure: Flack (1983) |
322 parameters | Absolute structure parameter: 0.001 (18) |
13 restraints |
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 | Occ. (<1) | |
Ag1 | 0.0000 | 0.31917 (5) | 0.0000 | 0.04457 (14) | |
Co1 | 0.21020 (3) | 0.48714 (5) | 0.22914 (3) | 0.02666 (12) | |
S1 | 0.14873 (5) | 0.30161 (10) | 0.11542 (6) | 0.03258 (19) | |
O1 | 0.0811 (2) | 0.0540 (4) | 0.3873 (3) | 0.0581 (9) | |
O2 | 0.22302 (18) | 0.1037 (4) | 0.4561 (2) | 0.0458 (7) | |
N1 | 0.2271 (2) | 0.6004 (4) | 0.1154 (2) | 0.0395 (7) | |
H1 | 0.1798 | 0.5912 | 0.0564 | 0.047* | |
H2 | 0.2340 | 0.6967 | 0.1327 | 0.047* | |
N2 | 0.3263 (2) | 0.4071 (4) | 0.2530 (3) | 0.0396 (7) | |
H3 | 0.3576 | 0.4039 | 0.3222 | 0.048* | |
H4 | 0.3216 | 0.3145 | 0.2277 | 0.048* | |
N3 | 0.09835 (19) | 0.5808 (4) | 0.2088 (3) | 0.0383 (7) | |
H5 | 0.0783 | 0.6268 | 0.1463 | 0.046* | |
H6 | 0.0595 | 0.5112 | 0.2089 | 0.046* | |
N4 | 0.2594 (2) | 0.6494 (4) | 0.3304 (2) | 0.0364 (6) | |
H7 | 0.2765 | 0.6141 | 0.3961 | 0.044* | |
H8 | 0.3061 | 0.6878 | 0.3207 | 0.044* | |
N5 | 0.1989 (2) | 0.3614 (3) | 0.3410 (2) | 0.0322 (6) | |
H9 | 0.2515 | 0.3238 | 0.3787 | 0.039* | |
H10 | 0.1825 | 0.4186 | 0.3842 | 0.039* | |
C1 | 0.1504 (3) | 0.1644 (4) | 0.2126 (3) | 0.0372 (8) | |
H11 | 0.1051 | 0.0919 | 0.1813 | 0.045* | |
H12 | 0.2059 | 0.1135 | 0.2369 | 0.045* | |
C2 | 0.1364 (2) | 0.2377 (4) | 0.3044 (3) | 0.0317 (7) | |
H13 | 0.0771 | 0.2771 | 0.2810 | 0.038* | |
C3 | 0.1481 (2) | 0.1233 (4) | 0.3914 (3) | 0.0361 (8) | |
C4 | 0.3050 (3) | 0.5450 (7) | 0.0968 (4) | 0.0573 (13) | |
H14 | 0.2897 | 0.4603 | 0.0502 | 0.069* | |
H15 | 0.3280 | 0.6216 | 0.0648 | 0.069* | |
C5 | 0.3707 (3) | 0.5023 (7) | 0.2000 (4) | 0.0551 (12) | |
H16 | 0.4181 | 0.4487 | 0.1904 | 0.066* | |
H17 | 0.3943 | 0.5896 | 0.2417 | 0.066* | |
C6 | 0.1082 (3) | 0.6900 (5) | 0.2938 (4) | 0.0477 (10) | |
H18 | 0.0610 | 0.7610 | 0.2716 | 0.057* | |
H19 | 0.1078 | 0.6402 | 0.3562 | 0.057* | |
C7 | 0.1931 (3) | 0.7657 (4) | 0.3154 (4) | 0.0456 (10) | |
H20 | 0.1900 | 0.8290 | 0.2571 | 0.055* | |
H21 | 0.2078 | 0.8261 | 0.3779 | 0.055* | |
Cl1 | 0.0000 | 0.86644 (15) | 0.0000 | 0.0397 (3) | |
O3 | 0.0194 (6) | 0.8851 (10) | 0.1120 (5) | 0.070 (2) | 0.50 |
O4 | 0.0409 (7) | 0.7347 (13) | −0.0117 (9) | 0.112 (4) | 0.50 |
O5 | −0.0919 (4) | 0.8481 (10) | −0.0499 (6) | 0.067 (2) | 0.50 |
O6 | 0.0282 (5) | 0.9912 (12) | −0.0383 (7) | 0.079 (2) | 0.50 |
Cl2 | 0.37527 (6) | 0.98034 (14) | 0.19897 (9) | 0.0495 (2) | |
O7 | 0.3094 (11) | 0.898 (2) | 0.2056 (16) | 0.115 (6) | 0.50 |
O8 | 0.3534 (12) | 1.1056 (13) | 0.1333 (12) | 0.121 (6) | 0.50 |
O9 | 0.4166 (17) | 1.056 (3) | 0.2960 (10) | 0.168 (10) | 0.50 |
O10 | 0.4352 (8) | 0.8937 (16) | 0.1788 (16) | 0.097 (6) | 0.50 |
O11 | 0.2889 (9) | 0.919 (2) | 0.1446 (11) | 0.084 (4) | 0.50 |
O12 | 0.3949 (13) | 1.028 (5) | 0.1154 (12) | 0.218 (17) | 0.50 |
O13 | 0.3750 (11) | 1.080 (2) | 0.2633 (16) | 0.159 (10) | 0.50 |
O14 | 0.4421 (13) | 0.887 (2) | 0.248 (2) | 0.193 (13) | 0.50 |
O15 | 0.4028 (2) | 0.3330 (6) | 0.4736 (3) | 0.0604 (9) | |
H22 | 0.403 (4) | 0.389 (6) | 0.524 (4) | 0.091* | |
H23 | 0.419 (11) | 0.247 (6) | 0.497 (7) | 0.091* | 0.50 |
H24 | 0.454 (3) | 0.309 (17) | 0.482 (8) | 0.091* | 0.50 |
O16 | 0.1116 (4) | 0.4563 (10) | 0.4944 (4) | 0.115 (2) | |
H25 | 0.083 (6) | 0.438 (14) | 0.534 (6) | 0.173* | |
H26 | 0.156 (4) | 0.510 (12) | 0.530 (7) | 0.173* | |
O17 | 0.0413 (7) | 0.2037 (15) | 0.5497 (11) | 0.096 (3) | 0.50 |
H27 | −0.013 (3) | 0.20 (2) | 0.538 (15) | 0.144* | 0.50 |
H28 | 0.053 (12) | 0.131 (15) | 0.517 (16) | 0.144* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.0396 (2) | 0.0497 (3) | 0.0313 (2) | 0.000 | −0.00251 (16) | 0.000 |
Co1 | 0.0272 (2) | 0.0267 (2) | 0.0234 (2) | 0.00172 (18) | 0.00598 (16) | −0.00014 (18) |
S1 | 0.0351 (4) | 0.0334 (4) | 0.0248 (4) | −0.0001 (4) | 0.0058 (3) | −0.0024 (4) |
O1 | 0.0459 (17) | 0.067 (2) | 0.064 (2) | −0.0068 (15) | 0.0227 (15) | 0.0198 (17) |
O2 | 0.0473 (15) | 0.0469 (16) | 0.0363 (13) | 0.0033 (14) | 0.0072 (11) | 0.0092 (13) |
N1 | 0.0432 (16) | 0.0415 (17) | 0.0322 (14) | −0.0023 (15) | 0.0119 (13) | 0.0047 (14) |
N2 | 0.0345 (15) | 0.0474 (19) | 0.0366 (16) | 0.0048 (14) | 0.0124 (13) | 0.0015 (15) |
N3 | 0.0332 (15) | 0.0337 (15) | 0.0421 (17) | 0.0054 (13) | 0.0068 (13) | −0.0008 (14) |
N4 | 0.0412 (16) | 0.0320 (15) | 0.0321 (14) | −0.0028 (13) | 0.0086 (12) | −0.0044 (13) |
N5 | 0.0379 (15) | 0.0315 (15) | 0.0264 (13) | 0.0027 (12) | 0.0109 (12) | −0.0027 (11) |
C1 | 0.044 (2) | 0.0312 (18) | 0.0295 (17) | 0.0022 (16) | 0.0056 (15) | 0.0003 (15) |
C2 | 0.0305 (17) | 0.0318 (17) | 0.0316 (17) | 0.0029 (14) | 0.0100 (14) | 0.0057 (14) |
C3 | 0.0417 (18) | 0.031 (2) | 0.0365 (17) | 0.0003 (16) | 0.0159 (15) | 0.0012 (15) |
C4 | 0.062 (3) | 0.072 (3) | 0.050 (2) | 0.008 (2) | 0.035 (2) | 0.016 (2) |
C5 | 0.038 (2) | 0.074 (3) | 0.060 (3) | 0.001 (2) | 0.0259 (19) | 0.007 (3) |
C6 | 0.048 (2) | 0.042 (2) | 0.054 (3) | 0.0119 (19) | 0.019 (2) | −0.0067 (19) |
C7 | 0.059 (3) | 0.0250 (17) | 0.050 (2) | 0.0016 (16) | 0.016 (2) | −0.0096 (16) |
Cl1 | 0.0393 (6) | 0.0405 (7) | 0.0334 (6) | 0.000 | 0.0064 (5) | 0.000 |
O3 | 0.093 (5) | 0.078 (5) | 0.034 (3) | −0.023 (5) | 0.017 (3) | −0.007 (3) |
O4 | 0.117 (9) | 0.099 (7) | 0.088 (7) | 0.074 (6) | −0.002 (6) | −0.025 (6) |
O5 | 0.038 (3) | 0.080 (6) | 0.069 (4) | −0.008 (4) | 0.002 (3) | −0.008 (4) |
O6 | 0.073 (5) | 0.083 (6) | 0.090 (6) | −0.017 (5) | 0.039 (4) | 0.026 (6) |
Cl2 | 0.0404 (5) | 0.0508 (6) | 0.0594 (6) | −0.0013 (5) | 0.0209 (4) | −0.0041 (5) |
O7 | 0.107 (13) | 0.077 (8) | 0.215 (19) | −0.032 (9) | 0.120 (14) | −0.020 (13) |
O8 | 0.185 (17) | 0.056 (6) | 0.096 (10) | 0.015 (7) | 0.021 (9) | 0.039 (6) |
O9 | 0.25 (2) | 0.159 (18) | 0.050 (6) | −0.088 (18) | 0.008 (11) | −0.023 (8) |
O10 | 0.060 (7) | 0.075 (7) | 0.174 (16) | −0.003 (6) | 0.063 (10) | −0.041 (10) |
O11 | 0.054 (5) | 0.083 (8) | 0.108 (9) | −0.021 (5) | 0.021 (6) | −0.006 (8) |
O12 | 0.135 (15) | 0.45 (5) | 0.067 (7) | −0.13 (2) | 0.039 (9) | 0.004 (18) |
O13 | 0.097 (9) | 0.140 (13) | 0.173 (19) | 0.042 (9) | −0.028 (10) | −0.103 (14) |
O14 | 0.112 (12) | 0.132 (15) | 0.26 (3) | 0.089 (11) | −0.015 (15) | −0.002 (18) |
O15 | 0.062 (2) | 0.076 (3) | 0.0410 (16) | −0.007 (2) | 0.0156 (15) | −0.0118 (19) |
O16 | 0.104 (4) | 0.169 (7) | 0.089 (3) | −0.027 (4) | 0.054 (3) | −0.029 (4) |
O17 | 0.083 (6) | 0.113 (9) | 0.109 (9) | −0.020 (6) | 0.054 (6) | −0.028 (7) |
Ag1—S1i | 2.3938 (9) | C2—H13 | 0.9800 |
Ag1—S1 | 2.3938 (9) | C4—C5 | 1.486 (7) |
Co1—N3 | 1.960 (3) | C4—H14 | 0.9700 |
Co1—N2 | 1.964 (3) | C4—H15 | 0.9700 |
Co1—N1 | 1.972 (3) | C5—H16 | 0.9700 |
Co1—N5 | 1.975 (3) | C5—H17 | 0.9700 |
Co1—N4 | 1.980 (3) | C6—C7 | 1.492 (6) |
Co1—S1 | 2.2642 (10) | C6—H18 | 0.9700 |
S1—C1 | 1.815 (4) | C6—H19 | 0.9700 |
O1—C3 | 1.256 (5) | C7—H20 | 0.9700 |
O2—C3 | 1.245 (5) | C7—H21 | 0.9700 |
N1—C4 | 1.490 (5) | Cl1—O6 | 1.396 (8) |
N1—H1 | 0.9000 | Cl1—O4 | 1.409 (8) |
N1—H2 | 0.9000 | Cl1—O5 | 1.430 (6) |
N2—C5 | 1.486 (6) | Cl1—O3 | 1.462 (6) |
N2—H3 | 0.9000 | Cl2—O13 | 1.264 (15) |
N2—H4 | 0.9000 | Cl2—O7 | 1.351 (14) |
N3—C6 | 1.492 (5) | Cl2—O14 | 1.359 (16) |
N3—H5 | 0.9000 | Cl2—O10 | 1.370 (11) |
N3—H6 | 0.9000 | Cl2—O12 | 1.372 (15) |
N4—C7 | 1.479 (5) | Cl2—O8 | 1.410 (10) |
N4—H7 | 0.9000 | Cl2—O9 | 1.430 (15) |
N4—H8 | 0.9000 | Cl2—O11 | 1.459 (14) |
N5—C2 | 1.482 (5) | O15—H22 | 0.85 (5) |
N5—H9 | 0.9000 | O15—H23 | 0.84 (2) |
N5—H10 | 0.9000 | O15—H24 | 0.84 (2) |
C1—C2 | 1.516 (5) | O16—H25 | 0.85 (9) |
C1—H11 | 0.9700 | O16—H26 | 0.86 (10) |
C1—H12 | 0.9700 | O17—H27 | 0.85 (2) |
C2—C3 | 1.538 (5) | O17—H28 | 0.85 (2) |
S1i—Ag1—S1 | 172.38 (5) | N5—C2—C1 | 108.2 (3) |
N3—Co1—N2 | 175.89 (16) | N5—C2—C3 | 111.8 (3) |
N3—Co1—N1 | 93.59 (14) | C1—C2—C3 | 109.7 (3) |
N2—Co1—N1 | 84.87 (14) | N5—C2—H13 | 109.0 |
N3—Co1—N5 | 90.38 (13) | C1—C2—H13 | 109.0 |
N2—Co1—N5 | 91.31 (14) | C3—C2—H13 | 109.0 |
N1—Co1—N5 | 175.53 (14) | O2—C3—O1 | 126.4 (4) |
N3—Co1—N4 | 84.43 (14) | O2—C3—C2 | 117.3 (3) |
N2—Co1—N4 | 91.80 (14) | O1—C3—C2 | 116.3 (3) |
N1—Co1—N4 | 91.68 (15) | C5—C4—N1 | 107.5 (4) |
N5—Co1—N4 | 90.76 (13) | C5—C4—H14 | 110.2 |
N3—Co1—S1 | 93.46 (10) | N1—C4—H14 | 110.2 |
N2—Co1—S1 | 90.35 (11) | C5—C4—H15 | 110.2 |
N1—Co1—S1 | 89.86 (11) | N1—C4—H15 | 110.2 |
N5—Co1—S1 | 87.84 (9) | H14—C4—H15 | 108.5 |
N4—Co1—S1 | 177.46 (10) | N2—C5—C4 | 107.3 (4) |
C1—S1—Co1 | 96.81 (12) | N2—C5—H16 | 110.3 |
C1—S1—Ag1 | 105.49 (13) | C4—C5—H16 | 110.3 |
Co1—S1—Ag1 | 120.00 (4) | N2—C5—H17 | 110.3 |
C4—N1—Co1 | 110.1 (3) | C4—C5—H17 | 110.3 |
C4—N1—H1 | 109.6 | H16—C5—H17 | 108.5 |
Co1—N1—H1 | 109.6 | C7—C6—N3 | 106.6 (3) |
C4—N1—H2 | 109.6 | C7—C6—H18 | 110.4 |
Co1—N1—H2 | 109.6 | N3—C6—H18 | 110.4 |
H1—N1—H2 | 108.2 | C7—C6—H19 | 110.4 |
C5—N2—Co1 | 109.5 (3) | N3—C6—H19 | 110.4 |
C5—N2—H3 | 109.8 | H18—C6—H19 | 108.6 |
Co1—N2—H3 | 109.8 | N4—C7—C6 | 107.2 (3) |
C5—N2—H4 | 109.8 | N4—C7—H20 | 110.3 |
Co1—N2—H4 | 109.8 | C6—C7—H20 | 110.3 |
H3—N2—H4 | 108.2 | N4—C7—H21 | 110.3 |
C6—N3—Co1 | 110.4 (2) | C6—C7—H21 | 110.3 |
C6—N3—H5 | 109.6 | H20—C7—H21 | 108.5 |
Co1—N3—H5 | 109.6 | O6—Cl1—O4 | 113.6 (7) |
C6—N3—H6 | 109.6 | O6—Cl1—O5 | 110.9 (5) |
Co1—N3—H6 | 109.6 | O4—Cl1—O5 | 108.5 (6) |
H5—N3—H6 | 108.1 | O6—Cl1—O3 | 109.1 (5) |
C7—N4—Co1 | 109.7 (2) | O4—Cl1—O3 | 106.8 (6) |
C7—N4—H7 | 109.7 | O5—Cl1—O3 | 107.5 (5) |
Co1—N4—H7 | 109.7 | O13—Cl2—O14 | 107.9 (13) |
C7—N4—H8 | 109.7 | O7—Cl2—O10 | 111.0 (10) |
Co1—N4—H8 | 109.7 | O13—Cl2—O12 | 115 (2) |
H7—N4—H8 | 108.2 | O14—Cl2—O12 | 102.4 (17) |
C2—N5—Co1 | 115.1 (2) | O7—Cl2—O8 | 117.5 (11) |
C2—N5—H9 | 108.5 | O10—Cl2—O8 | 111.5 (10) |
Co1—N5—H9 | 108.5 | O7—Cl2—O9 | 108.9 (12) |
C2—N5—H10 | 108.5 | O10—Cl2—O9 | 109.2 (13) |
Co1—N5—H10 | 108.5 | O8—Cl2—O9 | 97.6 (11) |
H9—N5—H10 | 107.5 | O13—Cl2—O11 | 112.1 (11) |
C2—C1—S1 | 110.2 (3) | O14—Cl2—O11 | 118.9 (13) |
C2—C1—H11 | 109.6 | O12—Cl2—O11 | 100.4 (9) |
S1—C1—H11 | 109.6 | H22—O15—H23 | 109 (4) |
C2—C1—H12 | 109.6 | H22—O15—H24 | 109 (4) |
S1—C1—H12 | 109.6 | H25—O16—H26 | 108 (9) |
H11—C1—H12 | 108.1 | H27—O17—H28 | 108 (4) |
N3—Co1—S1—C1 | −98.88 (17) | N1—Co1—N4—C7 | 79.2 (3) |
N2—Co1—S1—C1 | 82.67 (17) | N5—Co1—N4—C7 | −104.6 (3) |
N1—Co1—S1—C1 | 167.53 (16) | N3—Co1—N5—C2 | 75.3 (3) |
N5—Co1—S1—C1 | −8.63 (16) | N2—Co1—N5—C2 | −108.4 (3) |
N3—Co1—S1—Ag1 | 13.43 (11) | N4—Co1—N5—C2 | 159.7 (2) |
N2—Co1—S1—Ag1 | −165.03 (11) | S1—Co1—N5—C2 | −18.1 (2) |
N1—Co1—S1—Ag1 | −80.16 (11) | Co1—S1—C1—C2 | 34.0 (3) |
N5—Co1—S1—Ag1 | 103.68 (10) | Ag1—S1—C1—C2 | −89.7 (3) |
N3—Co1—N1—C4 | −173.1 (3) | Co1—N5—C2—C1 | 44.4 (3) |
N2—Co1—N1—C4 | 10.7 (3) | Co1—N5—C2—C3 | 165.4 (2) |
N4—Co1—N1—C4 | 102.4 (3) | S1—C1—C2—N5 | −51.5 (3) |
S1—Co1—N1—C4 | −79.7 (3) | S1—C1—C2—C3 | −173.7 (3) |
N1—Co1—N2—C5 | 16.7 (3) | N5—C2—C3—O2 | −32.8 (5) |
N5—Co1—N2—C5 | −165.6 (3) | C1—C2—C3—O2 | 87.2 (4) |
N4—Co1—N2—C5 | −74.8 (3) | N5—C2—C3—O1 | 150.2 (4) |
S1—Co1—N2—C5 | 106.5 (3) | C1—C2—C3—O1 | −89.7 (4) |
N1—Co1—N3—C6 | −105.3 (3) | Co1—N1—C4—C5 | −35.7 (5) |
N5—Co1—N3—C6 | 76.8 (3) | Co1—N2—C5—C4 | −40.6 (5) |
N4—Co1—N3—C6 | −14.0 (3) | N1—C4—C5—N2 | 49.3 (6) |
S1—Co1—N3—C6 | 164.6 (3) | Co1—N3—C6—C7 | 38.9 (4) |
N3—Co1—N4—C7 | −14.3 (3) | Co1—N4—C7—C6 | 39.3 (4) |
N2—Co1—N4—C7 | 164.1 (3) | N3—C6—C7—N4 | −50.3 (5) |
Symmetry code: (i) −x, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O12ii | 0.90 | 2.30 | 3.14 (2) | 155 |
N1—H2···O11 | 0.90 | 2.19 | 3.034 (19) | 157 |
N1—H2···O7 | 0.90 | 2.23 | 3.066 (18) | 155 |
N2—H3···O15 | 0.90 | 2.04 | 2.899 (5) | 160 |
N2—H4···O13iii | 0.90 | 2.28 | 3.057 (19) | 144 |
N3—H5···O4 | 0.90 | 2.25 | 3.146 (13) | 174 |
N3—H6···O10iv | 0.90 | 2.21 | 3.083 (12) | 162 |
N4—H7···O2v | 0.90 | 2.03 | 2.868 (4) | 155 |
N4—H8···O7 | 0.90 | 2.49 | 3.117 (16) | 128 |
N4—H8···O17v | 0.90 | 2.50 | 3.138 (13) | 128 |
N5—H9···O15 | 0.90 | 2.36 | 3.201 (5) | 155 |
N5—H10···O16 | 0.90 | 2.25 | 3.079 (6) | 152 |
O15—H22···O1v | 0.85 (5) | 1.89 (3) | 2.711 (5) | 162 (7) |
O15—H24···O15vi | 0.84 (2) | 2.23 (5) | 3.027 (8) | 158 (12) |
O16—H25···O17 | 0.85 (9) | 2.27 (11) | 2.794 (15) | 120 (10) |
O16—H26···O2v | 0.86 (10) | 2.12 (4) | 2.891 (7) | 149 (7) |
O17—H27···O1vii | 0.85 (2) | 2.2 (2) | 2.822 (12) | 126 (19) |
O17—H28···O1 | 0.85 (2) | 2.12 (12) | 2.884 (12) | 149 (19) |
Symmetry codes: (ii) −x+1/2, y−1/2, −z; (iii) x, y−1, z; (iv) x−1/2, y−1/2, z; (v) −x+1/2, y+1/2, −z+1; (vi) −x+1, y, −z+1; (vii) −x, y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [AgCo2(C3H5NO2S)2(C2H8N2)4](ClO4)3·5H2O |
Mr | 1092.86 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 296 |
a, b, c (Å) | 16.542 (2), 9.050 (2), 13.728 (2) |
β (°) | 111.507 (10) |
V (Å3) | 1912.0 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.77 |
Crystal size (mm) | 0.40 × 0.18 × 0.18 |
Data collection | |
Diffractometer | Rigaku AFC-7S |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.537, 0.741 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2426, 2346, 2219 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.060, 1.05 |
No. of reflections | 2346 |
No. of parameters | 322 |
No. of restraints | 13 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.25 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.001 (18) |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control Software, CrystalStructure (Rigaku/MSC, 2004), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Ag1—S1 | 2.3938 (9) | Co1—N5 | 1.975 (3) |
Co1—N3 | 1.960 (3) | Co1—N4 | 1.980 (3) |
Co1—N2 | 1.964 (3) | Co1—S1 | 2.2642 (10) |
Co1—N1 | 1.972 (3) | ||
S1i—Ag1—S1 | 172.38 (5) | N1—Co1—N5 | 175.53 (14) |
N3—Co1—N2 | 175.89 (16) | N4—Co1—S1 | 177.46 (10) |
Symmetry code: (i) −x, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O12ii | 0.90 | 2.30 | 3.14 (2) | 155.4 |
N1—H2···O11 | 0.90 | 2.19 | 3.034 (19) | 156.9 |
N1—H2···O7 | 0.90 | 2.23 | 3.066 (18) | 155.1 |
N2—H3···O15 | 0.90 | 2.04 | 2.899 (5) | 160.1 |
N2—H4···O13iii | 0.90 | 2.28 | 3.057 (19) | 144.2 |
N3—H5···O4 | 0.90 | 2.25 | 3.146 (13) | 174.1 |
N3—H6···O10iv | 0.90 | 2.21 | 3.083 (12) | 161.9 |
N4—H7···O2v | 0.90 | 2.03 | 2.868 (4) | 154.7 |
N4—H8···O7 | 0.90 | 2.49 | 3.117 (16) | 127.5 |
N4—H8···O17v | 0.90 | 2.50 | 3.138 (13) | 127.9 |
N5—H9···O15 | 0.90 | 2.36 | 3.201 (5) | 155.4 |
N5—H10···O16 | 0.90 | 2.25 | 3.079 (6) | 152.2 |
O15—H22···O1v | 0.85 (5) | 1.89 (3) | 2.711 (5) | 162 (7) |
O16—H26···O2v | 0.86 (10) | 2.12 (4) | 2.891 (7) | 149 (7) |
O17—H27···O1vi | 0.85 (2) | 2.2 (2) | 2.822 (12) | 126 (19) |
O17—H28···O1 | 0.85 (2) | 2.12 (12) | 2.884 (12) | 149 (19) |
Symmetry codes: (ii) −x+1/2, y−1/2, −z; (iii) x, y−1, z; (iv) x−1/2, y−1/2, z; (v) −x+1/2, y+1/2, −z+1; (vi) −x, y, −z+1. |
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Thiolato groups coordinated to a metal center possess relatively strong Lewis basicity, which allows them to bind with a second metal center (Konno, 2004). Previously, Konno et al. (2001) reported ΛL-[Co(L-cys-N,S)(en)2]+ (L-cys = L-cysteinate, en = ethylenediamine) reacts with AgNO3 to give an S-bridged (CoIIIAgI)n coordination polymer, {ΛL-[Ag{Co(L-cys-N,S)(en)2}](NO3)2}n.H2O (II). In this compound, the ΛL-[Co(L-cys-N,S)(en)2]+ unit binds with two AgI atoms through sulfur and with another AgI atom through a carboxylate group, to give a sheet-like structure. In this paper, we report on the structure of ΛLΛL-[Ag{Co(L-cys-N,S)(en)2}2](ClO4)3.5H2O (I), which was obtained by the 2:1 reaction of ΛL-[Co(L-cys-N,S)(en)2]+ with AgClO4.
The cation is composed of two octahedral [Co(L-cys-N,S)(en)2]+ units that are linked by an AgI atom through the S atoms to form a linear-type S-bridged CoIIIAgICoIII trinuclear structure in [Ag{Co(L-cys-N,S)(en)2}2]3+ (Fig. 1). The AgI atom, which is locate on a twofold axis, adopts an almost linear coordination geometry, unlike an angular geometry found in (II) (S—Ag—S = 149.62 (7) °). Furthermore, the Ag—S bonds in (I) are appreciably shorter than those in (II) (Ag—S = 2.501 (3), 2.511 (3) Å). These differences are ascribed to the fact that the AgI center in (II) is coordinated by a carboxylate group (Ag—O = 2.598 (1), 2.490 (8) Å), besides two thiolato groups. Other bond distances and angles in (I) are similar to those in (II) (Table 1). The two [Co(L-cys-N,S)(en)2]+ units in (I) have an Λ configuration because of the configuration of the mononuclear ΛL-[Co(L-cys-N,S)(en)2]+ reactant. The L-cys N,S-chelate ring adopts a λ conformation; the two en N,N-chelate rings adopt δ and λ conformations.
The cation is connected with to four adjacent cations through N–H···O hydrogen bonds between coordinated amine groups and non-coordinated carboxylate groups to give a sheet-like structure (Fig. 2). The sheets are further linked through the perchlorate anions and water molecules through hydrogen bonds.