The structure of the novel cadmium phenanthroline thiosulfate poly[[(1,10-phenanthroline-κ
2N,
N′)cadmium(II)]-μ
3-thiosulfato-κ
3S:
S:
O], [Cd(S
2O
3)(C
12H
8N
2)]
n, with a pentacoordinated Cd centre, is reported. It forms linear chains built up around a 2
1 axis and is isostructural with the known bipyridine homologue. The structure is also compared with a previously reported closely related monoaqua monohydrated phase, where the Cd
2+ cation is hexacoordinated. The incidence of weak C—H
O interactions in the determination of its general packing properties is discussed.
Supporting information
CCDC reference: 233114
In a trial to obtain a cadmium dithionite, a methanolic solution of phenanthroline monohydrate was allowed to diffuse into a water solution of cadmium acetate dihydrate and sodium dithionite (all concentrations being 0.025M). Due to the unplanned dithionite decomposition, colourless prisms of the title thiosulfate, (I), suitable for X-ray diffraction, appeared after a few days.
All H atoms in the structure were defined by the stereochemistry and they were accordingly located at their calculated positions riding on their host atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick,1994); software used to prepare material for publication: SHELXL97.
(1,10-phenantholine-
κ2N,
N')(µ
3-thiosulfato-
κ3S:
S:
O)cadmium(II)
top
Crystal data top
[Cd(S2O3)(C12H8N2)] | F(000) = 792 |
Mr = 404.72 | Dx = 2.148 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 6.5200 (13) Å | θ = 7.5–15° |
b = 10.172 (2) Å | µ = 2.09 mm−1 |
c = 18.871 (4) Å | T = 293 K |
V = 1251.6 (4) Å3 | Needle, colourless |
Z = 4 | 0.50 × 0.15 × 0.15 mm |
Data collection top
Rigaku AFC-7S diffractometer | 2013 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 27.5°, θmin = 2.2° |
ω/2θ scans | h = −1→8 |
Absorption correction: ψ-scan MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) | k = −1→13 |
Tmin = 0.35, Tmax = 0.73 | l = −1→24 |
2276 measured reflections | 3 standard reflections every 150 reflections |
2093 independent reflections | intensity decay: <3% |
Refinement top
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)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0894P)2 + 7.6222P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.008 |
2093 reflections | Δρmax = 1.21 e Å−3 |
182 parameters | Δρmin = −1.04 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.43 (7) |
Crystal data top
[Cd(S2O3)(C12H8N2)] | V = 1251.6 (4) Å3 |
Mr = 404.72 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.5200 (13) Å | µ = 2.09 mm−1 |
b = 10.172 (2) Å | T = 293 K |
c = 18.871 (4) Å | 0.50 × 0.15 × 0.15 mm |
Data collection top
Rigaku AFC-7S diffractometer | 2013 reflections with I > 2σ(I) |
Absorption correction: ψ-scan MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) | Rint = 0.018 |
Tmin = 0.35, Tmax = 0.73 | 3 standard reflections every 150 reflections |
2276 measured reflections | intensity decay: <3% |
2093 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.140 | Δρmax = 1.21 e Å−3 |
S = 1.01 | Δρmin = −1.04 e Å−3 |
2093 reflections | Absolute structure: Flack (1983) |
182 parameters | Absolute structure parameter: 0.43 (7) |
0 restraints | |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cd | 0.68554 (10) | 0.35218 (6) | 0.44820 (3) | 0.0310 (2) | |
S1 | 1.0076 (3) | 0.3703 (2) | 0.52507 (11) | 0.0318 (4) | |
S2 | 1.2289 (3) | 0.46992 (19) | 0.46632 (10) | 0.0289 (4) | |
O1 | 1.2529 (14) | 0.4036 (7) | 0.3985 (3) | 0.0493 (19) | |
O2 | 1.1586 (12) | 0.6055 (7) | 0.4621 (4) | 0.0481 (17) | |
O3 | 1.4146 (10) | 0.4554 (7) | 0.5101 (3) | 0.0385 (14) | |
N1 | 0.7066 (13) | 0.5455 (7) | 0.3847 (4) | 0.0316 (15) | |
N2 | 0.7294 (12) | 0.2975 (7) | 0.3296 (4) | 0.0289 (14) | |
C1 | 0.6982 (16) | 0.6676 (9) | 0.4119 (5) | 0.042 (2) | |
H1A | 0.6820 | 0.6776 | 0.4606 | 0.050* | |
C2 | 0.7129 (18) | 0.7810 (9) | 0.3694 (6) | 0.047 (3) | |
H2A | 0.7068 | 0.8643 | 0.3897 | 0.057* | |
C3 | 0.7361 (17) | 0.7667 (11) | 0.2989 (6) | 0.047 (3) | |
H3A | 0.7453 | 0.8410 | 0.2703 | 0.057* | |
C4 | 0.7464 (14) | 0.6424 (10) | 0.2683 (5) | 0.0362 (18) | |
C5 | 0.7762 (17) | 0.6216 (12) | 0.1938 (5) | 0.048 (3) | |
H5A | 0.7873 | 0.6934 | 0.1635 | 0.057* | |
C6 | 0.7881 (16) | 0.4989 (11) | 0.1675 (5) | 0.043 (2) | |
H6A | 0.8086 | 0.4878 | 0.1191 | 0.052* | |
C7 | 0.7702 (14) | 0.3843 (10) | 0.2118 (4) | 0.0347 (19) | |
C8 | 0.7736 (17) | 0.2551 (11) | 0.1851 (5) | 0.045 (2) | |
H8A | 0.7885 | 0.2398 | 0.1367 | 0.055* | |
C9 | 0.7548 (15) | 0.1534 (12) | 0.2310 (5) | 0.044 (2) | |
H9A | 0.7561 | 0.0672 | 0.2146 | 0.053* | |
C10 | 0.7335 (15) | 0.1794 (9) | 0.3033 (5) | 0.038 (2) | |
H10A | 0.7218 | 0.1086 | 0.3343 | 0.046* | |
C11 | 0.7437 (13) | 0.4027 (9) | 0.2851 (4) | 0.0292 (17) | |
C12 | 0.7343 (13) | 0.5335 (9) | 0.3127 (5) | 0.0303 (18) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd | 0.0341 (3) | 0.0341 (3) | 0.0247 (3) | 0.0010 (3) | 0.0016 (2) | 0.0042 (2) |
S1 | 0.0296 (9) | 0.0348 (10) | 0.0310 (9) | 0.0003 (9) | 0.0008 (8) | 0.0102 (8) |
S2 | 0.0336 (10) | 0.0273 (8) | 0.0257 (9) | −0.0017 (8) | 0.0018 (8) | 0.0011 (7) |
O1 | 0.067 (5) | 0.051 (4) | 0.030 (3) | −0.008 (4) | 0.016 (3) | −0.013 (3) |
O2 | 0.051 (4) | 0.035 (3) | 0.059 (4) | 0.006 (3) | 0.003 (4) | 0.014 (3) |
O3 | 0.032 (3) | 0.046 (3) | 0.038 (3) | 0.005 (3) | −0.001 (3) | −0.001 (3) |
N1 | 0.034 (4) | 0.028 (3) | 0.033 (3) | 0.004 (3) | −0.002 (3) | 0.001 (3) |
N2 | 0.032 (4) | 0.027 (3) | 0.027 (3) | 0.005 (3) | 0.003 (3) | 0.001 (3) |
C1 | 0.042 (5) | 0.042 (5) | 0.042 (4) | −0.003 (5) | −0.004 (4) | −0.004 (4) |
C2 | 0.045 (6) | 0.023 (4) | 0.075 (7) | −0.007 (4) | −0.008 (6) | 0.005 (4) |
C3 | 0.040 (6) | 0.043 (5) | 0.059 (6) | −0.006 (5) | −0.009 (5) | 0.009 (5) |
C4 | 0.032 (4) | 0.038 (4) | 0.039 (4) | 0.001 (4) | −0.002 (4) | 0.000 (4) |
C5 | 0.043 (5) | 0.063 (6) | 0.037 (5) | 0.012 (5) | 0.001 (4) | 0.028 (5) |
C6 | 0.038 (5) | 0.060 (6) | 0.031 (4) | 0.003 (5) | −0.006 (4) | 0.013 (4) |
C7 | 0.027 (4) | 0.051 (5) | 0.026 (4) | 0.000 (4) | 0.001 (3) | 0.003 (3) |
C8 | 0.040 (6) | 0.061 (6) | 0.035 (5) | 0.000 (5) | −0.001 (4) | −0.011 (4) |
C9 | 0.034 (4) | 0.054 (5) | 0.044 (5) | −0.003 (5) | 0.001 (4) | −0.026 (5) |
C10 | 0.035 (5) | 0.034 (4) | 0.046 (5) | 0.002 (4) | 0.009 (4) | 0.009 (4) |
C11 | 0.025 (4) | 0.041 (4) | 0.022 (3) | 0.002 (3) | −0.002 (3) | −0.001 (3) |
C12 | 0.022 (4) | 0.036 (4) | 0.033 (4) | 0.001 (4) | −0.002 (3) | 0.007 (3) |
Geometric parameters (Å, º) top
Cd—S1i | 2.593 (2) | C3—C4 | 1.393 (15) |
Cd—S1 | 2.559 (2) | C3—H3A | 0.9300 |
Cd—N1 | 2.306 (7) | C4—C12 | 1.391 (12) |
Cd—N2 | 2.323 (7) | C4—C5 | 1.434 (13) |
Cd—O3ii | 2.363 (7) | C5—C6 | 1.345 (16) |
S1—S2 | 2.083 (3) | C5—H5A | 0.9300 |
S2—O2 | 1.455 (7) | C6—C7 | 1.439 (13) |
S2—O1 | 1.455 (6) | C6—H6A | 0.9300 |
S2—O3 | 1.473 (7) | C7—C11 | 1.407 (12) |
N1—C1 | 1.345 (12) | C7—C8 | 1.408 (14) |
N1—C12 | 1.376 (11) | C8—C9 | 1.356 (16) |
N2—C10 | 1.300 (11) | C8—H8A | 0.9300 |
N2—C11 | 1.364 (11) | C9—C10 | 1.397 (13) |
C1—C2 | 1.408 (13) | C9—H9A | 0.9300 |
C1—H1A | 0.9300 | C10—H10A | 0.9300 |
C2—C3 | 1.347 (17) | C11—C12 | 1.430 (13) |
C2—H2A | 0.9300 | | |
| | | |
N1—Cd—S1i | 150.7 (2) | C2—C3—H3A | 119.5 |
N2—Cd—S1i | 91.91 (18) | C4—C3—H3A | 119.5 |
O3ii—Cd—S1i | 87.55 (18) | C12—C4—C3 | 118.0 (8) |
S1—Cd—S1i | 108.66 (5) | C12—C4—C5 | 118.8 (9) |
N1—Cd—N2 | 72.4 (2) | C3—C4—C5 | 123.2 (10) |
N1—Cd—O3ii | 85.5 (3) | C6—C5—C4 | 120.4 (9) |
N2—Cd—O3ii | 132.4 (2) | C6—C5—H5A | 119.8 |
N1—Cd—S1 | 100.6 (2) | C4—C5—H5A | 119.8 |
N2—Cd—S1 | 117.5 (2) | C5—C6—C7 | 122.2 (9) |
O3ii—Cd—S1 | 107.52 (17) | C5—C6—H6A | 118.9 |
S2—S1—Cd | 107.57 (10) | C7—C6—H6A | 118.9 |
O2—S2—O1 | 115.1 (5) | C11—C7—C8 | 118.6 (9) |
O2—S2—O3 | 112.7 (4) | C11—C7—C6 | 118.3 (9) |
O1—S2—O3 | 111.0 (5) | C8—C7—C6 | 123.1 (9) |
O2—S2—S1 | 105.8 (3) | C9—C8—C7 | 118.8 (9) |
O1—S2—S1 | 108.5 (3) | C9—C8—H8A | 120.6 |
O3—S2—S1 | 102.8 (3) | C7—C8—H8A | 120.6 |
C1—N1—C12 | 117.6 (8) | C8—C9—C10 | 119.3 (10) |
C1—N1—Cd | 125.9 (6) | C8—C9—H9A | 120.3 |
C12—N1—Cd | 116.4 (6) | C10—C9—H9A | 120.3 |
C10—N2—C11 | 119.3 (7) | N2—C10—C9 | 123.3 (9) |
C10—N2—Cd | 126.3 (6) | N2—C10—H10A | 118.3 |
C11—N2—Cd | 114.4 (5) | C9—C10—H10A | 118.3 |
N1—C1—C2 | 122.4 (9) | N2—C11—C7 | 120.7 (8) |
N1—C1—H1A | 118.8 | N2—C11—C12 | 120.2 (7) |
C2—C1—H1A | 118.8 | C7—C11—C12 | 119.2 (8) |
C3—C2—C1 | 118.8 (10) | N1—C12—C4 | 122.2 (8) |
C3—C2—H2A | 120.6 | N1—C12—C11 | 116.6 (8) |
C1—C2—H2A | 120.6 | C4—C12—C11 | 121.2 (8) |
C2—C3—C4 | 120.9 (10) | | |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | [Cd(S2O3)(C12H8N2)] |
Mr | 404.72 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 6.5200 (13), 10.172 (2), 18.871 (4) |
V (Å3) | 1251.6 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.09 |
Crystal size (mm) | 0.50 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | ψ-scan MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) |
Tmin, Tmax | 0.35, 0.73 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2276, 2093, 2013 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.140, 1.01 |
No. of reflections | 2093 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.21, −1.04 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.43 (7) |
Selected bond angles (º) topN1—Cd—S1i | 150.7 (2) | N1—Cd—O3ii | 85.5 (3) |
N2—Cd—S1i | 91.91 (18) | N2—Cd—O3ii | 132.4 (2) |
O3ii—Cd—S1i | 87.55 (18) | N1—Cd—S1 | 100.6 (2) |
S1—Cd—S1i | 108.66 (5) | N2—Cd—S1 | 117.5 (2) |
N1—Cd—N2 | 72.4 (2) | O3ii—Cd—S1 | 107.52 (17) |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x−1, y, z. |
Coordination bond lengths (Å) and bond valences for compounds (I), (II) and (III) top | Bond Lengths | | | Bond Valences | | |
| (I) | (II) | (III) | (I) | (II) | (III) |
| | | | | | |
S1-Cd | 2.559 (2) | 2.595 (2) | 2.5744 (9) | 0.502 | 0.455 | 0.482 |
S1i-Cd | 2.593 (2) | 2.698 (2) | 2.5866 (8) | 0.458 | 0.345 | 0.466 |
O3ii-Cd | 2.364 (7) | 2.549 (4) | 2.365 (2) | 0.288 | 0.175 | 0.288 |
N1-Cd | 2.307 (7) | 2.351 (4) | 2.311 (3) | 0.391 | 0.348 | 0.386 |
N2-Cd | 2.324 (7) | 2.346 (4) | 2.310 (3) | 0.374 | 0.352 | 0.378 |
O1W-Cd | | 2.272 (4) | | | 0.370 | |
| | | | —– | —– | —– |
| | | | 2.013 | 2.045 | 2.000 |
| | | | | | |
S1-S2 | 2.0825 (3) | 2.054 (2) | 2.0840 (11) | | | |
S2-O1 | 1.455 (6) | 1.463 (4) | 1.445 (2) | | | |
S2-O2 | 1.455 (7) | 1.469 (4) | 1.454 (2) | | | |
S2-O3 | 1.474 (7) | 1.466 (4) | 1.478 (2) | | | |
Symmetry codes: see Table 1. |
Hydrogen-bond geometry (Å, °) in (I) and (III) topD-H···A | D-H | H···A | D···A | D-H···A |
(I) | | | | |
C1-H1A···O2i | 0.93 | 2.65 | 3.323 (12) | 130 |
C5-H5A···O1ii | 0.93 | 2.45 | 3.357 (12) | 166 |
C8-H8A···O2iii | 0.93 | 2.34 | 3.195 (13) | 154 |
C9-H9A···O1iii | 0.93 | 2.71 | 3.526 (12) | 147 |
| | | | |
(III) | | | | |
C4-H4A···O2iv | 0.93 | 2.66 | 3.587 (9) | 179 |
C7-H7A···O2iv | 0.93 | 2.49 | 3.413 (9) | 171 |
C8-H8A···O3v | 0.93 | 2.61 | 3.435 (8) | 148 |
C9-H9A···O1vi | 0.93 | 2.68 | 3.601 (9) | 169 |
Symmetry codes: (i) x − 3/2, −y + 1/2, z + 1/2; (ii) −x + 2, y + 1/2, −z + 1/2; (iii) −x + 2, y − 1/2, −z + 1/2; (iv) −x − 1, −y − 1, −z − 2; (v) x − 1/2, −y − 3/2, z − 1/2; (vi) −x − 2, −y − 1, −z − 2. Codes (i)-(iii) correspond to compound (I) [space group P212121]. Codes (iv)-(vi) correspond to compound (III) [space group P21/n] |
The dithionite anion is quite unstable even in the absence of air and it can gradually decompose, breaking up easily into thiosulfate plus pyrosulfite (Remy, 1956). During an exploration of the Cd+2-dithionite-phenanthroline system, and as part of a search for a synthetic route to the elusive cadmium dithionite complexes, we unwittingly obtained the title novel anhydrous five-coordinate cadmium phenanthroline thiosulfate, (I). The compound is polymeric and crystallizes in the form of double chains, or strips, built up around the 21 axis running along a. This motif is not unusual, being shared by a number of related compounds, viz. the aqua monohydrated six-coordinate cadmium phenanthroline (phen) thiosulfate, (II) (Baggio et al., 1998) and the anhydrous cadmium bipyridine (bpy) thiosulfate, (III) (Baggio et al., 1997). In spite of belonging to an enanthiomorphic class (222), no definite handedness could be ascribed to the structure of (I), the best model for refinement being a racemic twin with a 0.43 (7):0.57 (7) ratio. \sch
A displacement ellipsoid plot of the ensemble (I) is shown in Fig 1. The bonds to the five-coordinate Cd centre are provided by two N atoms from the chelating dinitrogenated base, and two S atoms and one O atom from three different thiosulfate groups. The anion acts in two different bridging modes: as a short bridge through the terminal S1 atom (shared by two different Cd centres) and as a long bridge through the whole S1—S2—O3 arm. The geometry of the anion is normal for this type of coordination. Comparison of (I) with the closely related structures (II) and (III) reveals that, beyond the overall similarities, there are some minor subtle points differentiating them.
Structure (II) presents a six-coordinate Cd centre surrounded by the same ligands as in (I) but with the sixth place occupied by one aqua molecule and with a stabilizing hydration water molecule. In spite of the obvious differences that the larger coordination number introduces, the general structural trend is the same in both compounds: there are one-dimensional chains built up along one of the crystallographic axes, the axial length along the chains being defined by the doubling of the motif through the 21 axis, and with interleaving of the phen groups normal to this axis in the usual gear-like mode. As expected, the larger coordination number in (II) results in an elongation of the coordination bonds (Table 2). The effect is reflected in the concomitant enlargement of the associated cell parameter, which in (II) is ~8% larger than in (I) [7.051 (2) versus 6.520 (1) Å]. The relative weakening of the coordination bonds can be quantitatively analyzed in terms of the `bond valence' (Brown & Altermatt, 1985) associated with each of these interactions, those corresponding to bonds in (II) being consistently smaller than their homologues in (I) (Table 2). In both cases, the sum around the cation (2.013 and 2.045) is consistent with the divalent character of Cd. These differences in coordination strength propagate to the thiosulfate group: the larger involvement in coordination of atom S1 in structure (I) slightly weakens the S1—S2 bond in the anion, and this is reflected in its consequent enlargement and the associated evenness of the S—O bond lengths compared with those in (II) (Table 2).
Compound (III) is the bpy homologue of (I). Although it presents an almost exactly isostructural double chain (see Fig 2 for an overlap view) and a very similar density [2.16, versus 2.15 Mgm−3 in (I)], it crystallizes in a different space group (P21/n). Even though all the strips run in a unique crystallographic 21 screw-axis direction in both unit cells [the a axis in (I) and the b axis in (III)], two different orientations for the strip widths appear in the former (Fig. 3) while a single one appears in the latter, due to the different symmetry-element dispositions. This enables different ways of interaction between neighbouring chains. In fact, the weak C—H···O bonds present in the structures (Table 3) involve some H atoms which exist in just one of the ligands but not in the other. Thus, atom H4 in bpy has no counterpart in phen and atom H5A (C5) in phen has no counterpart in bpy, both H atoms being actively engaged in C—H···O bonds. Thus it seems that it is the different geometry (and, accordingly, the external hydrogen `shield' of each ligand) which favours one or the other packing mode. This is not a novel fact; we have recently reported (Harvey et al., 2003) a very similar situation where the presence (or absence) of some H atoms in the bpy or phen ligands in two otherwise absolutely isostructural compounds determined differences in weak interactions leading to measurable effects on some crystallographic properties, viz. the cell dimensions. In the present case, these modifications are more extensive, involving not only the cell parameters but also the crystal system and space group as well. The planar aromatic groups stack in the usual gear-like mode, leading to the classical 6.5 Å spacing. Here, however, the offset is rather large (Fig. 3), with almost no overlapping areas along the normal to the aromatic planes.