Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108028072/ga3106sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108028072/ga3106Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108028072/ga3106IIsup3.hkl |
CCDC references: 687109; 687110
To prepare compound (I), a mixture of AgNO3 (56 mg, 0.33 mmol), 3-sulfophenylphosphonic acid (67 mg, 0.28 mmol) and 4,4'-bipy (52 mg, 0.33 mmol) in distilled water (10 ml) was placed in a Parr Teflon-lined autoclave (23 ml) and heated at 423 K for 4 d. Colourless column-shaped crystals of (I) were collected in a ca 72% yield based on Ag. Analysis, calculated for C26H27N4O9P1S1Ag2: C 38.16, H 3.33, N 6.85%; found: C 38.10, H 3.40, N 6.82%. IR data (KBr, ν, cm-1): 3429 (s), 3039 (m), 1599 (s), 1528 (m), 1486 (m), 1406 (m), 1217 (vs), 1190 (vs), 1107 (s), 1071 (m), 1037 (s), 995 (m), 904 (m), 851 (m), 803 (s), 732 (m), 689 (m), 618 (m), 564 (m), 531 (m).
To prepare compound (II), a mixture of CoCO3 (36 mg, 0.30 mmol), 3-sulfophenylphosphonic acid (83 mg, 0.35 mmol) and 4,4'-bipy (47 mg, 0.30 mmol) in distilled water (10 ml) was placed in a Parr Teflon-lined autoclave (23 ml) and heated at 413 K for 4 d. Orange brick-shaped crystals of (II) were collected in a ca 55% yield based on Co. Analysis, calculated for C16H21N2O10P1S1Co1: C 36.72, H 4.04, N 5.35%; found: C 36.68, H 4.11, N 5.31%. IR data (KBr, ν, cm-1): 3401 (s), 3071 (m), 1607 (s), 1534 (m), 1490 (m), 1414 (m), 1219 (m), 1171 (s), 1100 (vs), 1067 (s), 1030 (vs), 997 (s), 862 (m), 810 (m), 732 (m), 688 (m), 618 (m), 559 (m).
H atoms bonded to C atoms were positioned geometrically (C—H = 0.93 Å) and included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C). Water H atoms and H atoms of protonated PO3 were located in a difference map and refined with Uiso(H) = 1.5Ueq(O). Atoms C7, C8, C15 and C16 of the same benzene ring in (I) were found to be disordered and were modelled over two sets of positions (A and B), giving refined occupancies of 0.531 (6) and 0.469 (4)%, respectively. The anisotropic displacement parameters of atoms C15B and C16B were restrained due to their larger thermal parameter.
For both compounds, data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Ag2(C10H8N2)2](C6H5O6PS)·3H2O | Dx = 1.892 Mg m−3 |
Mr = 818.29 | Melting point: not measured K |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 7948 reflections |
a = 14.539 (3) Å | θ = 2.0–27.5° |
b = 17.472 (4) Å | µ = 1.55 mm−1 |
c = 22.623 (4) Å | T = 293 K |
V = 5747 (2) Å3 | Column, colourless |
Z = 8 | 0.50 × 0.12 × 0.12 mm |
F(000) = 3264 |
Rigaku Mercury70 diffractometer | 6577 independent reflections |
Radiation source: fine-focus sealed tube | 6186 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ω scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan (CrystalClear; Molecular Structure Corporation & Rigaku, 2000) | h = −18→18 |
Tmin = 0.796, Tmax = 0.834 | k = −22→22 |
42765 measured reflections | l = −28→29 |
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)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.027P)2 + 8.9577P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
6577 reflections | Δρmax = 0.55 e Å−3 |
434 parameters | Δρmin = −0.44 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00031 (4) |
[Ag2(C10H8N2)2](C6H5O6PS)·3H2O | V = 5747 (2) Å3 |
Mr = 818.29 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 14.539 (3) Å | µ = 1.55 mm−1 |
b = 17.472 (4) Å | T = 293 K |
c = 22.623 (4) Å | 0.50 × 0.12 × 0.12 mm |
Rigaku Mercury70 diffractometer | 6577 independent reflections |
Absorption correction: multi-scan (CrystalClear; Molecular Structure Corporation & Rigaku, 2000) | 6186 reflections with I > 2σ(I) |
Tmin = 0.796, Tmax = 0.834 | Rint = 0.023 |
42765 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 3 restraints |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.55 e Å−3 |
6577 reflections | Δρmin = −0.44 e Å−3 |
434 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 | Occ. (<1) | |
Ag1 | 0.11592 (2) | 0.52605 (2) | 0.263230 (10) | 0.06095 (10) | |
Ag2 | 0.111672 (17) | 0.004184 (14) | 0.494212 (9) | 0.04443 (8) | |
S1 | −0.01092 (4) | 0.21176 (4) | 0.48855 (3) | 0.03244 (14) | |
P1 | 0.13992 (5) | 0.28290 (4) | 0.27070 (3) | 0.03245 (15) | |
N1 | 0.11647 (18) | 0.52311 (15) | 0.35801 (10) | 0.0421 (6) | |
N2 | 0.12518 (18) | 0.48507 (15) | 0.66924 (10) | 0.0441 (6) | |
N3 | 0.12372 (16) | −0.00461 (13) | 0.40033 (9) | 0.0356 (5) | |
N4 | 0.12292 (17) | −0.01041 (13) | 0.08803 (9) | 0.0372 (5) | |
C1 | 0.08605 (17) | 0.23371 (13) | 0.44416 (10) | 0.0275 (5) | |
C2 | 0.07593 (17) | 0.24737 (14) | 0.38402 (10) | 0.0283 (5) | |
H2A | 0.0178 | 0.2460 | 0.3670 | 0.034* | |
C3 | 0.15287 (17) | 0.26311 (14) | 0.34914 (10) | 0.0287 (5) | |
C4 | 0.23881 (18) | 0.26421 (17) | 0.37578 (11) | 0.0381 (6) | |
H4A | 0.2907 | 0.2742 | 0.3530 | 0.046* | |
C5 | 0.24829 (19) | 0.25064 (18) | 0.43591 (13) | 0.0427 (7) | |
H5A | 0.3064 | 0.2518 | 0.4531 | 0.051* | |
C6 | 0.17227 (19) | 0.23539 (16) | 0.47053 (11) | 0.0366 (6) | |
H6A | 0.1787 | 0.2264 | 0.5108 | 0.044* | |
C7A | 0.1496 (11) | 0.4583 (4) | 0.3829 (3) | 0.043 (2) | 0.58 (3) |
H7A | 0.1692 | 0.4187 | 0.3585 | 0.051* | 0.58 (3) |
C8A | 0.1554 (10) | 0.4490 (5) | 0.4432 (4) | 0.0392 (19) | 0.58 (3) |
H8A | 0.1781 | 0.4036 | 0.4589 | 0.047* | 0.58 (3) |
C7B | 0.1045 (14) | 0.4563 (7) | 0.3862 (5) | 0.045 (3) | 0.42 (3) |
H7B | 0.0904 | 0.4137 | 0.3633 | 0.053* | 0.42 (3) |
C8B | 0.1113 (15) | 0.4460 (7) | 0.4459 (5) | 0.041 (3) | 0.42 (3) |
H8B | 0.1057 | 0.3974 | 0.4624 | 0.049* | 0.42 (3) |
C9 | 0.12655 (18) | 0.50898 (14) | 0.48123 (11) | 0.0314 (5) | |
C10 | 0.12840 (18) | 0.50078 (15) | 0.54629 (11) | 0.0316 (5) | |
C11 | 0.1402 (3) | 0.43129 (18) | 0.57361 (13) | 0.0534 (8) | |
H11A | 0.1492 | 0.3875 | 0.5509 | 0.064* | |
C12 | 0.1389 (3) | 0.4258 (2) | 0.63420 (14) | 0.0649 (8) | |
H12A | 0.1480 | 0.3781 | 0.6513 | 0.078* | |
C13 | 0.1154 (3) | 0.5524 (2) | 0.64329 (14) | 0.0649 (8) | |
H13A | 0.1075 | 0.5953 | 0.6672 | 0.078* | |
C14 | 0.1162 (3) | 0.56266 (19) | 0.58311 (13) | 0.0689 (12) | |
H14A | 0.1086 | 0.6114 | 0.5673 | 0.083* | |
C15A | 0.0996 (8) | 0.5748 (7) | 0.4534 (6) | 0.037 (2) | 0.58 (3) |
H15A | 0.0842 | 0.6176 | 0.4758 | 0.044* | 0.58 (3) |
C16A | 0.0951 (9) | 0.5783 (8) | 0.3922 (6) | 0.039 (2) | 0.58 (3) |
H16A | 0.0753 | 0.6238 | 0.3750 | 0.047* | 0.58 (3) |
C15B | 0.1295 (14) | 0.5809 (11) | 0.4549 (9) | 0.040 (3) | 0.42 (3) |
H15B | 0.1362 | 0.6245 | 0.4781 | 0.048* | 0.42 (3) |
C16B | 0.1226 (14) | 0.5878 (11) | 0.3946 (8) | 0.040 (3) | 0.42 (3) |
H16B | 0.1219 | 0.6363 | 0.3777 | 0.048* | 0.42 (3) |
C17 | 0.1516 (2) | 0.05572 (16) | 0.36856 (11) | 0.0392 (6) | |
H17A | 0.1684 | 0.1002 | 0.3884 | 0.047* | |
C18 | 0.1564 (2) | 0.05479 (15) | 0.30776 (11) | 0.0380 (6) | |
H18A | 0.1760 | 0.0981 | 0.2875 | 0.046* | |
C19 | 0.13214 (18) | −0.01066 (14) | 0.27667 (11) | 0.0308 (5) | |
C20 | 0.13086 (18) | −0.01127 (14) | 0.21143 (11) | 0.0304 (5) | |
C21 | 0.1141 (2) | 0.05544 (16) | 0.18024 (12) | 0.0426 (7) | |
H21A | 0.1052 | 0.1013 | 0.2003 | 0.051* | |
C22 | 0.1106 (2) | 0.05355 (16) | 0.11946 (12) | 0.0458 (7) | |
H22A | 0.0992 | 0.0989 | 0.0993 | 0.055* | |
C23 | 0.1400 (2) | −0.07456 (17) | 0.11810 (12) | 0.0467 (7) | |
H23A | 0.1492 | −0.1196 | 0.0970 | 0.056* | |
C24 | 0.1446 (2) | −0.07733 (16) | 0.17894 (12) | 0.0433 (7) | |
H24A | 0.1569 | −0.1234 | 0.1980 | 0.052* | |
C25 | 0.1046 (2) | −0.07358 (15) | 0.31007 (11) | 0.0392 (6) | |
H25A | 0.0887 | −0.1191 | 0.2914 | 0.047* | |
C26 | 0.1008 (2) | −0.06836 (16) | 0.37082 (12) | 0.0416 (7) | |
H26A | 0.0815 | −0.1109 | 0.3922 | 0.050* | |
O1 | −0.00692 (16) | 0.13015 (12) | 0.49898 (10) | 0.0531 (6) | |
O1W | −0.2535 (2) | 0.2516 (2) | 0.38081 (12) | 0.0703 (8) | |
H11 | −0.202 (4) | 0.242 (3) | 0.398 (2) | 0.105* | |
H12 | −0.241 (4) | 0.256 (3) | 0.349 (2) | 0.105* | |
O2 | −0.00010 (16) | 0.25587 (15) | 0.54226 (9) | 0.0568 (6) | |
O2W | −0.0040 (2) | 0.24892 (17) | 0.66573 (12) | 0.0663 (7) | |
H21 | 0.011 (3) | 0.250 (3) | 0.631 (2) | 0.099* | |
H22 | 0.044 (4) | 0.262 (3) | 0.678 (2) | 0.099* | |
O3 | −0.09055 (14) | 0.23458 (15) | 0.45456 (9) | 0.0552 (6) | |
O3W | 0.3752 (2) | 0.18899 (18) | 0.25093 (13) | 0.0672 (8) | |
H31 | 0.401 (4) | 0.206 (3) | 0.274 (2) | 0.101* | |
H32 | 0.326 (4) | 0.219 (3) | 0.250 (2) | 0.101* | |
O4 | 0.08479 (15) | 0.21668 (11) | 0.24432 (8) | 0.0398 (4) | |
H4 | 0.0000 | 0.223 (3) | 0.2500 | 0.060* | |
O5 | 0.08278 (14) | 0.35699 (10) | 0.26710 (8) | 0.0385 (4) | |
H5 | 0.0000 | 0.348 (3) | 0.2500 | 0.058* | |
O6 | 0.23315 (15) | 0.28959 (14) | 0.24400 (9) | 0.0525 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ag1 | 0.07049 (18) | 0.0959 (2) | 0.01643 (12) | 0.00276 (15) | −0.00092 (10) | −0.00254 (11) |
Ag2 | 0.06214 (15) | 0.05730 (15) | 0.01386 (10) | −0.00112 (11) | 0.00122 (9) | −0.00027 (8) |
S1 | 0.0391 (3) | 0.0384 (3) | 0.0198 (3) | 0.0014 (3) | 0.0049 (2) | 0.0009 (2) |
P1 | 0.0406 (4) | 0.0379 (3) | 0.0188 (3) | −0.0024 (3) | 0.0021 (3) | 0.0030 (2) |
N1 | 0.0589 (15) | 0.0484 (14) | 0.0190 (11) | −0.0034 (12) | −0.0009 (10) | −0.0028 (9) |
N2 | 0.0577 (15) | 0.0571 (15) | 0.0177 (11) | −0.0049 (12) | −0.0015 (10) | 0.0028 (10) |
N3 | 0.0527 (14) | 0.0390 (12) | 0.0152 (10) | 0.0045 (10) | 0.0000 (9) | 0.0015 (8) |
N4 | 0.0548 (14) | 0.0416 (12) | 0.0152 (10) | 0.0038 (10) | 0.0005 (9) | −0.0017 (8) |
C1 | 0.0356 (12) | 0.0263 (11) | 0.0204 (11) | −0.0003 (9) | 0.0002 (9) | 0.0002 (9) |
C2 | 0.0307 (12) | 0.0332 (12) | 0.0210 (11) | 0.0008 (10) | −0.0028 (9) | 0.0015 (9) |
C3 | 0.0349 (12) | 0.0308 (12) | 0.0205 (11) | −0.0010 (10) | 0.0000 (10) | 0.0024 (9) |
C4 | 0.0338 (13) | 0.0492 (16) | 0.0313 (14) | −0.0076 (11) | 0.0014 (11) | 0.0018 (11) |
C5 | 0.0336 (13) | 0.0601 (18) | 0.0345 (14) | −0.0048 (13) | −0.0108 (11) | 0.0011 (13) |
C6 | 0.0457 (15) | 0.0426 (14) | 0.0216 (12) | 0.0019 (12) | −0.0058 (11) | 0.0020 (10) |
C7A | 0.068 (6) | 0.040 (3) | 0.019 (2) | 0.005 (4) | 0.006 (4) | −0.008 (2) |
C8A | 0.061 (6) | 0.030 (3) | 0.026 (3) | 0.005 (4) | 0.003 (4) | −0.0013 (19) |
C7B | 0.059 (8) | 0.044 (5) | 0.030 (4) | 0.007 (5) | 0.003 (5) | −0.013 (3) |
C8B | 0.072 (9) | 0.032 (4) | 0.019 (3) | 0.003 (5) | −0.001 (5) | −0.006 (3) |
C9 | 0.0436 (14) | 0.0338 (13) | 0.0168 (11) | −0.0007 (11) | −0.0010 (10) | −0.0033 (9) |
C10 | 0.0394 (13) | 0.0364 (13) | 0.0188 (12) | −0.0027 (11) | 0.0000 (10) | −0.0028 (9) |
C11 | 0.096 (3) | 0.0379 (15) | 0.0266 (14) | 0.0043 (16) | 0.0037 (15) | −0.0017 (12) |
C12 | 0.122 (2) | 0.0468 (13) | 0.0257 (11) | 0.0051 (14) | 0.0015 (13) | −0.0007 (9) |
C13 | 0.122 (2) | 0.0468 (13) | 0.0257 (11) | 0.0051 (14) | 0.0015 (13) | −0.0007 (9) |
C14 | 0.148 (4) | 0.0364 (16) | 0.0221 (14) | 0.007 (2) | −0.0016 (18) | −0.0048 (12) |
C15A | 0.053 (5) | 0.032 (4) | 0.025 (3) | 0.003 (4) | 0.003 (4) | −0.002 (2) |
C16A | 0.056 (5) | 0.033 (5) | 0.029 (3) | −0.004 (3) | −0.003 (4) | 0.003 (3) |
C15B | 0.067 (8) | 0.033 (3) | 0.021 (3) | −0.015 (5) | −0.001 (5) | −0.002 (2) |
C16B | 0.067 (8) | 0.033 (3) | 0.021 (3) | −0.015 (5) | −0.001 (5) | −0.002 (2) |
C17 | 0.0614 (18) | 0.0336 (13) | 0.0225 (12) | 0.0006 (12) | −0.0023 (12) | −0.0016 (10) |
C18 | 0.0607 (17) | 0.0331 (13) | 0.0200 (12) | −0.0037 (12) | −0.0013 (12) | 0.0023 (10) |
C19 | 0.0447 (14) | 0.0317 (13) | 0.0160 (11) | 0.0042 (10) | 0.0004 (10) | 0.0012 (9) |
C20 | 0.0418 (14) | 0.0343 (13) | 0.0153 (11) | 0.0024 (10) | 0.0013 (9) | 0.0004 (9) |
C21 | 0.077 (2) | 0.0306 (13) | 0.0202 (12) | 0.0047 (13) | −0.0021 (13) | −0.0026 (10) |
C22 | 0.081 (2) | 0.0345 (14) | 0.0221 (13) | 0.0045 (14) | −0.0052 (13) | 0.0029 (10) |
C23 | 0.078 (2) | 0.0396 (15) | 0.0227 (13) | 0.0151 (15) | 0.0002 (13) | −0.0063 (11) |
C24 | 0.075 (2) | 0.0333 (14) | 0.0216 (12) | 0.0140 (14) | −0.0029 (13) | −0.0009 (10) |
C25 | 0.0664 (19) | 0.0314 (13) | 0.0198 (12) | −0.0029 (13) | 0.0006 (12) | −0.0003 (10) |
C26 | 0.0645 (19) | 0.0374 (14) | 0.0229 (13) | −0.0027 (13) | 0.0031 (12) | 0.0051 (10) |
O1 | 0.0661 (14) | 0.0409 (12) | 0.0523 (13) | −0.0069 (10) | 0.0152 (11) | 0.0120 (10) |
O1W | 0.0633 (16) | 0.103 (2) | 0.0443 (15) | 0.0079 (15) | 0.0049 (13) | 0.0088 (15) |
O2 | 0.0685 (15) | 0.0720 (16) | 0.0299 (11) | −0.0028 (12) | 0.0116 (10) | −0.0186 (10) |
O2W | 0.089 (2) | 0.0716 (17) | 0.0388 (13) | −0.0074 (15) | 0.0056 (13) | −0.0009 (12) |
O3 | 0.0370 (11) | 0.0911 (18) | 0.0375 (12) | 0.0118 (11) | 0.0049 (9) | 0.0142 (11) |
O3W | 0.0784 (19) | 0.0725 (18) | 0.0507 (15) | 0.0123 (15) | −0.0045 (13) | −0.0157 (13) |
O4 | 0.0538 (12) | 0.0331 (10) | 0.0326 (10) | 0.0054 (9) | −0.0071 (9) | −0.0077 (8) |
O5 | 0.0569 (11) | 0.0286 (9) | 0.0301 (10) | −0.0037 (8) | −0.0063 (9) | 0.0021 (7) |
O6 | 0.0484 (12) | 0.0772 (16) | 0.0319 (10) | −0.0050 (11) | 0.0109 (9) | 0.0102 (10) |
Ag1—N2i | 2.139 (2) | C9—C15A | 1.369 (13) |
Ag1—N1 | 2.145 (2) | C9—C15B | 1.392 (19) |
Ag2—N4ii | 2.131 (2) | C9—C10 | 1.479 (4) |
Ag2—N3 | 2.137 (2) | C10—C11 | 1.373 (4) |
Ag2—Ag2iii | 3.2610 (8) | C10—C14 | 1.376 (4) |
S1—O3 | 1.446 (2) | C11—C12 | 1.374 (4) |
S1—O1 | 1.446 (2) | C11—H11A | 0.9300 |
S1—O2 | 1.447 (2) | C12—H12A | 0.9300 |
S1—C1 | 1.773 (3) | C13—C14 | 1.373 (4) |
P1—O6 | 1.488 (2) | C13—H13A | 0.9300 |
P1—O4 | 1.529 (2) | C14—H14A | 0.9300 |
P1—O5 | 1.540 (2) | C15A—C16A | 1.389 (10) |
P1—C3 | 1.818 (2) | C15A—H15A | 0.9300 |
N1—C16A | 1.274 (14) | C16A—H16A | 0.9300 |
N1—C7B | 1.342 (14) | C15B—C16B | 1.372 (16) |
N1—C7A | 1.353 (10) | C15B—H15B | 0.9300 |
N1—C16B | 1.404 (18) | C16B—H16B | 0.9300 |
N2—C12 | 1.319 (4) | C17—C18 | 1.377 (3) |
N2—C13 | 1.323 (4) | C17—H17A | 0.9300 |
N2—Ag1iv | 2.139 (2) | C18—C19 | 1.388 (4) |
N3—C17 | 1.339 (3) | C18—H18A | 0.9300 |
N3—C26 | 1.341 (4) | C19—C25 | 1.393 (4) |
N4—C23 | 1.334 (4) | C19—C20 | 1.476 (3) |
N4—C22 | 1.337 (4) | C20—C24 | 1.383 (4) |
N4—Ag2v | 2.131 (2) | C20—C21 | 1.384 (4) |
C1—C6 | 1.389 (4) | C21—C22 | 1.376 (4) |
C1—C2 | 1.389 (3) | C21—H21A | 0.9300 |
C2—C3 | 1.396 (3) | C22—H22A | 0.9300 |
C2—H2A | 0.9300 | C23—C24 | 1.379 (4) |
C3—C4 | 1.387 (4) | C23—H23A | 0.9300 |
C4—C5 | 1.388 (4) | C24—H24A | 0.9300 |
C4—H4A | 0.9300 | C25—C26 | 1.378 (4) |
C5—C6 | 1.380 (4) | C25—H25A | 0.9300 |
C5—H5A | 0.9300 | C26—H26A | 0.9300 |
C6—H6A | 0.9300 | O1W—H11 | 0.87 (5) |
C7A—C8A | 1.375 (11) | O1W—H12 | 0.74 (5) |
C7A—H7A | 0.9300 | O2W—H21 | 0.82 (5) |
C8A—C9 | 1.419 (9) | O2W—H22 | 0.78 (5) |
C8A—H8A | 0.9300 | O3W—H31 | 0.71 (5) |
C7B—C8B | 1.366 (16) | O3W—H32 | 0.88 (5) |
C7B—H7B | 0.9300 | O4—H4 | 1.245 (5) |
C8B—C9 | 1.378 (11) | O5—H5 | 1.273 (6) |
C8B—H8B | 0.9300 | ||
N2i—Ag1—N1 | 172.38 (10) | C15A—C9—C10 | 123.0 (6) |
N4ii—Ag2—N3 | 170.82 (9) | C8B—C9—C10 | 120.1 (6) |
N4ii—Ag2—Ag2iii | 89.93 (7) | C15B—C9—C10 | 120.9 (8) |
N3—Ag2—Ag2iii | 99.10 (6) | C8A—C9—C10 | 121.8 (4) |
O3—S1—O1 | 113.00 (15) | C11—C10—C14 | 116.0 (3) |
O3—S1—O2 | 112.75 (15) | C11—C10—C9 | 122.4 (2) |
O1—S1—O2 | 112.55 (14) | C14—C10—C9 | 121.6 (3) |
O3—S1—C1 | 106.02 (12) | C10—C11—C12 | 120.6 (3) |
O1—S1—C1 | 105.88 (12) | C10—C11—H11A | 119.7 |
O2—S1—C1 | 105.90 (13) | C12—C11—H11A | 119.7 |
O6—P1—O4 | 112.24 (13) | N2—C12—C11 | 123.2 (3) |
O6—P1—O5 | 113.81 (13) | N2—C12—H12A | 118.4 |
O4—P1—O5 | 109.43 (11) | C11—C12—H12A | 118.4 |
O6—P1—C3 | 108.46 (12) | N2—C13—C14 | 123.7 (3) |
O4—P1—C3 | 106.94 (11) | N2—C13—H13A | 118.1 |
O5—P1—C3 | 105.51 (11) | C14—C13—H13A | 118.1 |
C16A—N1—C7B | 109.8 (8) | C13—C14—C10 | 119.9 (3) |
C16A—N1—C7A | 117.9 (7) | C13—C14—H14A | 120.0 |
C7B—N1—C16B | 115.3 (9) | C10—C14—H14A | 120.0 |
C7A—N1—C16B | 113.9 (9) | C9—C15A—C16A | 120.6 (8) |
C16A—N1—Ag1 | 126.0 (6) | C9—C15A—H15A | 119.7 |
C7B—N1—Ag1 | 119.7 (5) | C16A—C15A—H15A | 119.7 |
C7A—N1—Ag1 | 116.0 (4) | N1—C16A—C15A | 124.1 (8) |
C16B—N1—Ag1 | 124.8 (8) | N1—C16A—H16A | 118.0 |
C12—N2—C13 | 116.6 (3) | C15A—C16A—H16A | 118.0 |
C12—N2—Ag1iv | 122.4 (2) | C16B—C15B—C9 | 120.1 (12) |
C13—N2—Ag1iv | 121.0 (2) | C16B—C15B—H15B | 119.9 |
C17—N3—C26 | 117.5 (2) | C9—C15B—H15B | 119.9 |
C17—N3—Ag2 | 120.13 (18) | C15B—C16B—N1 | 121.4 (13) |
C26—N3—Ag2 | 122.30 (18) | C15B—C16B—H16B | 119.3 |
C23—N4—C22 | 117.1 (2) | N1—C16B—H16B | 119.3 |
C23—N4—Ag2v | 124.39 (18) | N3—C17—C18 | 122.8 (3) |
C22—N4—Ag2v | 118.48 (18) | N3—C17—H17A | 118.6 |
C6—C1—C2 | 120.8 (2) | C18—C17—H17A | 118.6 |
C6—C1—S1 | 118.63 (19) | C17—C18—C19 | 120.2 (2) |
C2—C1—S1 | 120.51 (19) | C17—C18—H18A | 119.9 |
C1—C2—C3 | 120.2 (2) | C19—C18—H18A | 119.9 |
C1—C2—H2A | 119.9 | C18—C19—C25 | 116.7 (2) |
C3—C2—H2A | 119.9 | C18—C19—C20 | 121.0 (2) |
C4—C3—C2 | 118.6 (2) | C25—C19—C20 | 122.2 (2) |
C4—C3—P1 | 120.98 (19) | C24—C20—C21 | 117.2 (2) |
C2—C3—P1 | 120.41 (19) | C24—C20—C19 | 122.4 (2) |
C3—C4—C5 | 120.9 (2) | C21—C20—C19 | 120.4 (2) |
C3—C4—H4A | 119.6 | C22—C21—C20 | 119.7 (3) |
C5—C4—H4A | 119.6 | C22—C21—H21A | 120.1 |
C6—C5—C4 | 120.6 (3) | C20—C21—H21A | 120.1 |
C6—C5—H5A | 119.7 | N4—C22—C21 | 123.1 (3) |
C4—C5—H5A | 119.7 | N4—C22—H22A | 118.4 |
C5—C6—C1 | 118.9 (2) | C21—C22—H22A | 118.4 |
C5—C6—H6A | 120.6 | N4—C23—C24 | 123.2 (3) |
C1—C6—H6A | 120.6 | N4—C23—H23A | 118.4 |
N1—C7A—C8A | 122.2 (7) | C24—C23—H23A | 118.4 |
N1—C7A—H7A | 118.9 | C23—C24—C20 | 119.6 (3) |
C8A—C7A—H7A | 118.9 | C23—C24—H24A | 120.2 |
C7A—C8A—C9 | 119.7 (7) | C20—C24—H24A | 120.2 |
C7A—C8A—H8A | 120.1 | C26—C25—C19 | 120.0 (3) |
C9—C8A—H8A | 120.1 | C26—C25—H25A | 120.0 |
N1—C7B—C8B | 125.2 (10) | C19—C25—H25A | 120.0 |
N1—C7B—H7B | 117.4 | N3—C26—C25 | 122.8 (3) |
C8B—C7B—H7B | 117.4 | N3—C26—H26A | 118.6 |
C7B—C8B—C9 | 118.6 (10) | C25—C26—H26A | 118.6 |
C7B—C8B—H8B | 120.7 | H11—O1W—H12 | 104 (5) |
C9—C8B—H8B | 120.7 | H21—O2W—H22 | 96 (5) |
C15A—C9—C8B | 111.1 (7) | H31—O3W—H32 | 101 (5) |
C8B—C9—C15B | 118.6 (9) | P1—O4—H4 | 114 (2) |
C15A—C9—C8A | 115.2 (7) | P1—O5—H5 | 115 (2) |
C15B—C9—C8A | 113.4 (9) |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y, z+1/2; (iii) −x, −y, −z+1; (iv) x, −y+1, z+1/2; (v) x, −y, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H11···O3 | 0.87 (5) | 2.06 (5) | 2.913 (4) | 167 (5) |
O1W—H12···O6vi | 0.74 (5) | 2.19 (5) | 2.916 (3) | 166 (6) |
O2W—H22···O3Wvii | 0.78 (5) | 2.20 (5) | 2.898 (4) | 149 (5) |
O2W—H21···O2 | 0.82 (5) | 2.01 (5) | 2.796 (3) | 161 (5) |
O3W—H32···O6 | 0.88 (5) | 1.84 (5) | 2.717 (4) | 174 (5) |
O3W—H31···O2Wviii | 0.71 (5) | 2.09 (5) | 2.795 (4) | 171 (6) |
O5—H5···O5vi | 1.27 (1) | 1.27 (1) | 2.528 (4) | 166 (5) |
Symmetry codes: (vi) −x, y, −z+1/2; (vii) −x+1/2, −y+1/2, z+1/2; (viii) x+1/2, −y+1/2, −z+1. |
[Co(C10H8N2)2(H2O)4](C6H5O6PS) | Dx = 1.693 Mg m−3 |
Mr = 523.31 | Melting point: not measured K |
Orthorhombic, Cmca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2bc 2 | Cell parameters from 4587 reflections |
a = 14.9569 (8) Å | θ = 3.0–27.5° |
b = 22.5625 (11) Å | µ = 1.07 mm−1 |
c = 12.1697 (7) Å | T = 293 K |
V = 4106.8 (4) Å3 | Brick, orange |
Z = 8 | 0.43 × 0.20 × 0.20 mm |
F(000) = 2152 |
Rigaku Mercury70 diffractometer | 2446 independent reflections |
Radiation source: fine-focus sealed tube | 2337 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan CrystalClear (Molecular Structure Corporation & Rigaku, 2000) | h = −19→16 |
Tmin = 0.771, Tmax = 0.811 | k = −29→29 |
15395 measured reflections | l = −15→15 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0409P)2 + 9.3696P] where P = (Fo2 + 2Fc2)/3 |
2446 reflections | (Δ/σ)max = 0.001 |
171 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
[Co(C10H8N2)2(H2O)4](C6H5O6PS) | V = 4106.8 (4) Å3 |
Mr = 523.31 | Z = 8 |
Orthorhombic, Cmca | Mo Kα radiation |
a = 14.9569 (8) Å | µ = 1.07 mm−1 |
b = 22.5625 (11) Å | T = 293 K |
c = 12.1697 (7) Å | 0.43 × 0.20 × 0.20 mm |
Rigaku Mercury70 diffractometer | 2446 independent reflections |
Absorption correction: multi-scan CrystalClear (Molecular Structure Corporation & Rigaku, 2000) | 2337 reflections with I > 2σ(I) |
Tmin = 0.771, Tmax = 0.811 | Rint = 0.030 |
15395 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.51 e Å−3 |
2446 reflections | Δρmin = −0.42 e Å−3 |
171 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 | ||
Co1 | 0.2500 | 0.128788 (15) | 0.2500 | 0.02164 (13) | |
S1 | 0.0000 | 0.27459 (3) | 0.04910 (7) | 0.02563 (18) | |
P1 | 0.0000 | 0.51061 (3) | 0.16795 (7) | 0.02425 (19) | |
N1 | 0.2500 | 0.22178 (10) | 0.2500 | 0.0234 (5) | |
N2 | 0.2500 | 0.53483 (10) | 0.2500 | 0.0232 (5) | |
C1 | 0.0000 | 0.32943 (13) | 0.1546 (3) | 0.0270 (6) | |
C2 | 0.0000 | 0.31315 (16) | 0.2636 (3) | 0.0394 (8) | |
H2A | 0.0000 | 0.2733 | 0.2831 | 0.047* | |
C3 | 0.0000 | 0.35676 (18) | 0.3442 (3) | 0.0448 (9) | |
H3A | 0.0000 | 0.3460 | 0.4179 | 0.054* | |
C4 | 0.0000 | 0.41636 (15) | 0.3155 (3) | 0.0350 (7) | |
H4A | 0.0000 | 0.4452 | 0.3701 | 0.042* | |
C5 | 0.0000 | 0.43303 (13) | 0.2062 (3) | 0.0253 (6) | |
C6 | 0.0000 | 0.38905 (13) | 0.1249 (3) | 0.0264 (6) | |
H6A | 0.0000 | 0.3997 | 0.0511 | 0.032* | |
C7 | 0.23873 (16) | 0.25250 (10) | 0.15735 (19) | 0.0301 (5) | |
H7A | 0.2301 | 0.2317 | 0.0922 | 0.036* | |
C8 | 0.23925 (17) | 0.31367 (9) | 0.15357 (19) | 0.0301 (5) | |
H8A | 0.2324 | 0.3333 | 0.0869 | 0.036* | |
C9 | 0.2500 | 0.34546 (12) | 0.2500 | 0.0233 (6) | |
C10 | 0.2500 | 0.41125 (12) | 0.2500 | 0.0228 (6) | |
C11 | 0.27934 (16) | 0.44286 (9) | 0.15931 (18) | 0.0279 (5) | |
H11A | 0.2994 | 0.4232 | 0.0968 | 0.033* | |
C12 | 0.27836 (15) | 0.50412 (9) | 0.16307 (19) | 0.0276 (5) | |
H12A | 0.2985 | 0.5249 | 0.1019 | 0.033* | |
O1 | 0.08066 (12) | 0.28361 (7) | −0.01479 (15) | 0.0407 (4) | |
O2 | 0.0000 | 0.21758 (9) | 0.1056 (2) | 0.0348 (5) | |
O3 | −0.08390 (10) | 0.52101 (6) | 0.09627 (14) | 0.0300 (4) | |
H3 | −0.084 (3) | 0.5000 | 0.0000 | 0.045* | |
O4 | 0.0000 | 0.54849 (10) | 0.2688 (2) | 0.0330 (5) | |
O1W | 0.12786 (12) | 0.12656 (7) | 0.15875 (16) | 0.0341 (4) | |
H11 | 0.101 (2) | 0.1545 (15) | 0.146 (3) | 0.051* | |
H12 | 0.091 (2) | 0.1036 (14) | 0.184 (3) | 0.051* | |
O2W | 0.32333 (12) | 0.12520 (7) | 0.10323 (15) | 0.0307 (4) | |
H21 | 0.356 (2) | 0.1501 (13) | 0.082 (3) | 0.046* | |
H22 | 0.351 (2) | 0.0959 (13) | 0.097 (3) | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0267 (2) | 0.01170 (19) | 0.0265 (2) | 0.000 | 0.00236 (16) | 0.000 |
S1 | 0.0298 (4) | 0.0163 (3) | 0.0309 (4) | 0.000 | 0.000 | 0.0021 (3) |
P1 | 0.0241 (4) | 0.0171 (4) | 0.0316 (4) | 0.000 | 0.000 | −0.0045 (3) |
N1 | 0.0314 (13) | 0.0124 (11) | 0.0263 (13) | 0.000 | 0.0000 (10) | 0.000 |
N2 | 0.0291 (13) | 0.0121 (10) | 0.0285 (13) | 0.000 | −0.0041 (10) | 0.000 |
C1 | 0.0260 (15) | 0.0219 (14) | 0.0330 (17) | 0.000 | 0.000 | 0.0002 (12) |
C2 | 0.057 (2) | 0.0239 (15) | 0.038 (2) | 0.000 | 0.000 | 0.0073 (14) |
C3 | 0.068 (3) | 0.040 (2) | 0.0263 (18) | 0.000 | 0.000 | 0.0051 (15) |
C4 | 0.0432 (19) | 0.0292 (16) | 0.0327 (18) | 0.000 | 0.000 | −0.0030 (14) |
C5 | 0.0232 (14) | 0.0216 (13) | 0.0310 (16) | 0.000 | 0.000 | 0.0004 (12) |
C6 | 0.0318 (16) | 0.0201 (13) | 0.0274 (16) | 0.000 | 0.000 | 0.0011 (12) |
C7 | 0.0486 (14) | 0.0161 (9) | 0.0257 (11) | 0.0008 (9) | −0.0023 (10) | −0.0023 (8) |
C8 | 0.0473 (14) | 0.0165 (10) | 0.0266 (11) | 0.0006 (9) | −0.0041 (10) | 0.0028 (8) |
C9 | 0.0269 (14) | 0.0147 (13) | 0.0284 (15) | 0.000 | −0.0013 (12) | 0.000 |
C10 | 0.0252 (14) | 0.0161 (12) | 0.0273 (15) | 0.000 | −0.0047 (12) | 0.000 |
C11 | 0.0371 (12) | 0.0176 (10) | 0.0289 (11) | 0.0017 (8) | 0.0017 (10) | −0.0008 (8) |
C12 | 0.0364 (11) | 0.0190 (10) | 0.0276 (11) | −0.0003 (9) | 0.0008 (10) | 0.0029 (8) |
O1 | 0.0442 (10) | 0.0322 (9) | 0.0458 (11) | −0.0081 (7) | 0.0137 (8) | −0.0035 (8) |
O2 | 0.0446 (14) | 0.0183 (10) | 0.0414 (14) | 0.000 | 0.000 | 0.0044 (9) |
O3 | 0.0265 (8) | 0.0248 (7) | 0.0388 (9) | 0.0052 (6) | −0.0029 (7) | −0.0042 (7) |
O4 | 0.0337 (12) | 0.0254 (11) | 0.0400 (14) | 0.000 | 0.000 | −0.0114 (10) |
O1W | 0.0286 (9) | 0.0224 (8) | 0.0514 (11) | 0.0006 (6) | −0.0036 (8) | 0.0081 (7) |
O2W | 0.0337 (9) | 0.0210 (7) | 0.0374 (9) | 0.0015 (6) | 0.0110 (7) | 0.0041 (7) |
Co1—N1 | 2.098 (2) | C3—C4 | 1.389 (5) |
Co1—O2W | 2.0976 (17) | C3—H3A | 0.9300 |
Co1—O2Wi | 2.0976 (17) | C4—C5 | 1.382 (5) |
Co1—N2ii | 2.120 (2) | C4—H4A | 0.9300 |
Co1—O1Wi | 2.1384 (18) | C5—C6 | 1.401 (4) |
Co1—O1W | 2.1384 (18) | C6—H6A | 0.9300 |
S1—O1 | 1.4497 (18) | C7—C8 | 1.381 (3) |
S1—O1iii | 1.4498 (18) | C7—H7A | 0.9300 |
S1—O2 | 1.458 (2) | C8—C9 | 1.385 (3) |
S1—C1 | 1.783 (3) | C8—H8A | 0.9300 |
P1—O4 | 1.496 (2) | C9—C8i | 1.385 (3) |
P1—O3 | 1.5462 (16) | C9—C10 | 1.484 (4) |
P1—O3iii | 1.5462 (16) | C10—C11i | 1.385 (3) |
P1—C5 | 1.811 (3) | C10—C11 | 1.385 (3) |
N1—C7i | 1.334 (3) | C11—C12 | 1.383 (3) |
N1—C7 | 1.334 (3) | C11—H11A | 0.9300 |
N2—C12 | 1.334 (3) | C12—H12A | 0.9300 |
N2—C12i | 1.334 (3) | O3—H3 | 1.2638 (16) |
N2—Co1iv | 2.120 (2) | O1W—H11 | 0.76 (3) |
C1—C2 | 1.376 (5) | O1W—H12 | 0.82 (3) |
C1—C6 | 1.393 (4) | O2W—H21 | 0.79 (3) |
C2—C3 | 1.389 (5) | O2W—H22 | 0.78 (3) |
C2—H2A | 0.9300 | ||
N1—Co1—O2W | 92.21 (4) | C3—C2—H2A | 120.3 |
N1—Co1—O2Wi | 92.21 (4) | C2—C3—C4 | 120.5 (3) |
O2W—Co1—O2Wi | 175.58 (9) | C2—C3—H3A | 119.7 |
N1—Co1—N2ii | 180.0 | C4—C3—H3A | 119.7 |
O2W—Co1—N2ii | 87.79 (4) | C5—C4—C3 | 120.4 (3) |
O2Wi—Co1—N2ii | 87.79 (4) | C5—C4—H4A | 119.8 |
N1—Co1—O1Wi | 91.35 (4) | C3—C4—H4A | 119.8 |
O2W—Co1—O1Wi | 89.69 (7) | C4—C5—C6 | 119.1 (3) |
O2Wi—Co1—O1Wi | 90.21 (7) | C4—C5—P1 | 120.7 (2) |
N2ii—Co1—O1Wi | 88.65 (4) | C6—C5—P1 | 120.2 (2) |
N1—Co1—O1W | 91.35 (4) | C1—C6—C5 | 120.1 (3) |
O2W—Co1—O1W | 90.21 (7) | C1—C6—H6A | 120.0 |
O2Wi—Co1—O1W | 89.69 (7) | C5—C6—H6A | 120.0 |
N2ii—Co1—O1W | 88.65 (4) | N1—C7—C8 | 123.1 (2) |
O1Wi—Co1—O1W | 177.30 (9) | N1—C7—H7A | 118.4 |
O1—S1—O1iii | 112.65 (16) | C8—C7—H7A | 118.4 |
O1—S1—O2 | 112.13 (9) | C7—C8—C9 | 119.3 (2) |
O1iii—S1—O2 | 112.13 (9) | C7—C8—H8A | 120.3 |
O1—S1—C1 | 106.78 (9) | C9—C8—H8A | 120.3 |
O1iii—S1—C1 | 106.78 (9) | C8i—C9—C8 | 117.6 (3) |
O2—S1—C1 | 105.82 (15) | C8i—C9—C10 | 121.20 (13) |
O4—P1—O3 | 112.11 (8) | C8—C9—C10 | 121.20 (13) |
O4—P1—O3iii | 112.11 (8) | C11i—C10—C11 | 118.0 (3) |
O3—P1—O3iii | 108.50 (13) | C11i—C10—C9 | 120.98 (13) |
O4—P1—C5 | 109.96 (15) | C11—C10—C9 | 120.98 (13) |
O3—P1—C5 | 106.95 (8) | C12—C11—C10 | 119.0 (2) |
O3iii—P1—C5 | 106.95 (8) | C12—C11—H11A | 120.5 |
C7i—N1—C7 | 117.4 (3) | C10—C11—H11A | 120.5 |
C7i—N1—Co1 | 121.30 (13) | N2—C12—C11 | 123.3 (2) |
C7—N1—Co1 | 121.30 (13) | N2—C12—H12A | 118.4 |
C12—N2—C12i | 117.4 (2) | C11—C12—H12A | 118.4 |
C12—N2—Co1iv | 121.30 (12) | P1—O3—H3 | 117.8 (17) |
C12i—N2—Co1iv | 121.30 (12) | Co1—O1W—H11 | 122 (2) |
C2—C1—C6 | 120.5 (3) | Co1—O1W—H12 | 113 (2) |
C2—C1—S1 | 120.6 (2) | H11—O1W—H12 | 104 (3) |
C6—C1—S1 | 118.9 (3) | Co1—O2W—H21 | 125 (2) |
C1—C2—C3 | 119.4 (3) | Co1—O2W—H22 | 113 (2) |
C1—C2—H2A | 120.3 | H21—O2W—H22 | 104 (3) |
Symmetry codes: (i) −x+1/2, y, −z+1/2; (ii) x, y−1/2, −z+1/2; (iii) −x, y, z; (iv) x, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H11···O2 | 0.76 (3) | 2.13 (3) | 2.880 (2) | 166 (3) |
O1W—H12···O4ii | 0.82 (3) | 1.93 (3) | 2.745 (2) | 175 (3) |
O2W—H21···O1v | 0.79 (3) | 1.95 (3) | 2.730 (2) | 170 (3) |
O2W—H22···O3vi | 0.78 (3) | 1.95 (3) | 2.731 (2) | 174 (3) |
O3—H3···O3vii | 1.26 (1) | 1.26 (1) | 2.528 (3) | 180 (4) |
Symmetry codes: (ii) x, y−1/2, −z+1/2; (v) −x+1/2, −y+1/2, −z; (vi) x+1/2, y−1/2, z; (vii) x, −y+1, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Ag2(C10H8N2)2](C6H5O6PS)·3H2O | [Co(C10H8N2)2(H2O)4](C6H5O6PS) |
Mr | 818.29 | 523.31 |
Crystal system, space group | Orthorhombic, Pbcn | Orthorhombic, Cmca |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 14.539 (3), 17.472 (4), 22.623 (4) | 14.9569 (8), 22.5625 (11), 12.1697 (7) |
V (Å3) | 5747 (2) | 4106.8 (4) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.55 | 1.07 |
Crystal size (mm) | 0.50 × 0.12 × 0.12 | 0.43 × 0.20 × 0.20 |
Data collection | ||
Diffractometer | Rigaku Mercury70 diffractometer | Rigaku Mercury70 diffractometer |
Absorption correction | Multi-scan (CrystalClear; Molecular Structure Corporation & Rigaku, 2000) | Multi-scan CrystalClear (Molecular Structure Corporation & Rigaku, 2000) |
Tmin, Tmax | 0.796, 0.834 | 0.771, 0.811 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42765, 6577, 6186 | 15395, 2446, 2337 |
Rint | 0.023 | 0.030 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.078, 1.04 | 0.040, 0.092, 1.06 |
No. of reflections | 6577 | 2446 |
No. of parameters | 434 | 171 |
No. of restraints | 3 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.44 | 0.51, −0.42 |
Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).
Ag1—N2i | 2.139 (2) | Ag2—N3 | 2.137 (2) |
Ag1—N1 | 2.145 (2) | Ag2—Ag2iii | 3.2610 (8) |
Ag2—N4ii | 2.131 (2) | ||
N2i—Ag1—N1 | 172.38 (10) | N4ii—Ag2—N3 | 170.82 (9) |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y, z+1/2; (iii) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H11···O3 | 0.87 (5) | 2.06 (5) | 2.913 (4) | 167 (5) |
O1W—H12···O6iv | 0.74 (5) | 2.19 (5) | 2.916 (3) | 166 (6) |
O2W—H22···O3Wv | 0.78 (5) | 2.20 (5) | 2.898 (4) | 149 (5) |
O2W—H21···O2 | 0.82 (5) | 2.01 (5) | 2.796 (3) | 161 (5) |
O3W—H32···O6 | 0.88 (5) | 1.84 (5) | 2.717 (4) | 174 (5) |
O3W—H31···O2Wvi | 0.71 (5) | 2.09 (5) | 2.795 (4) | 171 (6) |
O5—H5···O5iv | 1.273 (6) | 1.273 (6) | 2.528 (4) | 166 (5) |
Symmetry codes: (iv) −x, y, −z+1/2; (v) −x+1/2, −y+1/2, z+1/2; (vi) x+1/2, −y+1/2, −z+1. |
Co1—N1 | 2.098 (2) | Co1—N2i | 2.120 (2) |
Co1—O2W | 2.0976 (17) | Co1—O1W | 2.1384 (18) |
Symmetry code: (i) x, y−1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H11···O2 | 0.76 (3) | 2.13 (3) | 2.880 (2) | 166 (3) |
O1W—H12···O4i | 0.82 (3) | 1.93 (3) | 2.745 (2) | 175 (3) |
O2W—H21···O1ii | 0.79 (3) | 1.95 (3) | 2.730 (2) | 170 (3) |
O2W—H22···O3iii | 0.78 (3) | 1.95 (3) | 2.731 (2) | 174 (3) |
O3—H3···O3iv | 1.2638 (16) | 1.2638 (16) | 2.528 (3) | 180 (4) |
Symmetry codes: (i) x, y−1/2, −z+1/2; (ii) −x+1/2, −y+1/2, −z; (iii) x+1/2, y−1/2, z; (iv) x, −y+1, −z. |
During the past few years, interest in the design, synthesis, characterization and functions of hybrid inorganic–organic supramolecular compounds has been growing (Lehn, 1995). Usually, hydrogen bonding and π–π stacking interactions are important in solid-state assembly. In the case of ionic supramolecular compounds, the counterions play an important role in the stabilization of their structures through electrostatic interaction (Min & Suh, 2000; Noro et al., 2002). In general, small anions, such as NO3-, BF4-, ClO4-, PF6- etc., are used as counterions for cationic metal components. Reports on the use of phosphonic acids as a building block for supramolecular complexes are rare, although they have been shown to form extremely strong hydrogen bonds in their solid-state structures (Clearfield et al., 2001; Sharma & Clearfield, 2001). 3-Sulfophenylphosphonic acid, HO3S-C6H4-PO3H2, the first sulfonate–phosphonate ligand to be investigated, has recently been employed as a metal–organic coordination fragment due to its diverse coordination modes (Du et al., 2006a,b; Du, Li et al., 2007; Du, Prosvirin & Mao, 2007; Du, Xie & Wen, 2007; Du, Xu et al., 2007). When the deprotonated 3-sulfophenylphosphonic acid is not coordinated, it can also be employed as an organic counterion for constructing hybrid inorganic–organic supramolecular arrays. Here, we report the two title compounds, (I) and (II), which are the first examples illustrating two novel lattice architectures resulting from the association of metal–organic units with the [O3S-C6H4-PO3H]2- anion and water molecules.
The structure of compound (I) features one-dimensional chains of {[Ag(4,4'-bipy)]22+}n (4,4'-bipy is 4,4'-bipyridine) with [O3S-C6H4-PO3H]2- anions as counterions. There are two independent AgI ions in the asymmetric unit of (I) (Fig. 1). Both AgI ions are two-coordinated by two N atoms from two 4,4'-bipy ligands in a linear geometry (Table 1). The interconnection of the AgI ions by the bidentate bridging 4,4'-bipy ligands results in the formation of one-dimensional chains along the c axis. These chains are further assembled into a two-dimensional supramolecular layered architecture via weak π–π packing interactions (Fig. 2). One aryl ring in the 4,4'-bipy ligand is disordered, displaying two ring orientations (C7A/C8A/C9/C15A/C16A/N1 and C7B/C8B/C9/C15B/C16B/N1) (Fig. 1).
The [O3S-C6H4-PO3H]2- anion in (I) forms a dimer through two short hydrogen bonds between two pairs of twofold symmetry-related phosphonate O atoms, with the bonded H atoms (H4 and H5) located on a twofold axis (Fig. 3a and Table 2). This is a unique arrangement, with the most similar example being seen in diprotonated phosphonate groups (see, for example, Clarke et al., 2005). It is noted that symmetrical hydrogen bonds and hydrogen-bonded dimers with similar dimensions of other phosphonic acids have also been reported previously (Sharma & Clearfield, 2000a,b; Bowes et al., 2003; Man et al., 2006; Courtney et al., 2006; Latham et al., 2007). The dimer is further stabilized by extensive hydrogen bonding with solvent water molecules, using one phosphonate and two sulfonate O atoms as acceptors (Table 2). Coupled with this is a cyclic water tetramer formed by hydrogen-bonding associations between two O2W atoms and two O3W atoms (Fig. 4 and Table 1); the four O atoms are not coplanar, with the torsion angle O2Wii—O3W—O2Wiii—O3Wiv being ca 42.6° [symmetry codes: (ii) 1/2 - x, 1/2 - y, -1/2 + z; (iii) 1/2 + x, 1/2 - y, 1 - z; (iv) 1 - x, y, 1/2 - z Please check added text]. All water molecules act as a hydrogen-bond acceptor and two hydrogen-bond donors.
The hydrogen-bond interactions of these [O3S-C6H4-PO3H]2- dimers and water tetramers in (I) lead to the formation of a novel two-dimensional supramolecular layer aggregate (Fig. 4). The layer features two kinds of rings, dicussed according to graph-set analysis nomenclature (Bernstein et al., 1995). One ring, including one solvent water molecule, one [O3S-C6H4-PO3H]2- anion and one phosphonate group from another [O3S-C6H4-PO3H]2- anion, can be specified as having an R34(14) pattern, whereas the other ring, including five solvent water molecules, one [O3S-C6H4-PO3H]2- anion, and one phosphonate group and one sulfonate group from two other [O3S-C6H4-PO3H]2- anions, can be specified as having an R85(24) pattern. The whole packing scheme of (I) thus presents a layer structure following the alternating array pattern of ···ABAB···, where A is an [Ag(4,4'-bipy)]2 layer and B is an [(O3S-C6H4-PO3H).3(H2O)] layer.
The structure of compound (II) features one-dimensional cationic chains of {[Co(4,4'-bipy)(H2O)4]2+}n with similar dimer [O3S-C6H4-PO3H]2- anions as in (I). The cationic unit possesses twofold crystallographic symmetry, while the [O3S-C6H4-PO3H]2- anion is constrained to a mirror plane. The CoII ion is octahedrally coordinated by two N atoms from two symmetry-related 4,4'-bipy ligands and by two pairs of symmetry-related water molecules (Fig. 5 and Table 3). Although cationic {[Co(4,4'-bipy)(H2O)4]2+}n chains are commonly observed (see, for example, Wang et al., 2006), their supramolecular arrays are diverse and strongly affected by the different counterions being employed.
The dimer anions in (II) are similar to those in (I) through the common twofold symmetry relationship between each hydrogen-bonded [O3S-C6H4-PO3H]2- dimer centred on the bonded H atom (H3) (Table 4; Fig. 3b). In addition, the phenyl rings are all ordered and constrained to have mirror plane symmetry, so the dihedral angle bwteen the two phenyl rings in the dimer anion is 0°, whereas that in (I) is 24.5 (1)° for the ordered molecule. The dimer is stabilized by hydrogen bonding to two pairs of O2W water molecules, utilizing two pairs of sulfonate and two pairs of phosphonate O atoms as receptors. This dimer further utilizes its remaining one pair of sulfonate and one pair of phosphonate O atoms as receptors and is connected to four neighbouring dimers via the hydrogen-bonding associations of four pairs of O1W water molecules, leading to the formation of a novel two-dimensional supramolecular layer aggregate (Table 4; Fig. 6). This layer contains graph-set rings such as R24(8) and R44(12) etc., which are completely different to the supramolecular layer structure in (I). It is noted that all aqua molecules here act as hydrogen-bond donors and each is hydrogen-bonded to one phosphonate and one sulfonate O atom.
The interconnection of the CoII ions of (II) by the bidentate bridging 4,4'-bipy ligands results in the formation of one-dimensional chains along the b axis, which are further assembled into an extensive three-dimensional supramolecular architecture via the hydrogen-bond interactions described above (Fig. 7; Table 4).
In summary, two novel hydrogen-bonded layers directed by [O3S-C6H4-PO3H]2- anions have been observed in compounds (I) and (II). The [O3S-C6H4-PO3H]2- anions in both compounds form unique dimers via two short hydrogen bonds between two pairs of phosphonate O atoms, and are further hydrogen-bonded to solvent water or aqua molecules.