The title complexes [
M(sac)
2(mpy)
2] [sac is saccharinate (C
7H
4NO
3S) and mpy is 2-pyridylmethanol (C
6H
7NO)], with
M = Zn
II and Cd
II, are isostructural and consist of neutral molecules. The Zn
II or Cd
II cations are octahedrally coordinated by the two neutral mpy and two anionic sac ligands. The mpy ligand acts as a bidentate donor through the amine N and hydroxyl O atoms. The sac ligands exhibit an ambidentate coordination behaviour; one is
N-coordinated and the other is
O-coordinated within the same coordination octahedron. The crystal packing is determined by C-H
O-type hydrogen bonding, as well as by weak py-py and sac-sac aromatic
-
-stacking interactions.
Supporting information
CCDC references: 193396; 193397
The mpy ligand (0.218 g, 2.0 mmol) dissolved in methanol (15 ml) was added
dropwise to solutions of tetraaquabis(saccharinato)zinc(II) and
tetraaquabis(saccharinato)cadmium(II) dihydrate (1 mmol) dissolved in
methanol–2-propanol mixtures (v:v, 1:1, 30 ml) with continuous stirring at
room temperature. The resulting solutions were left to stand at room
temperature and allowed to evaporate slowly over a period of afew days
whereupon crystallization occurred. Crystals of both compounds suitable for
X-ray diffraction analysis were collected by suction filtration, washed with
acetone and dried in air.
Hydroxyl H atoms were refined with restraints starting from their locations in a
difference map [Uiso(H) = 1.2Ueq(O)]. The remaining H-atom
positions were calculated [C—H = 0.95 (CH) and 0.99 Å (CH2), and
Uiso(H) = 1.2Ueq(C)].
For both compounds, data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR97 (Altomare et al.,1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(I) Bis(2-pyridylmethanol)bis(saccharinato)zinc(II)
top
Crystal data top
[Zn(C7H4NO3S)2(C6H7NO)2] | Z = 2 |
Mr = 647.97 | F(000) = 664 |
Triclinic, P1 | Dx = 1.665 Mg m−3 |
a = 8.9874 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.1630 (2) Å | Cell parameters from 11819 reflections |
c = 13.1879 (3) Å | θ = 2.9–27.5° |
α = 99.1532 (8)° | µ = 1.17 mm−1 |
β = 95.0138 (9)° | T = 120 K |
γ = 95.729 (2)° | Needle, colourless |
V = 1292.52 (5) Å3 | 0.25 × 0.10 × 0.05 mm |
Data collection top
Enraf–Nonius KappaCCD area-detector diffractometer | 5684 independent reflections |
Radiation source: Enraf–Nonius FR591 rotating anode | 4863 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans to fill Ewald sphere | h = −10→11 |
Absorption correction: multi-scan (Blessing, 1995) | k = −14→14 |
Tmin = 0.869, Tmax = 0.943 | l = −17→17 |
16550 measured reflections | |
Refinement top
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)] = 0.034 | Hydrogen site location: mixed |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0312P)2 + 0.9518P] where P = (Fo2 + 2Fc2)/3 |
5684 reflections | (Δ/σ)max = 0.001 |
376 parameters | Δρmax = 0.38 e Å−3 |
2 restraints | Δρmin = −0.53 e Å−3 |
Crystal data top
[Zn(C7H4NO3S)2(C6H7NO)2] | γ = 95.729 (2)° |
Mr = 647.97 | V = 1292.52 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9874 (2) Å | Mo Kα radiation |
b = 11.1630 (2) Å | µ = 1.17 mm−1 |
c = 13.1879 (3) Å | T = 120 K |
α = 99.1532 (8)° | 0.25 × 0.10 × 0.05 mm |
β = 95.0138 (9)° | |
Data collection top
Enraf–Nonius KappaCCD area-detector diffractometer | 5684 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 4863 reflections with I > 2σ(I) |
Tmin = 0.869, Tmax = 0.943 | Rint = 0.042 |
16550 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 2 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.38 e Å−3 |
5684 reflections | Δρmin = −0.53 e Å−3 |
376 parameters | |
Special details top
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the
entire data set is used to refine the cell, which is indexed from all observed
reflections in a 10 degree phi range. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Zn1 | 0.38648 (2) | 0.29128 (2) | 0.223516 (17) | 0.01324 (8) | |
O1 | 0.52823 (16) | 0.35896 (13) | 0.11421 (11) | 0.0169 (3) | |
H1O | 0.477 (2) | 0.4124 (17) | 0.0969 (18) | 0.020* | |
O2 | 0.57861 (16) | 0.19005 (13) | 0.26526 (11) | 0.0169 (3) | |
H2O | 0.537 (3) | 0.1311 (16) | 0.2869 (18) | 0.020* | |
N1 | 0.33447 (19) | 0.15621 (15) | 0.08872 (13) | 0.0133 (3) | |
N2 | 0.52242 (18) | 0.41856 (15) | 0.33549 (13) | 0.0139 (3) | |
C1 | 0.2202 (2) | 0.06560 (18) | 0.07478 (16) | 0.0157 (4) | |
H1 | 0.1584 | 0.0595 | 0.1290 | 0.019* | |
C2 | 0.1891 (2) | −0.01850 (19) | −0.01478 (16) | 0.0175 (4) | |
H2 | 0.1089 | −0.0824 | −0.0216 | 0.021* | |
C3 | 0.2771 (2) | −0.0082 (2) | −0.09490 (17) | 0.0198 (5) | |
H3 | 0.2577 | −0.0647 | −0.1578 | 0.024* | |
C4 | 0.3932 (2) | 0.0851 (2) | −0.08186 (17) | 0.0203 (5) | |
H4 | 0.4544 | 0.0943 | −0.1359 | 0.024* | |
C5 | 0.4196 (2) | 0.16557 (18) | 0.01131 (16) | 0.0153 (4) | |
C6 | 0.5469 (2) | 0.26750 (18) | 0.02996 (16) | 0.0174 (4) | |
H6A | 0.6428 | 0.2336 | 0.0441 | 0.021* | |
H6B | 0.5527 | 0.3047 | −0.0331 | 0.021* | |
C7 | 0.4957 (2) | 0.53560 (18) | 0.36046 (16) | 0.0162 (4) | |
H7 | 0.4078 | 0.5606 | 0.3285 | 0.019* | |
C8 | 0.5902 (2) | 0.62052 (19) | 0.43032 (16) | 0.0169 (4) | |
H8 | 0.5678 | 0.7024 | 0.4463 | 0.020* | |
C9 | 0.7185 (2) | 0.58450 (19) | 0.47681 (16) | 0.0177 (4) | |
H9 | 0.7849 | 0.6409 | 0.5261 | 0.021* | |
C10 | 0.7484 (2) | 0.46528 (19) | 0.45035 (16) | 0.0171 (4) | |
H10 | 0.8370 | 0.4390 | 0.4801 | 0.021* | |
C11 | 0.6475 (2) | 0.38429 (18) | 0.37973 (15) | 0.0139 (4) | |
C12 | 0.6761 (2) | 0.25316 (19) | 0.35234 (16) | 0.0181 (4) | |
H12A | 0.7818 | 0.2502 | 0.3372 | 0.022* | |
H12B | 0.6615 | 0.2115 | 0.4122 | 0.022* | |
S1 | 0.34019 (6) | −0.11760 (5) | 0.33629 (4) | 0.01998 (13) | |
N3 | 0.3809 (2) | 0.02314 (15) | 0.31906 (14) | 0.0175 (4) | |
O3 | 0.25978 (16) | 0.19410 (12) | 0.31380 (11) | 0.0163 (3) | |
O4 | 0.4161 (2) | −0.13807 (15) | 0.43137 (13) | 0.0317 (4) | |
O5 | 0.35998 (19) | −0.20078 (14) | 0.24490 (13) | 0.0305 (4) | |
C13 | 0.2614 (2) | 0.08481 (18) | 0.32599 (15) | 0.0151 (4) | |
C14 | 0.1231 (2) | 0.01129 (19) | 0.34554 (16) | 0.0177 (4) | |
C15 | −0.0176 (3) | 0.0489 (2) | 0.35650 (18) | 0.0255 (5) | |
H15 | −0.0349 | 0.1310 | 0.3540 | 0.031* | |
C16 | −0.1325 (3) | −0.0373 (2) | 0.3712 (2) | 0.0317 (6) | |
H16 | −0.2302 | −0.0140 | 0.3791 | 0.038* | |
C17 | −0.1066 (3) | −0.1569 (2) | 0.37455 (19) | 0.0317 (6) | |
H17 | −0.1874 | −0.2144 | 0.3839 | 0.038* | |
C18 | 0.0349 (3) | −0.1949 (2) | 0.36452 (18) | 0.0281 (5) | |
H18 | 0.0529 | −0.2768 | 0.3673 | 0.034* | |
C19 | 0.1479 (3) | −0.10767 (19) | 0.35033 (16) | 0.0197 (4) | |
S2 | 0.04298 (5) | 0.37705 (4) | 0.22439 (4) | 0.01333 (11) | |
N4 | 0.21309 (18) | 0.39888 (15) | 0.19066 (13) | 0.0134 (3) | |
O6 | 0.34309 (16) | 0.52299 (13) | 0.09695 (11) | 0.0192 (3) | |
O7 | −0.03371 (16) | 0.26245 (13) | 0.17043 (11) | 0.0199 (3) | |
O8 | 0.04240 (16) | 0.39778 (14) | 0.33447 (11) | 0.0190 (3) | |
C20 | 0.2284 (2) | 0.49276 (18) | 0.13616 (15) | 0.0145 (4) | |
C21 | 0.0901 (2) | 0.55604 (18) | 0.12855 (15) | 0.0148 (4) | |
C22 | 0.0676 (2) | 0.65791 (19) | 0.08383 (17) | 0.0194 (4) | |
H22 | 0.1457 | 0.6977 | 0.0528 | 0.023* | |
C23 | −0.0722 (3) | 0.7000 (2) | 0.08575 (17) | 0.0221 (5) | |
H23 | −0.0903 | 0.7695 | 0.0553 | 0.027* | |
C24 | −0.1868 (2) | 0.6424 (2) | 0.13157 (18) | 0.0226 (5) | |
H24 | −0.2814 | 0.6734 | 0.1321 | 0.027* | |
C25 | −0.1647 (2) | 0.54010 (19) | 0.17650 (17) | 0.0188 (4) | |
H25 | −0.2422 | 0.4998 | 0.2076 | 0.023* | |
C26 | −0.0245 (2) | 0.50023 (18) | 0.17353 (15) | 0.0149 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.01296 (13) | 0.01078 (13) | 0.01609 (13) | 0.00128 (9) | 0.00212 (9) | 0.00237 (9) |
O1 | 0.0161 (8) | 0.0135 (7) | 0.0222 (8) | 0.0021 (6) | 0.0038 (6) | 0.0052 (6) |
O2 | 0.0164 (8) | 0.0132 (7) | 0.0212 (8) | 0.0023 (6) | 0.0028 (6) | 0.0021 (6) |
N1 | 0.0141 (9) | 0.0119 (8) | 0.0146 (9) | 0.0035 (6) | 0.0024 (6) | 0.0028 (7) |
N2 | 0.0127 (9) | 0.0129 (8) | 0.0172 (9) | 0.0025 (6) | 0.0033 (6) | 0.0041 (7) |
C1 | 0.0168 (11) | 0.0130 (10) | 0.0182 (11) | 0.0028 (8) | 0.0036 (8) | 0.0041 (8) |
C2 | 0.0166 (11) | 0.0131 (10) | 0.0218 (11) | 0.0018 (8) | −0.0012 (8) | 0.0017 (8) |
C3 | 0.0222 (12) | 0.0178 (11) | 0.0190 (11) | 0.0077 (9) | 0.0011 (8) | −0.0007 (9) |
C4 | 0.0244 (12) | 0.0206 (11) | 0.0187 (11) | 0.0102 (9) | 0.0071 (9) | 0.0047 (9) |
C5 | 0.0164 (11) | 0.0141 (10) | 0.0180 (11) | 0.0061 (8) | 0.0040 (8) | 0.0069 (8) |
C6 | 0.0195 (11) | 0.0142 (10) | 0.0209 (11) | 0.0040 (8) | 0.0087 (8) | 0.0052 (8) |
C7 | 0.0160 (11) | 0.0138 (10) | 0.0199 (11) | 0.0039 (8) | 0.0032 (8) | 0.0035 (8) |
C8 | 0.0173 (11) | 0.0123 (10) | 0.0219 (11) | 0.0022 (8) | 0.0050 (8) | 0.0036 (8) |
C9 | 0.0184 (11) | 0.0170 (11) | 0.0169 (11) | −0.0006 (8) | 0.0026 (8) | 0.0018 (8) |
C10 | 0.0150 (11) | 0.0194 (11) | 0.0180 (11) | 0.0034 (8) | 0.0010 (8) | 0.0060 (8) |
C11 | 0.0137 (10) | 0.0136 (10) | 0.0163 (10) | 0.0028 (8) | 0.0056 (8) | 0.0052 (8) |
C12 | 0.0169 (11) | 0.0149 (10) | 0.0227 (11) | 0.0044 (8) | 0.0005 (8) | 0.0029 (8) |
S1 | 0.0242 (3) | 0.0115 (2) | 0.0258 (3) | 0.0049 (2) | 0.0049 (2) | 0.0046 (2) |
N3 | 0.0188 (10) | 0.0113 (8) | 0.0236 (10) | 0.0031 (7) | 0.0033 (7) | 0.0051 (7) |
O3 | 0.0197 (8) | 0.0118 (7) | 0.0198 (8) | 0.0044 (6) | 0.0061 (6) | 0.0060 (6) |
O4 | 0.0383 (11) | 0.0242 (9) | 0.0362 (10) | 0.0109 (7) | −0.0017 (8) | 0.0143 (8) |
O5 | 0.0361 (10) | 0.0167 (8) | 0.0386 (10) | 0.0042 (7) | 0.0141 (8) | −0.0024 (7) |
C13 | 0.0194 (11) | 0.0146 (10) | 0.0119 (10) | 0.0034 (8) | 0.0021 (8) | 0.0027 (8) |
C14 | 0.0208 (11) | 0.0176 (11) | 0.0157 (11) | 0.0030 (8) | 0.0024 (8) | 0.0055 (8) |
C15 | 0.0253 (13) | 0.0240 (12) | 0.0312 (13) | 0.0060 (9) | 0.0091 (9) | 0.0116 (10) |
C16 | 0.0230 (13) | 0.0346 (14) | 0.0409 (15) | 0.0020 (10) | 0.0104 (10) | 0.0142 (12) |
C17 | 0.0304 (14) | 0.0299 (14) | 0.0358 (15) | −0.0056 (11) | 0.0089 (11) | 0.0110 (11) |
C18 | 0.0375 (15) | 0.0175 (11) | 0.0297 (13) | −0.0022 (10) | 0.0087 (10) | 0.0064 (10) |
C19 | 0.0261 (12) | 0.0162 (11) | 0.0182 (11) | 0.0034 (9) | 0.0055 (8) | 0.0053 (8) |
S2 | 0.0121 (3) | 0.0125 (2) | 0.0160 (3) | 0.00139 (18) | 0.00106 (18) | 0.00418 (19) |
N4 | 0.0111 (9) | 0.0131 (8) | 0.0169 (9) | 0.0017 (6) | 0.0025 (6) | 0.0050 (7) |
O6 | 0.0178 (8) | 0.0153 (7) | 0.0272 (8) | 0.0026 (6) | 0.0083 (6) | 0.0080 (6) |
O7 | 0.0182 (8) | 0.0130 (7) | 0.0271 (8) | −0.0032 (6) | −0.0001 (6) | 0.0037 (6) |
O8 | 0.0190 (8) | 0.0240 (8) | 0.0165 (8) | 0.0067 (6) | 0.0033 (6) | 0.0072 (6) |
C20 | 0.0169 (11) | 0.0095 (9) | 0.0164 (10) | 0.0013 (8) | 0.0004 (8) | 0.0014 (8) |
C21 | 0.0163 (11) | 0.0127 (10) | 0.0150 (10) | 0.0015 (8) | −0.0003 (8) | 0.0020 (8) |
C22 | 0.0195 (11) | 0.0171 (11) | 0.0225 (11) | 0.0014 (8) | 0.0025 (8) | 0.0064 (9) |
C23 | 0.0232 (12) | 0.0185 (11) | 0.0269 (12) | 0.0054 (9) | −0.0014 (9) | 0.0111 (9) |
C24 | 0.0167 (11) | 0.0234 (12) | 0.0285 (12) | 0.0068 (9) | −0.0023 (9) | 0.0061 (9) |
C25 | 0.0143 (11) | 0.0185 (11) | 0.0235 (11) | 0.0009 (8) | 0.0011 (8) | 0.0040 (9) |
C26 | 0.0160 (11) | 0.0120 (10) | 0.0155 (10) | 0.0007 (8) | −0.0018 (8) | 0.0007 (8) |
Geometric parameters (Å, º) top
Zn1—O3 | 2.0717 (14) | C12—H12B | 0.9900 |
Zn1—N2 | 2.0887 (17) | S1—O5 | 1.4356 (17) |
Zn1—N4 | 2.1167 (16) | S1—O4 | 1.4363 (17) |
Zn1—N1 | 2.1244 (17) | S1—N3 | 1.6330 (18) |
Zn1—O1 | 2.1788 (14) | S1—C19 | 1.767 (2) |
Zn1—O2 | 2.2323 (14) | N3—C13 | 1.334 (3) |
O1—C6 | 1.418 (2) | O3—C13 | 1.257 (2) |
O1—H1O | 0.834 (10) | C13—C14 | 1.485 (3) |
O2—C12 | 1.423 (2) | C14—C19 | 1.378 (3) |
O2—H2O | 0.828 (10) | C14—C15 | 1.384 (3) |
N1—C5 | 1.339 (3) | C15—C16 | 1.388 (3) |
N1—C1 | 1.346 (3) | C15—H15 | 0.9500 |
N2—C11 | 1.339 (3) | C16—C17 | 1.385 (4) |
N2—C7 | 1.346 (3) | C16—H16 | 0.9500 |
C1—C2 | 1.375 (3) | C17—C18 | 1.390 (4) |
C1—H1 | 0.9500 | C17—H17 | 0.9500 |
C2—C3 | 1.386 (3) | C18—C19 | 1.382 (3) |
C2—H2 | 0.9500 | C18—H18 | 0.9500 |
C3—C4 | 1.378 (3) | S2—O8 | 1.4338 (15) |
C3—H3 | 0.9500 | S2—O7 | 1.4376 (15) |
C4—C5 | 1.389 (3) | S2—N4 | 1.6351 (17) |
C4—H4 | 0.9500 | S2—C26 | 1.760 (2) |
C5—C6 | 1.506 (3) | N4—C20 | 1.364 (3) |
C6—H6A | 0.9900 | O6—C20 | 1.234 (2) |
C6—H6B | 0.9900 | C20—C21 | 1.493 (3) |
C7—C8 | 1.376 (3) | C21—C26 | 1.378 (3) |
C7—H7 | 0.9500 | C21—C22 | 1.386 (3) |
C8—C9 | 1.384 (3) | C22—C23 | 1.386 (3) |
C8—H8 | 0.9500 | C22—H22 | 0.9500 |
C9—C10 | 1.380 (3) | C23—C24 | 1.393 (3) |
C9—H9 | 0.9500 | C23—H23 | 0.9500 |
C10—C11 | 1.389 (3) | C24—C25 | 1.390 (3) |
C10—H10 | 0.9500 | C24—H24 | 0.9500 |
C11—C12 | 1.504 (3) | C25—C26 | 1.380 (3) |
C12—H12A | 0.9900 | C25—H25 | 0.9500 |
| | | |
O3—Zn1—N2 | 101.67 (6) | O2—C12—H12A | 109.2 |
O3—Zn1—N4 | 93.40 (6) | C11—C12—H12A | 109.2 |
N2—Zn1—N4 | 99.10 (6) | O2—C12—H12B | 109.2 |
O3—Zn1—N1 | 94.17 (6) | C11—C12—H12B | 109.2 |
N2—Zn1—N1 | 156.92 (6) | H12A—C12—H12B | 107.9 |
N4—Zn1—N1 | 96.58 (6) | O5—S1—O4 | 116.39 (10) |
O3—Zn1—O1 | 168.97 (5) | O5—S1—N3 | 110.06 (10) |
N2—Zn1—O1 | 85.38 (6) | O4—S1—N3 | 111.01 (10) |
N4—Zn1—O1 | 93.84 (6) | O5—S1—C19 | 111.56 (10) |
N1—Zn1—O1 | 76.74 (6) | O4—S1—C19 | 109.72 (10) |
O3—Zn1—O2 | 88.05 (5) | N3—S1—C19 | 96.29 (9) |
N2—Zn1—O2 | 76.74 (6) | C13—N3—S1 | 111.22 (14) |
N4—Zn1—O2 | 175.80 (6) | C13—O3—Zn1 | 128.87 (13) |
N1—Zn1—O2 | 87.24 (6) | O3—C13—N3 | 124.82 (19) |
O1—Zn1—O2 | 85.32 (5) | O3—C13—C14 | 121.05 (18) |
C6—O1—Zn1 | 112.97 (11) | N3—C13—C14 | 114.09 (18) |
C6—O1—H1O | 112.9 (17) | C19—C14—C15 | 120.8 (2) |
Zn1—O1—H1O | 99.2 (17) | C19—C14—C13 | 111.43 (18) |
C12—O2—Zn1 | 113.28 (11) | C15—C14—C13 | 127.79 (19) |
C12—O2—H2O | 103.7 (17) | C14—C15—C16 | 117.8 (2) |
Zn1—O2—H2O | 102.5 (18) | C14—C15—H15 | 121.1 |
C5—N1—C1 | 118.36 (18) | C16—C15—H15 | 121.1 |
C5—N1—Zn1 | 116.78 (14) | C17—C16—C15 | 120.8 (2) |
C1—N1—Zn1 | 124.82 (13) | C17—C16—H16 | 119.6 |
C11—N2—C7 | 118.32 (18) | C15—C16—H16 | 119.6 |
C11—N2—Zn1 | 118.38 (13) | C16—C17—C18 | 121.6 (2) |
C7—N2—Zn1 | 123.16 (13) | C16—C17—H17 | 119.2 |
N1—C1—C2 | 122.72 (19) | C18—C17—H17 | 119.2 |
N1—C1—H1 | 118.6 | C19—C18—C17 | 116.7 (2) |
C2—C1—H1 | 118.6 | C19—C18—H18 | 121.6 |
C1—C2—C3 | 118.7 (2) | C17—C18—H18 | 121.6 |
C1—C2—H2 | 120.6 | C14—C19—C18 | 122.3 (2) |
C3—C2—H2 | 120.6 | C14—C19—S1 | 106.89 (16) |
C4—C3—C2 | 119.0 (2) | C18—C19—S1 | 130.82 (18) |
C4—C3—H3 | 120.5 | O8—S2—O7 | 115.93 (9) |
C2—C3—H3 | 120.5 | O8—S2—N4 | 111.69 (9) |
C3—C4—C5 | 119.2 (2) | O7—S2—N4 | 110.72 (9) |
C3—C4—H4 | 120.4 | O8—S2—C26 | 109.78 (9) |
C5—C4—H4 | 120.4 | O7—S2—C26 | 110.98 (9) |
N1—C5—C4 | 122.02 (19) | N4—S2—C26 | 95.97 (9) |
N1—C5—C6 | 116.86 (18) | C20—N4—S2 | 111.71 (14) |
C4—C5—C6 | 121.12 (18) | C20—N4—Zn1 | 124.11 (13) |
O1—C6—C5 | 111.91 (16) | S2—N4—Zn1 | 124.16 (9) |
O1—C6—H6A | 109.2 | O6—C20—N4 | 124.35 (18) |
C5—C6—H6A | 109.2 | O6—C20—C21 | 123.05 (18) |
O1—C6—H6B | 109.2 | N4—C20—C21 | 112.59 (17) |
C5—C6—H6B | 109.2 | C26—C21—C22 | 119.98 (19) |
H6A—C6—H6B | 107.9 | C26—C21—C20 | 111.52 (17) |
N2—C7—C8 | 122.79 (19) | C22—C21—C20 | 128.50 (19) |
N2—C7—H7 | 118.6 | C21—C22—C23 | 117.98 (19) |
C8—C7—H7 | 118.6 | C21—C22—H22 | 121.0 |
C7—C8—C9 | 118.77 (19) | C23—C22—H22 | 121.0 |
C7—C8—H8 | 120.6 | C22—C23—C24 | 121.2 (2) |
C9—C8—H8 | 120.6 | C22—C23—H23 | 119.4 |
C8—C9—C10 | 118.92 (19) | C24—C23—H23 | 119.4 |
C8—C9—H9 | 120.5 | C25—C24—C23 | 121.0 (2) |
C10—C9—H9 | 120.5 | C25—C24—H24 | 119.5 |
C9—C10—C11 | 119.19 (19) | C23—C24—H24 | 119.5 |
C9—C10—H10 | 120.4 | C26—C25—C24 | 116.5 (2) |
C11—C10—H10 | 120.4 | C26—C25—H25 | 121.7 |
N2—C11—C10 | 122.00 (18) | C24—C25—H25 | 121.7 |
N2—C11—C12 | 118.09 (18) | C21—C26—C25 | 123.27 (19) |
C10—C11—C12 | 119.90 (18) | C21—C26—S2 | 108.05 (15) |
O2—C12—C11 | 111.98 (16) | C25—C26—S2 | 128.67 (16) |
| | | |
O3—Zn1—O1—C6 | 17.2 (4) | Zn1—O3—C13—N3 | 29.1 (3) |
N2—Zn1—O1—C6 | 147.42 (13) | Zn1—O3—C13—C14 | −148.21 (15) |
N4—Zn1—O1—C6 | −113.74 (13) | S1—N3—C13—O3 | −178.41 (16) |
N1—Zn1—O1—C6 | −17.88 (13) | S1—N3—C13—C14 | −0.9 (2) |
O2—Zn1—O1—C6 | 70.38 (13) | O3—C13—C14—C19 | 176.36 (19) |
O3—Zn1—O2—C12 | −93.63 (13) | N3—C13—C14—C19 | −1.2 (3) |
N2—Zn1—O2—C12 | 8.84 (13) | O3—C13—C14—C15 | −2.4 (3) |
N1—Zn1—O2—C12 | 172.09 (14) | N3—C13—C14—C15 | 180.0 (2) |
O1—Zn1—O2—C12 | 95.18 (13) | C19—C14—C15—C16 | −0.7 (3) |
O3—Zn1—N1—C5 | −165.52 (14) | C13—C14—C15—C16 | 178.0 (2) |
N2—Zn1—N1—C5 | −32.0 (2) | C14—C15—C16—C17 | −0.1 (4) |
N4—Zn1—N1—C5 | 100.57 (14) | C15—C16—C17—C18 | 0.7 (4) |
O1—Zn1—N1—C5 | 8.16 (13) | C16—C17—C18—C19 | −0.4 (4) |
O2—Zn1—N1—C5 | −77.68 (14) | C15—C14—C19—C18 | 1.0 (3) |
O3—Zn1—N1—C1 | 16.83 (16) | C13—C14—C19—C18 | −177.9 (2) |
N2—Zn1—N1—C1 | 150.32 (16) | C15—C14—C19—S1 | −178.56 (18) |
N4—Zn1—N1—C1 | −77.09 (16) | C13—C14—C19—S1 | 2.6 (2) |
O1—Zn1—N1—C1 | −169.50 (17) | C17—C18—C19—C14 | −0.4 (3) |
O2—Zn1—N1—C1 | 104.66 (16) | C17—C18—C19—S1 | 179.04 (19) |
O3—Zn1—N2—C11 | 83.07 (15) | O5—S1—C19—C14 | −117.26 (16) |
N4—Zn1—N2—C11 | 178.49 (14) | O4—S1—C19—C14 | 112.24 (16) |
N1—Zn1—N2—C11 | −49.3 (2) | N3—S1—C19—C14 | −2.77 (16) |
O1—Zn1—N2—C11 | −88.35 (14) | O5—S1—C19—C18 | 63.2 (2) |
O2—Zn1—N2—C11 | −2.08 (14) | O4—S1—C19—C18 | −67.3 (2) |
O3—Zn1—N2—C7 | −101.43 (16) | N3—S1—C19—C18 | 177.7 (2) |
N4—Zn1—N2—C7 | −6.02 (17) | O8—S2—N4—C20 | −117.13 (15) |
N1—Zn1—N2—C7 | 126.19 (18) | O7—S2—N4—C20 | 112.05 (14) |
O1—Zn1—N2—C7 | 87.14 (16) | C26—S2—N4—C20 | −3.06 (15) |
O2—Zn1—N2—C7 | 173.41 (17) | O8—S2—N4—Zn1 | 64.62 (13) |
C5—N1—C1—C2 | 1.1 (3) | O7—S2—N4—Zn1 | −66.20 (13) |
Zn1—N1—C1—C2 | 178.73 (15) | C26—S2—N4—Zn1 | 178.69 (11) |
N1—C1—C2—C3 | −1.4 (3) | O3—Zn1—N4—C20 | 175.52 (15) |
C1—C2—C3—C4 | 0.5 (3) | N2—Zn1—N4—C20 | 73.13 (16) |
C2—C3—C4—C5 | 0.5 (3) | N1—Zn1—N4—C20 | −89.88 (16) |
C1—N1—C5—C4 | 0.0 (3) | O1—Zn1—N4—C20 | −12.80 (16) |
Zn1—N1—C5—C4 | −177.83 (15) | O3—Zn1—N4—S2 | −6.44 (11) |
C1—N1—C5—C6 | −179.63 (17) | N2—Zn1—N4—S2 | −108.84 (11) |
Zn1—N1—C5—C6 | 2.6 (2) | N1—Zn1—N4—S2 | 88.16 (11) |
C3—C4—C5—N1 | −0.8 (3) | O1—Zn1—N4—S2 | 165.23 (11) |
C3—C4—C5—C6 | 178.80 (19) | S2—N4—C20—O6 | −175.72 (16) |
Zn1—O1—C6—C5 | 24.1 (2) | Zn1—N4—C20—O6 | 2.5 (3) |
N1—C5—C6—O1 | −18.0 (2) | S2—N4—C20—C21 | 4.2 (2) |
C4—C5—C6—O1 | 162.34 (18) | Zn1—N4—C20—C21 | −177.55 (12) |
C11—N2—C7—C8 | −0.9 (3) | O6—C20—C21—C26 | 176.44 (19) |
Zn1—N2—C7—C8 | −176.42 (15) | N4—C20—C21—C26 | −3.5 (2) |
N2—C7—C8—C9 | 0.2 (3) | O6—C20—C21—C22 | −3.5 (3) |
C7—C8—C9—C10 | 1.0 (3) | N4—C20—C21—C22 | 176.6 (2) |
C8—C9—C10—C11 | −1.4 (3) | C26—C21—C22—C23 | −0.3 (3) |
C7—N2—C11—C10 | 0.5 (3) | C20—C21—C22—C23 | 179.6 (2) |
Zn1—N2—C11—C10 | 176.18 (15) | C21—C22—C23—C24 | 0.3 (3) |
C7—N2—C11—C12 | 179.42 (18) | C22—C23—C24—C25 | −0.3 (3) |
Zn1—N2—C11—C12 | −4.9 (2) | C23—C24—C25—C26 | 0.3 (3) |
C9—C10—C11—N2 | 0.7 (3) | C22—C21—C26—C25 | 0.4 (3) |
C9—C10—C11—C12 | −178.22 (19) | C20—C21—C26—C25 | −179.58 (19) |
Zn1—O2—C12—C11 | −13.4 (2) | C22—C21—C26—S2 | −178.87 (16) |
N2—C11—C12—O2 | 12.4 (3) | C20—C21—C26—S2 | 1.2 (2) |
C10—C11—C12—O2 | −168.60 (18) | C24—C25—C26—C21 | −0.4 (3) |
O5—S1—N3—C13 | 117.84 (16) | C24—C25—C26—S2 | 178.69 (17) |
O4—S1—N3—C13 | −111.83 (16) | O8—S2—C26—C21 | 116.62 (15) |
C19—S1—N3—C13 | 2.13 (16) | O7—S2—C26—C21 | −113.92 (15) |
N2—Zn1—O3—C13 | −112.53 (17) | N4—S2—C26—C21 | 0.99 (16) |
N4—Zn1—O3—C13 | 147.45 (17) | O8—S2—C26—C25 | −62.6 (2) |
N1—Zn1—O3—C13 | 50.59 (17) | O7—S2—C26—C25 | 66.9 (2) |
O1—Zn1—O3—C13 | 16.5 (4) | N4—S2—C26—C25 | −178.2 (2) |
O2—Zn1—O3—C13 | −36.49 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O6 | 0.83 (1) | 1.81 (1) | 2.617 (2) | 162 (2) |
O2—H2O···N3 | 0.83 (1) | 1.88 (1) | 2.667 (2) | 159 (2) |
C6—H6B···O6i | 0.99 | 2.36 | 3.213 (2) | 144 |
C8—H8···O4ii | 0.95 | 2.37 | 3.247 (3) | 153 |
C12—H12B···O4iii | 0.99 | 2.47 | 3.441 (3) | 168 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+1, −y, −z+1. |
(II) Bis(2-pyridylmethanol)bis(saccharinato)cadmium(II)
top
Crystal data top
[Cd(C7H4NO3S)2(C6H7NO)2] | Z = 2 |
Mr = 695.00 | F(000) = 700 |
Triclinic, P1 | Dx = 1.747 Mg m−3 |
a = 8.7516 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.4547 (1) Å | Cell parameters from 24147 reflections |
c = 13.5442 (2) Å | θ = 2.9–27.5° |
α = 99.8079 (6)° | µ = 1.04 mm−1 |
β = 96.5191 (5)° | T = 120 K |
γ = 95.1327 (5)° | Block, colourless |
V = 1321.03 (3) Å3 | 0.35 × 0.25 × 0.20 mm |
Data collection top
Enraf Nonius KappaCCD area-detector diffractometer | 5886 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 5437 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans to fill Ewald sphere | h = −11→11 |
Absorption correction: multi-scan (Blessing, 1995) | k = −14→14 |
Tmin = 0.738, Tmax = 0.812 | l = −16→17 |
18640 measured reflections | |
Refinement top
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)] = 0.027 | Hydrogen site location: mixed |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0261P)2 + 1.0424P] where P = (Fo2 + 2Fc2)/3 |
5886 reflections | (Δ/σ)max = 0.001 |
376 parameters | Δρmax = 0.40 e Å−3 |
2 restraints | Δρmin = −0.85 e Å−3 |
Crystal data top
[Cd(C7H4NO3S)2(C6H7NO)2] | γ = 95.1327 (5)° |
Mr = 695.00 | V = 1321.03 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.7516 (1) Å | Mo Kα radiation |
b = 11.4547 (1) Å | µ = 1.04 mm−1 |
c = 13.5442 (2) Å | T = 120 K |
α = 99.8079 (6)° | 0.35 × 0.25 × 0.20 mm |
β = 96.5191 (5)° | |
Data collection top
Enraf Nonius KappaCCD area-detector diffractometer | 5886 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 5437 reflections with I > 2σ(I) |
Tmin = 0.738, Tmax = 0.812 | Rint = 0.049 |
18640 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | 2 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.40 e Å−3 |
5886 reflections | Δρmin = −0.85 e Å−3 |
376 parameters | |
Special details top
Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the
entire data set is used to refine the cell, which is indexed from all observed
reflections in a 10 degree phi range. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cd1 | 0.383860 (15) | 0.289946 (12) | 0.224030 (10) | 0.01435 (6) | |
O1 | 0.52788 (17) | 0.35684 (13) | 0.10290 (11) | 0.0185 (3) | |
H1O | 0.474 (2) | 0.4068 (18) | 0.0829 (19) | 0.022* | |
O2 | 0.59897 (16) | 0.19382 (13) | 0.28767 (11) | 0.0183 (3) | |
H2O | 0.554 (3) | 0.1342 (16) | 0.3058 (19) | 0.022* | |
N1 | 0.34002 (18) | 0.14766 (14) | 0.07946 (12) | 0.0138 (3) | |
N2 | 0.53985 (18) | 0.42437 (14) | 0.34415 (12) | 0.0146 (3) | |
C1 | 0.2287 (2) | 0.05520 (17) | 0.06548 (15) | 0.0161 (4) | |
H1 | 0.1693 | 0.0466 | 0.1188 | 0.019* | |
C2 | 0.1972 (2) | −0.02729 (18) | −0.02279 (16) | 0.0178 (4) | |
H2 | 0.1178 | −0.0916 | −0.0304 | 0.021* | |
C3 | 0.2844 (2) | −0.01428 (19) | −0.10073 (16) | 0.0205 (4) | |
H3 | 0.2661 | −0.0702 | −0.1624 | 0.025* | |
C4 | 0.3979 (2) | 0.08090 (18) | −0.08736 (16) | 0.0183 (4) | |
H4 | 0.4583 | 0.0915 | −0.1398 | 0.022* | |
C5 | 0.4227 (2) | 0.16113 (17) | 0.00404 (15) | 0.0141 (4) | |
C6 | 0.5484 (2) | 0.26559 (18) | 0.02194 (16) | 0.0179 (4) | |
H6A | 0.6502 | 0.2364 | 0.0367 | 0.021* | |
H6B | 0.5492 | 0.2995 | −0.0406 | 0.021* | |
C7 | 0.5122 (2) | 0.53910 (18) | 0.36433 (16) | 0.0167 (4) | |
H7 | 0.4261 | 0.5633 | 0.3268 | 0.020* | |
C8 | 0.6033 (2) | 0.62260 (18) | 0.43697 (16) | 0.0176 (4) | |
H8 | 0.5795 | 0.7026 | 0.4504 | 0.021* | |
C9 | 0.7312 (2) | 0.58764 (18) | 0.49053 (15) | 0.0177 (4) | |
H9 | 0.7966 | 0.6433 | 0.5413 | 0.021* | |
C10 | 0.7614 (2) | 0.47049 (18) | 0.46842 (15) | 0.0174 (4) | |
H10 | 0.8492 | 0.4449 | 0.5031 | 0.021* | |
C11 | 0.6626 (2) | 0.39011 (17) | 0.39519 (15) | 0.0144 (4) | |
C12 | 0.6916 (2) | 0.26099 (18) | 0.37513 (16) | 0.0191 (4) | |
H12A | 0.8020 | 0.2564 | 0.3671 | 0.023* | |
H12B | 0.6706 | 0.2250 | 0.4344 | 0.023* | |
S1 | 0.35988 (6) | −0.11532 (4) | 0.33596 (4) | 0.02063 (12) | |
N3 | 0.3866 (2) | 0.02229 (15) | 0.31852 (13) | 0.0181 (4) | |
O3 | 0.24371 (17) | 0.18041 (13) | 0.31316 (11) | 0.0200 (3) | |
O4 | 0.4498 (2) | −0.13017 (15) | 0.42793 (14) | 0.0327 (4) | |
O5 | 0.3788 (2) | −0.19639 (14) | 0.24603 (14) | 0.0325 (4) | |
C13 | 0.2576 (2) | 0.07537 (18) | 0.32498 (15) | 0.0159 (4) | |
C14 | 0.1230 (2) | −0.00286 (19) | 0.34535 (16) | 0.0197 (4) | |
C15 | −0.0249 (3) | 0.0262 (2) | 0.35524 (19) | 0.0290 (5) | |
H15 | −0.0519 | 0.1036 | 0.3499 | 0.035* | |
C16 | −0.1327 (3) | −0.0615 (3) | 0.3732 (2) | 0.0392 (6) | |
H16 | −0.2349 | −0.0439 | 0.3816 | 0.047* | |
C17 | −0.0926 (3) | −0.1747 (3) | 0.3789 (2) | 0.0411 (7) | |
H17 | −0.1689 | −0.2339 | 0.3898 | 0.049* | |
C18 | 0.0566 (3) | −0.2037 (2) | 0.36918 (18) | 0.0314 (5) | |
H18 | 0.0843 | −0.2811 | 0.3738 | 0.038* | |
C19 | 0.1622 (3) | −0.11500 (19) | 0.35246 (16) | 0.0209 (4) | |
S2 | 0.01977 (5) | 0.38779 (4) | 0.21705 (4) | 0.01421 (10) | |
N4 | 0.19338 (19) | 0.40329 (15) | 0.18416 (13) | 0.0160 (3) | |
O6 | 0.33053 (17) | 0.52036 (13) | 0.09539 (12) | 0.0234 (3) | |
O7 | −0.06543 (17) | 0.27863 (13) | 0.16268 (12) | 0.0233 (3) | |
O8 | 0.02562 (17) | 0.40667 (14) | 0.32496 (11) | 0.0211 (3) | |
C20 | 0.2130 (2) | 0.49513 (18) | 0.13289 (15) | 0.0172 (4) | |
C21 | 0.0747 (2) | 0.56276 (18) | 0.12757 (15) | 0.0161 (4) | |
C22 | 0.0566 (3) | 0.66502 (19) | 0.08748 (17) | 0.0215 (4) | |
H22 | 0.1367 | 0.7005 | 0.0567 | 0.026* | |
C23 | −0.0824 (3) | 0.7140 (2) | 0.09372 (18) | 0.0254 (5) | |
H23 | −0.0976 | 0.7841 | 0.0669 | 0.030* | |
C24 | −0.2000 (3) | 0.6619 (2) | 0.13873 (19) | 0.0264 (5) | |
H24 | −0.2936 | 0.6976 | 0.1426 | 0.032* | |
C25 | −0.1830 (2) | 0.55904 (19) | 0.17800 (17) | 0.0214 (4) | |
H25 | −0.2631 | 0.5226 | 0.2081 | 0.026* | |
C26 | −0.0439 (2) | 0.51231 (17) | 0.17117 (15) | 0.0155 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.01617 (8) | 0.01129 (8) | 0.01493 (9) | −0.00037 (5) | 0.00189 (6) | 0.00160 (6) |
O1 | 0.0198 (7) | 0.0134 (7) | 0.0227 (8) | 0.0003 (5) | 0.0044 (6) | 0.0045 (6) |
O2 | 0.0196 (7) | 0.0118 (7) | 0.0224 (8) | 0.0004 (6) | 0.0042 (6) | −0.0006 (6) |
N1 | 0.0132 (8) | 0.0128 (8) | 0.0154 (8) | 0.0021 (6) | 0.0015 (6) | 0.0027 (6) |
N2 | 0.0140 (8) | 0.0135 (8) | 0.0158 (8) | 0.0001 (6) | 0.0029 (6) | 0.0017 (7) |
C1 | 0.0159 (9) | 0.0139 (9) | 0.0187 (10) | 0.0008 (7) | 0.0034 (8) | 0.0030 (8) |
C2 | 0.0155 (10) | 0.0134 (9) | 0.0227 (10) | 0.0012 (7) | −0.0010 (8) | 0.0007 (8) |
C3 | 0.0241 (11) | 0.0186 (10) | 0.0174 (10) | 0.0079 (8) | −0.0006 (8) | −0.0015 (8) |
C4 | 0.0197 (10) | 0.0204 (10) | 0.0167 (10) | 0.0078 (8) | 0.0045 (8) | 0.0047 (8) |
C5 | 0.0117 (9) | 0.0141 (9) | 0.0180 (10) | 0.0045 (7) | 0.0023 (7) | 0.0052 (8) |
C6 | 0.0166 (10) | 0.0168 (10) | 0.0215 (10) | 0.0015 (8) | 0.0063 (8) | 0.0047 (8) |
C7 | 0.0162 (9) | 0.0144 (9) | 0.0203 (10) | 0.0031 (7) | 0.0044 (8) | 0.0035 (8) |
C8 | 0.0205 (10) | 0.0116 (9) | 0.0207 (10) | 0.0005 (7) | 0.0073 (8) | 0.0010 (8) |
C9 | 0.0187 (10) | 0.0167 (10) | 0.0164 (10) | −0.0024 (8) | 0.0027 (8) | 0.0010 (8) |
C10 | 0.0178 (10) | 0.0182 (10) | 0.0160 (10) | 0.0005 (8) | 0.0006 (8) | 0.0043 (8) |
C11 | 0.0139 (9) | 0.0151 (9) | 0.0153 (9) | 0.0005 (7) | 0.0062 (7) | 0.0035 (8) |
C12 | 0.0191 (10) | 0.0140 (10) | 0.0240 (11) | 0.0031 (8) | 0.0004 (8) | 0.0037 (8) |
S1 | 0.0264 (3) | 0.0119 (2) | 0.0240 (3) | 0.00258 (19) | 0.0034 (2) | 0.0043 (2) |
N3 | 0.0203 (9) | 0.0126 (8) | 0.0222 (9) | 0.0012 (7) | 0.0037 (7) | 0.0053 (7) |
O3 | 0.0254 (8) | 0.0144 (7) | 0.0237 (8) | 0.0041 (6) | 0.0090 (6) | 0.0082 (6) |
O4 | 0.0386 (10) | 0.0239 (9) | 0.0363 (10) | 0.0085 (7) | −0.0059 (8) | 0.0120 (8) |
O5 | 0.0425 (10) | 0.0187 (8) | 0.0363 (9) | 0.0034 (7) | 0.0147 (8) | −0.0016 (7) |
C13 | 0.0215 (10) | 0.0150 (10) | 0.0115 (9) | 0.0026 (8) | 0.0020 (7) | 0.0027 (8) |
C14 | 0.0222 (10) | 0.0207 (10) | 0.0176 (10) | −0.0005 (8) | 0.0056 (8) | 0.0069 (8) |
C15 | 0.0236 (11) | 0.0325 (13) | 0.0331 (13) | 0.0017 (10) | 0.0083 (10) | 0.0102 (11) |
C16 | 0.0244 (13) | 0.0492 (17) | 0.0455 (16) | −0.0037 (11) | 0.0134 (11) | 0.0115 (13) |
C17 | 0.0367 (15) | 0.0456 (16) | 0.0390 (15) | −0.0198 (12) | 0.0113 (12) | 0.0105 (13) |
C18 | 0.0433 (14) | 0.0230 (12) | 0.0263 (12) | −0.0110 (10) | 0.0048 (10) | 0.0071 (10) |
C19 | 0.0266 (11) | 0.0199 (10) | 0.0160 (10) | −0.0027 (8) | 0.0046 (8) | 0.0045 (8) |
S2 | 0.0140 (2) | 0.0131 (2) | 0.0152 (2) | −0.00044 (17) | 0.00057 (18) | 0.00373 (18) |
N4 | 0.0152 (8) | 0.0143 (8) | 0.0200 (9) | 0.0024 (6) | 0.0048 (7) | 0.0057 (7) |
O6 | 0.0247 (8) | 0.0174 (7) | 0.0325 (9) | 0.0039 (6) | 0.0152 (7) | 0.0084 (7) |
O7 | 0.0233 (8) | 0.0146 (7) | 0.0294 (8) | −0.0051 (6) | −0.0015 (6) | 0.0034 (6) |
O8 | 0.0216 (7) | 0.0282 (8) | 0.0152 (7) | 0.0052 (6) | 0.0041 (6) | 0.0069 (6) |
C20 | 0.0228 (10) | 0.0119 (9) | 0.0168 (10) | 0.0013 (8) | 0.0043 (8) | 0.0020 (8) |
C21 | 0.0191 (10) | 0.0138 (9) | 0.0145 (9) | 0.0004 (7) | 0.0000 (8) | 0.0018 (8) |
C22 | 0.0252 (11) | 0.0181 (10) | 0.0223 (11) | 0.0013 (8) | 0.0030 (9) | 0.0072 (9) |
C23 | 0.0256 (11) | 0.0215 (11) | 0.0311 (12) | 0.0044 (9) | −0.0018 (9) | 0.0133 (10) |
C24 | 0.0171 (10) | 0.0259 (12) | 0.0362 (13) | 0.0050 (9) | −0.0035 (9) | 0.0091 (10) |
C25 | 0.0154 (10) | 0.0212 (11) | 0.0261 (11) | −0.0015 (8) | −0.0014 (8) | 0.0052 (9) |
C26 | 0.0176 (10) | 0.0124 (9) | 0.0149 (9) | −0.0008 (7) | −0.0039 (7) | 0.0032 (8) |
Geometric parameters (Å, º) top
Cd1—O3 | 2.2612 (14) | C12—H12B | 0.9900 |
Cd1—N2 | 2.2688 (16) | S1—O5 | 1.4357 (17) |
Cd1—N4 | 2.2755 (17) | S1—O4 | 1.4400 (17) |
Cd1—N1 | 2.2952 (16) | S1—N3 | 1.6336 (17) |
Cd1—O1 | 2.3648 (14) | S1—C19 | 1.770 (2) |
Cd1—O2 | 2.4136 (15) | N3—C13 | 1.334 (3) |
O1—C6 | 1.420 (2) | O3—C13 | 1.255 (2) |
O1—H1O | 0.833 (10) | C13—C14 | 1.495 (3) |
O2—C12 | 1.418 (2) | C14—C19 | 1.375 (3) |
O2—H2O | 0.843 (10) | C14—C15 | 1.380 (3) |
N1—C5 | 1.339 (3) | C15—C16 | 1.388 (3) |
N1—C1 | 1.346 (2) | C15—H15 | 0.9500 |
N2—C11 | 1.336 (3) | C16—C17 | 1.385 (4) |
N2—C7 | 1.345 (3) | C16—H16 | 0.9500 |
C1—C2 | 1.375 (3) | C17—C18 | 1.391 (4) |
C1—H1 | 0.9500 | C17—H17 | 0.9500 |
C2—C3 | 1.391 (3) | C18—C19 | 1.377 (3) |
C2—H2 | 0.9500 | C18—H18 | 0.9500 |
C3—C4 | 1.381 (3) | S2—O7 | 1.4340 (15) |
C3—H3 | 0.9500 | S2—O8 | 1.4349 (15) |
C4—C5 | 1.393 (3) | S2—N4 | 1.6343 (17) |
C4—H4 | 0.9500 | S2—C26 | 1.760 (2) |
C5—C6 | 1.519 (3) | N4—C20 | 1.365 (3) |
C6—H6A | 0.9900 | O6—C20 | 1.231 (2) |
C6—H6B | 0.9900 | C20—C21 | 1.496 (3) |
C7—C8 | 1.372 (3) | C21—C26 | 1.381 (3) |
C7—H7 | 0.9500 | C21—C22 | 1.386 (3) |
C8—C9 | 1.391 (3) | C22—C23 | 1.390 (3) |
C8—H8 | 0.9500 | C22—H22 | 0.9500 |
C9—C10 | 1.380 (3) | C23—C24 | 1.394 (3) |
C9—H9 | 0.9500 | C23—H23 | 0.9500 |
C10—C11 | 1.390 (3) | C24—C25 | 1.386 (3) |
C10—H10 | 0.9500 | C24—H24 | 0.9500 |
C11—C12 | 1.507 (3) | C25—C26 | 1.379 (3) |
C12—H12A | 0.9900 | C25—H25 | 0.9500 |
| | | |
O3—Cd1—N2 | 104.10 (6) | O2—C12—H12A | 109.0 |
O3—Cd1—N4 | 95.69 (6) | C11—C12—H12A | 109.0 |
N2—Cd1—N4 | 100.16 (6) | O2—C12—H12B | 109.0 |
O3—Cd1—N1 | 94.13 (6) | C11—C12—H12B | 109.0 |
N2—Cd1—N1 | 152.70 (6) | H12A—C12—H12B | 107.8 |
N4—Cd1—N1 | 98.02 (6) | O5—S1—O4 | 116.24 (11) |
O3—Cd1—O1 | 165.28 (5) | O5—S1—N3 | 110.33 (10) |
N2—Cd1—O1 | 87.82 (5) | O4—S1—N3 | 110.90 (10) |
N4—Cd1—O1 | 90.56 (6) | O5—S1—C19 | 111.05 (10) |
N1—Cd1—O1 | 71.76 (5) | O4—S1—C19 | 110.21 (11) |
O3—Cd1—O2 | 84.99 (5) | N3—S1—C19 | 96.35 (10) |
N2—Cd1—O2 | 71.37 (5) | C13—N3—S1 | 111.22 (14) |
N4—Cd1—O2 | 171.35 (5) | C13—O3—Cd1 | 127.37 (13) |
N1—Cd1—O2 | 90.52 (5) | O3—C13—N3 | 125.08 (19) |
O1—Cd1—O2 | 90.83 (5) | O3—C13—C14 | 120.79 (18) |
C6—O1—Cd1 | 114.12 (11) | N3—C13—C14 | 114.11 (18) |
C6—O1—H1O | 111.5 (18) | C19—C14—C15 | 121.3 (2) |
Cd1—O1—H1O | 101.9 (18) | C19—C14—C13 | 111.18 (18) |
C12—O2—Cd1 | 114.62 (11) | C15—C14—C13 | 127.5 (2) |
C12—O2—H2O | 106.5 (18) | C14—C15—C16 | 117.7 (2) |
Cd1—O2—H2O | 102.4 (17) | C14—C15—H15 | 121.2 |
C5—N1—C1 | 118.86 (17) | C16—C15—H15 | 121.2 |
C5—N1—Cd1 | 118.50 (13) | C17—C16—C15 | 120.6 (2) |
C1—N1—Cd1 | 122.53 (13) | C17—C16—H16 | 119.7 |
C11—N2—C7 | 119.03 (17) | C15—C16—H16 | 119.7 |
C11—N2—Cd1 | 119.85 (13) | C16—C17—C18 | 121.6 (2) |
C7—N2—Cd1 | 121.12 (13) | C16—C17—H17 | 119.2 |
N1—C1—C2 | 122.78 (19) | C18—C17—H17 | 119.2 |
N1—C1—H1 | 118.6 | C19—C18—C17 | 116.8 (2) |
C2—C1—H1 | 118.6 | C19—C18—H18 | 121.6 |
C1—C2—C3 | 118.41 (19) | C17—C18—H18 | 121.6 |
C1—C2—H2 | 120.8 | C14—C19—C18 | 122.0 (2) |
C3—C2—H2 | 120.8 | C14—C19—S1 | 107.12 (15) |
C4—C3—C2 | 119.18 (19) | C18—C19—S1 | 130.9 (2) |
C4—C3—H3 | 120.4 | O7—S2—O8 | 115.89 (9) |
C2—C3—H3 | 120.4 | O7—S2—N4 | 110.70 (9) |
C3—C4—C5 | 119.14 (19) | O8—S2—N4 | 111.05 (9) |
C3—C4—H4 | 120.4 | O7—S2—C26 | 111.63 (9) |
C5—C4—H4 | 120.4 | O8—S2—C26 | 109.91 (9) |
N1—C5—C4 | 121.61 (18) | N4—S2—C26 | 95.90 (9) |
N1—C5—C6 | 117.86 (17) | C20—N4—S2 | 112.15 (14) |
C4—C5—C6 | 120.51 (18) | C20—N4—Cd1 | 123.66 (13) |
O1—C6—C5 | 112.82 (16) | S2—N4—Cd1 | 124.16 (9) |
O1—C6—H6A | 109.0 | O6—C20—N4 | 124.38 (19) |
C5—C6—H6A | 109.0 | O6—C20—C21 | 123.48 (19) |
O1—C6—H6B | 109.0 | N4—C20—C21 | 112.15 (17) |
C5—C6—H6B | 109.0 | C26—C21—C22 | 120.01 (19) |
H6A—C6—H6B | 107.8 | C26—C21—C20 | 111.67 (18) |
N2—C7—C8 | 122.71 (19) | C22—C21—C20 | 128.31 (19) |
N2—C7—H7 | 118.6 | C21—C22—C23 | 117.9 (2) |
C8—C7—H7 | 118.6 | C21—C22—H22 | 121.1 |
C7—C8—C9 | 118.61 (19) | C23—C22—H22 | 121.1 |
C7—C8—H8 | 120.7 | C22—C23—C24 | 121.1 (2) |
C9—C8—H8 | 120.7 | C22—C23—H23 | 119.5 |
C10—C9—C8 | 118.68 (19) | C24—C23—H23 | 119.5 |
C10—C9—H9 | 120.7 | C25—C24—C23 | 121.2 (2) |
C8—C9—H9 | 120.7 | C25—C24—H24 | 119.4 |
C9—C10—C11 | 119.66 (19) | C23—C24—H24 | 119.4 |
C9—C10—H10 | 120.2 | C26—C25—C24 | 116.6 (2) |
C11—C10—H10 | 120.2 | C26—C25—H25 | 121.7 |
N2—C11—C10 | 121.28 (18) | C24—C25—H25 | 121.7 |
N2—C11—C12 | 119.30 (17) | C25—C26—C21 | 123.19 (19) |
C10—C11—C12 | 119.39 (18) | C25—C26—S2 | 128.80 (16) |
O2—C12—C11 | 113.12 (17) | C21—C26—S2 | 107.97 (15) |
| | | |
O3—Cd1—O1—C6 | −0.4 (3) | Cd1—O3—C13—N3 | 24.8 (3) |
N2—Cd1—O1—C6 | 144.15 (13) | Cd1—O3—C13—C14 | −153.41 (14) |
N4—Cd1—O1—C6 | −115.71 (13) | S1—N3—C13—O3 | −178.79 (17) |
N1—Cd1—O1—C6 | −17.45 (12) | S1—N3—C13—C14 | −0.4 (2) |
O2—Cd1—O1—C6 | 72.83 (13) | O3—C13—C14—C19 | 178.01 (19) |
O3—Cd1—O2—C12 | −96.36 (13) | N3—C13—C14—C19 | −0.4 (3) |
N2—Cd1—O2—C12 | 10.36 (13) | O3—C13—C14—C15 | −1.1 (3) |
N1—Cd1—O2—C12 | 169.54 (13) | N3—C13—C14—C15 | −179.5 (2) |
O1—Cd1—O2—C12 | 97.78 (13) | C19—C14—C15—C16 | 0.3 (4) |
O3—Cd1—N1—C5 | −168.86 (14) | C13—C14—C15—C16 | 179.4 (2) |
N2—Cd1—N1—C5 | −36.6 (2) | C14—C15—C16—C17 | −1.2 (4) |
N4—Cd1—N1—C5 | 94.79 (14) | C15—C16—C17—C18 | 1.4 (4) |
O1—Cd1—N1—C5 | 6.86 (13) | C16—C17—C18—C19 | −0.7 (4) |
O2—Cd1—N1—C5 | −83.84 (14) | C15—C14—C19—C18 | 0.3 (3) |
O3—Cd1—N1—C1 | 15.02 (15) | C13—C14—C19—C18 | −178.8 (2) |
N2—Cd1—N1—C1 | 147.27 (15) | C15—C14—C19—S1 | −179.86 (19) |
N4—Cd1—N1—C1 | −81.33 (15) | C13—C14—C19—S1 | 1.0 (2) |
O1—Cd1—N1—C1 | −169.26 (16) | C17—C18—C19—C14 | −0.2 (4) |
O2—Cd1—N1—C1 | 100.04 (15) | C17—C18—C19—S1 | −179.92 (19) |
O3—Cd1—N2—C11 | 75.63 (15) | O5—S1—C19—C14 | −115.77 (16) |
N4—Cd1—N2—C11 | 174.19 (14) | O4—S1—C19—C14 | 113.95 (16) |
N1—Cd1—N2—C11 | −54.8 (2) | N3—S1—C19—C14 | −1.10 (17) |
O1—Cd1—N2—C11 | −95.64 (14) | O5—S1—C19—C18 | 64.0 (2) |
O2—Cd1—N2—C11 | −4.03 (13) | O4—S1—C19—C18 | −66.3 (2) |
O3—Cd1—N2—C7 | −105.21 (15) | N3—S1—C19—C18 | 178.7 (2) |
N4—Cd1—N2—C7 | −6.66 (16) | O7—S2—N4—C20 | 112.26 (15) |
N1—Cd1—N2—C7 | 124.35 (16) | O8—S2—N4—C20 | −117.54 (15) |
O1—Cd1—N2—C7 | 83.52 (15) | C26—S2—N4—C20 | −3.54 (16) |
O2—Cd1—N2—C7 | 175.13 (16) | O7—S2—N4—Cd1 | −69.91 (13) |
C5—N1—C1—C2 | 0.8 (3) | O8—S2—N4—Cd1 | 60.29 (13) |
Cd1—N1—C1—C2 | 176.95 (15) | C26—S2—N4—Cd1 | 174.29 (11) |
N1—C1—C2—C3 | 0.0 (3) | O3—Cd1—N4—C20 | 176.09 (16) |
C1—C2—C3—C4 | −0.6 (3) | N2—Cd1—N4—C20 | 70.63 (16) |
C2—C3—C4—C5 | 0.3 (3) | N1—Cd1—N4—C20 | −88.92 (16) |
C1—N1—C5—C4 | −1.1 (3) | O1—Cd1—N4—C20 | −17.26 (16) |
Cd1—N1—C5—C4 | −177.38 (14) | O3—Cd1—N4—S2 | −1.50 (12) |
C1—N1—C5—C6 | −179.55 (17) | N2—Cd1—N4—S2 | −106.96 (11) |
Cd1—N1—C5—C6 | 4.2 (2) | N1—Cd1—N4—S2 | 93.50 (11) |
C3—C4—C5—N1 | 0.5 (3) | O1—Cd1—N4—S2 | 165.15 (11) |
C3—C4—C5—C6 | 178.94 (18) | S2—N4—C20—O6 | −175.79 (17) |
Cd1—O1—C6—C5 | 25.0 (2) | Cd1—N4—C20—O6 | 6.4 (3) |
N1—C5—C6—O1 | −19.9 (3) | S2—N4—C20—C21 | 4.4 (2) |
C4—C5—C6—O1 | 161.67 (18) | Cd1—N4—C20—C21 | −173.41 (12) |
C11—N2—C7—C8 | −1.4 (3) | O6—C20—C21—C26 | 177.0 (2) |
Cd1—N2—C7—C8 | 179.46 (15) | N4—C20—C21—C26 | −3.3 (2) |
N2—C7—C8—C9 | 1.3 (3) | O6—C20—C21—C22 | −4.2 (3) |
C7—C8—C9—C10 | 0.0 (3) | N4—C20—C21—C22 | 175.6 (2) |
C8—C9—C10—C11 | −1.2 (3) | C26—C21—C22—C23 | 0.5 (3) |
C7—N2—C11—C10 | 0.1 (3) | C20—C21—C22—C23 | −178.3 (2) |
Cd1—N2—C11—C10 | 179.27 (14) | C21—C22—C23—C24 | −0.1 (3) |
C7—N2—C11—C12 | 178.22 (18) | C22—C23—C24—C25 | −0.6 (4) |
Cd1—N2—C11—C12 | −2.6 (2) | C23—C24—C25—C26 | 0.7 (3) |
C9—C10—C11—N2 | 1.2 (3) | C24—C25—C26—C21 | −0.3 (3) |
C9—C10—C11—C12 | −176.92 (18) | C24—C25—C26—S2 | 177.19 (17) |
Cd1—O2—C12—C11 | −14.8 (2) | C22—C21—C26—C25 | −0.4 (3) |
N2—C11—C12—O2 | 12.0 (3) | C20—C21—C26—C25 | 178.60 (19) |
C10—C11—C12—O2 | −169.85 (17) | C22—C21—C26—S2 | −178.27 (16) |
O5—S1—N3—C13 | 116.15 (16) | C20—C21—C26—S2 | 0.7 (2) |
O4—S1—N3—C13 | −113.60 (16) | O7—S2—C26—C25 | 68.7 (2) |
C19—S1—N3—C13 | 0.89 (16) | O8—S2—C26—C25 | −61.3 (2) |
N2—Cd1—O3—C13 | −106.71 (17) | N4—S2—C26—C25 | −176.2 (2) |
N4—Cd1—O3—C13 | 151.30 (17) | O7—S2—C26—C21 | −113.49 (15) |
N1—Cd1—O3—C13 | 52.80 (17) | O8—S2—C26—C21 | 116.48 (15) |
O1—Cd1—O3—C13 | 36.6 (3) | N4—S2—C26—C21 | 1.55 (15) |
O2—Cd1—O3—C13 | −37.36 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O6 | 0.83 (1) | 1.89 (1) | 2.666 (2) | 155 (3) |
O2—H2O···N3 | 0.84 (1) | 1.90 (1) | 2.700 (2) | 157 (2) |
C6—H6B···O6i | 0.99 | 2.50 | 3.302 (2) | 138 |
C8—H8···O4ii | 0.95 | 2.36 | 3.256 (3) | 158 |
C12—H12B···O4iii | 0.99 | 2.59 | 3.560 (3) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+1, −y, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Zn(C7H4NO3S)2(C6H7NO)2] | [Cd(C7H4NO3S)2(C6H7NO)2] |
Mr | 647.97 | 695.00 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 8.9874 (2), 11.1630 (2), 13.1879 (3) | 8.7516 (1), 11.4547 (1), 13.5442 (2) |
α, β, γ (°) | 99.1532 (8), 95.0138 (9), 95.729 (2) | 99.8079 (6), 96.5191 (5), 95.1327 (5) |
V (Å3) | 1292.52 (5) | 1321.03 (3) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.17 | 1.04 |
Crystal size (mm) | 0.25 × 0.10 × 0.05 | 0.35 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Enraf–Nonius KappaCCD area-detector diffractometer | Enraf Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.869, 0.943 | 0.738, 0.812 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16550, 5684, 4863 | 18640, 5886, 5437 |
Rint | 0.042 | 0.049 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.081, 1.04 | 0.027, 0.066, 1.06 |
No. of reflections | 5684 | 5886 |
No. of parameters | 376 | 376 |
No. of restraints | 2 | 2 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.53 | 0.40, −0.85 |
Selected geometric parameters (Å, º) for (I) topZn1—O3 | 2.0717 (14) | Zn1—N1 | 2.1244 (17) |
Zn1—N2 | 2.0887 (17) | Zn1—O1 | 2.1788 (14) |
Zn1—N4 | 2.1167 (16) | Zn1—O2 | 2.2323 (14) |
| | | |
O3—Zn1—N2 | 101.67 (6) | N4—Zn1—O1 | 93.84 (6) |
O3—Zn1—N4 | 93.40 (6) | N1—Zn1—O1 | 76.74 (6) |
N2—Zn1—N4 | 99.10 (6) | O3—Zn1—O2 | 88.05 (5) |
O3—Zn1—N1 | 94.17 (6) | N2—Zn1—O2 | 76.74 (6) |
N2—Zn1—N1 | 156.92 (6) | N4—Zn1—O2 | 175.80 (6) |
N4—Zn1—N1 | 96.58 (6) | N1—Zn1—O2 | 87.24 (6) |
O3—Zn1—O1 | 168.97 (5) | O1—Zn1—O2 | 85.32 (5) |
N2—Zn1—O1 | 85.38 (6) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O6 | 0.834 (10) | 1.811 (12) | 2.617 (2) | 162 (2) |
O2—H2O···N3 | 0.828 (10) | 1.876 (13) | 2.667 (2) | 159 (2) |
C6—H6B···O6i | 0.99 | 2.36 | 3.213 (2) | 144 |
C8—H8···O4ii | 0.95 | 2.37 | 3.247 (3) | 153 |
C12—H12B···O4iii | 0.99 | 2.47 | 3.441 (3) | 168 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+1, −y, −z+1. |
Selected geometric parameters (Å, º) for (II) topCd1—O3 | 2.2612 (14) | Cd1—N1 | 2.2952 (16) |
Cd1—N2 | 2.2688 (16) | Cd1—O1 | 2.3648 (14) |
Cd1—N4 | 2.2755 (17) | Cd1—O2 | 2.4136 (15) |
| | | |
O3—Cd1—N2 | 104.10 (6) | N4—Cd1—O1 | 90.56 (6) |
O3—Cd1—N4 | 95.69 (6) | N1—Cd1—O1 | 71.76 (5) |
N2—Cd1—N4 | 100.16 (6) | O3—Cd1—O2 | 84.99 (5) |
O3—Cd1—N1 | 94.13 (6) | N2—Cd1—O2 | 71.37 (5) |
N2—Cd1—N1 | 152.70 (6) | N4—Cd1—O2 | 171.35 (5) |
N4—Cd1—N1 | 98.02 (6) | N1—Cd1—O2 | 90.52 (5) |
O3—Cd1—O1 | 165.28 (5) | O1—Cd1—O2 | 90.83 (5) |
N2—Cd1—O1 | 87.82 (5) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O6 | 0.833 (10) | 1.889 (14) | 2.666 (2) | 155 (3) |
O2—H2O···N3 | 0.843 (10) | 1.904 (13) | 2.700 (2) | 157 (2) |
C6—H6B···O6i | 0.99 | 2.50 | 3.302 (2) | 138 |
C8—H8···O4ii | 0.95 | 2.36 | 3.256 (3) | 158 |
C12—H12B···O4iii | 0.99 | 2.59 | 3.560 (3) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y+1, z; (iii) −x+1, −y, −z+1. |
Saccharin and its deprotonated form, saccharinate (sac), are versatile polyfunctional ligands in coordination chemistry. Sac may bond to metals through four sites, viz. the negatively charged imino N atom, one carbonyl and two sulfonyl O atoms. The sac ligand can behave as a mono- or bidentate ligand and, in some cases, can as a bridging ligand between two metals. In this work, we report the crystal structures of new bis(saccharinato)zinc(II) and cadmium(II) complexes with 2-pyridylmethanol (mpy), namely [Zn(sac)2(mpy)2], (I), and [Cd(sac)2(mpy)2], (II), containing ambidentate N– and O-coordinated sac ligands within a coordination polyhedron.
The molecular structures of [Zn(sac)2(mpy)2] and [Cd(sac)2(mpy)2] are given in Figs. 1 and 2, respectively. The crystal structures are isomorphous and consist of individual neutral molecules of [M(sac)2(mpy)2]. The ZnII and CdII are six-coordinated by two mpy and two sac ligands, forming an MN3O3 core. The mpy ligand behaves as a bidentate donor through the amine N and methanol O atoms, forming a five-membered chelate ring. The N atoms of the two mpy ligands are in trans positions, while the hydroxyl O atoms occupy the cis positions of the octahedron. The sac anion usually interacts with transition metal ions through its deprotonated N atom. The coordination of sac to the transition metal ions through donor groups other than the amine N atom is unusual and there are only a few examples of O-coordination of sac reported previously, i.e. in metal–sac complexes with pyridine (Cotton et al., 1986; Quinzani et al., 1999), dipyridylamine (Deng et al., 2001) and triphenylphosphine (Falvello et al., 2001). Recently, O-coordinated sac complexes of trivalent lanthanides and yttrium have been reported by Piro et al. (2002). Therefore, the most interesting feature of complexes (I) and (II) is the coordination of the sac ligands, which occur in two distinct manners. Both sac ligands are monodentate, one being N-coordinated and the other O-coordinated.
The Zn—Nsac bond distance in (I) is significantly longer than the distance of 1.977 (2) Å found in [Zn(sac)2(py)2] (py is pyridine; Quinzani et al., 1997), but also markedly shorter the distances of 2.157 (5) and 2.2423 (9) Å reported for [Zn(sac)2(bipy)2]·H2O (bipy is 2,2'-bipyridine; Johns et al., 2001) and [Zn(sac)2(mea)2] (mea is monoethanolamine; Yilmaz et al., 2001), respectively. The Cd—Nsac bond distance in (II) is much shorter than that observed in [Cd(sac)2(HydEt-en)2] (Yilmaz et al., 2002), where HydEt-en is N-(2-hydroxyethyl)-ethylenediamine, while it is longer than those found in [Cd(sac)2(bipy)2] (Johns et al., 2001) and [Cd2(sac)4(im)2] (im is imidazole; Jianmin et al., 1997). It seems that the differences in the M—Nsac bond distances in these structures are a consequence of the steric effects of the co-ligands, such as bipy, mea, HydEt-en and im. Large distortions in the coordination polyhedra from ideal octahedral geometry are clearly evident from the N—M—N, N—M—O and O—M—O bond angles. The bite angles of the mpy ligand in the ZnII and CdII complexes are significantly smaller than the ideal cis angles of a regular octahedron (90°), and as a result, these complexes may be regarded as having a distorted octahedral structure.
The sac ligands in the two complexes are essentially planar, with an r.m.s. deviation of ca 0.03 Å. The py rings of the mpy ligands are also planar, with an r.m.s. deviation of ca 0.01 Å, but the hydroxyl O and methylene C atoms deviate slightly from the py planes by ca 0.38 (2) and 0.02 (1) Å. The mpy ligands in (I) and (II) are roughly perpendicular to each other, with dihedral angles of 80.07 (5) and 87.46°, respectively, while the dihedral angle between the best planes of the sac ligands is 22.60° in (I) and 19.19 (5)° in (II). As the two structures are isomorphous, only the packing of only one of the structures, (I), is given (Fig. 3). The hydroxyl H atoms of the mpy ligands form strong intramolecular hydrogen bonds with the carbonyl O and the negatively charged N atoms of neighbouring sac ligands. The methylene and phenyl H atoms are involved in weak intermolecular C—H···O interactions with the sulfonyl and carbonyl O atoms. Furthermore, there are weak π–π interactions between the mpy-ring centroids (Cg) [Cg···Cgi: 3.443 (1) Å in (I) and 3.460 (1) Å in (II); symmetry code: (i) 1 - x, 1 - y, 1 - z] and the sac rings [Cg···Cgii: 3.801 (1) Å in (I) and 3.979 (1) Å in (II); symmetry code: (ii) -x, -y, 1 - z]. The molecules are held together by weak hydrogen bonds and π–π interactions thereby forming a three-dimensional network.