The title ZnII complex, [Zn(C4H4O5)(C6H6N4S2)(H2O)]·2H2O, with ligands consisting of an oxydiacetate dianion (ODA), a diaminobithiazole (DABT) molecule and a water molecule, displays a distorted octahedral coordination geometry. The tridentate ODA chelates to the ZnII in a meridional configuration, with the Zn—O(ether) distance of 2.216 (5) Å, much longer than the Zn—O(carboxyl) distances of 2.051 (5) and 2.071 (5) Å. The overlapped arrangement of parallel DABT ligands, with a separation of 3.509 (9) Å between neighboring DABT rings, suggests π–π stacking between neighboring molecules.
Supporting information
CCDC reference: 221640
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.012 Å
- H-atom completeness 88%
- Disorder in solvent or counterion
- R factor = 0.054
- wR factor = 0.189
- Data-to-parameter ratio = 15.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ......................... 33.00 Perc.
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C10 H16 N4 O8 S2 Zn1
Atom count from the _atom_site data: C10 H14 N4 O8 S2 Zn1
CELLZ_01
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C10 H16 N4 O8 S2 Zn
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 40.00 40.00 0.00
H 64.00 56.00 8.00
N 16.00 16.00 0.00
O 32.00 32.00 0.00
S 8.00 8.00 0.00
Zn 4.00 4.00 0.00
Difference between formula and atom_site contents detected.
WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
[Zn(C4H4O5)(C6H6N4S2)(H2O)]·2H2O | F(000) = 920 |
Mr = 449.76 | Dx = 1.680 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 20 reflections |
a = 16.682 (4) Å | θ = 4.8–10.2° |
b = 10.083 (3) Å | µ = 1.66 mm−1 |
c = 11.1718 (17) Å | T = 298 K |
β = 108.907 (2)° | Prism, colorless |
V = 1777.8 (7) Å3 | 0.30 × 0.25 × 0.14 mm |
Z = 4 | |
Data collection top
Rigaku AFC-7S diffractometer | 1589 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 26.0°, θmin = 2.4° |
ω/2θ scans | h = −20→19 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→0 |
Tmin = 0.602, Tmax = 0.790 | l = 0→13 |
3688 measured reflections | 3 standard reflections every 150 reflections |
3496 independent reflections | intensity decay: 1.5% |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.189 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0885P)2] where P = (Fo2 + 2Fc2)/3 |
3496 reflections | (Δ/σ)max < 0.001 |
225 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −0.53 e Å−3 |
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. |
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 | Occ. (<1) |
Zn | 0.16865 (5) | 0.47670 (8) | 0.39044 (8) | 0.0474 (3) | |
S1 | −0.08453 (15) | 0.2469 (3) | 0.2390 (3) | 0.0928 (9) | |
S1' | 0.1527 (2) | 0.4055 (3) | 0.7957 (3) | 0.0993 (9) | |
O1 | 0.1536 (3) | 0.6785 (4) | 0.3935 (5) | 0.0544 (12) | |
O2 | 0.2093 (3) | 0.8742 (5) | 0.3714 (5) | 0.0619 (14) | |
O3 | 0.2991 (3) | 0.5579 (4) | 0.4571 (4) | 0.0486 (12) | |
O4 | 0.2467 (3) | 0.3152 (4) | 0.3984 (4) | 0.0484 (11) | |
O5 | 0.3757 (3) | 0.2401 (5) | 0.4146 (5) | 0.0652 (14) | |
O6 | 0.1693 (3) | 0.5030 (4) | 0.1936 (4) | 0.0520 (12) | |
O7 | 0.3232 (5) | 0.5881 (7) | 0.9924 (6) | 0.104 (2) | |
O8a | 0.5082 (13) | 0.369 (2) | 0.329 (2) | 0.158 (7)* | 0.50 |
O8b | 0.4800 (15) | 0.437 (2) | 0.232 (2) | 0.177 (8)* | 0.50 |
N2 | 0.0097 (5) | 0.3649 (8) | 0.1134 (7) | 0.088 (2) | |
H21 | 0.0525 | 0.4099 | 0.1092 | 0.106* | |
H22 | −0.0276 | 0.3368 | 0.0452 | 0.106* | |
N2' | 0.2726 (5) | 0.5297 (8) | 0.7243 (6) | 0.086 (2) | |
H23 | 0.2947 | 0.5565 | 0.6690 | 0.103* | |
H24 | 0.2980 | 0.5445 | 0.8034 | 0.103* | |
N3 | 0.0545 (4) | 0.3766 (6) | 0.3369 (6) | 0.0575 (16) | |
N3' | 0.1559 (4) | 0.4386 (6) | 0.5704 (6) | 0.0613 (17) | |
C2 | 0.0012 (4) | 0.3389 (9) | 0.2238 (9) | 0.069 (2) | |
C2' | 0.1973 (6) | 0.4640 (8) | 0.6867 (8) | 0.069 (2) | |
C4 | 0.0266 (5) | 0.3331 (8) | 0.4356 (9) | 0.064 (2) | |
C4' | 0.0810 (5) | 0.3685 (7) | 0.5605 (9) | 0.068 (2) | |
C5 | −0.0460 (6) | 0.2658 (9) | 0.3976 (11) | 0.091 (3) | |
H5 | −0.0727 | 0.2327 | 0.4527 | 0.109* | |
C5' | 0.0698 (7) | 0.3445 (9) | 0.6734 (9) | 0.088 (3) | |
H5' | 0.0233 | 0.3006 | 0.6832 | 0.106* | |
C11 | 0.2135 (5) | 0.7506 (7) | 0.3905 (7) | 0.0513 (17) | |
C12 | 0.3004 (4) | 0.6911 (6) | 0.4123 (6) | 0.0465 (16) | |
H12A | 0.3138 | 0.6907 | 0.3341 | 0.056* | |
H12B | 0.3430 | 0.7428 | 0.4744 | 0.056* | |
C13 | 0.3615 (4) | 0.4687 (7) | 0.4385 (7) | 0.0563 (18) | |
H13A | 0.4121 | 0.4698 | 0.5123 | 0.068* | |
H13B | 0.3769 | 0.4965 | 0.3658 | 0.068* | |
C14 | 0.3243 (5) | 0.3301 (7) | 0.4174 (7) | 0.0506 (17) | |
H61 | 0.2077 | 0.4596 | 0.1646 | 0.100* | |
H62 | 0.1527 | 0.5776 | 0.1538 | 0.100* | |
H71 | 0.3720 | 0.5642 | 1.0678 | 0.100* | |
H72 | 0.2692 | 0.5605 | 1.0026 | 0.100* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn | 0.0496 (5) | 0.0406 (4) | 0.0537 (5) | −0.0020 (4) | 0.0192 (4) | 0.0033 (4) |
S1 | 0.0612 (14) | 0.0932 (18) | 0.127 (2) | −0.0263 (13) | 0.0345 (15) | −0.0023 (17) |
S1' | 0.163 (3) | 0.0791 (17) | 0.0775 (17) | −0.0015 (17) | 0.0690 (18) | 0.0122 (13) |
O1 | 0.061 (3) | 0.041 (3) | 0.067 (3) | 0.008 (2) | 0.029 (3) | 0.005 (2) |
O2 | 0.076 (4) | 0.043 (3) | 0.074 (4) | 0.002 (3) | 0.034 (3) | −0.002 (3) |
O3 | 0.051 (3) | 0.042 (3) | 0.051 (3) | 0.001 (2) | 0.013 (2) | 0.001 (2) |
O4 | 0.045 (3) | 0.040 (3) | 0.057 (3) | 0.002 (2) | 0.012 (2) | 0.002 (2) |
O5 | 0.054 (3) | 0.050 (3) | 0.078 (4) | 0.010 (2) | 0.002 (3) | −0.012 (3) |
O6 | 0.057 (3) | 0.050 (3) | 0.051 (3) | −0.003 (2) | 0.020 (2) | 0.003 (2) |
O7 | 0.159 (7) | 0.087 (5) | 0.080 (4) | −0.032 (5) | 0.056 (5) | −0.005 (4) |
N2 | 0.079 (5) | 0.115 (6) | 0.068 (5) | −0.039 (5) | 0.021 (4) | −0.004 (5) |
N2' | 0.119 (7) | 0.093 (5) | 0.045 (4) | 0.005 (5) | 0.024 (4) | 0.005 (4) |
N3 | 0.055 (4) | 0.049 (3) | 0.073 (4) | −0.006 (3) | 0.028 (4) | 0.000 (3) |
N3' | 0.087 (5) | 0.054 (4) | 0.047 (4) | −0.001 (3) | 0.028 (4) | 0.005 (3) |
C2 | 0.034 (4) | 0.078 (6) | 0.088 (7) | −0.014 (4) | 0.013 (4) | −0.007 (5) |
C2' | 0.095 (7) | 0.050 (5) | 0.068 (6) | −0.006 (5) | 0.034 (5) | −0.005 (4) |
C4 | 0.068 (5) | 0.052 (4) | 0.082 (6) | 0.000 (4) | 0.039 (5) | −0.001 (4) |
C4' | 0.089 (6) | 0.043 (4) | 0.100 (7) | −0.004 (4) | 0.068 (6) | 0.003 (4) |
C5 | 0.078 (6) | 0.069 (6) | 0.154 (10) | −0.015 (5) | 0.076 (7) | 0.004 (6) |
C5' | 0.130 (8) | 0.072 (6) | 0.086 (7) | −0.023 (6) | 0.066 (7) | −0.012 (5) |
C11 | 0.070 (5) | 0.042 (4) | 0.049 (4) | 0.000 (4) | 0.028 (4) | −0.008 (3) |
C12 | 0.055 (4) | 0.037 (4) | 0.046 (4) | −0.011 (3) | 0.014 (3) | −0.010 (3) |
C13 | 0.045 (4) | 0.056 (4) | 0.064 (5) | 0.000 (4) | 0.012 (3) | −0.007 (4) |
C14 | 0.054 (5) | 0.044 (4) | 0.045 (4) | 0.007 (3) | 0.003 (4) | −0.002 (3) |
Geometric parameters (Å, º) top
Zn—O1 | 2.051 (5) | N2—H21 | 0.860 |
Zn—N3 | 2.066 (6) | N2—H22 | 0.860 |
Zn—O4 | 2.069 (4) | N2'—C2' | 1.360 (11) |
Zn—N3' | 2.124 (6) | N2'—H23 | 0.860 |
Zn—O3 | 2.216 (5) | N2'—H24 | 0.860 |
Zn—O6 | 2.219 (4) | N3—C2 | 1.342 (10) |
S1—C5 | 1.689 (11) | N3—C4 | 1.399 (10) |
S1—C2 | 1.759 (8) | N3'—C2' | 1.285 (10) |
S1'—C5' | 1.712 (11) | N3'—C4' | 1.409 (10) |
S1'—C2' | 1.723 (9) | C4—C5 | 1.334 (12) |
O1—C11 | 1.245 (8) | C4—C4' | 1.440 (12) |
O2—C11 | 1.263 (8) | C4'—C5' | 1.355 (11) |
O3—C12 | 1.436 (8) | C5—H5 | 0.930 |
O3—C13 | 1.440 (8) | C5'—H5' | 0.930 |
O4—C14 | 1.251 (8) | C11—C12 | 1.513 (10) |
O5—C14 | 1.256 (8) | C12—H12A | 0.970 |
O6—H61 | 0.917 | C12—H12B | 0.970 |
O6—H62 | 0.872 | C13—C14 | 1.517 (10) |
O7—H71 | 0.993 | C13—H13A | 0.970 |
O7—H72 | 0.985 | C13—H13B | 0.970 |
N2—C2 | 1.313 (11) | | |
| | | |
O1—Zn—N3 | 112.6 (2) | C4'—N3'—Zn | 112.0 (5) |
O1—Zn—O4 | 149.13 (19) | N2—C2—N3 | 126.0 (7) |
N3—Zn—O4 | 97.8 (2) | N2—C2—S1 | 122.3 (7) |
O1—Zn—N3' | 96.5 (2) | N3—C2—S1 | 111.7 (7) |
N3—Zn—N3' | 79.6 (3) | N3'—C2'—N2' | 123.3 (8) |
O4—Zn—N3' | 94.1 (2) | N3'—C2'—S1' | 115.7 (7) |
O1—Zn—O3 | 74.93 (17) | N2'—C2'—S1' | 121.0 (7) |
N3—Zn—O3 | 172.3 (2) | C5—C4—N3 | 114.1 (9) |
O4—Zn—O3 | 74.95 (17) | C5—C4—C4' | 131.0 (8) |
N3'—Zn—O3 | 97.9 (2) | N3—C4—C4' | 114.9 (7) |
O1—Zn—O6 | 86.44 (17) | C5'—C4'—N3' | 113.7 (9) |
N3—Zn—O6 | 94.1 (2) | C5'—C4'—C4 | 128.6 (8) |
O4—Zn—O6 | 86.05 (17) | N3'—C4'—C4 | 117.7 (7) |
N3'—Zn—O6 | 173.7 (2) | C4—C5—S1 | 112.9 (7) |
O3—Zn—O6 | 88.23 (16) | C4—C5—H5 | 123.6 |
C5—S1—C2 | 89.8 (4) | S1—C5—H5 | 123.6 |
C5'—S1'—C2' | 88.9 (4) | C4'—C5'—S1' | 111.1 (7) |
C11—O1—Zn | 118.4 (4) | C4'—C5'—H5' | 124.4 |
C12—O3—C13 | 116.1 (5) | S1'—C5'—H5' | 124.4 |
C12—O3—Zn | 110.6 (4) | O1—C11—O2 | 125.4 (7) |
C13—O3—Zn | 113.5 (4) | O1—C11—C12 | 119.9 (6) |
C14—O4—Zn | 121.0 (4) | O2—C11—C12 | 114.7 (7) |
Zn—O6—H61 | 121.5 | O3—C12—C11 | 107.8 (5) |
Zn—O6—H62 | 120.3 | O3—C12—H12A | 110.1 |
H61—O6—H62 | 112.0 | C11—C12—H12A | 110.1 |
H71—O7—H72 | 111.2 | O3—C12—H12B | 110.1 |
C2—N2—H21 | 120.0 | C11—C12—H12B | 110.1 |
C2—N2—H22 | 120.0 | H12A—C12—H12B | 108.5 |
H21—N2—H22 | 120.0 | O3—C13—C14 | 108.6 (6) |
C2'—N2'—H23 | 120.0 | O3—C13—H13A | 110.0 |
C2'—N2'—H24 | 120.0 | C14—C13—H13A | 110.0 |
H23—N2'—H24 | 120.0 | O3—C13—H13B | 110.0 |
C2—N3—C4 | 111.5 (7) | C14—C13—H13B | 110.0 |
C2—N3—Zn | 132.7 (5) | H13A—C13—H13B | 108.3 |
C4—N3—Zn | 115.8 (5) | O4—C14—O5 | 125.9 (7) |
C2'—N3'—C4' | 110.6 (7) | O4—C14—C13 | 119.0 (6) |
C2'—N3'—Zn | 137.4 (6) | O5—C14—C13 | 115.0 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O6 | 0.86 | 2.09 | 2.878 (10) | 152 |
N2—H22···O5i | 0.86 | 1.95 | 2.799 (10) | 168 |
N2′—H23···O3 | 0.86 | 2.39 | 3.169 (8) | 151 |
N2′—H24···O7 | 0.86 | 2.06 | 2.897 (9) | 163 |
O6—H61···O2ii | 0.92 | 1.78 | 2.696 (7) | 173 |
O6—H62···O5iii | 0.87 | 1.81 | 2.674 (7) | 174 |
O7—H71···O8biv | 0.99 | 2.47 | 3.43 (2) | 163 |
O7—H72···O2v | 0.98 | 2.31 | 2.792 (9) | 110 |
C5′—H5′···O8avi | 0.93 | 2.43 | 3.14 (2) | 133 |
C13—H13A···O8avii | 0.97 | 2.46 | 3.24 (2) | 138 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, y, z+1; (v) −x+1/2, y−1/2, −z+3/2; (vi) x−1/2, −y+1/2, z+1/2; (vii) −x+1, −y+1, −z+1. |