Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005889/bt6251sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005889/bt62512sup2.hkl |
CCDC reference: 209888
The title complex, (2), precipitated as a microcrystalline solid upon addition of a solution of zinc chloride in ether to a solution of (1) (Beckmann, 1998) and the strong base 1,8-diazabicyclo[5.4.0]undec-7-ene in acetonitrile. A single-crystal was obtained by slow evaporation of a solution in acetonitrile. The stoichiometric composition of (2) can be described as [(1) + ZnCl2 - HCl]2.
H atoms of NH groups were identified in difference syntheses and refined freely, but with a common N—H distance restraint. Other H atoms were included using a riding model with fixed C—H bond lengths of 1.00 (CH) or 0.99 Å (CH2); Uiso(H) values were fixed at 1.2Ueq of the parent atom.
Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
[Zn2(C13H22N3O4)2]Cl2 | F(000) = 800 |
Mr = 770.31 | Dx = 1.720 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 56 reflections |
a = 12.706 (2) Å | θ = 10–11.5° |
b = 9.2379 (16) Å | µ = 1.85 mm−1 |
c = 13.050 (2) Å | T = 143 K |
β = 103.849 (12)° | Tablet, colourless |
V = 1487.3 (4) Å3 | 0.6 × 0.5 × 0.25 mm |
Z = 2 |
Stoe STADI-4 diffractometer | 3146 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 27.6°, θmin = 3.2° |
ω/θ scans | h = 0→16 |
Absorption correction: ψ scans (XEMP; Siemens, 1994) | k = −12→1 |
Tmin = 0.611, Tmax = 0.988 | l = −16→16 |
3862 measured reflections | 3 standard reflections every 60 min |
3416 independent reflections | intensity decay: none |
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: inferred from neighbouring sites |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0324P)2 + 1.1834P] where P = (Fo2 + 2Fc2)/3 |
3416 reflections | (Δ/σ)max < 0.001 |
211 parameters | Δρmax = 0.42 e Å−3 |
3 restraints | Δρmin = −0.44 e Å−3 |
[Zn2(C13H22N3O4)2]Cl2 | V = 1487.3 (4) Å3 |
Mr = 770.31 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.706 (2) Å | µ = 1.85 mm−1 |
b = 9.2379 (16) Å | T = 143 K |
c = 13.050 (2) Å | 0.6 × 0.5 × 0.25 mm |
β = 103.849 (12)° |
Stoe STADI-4 diffractometer | 3146 reflections with I > 2σ(I) |
Absorption correction: ψ scans (XEMP; Siemens, 1994) | Rint = 0.017 |
Tmin = 0.611, Tmax = 0.988 | 3 standard reflections every 60 min |
3862 measured reflections | intensity decay: none |
3416 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | 3 restraints |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.42 e Å−3 |
3416 reflections | Δρmin = −0.44 e Å−3 |
211 parameters |
Experimental. rac-bis[µ-(1R,2S,12R,13S,15S,17S,18R)-14,16,19-trioxa- 3,7,11-triazatetracyclo-[13.3.1.02,13.012,17]nonadecan-18- olato-κ3N3,N7,N11;1:2κ2O18]dizinc(II) dichloride |
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 | ||
Zn | 0.498964 (15) | 0.44126 (2) | 0.385526 (15) | 0.01346 (7) | |
Cl | 0.65088 (4) | 0.21840 (5) | 0.67527 (4) | 0.02150 (11) | |
O1 | 0.87749 (10) | 0.53912 (15) | 0.53455 (10) | 0.0196 (3) | |
O2 | 0.81912 (11) | 0.74399 (16) | 0.43401 (11) | 0.0224 (3) | |
O3 | 0.84961 (11) | 0.53008 (16) | 0.35162 (11) | 0.0220 (3) | |
O4 | 0.58556 (10) | 0.58286 (14) | 0.50926 (10) | 0.0148 (3) | |
N1 | 0.55061 (12) | 0.59639 (18) | 0.28969 (12) | 0.0153 (3) | |
H01 | 0.5192 (16) | 0.667 (2) | 0.3124 (16) | 0.011 (5)* | |
N2 | 0.41100 (13) | 0.30671 (18) | 0.26391 (12) | 0.0180 (3) | |
H02 | 0.3442 (15) | 0.328 (3) | 0.260 (2) | 0.029 (7)* | |
N3 | 0.63507 (12) | 0.31357 (17) | 0.43133 (12) | 0.0146 (3) | |
H03 | 0.6338 (19) | 0.295 (3) | 0.4958 (14) | 0.020 (6)* | |
C1 | 0.73659 (14) | 0.3908 (2) | 0.43370 (14) | 0.0153 (3) | |
H1 | 0.7952 | 0.3166 | 0.4406 | 0.018* | |
C2 | 0.73790 (14) | 0.4834 (2) | 0.33574 (14) | 0.0168 (4) | |
H2 | 0.7170 | 0.4227 | 0.2706 | 0.020* | |
C3 | 0.66890 (14) | 0.6228 (2) | 0.32190 (14) | 0.0166 (4) | |
H3 | 0.6887 | 0.6806 | 0.2645 | 0.020* | |
C4 | 0.51156 (17) | 0.5955 (2) | 0.17239 (15) | 0.0236 (4) | |
H4A | 0.5691 | 0.5553 | 0.1413 | 0.028* | |
H4B | 0.4977 | 0.6963 | 0.1471 | 0.028* | |
C5 | 0.40929 (17) | 0.5075 (2) | 0.13450 (15) | 0.0244 (4) | |
H5A | 0.3825 | 0.5204 | 0.0573 | 0.029* | |
H5B | 0.3528 | 0.5442 | 0.1686 | 0.029* | |
C6 | 0.42703 (18) | 0.3467 (2) | 0.15888 (15) | 0.0244 (4) | |
H6A | 0.3762 | 0.2901 | 0.1042 | 0.029* | |
H6B | 0.5017 | 0.3204 | 0.1555 | 0.029* | |
C7 | 0.42644 (16) | 0.1468 (2) | 0.28289 (16) | 0.0234 (4) | |
H7A | 0.4407 | 0.1019 | 0.2187 | 0.028* | |
H7B | 0.3578 | 0.1056 | 0.2932 | 0.028* | |
C8 | 0.51733 (17) | 0.1040 (2) | 0.37669 (16) | 0.0234 (4) | |
H8A | 0.4963 | 0.1320 | 0.4423 | 0.028* | |
H8B | 0.5249 | −0.0027 | 0.3771 | 0.028* | |
C9 | 0.62685 (16) | 0.1708 (2) | 0.37839 (16) | 0.0221 (4) | |
H9A | 0.6854 | 0.1064 | 0.4167 | 0.027* | |
H9B | 0.6351 | 0.1827 | 0.3053 | 0.027* | |
C10 | 0.88142 (15) | 0.6159 (2) | 0.44320 (16) | 0.0224 (4) | |
H10 | 0.9585 | 0.6451 | 0.4496 | 0.027* | |
C11 | 0.76778 (14) | 0.4913 (2) | 0.52973 (14) | 0.0157 (3) | |
H11 | 0.7663 | 0.4358 | 0.5952 | 0.019* | |
C12 | 0.69349 (14) | 0.6238 (2) | 0.52120 (14) | 0.0156 (3) | |
H12 | 0.7170 | 0.6850 | 0.5858 | 0.019* | |
C13 | 0.70556 (15) | 0.7096 (2) | 0.42425 (15) | 0.0175 (4) | |
H13 | 0.6626 | 0.8012 | 0.4189 | 0.021* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.01175 (11) | 0.01631 (12) | 0.01290 (11) | −0.00067 (8) | 0.00410 (7) | −0.00177 (8) |
Cl | 0.0173 (2) | 0.0245 (2) | 0.0222 (2) | 0.00080 (18) | 0.00380 (16) | 0.00437 (18) |
O1 | 0.0105 (6) | 0.0274 (7) | 0.0207 (6) | −0.0029 (5) | 0.0031 (5) | 0.0053 (6) |
O2 | 0.0169 (6) | 0.0222 (7) | 0.0283 (7) | −0.0061 (5) | 0.0056 (5) | 0.0051 (6) |
O3 | 0.0155 (6) | 0.0307 (8) | 0.0224 (7) | 0.0001 (6) | 0.0099 (5) | 0.0047 (6) |
O4 | 0.0114 (6) | 0.0189 (6) | 0.0152 (6) | −0.0028 (5) | 0.0053 (5) | −0.0023 (5) |
N1 | 0.0142 (7) | 0.0164 (7) | 0.0148 (7) | 0.0016 (6) | 0.0024 (6) | 0.0018 (6) |
N2 | 0.0172 (8) | 0.0199 (8) | 0.0164 (7) | −0.0002 (6) | 0.0030 (6) | −0.0022 (6) |
N3 | 0.0173 (7) | 0.0139 (7) | 0.0131 (7) | −0.0008 (6) | 0.0047 (6) | −0.0006 (6) |
C1 | 0.0120 (8) | 0.0175 (8) | 0.0165 (8) | 0.0024 (7) | 0.0036 (6) | 0.0018 (7) |
C2 | 0.0140 (8) | 0.0220 (9) | 0.0155 (8) | 0.0016 (7) | 0.0059 (6) | 0.0014 (7) |
C3 | 0.0161 (8) | 0.0190 (9) | 0.0154 (8) | 0.0003 (7) | 0.0049 (6) | 0.0057 (7) |
C4 | 0.0267 (10) | 0.0272 (10) | 0.0153 (9) | −0.0022 (9) | 0.0016 (7) | 0.0047 (8) |
C5 | 0.0247 (10) | 0.0294 (11) | 0.0151 (9) | 0.0004 (9) | −0.0028 (7) | 0.0018 (8) |
C6 | 0.0304 (10) | 0.0272 (11) | 0.0159 (9) | −0.0036 (9) | 0.0059 (8) | −0.0049 (8) |
C7 | 0.0223 (9) | 0.0199 (10) | 0.0249 (10) | −0.0044 (8) | −0.0006 (8) | −0.0029 (8) |
C8 | 0.0277 (10) | 0.0142 (9) | 0.0256 (10) | −0.0030 (8) | 0.0009 (8) | 0.0004 (8) |
C9 | 0.0204 (9) | 0.0168 (9) | 0.0272 (10) | 0.0039 (8) | 0.0019 (8) | −0.0055 (8) |
C10 | 0.0138 (8) | 0.0295 (11) | 0.0247 (9) | −0.0034 (8) | 0.0063 (7) | 0.0064 (8) |
C11 | 0.0100 (8) | 0.0206 (9) | 0.0165 (8) | −0.0036 (7) | 0.0034 (6) | 0.0035 (7) |
C12 | 0.0135 (8) | 0.0179 (9) | 0.0158 (8) | −0.0035 (7) | 0.0039 (6) | −0.0013 (7) |
C13 | 0.0140 (8) | 0.0162 (9) | 0.0227 (9) | −0.0027 (7) | 0.0049 (7) | 0.0011 (7) |
Zn—O4i | 1.9480 (13) | C2—H2 | 1.0000 |
Zn—N3 | 2.0603 (16) | C3—C13 | 1.532 (3) |
Zn—N1 | 2.1074 (16) | C3—H3 | 1.0000 |
Zn—N2 | 2.1128 (16) | C4—C5 | 1.512 (3) |
Zn—O4 | 2.1629 (13) | C4—H4A | 0.9900 |
O1—C10 | 1.398 (2) | C4—H4B | 0.9900 |
O1—C11 | 1.449 (2) | C5—C6 | 1.524 (3) |
O2—C10 | 1.413 (3) | C5—H5A | 0.9900 |
O2—C13 | 1.453 (2) | C5—H5B | 0.9900 |
O3—C10 | 1.410 (3) | C6—H6A | 0.9900 |
O3—C2 | 1.450 (2) | C6—H6B | 0.9900 |
O4—C12 | 1.395 (2) | C7—C8 | 1.520 (3) |
O4—Zni | 1.9480 (13) | C7—H7A | 0.9900 |
N1—C3 | 1.481 (2) | C7—H7B | 0.9900 |
N1—C4 | 1.492 (2) | C8—C9 | 1.518 (3) |
N1—H01 | 0.855 (17) | C8—H8A | 0.9900 |
N2—C6 | 1.480 (2) | C8—H8B | 0.9900 |
N2—C7 | 1.503 (3) | C9—H9A | 0.9900 |
N2—H02 | 0.860 (18) | C9—H9B | 0.9900 |
N3—C1 | 1.468 (2) | C10—H10 | 1.0000 |
N3—C9 | 1.481 (2) | C11—C12 | 1.533 (3) |
N3—H03 | 0.862 (17) | C11—H11 | 1.0000 |
C1—C11 | 1.533 (3) | C12—C13 | 1.532 (3) |
C1—C2 | 1.541 (2) | C12—H12 | 1.0000 |
C1—H1 | 1.0000 | C13—H13 | 1.0000 |
C2—C3 | 1.544 (3) | ||
O4i—Zn—N3 | 107.23 (6) | C5—C4—H4B | 109.0 |
O4i—Zn—N1 | 143.00 (6) | H4A—C4—H4B | 107.8 |
N3—Zn—N1 | 101.68 (6) | C4—C5—C6 | 112.52 (17) |
O4i—Zn—N2 | 100.39 (6) | C4—C5—H5A | 109.1 |
N3—Zn—N2 | 97.90 (6) | C6—C5—H5A | 109.1 |
N1—Zn—N2 | 97.94 (6) | C4—C5—H5B | 109.1 |
O4i—Zn—O4 | 79.09 (5) | C6—C5—H5B | 109.1 |
N3—Zn—O4 | 83.57 (6) | H5A—C5—H5B | 107.8 |
N1—Zn—O4 | 81.77 (6) | N2—C6—C5 | 112.98 (17) |
N2—Zn—O4 | 178.53 (6) | N2—C6—H6A | 109.0 |
C10—O1—C11 | 110.36 (13) | C5—C6—H6A | 109.0 |
C10—O2—C13 | 110.43 (14) | N2—C6—H6B | 109.0 |
C10—O3—C2 | 111.14 (14) | C5—C6—H6B | 109.0 |
C12—O4—Zni | 130.20 (11) | H6A—C6—H6B | 107.8 |
C12—O4—Zn | 123.92 (11) | N2—C7—C8 | 115.61 (16) |
Zni—O4—Zn | 100.91 (5) | N2—C7—H7A | 108.4 |
C3—N1—C4 | 110.97 (14) | C8—C7—H7A | 108.4 |
C3—N1—Zn | 112.49 (11) | N2—C7—H7B | 108.4 |
C4—N1—Zn | 122.06 (12) | C8—C7—H7B | 108.4 |
C3—N1—H01 | 107.5 (14) | H7A—C7—H7B | 107.4 |
C4—N1—H01 | 106.9 (14) | C9—C8—C7 | 115.03 (17) |
Zn—N1—H01 | 94.5 (14) | C9—C8—H8A | 108.5 |
C6—N2—C7 | 110.89 (16) | C7—C8—H8A | 108.5 |
C6—N2—Zn | 112.54 (12) | C9—C8—H8B | 108.5 |
C7—N2—Zn | 115.45 (12) | C7—C8—H8B | 108.5 |
C6—N2—H02 | 103.8 (17) | H8A—C8—H8B | 107.5 |
C7—N2—H02 | 108.8 (18) | N3—C9—C8 | 109.34 (16) |
Zn—N2—H02 | 104.3 (17) | N3—C9—H9A | 109.8 |
C1—N3—C9 | 113.97 (14) | C8—C9—H9A | 109.8 |
C1—N3—Zn | 113.58 (11) | N3—C9—H9B | 109.8 |
C9—N3—Zn | 114.45 (11) | C8—C9—H9B | 109.8 |
C1—N3—H03 | 107.3 (16) | H9A—C9—H9B | 108.3 |
C9—N3—H03 | 105.3 (16) | O1—C10—O3 | 112.06 (17) |
Zn—N3—H03 | 100.7 (16) | O1—C10—O2 | 111.32 (16) |
N3—C1—C11 | 111.44 (14) | O3—C10—O2 | 110.97 (15) |
N3—C1—C2 | 115.85 (14) | O1—C10—H10 | 107.4 |
C11—C1—C2 | 106.87 (15) | O3—C10—H10 | 107.4 |
N3—C1—H1 | 107.4 | O2—C10—H10 | 107.4 |
C11—C1—H1 | 107.4 | O1—C11—C12 | 109.22 (15) |
C2—C1—H1 | 107.4 | O1—C11—C1 | 106.12 (14) |
O3—C2—C1 | 104.53 (14) | C12—C11—C1 | 112.92 (14) |
O3—C2—C3 | 106.13 (15) | O1—C11—H11 | 109.5 |
C1—C2—C3 | 116.17 (15) | C12—C11—H11 | 109.5 |
O3—C2—H2 | 109.9 | C1—C11—H11 | 109.5 |
C1—C2—H2 | 109.9 | O4—C12—C13 | 109.76 (14) |
C3—C2—H2 | 109.9 | O4—C12—C11 | 111.34 (15) |
N1—C3—C13 | 114.20 (15) | C13—C12—C11 | 106.95 (14) |
N1—C3—C2 | 113.91 (15) | O4—C12—H12 | 109.6 |
C13—C3—C2 | 106.80 (15) | C13—C12—H12 | 109.6 |
N1—C3—H3 | 107.2 | C11—C12—H12 | 109.6 |
C13—C3—H3 | 107.2 | O2—C13—C12 | 109.54 (14) |
C2—C3—H3 | 107.2 | O2—C13—C3 | 106.22 (15) |
N1—C4—C5 | 112.79 (16) | C12—C13—C3 | 112.30 (15) |
N1—C4—H4A | 109.0 | O2—C13—H13 | 109.6 |
C5—C4—H4A | 109.0 | C12—C13—H13 | 109.6 |
N1—C4—H4B | 109.0 | C3—C13—H13 | 109.6 |
O4i—Zn—O4—C12 | 157.20 (16) | O3—C2—C3—C13 | −61.16 (17) |
N3—Zn—O4—C12 | 48.22 (13) | C1—C2—C3—C13 | 54.5 (2) |
N1—Zn—O4—C12 | −54.62 (13) | C3—N1—C4—C5 | 154.52 (17) |
O4i—Zn—O4—Zni | 0.0 | Zn—N1—C4—C5 | 18.2 (2) |
N3—Zn—O4—Zni | −108.98 (6) | N1—C4—C5—C6 | −65.5 (2) |
N1—Zn—O4—Zni | 148.18 (7) | C7—N2—C6—C5 | 178.47 (16) |
O4i—Zn—N1—C3 | 111.81 (13) | Zn—N2—C6—C5 | −50.5 (2) |
N3—Zn—N1—C3 | −29.17 (13) | C4—C5—C6—N2 | 88.6 (2) |
N2—Zn—N1—C3 | −128.99 (12) | C6—N2—C7—C8 | 119.12 (19) |
O4—Zn—N1—C3 | 52.47 (12) | Zn—N2—C7—C8 | −10.4 (2) |
O4i—Zn—N1—C4 | −112.43 (15) | N2—C7—C8—C9 | −52.5 (2) |
N3—Zn—N1—C4 | 106.59 (15) | C1—N3—C9—C8 | −177.71 (15) |
N2—Zn—N1—C4 | 6.76 (15) | Zn—N3—C9—C8 | −44.62 (18) |
O4—Zn—N1—C4 | −171.78 (15) | C7—C8—C9—N3 | 87.3 (2) |
O4i—Zn—N2—C6 | 156.58 (13) | C11—O1—C10—O3 | −61.4 (2) |
N3—Zn—N2—C6 | −94.19 (14) | C11—O1—C10—O2 | 63.6 (2) |
N1—Zn—N2—C6 | 8.86 (14) | C2—O3—C10—O1 | 62.59 (19) |
O4i—Zn—N2—C7 | −74.73 (14) | C2—O3—C10—O2 | −62.54 (19) |
N3—Zn—N2—C7 | 34.50 (14) | C13—O2—C10—O1 | −62.70 (19) |
N1—Zn—N2—C7 | 137.55 (13) | C13—O2—C10—O3 | 62.85 (18) |
O4i—Zn—N3—C1 | −129.11 (11) | C10—O1—C11—C12 | −60.62 (19) |
N1—Zn—N3—C1 | 27.52 (13) | C10—O1—C11—C1 | 61.39 (19) |
N2—Zn—N3—C1 | 127.38 (12) | N3—C1—C11—O1 | 169.34 (14) |
O4—Zn—N3—C1 | −52.66 (11) | C2—C1—C11—O1 | −63.18 (17) |
O4i—Zn—N3—C9 | 97.62 (13) | N3—C1—C11—C12 | −71.04 (19) |
N1—Zn—N3—C9 | −105.75 (13) | C2—C1—C11—C12 | 56.44 (18) |
N2—Zn—N3—C9 | −5.90 (14) | Zni—O4—C12—C13 | −147.22 (12) |
O4—Zn—N3—C9 | 174.07 (13) | Zn—O4—C12—C13 | 62.66 (18) |
C9—N3—C1—C11 | −151.50 (15) | Zni—O4—C12—C11 | 94.55 (17) |
Zn—N3—C1—C11 | 75.00 (16) | Zn—O4—C12—C11 | −55.56 (18) |
C9—N3—C1—C2 | 86.05 (19) | O1—C11—C12—O4 | 176.04 (13) |
Zn—N3—C1—C2 | −47.45 (18) | C1—C11—C12—O4 | 58.22 (19) |
C10—O3—C2—C1 | −62.02 (18) | O1—C11—C12—C13 | 56.13 (18) |
C10—O3—C2—C3 | 61.29 (18) | C1—C11—C12—C13 | −61.69 (18) |
N3—C1—C2—O3 | −172.28 (15) | C10—O2—C13—C12 | 58.95 (19) |
C11—C1—C2—O3 | 62.88 (17) | C10—O2—C13—C3 | −62.55 (18) |
N3—C1—C2—C3 | 71.2 (2) | O4—C12—C13—O2 | −176.40 (14) |
C11—C1—C2—C3 | −53.7 (2) | C11—C12—C13—O2 | −55.49 (19) |
C4—N1—C3—C13 | 146.22 (16) | O4—C12—C13—C3 | −58.6 (2) |
Zn—N1—C3—C13 | −73.08 (17) | C11—C12—C13—C3 | 62.28 (19) |
C4—N1—C3—C2 | −90.69 (18) | N1—C3—C13—O2 | −171.23 (14) |
Zn—N1—C3—C2 | 50.01 (17) | C2—C3—C13—O2 | 61.90 (18) |
O3—C2—C3—N1 | 171.81 (14) | N1—C3—C13—C12 | 69.0 (2) |
C1—C2—C3—N1 | −72.5 (2) | C2—C3—C13—C12 | −57.82 (19) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···Cli | 0.86 (2) | 2.45 (2) | 3.2017 (17) | 148 (2) |
N2—H02···Clii | 0.86 (2) | 2.48 (2) | 3.2382 (18) | 148 (2) |
N3—H03···Cl | 0.86 (2) | 2.41 (2) | 3.2622 (16) | 172 (2) |
C10—H10···O1iii | 1.00 | 2.66 | 3.331 (2) | 125 |
C9—H9B···O3iv | 0.99 | 2.53 | 3.350 (2) | 140 |
C8—H8B···Clv | 0.99 | 2.95 | 3.634 (2) | 127 |
C5—H5B···Cli | 0.99 | 3.00 | 3.751 (2) | 133 |
C11—H11···Cl | 1.00 | 2.83 | 3.6770 (19) | 143 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C13H22N3O4)2]Cl2 |
Mr | 770.31 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 143 |
a, b, c (Å) | 12.706 (2), 9.2379 (16), 13.050 (2) |
β (°) | 103.849 (12) |
V (Å3) | 1487.3 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.85 |
Crystal size (mm) | 0.6 × 0.5 × 0.25 |
Data collection | |
Diffractometer | Stoe STADI-4 diffractometer |
Absorption correction | ψ scans (XEMP; Siemens, 1994) |
Tmin, Tmax | 0.611, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3862, 3416, 3146 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.068, 1.05 |
No. of reflections | 3416 |
No. of parameters | 211 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.42, −0.44 |
Computer programs: DIF4 (Stoe & Cie, 1992), DIF4, REDU4 (Stoe & Cie, 1992), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
Zn—O4i | 1.9480 (13) | Zn—N2 | 2.1128 (16) |
Zn—N3 | 2.0603 (16) | Zn—O4 | 2.1629 (13) |
Zn—N1 | 2.1074 (16) | ||
O4i—Zn—N3 | 107.23 (6) | C12—O4—Zn | 123.92 (11) |
O4i—Zn—N1 | 143.00 (6) | Zni—O4—Zn | 100.91 (5) |
N3—Zn—N1 | 101.68 (6) | C3—N1—C4 | 110.97 (14) |
O4i—Zn—N2 | 100.39 (6) | C3—N1—Zn | 112.49 (11) |
N3—Zn—N2 | 97.90 (6) | C4—N1—Zn | 122.06 (12) |
N1—Zn—N2 | 97.94 (6) | C6—N2—C7 | 110.89 (16) |
O4i—Zn—O4 | 79.09 (5) | C6—N2—Zn | 112.54 (12) |
N3—Zn—O4 | 83.57 (6) | C7—N2—Zn | 115.45 (12) |
N1—Zn—O4 | 81.77 (6) | C1—N3—C9 | 113.97 (14) |
N2—Zn—O4 | 178.53 (6) | C1—N3—Zn | 113.58 (11) |
C12—O4—Zni | 130.20 (11) | C9—N3—Zn | 114.45 (11) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H01···Cli | 0.855 (17) | 2.445 (18) | 3.2017 (17) | 147.8 (18) |
N2—H02···Clii | 0.860 (18) | 2.48 (2) | 3.2382 (18) | 148 (2) |
N3—H03···Cl | 0.862 (17) | 2.407 (18) | 3.2622 (16) | 172 (2) |
C10—H10···O1iii | 1.00 | 2.66 | 3.331 (2) | 125 |
C9—H9B···O3iv | 0.99 | 2.53 | 3.350 (2) | 140 |
C8—H8B···Clv | 0.99 | 2.95 | 3.634 (2) | 127 |
C5—H5B···Cli | 0.99 | 3.00 | 3.751 (2) | 133 |
C11—H11···Cl | 1.00 | 2.83 | 3.6770 (19) | 143 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+1, −y, −z+1. |
Many hydrolytic enzymes, particularly those that catalyse phosphoryl transfer reactions, use metal ions as cofactors (Bertini & Luchinat, 1994). The metal ion most commonly found in the active site of hydrolytic enzymes is Zn2+ (Vallee & Auld, 1993). The cations generally act as Lewis acid or electrophilic catalysts, withdrawing electron density from the coordinated substrate or stabilizing the negative charge that usually develops on the `leaving group' in hydrolytic reactions. However, the binding of metal ions to anionic, even bidentate, substrate groups such as carboxylates or phosphates, is not strong in aqueous solution (Fraústo da Silva & Williams, 1992) and enzyme structures have evolved to bind the cation in close and productive proximity to the substrate. We report the structure of a model system, designed to achieve this aim.
Enzyme model systems can only be expected to shed light on enzyme reaction mechanisms if they themselves are properly understood. If the model system features metal ion complexation, the structure and stability of the complex formed are fundamental to this understanding. We report here the structure of the zinc complex, (2), of the deprotonated triaminoalcohol ligand [(1), LOH], designed as a potential leaving group from phosphate mono- and diesters when a metal cation is bound.
The zinc cation (Fig. 1) is coordinated, as designed, to the alcohol O atom (which has lost its proton) and also to the three N atoms of the ligand (LO-). The coordination number of the metal ion is made up to five by the formation of an inversion-symmetric dimer {[Zn2(LO)2]2+}, with the alkoxide O atoms acting as bridging ligands in the central four-membered ring (which is exactly planar by symmetry). The coordination geometry of Zn2+ (for exact values and s.u.'s, see Table 1) is that of a distorted trigonal bipyramid; the axial angle N2—Zn—O4ax is 178.5° and the sum of the three equatorial angles at Zn is ca 351°. The three Zn—N distances are similar (between 2.06 and 2.11 Å), but the axial Zn—O4 distance (2.16 Å) is markedly longer than that to the bridging equatorial O atom (Zn—O4i 1.95 Å). The six-membered ring Zn—N3—C1—C11—C12—O4 displays a chair conformation, whereas Zn—N1—C3—C2—C1—N3 is a chair flattened around zinc, and Zn—N1—C4—C5—C6—N2 a distorted half-chair.
The overall 2+ charge of the dimer unit is balanced by two chloride anions. These participate in three classical hydrogen bonds N—H···Cl- (Table 2), the net effect of which is to form layers of anions and cations parallel to (101) (Fig. 2). There is also a Zn···Cli contact (not shown in Fig. 2) of 3.6628 (7) Å.
The following paper (Jones et al., 2003) reports the structure of another compound containing the same cation.