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Valinomycin is a naturally occurring cyclic dodecadepsipeptide with the formula
cyclo-[
D-HiVA
L-Val
L-LA
L-Val]
3 (
D-HiVA is
D-
-hydroxyisovaleic acid, Val is valine and LA is lactic acid), which binds a K
+ ion with high selectively. In the past, several cation-binding modes have been revealed by X-ray crystallography. In the K
+, Rb
+ and Cs
+ complexes, the ester O atoms coordinate the cation with a trigonal antiprismatic geometry, while the six amide groups form intramolecular hydrogen bonds and the network that is formed has a bracelet-like conformation (Type 1 binding). Type 2 binding is seen with the Na
+ cation, in which the valinomycin molecule retains the bracelet conformation but the cations are coordinated by only three ester carbonyl groups and are not centrally located. In addition, a picrate counter-ion and a water molecule is found at the center of the valinomycin bracelet. Type 3 binding is observed with divalent Ba
2+, in which two cations are incorporated, bridged by two anions, and coordinated by amide carbonyl groups, and there are no intramolecular amide hydrogen bonds. In this paper, we present a new Type 4 cation-binding mode, observed in valinomycin hexaaquamagnesium bis(trifluoromethanesulfonate) trihydrate, C
54H
90N
6O
18·[Mg(H
2O)
6](CF
3SO
3)
2·3H
2O, in which the valinomycin molecule incorporates a whole hexaaquamagnesium ion, [Mg(H
2O)
6]
2+,
via hydrogen bonding between the amide carbonyl groups and the hydrate water H atoms. In this complex, valinomycin retains the threefold symmetry observed in Type 1 binding, but the amide hydrogen-bond network is lost; the hexaaquamagnesium cation is hydrogen bonded by six amide carbonyl groups.
1H NMR titration data is consistent with the 1:1 binding stoichiometry in acetonitrile solution. This new cation-binding mode of binding a whole hexaaquamagnesium ion by a cyclic polypeptide is likely to have important implications for the study of metal binding with biological models under physiological conditions.
Supporting information
CCDC reference: 1489496
Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
Valinomycin hexaaquamagnesium bis(trifluoromethanesulfonate) trihydrate
top
Crystal data top
C54H90N6O18·[Mg(H2O)6](CF3O3S)2·3H2O | Dx = 1.284 Mg m−3 |
Mr = 1595.91 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3 | Cell parameters from 9973 reflections |
a = 16.4188 (5) Å | θ = 2.5–31.5° |
c = 8.8395 (3) Å | µ = 0.16 mm−1 |
V = 2063.67 (14) Å3 | T = 100 K |
Z = 1 | Prism, colourless |
F(000) = 848 | 0.66 × 0.46 × 0.24 mm |
Data collection top
Bruker APEXII CCD diffractometer | 8681 independent reflections |
Radiation source: fine-focus sealed tube | 7479 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 512 pixels mm-1 | θmax = 31.5°, θmin = 1.4° |
φ and ω scans | h = −23→19 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −23→24 |
Tmin = 0.642, Tmax = 0.746 | l = −12→12 |
19702 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0586P)2 + 0.5419P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.120 | (Δ/σ)max = 0.006 |
S = 1.04 | Δρmax = 0.42 e Å−3 |
8681 reflections | Δρmin = −0.28 e Å−3 |
324 parameters | Absolute structure: Flack x determined using 3081 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013); Hooft y determined using 4154
Bijvoet pairs
(Hooft et al., 2008) |
10 restraints | Absolute structure parameter: 0.08 (4) |
Special details top
Experimental. SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1337 before and 0.0601 after correction.
The Ratio of minimum to maximum transmission is 0.8598.
The λ/2 correction factor is 0.00150. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.6667 | 0.3333 | 0.66117 (12) | 0.0184 (2) | |
F1 | 0.60558 (17) | 0.35704 (17) | 0.9207 (2) | 0.0438 (5) | |
O1 | 0.69848 (16) | 0.43012 (16) | 0.6250 (3) | 0.0285 (5) | |
C1 | 0.6667 | 0.3333 | 0.8658 (6) | 0.0265 (10) | |
S2 | 1.0000 | 1.0000 | 0.30056 (11) | 0.01403 (19) | |
F2 | 0.91560 (14) | 0.93744 (14) | 0.0403 (2) | 0.0336 (4) | |
O2 | 0.93719 (14) | 1.03489 (14) | 0.3376 (2) | 0.0204 (4) | |
C2 | 1.0000 | 1.0000 | 0.0944 (5) | 0.0222 (9) | |
Mg1 | 0.3333 | 0.6667 | 0.44311 (17) | 0.0187 (3) | |
H4A | 0.2937 (14) | 0.5084 (13) | 0.587 (5) | 0.060 (10)* | |
H4B | 0.4026 (16) | 0.567 (2) | 0.559 (4) | 0.060 (10)* | |
O3 | 0.44327 (15) | 0.67964 (16) | 0.3086 (3) | 0.0282 (5) | |
H3A | 0.5057 (11) | 0.725 (2) | 0.333 (3) | 0.042* | |
H3B | 0.4351 (19) | 0.671 (3) | 0.2020 (16) | 0.042* | |
O4 | 0.34675 (16) | 0.57098 (16) | 0.5779 (3) | 0.0319 (5) | |
O5 | 0.39800 (13) | 0.41075 (14) | 0.6719 (2) | 0.0205 (4) | |
O6 | 0.40520 (14) | 0.34550 (14) | 0.4513 (2) | 0.0222 (4) | |
O7 | 0.50107 (16) | 0.56902 (15) | 0.4816 (3) | 0.0287 (5) | |
O8 | 0.67291 (13) | 0.73269 (13) | 0.2606 (2) | 0.0192 (4) | |
O9 | 0.59991 (15) | 0.82266 (16) | 0.4373 (3) | 0.0352 (6) | |
O10 | 0.72909 (15) | 0.73641 (14) | 0.4949 (2) | 0.0261 (5) | |
N1 | 0.61651 (16) | 0.53350 (16) | 0.4809 (3) | 0.0195 (4) | |
H1 | 0.6406 | 0.5019 | 0.5236 | 0.023* | |
N2 | 0.74635 (16) | 0.94657 (16) | 0.4611 (3) | 0.0186 (4) | |
H2 | 0.8033 | 0.9777 | 0.4228 | 0.022* | |
C3 | 0.36146 (19) | 0.34741 (19) | 0.5583 (3) | 0.0174 (5) | |
C4 | 0.49917 (19) | 0.4676 (2) | 0.6805 (3) | 0.0211 (5) | |
H4 | 0.5273 | 0.4264 | 0.6949 | 0.025* | |
C5 | 0.53817 (19) | 0.52612 (19) | 0.5368 (3) | 0.0204 (5) | |
C6 | 0.66311 (19) | 0.59238 (18) | 0.3489 (3) | 0.0185 (5) | |
H6 | 0.6192 | 0.5691 | 0.2606 | 0.022* | |
C7 | 0.69074 (19) | 0.69393 (19) | 0.3818 (3) | 0.0188 (5) | |
C8 | 0.71813 (19) | 0.83473 (18) | 0.2629 (3) | 0.0202 (5) | |
H8 | 0.7878 | 0.8625 | 0.2702 | 0.024* | |
C9 | 0.68318 (19) | 0.86665 (19) | 0.3973 (3) | 0.0210 (5) | |
C10 | 0.72384 (18) | 0.98310 (19) | 0.5948 (3) | 0.0173 (5) | |
H10 | 0.6964 | 0.9324 | 0.6731 | 0.021* | |
C11 | 0.8147 (2) | 1.0665 (2) | 0.6580 (3) | 0.0223 (5) | |
H11 | 0.8483 | 1.1113 | 0.5733 | 0.027* | |
C12 | 0.8787 (2) | 1.0314 (3) | 0.7201 (4) | 0.0329 (7) | |
H12A | 0.8472 | 0.9880 | 0.8043 | 0.049* | |
H12B | 0.9377 | 1.0850 | 0.7558 | 0.049* | |
H12C | 0.8922 | 0.9986 | 0.6399 | 0.049* | |
C13 | 0.7937 (2) | 1.1190 (2) | 0.7812 (4) | 0.0336 (7) | |
H13A | 0.7593 | 1.1476 | 0.7370 | 0.050* | |
H13B | 0.8530 | 1.1682 | 0.8247 | 0.050* | |
H13C | 0.7555 | 1.0747 | 0.8607 | 0.050* | |
C14 | 0.6938 (2) | 0.8632 (2) | 0.1151 (4) | 0.0301 (6) | |
H14A | 0.7150 | 0.8396 | 0.0309 | 0.045* | |
H14B | 0.7250 | 0.9320 | 0.1096 | 0.045* | |
H14C | 0.6255 | 0.8366 | 0.1087 | 0.045* | |
C15 | 0.75134 (19) | 0.58643 (18) | 0.3117 (3) | 0.0191 (5) | |
H15 | 0.7868 | 0.5952 | 0.4080 | 0.023* | |
C16 | 0.7239 (2) | 0.4894 (2) | 0.2484 (4) | 0.0280 (6) | |
H16A | 0.7806 | 0.4846 | 0.2343 | 0.042* | |
H16B | 0.6921 | 0.4806 | 0.1509 | 0.042* | |
H16C | 0.6814 | 0.4408 | 0.3194 | 0.042* | |
C17 | 0.8166 (2) | 0.6631 (2) | 0.2011 (3) | 0.0271 (6) | |
H17A | 0.8720 | 0.6570 | 0.1813 | 0.041* | |
H17B | 0.8364 | 0.7251 | 0.2451 | 0.041* | |
H17C | 0.7831 | 0.6564 | 0.1060 | 0.041* | |
C18 | 0.5194 (2) | 0.5312 (2) | 0.8198 (3) | 0.0296 (6) | |
H18 | 0.4914 | 0.5721 | 0.8010 | 0.035* | |
C19 | 0.6254 (2) | 0.5952 (3) | 0.8420 (4) | 0.0375 (7) | |
H19A | 0.6550 | 0.5566 | 0.8559 | 0.056* | |
H19B | 0.6368 | 0.6346 | 0.9316 | 0.056* | |
H19C | 0.6522 | 0.6353 | 0.7527 | 0.056* | |
C20 | 0.4742 (3) | 0.4738 (3) | 0.9613 (4) | 0.0430 (9) | |
H20A | 0.4061 | 0.4351 | 0.9459 | 0.064* | |
H20B | 0.4866 | 0.5163 | 1.0471 | 0.064* | |
H20C | 0.5006 | 0.4331 | 0.9823 | 0.064* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0195 (3) | 0.0195 (3) | 0.0164 (5) | 0.00973 (16) | 0.000 | 0.000 |
F1 | 0.0497 (14) | 0.0575 (14) | 0.0289 (10) | 0.0304 (12) | 0.0095 (9) | −0.0088 (9) |
O1 | 0.0300 (12) | 0.0229 (10) | 0.0316 (11) | 0.0126 (9) | −0.0047 (9) | 0.0055 (8) |
C1 | 0.0315 (16) | 0.0315 (16) | 0.016 (2) | 0.0158 (8) | 0.000 | 0.000 |
S2 | 0.0134 (3) | 0.0134 (3) | 0.0152 (4) | 0.00671 (14) | 0.000 | 0.000 |
F2 | 0.0307 (10) | 0.0400 (11) | 0.0225 (9) | 0.0120 (9) | −0.0100 (7) | −0.0052 (8) |
O2 | 0.0173 (9) | 0.0204 (9) | 0.0250 (9) | 0.0107 (8) | 0.0037 (7) | 0.0002 (7) |
C2 | 0.0248 (15) | 0.0248 (15) | 0.017 (2) | 0.0124 (7) | 0.000 | 0.000 |
Mg1 | 0.0130 (4) | 0.0130 (4) | 0.0301 (9) | 0.00652 (19) | 0.000 | 0.000 |
O3 | 0.0173 (9) | 0.0309 (11) | 0.0354 (11) | 0.0112 (9) | 0.0015 (8) | −0.0006 (9) |
O4 | 0.0283 (11) | 0.0263 (11) | 0.0436 (13) | 0.0156 (9) | −0.0039 (9) | 0.0054 (9) |
O5 | 0.0134 (8) | 0.0220 (9) | 0.0239 (9) | 0.0074 (7) | −0.0026 (7) | −0.0050 (7) |
O6 | 0.0174 (9) | 0.0208 (10) | 0.0261 (10) | 0.0078 (8) | 0.0010 (7) | −0.0023 (8) |
O7 | 0.0243 (10) | 0.0237 (11) | 0.0420 (12) | 0.0149 (9) | −0.0021 (9) | 0.0035 (9) |
O8 | 0.0184 (9) | 0.0117 (8) | 0.0250 (9) | 0.0056 (7) | −0.0027 (7) | −0.0009 (7) |
O9 | 0.0151 (10) | 0.0256 (11) | 0.0528 (14) | 0.0010 (9) | 0.0104 (9) | −0.0101 (10) |
O10 | 0.0284 (11) | 0.0183 (10) | 0.0266 (10) | 0.0080 (9) | −0.0070 (8) | −0.0060 (8) |
N1 | 0.0157 (10) | 0.0170 (11) | 0.0252 (11) | 0.0078 (9) | −0.0033 (8) | 0.0003 (8) |
N2 | 0.0130 (10) | 0.0139 (10) | 0.0280 (11) | 0.0059 (8) | 0.0052 (8) | 0.0003 (8) |
C3 | 0.0153 (11) | 0.0168 (11) | 0.0219 (12) | 0.0094 (9) | −0.0028 (9) | −0.0001 (9) |
C4 | 0.0126 (11) | 0.0237 (13) | 0.0245 (12) | 0.0071 (10) | −0.0034 (9) | −0.0015 (10) |
C5 | 0.0180 (12) | 0.0145 (12) | 0.0267 (13) | 0.0066 (10) | −0.0058 (10) | −0.0030 (9) |
C6 | 0.0189 (12) | 0.0129 (11) | 0.0206 (12) | 0.0056 (10) | −0.0079 (9) | −0.0026 (9) |
C7 | 0.0160 (12) | 0.0139 (11) | 0.0237 (12) | 0.0054 (9) | −0.0008 (9) | 0.0001 (9) |
C8 | 0.0170 (12) | 0.0106 (11) | 0.0294 (13) | 0.0042 (9) | 0.0023 (9) | 0.0000 (9) |
C9 | 0.0132 (11) | 0.0140 (12) | 0.0343 (14) | 0.0057 (10) | 0.0038 (10) | 0.0005 (9) |
C10 | 0.0159 (11) | 0.0158 (11) | 0.0215 (12) | 0.0090 (10) | 0.0027 (9) | 0.0023 (9) |
C11 | 0.0215 (13) | 0.0216 (13) | 0.0223 (13) | 0.0096 (11) | −0.0033 (9) | 0.0003 (10) |
C12 | 0.0295 (16) | 0.049 (2) | 0.0270 (14) | 0.0249 (15) | −0.0061 (12) | 0.0040 (13) |
C13 | 0.0300 (16) | 0.0324 (16) | 0.0358 (16) | 0.0137 (13) | −0.0094 (12) | −0.0139 (13) |
C14 | 0.0334 (16) | 0.0236 (14) | 0.0327 (15) | 0.0139 (13) | 0.0036 (12) | 0.0064 (11) |
C15 | 0.0213 (12) | 0.0170 (12) | 0.0191 (11) | 0.0096 (10) | −0.0019 (9) | −0.0023 (9) |
C16 | 0.0343 (16) | 0.0226 (14) | 0.0283 (14) | 0.0151 (12) | −0.0006 (12) | −0.0049 (11) |
C17 | 0.0266 (15) | 0.0256 (14) | 0.0282 (14) | 0.0124 (12) | 0.0042 (11) | 0.0047 (11) |
C18 | 0.0231 (14) | 0.0355 (16) | 0.0282 (14) | 0.0132 (13) | −0.0077 (11) | −0.0131 (12) |
C19 | 0.0256 (15) | 0.0432 (19) | 0.0356 (16) | 0.0111 (14) | −0.0109 (12) | −0.0128 (14) |
C20 | 0.0320 (17) | 0.064 (2) | 0.0268 (15) | 0.0199 (17) | −0.0032 (12) | −0.0098 (15) |
Geometric parameters (Å, º) top
S1—O1i | 1.439 (2) | C4—C18 | 1.539 (4) |
S1—O1 | 1.439 (2) | C6—H6 | 1.0000 |
S1—O1ii | 1.439 (2) | C6—C7 | 1.521 (4) |
S1—C1 | 1.809 (5) | C6—C15 | 1.535 (4) |
F1—C1 | 1.336 (3) | C8—H8 | 1.0000 |
C1—F1ii | 1.336 (3) | C8—C9 | 1.522 (4) |
C1—F1i | 1.336 (3) | C8—C14 | 1.507 (4) |
S2—O2iii | 1.446 (2) | C10—C3vi | 1.525 (4) |
S2—O2iv | 1.446 (2) | C10—H10 | 1.0000 |
S2—O2 | 1.446 (2) | C10—C11 | 1.540 (4) |
S2—C2 | 1.822 (5) | C11—H11 | 1.0000 |
F2—C2 | 1.334 (2) | C11—C12 | 1.532 (4) |
C2—F2iv | 1.334 (2) | C11—C13 | 1.531 (4) |
C2—F2iii | 1.334 (2) | C12—H12A | 0.9800 |
Mg1—O3v | 2.082 (2) | C12—H12B | 0.9800 |
Mg1—O3vi | 2.082 (2) | C12—H12C | 0.9800 |
Mg1—O3 | 2.082 (2) | C13—H13A | 0.9800 |
Mg1—O4vi | 2.070 (2) | C13—H13B | 0.9800 |
Mg1—O4 | 2.070 (2) | C13—H13C | 0.9800 |
Mg1—O4v | 2.070 (2) | C14—H14A | 0.9800 |
O3—H3A | 0.944 (13) | C14—H14B | 0.9800 |
O3—H3B | 0.953 (13) | C14—H14C | 0.9800 |
O4—H4A | 0.962 (13) | C15—H15 | 1.0000 |
O4—H4B | 0.966 (10) | C15—C16 | 1.529 (4) |
O5—C3 | 1.351 (3) | C15—C17 | 1.530 (4) |
O5—C4 | 1.444 (3) | C16—H16A | 0.9800 |
O6—C3 | 1.197 (3) | C16—H16B | 0.9800 |
O7—C5 | 1.239 (3) | C16—H16C | 0.9800 |
O8—C7 | 1.351 (3) | C17—H17A | 0.9800 |
O8—C8 | 1.454 (3) | C17—H17B | 0.9800 |
O9—C9 | 1.236 (3) | C17—H17C | 0.9800 |
O10—C7 | 1.201 (3) | C18—H18 | 1.0000 |
N1—H1 | 0.8791 | C18—C19 | 1.531 (4) |
N1—C5 | 1.326 (4) | C18—C20 | 1.517 (5) |
N1—C6 | 1.463 (4) | C19—H19A | 0.9800 |
N2—H2 | 0.8790 | C19—H19B | 0.9800 |
N2—C9 | 1.325 (4) | C19—H19C | 0.9800 |
N2—C10 | 1.454 (3) | C20—H20A | 0.9800 |
C3—C10v | 1.525 (4) | C20—H20B | 0.9800 |
C4—H4 | 1.0000 | C20—H20C | 0.9800 |
C4—C5 | 1.527 (4) | | |
| | | |
O1i—S1—O1ii | 115.20 (7) | O8—C8—C9 | 110.1 (2) |
O1i—S1—O1 | 115.20 (7) | O8—C8—C14 | 106.5 (2) |
O1ii—S1—O1 | 115.20 (7) | C9—C8—H8 | 109.6 |
O1i—S1—C1 | 102.85 (10) | C14—C8—H8 | 109.6 |
O1ii—S1—C1 | 102.85 (10) | C14—C8—C9 | 111.4 (2) |
O1—S1—C1 | 102.85 (10) | O9—C9—N2 | 123.1 (3) |
F1—C1—S1 | 111.3 (2) | O9—C9—C8 | 121.3 (3) |
F1i—C1—S1 | 111.3 (2) | N2—C9—C8 | 115.5 (2) |
F1ii—C1—S1 | 111.3 (2) | N2—C10—C3vi | 111.2 (2) |
F1i—C1—F1 | 107.6 (2) | N2—C10—H10 | 108.8 |
F1ii—C1—F1 | 107.6 (2) | N2—C10—C11 | 109.2 (2) |
F1ii—C1—F1i | 107.6 (2) | C3vi—C10—H10 | 108.8 |
O2iii—S2—O2 | 115.01 (7) | C3vi—C10—C11 | 110.1 (2) |
O2iv—S2—O2 | 115.01 (7) | C11—C10—H10 | 108.8 |
O2iii—S2—O2iv | 115.01 (7) | C10—C11—H11 | 108.4 |
O2iii—S2—C2 | 103.11 (9) | C12—C11—C10 | 109.7 (2) |
O2iv—S2—C2 | 103.11 (9) | C12—C11—H11 | 108.4 |
O2—S2—C2 | 103.11 (9) | C13—C11—C10 | 111.6 (2) |
F2iv—C2—S2 | 111.01 (19) | C13—C11—H11 | 108.4 |
F2iii—C2—S2 | 111.01 (19) | C13—C11—C12 | 110.3 (3) |
F2—C2—S2 | 111.01 (19) | C11—C12—H12A | 109.5 |
F2iii—C2—F2 | 107.9 (2) | C11—C12—H12B | 109.5 |
F2iii—C2—F2iv | 107.9 (2) | C11—C12—H12C | 109.5 |
F2iv—C2—F2 | 107.9 (2) | H12A—C12—H12B | 109.5 |
O3vi—Mg1—O3v | 90.60 (10) | H12A—C12—H12C | 109.5 |
O3v—Mg1—O3 | 90.60 (10) | H12B—C12—H12C | 109.5 |
O3vi—Mg1—O3 | 90.60 (10) | C11—C13—H13A | 109.5 |
O4v—Mg1—O3vi | 89.78 (9) | C11—C13—H13B | 109.5 |
O4vi—Mg1—O3v | 179.61 (11) | C11—C13—H13C | 109.5 |
O4vi—Mg1—O3 | 89.78 (9) | H13A—C13—H13B | 109.5 |
O4vi—Mg1—O3vi | 89.46 (10) | H13A—C13—H13C | 109.5 |
O4v—Mg1—O3 | 179.61 (11) | H13B—C13—H13C | 109.5 |
O4—Mg1—O3vi | 179.61 (12) | C8—C14—H14A | 109.5 |
O4—Mg1—O3 | 89.46 (10) | C8—C14—H14B | 109.5 |
O4v—Mg1—O3v | 89.46 (10) | C8—C14—H14C | 109.5 |
O4—Mg1—O3v | 89.78 (9) | H14A—C14—H14B | 109.5 |
O4vi—Mg1—O4 | 90.15 (11) | H14A—C14—H14C | 109.5 |
O4v—Mg1—O4vi | 90.15 (11) | H14B—C14—H14C | 109.5 |
O4v—Mg1—O4 | 90.15 (11) | C6—C15—H15 | 108.0 |
Mg1—O3—H3A | 119.3 (17) | C16—C15—C6 | 110.4 (2) |
Mg1—O3—H3B | 120.1 (17) | C16—C15—H15 | 108.0 |
H3A—O3—H3B | 112 (2) | C16—C15—C17 | 110.1 (2) |
Mg1—O4—H4A | 118 (2) | C17—C15—C6 | 112.3 (2) |
Mg1—O4—H4B | 114.4 (18) | C17—C15—H15 | 108.0 |
H4A—O4—H4B | 109.0 (19) | C15—C16—H16A | 109.5 |
C3—O5—C4 | 117.5 (2) | C15—C16—H16B | 109.5 |
C7—O8—C8 | 115.2 (2) | C15—C16—H16C | 109.5 |
C5—N1—H1 | 119.2 | H16A—C16—H16B | 109.5 |
C5—N1—C6 | 121.4 (2) | H16A—C16—H16C | 109.5 |
C6—N1—H1 | 119.4 | H16B—C16—H16C | 109.5 |
C9—N2—H2 | 119.3 | C15—C17—H17A | 109.5 |
C9—N2—C10 | 121.4 (2) | C15—C17—H17B | 109.5 |
C10—N2—H2 | 119.3 | C15—C17—H17C | 109.5 |
O5—C3—C10v | 109.2 (2) | H17A—C17—H17B | 109.5 |
O6—C3—O5 | 124.4 (2) | H17A—C17—H17C | 109.5 |
O6—C3—C10v | 126.3 (2) | H17B—C17—H17C | 109.5 |
O5—C4—H4 | 110.0 | C4—C18—H18 | 107.9 |
O5—C4—C5 | 110.3 (2) | C19—C18—C4 | 110.7 (2) |
O5—C4—C18 | 105.6 (2) | C19—C18—H18 | 107.9 |
C5—C4—H4 | 110.0 | C20—C18—C4 | 111.4 (3) |
C5—C4—C18 | 111.0 (2) | C20—C18—H18 | 107.9 |
C18—C4—H4 | 110.0 | C20—C18—C19 | 110.8 (3) |
O7—C5—N1 | 122.1 (3) | C18—C19—H19A | 109.5 |
O7—C5—C4 | 121.0 (3) | C18—C19—H19B | 109.5 |
N1—C5—C4 | 116.7 (2) | C18—C19—H19C | 109.5 |
N1—C6—H6 | 109.3 | H19A—C19—H19B | 109.5 |
N1—C6—C7 | 110.0 (2) | H19A—C19—H19C | 109.5 |
N1—C6—C15 | 109.1 (2) | H19B—C19—H19C | 109.5 |
C7—C6—H6 | 109.3 | C18—C20—H20A | 109.5 |
C7—C6—C15 | 109.7 (2) | C18—C20—H20B | 109.5 |
C15—C6—H6 | 109.3 | C18—C20—H20C | 109.5 |
O8—C7—C6 | 110.4 (2) | H20A—C20—H20B | 109.5 |
O10—C7—O8 | 124.1 (2) | H20A—C20—H20C | 109.5 |
O10—C7—C6 | 125.3 (2) | H20B—C20—H20C | 109.5 |
O8—C8—H8 | 109.6 | | |
| | | |
O1i—S1—C1—F1ii | −56.91 (15) | N2—C10—C11—C13 | 169.9 (2) |
O1ii—S1—C1—F1i | −176.91 (15) | C3—O5—C4—C5 | 60.6 (3) |
O1i—S1—C1—F1 | −176.91 (15) | C3—O5—C4—C18 | −179.4 (2) |
O1ii—S1—C1—F1ii | 63.09 (15) | C3vi—C10—C11—C12 | 170.1 (2) |
O1—S1—C1—F1i | −56.91 (15) | C3vi—C10—C11—C13 | 47.5 (3) |
O1—S1—C1—F1ii | −176.91 (15) | C4—O5—C3—O6 | −12.8 (4) |
O1ii—S1—C1—F1 | −56.91 (15) | C4—O5—C3—C10v | 163.1 (2) |
O1i—S1—C1—F1i | 63.09 (15) | C5—N1—C6—C7 | 59.6 (3) |
O1—S1—C1—F1 | 63.09 (15) | C5—N1—C6—C15 | −180.0 (2) |
O2iii—S2—C2—F2iii | −66.20 (12) | C5—C4—C18—C19 | −60.7 (3) |
O2iv—S2—C2—F2iv | −66.20 (13) | C5—C4—C18—C20 | 175.4 (3) |
O2iv—S2—C2—F2 | 53.80 (12) | C6—N1—C5—O7 | −0.7 (4) |
O2iv—S2—C2—F2iii | 173.80 (12) | C6—N1—C5—C4 | −176.3 (2) |
O2iii—S2—C2—F2 | 173.80 (12) | C7—O8—C8—C9 | −62.2 (3) |
O2—S2—C2—F2iii | 53.80 (13) | C7—O8—C8—C14 | 176.8 (2) |
O2—S2—C2—F2 | −66.20 (12) | C7—C6—C15—C16 | −168.9 (2) |
O2iii—S2—C2—F2iv | 53.80 (13) | C7—C6—C15—C17 | −45.6 (3) |
O2—S2—C2—F2iv | 173.80 (13) | C8—O8—C7—O10 | 10.6 (4) |
O5—C4—C5—O7 | 45.2 (4) | C8—O8—C7—C6 | −164.6 (2) |
O5—C4—C5—N1 | −139.1 (2) | C9—N2—C10—C3vi | −67.9 (3) |
O5—C4—C18—C19 | 179.7 (3) | C9—N2—C10—C11 | 170.4 (2) |
O5—C4—C18—C20 | 55.9 (3) | C10—N2—C9—O9 | 6.7 (5) |
O8—C8—C9—O9 | −38.7 (4) | C10—N2—C9—C8 | −177.1 (2) |
O8—C8—C9—N2 | 145.1 (2) | C14—C8—C9—O9 | 79.3 (3) |
N1—C6—C7—O8 | −138.5 (2) | C14—C8—C9—N2 | −97.0 (3) |
N1—C6—C7—O10 | 46.4 (4) | C15—C6—C7—O8 | 101.5 (2) |
N1—C6—C15—C16 | 70.5 (3) | C15—C6—C7—O10 | −73.6 (3) |
N1—C6—C15—C17 | −166.2 (2) | C18—C4—C5—O7 | −71.5 (3) |
N2—C10—C11—C12 | −67.6 (3) | C18—C4—C5—N1 | 104.2 (3) |
Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, x−y, z; (iii) −x+y+1, −x+2, z; (iv) −y+2, x−y+1, z; (v) −x+y, −x+1, z; (vi) −y+1, x−y+1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O9v | 0.96 (1) | 2.05 (3) | 2.802 (3) | 134 (4) |
O4—H4B···O7 | 0.97 (1) | 1.74 (1) | 2.688 (3) | 167 (3) |
O3—H3A···O9 | 0.94 (1) | 1.82 (2) | 2.717 (3) | 157 (3) |
N1—H1···O1 | 0.88 | 2.05 | 2.933 (4) | 179 |
N2—H2···O2 | 0.88 | 2.05 | 2.927 (4) | 173 |
Symmetry code: (v) −x+y, −x+1, z. |
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