Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113024323/cu3036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113024323/cu3036Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113024323/cu3036IIsup3.hkl |
CCDC references: 969472; 969473
Triptans are selective serotonin receptor agonists designed to treat acute migraine. There are currently seven triptans, namely sumatriptan, rizatriptan, zolmitriptan, eletriptan, naratriptan, almotriptan and frovatriptan, available on the market. They differ from each other with respect to their pharmacological profiles: complete pain relief, speed of pain relief, rate of migraine recurrence, relief of associated symptoms and adverse effects (Belvís et al., 2009). Zolmitriptan [(S)-4-({3-[2-(dimethylamino)ethyl]-1H-indol-5-yl}methyl)-1,3-oxazolidin-2-one] is a novel and selective centrally and peripherally acting 5-HT1B/D receptor agonist in development for the acute treatment of migraine (Martin, 1994). We have been studying the series of zolmitriptan (Ravikumar et al., 2007) and its solvates with chloroform (Sridhar et al., 2007), benzene and phenol (Swamy et al., 2007), and pyridine and propiophenone (Sridhar et al., 2010). In the present study, we report two salts of zolmitriptan for the first time, namely zolmitriptan oxalate, (I), and zolmitriptan camphorsulfonate, (II).
Crystals of (I) suitable for X-ray diffraction were obtained by disssolving zolmitriptan (SMS Pharma Research Centre, Hyderabad) and oxalic acid [Ratio?] in methanol–water (85:15 v/v, 20 ml) and allowing the solution to evaporate slowly. Crystals of (II) were obtained by slow evaporation of a solution of zolmitriptan and S-camphor sulfonic acid [Ratio?] in methanol.
Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. All N-bound H atoms of the zolmitriptan cations in (I) and (II) were located in a difference density map and refined isotropically. The C-bound H atoms of (I) and (II) were located in difference density maps but were positioned geometrically and included as riding atoms, with C—H = 0.93–0.98 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. For the methyl H atoms, the AFIX 137 command was used (Sheldrick, 2008) [Please do not use software-specific terms - rephrase in more general language]. Compound (I) shows a meaningless Flack parameter (Flack & Bernardinelli, 2000) value of -0.4 (6). This is due to the molecular structure of (I) having light atoms (<Si) with no significant anomalous scattering effects. In this case, the Flack parameter is indeterminate with Mo radiation and hence the absolute structure cannot be determined. However, the absolute configuration of the procured material was known in advance and was confirmed by unambiguous refinement of the absolute structure parameter (Flack & Bernardinelli, 2000) in (II).
The asymmetric unit of (I) contains two crystallographically independent protonated zolmitriptan molecules (unprimed and primed atom labels) and two oxalate monoanions (labelled A and B) (Fig. 1), while that of (II) comprises one protonated zolmitriptan molecule and one camphorsulfonate anion (Fig. 2). Protonation occurs at atom N2 of the ethylamine side chain of the zolmitriptan for both (I) and (II) and shows quaternary character. The sums of the angles at N2 are 334.3 (2) and 333.6 (2)° for the unprimed and primed cations of (I), and 334.4 (2)° for (II). The corresponding angle for the unprotonated N2 atom of zolmitriptan is 329.8 (2)° (Ravikumar et al., 2007). The bond lengths and angles of the zolmitriptan cations in (I) and (II) are similar. Except for the geometry around atom N2 due to protonation, all other geometries agree well with the values found in the related structures of zolmitriptan base and its solvates. In (II), the two five-membered rings (C18—C22 and C18–C20/C23/C24) of the camphorsulfonate anion adopt an envelope conformation. The dihedral angles of the bridged three-atom (C18/C19/C20) plane of the camphorsulfonate anion of (II) to the four-atom planes (C18/C22/C21/C20 and C18/C24/C23/C20) are 54.4 (3) and 56.1 (3)°, respectively.
The zolmitriptan molecule is composed of three linked groups, viz. a planar indole ring system, an ethylamine side chain and an oxazolidinone unit. In (I), both the ethylamine side chain and the oxazolidinone unit are oriented in opposite directions with respect to the planar indole ring for the two independent molecules, thereby giving the molecule a step-like appearance. However, in (II), both these side chains are folded in the same direction, giving the molecule a cup-like appearance. The conformation of the oxazolidinone ring of the unprimed cation of (I) is different from the other two cations [the primed cation of (I) and the cation of (II)]. It adopts an envelope conformation in the unprimed cation of (I), while the primed cation of (I) and the cation of (II) adopt twisted conformations. The ethylamine side-chain conformation is different for (I) and (II), as can be seen from three torsion angles, viz. C1—C2—C9—C10, C2—C9—C10—N2 and C9—C10—N2—C11. In (I), it adopts an ac (anticlinal, ±90–150°; Boeyens, 1978), ap (antiperiplanar, ±150–180°), ap conformation for both unprimed and primed cations of (I), respectively. In (II), it is in an ac, ap, sc (synclinal, ±30–90°) conformation.
The orientation of the oxazolidinone ring can be defined by the C4—C5—C13—C14 torsion angle with respect to the planar indole ring. It is in an ac conformation for the unprimed cation of (I), while both the primed cation of (I) and the cation of (II) adopt an sc conformation. The planes of the ethylamine group (τ1) and the oxazolidinone ring (τ2) make dihedral angles of 55.86 (10) and 68.25 (9), and 53.16 (9) and 84.86 (9)°, for the unprimed and primed cations of (I), respectvely, and 43.38 (15) and 69.78 (14)° for the cation of (II), with respect to the planar indole ring. Similarly, the dihedral angles between the planes of the ethylamine group and the oxazolidinone ring (τ3) are 79.18 (12) and 74.20 (11)°, respectively, for the unprimed and primed cations of (I), and 68.04 (18)° for the cation of (II).
In (I), cation–cation, anion–anion and cation–anion interactions stabilize the crystal structure (Table 2), while in (II) there are cation–cation and cation–anion interactions (Table 3). Both independent cations of (I) are held together by N—H···O hydrogen bonds involving atoms N3 and O2 of the oxazolidinone ring, forming an R22(8) dimer (Etter, 1990; Etter et al., 1990; Bernstein et al., 1995). Each oxalate anion (A or B) is linked by short hydrogen bonds to its translation-related anion, forming an independent one-dimensional chain running parallel to the [100] direction (Fig. 3). The cationic dimer links the four anionic chains through four N—H···O hydrogen bonds. In these, atoms N1/N2 and N1'/N2' of the two cations are involved in a three-centred hydrogen-bonding pattern (Jeffrey & Saenger, 1991), forming an R12(5) motif. The anionic chains interlink pairs of cation dimers and extend them into a three-dimensional hydrogen-bonded network.
The cation of (II) is involved in a one-dimensional helical chain of C(11) type along the c, axis involving atom N1 of the indole ring and atom O2 of the oxazolidinone ring (Fig. 4). Each zolmitriptan cation (atoms N2 of the ethylamine side chain and N3 of the oxazolidinone ring) in the helical chain is further linked by atoms O4 and O5 of the camphorsulfonate anion, thereby forming an R22(15) ring motif.
We have also reported the structures of zolmitriptan and five of its solvates. Based on these reported data and the present structures of (I) and (II), zolmitriptan can be viewed in three configurations from a molecular perspective, viz. cup, L and step-like shapes. Both the base and (II) have a cup-like appearance, while the solvates of zolmitriptan fall into the L-shaped category. Interestingly, (I) is different from these two groups and has a step-like appearance. The five solvate structures have more or less similar conformational features for the ethylamine side chain and the oxazolidinone ring. In all these cases, the ethylamine side chain has sp (synperiplanar, ±0–30°), ap and ap conformations for the three torsion angles discussed above. Except for the chloroform solvate, where it is in a twisted conformation, the oxazolidinone ring is planar in all the solvates. Another similarity in the solvate structures is the position of atom N2 of the ethylamine side chain with respect to the planar indole ring (τ4): it is intra, being almost coplanar with the indole ring.
The zolmitriptan base has different conformational features compared with the solvate structures. The ethylamine side chain is in an ac, sc, ap conformation, the oxazolidinone ring is in a twisted conformation and, finally, atom N2 is not coplanar with the indole ring.
Both (I) and (II) are salts and show significant conformational differences compared with the solvate structures. The conformation of the oxazolidinone ring matches that of the zolmitriptan base [except for the unprimed cation of (I), which is in an envelope conformation]. However, the ethylamine side chain has different conformations in (I) and (II), as well as differing from the zolmitriptan base and solvates. An overlay of all currently known zolmitriptan structures (Fig. 5), superimposing the planar indole systems, reveals these conformational and orientational differences.
The conformational flexibility of the zolmitriptan molecule can facilitate different kinds of hydrogen-bonding pattern. The cup-shaped and L-shaped configurations observed in the zolmitriptan base, (II) and the solvate structures exhibit a helical chain in the crystal packing. However, (I), which is in step-like configuration, forms a dimer.
Based on the theoretical 5-HT1B-like receptor model (Moloney et al., 1999), the distance from atom N2 to the centroid of the C3—C8 aromatic ring (d1), the distance from atom N3 to the centroid of the C3—C8 aromatic ring (d2) and the N2···N3 distance (d3) were calculated for both (I) and (II) and the six previously reported structures (Table 4). It is very clear that the values are almost equal for all structures, except the d3 value of (II).
In conclusion, the crystal structures of the oxalate and camphor sulfonate salts of zolmitriptan depict two different configurations of the zolmitriptan molecule, which in turn leads to different hydrogen-bonding interactions. In (I), it forms a dimer, while in (II) it leads to a helical chain. From the present study it is clear that the conformational flexibility of the zolmitriptan molecule is highly dependent on the co-formers, such as salts, solvates etc., in the crystal lattice.
For related literature, see: Belvís et al. (2009); Bernstein et al. (1995); Boeyens (1978); Etter (1990); Etter, MacDonald & Bernstein (1990); Flack & Bernardinelli (2000); Jeffrey & Saenger (1991); Martin (1994); Moloney et al. (1999); Ravikumar et al. (2007); Sheldrick (2008); Sridhar et al. (2007, 2010); Swamy et al. (2007).
For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C16H22N3O2+·C2HO4− | F(000) = 800 |
Mr = 377.39 | Dx = 1.356 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 6021 reflections |
a = 5.5944 (4) Å | θ = 2.2–27.8° |
b = 17.9908 (14) Å | µ = 0.10 mm−1 |
c = 18.3844 (15) Å | T = 294 K |
β = 92.220 (1)° | Block, colourless |
V = 1849.0 (2) Å3 | 0.19 × 0.17 × 0.09 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 7991 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 28.0°, θmin = 1.1° |
ω scans | h = −7→7 |
21294 measured reflections | k = −23→22 |
8509 independent reflections | l = −23→24 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0594P)2 + 0.1495P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
8509 reflections | Δρmax = 0.28 e Å−3 |
523 parameters | Δρmin = −0.20 e Å−3 |
1 restraint | Absolute structure: Flack & Bernardinelli (2000), with 4320 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.4 (6) |
C16H22N3O2+·C2HO4− | V = 1849.0 (2) Å3 |
Mr = 377.39 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.5944 (4) Å | µ = 0.10 mm−1 |
b = 17.9908 (14) Å | T = 294 K |
c = 18.3844 (15) Å | 0.19 × 0.17 × 0.09 mm |
β = 92.220 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 7991 reflections with I > 2σ(I) |
21294 measured reflections | Rint = 0.018 |
8509 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.099 | Δρmax = 0.28 e Å−3 |
S = 1.04 | Δρmin = −0.20 e Å−3 |
8509 reflections | Absolute structure: Flack & Bernardinelli (2000), with 4320 Friedel pairs |
523 parameters | Absolute structure parameter: −0.4 (6) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1178 (4) | 0.48893 (11) | 1.05952 (10) | 0.0593 (5) | |
H1 | 0.0358 | 0.4759 | 1.1007 | 0.071* | |
C2 | 0.0572 (3) | 0.46634 (9) | 0.99053 (9) | 0.0481 (4) | |
C3 | 0.2275 (3) | 0.50016 (8) | 0.94457 (8) | 0.0445 (3) | |
C4 | 0.2590 (3) | 0.50067 (9) | 0.86961 (8) | 0.0458 (3) | |
H4 | 0.1533 | 0.4748 | 0.8386 | 0.055* | |
C5 | 0.4465 (3) | 0.53950 (9) | 0.84163 (10) | 0.0514 (4) | |
C6 | 0.6071 (4) | 0.57867 (10) | 0.88899 (12) | 0.0592 (4) | |
H6 | 0.7344 | 0.6043 | 0.8697 | 0.071* | |
C7 | 0.5795 (4) | 0.57969 (10) | 0.96265 (12) | 0.0617 (5) | |
H7 | 0.6863 | 0.6054 | 0.9934 | 0.074* | |
C8 | 0.3879 (3) | 0.54136 (8) | 0.99009 (9) | 0.0511 (4) | |
C9 | −0.1344 (3) | 0.41138 (10) | 0.96832 (9) | 0.0489 (4) | |
H9A | −0.2164 | 0.4277 | 0.9237 | 0.059* | |
H9B | −0.2509 | 0.4079 | 1.0059 | 0.059* | |
C10 | −0.0204 (2) | 0.33632 (9) | 0.95690 (7) | 0.0406 (3) | |
H10C | 0.1025 | 0.3416 | 0.9215 | 0.049* | |
H10D | 0.0571 | 0.3204 | 1.0024 | 0.049* | |
C11 | −0.0594 (4) | 0.21036 (11) | 0.90778 (12) | 0.0637 (5) | |
H11D | −0.1702 | 0.1755 | 0.8858 | 0.096* | |
H11E | 0.0211 | 0.1878 | 0.9492 | 0.096* | |
H11F | 0.0560 | 0.2245 | 0.8730 | 0.096* | |
C12 | −0.3674 (4) | 0.25819 (15) | 0.98702 (12) | 0.0735 (6) | |
H12D | −0.2842 | 0.2413 | 1.0306 | 0.110* | |
H12E | −0.4716 | 0.2196 | 0.9686 | 0.110* | |
H12F | −0.4602 | 0.3014 | 0.9978 | 0.110* | |
C13 | 0.4870 (4) | 0.53911 (10) | 0.76110 (10) | 0.0591 (4) | |
H13C | 0.3674 | 0.5074 | 0.7373 | 0.071* | |
H13D | 0.6424 | 0.5173 | 0.7532 | 0.071* | |
C14 | 0.4768 (3) | 0.61495 (10) | 0.72522 (10) | 0.0539 (4) | |
H14 | 0.5965 | 0.6480 | 0.7483 | 0.065* | |
C15 | 0.5108 (4) | 0.61121 (12) | 0.64302 (11) | 0.0619 (4) | |
H15C | 0.6690 | 0.6286 | 0.6314 | 0.074* | |
H15D | 0.4912 | 0.5606 | 0.6255 | 0.074* | |
C16 | 0.1742 (3) | 0.67836 (10) | 0.66121 (10) | 0.0543 (4) | |
N1 | 0.3156 (3) | 0.53324 (9) | 1.05980 (8) | 0.0631 (4) | |
H1A | 0.396 (5) | 0.5533 (16) | 1.1012 (16) | 0.098 (9)* | |
N2 | −0.1911 (2) | 0.27725 (8) | 0.93141 (7) | 0.0412 (3) | |
H2 | −0.270 (4) | 0.2943 (12) | 0.8900 (11) | 0.054 (5)* | |
N3 | 0.2413 (3) | 0.64940 (11) | 0.72528 (10) | 0.0650 (4) | |
H3 | 0.184 (4) | 0.6669 (13) | 0.7630 (13) | 0.063 (6)* | |
O1 | 0.3299 (3) | 0.65870 (9) | 0.61063 (7) | 0.0663 (4) | |
O2 | 0.0011 (3) | 0.71656 (9) | 0.64548 (8) | 0.0697 (4) | |
C1' | −0.0926 (3) | 0.96641 (9) | 0.42953 (9) | 0.0509 (4) | |
H1' | 0.0050 | 0.9834 | 0.3933 | 0.061* | |
C2' | −0.0631 (3) | 0.98331 (8) | 0.50177 (9) | 0.0433 (3) | |
C3' | −0.2477 (3) | 0.94457 (8) | 0.53859 (8) | 0.0403 (3) | |
C4' | −0.3066 (3) | 0.93685 (9) | 0.61140 (9) | 0.0442 (3) | |
H4' | −0.2177 | 0.9614 | 0.6478 | 0.053* | |
C5' | −0.4981 (3) | 0.89241 (9) | 0.62887 (9) | 0.0468 (3) | |
C6' | −0.6339 (3) | 0.85668 (9) | 0.57247 (10) | 0.0526 (4) | |
H6' | −0.7627 | 0.8271 | 0.5846 | 0.063* | |
C7' | −0.5818 (3) | 0.86421 (8) | 0.50081 (10) | 0.0521 (4) | |
H7' | −0.6758 | 0.8414 | 0.4644 | 0.062* | |
C8' | −0.3855 (3) | 0.90667 (8) | 0.48402 (9) | 0.0453 (3) | |
C9' | 0.1207 (3) | 1.03475 (9) | 0.53522 (8) | 0.0442 (3) | |
H9'A | 0.2488 | 1.0422 | 0.5019 | 0.053* | |
H9'B | 0.1886 | 1.0131 | 0.5797 | 0.053* | |
C10' | 0.0051 (2) | 1.10877 (8) | 0.55192 (7) | 0.0361 (3) | |
H10A | −0.0652 | 1.1291 | 0.5071 | 0.043* | |
H10B | −0.1234 | 1.1004 | 0.5849 | 0.043* | |
C11' | 0.0402 (4) | 1.22955 (10) | 0.61224 (12) | 0.0611 (5) | |
H11A | −0.0813 | 1.2127 | 0.6438 | 0.092* | |
H11B | −0.0331 | 1.2558 | 0.5718 | 0.092* | |
H11C | 0.1484 | 1.2621 | 0.6386 | 0.092* | |
C12' | 0.3578 (3) | 1.18876 (13) | 0.53422 (11) | 0.0622 (5) | |
H12A | 0.2814 | 1.2120 | 0.4925 | 0.093* | |
H12B | 0.4469 | 1.1463 | 0.5190 | 0.093* | |
H12C | 0.4643 | 1.2236 | 0.5583 | 0.093* | |
C13' | −0.5762 (3) | 0.88265 (11) | 0.70621 (10) | 0.0570 (4) | |
H13A | −0.6718 | 0.9254 | 0.7188 | 0.068* | |
H13B | −0.6786 | 0.8392 | 0.7078 | 0.068* | |
C14' | −0.3783 (3) | 0.87389 (10) | 0.76343 (9) | 0.0509 (4) | |
H14' | −0.2737 | 0.9176 | 0.7634 | 0.061* | |
C15' | −0.4672 (4) | 0.86095 (12) | 0.83974 (10) | 0.0608 (4) | |
H15A | −0.4784 | 0.9075 | 0.8660 | 0.073* | |
H15B | −0.6231 | 0.8373 | 0.8376 | 0.073* | |
C16' | −0.1684 (3) | 0.77853 (11) | 0.82199 (9) | 0.0541 (4) | |
N1' | −0.2867 (3) | 0.92085 (8) | 0.41821 (8) | 0.0551 (4) | |
H1'A | −0.329 (4) | 0.9032 (13) | 0.3783 (13) | 0.062 (6)* | |
N2' | 0.1738 (2) | 1.16472 (7) | 0.58515 (6) | 0.0364 (2) | |
H2' | 0.248 (3) | 1.1444 (11) | 0.6215 (10) | 0.045 (5)* | |
N3' | −0.2362 (3) | 0.80660 (9) | 0.75675 (8) | 0.0565 (4) | |
H3' | −0.166 (4) | 0.7951 (13) | 0.7192 (12) | 0.067 (6)* | |
O1' | −0.2902 (3) | 0.81285 (9) | 0.87432 (7) | 0.0646 (3) | |
O2' | −0.0229 (3) | 0.73009 (10) | 0.83680 (8) | 0.0747 (4) | |
C1A | 0.4576 (2) | 0.59818 (9) | 1.25933 (7) | 0.0385 (3) | |
C2A | 0.7041 (2) | 0.58769 (10) | 1.22487 (8) | 0.0440 (3) | |
O1A | 0.28356 (17) | 0.57559 (8) | 1.21965 (6) | 0.0526 (3) | |
O2A | 0.45024 (18) | 0.62586 (9) | 1.31947 (6) | 0.0578 (3) | |
O3A | 0.7178 (2) | 0.57763 (13) | 1.16093 (7) | 0.0897 (6) | |
O4A | 0.88152 (17) | 0.59359 (9) | 1.27115 (6) | 0.0563 (3) | |
H4A | 1.038 (5) | 0.5849 (17) | 1.2478 (13) | 0.090 (8)* | |
C1B | −0.4432 (2) | 0.83410 (8) | 0.22797 (7) | 0.0340 (3) | |
C2B | −0.6904 (2) | 0.84566 (8) | 0.26195 (7) | 0.0351 (3) | |
O1B | −0.43716 (18) | 0.80688 (8) | 0.16686 (6) | 0.0528 (3) | |
O2B | −0.26933 (16) | 0.85491 (7) | 0.26806 (5) | 0.0420 (2) | |
O3B | −0.70775 (19) | 0.86045 (11) | 0.32431 (6) | 0.0711 (4) | |
O4B | −0.86758 (17) | 0.83753 (8) | 0.21520 (6) | 0.0523 (3) | |
H4B | −1.006 (5) | 0.8480 (16) | 0.2332 (14) | 0.088 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0779 (12) | 0.0584 (10) | 0.0410 (8) | 0.0229 (9) | −0.0056 (8) | −0.0096 (7) |
C2 | 0.0515 (9) | 0.0496 (8) | 0.0425 (8) | 0.0152 (7) | −0.0062 (6) | −0.0092 (7) |
C3 | 0.0482 (8) | 0.0386 (7) | 0.0456 (8) | 0.0102 (6) | −0.0113 (6) | −0.0086 (6) |
C4 | 0.0526 (8) | 0.0398 (7) | 0.0442 (8) | 0.0023 (6) | −0.0091 (6) | −0.0076 (6) |
C5 | 0.0603 (10) | 0.0365 (7) | 0.0570 (9) | 0.0038 (7) | −0.0035 (7) | −0.0017 (7) |
C6 | 0.0566 (10) | 0.0426 (8) | 0.0774 (12) | −0.0028 (7) | −0.0108 (9) | 0.0002 (8) |
C7 | 0.0654 (11) | 0.0381 (8) | 0.0788 (13) | 0.0007 (8) | −0.0307 (9) | −0.0097 (8) |
C8 | 0.0622 (10) | 0.0385 (7) | 0.0507 (9) | 0.0137 (7) | −0.0216 (7) | −0.0127 (7) |
C9 | 0.0419 (8) | 0.0576 (9) | 0.0474 (8) | 0.0098 (7) | 0.0027 (6) | −0.0023 (7) |
C10 | 0.0322 (6) | 0.0545 (8) | 0.0348 (6) | 0.0022 (6) | −0.0023 (5) | 0.0009 (6) |
C11 | 0.0611 (11) | 0.0496 (9) | 0.0797 (13) | 0.0006 (8) | −0.0075 (9) | 0.0015 (9) |
C12 | 0.0524 (10) | 0.1088 (18) | 0.0598 (11) | −0.0208 (11) | 0.0098 (9) | 0.0269 (11) |
C13 | 0.0717 (11) | 0.0461 (9) | 0.0600 (10) | −0.0019 (8) | 0.0090 (9) | −0.0043 (8) |
C14 | 0.0552 (9) | 0.0493 (9) | 0.0573 (9) | −0.0104 (7) | 0.0039 (7) | −0.0040 (7) |
C15 | 0.0588 (10) | 0.0672 (11) | 0.0609 (10) | −0.0106 (9) | 0.0158 (8) | −0.0019 (9) |
C16 | 0.0566 (10) | 0.0541 (10) | 0.0524 (10) | −0.0170 (8) | 0.0044 (8) | 0.0005 (7) |
N1 | 0.0864 (12) | 0.0525 (8) | 0.0483 (8) | 0.0152 (8) | −0.0252 (8) | −0.0186 (7) |
N2 | 0.0338 (6) | 0.0530 (7) | 0.0366 (6) | −0.0027 (5) | −0.0020 (5) | 0.0093 (5) |
N3 | 0.0725 (11) | 0.0741 (11) | 0.0491 (8) | 0.0114 (9) | 0.0126 (8) | 0.0057 (8) |
O1 | 0.0738 (9) | 0.0771 (9) | 0.0487 (7) | −0.0054 (7) | 0.0121 (6) | 0.0021 (6) |
O2 | 0.0637 (8) | 0.0787 (10) | 0.0665 (8) | −0.0003 (7) | −0.0003 (7) | 0.0083 (7) |
C1' | 0.0608 (10) | 0.0476 (8) | 0.0440 (8) | 0.0071 (7) | −0.0019 (7) | −0.0049 (7) |
C2' | 0.0441 (8) | 0.0416 (7) | 0.0439 (7) | 0.0080 (6) | −0.0029 (6) | −0.0060 (6) |
C3' | 0.0419 (7) | 0.0353 (6) | 0.0430 (7) | 0.0066 (6) | −0.0087 (6) | −0.0061 (5) |
C4' | 0.0435 (8) | 0.0446 (7) | 0.0438 (8) | 0.0021 (6) | −0.0096 (6) | −0.0080 (6) |
C5' | 0.0471 (8) | 0.0430 (8) | 0.0497 (8) | 0.0038 (6) | −0.0069 (7) | 0.0002 (6) |
C6' | 0.0509 (9) | 0.0377 (7) | 0.0681 (10) | −0.0040 (7) | −0.0128 (7) | 0.0002 (7) |
C7' | 0.0599 (9) | 0.0358 (7) | 0.0587 (9) | −0.0012 (7) | −0.0218 (8) | −0.0086 (6) |
C8' | 0.0549 (9) | 0.0335 (7) | 0.0463 (8) | 0.0070 (6) | −0.0134 (6) | −0.0073 (6) |
C9' | 0.0351 (7) | 0.0505 (8) | 0.0469 (8) | 0.0042 (6) | −0.0002 (6) | −0.0063 (6) |
C10' | 0.0287 (6) | 0.0433 (7) | 0.0360 (6) | −0.0008 (5) | −0.0028 (5) | −0.0017 (5) |
C11' | 0.0622 (11) | 0.0440 (8) | 0.0762 (12) | 0.0041 (8) | −0.0068 (9) | −0.0148 (8) |
C12' | 0.0487 (9) | 0.0807 (13) | 0.0573 (10) | −0.0216 (9) | 0.0040 (8) | 0.0153 (9) |
C13' | 0.0494 (9) | 0.0628 (10) | 0.0585 (10) | −0.0020 (8) | 0.0000 (8) | 0.0010 (8) |
C14' | 0.0559 (9) | 0.0478 (8) | 0.0491 (8) | −0.0110 (7) | 0.0014 (7) | −0.0016 (6) |
C15' | 0.0694 (11) | 0.0630 (11) | 0.0505 (9) | −0.0022 (9) | 0.0062 (8) | −0.0083 (8) |
C16' | 0.0583 (10) | 0.0598 (10) | 0.0443 (8) | −0.0095 (8) | 0.0025 (7) | 0.0036 (7) |
N1' | 0.0731 (10) | 0.0497 (8) | 0.0412 (7) | 0.0035 (7) | −0.0125 (7) | −0.0120 (6) |
N2' | 0.0322 (5) | 0.0435 (6) | 0.0331 (6) | −0.0018 (5) | −0.0043 (4) | 0.0031 (5) |
N3' | 0.0599 (9) | 0.0673 (9) | 0.0426 (7) | 0.0057 (7) | 0.0072 (6) | 0.0052 (7) |
O1' | 0.0785 (9) | 0.0740 (8) | 0.0413 (6) | −0.0018 (7) | 0.0019 (6) | −0.0012 (6) |
O2' | 0.0812 (10) | 0.0840 (10) | 0.0587 (8) | 0.0152 (8) | 0.0011 (7) | 0.0149 (7) |
C1A | 0.0221 (5) | 0.0597 (9) | 0.0336 (6) | −0.0005 (6) | 0.0020 (5) | −0.0018 (6) |
C2A | 0.0247 (6) | 0.0710 (10) | 0.0366 (7) | −0.0057 (6) | 0.0030 (5) | −0.0137 (7) |
O1A | 0.0241 (4) | 0.0922 (9) | 0.0415 (5) | −0.0058 (5) | −0.0006 (4) | −0.0169 (6) |
O2A | 0.0297 (5) | 0.1041 (10) | 0.0398 (5) | −0.0024 (6) | 0.0028 (4) | −0.0228 (6) |
O3A | 0.0358 (6) | 0.1872 (19) | 0.0465 (7) | −0.0086 (9) | 0.0059 (5) | −0.0424 (9) |
O4A | 0.0222 (4) | 0.1086 (10) | 0.0381 (5) | −0.0010 (5) | 0.0007 (4) | −0.0136 (6) |
C1B | 0.0229 (5) | 0.0468 (7) | 0.0326 (6) | 0.0013 (5) | 0.0024 (4) | 0.0017 (5) |
C2B | 0.0243 (5) | 0.0483 (7) | 0.0328 (6) | −0.0022 (5) | 0.0030 (4) | −0.0032 (5) |
O1B | 0.0290 (5) | 0.0900 (9) | 0.0396 (5) | 0.0014 (5) | 0.0026 (4) | −0.0202 (6) |
O2B | 0.0221 (4) | 0.0665 (7) | 0.0372 (5) | −0.0008 (4) | −0.0012 (3) | −0.0067 (5) |
O3B | 0.0334 (5) | 0.1420 (14) | 0.0381 (6) | −0.0091 (7) | 0.0042 (4) | −0.0287 (7) |
O4B | 0.0210 (4) | 0.1008 (9) | 0.0351 (5) | 0.0017 (5) | 0.0016 (4) | −0.0116 (5) |
C1—C2 | 1.362 (2) | C3'—C8' | 1.416 (2) |
C1—N1 | 1.364 (3) | C4'—C5' | 1.384 (2) |
C1—H1 | 0.9300 | C4'—H4' | 0.9300 |
C2—C3 | 1.433 (3) | C5'—C6' | 1.416 (2) |
C2—C9 | 1.503 (2) | C5'—C13' | 1.514 (2) |
C3—C4 | 1.396 (2) | C6'—C7' | 1.367 (3) |
C3—C8 | 1.413 (2) | C6'—H6' | 0.9300 |
C4—C5 | 1.376 (3) | C7'—C8' | 1.383 (3) |
C4—H4 | 0.9300 | C7'—H7' | 0.9300 |
C5—C6 | 1.415 (3) | C8'—N1' | 1.373 (2) |
C5—C13 | 1.506 (2) | C9'—C10' | 1.517 (2) |
C6—C7 | 1.369 (3) | C9'—H9'A | 0.9700 |
C6—H6 | 0.9300 | C9'—H9'B | 0.9700 |
C7—C8 | 1.386 (3) | C10'—N2' | 1.4941 (17) |
C7—H7 | 0.9300 | C10'—H10A | 0.9700 |
C8—N1 | 1.366 (3) | C10'—H10B | 0.9700 |
C9—C10 | 1.512 (2) | C11'—N2' | 1.482 (2) |
C9—H9A | 0.9700 | C11'—H11A | 0.9600 |
C9—H9B | 0.9700 | C11'—H11B | 0.9600 |
C10—N2 | 1.492 (2) | C11'—H11C | 0.9600 |
C10—H10C | 0.9700 | C12'—N2' | 1.483 (2) |
C10—H10D | 0.9700 | C12'—H12A | 0.9600 |
C11—N2 | 1.485 (2) | C12'—H12B | 0.9600 |
C11—H11D | 0.9600 | C12'—H12C | 0.9600 |
C11—H11E | 0.9600 | C13'—C14' | 1.505 (3) |
C11—H11F | 0.9600 | C13'—H13A | 0.9700 |
C12—N2 | 1.488 (2) | C13'—H13B | 0.9700 |
C12—H12D | 0.9600 | C14'—N3' | 1.456 (2) |
C12—H12E | 0.9600 | C14'—C15' | 1.524 (2) |
C12—H12F | 0.9600 | C14'—H14' | 0.9800 |
C13—C14 | 1.515 (3) | C15'—O1' | 1.444 (3) |
C13—H13C | 0.9700 | C15'—H15A | 0.9700 |
C13—H13D | 0.9700 | C15'—H15B | 0.9700 |
C14—N3 | 1.456 (3) | C16'—O2' | 1.216 (2) |
C14—C15 | 1.532 (3) | C16'—N3' | 1.343 (2) |
C14—H14 | 0.9800 | C16'—O1' | 1.350 (2) |
C15—O1 | 1.436 (3) | N1'—H1'A | 0.83 (2) |
C15—H15C | 0.9700 | N2'—H2' | 0.86 (2) |
C15—H15D | 0.9700 | N3'—H3' | 0.83 (2) |
C16—O2 | 1.213 (2) | C1A—O2A | 1.2147 (17) |
C16—N3 | 1.329 (3) | C1A—O1A | 1.2612 (17) |
C16—O1 | 1.346 (2) | C1A—C2A | 1.5514 (17) |
N1—H1A | 0.94 (3) | C2A—O3A | 1.1946 (19) |
N2—H2 | 0.92 (2) | C2A—O4A | 1.2864 (17) |
N3—H3 | 0.84 (2) | O4A—H4A | 1.00 (3) |
C1'—C2' | 1.366 (2) | C1B—O1B | 1.2273 (17) |
C1'—N1' | 1.370 (3) | C1B—O2B | 1.2548 (16) |
C1'—H1' | 0.9300 | C1B—C2B | 1.5531 (16) |
C2'—C3' | 1.437 (2) | C2B—O3B | 1.1846 (17) |
C2'—C9' | 1.498 (2) | C2B—O4B | 1.2949 (16) |
C3'—C4' | 1.398 (2) | O4B—H4B | 0.87 (3) |
C2—C1—N1 | 110.53 (18) | C4'—C3'—C2' | 134.41 (14) |
C2—C1—H1 | 124.7 | C8'—C3'—C2' | 106.33 (14) |
N1—C1—H1 | 124.7 | C5'—C4'—C3' | 119.52 (14) |
C1—C2—C3 | 105.96 (16) | C5'—C4'—H4' | 120.2 |
C1—C2—C9 | 126.76 (18) | C3'—C4'—H4' | 120.2 |
C3—C2—C9 | 127.04 (14) | C4'—C5'—C6' | 119.37 (16) |
C4—C3—C8 | 118.67 (16) | C4'—C5'—C13' | 122.60 (15) |
C4—C3—C2 | 134.17 (14) | C6'—C5'—C13' | 117.98 (16) |
C8—C3—C2 | 107.15 (14) | C7'—C6'—C5' | 122.18 (16) |
C5—C4—C3 | 119.95 (14) | C7'—C6'—H6' | 118.9 |
C5—C4—H4 | 120.0 | C5'—C6'—H6' | 118.9 |
C3—C4—H4 | 120.0 | C6'—C7'—C8' | 118.08 (14) |
C4—C5—C6 | 119.86 (17) | C6'—C7'—H7' | 121.0 |
C4—C5—C13 | 120.72 (16) | C8'—C7'—H7' | 121.0 |
C6—C5—C13 | 119.39 (17) | N1'—C8'—C7' | 130.51 (15) |
C7—C6—C5 | 121.46 (19) | N1'—C8'—C3' | 107.95 (15) |
C7—C6—H6 | 119.3 | C7'—C8'—C3' | 121.54 (16) |
C5—C6—H6 | 119.3 | C2'—C9'—C10' | 109.52 (11) |
C6—C7—C8 | 118.17 (16) | C2'—C9'—H9'A | 109.8 |
C6—C7—H7 | 120.9 | C10'—C9'—H9'A | 109.8 |
C8—C7—H7 | 120.9 | C2'—C9'—H9'B | 109.8 |
N1—C8—C7 | 130.97 (16) | C10'—C9'—H9'B | 109.8 |
N1—C8—C3 | 107.18 (17) | H9'A—C9'—H9'B | 108.2 |
C7—C8—C3 | 121.84 (16) | N2'—C10'—C9' | 113.99 (11) |
C2—C9—C10 | 108.97 (12) | N2'—C10'—H10A | 108.8 |
C2—C9—H9A | 109.9 | C9'—C10'—H10A | 108.8 |
C10—C9—H9A | 109.9 | N2'—C10'—H10B | 108.8 |
C2—C9—H9B | 109.9 | C9'—C10'—H10B | 108.8 |
C10—C9—H9B | 109.9 | H10A—C10'—H10B | 107.6 |
H9A—C9—H9B | 108.3 | N2'—C11'—H11A | 109.5 |
N2—C10—C9 | 114.30 (12) | N2'—C11'—H11B | 109.5 |
N2—C10—H10C | 108.7 | H11A—C11'—H11B | 109.5 |
C9—C10—H10C | 108.7 | N2'—C11'—H11C | 109.5 |
N2—C10—H10D | 108.7 | H11A—C11'—H11C | 109.5 |
C9—C10—H10D | 108.7 | H11B—C11'—H11C | 109.5 |
H10C—C10—H10D | 107.6 | N2'—C12'—H12A | 109.5 |
N2—C11—H11D | 109.5 | N2'—C12'—H12B | 109.5 |
N2—C11—H11E | 109.5 | H12A—C12'—H12B | 109.5 |
H11D—C11—H11E | 109.5 | N2'—C12'—H12C | 109.5 |
N2—C11—H11F | 109.5 | H12A—C12'—H12C | 109.5 |
H11D—C11—H11F | 109.5 | H12B—C12'—H12C | 109.5 |
H11E—C11—H11F | 109.5 | C14'—C13'—C5' | 115.94 (15) |
N2—C12—H12D | 109.5 | C14'—C13'—H13A | 108.3 |
N2—C12—H12E | 109.5 | C5'—C13'—H13A | 108.3 |
H12D—C12—H12E | 109.5 | C14'—C13'—H13B | 108.3 |
N2—C12—H12F | 109.5 | C5'—C13'—H13B | 108.3 |
H12D—C12—H12F | 109.5 | H13A—C13'—H13B | 107.4 |
H12E—C12—H12F | 109.5 | N3'—C14'—C13' | 114.66 (15) |
C5—C13—C14 | 114.77 (15) | N3'—C14'—C15' | 98.58 (14) |
C5—C13—H13C | 108.6 | C13'—C14'—C15' | 113.69 (16) |
C14—C13—H13C | 108.6 | N3'—C14'—H14' | 109.8 |
C5—C13—H13D | 108.6 | C13'—C14'—H14' | 109.8 |
C14—C13—H13D | 108.6 | C15'—C14'—H14' | 109.8 |
H13C—C13—H13D | 107.6 | O1'—C15'—C14' | 104.72 (15) |
N3—C14—C13 | 113.70 (16) | O1'—C15'—H15A | 110.8 |
N3—C14—C15 | 99.58 (15) | C14'—C15'—H15A | 110.8 |
C13—C14—C15 | 112.69 (15) | O1'—C15'—H15B | 110.8 |
N3—C14—H14 | 110.2 | C14'—C15'—H15B | 110.8 |
C13—C14—H14 | 110.2 | H15A—C15'—H15B | 108.9 |
C15—C14—H14 | 110.2 | O2'—C16'—N3' | 129.27 (18) |
O1—C15—C14 | 105.69 (15) | O2'—C16'—O1' | 121.34 (16) |
O1—C15—H15C | 110.6 | N3'—C16'—O1' | 109.39 (17) |
C14—C15—H15C | 110.6 | C1'—N1'—C8' | 108.71 (14) |
O1—C15—H15D | 110.6 | C1'—N1'—H1'A | 124.4 (16) |
C14—C15—H15D | 110.6 | C8'—N1'—H1'A | 126.8 (16) |
H15C—C15—H15D | 108.7 | C11'—N2'—C12' | 110.75 (15) |
O2—C16—N3 | 128.96 (18) | C11'—N2'—C10' | 110.42 (12) |
O2—C16—O1 | 121.09 (17) | C12'—N2'—C10' | 112.41 (12) |
N3—C16—O1 | 109.94 (18) | C11'—N2'—H2' | 108.1 (12) |
C1—N1—C8 | 109.17 (14) | C12'—N2'—H2' | 106.7 (13) |
C1—N1—H1A | 126.2 (18) | C10'—N2'—H2' | 108.3 (13) |
C8—N1—H1A | 124.6 (19) | C16'—N3'—C14' | 111.94 (16) |
C11—N2—C12 | 111.34 (17) | C16'—N3'—H3' | 121.3 (16) |
C11—N2—C10 | 110.51 (12) | C14'—N3'—H3' | 123.6 (17) |
C12—N2—C10 | 112.43 (14) | C16'—O1'—C15' | 108.47 (13) |
C11—N2—H2 | 104.8 (13) | O2A—C1A—O1A | 127.30 (12) |
C12—N2—H2 | 109.8 (13) | O2A—C1A—C2A | 118.92 (12) |
C10—N2—H2 | 107.6 (13) | O1A—C1A—C2A | 113.78 (12) |
C16—N3—C14 | 113.01 (17) | O3A—C2A—O4A | 125.89 (13) |
C16—N3—H3 | 118.9 (16) | O3A—C2A—C1A | 120.80 (13) |
C14—N3—H3 | 122.4 (16) | O4A—C2A—C1A | 113.26 (11) |
C16—O1—C15 | 109.55 (15) | C2A—O4A—H4A | 111.6 (14) |
C2'—C1'—N1' | 110.24 (17) | O1B—C1B—O2B | 127.48 (12) |
C2'—C1'—H1' | 124.9 | O1B—C1B—C2B | 118.58 (11) |
N1'—C1'—H1' | 124.9 | O2B—C1B—C2B | 113.95 (11) |
C1'—C2'—C3' | 106.75 (14) | O3B—C2B—O4B | 125.34 (12) |
C1'—C2'—C9' | 126.28 (16) | O3B—C2B—C1B | 121.80 (12) |
C3'—C2'—C9' | 126.93 (14) | O4B—C2B—C1B | 112.86 (11) |
C4'—C3'—C8' | 119.25 (15) | C2B—O4B—H4B | 113.0 (17) |
N1—C1—C2—C3 | −1.02 (18) | C1'—C2'—C3'—C8' | −1.34 (17) |
N1—C1—C2—C9 | 173.66 (15) | C9'—C2'—C3'—C8' | 176.45 (14) |
C1—C2—C3—C4 | −177.98 (17) | C8'—C3'—C4'—C5' | 0.0 (2) |
C9—C2—C3—C4 | 7.4 (3) | C2'—C3'—C4'—C5' | −178.15 (16) |
C1—C2—C3—C8 | 0.97 (16) | C3'—C4'—C5'—C6' | −1.2 (2) |
C9—C2—C3—C8 | −173.69 (14) | C3'—C4'—C5'—C13' | −178.61 (15) |
C8—C3—C4—C5 | 1.4 (2) | C4'—C5'—C6'—C7' | 0.3 (2) |
C2—C3—C4—C5 | −179.76 (16) | C13'—C5'—C6'—C7' | 177.83 (16) |
C3—C4—C5—C6 | 0.1 (2) | C5'—C6'—C7'—C8' | 1.8 (2) |
C3—C4—C5—C13 | 178.44 (15) | C6'—C7'—C8'—N1' | 176.78 (16) |
C4—C5—C6—C7 | −0.7 (3) | C6'—C7'—C8'—C3' | −3.1 (2) |
C13—C5—C6—C7 | −179.04 (16) | C4'—C3'—C8'—N1' | −177.67 (14) |
C5—C6—C7—C8 | −0.3 (3) | C2'—C3'—C8'—N1' | 0.94 (16) |
C6—C7—C8—N1 | −179.40 (16) | C4'—C3'—C8'—C7' | 2.2 (2) |
C6—C7—C8—C3 | 1.9 (2) | C2'—C3'—C8'—C7' | −179.16 (14) |
C4—C3—C8—N1 | 178.56 (14) | C1'—C2'—C9'—C10' | 101.99 (17) |
C2—C3—C8—N1 | −0.58 (16) | C3'—C2'—C9'—C10' | −75.38 (19) |
C4—C3—C8—C7 | −2.5 (2) | C2'—C9'—C10'—N2' | −179.60 (12) |
C2—C3—C8—C7 | 178.40 (14) | C4'—C5'—C13'—C14' | −41.4 (2) |
C1—C2—C9—C10 | −98.35 (18) | C6'—C5'—C13'—C14' | 141.11 (16) |
C3—C2—C9—C10 | 75.24 (19) | C5'—C13'—C14'—N3' | −65.1 (2) |
C2—C9—C10—N2 | −177.47 (12) | C5'—C13'—C14'—C15' | −177.52 (16) |
C4—C5—C13—C14 | 119.89 (18) | N3'—C14'—C15'—O1' | 25.04 (17) |
C6—C5—C13—C14 | −61.8 (2) | C13'—C14'—C15'—O1' | 146.84 (16) |
C5—C13—C14—N3 | −65.7 (2) | C2'—C1'—N1'—C8' | −0.70 (19) |
C5—C13—C14—C15 | −178.09 (16) | C7'—C8'—N1'—C1' | 179.93 (16) |
N3—C14—C15—O1 | 14.00 (18) | C3'—C8'—N1'—C1' | −0.18 (18) |
C13—C14—C15—O1 | 134.82 (17) | C9'—C10'—N2'—C11' | −169.42 (14) |
C2—C1—N1—C8 | 0.7 (2) | C9'—C10'—N2'—C12' | 66.36 (17) |
C7—C8—N1—C1 | −178.89 (17) | O2'—C16'—N3'—C14' | −168.4 (2) |
C3—C8—N1—C1 | −0.04 (18) | O1'—C16'—N3'—C14' | 11.7 (2) |
C9—C10—N2—C11 | 168.80 (14) | C13'—C14'—N3'—C16' | −144.04 (16) |
C9—C10—N2—C12 | −66.11 (18) | C15'—C14'—N3'—C16' | −22.95 (19) |
O2—C16—N3—C14 | −172.21 (18) | O2'—C16'—O1'—C15' | −173.52 (18) |
O1—C16—N3—C14 | 8.5 (2) | N3'—C16'—O1'—C15' | 6.4 (2) |
C13—C14—N3—C16 | −134.08 (18) | C14'—C15'—O1'—C16' | −20.66 (19) |
C15—C14—N3—C16 | −14.0 (2) | O2A—C1A—C2A—O3A | −162.2 (2) |
O2—C16—O1—C15 | −177.52 (17) | O1A—C1A—C2A—O3A | 18.1 (3) |
N3—C16—O1—C15 | 1.8 (2) | O2A—C1A—C2A—O4A | 15.6 (2) |
C14—C15—O1—C16 | −10.54 (19) | O1A—C1A—C2A—O4A | −164.11 (16) |
N1'—C1'—C2'—C3' | 1.27 (18) | O1B—C1B—C2B—O3B | 167.90 (18) |
N1'—C1'—C2'—C9' | −176.54 (14) | O2B—C1B—C2B—O3B | −12.4 (2) |
C1'—C2'—C3'—C4' | 176.95 (16) | O1B—C1B—C2B—O4B | −12.2 (2) |
C9'—C2'—C3'—C4' | −5.3 (3) | O2B—C1B—C2B—O4B | 167.48 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3A | 0.94 (3) | 2.12 (3) | 2.972 (2) | 150 (2) |
N1—H1A···O1A | 0.94 (3) | 2.32 (3) | 3.048 (2) | 133 (2) |
N2—H2···O1Bi | 0.92 (2) | 1.92 (2) | 2.754 (2) | 150 (2) |
N2—H2···O4Bi | 0.92 (2) | 2.25 (2) | 2.936 (2) | 131 (2) |
N3—H3···O2′ | 0.84 (2) | 2.14 (2) | 2.954 (2) | 163 (2) |
N1′—H1′A···O2B | 0.83 (2) | 2.24 (2) | 3.010 (2) | 155 (2) |
N1′—H1′A···O3B | 0.83 (2) | 2.43 (2) | 3.065 (2) | 135 (2) |
N2′—H2′···O2Aii | 0.86 (2) | 2.00 (2) | 2.775 (2) | 151 (2) |
N2′—H2′···O4Aii | 0.86 (2) | 2.317 (19) | 2.962 (2) | 132 (2) |
N3′—H3′···O2 | 0.83 (2) | 2.19 (2) | 2.963 (2) | 154 (2) |
O4A—H4A···O1Aiii | 1.00 (3) | 1.49 (3) | 2.495 (1) | 174 (2) |
O4B—H4B···O2Biv | 0.87 (3) | 1.63 (3) | 2.503 (1) | 172 (3) |
Symmetry codes: (i) −x−1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+2; (iii) x+1, y, z; (iv) x−1, y, z. |
C16H22N3O2+·C10H15O4S− | F(000) = 1112 |
Mr = 519.65 | Dx = 1.298 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 1398 reflections |
a = 9.5992 (15) Å | θ = 2.4–20.5° |
b = 16.361 (3) Å | µ = 0.17 mm−1 |
c = 16.927 (2) Å | T = 294 K |
V = 2658.4 (7) Å3 | Needle, colourless |
Z = 4 | 0.17 × 0.12 × 0.09 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5280 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 28.0°, θmin = 1.7° |
ω scans | h = −12→12 |
31108 measured reflections | k = −21→21 |
6314 independent reflections | l = −21→21 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0582P)2 + 0.5005P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
6314 reflections | Δρmax = 0.32 e Å−3 |
341 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Absolute structure: Flack & Bernardinelli (2000), with 2812 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (9) |
C16H22N3O2+·C10H15O4S− | V = 2658.4 (7) Å3 |
Mr = 519.65 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.5992 (15) Å | µ = 0.17 mm−1 |
b = 16.361 (3) Å | T = 294 K |
c = 16.927 (2) Å | 0.17 × 0.12 × 0.09 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5280 reflections with I > 2σ(I) |
31108 measured reflections | Rint = 0.048 |
6314 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.132 | Δρmax = 0.32 e Å−3 |
S = 1.10 | Δρmin = −0.16 e Å−3 |
6314 reflections | Absolute structure: Flack & Bernardinelli (2000), with 2812 Friedel pairs |
341 parameters | Absolute structure parameter: 0.00 (9) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.0768 (3) | 0.5166 (2) | 0.48754 (18) | 0.0563 (8) | |
H1 | −0.1409 | 0.5592 | 0.4858 | 0.068* | |
C2 | −0.0661 (3) | 0.46101 (16) | 0.54777 (15) | 0.0415 (6) | |
C3 | 0.0456 (3) | 0.40754 (16) | 0.52645 (14) | 0.0389 (6) | |
C4 | 0.1087 (3) | 0.34038 (15) | 0.56393 (14) | 0.0381 (6) | |
H4 | 0.0733 | 0.3210 | 0.6115 | 0.046* | |
C5 | 0.2239 (3) | 0.30303 (17) | 0.53001 (16) | 0.0454 (7) | |
C6 | 0.2724 (4) | 0.3318 (2) | 0.45648 (17) | 0.0588 (9) | |
H6 | 0.3489 | 0.3062 | 0.4336 | 0.071* | |
C7 | 0.2118 (4) | 0.3958 (2) | 0.41731 (16) | 0.0606 (9) | |
H7 | 0.2451 | 0.4129 | 0.3684 | 0.073* | |
C8 | 0.0986 (3) | 0.43466 (18) | 0.45303 (15) | 0.0476 (7) | |
C9 | −0.1475 (3) | 0.45724 (17) | 0.62329 (16) | 0.0441 (6) | |
H9A | −0.1889 | 0.4035 | 0.6290 | 0.053* | |
H9B | −0.2220 | 0.4972 | 0.6219 | 0.053* | |
C10 | −0.0528 (3) | 0.47443 (15) | 0.69317 (14) | 0.0376 (6) | |
H10A | 0.0312 | 0.4419 | 0.6877 | 0.045* | |
H10B | −0.0257 | 0.5315 | 0.6919 | 0.045* | |
C11 | −0.2416 (3) | 0.5081 (2) | 0.78690 (19) | 0.0570 (8) | |
H11A | −0.2708 | 0.5011 | 0.8407 | 0.085* | |
H11B | −0.3158 | 0.4922 | 0.7521 | 0.085* | |
H11C | −0.2184 | 0.5644 | 0.7778 | 0.085* | |
C12 | −0.0137 (4) | 0.46369 (19) | 0.83555 (17) | 0.0582 (8) | |
H12A | 0.0173 | 0.5193 | 0.8392 | 0.087* | |
H12B | 0.0643 | 0.4289 | 0.8243 | 0.087* | |
H12C | −0.0552 | 0.4476 | 0.8847 | 0.087* | |
C13 | 0.2974 (3) | 0.23536 (18) | 0.57302 (18) | 0.0545 (8) | |
H13A | 0.3480 | 0.2028 | 0.5346 | 0.065* | |
H13B | 0.2277 | 0.2003 | 0.5969 | 0.065* | |
C14 | 0.3990 (3) | 0.26222 (18) | 0.63721 (18) | 0.0507 (7) | |
H14 | 0.4443 | 0.2137 | 0.6594 | 0.061* | |
C15 | 0.5111 (3) | 0.3232 (2) | 0.6119 (2) | 0.0620 (8) | |
H15A | 0.6009 | 0.2963 | 0.6079 | 0.074* | |
H15B | 0.4883 | 0.3468 | 0.5609 | 0.074* | |
C16 | 0.4055 (3) | 0.37482 (18) | 0.72109 (17) | 0.0493 (7) | |
N1 | 0.0205 (3) | 0.50032 (18) | 0.43012 (15) | 0.0629 (8) | |
H1N | 0.033 (3) | 0.5304 (17) | 0.3909 (18) | 0.045 (8)* | |
N2 | −0.1176 (2) | 0.45637 (13) | 0.77153 (14) | 0.0409 (5) | |
H2N | −0.140 (3) | 0.410 (2) | 0.7665 (18) | 0.055 (9)* | |
N3 | 0.3355 (3) | 0.30845 (16) | 0.70100 (14) | 0.0475 (6) | |
H3N | 0.267 (3) | 0.2929 (18) | 0.7295 (17) | 0.045 (8)* | |
O1 | 0.5145 (2) | 0.38531 (14) | 0.67156 (14) | 0.0645 (6) | |
O2 | 0.3834 (3) | 0.42235 (15) | 0.77492 (14) | 0.0745 (7) | |
C17 | −0.1137 (3) | 0.19909 (16) | 0.86265 (14) | 0.0408 (6) | |
H17A | −0.0781 | 0.1468 | 0.8807 | 0.049* | |
H17B | −0.0861 | 0.2398 | 0.9013 | 0.049* | |
C18 | −0.2717 (3) | 0.19445 (14) | 0.86231 (14) | 0.0348 (5) | |
C19 | −0.3411 (3) | 0.14104 (17) | 0.92874 (16) | 0.0435 (6) | |
C20 | −0.4911 (3) | 0.1638 (2) | 0.9037 (2) | 0.0604 (8) | |
H20 | −0.5641 | 0.1395 | 0.9366 | 0.072* | |
C21 | −0.4904 (4) | 0.2560 (2) | 0.9033 (2) | 0.0783 (11) | |
H21A | −0.5111 | 0.2777 | 0.9553 | 0.094* | |
H21B | −0.5571 | 0.2775 | 0.8656 | 0.094* | |
C22 | −0.3429 (4) | 0.27545 (19) | 0.87891 (19) | 0.0620 (9) | |
C23 | −0.4940 (4) | 0.1362 (3) | 0.8170 (2) | 0.0751 (10) | |
H23A | −0.5663 | 0.1643 | 0.7876 | 0.090* | |
H23B | −0.5083 | 0.0777 | 0.8128 | 0.090* | |
C24 | −0.3464 (3) | 0.1611 (2) | 0.78774 (17) | 0.0558 (8) | |
H24A | −0.2972 | 0.1143 | 0.7664 | 0.067* | |
H24B | −0.3525 | 0.2029 | 0.7472 | 0.067* | |
C25 | −0.3082 (4) | 0.0502 (2) | 0.9218 (3) | 0.0792 (12) | |
H25A | −0.2127 | 0.0409 | 0.9360 | 0.119* | |
H25B | −0.3235 | 0.0326 | 0.8684 | 0.119* | |
H25C | −0.3678 | 0.0199 | 0.9566 | 0.119* | |
C26 | −0.3051 (4) | 0.1701 (3) | 1.01219 (18) | 0.0801 (12) | |
H26A | −0.3063 | 0.2288 | 1.0137 | 0.120* | |
H26B | −0.2140 | 0.1508 | 1.0263 | 0.120* | |
H26C | −0.3723 | 0.1490 | 1.0489 | 0.120* | |
O3 | −0.0361 (2) | 0.15236 (11) | 0.72175 (11) | 0.0573 (5) | |
O4 | 0.1100 (3) | 0.2448 (2) | 0.79331 (14) | 0.1048 (11) | |
O5 | −0.1058 (3) | 0.29142 (12) | 0.73597 (13) | 0.0749 (8) | |
O6 | −0.2914 (4) | 0.34217 (14) | 0.8749 (2) | 0.1083 (12) | |
S1 | −0.02957 (8) | 0.22350 (4) | 0.77060 (4) | 0.04460 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0593 (19) | 0.0592 (18) | 0.0505 (17) | −0.0088 (15) | −0.0212 (15) | 0.0166 (15) |
C2 | 0.0432 (15) | 0.0447 (15) | 0.0365 (13) | −0.0087 (12) | −0.0120 (11) | 0.0081 (11) |
C3 | 0.0436 (14) | 0.0465 (14) | 0.0265 (11) | −0.0161 (12) | −0.0052 (10) | −0.0010 (10) |
C4 | 0.0453 (14) | 0.0422 (14) | 0.0267 (11) | −0.0141 (12) | −0.0002 (11) | −0.0047 (10) |
C5 | 0.0464 (15) | 0.0500 (15) | 0.0397 (14) | −0.0106 (13) | 0.0026 (12) | −0.0189 (12) |
C6 | 0.0571 (18) | 0.080 (2) | 0.0391 (15) | −0.0181 (17) | 0.0099 (14) | −0.0234 (16) |
C7 | 0.069 (2) | 0.086 (2) | 0.0270 (13) | −0.0355 (19) | 0.0087 (14) | −0.0131 (15) |
C8 | 0.0574 (17) | 0.0586 (17) | 0.0267 (12) | −0.0257 (15) | −0.0096 (12) | 0.0046 (12) |
C9 | 0.0379 (14) | 0.0460 (15) | 0.0483 (15) | 0.0014 (12) | −0.0050 (12) | 0.0090 (12) |
C10 | 0.0427 (14) | 0.0321 (12) | 0.0381 (13) | −0.0045 (11) | 0.0017 (11) | 0.0039 (10) |
C11 | 0.0527 (17) | 0.0578 (18) | 0.0604 (19) | 0.0066 (14) | 0.0148 (14) | −0.0020 (15) |
C12 | 0.076 (2) | 0.0569 (18) | 0.0416 (15) | −0.0020 (16) | −0.0107 (15) | 0.0068 (13) |
C13 | 0.0559 (18) | 0.0446 (16) | 0.0631 (18) | 0.0028 (14) | 0.0102 (14) | −0.0240 (14) |
C14 | 0.0463 (16) | 0.0484 (16) | 0.0575 (17) | 0.0079 (13) | 0.0056 (13) | −0.0049 (14) |
C15 | 0.0440 (17) | 0.077 (2) | 0.0649 (19) | −0.0053 (16) | 0.0100 (15) | −0.0075 (17) |
C16 | 0.0509 (16) | 0.0526 (16) | 0.0443 (16) | 0.0047 (14) | −0.0071 (14) | 0.0004 (14) |
N1 | 0.0788 (19) | 0.0745 (18) | 0.0354 (13) | −0.0276 (16) | −0.0188 (13) | 0.0234 (13) |
N2 | 0.0527 (14) | 0.0253 (10) | 0.0448 (12) | −0.0034 (10) | 0.0037 (11) | 0.0049 (10) |
N3 | 0.0419 (13) | 0.0567 (14) | 0.0440 (13) | −0.0070 (11) | 0.0081 (11) | −0.0072 (11) |
O1 | 0.0548 (14) | 0.0652 (13) | 0.0734 (14) | −0.0148 (11) | 0.0107 (12) | −0.0099 (11) |
O2 | 0.0937 (18) | 0.0658 (14) | 0.0641 (14) | −0.0052 (13) | 0.0040 (14) | −0.0220 (12) |
C17 | 0.0480 (15) | 0.0470 (15) | 0.0273 (12) | −0.0089 (12) | 0.0093 (11) | 0.0026 (11) |
C18 | 0.0429 (13) | 0.0299 (11) | 0.0317 (12) | −0.0003 (10) | 0.0062 (10) | 0.0021 (10) |
C19 | 0.0394 (14) | 0.0481 (15) | 0.0429 (14) | −0.0086 (12) | −0.0015 (11) | 0.0141 (12) |
C20 | 0.0378 (16) | 0.080 (2) | 0.0634 (19) | −0.0016 (15) | 0.0032 (14) | 0.0246 (17) |
C21 | 0.073 (2) | 0.083 (2) | 0.079 (2) | 0.031 (2) | 0.029 (2) | 0.0216 (19) |
C22 | 0.085 (2) | 0.0398 (16) | 0.0612 (19) | 0.0119 (17) | 0.0350 (17) | 0.0041 (15) |
C23 | 0.050 (2) | 0.102 (3) | 0.074 (2) | −0.0079 (19) | −0.0205 (17) | 0.013 (2) |
C24 | 0.0520 (17) | 0.073 (2) | 0.0422 (16) | 0.0025 (15) | −0.0098 (13) | 0.0023 (15) |
C25 | 0.070 (2) | 0.054 (2) | 0.115 (3) | −0.0042 (17) | −0.005 (2) | 0.041 (2) |
C26 | 0.065 (2) | 0.136 (3) | 0.0394 (17) | −0.029 (2) | 0.0016 (16) | 0.021 (2) |
O3 | 0.0829 (14) | 0.0450 (10) | 0.0439 (11) | 0.0185 (10) | 0.0155 (11) | 0.0001 (9) |
O4 | 0.0706 (17) | 0.185 (3) | 0.0594 (15) | −0.056 (2) | 0.0212 (13) | −0.0065 (18) |
O5 | 0.138 (2) | 0.0327 (10) | 0.0540 (12) | 0.0138 (12) | 0.0425 (14) | 0.0078 (9) |
O6 | 0.155 (3) | 0.0355 (12) | 0.134 (3) | 0.0033 (16) | 0.089 (2) | −0.0099 (14) |
S1 | 0.0568 (4) | 0.0423 (3) | 0.0347 (3) | −0.0072 (3) | 0.0152 (3) | 0.0009 (3) |
C1—C2 | 1.370 (4) | C15—H15B | 0.9700 |
C1—N1 | 1.374 (4) | C16—O2 | 1.217 (4) |
C1—H1 | 0.9300 | C16—N3 | 1.321 (4) |
C2—C3 | 1.430 (4) | C16—O1 | 1.351 (4) |
C2—C9 | 1.499 (4) | N1—H1N | 0.83 (3) |
C3—C4 | 1.406 (4) | N2—H2N | 0.79 (3) |
C3—C8 | 1.414 (4) | N3—H3N | 0.85 (3) |
C4—C5 | 1.388 (4) | C17—C18 | 1.519 (4) |
C4—H4 | 0.9300 | C17—S1 | 1.800 (2) |
C5—C6 | 1.410 (4) | C17—H17A | 0.9700 |
C5—C13 | 1.501 (4) | C17—H17B | 0.9700 |
C6—C7 | 1.369 (5) | C18—C22 | 1.517 (4) |
C6—H6 | 0.9300 | C18—C24 | 1.551 (4) |
C7—C8 | 1.396 (5) | C18—C19 | 1.572 (3) |
C7—H7 | 0.9300 | C19—C25 | 1.524 (4) |
C8—N1 | 1.366 (4) | C19—C26 | 1.530 (4) |
C9—C10 | 1.518 (4) | C19—C20 | 1.547 (4) |
C9—H9A | 0.9700 | C20—C21 | 1.508 (5) |
C9—H9B | 0.9700 | C20—C23 | 1.535 (5) |
C10—N2 | 1.495 (3) | C20—H20 | 0.9800 |
C10—H10A | 0.9700 | C21—C22 | 1.509 (5) |
C10—H10B | 0.9700 | C21—H21A | 0.9700 |
C11—N2 | 1.483 (4) | C21—H21B | 0.9700 |
C11—H11A | 0.9600 | C22—O6 | 1.200 (4) |
C11—H11B | 0.9600 | C23—C24 | 1.555 (5) |
C11—H11C | 0.9600 | C23—H23A | 0.9700 |
C12—N2 | 1.478 (4) | C23—H23B | 0.9700 |
C12—H12A | 0.9600 | C24—H24A | 0.9700 |
C12—H12B | 0.9600 | C24—H24B | 0.9700 |
C12—H12C | 0.9600 | C25—H25A | 0.9600 |
C13—C14 | 1.525 (4) | C25—H25B | 0.9600 |
C13—H13A | 0.9700 | C25—H25C | 0.9600 |
C13—H13B | 0.9700 | C26—H26A | 0.9600 |
C14—N3 | 1.452 (4) | C26—H26B | 0.9600 |
C14—C15 | 1.528 (4) | C26—H26C | 0.9600 |
C14—H14 | 0.9800 | O3—S1 | 1.429 (2) |
C15—O1 | 1.433 (4) | O4—S1 | 1.437 (3) |
C15—H15A | 0.9700 | O5—S1 | 1.454 (2) |
C2—C1—N1 | 110.3 (3) | C12—N2—C10 | 110.7 (2) |
C2—C1—H1 | 124.9 | C11—N2—C10 | 112.2 (2) |
N1—C1—H1 | 124.9 | C12—N2—H2N | 110 (2) |
C1—C2—C3 | 105.9 (3) | C11—N2—H2N | 111 (2) |
C1—C2—C9 | 128.5 (3) | C10—N2—H2N | 102 (2) |
C3—C2—C9 | 125.5 (2) | C16—N3—C14 | 113.9 (3) |
C4—C3—C8 | 119.1 (3) | C16—N3—H3N | 119 (2) |
C4—C3—C2 | 133.4 (2) | C14—N3—H3N | 126 (2) |
C8—C3—C2 | 107.4 (2) | C16—O1—C15 | 109.2 (2) |
C5—C4—C3 | 120.1 (2) | C18—C17—S1 | 117.12 (19) |
C5—C4—H4 | 120.0 | C18—C17—H17A | 108.0 |
C3—C4—H4 | 120.0 | S1—C17—H17A | 108.0 |
C4—C5—C6 | 118.8 (3) | C18—C17—H17B | 108.0 |
C4—C5—C13 | 119.9 (3) | S1—C17—H17B | 108.0 |
C6—C5—C13 | 121.3 (3) | H17A—C17—H17B | 107.3 |
C7—C6—C5 | 122.9 (3) | C22—C18—C17 | 113.9 (2) |
C7—C6—H6 | 118.6 | C22—C18—C24 | 104.5 (3) |
C5—C6—H6 | 118.6 | C17—C18—C24 | 118.9 (2) |
C6—C7—C8 | 118.0 (3) | C22—C18—C19 | 99.3 (2) |
C6—C7—H7 | 121.0 | C17—C18—C19 | 116.6 (2) |
C8—C7—H7 | 121.0 | C24—C18—C19 | 101.0 (2) |
N1—C8—C7 | 131.4 (3) | C25—C19—C26 | 109.1 (3) |
N1—C8—C3 | 107.4 (3) | C25—C19—C20 | 114.0 (3) |
C7—C8—C3 | 121.2 (3) | C26—C19—C20 | 112.9 (3) |
C2—C9—C10 | 110.2 (2) | C25—C19—C18 | 113.5 (3) |
C2—C9—H9A | 109.6 | C26—C19—C18 | 113.0 (2) |
C10—C9—H9A | 109.6 | C20—C19—C18 | 93.7 (2) |
C2—C9—H9B | 109.6 | C21—C20—C23 | 106.9 (3) |
C10—C9—H9B | 109.6 | C21—C20—C19 | 103.8 (3) |
H9A—C9—H9B | 108.1 | C23—C20—C19 | 102.0 (3) |
N2—C10—C9 | 113.9 (2) | C21—C20—H20 | 114.3 |
N2—C10—H10A | 108.8 | C23—C20—H20 | 114.3 |
C9—C10—H10A | 108.8 | C19—C20—H20 | 114.3 |
N2—C10—H10B | 108.8 | C20—C21—C22 | 102.5 (3) |
C9—C10—H10B | 108.8 | C20—C21—H21A | 111.3 |
H10A—C10—H10B | 107.7 | C22—C21—H21A | 111.3 |
N2—C11—H11A | 109.5 | C20—C21—H21B | 111.3 |
N2—C11—H11B | 109.5 | C22—C21—H21B | 111.3 |
H11A—C11—H11B | 109.5 | H21A—C21—H21B | 109.2 |
N2—C11—H11C | 109.5 | O6—C22—C21 | 126.5 (3) |
H11A—C11—H11C | 109.5 | O6—C22—C18 | 126.7 (3) |
H11B—C11—H11C | 109.5 | C21—C22—C18 | 106.8 (3) |
N2—C12—H12A | 109.5 | C20—C23—C24 | 102.2 (3) |
N2—C12—H12B | 109.5 | C20—C23—H23A | 111.3 |
H12A—C12—H12B | 109.5 | C24—C23—H23A | 111.3 |
N2—C12—H12C | 109.5 | C20—C23—H23B | 111.3 |
H12A—C12—H12C | 109.5 | C24—C23—H23B | 111.3 |
H12B—C12—H12C | 109.5 | H23A—C23—H23B | 109.2 |
C5—C13—C14 | 115.7 (2) | C18—C24—C23 | 104.7 (2) |
C5—C13—H13A | 108.4 | C18—C24—H24A | 110.8 |
C14—C13—H13A | 108.4 | C23—C24—H24A | 110.8 |
C5—C13—H13B | 108.4 | C18—C24—H24B | 110.8 |
C14—C13—H13B | 108.4 | C23—C24—H24B | 110.8 |
H13A—C13—H13B | 107.4 | H24A—C24—H24B | 108.9 |
N3—C14—C13 | 114.3 (2) | C19—C25—H25A | 109.5 |
N3—C14—C15 | 99.4 (2) | C19—C25—H25B | 109.5 |
C13—C14—C15 | 116.0 (3) | H25A—C25—H25B | 109.5 |
N3—C14—H14 | 108.9 | C19—C25—H25C | 109.5 |
C13—C14—H14 | 108.9 | H25A—C25—H25C | 109.5 |
C15—C14—H14 | 108.9 | H25B—C25—H25C | 109.5 |
O1—C15—C14 | 106.3 (2) | C19—C26—H26A | 109.5 |
O1—C15—H15A | 110.5 | C19—C26—H26B | 109.5 |
C14—C15—H15A | 110.5 | H26A—C26—H26B | 109.5 |
O1—C15—H15B | 110.5 | C19—C26—H26C | 109.5 |
C14—C15—H15B | 110.5 | H26A—C26—H26C | 109.5 |
H15A—C15—H15B | 108.7 | H26B—C26—H26C | 109.5 |
O2—C16—N3 | 129.0 (3) | O3—S1—O4 | 113.13 (18) |
O2—C16—O1 | 121.3 (3) | O3—S1—O5 | 111.55 (13) |
N3—C16—O1 | 109.8 (3) | O4—S1—O5 | 113.1 (2) |
C8—N1—C1 | 108.9 (2) | O3—S1—C17 | 107.50 (12) |
C8—N1—H1N | 128 (2) | O4—S1—C17 | 103.92 (14) |
C1—N1—H1N | 123 (2) | O5—S1—C17 | 107.01 (13) |
C12—N2—C11 | 111.5 (2) | ||
N1—C1—C2—C3 | 0.5 (3) | C14—C15—O1—C16 | −9.2 (3) |
N1—C1—C2—C9 | 177.7 (2) | S1—C17—C18—C22 | −88.9 (3) |
C1—C2—C3—C4 | 178.3 (3) | S1—C17—C18—C24 | 34.9 (3) |
C9—C2—C3—C4 | 0.9 (4) | S1—C17—C18—C19 | 156.25 (19) |
C1—C2—C3—C8 | 0.6 (3) | C22—C18—C19—C25 | 171.4 (3) |
C9—C2—C3—C8 | −176.8 (2) | C17—C18—C19—C25 | −65.7 (3) |
C8—C3—C4—C5 | 1.8 (3) | C24—C18—C19—C25 | 64.6 (3) |
C2—C3—C4—C5 | −175.7 (3) | C22—C18—C19—C26 | −63.6 (3) |
C3—C4—C5—C6 | −2.3 (4) | C17—C18—C19—C26 | 59.3 (3) |
C3—C4—C5—C13 | 175.5 (2) | C24—C18—C19—C26 | −170.4 (3) |
C4—C5—C6—C7 | 0.8 (4) | C22—C18—C19—C20 | 53.2 (3) |
C13—C5—C6—C7 | −176.9 (3) | C17—C18—C19—C20 | 176.1 (2) |
C5—C6—C7—C8 | 1.1 (4) | C24—C18—C19—C20 | −53.6 (3) |
C6—C7—C8—N1 | 177.9 (3) | C25—C19—C20—C21 | −171.3 (3) |
C6—C7—C8—C3 | −1.6 (4) | C26—C19—C20—C21 | 63.4 (3) |
C4—C3—C8—N1 | −179.5 (2) | C18—C19—C20—C21 | −53.5 (3) |
C2—C3—C8—N1 | −1.4 (3) | C25—C19—C20—C23 | −60.4 (3) |
C4—C3—C8—C7 | 0.2 (4) | C26—C19—C20—C23 | 174.4 (3) |
C2—C3—C8—C7 | 178.3 (2) | C18—C19—C20—C23 | 57.4 (3) |
C1—C2—C9—C10 | −113.1 (3) | C23—C20—C21—C22 | −74.8 (4) |
C3—C2—C9—C10 | 63.7 (3) | C19—C20—C21—C22 | 32.5 (4) |
C2—C9—C10—N2 | −168.9 (2) | C20—C21—C22—O6 | −175.5 (4) |
C4—C5—C13—C14 | −80.6 (3) | C20—C21—C22—C18 | 3.3 (4) |
C6—C5—C13—C14 | 97.2 (3) | C17—C18—C22—O6 | 17.3 (5) |
C5—C13—C14—N3 | 60.9 (3) | C24—C18—C22—O6 | −113.9 (4) |
C5—C13—C14—C15 | −53.9 (3) | C19—C18—C22—O6 | 142.1 (4) |
N3—C14—C15—O1 | 10.8 (3) | C17—C18—C22—C21 | −161.4 (3) |
C13—C14—C15—O1 | 133.9 (3) | C24—C18—C22—C21 | 67.3 (3) |
C7—C8—N1—C1 | −177.9 (3) | C19—C18—C22—C21 | −36.7 (3) |
C3—C8—N1—C1 | 1.6 (3) | C21—C20—C23—C24 | 69.4 (3) |
C2—C1—N1—C8 | −1.3 (3) | C19—C20—C23—C24 | −39.1 (3) |
C9—C10—N2—C12 | 172.2 (2) | C22—C18—C24—C23 | −71.1 (3) |
C9—C10—N2—C11 | −62.5 (3) | C17—C18—C24—C23 | 160.6 (3) |
O2—C16—N3—C14 | −175.0 (3) | C19—C18—C24—C23 | 31.7 (3) |
O1—C16—N3—C14 | 4.7 (3) | C20—C23—C24—C18 | 4.0 (3) |
C13—C14—N3—C16 | −134.0 (3) | C18—C17—S1—O3 | −74.7 (2) |
C15—C14—N3—C16 | −9.7 (3) | C18—C17—S1—O4 | 165.1 (2) |
O2—C16—O1—C15 | −177.1 (3) | C18—C17—S1—O5 | 45.2 (2) |
N3—C16—O1—C15 | 3.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.83 (3) | 2.26 (3) | 3.059 (4) | 161 (3) |
N2—H2N···O5 | 0.79 (3) | 2.03 (3) | 2.767 (3) | 154 (3) |
N3—H3N···O4 | 0.85 (3) | 2.01 (3) | 2.866 (3) | 174 (3) |
Symmetry code: (i) −x+1/2, −y+1, z−1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C16H22N3O2+·C2HO4− | C16H22N3O2+·C10H15O4S− |
Mr | 377.39 | 519.65 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 294 | 294 |
a, b, c (Å) | 5.5944 (4), 17.9908 (14), 18.3844 (15) | 9.5992 (15), 16.361 (3), 16.927 (2) |
α, β, γ (°) | 90, 92.220 (1), 90 | 90, 90, 90 |
V (Å3) | 1849.0 (2) | 2658.4 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.17 |
Crystal size (mm) | 0.19 × 0.17 × 0.09 | 0.17 × 0.12 × 0.09 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21294, 8509, 7991 | 31108, 6314, 5280 |
Rint | 0.018 | 0.048 |
(sin θ/λ)max (Å−1) | 0.660 | 0.660 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.099, 1.04 | 0.062, 0.132, 1.10 |
No. of reflections | 8509 | 6314 |
No. of parameters | 523 | 341 |
No. of restraints | 1 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.20 | 0.32, −0.16 |
Absolute structure | Flack & Bernardinelli (2000), with 4320 Friedel pairs | Flack & Bernardinelli (2000), with 2812 Friedel pairs |
Absolute structure parameter | −0.4 (6) | 0.00 (9) |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3A | 0.94 (3) | 2.12 (3) | 2.972 (2) | 150 (2) |
N1—H1A···O1A | 0.94 (3) | 2.32 (3) | 3.048 (2) | 133 (2) |
N2—H2···O1Bi | 0.92 (2) | 1.92 (2) | 2.754 (2) | 150 (2) |
N2—H2···O4Bi | 0.92 (2) | 2.25 (2) | 2.936 (2) | 131 (2) |
N3—H3···O2' | 0.84 (2) | 2.14 (2) | 2.954 (2) | 163 (2) |
N1'—H1'A···O2B | 0.83 (2) | 2.24 (2) | 3.010 (2) | 155 (2) |
N1'—H1'A···O3B | 0.83 (2) | 2.43 (2) | 3.065 (2) | 135 (2) |
N2'—H2'···O2Aii | 0.86 (2) | 2.00 (2) | 2.775 (2) | 151 (2) |
N2'—H2'···O4Aii | 0.86 (2) | 2.317 (19) | 2.962 (2) | 132 (2) |
N3'—H3'···O2 | 0.83 (2) | 2.19 (2) | 2.963 (2) | 154 (2) |
O4A—H4A···O1Aiii | 1.00 (3) | 1.49 (3) | 2.495 (1) | 174 (2) |
O4B—H4B···O2Biv | 0.87 (3) | 1.63 (3) | 2.503 (1) | 172 (3) |
Symmetry codes: (i) −x−1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+2; (iii) x+1, y, z; (iv) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.83 (3) | 2.26 (3) | 3.059 (4) | 161 (3) |
N2—H2N···O5 | 0.79 (3) | 2.03 (3) | 2.767 (3) | 154 (3) |
N3—H3N···O4 | 0.85 (3) | 2.01 (3) | 2.866 (3) | 174 (3) |
Symmetry code: (i) −x+1/2, −y+1, z−1/2. |
Parameter | (I), molecule A | (I), molecule B | (II) | 1 | 2 | 3a | 4 | 5 | 6a |
Shape | Step-like | Step-like | Cup | Cup | L-shaped | L-shaped | L-shaped | L-shaped | L-shaped |
Oxazolidinone ring | Envelope | Twisted | Twisted | Twisted | Twisted | Planar | Planar | Planar | Planar |
Ethylamide chainb | ac, ap, ap | ac, ap, ap | ac, ap, sc | ac, sc, ap | sp, ap, ap | sp, ap, ap | sp, ap, ap | sp, ap, ap | sp, ap, ap |
τ1 | 55.86 (10) | 53.16 (9) | 43.38 (15) | 77.18 (16) | 44.9 (3) | 49.98 (15) | 49.21 (11) | 48.78 (12) | 57.5 (2) |
τ2 | 68.25 (9) | 84.86 (9) | 69.78 (14) | 69.89 (12) | 48.8 (2) | 64.59 (13) | 64.29 (9) | 60.83 (12) | 59.59 (14) |
τ3 | 79.18 (12) | 74.20 (11) | 68.04 (18) | 68.88 (18) | 68.1 (3) | 65.55 (19) | 63.55 (13) | 63.46 (16) | 57.3 (3) |
τ4 | 1.883 (2) | 1.7205 (12) | 1.424 (2) | 2.430 (2) | 0.111 (4) | 1.074 (2) | 0.1590 (15) | 0.2081 (17) | 0.579 (3) |
d1 | 6.02 | 5.71 | 5.63 | 5.54 | 6.34 | 4.05 | 6.44 | 6.44 | 6.46 |
d2 | 4.04 | 4.23 | 4.05 | 3.90 | 3.99 | 6.47 | 4.05 | 4.04 | 4.02 |
d3 | 8.11 | 7.57 | 5.12 | 7.57 | 8.15 | 8.77 | 8.66 | 8.61 | 8.62 |
Notes: (I) and (II) = present structures; 1 = zolmitriptan base; 2 = zolmitriptan chloroform solvate; 3 = zolmitriptan phenol solvate; 4 = zolmitriptan benzene solvate; 5 = zolmitriptan pyridine solvate; 6 = zolmitriptan propiophenone solvate; τ1 = dihedral angle between the planes of the ethylamine group and the indole ring; τ2 = dihedral angle between the planes of the oxazolidinone and indole rings; τ3 = dihedral angle between the planes of the ethylamine group and the oxazolidinone ring; τ4 = distance from atom N2 to the plane of the indole ring; d1 = distance from atom N2 to the centroid of the C3–C8 ring; d2 = distance from atom N3 to the centroid of the C3–C8 ring; d3 = N2···N3 distance. (a) Only one zolmitriptan molecule has been taken for comparison. (b) Calculated from three torsion angles, viz.. C1—C2—C9—C10, C2—C9—C10—N2 and C9—C10—N2—C11. |
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