Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019083/bt2337sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019083/bt2337IIIsup2.hkl |
CCDC reference: 647614
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.012 Å
- R factor = 0.067
- wR factor = 0.186
- Data-to-parameter ratio = 9.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 4.02 Ratio PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.54 Ratio PLAT340_ALERT_3_B Low Bond Precision on C-C bonds (x 1000) Ang ... 12 PLAT360_ALERT_2_B Short C(sp3)-C(sp3) Bond C8A - C9A ... 1.32 Ang.
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.88 Ratio PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.85 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.59 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.45 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C8D - C9D .. 5.51 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7A PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8A PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7D PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C8D PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C8D - C9D ... 1.42 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C6C - C7C ... 1.55 Ang. PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 28
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.51 From the CIF: _reflns_number_total 6753 Count of symmetry unique reflns 6763 Completeness (_total/calc) 99.85% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT792_ALERT_1_G Check the Absolute Configuration of C5A = ... R PLAT792_ALERT_1_G Check the Absolute Configuration of C5B = ... S PLAT792_ALERT_1_G Check the Absolute Configuration of C5C = ... S PLAT792_ALERT_1_G Check the Absolute Configuration of C5D = ... R
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 13 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 12 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The present structure can be compared with 6 compounds incorporating the 1-carbonyl-5-phenylpyrazoline substructure as retrieved from the Cambridge Structural Database (Allen, 2002). In all seven structures the carbonyl function is, due to its conjugation with the neighbouring N atom, coplanar with the mean plane of the pyrazoline ring. By contrast, the conformation on the bond linking the phenyl and pyrazoline rings varies within two limiting cases: (1) the conformation in which the plane of the phenyl ring bisects the heterocycle (the N2=C3 double bond) as observed for the title derivative and (2) the conformation where the phenyl plane eclipses the N1—C5 bond as reported for 1-acetyl-5-(2-methoxyphenyl)-3-(2-methoxystyryl)-2-pyrazoline (Krishnakumar et al., 2004).
For related literature, see: Allen et al. (1987); Burke-Laing & Laing (1976); Kalinowski et al. (1984); Lambert et al. (1998); Shmueli et al. (1973); Světlík et al. (2005).
The title compound was prepared by refluxing pyrazoline (I) (352 mg, 2 mmol) in diethyl oxalate (15 ml) for 2.5 h. After evaporation of the solvent, the resultant oil was dissolved in ether and left to crystallize to give colourless crystals (46% yield; m.p. 415–417 K). IR (KBr): 3165 (OH), 1746 (ester CO), 1641 (amide CO), 1600 (C=C/C=N) cm-1. 1H NMR (CDCl3): δ 1.39 (3H, t, ester Me), 2.07 (3H, s, Me), 2.78 (1H, dd, J = 3.3 and 18.6 Hz, H of CH2), 3.39 (1H, dd, J = 11.1 and 18.6 Hz, H of CH2), 4.42 (2H, q, ester CH2), 5.76 (1H, dd, J = 3.3 and 11.1 Hz, CH), 6.50 (1H, t, Har), 6.77 (1H, t, Har), 6.91 (2H, m, Har), 8.00 (1H, brs, OH). 13C NMR (CDCl3): δ 14.0 (ester Me), 16.0 (Me), 45.2 (CH2), 54.2 (CH), 62.4 (ester CH2), 116.9 (CH-3'), 120.2 (CH-5'), 124.6 (CH-6'), 125.0 (C-1'), 129.3 (CH-4'), 153.9 (C-2'), 159.2 (C=N), 161.6 and 162.2 (C=O ester/amide).
H atoms were visible in difference maps and were subsequently treated as riding atoms with distances C—H = 0.93 (Carom), 0.98 (Ctertiary), 0.97 (CH2), 0.96 (CH3) and 0.82 Å (OH); Uiso of the H atoms were set to 1.2 (1.5 for the methyl H atoms) times Ueq of the parent atom. Reflection 002, affected by secondary extinction, was deleted and the Friedel pairs merged before the least-squares refinement.
As a continuation of our project aimed at developing new therapeutic agents, we attempted to prepare, by the reaction of 4,5-dihydro-3-methyl-5-(2-hydroxyphenyl)-1H-pyrazole (I) (Světlík et al., 2005) with diethyl oxalate, the tricyclic compound (II) possessing 1,4-oxazepine core. However, 1H and 13C NMR spectra were consistent with the structure (III) or (IV), but it was difficult to distinguish between these two alternatives from the NMR spectral data (Kalinowski et al., 1984); on the other hand, the IR spectrum matches better the structure (III) (Lambert et al., 1998). To confirm our presumption and to establish conformational features of the molecule, an X-ray analysis of the reaction product was undertaken.
The structure determination has shown that the four independent molecules (denoted as A - D) are, except for the terminal ethyl groups, identical to within 5/s as far as bond distances and angles are concerned. Thus, only one molecule (A) is shown in Fig. 2. As can be seen, the compound has the structure (III).
The sp2-hybridized N1 atom is involved in conjugation with the adjacent carbonyl function, as found for amides (Allen et al., 1987), rather than the pyrazoline double bond (Burke-Laing & Laing, 1976). In all four molecules the C6—C7 bond lengths are close to the value of 1.487 (5) Å reported for a Csp2—Csp2 single bond (Shmueli et al., 1973). Other bond distances are close to those generally expected.
As mentioned above, the conformational properties of the molecule is of prime interest here. The conformation of the hydroxyphenylpyrazoline portion in all independent molecules is the same: the pyrazoline ring is approximately planar with slight but significant distortion towards the C5-envelope; the phenyl ring occupies the pseudoaxial position and bisects the heterocycle. However, relative configuration on C5 in molecules B and C is opposite relative to molecules A and D. Another source of asymmetry is imposed by the approximatelly perpendicular orientation of the ethyl ester group relative to the mean plane of the carbonylpyrazoline moiety. As shown by the torsion angle N1—C6—C7—O2, both 'enantiomeric' values (ca ±90°) are equally populated. The third difference among the independent molecules concerns the rotation around the O3—C8 bond.
The crystal packing is dominated by hydrogen bonding. As shown in Table 1, the hydroxy group of all independent molecules is involved in an H-bond interaction with the carbonyl atom adjacent to the heterocycle of a neighbouring molecule.
The present structure can be compared with 6 compounds incorporating the 1-carbonyl-5-phenylpyrazoline substructure as retrieved from the Cambridge Structural Database (Allen, 2002). In all seven structures the carbonyl function is, due to its conjugation with the neighbouring N atom, coplanar with the mean plane of the pyrazoline ring. By contrast, the conformation on the bond linking the phenyl and pyrazoline rings varies within two limiting cases: (1) the conformation in which the plane of the phenyl ring bisects the heterocycle (the N2=C3 double bond) as observed for the title derivative and (2) the conformation where the phenyl plane eclipses the N1—C5 bond as reported for 1-acetyl-5-(2-methoxyphenyl)-3-(2-methoxystyryl)-2-pyrazoline (Krishnakumar et al., 2004).
For related literature, see: Allen et al. (1987); Burke-Laing & Laing (1976); Kalinowski et al. (1984); Lambert et al. (1998); Shmueli et al. (1973); Světlík et al. (2005).
Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C14H16N2O4 | F(000) = 2336 |
Mr = 276.29 | Dx = 1.249 Mg m−3 |
Monoclinic, Cc | Melting point: 416 K |
Hall symbol: C -2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 17.133 (3) Å | Cell parameters from 20 reflections |
b = 17.062 (3) Å | θ = 7–18° |
c = 20.130 (4) Å | µ = 0.09 mm−1 |
β = 93.02 (4)° | T = 296 K |
V = 5876.3 (19) Å3 | Prism, colourless |
Z = 16 | 0.30 × 0.20 × 0.15 mm |
Siemens P4 diffractometer | Rint = 0.027 |
Radiation source: fine-focus sealed tube | θmax = 27.5°, θmin = 1.7° |
Graphite monochromator | h = 0→22 |
ω/2θ scans | k = −1→22 |
7430 measured reflections | l = −26→26 |
6753 independent reflections | 3 standard reflections every 97 reflections |
3465 reflections with I > 2σ(I) | 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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0683P)2 + 4.0502P] where P = (Fo2 + 2Fc2)/3 |
6753 reflections | (Δ/σ)max = 0.002 |
733 parameters | Δρmax = 0.19 e Å−3 |
2 restraints | Δρmin = −0.24 e Å−3 |
C14H16N2O4 | V = 5876.3 (19) Å3 |
Mr = 276.29 | Z = 16 |
Monoclinic, Cc | Mo Kα radiation |
a = 17.133 (3) Å | µ = 0.09 mm−1 |
b = 17.062 (3) Å | T = 296 K |
c = 20.130 (4) Å | 0.30 × 0.20 × 0.15 mm |
β = 93.02 (4)° |
Siemens P4 diffractometer | Rint = 0.027 |
7430 measured reflections | 3 standard reflections every 97 reflections |
6753 independent reflections | intensity decay: none |
3465 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.067 | 2 restraints |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.19 e Å−3 |
6753 reflections | Δρmin = −0.24 e Å−3 |
733 parameters |
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 | ||
N1A | 0.6208 (3) | 0.5326 (3) | 0.3151 (2) | 0.0548 (13) | |
N2A | 0.6596 (3) | 0.5108 (3) | 0.2578 (3) | 0.0632 (14) | |
C3A | 0.7331 (4) | 0.5083 (4) | 0.2753 (4) | 0.0702 (19) | |
C4A | 0.7541 (4) | 0.5291 (5) | 0.3457 (4) | 0.075 (2) | |
H4A1 | 0.7861 | 0.5760 | 0.3485 | 0.090* | |
H4A2 | 0.7819 | 0.4866 | 0.3685 | 0.090* | |
C5A | 0.6731 (4) | 0.5435 (4) | 0.3758 (3) | 0.0601 (16) | |
H5A | 0.6699 | 0.5977 | 0.3913 | 0.072* | |
C6A | 0.5445 (4) | 0.5430 (4) | 0.3117 (4) | 0.0636 (17) | |
O1A | 0.5076 (3) | 0.5656 (3) | 0.3592 (2) | 0.0799 (14) | |
C7A | 0.5008 (4) | 0.5283 (5) | 0.2465 (4) | 0.073 (2) | |
O2A | 0.4738 (5) | 0.4655 (4) | 0.2317 (3) | 0.129 (3) | |
O3A | 0.4921 (4) | 0.5881 (4) | 0.2090 (3) | 0.114 (2) | |
C8A | 0.4415 (8) | 0.5814 (8) | 0.1472 (5) | 0.147 (5) | |
H8A1 | 0.4705 | 0.5984 | 0.1097 | 0.177* | |
H8A2 | 0.4271 | 0.5269 | 0.1401 | 0.177* | |
C9A | 0.3776 (7) | 0.6240 (12) | 0.1503 (7) | 0.218 (9) | |
H9A1 | 0.3569 | 0.6182 | 0.1933 | 0.327* | |
H9A2 | 0.3396 | 0.6067 | 0.1167 | 0.327* | |
H9A3 | 0.3900 | 0.6781 | 0.1429 | 0.327* | |
C10A | 0.7932 (5) | 0.4856 (6) | 0.2279 (5) | 0.101 (3) | |
H10A | 0.7690 | 0.4811 | 0.1839 | 0.152* | |
H10B | 0.8158 | 0.4361 | 0.2410 | 0.152* | |
H10C | 0.8333 | 0.5248 | 0.2281 | 0.152* | |
C11A | 0.6556 (3) | 0.4882 (4) | 0.4315 (3) | 0.0557 (16) | |
C12A | 0.6539 (4) | 0.4063 (4) | 0.4235 (3) | 0.0540 (15) | |
C13A | 0.6403 (4) | 0.3569 (4) | 0.4755 (4) | 0.0688 (19) | |
H13A | 0.6405 | 0.3029 | 0.4690 | 0.083* | |
C14A | 0.6265 (4) | 0.3866 (5) | 0.5364 (4) | 0.081 (2) | |
H14A | 0.6162 | 0.3531 | 0.5714 | 0.098* | |
C15A | 0.6279 (4) | 0.4667 (6) | 0.5461 (4) | 0.082 (2) | |
H15A | 0.6195 | 0.4869 | 0.5881 | 0.099* | |
C16A | 0.6417 (4) | 0.5175 (4) | 0.4941 (4) | 0.0707 (19) | |
H16A | 0.6416 | 0.5713 | 0.5013 | 0.085* | |
O4A | 0.6686 (3) | 0.3799 (3) | 0.3611 (2) | 0.0742 (14) | |
H4A | 0.6640 | 0.3321 | 0.3598 | 0.111* | |
N1B | 0.0299 (3) | 0.2709 (3) | 0.3752 (2) | 0.0547 (13) | |
N2B | −0.0143 (3) | 0.2907 (3) | 0.4300 (3) | 0.0655 (14) | |
C3B | −0.0860 (4) | 0.2896 (5) | 0.4081 (4) | 0.0701 (19) | |
C4B | −0.0990 (4) | 0.2713 (5) | 0.3368 (4) | 0.075 (2) | |
H4B1 | −0.1266 | 0.3137 | 0.3137 | 0.090* | |
H4B2 | −0.1290 | 0.2235 | 0.3307 | 0.090* | |
C5B | −0.0172 (4) | 0.2614 (4) | 0.3116 (3) | 0.0588 (16) | |
H5B | −0.0110 | 0.2080 | 0.2947 | 0.071* | |
C6B | 0.1060 (4) | 0.2630 (4) | 0.3823 (3) | 0.0610 (17) | |
O1B | 0.1473 (3) | 0.2434 (3) | 0.3372 (2) | 0.0810 (15) | |
C7B | 0.1422 (4) | 0.2772 (5) | 0.4508 (4) | 0.072 (2) | |
O2B | 0.1578 (4) | 0.2268 (3) | 0.4906 (3) | 0.0984 (18) | |
O3B | 0.1592 (3) | 0.3520 (3) | 0.4600 (3) | 0.0934 (17) | |
C8B | 0.1969 (7) | 0.3777 (6) | 0.5239 (5) | 0.125 (4) | |
H8B1 | 0.2250 | 0.3345 | 0.5454 | 0.150* | |
H8B2 | 0.2335 | 0.4198 | 0.5167 | 0.150* | |
C9B | 0.1352 (10) | 0.4046 (7) | 0.5649 (6) | 0.170 (6) | |
H9B1 | 0.1158 | 0.4541 | 0.5485 | 0.255* | |
H9B2 | 0.1554 | 0.4105 | 0.6100 | 0.255* | |
H9B3 | 0.0934 | 0.3670 | 0.5633 | 0.255* | |
C10B | −0.1490 (5) | 0.3111 (6) | 0.4520 (4) | 0.100 (3) | |
H10D | −0.1267 | 0.3242 | 0.4953 | 0.150* | |
H10E | −0.1841 | 0.2676 | 0.4555 | 0.150* | |
H10F | −0.1771 | 0.3554 | 0.4337 | 0.150* | |
C11B | 0.0054 (4) | 0.3198 (4) | 0.2594 (3) | 0.0632 (17) | |
C12B | −0.0021 (4) | 0.4012 (4) | 0.2695 (4) | 0.0672 (19) | |
C13B | 0.0167 (5) | 0.4515 (5) | 0.2185 (4) | 0.081 (2) | |
H13B | 0.0122 | 0.5053 | 0.2242 | 0.097* | |
C14B | 0.0417 (5) | 0.4224 (6) | 0.1598 (4) | 0.093 (3) | |
H14B | 0.0537 | 0.4571 | 0.1262 | 0.112* | |
C15B | 0.0494 (5) | 0.3438 (7) | 0.1495 (4) | 0.097 (3) | |
H15B | 0.0661 | 0.3248 | 0.1093 | 0.116* | |
C16B | 0.0321 (4) | 0.2936 (5) | 0.1996 (4) | 0.076 (2) | |
H16B | 0.0385 | 0.2400 | 0.1933 | 0.091* | |
O4B | −0.0273 (3) | 0.4245 (3) | 0.3280 (3) | 0.0868 (16) | |
H4B | −0.0137 | 0.4700 | 0.3351 | 0.130* | |
N1C | 0.1945 (3) | 0.6096 (3) | 0.3077 (3) | 0.0547 (12) | |
N2C | 0.2132 (3) | 0.5688 (3) | 0.2509 (3) | 0.0612 (14) | |
C3C | 0.2186 (4) | 0.4959 (4) | 0.2688 (4) | 0.0672 (18) | |
C4C | 0.2005 (4) | 0.4792 (4) | 0.3373 (4) | 0.076 (2) | |
H4C1 | 0.2438 | 0.4524 | 0.3605 | 0.091* | |
H4C2 | 0.1542 | 0.4466 | 0.3386 | 0.091* | |
C5C | 0.1867 (4) | 0.5588 (4) | 0.3684 (3) | 0.0594 (16) | |
H5C | 0.1329 | 0.5616 | 0.3827 | 0.071* | |
C6C | 0.1797 (3) | 0.6850 (4) | 0.3058 (3) | 0.0599 (17) | |
O1C | 0.1572 (3) | 0.7236 (3) | 0.3536 (2) | 0.0717 (13) | |
C7C | 0.1940 (4) | 0.7306 (4) | 0.2412 (3) | 0.0616 (17) | |
O2C | 0.2570 (3) | 0.7490 (4) | 0.2253 (3) | 0.0956 (18) | |
O3C | 0.1275 (3) | 0.7527 (3) | 0.2119 (2) | 0.0760 (13) | |
C8C | 0.1321 (5) | 0.8098 (5) | 0.1566 (4) | 0.087 (2) | |
H8C1 | 0.1551 | 0.8585 | 0.1731 | 0.105* | |
H8C2 | 0.1647 | 0.7890 | 0.1228 | 0.105* | |
C9C | 0.0530 (5) | 0.8240 (6) | 0.1283 (5) | 0.109 (3) | |
H9C1 | 0.0365 | 0.7802 | 0.1011 | 0.164* | |
H9C2 | 0.0527 | 0.8706 | 0.1016 | 0.164* | |
H9C3 | 0.0180 | 0.8304 | 0.1636 | 0.164* | |
C10C | 0.2412 (6) | 0.4351 (6) | 0.2200 (5) | 0.114 (3) | |
H10G | 0.2381 | 0.4570 | 0.1760 | 0.171* | |
H10H | 0.2062 | 0.3913 | 0.2217 | 0.171* | |
H10I | 0.2936 | 0.4180 | 0.2309 | 0.171* | |
C11C | 0.2427 (4) | 0.5834 (4) | 0.4250 (3) | 0.0590 (16) | |
C12C | 0.3232 (4) | 0.5804 (4) | 0.4209 (3) | 0.0552 (15) | |
C13C | 0.3722 (4) | 0.5998 (4) | 0.4749 (4) | 0.074 (2) | |
H13C | 0.4261 | 0.5974 | 0.4715 | 0.089* | |
C14C | 0.3421 (5) | 0.6226 (5) | 0.5332 (4) | 0.089 (2) | |
H14C | 0.3757 | 0.6353 | 0.5694 | 0.107* | |
C15C | 0.2625 (5) | 0.6271 (5) | 0.5392 (3) | 0.085 (2) | |
H15C | 0.2420 | 0.6426 | 0.5790 | 0.102* | |
C16C | 0.2142 (4) | 0.6082 (5) | 0.4853 (4) | 0.074 (2) | |
H16C | 0.1605 | 0.6121 | 0.4889 | 0.088* | |
O4C | 0.3502 (2) | 0.5602 (3) | 0.3606 (2) | 0.0671 (12) | |
H4C | 0.3976 | 0.5668 | 0.3612 | 0.101* | |
N1D | 0.4548 (3) | 0.2007 (3) | 0.3763 (3) | 0.0614 (14) | |
N2D | 0.4413 (3) | 0.2486 (4) | 0.4311 (3) | 0.0675 (15) | |
C3D | 0.4410 (4) | 0.3186 (5) | 0.4079 (4) | 0.079 (2) | |
C4D | 0.4574 (4) | 0.3284 (4) | 0.3361 (4) | 0.080 (2) | |
H4D1 | 0.5064 | 0.3555 | 0.3309 | 0.096* | |
H4D2 | 0.4156 | 0.3567 | 0.3122 | 0.096* | |
C5D | 0.4616 (4) | 0.2432 (4) | 0.3125 (3) | 0.0632 (18) | |
H5D | 0.5138 | 0.2336 | 0.2964 | 0.076* | |
C6D | 0.4642 (4) | 0.1239 (4) | 0.3856 (4) | 0.0611 (17) | |
O1D | 0.4816 (3) | 0.0799 (3) | 0.3401 (3) | 0.0841 (15) | |
C7D | 0.4557 (4) | 0.0937 (4) | 0.4561 (4) | 0.0666 (18) | |
O2D | 0.5106 (3) | 0.0790 (4) | 0.4930 (3) | 0.1012 (19) | |
O3D | 0.3816 (3) | 0.0847 (4) | 0.4680 (3) | 0.0953 (18) | |
C8D | 0.3637 (6) | 0.0641 (7) | 0.5346 (5) | 0.115 (3) | |
H8D1 | 0.3203 | 0.0276 | 0.5338 | 0.138* | |
H8D2 | 0.4085 | 0.0393 | 0.5573 | 0.138* | |
C9D | 0.3438 (8) | 0.1338 (11) | 0.5686 (6) | 0.175 (7) | |
H9D1 | 0.3899 | 0.1650 | 0.5770 | 0.262* | |
H9D2 | 0.3218 | 0.1205 | 0.6100 | 0.262* | |
H9D3 | 0.3063 | 0.1631 | 0.5415 | 0.262* | |
C10D | 0.4278 (6) | 0.3889 (5) | 0.4516 (4) | 0.104 (3) | |
H10J | 0.3784 | 0.4124 | 0.4389 | 0.156* | |
H10K | 0.4688 | 0.4264 | 0.4465 | 0.156* | |
H10L | 0.4279 | 0.3725 | 0.4973 | 0.156* | |
C11D | 0.4019 (4) | 0.2188 (4) | 0.2593 (3) | 0.0635 (18) | |
C12D | 0.3230 (4) | 0.2271 (4) | 0.2667 (4) | 0.0708 (19) | |
C13D | 0.2697 (5) | 0.2077 (5) | 0.2147 (5) | 0.090 (2) | |
H13D | 0.2165 | 0.2153 | 0.2189 | 0.107* | |
C14D | 0.2965 (6) | 0.1771 (6) | 0.1570 (4) | 0.103 (3) | |
H14D | 0.2608 | 0.1641 | 0.1223 | 0.123* | |
C15D | 0.3757 (6) | 0.1653 (6) | 0.1492 (4) | 0.106 (3) | |
H15D | 0.3933 | 0.1438 | 0.1102 | 0.127* | |
C16D | 0.4278 (5) | 0.1863 (5) | 0.2012 (4) | 0.087 (2) | |
H16D | 0.4810 | 0.1786 | 0.1971 | 0.104* | |
O4D | 0.3009 (3) | 0.2567 (4) | 0.3255 (3) | 0.0879 (16) | |
H4D | 0.2556 | 0.2439 | 0.3312 | 0.132* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.055 (3) | 0.050 (3) | 0.059 (3) | 0.010 (2) | −0.003 (2) | 0.004 (2) |
N2A | 0.061 (3) | 0.051 (3) | 0.078 (4) | −0.005 (3) | 0.003 (3) | −0.004 (3) |
C3A | 0.064 (4) | 0.065 (5) | 0.082 (5) | 0.000 (4) | 0.004 (4) | 0.014 (4) |
C4A | 0.045 (4) | 0.083 (5) | 0.095 (6) | −0.016 (3) | −0.002 (3) | 0.011 (4) |
C5A | 0.059 (4) | 0.051 (4) | 0.069 (4) | 0.004 (3) | −0.009 (3) | −0.001 (3) |
C6A | 0.053 (4) | 0.069 (4) | 0.068 (5) | 0.011 (3) | −0.005 (3) | 0.007 (4) |
O1A | 0.050 (3) | 0.113 (4) | 0.076 (3) | 0.015 (3) | −0.004 (2) | −0.009 (3) |
C7A | 0.070 (5) | 0.064 (5) | 0.085 (5) | 0.008 (4) | −0.002 (4) | 0.012 (4) |
O2A | 0.163 (6) | 0.101 (5) | 0.119 (5) | −0.048 (4) | −0.047 (4) | 0.023 (4) |
O3A | 0.161 (6) | 0.088 (4) | 0.086 (4) | 0.008 (4) | −0.059 (4) | 0.004 (3) |
C8A | 0.181 (12) | 0.164 (11) | 0.088 (7) | 0.029 (9) | −0.069 (7) | 0.010 (7) |
C9A | 0.114 (9) | 0.38 (3) | 0.151 (11) | 0.120 (13) | −0.047 (8) | −0.041 (14) |
C10A | 0.072 (5) | 0.120 (7) | 0.113 (7) | 0.020 (5) | 0.028 (5) | 0.012 (6) |
C11A | 0.046 (3) | 0.062 (4) | 0.058 (4) | 0.015 (3) | −0.009 (3) | −0.006 (3) |
C12A | 0.054 (4) | 0.058 (4) | 0.049 (4) | 0.009 (3) | −0.002 (3) | −0.004 (3) |
C13A | 0.071 (5) | 0.058 (4) | 0.077 (5) | 0.014 (3) | 0.003 (4) | 0.010 (4) |
C14A | 0.070 (5) | 0.096 (7) | 0.078 (6) | 0.020 (4) | 0.006 (4) | 0.011 (5) |
C15A | 0.078 (5) | 0.115 (7) | 0.053 (4) | 0.020 (5) | 0.006 (4) | −0.010 (4) |
C16A | 0.070 (4) | 0.066 (4) | 0.075 (5) | 0.005 (3) | −0.007 (3) | −0.009 (4) |
O4A | 0.092 (4) | 0.063 (3) | 0.069 (3) | 0.011 (3) | 0.011 (3) | 0.005 (3) |
N1B | 0.049 (3) | 0.055 (3) | 0.059 (3) | 0.002 (2) | −0.009 (2) | 0.007 (2) |
N2B | 0.065 (4) | 0.072 (4) | 0.060 (3) | 0.008 (3) | 0.002 (3) | 0.006 (3) |
C3B | 0.049 (4) | 0.082 (5) | 0.080 (5) | 0.008 (3) | 0.009 (3) | 0.024 (4) |
C4B | 0.058 (4) | 0.086 (5) | 0.080 (5) | −0.015 (4) | −0.003 (4) | 0.013 (4) |
C5B | 0.062 (4) | 0.066 (4) | 0.046 (3) | −0.013 (3) | −0.018 (3) | −0.007 (3) |
C6B | 0.050 (4) | 0.077 (5) | 0.055 (4) | 0.001 (3) | −0.003 (3) | 0.004 (4) |
O1B | 0.062 (3) | 0.109 (4) | 0.072 (3) | 0.008 (3) | 0.004 (3) | −0.011 (3) |
C7B | 0.070 (5) | 0.074 (5) | 0.072 (5) | 0.010 (4) | −0.009 (4) | 0.006 (4) |
O2B | 0.114 (4) | 0.084 (4) | 0.093 (4) | 0.004 (3) | −0.033 (3) | 0.016 (3) |
O3B | 0.116 (4) | 0.067 (3) | 0.093 (4) | −0.015 (3) | −0.039 (3) | 0.003 (3) |
C8B | 0.174 (10) | 0.079 (6) | 0.114 (8) | −0.029 (6) | −0.070 (7) | −0.005 (6) |
C9B | 0.266 (18) | 0.110 (9) | 0.130 (10) | 0.045 (10) | −0.030 (11) | −0.031 (8) |
C10B | 0.084 (6) | 0.122 (8) | 0.097 (6) | 0.015 (5) | 0.024 (5) | 0.021 (5) |
C11B | 0.060 (4) | 0.072 (5) | 0.056 (4) | −0.011 (3) | −0.012 (3) | 0.001 (4) |
C12B | 0.063 (4) | 0.068 (5) | 0.069 (5) | −0.009 (4) | −0.015 (4) | 0.006 (4) |
C13B | 0.090 (6) | 0.077 (5) | 0.075 (5) | −0.011 (4) | −0.013 (4) | 0.014 (4) |
C14B | 0.098 (6) | 0.117 (8) | 0.064 (5) | −0.027 (5) | −0.004 (4) | 0.022 (5) |
C15B | 0.104 (6) | 0.127 (9) | 0.061 (5) | −0.023 (6) | 0.013 (4) | −0.006 (5) |
C16B | 0.090 (5) | 0.066 (5) | 0.071 (5) | −0.018 (4) | −0.010 (4) | −0.007 (4) |
O4B | 0.108 (4) | 0.074 (4) | 0.079 (4) | −0.004 (3) | 0.008 (3) | −0.008 (3) |
N1C | 0.050 (3) | 0.056 (3) | 0.058 (3) | −0.006 (2) | −0.001 (2) | 0.000 (3) |
N2C | 0.065 (3) | 0.059 (3) | 0.059 (3) | 0.008 (3) | −0.011 (3) | −0.007 (3) |
C3C | 0.059 (4) | 0.058 (4) | 0.083 (5) | 0.013 (3) | −0.011 (3) | −0.003 (4) |
C4C | 0.072 (4) | 0.069 (5) | 0.084 (5) | −0.022 (4) | −0.019 (4) | −0.006 (4) |
C5C | 0.059 (4) | 0.057 (4) | 0.062 (4) | −0.009 (3) | −0.005 (3) | 0.009 (3) |
C6C | 0.048 (3) | 0.071 (5) | 0.059 (4) | 0.014 (3) | −0.010 (3) | 0.000 (4) |
O1C | 0.086 (3) | 0.066 (3) | 0.063 (3) | 0.016 (3) | 0.004 (2) | −0.002 (3) |
C7C | 0.051 (4) | 0.066 (4) | 0.066 (4) | 0.010 (3) | −0.011 (3) | 0.003 (3) |
O2C | 0.056 (3) | 0.128 (5) | 0.102 (4) | −0.013 (3) | −0.008 (3) | 0.034 (4) |
O3C | 0.062 (3) | 0.085 (3) | 0.080 (3) | 0.004 (2) | 0.003 (2) | 0.031 (3) |
C8C | 0.101 (6) | 0.098 (6) | 0.062 (4) | −0.021 (5) | −0.003 (4) | 0.032 (4) |
C9C | 0.090 (6) | 0.113 (7) | 0.122 (7) | 0.019 (5) | −0.015 (5) | 0.056 (6) |
C10C | 0.120 (7) | 0.095 (7) | 0.122 (7) | 0.025 (6) | −0.033 (6) | −0.044 (6) |
C11C | 0.059 (4) | 0.054 (4) | 0.064 (4) | 0.006 (3) | 0.001 (3) | 0.007 (3) |
C12C | 0.057 (4) | 0.051 (4) | 0.057 (4) | 0.007 (3) | 0.002 (3) | 0.001 (3) |
C13C | 0.065 (4) | 0.066 (4) | 0.089 (6) | 0.007 (4) | −0.014 (4) | −0.004 (4) |
C14C | 0.095 (6) | 0.104 (6) | 0.066 (5) | 0.017 (5) | −0.019 (4) | −0.017 (5) |
C15C | 0.105 (6) | 0.108 (6) | 0.043 (4) | 0.025 (5) | 0.003 (4) | 0.002 (4) |
C16C | 0.072 (4) | 0.091 (5) | 0.059 (4) | 0.009 (4) | 0.016 (4) | 0.012 (4) |
O4C | 0.052 (2) | 0.077 (3) | 0.072 (3) | 0.007 (2) | −0.003 (2) | −0.007 (3) |
N1D | 0.061 (3) | 0.070 (4) | 0.053 (3) | 0.004 (3) | −0.001 (3) | 0.010 (3) |
N2D | 0.065 (3) | 0.080 (4) | 0.057 (3) | 0.004 (3) | −0.007 (3) | 0.001 (3) |
C3D | 0.073 (5) | 0.091 (6) | 0.073 (5) | 0.007 (4) | −0.020 (4) | 0.007 (5) |
C4D | 0.077 (5) | 0.058 (4) | 0.103 (6) | −0.020 (4) | −0.025 (4) | 0.006 (4) |
C5D | 0.047 (3) | 0.089 (5) | 0.053 (4) | −0.006 (3) | 0.001 (3) | 0.021 (4) |
C6D | 0.047 (3) | 0.065 (4) | 0.071 (5) | −0.010 (3) | −0.002 (3) | 0.017 (4) |
O1D | 0.103 (4) | 0.075 (4) | 0.074 (3) | 0.012 (3) | 0.007 (3) | −0.002 (3) |
C7D | 0.069 (5) | 0.065 (4) | 0.065 (4) | 0.003 (3) | −0.005 (4) | 0.011 (3) |
O2D | 0.074 (3) | 0.138 (5) | 0.089 (4) | 0.008 (3) | −0.023 (3) | 0.032 (4) |
O3D | 0.071 (3) | 0.139 (5) | 0.075 (3) | −0.024 (3) | −0.007 (3) | 0.035 (3) |
C8D | 0.100 (7) | 0.158 (10) | 0.089 (7) | −0.009 (7) | 0.016 (5) | 0.047 (7) |
C9D | 0.135 (10) | 0.29 (2) | 0.100 (9) | 0.023 (12) | 0.034 (7) | 0.054 (11) |
C10D | 0.121 (7) | 0.085 (6) | 0.105 (7) | 0.024 (5) | −0.023 (5) | −0.032 (5) |
C11D | 0.051 (4) | 0.079 (5) | 0.060 (4) | −0.015 (3) | −0.004 (3) | 0.025 (4) |
C12D | 0.064 (5) | 0.076 (5) | 0.071 (5) | 0.003 (4) | −0.013 (4) | 0.012 (4) |
C13D | 0.075 (5) | 0.096 (6) | 0.094 (6) | −0.006 (4) | −0.023 (5) | 0.005 (5) |
C14D | 0.114 (8) | 0.124 (8) | 0.066 (6) | −0.018 (6) | −0.039 (5) | 0.007 (5) |
C15D | 0.108 (8) | 0.142 (9) | 0.066 (5) | −0.022 (6) | −0.009 (5) | 0.005 (5) |
C16D | 0.097 (6) | 0.096 (6) | 0.068 (5) | −0.014 (5) | 0.001 (4) | 0.013 (4) |
O4D | 0.053 (3) | 0.114 (5) | 0.095 (4) | 0.000 (3) | −0.003 (3) | −0.010 (3) |
N1A—C6A | 1.318 (8) | N1C—C6C | 1.311 (8) |
N1A—N2A | 1.413 (7) | N1C—N2C | 1.390 (7) |
N1A—C5A | 1.488 (8) | N1C—C5C | 1.510 (8) |
N2A—C3A | 1.290 (9) | N2C—C3C | 1.297 (8) |
C3A—C10A | 1.492 (11) | C3C—C4C | 1.456 (10) |
C3A—C4A | 1.487 (11) | C3C—C10C | 1.493 (11) |
C4A—C5A | 1.561 (9) | C4C—C5C | 1.520 (10) |
C4A—H4A1 | 0.9700 | C4C—H4C1 | 0.9700 |
C4A—H4A2 | 0.9700 | C4C—H4C2 | 0.9700 |
C5A—C11A | 1.507 (9) | C5C—C11C | 1.509 (9) |
C5A—H5A | 0.9800 | C5C—H5C | 0.9800 |
C6A—O1A | 1.236 (8) | C6C—O1C | 1.245 (8) |
C6A—C7A | 1.497 (10) | C6C—C7C | 1.546 (10) |
C7A—O2A | 1.198 (9) | C7C—O2C | 1.183 (8) |
C7A—O3A | 1.273 (9) | C7C—O3C | 1.311 (7) |
O3A—C8A | 1.482 (10) | O3C—C8C | 1.484 (8) |
C8A—C9A | 1.318 (15) | C8C—C9C | 1.462 (11) |
C8A—H8A1 | 0.9700 | C8C—H8C1 | 0.9700 |
C8A—H8A2 | 0.9700 | C8C—H8C2 | 0.9700 |
C9A—H9A1 | 0.9600 | C9C—H9C1 | 0.9600 |
C9A—H9A2 | 0.9600 | C9C—H9C2 | 0.9600 |
C9A—H9A3 | 0.9600 | C9C—H9C3 | 0.9600 |
C10A—H10A | 0.9600 | C10C—H10G | 0.9600 |
C10A—H10B | 0.9600 | C10C—H10H | 0.9600 |
C10A—H10C | 0.9600 | C10C—H10I | 0.9600 |
C11A—C16A | 1.389 (9) | C11C—C12C | 1.386 (8) |
C11A—C12A | 1.407 (9) | C11C—C16C | 1.398 (9) |
C12A—O4A | 1.370 (7) | C12C—O4C | 1.366 (7) |
C12A—C13A | 1.373 (9) | C12C—C13C | 1.378 (10) |
C13A—C14A | 1.359 (10) | C13C—C14C | 1.364 (11) |
C13A—H13A | 0.9300 | C13C—H13C | 0.9300 |
C14A—C15A | 1.382 (12) | C14C—C15C | 1.378 (12) |
C14A—H14A | 0.9300 | C14C—H14C | 0.9300 |
C15A—C16A | 1.389 (11) | C15C—C16C | 1.368 (10) |
C15A—H15A | 0.9300 | C15C—H15C | 0.9300 |
C16A—H16A | 0.9300 | C16C—H16C | 0.9300 |
O4A—H4A | 0.8200 | O4C—H4C | 0.8200 |
N1B—C6B | 1.312 (8) | N1D—C6D | 1.333 (9) |
N1B—N2B | 1.412 (7) | N1D—N2D | 1.401 (8) |
N1B—C5B | 1.486 (7) | N1D—C5D | 1.485 (8) |
N2B—C3B | 1.284 (8) | N2D—C3D | 1.283 (10) |
C3B—C4B | 1.473 (10) | C3D—C4D | 1.497 (11) |
C3B—C10B | 1.477 (10) | C3D—C10D | 1.511 (11) |
C4B—C5B | 1.526 (10) | C4D—C5D | 1.532 (10) |
C4B—H4B1 | 0.9700 | C4D—H4D1 | 0.9700 |
C4B—H4B2 | 0.9700 | C4D—H4D2 | 0.9700 |
C5B—C11B | 1.512 (9) | C5D—C11D | 1.500 (9) |
C5B—H5B | 0.9800 | C5D—H5D | 0.9800 |
C6B—O1B | 1.226 (7) | C6D—O1D | 1.233 (8) |
C6B—C7B | 1.502 (10) | C6D—C7D | 1.524 (10) |
C7B—O2B | 1.195 (8) | C7D—O2D | 1.194 (8) |
C7B—O3B | 1.320 (9) | C7D—O3D | 1.314 (8) |
O3B—C8B | 1.475 (10) | O3D—C8D | 1.435 (10) |
C8B—C9B | 1.449 (17) | C8D—C9D | 1.422 (17) |
C8B—H8B1 | 0.9700 | C8D—H8D1 | 0.9700 |
C8B—H8B2 | 0.9700 | C8D—H8D2 | 0.9700 |
C9B—H9B1 | 0.9600 | C9D—H9D1 | 0.9600 |
C9B—H9B2 | 0.9600 | C9D—H9D2 | 0.9600 |
C9B—H9B3 | 0.9600 | C9D—H9D3 | 0.9600 |
C10B—H10D | 0.9600 | C10D—H10J | 0.9600 |
C10B—H10E | 0.9600 | C10D—H10K | 0.9600 |
C10B—H10F | 0.9600 | C10D—H10L | 0.9600 |
C11B—C16B | 1.385 (10) | C11D—C12D | 1.374 (9) |
C11B—C12B | 1.410 (10) | C11D—C16D | 1.388 (10) |
C12B—O4B | 1.335 (9) | C12D—O4D | 1.358 (9) |
C12B—C13B | 1.389 (10) | C12D—C13D | 1.393 (10) |
C13B—C14B | 1.371 (12) | C13D—C14D | 1.374 (12) |
C13B—H13B | 0.9300 | C13D—H13D | 0.9300 |
C14B—C15B | 1.366 (13) | C14D—C15D | 1.388 (13) |
C14B—H14B | 0.9300 | C14D—H14D | 0.9300 |
C15B—C16B | 1.367 (11) | C15D—C16D | 1.387 (11) |
C15B—H15B | 0.9300 | C15D—H15D | 0.9300 |
C16B—H16B | 0.9300 | C16D—H16D | 0.9300 |
O4B—H4B | 0.8200 | O4D—H4D | 0.8200 |
C6A—N1A—N2A | 120.1 (5) | C6C—N1C—N2C | 121.3 (6) |
C6A—N1A—C5A | 125.4 (5) | C6C—N1C—C5C | 124.2 (6) |
N2A—N1A—C5A | 114.5 (5) | N2C—N1C—C5C | 114.4 (5) |
C3A—N2A—N1A | 106.2 (6) | C3C—N2C—N1C | 105.5 (6) |
N2A—C3A—C10A | 122.0 (8) | N2C—C3C—C4C | 115.8 (7) |
N2A—C3A—C4A | 115.9 (7) | N2C—C3C—C10C | 120.0 (8) |
C10A—C3A—C4A | 122.2 (7) | C4C—C3C—C10C | 124.2 (8) |
C3A—C4A—C5A | 103.4 (6) | C3C—C4C—C5C | 105.1 (6) |
C3A—C4A—H4A1 | 111.1 | C3C—C4C—H4C1 | 110.7 |
C5A—C4A—H4A1 | 111.1 | C5C—C4C—H4C1 | 110.7 |
C3A—C4A—H4A2 | 111.1 | C3C—C4C—H4C2 | 110.7 |
C5A—C4A—H4A2 | 111.1 | C5C—C4C—H4C2 | 110.7 |
H4A1—C4A—H4A2 | 109.0 | H4C1—C4C—H4C2 | 108.8 |
N1A—C5A—C11A | 113.4 (5) | N1C—C5C—C11C | 111.7 (5) |
N1A—C5A—C4A | 99.8 (5) | N1C—C5C—C4C | 99.0 (5) |
C11A—C5A—C4A | 114.0 (5) | C11C—C5C—C4C | 116.9 (5) |
N1A—C5A—H5A | 109.7 | N1C—C5C—H5C | 109.6 |
C11A—C5A—H5A | 109.7 | C11C—C5C—H5C | 109.6 |
C4A—C5A—H5A | 109.7 | C4C—C5C—H5C | 109.6 |
O1A—C6A—N1A | 123.2 (6) | O1C—C6C—N1C | 124.3 (6) |
O1A—C6A—C7A | 118.6 (6) | O1C—C6C—C7C | 116.9 (6) |
N1A—C6A—C7A | 118.2 (7) | N1C—C6C—C7C | 118.7 (6) |
O2A—C7A—O3A | 122.5 (8) | O2C—C7C—O3C | 125.8 (7) |
O2A—C7A—C6A | 122.5 (7) | O2C—C7C—C6C | 123.2 (6) |
O3A—C7A—C6A | 115.0 (7) | O3C—C7C—C6C | 110.6 (6) |
C7A—O3A—C8A | 118.7 (8) | C7C—O3C—C8C | 116.5 (5) |
C9A—C8A—O3A | 111.7 (11) | C9C—C8C—O3C | 108.4 (6) |
C9A—C8A—H8A1 | 109.3 | C9C—C8C—H8C1 | 110.0 |
O3A—C8A—H8A1 | 109.3 | O3C—C8C—H8C1 | 110.0 |
C9A—C8A—H8A2 | 109.3 | C9C—C8C—H8C2 | 110.0 |
O3A—C8A—H8A2 | 109.3 | O3C—C8C—H8C2 | 110.0 |
H8A1—C8A—H8A2 | 107.9 | H8C1—C8C—H8C2 | 108.4 |
C8A—C9A—H9A1 | 109.5 | C8C—C9C—H9C1 | 109.5 |
C8A—C9A—H9A2 | 109.5 | C8C—C9C—H9C2 | 109.5 |
H9A1—C9A—H9A2 | 109.5 | H9C1—C9C—H9C2 | 109.5 |
C8A—C9A—H9A3 | 109.5 | C8C—C9C—H9C3 | 109.5 |
H9A1—C9A—H9A3 | 109.5 | H9C1—C9C—H9C3 | 109.5 |
H9A2—C9A—H9A3 | 109.5 | H9C2—C9C—H9C3 | 109.5 |
C3A—C10A—H10A | 109.5 | C3C—C10C—H10G | 109.5 |
C3A—C10A—H10B | 109.5 | C3C—C10C—H10H | 109.5 |
H10A—C10A—H10B | 109.5 | H10G—C10C—H10H | 109.5 |
C3A—C10A—H10C | 109.5 | C3C—C10C—H10I | 109.5 |
H10A—C10A—H10C | 109.5 | H10G—C10C—H10I | 109.5 |
H10B—C10A—H10C | 109.5 | H10H—C10C—H10I | 109.5 |
C16A—C11A—C12A | 117.2 (6) | C12C—C11C—C16C | 117.1 (6) |
C16A—C11A—C5A | 120.0 (6) | C12C—C11C—C5C | 122.7 (6) |
C12A—C11A—C5A | 122.7 (6) | C16C—C11C—C5C | 120.1 (6) |
O4A—C12A—C13A | 122.9 (6) | O4C—C12C—C13C | 122.7 (6) |
O4A—C12A—C11A | 115.3 (6) | O4C—C12C—C11C | 116.5 (6) |
C13A—C12A—C11A | 121.8 (6) | C13C—C12C—C11C | 120.8 (6) |
C14A—C13A—C12A | 120.2 (7) | C14C—C13C—C12C | 120.3 (7) |
C14A—C13A—H13A | 119.9 | C14C—C13C—H13C | 119.9 |
C12A—C13A—H13A | 119.9 | C12C—C13C—H13C | 119.9 |
C13A—C14A—C15A | 119.6 (8) | C13C—C14C—C15C | 120.8 (7) |
C13A—C14A—H14A | 120.2 | C13C—C14C—H14C | 119.6 |
C15A—C14A—H14A | 120.2 | C15C—C14C—H14C | 119.6 |
C14A—C15A—C16A | 120.8 (7) | C16C—C15C—C14C | 118.5 (7) |
C14A—C15A—H15A | 119.6 | C16C—C15C—H15C | 120.7 |
C16A—C15A—H15A | 119.6 | C14C—C15C—H15C | 120.7 |
C11A—C16A—C15A | 120.3 (7) | C15C—C16C—C11C | 122.4 (7) |
C11A—C16A—H16A | 119.9 | C15C—C16C—H16C | 118.8 |
C15A—C16A—H16A | 119.9 | C11C—C16C—H16C | 118.8 |
C12A—O4A—H4A | 109.5 | C12C—O4C—H4C | 109.5 |
C6B—N1B—N2B | 120.7 (5) | C6D—N1D—N2D | 119.2 (6) |
C6B—N1B—C5B | 125.0 (6) | C6D—N1D—C5D | 125.8 (6) |
N2B—N1B—C5B | 114.3 (5) | N2D—N1D—C5D | 114.9 (6) |
C3B—N2B—N1B | 105.7 (5) | C3D—N2D—N1D | 104.7 (6) |
N2B—C3B—C4B | 115.5 (6) | N2D—C3D—C4D | 117.2 (7) |
N2B—C3B—C10B | 120.4 (7) | N2D—C3D—C10D | 121.7 (7) |
C4B—C3B—C10B | 123.9 (7) | C4D—C3D—C10D | 121.0 (8) |
C3B—C4B—C5B | 104.7 (6) | C3D—C4D—C5D | 102.0 (6) |
C3B—C4B—H4B1 | 110.8 | C3D—C4D—H4D1 | 111.4 |
C5B—C4B—H4B1 | 110.8 | C5D—C4D—H4D1 | 111.4 |
C3B—C4B—H4B2 | 110.8 | C3D—C4D—H4D2 | 111.4 |
C5B—C4B—H4B2 | 110.8 | C5D—C4D—H4D2 | 111.4 |
H4B1—C4B—H4B2 | 108.9 | H4D1—C4D—H4D2 | 109.2 |
N1B—C5B—C11B | 112.3 (5) | N1D—C5D—C11D | 113.6 (5) |
N1B—C5B—C4B | 99.6 (5) | N1D—C5D—C4D | 100.8 (6) |
C11B—C5B—C4B | 115.5 (6) | C11D—C5D—C4D | 116.2 (6) |
N1B—C5B—H5B | 109.7 | N1D—C5D—H5D | 108.6 |
C11B—C5B—H5B | 109.7 | C11D—C5D—H5D | 108.6 |
C4B—C5B—H5B | 109.7 | C4D—C5D—H5D | 108.6 |
O1B—C6B—N1B | 123.8 (6) | O1D—C6D—N1D | 121.9 (6) |
O1B—C6B—C7B | 119.8 (6) | O1D—C6D—C7D | 121.6 (7) |
N1B—C6B—C7B | 116.4 (6) | N1D—C6D—C7D | 116.5 (7) |
O2B—C7B—O3B | 124.2 (7) | O2D—C7D—O3D | 126.7 (7) |
O2B—C7B—C6B | 124.5 (8) | O2D—C7D—C6D | 122.7 (7) |
O3B—C7B—C6B | 111.2 (7) | O3D—C7D—C6D | 110.6 (6) |
C7B—O3B—C8B | 119.5 (6) | C7D—O3D—C8D | 117.2 (6) |
C9B—C8B—O3B | 107.0 (10) | C9D—C8D—O3D | 108.2 (9) |
C9B—C8B—H8B1 | 110.3 | C9D—C8D—H8D1 | 110.1 |
O3B—C8B—H8B1 | 110.3 | O3D—C8D—H8D1 | 110.1 |
C9B—C8B—H8B2 | 110.3 | C9D—C8D—H8D2 | 110.1 |
O3B—C8B—H8B2 | 110.3 | O3D—C8D—H8D2 | 110.1 |
H8B1—C8B—H8B2 | 108.6 | H8D1—C8D—H8D2 | 108.4 |
C8B—C9B—H9B1 | 109.5 | C8D—C9D—H9D1 | 109.5 |
C8B—C9B—H9B2 | 109.5 | C8D—C9D—H9D2 | 109.5 |
H9B1—C9B—H9B2 | 109.5 | H9D1—C9D—H9D2 | 109.5 |
C8B—C9B—H9B3 | 109.5 | C8D—C9D—H9D3 | 109.5 |
H9B1—C9B—H9B3 | 109.5 | H9D1—C9D—H9D3 | 109.5 |
H9B2—C9B—H9B3 | 109.5 | H9D2—C9D—H9D3 | 109.5 |
C3B—C10B—H10D | 109.5 | C3D—C10D—H10J | 109.5 |
C3B—C10B—H10E | 109.5 | C3D—C10D—H10K | 109.5 |
H10D—C10B—H10E | 109.5 | H10J—C10D—H10K | 109.5 |
C3B—C10B—H10F | 109.5 | C3D—C10D—H10L | 109.5 |
H10D—C10B—H10F | 109.5 | H10J—C10D—H10L | 109.5 |
H10E—C10B—H10F | 109.5 | H10K—C10D—H10L | 109.5 |
C16B—C11B—C12B | 118.7 (7) | C12D—C11D—C16D | 119.5 (7) |
C16B—C11B—C5B | 119.9 (7) | C12D—C11D—C5D | 122.2 (7) |
C12B—C11B—C5B | 121.4 (6) | C16D—C11D—C5D | 118.4 (6) |
O4B—C12B—C13B | 124.5 (7) | O4D—C12D—C11D | 116.9 (6) |
O4B—C12B—C11B | 117.2 (7) | O4D—C12D—C13D | 122.8 (7) |
C13B—C12B—C11B | 118.4 (8) | C11D—C12D—C13D | 120.2 (8) |
C14B—C13B—C12B | 120.6 (8) | C14D—C13D—C12D | 119.5 (8) |
C14B—C13B—H13B | 119.7 | C14D—C13D—H13D | 120.3 |
C12B—C13B—H13B | 119.7 | C12D—C13D—H13D | 120.3 |
C15B—C14B—C13B | 121.6 (8) | C13D—C14D—C15D | 121.5 (8) |
C15B—C14B—H14B | 119.2 | C13D—C14D—H14D | 119.3 |
C13B—C14B—H14B | 119.2 | C15D—C14D—H14D | 119.3 |
C14B—C15B—C16B | 118.5 (8) | C16D—C15D—C14D | 118.1 (9) |
C14B—C15B—H15B | 120.8 | C16D—C15D—H15D | 121.0 |
C16B—C15B—H15B | 120.8 | C14D—C15D—H15D | 121.0 |
C15B—C16B—C11B | 122.2 (8) | C11D—C16D—C15D | 121.2 (9) |
C15B—C16B—H16B | 118.9 | C11D—C16D—H16D | 119.4 |
C11B—C16B—H16B | 118.9 | C15D—C16D—H16D | 119.4 |
C12B—O4B—H4B | 109.5 | C12D—O4D—H4D | 109.5 |
C6A—N1A—N2A—C3A | 177.3 (6) | C6C—N1C—N2C—C3C | −175.5 (6) |
C5A—N1A—N2A—C3A | −1.5 (7) | C5C—N1C—N2C—C3C | −0.3 (7) |
N1A—N2A—C3A—C10A | 178.8 (6) | N1C—N2C—C3C—C4C | 3.1 (7) |
N1A—N2A—C3A—C4A | −1.0 (8) | N1C—N2C—C3C—C10C | −177.8 (6) |
N2A—C3A—C4A—C5A | 2.9 (8) | N2C—C3C—C4C—C5C | −4.7 (8) |
C10A—C3A—C4A—C5A | −176.9 (7) | C10C—C3C—C4C—C5C | 176.2 (7) |
C6A—N1A—C5A—C11A | 62.7 (8) | C6C—N1C—C5C—C11C | −63.4 (8) |
N2A—N1A—C5A—C11A | −118.6 (6) | N2C—N1C—C5C—C11C | 121.5 (6) |
C6A—N1A—C5A—C4A | −175.7 (6) | C6C—N1C—C5C—C4C | 172.8 (6) |
N2A—N1A—C5A—C4A | 3.1 (7) | N2C—N1C—C5C—C4C | −2.3 (6) |
C3A—C4A—C5A—N1A | −3.2 (7) | C3C—C4C—C5C—N1C | 3.7 (6) |
C3A—C4A—C5A—C11A | 118.0 (6) | C3C—C4C—C5C—C11C | −116.3 (6) |
N2A—N1A—C6A—O1A | −176.6 (6) | N2C—N1C—C6C—O1C | 174.5 (6) |
C5A—N1A—C6A—O1A | 2.1 (11) | C5C—N1C—C6C—O1C | −0.3 (10) |
N2A—N1A—C6A—C7A | 2.1 (9) | N2C—N1C—C6C—C7C | −8.1 (8) |
C5A—N1A—C6A—C7A | −179.1 (6) | C5C—N1C—C6C—C7C | 177.1 (5) |
O1A—C6A—C7A—O2A | −90.6 (11) | O1C—C6C—C7C—O2C | 101.3 (8) |
N1A—C6A—C7A—O2A | 90.6 (10) | N1C—C6C—C7C—O2C | −76.3 (9) |
O1A—C6A—C7A—O3A | 87.0 (9) | O1C—C6C—C7C—O3C | −71.8 (8) |
N1A—C6A—C7A—O3A | −91.7 (9) | N1C—C6C—C7C—O3C | 110.6 (6) |
O2A—C7A—O3A—C8A | 4.9 (14) | O2C—C7C—O3C—C8C | −4.1 (11) |
C6A—C7A—O3A—C8A | −172.7 (9) | C6C—C7C—O3C—C8C | 168.7 (6) |
C7A—O3A—C8A—C9A | 112.3 (15) | C7C—O3C—C8C—C9C | 177.1 (7) |
N1A—C5A—C11A—C16A | −126.0 (6) | N1C—C5C—C11C—C12C | −62.8 (8) |
C4A—C5A—C11A—C16A | 120.7 (7) | C4C—C5C—C11C—C12C | 50.3 (8) |
N1A—C5A—C11A—C12A | 55.3 (8) | N1C—C5C—C11C—C16C | 119.3 (7) |
C4A—C5A—C11A—C12A | −58.0 (8) | C4C—C5C—C11C—C16C | −127.7 (7) |
C16A—C11A—C12A—O4A | −179.4 (6) | C16C—C11C—C12C—O4C | −176.5 (6) |
C5A—C11A—C12A—O4A | −0.7 (8) | C5C—C11C—C12C—O4C | 5.5 (9) |
C16A—C11A—C12A—C13A | −0.9 (9) | C16C—C11C—C12C—C13C | 1.2 (9) |
C5A—C11A—C12A—C13A | 177.8 (6) | C5C—C11C—C12C—C13C | −176.8 (6) |
O4A—C12A—C13A—C14A | 179.6 (6) | O4C—C12C—C13C—C14C | 177.3 (7) |
C11A—C12A—C13A—C14A | 1.1 (10) | C11C—C12C—C13C—C14C | −0.2 (11) |
C12A—C13A—C14A—C15A | −1.3 (11) | C12C—C13C—C14C—C15C | −0.4 (13) |
C13A—C14A—C15A—C16A | 1.3 (11) | C13C—C14C—C15C—C16C | 0.0 (13) |
C12A—C11A—C16A—C15A | 0.8 (9) | C14C—C15C—C16C—C11C | 1.1 (13) |
C5A—C11A—C16A—C15A | −177.9 (6) | C12C—C11C—C16C—C15C | −1.7 (11) |
C14A—C15A—C16A—C11A | −1.1 (11) | C5C—C11C—C16C—C15C | 176.4 (7) |
C6B—N1B—N2B—C3B | −176.4 (6) | C6D—N1D—N2D—C3D | 174.9 (6) |
C5B—N1B—N2B—C3B | 4.2 (7) | C5D—N1D—N2D—C3D | −1.7 (7) |
N1B—N2B—C3B—C4B | −1.5 (8) | N1D—N2D—C3D—C4D | −2.5 (8) |
N1B—N2B—C3B—C10B | −177.4 (7) | N1D—N2D—C3D—C10D | 179.7 (6) |
N2B—C3B—C4B—C5B | −1.5 (9) | N2D—C3D—C4D—C5D | 5.4 (8) |
C10B—C3B—C4B—C5B | 174.2 (7) | C10D—C3D—C4D—C5D | −176.9 (7) |
C6B—N1B—C5B—C11B | −61.4 (8) | C6D—N1D—C5D—C11D | 63.3 (8) |
N2B—N1B—C5B—C11B | 118.0 (6) | N2D—N1D—C5D—C11D | −120.3 (6) |
C6B—N1B—C5B—C4B | 175.8 (6) | C6D—N1D—C5D—C4D | −171.6 (6) |
N2B—N1B—C5B—C4B | −4.8 (7) | N2D—N1D—C5D—C4D | 4.7 (6) |
C3B—C4B—C5B—N1B | 3.5 (7) | C3D—C4D—C5D—N1D | −5.3 (6) |
C3B—C4B—C5B—C11B | −117.0 (6) | C3D—C4D—C5D—C11D | 117.9 (6) |
N2B—N1B—C6B—O1B | 177.5 (6) | N2D—N1D—C6D—O1D | −174.9 (6) |
C5B—N1B—C6B—O1B | −3.2 (10) | C5D—N1D—C6D—O1D | 1.4 (10) |
N2B—N1B—C6B—C7B | −0.9 (9) | N2D—N1D—C6D—C7D | 2.7 (8) |
C5B—N1B—C6B—C7B | 178.5 (6) | C5D—N1D—C6D—C7D | 179.0 (5) |
O1B—C6B—C7B—O2B | −82.0 (10) | O1D—C6D—C7D—O2D | 77.0 (10) |
N1B—C6B—C7B—O2B | 96.4 (9) | N1D—C6D—C7D—O2D | −100.6 (8) |
O1B—C6B—C7B—O3B | 94.0 (8) | O1D—C6D—C7D—O3D | −101.2 (8) |
N1B—C6B—C7B—O3B | −87.6 (8) | N1D—C6D—C7D—O3D | 81.2 (8) |
O2B—C7B—O3B—C8B | −2.7 (13) | O2D—C7D—O3D—C8D | 8.0 (13) |
C6B—C7B—O3B—C8B | −178.7 (8) | C6D—C7D—O3D—C8D | −173.9 (8) |
C7B—O3B—C8B—C9B | −95.6 (10) | C7D—O3D—C8D—C9D | 97.2 (11) |
N1B—C5B—C11B—C16B | 120.4 (7) | N1D—C5D—C11D—C12D | 60.7 (9) |
C4B—C5B—C11B—C16B | −126.3 (7) | C4D—C5D—C11D—C12D | −55.6 (9) |
N1B—C5B—C11B—C12B | −61.2 (8) | N1D—C5D—C11D—C16D | −118.7 (7) |
C4B—C5B—C11B—C12B | 52.1 (8) | C4D—C5D—C11D—C16D | 125.0 (8) |
C16B—C11B—C12B—O4B | −179.3 (6) | C16D—C11D—C12D—O4D | 177.8 (7) |
C5B—C11B—C12B—O4B | 2.3 (9) | C5D—C11D—C12D—O4D | −1.6 (10) |
C16B—C11B—C12B—C13B | 0.9 (10) | C16D—C11D—C12D—C13D | −4.1 (11) |
C5B—C11B—C12B—C13B | −177.4 (6) | C5D—C11D—C12D—C13D | 176.5 (7) |
O4B—C12B—C13B—C14B | −179.6 (7) | O4D—C12D—C13D—C14D | −179.2 (8) |
C11B—C12B—C13B—C14B | 0.1 (11) | C11D—C12D—C13D—C14D | 2.7 (12) |
C12B—C13B—C14B—C15B | −0.3 (13) | C12D—C13D—C14D—C15D | −0.2 (14) |
C13B—C14B—C15B—C16B | −0.5 (14) | C13D—C14D—C15D—C16D | −1.0 (15) |
C14B—C15B—C16B—C11B | 1.6 (13) | C12D—C11D—C16D—C15D | 3.0 (12) |
C12B—C11B—C16B—C15B | −1.8 (11) | C5D—C11D—C16D—C15D | −177.6 (8) |
C5B—C11B—C16B—C15B | 176.6 (7) | C14D—C15D—C16D—C11D | −0.4 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4A—H4A···O1Ci | 0.82 | 1.86 | 2.678 (7) | 177 |
O4B—H4B···O1Dii | 0.82 | 1.88 | 2.665 (7) | 160 |
O4C—H4C···O1A | 0.82 | 1.89 | 2.700 (6) | 171 |
O4D—H4D···O1B | 0.82 | 1.87 | 2.664 (7) | 164 |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x−1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C14H16N2O4 |
Mr | 276.29 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 296 |
a, b, c (Å) | 17.133 (3), 17.062 (3), 20.130 (4) |
β (°) | 93.02 (4) |
V (Å3) | 5876.3 (19) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Siemens P4 |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7430, 6753, 3465 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.186, 1.04 |
No. of reflections | 6753 |
No. of parameters | 733 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.24 |
Computer programs: XSCANS (Siemens, 1991), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O4A—H4A···O1Ci | 0.82 | 1.86 | 2.678 (7) | 177.1 |
O4B—H4B···O1Dii | 0.82 | 1.88 | 2.665 (7) | 160.0 |
O4C—H4C···O1A | 0.82 | 1.89 | 2.700 (6) | 171.1 |
O4D—H4D···O1B | 0.82 | 1.87 | 2.664 (7) | 164.3 |
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) x−1/2, y+1/2, z. |
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As a continuation of our project aimed at developing new therapeutic agents, we attempted to prepare, by the reaction of 4,5-dihydro-3-methyl-5-(2-hydroxyphenyl)-1H-pyrazole (I) (Světlík et al., 2005) with diethyl oxalate, the tricyclic compound (II) possessing 1,4-oxazepine core. However, 1H and 13C NMR spectra were consistent with the structure (III) or (IV), but it was difficult to distinguish between these two alternatives from the NMR spectral data (Kalinowski et al., 1984); on the other hand, the IR spectrum matches better the structure (III) (Lambert et al., 1998). To confirm our presumption and to establish conformational features of the molecule, an X-ray analysis of the reaction product was undertaken.
The structure determination has shown that the four independent molecules (denoted as A - D) are, except for the terminal ethyl groups, identical to within 5/s as far as bond distances and angles are concerned. Thus, only one molecule (A) is shown in Fig. 2. As can be seen, the compound has the structure (III).
The sp2-hybridized N1 atom is involved in conjugation with the adjacent carbonyl function, as found for amides (Allen et al., 1987), rather than the pyrazoline double bond (Burke-Laing & Laing, 1976). In all four molecules the C6—C7 bond lengths are close to the value of 1.487 (5) Å reported for a Csp2—Csp2 single bond (Shmueli et al., 1973). Other bond distances are close to those generally expected.
As mentioned above, the conformational properties of the molecule is of prime interest here. The conformation of the hydroxyphenylpyrazoline portion in all independent molecules is the same: the pyrazoline ring is approximately planar with slight but significant distortion towards the C5-envelope; the phenyl ring occupies the pseudoaxial position and bisects the heterocycle. However, relative configuration on C5 in molecules B and C is opposite relative to molecules A and D. Another source of asymmetry is imposed by the approximatelly perpendicular orientation of the ethyl ester group relative to the mean plane of the carbonylpyrazoline moiety. As shown by the torsion angle N1—C6—C7—O2, both 'enantiomeric' values (ca ±90°) are equally populated. The third difference among the independent molecules concerns the rotation around the O3—C8 bond.
The crystal packing is dominated by hydrogen bonding. As shown in Table 1, the hydroxy group of all independent molecules is involved in an H-bond interaction with the carbonyl atom adjacent to the heterocycle of a neighbouring molecule.