research communications
New insights in the discovery of novel h-MAO-B inhibitors: structural characterization of a series of N-phenyl-4-oxo-4H-chromene-3-carboxamide derivatives
aFP-ENAS-Faculdade de Ciências de Saúde, Escola Superior de Saúde da UFP, Universidade Fernando Pessoa, Rua Carlos da Maia, 296, P-4200-150 Porto, Portugal, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cCIQ/Departamento de Quιmica e Bioquιmica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal
*Correspondence e-mail: jnlow111@gmail.com
Six N-substituted-phenyl 4-oxo-4H-chromene-3-carboxamides, namely N-(2-nitrophenyl)-4-oxo-4H-chromene-3-carboxamide, C16H10N2O5 (2b), N-(3-methoxyphenyl)-4-oxo-4H-chromene-3-carboxamide, C17H13NO4, (3a), N-(3-bromophenyl)-4-oxo-4H-chromene-3-carboxamide, C16H10BrNO3, (3b), N-(4-methoxyphenyl)-4-oxo-4H-chromene-3-carboxamide, C17H13NO4, (4a), N-(4-methylphenyl)-4-oxo-4H-chromene-3-carboxamide, C17H13NO3, (4d), and N-(4-hydroxyphenyl)-4-oxo-4H-chromene-3-carboxamide, C16H11NO4, (4e), have been structurally characterized. All compounds exhibit an anti conformation with respect to the C—N rotamer of the amide and a trans-related conformation with the carbonyl groups of the chromone ring of the amide. These structures present an intramolecular hydrogen-bonded network comprising an N—H⋯O hydrogen bond between the amide N atom and the O atom of the carbonyl group of the pyrone ring, forming an S(6) ring, and a weak Car—H⋯O hydrogen bond in which the carbonyl group of the amide acts as acceptor for the H atom of an ortho-C atom of the exocyclic phenyl ring, which results in another S(6) ring. The N—H⋯O intramolecular hydrogen bond constrains the carboxamide moiety such that it is virtually coplanar with the chromone ring.
1. Chemical context
Chromones are a group of natural and synthetic oxygen h-MAO-B. Recent data (Cagide et al., 2015) suggest that the activity and selectivity towards that enzyme is dependent on the nature and position of the substituent located in the exocyclic phenyl ring. When compared with the unsubstituted compound (1), the para substitution in the exocyclic phenyl ring seems to play an important role in the enzymatic interaction: the presence of para-Cl (4c) and –CH3 (4d) substituents favours the potency while an –OH (4e) substituent has the opposite effect. The data acquired so far point out the importance of a structure–activity relationship study to optimize the potency vs selectivity of this type of inhibitor, namely performing structural and electronic changes in the substituents.
having a high degree of chemical diversity that is frequently linked to a broad array of biological activities. The chromone-3-(phenyl)carboxamide derivatives, depicted the scheme, have emerged as promising compounds for the management of neurodegenerative diseases such as Alzheimer's and Parkinson's since they display activities againstThus, the results for the structural characterization of some chromone-3-phenylcarboxamide derivatives are presented and discussed. These compounds are as follows – (1): N-phenyl-4-oxo-4H-chromene-3-carboxamide (Cagide et al., 2015); (2a): N-(2-methoxyphenyl)-4-oxo-4H-chromene-3-carboxamide (Gomes et al., 2013); (2b): N-(2-nitrophenyl)-4-oxo-4H-chromone-3-carboxamide (CCDC 1025354); (3a): N-(3-methoxyphenyl)-4-oxo-4H-chromene-3-carboxamide (CCDC 102353); (3b): N-(3-bromophenyl)-4-oxo-4H-chromene-3-carboxamide (CCDC 1025352); (4a): N-(4-methoxyphenyl)-4-oxo-4H-chromene-3-carboxamide (CCDC 1025355); (4b): N-(4-bromophenyl)-4-oxo-4H-chromene-3-carboxamide (Gomes et al., 2015); (4c): N-(4-chlorophenyl)-4-oxo-4H-chromene-3-carboxamide (Gomes et al., 2015); (4d): N-(4-methylphenyl)-4-oxo-4H-chromene-3-carboxamide; (4e): N-(4-hydroxyphenyl)-4-oxo-4H-chromene-3-carboxamide (CCDC 102524). Compounds with CCDC numbers given were deposited by the current authors, Gomes, Borges and Low, in the Cambridge Structural Database (CSD; Groom & Allen, 2014).
2. Structural commentary
2.1. Molecular structures
Conformations and intramolecular hydrogen-bond network
The structural analysis confirms that the molecules are 4-chromone derivatives with a phenylamide substituent on position number 3 of the pyrone ring. Fig. 1 to 6 show the displacement ellipsoid diagrams with the adopted labelling scheme for (2b), (3a), (3b), (4a), (4d) and (4e), the structurally characterized compounds in this work. As seen, the molecules exhibit an anti conformation with respect to the C–N rotamer of the amide following a pattern given by compound (1), which was previously described by Cagide et al. (2015). Due to the asymmetry of the chromone residue, the anti conformation can assume several geometries depending on the relative position of the carbonyl groups of the chromone ring and the amide group which can be cis or trans related. Compounds (1)–(4) exhibit a trans relation between these bonds as can be seen in Figs. 1 to 6. This molecular conformation allows the establishment of two or three intramolecular hydrogen bonds. Details of the intramolecular hydrogen bonding are given in Tables 2–7. Generally, as seen in the scheme below, there is an intramolecular hydrogen bond involving the amide and the chromone where the amide nitrogen atom acts as donor to the oxo oxygen atom of the chromone ring, forming an S(6) ring; the carboxyl oxygen of the amide acts as acceptor for a weak H interaction with the C–H group located at the ortho position of the phenyl ring, forming another S(6) ring. This hydrogen-bonding network probably enhances the planarity of the molecules and may prevent them from adopting some other possible conformations by restraining their geometries. Compounds (2a) and (2b) have substituents located at the ortho position on the benzyl ring with oxygen atoms (methoxy and nitro, respectively) that act as acceptors for the amide nitrogen atom of the carboxamide residue, hence forming a third intramolecular hydrogen bond (see scheme).
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Molecular geometries
The values for bond lengths involving the atoms of the carboxamide residue assume the expected ranges for sp3—Csp3 bond (Allen et al., 1987). The C31—O3 bond lengths range from 1.22 to 1.25 Å and the C31—N3 bond lengths are within the 1.33 to 1.37 Å interval, showing the the partial sp2 character of the amide nitrogen atom attributed to those compounds.
with aromatic substituents. The C3—C31 bond ranges from 1.49 to 1.51 Å, which are the typical range values for an CTable 1 details selected dihedral angles between the mean planes of aromatic rings, θChr-Phe, between the chromone ring and the amide moiety (the plane defined by atoms O3, C31and N3), θChr-amide, and between the exocyclic phenyl ring and the amide, θPhe-amide. Those dihedral angles are primarily due to the rotation of the rings around the C3—C31 and N3—C311 bonds with exception of (3a) that assumes mainly a bent conformation between the rings. The structural analysis of (1) performed previously (Cagide et al., 2015) revealed that the amide moiety is practically planar with the chromone ring: it makes a dihedral angle of 4.31 (12)° with the plane defined by the O, C and N atoms of the amide residue. The loss of planarity for the overall molecule results from the slight twist of the exocyclic phenyl substituent around the amidic N—C bond, which is the main factor affecting the value for the dihedral angle of 9.48 (12)° between the best plane of the exocyclic phenyl ring and the O—C—N amidic plane. The dihedral angle between the mean plane of the chromone ring and that of the exocyclic phenyl ring is 10.77 (4)°. The θChr-amide dihedral angles for the substituted compounds are below 15° for all the compounds, suggesting that the amide moiety is essentially planar with the chromone ring. The strong N3—H3⋯O4 hydrogen contact may preclude higher rotations around the C3—C31 bond in spite of its Csp3—Csp3 character. The θPhe-amide angles present more widely spread values, ranging between 2 and 33°. The substituents with oxygen atoms located at the ortho position on the exocyclic phenyl ring in (2) which, simultaneously, cause and act as acceptors for the hydrogen atom of the amide, thus forming an intramolecular hydrogen bond, suggest that a tricky balance between those two factors allows the formation of several energetically accessible rotated conformations. This fact is especially noticeable in the various conformation polymorphs of (2a).
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The remaining compounds are not constrained by ortho-substituents but they still present a wide range of values for the θPhe-amide dihedral angles (between 3 and 24°). The θChr-Phe values may be used as a measure of the relative positioning of the two aromatic rings which may define the primary conformation for the molecules. The aromatic rings are usually rotated or co-planar, with exception of (3a) where they are bent with respect to each other. The chromones with halogen substituents assume the most planar conformations, probably related to the typical positive mesomeric effects on the π system. Considering the fact that the para-substituent on the exocyclic phenyl ring for chromone-3-phenylcarboxamides has a positive effect on their activity, and the requirement of establishing the factors that can modulate the enzyme–ligand interaction, it can be assumed their h-MAO-B activity is strongly dependent on the electronic environment of the substituent. This is not a preferred conformation that reduces or enhances the activity, so it may be assumed that the electronic environment provided by the substituent is the primary condition for the pharmacological activities displayed by those molecules.
of theIn compound (3b) there are two molecules in the A calculation using Molfit with Quaternion Transformation Method (Mackay, 1984) gave the following fit: weighted/unit weight r.m.s. fits: 0.133/0.144 Å for 23 atoms with molecule 1 inverted on molecule 2, 21 atoms. The largest individual displacement is 0.178 Å(Br13/Br23). The r.m.s. bond fit = 0.0052 Å and the r.m.s. angle fit = 0.437°.
3. Supramolecular features
The carboxamide H atom is not involved in any intermolecular interaction in any of the compounds.
In (2b), the molecules are linked by C8—H8⋯O32(−x, y + , −z + ), C5—H5⋯O1(−x, y − , −z + ) and C313—H313⋯O3(−x, y − , −z + ) hydrogen bonds which, by the action of twofold screw axes running parallel to the b axis, link the molecules into corrugated sheets which lie parallel to the (10) plane, and which form a distorted chequerboard pattern comprised of R22(15) and R44(23) rings (Table 2 and Fig. 7).
In (3a), the molecules are linked by the C2—H2⋯O3(−x + 1, −y + 1, −z + 1) hydrogen bond, forming centrosymmetric dimers across the inversion centre at (1/2, 1/2, 1/2) (Table 3 and Fig. 8).
In (3b), independent ladders of molecule 1 and molecule 2 are propagated along the a-axis direction by unit translation. These are formed by chains of R22(13) rings produced by the weak Cx2—Hx2⋯Ox4(x + 1, y, z) and Cx36—Hx36⋯Ox3(x − 1, y, z) interactions, where x = 1 or 2 (Table 4 and Fig. 9).
A common feature found for compounds with para substituents, (4a)–(4d) is the formation of a ladder structure composed of molecules propagated by unit axial translations involving intermolecular hydrogen bonds between C2 and O4 of the chromone ring and the C atom located at the ortho position of the exocyclic phenyl ring and the carboxamide O atom. This is also found in (1) and in compound (3b), which has a Br substituent located at the meta position, in which the ladder structure is supplemented by an intermolecular hydrogen bond between C5 and O1 of the chromone moiety. In (4a), the molecules are linked by C2—H2⋯O4 (x, y − 1, z) and C316—H316⋯O3 (x, y + 1, z) hydrogen bonds, forming R22(13) rings structures which are propagated along the b-axis direction by unit translation (Table 5 and Fig. 10). In (4d), the molecules are linked by C2—H2⋯O4(x + 1, y, z) and C316—H316⋯O3(x − 1, y, z) hydrogen bonds, forming R22(13) ring structures which are propagated along the a-axis direction by unit translation (Table 6 and Fig. 11).
In the hydroxyl compound (4e), the molecules in the are linked by the O114—H114⋯O23 hydrogen bond, forming a dimer. These dimers are linked by the O214—H214⋯O13(x − 1,1 + y, z) and weak C16—H16⋯O114(x, y, z − 1), C18—H18⋯O24(x + 1, y − 1, z − 1), C26—H26⋯O214(x, y, z + 1) and C28—H28⋯O14(x, y, z + 1) hydrogen bonds, which link the molecules into sheets that form a chequerboard pattern and which lie parallel to the (10) plane, comprised of R32(15) and R33(24) rings (Table 7 and Fig. 12).
Selected π–π contacts, with centroid-to-centroid distances less than 4.0 Å and with angles between planes of less than 10° for compounds (2b), (3b), (4a) and (4d) are listed in Table 8. No interactions were found for (3a).
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4. Synthesis and crystallization
The compounds were obtained by synthetic strategies described elsewhere (Cagide et al., 2011). Chromone-3-carboxamide derivatives were synthesized using chromone-3-carboxylic acid as starting material which, after in situ activation with phosphorus(V) oxychloride (POCl3) in dimethylformamide, react with the different substituted anilines. Crystals were recrystallized from ethylacetate forming colourless plates whose dimensions are given in Table 9.
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5. Refinement
Crystal data, data collection and structure .
details are summarized in Table 9In (3b) there are two molecules in the The largest difference map peaks are associated with the Br atoms.
In all compounds, H atoms attached to C atoms were treated as riding atoms with C—H(aromatic) = 0.95 Å with Uiso(H) = 1.2Ueq(C); C—H(methyl), = 0.98 Å with Uiso= 1.5Ueq(C). In all compounds, the amino H atoms were refined with the exception of (3b) where these atoms were refined as riding atoms with N—H = 0.88 Å with Uiso = 1.2Ueq(C) and in (4e) in which the positional parameters of the amino and hydroxyl H atoms were refined but their Uiso values were constrained to be Uiso(N) = 1.2Ueq(N) and Uiso(O)b= 1.5Ueq(O). The final positions of these atoms were checked in a difference Fourier map, as were the positions of the H atoms in any methyl groups. The quality of the crystals for (4e) was poor and the crystals were twinned. The completeness is 97%. The crystal studied was refined as a two-component twin [twin law: 2-axis (001) [05], BASF = 0.40].
Supporting information
https://doi.org/10.1107/S2056989015007859/lh5762sup1.cif
contains datablocks 2b, 3a, 3b, 4a, 4d, 4e, global. DOI:Structure factors: contains datablock 2b. DOI: https://doi.org/10.1107/S2056989015007859/lh57622bsup2.hkl
Structure factors: contains datablock 3a. DOI: https://doi.org/10.1107/S2056989015007859/lh57623asup3.hkl
Structure factors: contains datablock 3b. DOI: https://doi.org/10.1107/S2056989015007859/lh57623bsup4.hkl
Structure factors: contains datablock 4a. DOI: https://doi.org/10.1107/S2056989015007859/lh57624asup5.hkl
Structure factors: contains datablock 4d. DOI: https://doi.org/10.1107/S2056989015007859/lh57624dsup6.hkl
Structure factors: contains datablock 4e. DOI: https://doi.org/10.1107/S2056989015007859/lh57624esup7.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015007859/lh57622bsup8.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989015007859/lh57623asup9.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989015007859/lh57623bsup10.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989015007859/lh57624asup11.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989015007859/lh57624dsup12.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989015007859/lh57624esup13.cml
For all compounds, data collection: CrystalClear-SM Expert (Rigaku, 2012); cell
CrystalClear-SM Expert (Rigaku, 2012); data reduction: CrystalClear-SM Expert (Rigaku, 2012). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and Flipper 25 (Oszlányi & Sütő, 2004) for (2b), (3a), (4a), (4d), (4e); SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and Flipper 25 (Oszlányi & Sütő, 2004); for (3b). Program(s) used to refine structure: OSCAIL (McArdle et al., 2004), ShelXle (Hübschle et al., 2011) and SHELXL2014 (Sheldrick, 2015) for (2b), (3a), (4a), (4d), (4e); OSCAIL (McArdle et al., 2004), ShelXle (Hübschle et al., 2011) and SHELXL (Sheldrick, 2015) for (3b). For all compounds, molecular graphics: Mercury (Macrae et al., 2006). Software used to prepare material for publication: OSCAIL (McArdle et al., 2004), SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009) for (2b), (3a), (4a), (4d), (4e); OSCAIL (McArdle et al., 2004), SHELXL (Sheldrick, 2015) and PLATON (Spek, 2009) for (3b).C16H10N2O5 | F(000) = 640 |
Mr = 310.26 | Dx = 1.593 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
a = 14.104 (9) Å | Cell parameters from 3262 reflections |
b = 12.692 (8) Å | θ = 2.2–31.3° |
c = 7.340 (5) Å | µ = 0.12 mm−1 |
β = 100.065 (13)° | T = 100 K |
V = 1293.7 (15) Å3 | Rod, yellow |
Z = 4 | 0.09 × 0.02 × 0.01 mm |
Rigaku Saturn724+ (2x2 bin mode) diffractometer | 2947 independent reflections |
Radiation source: Rotating Anode | 2215 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.061 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
profile data from ω–scans | h = −18→18 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | k = −16→15 |
Tmin = 0.989, Tmax = 0.999 | l = −9→9 |
8466 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.0365P)2 + 1.6526P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
2947 reflections | Δρmax = 0.24 e Å−3 |
212 parameters | Δρmin = −0.31 e Å−3 |
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 | ||
O1 | 0.06264 (13) | 0.90167 (15) | 0.2131 (3) | 0.0216 (5) | |
O3 | 0.33472 (14) | 0.85362 (16) | 0.4843 (3) | 0.0253 (5) | |
O4 | 0.15266 (14) | 0.59520 (16) | 0.2912 (3) | 0.0261 (5) | |
O31 | 0.37222 (16) | 0.41995 (16) | 0.8305 (3) | 0.0296 (5) | |
O32 | 0.27802 (14) | 0.48771 (16) | 0.5956 (3) | 0.0261 (5) | |
N3 | 0.32255 (17) | 0.67310 (19) | 0.4733 (3) | 0.0200 (5) | |
H3 | 0.278 (3) | 0.616 (3) | 0.447 (5) | 0.049 (11)* | |
N31 | 0.35685 (17) | 0.48317 (19) | 0.7022 (3) | 0.0219 (6) | |
C2 | 0.1510 (2) | 0.8769 (2) | 0.3047 (4) | 0.0209 (6) | |
H2 | 0.1918 | 0.9337 | 0.3523 | 0.025* | |
C3 | 0.18677 (19) | 0.7789 (2) | 0.3351 (4) | 0.0180 (6) | |
C4 | 0.1266 (2) | 0.6879 (2) | 0.2674 (4) | 0.0201 (6) | |
C4A | 0.03017 (19) | 0.7160 (2) | 0.1659 (4) | 0.0191 (6) | |
C5 | −0.0351 (2) | 0.6377 (2) | 0.0908 (4) | 0.0206 (6) | |
H5 | −0.0180 | 0.5655 | 0.1071 | 0.025* | |
C6 | −0.1244 (2) | 0.6653 (2) | −0.0068 (4) | 0.0249 (7) | |
H6 | −0.1681 | 0.6119 | −0.0588 | 0.030* | |
C7 | −0.1509 (2) | 0.7710 (3) | −0.0296 (4) | 0.0246 (7) | |
H7 | −0.2126 | 0.7889 | −0.0969 | 0.030* | |
C8 | −0.0884 (2) | 0.8501 (2) | 0.0448 (4) | 0.0232 (6) | |
H8 | −0.1063 | 0.9222 | 0.0311 | 0.028* | |
C8A | 0.0017 (2) | 0.8203 (2) | 0.1405 (4) | 0.0212 (6) | |
C31 | 0.2891 (2) | 0.7728 (2) | 0.4371 (4) | 0.0211 (6) | |
C311 | 0.4162 (2) | 0.6460 (2) | 0.5629 (4) | 0.0202 (6) | |
C312 | 0.43423 (19) | 0.5536 (2) | 0.6708 (4) | 0.0196 (6) | |
C313 | 0.5268 (2) | 0.5248 (2) | 0.7552 (4) | 0.0221 (6) | |
H313 | 0.5367 | 0.4627 | 0.8284 | 0.027* | |
C314 | 0.6038 (2) | 0.5870 (2) | 0.7320 (4) | 0.0250 (7) | |
H314 | 0.6673 | 0.5677 | 0.7880 | 0.030* | |
C315 | 0.5883 (2) | 0.6778 (2) | 0.6266 (4) | 0.0236 (7) | |
H315 | 0.6416 | 0.7203 | 0.6103 | 0.028* | |
C316 | 0.4957 (2) | 0.7078 (2) | 0.5439 (4) | 0.0223 (6) | |
H316 | 0.4866 | 0.7711 | 0.4739 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0174 (10) | 0.0192 (10) | 0.0275 (12) | 0.0018 (8) | 0.0020 (8) | 0.0005 (9) |
O3 | 0.0215 (11) | 0.0186 (10) | 0.0348 (13) | −0.0029 (9) | 0.0027 (9) | −0.0010 (9) |
O4 | 0.0214 (11) | 0.0163 (10) | 0.0381 (13) | 0.0011 (9) | −0.0016 (9) | 0.0017 (9) |
O31 | 0.0355 (12) | 0.0219 (11) | 0.0300 (13) | 0.0006 (10) | 0.0022 (10) | 0.0077 (10) |
O32 | 0.0190 (10) | 0.0229 (11) | 0.0341 (13) | −0.0012 (9) | −0.0017 (9) | 0.0027 (9) |
N3 | 0.0160 (12) | 0.0170 (12) | 0.0258 (14) | 0.0010 (10) | 0.0004 (10) | 0.0022 (10) |
N31 | 0.0217 (12) | 0.0191 (12) | 0.0256 (14) | 0.0015 (10) | 0.0057 (11) | 0.0013 (10) |
C2 | 0.0169 (14) | 0.0236 (15) | 0.0223 (16) | 0.0015 (12) | 0.0033 (12) | −0.0012 (12) |
C3 | 0.0173 (13) | 0.0185 (13) | 0.0182 (14) | −0.0004 (12) | 0.0029 (11) | 0.0009 (12) |
C4 | 0.0190 (14) | 0.0209 (14) | 0.0210 (15) | 0.0016 (12) | 0.0053 (11) | 0.0029 (12) |
C4A | 0.0162 (13) | 0.0221 (14) | 0.0189 (15) | −0.0015 (12) | 0.0028 (11) | 0.0005 (12) |
C5 | 0.0209 (14) | 0.0182 (14) | 0.0229 (15) | 0.0010 (12) | 0.0042 (12) | 0.0002 (12) |
C6 | 0.0233 (15) | 0.0272 (16) | 0.0238 (16) | −0.0018 (13) | 0.0033 (12) | −0.0020 (13) |
C7 | 0.0187 (14) | 0.0318 (16) | 0.0236 (16) | 0.0039 (14) | 0.0044 (12) | 0.0003 (13) |
C8 | 0.0238 (15) | 0.0252 (15) | 0.0215 (15) | 0.0046 (13) | 0.0062 (12) | 0.0007 (13) |
C8A | 0.0197 (14) | 0.0231 (15) | 0.0212 (15) | −0.0005 (12) | 0.0048 (11) | −0.0019 (12) |
C31 | 0.0204 (14) | 0.0217 (14) | 0.0220 (16) | −0.0012 (12) | 0.0063 (12) | 0.0004 (12) |
C311 | 0.0174 (13) | 0.0217 (14) | 0.0207 (15) | 0.0014 (12) | 0.0014 (11) | −0.0012 (12) |
C312 | 0.0177 (13) | 0.0187 (14) | 0.0225 (15) | −0.0012 (12) | 0.0034 (11) | −0.0003 (12) |
C313 | 0.0230 (15) | 0.0211 (14) | 0.0216 (16) | 0.0023 (12) | 0.0021 (12) | −0.0018 (12) |
C314 | 0.0199 (14) | 0.0270 (16) | 0.0264 (17) | 0.0041 (13) | −0.0005 (12) | −0.0063 (13) |
C315 | 0.0175 (14) | 0.0263 (15) | 0.0273 (16) | −0.0025 (13) | 0.0048 (12) | −0.0057 (13) |
C316 | 0.0181 (14) | 0.0217 (15) | 0.0269 (17) | −0.0006 (12) | 0.0033 (12) | −0.0016 (12) |
O1—C2 | 1.346 (3) | C5—H5 | 0.9500 |
O1—C8A | 1.389 (3) | C6—C7 | 1.395 (4) |
O3—C31 | 1.228 (4) | C6—H6 | 0.9500 |
O4—C4 | 1.235 (3) | C7—C8 | 1.384 (4) |
O31—N31 | 1.227 (3) | C7—H7 | 0.9500 |
O32—N31 | 1.244 (3) | C8—C8A | 1.392 (4) |
N3—C31 | 1.360 (4) | C8—H8 | 0.9500 |
N3—C311 | 1.411 (4) | C311—C316 | 1.396 (4) |
N3—H3 | 0.96 (4) | C311—C312 | 1.413 (4) |
N31—C312 | 1.460 (4) | C312—C313 | 1.392 (4) |
C2—C3 | 1.346 (4) | C313—C314 | 1.378 (4) |
C2—H2 | 0.9500 | C313—H313 | 0.9500 |
C3—C4 | 1.468 (4) | C314—C315 | 1.383 (4) |
C3—C31 | 1.508 (4) | C314—H314 | 0.9500 |
C4—C4A | 1.476 (4) | C315—C316 | 1.394 (4) |
C4A—C8A | 1.385 (4) | C315—H315 | 0.9500 |
C4A—C5 | 1.401 (4) | C316—H316 | 0.9500 |
C5—C6 | 1.381 (4) | ||
C2—O1—C8A | 118.3 (2) | C7—C8—C8A | 117.7 (3) |
C31—N3—C311 | 125.6 (2) | C7—C8—H8 | 121.2 |
C31—N3—H3 | 118 (2) | C8A—C8—H8 | 121.2 |
C311—N3—H3 | 116 (2) | C4A—C8A—O1 | 120.9 (3) |
O31—N31—O32 | 122.1 (2) | C4A—C8A—C8 | 123.0 (3) |
O31—N31—C312 | 119.0 (2) | O1—C8A—C8 | 116.1 (3) |
O32—N31—C312 | 118.9 (2) | O3—C31—N3 | 125.1 (3) |
O1—C2—C3 | 125.9 (3) | O3—C31—C3 | 120.4 (3) |
O1—C2—H2 | 117.1 | N3—C31—C3 | 114.5 (2) |
C3—C2—H2 | 117.1 | C316—C311—N3 | 121.3 (3) |
C2—C3—C4 | 119.6 (3) | C316—C311—C312 | 117.0 (3) |
C2—C3—C31 | 115.4 (3) | N3—C311—C312 | 121.8 (3) |
C4—C3—C31 | 125.0 (3) | C313—C312—C311 | 122.0 (3) |
O4—C4—C3 | 124.2 (3) | C313—C312—N31 | 115.9 (3) |
O4—C4—C4A | 121.8 (3) | C311—C312—N31 | 122.0 (2) |
C3—C4—C4A | 114.0 (2) | C314—C313—C312 | 119.5 (3) |
C8A—C4A—C5 | 118.0 (3) | C314—C313—H313 | 120.2 |
C8A—C4A—C4 | 121.3 (3) | C312—C313—H313 | 120.2 |
C5—C4A—C4 | 120.7 (3) | C313—C314—C315 | 119.7 (3) |
C6—C5—C4A | 120.1 (3) | C313—C314—H314 | 120.2 |
C6—C5—H5 | 120.0 | C315—C314—H314 | 120.2 |
C4A—C5—H5 | 120.0 | C314—C315—C316 | 121.1 (3) |
C5—C6—C7 | 120.5 (3) | C314—C315—H315 | 119.5 |
C5—C6—H6 | 119.8 | C316—C315—H315 | 119.5 |
C7—C6—H6 | 119.8 | C315—C316—C311 | 120.7 (3) |
C8—C7—C6 | 120.7 (3) | C315—C316—H316 | 119.7 |
C8—C7—H7 | 119.6 | C311—C316—H316 | 119.7 |
C6—C7—H7 | 119.6 | ||
C8A—O1—C2—C3 | −0.6 (4) | C311—N3—C31—O3 | −3.2 (5) |
O1—C2—C3—C4 | −0.9 (5) | C311—N3—C31—C3 | 178.5 (3) |
O1—C2—C3—C31 | 178.3 (3) | C2—C3—C31—O3 | −1.0 (4) |
C2—C3—C4—O4 | −178.8 (3) | C4—C3—C31—O3 | 178.1 (3) |
C31—C3—C4—O4 | 2.0 (5) | C2—C3—C31—N3 | 177.3 (3) |
C2—C3—C4—C4A | 1.3 (4) | C4—C3—C31—N3 | −3.5 (4) |
C31—C3—C4—C4A | −177.9 (3) | C31—N3—C311—C316 | −32.2 (4) |
O4—C4—C4A—C8A | 179.8 (3) | C31—N3—C311—C312 | 149.8 (3) |
C3—C4—C4A—C8A | −0.3 (4) | C316—C311—C312—C313 | 0.1 (4) |
O4—C4—C4A—C5 | −0.7 (4) | N3—C311—C312—C313 | 178.1 (3) |
C3—C4—C4A—C5 | 179.2 (3) | C316—C311—C312—N31 | 179.4 (3) |
C8A—C4A—C5—C6 | 0.7 (4) | N3—C311—C312—N31 | −2.6 (4) |
C4—C4A—C5—C6 | −178.8 (3) | O31—N31—C312—C313 | 17.2 (4) |
C4A—C5—C6—C7 | −0.8 (4) | O32—N31—C312—C313 | −161.3 (3) |
C5—C6—C7—C8 | 0.1 (5) | O31—N31—C312—C311 | −162.2 (3) |
C6—C7—C8—C8A | 0.8 (4) | O32—N31—C312—C311 | 19.3 (4) |
C5—C4A—C8A—O1 | 179.3 (3) | C311—C312—C313—C314 | −0.8 (4) |
C4—C4A—C8A—O1 | −1.2 (4) | N31—C312—C313—C314 | 179.8 (3) |
C5—C4A—C8A—C8 | 0.2 (4) | C312—C313—C314—C315 | 0.6 (4) |
C4—C4A—C8A—C8 | 179.7 (3) | C313—C314—C315—C316 | 0.3 (5) |
C2—O1—C8A—C4A | 1.7 (4) | C314—C315—C316—C311 | −1.1 (5) |
C2—O1—C8A—C8 | −179.2 (3) | N3—C311—C316—C315 | −177.2 (3) |
C7—C8—C8A—C4A | −0.9 (5) | C312—C311—C316—C315 | 0.8 (4) |
C7—C8—C8A—O1 | 179.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4 | 0.96 (4) | 1.95 (4) | 2.718 (3) | 136 (3) |
N3—H3···O32 | 0.96 (4) | 1.96 (4) | 2.633 (3) | 126 (3) |
C316—H316···O3 | 0.95 | 2.40 | 2.902 (4) | 113 |
C8—H8···O32i | 0.95 | 2.58 | 3.210 (4) | 124 |
C5—H5···O1ii | 0.95 | 2.60 | 3.375 (4) | 139 |
C313—H313···O3iii | 0.95 | 2.49 | 3.299 (4) | 143 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y−1/2, −z+3/2. |
C17H13NO4 | F(000) = 616 |
Mr = 295.28 | Dx = 1.487 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
a = 9.6903 (2) Å | Cell parameters from 7535 reflections |
b = 5.5303 (4) Å | θ = 2.4–27.5° |
c = 24.9335 (18) Å | µ = 0.11 mm−1 |
β = 99.162 (5)° | T = 100 K |
V = 1319.15 (14) Å3 | Plate, yellow |
Z = 4 | 0.16 × 0.11 × 0.02 mm |
Rigaku Saturn724+ (2x2 bin mode) diffractometer | 2665 independent reflections |
Graphite Monochromator monochromator | 1952 reflections with I > 2σ(I) |
Detector resolution: 28.5714 pixels mm-1 | Rint = 0.055 |
profile data from ω–scans | θmax = 26.4°, θmin = 3.0° |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | h = −8→12 |
Tmin = 0.983, Tmax = 0.998 | k = −6→4 |
7859 measured reflections | l = −31→31 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0608P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
2665 reflections | Δρmax = 0.27 e Å−3 |
205 parameters | Δρmin = −0.28 e Å−3 |
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 | ||
O1 | 0.26521 (11) | 0.7928 (2) | 0.57868 (4) | 0.0171 (3) | |
O3 | 0.44760 (12) | 0.7936 (2) | 0.44346 (5) | 0.0232 (3) | |
O4 | 0.18474 (11) | 0.2131 (2) | 0.47561 (5) | 0.0180 (3) | |
O31 | 0.59354 (12) | 0.7141 (2) | 0.26613 (5) | 0.0203 (3) | |
N3 | 0.35790 (14) | 0.4246 (3) | 0.41394 (6) | 0.0165 (3) | |
H3 | 0.301 (2) | 0.299 (4) | 0.4246 (9) | 0.041 (6)* | |
C2 | 0.32706 (16) | 0.7700 (3) | 0.53426 (7) | 0.0161 (4) | |
H2 | 0.3919 | 0.8917 | 0.5280 | 0.022 (5)* | |
C3 | 0.30423 (16) | 0.5879 (3) | 0.49791 (6) | 0.0142 (4) | |
C4 | 0.20852 (16) | 0.3913 (3) | 0.50574 (6) | 0.0142 (4) | |
C4A | 0.13765 (16) | 0.4230 (3) | 0.55341 (6) | 0.0145 (4) | |
C5 | 0.03520 (16) | 0.2597 (3) | 0.56506 (7) | 0.0166 (4) | |
H5 | 0.0134 | 0.1214 | 0.5427 | 0.020* | |
C6 | −0.03398 (17) | 0.2980 (3) | 0.60851 (7) | 0.0171 (4) | |
H6 | −0.1032 | 0.1868 | 0.6159 | 0.020* | |
C7 | −0.00212 (17) | 0.5010 (3) | 0.64171 (7) | 0.0187 (4) | |
H7 | −0.0508 | 0.5275 | 0.6714 | 0.022* | |
C8 | 0.09905 (17) | 0.6627 (3) | 0.63182 (7) | 0.0177 (4) | |
H8 | 0.1221 | 0.7986 | 0.6548 | 0.021* | |
C8A | 0.16685 (16) | 0.6224 (3) | 0.58735 (7) | 0.0152 (4) | |
C31 | 0.37825 (16) | 0.6126 (3) | 0.44949 (6) | 0.0159 (4) | |
C311 | 0.39490 (16) | 0.4120 (3) | 0.36136 (6) | 0.0158 (4) | |
C312 | 0.48345 (16) | 0.5805 (3) | 0.34230 (7) | 0.0158 (4) | |
H312 | 0.5242 | 0.7080 | 0.3650 | 0.019* | |
C313 | 0.51050 (16) | 0.5572 (3) | 0.28940 (7) | 0.0160 (4) | |
C314 | 0.45126 (17) | 0.3717 (3) | 0.25555 (7) | 0.0181 (4) | |
H314 | 0.4695 | 0.3599 | 0.2193 | 0.022* | |
C315 | 0.36543 (17) | 0.2046 (3) | 0.27535 (7) | 0.0190 (4) | |
H315 | 0.3256 | 0.0763 | 0.2527 | 0.023* | |
C316 | 0.33721 (17) | 0.2231 (3) | 0.32799 (7) | 0.0181 (4) | |
H316 | 0.2787 | 0.1074 | 0.3413 | 0.022* | |
C317 | 0.67728 (17) | 0.8800 (3) | 0.30136 (7) | 0.0203 (4) | |
H31A | 0.7369 | 0.9724 | 0.2805 | 0.030* | |
H31B | 0.7359 | 0.7902 | 0.3303 | 0.030* | |
H31C | 0.6164 | 0.9911 | 0.3174 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0184 (6) | 0.0160 (6) | 0.0181 (6) | −0.0038 (5) | 0.0064 (5) | −0.0022 (5) |
O3 | 0.0268 (7) | 0.0212 (7) | 0.0243 (7) | −0.0100 (6) | 0.0118 (5) | −0.0044 (5) |
O4 | 0.0198 (6) | 0.0159 (6) | 0.0192 (6) | −0.0040 (5) | 0.0059 (5) | −0.0033 (5) |
O31 | 0.0223 (6) | 0.0216 (7) | 0.0188 (6) | −0.0063 (5) | 0.0087 (5) | −0.0010 (5) |
N3 | 0.0148 (7) | 0.0169 (8) | 0.0192 (8) | −0.0037 (6) | 0.0064 (6) | −0.0013 (6) |
C2 | 0.0131 (8) | 0.0182 (9) | 0.0174 (9) | −0.0007 (7) | 0.0036 (7) | 0.0043 (7) |
C3 | 0.0110 (8) | 0.0155 (8) | 0.0162 (8) | 0.0008 (7) | 0.0019 (6) | 0.0021 (7) |
C4 | 0.0121 (8) | 0.0160 (9) | 0.0136 (8) | 0.0028 (7) | −0.0011 (6) | 0.0031 (7) |
C4A | 0.0119 (8) | 0.0149 (8) | 0.0165 (8) | 0.0022 (7) | 0.0012 (6) | 0.0022 (7) |
C5 | 0.0144 (8) | 0.0162 (9) | 0.0184 (9) | −0.0013 (7) | 0.0001 (7) | 0.0020 (7) |
C6 | 0.0133 (8) | 0.0195 (9) | 0.0185 (9) | −0.0010 (7) | 0.0026 (7) | 0.0056 (7) |
C7 | 0.0172 (9) | 0.0224 (10) | 0.0171 (9) | 0.0040 (7) | 0.0049 (7) | 0.0043 (7) |
C8 | 0.0199 (9) | 0.0152 (9) | 0.0176 (9) | 0.0020 (7) | 0.0020 (7) | −0.0010 (7) |
C8A | 0.0119 (8) | 0.0150 (9) | 0.0183 (8) | −0.0009 (7) | 0.0015 (6) | 0.0050 (7) |
C31 | 0.0118 (8) | 0.0171 (9) | 0.0185 (9) | 0.0001 (7) | 0.0012 (6) | 0.0021 (7) |
C311 | 0.0123 (8) | 0.0175 (9) | 0.0179 (9) | 0.0032 (7) | 0.0037 (6) | 0.0009 (7) |
C312 | 0.0123 (8) | 0.0162 (9) | 0.0188 (9) | −0.0007 (7) | 0.0026 (6) | −0.0006 (7) |
C313 | 0.0108 (8) | 0.0166 (9) | 0.0213 (9) | 0.0024 (7) | 0.0047 (6) | 0.0023 (7) |
C314 | 0.0172 (9) | 0.0209 (9) | 0.0169 (8) | 0.0036 (7) | 0.0049 (7) | −0.0003 (7) |
C315 | 0.0168 (9) | 0.0185 (9) | 0.0214 (9) | −0.0011 (7) | 0.0024 (7) | −0.0050 (7) |
C316 | 0.0152 (8) | 0.0167 (9) | 0.0235 (9) | −0.0018 (7) | 0.0068 (7) | −0.0004 (7) |
C317 | 0.0174 (9) | 0.0210 (10) | 0.0232 (9) | −0.0051 (7) | 0.0056 (7) | −0.0001 (8) |
O1—C2 | 1.3464 (18) | C6—H6 | 0.9500 |
O1—C8A | 1.3815 (19) | C7—C8 | 1.378 (2) |
O3—C31 | 1.228 (2) | C7—H7 | 0.9500 |
O4—C4 | 1.239 (2) | C8—C8A | 1.394 (2) |
O31—C313 | 1.3733 (19) | C8—H8 | 0.9500 |
O31—C317 | 1.430 (2) | C311—C316 | 1.396 (2) |
N3—C31 | 1.360 (2) | C311—C312 | 1.400 (2) |
N3—C311 | 1.4146 (19) | C312—C313 | 1.391 (2) |
N3—H3 | 0.95 (2) | C312—H312 | 0.9500 |
C2—C3 | 1.349 (2) | C313—C314 | 1.393 (2) |
C2—H2 | 0.9500 | C314—C315 | 1.386 (2) |
C3—C4 | 1.462 (2) | C314—H314 | 0.9500 |
C3—C31 | 1.506 (2) | C315—C316 | 1.386 (2) |
C4—C4A | 1.475 (2) | C315—H315 | 0.9500 |
C4A—C8A | 1.391 (2) | C316—H316 | 0.9500 |
C4A—C5 | 1.406 (2) | C317—H31A | 0.9800 |
C5—C6 | 1.378 (2) | C317—H31B | 0.9800 |
C5—H5 | 0.9500 | C317—H31C | 0.9800 |
C6—C7 | 1.400 (2) | ||
C2—O1—C8A | 118.25 (13) | O1—C8A—C8 | 116.09 (14) |
C313—O31—C317 | 117.35 (13) | C4A—C8A—C8 | 122.32 (15) |
C31—N3—C311 | 127.55 (14) | O3—C31—N3 | 124.66 (14) |
C31—N3—H3 | 114.0 (13) | O3—C31—C3 | 120.80 (15) |
C311—N3—H3 | 117.9 (13) | N3—C31—C3 | 114.51 (14) |
O1—C2—C3 | 125.13 (15) | C316—C311—C312 | 120.30 (14) |
O1—C2—H2 | 117.4 | C316—C311—N3 | 116.92 (14) |
C3—C2—H2 | 117.4 | C312—C311—N3 | 122.78 (15) |
C2—C3—C4 | 120.32 (14) | C313—C312—C311 | 118.59 (15) |
C2—C3—C31 | 115.01 (15) | C313—C312—H312 | 120.7 |
C4—C3—C31 | 124.61 (14) | C311—C312—H312 | 120.7 |
O4—C4—C3 | 124.85 (14) | O31—C313—C312 | 123.62 (15) |
O4—C4—C4A | 121.19 (14) | O31—C313—C314 | 114.96 (14) |
C3—C4—C4A | 113.96 (14) | C312—C313—C314 | 121.40 (15) |
C8A—C4A—C5 | 117.72 (14) | C315—C314—C313 | 119.22 (15) |
C8A—C4A—C4 | 120.57 (14) | C315—C314—H314 | 120.4 |
C5—C4A—C4 | 121.67 (15) | C313—C314—H314 | 120.4 |
C6—C5—C4A | 120.76 (16) | C314—C315—C316 | 120.53 (16) |
C6—C5—H5 | 119.6 | C314—C315—H315 | 119.7 |
C4A—C5—H5 | 119.6 | C316—C315—H315 | 119.7 |
C5—C6—C7 | 119.94 (15) | C315—C316—C311 | 119.94 (15) |
C5—C6—H6 | 120.0 | C315—C316—H316 | 120.0 |
C7—C6—H6 | 120.0 | C311—C316—H316 | 120.0 |
C8—C7—C6 | 120.73 (15) | O31—C317—H31A | 109.5 |
C8—C7—H7 | 119.6 | O31—C317—H31B | 109.5 |
C6—C7—H7 | 119.6 | H31A—C317—H31B | 109.5 |
C7—C8—C8A | 118.52 (15) | O31—C317—H31C | 109.5 |
C7—C8—H8 | 120.7 | H31A—C317—H31C | 109.5 |
C8A—C8—H8 | 120.7 | H31B—C317—H31C | 109.5 |
O1—C8A—C4A | 121.59 (14) | ||
C8A—O1—C2—C3 | −2.3 (2) | C7—C8—C8A—O1 | 178.69 (14) |
O1—C2—C3—C4 | −1.6 (3) | C7—C8—C8A—C4A | −1.2 (3) |
O1—C2—C3—C31 | 175.74 (14) | C311—N3—C31—O3 | −8.8 (3) |
C2—C3—C4—O4 | −177.46 (16) | C311—N3—C31—C3 | 169.44 (14) |
C31—C3—C4—O4 | 5.5 (3) | C2—C3—C31—O3 | −3.5 (2) |
C2—C3—C4—C4A | 3.5 (2) | C4—C3—C31—O3 | 173.63 (15) |
C31—C3—C4—C4A | −173.52 (14) | C2—C3—C31—N3 | 178.11 (15) |
O4—C4—C4A—C8A | 179.08 (15) | C4—C3—C31—N3 | −4.7 (2) |
C3—C4—C4A—C8A | −1.8 (2) | C31—N3—C311—C316 | −166.55 (16) |
O4—C4—C4A—C5 | −3.4 (2) | C31—N3—C311—C312 | 12.6 (2) |
C3—C4—C4A—C5 | 175.72 (14) | C316—C311—C312—C313 | 1.0 (2) |
C8A—C4A—C5—C6 | 0.4 (2) | N3—C311—C312—C313 | −178.12 (14) |
C4—C4A—C5—C6 | −177.26 (15) | C317—O31—C313—C312 | 12.6 (2) |
C4A—C5—C6—C7 | −0.2 (2) | C317—O31—C313—C314 | −168.72 (14) |
C5—C6—C7—C8 | −0.7 (3) | C311—C312—C313—O31 | 178.79 (15) |
C6—C7—C8—C8A | 1.3 (2) | C311—C312—C313—C314 | 0.2 (2) |
C2—O1—C8A—C4A | 4.0 (2) | O31—C313—C314—C315 | −179.81 (14) |
C2—O1—C8A—C8 | −175.85 (14) | C312—C313—C314—C315 | −1.1 (2) |
C5—C4A—C8A—O1 | −179.53 (14) | C313—C314—C315—C316 | 0.8 (2) |
C4—C4A—C8A—O1 | −1.9 (2) | C314—C315—C316—C311 | 0.3 (2) |
C5—C4A—C8A—C8 | 0.4 (2) | C312—C311—C316—C315 | −1.2 (2) |
C4—C4A—C8A—C8 | 178.01 (15) | N3—C311—C316—C315 | 177.90 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4 | 0.95 (2) | 1.89 (2) | 2.7147 (17) | 143.8 (18) |
C312—H312···O3 | 0.95 | 2.25 | 2.855 (2) | 121 |
C2—H2···O3i | 0.95 | 2.37 | 3.243 (2) | 153 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
C16H10BrNO3 | Z = 4 |
Mr = 344.16 | F(000) = 688 |
Triclinic, P1 | Dx = 1.759 Mg m−3 |
a = 6.7435 (1) Å | Mo Kα radiation, λ = 0.71075 Å |
b = 7.3012 (1) Å | Cell parameters from 6848 reflections |
c = 28.0740 (9) Å | θ = 1.5–27.5° |
α = 85.309 (4)° | µ = 3.17 mm−1 |
β = 89.164 (4)° | T = 120 K |
γ = 70.645 (3)° | Plate, colourless |
V = 1299.64 (5) Å3 | 0.38 × 0.34 × 0.06 mm |
Rigaku RAXIS conversion diffractometer | 5939 independent reflections |
Radiation source: Sealed Tube | 5633 reflections with I > 2σ(I) |
Graphite Monochromator monochromator | Rint = 0.045 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 27.5°, θmin = 1.5° |
profile data from ω–scans | h = −7→8 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | k = −9→9 |
Tmin = 0.379, Tmax = 0.833 | l = −36→36 |
16781 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.116 | w = 1/[σ2(Fo2) + (0.0487P)2 + 2.2824P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
5939 reflections | Δρmax = 1.79 e Å−3 |
379 parameters | Δρmin = −0.86 e Å−3 |
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 | ||
Br13 | 0.19823 (5) | 0.50533 (5) | 0.21591 (2) | 0.02468 (10) | |
O11 | 0.1612 (3) | 0.1960 (3) | −0.09282 (8) | 0.0234 (5) | |
O14 | 0.7153 (3) | 0.1950 (3) | −0.03480 (8) | 0.0242 (5) | |
O131 | 0.1525 (4) | 0.3349 (4) | 0.04468 (8) | 0.0256 (5) | |
N13 | 0.5020 (4) | 0.3021 (4) | 0.04552 (9) | 0.0199 (5) | |
H13 | 0.6134 | 0.2758 | 0.0272 | 0.024* | |
C12 | 0.1726 (5) | 0.2403 (4) | −0.04764 (10) | 0.0213 (6) | |
H12 | 0.0470 | 0.2721 | −0.0297 | 0.026* | |
C13 | 0.3488 (5) | 0.2431 (4) | −0.02576 (10) | 0.0187 (6) | |
C14 | 0.5473 (5) | 0.1936 (4) | −0.05181 (10) | 0.0182 (6) | |
C14A | 0.5333 (5) | 0.1413 (4) | −0.10070 (10) | 0.0193 (6) | |
C15 | 0.7097 (5) | 0.0851 (4) | −0.12974 (11) | 0.0217 (6) | |
H15 | 0.8429 | 0.0789 | −0.1177 | 0.026* | |
C16 | 0.6925 (5) | 0.0387 (5) | −0.17555 (11) | 0.0258 (7) | |
H16 | 0.8131 | 0.0022 | −0.1951 | 0.031* | |
C17 | 0.4978 (5) | 0.0448 (5) | −0.19347 (11) | 0.0248 (6) | |
H17 | 0.4873 | 0.0114 | −0.2251 | 0.030* | |
C18 | 0.3209 (5) | 0.0991 (4) | −0.16563 (11) | 0.0227 (6) | |
H18 | 0.1882 | 0.1043 | −0.1778 | 0.027* | |
C18A | 0.3417 (5) | 0.1459 (4) | −0.11934 (10) | 0.0203 (6) | |
C131 | 0.5316 (5) | 0.3428 (4) | 0.09256 (10) | 0.0185 (6) | |
C132 | 0.3685 (5) | 0.4007 (4) | 0.12504 (10) | 0.0190 (6) | |
H132 | 0.2278 | 0.4166 | 0.1163 | 0.023* | |
C133 | 0.4191 (5) | 0.4344 (4) | 0.17065 (10) | 0.0203 (6) | |
C134 | 0.6201 (5) | 0.4156 (4) | 0.18499 (11) | 0.0224 (6) | |
H134 | 0.6488 | 0.4403 | 0.2164 | 0.027* | |
C135 | 0.7799 (5) | 0.3588 (5) | 0.15156 (11) | 0.0234 (6) | |
H135 | 0.9200 | 0.3447 | 0.1604 | 0.028* | |
C136 | 0.7379 (5) | 0.3226 (4) | 0.10580 (11) | 0.0217 (6) | |
H136 | 0.8483 | 0.2842 | 0.0835 | 0.026* | |
C137 | 0.3224 (5) | 0.2985 (4) | 0.02492 (10) | 0.0192 (6) | |
Br23 | −0.07137 (5) | 1.08718 (5) | 0.28460 (2) | 0.02772 (10) | |
O21 | −0.0747 (3) | 0.5655 (3) | 0.59280 (7) | 0.0223 (4) | |
O24 | 0.4533 (4) | 0.6676 (3) | 0.54070 (8) | 0.0259 (5) | |
O231 | −0.1079 (4) | 0.8225 (4) | 0.45807 (8) | 0.0276 (5) | |
N23 | 0.2310 (4) | 0.8203 (4) | 0.45937 (9) | 0.0218 (5) | |
H23 | 0.3452 | 0.7817 | 0.4775 | 0.026* | |
C22 | −0.0700 (5) | 0.6501 (4) | 0.54886 (10) | 0.0211 (6) | |
H22 | −0.1952 | 0.6861 | 0.5301 | 0.025* | |
C23 | 0.0968 (5) | 0.6891 (4) | 0.52871 (10) | 0.0202 (6) | |
C24 | 0.2927 (5) | 0.6380 (4) | 0.55608 (11) | 0.0204 (6) | |
C24A | 0.2867 (5) | 0.5466 (4) | 0.60466 (10) | 0.0197 (6) | |
C25 | 0.4612 (5) | 0.4903 (4) | 0.63557 (11) | 0.0224 (6) | |
H25 | 0.5876 | 0.5111 | 0.6254 | 0.027* | |
C26 | 0.4502 (5) | 0.4048 (5) | 0.68070 (11) | 0.0249 (6) | |
H26 | 0.5692 | 0.3671 | 0.7015 | 0.030* | |
C27 | 0.2653 (5) | 0.3732 (5) | 0.69597 (11) | 0.0244 (6) | |
H27 | 0.2594 | 0.3149 | 0.7272 | 0.029* | |
C28 | 0.0911 (5) | 0.4256 (5) | 0.66619 (11) | 0.0231 (6) | |
H28 | −0.0345 | 0.4031 | 0.6763 | 0.028* | |
C28A | 0.1050 (5) | 0.5124 (4) | 0.62079 (10) | 0.0206 (6) | |
C231 | 0.2488 (5) | 0.9119 (4) | 0.41434 (11) | 0.0213 (6) | |
C232 | 0.0957 (5) | 0.9487 (4) | 0.37790 (10) | 0.0212 (6) | |
H232 | −0.0274 | 0.9138 | 0.3826 | 0.025* | |
C233 | 0.1333 (5) | 1.0386 (5) | 0.33470 (11) | 0.0230 (6) | |
C234 | 0.3077 (5) | 1.0949 (5) | 0.32614 (11) | 0.0253 (6) | |
H234 | 0.3257 | 1.1583 | 0.2963 | 0.030* | |
C235 | 0.4566 (5) | 1.0555 (5) | 0.36291 (12) | 0.0259 (7) | |
H235 | 0.5788 | 1.0917 | 0.3580 | 0.031* | |
C236 | 0.4281 (5) | 0.9640 (5) | 0.40655 (11) | 0.0239 (6) | |
H236 | 0.5315 | 0.9367 | 0.4312 | 0.029* | |
C237 | 0.0609 (5) | 0.7833 (4) | 0.47874 (10) | 0.0208 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br13 | 0.02787 (18) | 0.03148 (18) | 0.01601 (16) | −0.01088 (13) | 0.00215 (11) | −0.00539 (12) |
O11 | 0.0200 (11) | 0.0311 (12) | 0.0190 (10) | −0.0076 (9) | −0.0011 (8) | −0.0052 (9) |
O14 | 0.0211 (11) | 0.0323 (12) | 0.0204 (11) | −0.0096 (9) | 0.0003 (8) | −0.0056 (9) |
O131 | 0.0242 (11) | 0.0364 (13) | 0.0187 (10) | −0.0122 (10) | 0.0021 (8) | −0.0068 (9) |
N13 | 0.0217 (13) | 0.0238 (13) | 0.0145 (11) | −0.0073 (10) | 0.0007 (9) | −0.0039 (9) |
C12 | 0.0237 (15) | 0.0239 (15) | 0.0160 (13) | −0.0072 (12) | 0.0009 (11) | −0.0038 (11) |
C13 | 0.0200 (14) | 0.0178 (13) | 0.0183 (13) | −0.0062 (11) | −0.0012 (10) | −0.0016 (10) |
C14 | 0.0221 (14) | 0.0149 (13) | 0.0169 (13) | −0.0054 (11) | −0.0001 (10) | −0.0002 (10) |
C14A | 0.0245 (15) | 0.0157 (13) | 0.0174 (13) | −0.0063 (11) | 0.0011 (11) | −0.0006 (10) |
C15 | 0.0210 (15) | 0.0207 (14) | 0.0227 (15) | −0.0061 (11) | 0.0019 (11) | −0.0015 (11) |
C16 | 0.0332 (17) | 0.0206 (15) | 0.0210 (15) | −0.0051 (12) | 0.0065 (12) | −0.0039 (11) |
C17 | 0.0367 (18) | 0.0205 (15) | 0.0155 (14) | −0.0070 (13) | −0.0001 (12) | −0.0027 (11) |
C18 | 0.0271 (16) | 0.0200 (14) | 0.0190 (14) | −0.0052 (12) | −0.0045 (11) | −0.0008 (11) |
C18A | 0.0265 (15) | 0.0173 (13) | 0.0155 (13) | −0.0052 (11) | −0.0008 (11) | 0.0001 (10) |
C131 | 0.0253 (15) | 0.0158 (13) | 0.0148 (13) | −0.0075 (11) | −0.0018 (11) | 0.0000 (10) |
C132 | 0.0221 (14) | 0.0183 (14) | 0.0164 (13) | −0.0067 (11) | −0.0004 (11) | −0.0004 (10) |
C133 | 0.0247 (15) | 0.0177 (13) | 0.0177 (14) | −0.0055 (11) | −0.0009 (11) | −0.0023 (10) |
C134 | 0.0292 (16) | 0.0195 (14) | 0.0180 (14) | −0.0069 (12) | −0.0052 (11) | −0.0024 (11) |
C135 | 0.0196 (15) | 0.0237 (15) | 0.0276 (16) | −0.0077 (12) | −0.0059 (11) | −0.0026 (12) |
C136 | 0.0212 (15) | 0.0223 (15) | 0.0217 (14) | −0.0072 (11) | 0.0006 (11) | −0.0016 (11) |
C137 | 0.0226 (14) | 0.0177 (14) | 0.0169 (13) | −0.0059 (11) | −0.0011 (11) | −0.0016 (10) |
Br23 | 0.02983 (19) | 0.03229 (19) | 0.01703 (16) | −0.00573 (13) | −0.00026 (12) | 0.00149 (12) |
O21 | 0.0225 (11) | 0.0276 (11) | 0.0171 (10) | −0.0087 (9) | −0.0008 (8) | −0.0010 (8) |
O24 | 0.0219 (11) | 0.0330 (13) | 0.0234 (11) | −0.0108 (9) | −0.0011 (8) | 0.0012 (9) |
O231 | 0.0235 (12) | 0.0375 (13) | 0.0202 (11) | −0.0089 (10) | −0.0036 (9) | 0.0018 (9) |
N23 | 0.0230 (13) | 0.0256 (13) | 0.0151 (11) | −0.0061 (10) | −0.0028 (9) | 0.0005 (10) |
C22 | 0.0247 (15) | 0.0206 (14) | 0.0169 (13) | −0.0057 (11) | 0.0007 (11) | −0.0039 (11) |
C23 | 0.0229 (15) | 0.0192 (14) | 0.0164 (13) | −0.0038 (11) | −0.0002 (11) | −0.0029 (11) |
C24 | 0.0218 (15) | 0.0175 (13) | 0.0203 (14) | −0.0039 (11) | 0.0002 (11) | −0.0040 (11) |
C24A | 0.0220 (14) | 0.0170 (13) | 0.0192 (14) | −0.0046 (11) | 0.0007 (11) | −0.0041 (10) |
C25 | 0.0223 (15) | 0.0206 (14) | 0.0230 (15) | −0.0046 (11) | −0.0018 (11) | −0.0048 (11) |
C26 | 0.0281 (16) | 0.0216 (15) | 0.0228 (15) | −0.0046 (12) | −0.0040 (12) | −0.0046 (12) |
C27 | 0.0324 (17) | 0.0221 (15) | 0.0160 (14) | −0.0056 (12) | 0.0003 (12) | −0.0012 (11) |
C28 | 0.0262 (16) | 0.0231 (15) | 0.0196 (14) | −0.0072 (12) | 0.0022 (11) | −0.0035 (11) |
C28A | 0.0213 (14) | 0.0201 (14) | 0.0188 (14) | −0.0039 (11) | −0.0013 (11) | −0.0042 (11) |
C231 | 0.0247 (15) | 0.0174 (14) | 0.0191 (14) | −0.0030 (11) | 0.0021 (11) | −0.0026 (11) |
C232 | 0.0245 (15) | 0.0185 (14) | 0.0183 (14) | −0.0039 (11) | 0.0022 (11) | −0.0018 (11) |
C233 | 0.0219 (15) | 0.0219 (15) | 0.0204 (14) | −0.0007 (11) | 0.0027 (11) | −0.0026 (11) |
C234 | 0.0273 (16) | 0.0222 (15) | 0.0229 (15) | −0.0040 (12) | 0.0069 (12) | −0.0010 (12) |
C235 | 0.0272 (16) | 0.0223 (15) | 0.0281 (16) | −0.0076 (12) | 0.0073 (12) | −0.0060 (12) |
C236 | 0.0240 (15) | 0.0225 (15) | 0.0245 (15) | −0.0065 (12) | 0.0006 (12) | −0.0039 (12) |
C237 | 0.0247 (15) | 0.0194 (14) | 0.0169 (13) | −0.0050 (11) | −0.0003 (11) | −0.0030 (11) |
Br13—C133 | 1.909 (3) | Br23—C233 | 1.913 (3) |
O11—C12 | 1.344 (4) | O21—C22 | 1.339 (4) |
O11—C18A | 1.376 (4) | O21—C28A | 1.380 (4) |
O14—C14 | 1.240 (4) | O24—C24 | 1.238 (4) |
O131—C137 | 1.223 (4) | O231—C237 | 1.221 (4) |
N13—C137 | 1.359 (4) | N23—C237 | 1.359 (4) |
N13—C131 | 1.408 (4) | N23—C231 | 1.404 (4) |
N13—H13 | 0.8800 | N23—H23 | 0.8800 |
C12—C13 | 1.352 (4) | C22—C23 | 1.354 (4) |
C12—H12 | 0.9500 | C22—H22 | 0.9500 |
C13—C14 | 1.467 (4) | C23—C24 | 1.460 (4) |
C13—C137 | 1.503 (4) | C23—C237 | 1.497 (4) |
C14—C14A | 1.467 (4) | C24—C24A | 1.475 (4) |
C14A—C18A | 1.390 (4) | C24A—C28A | 1.391 (4) |
C14A—C15 | 1.397 (4) | C24A—C25 | 1.399 (4) |
C15—C16 | 1.373 (4) | C25—C26 | 1.378 (5) |
C15—H15 | 0.9500 | C25—H25 | 0.9500 |
C16—C17 | 1.398 (5) | C26—C27 | 1.397 (5) |
C16—H16 | 0.9500 | C26—H26 | 0.9500 |
C17—C18 | 1.379 (5) | C27—C28 | 1.380 (5) |
C17—H17 | 0.9500 | C27—H27 | 0.9500 |
C18—C18A | 1.391 (4) | C28—C28A | 1.393 (4) |
C18—H18 | 0.9500 | C28—H28 | 0.9500 |
C131—C132 | 1.395 (4) | C231—C236 | 1.392 (5) |
C131—C136 | 1.402 (4) | C231—C232 | 1.409 (4) |
C132—C133 | 1.391 (4) | C232—C233 | 1.392 (4) |
C132—H132 | 0.9500 | C232—H232 | 0.9500 |
C133—C134 | 1.379 (5) | C233—C234 | 1.380 (5) |
C134—C135 | 1.397 (5) | C234—C235 | 1.395 (5) |
C134—H134 | 0.9500 | C234—H234 | 0.9500 |
C135—C136 | 1.384 (4) | C235—C236 | 1.389 (5) |
C135—H135 | 0.9500 | C235—H235 | 0.9500 |
C136—H136 | 0.9500 | C236—H236 | 0.9500 |
C12—O11—C18A | 118.6 (2) | C22—O21—C28A | 118.1 (2) |
C137—N13—C131 | 128.0 (3) | C237—N23—C231 | 128.6 (3) |
C137—N13—H13 | 116.0 | C237—N23—H23 | 115.7 |
C131—N13—H13 | 116.0 | C231—N23—H23 | 115.7 |
O11—C12—C13 | 125.2 (3) | O21—C22—C23 | 126.0 (3) |
O11—C12—H12 | 117.4 | O21—C22—H22 | 117.0 |
C13—C12—H12 | 117.4 | C23—C22—H22 | 117.0 |
C12—C13—C14 | 119.6 (3) | C22—C23—C24 | 119.3 (3) |
C12—C13—C137 | 115.5 (3) | C22—C23—C237 | 115.3 (3) |
C14—C13—C137 | 124.9 (3) | C24—C23—C237 | 125.4 (3) |
O14—C14—C13 | 123.9 (3) | O24—C24—C23 | 124.0 (3) |
O14—C14—C14A | 121.5 (3) | O24—C24—C24A | 121.4 (3) |
C13—C14—C14A | 114.6 (3) | C23—C24—C24A | 114.6 (3) |
C18A—C14A—C15 | 118.1 (3) | C28A—C24A—C25 | 118.1 (3) |
C18A—C14A—C14 | 120.3 (3) | C28A—C24A—C24 | 120.2 (3) |
C15—C14A—C14 | 121.6 (3) | C25—C24A—C24 | 121.7 (3) |
C16—C15—C14A | 120.6 (3) | C26—C25—C24A | 120.2 (3) |
C16—C15—H15 | 119.7 | C26—C25—H25 | 119.9 |
C14A—C15—H15 | 119.7 | C24A—C25—H25 | 119.9 |
C15—C16—C17 | 120.2 (3) | C25—C26—C27 | 120.4 (3) |
C15—C16—H16 | 119.9 | C25—C26—H26 | 119.8 |
C17—C16—H16 | 119.9 | C27—C26—H26 | 119.8 |
C18—C17—C16 | 120.6 (3) | C28—C27—C26 | 120.8 (3) |
C18—C17—H17 | 119.7 | C28—C27—H27 | 119.6 |
C16—C17—H17 | 119.7 | C26—C27—H27 | 119.6 |
C17—C18—C18A | 118.3 (3) | C27—C28—C28A | 117.9 (3) |
C17—C18—H18 | 120.8 | C27—C28—H28 | 121.0 |
C18A—C18—H18 | 120.8 | C28A—C28—H28 | 121.0 |
O11—C18A—C14A | 121.8 (3) | O21—C28A—C24A | 121.8 (3) |
O11—C18A—C18 | 116.0 (3) | O21—C28A—C28 | 115.6 (3) |
C14A—C18A—C18 | 122.2 (3) | C24A—C28A—C28 | 122.6 (3) |
C132—C131—C136 | 120.4 (3) | C236—C231—N23 | 116.9 (3) |
C132—C131—N13 | 123.3 (3) | C236—C231—C232 | 120.5 (3) |
C136—C131—N13 | 116.3 (3) | N23—C231—C232 | 122.5 (3) |
C133—C132—C131 | 117.7 (3) | C233—C232—C231 | 116.8 (3) |
C133—C132—H132 | 121.2 | C233—C232—H232 | 121.6 |
C131—C132—H132 | 121.2 | C231—C232—H232 | 121.6 |
C134—C133—C132 | 123.5 (3) | C234—C233—C232 | 124.0 (3) |
C134—C133—Br13 | 118.6 (2) | C234—C233—Br23 | 118.6 (2) |
C132—C133—Br13 | 117.9 (2) | C232—C233—Br23 | 117.4 (2) |
C133—C134—C135 | 117.5 (3) | C233—C234—C235 | 117.6 (3) |
C133—C134—H134 | 121.3 | C233—C234—H234 | 121.2 |
C135—C134—H134 | 121.3 | C235—C234—H234 | 121.2 |
C136—C135—C134 | 121.2 (3) | C236—C235—C234 | 120.7 (3) |
C136—C135—H135 | 119.4 | C236—C235—H235 | 119.6 |
C134—C135—H135 | 119.4 | C234—C235—H235 | 119.6 |
C135—C136—C131 | 119.7 (3) | C235—C236—C231 | 120.2 (3) |
C135—C136—H136 | 120.2 | C235—C236—H236 | 119.9 |
C131—C136—H136 | 120.2 | C231—C236—H236 | 119.9 |
O131—C137—N13 | 124.8 (3) | O231—C237—N23 | 124.2 (3) |
O131—C137—C13 | 121.3 (3) | O231—C237—C23 | 121.8 (3) |
N13—C137—C13 | 113.8 (3) | N23—C237—C23 | 114.0 (3) |
C18A—O11—C12—C13 | 1.2 (5) | C28A—O21—C22—C23 | 0.2 (4) |
O11—C12—C13—C14 | −0.5 (5) | O21—C22—C23—C24 | −0.4 (5) |
O11—C12—C13—C137 | 179.6 (3) | O21—C22—C23—C237 | 179.5 (3) |
C12—C13—C14—O14 | 179.0 (3) | C22—C23—C24—O24 | 179.9 (3) |
C137—C13—C14—O14 | −1.2 (5) | C237—C23—C24—O24 | 0.0 (5) |
C12—C13—C14—C14A | −0.9 (4) | C22—C23—C24—C24A | −0.2 (4) |
C137—C13—C14—C14A | 179.0 (3) | C237—C23—C24—C24A | 179.9 (3) |
O14—C14—C14A—C18A | −178.3 (3) | O24—C24—C24A—C28A | −179.1 (3) |
C13—C14—C14A—C18A | 1.6 (4) | C23—C24—C24A—C28A | 1.1 (4) |
O14—C14—C14A—C15 | 2.0 (5) | O24—C24—C24A—C25 | 0.3 (4) |
C13—C14—C14A—C15 | −178.2 (3) | C23—C24—C24A—C25 | −179.5 (3) |
C18A—C14A—C15—C16 | 0.9 (5) | C28A—C24A—C25—C26 | −0.4 (4) |
C14—C14A—C15—C16 | −179.3 (3) | C24—C24A—C25—C26 | −179.8 (3) |
C14A—C15—C16—C17 | −0.8 (5) | C24A—C25—C26—C27 | 0.1 (5) |
C15—C16—C17—C18 | 0.6 (5) | C25—C26—C27—C28 | 0.4 (5) |
C16—C17—C18—C18A | −0.4 (5) | C26—C27—C28—C28A | −0.7 (5) |
C12—O11—C18A—C14A | −0.4 (4) | C22—O21—C28A—C24A | 0.7 (4) |
C12—O11—C18A—C18 | 179.2 (3) | C22—O21—C28A—C28 | 179.8 (3) |
C15—C14A—C18A—O11 | 178.8 (3) | C25—C24A—C28A—O21 | 179.2 (3) |
C14—C14A—C18A—O11 | −1.0 (4) | C24—C24A—C28A—O21 | −1.4 (4) |
C15—C14A—C18A—C18 | −0.8 (4) | C25—C24A—C28A—C28 | 0.2 (4) |
C14—C14A—C18A—C18 | 179.4 (3) | C24—C24A—C28A—C28 | 179.6 (3) |
C17—C18—C18A—O11 | −179.0 (3) | C27—C28—C28A—O21 | −178.7 (3) |
C17—C18—C18A—C14A | 0.6 (5) | C27—C28—C28A—C24A | 0.3 (5) |
C137—N13—C131—C132 | −4.7 (5) | C237—N23—C231—C236 | 168.5 (3) |
C137—N13—C131—C136 | 175.4 (3) | C237—N23—C231—C232 | −12.4 (5) |
C136—C131—C132—C133 | −0.8 (4) | C236—C231—C232—C233 | −0.2 (4) |
N13—C131—C132—C133 | 179.3 (3) | N23—C231—C232—C233 | −179.3 (3) |
C131—C132—C133—C134 | 0.7 (5) | C231—C232—C233—C234 | −1.0 (4) |
C131—C132—C133—Br13 | −178.0 (2) | C231—C232—C233—Br23 | 179.4 (2) |
C132—C133—C134—C135 | −0.3 (5) | C232—C233—C234—C235 | 1.3 (5) |
Br13—C133—C134—C135 | 178.4 (2) | Br23—C233—C234—C235 | −179.0 (2) |
C133—C134—C135—C136 | −0.1 (5) | C233—C234—C235—C236 | −0.4 (5) |
C134—C135—C136—C131 | −0.1 (5) | C234—C235—C236—C231 | −0.7 (5) |
C132—C131—C136—C135 | 0.5 (5) | N23—C231—C236—C235 | −179.9 (3) |
N13—C131—C136—C135 | −179.6 (3) | C232—C231—C236—C235 | 1.0 (4) |
C131—N13—C137—O131 | 1.5 (5) | C231—N23—C237—O231 | 2.0 (5) |
C131—N13—C137—C13 | −178.2 (3) | C231—N23—C237—C23 | −177.8 (3) |
C12—C13—C137—O131 | 1.1 (4) | C22—C23—C237—O231 | 0.4 (4) |
C14—C13—C137—O131 | −178.8 (3) | C24—C23—C237—O231 | −179.8 (3) |
C12—C13—C137—N13 | −179.2 (3) | C22—C23—C237—N23 | −179.8 (3) |
C14—C13—C137—N13 | 0.9 (4) | C24—C23—C237—N23 | 0.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O14 | 0.88 | 1.93 | 2.686 (3) | 143 |
N23—H23···O24 | 0.88 | 1.94 | 2.698 (3) | 143 |
C12—H12···O131 | 0.95 | 2.34 | 2.727 (4) | 104 |
C22—H22···O231 | 0.95 | 2.33 | 2.725 (4) | 104 |
C132—H132···O131 | 0.95 | 2.26 | 2.860 (4) | 121 |
C232—H232···O231 | 0.95 | 2.28 | 2.865 (4) | 119 |
C12—H12···O14i | 0.95 | 2.49 | 3.221 (4) | 134 |
C22—H22···O24i | 0.95 | 2.43 | 3.185 (4) | 136 |
C15—H15···O11ii | 0.95 | 2.68 | 3.587 (4) | 160 |
C25—H25···O21ii | 0.95 | 2.58 | 3.530 (4) | 177 |
C136—H136···O131ii | 0.95 | 2.43 | 3.282 (4) | 149 |
C236—H236···O231ii | 0.95 | 2.41 | 3.270 (4) | 151 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
C17H13NO4 | F(000) = 616 |
Mr = 295.28 | Dx = 1.506 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
a = 14.1629 (10) Å | Cell parameters from 15826 reflections |
b = 6.772 (5) Å | θ = 2.6–27.5° |
c = 15.1898 (11) Å | µ = 0.11 mm−1 |
β = 116.607 (11)° | T = 100 K |
V = 1302.6 (10) Å3 | Plate, colourless |
Z = 4 | 0.15 × 0.07 × 0.01 mm |
Rigaku Saturn724+ (2x2 bin mode) diffractometer | 2987 independent reflections |
Graphite Monochromator monochromator | 2617 reflections with I > 2σ(I) |
Detector resolution: 28.5714 pixels mm-1 | Rint = 0.042 |
profile data from ω–scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | h = −18→16 |
Tmin = 0.984, Tmax = 0.999 | k = −8→8 |
16554 measured reflections | l = −19→19 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0587P)2 + 0.664P] where P = (Fo2 + 2Fc2)/3 |
S = 0.92 | (Δ/σ)max = 0.005 |
2987 reflections | Δρmax = 0.39 e Å−3 |
204 parameters | Δρmin = −0.18 e Å−3 |
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 | ||
O1 | 0.61512 (6) | 0.04824 (12) | 0.04192 (6) | 0.0222 (2) | |
O4 | 0.63888 (6) | 0.60878 (12) | 0.15264 (6) | 0.0221 (2) | |
O314 | 0.64113 (7) | 0.68423 (13) | 0.66556 (6) | 0.0260 (2) | |
O3 | 0.61112 (8) | 0.10549 (13) | 0.30685 (7) | 0.0281 (2) | |
N3 | 0.63425 (8) | 0.44104 (15) | 0.31133 (7) | 0.0206 (2) | |
H3 | 0.6347 (12) | 0.541 (3) | 0.2725 (12) | 0.034 (4)* | |
C2 | 0.62017 (9) | 0.08077 (18) | 0.13108 (8) | 0.0207 (2) | |
H2 | 0.6193 | −0.0316 | 0.1681 | 0.025* | |
C3 | 0.62644 (8) | 0.26035 (17) | 0.17274 (8) | 0.0196 (2) | |
C4 | 0.63203 (8) | 0.43834 (17) | 0.12051 (8) | 0.0187 (2) | |
C4A | 0.62683 (8) | 0.40077 (17) | 0.02284 (8) | 0.0192 (2) | |
C5 | 0.62976 (9) | 0.55604 (18) | −0.03704 (9) | 0.0219 (2) | |
H5 | 0.6382 | 0.6881 | −0.0136 | 0.026* | |
C6 | 0.62051 (9) | 0.51790 (19) | −0.12981 (9) | 0.0239 (3) | |
H6 | 0.6233 | 0.6235 | −0.1697 | 0.029* | |
C7 | 0.60702 (9) | 0.32347 (19) | −0.16527 (9) | 0.0241 (3) | |
H7 | 0.5993 | 0.2987 | −0.2297 | 0.029* | |
C8 | 0.60487 (9) | 0.16788 (18) | −0.10756 (9) | 0.0233 (3) | |
H8 | 0.5961 | 0.0361 | −0.1314 | 0.028* | |
C8A | 0.61592 (8) | 0.20886 (17) | −0.01329 (8) | 0.0199 (2) | |
C31 | 0.62381 (9) | 0.25962 (17) | 0.27073 (9) | 0.0206 (2) | |
C311 | 0.63093 (8) | 0.49421 (17) | 0.40033 (8) | 0.0194 (2) | |
C312 | 0.64385 (9) | 0.36073 (18) | 0.47503 (8) | 0.0218 (2) | |
H312 | 0.6515 | 0.2237 | 0.4665 | 0.026* | |
C313 | 0.64547 (9) | 0.42952 (18) | 0.56178 (9) | 0.0221 (2) | |
H313 | 0.6542 | 0.3385 | 0.6125 | 0.027* | |
C314 | 0.63439 (9) | 0.63048 (18) | 0.57565 (8) | 0.0207 (2) | |
C315 | 0.61990 (9) | 0.76285 (17) | 0.50058 (8) | 0.0215 (2) | |
H315 | 0.6110 | 0.8996 | 0.5086 | 0.026* | |
C316 | 0.61854 (9) | 0.69445 (17) | 0.41378 (8) | 0.0208 (2) | |
H316 | 0.6090 | 0.7854 | 0.3629 | 0.025* | |
C317 | 0.62986 (11) | 0.88959 (19) | 0.67957 (9) | 0.0273 (3) | |
H31A | 0.6389 | 0.9118 | 0.7466 | 0.041* | |
H31B | 0.5594 | 0.9338 | 0.6321 | 0.041* | |
H31C | 0.6835 | 0.9643 | 0.6696 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0260 (4) | 0.0173 (4) | 0.0241 (4) | −0.0006 (3) | 0.0119 (3) | −0.0015 (3) |
O4 | 0.0272 (4) | 0.0173 (4) | 0.0224 (4) | −0.0011 (3) | 0.0116 (3) | −0.0010 (3) |
O314 | 0.0354 (5) | 0.0222 (4) | 0.0223 (4) | 0.0018 (4) | 0.0148 (4) | 0.0009 (3) |
O3 | 0.0406 (5) | 0.0187 (4) | 0.0294 (5) | −0.0028 (4) | 0.0195 (4) | 0.0016 (3) |
N3 | 0.0246 (5) | 0.0176 (5) | 0.0194 (5) | −0.0011 (4) | 0.0097 (4) | 0.0011 (4) |
C2 | 0.0205 (5) | 0.0191 (5) | 0.0222 (5) | 0.0002 (4) | 0.0092 (4) | 0.0010 (4) |
C3 | 0.0186 (5) | 0.0182 (5) | 0.0208 (5) | 0.0003 (4) | 0.0077 (4) | 0.0007 (4) |
C4 | 0.0158 (5) | 0.0180 (5) | 0.0205 (5) | 0.0001 (4) | 0.0065 (4) | −0.0002 (4) |
C4A | 0.0166 (5) | 0.0198 (5) | 0.0206 (5) | 0.0007 (4) | 0.0077 (4) | 0.0000 (4) |
C5 | 0.0211 (5) | 0.0204 (5) | 0.0242 (5) | 0.0006 (4) | 0.0100 (4) | 0.0008 (4) |
C6 | 0.0234 (5) | 0.0251 (6) | 0.0240 (6) | 0.0016 (5) | 0.0114 (5) | 0.0033 (5) |
C7 | 0.0224 (5) | 0.0301 (7) | 0.0209 (5) | 0.0009 (5) | 0.0106 (4) | −0.0019 (5) |
C8 | 0.0210 (5) | 0.0241 (6) | 0.0245 (6) | −0.0003 (4) | 0.0100 (4) | −0.0039 (5) |
C8A | 0.0170 (5) | 0.0196 (5) | 0.0227 (5) | 0.0003 (4) | 0.0084 (4) | 0.0002 (4) |
C31 | 0.0192 (5) | 0.0194 (5) | 0.0222 (5) | 0.0001 (4) | 0.0084 (4) | 0.0008 (4) |
C311 | 0.0184 (5) | 0.0203 (5) | 0.0187 (5) | −0.0014 (4) | 0.0077 (4) | −0.0004 (4) |
C312 | 0.0223 (5) | 0.0187 (5) | 0.0231 (6) | −0.0004 (4) | 0.0089 (4) | 0.0017 (4) |
C313 | 0.0236 (6) | 0.0207 (6) | 0.0218 (5) | −0.0001 (4) | 0.0100 (4) | 0.0041 (4) |
C314 | 0.0195 (5) | 0.0230 (6) | 0.0193 (5) | −0.0011 (4) | 0.0085 (4) | −0.0001 (4) |
C315 | 0.0219 (5) | 0.0189 (5) | 0.0226 (5) | 0.0008 (4) | 0.0088 (4) | 0.0002 (4) |
C316 | 0.0217 (5) | 0.0189 (5) | 0.0201 (5) | −0.0005 (4) | 0.0077 (4) | 0.0033 (4) |
C317 | 0.0366 (7) | 0.0231 (6) | 0.0255 (6) | 0.0020 (5) | 0.0166 (5) | −0.0013 (5) |
O1—C2 | 1.3420 (14) | C6—H6 | 0.9500 |
O1—C8A | 1.3767 (15) | C7—C8 | 1.3797 (19) |
O4—C4 | 1.2399 (16) | C7—H7 | 0.9500 |
O314—C314 | 1.3747 (14) | C8—C8A | 1.3969 (16) |
O314—C317 | 1.4266 (18) | C8—H8 | 0.9500 |
O3—C31 | 1.2293 (16) | C311—C316 | 1.3941 (19) |
N3—C31 | 1.3528 (17) | C311—C312 | 1.3971 (16) |
N3—C311 | 1.4201 (15) | C312—C313 | 1.3881 (17) |
N3—H3 | 0.901 (17) | C312—H312 | 0.9500 |
C2—C3 | 1.3553 (18) | C313—C314 | 1.3967 (19) |
C2—H2 | 0.9500 | C313—H313 | 0.9500 |
C3—C4 | 1.4645 (17) | C314—C315 | 1.3916 (17) |
C3—C31 | 1.5055 (16) | C315—C316 | 1.3894 (16) |
C4—C4A | 1.4742 (16) | C315—H315 | 0.9500 |
C4A—C8A | 1.3921 (18) | C316—H316 | 0.9500 |
C4A—C5 | 1.4031 (17) | C317—H31A | 0.9800 |
C5—C6 | 1.3799 (17) | C317—H31B | 0.9800 |
C5—H5 | 0.9500 | C317—H31C | 0.9800 |
C6—C7 | 1.403 (2) | ||
C2—O1—C8A | 118.29 (10) | O1—C8A—C8 | 116.09 (11) |
C314—O314—C317 | 116.34 (9) | C4A—C8A—C8 | 122.10 (11) |
C31—N3—C311 | 128.37 (10) | O3—C31—N3 | 125.15 (11) |
C31—N3—H3 | 114.6 (10) | O3—C31—C3 | 121.16 (11) |
C311—N3—H3 | 116.4 (10) | N3—C31—C3 | 113.68 (10) |
O1—C2—C3 | 125.53 (11) | C316—C311—C312 | 119.31 (11) |
O1—C2—H2 | 117.2 | C316—C311—N3 | 116.50 (10) |
C3—C2—H2 | 117.2 | C312—C311—N3 | 124.13 (11) |
C2—C3—C4 | 119.58 (11) | C313—C312—C311 | 119.62 (12) |
C2—C3—C31 | 115.67 (10) | C313—C312—H312 | 120.2 |
C4—C3—C31 | 124.72 (10) | C311—C312—H312 | 120.2 |
O4—C4—C3 | 124.51 (11) | C312—C313—C314 | 121.00 (11) |
O4—C4—C4A | 121.10 (10) | C312—C313—H313 | 119.5 |
C3—C4—C4A | 114.37 (10) | C314—C313—H313 | 119.5 |
C8A—C4A—C5 | 118.31 (11) | O314—C314—C315 | 124.24 (12) |
C8A—C4A—C4 | 120.31 (10) | O314—C314—C313 | 116.45 (10) |
C5—C4A—C4 | 121.36 (11) | C315—C314—C313 | 119.30 (11) |
C6—C5—C4A | 120.33 (11) | C316—C315—C314 | 119.81 (12) |
C6—C5—H5 | 119.8 | C316—C315—H315 | 120.1 |
C4A—C5—H5 | 119.8 | C314—C315—H315 | 120.1 |
C5—C6—C7 | 120.14 (11) | C315—C316—C311 | 120.94 (11) |
C5—C6—H6 | 119.9 | C315—C316—H316 | 119.5 |
C7—C6—H6 | 119.9 | C311—C316—H316 | 119.5 |
C8—C7—C6 | 120.71 (12) | O314—C317—H31A | 109.5 |
C8—C7—H7 | 119.6 | O314—C317—H31B | 109.5 |
C6—C7—H7 | 119.6 | H31A—C317—H31B | 109.5 |
C7—C8—C8A | 118.38 (12) | O314—C317—H31C | 109.5 |
C7—C8—H8 | 120.8 | H31A—C317—H31C | 109.5 |
C8A—C8—H8 | 120.8 | H31B—C317—H31C | 109.5 |
O1—C8A—C4A | 121.81 (11) | ||
C8A—O1—C2—C3 | −0.22 (17) | C7—C8—C8A—O1 | −178.88 (10) |
O1—C2—C3—C4 | −2.25 (18) | C7—C8—C8A—C4A | 1.28 (17) |
O1—C2—C3—C31 | 176.01 (10) | C311—N3—C31—O3 | −1.40 (19) |
C2—C3—C4—O4 | −179.33 (11) | C311—N3—C31—C3 | 177.21 (10) |
C31—C3—C4—O4 | 2.58 (18) | C2—C3—C31—O3 | −3.68 (17) |
C2—C3—C4—C4A | 1.79 (15) | C4—C3—C31—O3 | 174.48 (11) |
C31—C3—C4—C4A | −176.31 (10) | C2—C3—C31—N3 | 177.65 (10) |
O4—C4—C4A—C8A | −178.03 (10) | C4—C3—C31—N3 | −4.19 (16) |
C3—C4—C4A—C8A | 0.89 (15) | C31—N3—C311—C316 | −165.10 (11) |
O4—C4—C4A—C5 | 0.21 (17) | C31—N3—C311—C312 | 17.83 (18) |
C3—C4—C4A—C5 | 179.13 (10) | C316—C311—C312—C313 | −0.79 (17) |
C8A—C4A—C5—C6 | 0.89 (17) | N3—C311—C312—C313 | 176.21 (10) |
C4—C4A—C5—C6 | −177.38 (10) | C311—C312—C313—C314 | −0.02 (17) |
C4A—C5—C6—C7 | 0.64 (18) | C317—O314—C314—C315 | 1.46 (16) |
C5—C6—C7—C8 | −1.26 (18) | C317—O314—C314—C313 | 179.96 (11) |
C6—C7—C8—C8A | 0.31 (17) | C312—C313—C314—O314 | −177.58 (10) |
C2—O1—C8A—C4A | 3.11 (15) | C312—C313—C314—C315 | 1.00 (17) |
C2—O1—C8A—C8 | −176.72 (9) | O314—C314—C315—C316 | 177.30 (10) |
C5—C4A—C8A—O1 | 178.30 (10) | C313—C314—C315—C316 | −1.16 (17) |
C4—C4A—C8A—O1 | −3.41 (16) | C314—C315—C316—C311 | 0.36 (17) |
C5—C4A—C8A—C8 | −1.88 (16) | C312—C311—C316—C315 | 0.63 (17) |
C4—C4A—C8A—C8 | 176.42 (10) | N3—C311—C316—C315 | −176.60 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4 | 0.901 (17) | 1.903 (16) | 2.6919 (13) | 145.0 (15) |
C312—H312···O3 | 0.95 | 2.37 | 2.9441 (17) | 119 |
C2—H2···O4i | 0.95 | 2.47 | 3.212 (3) | 134 |
C316—H316···O3ii | 0.95 | 2.33 | 3.201 (2) | 152 |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
C17H13NO3 | Z = 2 |
Mr = 279.28 | F(000) = 292 |
Triclinic, P1 | Dx = 1.418 Mg m−3 |
a = 6.6106 (5) Å | Mo Kα radiation, λ = 0.71075 Å |
b = 7.0143 (5) Å | Cell parameters from 8940 reflections |
c = 15.3749 (11) Å | θ = 3.2–27.5° |
α = 91.444 (6)° | µ = 0.10 mm−1 |
β = 95.238 (6)° | T = 100 K |
γ = 112.551 (8)° | Plate, colourless |
V = 654.25 (9) Å3 | 0.16 × 0.09 × 0.02 mm |
Rigaku Saturn724+ (2x2 bin mode) diffractometer | 2986 independent reflections |
Radiation source: Sealed Tube | 2645 reflections with I > 2σ(I) |
Mirrors monochromator | Rint = 0.035 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.6°, θmin = 3.2° |
profile data from ω–scans | h = −8→8 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | k = −9→8 |
Tmin = 0.985, Tmax = 0.998 | l = −19→19 |
9400 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0687P)2 + 0.1454P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.004 |
2986 reflections | Δρmax = 0.33 e Å−3 |
196 parameters | Δρmin = −0.26 e Å−3 |
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 | ||
O1 | 0.82225 (13) | 0.28691 (13) | 0.53040 (5) | 0.0234 (2) | |
O3 | 0.75229 (13) | 0.36263 (14) | 0.27108 (6) | 0.0285 (2) | |
O4 | 0.21316 (13) | 0.23497 (13) | 0.42176 (5) | 0.0245 (2) | |
N3 | 0.38310 (16) | 0.28969 (15) | 0.26610 (6) | 0.0217 (2) | |
H3 | 0.282 (3) | 0.276 (3) | 0.3036 (11) | 0.043 (5)* | |
C2 | 0.78092 (18) | 0.30515 (17) | 0.44464 (8) | 0.0220 (2) | |
H2 | 0.8985 | 0.3286 | 0.4097 | 0.032 (4)* | |
C3 | 0.58640 (17) | 0.29301 (16) | 0.40379 (7) | 0.0197 (2) | |
C4 | 0.39777 (18) | 0.24920 (16) | 0.45362 (7) | 0.0198 (2) | |
C4A | 0.44234 (18) | 0.22256 (16) | 0.54690 (7) | 0.0197 (2) | |
C5 | 0.27553 (19) | 0.17259 (18) | 0.60293 (8) | 0.0230 (2) | |
H5 | 0.1298 | 0.1528 | 0.5803 | 0.028* | |
C6 | 0.3225 (2) | 0.15213 (19) | 0.69049 (8) | 0.0264 (3) | |
H6 | 0.2086 | 0.1160 | 0.7279 | 0.032* | |
C7 | 0.5381 (2) | 0.18446 (19) | 0.72459 (8) | 0.0274 (3) | |
H7 | 0.5697 | 0.1734 | 0.7853 | 0.033* | |
C8 | 0.7048 (2) | 0.23214 (18) | 0.67093 (8) | 0.0256 (3) | |
H8 | 0.8509 | 0.2541 | 0.6939 | 0.031* | |
C8A | 0.65314 (18) | 0.24727 (17) | 0.58227 (8) | 0.0210 (2) | |
C311 | 0.32431 (18) | 0.28817 (17) | 0.17506 (7) | 0.0222 (2) | |
C312 | 0.4436 (2) | 0.24849 (19) | 0.11163 (8) | 0.0271 (3) | |
H312 | 0.5759 | 0.2289 | 0.1284 | 0.032* | |
C313 | 0.3675 (2) | 0.23785 (19) | 0.02375 (8) | 0.0296 (3) | |
H313 | 0.4502 | 0.2118 | −0.0191 | 0.036* | |
C314 | 0.1735 (2) | 0.26422 (18) | −0.00357 (8) | 0.0273 (3) | |
C315 | 0.0570 (2) | 0.30296 (19) | 0.06084 (8) | 0.0263 (3) | |
H315 | −0.0762 | 0.3208 | 0.0440 | 0.032* | |
C316 | 0.13057 (19) | 0.31625 (18) | 0.14920 (8) | 0.0241 (3) | |
H316 | 0.0489 | 0.3445 | 0.1919 | 0.029* | |
C317 | 0.0915 (2) | 0.2486 (2) | −0.09925 (8) | 0.0335 (3) | |
H31C | −0.0432 | 0.2766 | −0.1057 | 0.050* | |
H31D | 0.0598 | 0.1090 | −0.1244 | 0.050* | |
H31E | 0.2045 | 0.3500 | −0.1299 | 0.050* | |
C31 | 0.58315 (18) | 0.31961 (17) | 0.30716 (8) | 0.0216 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0174 (4) | 0.0264 (4) | 0.0264 (4) | 0.0091 (3) | 0.0004 (3) | 0.0004 (3) |
O3 | 0.0202 (4) | 0.0359 (5) | 0.0297 (5) | 0.0098 (4) | 0.0080 (3) | 0.0047 (4) |
O4 | 0.0174 (4) | 0.0332 (5) | 0.0252 (4) | 0.0120 (3) | 0.0028 (3) | 0.0048 (3) |
N3 | 0.0194 (5) | 0.0256 (5) | 0.0213 (5) | 0.0096 (4) | 0.0042 (4) | 0.0033 (4) |
C2 | 0.0188 (5) | 0.0203 (5) | 0.0261 (6) | 0.0068 (4) | 0.0027 (4) | 0.0001 (4) |
C3 | 0.0182 (5) | 0.0166 (5) | 0.0245 (6) | 0.0069 (4) | 0.0033 (4) | 0.0010 (4) |
C4 | 0.0178 (5) | 0.0172 (5) | 0.0249 (5) | 0.0073 (4) | 0.0021 (4) | 0.0013 (4) |
C4A | 0.0201 (5) | 0.0168 (5) | 0.0226 (5) | 0.0080 (4) | 0.0011 (4) | 0.0001 (4) |
C5 | 0.0222 (5) | 0.0221 (5) | 0.0264 (6) | 0.0104 (4) | 0.0031 (4) | 0.0011 (4) |
C6 | 0.0296 (6) | 0.0267 (6) | 0.0254 (6) | 0.0129 (5) | 0.0060 (5) | 0.0014 (4) |
C7 | 0.0343 (6) | 0.0268 (6) | 0.0221 (5) | 0.0140 (5) | −0.0007 (5) | −0.0006 (4) |
C8 | 0.0251 (6) | 0.0250 (6) | 0.0267 (6) | 0.0114 (5) | −0.0042 (4) | −0.0026 (4) |
C8A | 0.0202 (5) | 0.0175 (5) | 0.0257 (6) | 0.0078 (4) | 0.0020 (4) | −0.0004 (4) |
C311 | 0.0224 (5) | 0.0203 (5) | 0.0218 (5) | 0.0058 (4) | 0.0036 (4) | 0.0020 (4) |
C312 | 0.0245 (6) | 0.0278 (6) | 0.0285 (6) | 0.0091 (5) | 0.0059 (4) | 0.0011 (5) |
C313 | 0.0313 (6) | 0.0297 (6) | 0.0253 (6) | 0.0077 (5) | 0.0102 (5) | −0.0003 (5) |
C314 | 0.0318 (6) | 0.0217 (5) | 0.0228 (6) | 0.0040 (5) | 0.0037 (5) | 0.0019 (4) |
C315 | 0.0269 (6) | 0.0256 (6) | 0.0253 (6) | 0.0093 (5) | 0.0012 (4) | 0.0025 (4) |
C316 | 0.0245 (6) | 0.0252 (6) | 0.0233 (6) | 0.0099 (5) | 0.0044 (4) | 0.0020 (4) |
C317 | 0.0425 (7) | 0.0301 (6) | 0.0224 (6) | 0.0083 (6) | 0.0029 (5) | 0.0009 (5) |
C31 | 0.0201 (5) | 0.0198 (5) | 0.0257 (6) | 0.0078 (4) | 0.0047 (4) | 0.0026 (4) |
O1—C2 | 1.3414 (14) | C7—C8 | 1.3799 (18) |
O1—C8A | 1.3779 (14) | C7—H7 | 0.9500 |
O3—C31 | 1.2296 (14) | C8—C8A | 1.3914 (16) |
O4—C4 | 1.2386 (13) | C8—H8 | 0.9500 |
N3—C31 | 1.3488 (14) | C311—C316 | 1.3935 (16) |
N3—C311 | 1.4168 (14) | C311—C312 | 1.3948 (16) |
N3—H3 | 0.900 (18) | C312—C313 | 1.3878 (17) |
C2—C3 | 1.3494 (15) | C312—H312 | 0.9500 |
C2—H2 | 0.9500 | C313—C314 | 1.3939 (18) |
C3—C4 | 1.4590 (15) | C313—H313 | 0.9500 |
C3—C31 | 1.5013 (16) | C314—C315 | 1.3907 (17) |
C4—C4A | 1.4688 (15) | C314—C317 | 1.5068 (16) |
C4A—C8A | 1.3926 (15) | C315—C316 | 1.3889 (16) |
C4A—C5 | 1.4047 (16) | C315—H315 | 0.9500 |
C5—C6 | 1.3773 (16) | C316—H316 | 0.9500 |
C5—H5 | 0.9500 | C317—H31C | 0.9800 |
C6—C7 | 1.4023 (17) | C317—H31D | 0.9800 |
C6—H6 | 0.9500 | C317—H31E | 0.9800 |
C2—O1—C8A | 118.52 (9) | O1—C8A—C4A | 121.24 (10) |
C31—N3—C311 | 127.52 (10) | C8—C8A—C4A | 122.38 (11) |
C31—N3—H3 | 112.7 (11) | C316—C311—C312 | 119.49 (11) |
C311—N3—H3 | 119.7 (11) | C316—C311—N3 | 117.29 (10) |
O1—C2—C3 | 125.51 (10) | C312—C311—N3 | 123.11 (10) |
O1—C2—H2 | 117.2 | C313—C312—C311 | 119.44 (11) |
C3—C2—H2 | 117.2 | C313—C312—H312 | 120.3 |
C2—C3—C4 | 119.57 (10) | C311—C312—H312 | 120.3 |
C2—C3—C31 | 115.13 (10) | C312—C313—C314 | 122.04 (11) |
C4—C3—C31 | 125.27 (10) | C312—C313—H313 | 119.0 |
O4—C4—C3 | 124.11 (10) | C314—C313—H313 | 119.0 |
O4—C4—C4A | 121.31 (10) | C315—C314—C313 | 117.49 (11) |
C3—C4—C4A | 114.58 (9) | C315—C314—C317 | 121.24 (12) |
C8A—C4A—C5 | 118.12 (10) | C313—C314—C317 | 121.26 (12) |
C8A—C4A—C4 | 120.48 (10) | C316—C315—C314 | 121.62 (11) |
C5—C4A—C4 | 121.39 (10) | C316—C315—H315 | 119.2 |
C6—C5—C4A | 120.25 (11) | C314—C315—H315 | 119.2 |
C6—C5—H5 | 119.9 | C315—C316—C311 | 119.91 (11) |
C4A—C5—H5 | 119.9 | C315—C316—H316 | 120.0 |
C5—C6—C7 | 120.20 (11) | C311—C316—H316 | 120.0 |
C5—C6—H6 | 119.9 | C314—C317—H31C | 109.5 |
C7—C6—H6 | 119.9 | C314—C317—H31D | 109.5 |
C8—C7—C6 | 120.76 (11) | H31C—C317—H31D | 109.5 |
C8—C7—H7 | 119.6 | C314—C317—H31E | 109.5 |
C6—C7—H7 | 119.6 | H31C—C317—H31E | 109.5 |
C7—C8—C8A | 118.23 (11) | H31D—C317—H31E | 109.5 |
C7—C8—H8 | 120.9 | O3—C31—N3 | 124.93 (11) |
C8A—C8—H8 | 120.9 | O3—C31—C3 | 120.73 (10) |
O1—C8A—C8 | 116.38 (10) | N3—C31—C3 | 114.33 (9) |
C8A—O1—C2—C3 | 1.72 (17) | C4—C4A—C8A—O1 | −3.26 (16) |
O1—C2—C3—C4 | −2.37 (17) | C5—C4A—C8A—C8 | −2.55 (17) |
O1—C2—C3—C31 | 179.75 (9) | C4—C4A—C8A—C8 | 177.21 (10) |
C2—C3—C4—O4 | −179.91 (10) | C31—N3—C311—C316 | −161.26 (11) |
C31—C3—C4—O4 | −2.27 (18) | C31—N3—C311—C312 | 22.52 (18) |
C2—C3—C4—C4A | 0.18 (15) | C316—C311—C312—C313 | 0.07 (18) |
C31—C3—C4—C4A | 177.83 (9) | N3—C311—C312—C313 | 176.21 (10) |
O4—C4—C4A—C8A | −177.42 (10) | C311—C312—C313—C314 | −0.46 (19) |
C3—C4—C4A—C8A | 2.48 (15) | C312—C313—C314—C315 | 0.26 (19) |
O4—C4—C4A—C5 | 2.32 (17) | C312—C313—C314—C317 | −178.96 (11) |
C3—C4—C4A—C5 | −177.77 (10) | C313—C314—C315—C316 | 0.35 (18) |
C8A—C4A—C5—C6 | 0.93 (17) | C317—C314—C315—C316 | 179.57 (11) |
C4—C4A—C5—C6 | −178.83 (10) | C314—C315—C316—C311 | −0.73 (18) |
C4A—C5—C6—C7 | 1.07 (18) | C312—C311—C316—C315 | 0.51 (18) |
C5—C6—C7—C8 | −1.57 (18) | N3—C311—C316—C315 | −175.85 (10) |
C6—C7—C8—C8A | 0.02 (18) | C311—N3—C31—O3 | 4.35 (19) |
C2—O1—C8A—C8 | −179.25 (9) | C311—N3—C31—C3 | −174.78 (10) |
C2—O1—C8A—C4A | 1.19 (15) | C2—C3—C31—O3 | −4.51 (16) |
C7—C8—C8A—O1 | −177.48 (10) | C4—C3—C31—O3 | 177.76 (10) |
C7—C8—C8A—C4A | 2.07 (17) | C2—C3—C31—N3 | 174.67 (10) |
C5—C4A—C8A—O1 | 176.98 (10) | C4—C3—C31—N3 | −3.07 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O4 | 0.900 (18) | 1.916 (18) | 2.7098 (13) | 146.1 (15) |
C312—H312···O3 | 0.95 | 2.37 | 2.9240 (16) | 116 |
C2—H2···O4i | 0.95 | 2.40 | 3.1280 (14) | 133 |
C316—H316···O3ii | 0.95 | 2.44 | 3.3644 (14) | 164 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z. |
C16H11NO4 | Z = 4 |
Mr = 281.26 | F(000) = 584 |
Triclinic, P1 | Dx = 1.494 Mg m−3 |
a = 7.0756 (5) Å | Mo Kα radiation, λ = 0.71075 Å |
b = 12.5125 (9) Å | Cell parameters from 14545 reflections |
c = 14.2944 (10) Å | θ = 2.9–27.5° |
α = 86.267 (8)° | µ = 0.11 mm−1 |
β = 83.839 (8)° | T = 100 K |
γ = 84.588 (8)° | Block, colourless |
V = 1250.68 (16) Å3 | 0.14 × 0.04 × 0.04 mm |
Rigaku Saturn724+ (2x2 bin mode) diffractometer | 5627 measured reflections |
Radiation source: Sealed Tube | 5627 independent reflections |
Mirrors monochromator | 4343 reflections with I > 2σ(I) |
Detector resolution: 28.5714 pixels mm-1 | θmax = 27.6°, θmin = 2.9° |
profile data from ω–scans | h = −9→9 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | k = −16→16 |
Tmin = 0.985, Tmax = 0.996 | l = −4→18 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.252 | w = 1/[σ2(Fo2) + (0.1127P)2 + 0.9725P] where P = (Fo2 + 2Fc2)/3 |
S = 1.18 | (Δ/σ)max < 0.001 |
5627 reflections | Δρmax = 0.41 e Å−3 |
392 parameters | Δρmin = −0.38 e Å−3 |
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. Refined as a 2-component twin. 2-axis (0 0 1) [-1 0 5], Angle () [] = 3.22 Deg, Freq = 48 ************* (-1.000 0.000 0.000) (h1) (h2) Nr Overlap = 1085 (0.000 - 1.000 0.000) * (k1) = (k2) BASF = 0.40 (-0.412 - 0.127 1.000) (l1) (l2) DEL-R =-0.068 |
x | y | z | Uiso*/Ueq | ||
O11 | 0.8738 (4) | −0.0689 (2) | −0.21765 (17) | 0.0295 (6) | |
O13 | 0.7750 (4) | −0.0154 (2) | 0.06141 (17) | 0.0339 (6) | |
O14 | 0.5168 (4) | 0.1945 (2) | −0.14104 (17) | 0.0311 (6) | |
O114 | 0.4248 (4) | 0.2817 (2) | 0.40213 (18) | 0.0379 (7) | |
H114 | 0.353 (8) | 0.344 (5) | 0.412 (4) | 0.057* | |
N13 | 0.5991 (4) | 0.1441 (2) | 0.0370 (2) | 0.0270 (6) | |
H13 | 0.546 (6) | 0.188 (3) | −0.011 (3) | 0.032* | |
C12 | 0.8371 (5) | −0.0430 (3) | −0.1277 (2) | 0.0280 (7) | |
H12 | 0.8983 | −0.0883 | −0.0820 | 0.034* | |
C13 | 0.7215 (5) | 0.0413 (3) | −0.0963 (2) | 0.0254 (7) | |
C14 | 0.6239 (5) | 0.1147 (3) | −0.1638 (2) | 0.0258 (7) | |
C14A | 0.6635 (5) | 0.0847 (3) | −0.2619 (2) | 0.0259 (7) | |
C15 | 0.5814 (5) | 0.1460 (3) | −0.3350 (3) | 0.0311 (8) | |
H15 | 0.4998 | 0.2090 | −0.3212 | 0.037* | |
C16 | 0.6177 (6) | 0.1161 (3) | −0.4271 (3) | 0.0342 (8) | |
H16 | 0.5602 | 0.1578 | −0.4761 | 0.041* | |
C17 | 0.7399 (6) | 0.0235 (3) | −0.4478 (3) | 0.0360 (8) | |
H17 | 0.7644 | 0.0031 | −0.5111 | 0.043* | |
C18 | 0.8250 (5) | −0.0382 (3) | −0.3772 (3) | 0.0330 (8) | |
H18 | 0.9083 | −0.1005 | −0.3910 | 0.040* | |
C18A | 0.7842 (5) | −0.0058 (3) | −0.2852 (2) | 0.0274 (7) | |
C111 | 0.5570 (5) | 0.1758 (3) | 0.1308 (2) | 0.0252 (7) | |
C112 | 0.6421 (5) | 0.1236 (3) | 0.2077 (2) | 0.0282 (7) | |
H112 | 0.7315 | 0.0626 | 0.1985 | 0.034* | |
C113 | 0.5955 (5) | 0.1611 (3) | 0.2966 (2) | 0.0294 (7) | |
H113 | 0.6544 | 0.1259 | 0.3482 | 0.035* | |
C114 | 0.4642 (5) | 0.2494 (3) | 0.3121 (2) | 0.0288 (7) | |
C115 | 0.3799 (5) | 0.3017 (3) | 0.2363 (3) | 0.0295 (8) | |
H115 | 0.2910 | 0.3628 | 0.2458 | 0.035* | |
C116 | 0.4259 (5) | 0.2644 (3) | 0.1463 (2) | 0.0288 (7) | |
H116 | 0.3669 | 0.2999 | 0.0948 | 0.035* | |
C131 | 0.7013 (5) | 0.0543 (3) | 0.0076 (2) | 0.0256 (7) | |
O21 | 0.3577 (4) | 0.4196 (2) | 0.68202 (17) | 0.0291 (6) | |
O23 | 0.2438 (4) | 0.4764 (2) | 0.40951 (18) | 0.0340 (6) | |
O24 | 0.0699 (4) | 0.7076 (2) | 0.61185 (18) | 0.0329 (6) | |
O214 | −0.0597 (4) | 0.7840 (2) | 0.07027 (17) | 0.0335 (6) | |
H214 | −0.127 (7) | 0.846 (4) | 0.061 (4) | 0.050* | |
N23 | 0.1222 (4) | 0.6485 (2) | 0.4321 (2) | 0.0271 (6) | |
H23 | 0.083 (6) | 0.697 (4) | 0.476 (3) | 0.033* | |
C22 | 0.3224 (5) | 0.4471 (3) | 0.5933 (2) | 0.0279 (7) | |
H22 | 0.3692 | 0.3977 | 0.5467 | 0.033* | |
C23 | 0.2255 (5) | 0.5396 (3) | 0.5643 (2) | 0.0251 (7) | |
C24 | 0.1521 (5) | 0.6191 (3) | 0.6325 (2) | 0.0269 (7) | |
C24A | 0.1811 (5) | 0.5846 (3) | 0.7308 (2) | 0.0265 (7) | |
C25 | 0.1072 (5) | 0.6482 (3) | 0.8058 (2) | 0.0292 (7) | |
H25 | 0.0377 | 0.7154 | 0.7934 | 0.035* | |
C26 | 0.1346 (6) | 0.6140 (3) | 0.8973 (3) | 0.0339 (8) | |
H26 | 0.0833 | 0.6574 | 0.9476 | 0.041* | |
C27 | 0.2386 (6) | 0.5147 (3) | 0.9163 (3) | 0.0358 (9) | |
H27 | 0.2567 | 0.4913 | 0.9796 | 0.043* | |
C28 | 0.3146 (6) | 0.4509 (3) | 0.8432 (3) | 0.0310 (8) | |
H28 | 0.3866 | 0.3844 | 0.8552 | 0.037* | |
C28A | 0.2824 (5) | 0.4874 (3) | 0.7521 (2) | 0.0269 (7) | |
C211 | 0.0775 (5) | 0.6804 (3) | 0.3389 (2) | 0.0267 (7) | |
C212 | 0.1618 (5) | 0.6283 (3) | 0.2592 (2) | 0.0282 (7) | |
H212 | 0.2525 | 0.5680 | 0.2658 | 0.034* | |
C213 | 0.1131 (5) | 0.6645 (3) | 0.1709 (3) | 0.0310 (8) | |
H213 | 0.1699 | 0.6284 | 0.1170 | 0.037* | |
C214 | −0.0177 (5) | 0.7531 (3) | 0.1599 (2) | 0.0273 (7) | |
C215 | −0.0999 (5) | 0.8059 (3) | 0.2387 (2) | 0.0281 (7) | |
H215 | −0.1887 | 0.8670 | 0.2317 | 0.034* | |
C216 | −0.0524 (5) | 0.7694 (3) | 0.3276 (2) | 0.0279 (7) | |
H216 | −0.1093 | 0.8057 | 0.3813 | 0.033* | |
C231 | 0.1984 (5) | 0.5522 (3) | 0.4620 (2) | 0.0257 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0371 (14) | 0.0262 (13) | 0.0243 (12) | 0.0048 (10) | −0.0052 (10) | −0.0025 (10) |
O13 | 0.0470 (16) | 0.0281 (14) | 0.0255 (12) | 0.0065 (11) | −0.0081 (11) | −0.0009 (10) |
O14 | 0.0372 (14) | 0.0265 (13) | 0.0289 (12) | 0.0033 (11) | −0.0047 (10) | −0.0017 (10) |
O114 | 0.0536 (17) | 0.0314 (15) | 0.0277 (13) | 0.0109 (12) | −0.0098 (12) | −0.0072 (11) |
N13 | 0.0329 (15) | 0.0240 (15) | 0.0234 (13) | 0.0013 (12) | −0.0042 (11) | 0.0009 (11) |
C12 | 0.0331 (18) | 0.0278 (18) | 0.0233 (16) | −0.0015 (14) | −0.0053 (13) | −0.0008 (13) |
C13 | 0.0286 (16) | 0.0230 (16) | 0.0253 (16) | −0.0045 (13) | −0.0052 (13) | 0.0004 (13) |
C14 | 0.0253 (16) | 0.0244 (17) | 0.0273 (16) | −0.0035 (13) | −0.0028 (13) | 0.0024 (13) |
C14A | 0.0292 (17) | 0.0231 (17) | 0.0254 (16) | −0.0047 (13) | −0.0022 (13) | −0.0001 (13) |
C15 | 0.0351 (19) | 0.0292 (19) | 0.0286 (17) | −0.0024 (15) | −0.0032 (14) | 0.0005 (14) |
C16 | 0.041 (2) | 0.035 (2) | 0.0261 (17) | −0.0012 (16) | −0.0059 (15) | 0.0024 (15) |
C17 | 0.045 (2) | 0.039 (2) | 0.0234 (16) | −0.0030 (17) | −0.0032 (15) | −0.0015 (15) |
C18 | 0.037 (2) | 0.033 (2) | 0.0286 (17) | −0.0003 (15) | −0.0015 (15) | −0.0049 (15) |
C18A | 0.0289 (17) | 0.0305 (18) | 0.0231 (15) | −0.0050 (14) | −0.0048 (13) | 0.0033 (13) |
C111 | 0.0290 (17) | 0.0232 (16) | 0.0240 (15) | −0.0033 (13) | −0.0029 (13) | −0.0034 (13) |
C112 | 0.0320 (18) | 0.0245 (17) | 0.0281 (16) | 0.0012 (14) | −0.0050 (13) | −0.0032 (13) |
C113 | 0.0398 (19) | 0.0228 (17) | 0.0259 (16) | 0.0016 (14) | −0.0096 (14) | 0.0006 (13) |
C114 | 0.0355 (18) | 0.0255 (17) | 0.0258 (16) | −0.0010 (14) | −0.0038 (14) | −0.0053 (13) |
C115 | 0.0342 (18) | 0.0230 (17) | 0.0313 (18) | 0.0040 (14) | −0.0077 (14) | −0.0039 (14) |
C116 | 0.0353 (18) | 0.0248 (17) | 0.0266 (16) | 0.0008 (14) | −0.0072 (14) | −0.0022 (13) |
C131 | 0.0300 (17) | 0.0216 (16) | 0.0253 (16) | −0.0020 (13) | −0.0045 (13) | −0.0003 (13) |
O21 | 0.0383 (14) | 0.0233 (12) | 0.0252 (12) | 0.0029 (10) | −0.0067 (10) | −0.0012 (10) |
O23 | 0.0462 (15) | 0.0276 (13) | 0.0275 (12) | 0.0057 (11) | −0.0067 (11) | −0.0044 (10) |
O24 | 0.0414 (15) | 0.0269 (13) | 0.0299 (13) | 0.0050 (11) | −0.0084 (11) | −0.0028 (10) |
O214 | 0.0446 (15) | 0.0296 (14) | 0.0250 (12) | 0.0064 (11) | −0.0081 (11) | 0.0007 (10) |
N23 | 0.0357 (16) | 0.0221 (15) | 0.0238 (14) | 0.0006 (12) | −0.0068 (12) | −0.0009 (11) |
C22 | 0.0329 (18) | 0.0267 (18) | 0.0249 (16) | −0.0022 (14) | −0.0055 (13) | −0.0031 (14) |
C23 | 0.0281 (16) | 0.0226 (16) | 0.0248 (15) | −0.0009 (13) | −0.0047 (13) | −0.0030 (13) |
C24 | 0.0298 (17) | 0.0245 (17) | 0.0270 (16) | −0.0016 (13) | −0.0065 (13) | −0.0005 (13) |
C24A | 0.0296 (17) | 0.0243 (17) | 0.0261 (16) | −0.0035 (13) | −0.0035 (13) | −0.0015 (13) |
C25 | 0.0345 (18) | 0.0258 (18) | 0.0276 (17) | −0.0008 (14) | −0.0055 (14) | −0.0027 (14) |
C26 | 0.043 (2) | 0.0299 (19) | 0.0290 (18) | −0.0007 (16) | −0.0042 (15) | −0.0051 (15) |
C27 | 0.050 (2) | 0.034 (2) | 0.0243 (17) | −0.0014 (17) | −0.0085 (16) | 0.0007 (15) |
C28 | 0.041 (2) | 0.0238 (17) | 0.0287 (17) | −0.0023 (15) | −0.0056 (15) | 0.0010 (14) |
C28A | 0.0318 (17) | 0.0247 (17) | 0.0247 (16) | −0.0036 (14) | −0.0038 (13) | −0.0027 (13) |
C211 | 0.0302 (17) | 0.0250 (17) | 0.0253 (16) | −0.0033 (13) | −0.0052 (13) | 0.0005 (13) |
C212 | 0.0314 (17) | 0.0239 (17) | 0.0285 (17) | 0.0038 (13) | −0.0046 (14) | −0.0017 (14) |
C213 | 0.0369 (19) | 0.0283 (18) | 0.0270 (17) | 0.0025 (15) | −0.0021 (14) | −0.0042 (14) |
C214 | 0.0312 (17) | 0.0262 (17) | 0.0246 (16) | −0.0014 (14) | −0.0066 (13) | 0.0018 (13) |
C215 | 0.0305 (17) | 0.0229 (17) | 0.0306 (17) | 0.0006 (13) | −0.0054 (14) | −0.0005 (13) |
C216 | 0.0328 (18) | 0.0247 (17) | 0.0263 (16) | −0.0014 (14) | −0.0041 (13) | −0.0026 (13) |
C231 | 0.0292 (17) | 0.0243 (17) | 0.0236 (15) | −0.0003 (13) | −0.0046 (12) | −0.0022 (13) |
O11—C12 | 1.339 (4) | O21—C22 | 1.336 (4) |
O11—C18A | 1.377 (4) | O21—C28A | 1.384 (4) |
O13—C131 | 1.241 (4) | O23—C231 | 1.244 (4) |
O14—C14 | 1.235 (4) | O24—C24 | 1.234 (4) |
O114—C114 | 1.366 (4) | O214—C214 | 1.369 (4) |
O114—H114 | 0.91 (6) | O214—H214 | 0.88 (5) |
N13—C131 | 1.343 (4) | N23—C231 | 1.337 (4) |
N13—C111 | 1.416 (4) | N23—C211 | 1.424 (4) |
N13—H13 | 0.94 (4) | N23—H23 | 0.90 (4) |
C12—C13 | 1.343 (5) | C22—C23 | 1.353 (5) |
C12—H12 | 0.9500 | C22—H22 | 0.9500 |
C13—C14 | 1.469 (5) | C23—C24 | 1.459 (5) |
C13—C131 | 1.495 (5) | C23—C231 | 1.492 (5) |
C14—C14A | 1.466 (5) | C24—C24A | 1.473 (5) |
C14A—C18A | 1.389 (5) | C24A—C28A | 1.386 (5) |
C14A—C15 | 1.401 (5) | C24A—C25 | 1.403 (5) |
C15—C16 | 1.383 (5) | C25—C26 | 1.377 (5) |
C15—H15 | 0.9500 | C25—H25 | 0.9500 |
C16—C17 | 1.406 (6) | C26—C27 | 1.409 (5) |
C16—H16 | 0.9500 | C26—H26 | 0.9500 |
C17—C18 | 1.385 (5) | C27—C28 | 1.388 (5) |
C17—H17 | 0.9500 | C27—H27 | 0.9500 |
C18—C18A | 1.394 (5) | C28—C28A | 1.387 (5) |
C18—H18 | 0.9500 | C28—H28 | 0.9500 |
C111—C116 | 1.390 (5) | C211—C216 | 1.388 (5) |
C111—C112 | 1.405 (5) | C211—C212 | 1.399 (5) |
C112—C113 | 1.379 (5) | C212—C213 | 1.381 (5) |
C112—H112 | 0.9500 | C212—H212 | 0.9500 |
C113—C114 | 1.388 (5) | C213—C214 | 1.387 (5) |
C113—H113 | 0.9500 | C213—H213 | 0.9500 |
C114—C115 | 1.389 (5) | C214—C215 | 1.388 (5) |
C115—C116 | 1.392 (5) | C215—C216 | 1.388 (5) |
C115—H115 | 0.9500 | C215—H215 | 0.9500 |
C116—H116 | 0.9500 | C216—H216 | 0.9500 |
C12—O11—C18A | 118.3 (3) | C22—O21—C28A | 118.5 (3) |
C114—O114—H114 | 119 (3) | C214—O214—H214 | 118 (3) |
C131—N13—C111 | 127.5 (3) | C231—N23—C211 | 126.8 (3) |
C131—N13—H13 | 114 (3) | C231—N23—H23 | 118 (3) |
C111—N13—H13 | 118 (3) | C211—N23—H23 | 115 (3) |
O11—C12—C13 | 125.8 (3) | O21—C22—C23 | 125.3 (3) |
O11—C12—H12 | 117.1 | O21—C22—H22 | 117.3 |
C13—C12—H12 | 117.1 | C23—C22—H22 | 117.3 |
C12—C13—C14 | 119.6 (3) | C22—C23—C24 | 119.8 (3) |
C12—C13—C131 | 116.6 (3) | C22—C23—C231 | 116.2 (3) |
C14—C13—C131 | 123.8 (3) | C24—C23—C231 | 124.0 (3) |
O14—C14—C14A | 122.2 (3) | O24—C24—C23 | 124.3 (3) |
O14—C14—C13 | 123.7 (3) | O24—C24—C24A | 121.5 (3) |
C14A—C14—C13 | 114.0 (3) | C23—C24—C24A | 114.2 (3) |
C18A—C14A—C15 | 117.8 (3) | C28A—C24A—C25 | 117.8 (3) |
C18A—C14A—C14 | 120.9 (3) | C28A—C24A—C24 | 120.7 (3) |
C15—C14A—C14 | 121.3 (3) | C25—C24A—C24 | 121.6 (3) |
C16—C15—C14A | 120.8 (4) | C26—C25—C24A | 120.6 (3) |
C16—C15—H15 | 119.6 | C26—C25—H25 | 119.7 |
C14A—C15—H15 | 119.6 | C24A—C25—H25 | 119.7 |
C15—C16—C17 | 119.7 (3) | C25—C26—C27 | 120.1 (3) |
C15—C16—H16 | 120.2 | C25—C26—H26 | 120.0 |
C17—C16—H16 | 120.2 | C27—C26—H26 | 120.0 |
C18—C17—C16 | 121.0 (3) | C28—C27—C26 | 120.3 (3) |
C18—C17—H17 | 119.5 | C28—C27—H27 | 119.8 |
C16—C17—H17 | 119.5 | C26—C27—H27 | 119.8 |
C17—C18—C18A | 117.7 (4) | C28A—C28—C27 | 118.0 (3) |
C17—C18—H18 | 121.1 | C28A—C28—H28 | 121.0 |
C18A—C18—H18 | 121.1 | C27—C28—H28 | 121.0 |
O11—C18A—C14A | 121.3 (3) | O21—C28A—C24A | 121.2 (3) |
O11—C18A—C18 | 115.6 (3) | O21—C28A—C28 | 115.6 (3) |
C14A—C18A—C18 | 123.1 (3) | C24A—C28A—C28 | 123.2 (3) |
C116—C111—C112 | 118.9 (3) | C216—C211—C212 | 119.1 (3) |
C116—C111—N13 | 117.5 (3) | C216—C211—N23 | 117.7 (3) |
C112—C111—N13 | 123.5 (3) | C212—C211—N23 | 123.2 (3) |
C113—C112—C111 | 119.7 (3) | C213—C212—C211 | 120.0 (3) |
C113—C112—H112 | 120.1 | C213—C212—H212 | 120.0 |
C111—C112—H112 | 120.1 | C211—C212—H212 | 120.0 |
C112—C113—C114 | 121.3 (3) | C212—C213—C214 | 120.8 (3) |
C112—C113—H113 | 119.3 | C212—C213—H213 | 119.6 |
C114—C113—H113 | 119.3 | C214—C213—H213 | 119.6 |
O114—C114—C113 | 117.9 (3) | O214—C214—C213 | 117.5 (3) |
O114—C114—C115 | 122.8 (3) | O214—C214—C215 | 123.1 (3) |
C113—C114—C115 | 119.3 (3) | C213—C214—C215 | 119.4 (3) |
C114—C115—C116 | 119.8 (3) | C216—C215—C214 | 120.0 (3) |
C114—C115—H115 | 120.1 | C216—C215—H215 | 120.0 |
C116—C115—H115 | 120.1 | C214—C215—H215 | 120.0 |
C111—C116—C115 | 120.9 (3) | C215—C216—C211 | 120.7 (3) |
C111—C116—H116 | 119.5 | C215—C216—H216 | 119.7 |
C115—C116—H116 | 119.5 | C211—C216—H216 | 119.7 |
O13—C131—N13 | 123.6 (3) | O23—C231—N23 | 123.3 (3) |
O13—C131—C13 | 120.5 (3) | O23—C231—C23 | 121.0 (3) |
N13—C131—C13 | 115.9 (3) | N23—C231—C23 | 115.6 (3) |
C18A—O11—C12—C13 | −1.2 (5) | C28A—O21—C22—C23 | 3.5 (5) |
O11—C12—C13—C14 | −0.4 (6) | O21—C22—C23—C24 | 0.6 (6) |
O11—C12—C13—C131 | 179.8 (3) | O21—C22—C23—C231 | −178.4 (3) |
C12—C13—C14—O14 | −179.3 (3) | C22—C23—C24—O24 | 176.5 (4) |
C131—C13—C14—O14 | 0.5 (5) | C231—C23—C24—O24 | −4.6 (6) |
C12—C13—C14—C14A | 1.1 (5) | C22—C23—C24—C24A | −4.4 (5) |
C131—C13—C14—C14A | −179.2 (3) | C231—C23—C24—C24A | 174.6 (3) |
O14—C14—C14A—C18A | −179.8 (3) | O24—C24—C24A—C28A | −176.6 (3) |
C13—C14—C14A—C18A | −0.2 (5) | C23—C24—C24A—C28A | 4.3 (5) |
O14—C14—C14A—C15 | 0.2 (5) | O24—C24—C24A—C25 | 3.7 (5) |
C13—C14—C14A—C15 | 179.9 (3) | C23—C24—C24A—C25 | −175.4 (3) |
C18A—C14A—C15—C16 | 1.0 (5) | C28A—C24A—C25—C26 | −0.3 (5) |
C14—C14A—C15—C16 | −179.1 (3) | C24—C24A—C25—C26 | 179.4 (3) |
C14A—C15—C16—C17 | −0.6 (6) | C24A—C25—C26—C27 | 0.4 (6) |
C15—C16—C17—C18 | −0.1 (6) | C25—C26—C27—C28 | 0.2 (6) |
C16—C17—C18—C18A | 0.4 (6) | C26—C27—C28—C28A | −0.9 (6) |
C12—O11—C18A—C14A | 2.1 (5) | C22—O21—C28A—C24A | −3.5 (5) |
C12—O11—C18A—C18 | −178.7 (3) | C22—O21—C28A—C28 | 176.2 (3) |
C15—C14A—C18A—O11 | 178.6 (3) | C25—C24A—C28A—O21 | 179.2 (3) |
C14—C14A—C18A—O11 | −1.4 (5) | C24—C24A—C28A—O21 | −0.5 (5) |
C15—C14A—C18A—C18 | −0.6 (5) | C25—C24A—C28A—C28 | −0.5 (5) |
C14—C14A—C18A—C18 | 179.4 (3) | C24—C24A—C28A—C28 | 179.8 (3) |
C17—C18—C18A—O11 | −179.3 (3) | C27—C28—C28A—O21 | −178.6 (3) |
C17—C18—C18A—C14A | −0.1 (6) | C27—C28—C28A—C24A | 1.1 (6) |
C131—N13—C111—C116 | −170.9 (3) | C231—N23—C211—C216 | 160.2 (3) |
C131—N13—C111—C112 | 9.9 (6) | C231—N23—C211—C212 | −21.6 (6) |
C116—C111—C112—C113 | −0.4 (5) | C216—C211—C212—C213 | −1.0 (5) |
N13—C111—C112—C113 | 178.8 (3) | N23—C211—C212—C213 | −179.2 (3) |
C111—C112—C113—C114 | 0.6 (6) | C211—C212—C213—C214 | 0.6 (6) |
C112—C113—C114—O114 | 179.8 (3) | C212—C213—C214—O214 | −179.6 (3) |
C112—C113—C114—C115 | −0.8 (6) | C212—C213—C214—C215 | 0.2 (6) |
O114—C114—C115—C116 | −179.8 (4) | O214—C214—C215—C216 | 179.2 (3) |
C113—C114—C115—C116 | 0.8 (6) | C213—C214—C215—C216 | −0.6 (5) |
C112—C111—C116—C115 | 0.5 (5) | C214—C215—C216—C211 | 0.2 (5) |
N13—C111—C116—C115 | −178.8 (3) | C212—C211—C216—C215 | 0.6 (5) |
C114—C115—C116—C111 | −0.7 (6) | N23—C211—C216—C215 | 178.9 (3) |
C111—N13—C131—O13 | 0.1 (6) | C211—N23—C231—O23 | 1.2 (6) |
C111—N13—C131—C13 | 179.5 (3) | C211—N23—C231—C23 | −178.4 (3) |
C12—C13—C131—O13 | −6.3 (5) | C22—C23—C231—O23 | 7.8 (5) |
C14—C13—C131—O13 | 173.9 (3) | C24—C23—C231—O23 | −171.1 (3) |
C12—C13—C131—N13 | 174.3 (3) | C22—C23—C231—N23 | −172.6 (3) |
C14—C13—C131—N13 | −5.5 (5) | C24—C23—C231—N23 | 8.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O14 | 0.94 (4) | 1.88 (4) | 2.693 (4) | 143 (4) |
N23—H23···O24 | 0.90 (4) | 1.95 (4) | 2.698 (4) | 139 (4) |
C112—H112···O13 | 0.95 | 2.23 | 2.833 (4) | 121 |
C212—H212···O23 | 0.95 | 2.28 | 2.845 (4) | 117 |
O114—H114···O23 | 0.91 (6) | 1.76 (6) | 2.647 (4) | 167 (5) |
O214—H214···O13i | 0.88 (5) | 1.81 (5) | 2.668 (4) | 165 (5) |
C16—H16···O114ii | 0.95 | 2.46 | 3.411 (5) | 174 |
C18—H18···O24iii | 0.95 | 2.56 | 3.481 (5) | 163 |
C22—H22···O114 | 0.95 | 2.58 | 3.508 (4) | 166 |
C26—H26···O214iv | 0.95 | 2.51 | 3.454 (5) | 175 |
C28—H28···O14iv | 0.95 | 2.46 | 3.391 (5) | 165 |
Symmetry codes: (i) x−1, y+1, z; (ii) x, y, z−1; (iii) x+1, y−1, z−1; (iv) x, y, z+1. |
θChr-Phe is the dihedral angle between the mean planes of the chromene and the phenyl ring. θChr-amide is the dihedral angle between the mean planes of the chromone ring and the plane defined by atoms O3, C31 and N3. θamide-Phe is the dihedral angle between the mean planes of the phenyl ring and the plane defined by atoms O3, C31 and N3. The suffices A and B for compound (2a) denote the polymeric forms. Basic Conf. denotes the primary shape given by the relative position of the aromatic rings around the carboxamide linkage. |
Compound | θChr-Phe | θChr-amide | θamide-Phe | Basic Conf. |
(1) | 10.77 (4) | 4.31 (12) | 9.48 (12) | Rotation |
(2a mol1A | 11.64 (5) | 8.72 (14) | 20.35 (13) | Rotation |
(2a mol2A | 2.47 (5) | 1.75 (2) | 2.2 (2) | Planar |
(2a mol1B | 6.50 (18) | 15.0 (5) | 10.1 (6) | Rotation |
(2a mol2B | 10.52 (17) | 1.8 (6) | 12.27 (6) | Rotation |
(2b) | 35.96 (9) | 2.35 (4) | 33.6 (2) | Rotation |
(3a) | 15.61 (8) | 9.3 (3) | 11.7 (2) | Bent |
(3b) mol1 | 2.68 (10) | 2.0 (4) | 4.0 (4) | Planar |
(3b) mol2 | 10.31 (12) | 0.6 (4) | 10.42 (12) | Rotation |
(4a) | 11.48 (6) | 5.2 (5) | 6.5 (4) | Rotation |
(4b) | 4.90 (10) | 2.0 (4) | 2.9 (4) | Planar |
(4c) | 1.95 (7) | 5.7 (3) | 4.4 (3) | Planar |
(4d) | 22.88 (4) | 2.71 (8) | 23.90 (5) | Rotation |
(44e) mol1 | 3.58 (17) | 5.9 (2) | 9.5 (3) | Rotation |
(44e) mol2 | 10.02 (15) | 10.69 (2) | 19.8 (2) | Rotation |
Cg1, Cg2 and Cg3(Cg7) are the centroids of the pyrone, of the chromone phenyl and of the carboxamide phenyl rings, respectively. * indicates contacts in which the planes involved are inclined to each other, the perpendicular distance between the planes is an average value and the angle between the planes is given in place of a slippage. Only interplanar interactions with Cg···Cg distances less than or equal to 4.0 Å or with angles between the planes of less than 10° are included. |
Compound | contacts | distance | perp. distance | Slippage* |
(2b) | Cg1···Cg1iii | 3.859 (3) | 3.4223*) | 4.0 (13)* |
Cg1···Cg2iv | 3.564 (3) | 3.3951* | 3.86 (13)* | |
Cg2···Cg2iv | 3.674 (3) | 3.4035* | 4.0 (13)* | |
Cg3···Cg3i | 3.649 (3) | 3.3049 (11) | 1.546 | |
(3b) | Cg1···Cg3v | 3.6621 (17) | 3.4150* | 2.91 (13) |
Cg2···Cg3vi | 3.6851 (18) | 3.3587*' | 2.47 (14)* | |
Cg2···Cg3v | 3.7278 (17) | 3.4360* | 2.47 (14)* | |
(4a) | Cg2···Cg3ii | 3.780 (3) | 3.383* | 1.90 (6)* |
(4d) | Cg1···Cg1vii | 3.4831 (7) | 3.3257 (4) | 1.035 |
Cg1···Cg2Vii | 3.6037 (7) | 3.3137* | 2.46 (5)* | |
(4e) | Cg1···Cg3vi | 3.669 (2) | 3.3741*) | 3.50 (17)* |
Cg1···Cg7v | 3.768 (2) | 3.3792* | 3.09 (17)* |
Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) 3/2 - x, -1/2 + y, 1/2 - z; (iii) x, 3/2 - y, -1/2 + z; (iv) x, 3/2 - y, 1/2 + z; (v) 1 - x, 1 - y, -z; (vi) 1 - x, -y, -z; (vii) 1 - x, -y, 1 - z. |
Acknowledgements
The authors thank the National Crystallographic Service, University of Southampton for the data collection and for their help and advice (Coles & Gale, 2012) and the Foundation for Science and Technology (FCT), Portugal, for financial support. FC (grant SFRH/BPDF/QUI-QUI/74491/2010) is also supported by the FCT.
References
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