Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614018713/sk3561sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614018713/sk3561Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614018713/sk3561IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614018713/sk3561IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614018713/sk3561IVsup5.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614018713/sk3561Isup6.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614018713/sk3561IIsup7.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614018713/sk3561IIIsup8.cml | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614018713/sk3561IVsup9.cml |
CCDC references: 1019820; 1019821; 1019822; 1019823
Substituted acetamides of the type R1CH2CONHR2, where R1 and R2 are aromatic substituents are of interest as they have some resemblance to benzyl penicillins ((Pitt, 1952; Csöregh & Palm, 1977; Kojić-Prodić & Rużoć-Toroš, 1978; Mijin & Marinkovic, 2006; Mijin et al., 2008). We report here the molecular structures and supramolecular assembly of four closely related amides, namely N-(4-chloro-3-methylphenyl)-2-phenylacetamide, (I), N-(4-bromo-3-methylphenyl)-2-phenylacetamide, (II), N-(4-chloro-3-methylphenyl)-2-(2,4-dichlorophenyl)acetamide, (III), and N-(4-bromo-3-methylphenyl)-2-(2-chlorophenyl)acetamide, (IV) (see Scheme 1). The purposes of this study are the comparison of the molecular conformations and the supramolecular assembly across a series of amides of the type R1CH2CONHR2, where R1 and R2 represent either phenyl (in the case of R1) or halogeno-substituted phenyl groups (for both R1 and R2), including not only compounds (I)–(IV) but also their recently reported analogues (V)–(VII) (see Scheme 1); and the extension of this comparison of supramolecular assembly patterns to include analogues where R1 represents the naphthalen-1-yl unit, compounds (VIII)–(XI) (see Scheme 2), where there is greater scope for the occurrence of π–π stacking interactions. Compounds (V)–(XI) have all been the subject of individual structure reports, some of them quite brief, and no comparisons between them have been drawn. Accordingly, it is worthwhile to draw together these disparate structural reports for the purposes of comparison, and this we undertake here. We also briefly consider the effects on the supramolecular assembly when R2 represents an N-heterocyclic group, thereby introducing into the molecular constitution one or more further potential hydrogen-bond acceptors. Compounds (I)–(IV) were all prepared by a condensation reaction between a substituted aniline and either phenylacetic acid, for compounds (I) and (II), or a substituted phenylacetic acid, for compounds (III) and (IV), using a tenfold molar excess of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride as the amide coupling agent.
For the synthesis of compounds (I)–(IV), a mixture of 1 mmol each of the appropriately substituted phenylacetic acid and aniline precursors were dissolved in dichloromethane (20 ml) in the presence of 3-(3-dimethylaminopropyl)-1-ethylcarbodiimide hydrochloride (1.0 g, 10 mmol) and triethylamine (2 mmol). The mixtures were stirred at 273 K for 3 h, and then each was poured with stirring into ice-cold aqueous hydrogen chloride solution (100 ml of 10% solution). The resulting mixtures were extracted with dichloromethane (3 × 20 ml); each of the combined organic extracts was then washed with excess of aqueous sodium hydrogen carbonate solution and with brine, after which the solvent was removed under reduced pressure. Slow evaporation, at ambient temperature and in the presence of air, of solution in methanol gave colourless crystals of compounds (I)–(IV) suitable for single-crystal X-ray diffraction. Compound (I): yield 77%, m.p. 397–399 K; analysis found: C 69.3, H 5.5, N 5.4%; C15H14ClNO requires: C 69.4, H 5.4, N 5.4%. Compound (II): yield 80%, m.p. 457–459 K; analysis found: C 54.8, H 3.7, N 4.2%; C15H12Cl3NO requires: C 54.8, H 3.7, N 4.3%. Compound (III): yield 80%, m.p. 457–459 K; analysis found: C 54.8, H 3.7, N 4.2%; C15H12Cl3NO requires: C 54.8, H 3.7, N 4.3%. Compound (IV): yield 83%, m.p. 454–456 K; analysis found: C 53.2, H 3.9, N 4.2%; C15H13BrClNO requires: C 53.2, H 3.9, N 4.1%.
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps and then treated as riding atoms, with C—H = 0.95 (aromatic), 0.98 (CH3) or 0.99 Å (CH2) and N—H = 0.88 Å, and with Uiso(H) = kUeq(N,O), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. For compound (IV), the low-angle reflection 200, which had been attenuated by the beam stop, was omitted from the final refinement. The absolute configuration of (III) in the crystal selected for data collection was established by means of the Flack x parameter (Flack, 1983), x = 0.02 (4), calculated by the use of 697 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013).
Compounds (I) (Fig. 1) and (II) (Fig. 2) are isostructural in the space group P1, while compounds (III) (Fig. 3) and (IV) (Fig. 4) both crystallize in monoclinic space groups, P21 and P21/c respectively. Compound (V) also crystallizes in P21/c (Fun, Shahani et al., 2012), while compounds (VI) (Praveen et al., 2013b) and (VII) (Praveen et al., 2013a) are isostructural in the space group P212121, although neither of the original structure reports on (VI) and (VII) mentioned the other one.
The 4-halogeno-3-methylphenyl units in compounds (III) and (IV) adopt a different orientation from those in compounds (I) and (II), corresponding to a rotation of approximately 180° around the bond N1—C11 (cf. Figs. 1–4). Apart from this difference, however, the molecular conformations of compounds (I)–(VII) are all very similar, as demonstrated by the torsion angles (Table 2) which define the orientation of the phenyl and benzyl substituents relative to the central trans-planar amide unit. The conformational similarity is confirmed by the narrow rings spanned by the dihedral angle between the two aryl rings in each compound, ranging from 60.1 (2)° in compound (IV) to 72.03 (14)° in compound (II). The molecular conformations in (I)–(VII) thus appear to be largely independent of the number, nature and location of the halogeno substituents. The molecules of compounds (I)–(VII) are all conformationallly chiral, and the centrosymmetric space groups for compounds (I), (II), (IV) and (V) confirm that equal numbers of the two conformational enantiomers are present in each case. For compounds (III), (VI) and (VII), on the other hand, which all crystallize in Sohncke space groups, only one conformational enantiomer is present in each crystal, provided that these crystals are untwinned, which appears to be the case for all of them. For each of these compounds, the absolute configuration of the molecules in the crystals selected for data collection was established by means of the Flack x parameter (Flack, 1983; Parsons et al., 2013), but it seems probable that all three crystallize as conformational conglomerates, rather than as conformational racemates, as for compounds (I), (II), (IV) and (V).
In each of the isomorphous compounds (I) and (II), molecules related by translation are linked by N—H···O hydrogen bonds (Table 3) to form C(4) (Bernstein et al., 1995) chains running parallel to the [100] direction. These chains are modestly reinforced by a C—H···π(arene) interaction, also involving molecules related by translation, so forming a chain of rings (Fig. 5). Two chains of this type pass through each unit cell but there are no direction-specific interactions between adjacent chains. The molecules in compounds (III) and (IV) are also linked into C(4) chains by N—H···O hydrogen bonds, in each case running parallel to the [010] direction. Despite the presence of 21 screw axes in (III) and (IV), the chains again comprise molecules related by translation. However, the intermolecular C—H···π(arene) contacts in (III) and (IV) have rather long H···Cg distances and small C—H···Cg angles (Table 3), and they are probably not structurally significant. Hence, the supramolecular assembly in (III) and (IV) consists of simple C(4) chains (Figs. 6 and 7), rather than chains of rings: again, there are no direction-specific interactions between adjacent chains.
In the structure of compound (IV), there is a short intermolecular Br···Br contact between inversion-related molecules, with Br14···Br14i = 3.4303 (8) Å and C14—Br14···Br14i= 158.60 (13)° [symmetry code: (i) -x+1, -y+2, -z]. A database study of the angular distribution of such contacts (Ramasubbu et al., 1986) has shown that the C—X···X angles (where = Cl, Br or I) are clustered either around 100° or around 165°, and the angle observed in compound (IV) is consistent with this finding. Although the observed Br···Br distance in (IV) is shorter that the conventional sum of van der Waals radii (3.70 Å; Rowland & Taylor, 1996), a database study of the nonbonded distances in such contacts (Nyburg & Faerman, 1985) found that atoms such as halogens bonded to C atoms do not behave in this context as though they were spherical but instead they behave as oblate ellipsoids, with the major axis normal to the direction of the C—X bond and the minor axis parallel to the C—X bond. For Br, these characteristic radii were found to be 2.01 and 1.64 Å, respectively, and, on this basis, the observed Br···Br distance in compound (IV) does not seem to be exceptional.
Simple C(4) chains containing molecules related by translation are also found in compounds (V)–(VII). In compound (V) (Fun, Shahani et al., 2012), the chains run parallel to [010] in P21/c, as in (IV), while in the isostructural compounds (VI) and (VII) (Praveen et al., 2013a,b), the chains run parallel to the [100] direction.
Unlike compounds (I) and (II), compounds (VIII) (Fun, Quah et al., 2012) and (IX) (Fun et al., 2011a) (see Scheme 2) are not isostructural, although in each pair, the analogues differ only in that compounds (II) and (IX) contain a bromo substituent in place of the chloro substituent in each of compounds (I) and (VIII). Compounds (VIII) and (IX) crystallize in the space groups P21/c and Pbca, respectively and, whereas in (VIII), molecules related by translation are linked into simple C(4) chains by N—H···O hydrogen bonds, in (IX) molecules related by a b-glide plane are linked by N—H···O hydrogen bonds modestly reinforced by C—H···O hydrogen bonds to form a C(4)C(4)[R21(6)] chain of rings.
In each of compounds (X) (Praveen et al., 2011) and (XI) (Fun et al., 2011b), molecules related by n-glide and c-glide planes, respectively, are linked by N—H···O hydrogen bonds to form C(4) chains running parallel to [101] and [001] respectively. In addition, there are two aromatic π–π stacking interactions in each structure, although these were not mentioned in the original structure reports. In each case, one such interaction reinforces the hydrogen-bonded chains and the other links these chains into sheets which lie parallel to (010) in both structures (Figs. 8 and 9).
The C(4) motif found in compounds (I)–(XI) appears to be characteristic of amides containing only hydrocarbyl substituents from which other potential hydrogen-bond acceptors are absent (Kashino et al., 1979; Bowes et al., 2003; Glidewell et al., 2003; Kumar et al., 2004; Garden et al., 2005; Cuffini et al., 2006; Wardell et al., 2006). It is noteworthy that in each of compounds (I)–(VII) the repeat vector parallel to the direction of the chain is short, ranging from b = 4.7282 (3) Å in compound (IV) to a = 5.0039 (7) Å in compound (I), and this behaviour is also found in compound (VIII), where b = 5.0458 (11) Å. However, in the other naphthyl derivatives, compounds (IX)–(XI), the repeat distance parallel to the chain direction is very much longer (>9 Å in each case) and in each of these three the chain consists of molecules related by glide planes, rather than by translation as in compounds (I)–(VIII).
When, however, the N-aryl group is replaced by a nitrogen-containing hererocyclic unit (Nayak et al., 2013, 2013a,b,c), N—H···O hydrogen bonds are absent from the structures and the supramolecular assembly is determined by N—H···N hydrogen bonds together with some combination of C—H···N and C—H···O hydrogen bonds and, in some cases, π–π stacking interactions. An exception is provided by the pyrimidine derivative, N-(4,6-dimethoxypyrimidin-2-yl)-2-(3-methylphenyl)acetamide (Praveen et al., 2012); this is an example of a cis-amide (although, unfortunately, the schematic diagram in the original structure report depicts this as a trans-amide) and inversion-related pairs of N—H···O hydrogen bonds link pairs of molecules into centrosymmetric R22(8) dimers.
For all compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2014) and PLATON (Spek, 2009).
C15H14ClNO | Z = 2 |
Mr = 259.72 | F(000) = 272 |
Triclinic, P1 | Dx = 1.342 Mg m−3 |
a = 5.0039 (7) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 10.7525 (12) Å | Cell parameters from 2447 reflections |
c = 12.6177 (12) Å | θ = 3.7–72.4° |
α = 108.615 (10)° | µ = 2.51 mm−1 |
β = 91.771 (11)° | T = 173 K |
γ = 90.167 (11)° | Block, colourless |
V = 643.01 (14) Å3 | 0.28 × 0.16 × 0.08 mm |
Agilent Eos Gemini diffractometer | 1865 reflections with I > 2σ(I) |
Radiation source: Enhance (Cu) X-ray Source | Rint = 0.032 |
ω scans | θmax = 72.4°, θmin = 3.7° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −6→5 |
Tmin = 0.413, Tmax = 0.818 | k = −13→12 |
3772 measured reflections | l = −11→15 |
2447 independent reflections |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.093P)2 + 0.0997P] where P = (Fo2 + 2Fc2)/3 |
2447 reflections | (Δ/σ)max < 0.001 |
164 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C15H14ClNO | γ = 90.167 (11)° |
Mr = 259.72 | V = 643.01 (14) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.0039 (7) Å | Cu Kα radiation |
b = 10.7525 (12) Å | µ = 2.51 mm−1 |
c = 12.6177 (12) Å | T = 173 K |
α = 108.615 (10)° | 0.28 × 0.16 × 0.08 mm |
β = 91.771 (11)° |
Agilent Eos Gemini diffractometer | 2447 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 1865 reflections with I > 2σ(I) |
Tmin = 0.413, Tmax = 0.818 | Rint = 0.032 |
3772 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.187 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.37 e Å−3 |
2447 reflections | Δρmin = −0.30 e Å−3 |
164 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2965 (6) | 0.7657 (3) | 0.5498 (3) | 0.0381 (7) | |
O1 | 0.0598 (4) | 0.7371 (2) | 0.5294 (2) | 0.0474 (6) | |
N1 | 0.4929 (5) | 0.7032 (2) | 0.4826 (2) | 0.0382 (6) | |
H1 | 0.6572 | 0.7331 | 0.5018 | 0.046* | |
C2 | 0.3951 (6) | 0.8735 (3) | 0.6541 (3) | 0.0476 (8) | |
H2A | 0.4673 | 0.8326 | 0.7089 | 0.057* | |
H2B | 0.5436 | 0.9219 | 0.6341 | 0.057* | |
C11 | 0.4580 (6) | 0.5937 (3) | 0.3837 (2) | 0.0352 (6) | |
C12 | 0.6223 (6) | 0.5854 (3) | 0.2949 (3) | 0.0412 (7) | |
H12 | 0.7489 | 0.6539 | 0.3022 | 0.049* | |
C13 | 0.6082 (6) | 0.4808 (3) | 0.1961 (3) | 0.0406 (7) | |
C14 | 0.4197 (6) | 0.3831 (3) | 0.1900 (3) | 0.0410 (7) | |
Cl14 | 0.38569 (19) | 0.24733 (8) | 0.06853 (7) | 0.0578 (3) | |
C15 | 0.2555 (7) | 0.3892 (3) | 0.2774 (3) | 0.0440 (7) | |
H15 | 0.1298 | 0.3205 | 0.2705 | 0.053* | |
C16 | 0.2731 (6) | 0.4949 (3) | 0.3751 (3) | 0.0395 (7) | |
H16 | 0.1599 | 0.4995 | 0.4353 | 0.047* | |
C17 | 0.7884 (7) | 0.4765 (4) | 0.1016 (3) | 0.0578 (9) | |
H17A | 0.6812 | 0.4862 | 0.0385 | 0.087* | |
H17B | 0.8806 | 0.3923 | 0.0780 | 0.087* | |
H17C | 0.9205 | 0.5483 | 0.1269 | 0.087* | |
C21 | 0.1835 (6) | 0.9697 (3) | 0.7089 (3) | 0.0398 (7) | |
C22 | 0.0824 (7) | 0.9718 (3) | 0.8102 (3) | 0.0450 (7) | |
H22 | 0.1475 | 0.9119 | 0.8459 | 0.054* | |
C23 | −0.1131 (7) | 1.0605 (3) | 0.8601 (3) | 0.0523 (9) | |
H23 | −0.1815 | 1.0603 | 0.9294 | 0.063* | |
C24 | −0.2089 (7) | 1.1487 (3) | 0.8104 (3) | 0.0498 (8) | |
H24 | −0.3424 | 1.2095 | 0.8450 | 0.060* | |
C25 | −0.1088 (7) | 1.1479 (3) | 0.7095 (3) | 0.0493 (8) | |
H25 | −0.1742 | 1.2082 | 0.6742 | 0.059* | |
C26 | 0.0868 (7) | 1.0597 (3) | 0.6596 (3) | 0.0459 (8) | |
H26 | 0.1558 | 1.0607 | 0.5906 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0324 (16) | 0.0370 (14) | 0.0442 (17) | 0.0064 (12) | 0.0039 (12) | 0.0117 (13) |
O1 | 0.0277 (11) | 0.0470 (12) | 0.0580 (14) | 0.0048 (9) | 0.0050 (9) | 0.0031 (10) |
N1 | 0.0247 (12) | 0.0414 (13) | 0.0483 (15) | 0.0039 (10) | 0.0039 (10) | 0.0140 (11) |
C2 | 0.0345 (17) | 0.0472 (17) | 0.054 (2) | 0.0058 (13) | −0.0031 (14) | 0.0061 (15) |
C11 | 0.0292 (14) | 0.0379 (14) | 0.0407 (15) | 0.0127 (11) | 0.0041 (11) | 0.0152 (12) |
C12 | 0.0323 (16) | 0.0466 (17) | 0.0504 (18) | 0.0067 (12) | 0.0068 (13) | 0.0230 (15) |
C13 | 0.0347 (16) | 0.0516 (17) | 0.0406 (16) | 0.0156 (13) | 0.0072 (12) | 0.0211 (14) |
C14 | 0.0427 (17) | 0.0415 (16) | 0.0389 (16) | 0.0155 (13) | 0.0063 (13) | 0.0125 (13) |
Cl14 | 0.0660 (6) | 0.0503 (5) | 0.0489 (5) | 0.0115 (4) | 0.0099 (4) | 0.0033 (4) |
C15 | 0.0432 (18) | 0.0374 (15) | 0.0531 (19) | 0.0048 (13) | 0.0083 (14) | 0.0160 (14) |
C16 | 0.0359 (16) | 0.0404 (15) | 0.0458 (17) | 0.0091 (12) | 0.0103 (13) | 0.0181 (14) |
C17 | 0.050 (2) | 0.075 (2) | 0.053 (2) | 0.0121 (18) | 0.0143 (16) | 0.0248 (19) |
C21 | 0.0340 (16) | 0.0347 (14) | 0.0456 (17) | 0.0002 (12) | −0.0002 (13) | 0.0059 (13) |
C22 | 0.0482 (19) | 0.0437 (17) | 0.0441 (18) | 0.0057 (14) | −0.0015 (14) | 0.0159 (14) |
C23 | 0.056 (2) | 0.055 (2) | 0.0402 (18) | 0.0023 (16) | 0.0084 (15) | 0.0066 (15) |
C24 | 0.0439 (19) | 0.0393 (16) | 0.056 (2) | 0.0086 (14) | 0.0053 (15) | −0.0002 (15) |
C25 | 0.0466 (19) | 0.0383 (16) | 0.064 (2) | 0.0072 (14) | −0.0011 (16) | 0.0180 (15) |
C26 | 0.0455 (18) | 0.0460 (17) | 0.0480 (18) | 0.0017 (14) | 0.0054 (14) | 0.0174 (15) |
C1—O1 | 1.221 (4) | C15—H15 | 0.9500 |
C1—N1 | 1.352 (4) | C16—H16 | 0.9500 |
C1—C2 | 1.517 (4) | C17—H17A | 0.9800 |
N1—C11 | 1.422 (4) | C17—H17B | 0.9800 |
N1—H1 | 0.8800 | C17—H17C | 0.9800 |
C2—C21 | 1.505 (4) | C21—C22 | 1.383 (5) |
C2—H2A | 0.9900 | C21—C26 | 1.387 (5) |
C2—H2B | 0.9900 | C22—C23 | 1.387 (4) |
C11—C16 | 1.382 (4) | C22—H22 | 0.9500 |
C11—C12 | 1.391 (4) | C23—C24 | 1.373 (5) |
C12—C13 | 1.386 (4) | C23—H23 | 0.9500 |
C12—H12 | 0.9500 | C24—C25 | 1.379 (5) |
C13—C14 | 1.392 (5) | C24—H24 | 0.9500 |
C13—C17 | 1.506 (4) | C25—C26 | 1.385 (5) |
C14—C15 | 1.381 (4) | C25—H25 | 0.9500 |
C14—Cl14 | 1.750 (3) | C26—H26 | 0.9500 |
C15—C16 | 1.385 (4) | ||
O1—C1—N1 | 123.1 (3) | C11—C16—C15 | 119.0 (3) |
O1—C1—C2 | 122.6 (3) | C11—C16—H16 | 120.5 |
N1—C1—C2 | 114.3 (3) | C15—C16—H16 | 120.5 |
C1—N1—C11 | 125.9 (2) | C13—C17—H17A | 109.5 |
C1—N1—H1 | 117.0 | C13—C17—H17B | 109.5 |
C11—N1—H1 | 117.0 | H17A—C17—H17B | 109.5 |
C21—C2—C1 | 114.1 (3) | C13—C17—H17C | 109.5 |
C21—C2—H2A | 108.7 | H17A—C17—H17C | 109.5 |
C1—C2—H2A | 108.7 | H17B—C17—H17C | 109.5 |
C21—C2—H2B | 108.7 | C22—C21—C26 | 118.2 (3) |
C1—C2—H2B | 108.7 | C22—C21—C2 | 120.9 (3) |
H2A—C2—H2B | 107.6 | C26—C21—C2 | 120.8 (3) |
C16—C11—C12 | 119.8 (3) | C21—C22—C23 | 120.6 (3) |
C16—C11—N1 | 122.1 (3) | C21—C22—H22 | 119.7 |
C12—C11—N1 | 118.1 (3) | C23—C22—H22 | 119.7 |
C13—C12—C11 | 122.4 (3) | C24—C23—C22 | 120.7 (3) |
C13—C12—H12 | 118.8 | C24—C23—H23 | 119.6 |
C11—C12—H12 | 118.8 | C22—C23—H23 | 119.6 |
C12—C13—C14 | 116.4 (3) | C23—C24—C25 | 119.2 (3) |
C12—C13—C17 | 120.6 (3) | C23—C24—H24 | 120.4 |
C14—C13—C17 | 123.0 (3) | C25—C24—H24 | 120.4 |
C15—C14—C13 | 122.1 (3) | C24—C25—C26 | 120.3 (3) |
C15—C14—Cl14 | 118.0 (3) | C24—C25—H25 | 119.9 |
C13—C14—Cl14 | 119.9 (2) | C26—C25—H25 | 119.9 |
C14—C15—C16 | 120.4 (3) | C25—C26—C21 | 121.0 (3) |
C14—C15—H15 | 119.8 | C25—C26—H26 | 119.5 |
C16—C15—H15 | 119.8 | C21—C26—H26 | 119.5 |
O1—C1—N1—C11 | −3.2 (5) | Cl14—C14—C15—C16 | −179.6 (2) |
C2—C1—N1—C11 | 175.8 (3) | C12—C11—C16—C15 | −0.1 (4) |
O1—C1—C2—C21 | −19.4 (5) | N1—C11—C16—C15 | −178.1 (3) |
N1—C1—C2—C21 | 161.5 (3) | C14—C15—C16—C11 | −0.3 (5) |
C1—N1—C11—C16 | −37.5 (4) | C1—C2—C21—C22 | 109.2 (4) |
C1—N1—C11—C12 | 144.4 (3) | C1—C2—C21—C26 | −71.5 (4) |
C16—C11—C12—C13 | 0.2 (4) | C26—C21—C22—C23 | 0.9 (5) |
N1—C11—C12—C13 | 178.4 (3) | C2—C21—C22—C23 | −179.8 (3) |
C11—C12—C13—C14 | −0.1 (4) | C21—C22—C23—C24 | −0.5 (5) |
C11—C12—C13—C17 | 179.4 (3) | C22—C23—C24—C25 | 0.2 (5) |
C12—C13—C14—C15 | −0.2 (4) | C23—C24—C25—C26 | −0.3 (5) |
C17—C13—C14—C15 | −179.7 (3) | C24—C25—C26—C21 | 0.7 (5) |
C12—C13—C14—Cl14 | 179.8 (2) | C22—C21—C26—C25 | −1.0 (5) |
C17—C13—C14—Cl14 | 0.3 (4) | C2—C21—C26—C25 | 179.7 (3) |
C13—C14—C15—C16 | 0.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 2.03 | 2.878 (3) | 161 |
C2—H2B···Cg1i | 0.99 | 2.81 | 3.546 (4) | 132 |
Symmetry code: (i) x+1, y, z. |
C15H14BrNO | Z = 2 |
Mr = 304.18 | F(000) = 308 |
Triclinic, P1 | Dx = 1.542 Mg m−3 |
a = 4.9995 (3) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 10.8392 (4) Å | Cell parameters from 2515 reflections |
c = 12.7301 (7) Å | θ = 4.3–72.4° |
α = 108.149 (4)° | µ = 4.16 mm−1 |
β = 91.968 (5)° | T = 173 K |
γ = 90.310 (4)° | Plate, colourless |
V = 655.05 (6) Å3 | 0.32 × 0.18 × 0.08 mm |
Agilent Eos Gemini diffractometer | 2276 reflections with I > 2σ(I) |
Radiation source: Enhance (Cu) X-ray Source | Rint = 0.039 |
ω scans | θmax = 72.4°, θmin = 4.3° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −6→6 |
Tmin = 0.286, Tmax = 0.818 | k = −13→8 |
3876 measured reflections | l = −15→15 |
2515 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0697P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2515 reflections | Δρmax = 0.72 e Å−3 |
164 parameters | Δρmin = −0.45 e Å−3 |
C15H14BrNO | γ = 90.310 (4)° |
Mr = 304.18 | V = 655.05 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.9995 (3) Å | Cu Kα radiation |
b = 10.8392 (4) Å | µ = 4.16 mm−1 |
c = 12.7301 (7) Å | T = 173 K |
α = 108.149 (4)° | 0.32 × 0.18 × 0.08 mm |
β = 91.968 (5)° |
Agilent Eos Gemini diffractometer | 2515 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 2276 reflections with I > 2σ(I) |
Tmin = 0.286, Tmax = 0.818 | Rint = 0.039 |
3876 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.72 e Å−3 |
2515 reflections | Δρmin = −0.45 e Å−3 |
164 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2977 (5) | 0.7638 (2) | 0.5510 (2) | 0.0290 (5) | |
O1 | 0.0594 (4) | 0.7346 (2) | 0.53092 (18) | 0.0398 (5) | |
N1 | 0.4932 (4) | 0.7035 (2) | 0.48448 (19) | 0.0302 (5) | |
H1 | 0.6577 | 0.7332 | 0.5037 | 0.036* | |
C2 | 0.3984 (5) | 0.8692 (3) | 0.6554 (2) | 0.0369 (6) | |
H2A | 0.4635 | 0.8277 | 0.7104 | 0.044* | |
H2B | 0.5519 | 0.9158 | 0.6370 | 0.044* | |
C11 | 0.4584 (5) | 0.5970 (2) | 0.3866 (2) | 0.0273 (5) | |
C12 | 0.6214 (5) | 0.5910 (3) | 0.2990 (2) | 0.0318 (5) | |
H12 | 0.7472 | 0.6595 | 0.3066 | 0.038* | |
C13 | 0.6073 (5) | 0.4886 (3) | 0.2008 (2) | 0.0334 (5) | |
C14 | 0.4191 (5) | 0.3906 (3) | 0.1937 (2) | 0.0315 (5) | |
Br14 | 0.37906 (7) | 0.24603 (3) | 0.06240 (2) | 0.04614 (15) | |
C15 | 0.2543 (6) | 0.3946 (3) | 0.2798 (2) | 0.0341 (6) | |
H15 | 0.1284 | 0.3261 | 0.2723 | 0.041* | |
C16 | 0.2720 (5) | 0.4974 (3) | 0.3765 (2) | 0.0319 (5) | |
H16 | 0.1586 | 0.5003 | 0.4356 | 0.038* | |
C17 | 0.7862 (7) | 0.4883 (4) | 0.1079 (3) | 0.0470 (7) | |
H17A | 0.8685 | 0.4031 | 0.0793 | 0.071* | |
H17B | 0.9266 | 0.5552 | 0.1356 | 0.071* | |
H17C | 0.6801 | 0.5066 | 0.0485 | 0.071* | |
C21 | 0.1876 (5) | 0.9661 (3) | 0.7065 (2) | 0.0307 (5) | |
C22 | 0.0826 (6) | 0.9695 (3) | 0.8069 (2) | 0.0371 (6) | |
H22 | 0.1438 | 0.9100 | 0.8432 | 0.045* | |
C23 | −0.1117 (6) | 1.0592 (3) | 0.8550 (2) | 0.0422 (7) | |
H23 | −0.1816 | 1.0606 | 0.9238 | 0.051* | |
C24 | −0.2022 (6) | 1.1455 (3) | 0.8029 (3) | 0.0423 (7) | |
H24 | −0.3340 | 1.2069 | 0.8357 | 0.051* | |
C25 | −0.1001 (6) | 1.1423 (3) | 0.7023 (3) | 0.0405 (6) | |
H25 | −0.1631 | 1.2013 | 0.6658 | 0.049* | |
C26 | 0.0933 (6) | 1.0535 (3) | 0.6548 (2) | 0.0365 (6) | |
H26 | 0.1624 | 1.0524 | 0.5860 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0263 (12) | 0.0263 (12) | 0.0337 (13) | 0.0012 (9) | 0.0029 (9) | 0.0081 (10) |
O1 | 0.0231 (9) | 0.0364 (11) | 0.0489 (11) | 0.0001 (7) | 0.0038 (8) | −0.0030 (9) |
N1 | 0.0219 (9) | 0.0298 (11) | 0.0374 (11) | −0.0007 (8) | 0.0013 (8) | 0.0083 (9) |
C2 | 0.0277 (12) | 0.0361 (14) | 0.0400 (14) | 0.0011 (11) | −0.0006 (11) | 0.0018 (12) |
C11 | 0.0239 (11) | 0.0267 (12) | 0.0321 (12) | 0.0041 (9) | 0.0025 (9) | 0.0101 (10) |
C12 | 0.0253 (12) | 0.0339 (14) | 0.0392 (14) | −0.0009 (10) | 0.0041 (10) | 0.0154 (11) |
C13 | 0.0306 (12) | 0.0370 (14) | 0.0360 (13) | 0.0078 (10) | 0.0059 (10) | 0.0154 (11) |
C14 | 0.0389 (14) | 0.0253 (12) | 0.0285 (12) | 0.0072 (10) | 0.0040 (10) | 0.0054 (10) |
Br14 | 0.0619 (3) | 0.0346 (2) | 0.0363 (2) | 0.00613 (14) | 0.00912 (14) | 0.00200 (13) |
C15 | 0.0375 (14) | 0.0265 (13) | 0.0382 (14) | −0.0001 (10) | 0.0059 (11) | 0.0093 (11) |
C16 | 0.0337 (13) | 0.0294 (13) | 0.0349 (13) | 0.0026 (10) | 0.0106 (10) | 0.0123 (11) |
C17 | 0.0439 (16) | 0.060 (2) | 0.0400 (16) | 0.0038 (14) | 0.0135 (13) | 0.0182 (14) |
C21 | 0.0284 (12) | 0.0254 (12) | 0.0342 (13) | −0.0027 (10) | −0.0001 (10) | 0.0035 (10) |
C22 | 0.0436 (15) | 0.0334 (14) | 0.0337 (14) | −0.0008 (11) | −0.0008 (11) | 0.0097 (11) |
C23 | 0.0469 (17) | 0.0439 (17) | 0.0299 (13) | 0.0004 (13) | 0.0076 (12) | 0.0020 (12) |
C24 | 0.0405 (15) | 0.0307 (14) | 0.0472 (16) | 0.0035 (11) | 0.0048 (12) | −0.0008 (12) |
C25 | 0.0445 (15) | 0.0270 (14) | 0.0509 (17) | 0.0006 (11) | −0.0022 (13) | 0.0137 (12) |
C26 | 0.0389 (14) | 0.0356 (14) | 0.0364 (14) | −0.0040 (11) | 0.0058 (11) | 0.0127 (11) |
C1—O1 | 1.228 (3) | C15—H15 | 0.9500 |
C1—N1 | 1.348 (3) | C16—H16 | 0.9500 |
C1—C2 | 1.526 (4) | C17—H17A | 0.9800 |
N1—C11 | 1.415 (3) | C17—H17B | 0.9800 |
N1—H1 | 0.8800 | C17—H17C | 0.9800 |
C2—C21 | 1.507 (4) | C21—C26 | 1.387 (4) |
C2—H2A | 0.9900 | C21—C22 | 1.388 (4) |
C2—H2B | 0.9900 | C22—C23 | 1.394 (4) |
C11—C12 | 1.389 (4) | C22—H22 | 0.9500 |
C11—C16 | 1.395 (4) | C23—C24 | 1.375 (5) |
C12—C13 | 1.389 (4) | C23—H23 | 0.9500 |
C12—H12 | 0.9500 | C24—C25 | 1.385 (5) |
C13—C14 | 1.394 (4) | C24—H24 | 0.9500 |
C13—C17 | 1.506 (4) | C25—C26 | 1.383 (4) |
C14—C15 | 1.384 (4) | C25—H25 | 0.9500 |
C14—Br14 | 1.905 (3) | C26—H26 | 0.9500 |
C15—C16 | 1.379 (4) | ||
O1—C1—N1 | 123.2 (2) | C15—C16—C11 | 119.2 (2) |
O1—C1—C2 | 122.6 (2) | C15—C16—H16 | 120.4 |
N1—C1—C2 | 114.2 (2) | C11—C16—H16 | 120.4 |
C1—N1—C11 | 126.1 (2) | C13—C17—H17A | 109.5 |
C1—N1—H1 | 117.0 | C13—C17—H17B | 109.5 |
C11—N1—H1 | 117.0 | H17A—C17—H17B | 109.5 |
C21—C2—C1 | 113.3 (2) | C13—C17—H17C | 109.5 |
C21—C2—H2A | 108.9 | H17A—C17—H17C | 109.5 |
C1—C2—H2A | 108.9 | H17B—C17—H17C | 109.5 |
C21—C2—H2B | 108.9 | C26—C21—C22 | 118.4 (3) |
C1—C2—H2B | 108.9 | C26—C21—C2 | 121.2 (3) |
H2A—C2—H2B | 107.7 | C22—C21—C2 | 120.4 (3) |
C12—C11—C16 | 119.4 (2) | C21—C22—C23 | 120.8 (3) |
C12—C11—N1 | 118.2 (2) | C21—C22—H22 | 119.6 |
C16—C11—N1 | 122.3 (2) | C23—C22—H22 | 119.6 |
C11—C12—C13 | 122.4 (2) | C24—C23—C22 | 120.0 (3) |
C11—C12—H12 | 118.8 | C24—C23—H23 | 120.0 |
C13—C12—H12 | 118.8 | C22—C23—H23 | 120.0 |
C12—C13—C14 | 116.6 (2) | C23—C24—C25 | 119.6 (3) |
C12—C13—C17 | 120.1 (3) | C23—C24—H24 | 120.2 |
C14—C13—C17 | 123.3 (3) | C25—C24—H24 | 120.2 |
C15—C14—C13 | 122.0 (3) | C26—C25—C24 | 120.3 (3) |
C15—C14—Br14 | 117.6 (2) | C26—C25—H25 | 119.9 |
C13—C14—Br14 | 120.4 (2) | C24—C25—H25 | 119.9 |
C16—C15—C14 | 120.4 (2) | C25—C26—C21 | 120.8 (3) |
C16—C15—H15 | 119.8 | C25—C26—H26 | 119.6 |
C14—C15—H15 | 119.8 | C21—C26—H26 | 119.6 |
O1—C1—N1—C11 | −2.7 (4) | Br14—C14—C15—C16 | −179.4 (2) |
C2—C1—N1—C11 | 175.6 (2) | C14—C15—C16—C11 | −0.2 (4) |
O1—C1—C2—C21 | −22.5 (4) | C12—C11—C16—C15 | 0.3 (4) |
N1—C1—C2—C21 | 159.1 (2) | N1—C11—C16—C15 | −178.1 (2) |
C1—N1—C11—C12 | 144.2 (3) | C1—C2—C21—C26 | −69.4 (3) |
C1—N1—C11—C16 | −37.4 (4) | C1—C2—C21—C22 | 110.5 (3) |
C16—C11—C12—C13 | −0.3 (4) | C26—C21—C22—C23 | −0.4 (4) |
N1—C11—C12—C13 | 178.2 (2) | C2—C21—C22—C23 | 179.7 (3) |
C11—C12—C13—C14 | 0.1 (4) | C21—C22—C23—C24 | 0.2 (4) |
C11—C12—C13—C17 | 179.1 (3) | C22—C23—C24—C25 | 0.3 (5) |
C12—C13—C14—C15 | −0.1 (4) | C23—C24—C25—C26 | −0.5 (5) |
C17—C13—C14—C15 | −178.9 (3) | C24—C25—C26—C21 | 0.2 (4) |
C12—C13—C14—Br14 | 179.40 (18) | C22—C21—C26—C25 | 0.2 (4) |
C17—C13—C14—Br14 | 0.5 (4) | C2—C21—C26—C25 | −179.9 (3) |
C13—C14—C15—C16 | 0.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 2.03 | 2.868 (3) | 160 |
C2—H2B···Cg1i | 0.99 | 2.78 | 3.546 (3) | 135 |
Symmetry code: (i) x+1, y, z. |
C15H12Cl3NO | F(000) = 336 |
Mr = 328.61 | Dx = 1.517 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54184 Å |
a = 11.8441 (7) Å | Cell parameters from 2566 reflections |
b = 4.7288 (3) Å | θ = 3.4–72.2° |
c = 13.0981 (7) Å | µ = 5.71 mm−1 |
β = 101.310 (6)° | T = 173 K |
V = 719.36 (7) Å3 | Block, colourless |
Z = 2 | 0.16 × 0.08 × 0.06 mm |
Agilent Eos Gemini diffractometer | 2214 reflections with I > 2σ(I) |
Radiation source: Enhance (Cu) X-ray Source | Rint = 0.039 |
ω scans | θmax = 72.2°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −7→14 |
Tmin = 0.256, Tmax = 0.710 | k = −5→5 |
4196 measured reflections | l = −15→16 |
2566 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.058 | w = 1/[σ2(Fo2) + (0.074P)2 + 0.1558P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.155 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.55 e Å−3 |
2566 reflections | Δρmin = −0.29 e Å−3 |
182 parameters | Absolute structure: Flack x determined using 697 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
1 restraint | Absolute structure parameter: −0.02 (4) |
C15H12Cl3NO | V = 719.36 (7) Å3 |
Mr = 328.61 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 11.8441 (7) Å | µ = 5.71 mm−1 |
b = 4.7288 (3) Å | T = 173 K |
c = 13.0981 (7) Å | 0.16 × 0.08 × 0.06 mm |
β = 101.310 (6)° |
Agilent Eos Gemini diffractometer | 2566 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 2214 reflections with I > 2σ(I) |
Tmin = 0.256, Tmax = 0.710 | Rint = 0.039 |
4196 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.155 | Δρmax = 0.55 e Å−3 |
S = 1.07 | Δρmin = −0.29 e Å−3 |
2566 reflections | Absolute structure: Flack x determined using 697 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
182 parameters | Absolute structure parameter: −0.02 (4) |
1 restraint |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2642 (5) | 0.4768 (13) | 0.5713 (5) | 0.0269 (12) | |
O1 | 0.2599 (4) | 0.7328 (11) | 0.5588 (4) | 0.0396 (11) | |
N1 | 0.2985 (4) | 0.2962 (11) | 0.5045 (4) | 0.0279 (11) | |
H1 | 0.2980 | 0.1145 | 0.5189 | 0.034* | |
C2 | 0.2333 (7) | 0.3377 (15) | 0.6672 (5) | 0.0374 (15) | |
H2A | 0.1727 | 0.1939 | 0.6448 | 0.045* | |
H2B | 0.3020 | 0.2398 | 0.7069 | 0.045* | |
C11 | 0.3360 (5) | 0.3802 (13) | 0.4110 (5) | 0.0260 (12) | |
C12 | 0.2736 (5) | 0.5755 (14) | 0.3438 (5) | 0.0288 (12) | |
H12 | 0.2065 | 0.6576 | 0.3608 | 0.035* | |
C13 | 0.3077 (5) | 0.6540 (14) | 0.2516 (5) | 0.0317 (14) | |
C14 | 0.4081 (5) | 0.5313 (18) | 0.2321 (5) | 0.0383 (16) | |
Cl14 | 0.45559 (16) | 0.6230 (6) | 0.11761 (14) | 0.0585 (7) | |
C15 | 0.4702 (6) | 0.3367 (18) | 0.2978 (5) | 0.0409 (16) | |
H15 | 0.5377 | 0.2550 | 0.2814 | 0.049* | |
C16 | 0.4341 (6) | 0.2593 (16) | 0.3887 (5) | 0.0367 (15) | |
H16 | 0.4766 | 0.1248 | 0.4348 | 0.044* | |
C17 | 0.2369 (7) | 0.8607 (18) | 0.1784 (6) | 0.0434 (17) | |
H17A | 0.2041 | 0.7649 | 0.1130 | 0.065* | |
H17B | 0.2860 | 1.0171 | 0.1644 | 0.065* | |
H17C | 0.1746 | 0.9347 | 0.2102 | 0.065* | |
C21 | 0.1914 (5) | 0.5477 (14) | 0.7367 (5) | 0.0311 (13) | |
C22 | 0.0803 (6) | 0.6557 (13) | 0.7175 (5) | 0.0323 (14) | |
Cl22 | −0.01755 (16) | 0.5362 (5) | 0.60924 (14) | 0.0496 (5) | |
C23 | 0.0429 (6) | 0.8549 (15) | 0.7797 (5) | 0.0327 (13) | |
H23 | −0.0341 | 0.9223 | 0.7644 | 0.039* | |
C24 | 0.1211 (6) | 0.9555 (13) | 0.8660 (5) | 0.0310 (14) | |
Cl24 | 0.07578 (15) | 1.2083 (4) | 0.94506 (12) | 0.0401 (4) | |
C25 | 0.2322 (6) | 0.8551 (16) | 0.8878 (5) | 0.0336 (14) | |
H25 | 0.2854 | 0.9257 | 0.9461 | 0.040* | |
C26 | 0.2663 (5) | 0.6515 (14) | 0.8247 (5) | 0.0333 (15) | |
H26 | 0.3426 | 0.5798 | 0.8416 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.031 (3) | 0.022 (3) | 0.028 (3) | −0.003 (2) | 0.009 (2) | 0.002 (2) |
O1 | 0.062 (3) | 0.024 (2) | 0.038 (2) | −0.001 (2) | 0.022 (2) | 0.002 (2) |
N1 | 0.035 (3) | 0.019 (2) | 0.030 (3) | −0.001 (2) | 0.010 (2) | 0.001 (2) |
C2 | 0.052 (4) | 0.029 (3) | 0.035 (3) | 0.001 (3) | 0.020 (3) | 0.006 (3) |
C11 | 0.027 (3) | 0.023 (3) | 0.027 (3) | 0.000 (2) | 0.004 (2) | −0.003 (2) |
C12 | 0.028 (3) | 0.029 (3) | 0.030 (3) | 0.001 (3) | 0.007 (2) | −0.003 (3) |
C13 | 0.029 (3) | 0.036 (4) | 0.029 (3) | −0.001 (2) | 0.004 (2) | 0.003 (3) |
C14 | 0.035 (3) | 0.056 (5) | 0.026 (3) | −0.004 (3) | 0.011 (2) | 0.003 (3) |
Cl14 | 0.0456 (9) | 0.0954 (18) | 0.0388 (8) | 0.0073 (10) | 0.0183 (7) | 0.0197 (10) |
C15 | 0.032 (3) | 0.055 (4) | 0.038 (3) | 0.010 (3) | 0.014 (3) | 0.000 (3) |
C16 | 0.037 (3) | 0.039 (4) | 0.033 (3) | 0.004 (3) | 0.006 (3) | 0.008 (3) |
C17 | 0.046 (4) | 0.049 (4) | 0.036 (3) | 0.007 (3) | 0.007 (3) | 0.012 (3) |
C21 | 0.041 (3) | 0.024 (3) | 0.032 (3) | −0.004 (3) | 0.017 (2) | 0.007 (3) |
C22 | 0.040 (3) | 0.029 (4) | 0.028 (3) | −0.010 (3) | 0.006 (2) | 0.008 (3) |
Cl22 | 0.0483 (10) | 0.0577 (12) | 0.0400 (9) | −0.0107 (9) | 0.0018 (7) | −0.0027 (9) |
C23 | 0.036 (3) | 0.029 (3) | 0.036 (3) | 0.002 (3) | 0.013 (3) | 0.005 (3) |
C24 | 0.042 (3) | 0.023 (3) | 0.033 (3) | 0.002 (3) | 0.021 (3) | 0.004 (2) |
Cl24 | 0.0554 (10) | 0.0309 (8) | 0.0406 (8) | 0.0052 (7) | 0.0257 (7) | 0.0016 (7) |
C25 | 0.038 (3) | 0.037 (4) | 0.028 (3) | −0.005 (3) | 0.011 (3) | 0.003 (3) |
C26 | 0.032 (3) | 0.037 (4) | 0.033 (3) | 0.002 (3) | 0.010 (2) | 0.011 (3) |
C1—O1 | 1.221 (8) | C15—H15 | 0.9500 |
C1—N1 | 1.341 (8) | C16—H16 | 0.9500 |
C1—C2 | 1.526 (8) | C17—H17A | 0.9800 |
N1—C11 | 1.439 (7) | C17—H17B | 0.9800 |
N1—H1 | 0.8800 | C17—H17C | 0.9800 |
C2—C21 | 1.495 (9) | C21—C22 | 1.387 (9) |
C2—H2A | 0.9900 | C21—C26 | 1.399 (9) |
C2—H2B | 0.9900 | C22—C23 | 1.375 (9) |
C11—C16 | 1.377 (9) | C22—Cl22 | 1.740 (6) |
C11—C12 | 1.385 (9) | C23—C24 | 1.397 (10) |
C12—C13 | 1.397 (8) | C23—H23 | 0.9500 |
C12—H12 | 0.9500 | C24—C25 | 1.376 (9) |
C13—C14 | 1.391 (9) | C24—Cl24 | 1.734 (6) |
C13—C17 | 1.504 (9) | C25—C26 | 1.379 (9) |
C14—C15 | 1.372 (11) | C25—H25 | 0.9500 |
C14—Cl14 | 1.756 (6) | C26—H26 | 0.9500 |
C15—C16 | 1.390 (9) | ||
O1—C1—N1 | 123.6 (6) | C11—C16—C15 | 119.1 (6) |
O1—C1—C2 | 121.8 (6) | C11—C16—H16 | 120.4 |
N1—C1—C2 | 114.5 (5) | C15—C16—H16 | 120.4 |
C1—N1—C11 | 124.3 (5) | C13—C17—H17A | 109.5 |
C1—N1—H1 | 117.9 | C13—C17—H17B | 109.5 |
C11—N1—H1 | 117.9 | H17A—C17—H17B | 109.5 |
C21—C2—C1 | 112.1 (6) | C13—C17—H17C | 109.5 |
C21—C2—H2A | 109.2 | H17A—C17—H17C | 109.5 |
C1—C2—H2A | 109.2 | H17B—C17—H17C | 109.5 |
C21—C2—H2B | 109.2 | C22—C21—C26 | 116.4 (6) |
C1—C2—H2B | 109.2 | C22—C21—C2 | 123.4 (6) |
H2A—C2—H2B | 107.9 | C26—C21—C2 | 120.1 (6) |
C16—C11—C12 | 120.6 (6) | C23—C22—C21 | 123.3 (6) |
C16—C11—N1 | 118.7 (5) | C23—C22—Cl22 | 117.7 (5) |
C12—C11—N1 | 120.6 (5) | C21—C22—Cl22 | 119.0 (5) |
C11—C12—C13 | 121.2 (5) | C22—C23—C24 | 118.3 (6) |
C11—C12—H12 | 119.4 | C22—C23—H23 | 120.9 |
C13—C12—H12 | 119.4 | C24—C23—H23 | 120.9 |
C14—C13—C12 | 116.8 (6) | C25—C24—C23 | 120.4 (6) |
C14—C13—C17 | 122.9 (6) | C25—C24—Cl24 | 120.6 (6) |
C12—C13—C17 | 120.3 (6) | C23—C24—Cl24 | 119.0 (5) |
C15—C14—C13 | 122.5 (6) | C24—C25—C26 | 119.8 (6) |
C15—C14—Cl14 | 118.7 (5) | C24—C25—H25 | 120.1 |
C13—C14—Cl14 | 118.9 (5) | C26—C25—H25 | 120.1 |
C14—C15—C16 | 119.8 (6) | C25—C26—C21 | 121.8 (6) |
C14—C15—H15 | 120.1 | C25—C26—H26 | 119.1 |
C16—C15—H15 | 120.1 | C21—C26—H26 | 119.1 |
O1—C1—N1—C11 | 0.9 (10) | N1—C11—C16—C15 | 179.2 (6) |
C2—C1—N1—C11 | −177.5 (5) | C14—C15—C16—C11 | 0.0 (12) |
O1—C1—C2—C21 | 3.8 (10) | C1—C2—C21—C22 | 79.3 (8) |
N1—C1—C2—C21 | −177.8 (6) | C1—C2—C21—C26 | −98.9 (7) |
C1—N1—C11—C16 | 134.5 (7) | C26—C21—C22—C23 | 0.2 (9) |
C1—N1—C11—C12 | −46.5 (9) | C2—C21—C22—C23 | −178.0 (6) |
C16—C11—C12—C13 | 0.4 (10) | C26—C21—C22—Cl22 | −180.0 (4) |
N1—C11—C12—C13 | −178.5 (6) | C2—C21—C22—Cl22 | 1.8 (8) |
C11—C12—C13—C14 | −1.3 (10) | C21—C22—C23—C24 | 0.7 (10) |
C11—C12—C13—C17 | 178.3 (6) | Cl22—C22—C23—C24 | −179.1 (5) |
C12—C13—C14—C15 | 1.6 (11) | C22—C23—C24—C25 | −0.4 (9) |
C17—C13—C14—C15 | −178.0 (7) | C22—C23—C24—Cl24 | 179.6 (5) |
C12—C13—C14—Cl14 | −179.7 (5) | C23—C24—C25—C26 | −0.7 (9) |
C17—C13—C14—Cl14 | 0.6 (10) | Cl24—C24—C25—C26 | 179.2 (5) |
C13—C14—C15—C16 | −1.0 (12) | C24—C25—C26—C21 | 1.7 (9) |
Cl14—C14—C15—C16 | −179.7 (6) | C22—C21—C26—C25 | −1.4 (9) |
C12—C11—C16—C15 | 0.2 (10) | C2—C21—C26—C25 | 176.9 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.96 | 2.818 (7) | 166 |
C2—H2A···Cg1i | 0.99 | 2.96 | 3.498 (8) | 115 |
Symmetry code: (i) x, y−1, z. |
C15H13BrClNO | F(000) = 680 |
Mr = 338.62 | Dx = 1.618 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8458 (8) Å | Cell parameters from 4745 reflections |
b = 4.7282 (3) Å | θ = 3.3–33.0° |
c = 25.0757 (15) Å | µ = 3.14 mm−1 |
β = 98.133 (5)° | T = 173 K |
V = 1390.35 (15) Å3 | Needle, colourless |
Z = 4 | 0.38 × 0.12 × 0.08 mm |
Agilent Eos Gemini diffractometer | 2177 reflections with I > 2σ(I) |
Radiation source: Enhance (Mo) X-ray Source | Rint = 0.084 |
ω scans | θmax = 27.6°, θmin = 3.3° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −15→15 |
Tmin = 0.373, Tmax = 0.778 | k = −5→6 |
10821 measured reflections | l = −30→32 |
3201 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.064 | H-atom parameters constrained |
wR(F2) = 0.141 | w = 1/[σ2(Fo2) + (0.0429P)2 + 0.2861P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
3201 reflections | Δρmax = 0.58 e Å−3 |
173 parameters | Δρmin = −0.67 e Å−3 |
C15H13BrClNO | V = 1390.35 (15) Å3 |
Mr = 338.62 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.8458 (8) Å | µ = 3.14 mm−1 |
b = 4.7282 (3) Å | T = 173 K |
c = 25.0757 (15) Å | 0.38 × 0.12 × 0.08 mm |
β = 98.133 (5)° |
Agilent Eos Gemini diffractometer | 3201 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 2177 reflections with I > 2σ(I) |
Tmin = 0.373, Tmax = 0.778 | Rint = 0.084 |
10821 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.58 e Å−3 |
3201 reflections | Δρmin = −0.67 e Å−3 |
173 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2579 (3) | 0.6288 (9) | 0.29380 (16) | 0.0230 (9) | |
O1 | 0.2592 (3) | 0.8859 (6) | 0.28824 (12) | 0.0346 (8) | |
N1 | 0.2915 (3) | 0.4470 (7) | 0.25784 (13) | 0.0235 (8) | |
H1 | 0.2877 | 0.2651 | 0.2648 | 0.028* | |
C2 | 0.2236 (4) | 0.4897 (9) | 0.34319 (17) | 0.0305 (10) | |
H2A | 0.2910 | 0.3969 | 0.3638 | 0.037* | |
H2B | 0.1660 | 0.3417 | 0.3320 | 0.037* | |
C11 | 0.3328 (3) | 0.5284 (8) | 0.20926 (16) | 0.0203 (9) | |
C12 | 0.2722 (4) | 0.7259 (8) | 0.17483 (17) | 0.0243 (9) | |
H12 | 0.2036 | 0.8044 | 0.1839 | 0.029* | |
C13 | 0.3114 (4) | 0.8082 (8) | 0.12760 (17) | 0.0234 (9) | |
C14 | 0.4118 (4) | 0.6899 (9) | 0.11661 (16) | 0.0247 (9) | |
Br14 | 0.47195 (4) | 0.79352 (12) | 0.05281 (2) | 0.0442 (2) | |
C15 | 0.4720 (4) | 0.4935 (10) | 0.14980 (17) | 0.0301 (10) | |
H15 | 0.5409 | 0.4160 | 0.1409 | 0.036* | |
C16 | 0.4307 (4) | 0.4104 (9) | 0.19651 (17) | 0.0272 (10) | |
H16 | 0.4704 | 0.2722 | 0.2195 | 0.033* | |
C17 | 0.2426 (4) | 1.0184 (9) | 0.09054 (18) | 0.0318 (11) | |
H17A | 0.2168 | 0.9282 | 0.0558 | 0.048* | |
H17B | 0.2904 | 1.1822 | 0.0851 | 0.048* | |
H17C | 0.1763 | 1.0805 | 0.1068 | 0.048* | |
C21 | 0.1750 (4) | 0.7001 (8) | 0.37901 (17) | 0.0251 (9) | |
C22 | 0.0654 (4) | 0.8118 (10) | 0.36675 (18) | 0.0313 (10) | |
Cl22 | −0.01863 (11) | 0.7074 (3) | 0.30764 (5) | 0.0498 (4) | |
C23 | 0.0216 (4) | 1.0041 (10) | 0.4003 (2) | 0.0383 (12) | |
H23 | −0.0539 | 1.0738 | 0.3914 | 0.046* | |
C24 | 0.0888 (5) | 1.0927 (10) | 0.4464 (2) | 0.0405 (12) | |
H24 | 0.0598 | 1.2268 | 0.4693 | 0.049* | |
C25 | 0.1984 (4) | 0.9884 (11) | 0.4600 (2) | 0.0408 (12) | |
H25 | 0.2444 | 1.0488 | 0.4921 | 0.049* | |
C26 | 0.2400 (4) | 0.7939 (9) | 0.42601 (18) | 0.0326 (11) | |
H26 | 0.3153 | 0.7232 | 0.4353 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.025 (2) | 0.021 (2) | 0.023 (2) | −0.0002 (17) | 0.0062 (16) | 0.0026 (16) |
O1 | 0.063 (2) | 0.0094 (15) | 0.0360 (19) | −0.0026 (14) | 0.0208 (15) | 0.0031 (12) |
N1 | 0.037 (2) | 0.0104 (18) | 0.024 (2) | −0.0017 (14) | 0.0070 (15) | 0.0050 (13) |
C2 | 0.042 (3) | 0.023 (2) | 0.029 (3) | 0.006 (2) | 0.015 (2) | 0.0035 (18) |
C11 | 0.025 (2) | 0.013 (2) | 0.022 (2) | −0.0036 (16) | 0.0009 (16) | 0.0006 (15) |
C12 | 0.026 (2) | 0.020 (2) | 0.027 (2) | −0.0006 (17) | 0.0046 (17) | 0.0011 (16) |
C13 | 0.029 (2) | 0.015 (2) | 0.026 (2) | −0.0026 (17) | 0.0004 (17) | 0.0012 (16) |
C14 | 0.025 (2) | 0.028 (2) | 0.022 (2) | −0.0089 (18) | 0.0053 (16) | −0.0027 (17) |
Br14 | 0.0441 (3) | 0.0629 (4) | 0.0279 (3) | −0.0102 (3) | 0.0128 (2) | 0.0054 (2) |
C15 | 0.025 (2) | 0.037 (3) | 0.029 (3) | −0.0005 (19) | 0.0035 (18) | −0.0037 (19) |
C16 | 0.024 (2) | 0.024 (2) | 0.033 (3) | 0.0054 (18) | 0.0050 (18) | 0.0010 (18) |
C17 | 0.041 (3) | 0.023 (3) | 0.031 (3) | 0.001 (2) | 0.002 (2) | 0.0061 (18) |
C21 | 0.033 (3) | 0.018 (2) | 0.026 (2) | 0.0011 (18) | 0.0109 (18) | 0.0037 (17) |
C22 | 0.035 (3) | 0.032 (3) | 0.027 (3) | −0.012 (2) | 0.0063 (19) | 0.0043 (19) |
Cl22 | 0.0424 (8) | 0.0640 (10) | 0.0407 (8) | −0.0137 (6) | −0.0021 (6) | −0.0001 (6) |
C23 | 0.037 (3) | 0.035 (3) | 0.046 (3) | 0.003 (2) | 0.016 (2) | 0.006 (2) |
C24 | 0.056 (3) | 0.027 (3) | 0.044 (3) | 0.004 (2) | 0.025 (2) | −0.003 (2) |
C25 | 0.055 (3) | 0.039 (3) | 0.029 (3) | −0.002 (2) | 0.009 (2) | −0.007 (2) |
C26 | 0.039 (3) | 0.031 (3) | 0.029 (3) | 0.002 (2) | 0.007 (2) | 0.0017 (19) |
C1—O1 | 1.224 (5) | C15—H15 | 0.9500 |
C1—N1 | 1.346 (5) | C16—H16 | 0.9500 |
C1—C2 | 1.508 (5) | C17—H17A | 0.9800 |
N1—C11 | 1.428 (5) | C17—H17B | 0.9800 |
N1—H1 | 0.8800 | C17—H17C | 0.9800 |
C2—C21 | 1.508 (6) | C21—C26 | 1.387 (6) |
C2—H2A | 0.9900 | C21—C22 | 1.395 (6) |
C2—H2B | 0.9900 | C22—C23 | 1.388 (6) |
C11—C16 | 1.365 (6) | C22—Cl22 | 1.736 (5) |
C11—C12 | 1.399 (5) | C23—C24 | 1.374 (7) |
C12—C13 | 1.387 (6) | C23—H23 | 0.9500 |
C12—H12 | 0.9500 | C24—C25 | 1.385 (7) |
C13—C14 | 1.377 (6) | C24—H24 | 0.9500 |
C13—C17 | 1.517 (5) | C25—C26 | 1.391 (6) |
C14—C15 | 1.377 (6) | C25—H25 | 0.9500 |
C14—Br14 | 1.905 (4) | C26—H26 | 0.9500 |
C15—C16 | 1.388 (6) | ||
O1—C1—N1 | 123.3 (4) | C11—C16—C15 | 119.6 (4) |
O1—C1—C2 | 122.4 (4) | C11—C16—H16 | 120.2 |
N1—C1—C2 | 114.3 (4) | C15—C16—H16 | 120.2 |
C1—N1—C11 | 124.7 (3) | C13—C17—H17A | 109.5 |
C1—N1—H1 | 117.7 | C13—C17—H17B | 109.5 |
C11—N1—H1 | 117.7 | H17A—C17—H17B | 109.5 |
C1—C2—C21 | 111.8 (3) | C13—C17—H17C | 109.5 |
C1—C2—H2A | 109.3 | H17A—C17—H17C | 109.5 |
C21—C2—H2A | 109.3 | H17B—C17—H17C | 109.5 |
C1—C2—H2B | 109.3 | C26—C21—C22 | 117.0 (4) |
C21—C2—H2B | 109.3 | C26—C21—C2 | 120.3 (4) |
H2A—C2—H2B | 107.9 | C22—C21—C2 | 122.7 (4) |
C16—C11—C12 | 120.5 (4) | C23—C22—C21 | 122.0 (4) |
C16—C11—N1 | 119.6 (4) | C23—C22—Cl22 | 119.0 (4) |
C12—C11—N1 | 119.9 (4) | C21—C22—Cl22 | 118.9 (4) |
C13—C12—C11 | 120.7 (4) | C24—C23—C22 | 119.3 (5) |
C13—C12—H12 | 119.7 | C24—C23—H23 | 120.4 |
C11—C12—H12 | 119.7 | C22—C23—H23 | 120.4 |
C14—C13—C12 | 117.3 (4) | C23—C24—C25 | 120.6 (5) |
C14—C13—C17 | 123.2 (4) | C23—C24—H24 | 119.7 |
C12—C13—C17 | 119.5 (4) | C25—C24—H24 | 119.7 |
C13—C14—C15 | 122.8 (4) | C24—C25—C26 | 119.1 (5) |
C13—C14—Br14 | 120.0 (3) | C24—C25—H25 | 120.4 |
C15—C14—Br14 | 117.2 (3) | C26—C25—H25 | 120.4 |
C14—C15—C16 | 119.1 (4) | C21—C26—C25 | 122.0 (5) |
C14—C15—H15 | 120.5 | C21—C26—H26 | 119.0 |
C16—C15—H15 | 120.5 | C25—C26—H26 | 119.0 |
O1—C1—N1—C11 | 0.3 (6) | C12—C11—C16—C15 | 1.9 (6) |
C2—C1—N1—C11 | −177.0 (4) | N1—C11—C16—C15 | −178.8 (4) |
O1—C1—C2—C21 | 8.9 (6) | C14—C15—C16—C11 | −1.3 (7) |
N1—C1—C2—C21 | −173.8 (4) | C1—C2—C21—C26 | −103.7 (5) |
C1—N1—C11—C16 | 131.9 (4) | C1—C2—C21—C22 | 75.5 (5) |
C1—N1—C11—C12 | −48.7 (6) | C26—C21—C22—C23 | −1.2 (6) |
C16—C11—C12—C13 | −0.9 (6) | C2—C21—C22—C23 | 179.6 (4) |
N1—C11—C12—C13 | 179.7 (4) | C26—C21—C22—Cl22 | 178.6 (3) |
C11—C12—C13—C14 | −0.6 (6) | C2—C21—C22—Cl22 | −0.5 (6) |
C11—C12—C13—C17 | 178.8 (4) | C21—C22—C23—C24 | 1.4 (7) |
C12—C13—C14—C15 | 1.1 (6) | Cl22—C22—C23—C24 | −178.4 (4) |
C17—C13—C14—C15 | −178.2 (4) | C22—C23—C24—C25 | −1.0 (7) |
C12—C13—C14—Br14 | −179.6 (3) | C23—C24—C25—C26 | 0.5 (7) |
C17—C13—C14—Br14 | 1.1 (6) | C22—C21—C26—C25 | 0.6 (7) |
C13—C14—C15—C16 | −0.2 (7) | C2—C21—C26—C25 | 179.8 (4) |
Br14—C14—C15—C16 | −179.5 (3) | C24—C25—C26—C21 | −0.3 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.88 | 1.93 | 2.802 (4) | 170 |
C2—H2B···Cg1i | 0.99 | 2.99 | 3.552 (5) | 117 |
Symmetry code: (i) x, y−1, z. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C15H14ClNO | C15H14BrNO | C15H12Cl3NO | C15H13BrClNO |
Mr | 259.72 | 304.18 | 328.61 | 338.62 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Monoclinic, P21 | Monoclinic, P21/c |
Temperature (K) | 173 | 173 | 173 | 173 |
a, b, c (Å) | 5.0039 (7), 10.7525 (12), 12.6177 (12) | 4.9995 (3), 10.8392 (4), 12.7301 (7) | 11.8441 (7), 4.7288 (3), 13.0981 (7) | 11.8458 (8), 4.7282 (3), 25.0757 (15) |
α, β, γ (°) | 108.615 (10), 91.771 (11), 90.167 (11) | 108.149 (4), 91.968 (5), 90.310 (4) | 90, 101.310 (6), 90 | 90, 98.133 (5), 90 |
V (Å3) | 643.01 (14) | 655.05 (6) | 719.36 (7) | 1390.35 (15) |
Z | 2 | 2 | 2 | 4 |
Radiation type | Cu Kα | Cu Kα | Cu Kα | Mo Kα |
µ (mm−1) | 2.51 | 4.16 | 5.71 | 3.14 |
Crystal size (mm) | 0.28 × 0.16 × 0.08 | 0.32 × 0.18 × 0.08 | 0.16 × 0.08 × 0.06 | 0.38 × 0.12 × 0.08 |
Data collection | ||||
Diffractometer | Agilent Eos Gemini diffractometer | Agilent Eos Gemini diffractometer | Agilent Eos Gemini diffractometer | Agilent Eos Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) | Multi-scan (CrysAlis PRO; Agilent, 2012) | Multi-scan (CrysAlis PRO; Agilent, 2012) | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.413, 0.818 | 0.286, 0.818 | 0.256, 0.710 | 0.373, 0.778 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3772, 2447, 1865 | 3876, 2515, 2276 | 4196, 2566, 2214 | 10821, 3201, 2177 |
Rint | 0.032 | 0.039 | 0.039 | 0.084 |
(sin θ/λ)max (Å−1) | 0.618 | 0.618 | 0.617 | 0.651 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.187, 1.09 | 0.042, 0.110, 1.07 | 0.058, 0.155, 1.07 | 0.064, 0.141, 1.08 |
No. of reflections | 2447 | 2515 | 2566 | 3201 |
No. of parameters | 164 | 164 | 182 | 173 |
No. of restraints | 0 | 0 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.30 | 0.72, −0.45 | 0.55, −0.29 | 0.58, −0.67 |
Absolute structure | ? | ? | Flack x determined using 697 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) | ? |
Absolute structure parameter | ? | ? | −0.02 (4) | ? |
Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL2014 (Sheldrick, 2014) and PLATON (Spek, 2009).
Compound | θ1 | θ2 | θ3 | θ4 | θ5 |
(I) | 175.8 (3) | 144.4 (3) | 161.6 (3) | 109.2 (4) | 71.96 (16) |
(II) | 175.6 (1) | 144.2 (3) | 159.1 (2) | 110.5 (3) | 72.03 (14) |
(III) | -177.5 (5) | 134.5 (7) | -177.8 (6) | 79.3 (8) | 63.5 (3) |
(IV) | -177.0 (4) | 131.9 (4) | -173.8 (4) | 75.5 (5) | 60.1 (2) |
(V) | -177.6 (4) | 133.5 (4) | 174.7 (4) | 89.9 (5) | 68.21 (19) |
(VI) | -173.4 (3) | 139.2 (4) | -175.1 (3) | 80.6 (4) | 65.21 (18) |
(VII) | -173.6 (5) | 138.7 (6) | -175.4 (5) | 83.5 (7) | 66.4 (3) |
Notes: θ1 represents the torsion angle C2—C1—N1—C11; θ2 represents the torsion angle C1—N1—C11—C12 for compounds (I) and (II) and the torsion angle C1—N1—C11—C16 for compounds (III) and (IV); θ3 represents the torsion angle N1—C1—C2—C21; θ4 represents the torsion angle C1—C2—C21—C22; θ5 represents the dihedral angle between the two ring planes. For compounds (V)–(VII), the original atom numbering has been modified to match that in compound (I) |
Compound | D—H···A | D—H | H···A | D···A | D—H···A | |
(I) | N1—H1···O1i | 0.88 | 2.03 | 2.878 (3) | 161 | |
C2—H2B···Cg1i | 0.99 | 2.81 | 3.546 (4) | 132 | ||
(II) | N1—H1···O1i | 0.88 | 2.03 | 2.868 (3) | 160 | |
C2—H2B···Cg1i | 0.99 | 2.78 | 3.546 (3) | 135 | ||
(III) | N1—H1···O1ii | 0.88 | 1.96 | 2.818 (7) | 166 | |
C2—H2A···Cg1ii | 0.99 | 2.96 | 3.498 (8) | 115 | ||
(IV) | N1—H1···O1ii | 0.88 | 1.93 | 2.802 (4) | 170 | |
C2—H2B···Cg1ii | 0.99 | 2.99 | 3.552 (5) | 117 |
Symmetry codes: (i) x+1, y, z; (ii) x, y-1, z. Cg1 represents the centroid of the C21–C26 ring. |