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The crystal structures of five new salts of 2-chloro-4-nitroaniline (2Cl4na) and 2-methyl-6-nitroaniline (2m6na) with inorganic acids, namely, 2-chloro-4-nitroanilinium bromide, C
6H
6ClN
2O
2+·Br
− (
1), 2-chloro-4-nitroanilinium hydrogen sulfate, C
6H
6ClN
2O
2+·HSO
4− (
2), 2-methyl-6-nitroanilinium bromide, C
7H
9N
2O
2+·Br
− (
3), 2-methyl-6-nitroanilinium triiodide, C
7H
9N
2O
2+·I
3− (
4), and 2-methyl-6-nitroanilinium hydrogen sulfate, C
7H
9N
2O
2+·HSO
4− (
5), were determined by single-crystal X-ray diffraction. Theoretical calculations of the relaxed potential energy surface (rPES) revealed that the energy barriers for the rotation of the nitro group for isolated H2Cl4na
+ and H2m6na
+ cations are 4.6 and 11.6 kcal mol
−1, respectively. The ammonium group and respective anions form hydrogen bonds which are the most important interactions and are arranged in zero- (in
3), one- (in
1 and
4) or two-dimensional (in
2 and
5) networks. Hydrogen-bonding patterns were analyzed by means of mathematical relationships between graph-set descriptors and compared with previously reported nitroaniline salts. Hirshfeld surface analysis indicates that the nitro group plays a dominant role among the weak interactions,
i.e. C—H
O(NO
2), NO
2π(Ar) and O(NO
2)
π(NO
2). The frequency of the ν
sNO
2 vibration is correlated with the type of interaction in which the NO
2 group is involved. Analysis of the ν
sNO
2 band observed in the IR and Raman spectra allowed an assessment of its shift in the sequence (H2m6na)I
3 (
4) < (H2m6na)HSO
4 (
5) < (H2m6na)Br (
3) < (H2Cl4na)Br (
1) < (H2Cl4na)HSO
4 (
2).
Supporting information
CCDC references: 2043369; 2043368; 2043367; 2043366; 2043365
Data collection: CrysAlis PRO (Rigaku OD, 2015) for (1), (2), (3), (5); CrysAlis PRO (Rigaku OD, 2018) for (4). Cell refinement: CrysAlis PRO (Rigaku OD, 2015) for (1), (2), (3), (5); CrysAlis PRO (Rigaku OD, 2018) for (4). Data reduction: CrysAlis PRO (Rigaku OD, 2015) for (1), (2), (3), (5); CrysAlis PRO (Rigaku OD, 2018) for (4). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (1), (2); SHELXT (Sheldrick, 2015a) for (3), (4), (5). For all structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2008) and OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
2-Chloro-4-nitroanilinium bromide (1)
top
Crystal data top
C6H6ClN2O2+·Br− | Dx = 1.837 Mg m−3 |
Mr = 253.49 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 7548 reflections |
a = 5.72152 (9) Å | θ = 2.8–27.4° |
b = 7.90017 (17) Å | µ = 4.74 mm−1 |
c = 20.2729 (4) Å | T = 295 K |
V = 916.35 (3) Å3 | Block, clear yellowish colourless |
Z = 4 | 0.36 × 0.26 × 0.22 mm |
F(000) = 496 | |
Data collection top
Rigaku Xcalibur Atlas diffractometer | 2669 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 2340 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 10.6249 pixels mm-1 | θmax = 30.0°, θmin = 2.8° |
ω scans | h = −8→8 |
Absorption correction: analytical {CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by
Clark & Reid (1995)] | k = −11→11 |
Tmin = 0.300, Tmax = 0.446 | l = −28→28 |
18773 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0322P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.062 | (Δ/σ)max = 0.002 |
S = 1.13 | Δρmax = 0.33 e Å−3 |
2669 reflections | Δρmin = −0.70 e Å−3 |
113 parameters | Absolute structure: Flack x determined using 881 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
0 restraints | Absolute structure parameter: −0.008 (4) |
Primary atom site location: structure-invariant direct methods | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. X-ray diffraction data were collected on an Oxford Diffraction
four-circle single crystal diffractometer equipped with a CCD detector using
graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw
data were treated with the CrysAlis Data Reduction Program, version
1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected
for Lorentz and polarization effects. The crystal structures were solved by
direct methods (Sheldrick, 2008) and refined by full-matrix least-squares
methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software
(Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.52443 (5) | 0.84406 (4) | 0.58461 (2) | 0.04093 (10) | |
Cl1 | −0.31036 (14) | 0.35586 (13) | 0.53964 (4) | 0.0489 (2) | |
O1 | 0.0516 (5) | −0.1126 (3) | 0.68972 (13) | 0.0555 (7) | |
O2 | 0.2906 (5) | 0.0104 (4) | 0.75612 (13) | 0.0684 (8) | |
N1 | 0.0211 (4) | 0.6339 (3) | 0.57628 (13) | 0.0376 (6) | |
H1A | 0.139212 | 0.703405 | 0.585339 | 0.051 (11)* | |
H1B | −0.112446 | 0.680764 | 0.589483 | 0.061 (12)* | |
H1C | 0.015304 | 0.615323 | 0.533010 | 0.058 (12)* | |
N2 | 0.1576 (5) | 0.0117 (4) | 0.70883 (14) | 0.0435 (7) | |
C1 | 0.0557 (5) | 0.4735 (4) | 0.61076 (14) | 0.0315 (6) | |
C2 | −0.0893 (5) | 0.3361 (4) | 0.59723 (13) | 0.0316 (6) | |
C3 | −0.0560 (5) | 0.1838 (4) | 0.62907 (14) | 0.0353 (6) | |
H3 | −0.150708 | 0.090853 | 0.620220 | 0.042* | |
C4 | 0.1227 (5) | 0.1743 (4) | 0.67451 (14) | 0.0336 (6) | |
C5 | 0.2665 (6) | 0.3069 (5) | 0.68918 (16) | 0.0411 (8) | |
H5 | 0.385125 | 0.295483 | 0.720224 | 0.049* | |
C6 | 0.2312 (6) | 0.4597 (4) | 0.65653 (15) | 0.0384 (7) | |
H6 | 0.326256 | 0.552208 | 0.665712 | 0.046* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.03208 (15) | 0.03898 (17) | 0.05173 (17) | −0.00640 (13) | −0.00074 (12) | 0.00111 (15) |
Cl1 | 0.0427 (4) | 0.0490 (5) | 0.0550 (4) | −0.0100 (4) | −0.0201 (3) | 0.0017 (4) |
O1 | 0.0662 (17) | 0.0372 (14) | 0.0631 (15) | −0.0065 (13) | 0.0010 (13) | 0.0077 (11) |
O2 | 0.073 (2) | 0.064 (2) | 0.0680 (17) | 0.0007 (16) | −0.0280 (15) | 0.0191 (16) |
N1 | 0.0321 (12) | 0.0338 (13) | 0.0470 (14) | −0.0041 (11) | −0.0043 (11) | 0.0024 (11) |
N2 | 0.0447 (16) | 0.0424 (18) | 0.0433 (14) | 0.0014 (14) | 0.0024 (13) | 0.0069 (14) |
C1 | 0.0283 (14) | 0.0320 (15) | 0.0342 (13) | −0.0022 (12) | 0.0033 (11) | 0.0001 (12) |
C2 | 0.0273 (12) | 0.0336 (15) | 0.0339 (13) | −0.0016 (12) | −0.0019 (9) | −0.0050 (14) |
C3 | 0.0364 (14) | 0.0300 (16) | 0.0395 (14) | −0.0072 (12) | 0.0003 (12) | −0.0037 (13) |
C4 | 0.0358 (14) | 0.0310 (16) | 0.0340 (13) | −0.0002 (14) | 0.0020 (11) | 0.0009 (14) |
C5 | 0.0368 (16) | 0.046 (2) | 0.0409 (16) | −0.0033 (15) | −0.0098 (13) | 0.0050 (15) |
C6 | 0.0343 (16) | 0.0383 (18) | 0.0424 (15) | −0.0106 (14) | −0.0076 (13) | 0.0005 (15) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.729 (3) | C1—C6 | 1.371 (4) |
O1—N2 | 1.217 (4) | C2—C3 | 1.379 (4) |
O2—N2 | 1.224 (4) | C3—H3 | 0.9300 |
N1—H1A | 0.8900 | C3—C4 | 1.378 (4) |
N1—H1B | 0.8900 | C4—C5 | 1.365 (5) |
N1—H1C | 0.8900 | C5—H5 | 0.9300 |
N1—C1 | 1.461 (4) | C5—C6 | 1.391 (5) |
N2—C4 | 1.475 (4) | C6—H6 | 0.9300 |
C1—C2 | 1.393 (4) | | |
| | | |
H1A—N1—H1B | 109.5 | C3—C2—C1 | 120.4 (3) |
H1A—N1—H1C | 109.5 | C2—C3—H3 | 121.2 |
H1B—N1—H1C | 109.5 | C4—C3—C2 | 117.6 (3) |
C1—N1—H1A | 109.5 | C4—C3—H3 | 121.2 |
C1—N1—H1B | 109.5 | C3—C4—N2 | 117.6 (3) |
C1—N1—H1C | 109.5 | C5—C4—N2 | 119.0 (3) |
O1—N2—O2 | 123.5 (3) | C5—C4—C3 | 123.4 (3) |
O1—N2—C4 | 119.0 (3) | C4—C5—H5 | 120.8 |
O2—N2—C4 | 117.5 (3) | C4—C5—C6 | 118.3 (3) |
C2—C1—N1 | 120.1 (3) | C6—C5—H5 | 120.8 |
C6—C1—N1 | 119.5 (3) | C1—C6—C5 | 119.8 (3) |
C6—C1—C2 | 120.5 (3) | C1—C6—H6 | 120.1 |
C1—C2—Cl1 | 119.9 (2) | C5—C6—H6 | 120.1 |
C3—C2—Cl1 | 119.7 (2) | | |
| | | |
Cl1—C2—C3—C4 | 179.9 (2) | C1—C2—C3—C4 | 0.6 (4) |
O1—N2—C4—C3 | 10.1 (5) | C2—C1—C6—C5 | 0.7 (5) |
O1—N2—C4—C5 | −170.2 (3) | C2—C3—C4—N2 | 179.7 (3) |
O2—N2—C4—C3 | −168.8 (3) | C2—C3—C4—C5 | −0.1 (5) |
O2—N2—C4—C5 | 10.9 (5) | C3—C4—C5—C6 | −0.1 (5) |
N1—C1—C2—Cl1 | −0.1 (4) | C4—C5—C6—C1 | −0.2 (5) |
N1—C1—C2—C3 | 179.3 (3) | C6—C1—C2—Cl1 | 179.7 (2) |
N1—C1—C6—C5 | −179.5 (3) | C6—C1—C2—C3 | −0.9 (4) |
N2—C4—C5—C6 | −179.8 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br1 | 0.89 | 2.47 | 3.329 (2) | 163 |
N1—H1B···Br1i | 0.89 | 2.45 | 3.295 (2) | 159 |
N1—H1C···Br1ii | 0.89 | 2.41 | 3.266 (3) | 163 |
C3—H3···Br1iii | 0.93 | 2.79 | 3.712 (3) | 172 |
C5—H5···O2iv | 0.93 | 2.56 | 3.199 (4) | 126 |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z+1; (iii) x−1, y−1, z; (iv) −x+1, y+1/2, −z+3/2. |
2-Chloro-4-nitroanilinium hydrogen sulfate (2)
top
Crystal data top
C6H6ClN2O2+·HSO4− | F(000) = 552 |
Mr = 270.65 | Dx = 1.783 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.1771 (6) Å | Cell parameters from 1898 reflections |
b = 4.95335 (16) Å | θ = 3.2–31.7° |
c = 12.8431 (5) Å | µ = 0.60 mm−1 |
β = 101.584 (4)° | T = 295 K |
V = 1008.17 (7) Å3 | Plate, clear light colourless |
Z = 4 | 0.56 × 0.46 × 0.06 mm |
Data collection top
Rigaku Xcalibur Atlas diffractometer | 2923 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 2351 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 10.6249 pixels mm-1 | θmax = 30.0°, θmin = 2.6° |
ω scans | h = −22→22 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −6→6 |
Tmin = 0.967, Tmax = 1.000 | l = −9→18 |
6028 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.036 | Hetero |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0452P)2 + 0.2615P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2923 reflections | Δρmax = 0.52 e Å−3 |
161 parameters | Δρmin = −0.55 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. X-ray diffraction data were collected on an Oxford Diffraction
four-circle single crystal diffractometer equipped with a CCD detector using
graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw
data were treated with the CrysAlis Data Reduction Program, version
1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected
for Lorentz and polarization effects. The crystal structures were solved by
direct methods (Sheldrick, 2008) and refined by full-matrix least-squares
methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software
(Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.23626 (3) | 0.96745 (10) | −0.12914 (4) | 0.03739 (14) | |
O1 | 0.53464 (9) | 0.7499 (4) | 0.09311 (14) | 0.0535 (4) | |
O2 | 0.52394 (9) | 0.4068 (4) | 0.19099 (14) | 0.0506 (4) | |
N1 | 0.14105 (9) | 0.5553 (3) | −0.03115 (12) | 0.0241 (3) | |
H1A | 0.1199 (14) | 0.422 (5) | 0.0078 (17) | 0.035 (6)* | |
H1B | 0.1317 (16) | 0.517 (5) | −0.101 (2) | 0.054 (8)* | |
H1C | 0.1168 (16) | 0.706 (5) | −0.021 (2) | 0.052 (7)* | |
N2 | 0.49334 (10) | 0.5802 (4) | 0.12857 (14) | 0.0347 (4) | |
C1 | 0.23101 (10) | 0.5733 (3) | 0.01443 (13) | 0.0224 (3) | |
C2 | 0.28109 (11) | 0.7520 (3) | −0.02814 (13) | 0.0251 (3) | |
C3 | 0.36733 (11) | 0.7586 (4) | 0.01055 (15) | 0.0295 (4) | |
H3 | 0.401763 | 0.877371 | −0.017358 | 0.035* | |
C4 | 0.40055 (11) | 0.5844 (4) | 0.09144 (14) | 0.0275 (4) | |
C5 | 0.35195 (12) | 0.4124 (4) | 0.13820 (15) | 0.0322 (4) | |
H5 | 0.376323 | 0.302298 | 0.194717 | 0.039* | |
C6 | 0.26607 (11) | 0.4079 (4) | 0.09890 (14) | 0.0299 (4) | |
H6 | 0.231691 | 0.293888 | 0.129073 | 0.036* | |
S1 | 0.06905 (2) | 0.00369 (7) | 0.15958 (3) | 0.01902 (11) | |
O3 | 0.09583 (8) | 0.0670 (2) | 0.06133 (9) | 0.0258 (3) | |
O4 | 0.06204 (9) | −0.3111 (3) | 0.15478 (11) | 0.0306 (3) | |
H4 | 0.0475 (16) | −0.361 (5) | 0.207 (2) | 0.053 (8)* | |
O5 | −0.01424 (8) | 0.1079 (3) | 0.16332 (10) | 0.0300 (3) | |
O6 | 0.13091 (8) | 0.0741 (3) | 0.25338 (10) | 0.0318 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0396 (3) | 0.0372 (3) | 0.0332 (3) | −0.0025 (2) | 0.0022 (2) | 0.0149 (2) |
O1 | 0.0321 (7) | 0.0656 (11) | 0.0619 (11) | −0.0164 (7) | 0.0077 (7) | 0.0142 (9) |
O2 | 0.0323 (8) | 0.0582 (10) | 0.0568 (10) | 0.0050 (7) | −0.0022 (7) | 0.0171 (9) |
N1 | 0.0234 (7) | 0.0278 (7) | 0.0210 (7) | 0.0009 (6) | 0.0043 (6) | 0.0016 (6) |
N2 | 0.0275 (8) | 0.0424 (9) | 0.0328 (8) | −0.0029 (7) | 0.0030 (7) | −0.0017 (7) |
C1 | 0.0219 (7) | 0.0256 (8) | 0.0195 (7) | −0.0003 (6) | 0.0039 (6) | −0.0016 (6) |
C2 | 0.0302 (8) | 0.0243 (8) | 0.0209 (8) | 0.0013 (7) | 0.0057 (7) | 0.0026 (6) |
C3 | 0.0292 (8) | 0.0304 (9) | 0.0300 (9) | −0.0057 (7) | 0.0082 (7) | 0.0026 (7) |
C4 | 0.0224 (8) | 0.0326 (9) | 0.0266 (8) | −0.0023 (7) | 0.0027 (7) | −0.0014 (7) |
C5 | 0.0285 (9) | 0.0369 (10) | 0.0289 (9) | −0.0017 (8) | 0.0000 (7) | 0.0108 (8) |
C6 | 0.0296 (9) | 0.0333 (9) | 0.0258 (8) | −0.0059 (7) | 0.0034 (7) | 0.0069 (7) |
S1 | 0.0229 (2) | 0.01866 (19) | 0.01607 (18) | −0.00072 (14) | 0.00517 (14) | −0.00065 (14) |
O3 | 0.0324 (6) | 0.0278 (6) | 0.0195 (6) | −0.0037 (5) | 0.0106 (5) | 0.0018 (5) |
O4 | 0.0476 (8) | 0.0195 (6) | 0.0290 (7) | −0.0035 (5) | 0.0176 (6) | −0.0006 (5) |
O5 | 0.0296 (6) | 0.0379 (7) | 0.0241 (6) | 0.0082 (6) | 0.0088 (5) | −0.0004 (5) |
O6 | 0.0331 (7) | 0.0390 (7) | 0.0207 (6) | −0.0071 (6) | −0.0005 (5) | −0.0011 (5) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.7233 (17) | C3—H3 | 0.9300 |
O1—N2 | 1.218 (2) | C3—C4 | 1.374 (3) |
O2—N2 | 1.211 (2) | C4—C5 | 1.376 (3) |
N1—H1A | 0.93 (2) | C5—H5 | 0.9300 |
N1—H1B | 0.90 (3) | C5—C6 | 1.380 (2) |
N1—H1C | 0.87 (3) | C6—H6 | 0.9300 |
N1—C1 | 1.458 (2) | S1—O3 | 1.4483 (12) |
N2—C4 | 1.481 (2) | S1—O4 | 1.5636 (13) |
C1—C2 | 1.384 (2) | S1—O5 | 1.4526 (12) |
C1—C6 | 1.387 (2) | S1—O6 | 1.4457 (12) |
C2—C3 | 1.384 (2) | O4—H4 | 0.79 (3) |
| | | |
H1A—N1—H1B | 112 (2) | C4—C3—H3 | 121.0 |
H1A—N1—H1C | 108 (2) | C3—C4—N2 | 117.99 (16) |
H1B—N1—H1C | 110 (2) | C3—C4—C5 | 123.21 (17) |
C1—N1—H1A | 105.8 (13) | C5—C4—N2 | 118.79 (17) |
C1—N1—H1B | 111.5 (16) | C4—C5—H5 | 120.9 |
C1—N1—H1C | 109.6 (17) | C4—C5—C6 | 118.16 (17) |
O1—N2—C4 | 117.82 (17) | C6—C5—H5 | 120.9 |
O2—N2—O1 | 123.73 (17) | C1—C6—H6 | 120.0 |
O2—N2—C4 | 118.45 (17) | C5—C6—C1 | 120.01 (16) |
C2—C1—N1 | 119.76 (15) | C5—C6—H6 | 120.0 |
C2—C1—C6 | 120.46 (16) | O3—S1—O4 | 102.32 (7) |
C6—C1—N1 | 119.77 (15) | O3—S1—O5 | 113.18 (8) |
C1—C2—Cl1 | 120.14 (13) | O5—S1—O4 | 107.17 (8) |
C3—C2—Cl1 | 119.80 (13) | O6—S1—O3 | 113.31 (8) |
C3—C2—C1 | 120.06 (16) | O6—S1—O4 | 107.83 (8) |
C2—C3—H3 | 121.0 | O6—S1—O5 | 112.21 (8) |
C4—C3—C2 | 117.99 (16) | S1—O4—H4 | 107.9 (19) |
| | | |
Cl1—C2—C3—C4 | 179.72 (14) | C1—C2—C3—C4 | −0.1 (3) |
O1—N2—C4—C3 | 7.3 (3) | C2—C1—C6—C5 | −2.8 (3) |
O1—N2—C4—C5 | −173.56 (19) | C2—C3—C4—N2 | 176.51 (16) |
O2—N2—C4—C3 | −171.69 (19) | C2—C3—C4—C5 | −2.6 (3) |
O2—N2—C4—C5 | 7.5 (3) | C3—C4—C5—C6 | 2.6 (3) |
N1—C1—C2—Cl1 | 4.0 (2) | C4—C5—C6—C1 | 0.1 (3) |
N1—C1—C2—C3 | −176.13 (16) | C6—C1—C2—Cl1 | −177.08 (14) |
N1—C1—C6—C5 | 176.11 (17) | C6—C1—C2—C3 | 2.8 (3) |
N2—C4—C5—C6 | −176.51 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3 | 0.93 (2) | 1.96 (2) | 2.854 (2) | 161 (2) |
N1—H1B···O6i | 0.90 (3) | 1.92 (3) | 2.813 (2) | 171 (2) |
N1—H1C···O3ii | 0.87 (3) | 2.14 (3) | 2.952 (2) | 156 (2) |
N1—H1C···O5iii | 0.87 (3) | 2.39 (3) | 2.911 (2) | 119 (2) |
C3—H3···O1iv | 0.93 | 2.41 | 3.326 (2) | 168 |
C6—H6···O3 | 0.93 | 2.47 | 3.184 (2) | 134 |
O4—H4···O5v | 0.79 (3) | 1.85 (3) | 2.6350 (18) | 167 (3) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y+1, z; (iii) −x, −y+1, −z; (iv) −x+1, −y+2, −z; (v) −x, y−1/2, −z+1/2. |
2-Methyl-6-nitroanilinium bromide (3)
top
Crystal data top
C7H9N2O2+·Br− | Z = 2 |
Mr = 233.07 | F(000) = 232 |
Triclinic, P1 | Dx = 1.775 Mg m−3 |
a = 6.8920 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.7281 (3) Å | Cell parameters from 6602 reflections |
c = 8.9210 (2) Å | θ = 2.8–29.2° |
α = 76.646 (3)° | µ = 4.67 mm−1 |
β = 73.897 (2)° | T = 295 K |
γ = 76.045 (2)° | Block, clear yellowish colourless |
V = 436.12 (2) Å3 | 0.46 × 0.33 × 0.18 mm |
Data collection top
Rigaku Xcalibur Atlas diffractometer | 2299 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 1986 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 10.6249 pixels mm-1 | θmax = 29.0°, θmin = 3.1° |
ω scans | h = −9→9 |
Absorption correction: gaussian {CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by
Clark & Reid (1995)] | k = −10→10 |
Tmin = 0.947, Tmax = 0.973 | l = −12→12 |
15285 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0284P)2 + 0.0941P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
2299 reflections | Δρmax = 0.33 e Å−3 |
122 parameters | Δρmin = −0.39 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. X-ray diffraction data were collected on an Oxford Diffraction
four-circle single crystal diffractometer equipped with a CCD detector using
graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw
data were treated with the CrysAlis Data Reduction Program, version
1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected
for Lorentz and polarization effects. The crystal structures were solved by
direct methods (Sheldrick, 2008) and refined by full-matrix least-squares
methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software
(Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.81600 (3) | 0.10038 (3) | 0.85182 (2) | 0.04788 (9) | |
O1 | 0.2903 (3) | 0.0584 (2) | 0.53501 (18) | 0.0519 (4) | |
N1 | 0.3605 (3) | 0.1243 (2) | 0.7969 (2) | 0.0356 (3) | |
H1A | 0.359 (4) | 0.044 (4) | 0.739 (3) | 0.062 (7)* | |
H1B | 0.281 (4) | 0.095 (3) | 0.889 (3) | 0.057 (7)* | |
H1C | 0.492 (4) | 0.108 (3) | 0.811 (3) | 0.052 (6)* | |
C1 | 0.2937 (2) | 0.3101 (2) | 0.7213 (2) | 0.0294 (3) | |
O2 | 0.3704 (3) | 0.2520 (2) | 0.32372 (17) | 0.0638 (5) | |
N2 | 0.3158 (2) | 0.2116 (2) | 0.46776 (19) | 0.0397 (4) | |
C2 | 0.2568 (3) | 0.4475 (2) | 0.8078 (2) | 0.0354 (4) | |
C3 | 0.1993 (3) | 0.6251 (3) | 0.7319 (3) | 0.0457 (5) | |
H3 | 0.168936 | 0.719362 | 0.788371 | 0.055* | |
C4 | 0.1863 (3) | 0.6645 (3) | 0.5753 (3) | 0.0484 (5) | |
H4 | 0.148182 | 0.784148 | 0.528182 | 0.058* | |
C5 | 0.2291 (3) | 0.5293 (3) | 0.4892 (2) | 0.0411 (4) | |
H5 | 0.224223 | 0.555655 | 0.383067 | 0.049* | |
C6 | 0.2799 (2) | 0.3522 (2) | 0.5636 (2) | 0.0316 (3) | |
C7 | 0.2796 (4) | 0.4061 (3) | 0.9765 (2) | 0.0500 (5) | |
H7A | 0.195481 | 0.320174 | 1.038442 | 0.075* | |
H7B | 0.237042 | 0.515587 | 1.020032 | 0.075* | |
H7C | 0.420924 | 0.356305 | 0.978274 | 0.075* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.04293 (13) | 0.05194 (14) | 0.04204 (12) | −0.01063 (9) | −0.01413 (9) | 0.01167 (9) |
O1 | 0.0688 (10) | 0.0404 (8) | 0.0518 (8) | −0.0171 (7) | −0.0158 (7) | −0.0094 (7) |
N1 | 0.0429 (9) | 0.0296 (8) | 0.0318 (8) | −0.0052 (7) | −0.0110 (7) | 0.0008 (6) |
C1 | 0.0251 (7) | 0.0285 (8) | 0.0321 (8) | −0.0079 (6) | −0.0049 (6) | 0.0004 (6) |
O2 | 0.0869 (12) | 0.0773 (12) | 0.0324 (7) | −0.0260 (10) | −0.0152 (8) | −0.0074 (8) |
N2 | 0.0372 (8) | 0.0496 (10) | 0.0364 (8) | −0.0109 (7) | −0.0127 (6) | −0.0078 (7) |
C2 | 0.0296 (8) | 0.0352 (9) | 0.0401 (9) | −0.0094 (7) | −0.0023 (7) | −0.0078 (7) |
C3 | 0.0372 (10) | 0.0312 (9) | 0.0673 (14) | −0.0099 (8) | −0.0045 (9) | −0.0116 (9) |
C4 | 0.0407 (10) | 0.0310 (9) | 0.0690 (14) | −0.0103 (8) | −0.0186 (10) | 0.0108 (9) |
C5 | 0.0355 (9) | 0.0397 (10) | 0.0463 (10) | −0.0140 (8) | −0.0167 (8) | 0.0116 (8) |
C6 | 0.0270 (8) | 0.0327 (8) | 0.0353 (9) | −0.0094 (7) | −0.0099 (7) | 0.0005 (7) |
C7 | 0.0571 (13) | 0.0552 (13) | 0.0402 (10) | −0.0122 (10) | −0.0065 (9) | −0.0177 (10) |
Geometric parameters (Å, º) top
O1—N2 | 1.228 (2) | C2—C7 | 1.508 (3) |
N1—H1A | 0.90 (3) | C3—H3 | 0.9300 |
N1—H1B | 0.86 (3) | C3—C4 | 1.383 (3) |
N1—H1C | 0.92 (3) | C4—H4 | 0.9300 |
N1—C1 | 1.461 (2) | C4—C5 | 1.366 (3) |
C1—C2 | 1.389 (3) | C5—H5 | 0.9300 |
C1—C6 | 1.394 (2) | C5—C6 | 1.383 (2) |
O2—N2 | 1.222 (2) | C7—H7A | 0.9600 |
N2—C6 | 1.467 (2) | C7—H7B | 0.9600 |
C2—C3 | 1.399 (3) | C7—H7C | 0.9600 |
| | | |
H1A—N1—H1B | 105 (2) | C4—C3—H3 | 119.1 |
H1A—N1—H1C | 108 (2) | C3—C4—H4 | 119.7 |
H1B—N1—H1C | 108 (2) | C5—C4—C3 | 120.57 (18) |
C1—N1—H1A | 111.5 (17) | C5—C4—H4 | 119.7 |
C1—N1—H1B | 112.9 (17) | C4—C5—H5 | 120.8 |
C1—N1—H1C | 110.7 (15) | C4—C5—C6 | 118.49 (18) |
C2—C1—N1 | 118.04 (15) | C6—C5—H5 | 120.8 |
C2—C1—C6 | 120.05 (16) | C1—C6—N2 | 122.02 (15) |
C6—C1—N1 | 121.77 (16) | C5—C6—C1 | 121.68 (17) |
O1—N2—C6 | 118.93 (15) | C5—C6—N2 | 116.30 (16) |
O2—N2—O1 | 122.57 (17) | C2—C7—H7A | 109.5 |
O2—N2—C6 | 118.50 (17) | C2—C7—H7B | 109.5 |
C1—C2—C3 | 117.32 (17) | C2—C7—H7C | 109.5 |
C1—C2—C7 | 121.11 (17) | H7A—C7—H7B | 109.5 |
C3—C2—C7 | 121.57 (18) | H7A—C7—H7C | 109.5 |
C2—C3—H3 | 119.1 | H7B—C7—H7C | 109.5 |
C4—C3—C2 | 121.83 (19) | | |
| | | |
O1—N2—C6—C1 | 24.5 (2) | C2—C1—C6—N2 | −179.47 (15) |
O1—N2—C6—C5 | −154.82 (17) | C2—C1—C6—C5 | −0.2 (3) |
N1—C1—C2—C3 | 178.02 (16) | C2—C3—C4—C5 | 0.3 (3) |
N1—C1—C2—C7 | −1.5 (3) | C3—C4—C5—C6 | 1.8 (3) |
N1—C1—C6—N2 | 4.9 (2) | C4—C5—C6—C1 | −1.8 (3) |
N1—C1—C6—C5 | −175.88 (16) | C4—C5—C6—N2 | 177.48 (16) |
C1—C2—C3—C4 | −2.3 (3) | C6—C1—C2—C3 | 2.2 (2) |
O2—N2—C6—C1 | −155.44 (18) | C6—C1—C2—C7 | −177.35 (17) |
O2—N2—C6—C5 | 25.3 (2) | C7—C2—C3—C4 | 177.29 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.90 (3) | 1.98 (3) | 2.693 (2) | 135 (2) |
N1—H1B···Br1i | 0.86 (3) | 2.47 (3) | 3.2717 (17) | 155 (2) |
N1—H1C···Br1 | 0.92 (3) | 2.34 (3) | 3.2650 (18) | 174 (2) |
Symmetry code: (i) −x+1, −y, −z+2. |
2-Methyl-6-nitroanilinium triiodide (4)
top
Crystal data top
C7H9N2O2+·I3− | F(000) = 960 |
Mr = 533.86 | Dx = 2.681 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0840 (2) Å | Cell parameters from 6876 reflections |
b = 11.5247 (4) Å | θ = 3.0–26.6° |
c = 16.3921 (6) Å | µ = 7.07 mm−1 |
β = 98.738 (3)° | T = 295 K |
V = 1322.73 (8) Å3 | Block, clear dark black |
Z = 4 | 0.21 × 0.11 × 0.09 mm |
Data collection top
Rigaku Xcalibur Atlas diffractometer | 5822 measured reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 5822 independent reflections |
Graphite monochromator | 3181 reflections with I > 2σ(I) |
Detector resolution: 10.6249 pixels mm-1 | θmax = 29.7°, θmin = 3.1° |
ω scans | h = −9→9 |
Absorption correction: gaussian {CrysAlis PRO (Rigaku OD, 2015), based on expressions derived by
Clark & Reid (1995)] | k = −15→15 |
Tmin = 0.966, Tmax = 0.988 | l = −22→22 |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0302P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.80 | (Δ/σ)max = 0.001 |
5822 reflections | Δρmax = 0.70 e Å−3 |
130 parameters | Δρmin = −0.78 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component twin. X-ray diffraction data were collected on an Oxford Diffraction
four-circle single crystal diffractometer equipped with a CCD detector using
graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw
data were treated with the CrysAlis Data Reduction Program, version
1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected
for Lorentz and polarization effects. The crystal structures were solved by
direct methods (Sheldrick, 2008) and refined by full-matrix least-squares
methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software
(Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.23412 (5) | 0.64676 (3) | 0.49174 (2) | 0.05463 (12) | |
O1 | 0.7268 (7) | 0.6352 (3) | 0.3066 (3) | 0.0872 (15) | |
N1 | 0.7262 (6) | 0.6691 (3) | 0.4628 (2) | 0.0498 (11) | |
H1A | 0.705654 | 0.624493 | 0.418041 | 0.060* | |
H1B | 0.632377 | 0.658951 | 0.492567 | 0.060* | |
H1C | 0.837132 | 0.649941 | 0.492907 | 0.060* | |
C1 | 0.7319 (7) | 0.7911 (4) | 0.4380 (3) | 0.0384 (11) | |
O2 | 0.6924 (7) | 0.7754 (4) | 0.2194 (3) | 0.0901 (15) | |
N2 | 0.7129 (7) | 0.7393 (5) | 0.2892 (3) | 0.0615 (13) | |
C2 | 0.7435 (7) | 0.8734 (4) | 0.5006 (3) | 0.0435 (12) | |
C3 | 0.7455 (7) | 0.9904 (4) | 0.4768 (3) | 0.0493 (13) | |
H3 | 0.750588 | 1.047841 | 0.516951 | 0.059* | |
C4 | 0.7403 (7) | 1.0219 (4) | 0.3964 (3) | 0.0562 (15) | |
H4 | 0.744029 | 1.099935 | 0.382326 | 0.067* | |
C5 | 0.7293 (7) | 0.9375 (5) | 0.3353 (3) | 0.0515 (13) | |
H5 | 0.724229 | 0.958706 | 0.280255 | 0.062* | |
C6 | 0.7262 (7) | 0.8236 (4) | 0.3568 (3) | 0.0405 (12) | |
C7 | 0.7513 (9) | 0.8411 (4) | 0.5907 (3) | 0.0653 (17) | |
H7A | 0.637762 | 0.799188 | 0.597706 | 0.098* | |
H7B | 0.759889 | 0.910330 | 0.623588 | 0.098* | |
H7C | 0.861188 | 0.793308 | 0.607767 | 0.098* | |
I2 | 0.25651 (6) | 0.48323 (3) | 0.33199 (2) | 0.06088 (13) | |
I3 | 0.28580 (6) | 0.33035 (3) | 0.20403 (2) | 0.06437 (13) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0485 (2) | 0.0462 (2) | 0.0689 (2) | −0.00020 (18) | 0.00820 (19) | −0.00626 (17) |
O1 | 0.126 (4) | 0.051 (3) | 0.089 (3) | −0.006 (3) | 0.033 (3) | −0.027 (2) |
N1 | 0.046 (3) | 0.039 (2) | 0.065 (3) | −0.001 (2) | 0.009 (2) | −0.002 (2) |
C1 | 0.031 (3) | 0.032 (2) | 0.052 (3) | 0.000 (2) | 0.005 (2) | −0.002 (2) |
O2 | 0.112 (4) | 0.109 (4) | 0.050 (3) | −0.001 (3) | 0.014 (3) | −0.021 (2) |
N2 | 0.051 (3) | 0.076 (4) | 0.060 (3) | −0.005 (3) | 0.017 (3) | −0.017 (3) |
C2 | 0.043 (3) | 0.039 (3) | 0.049 (3) | 0.001 (2) | 0.004 (2) | 0.005 (2) |
C3 | 0.056 (4) | 0.036 (3) | 0.057 (4) | 0.000 (3) | 0.010 (3) | −0.002 (2) |
C4 | 0.057 (4) | 0.038 (3) | 0.073 (4) | −0.004 (3) | 0.010 (3) | 0.014 (3) |
C5 | 0.047 (3) | 0.055 (3) | 0.053 (3) | 0.003 (3) | 0.008 (3) | 0.008 (3) |
C6 | 0.044 (3) | 0.041 (3) | 0.037 (3) | −0.002 (2) | 0.008 (2) | −0.010 (2) |
C7 | 0.097 (5) | 0.048 (3) | 0.050 (3) | −0.006 (3) | 0.008 (3) | 0.006 (3) |
I2 | 0.0549 (2) | 0.0456 (2) | 0.0798 (3) | −0.00325 (19) | 0.00274 (19) | 0.01677 (19) |
I3 | 0.0536 (3) | 0.0606 (3) | 0.0816 (3) | 0.0035 (2) | 0.0189 (2) | 0.0096 (2) |
Geometric parameters (Å, º) top
O1—N2 | 1.234 (6) | C3—H3 | 0.9300 |
N1—H1A | 0.8900 | C3—C4 | 1.363 (6) |
N1—H1B | 0.8900 | C4—H4 | 0.9300 |
N1—H1C | 0.8900 | C4—C5 | 1.389 (7) |
N1—C1 | 1.466 (5) | C5—H5 | 0.9300 |
C1—C2 | 1.391 (6) | C5—C6 | 1.360 (6) |
C1—C6 | 1.378 (6) | C7—H7A | 0.9600 |
O2—N2 | 1.205 (6) | C7—H7B | 0.9600 |
N2—C6 | 1.465 (6) | C7—H7C | 0.9600 |
C2—C3 | 1.405 (6) | I2—I3 | 2.7711 (6) |
C2—C7 | 1.515 (6) | | |
| | | |
H1A—N1—H1B | 109.5 | C4—C3—H3 | 119.2 |
H1A—N1—H1C | 109.5 | C3—C4—H4 | 119.9 |
H1B—N1—H1C | 109.5 | C3—C4—C5 | 120.1 (5) |
C1—N1—H1A | 109.5 | C5—C4—H4 | 119.9 |
C1—N1—H1B | 109.5 | C4—C5—H5 | 120.3 |
C1—N1—H1C | 109.5 | C6—C5—C4 | 119.4 (5) |
C2—C1—N1 | 116.7 (4) | C6—C5—H5 | 120.3 |
C6—C1—N1 | 122.1 (4) | C1—C6—N2 | 122.6 (4) |
C6—C1—C2 | 121.2 (4) | C5—C6—C1 | 120.9 (4) |
O1—N2—C6 | 118.5 (5) | C5—C6—N2 | 116.5 (5) |
O2—N2—O1 | 123.3 (5) | C2—C7—H7A | 109.5 |
O2—N2—C6 | 118.2 (5) | C2—C7—H7B | 109.5 |
C1—C2—C3 | 116.8 (4) | C2—C7—H7C | 109.5 |
C1—C2—C7 | 122.8 (4) | H7A—C7—H7B | 109.5 |
C3—C2—C7 | 120.4 (4) | H7A—C7—H7C | 109.5 |
C2—C3—H3 | 119.2 | H7B—C7—H7C | 109.5 |
C4—C3—C2 | 121.6 (4) | | |
| | | |
O1—N2—C6—C1 | −7.5 (8) | C2—C1—C6—N2 | −179.6 (5) |
O1—N2—C6—C5 | 173.6 (5) | C2—C1—C6—C5 | −0.8 (8) |
N1—C1—C2—C3 | −178.9 (4) | C2—C3—C4—C5 | 1.1 (8) |
N1—C1—C2—C7 | 0.4 (7) | C3—C4—C5—C6 | −0.7 (8) |
N1—C1—C6—N2 | 0.4 (7) | C4—C5—C6—C1 | 0.6 (8) |
N1—C1—C6—C5 | 179.2 (5) | C4—C5—C6—N2 | 179.5 (5) |
C1—C2—C3—C4 | −1.3 (8) | C6—C1—C2—C3 | 1.1 (7) |
O2—N2—C6—C1 | 173.9 (5) | C6—C1—C2—C7 | −179.6 (5) |
O2—N2—C6—C5 | −5.0 (7) | C7—C2—C3—C4 | 179.4 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.89 | 1.86 | 2.591 (6) | 138 |
N1—H1B···I1 | 0.89 | 2.82 | 3.598 (4) | 146 |
N1—H1C···I1i | 0.89 | 2.82 | 3.566 (4) | 143 |
C5—H5···O1ii | 0.93 | 2.54 | 3.304 (6) | 140 |
Symmetry codes: (i) x+1, y, z; (ii) −x+3/2, y+1/2, −z+1/2. |
2-Methyl-6-nitroanilinium hydrogen sulfate (5)
top
Crystal data top
C7H9N2O2+·HSO4− | F(000) = 520 |
Mr = 250.23 | Dx = 1.622 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0966 (5) Å | Cell parameters from 5045 reflections |
b = 8.3785 (8) Å | θ = 3.0–30.2° |
c = 17.5115 (18) Å | µ = 0.33 mm−1 |
β = 100.185 (9)° | T = 295 K |
V = 1024.81 (16) Å3 | Plate, clear light colourless |
Z = 4 | 0.42 × 0.32 × 0.09 mm |
Data collection top
Rigaku Xcalibur Atlas diffractometer | 4495 measured reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 4495 independent reflections |
Graphite monochromator | 3463 reflections with I > 2σ(I) |
Detector resolution: 10.6249 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015) | k = −10→10 |
Tmin = 0.939, Tmax = 1.000 | l = −22→22 |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.136 | w = 1/[σ2(Fo2) + (0.0891P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
4495 reflections | Δρmax = 0.66 e Å−3 |
149 parameters | Δρmin = −0.42 e Å−3 |
0 restraints | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component twin. X-ray diffraction data were collected on an Oxford Diffraction
four-circle single crystal diffractometer equipped with a CCD detector using
graphite-monochromatized Mo Kα radiation (λ = 0.71073 Å). The raw
data were treated with the CrysAlis Data Reduction Program, version
1.171.38.34a or 1.171.39.46. The intensities of the reflection were corrected
for Lorentz and polarization effects. The crystal structures were solved by
direct methods (Sheldrick, 2008) and refined by full-matrix least-squares
methods using the SHELXL2017 program (Sheldrick, 2015) and OLEX2 software
(Dolomanov et al., 2009). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.32295 (8) | 0.09177 (8) | 0.70227 (4) | 0.0348 (2) | |
O3 | 0.4440 (3) | 0.1334 (4) | 0.64969 (14) | 0.0759 (8) | |
O4 | 0.1257 (3) | 0.1015 (3) | 0.66720 (14) | 0.0616 (6) | |
O5 | 0.3759 (3) | −0.0587 (3) | 0.73916 (19) | 0.0826 (9) | |
O6 | 0.3636 (4) | 0.2094 (4) | 0.76979 (18) | 0.1056 (12) | |
H6 | 0.281061 | 0.278984 | 0.764211 | 0.158* | |
O1 | 0.6922 (3) | 0.5681 (3) | 0.70497 (17) | 0.0655 (7) | |
N1 | 0.7908 (3) | 0.2815 (3) | 0.66155 (12) | 0.0339 (5) | |
H1A | 0.814514 | 0.352634 | 0.699809 | 0.041* | |
H1B | 0.888031 | 0.213257 | 0.665312 | 0.041* | |
H1C | 0.683885 | 0.228555 | 0.664973 | 0.041* | |
C1 | 0.7677 (3) | 0.3634 (3) | 0.58742 (14) | 0.0296 (5) | |
O2 | 0.7360 (4) | 0.7746 (3) | 0.6394 (2) | 0.1016 (11) | |
N2 | 0.7261 (3) | 0.6306 (3) | 0.6464 (2) | 0.0544 (7) | |
C2 | 0.7659 (3) | 0.2709 (3) | 0.52187 (15) | 0.0376 (6) | |
C3 | 0.7550 (4) | 0.3499 (5) | 0.45104 (17) | 0.0550 (8) | |
H3 | 0.754673 | 0.289852 | 0.406357 | 0.066* | |
C4 | 0.7451 (4) | 0.5101 (5) | 0.4451 (2) | 0.0651 (10) | |
H4 | 0.742614 | 0.558246 | 0.397108 | 0.078* | |
C5 | 0.7385 (4) | 0.6028 (4) | 0.5088 (2) | 0.0549 (8) | |
H5 | 0.727814 | 0.713202 | 0.504282 | 0.066* | |
C6 | 0.7481 (3) | 0.5294 (3) | 0.58028 (18) | 0.0391 (6) | |
C7 | 0.7704 (4) | 0.0907 (4) | 0.52610 (19) | 0.0540 (8) | |
H7A | 0.888111 | 0.056721 | 0.557734 | 0.081* | |
H7B | 0.761790 | 0.047517 | 0.474816 | 0.081* | |
H7C | 0.664339 | 0.053420 | 0.548427 | 0.081* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0317 (3) | 0.0349 (3) | 0.0374 (4) | 0.0040 (2) | 0.0048 (3) | 0.0040 (3) |
O3 | 0.0534 (13) | 0.121 (2) | 0.0551 (15) | −0.0218 (12) | 0.0147 (10) | 0.0165 (16) |
O4 | 0.0349 (11) | 0.0726 (16) | 0.0731 (16) | 0.0129 (9) | −0.0023 (10) | −0.0071 (13) |
O5 | 0.0546 (13) | 0.0609 (16) | 0.124 (2) | −0.0057 (10) | −0.0065 (13) | 0.0485 (16) |
O6 | 0.104 (2) | 0.122 (3) | 0.074 (2) | 0.0560 (17) | −0.0328 (15) | −0.0527 (19) |
O1 | 0.0745 (15) | 0.0624 (17) | 0.0601 (16) | 0.0092 (11) | 0.0136 (12) | −0.0225 (14) |
N1 | 0.0335 (10) | 0.0397 (12) | 0.0282 (12) | 0.0023 (8) | 0.0046 (8) | 0.0031 (9) |
C1 | 0.0219 (11) | 0.0376 (13) | 0.0295 (12) | 0.0006 (9) | 0.0054 (9) | 0.0023 (10) |
O2 | 0.125 (2) | 0.0362 (15) | 0.134 (3) | 0.0110 (13) | −0.0042 (19) | −0.0145 (17) |
N2 | 0.0452 (13) | 0.0392 (15) | 0.072 (2) | 0.0068 (10) | −0.0080 (12) | −0.0099 (14) |
C2 | 0.0264 (12) | 0.0543 (17) | 0.0320 (14) | 0.0026 (10) | 0.0050 (10) | −0.0027 (12) |
C3 | 0.0445 (16) | 0.092 (3) | 0.0298 (16) | 0.0084 (15) | 0.0094 (11) | 0.0052 (16) |
C4 | 0.0482 (18) | 0.101 (3) | 0.046 (2) | 0.0019 (17) | 0.0090 (15) | 0.036 (2) |
C5 | 0.0390 (15) | 0.0520 (19) | 0.071 (2) | −0.0023 (12) | 0.0032 (14) | 0.0263 (18) |
C6 | 0.0276 (12) | 0.0373 (14) | 0.0498 (18) | −0.0007 (10) | 0.0002 (11) | 0.0044 (13) |
C7 | 0.0558 (18) | 0.0529 (19) | 0.0512 (18) | 0.0083 (13) | 0.0037 (14) | −0.0193 (16) |
Geometric parameters (Å, º) top
S1—O3 | 1.410 (2) | N2—C6 | 1.465 (4) |
S1—O4 | 1.428 (2) | C2—C3 | 1.396 (4) |
S1—O5 | 1.436 (2) | C2—C7 | 1.512 (4) |
S1—O6 | 1.527 (3) | C3—H3 | 0.9300 |
O6—H6 | 0.8200 | C3—C4 | 1.347 (5) |
O1—N2 | 1.213 (4) | C4—H4 | 0.9300 |
N1—H1A | 0.8900 | C4—C5 | 1.367 (5) |
N1—H1B | 0.8900 | C5—H5 | 0.9300 |
N1—H1C | 0.8900 | C5—C6 | 1.385 (4) |
N1—C1 | 1.452 (3) | C7—H7A | 0.9600 |
C1—C2 | 1.383 (3) | C7—H7B | 0.9600 |
C1—C6 | 1.401 (4) | C7—H7C | 0.9600 |
O2—N2 | 1.216 (3) | | |
| | | |
O3—S1—O4 | 111.65 (15) | C1—C2—C7 | 121.5 (2) |
O3—S1—O5 | 111.72 (17) | C3—C2—C7 | 121.0 (3) |
O3—S1—O6 | 107.0 (2) | C2—C3—H3 | 118.8 |
O4—S1—O5 | 113.72 (14) | C4—C3—C2 | 122.3 (3) |
O4—S1—O6 | 109.44 (14) | C4—C3—H3 | 118.8 |
O5—S1—O6 | 102.7 (2) | C3—C4—H4 | 119.6 |
S1—O6—H6 | 109.5 | C3—C4—C5 | 120.8 (3) |
H1A—N1—H1B | 109.5 | C5—C4—H4 | 119.6 |
H1A—N1—H1C | 109.5 | C4—C5—H5 | 120.6 |
H1B—N1—H1C | 109.5 | C4—C5—C6 | 118.8 (3) |
C1—N1—H1A | 109.5 | C6—C5—H5 | 120.6 |
C1—N1—H1B | 109.5 | C1—C6—N2 | 121.8 (3) |
C1—N1—H1C | 109.5 | C5—C6—C1 | 120.7 (3) |
C2—C1—N1 | 117.4 (2) | C5—C6—N2 | 117.5 (3) |
C2—C1—C6 | 119.7 (2) | C2—C7—H7A | 109.5 |
C6—C1—N1 | 122.9 (2) | C2—C7—H7B | 109.5 |
O1—N2—O2 | 122.5 (3) | C2—C7—H7C | 109.5 |
O1—N2—C6 | 118.9 (3) | H7A—C7—H7B | 109.5 |
O2—N2—C6 | 118.6 (4) | H7A—C7—H7C | 109.5 |
C1—C2—C3 | 117.5 (3) | H7B—C7—H7C | 109.5 |
| | | |
O1—N2—C6—C1 | −12.4 (4) | C2—C1—C6—N2 | 172.5 (2) |
O1—N2—C6—C5 | 164.2 (3) | C2—C1—C6—C5 | −3.9 (3) |
N1—C1—C2—C3 | −176.3 (2) | C2—C3—C4—C5 | −2.3 (4) |
N1—C1—C2—C7 | 5.2 (3) | C3—C4—C5—C6 | 1.9 (4) |
N1—C1—C6—N2 | −7.6 (3) | C4—C5—C6—C1 | 1.2 (4) |
N1—C1—C6—C5 | 175.9 (2) | C4—C5—C6—N2 | −175.5 (2) |
C1—C2—C3—C4 | −0.5 (4) | C6—C1—C2—C3 | 3.5 (3) |
O2—N2—C6—C1 | 170.0 (2) | C6—C1—C2—C7 | −175.0 (2) |
O2—N2—C6—C5 | −13.4 (4) | C7—C2—C3—C4 | 178.0 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O5i | 0.82 | 1.75 | 2.568 (3) | 173 |
N1—H1A···O5ii | 0.89 | 2.39 | 2.993 (3) | 126 |
N1—H1A···O1 | 0.89 | 2.01 | 2.650 (3) | 128 |
N1—H1B···O4iii | 0.89 | 1.92 | 2.802 (3) | 169 |
N1—H1C···O3 | 0.89 | 1.86 | 2.731 (3) | 167 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) x+1, y, z. |
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