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Three conformational polymorphs of 3-(azidomethyl)benzoic acid, C8H7N3O2, are reported. All three structures maintain similar carboxylic acid dimers and π–π stacking. Crystal structure analysis and computational evaluations highlight the azidomethyl group as a source of conformational polymorphism, thus having potential implications in the design of solid-state reactions.
Supporting information
CCDC references: 2241209; 2241210; 2241211
For all structures, data collection: APEX4 (Bruker, 2021); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016). Program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a) for A, C; SHELXT2018 (Sheldrick, 2015a) and SHELXS (Sheldrick, 2008) for B. For all structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
3-(Azidomethyl)benzoic acid (A)
top
Crystal data top
C8H7N3O2 | F(000) = 368 |
Mr = 177.17 | Dx = 1.473 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6327 (5) Å | Cell parameters from 7334 reflections |
b = 9.5561 (6) Å | θ = 2.8–28.0° |
c = 11.2899 (7) Å | µ = 0.11 mm−1 |
β = 104.095 (3)° | T = 100 K |
V = 798.68 (9) Å3 | Plate, colourless |
Z = 4 | 0.16 × 0.12 × 0.04 mm |
Data collection top
Bruker D8 VENTURE DUO diffractometer | 1988 independent reflections |
Radiation source: sealed tube, fine-focus | 1496 reflections with I > 2σ(I) |
TRIUMPH graphite monochromator | Rint = 0.059 |
Detector resolution: 7.39 pixels mm-1 | θmax = 28.4°, θmin = 2.8° |
ω and φ scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −12→12 |
Tmin = 0.675, Tmax = 0.746 | l = −15→15 |
21950 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0404P)2 + 0.4603P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1988 reflections | Δρmax = 0.32 e Å−3 |
122 parameters | Δρmin = −0.23 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. Data for all structures were collected at 100 K on a Bruker D8 VENTURE Duo
fixed-chi three-circle diffractometer using Mo Kα radiation (λ =
0.71073 Å). All data were integrated with SAINT (Bruker, 2016) and
corrected for absorption using SADABS (Krause et al., 2015).
The structures of polymorphs A and C were solved by dual methods
using SHELXT (Sheldrick, 2015a), while B was solved by
direct methods using SHELXS (Sheldrick, 2008). All structures were
refined by full-matrix least-squares methods against F2 using
SHELXL (Sheldrick, 2015b). All non-H atoms were refined with
anisotropic displacement parameters. Calculations and refinement of the structure was carried out using
APEX4 (Bruker, 2021) and OLEX2 (Dolomanov et al., 2009)
software. Crystal packing diagrams were generated using OLEX2.
Structure overlay diagrams and r.m.s. deviation values were obtained using
Mercury (Macrae et al., 2020). For polymorph B,
the TWINROTMAT routine within PLATON (Spek, 2020) indicated twinning.
The twin law was found to be (100, 010, 101). The BASF value refined to
0.5471 (16). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.93737 (15) | 0.86449 (11) | 0.40596 (9) | 0.0215 (3) | |
O2 | 0.90744 (16) | 0.88984 (12) | 0.59702 (9) | 0.0220 (3) | |
H2 | 0.962 (4) | 0.979 (3) | 0.591 (2) | 0.083 (9)* | |
N1 | 0.56587 (18) | 0.34979 (13) | 0.20286 (11) | 0.0219 (3) | |
N2 | 0.50663 (18) | 0.46363 (14) | 0.15900 (11) | 0.0208 (3) | |
N3 | 0.4361 (2) | 0.56102 (16) | 0.11360 (13) | 0.0306 (3) | |
C1 | 0.82040 (18) | 0.67382 (14) | 0.49777 (12) | 0.0137 (3) | |
C2 | 0.81239 (18) | 0.58766 (14) | 0.39627 (12) | 0.0137 (3) | |
H2A | 0.845507 | 0.623981 | 0.326465 | 0.016* | |
C3 | 0.75637 (18) | 0.44948 (15) | 0.39698 (12) | 0.0140 (3) | |
C4 | 0.70877 (19) | 0.39726 (15) | 0.50081 (13) | 0.0159 (3) | |
H4 | 0.671218 | 0.302652 | 0.502454 | 0.019* | |
C5 | 0.71607 (19) | 0.48268 (15) | 0.60125 (13) | 0.0172 (3) | |
H5 | 0.683240 | 0.446267 | 0.671121 | 0.021* | |
C6 | 0.77106 (19) | 0.62109 (15) | 0.60026 (12) | 0.0159 (3) | |
H6 | 0.775077 | 0.679528 | 0.668945 | 0.019* | |
C7 | 0.89182 (19) | 0.81756 (15) | 0.49687 (12) | 0.0152 (3) | |
C8 | 0.74914 (19) | 0.35650 (15) | 0.28813 (12) | 0.0172 (3) | |
H8A | 0.836393 | 0.391527 | 0.243022 | 0.021* | |
H8B | 0.786820 | 0.260833 | 0.317165 | 0.021* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0348 (6) | 0.0163 (5) | 0.0164 (5) | −0.0041 (5) | 0.0122 (5) | 0.0002 (4) |
O2 | 0.0371 (6) | 0.0158 (5) | 0.0147 (5) | −0.0060 (5) | 0.0096 (4) | −0.0044 (4) |
N1 | 0.0297 (7) | 0.0152 (6) | 0.0181 (6) | −0.0009 (5) | 0.0005 (5) | −0.0018 (5) |
N2 | 0.0271 (7) | 0.0236 (7) | 0.0119 (6) | 0.0010 (6) | 0.0055 (5) | −0.0040 (5) |
N3 | 0.0404 (9) | 0.0292 (8) | 0.0226 (7) | 0.0117 (7) | 0.0081 (6) | 0.0035 (6) |
C1 | 0.0150 (6) | 0.0132 (6) | 0.0126 (6) | 0.0006 (5) | 0.0028 (5) | 0.0012 (5) |
C2 | 0.0143 (6) | 0.0153 (7) | 0.0117 (6) | 0.0005 (5) | 0.0039 (5) | 0.0019 (5) |
C3 | 0.0137 (6) | 0.0144 (7) | 0.0138 (6) | 0.0016 (5) | 0.0030 (5) | −0.0005 (5) |
C4 | 0.0157 (7) | 0.0136 (7) | 0.0186 (7) | −0.0013 (5) | 0.0046 (5) | 0.0024 (5) |
C5 | 0.0190 (7) | 0.0203 (7) | 0.0137 (6) | 0.0000 (6) | 0.0067 (6) | 0.0030 (6) |
C6 | 0.0177 (7) | 0.0183 (7) | 0.0119 (6) | 0.0008 (6) | 0.0042 (5) | −0.0010 (5) |
C7 | 0.0176 (7) | 0.0153 (7) | 0.0121 (6) | 0.0010 (5) | 0.0028 (5) | −0.0003 (5) |
C8 | 0.0217 (7) | 0.0154 (7) | 0.0150 (6) | −0.0002 (6) | 0.0055 (6) | −0.0017 (5) |
Geometric parameters (Å, º) top
O1—C7 | 1.2446 (17) | C2—C3 | 1.389 (2) |
O2—H2 | 0.96 (3) | C3—C4 | 1.4010 (19) |
O2—C7 | 1.3054 (17) | C3—C8 | 1.5065 (19) |
N1—N2 | 1.2345 (18) | C4—H4 | 0.9500 |
N1—C8 | 1.4939 (19) | C4—C5 | 1.387 (2) |
N2—N3 | 1.1333 (19) | C5—H5 | 0.9500 |
C1—C2 | 1.4002 (19) | C5—C6 | 1.389 (2) |
C1—C6 | 1.3953 (19) | C6—H6 | 0.9500 |
C1—C7 | 1.479 (2) | C8—H8A | 0.9900 |
C2—H2A | 0.9500 | C8—H8B | 0.9900 |
| | | |
C7—O2—H2 | 111.0 (17) | C4—C5—H5 | 119.8 |
N2—N1—C8 | 114.49 (12) | C4—C5—C6 | 120.40 (13) |
N3—N2—N1 | 172.89 (16) | C6—C5—H5 | 119.8 |
C2—C1—C7 | 118.90 (12) | C1—C6—H6 | 120.2 |
C6—C1—C2 | 119.97 (13) | C5—C6—C1 | 119.59 (13) |
C6—C1—C7 | 121.03 (12) | C5—C6—H6 | 120.2 |
C1—C2—H2A | 119.8 | O1—C7—O2 | 122.59 (13) |
C3—C2—C1 | 120.44 (12) | O1—C7—C1 | 121.19 (12) |
C3—C2—H2A | 119.8 | O2—C7—C1 | 116.21 (12) |
C2—C3—C4 | 119.11 (12) | N1—C8—C3 | 113.18 (12) |
C2—C3—C8 | 120.42 (12) | N1—C8—H8A | 108.9 |
C4—C3—C8 | 120.46 (12) | N1—C8—H8B | 108.9 |
C3—C4—H4 | 119.8 | C3—C8—H8A | 108.9 |
C5—C4—C3 | 120.49 (13) | C3—C8—H8B | 108.9 |
C5—C4—H4 | 119.8 | H8A—C8—H8B | 107.8 |
| | | |
N2—N1—C8—C3 | 59.97 (17) | C4—C3—C8—N1 | 85.04 (16) |
C1—C2—C3—C4 | −0.3 (2) | C4—C5—C6—C1 | −0.5 (2) |
C1—C2—C3—C8 | −179.53 (12) | C6—C1—C2—C3 | −0.3 (2) |
C2—C1—C6—C5 | 0.7 (2) | C6—C1—C7—O1 | 179.39 (13) |
C2—C1—C7—O1 | 3.0 (2) | C6—C1—C7—O2 | 0.8 (2) |
C2—C1—C7—O2 | −175.56 (13) | C7—C1—C2—C3 | 176.11 (12) |
C2—C3—C4—C5 | 0.5 (2) | C7—C1—C6—C5 | −175.65 (13) |
C2—C3—C8—N1 | −95.73 (15) | C8—C3—C4—C5 | 179.75 (13) |
C3—C4—C5—C6 | −0.1 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.96 (3) | 1.68 (3) | 2.6334 (15) | 175 (3) |
Symmetry code: (i) −x+2, −y+2, −z+1. |
3-(Azidomethyl)benzoic acid (B)
top
Crystal data top
C8H7N3O2 | F(000) = 368 |
Mr = 177.17 | Dx = 1.464 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 3.7712 (3) Å | Cell parameters from 5546 reflections |
b = 6.1229 (5) Å | θ = 3.4–26.2° |
c = 34.868 (3) Å | µ = 0.11 mm−1 |
β = 93.099 (3)° | T = 100 K |
V = 803.96 (11) Å3 | Plate, colourless |
Z = 4 | 0.28 × 0.06 × 0.02 mm |
Data collection top
Bruker D8 VENTURE DUO diffractometer | 1656 independent reflections |
Radiation source: sealed tube, fine-focus | 1411 reflections with I > 2σ(I) |
TRIUMPH graphite monochromator | Rint = 0.036 |
Detector resolution: 7.39 pixels mm-1 | θmax = 26.4°, θmin = 2.9° |
ω and φ scans | h = −4→4 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −7→7 |
Tmin = 0.682, Tmax = 0.745 | l = −43→43 |
10613 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)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0299P)2 + 0.3387P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
1656 reflections | Δρmax = 0.25 e Å−3 |
123 parameters | Δρmin = −0.23 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. Data for all structures were collected at 100 K on a Bruker D8 VENTURE Duo
fixed-chi three-circle diffractometer using Mo Kα radiation (λ =
0.71073 Å). All data were integrated with SAINT (Bruker, 2016) and
corrected for absorption using SADABS (Krause et al., 2015).
The structures of polymorphs A and C were solved by dual methods
using SHELXT (Sheldrick, 2015a), while B was solved by
direct methods using SHELXS (Sheldrick, 2008). All structures were
refined by full-matrix least-squares methods against F2 using
SHELXL (Sheldrick, 2015b). All non-H atoms were refined with
anisotropic displacement parameters. Calculations and refinement of the structure was carried out using
APEX4 (Bruker, 2021) and OLEX2 (Dolomanov et al., 2009)
software. Crystal packing diagrams were generated using OLEX2.
Structure overlay diagrams and r.m.s. deviation values were obtained using
Mercury (Macrae et al., 2020). For polymorph B,
the TWINROTMAT routine within PLATON (Spek, 2020) indicated twinning.
The twin law was found to be (100, 010, 101). The BASF value refined to
0.5471 (16). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.0623 (4) | 0.4961 (2) | 0.04746 (4) | 0.0214 (4) | |
O2 | 0.7725 (4) | 0.2518 (3) | 0.00956 (4) | 0.0243 (4) | |
H1 | 0.832 (9) | 0.347 (5) | −0.0081 (9) | 0.072 (11)* | |
N1 | 0.7854 (5) | 0.4340 (3) | 0.19050 (5) | 0.0249 (5) | |
N2 | 0.9692 (6) | 0.5552 (3) | 0.21177 (5) | 0.0232 (5) | |
N3 | 1.1081 (7) | 0.6857 (3) | 0.22997 (6) | 0.0362 (6) | |
C1 | 0.8065 (6) | 0.1853 (3) | 0.07635 (6) | 0.0160 (5) | |
C2 | 0.8930 (5) | 0.2600 (3) | 0.11338 (5) | 0.0161 (5) | |
H2 | 1.002494 | 0.398639 | 0.117123 | 0.019* | |
C3 | 0.8194 (6) | 0.1319 (3) | 0.14487 (6) | 0.0156 (5) | |
C4 | 0.6584 (6) | −0.0703 (3) | 0.13902 (6) | 0.0178 (5) | |
H4 | 0.604339 | −0.157416 | 0.160482 | 0.021* | |
C5 | 0.5758 (6) | −0.1466 (3) | 0.10202 (6) | 0.0192 (5) | |
H5 | 0.469034 | −0.286048 | 0.098269 | 0.023* | |
C6 | 0.6495 (6) | −0.0188 (3) | 0.07071 (6) | 0.0173 (5) | |
H6 | 0.593077 | −0.070155 | 0.045407 | 0.021* | |
C7 | 0.8919 (6) | 0.3249 (3) | 0.04313 (6) | 0.0165 (5) | |
C8 | 0.9242 (6) | 0.2094 (3) | 0.18508 (6) | 0.0194 (5) | |
H8A | 0.825573 | 0.109447 | 0.204114 | 0.023* | |
H8B | 1.186115 | 0.209188 | 0.189068 | 0.023* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0269 (9) | 0.0196 (8) | 0.0177 (7) | −0.0068 (8) | 0.0005 (7) | −0.0012 (6) |
O2 | 0.0336 (10) | 0.0257 (9) | 0.0132 (8) | −0.0101 (9) | −0.0031 (7) | 0.0002 (7) |
N1 | 0.0306 (13) | 0.0214 (10) | 0.0217 (9) | 0.0026 (10) | −0.0081 (9) | −0.0047 (8) |
N2 | 0.0318 (12) | 0.0240 (10) | 0.0134 (9) | 0.0075 (10) | −0.0018 (9) | 0.0018 (9) |
N3 | 0.0509 (15) | 0.0262 (11) | 0.0299 (11) | 0.0041 (12) | −0.0112 (11) | −0.0117 (10) |
C1 | 0.0133 (11) | 0.0180 (11) | 0.0167 (10) | 0.0027 (10) | −0.0006 (10) | 0.0005 (8) |
C2 | 0.0156 (12) | 0.0134 (11) | 0.0191 (11) | −0.0004 (10) | −0.0011 (9) | −0.0022 (8) |
C3 | 0.0123 (12) | 0.0174 (11) | 0.0168 (11) | 0.0034 (10) | −0.0020 (9) | −0.0006 (8) |
C4 | 0.0146 (12) | 0.0182 (11) | 0.0208 (11) | 0.0019 (10) | 0.0023 (9) | 0.0043 (9) |
C5 | 0.0164 (12) | 0.0138 (11) | 0.0270 (12) | −0.0016 (11) | −0.0031 (10) | −0.0020 (9) |
C6 | 0.0148 (12) | 0.0195 (11) | 0.0174 (10) | 0.0019 (10) | −0.0007 (9) | −0.0027 (9) |
C7 | 0.0165 (12) | 0.0179 (11) | 0.0151 (10) | 0.0047 (11) | 0.0008 (9) | −0.0033 (8) |
C8 | 0.0218 (13) | 0.0171 (11) | 0.0189 (11) | 0.0015 (11) | −0.0015 (9) | 0.0009 (8) |
Geometric parameters (Å, º) top
O1—C7 | 1.235 (3) | C2—C3 | 1.390 (3) |
O2—H1 | 0.89 (3) | C3—C4 | 1.389 (3) |
O2—C7 | 1.310 (2) | C3—C8 | 1.512 (3) |
N1—N2 | 1.235 (3) | C4—H4 | 0.9500 |
N1—C8 | 1.487 (3) | C4—C5 | 1.391 (3) |
N2—N3 | 1.131 (3) | C5—H5 | 0.9500 |
C1—C2 | 1.392 (3) | C5—C6 | 1.384 (3) |
C1—C6 | 1.392 (3) | C6—H6 | 0.9500 |
C1—C7 | 1.489 (3) | C8—H8A | 0.9900 |
C2—H2 | 0.9500 | C8—H8B | 0.9900 |
| | | |
C7—O2—H1 | 108.0 (19) | C4—C5—H5 | 120.1 |
N2—N1—C8 | 116.23 (18) | C6—C5—C4 | 119.8 (2) |
N3—N2—N1 | 171.5 (2) | C6—C5—H5 | 120.1 |
C2—C1—C7 | 118.89 (19) | C1—C6—H6 | 120.1 |
C6—C1—C2 | 120.19 (19) | C5—C6—C1 | 119.89 (19) |
C6—C1—C7 | 120.91 (18) | C5—C6—H6 | 120.1 |
C1—C2—H2 | 120.0 | O1—C7—O2 | 123.42 (18) |
C3—C2—C1 | 120.05 (19) | O1—C7—C1 | 121.70 (18) |
C3—C2—H2 | 120.0 | O2—C7—C1 | 114.88 (19) |
C2—C3—C8 | 120.15 (18) | N1—C8—C3 | 109.37 (17) |
C4—C3—C2 | 119.42 (18) | N1—C8—H8A | 109.8 |
C4—C3—C8 | 120.40 (18) | N1—C8—H8B | 109.8 |
C3—C4—H4 | 119.7 | C3—C8—H8A | 109.8 |
C3—C4—C5 | 120.64 (19) | C3—C8—H8B | 109.8 |
C5—C4—H4 | 119.7 | H8A—C8—H8B | 108.2 |
| | | |
N2—N1—C8—C3 | −146.9 (2) | C4—C3—C8—N1 | −129.8 (2) |
C1—C2—C3—C4 | −0.1 (3) | C4—C5—C6—C1 | 0.1 (3) |
C1—C2—C3—C8 | 177.95 (19) | C6—C1—C2—C3 | −0.7 (3) |
C2—C1—C6—C5 | 0.7 (3) | C6—C1—C7—O1 | −172.7 (2) |
C2—C1—C7—O1 | 5.9 (3) | C6—C1—C7—O2 | 7.4 (3) |
C2—C1—C7—O2 | −173.96 (19) | C7—C1—C2—C3 | −179.4 (2) |
C2—C3—C4—C5 | 1.0 (3) | C7—C1—C6—C5 | 179.4 (2) |
C2—C3—C8—N1 | 52.1 (3) | C8—C3—C4—C5 | −177.1 (2) |
C3—C4—C5—C6 | −0.9 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H1···O1i | 0.89 (3) | 1.74 (3) | 2.619 (2) | 172 (3) |
Symmetry code: (i) −x+2, −y+1, −z. |
3-(Azidomethyl)benzoic acid (C)
top
Crystal data top
C8H7N3O2 | Z = 2 |
Mr = 177.17 | F(000) = 184 |
Triclinic, P1 | Dx = 1.486 Mg m−3 |
a = 3.8029 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.9199 (5) Å | Cell parameters from 4919 reflections |
c = 11.5709 (6) Å | θ = 3.5–25.0° |
α = 66.828 (2)° | µ = 0.11 mm−1 |
β = 82.168 (3)° | T = 100 K |
γ = 82.245 (2)° | Plate, colourless |
V = 395.96 (4) Å3 | 0.31 × 0.12 × 0.01 mm |
Data collection top
Bruker D8 VENTURE DUO diffractometer | 1405 independent reflections |
Radiation source: sealed tube, fine-focus | 1196 reflections with I > 2σ(I) |
TRIUMPH graphite monochromator | Rint = 0.039 |
Detector resolution: 7.39 pixels mm-1 | θmax = 25.1°, θmin = 2.3° |
ω and φ scans | h = −4→4 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −11→11 |
Tmin = 0.692, Tmax = 0.745 | l = −13→13 |
10604 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.186P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1405 reflections | Δρmax = 0.28 e Å−3 |
122 parameters | Δρmin = −0.22 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. Data for all structures were collected at 100 K on a Bruker D8 VENTURE Duo
fixed-chi three-circle diffractometer using Mo Kα radiation (λ =
0.71073 Å). All data were integrated with SAINT (Bruker, 2016) and
corrected for absorption using SADABS (Krause et al., 2015).
The structures of polymorphs A and C were solved by dual methods
using SHELXT (Sheldrick, 2015a), while B was solved by
direct methods using SHELXS (Sheldrick, 2008). All structures were
refined by full-matrix least-squares methods against F2 using
SHELXL (Sheldrick, 2015b). All non-H atoms were refined with
anisotropic displacement parameters. Calculations and refinement of the structure was carried out using
APEX4 (Bruker, 2021) and OLEX2 (Dolomanov et al., 2009)
software. Crystal packing diagrams were generated using OLEX2.
Structure overlay diagrams and r.m.s. deviation values were obtained using
Mercury (Macrae et al., 2020). For polymorph B,
the TWINROTMAT routine within PLATON (Spek, 2020) indicated twinning.
The twin law was found to be (100, 010, 101). The BASF value refined to
0.5471 (16). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.0326 (3) | 0.83827 (12) | 0.49082 (10) | 0.0198 (3) | |
O2 | 0.2904 (3) | 1.03789 (12) | 0.35458 (11) | 0.0227 (3) | |
H2 | 0.186 (6) | 1.078 (3) | 0.410 (2) | 0.054 (7)* | |
N1 | 0.3359 (4) | 0.40072 (15) | 0.21257 (14) | 0.0251 (4) | |
N2 | 0.5625 (4) | 0.33494 (15) | 0.16159 (13) | 0.0221 (3) | |
N3 | 0.7443 (4) | 0.27491 (18) | 0.10769 (15) | 0.0329 (4) | |
C1 | 0.3888 (4) | 0.82269 (17) | 0.30991 (14) | 0.0161 (3) | |
C2 | 0.3511 (4) | 0.67337 (17) | 0.34707 (14) | 0.0164 (3) | |
H2A | 0.223831 | 0.622462 | 0.425784 | 0.020* | |
C3 | 0.4970 (4) | 0.59800 (17) | 0.27054 (14) | 0.0169 (3) | |
C4 | 0.6811 (4) | 0.67547 (18) | 0.15490 (15) | 0.0186 (4) | |
H4 | 0.783049 | 0.625313 | 0.101590 | 0.022* | |
C5 | 0.7172 (4) | 0.82338 (18) | 0.11701 (15) | 0.0194 (4) | |
H5 | 0.841506 | 0.874346 | 0.037700 | 0.023* | |
C6 | 0.5730 (4) | 0.89857 (18) | 0.19389 (15) | 0.0184 (4) | |
H6 | 0.599376 | 1.000494 | 0.167874 | 0.022* | |
C7 | 0.2220 (4) | 0.89969 (17) | 0.39315 (14) | 0.0163 (3) | |
C8 | 0.4606 (4) | 0.43609 (17) | 0.31271 (15) | 0.0199 (4) | |
H8A | 0.694016 | 0.380445 | 0.335739 | 0.024* | |
H8B | 0.289201 | 0.404683 | 0.388834 | 0.024* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0233 (6) | 0.0168 (6) | 0.0193 (6) | −0.0012 (4) | 0.0030 (5) | −0.0088 (5) |
O2 | 0.0299 (6) | 0.0149 (6) | 0.0238 (6) | −0.0030 (5) | 0.0068 (5) | −0.0104 (5) |
N1 | 0.0233 (7) | 0.0237 (8) | 0.0357 (8) | 0.0019 (6) | −0.0050 (6) | −0.0198 (7) |
N2 | 0.0256 (7) | 0.0207 (7) | 0.0214 (7) | −0.0072 (6) | −0.0005 (6) | −0.0084 (6) |
N3 | 0.0339 (9) | 0.0411 (10) | 0.0325 (8) | −0.0096 (7) | 0.0085 (7) | −0.0250 (8) |
C1 | 0.0137 (7) | 0.0182 (8) | 0.0184 (8) | 0.0015 (6) | −0.0040 (6) | −0.0092 (6) |
C2 | 0.0122 (7) | 0.0207 (8) | 0.0169 (8) | 0.0006 (6) | −0.0011 (6) | −0.0085 (6) |
C3 | 0.0123 (7) | 0.0190 (8) | 0.0221 (8) | 0.0019 (6) | −0.0048 (6) | −0.0107 (6) |
C4 | 0.0144 (7) | 0.0246 (9) | 0.0204 (8) | 0.0013 (6) | −0.0012 (6) | −0.0136 (7) |
C5 | 0.0169 (7) | 0.0233 (9) | 0.0179 (8) | −0.0010 (6) | 0.0012 (6) | −0.0089 (7) |
C6 | 0.0170 (7) | 0.0182 (8) | 0.0204 (8) | 0.0002 (6) | −0.0028 (6) | −0.0081 (7) |
C7 | 0.0149 (7) | 0.0168 (8) | 0.0178 (8) | 0.0011 (6) | −0.0031 (6) | −0.0074 (6) |
C8 | 0.0187 (8) | 0.0209 (9) | 0.0220 (8) | −0.0020 (6) | 0.0011 (6) | −0.0111 (7) |
Geometric parameters (Å, º) top
O1—C7 | 1.2337 (18) | C2—C3 | 1.388 (2) |
O2—H2 | 0.90 (3) | C3—C4 | 1.397 (2) |
O2—C7 | 1.3151 (19) | C3—C8 | 1.504 (2) |
N1—N2 | 1.2364 (19) | C4—H4 | 0.9500 |
N1—C8 | 1.485 (2) | C4—C5 | 1.377 (2) |
N2—N3 | 1.1337 (19) | C5—H5 | 0.9500 |
C1—C2 | 1.392 (2) | C5—C6 | 1.388 (2) |
C1—C6 | 1.397 (2) | C6—H6 | 0.9500 |
C1—C7 | 1.482 (2) | C8—H8A | 0.9900 |
C2—H2A | 0.9500 | C8—H8B | 0.9900 |
| | | |
C7—O2—H2 | 110.5 (15) | C4—C5—H5 | 119.8 |
N2—N1—C8 | 115.34 (13) | C4—C5—C6 | 120.46 (14) |
N3—N2—N1 | 173.10 (16) | C6—C5—H5 | 119.8 |
C2—C1—C6 | 119.94 (14) | C1—C6—H6 | 120.4 |
C2—C1—C7 | 119.07 (13) | C5—C6—C1 | 119.25 (15) |
C6—C1—C7 | 120.97 (13) | C5—C6—H6 | 120.4 |
C1—C2—H2A | 119.6 | O1—C7—O2 | 122.90 (14) |
C3—C2—C1 | 120.81 (14) | O1—C7—C1 | 122.22 (13) |
C3—C2—H2A | 119.6 | O2—C7—C1 | 114.88 (13) |
C2—C3—C4 | 118.53 (14) | N1—C8—C3 | 111.77 (13) |
C2—C3—C8 | 120.37 (14) | N1—C8—H8A | 109.3 |
C4—C3—C8 | 121.10 (14) | N1—C8—H8B | 109.3 |
C3—C4—H4 | 119.5 | C3—C8—H8A | 109.3 |
C5—C4—C3 | 121.01 (14) | C3—C8—H8B | 109.3 |
C5—C4—H4 | 119.5 | H8A—C8—H8B | 107.9 |
| | | |
N2—N1—C8—C3 | 108.18 (15) | C4—C3—C8—N1 | −49.36 (18) |
C1—C2—C3—C4 | −0.4 (2) | C4—C5—C6—C1 | −0.4 (2) |
C1—C2—C3—C8 | 178.84 (13) | C6—C1—C2—C3 | 0.5 (2) |
C2—C1—C6—C5 | −0.1 (2) | C6—C1—C7—O1 | 173.70 (14) |
C2—C1—C7—O1 | −4.4 (2) | C6—C1—C7—O2 | −6.1 (2) |
C2—C1—C7—O2 | 175.81 (13) | C7—C1—C2—C3 | 178.66 (13) |
C2—C3—C4—C5 | −0.2 (2) | C7—C1—C6—C5 | −178.22 (13) |
C2—C3—C8—N1 | 131.44 (14) | C8—C3—C4—C5 | −179.37 (14) |
C3—C4—C5—C6 | 0.6 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.90 (3) | 1.73 (3) | 2.6346 (15) | 176 (2) |
Symmetry code: (i) −x, −y+2, −z+1. |
Computational values top | ΔEcrys–crys(X) (kcal mol-1) | ΔEcrys–gas(X) (kcal mol-1) | ΔEgas–gas(A–X) (kcal mol-1) | τ1-gas (°) | τ1-crys (°) | τ1Δθ (°) | τ2-gas (°) | τ2-crys (°) | τ2Δθ (°) |
A | 0.00 | 0.02 | 0.00 | -95.81 | -95.76 | | 62.01 | 59.93 | |
B | 1.66 | 0.57 | 1.11 | 140.58 | 52.06 | 147.82 | 172.31 | -146.85 | 153.22 |
C | 1.29 | 1.25 | 0.06 | -85.58 | -131.44 | 35.68 | -62.15 | -108.21 | 168.14 |
Notes: τ1-gas and τ2-gas are the torsion angles obtained from Xgas.
τ1-crys and τ2-crys are the torsion angles obtained from Xcrys.
Δθ is taken as the difference between the dihedral in Acrys and the
dihedral in Bcrys or Ccrys. |
Table of germane noncovalent parameters topParameter | A | B | C |
O—H···O (Å) hydrogen-bond parameters* | | | |
O—H (Å) | 0.96 (3) | 0.89 (3) | 0.90 (3) |
H···O (Å) | 1.68 (3) | 1.74 (3) | 1.73 (3) |
O···O (Å) | 2.6334 (15) | 2.619 (2) | 2.6346 (15) |
D—H···A (°) | 175 (3) | 172 (3) | 176 (2) |
| | | |
π–π stacking parameters | | | |
Distance between planes (Å) | 3.361 | 3.414 | 3.406 |
| 3.353 | | |
Centroid–centroid distance (Å) | 3.6568 (12) | 3.7712 (3) | 3.8029 (2) |
| 4.0950 (12) | | |
Closest C···C distance (Å) | 3.3714 (19) | 3.414 (3) | 3.419 (2) |
| 3.367 (2) | | |
Note: (*) symmetry transformations used to generate equivalent atoms for
carboxylic acid dimer hydrogen bonds.
Molecule A: -x+2, -y+2, -z+1;
molecule B: -x+2, -y+1, -z;
molecule C: -x, -y+2, -z+1. |
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