We have investigated the polymorphic phase transformations above ambient temperature for 3-chloro-trans-cinnamic acid (3-ClCA, C9H7ClO2) and a solid solution of 3-ClCA and 3-bromo-trans-cinnamic acid (3-BrCA, C9H7BrO2). At 413 K, the γ polymorph of 3-ClCA transforms to the β polymorph. Interestingly, the structure of the β polymorph of 3-ClCA obtained in this transformation is different from the structure of the β polymorph of 3-BrCA obtained in the corresponding polymorphic transformation from the γ polymorph of 3-BrCA, even though the γ polymorphs of 3-ClCA and 3-BrCA are isostructural. We also report a high-temperature phase transformation from a γ-type structure to a β-type structure for a solid solution of 3-ClCA and 3-BrCA (with a molar ratio close to 1:1). The γ polymorph of the solid solution is isostructural with the γ polymorphs of pure 3-ClCA and pure 3-BrCA, while the β-type structure produced in the phase transformation is structurally similar to the β polymorph of pure 3-BrCA.
Supporting information
CCDC references: 1828662; 1828663
For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015b).
3-(3-Chloro/bromophenyl)prop-2-enoic acid (I)
top
Crystal data top
C9H7Br0.43Cl0.57O2 | F(000) = 405 |
Mr = 201.49 | Dx = 1.540 Mg m−3 |
Monoclinic, P21/a | Cu Kα radiation, λ = 1.54184 Å |
a = 12.3957 (8) Å | Cell parameters from 1154 reflections |
b = 4.9381 (2) Å | θ = 6.2–72.3° |
c = 14.2102 (12) Å | µ = 4.63 mm−1 |
β = 94.871 (6)° | T = 296 K |
V = 866.68 (10) Å3 | Needle, colourless |
Z = 4 | 0.29 × 0.10 × 0.05 mm |
Data collection top
Agilent SuperNova Dual Source diffractometer with an Atlas detector | 1306 reflections with I > 2σ(I) |
ω scans | Rint = 0.044 |
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2015) | θmax = 73.9°, θmin = 6.3° |
Tmin = 0.893, Tmax = 0.969 | h = −14→15 |
2874 measured reflections | k = −4→5 |
1670 independent reflections | l = −17→15 |
Refinement top
Refinement on F2 | 20 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.058P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
1670 reflections | Δρmax = 0.26 e Å−3 |
123 parameters | Δρmin = −0.34 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.67233 (18) | −0.6465 (4) | 0.23649 (16) | 0.0493 (5) | |
C2 | 0.62396 (18) | −0.5315 (5) | 0.31173 (16) | 0.0528 (5) | |
H2 | 0.555859 | −0.589481 | 0.325993 | 0.063* | |
C3 | 0.6770 (2) | −0.3315 (5) | 0.36513 (16) | 0.0557 (6) | |
C4 | 0.7783 (2) | −0.2403 (5) | 0.34630 (19) | 0.0610 (6) | |
H4 | 0.813206 | −0.105848 | 0.383226 | 0.073* | |
C5 | 0.8267 (2) | −0.3534 (5) | 0.27113 (19) | 0.0629 (6) | |
H5 | 0.894935 | −0.294524 | 0.257509 | 0.075* | |
C6 | 0.77456 (18) | −0.5532 (5) | 0.21618 (17) | 0.0552 (6) | |
H6 | 0.807542 | −0.625904 | 0.165490 | 0.066* | |
C7 | 0.61382 (18) | −0.8594 (4) | 0.18165 (17) | 0.0510 (5) | |
H7 | 0.546210 | −0.906212 | 0.200428 | 0.061* | |
C8 | 0.64617 (17) | −0.9925 (5) | 0.10857 (15) | 0.0513 (5) | |
H8 | 0.712007 | −0.946555 | 0.085987 | 0.062* | |
C9 | 0.58153 (17) | −1.2110 (4) | 0.06175 (16) | 0.0471 (5) | |
O1 | 0.62133 (13) | −1.3381 (3) | −0.00454 (13) | 0.0589 (4) | |
O2 | 0.48893 (13) | −1.2659 (4) | 0.08900 (13) | 0.0594 (5) | |
Cl1 | 0.6164 (7) | −0.170 (2) | 0.4567 (5) | 0.0732 (12) | 0.575 (4) |
Br1 | 0.6053 (4) | −0.1842 (12) | 0.4661 (2) | 0.0710 (7) | 0.425 (4) |
H1O | 0.438 (4) | −1.450 (11) | 0.045 (3) | 0.145 (16)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0526 (11) | 0.0412 (11) | 0.0539 (11) | −0.0002 (9) | 0.0041 (9) | −0.0001 (9) |
C2 | 0.0543 (11) | 0.0489 (12) | 0.0557 (11) | 0.0021 (10) | 0.0071 (9) | 0.0010 (10) |
C3 | 0.0681 (14) | 0.0493 (12) | 0.0498 (11) | 0.0088 (11) | 0.0064 (10) | −0.0025 (10) |
C4 | 0.0654 (14) | 0.0528 (13) | 0.0634 (14) | −0.0014 (11) | −0.0032 (11) | −0.0090 (11) |
C5 | 0.0553 (13) | 0.0618 (15) | 0.0716 (15) | −0.0067 (11) | 0.0056 (11) | −0.0064 (12) |
C6 | 0.0534 (12) | 0.0523 (13) | 0.0608 (13) | −0.0004 (10) | 0.0096 (10) | −0.0089 (10) |
C7 | 0.0493 (11) | 0.0453 (11) | 0.0588 (12) | −0.0021 (9) | 0.0071 (9) | −0.0022 (10) |
C8 | 0.0486 (10) | 0.0474 (11) | 0.0587 (12) | −0.0053 (9) | 0.0090 (9) | −0.0025 (10) |
C9 | 0.0470 (10) | 0.0435 (10) | 0.0512 (11) | 0.0015 (9) | 0.0071 (9) | −0.0011 (9) |
O1 | 0.0573 (9) | 0.0563 (10) | 0.0656 (9) | −0.0072 (7) | 0.0193 (7) | −0.0138 (8) |
O2 | 0.0530 (9) | 0.0614 (9) | 0.0657 (10) | −0.0096 (7) | 0.0167 (7) | −0.0126 (8) |
Cl1 | 0.097 (2) | 0.0690 (15) | 0.0584 (15) | −0.0042 (11) | 0.0339 (11) | −0.0167 (14) |
Br1 | 0.0888 (13) | 0.0720 (11) | 0.0543 (8) | 0.0109 (12) | 0.0182 (9) | −0.0098 (7) |
Geometric parameters (Å, º) top
C1—C2 | 1.391 (3) | C5—C6 | 1.384 (3) |
C1—C6 | 1.401 (3) | C5—H5 | 0.9300 |
C1—C7 | 1.464 (3) | C6—H6 | 0.9300 |
C2—C3 | 1.378 (3) | C7—C8 | 1.320 (3) |
C2—H2 | 0.9300 | C7—H7 | 0.9300 |
C3—C4 | 1.381 (4) | C8—C9 | 1.469 (3) |
C3—Cl1 | 1.7504 (10) | C8—H8 | 0.9300 |
C3—Br1 | 1.896 (4) | C9—O1 | 1.266 (3) |
C4—C5 | 1.387 (4) | C9—O2 | 1.271 (3) |
C4—H4 | 0.9300 | O2—H1O | 1.24 (5) |
| | | |
C2—C1—C6 | 118.7 (2) | C6—C5—H5 | 119.7 |
C2—C1—C7 | 118.4 (2) | C4—C5—H5 | 119.7 |
C6—C1—C7 | 122.8 (2) | C5—C6—C1 | 120.4 (2) |
C3—C2—C1 | 120.0 (2) | C5—C6—H6 | 119.8 |
C3—C2—H2 | 120.0 | C1—C6—H6 | 119.8 |
C1—C2—H2 | 120.0 | C8—C7—C1 | 127.4 (2) |
C2—C3—C4 | 121.7 (2) | C8—C7—H7 | 116.3 |
C2—C3—Cl1 | 121.5 (4) | C1—C7—H7 | 116.3 |
C4—C3—Cl1 | 116.7 (4) | C7—C8—C9 | 122.11 (19) |
C2—C3—Br1 | 117.3 (3) | C7—C8—H8 | 118.9 |
C4—C3—Br1 | 120.9 (3) | C9—C8—H8 | 118.9 |
Cl1—C3—Br1 | 4.9 (6) | O1—C9—O2 | 122.7 (2) |
C3—C4—C5 | 118.6 (2) | O1—C9—C8 | 117.97 (18) |
C3—C4—H4 | 120.7 | O2—C9—C8 | 119.37 (19) |
C5—C4—H4 | 120.7 | C9—O2—H1O | 115.5 (19) |
C6—C5—C4 | 120.6 (2) | | |
3-(3-Chloro/bromophenyl)prop-2-enoic acid (II)
top
Crystal data top
C9H7Br0.49Cl0.51O2 | F(000) = 823 |
Mr = 204.38 | Dx = 1.578 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54184 Å |
a = 19.054 (5) Å | Cell parameters from 946 reflections |
b = 3.9451 (7) Å | θ = 3.9–71.3° |
c = 24.661 (5) Å | µ = 4.83 mm−1 |
β = 111.81 (3)° | T = 296 K |
V = 1721.1 (7) Å3 | Needle, colourless |
Z = 8 | 0.19 × 0.05 × 0.04 mm |
Data collection top
Agilent SuperNova Dual Source diffractometer with an Atlas detector | 1181 reflections with I > 2σ(I) |
ω scans | Rint = 0.052 |
Absorption correction: gaussian (CrysAlis PRO; Rigaku OD, 2015) | θmax = 74.4°, θmin = 3.9° |
Tmin = 0.961, Tmax = 0.987 | h = −14→23 |
5012 measured reflections | k = −4→4 |
1706 independent reflections | l = −30→26 |
Refinement top
Refinement on F2 | 22 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.152 | w = 1/[σ2(Fo2) + (0.074P)2 + 0.5938P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1706 reflections | Δρmax = 0.40 e Å−3 |
120 parameters | Δρmin = −0.42 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.5351 (2) | 0.6106 (11) | 0.61622 (17) | 0.0616 (10) | |
C2 | 0.5504 (2) | 0.5294 (10) | 0.67517 (15) | 0.0591 (9) | |
H2 | 0.514805 | 0.579375 | 0.691554 | 0.071* | |
C3 | 0.6161 (2) | 0.3799 (10) | 0.70801 (16) | 0.0616 (9) | |
C4 | 0.6709 (2) | 0.2960 (10) | 0.6851 (2) | 0.0679 (10) | |
H4 | 0.715608 | 0.188866 | 0.707907 | 0.081* | |
C5 | 0.6565 (3) | 0.3769 (13) | 0.6280 (2) | 0.0789 (13) | |
H5 | 0.692530 | 0.326609 | 0.612053 | 0.095* | |
C6 | 0.5904 (2) | 0.5301 (13) | 0.59378 (19) | 0.0719 (11) | |
H6 | 0.582205 | 0.581225 | 0.555083 | 0.086* | |
C7 | 0.4650 (2) | 0.7733 (10) | 0.57900 (17) | 0.0631 (10) | |
H7 | 0.460976 | 0.822057 | 0.541064 | 0.076* | |
C8 | 0.4064 (2) | 0.8600 (11) | 0.59242 (17) | 0.0646 (10) | |
H8 | 0.408265 | 0.812665 | 0.629870 | 0.078* | |
C9 | 0.3394 (2) | 1.0250 (12) | 0.55188 (16) | 0.0663 (10) | |
Cl1 | 0.6387 (4) | 0.293 (3) | 0.7821 (3) | 0.0674 (16) | 0.506 (7) |
Br1 | 0.6347 (3) | 0.2667 (15) | 0.78648 (14) | 0.0824 (12) | 0.494 (7) |
O1 | 0.28940 (18) | 1.1178 (10) | 0.57129 (13) | 0.0892 (11) | |
H1 | 0.254247 | 1.207587 | 0.544981 | 0.134* | 0.5 |
O2 | 0.33317 (19) | 1.0789 (11) | 0.49960 (12) | 0.0858 (10) | |
H2A | 0.293100 | 1.176290 | 0.482034 | 0.129* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.065 (2) | 0.066 (2) | 0.057 (2) | −0.0153 (18) | 0.0263 (17) | −0.0109 (17) |
C2 | 0.069 (2) | 0.060 (2) | 0.057 (2) | −0.0114 (17) | 0.0325 (18) | −0.0071 (17) |
C3 | 0.071 (2) | 0.059 (2) | 0.058 (2) | −0.0061 (18) | 0.0291 (18) | −0.0015 (17) |
C4 | 0.067 (2) | 0.060 (2) | 0.084 (3) | −0.0015 (18) | 0.035 (2) | −0.0032 (19) |
C5 | 0.076 (3) | 0.091 (3) | 0.085 (3) | −0.004 (2) | 0.047 (2) | −0.012 (2) |
C6 | 0.081 (3) | 0.081 (3) | 0.064 (2) | −0.014 (2) | 0.039 (2) | −0.009 (2) |
C7 | 0.077 (2) | 0.064 (2) | 0.052 (2) | −0.0116 (19) | 0.0271 (18) | −0.0058 (17) |
C8 | 0.076 (2) | 0.068 (2) | 0.051 (2) | −0.0069 (19) | 0.0248 (18) | 0.0009 (17) |
C9 | 0.071 (2) | 0.076 (3) | 0.051 (2) | −0.011 (2) | 0.0219 (18) | −0.0059 (19) |
Cl1 | 0.065 (2) | 0.073 (3) | 0.062 (3) | −0.0005 (17) | 0.020 (2) | 0.020 (2) |
Br1 | 0.106 (2) | 0.086 (2) | 0.0679 (12) | 0.0151 (14) | 0.0463 (12) | 0.0122 (10) |
O1 | 0.081 (2) | 0.128 (3) | 0.0655 (19) | 0.013 (2) | 0.0348 (16) | 0.0167 (18) |
O2 | 0.088 (2) | 0.120 (3) | 0.0515 (15) | 0.0137 (19) | 0.0292 (14) | 0.0065 (16) |
Geometric parameters (Å, º) top
C1—C6 | 1.396 (6) | C5—H5 | 0.9300 |
C1—C2 | 1.410 (5) | C6—H6 | 0.9300 |
C1—C7 | 1.459 (6) | C7—C8 | 1.321 (6) |
C2—C3 | 1.348 (6) | C7—H7 | 0.9300 |
C2—H2 | 0.9300 | C8—C9 | 1.451 (6) |
C3—C4 | 1.400 (6) | C8—H8 | 0.9300 |
C3—Cl1 | 1.748 (6) | C9—O2 | 1.268 (5) |
C3—Br1 | 1.887 (5) | C9—O1 | 1.269 (5) |
C4—C5 | 1.369 (7) | O1—H1 | 0.8200 |
C4—H4 | 0.9300 | O2—H2A | 0.8200 |
C5—C6 | 1.369 (7) | | |
| | | |
C6—C1—C2 | 117.4 (4) | C4—C5—H5 | 119.2 |
C6—C1—C7 | 120.0 (4) | C6—C5—H5 | 119.2 |
C2—C1—C7 | 122.6 (4) | C5—C6—C1 | 120.9 (4) |
C3—C2—C1 | 120.6 (3) | C5—C6—H6 | 119.6 |
C3—C2—H2 | 119.7 | C1—C6—H6 | 119.6 |
C1—C2—H2 | 119.7 | C8—C7—C1 | 128.1 (4) |
C2—C3—C4 | 121.8 (4) | C8—C7—H7 | 115.9 |
C2—C3—Cl1 | 121.8 (4) | C1—C7—H7 | 115.9 |
C4—C3—Cl1 | 116.4 (4) | C7—C8—C9 | 123.5 (4) |
C2—C3—Br1 | 119.9 (3) | C7—C8—H8 | 118.2 |
C4—C3—Br1 | 118.3 (4) | C9—C8—H8 | 118.2 |
Cl1—C3—Br1 | 3.8 (5) | O2—C9—O1 | 122.3 (4) |
C5—C4—C3 | 117.8 (4) | O2—C9—C8 | 120.2 (4) |
C5—C4—H4 | 121.1 | O1—C9—C8 | 117.5 (3) |
C3—C4—H4 | 121.1 | C9—O1—H1 | 109.5 |
C4—C5—C6 | 121.6 (4) | C9—O2—H2A | 109.5 |
Crystallographic data for the γ-type and β(Br)-type structures of the
3-(Cl/Br)CA solid solution determined before and after the phase
transformation from the γ-type structure to the β(Br)-type structure topCompound | 3-(Cl0.57/Br0.43)CA | 3-(Cl0.50/Br0.50)CA |
Polymorph | γ | β(Br) |
Mr | 200.99 | 204.38 |
T (K) | 296 (1) | 150 (1) |
Crystal system | Monoclinic | Monoclinic |
Space group | P21/a | C2/c |
a (Å) | 12.3957 (8) | 19.054 (5) |
b (Å) | 4.9381 (2) | 3.9451 (7) |
c (Å) | 14.2102 (12) | 24.661 (5) |
α (°) | 90 | 90 |
β (°) | 94.871 (6) | 111.81 (3) |
γ (°) | 90 | 90 |
V (Å3) | 866.68 (10) | 1721.1 (7) |
Z | 4 | 8 |
Wavelength (Å) | 1.54184 | 1.54184 |
σ(calc) (Mg m-3) | 1.540 | 1.578 |
µ (mm-1) | 4.627 | 4.828 |
Occupancies 3-ClCA/3-BrCA | 0.575 (4)/0.425 (4) | 0.506 (7)/0.494 (7) |
Crystal size (mm) | 0.289 × 0.098 × 0.048 | 0.185 × 0.052 × 0.043 |
Reflections collected | 2874 | 5012 |
Independent reflections | 1670 | 1706 |
Rint | 0.0440 | 0.0522 |
R1 [I > 2σ(I)] | 0.0372 | 0.0494 |
wR2 [I > 2σ(I)] | 0.0937 | 0.1308 |
R1 (all data) | 0.0484 | 0.0763 |
wR2 (all data) | 0.1015 | 0.1516 |
Crystallographic data for the β and γ polymorphs of pure 3-ClCA and
pure 3-BrCA reported in previous publications topCompound | 3-ClCA | 3-BrCA | 3-ClCA | 3-BrCA |
Polymorph | γ | γ | β | β |
Reference | Kariuki et al. (1996) | Ahn et al. (2001) | Kanao et al. (1990) | Kanao et al. (1990) |
T (K) | 293 | 293 | 295 | 295 |
Space group | P21/a | P21/a | P1? | C2/c |
a (Å) | 12.400 (1) | 12.389 (2) | 8.618 (4) | 19.191 (6) |
b (Å) | 4.9560 (4) | 4.933 (5) | 13.627 (5) | 3.9879 (3) |
c (Å) | 13.943 (1) | 14.411 (2) | 3.909 (1) | 24.798 (7) |
α (°) | 90 | 90 | 106.77 (3) | 90 |
β (°) | 94.265 (3) | 95.426 (5) | 96.26 (3) | 113.05 (2) |
γ (°) | 90 | 90 | 75.71 (3) | 90 |
V (Å3) | 854.486 | 876.781 | 425.586 | 1746.319 |