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Pharmaceutical salt-forming acid 1-hydroxy-2-naphthoic acid (HNA) is widely used in pharmaceutical co-crystal preparation. In this work, we report a new polymorph of HNA obtained during attempted co-crystallization experiments. The reported form and the new form were fully characterized and their thermodynamic relationship was also established to be monotropic with the new form being the more stable form.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520614026134/ry5063sup1.cif
Contains datablocks mo_I, mo_II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614026134/ry5063mo_Isup2.hkl
Contains datablock mo_2014195_0m

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520614026134/ry5063mo_IIsup3.hkl
Contains datablock mo_2014375_0m

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520614026134/ry5063sup4.pdf
Experimental section, figures and tables

CCDC references: 1036605; 1036606

Computing details top

For both compounds, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
(mo_I) top
Crystal data top
C11H8O3F(000) = 392
Mr = 188.17Dx = 1.436 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.9798 (9) ÅCell parameters from 1909 reflections
b = 3.8107 (6) Åθ = 2.5–26.2°
c = 32.790 (5) ŵ = 0.11 mm1
β = 93.901 (8)°T = 296 K
V = 870.1 (2) Å3Columnar, colorless
Z = 40.44 × 0.32 × 0.11 mm
Data collection top
Bruker APEX-II CCD
diffractometer
1020 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.038
Graphite monochromatorθmax = 25.0°, θmin = 2.5°
ϕ and ω scansh = 87
6187 measured reflectionsk = 43
1491 independent reflectionsl = 3038
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 0.96 w = 1/[σ2(Fo2) + (0.0538P)2]
where P = (Fo2 + 2Fc2)/3
1491 reflections(Δ/σ)max = 0.001
133 parametersΔρmax = 0.15 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C11H8O3V = 870.1 (2) Å3
Mr = 188.17Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.9798 (9) ŵ = 0.11 mm1
b = 3.8107 (6) ÅT = 296 K
c = 32.790 (5) Å0.44 × 0.32 × 0.11 mm
β = 93.901 (8)°
Data collection top
Bruker APEX-II CCD
diffractometer
1020 reflections with I > 2σ(I)
6187 measured reflectionsRint = 0.038
1491 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.15 e Å3
1491 reflectionsΔρmin = 0.16 e Å3
133 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O30.25506 (17)0.8378 (3)0.99359 (4)0.0618 (4)
H20.346 (3)0.937 (5)1.0124 (7)0.093*
O20.48854 (16)0.8996 (3)0.95134 (3)0.0557 (4)
O10.42771 (17)0.6877 (3)0.87621 (4)0.0566 (4)
H10.493 (3)0.780 (5)0.8993 (7)0.085*
C110.3227 (2)0.8048 (4)0.95749 (5)0.0418 (4)
C20.1919 (2)0.6527 (3)0.92614 (5)0.0379 (4)
C30.0036 (2)0.5550 (4)0.93476 (5)0.0441 (4)
H30.03710.59070.96090.053*
C40.1183 (2)0.4107 (4)0.90569 (5)0.0475 (4)
H40.24140.34790.91210.057*
C50.0614 (2)0.3540 (3)0.86576 (5)0.0421 (4)
C60.1863 (3)0.2058 (4)0.83462 (6)0.0541 (5)
H50.31040.14270.84030.065*
C70.1271 (3)0.1547 (4)0.79662 (6)0.0632 (6)
H60.21130.05710.77650.076*
C100.1249 (2)0.4484 (3)0.85586 (5)0.0397 (4)
C90.1826 (3)0.3905 (4)0.81634 (5)0.0545 (5)
H80.30620.45040.80990.065*
C80.0574 (3)0.2457 (5)0.78713 (5)0.0632 (5)
H70.09580.20830.76090.076*
C10.2516 (2)0.6003 (3)0.88710 (5)0.0392 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O30.0531 (8)0.0938 (9)0.0384 (8)0.0212 (6)0.0023 (6)0.0106 (6)
O20.0422 (7)0.0784 (8)0.0462 (8)0.0145 (6)0.0010 (5)0.0081 (5)
O10.0428 (7)0.0800 (8)0.0474 (8)0.0089 (6)0.0068 (6)0.0060 (6)
C110.0442 (10)0.0446 (8)0.0362 (10)0.0011 (7)0.0004 (7)0.0003 (7)
C20.0394 (9)0.0374 (8)0.0364 (9)0.0012 (6)0.0018 (7)0.0024 (6)
C30.0438 (10)0.0489 (9)0.0397 (10)0.0026 (7)0.0033 (7)0.0039 (7)
C40.0392 (9)0.0502 (9)0.0524 (12)0.0051 (7)0.0006 (8)0.0043 (8)
C50.0465 (10)0.0330 (7)0.0454 (11)0.0009 (7)0.0082 (8)0.0047 (6)
C60.0600 (12)0.0445 (9)0.0550 (13)0.0038 (8)0.0153 (9)0.0021 (8)
C70.0859 (16)0.0434 (9)0.0564 (13)0.0023 (9)0.0246 (11)0.0041 (8)
C100.0479 (10)0.0336 (7)0.0367 (9)0.0043 (6)0.0028 (7)0.0023 (6)
C90.0642 (12)0.0532 (10)0.0457 (11)0.0047 (8)0.0006 (9)0.0018 (8)
C80.0905 (16)0.0577 (10)0.0400 (12)0.0082 (10)0.0066 (10)0.0068 (8)
C10.0366 (9)0.0384 (8)0.0422 (10)0.0009 (7)0.0000 (7)0.0031 (7)
Geometric parameters (Å, º) top
O3—C111.3102 (19)C5—C101.408 (2)
O3—H20.93 (2)C5—C61.414 (2)
O2—C111.2417 (17)C6—C71.353 (3)
O1—C11.3447 (18)C6—H50.9300
O1—H10.92 (2)C7—C81.389 (3)
C11—C21.449 (2)C7—H60.9300
C2—C11.388 (2)C10—C91.400 (2)
C2—C31.413 (2)C10—C11.430 (2)
C3—C41.351 (2)C9—C81.368 (3)
C3—H30.9300C9—H80.9300
C4—C51.410 (2)C8—H70.9300
C4—H40.9300
C11—O3—H2111.4 (13)C7—C6—H5119.7
C1—O1—H1106.4 (13)C5—C6—H5119.7
O2—C11—O3121.08 (15)C6—C7—C8121.08 (17)
O2—C11—C2123.41 (14)C6—C7—H6119.5
O3—C11—C2115.51 (14)C8—C7—H6119.5
C1—C2—C3119.26 (14)C9—C10—C5120.07 (15)
C1—C2—C11119.84 (14)C9—C10—C1121.61 (15)
C3—C2—C11120.90 (14)C5—C10—C1118.32 (14)
C4—C3—C2121.05 (15)C8—C9—C10120.07 (18)
C4—C3—H3119.5C8—C9—H8120.0
C2—C3—H3119.5C10—C9—H8120.0
C3—C4—C5120.94 (15)C9—C8—C7120.11 (18)
C3—C4—H4119.5C9—C8—H7119.9
C5—C4—H4119.5C7—C8—H7119.9
C10—C5—C4119.83 (14)O1—C1—C2123.15 (14)
C10—C5—C6117.98 (15)O1—C1—C10116.24 (14)
C4—C5—C6122.19 (16)C2—C1—C10120.61 (14)
C7—C6—C5120.68 (18)
O2—C11—C2—C11.3 (2)C4—C5—C10—C10.1 (2)
O3—C11—C2—C1178.66 (13)C6—C5—C10—C1179.64 (12)
O2—C11—C2—C3178.95 (14)C5—C10—C9—C80.8 (2)
O3—C11—C2—C31.1 (2)C1—C10—C9—C8179.76 (14)
C1—C2—C3—C40.2 (2)C10—C9—C8—C70.2 (2)
C11—C2—C3—C4179.49 (13)C6—C7—C8—C90.2 (3)
C2—C3—C4—C50.2 (2)C3—C2—C1—O1179.56 (12)
C3—C4—C5—C100.0 (2)C11—C2—C1—O10.7 (2)
C3—C4—C5—C6179.54 (13)C3—C2—C1—C100.2 (2)
C10—C5—C6—C70.5 (2)C11—C2—C1—C10179.58 (12)
C4—C5—C6—C7179.97 (14)C9—C10—C1—O10.8 (2)
C5—C6—C7—C80.1 (2)C5—C10—C1—O1179.73 (11)
C4—C5—C10—C9179.55 (13)C9—C10—C1—C2179.47 (13)
C6—C5—C10—C90.9 (2)C5—C10—C1—C20.0 (2)
(mo_II) top
Crystal data top
C11H8O3F(000) = 784
Mr = 188.17Dx = 1.426 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 20.920 (5) ÅCell parameters from 2087 reflections
b = 6.9926 (14) Åθ = 2.4–27.4°
c = 14.688 (3) ŵ = 0.11 mm1
β = 125.339 (10)°T = 296 K
V = 1752.7 (6) Å3Columnar, colorless
Z = 80.42 × 0.34 × 0.11 mm
Data collection top
Bruker APEX-II CCD
diffractometer
1239 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.034
Graphite monochromatorθmax = 27.5°, θmin = 2.4°
ϕ and ω scansh = 2227
7678 measured reflectionsk = 98
2015 independent reflectionsl = 1918
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.068Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.226H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.1338P)2 + 0.4921P]
where P = (Fo2 + 2Fc2)/3
2015 reflections(Δ/σ)max < 0.001
133 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C11H8O3V = 1752.7 (6) Å3
Mr = 188.17Z = 8
Monoclinic, C2/cMo Kα radiation
a = 20.920 (5) ŵ = 0.11 mm1
b = 6.9926 (14) ÅT = 296 K
c = 14.688 (3) Å0.42 × 0.34 × 0.11 mm
β = 125.339 (10)°
Data collection top
Bruker APEX-II CCD
diffractometer
1239 reflections with I > 2σ(I)
7678 measured reflectionsRint = 0.034
2015 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0680 restraints
wR(F2) = 0.226H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.49 e Å3
2015 reflectionsΔρmin = 0.27 e Å3
133 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O30.51230 (9)0.1297 (2)0.13772 (13)0.0546 (5)
H20.474 (2)0.137 (3)0.152 (2)0.082*
O20.59661 (9)0.1364 (2)0.32339 (13)0.0473 (5)
O10.74661 (9)0.1404 (2)0.41035 (12)0.0465 (5)
H10.704 (2)0.140 (3)0.408 (2)0.070*
C110.58435 (12)0.1317 (3)0.22991 (17)0.0373 (5)
C20.64602 (12)0.1281 (2)0.21269 (17)0.0349 (5)
C10.72398 (12)0.1329 (2)0.30434 (17)0.0343 (5)
C100.78555 (12)0.1295 (2)0.28829 (17)0.0359 (5)
C90.86499 (13)0.1328 (3)0.3797 (2)0.0464 (6)
H80.87870.13640.45220.056*
C80.92190 (15)0.1306 (3)0.3609 (3)0.0589 (7)
H70.97440.13460.42110.071*
C70.90208 (15)0.1224 (3)0.2531 (3)0.0609 (8)
H60.94160.11930.24220.073*
C60.82553 (15)0.1186 (3)0.1625 (2)0.0532 (6)
H50.81340.11410.09080.064*
C50.76483 (13)0.1216 (2)0.17838 (18)0.0397 (5)
C40.68447 (14)0.1170 (3)0.08643 (18)0.0455 (6)
H40.67110.11250.01410.055*
C30.62756 (12)0.1190 (3)0.10299 (17)0.0406 (5)
H30.57540.11430.04190.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O30.0321 (9)0.0918 (13)0.0424 (9)0.0012 (7)0.0231 (8)0.0018 (7)
O20.0349 (8)0.0739 (11)0.0394 (8)0.0016 (6)0.0250 (7)0.0003 (6)
O10.0360 (8)0.0718 (11)0.0332 (8)0.0019 (7)0.0209 (7)0.0014 (6)
C110.0310 (10)0.0445 (11)0.0392 (11)0.0011 (8)0.0219 (9)0.0012 (8)
C20.0322 (11)0.0381 (10)0.0365 (11)0.0003 (7)0.0211 (9)0.0001 (7)
C10.0357 (11)0.0367 (10)0.0343 (10)0.0009 (8)0.0224 (9)0.0015 (7)
C100.0367 (11)0.0305 (10)0.0467 (12)0.0004 (7)0.0277 (10)0.0001 (7)
C90.0367 (12)0.0473 (12)0.0543 (13)0.0038 (9)0.0257 (11)0.0040 (9)
C80.0351 (13)0.0576 (14)0.0808 (19)0.0066 (10)0.0317 (13)0.0055 (12)
C70.0507 (16)0.0627 (15)0.094 (2)0.0070 (11)0.0560 (16)0.0072 (13)
C60.0624 (16)0.0528 (13)0.0700 (15)0.0018 (10)0.0531 (14)0.0017 (10)
C50.0449 (12)0.0354 (10)0.0509 (13)0.0033 (8)0.0348 (11)0.0024 (8)
C40.0519 (13)0.0546 (13)0.0393 (11)0.0017 (9)0.0317 (11)0.0003 (9)
C30.0352 (11)0.0513 (12)0.0331 (10)0.0001 (8)0.0185 (9)0.0010 (8)
Geometric parameters (Å, º) top
O3—C111.321 (3)C9—H80.9300
O3—H20.93 (4)C8—C71.387 (4)
O2—C111.243 (2)C8—H70.9300
O1—C11.341 (2)C7—C61.368 (4)
O1—H10.86 (3)C7—H60.9300
C11—C21.451 (3)C6—C51.418 (3)
C2—C11.391 (3)C6—H50.9300
C2—C31.425 (3)C5—C41.423 (3)
C1—C101.437 (3)C4—C31.346 (3)
C10—C91.408 (3)C4—H40.9300
C10—C51.410 (3)C3—H30.9300
C9—C81.368 (3)
C11—O3—H2112.9 (19)C9—C8—H7119.7
C1—O1—H1107 (2)C7—C8—H7119.7
O2—C11—O3121.11 (18)C6—C7—C8121.4 (2)
O2—C11—C2123.83 (18)C6—C7—H6119.3
O3—C11—C2115.06 (18)C8—C7—H6119.3
C1—C2—C3119.65 (18)C7—C6—C5119.7 (2)
C1—C2—C11119.61 (18)C7—C6—H5120.1
C3—C2—C11120.73 (18)C5—C6—H5120.1
O1—C1—C2123.61 (19)C10—C5—C6118.5 (2)
O1—C1—C10116.29 (18)C10—C5—C4119.98 (18)
C2—C1—C10120.10 (19)C6—C5—C4121.5 (2)
C9—C10—C5120.23 (19)C3—C4—C5120.7 (2)
C9—C10—C1121.3 (2)C3—C4—H4119.6
C5—C10—C1118.50 (19)C5—C4—H4119.6
C8—C9—C10119.5 (2)C4—C3—C2121.0 (2)
C8—C9—H8120.2C4—C3—H3119.5
C10—C9—H8120.2C2—C3—H3119.5
C9—C8—C7120.6 (2)
O2—C11—C2—C11.0 (3)C10—C9—C8—C71.0 (3)
O3—C11—C2—C1179.00 (15)C9—C8—C7—C60.8 (3)
O2—C11—C2—C3178.75 (16)C8—C7—C6—C50.5 (3)
O3—C11—C2—C31.3 (2)C9—C10—C5—C60.5 (2)
C3—C2—C1—O1179.61 (15)C1—C10—C5—C6179.90 (16)
C11—C2—C1—O10.1 (3)C9—C10—C5—C4179.56 (16)
C3—C2—C1—C100.3 (2)C1—C10—C5—C40.0 (2)
C11—C2—C1—C10179.97 (15)C7—C6—C5—C100.4 (3)
O1—C1—C10—C90.4 (2)C7—C6—C5—C4179.72 (18)
C2—C1—C10—C9179.53 (15)C10—C5—C4—C30.4 (3)
O1—C1—C10—C5179.99 (14)C6—C5—C4—C3179.68 (18)
C2—C1—C10—C50.1 (2)C5—C4—C3—C20.8 (3)
C5—C10—C9—C80.8 (3)C1—C2—C3—C40.7 (3)
C1—C10—C9—C8179.61 (16)C11—C2—C3—C4179.53 (17)

Experimental details

(mo_I)(mo_II)
Crystal data
Chemical formulaC11H8O3C11H8O3
Mr188.17188.17
Crystal system, space groupMonoclinic, P21/nMonoclinic, C2/c
Temperature (K)296296
a, b, c (Å)6.9798 (9), 3.8107 (6), 32.790 (5)20.920 (5), 6.9926 (14), 14.688 (3)
β (°) 93.901 (8) 125.339 (10)
V3)870.1 (2)1752.7 (6)
Z48
Radiation typeMo KαMo Kα
µ (mm1)0.110.11
Crystal size (mm)0.44 × 0.32 × 0.110.42 × 0.34 × 0.11
Data collection
DiffractometerBruker APEX-II CCD
diffractometer
Bruker APEX-II CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
6187, 1491, 1020 7678, 2015, 1239
Rint0.0380.034
(sin θ/λ)max1)0.5940.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.097, 0.96 0.068, 0.226, 1.04
No. of reflections14912015
No. of parameters133133
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.15, 0.160.49, 0.27

Computer programs: Bruker APEX2, Bruker SAINT, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Bruker SHELXTL.

 

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