Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807040846/ng2310sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807040846/ng2310Isup2.hkl |
CCDC reference: 660355
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.002 Å
- R factor = 0.023
- wR factor = 0.061
- Data-to-parameter ratio = 21.2
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.608 1.000 Tmin(prime) and Tmax expected: 0.511 0.706 RR(prime) = 0.840 Please check that your absorption correction is appropriate. PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.82 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.71 PLAT431_ALERT_2_C Short Inter HL..A Contact Br1 .. O2 .. 3.23 Ang.
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.706 Tmax scaled 0.706 Tmin scaled 0.429
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For the initial structure described in P21/n, see Vasudevan et al. (1991). For additional related literature see Wolff et al. (2003); Testa et al. (2000); Taylor et al. (1982).
3-(Bromoacetyl) coumarin was purchased from Aldrich (97%), and recrystallized by evaporation at room temperature from acetonitrile.
Hydrogen atoms were positioned geometrically (aromatic C—H = 0.95 Å and methylene C—H = 0.99 Å) and refined using a riding model. The hydrogen atom isotropic displacement parameters were fixed to Uiso(H) = 1.2 times Ueq of the parent carbon atom.
Differential Scanning Calorimetry (DSC): Data were collected on a Perkin Elmer Pyris 1 DSC with 3 cycles recorded over the temperature range 102 to 323 K at a rate of 10 K/min.
Coumarin and its derivatives have attracted much interest due to their optical (Wolff et al., 2003) and biological properties (Testa et al., 2000). The structure of the title compound (form A) has previously been determined at 300 K (Vasudevan et al., 1991), using crystals grown by evaporation from a chloroform solution. The new polymorph (form B) reported here was obtained unexpectedly during recrystallization from acetonitrile.
In (I) (Fig.1) all bond lengths and angles fall within the expected ranges. The coumarin moiety is essentially planar with a dihedral angle between the mean planes of the two rings (C(1) to C(6) and C(1) to O(1)) of 1.4 (1)°. Br(1) and O(3) are cis to each other with a torsion angle Br(1)—C(11)—C(10)—O(3) of -2.0 (2)°.
The initial structure (A) was reported in the monoclinic space group P21/n with the following cell parameters: a = 21.555 (2), b = 4.229 (2), c = 10.784 (1) Å, β = 93.89 (1)° and V = 980.8 Å3 (Vasudevan et al., 1991). In view of the fact that the structures of (A) and (B) were determined at 300 K and 120 K respectively, the possibility that the structural differences were the result of a temperature induced phase transition, was examined using differential scanning calorimetry; no phase transition was observed over the temperature range 102 to 323 K.
Although the molecular conformation of (I) in both structures is very similar, there are significant differences between the packing of the two forms. The molecules in alternate layers of (A) are rotated with respect to each other creating an angle of 74° between mean planes calculated through the coumarin moieties (C2—C10/O1) in the asymmetric unit and the symmetry related fragment (1/2 - x, 1/2 + y, 1/2 - z) (Fig. 2(i)). While in (B) the molecules of (I) are inclined away from each other resulting in an angle of 28° between the mean planes calculated through the coumarin moieties (C1—C9/O1) in the asu and the adjacent symmetry related fragment (1 - x, y - 1/2, 3/2 - z) (Fig. 2(ii)).
In the initial structure report for (A) the authors noted the presence of weak C—H···O interactions which link the molecules to create one dimensional chains through the crystal. The new polymorph also contains a number of short attractive C—H···O contacts, which fulfil the criteria proposed by Taylor et al. (1982), and result in the interacting molecules essentially forming two dimensional non-planar sheets.
For the initial structure described in P21/n, see Vasudevan et al. (1991). For additional related literature see Wolff et al. (2003); Testa et al. (2000); Taylor et al. (1982).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C11H7BrO3 | F(000) = 528 |
Mr = 267.08 | Dx = 1.885 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6159 reflections |
a = 5.2932 (1) Å | θ = 2.4–30.5° |
b = 18.4568 (5) Å | µ = 4.35 mm−1 |
c = 9.7473 (3) Å | T = 120 K |
β = 98.768 (1)° | Plate, colourless |
V = 941.14 (4) Å3 | 0.15 × 0.14 × 0.08 mm |
Z = 4 |
Bruker SMART 6K CCD detector diffractometer | 2879 independent reflections |
Radiation source: fine-focus sealed tube | 2547 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 8 pixels mm-1 | θmax = 30.5°, θmin = 2.2° |
ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | k = −26→26 |
Tmin = 0.608, Tmax = 1.000 | l = −13→13 |
14782 measured 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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0323P)2 + 0.2289P] where P = (Fo2 + 2Fc2)/3 |
2879 reflections | (Δ/σ)max = 0.001 |
136 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C11H7BrO3 | V = 941.14 (4) Å3 |
Mr = 267.08 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.2932 (1) Å | µ = 4.35 mm−1 |
b = 18.4568 (5) Å | T = 120 K |
c = 9.7473 (3) Å | 0.15 × 0.14 × 0.08 mm |
β = 98.768 (1)° |
Bruker SMART 6K CCD detector diffractometer | 2879 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 2547 reflections with I > 2σ(I) |
Tmin = 0.608, Tmax = 1.000 | Rint = 0.033 |
14782 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.47 e Å−3 |
2879 reflections | Δρmin = −0.39 e Å−3 |
136 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. |
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. Crystallized from acetonitrile. |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.01135 (3) | 0.757563 (8) | 0.371259 (15) | 0.02027 (6) | |
O1 | 0.3366 (2) | 0.59926 (6) | 0.76010 (11) | 0.0182 (2) | |
O2 | 0.4139 (2) | 0.70306 (6) | 0.66504 (12) | 0.0212 (2) | |
O3 | 0.9830 (2) | 0.60442 (6) | 0.46858 (12) | 0.0231 (2) | |
C1 | 0.3813 (3) | 0.52704 (8) | 0.78488 (14) | 0.0154 (3) | |
C2 | 0.2347 (3) | 0.49236 (8) | 0.87179 (15) | 0.0196 (3) | |
H2 | 0.1061 | 0.5180 | 0.9099 | 0.024* | |
C3 | 0.2795 (3) | 0.41990 (9) | 0.90167 (16) | 0.0206 (3) | |
H3 | 0.1803 | 0.3956 | 0.9608 | 0.025* | |
C4 | 0.4698 (3) | 0.38162 (9) | 0.84573 (17) | 0.0211 (3) | |
H4 | 0.5004 | 0.3320 | 0.8680 | 0.025* | |
C5 | 0.6117 (3) | 0.41663 (8) | 0.75828 (16) | 0.0188 (3) | |
H5 | 0.7394 | 0.3908 | 0.7196 | 0.023* | |
C6 | 0.5684 (3) | 0.49013 (8) | 0.72614 (14) | 0.0153 (3) | |
C7 | 0.7075 (3) | 0.53040 (8) | 0.63710 (15) | 0.0158 (3) | |
H7 | 0.8342 | 0.5064 | 0.5946 | 0.019* | |
C8 | 0.6642 (3) | 0.60189 (8) | 0.61151 (14) | 0.0147 (3) | |
C9 | 0.4701 (3) | 0.64004 (8) | 0.67601 (15) | 0.0157 (3) | |
C10 | 0.8224 (3) | 0.63904 (8) | 0.51699 (14) | 0.0159 (3) | |
C11 | 0.7784 (3) | 0.71852 (8) | 0.48718 (15) | 0.0180 (3) | |
H11A | 0.7992 | 0.7455 | 0.5760 | 0.022* | |
H11B | 0.6006 | 0.7257 | 0.4405 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.01892 (9) | 0.02206 (9) | 0.02101 (9) | −0.00114 (5) | 0.00687 (6) | 0.00582 (5) |
O1 | 0.0192 (5) | 0.0161 (5) | 0.0220 (5) | 0.0033 (4) | 0.0116 (4) | 0.0032 (4) |
O2 | 0.0230 (5) | 0.0160 (5) | 0.0269 (6) | 0.0034 (4) | 0.0115 (4) | 0.0012 (4) |
O3 | 0.0254 (6) | 0.0190 (5) | 0.0289 (6) | 0.0028 (4) | 0.0172 (5) | 0.0006 (4) |
C1 | 0.0153 (6) | 0.0151 (6) | 0.0165 (6) | −0.0006 (5) | 0.0044 (5) | 0.0004 (5) |
C2 | 0.0180 (7) | 0.0220 (7) | 0.0210 (7) | 0.0001 (6) | 0.0099 (6) | 0.0020 (5) |
C3 | 0.0202 (7) | 0.0210 (7) | 0.0220 (7) | −0.0031 (6) | 0.0082 (6) | 0.0031 (5) |
C4 | 0.0229 (8) | 0.0163 (7) | 0.0249 (7) | −0.0022 (6) | 0.0065 (6) | 0.0019 (5) |
C5 | 0.0194 (7) | 0.0155 (7) | 0.0224 (7) | −0.0004 (5) | 0.0066 (6) | −0.0012 (5) |
C6 | 0.0144 (6) | 0.0157 (6) | 0.0165 (6) | −0.0009 (5) | 0.0051 (5) | −0.0004 (5) |
C7 | 0.0148 (6) | 0.0160 (6) | 0.0178 (6) | −0.0009 (5) | 0.0066 (5) | −0.0014 (5) |
C8 | 0.0134 (6) | 0.0160 (6) | 0.0161 (6) | −0.0004 (5) | 0.0064 (5) | −0.0006 (5) |
C9 | 0.0145 (6) | 0.0171 (7) | 0.0165 (6) | 0.0000 (5) | 0.0056 (5) | −0.0005 (5) |
C10 | 0.0168 (6) | 0.0154 (6) | 0.0163 (6) | −0.0013 (5) | 0.0051 (5) | −0.0008 (5) |
C11 | 0.0192 (7) | 0.0168 (6) | 0.0197 (7) | −0.0001 (5) | 0.0089 (6) | 0.0020 (5) |
Br1—C11 | 1.9343 (14) | C4—H4 | 0.9500 |
O1—C1 | 1.3688 (17) | C5—C6 | 1.403 (2) |
O1—C9 | 1.3836 (17) | C5—H5 | 0.9500 |
O2—C9 | 1.2014 (18) | C6—C7 | 1.4293 (19) |
O3—C10 | 1.2146 (17) | C7—C8 | 1.3559 (19) |
C1—C2 | 1.3895 (19) | C7—H7 | 0.9500 |
C1—C6 | 1.3949 (19) | C8—C9 | 1.4638 (19) |
C2—C3 | 1.382 (2) | C8—C10 | 1.5020 (19) |
C2—H2 | 0.9500 | C10—C11 | 1.507 (2) |
C3—C4 | 1.407 (2) | C11—H11A | 0.9900 |
C3—H3 | 0.9500 | C11—H11B | 0.9900 |
C4—C5 | 1.380 (2) | ||
C1—O1—C9 | 122.97 (11) | C8—C7—C6 | 121.96 (13) |
O1—C1—C2 | 117.30 (13) | C8—C7—H7 | 119.0 |
O1—C1—C6 | 121.17 (12) | C6—C7—H7 | 119.0 |
C2—C1—C6 | 121.53 (13) | C7—C8—C9 | 119.96 (12) |
C3—C2—C1 | 118.72 (13) | C7—C8—C10 | 117.54 (12) |
C3—C2—H2 | 120.6 | C9—C8—C10 | 122.50 (13) |
C1—C2—H2 | 120.6 | O2—C9—O1 | 115.94 (12) |
C2—C3—C4 | 120.96 (14) | O2—C9—C8 | 127.45 (13) |
C2—C3—H3 | 119.5 | O1—C9—C8 | 116.61 (12) |
C4—C3—H3 | 119.5 | O3—C10—C8 | 119.14 (13) |
C5—C4—C3 | 119.60 (14) | O3—C10—C11 | 122.28 (13) |
C5—C4—H4 | 120.2 | C8—C10—C11 | 118.58 (12) |
C3—C4—H4 | 120.2 | C10—C11—Br1 | 112.44 (10) |
C4—C5—C6 | 120.33 (14) | C10—C11—H11A | 109.1 |
C4—C5—H5 | 119.8 | Br1—C11—H11A | 109.1 |
C6—C5—H5 | 119.8 | C10—C11—H11B | 109.1 |
C1—C6—C5 | 118.85 (13) | Br1—C11—H11B | 109.1 |
C1—C6—C7 | 117.32 (13) | H11A—C11—H11B | 107.8 |
C5—C6—C7 | 123.82 (13) | ||
Br1—C11—C10—O3 | −2.04 (19) | Br1—C11—C10—C8 | 177.10 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O2i | 0.95 | 2.45 | 3.3572 (19) | 159 |
C5—H5···O3ii | 0.95 | 2.52 | 3.3302 (18) | 143 |
C7—H7···O3ii | 0.95 | 2.38 | 3.2329 (17) | 149 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C11H7BrO3 |
Mr | 267.08 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 5.2932 (1), 18.4568 (5), 9.7473 (3) |
β (°) | 98.768 (1) |
V (Å3) | 941.14 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.35 |
Crystal size (mm) | 0.15 × 0.14 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART 6K CCD detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.608, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14782, 2879, 2547 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.715 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.061, 1.06 |
No. of reflections | 2879 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.39 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O2i | 0.95 | 2.45 | 3.3572 (19) | 159.1 |
C5—H5···O3ii | 0.95 | 2.52 | 3.3302 (18) | 143.1 |
C7—H7···O3ii | 0.95 | 2.38 | 3.2329 (17) | 148.7 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+1. |
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Coumarin and its derivatives have attracted much interest due to their optical (Wolff et al., 2003) and biological properties (Testa et al., 2000). The structure of the title compound (form A) has previously been determined at 300 K (Vasudevan et al., 1991), using crystals grown by evaporation from a chloroform solution. The new polymorph (form B) reported here was obtained unexpectedly during recrystallization from acetonitrile.
In (I) (Fig.1) all bond lengths and angles fall within the expected ranges. The coumarin moiety is essentially planar with a dihedral angle between the mean planes of the two rings (C(1) to C(6) and C(1) to O(1)) of 1.4 (1)°. Br(1) and O(3) are cis to each other with a torsion angle Br(1)—C(11)—C(10)—O(3) of -2.0 (2)°.
The initial structure (A) was reported in the monoclinic space group P21/n with the following cell parameters: a = 21.555 (2), b = 4.229 (2), c = 10.784 (1) Å, β = 93.89 (1)° and V = 980.8 Å3 (Vasudevan et al., 1991). In view of the fact that the structures of (A) and (B) were determined at 300 K and 120 K respectively, the possibility that the structural differences were the result of a temperature induced phase transition, was examined using differential scanning calorimetry; no phase transition was observed over the temperature range 102 to 323 K.
Although the molecular conformation of (I) in both structures is very similar, there are significant differences between the packing of the two forms. The molecules in alternate layers of (A) are rotated with respect to each other creating an angle of 74° between mean planes calculated through the coumarin moieties (C2—C10/O1) in the asymmetric unit and the symmetry related fragment (1/2 - x, 1/2 + y, 1/2 - z) (Fig. 2(i)). While in (B) the molecules of (I) are inclined away from each other resulting in an angle of 28° between the mean planes calculated through the coumarin moieties (C1—C9/O1) in the asu and the adjacent symmetry related fragment (1 - x, y - 1/2, 3/2 - z) (Fig. 2(ii)).
In the initial structure report for (A) the authors noted the presence of weak C—H···O interactions which link the molecules to create one dimensional chains through the crystal. The new polymorph also contains a number of short attractive C—H···O contacts, which fulfil the criteria proposed by Taylor et al. (1982), and result in the interacting molecules essentially forming two dimensional non-planar sheets.