The title compound, C
14H
12BrNO, crystallizes in a phenol–imine tautomeric form. The structure is stabilized by O—H
N intramolecular hydrogen bonds, C—H
π and π–π intermolecular interactions. The molecule is planar and intramolecular O—H
N hydrogen bonding generates an
S(6) ring motif.
Supporting information
CCDC reference: 648066
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.037
- wR factor = 0.081
- Data-to-parameter ratio = 18.9
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1
C14 H12 Br N O
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 27.94
From the CIF: _reflns_number_total 2971
Count of symmetry unique reflns 1743
Completeness (_total/calc) 170.45%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1228
Fraction of Friedel pairs measured 0.705
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 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
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: X-AREA (Stoe, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(
E)-2-[(3-Bromophenylimino)methyl]-6-methylphenol
top
Crystal data top
C14H12BrNO | Dx = 1.542 Mg m−3 |
Mr = 290.16 | Melting point = 352–354 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 8829 reflections |
a = 6.2637 (5) Å | θ = 2.0–28.0° |
b = 13.8902 (11) Å | µ = 3.28 mm−1 |
c = 14.3678 (15) Å | T = 296 K |
V = 1250.06 (19) Å3 | Prism, colourless |
Z = 4 | 0.57 × 0.46 × 0.33 mm |
F(000) = 584 | |
Data collection top
Stoe IPDS-2 diffractometer | 2971 independent reflections |
Radiation source: fine-focus sealed tube | 2326 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.039 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.9°, θmin = 2.0° |
rotation method scans | h = −8→8 |
Absorption correction: integration (X-RED32; Stoe, 2002) | k = −16→18 |
Tmin = 0.204, Tmax = 0.451 | l = −18→18 |
8829 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.034P)2 + 0.3P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2971 reflections | Δρmax = 0.24 e Å−3 |
157 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1228 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (1) |
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 | x | y | z | Uiso*/Ueq | |
C1 | 0.2420 (5) | 0.51673 (19) | 0.0927 (2) | 0.0396 (6) | |
C2 | 0.3307 (5) | 0.42368 (18) | 0.10281 (19) | 0.0397 (6) | |
C3 | 0.5189 (5) | 0.4091 (2) | 0.1516 (2) | 0.0442 (7) | |
C4 | 0.6181 (5) | 0.4886 (2) | 0.1910 (2) | 0.0470 (7) | |
H4 | 0.7446 | 0.4800 | 0.2238 | 0.056* | |
C5 | 0.5339 (5) | 0.5807 (2) | 0.1827 (2) | 0.0505 (7) | |
H5 | 0.6028 | 0.6327 | 0.2103 | 0.061* | |
C6 | 0.3494 (5) | 0.59454 (18) | 0.1340 (2) | 0.0469 (6) | |
H6 | 0.2940 | 0.6564 | 0.1281 | 0.056* | |
C7 | 0.0505 (5) | 0.5330 (2) | 0.0404 (2) | 0.0433 (7) | |
H7 | −0.0033 | 0.5953 | 0.0370 | 0.052* | |
C8 | −0.2366 (4) | 0.4827 (2) | −0.0530 (2) | 0.0389 (6) | |
C9 | −0.3303 (5) | 0.57328 (19) | −0.0655 (2) | 0.0449 (7) | |
H9 | −0.2681 | 0.6281 | −0.0400 | 0.054* | |
C10 | −0.5166 (5) | 0.5798 (2) | −0.1163 (2) | 0.0472 (7) | |
C11 | −0.6155 (5) | 0.5015 (2) | −0.1547 (2) | 0.0486 (7) | |
H11 | −0.7423 | 0.5079 | −0.1878 | 0.058* | |
C12 | −0.5202 (5) | 0.4122 (2) | −0.1426 (2) | 0.0530 (8) | |
H12 | −0.5826 | 0.3579 | −0.1689 | 0.064* | |
C13 | −0.3346 (5) | 0.4030 (2) | −0.0923 (2) | 0.0467 (7) | |
H13 | −0.2741 | 0.3424 | −0.0844 | 0.056* | |
C14 | 0.6148 (5) | 0.3100 (2) | 0.1597 (3) | 0.0590 (9) | |
H14A | 0.7329 | 0.3117 | 0.2023 | 0.089* | |
H14B | 0.6639 | 0.2892 | 0.0997 | 0.089* | |
H14C | 0.5088 | 0.2659 | 0.1823 | 0.089* | |
Br1 | −0.64870 (7) | 0.70215 (3) | −0.12948 (4) | 0.08215 (17) | |
N1 | −0.0492 (4) | 0.46608 (17) | −0.00172 (18) | 0.0427 (5) | |
O1 | 0.2335 (4) | 0.34625 (15) | 0.06529 (18) | 0.0564 (6) | |
H1 | 0.1264 | 0.3636 | 0.0371 | 0.085* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0363 (13) | 0.0403 (14) | 0.0420 (17) | 0.0004 (11) | 0.0032 (13) | 0.0008 (12) |
C2 | 0.0400 (14) | 0.0384 (12) | 0.0407 (16) | −0.0026 (11) | 0.0029 (13) | 0.0002 (10) |
C3 | 0.0448 (16) | 0.0449 (15) | 0.0428 (19) | 0.0018 (12) | 0.0001 (13) | 0.0040 (12) |
C4 | 0.0403 (17) | 0.0615 (18) | 0.0394 (17) | −0.0019 (14) | −0.0048 (13) | 0.0038 (13) |
C5 | 0.0509 (18) | 0.0513 (17) | 0.0492 (19) | −0.0102 (14) | −0.0018 (15) | −0.0024 (14) |
C6 | 0.0514 (15) | 0.0385 (12) | 0.0508 (17) | −0.0027 (13) | −0.0021 (17) | −0.0011 (13) |
C7 | 0.0420 (15) | 0.0388 (14) | 0.0492 (18) | 0.0020 (12) | −0.0005 (14) | 0.0019 (13) |
C8 | 0.0355 (13) | 0.0415 (14) | 0.0396 (16) | −0.0023 (11) | 0.0013 (12) | −0.0009 (12) |
C9 | 0.0437 (16) | 0.0394 (13) | 0.0517 (18) | −0.0023 (13) | −0.0089 (15) | −0.0052 (12) |
C10 | 0.0454 (15) | 0.0473 (15) | 0.0489 (19) | 0.0024 (12) | −0.0016 (15) | −0.0020 (14) |
C11 | 0.0389 (16) | 0.0593 (17) | 0.048 (2) | −0.0064 (13) | −0.0032 (14) | −0.0004 (13) |
C12 | 0.0549 (18) | 0.0520 (16) | 0.052 (2) | −0.0151 (14) | −0.0034 (16) | −0.0068 (15) |
C13 | 0.0514 (16) | 0.0402 (13) | 0.0484 (18) | −0.0057 (14) | 0.0039 (16) | −0.0007 (12) |
C14 | 0.057 (2) | 0.0489 (17) | 0.071 (2) | 0.0125 (15) | −0.0160 (16) | 0.0072 (15) |
Br1 | 0.0787 (3) | 0.0588 (2) | 0.1089 (3) | 0.01838 (19) | −0.0373 (3) | −0.0037 (2) |
N1 | 0.0367 (12) | 0.0436 (13) | 0.0478 (15) | 0.0002 (10) | −0.0005 (11) | 0.0001 (11) |
O1 | 0.0552 (13) | 0.0382 (10) | 0.0757 (17) | −0.0024 (10) | −0.0152 (12) | −0.0017 (11) |
Geometric parameters (Å, º) top
C1—C6 | 1.404 (4) | C8—C9 | 1.400 (4) |
C1—C2 | 1.414 (4) | C8—N1 | 1.405 (4) |
C1—C7 | 1.434 (4) | C9—C10 | 1.379 (4) |
C2—O1 | 1.348 (3) | C9—H9 | 0.9300 |
C2—C3 | 1.386 (4) | C10—C11 | 1.368 (4) |
C3—C4 | 1.388 (4) | C10—Br1 | 1.899 (3) |
C3—C14 | 1.507 (4) | C11—C12 | 1.388 (4) |
C4—C5 | 1.388 (4) | C11—H11 | 0.9300 |
C4—H4 | 0.9300 | C12—C13 | 1.375 (5) |
C5—C6 | 1.365 (4) | C12—H12 | 0.9300 |
C5—H5 | 0.9300 | C13—H13 | 0.9300 |
C6—H6 | 0.9300 | C14—H14A | 0.9600 |
C7—N1 | 1.273 (4) | C14—H14B | 0.9600 |
C7—H7 | 0.9300 | C14—H14C | 0.9600 |
C8—C13 | 1.386 (4) | O1—H1 | 0.8200 |
| | | |
C6—C1—C2 | 118.1 (3) | C10—C9—C8 | 118.8 (3) |
C6—C1—C7 | 120.1 (3) | C10—C9—H9 | 120.6 |
C2—C1—C7 | 121.8 (3) | C8—C9—H9 | 120.6 |
O1—C2—C3 | 118.0 (2) | C11—C10—C9 | 123.0 (3) |
O1—C2—C1 | 120.7 (3) | C11—C10—Br1 | 118.3 (2) |
C3—C2—C1 | 121.3 (2) | C9—C10—Br1 | 118.7 (2) |
C2—C3—C4 | 118.1 (3) | C10—C11—C12 | 117.7 (3) |
C2—C3—C14 | 120.8 (3) | C10—C11—H11 | 121.1 |
C4—C3—C14 | 121.1 (3) | C12—C11—H11 | 121.1 |
C3—C4—C5 | 121.9 (3) | C13—C12—C11 | 120.8 (3) |
C3—C4—H4 | 119.1 | C13—C12—H12 | 119.6 |
C5—C4—H4 | 119.1 | C11—C12—H12 | 119.6 |
C6—C5—C4 | 119.7 (3) | C12—C13—C8 | 120.9 (3) |
C6—C5—H5 | 120.2 | C12—C13—H13 | 119.5 |
C4—C5—H5 | 120.2 | C8—C13—H13 | 119.5 |
C5—C6—C1 | 120.9 (3) | C3—C14—H14A | 109.5 |
C5—C6—H6 | 119.5 | C3—C14—H14B | 109.5 |
C1—C6—H6 | 119.5 | H14A—C14—H14B | 109.5 |
N1—C7—C1 | 123.0 (3) | C3—C14—H14C | 109.5 |
N1—C7—H7 | 118.5 | H14A—C14—H14C | 109.5 |
C1—C7—H7 | 118.5 | H14B—C14—H14C | 109.5 |
C13—C8—C9 | 118.7 (3) | C7—N1—C8 | 122.6 (2) |
C13—C8—N1 | 116.9 (3) | C2—O1—H1 | 109.5 |
C9—C8—N1 | 124.4 (3) | | |
| | | |
C6—C1—C2—O1 | 179.5 (3) | C2—C1—C7—N1 | −1.5 (4) |
C7—C1—C2—O1 | −1.9 (4) | C13—C8—C9—C10 | 0.0 (4) |
C6—C1—C2—C3 | −0.3 (4) | N1—C8—C9—C10 | −179.0 (3) |
C7—C1—C2—C3 | 178.3 (3) | C8—C9—C10—C11 | 0.5 (5) |
O1—C2—C3—C4 | −179.4 (3) | C8—C9—C10—Br1 | 177.8 (2) |
C1—C2—C3—C4 | 0.4 (4) | C9—C10—C11—C12 | −1.1 (5) |
O1—C2—C3—C14 | 1.8 (4) | Br1—C10—C11—C12 | −178.4 (3) |
C1—C2—C3—C14 | −178.4 (3) | C10—C11—C12—C13 | 1.1 (5) |
C2—C3—C4—C5 | 0.1 (4) | C11—C12—C13—C8 | −0.7 (5) |
C14—C3—C4—C5 | 178.8 (3) | C9—C8—C13—C12 | 0.1 (4) |
C3—C4—C5—C6 | −0.6 (5) | N1—C8—C13—C12 | 179.2 (3) |
C4—C5—C6—C1 | 0.6 (5) | C1—C7—N1—C8 | −179.9 (3) |
C2—C1—C6—C5 | −0.2 (4) | C13—C8—N1—C7 | −177.3 (3) |
C7—C1—C6—C5 | −178.8 (3) | C9—C8—N1—C7 | 1.6 (5) |
C6—C1—C7—N1 | 177.1 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.88 | 2.614 (3) | 148 |
C4—H4···Cg2i | 0.93 | 2.75 | 3.529 (3) | 142 |
C11—H11···Cg1ii | 0.93 | 2.72 | 3.526 (3) | 146 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −x−1/2, −y+1, z−1/2. |