Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020922/wk2053sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020922/wk2053Isup2.hkl |
CCDC reference: 654896
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (Wave) = 0.000 Å
- R factor = 0.035
- wR factor = 0.117
- Data-to-parameter ratio = 13.1
checkCIF/PLATON results
No syntax errors found
Alert level B ABSTM02_ALERT_3_B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75 Tmin and Tmax reported: 0.510 0.990 Tmin(prime) and Tmax expected: 0.946 0.987 RR(prime) = 0.537 Please check that your absorption correction is appropriate. SYMMS01_ALERT_1_B The cell setting should be one of the following * triclinic * monoclinic * orthorhombic * tetragonal * rhombohedral * trigonal * hexagonal * cubic Cell setting given = monoclinic'
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
All solvents and reagents were used as received from Aldrich and Fisher. 1H and 13C NMR were obtained using a Bruker AC250 spectrometer at ambient temperature. Chemical shifts (δ) are reported in parts per million (p.p.m.) relative to internal standards. Fast atom bombardment mass spectrometry (FABMS) was carried out using a Kratos MS50TC spectrometer with a thioglycerol matrix. Analytical data was obtained from the University of St Andrews Microanalytical Service.
KOH (1.347 g, 20.4 mmol) and NH2OH·HCl (1.418 g, 20.4 mmol) were dissolved in EtOH, mixed thoroughly and a white KCl precipitate removed by filtration. 3-Hydroxysalicylaldehyde (2.500 g, 18.10 mmol) was added to the filtrate, and the mixture refluxed for 3 hr. The solvent was removed in vacuo, and the residue redissolved in CHCl3, washed with water 3 times and dried over MgSO4. The solvent was removed in vacuo to yield the crude product as a yellow powder which was then recrystallized from chloroform to give yellow needles (2.371 g, 85.6%). A yellow block suitable for x-ray diffraction was grown by slow evaporation of a hexane/chloroform solvent. (Anal. Calc. for C7H7NO3: C, 54.9; H, 4.6; N, 9.2. Found: C, 54.9; H, 4.3; N, 9.1%); 1H NMR (250 MHz, MeOD): δ(H) (p.p.m.) 6.80 (m, 3H, 3 x ArH), 8.22 (s, 1H, ArCHN); 13C NMR (63 MHz, MeOD) δ(C) (p.p.m.) 118.0 (1 C, aromatic CH), 119.5 (1 C, aromatic C-CHN), 121.0 (1 C, aromatic CH), 122.0 (1 C, aromatic CH), 146.5 (1 C, aromatic C—OH), 152.5 (1 C, ArCHN); FABMS m/z 154 (MH)+, 48%.
Following data collection (see Table 1) an absorption correction was applied using the program SADABS. Tmax/Tmin is larger than calculated on the basis of the crystal dimensions. However, multi-scan procedures (such as SADABS) correct for all systematic errors that lead to disparities in the intensities of equivalent data. It is possible that the larger than expected range of transmission is accounted for by crystal decay or absorption by the mounting fibre.
The hydrogen atoms were located in a Fourier difference map. The positional and isotropic displacement parameters were then refined subject to restraints [C—H = 0.93 (2) Å, O—H = 0.82 (2) Å and Uiso(H) = 1.5Ueq(C or O)]. In subsequent cycles of least squares the H-atoms attached to C were constrained to ride on their parent atoms. H1, H5 and H6 were refined subject to distance restraints equal to 0.84 (5) Å.
3-Hydroxysalicylaldoxime (I) crystallizes with one molecule in the asymmetric unit in the space group P21/c. The molecule forms an intramolecular phenolic OH···N hydrogen bond [O5···N2 = 2.651 (2) Å] (Figure 1) and an intermolecular oximic OH···O hydrogen bond [O1···O5 = 2.798 (2) Å] with a neighbouring molecule related by the 21 screw axis. These two interactions taken together form a secondary level C(5) chain running parallel to the crystallographic b axis (Figure 2). The molecules within the C(5) chain also interact with their next-but-one neighbours through π-π stacking contacts which are related by a translation in the direction of the b axis. The inter-plane separation in these stacking interactions, using a calculated least squares mean plane from the phenyl carbons in one molecule and measuring the distances to the phenyl carbons in another molecule, is between 3.458 (2) and 3.471 (2) Å and the dihedral angle between the two phenyl planes is 0° by symmetry.
Each chain interacts with a neighbouring chain through intermolecular OH···O hydrogen bonds [O6···O1 = 2.835 (2) Å] related through the c-glide perpendicular to the b axis. These interactions taken with the oximic OH···O contacts and their symmetry equivalents form hydrogen bonded ring motifs around an inversion centre for which the graph-set descriptor is R44(14) (Bernstein et al., 1995). The hydrogen bonded rings connect the chains into slabs in the bc plane with the phenyl groups at the edges of the slabs (Figure 3). There are no hydrogen bonding interactions between the slabs and the only interactions are van der Waals contacts.
Salicylaldoximes without large side groups usually form hydrogen-bonded dimers [e.g. Cambridge Structural Database (Allen, 2002) refcodes SALOXM (Pfluger & Harlow, 1973) and ABULIT (Xu et al., 2004)], whereas those bearing large substituents are generally found to form hydrogen-bonded chains [e.g. refcodes HEPKET10 (Koziol & Kosturkiewicz, 1984) and HELBOP (Maurin, 1994)], as shown by Smith et al. (2003). In common with 3-fluorosalicylaldoxime (Wood et al., 2007) and salicylaldoxime-III (Wood et al., 2006), the structure of 3-hydroxysalicylaldoxime (present work) is an exception to this rule.
For related literature, see: Bernstein et al. (1995).
Data collection: SMART (Siemens, 1993); cell refinement: SAINT; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: CRYSTALS.
C7H7NO3 | Z = 4 |
Mr = 153.14 | F(000) = 320 |
Monoclinic', P21/c | Dx = 1.492 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 13.4603 (10) Å | Cell parameters from 1756 reflections |
b = 3.7507 (3) Å | θ = 3–25° |
c = 14.8398 (11) Å | µ = 0.12 mm−1 |
α = 90° | T = 150 K |
β = 114.531 (5)° | Block, yellow |
γ = 90° | 0.46 × 0.13 × 0.11 mm |
V = 681.57 (9) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 904 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
φ and ω scans | θmax = 26.6°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2006) | h = −16→16 |
Tmin = 0.51, Tmax = 0.99 | k = −4→4 |
8183 measured reflections | l = −17→18 |
1424 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: geom/difmap (OH) |
R[F2 > 2σ(F2)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982)
[weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 51.1 83.1 48.9 19.2 3.34 Prince, E. (1982). Mathematical Techniques in Crystallography and Materials Science. New York: Springer-Verlag. Watkin, D. J. (1994). Acta Cryst. A50, 411–437. |
S = 0.99 | (Δ/σ)max = 0.000103 |
1424 reflections | Δρmax = 0.22 e Å−3 |
109 parameters | Δρmin = −0.15 e Å−3 |
3 restraints |
C7H7NO3 | γ = 90° |
Mr = 153.14 | V = 681.57 (9) Å3 |
Monoclinic', P21/c | Z = 4 |
a = 13.4603 (10) Å | Mo Kα radiation |
b = 3.7507 (3) Å | µ = 0.12 mm−1 |
c = 14.8398 (11) Å | T = 150 K |
α = 90° | 0.46 × 0.13 × 0.11 mm |
β = 114.531 (5)° |
Bruker SMART APEX CCD area-detector diffractometer | 1424 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2006) | 904 reflections with I > 2σ(I) |
Tmin = 0.51, Tmax = 0.99 | Rint = 0.029 |
8183 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 3 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.22 e Å−3 |
1424 reflections | Δρmin = −0.15 e Å−3 |
109 parameters |
Experimental. Used Oxford Cryosystems low temperature device. Data collection strategy optimized with COSMO. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.44009 (11) | 0.2386 (5) | 0.06215 (10) | 0.0333 | |
N2 | 0.39503 (12) | 0.3040 (5) | 0.13107 (11) | 0.0266 | |
C3 | 0.30117 (14) | 0.4508 (5) | 0.08998 (13) | 0.0258 | |
C4 | 0.23874 (15) | 0.5415 (5) | 0.14676 (13) | 0.0240 | |
C5 | 0.28033 (14) | 0.4911 (5) | 0.24936 (13) | 0.0226 | |
O5 | 0.38212 (10) | 0.3513 (4) | 0.30415 (10) | 0.0277 | |
C6 | 0.21770 (14) | 0.5813 (5) | 0.30083 (13) | 0.0241 | |
O6 | 0.25519 (12) | 0.5341 (4) | 0.40046 (10) | 0.0335 | |
C7 | 0.11473 (15) | 0.7240 (5) | 0.25057 (15) | 0.0272 | |
C8 | 0.07223 (15) | 0.7703 (5) | 0.14860 (15) | 0.0279 | |
C9 | 0.13386 (15) | 0.6814 (5) | 0.09742 (14) | 0.0276 | |
H1 | 0.501 (2) | 0.135 (8) | 0.099 (2) | 0.0512* | |
H3 | 0.2687 | 0.4989 | 0.0202 | 0.0300* | |
H5 | 0.410 (2) | 0.296 (7) | 0.261 (2) | 0.0424* | |
H6 | 0.315 (2) | 0.444 (8) | 0.423 (2) | 0.0511* | |
H7 | 0.0735 | 0.7879 | 0.2870 | 0.0341* | |
H8 | 0.0024 | 0.8643 | 0.1144 | 0.0319* | |
H9 | 0.1071 | 0.7129 | 0.0287 | 0.0318* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0246 (7) | 0.0531 (10) | 0.0249 (7) | 0.0044 (7) | 0.0129 (6) | 0.0003 (7) |
N2 | 0.0258 (8) | 0.0353 (10) | 0.0224 (8) | −0.0004 (7) | 0.0136 (6) | −0.0014 (7) |
C3 | 0.0262 (9) | 0.0291 (10) | 0.0207 (8) | −0.0015 (8) | 0.0084 (7) | 0.0015 (7) |
C4 | 0.0237 (9) | 0.0232 (9) | 0.0260 (9) | −0.0023 (7) | 0.0112 (7) | 0.0000 (7) |
C5 | 0.0178 (8) | 0.0229 (10) | 0.0249 (9) | −0.0022 (7) | 0.0065 (7) | −0.0002 (7) |
O5 | 0.0201 (6) | 0.0395 (9) | 0.0225 (6) | 0.0029 (6) | 0.0078 (5) | 0.0002 (6) |
C6 | 0.0235 (9) | 0.0254 (9) | 0.0240 (9) | −0.0029 (8) | 0.0104 (7) | −0.0012 (8) |
O6 | 0.0288 (7) | 0.0516 (10) | 0.0210 (7) | 0.0063 (7) | 0.0111 (6) | 0.0014 (7) |
C7 | 0.0262 (9) | 0.0254 (9) | 0.0333 (10) | −0.0018 (8) | 0.0156 (8) | −0.0028 (8) |
C8 | 0.0206 (9) | 0.0267 (10) | 0.0335 (10) | 0.0038 (8) | 0.0085 (8) | 0.0021 (8) |
C9 | 0.0276 (9) | 0.0266 (10) | 0.0250 (9) | 0.0015 (8) | 0.0073 (7) | 0.0033 (8) |
O1—N2 | 1.4103 (19) | O5—H5 | 0.89 (2) |
O1—H1 | 0.87 (3) | C6—O6 | 1.361 (2) |
N2—C3 | 1.277 (2) | C6—C7 | 1.380 (3) |
C3—C4 | 1.456 (2) | O6—H6 | 0.81 (3) |
C3—H3 | 0.959 | C7—C8 | 1.389 (3) |
C4—C5 | 1.400 (3) | C7—H7 | 0.952 |
C4—C9 | 1.395 (3) | C8—C9 | 1.378 (3) |
C5—O5 | 1.374 (2) | C8—H8 | 0.932 |
C5—C6 | 1.394 (2) | C9—H9 | 0.938 |
N2—O1—H1 | 101.7 (18) | C5—C6—C7 | 119.86 (17) |
O1—N2—C3 | 111.52 (14) | O6—C6—C7 | 118.27 (16) |
N2—C3—C4 | 121.25 (16) | C6—O6—H6 | 111.2 (19) |
N2—C3—H3 | 120.9 | C6—C7—C8 | 120.29 (17) |
C4—C3—H3 | 117.8 | C6—C7—H7 | 118.8 |
C3—C4—C5 | 122.11 (17) | C8—C7—H7 | 120.9 |
C3—C4—C9 | 119.06 (16) | C7—C8—C9 | 120.02 (18) |
C5—C4—C9 | 118.83 (17) | C7—C8—H8 | 120.4 |
C4—C5—O5 | 123.05 (16) | C9—C8—H8 | 119.5 |
C4—C5—C6 | 120.23 (17) | C4—C9—C8 | 120.75 (18) |
O5—C5—C6 | 116.72 (16) | C4—C9—H9 | 117.8 |
C5—O5—H5 | 106.0 (17) | C8—C9—H9 | 121.4 |
C5—C6—O6 | 121.87 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5i | 0.87 (2) | 1.95 (2) | 2.7984 (18) | 167 (3) |
O5—H5···N2 | 0.89 (3) | 1.85 (3) | 2.651 (2) | 148 (3) |
O6—H6···O1ii | 0.81 (3) | 2.16 (2) | 2.8353 (18) | 141 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C7H7NO3 |
Mr | 153.14 |
Crystal system, space group | Monoclinic', P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 13.4603 (10), 3.7507 (3), 14.8398 (11) |
α, β, γ (°) | 90, 114.531 (5), 90 |
V (Å3) | 681.57 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.46 × 0.13 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2006) |
Tmin, Tmax | 0.51, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8183, 1424, 904 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.631 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.117, 0.99 |
No. of reflections | 1424 |
No. of parameters | 109 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.15 |
Computer programs: SMART (Siemens, 1993), SAINT (Siemens, 1995), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), DIAMOND (Brandenburg, 2004), CRYSTALS.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O5i | 0.87 (2) | 1.95 (2) | 2.7984 (18) | 167 (3) |
O5—H5···N2 | 0.89 (3) | 1.85 (3) | 2.651 (2) | 148 (3) |
O6—H6···O1ii | 0.81 (3) | 2.16 (2) | 2.8353 (18) | 141 (3) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, −y+1/2, z+1/2. |
3-Hydroxysalicylaldoxime (I) crystallizes with one molecule in the asymmetric unit in the space group P21/c. The molecule forms an intramolecular phenolic OH···N hydrogen bond [O5···N2 = 2.651 (2) Å] (Figure 1) and an intermolecular oximic OH···O hydrogen bond [O1···O5 = 2.798 (2) Å] with a neighbouring molecule related by the 21 screw axis. These two interactions taken together form a secondary level C(5) chain running parallel to the crystallographic b axis (Figure 2). The molecules within the C(5) chain also interact with their next-but-one neighbours through π-π stacking contacts which are related by a translation in the direction of the b axis. The inter-plane separation in these stacking interactions, using a calculated least squares mean plane from the phenyl carbons in one molecule and measuring the distances to the phenyl carbons in another molecule, is between 3.458 (2) and 3.471 (2) Å and the dihedral angle between the two phenyl planes is 0° by symmetry.
Each chain interacts with a neighbouring chain through intermolecular OH···O hydrogen bonds [O6···O1 = 2.835 (2) Å] related through the c-glide perpendicular to the b axis. These interactions taken with the oximic OH···O contacts and their symmetry equivalents form hydrogen bonded ring motifs around an inversion centre for which the graph-set descriptor is R44(14) (Bernstein et al., 1995). The hydrogen bonded rings connect the chains into slabs in the bc plane with the phenyl groups at the edges of the slabs (Figure 3). There are no hydrogen bonding interactions between the slabs and the only interactions are van der Waals contacts.