The Baylis–Hillman adduct of 4-nitrobenzaldehyde and 2-cyclopenten-1-one yielded a racemic compound, C
12H
11NO
4, in which there is one is a stereogenic C atom. A strong intermolecular O—H
O hydrogen bond and a weak C—H
O hydrogen bond link the molecules into a three-dimensional framework.
Supporting information
CCDC reference: 238698
Key indicators
- Single-crystal X-ray study
- T = 183 K
- Mean (C-C) = 0.005 Å
- R factor = 0.069
- wR factor = 0.171
- Data-to-parameter ratio = 12.2
checkCIF/PLATON results
No syntax errors found
Alert level C
DIFMX01_ALERT_2_C The maximum difference density is > 0.1*ZMAX*0.75
_refine_diff_density_max given = 0.685
Test value = 0.600
DIFMX02_ALERT_1_C The minimum difference density is > 0.1*ZMAX*0.75
The relevant atom site should be identified.
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 3.48
PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............ 0.69 e/A 3
PLAT430_ALERT_2_C Short Inter D...A Contact O3 .. O3 .. 2.89 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
6 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 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
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker,2000); cell refinement: SMART; data reduction: SAINT and SHELXTL (Bruker,2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
2-[Hydroxy(4-nitrophenyl)methyl]-cyclopent-2-en-1-one
top
Crystal data top
C12H11NO4 | F(000) = 488 |
Mr = 233.22 | Dx = 1.445 Mg m−3 |
Monoclinic, P21/c | Melting point: 409 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.746 (4) Å | Cell parameters from 5880 reflections |
b = 11.657 (4) Å | θ = 2.4–21.2° |
c = 7.250 (2) Å | µ = 0.11 mm−1 |
β = 95.479 (4)° | T = 183 K |
V = 1072.2 (6) Å3 | Block, yellow |
Z = 4 | 0.20 × 0.20 × 0.10 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1885 independent reflections |
Radiation source: fine-focus sealed tube | 1379 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
Detector resolution: 100x100 microns pixels mm-1 | θmax = 25.0°, θmin = 1.6° |
ω scans | h = −15→14 |
Absorption correction: multi-scan (SADABS; Sheldrick,1996) | k = −13→13 |
Tmin = 0.978, Tmax = 0.989 | l = −8→8 |
4315 measured reflections | |
Refinement top
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0805P)2] where P = (Fo2 + 2Fc2)/3 |
1885 reflections | (Δ/σ)max < 0.001 |
155 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
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 | |
O1 | 0.61859 (19) | −0.04164 (19) | 1.0523 (3) | 0.0460 (7) | |
H1 | 0.5869 | −0.0039 | 1.1286 | 0.069* | |
O2 | 0.46854 (17) | −0.0920 (2) | 0.6870 (3) | 0.0467 (7) | |
O3 | 1.0076 (2) | 0.3986 (2) | 1.1147 (4) | 0.0679 (9) | |
O4 | 1.08198 (18) | 0.2501 (2) | 1.2363 (3) | 0.0568 (8) | |
N | 1.0091 (2) | 0.2973 (3) | 1.1467 (4) | 0.0392 (7) | |
C1 | 0.5601 (3) | −0.1017 (3) | 0.6488 (4) | 0.0342 (8) | |
C2 | 0.6522 (2) | −0.0430 (3) | 0.7399 (4) | 0.0294 (7) | |
C3 | 0.7351 (3) | −0.0700 (3) | 0.6512 (5) | 0.0394 (9) | |
H3 | 0.8039 | −0.0412 | 0.6860 | 0.047* | |
C4 | 0.7107 (3) | −0.1495 (3) | 0.4924 (5) | 0.0477 (10) | |
H4B | 0.7528 | −0.2207 | 0.5089 | 0.072* | |
H4A | 0.7249 | −0.1127 | 0.3742 | 0.072* | |
C5 | 0.5943 (2) | −0.1744 (3) | 0.4957 (4) | 0.0388 (9) | |
H5B | 0.5550 | −0.1537 | 0.3760 | 0.058* | |
H5A | 0.5825 | −0.2567 | 0.5206 | 0.058* | |
C6 | 0.6442 (2) | 0.0320 (3) | 0.9060 (4) | 0.0326 (8) | |
H6 | 0.5842 | 0.0865 | 0.8772 | 0.049* | |
C7 | 0.7421 (2) | 0.1014 (3) | 0.9632 (4) | 0.0298 (7) | |
C8 | 0.8318 (2) | 0.0493 (3) | 1.0491 (4) | 0.0336 (8) | |
H8 | 0.8322 | −0.0313 | 1.0686 | 0.040* | |
C9 | 0.9201 (2) | 0.1123 (3) | 1.1065 (4) | 0.0339 (8) | |
H9 | 0.9813 | 0.0763 | 1.1652 | 0.041* | |
C10 | 0.9174 (2) | 0.2287 (3) | 1.0768 (4) | 0.0310 (7) | |
C11 | 0.8300 (2) | 0.2843 (3) | 0.9913 (4) | 0.0337 (8) | |
H11 | 0.8305 | 0.3648 | 0.9713 | 0.040* | |
C12 | 0.7418 (2) | 0.2190 (3) | 0.9358 (4) | 0.0307 (7) | |
H12 | 0.6804 | 0.2553 | 0.8782 | 0.037* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0482 (15) | 0.0453 (15) | 0.0457 (15) | −0.0045 (12) | 0.0106 (11) | 0.0019 (12) |
O2 | 0.0354 (14) | 0.0536 (16) | 0.0513 (15) | −0.0083 (12) | 0.0050 (11) | −0.0138 (13) |
O3 | 0.077 (2) | 0.0379 (16) | 0.084 (2) | −0.0200 (15) | −0.0170 (16) | −0.0022 (15) |
O4 | 0.0377 (14) | 0.0641 (19) | 0.0655 (18) | −0.0100 (13) | −0.0114 (12) | 0.0124 (15) |
N | 0.0449 (18) | 0.0365 (18) | 0.0361 (16) | −0.0105 (14) | 0.0040 (13) | −0.0015 (14) |
C1 | 0.0376 (19) | 0.0291 (18) | 0.0362 (19) | 0.0024 (15) | 0.0043 (15) | 0.0055 (15) |
C2 | 0.0293 (17) | 0.0283 (18) | 0.0302 (17) | 0.0024 (14) | 0.0010 (14) | 0.0043 (14) |
C3 | 0.0357 (19) | 0.045 (2) | 0.0376 (19) | −0.0008 (16) | 0.0019 (15) | 0.0008 (16) |
C4 | 0.047 (2) | 0.054 (2) | 0.043 (2) | 0.0100 (18) | 0.0051 (17) | −0.0060 (18) |
C5 | 0.050 (2) | 0.0304 (19) | 0.0351 (18) | 0.0033 (16) | 0.0019 (15) | −0.0036 (15) |
C6 | 0.0309 (18) | 0.0333 (19) | 0.0338 (18) | −0.0017 (14) | 0.0032 (14) | 0.0034 (15) |
C7 | 0.0323 (17) | 0.0304 (18) | 0.0271 (16) | 0.0008 (14) | 0.0041 (13) | −0.0005 (14) |
C8 | 0.0365 (19) | 0.0226 (17) | 0.0416 (19) | 0.0034 (14) | 0.0036 (15) | 0.0018 (14) |
C9 | 0.0310 (17) | 0.035 (2) | 0.0358 (18) | 0.0043 (15) | 0.0023 (14) | 0.0015 (15) |
C10 | 0.0344 (18) | 0.0323 (19) | 0.0270 (16) | −0.0040 (15) | 0.0065 (14) | −0.0020 (14) |
C11 | 0.049 (2) | 0.0254 (17) | 0.0281 (16) | 0.0007 (16) | 0.0102 (15) | 0.0016 (14) |
C12 | 0.0314 (17) | 0.0325 (18) | 0.0281 (16) | 0.0087 (14) | 0.0018 (13) | 0.0002 (14) |
Geometric parameters (Å, º) top
O2—C1 | 1.230 (3) | N—C10 | 1.466 (4) |
C1—C2 | 1.461 (4) | O3—N | 1.204 (4) |
C2—C3 | 1.327 (4) | O4—N | 1.213 (3) |
C3—C4 | 1.488 (4) | C3—H3 | 0.9500 |
C4—C5 | 1.514 (4) | C4—H4B | 0.9900 |
C1—C5 | 1.494 (4) | C4—H4A | 0.9900 |
C2—C6 | 1.499 (4) | C5—H5B | 0.9900 |
O1—C6 | 1.427 (4) | C5—H5A | 0.9900 |
C6—C7 | 1.511 (4) | C6—H6 | 1.0000 |
C7—C8 | 1.389 (4) | C8—H8 | 0.9500 |
C8—C9 | 1.374 (4) | C9—H9 | 0.9500 |
C9—C10 | 1.374 (4) | C11—H11 | 0.9500 |
C10—C11 | 1.383 (4) | C12—H12 | 0.9500 |
C11—C12 | 1.386 (4) | O1—H1 | 0.8400 |
C7—C12 | 1.385 (4) | | |
| | | |
C3—C2—C6 | 130.2 (3) | C2—C3—H3 | 123.1 |
O2—C1—C2 | 126.4 (3) | C4—C3—H3 | 123.1 |
O2—C1—C5 | 124.7 (3) | C3—C4—H4B | 111.0 |
C1—C2—C6 | 121.5 (3) | C5—C4—H4B | 111.0 |
C2—C6—C7 | 114.5 (2) | C3—C4—H4A | 111.0 |
C2—C3—C4 | 113.9 (3) | C5—C4—H4A | 111.0 |
C2—C1—C5 | 108.8 (3) | C6—O1—H1 | 109.5 |
C3—C2—C1 | 108.2 (3) | H4B—C4—H4A | 109.0 |
C1—C5—C4 | 105.0 (3) | C1—C5—H5B | 110.7 |
C3—C4—C5 | 103.9 (3) | C4—C5—H5B | 110.7 |
O1—C6—C2 | 106.5 (2) | C1—C5—H5A | 110.7 |
O1—C6—C7 | 111.1 (3) | C4—C5—H5A | 110.7 |
O3—N—O4 | 123.1 (3) | H5B—C5—H5A | 108.8 |
C9—C10—C11 | 122.6 (3) | O1—C6—H6 | 108.2 |
C9—C8—C7 | 121.2 (3) | C2—C6—H6 | 108.2 |
C8—C7—C6 | 120.8 (3) | C7—C6—H6 | 108.2 |
C7—C12—C11 | 120.7 (3) | C9—C8—H8 | 119.4 |
C12—C7—C6 | 120.0 (3) | C7—C8—H8 | 119.4 |
C12—C7—C8 | 119.2 (3) | C8—C9—H9 | 120.9 |
O3—N—C10 | 118.1 (3) | C10—C9—H9 | 120.9 |
O4—N—C10 | 118.8 (3) | C10—C11—H11 | 121.0 |
C9—C10—N | 118.5 (3) | C12—C11—H11 | 121.0 |
C11—C10—N | 118.8 (3) | C7—C12—H12 | 119.6 |
C10—C11—C12 | 118.0 (3) | C11—C12—H12 | 119.6 |
C8—C9—C10 | 118.2 (3) | | |
| | | |
O2—C1—C2—C3 | −175.8 (3) | O1—C6—C7—C8 | 47.3 (4) |
C5—C1—C2—C3 | 2.6 (4) | C2—C6—C7—C8 | −73.4 (4) |
O2—C1—C2—C6 | 4.7 (5) | C12—C7—C8—C9 | −0.2 (4) |
C5—C1—C2—C6 | −176.9 (3) | C6—C7—C8—C9 | −178.1 (3) |
C1—C2—C3—C4 | −0.3 (4) | C7—C8—C9—C10 | 0.0 (4) |
C6—C2—C3—C4 | 179.1 (3) | C8—C9—C10—C11 | −0.2 (4) |
C2—C3—C4—C5 | −2.0 (4) | C8—C9—C10—N | 176.7 (3) |
O2—C1—C5—C4 | 174.8 (3) | O3—N—C10—C9 | 177.6 (3) |
C2—C1—C5—C4 | −3.7 (3) | O4—N—C10—C9 | −3.6 (4) |
C3—C4—C5—C1 | 3.3 (3) | O3—N—C10—C11 | −5.4 (4) |
C3—C2—C6—O1 | −112.8 (4) | O4—N—C10—C11 | 173.4 (3) |
C1—C2—C6—O1 | 66.5 (3) | C9—C10—C11—C12 | 0.6 (4) |
C3—C2—C6—C7 | 10.4 (5) | N—C10—C11—C12 | −176.3 (2) |
C1—C2—C6—C7 | −170.3 (3) | C8—C7—C12—C11 | 0.6 (4) |
O1—C6—C7—C12 | −130.5 (3) | C6—C7—C12—C11 | 178.5 (3) |
C2—C6—C7—C12 | 108.8 (3) | C10—C11—C12—C7 | −0.8 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.84 | 1.93 | 2.763 (3) | 173 |
C5—H5A···O1ii | 0.99 | 2.40 | 3.347 (4) | 159 |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) x, −y−1/2, z−1/2. |