Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030322/hb2448sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030322/hb2448Isup2.hkl |
CCDC reference: 657792
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- R factor = 0.058
- wR factor = 0.156
- Data-to-parameter ratio = 15.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 800 Deg. PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C10
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 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 1 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
A solution of 3-nitrobenzaldehyde and isopropyl acetoacetate in 2-propanol containing a catalytic amount of piperidinium acetate was stirred at 323–328 K for 1 h and left at room temperature for 48 h. The product was collected by filtration and was recrystallized from 2-propanol to yield colourless blocks of (I). Yield was 77%. m.p.: 365 K.
The H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
The title compound (I) is an intermediate in a synthesis of azelnidipine, which is a calcium antagonist for the treatment of hypertension (Takashi et al., 1995) and we report its crystal structure here (Fig. 1).
C1—C6, N1 and O2—O3 are almost coplanar, with an r.m.s. deviation from the mean plane of 0.008 (8) Å. C7—C9, C13—C14 and O5 are also almost coplanar, with an r.m.s. deviation of 0.055 (4) Å, forming a dihedral angle of 15.33 (8)° with the above plane. In addition, C8—C10 and O3—O4 are almost coplanar, with an r.m.s. deviation from the mean plane of 0.018 (7) Å, which is nearly orthogonal to the second plane (C7—C9, C13—C14 and O5) with a dihedral angle of 87.27 (9)°.
In the crystal of (I), the packing is consolidated by weak C—H···O interactions (Table 1).
For related literature, see: Takashi et al. (1995).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level (arbitrary spheres for the H atoms). |
C14H15NO5 | Z = 2 |
Mr = 277.27 | F(000) = 292 |
Triclinic, P1 | Dx = 1.335 Mg m−3 |
Hall symbol: -P 1 | Melting point: 365 K |
a = 7.545 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.240 (5) Å | Cell parameters from 1113 reflections |
c = 11.055 (6) Å | θ = 2.6–24.9° |
α = 103.598 (8)° | µ = 0.10 mm−1 |
β = 101.898 (8)° | T = 294 K |
γ = 105.876 (8)° | Block, colorless |
V = 689.7 (6) Å3 | 0.22 × 0.20 × 0.16 mm |
Bruker SMART CCD diffractometer | 2754 independent reflections |
Radiation source: fine-focus sealed tube | 1499 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→7 |
Tmin = 0.980, Tmax = 0.984 | k = −7→11 |
3816 measured reflections | l = −13→12 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0602P)2 + 0.2485P] where P = (Fo2 + 2Fc2)/3 |
2754 reflections | (Δ/σ)max = 0.001 |
184 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C14H15NO5 | γ = 105.876 (8)° |
Mr = 277.27 | V = 689.7 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.545 (4) Å | Mo Kα radiation |
b = 9.240 (5) Å | µ = 0.10 mm−1 |
c = 11.055 (6) Å | T = 294 K |
α = 103.598 (8)° | 0.22 × 0.20 × 0.16 mm |
β = 101.898 (8)° |
Bruker SMART CCD diffractometer | 2754 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1499 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.984 | Rint = 0.024 |
3816 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.23 e Å−3 |
2754 reflections | Δρmin = −0.19 e Å−3 |
184 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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.2135 (3) | 0.4164 (3) | 0.0034 (2) | 0.0825 (8) | |
O2 | −0.1935 (4) | 0.6589 (3) | 0.0411 (2) | 0.0917 (8) | |
O3 | 0.0432 (3) | 1.1048 (2) | 0.30423 (18) | 0.0577 (6) | |
O4 | 0.3410 (3) | 1.1135 (2) | 0.29935 (16) | 0.0479 (5) | |
O5 | 0.3443 (3) | 1.3493 (3) | 0.5663 (2) | 0.0745 (7) | |
N1 | −0.1550 (4) | 0.5522 (4) | 0.0740 (2) | 0.0612 (7) | |
C1 | 0.0380 (4) | 0.7413 (3) | 0.2841 (2) | 0.0443 (7) | |
H1 | 0.0055 | 0.8195 | 0.2543 | 0.053* | |
C2 | −0.0298 (4) | 0.5891 (3) | 0.2048 (3) | 0.0456 (7) | |
C3 | 0.0137 (4) | 0.4697 (3) | 0.2429 (3) | 0.0615 (8) | |
H3 | −0.0329 | 0.3668 | 0.1864 | 0.074* | |
C4 | 0.1277 (5) | 0.5056 (4) | 0.3664 (3) | 0.0703 (10) | |
H4 | 0.1584 | 0.4262 | 0.3951 | 0.084* | |
C5 | 0.1969 (4) | 0.6570 (3) | 0.4482 (3) | 0.0570 (8) | |
H5 | 0.2736 | 0.6789 | 0.5322 | 0.068* | |
C6 | 0.1554 (4) | 0.7794 (3) | 0.4089 (2) | 0.0431 (6) | |
C7 | 0.2365 (4) | 0.9379 (3) | 0.5013 (2) | 0.0445 (7) | |
H7 | 0.2807 | 0.9420 | 0.5875 | 0.053* | |
C8 | 0.2577 (3) | 1.0773 (3) | 0.4828 (2) | 0.0408 (6) | |
C9 | 0.1986 (4) | 1.0990 (3) | 0.3518 (2) | 0.0403 (6) | |
C10 | 0.3134 (4) | 1.1453 (3) | 0.1732 (3) | 0.0534 (8) | |
H10 | 0.2163 | 1.1969 | 0.1626 | 0.064* | |
C11 | 0.2471 (6) | 0.9911 (4) | 0.0685 (3) | 0.0818 (11) | |
H11A | 0.3449 | 0.9430 | 0.0772 | 0.123* | |
H11B | 0.2224 | 1.0083 | −0.0147 | 0.123* | |
H11C | 0.1311 | 0.9225 | 0.0756 | 0.123* | |
C12 | 0.5033 (5) | 1.2548 (5) | 0.1801 (4) | 0.0909 (12) | |
H12A | 0.5370 | 1.3512 | 0.2496 | 0.136* | |
H12B | 0.4962 | 1.2780 | 0.0993 | 0.136* | |
H12C | 0.5994 | 1.2061 | 0.1958 | 0.136* | |
C13 | 0.3435 (4) | 1.2283 (4) | 0.5895 (3) | 0.0508 (7) | |
C14 | 0.4305 (5) | 1.2290 (4) | 0.7243 (3) | 0.0683 (9) | |
H14A | 0.4829 | 1.3358 | 0.7816 | 0.103* | |
H14B | 0.5311 | 1.1841 | 0.7241 | 0.103* | |
H14C | 0.3332 | 1.1675 | 0.7534 | 0.103* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0826 (17) | 0.0679 (16) | 0.0576 (14) | −0.0046 (13) | 0.0022 (12) | −0.0004 (12) |
O2 | 0.109 (2) | 0.0929 (19) | 0.0554 (14) | 0.0409 (16) | −0.0158 (13) | 0.0165 (13) |
O3 | 0.0493 (12) | 0.0763 (15) | 0.0531 (12) | 0.0249 (11) | 0.0096 (10) | 0.0302 (10) |
O4 | 0.0483 (11) | 0.0634 (12) | 0.0365 (10) | 0.0210 (9) | 0.0122 (9) | 0.0213 (9) |
O5 | 0.0934 (18) | 0.0521 (13) | 0.0608 (14) | 0.0202 (12) | 0.0027 (12) | 0.0086 (11) |
N1 | 0.0585 (16) | 0.0657 (18) | 0.0432 (15) | 0.0086 (14) | 0.0065 (12) | 0.0090 (14) |
C1 | 0.0443 (15) | 0.0486 (17) | 0.0428 (15) | 0.0169 (13) | 0.0099 (12) | 0.0200 (13) |
C2 | 0.0422 (15) | 0.0473 (17) | 0.0435 (16) | 0.0109 (13) | 0.0107 (13) | 0.0135 (13) |
C3 | 0.063 (2) | 0.0455 (18) | 0.067 (2) | 0.0124 (15) | 0.0152 (17) | 0.0115 (15) |
C4 | 0.084 (2) | 0.051 (2) | 0.075 (2) | 0.0245 (18) | 0.0067 (19) | 0.0304 (18) |
C5 | 0.0620 (19) | 0.059 (2) | 0.0505 (17) | 0.0179 (16) | 0.0072 (14) | 0.0295 (16) |
C6 | 0.0417 (15) | 0.0499 (16) | 0.0400 (15) | 0.0141 (13) | 0.0114 (12) | 0.0203 (13) |
C7 | 0.0414 (15) | 0.0585 (18) | 0.0328 (14) | 0.0161 (13) | 0.0078 (12) | 0.0161 (13) |
C8 | 0.0380 (14) | 0.0478 (16) | 0.0354 (14) | 0.0135 (12) | 0.0087 (11) | 0.0135 (12) |
C9 | 0.0462 (16) | 0.0354 (14) | 0.0340 (14) | 0.0116 (12) | 0.0071 (13) | 0.0078 (11) |
C10 | 0.0618 (19) | 0.0653 (19) | 0.0381 (15) | 0.0212 (16) | 0.0131 (14) | 0.0266 (14) |
C11 | 0.108 (3) | 0.080 (2) | 0.048 (2) | 0.023 (2) | 0.0173 (19) | 0.0163 (18) |
C12 | 0.085 (3) | 0.103 (3) | 0.071 (2) | 0.001 (2) | 0.017 (2) | 0.046 (2) |
C13 | 0.0442 (16) | 0.0572 (19) | 0.0421 (17) | 0.0140 (14) | 0.0077 (13) | 0.0074 (14) |
C14 | 0.066 (2) | 0.082 (2) | 0.0420 (17) | 0.0256 (18) | 0.0004 (15) | 0.0051 (16) |
O1—N1 | 1.214 (3) | C7—C8 | 1.324 (3) |
O2—N1 | 1.212 (3) | C7—H7 | 0.9300 |
O3—C9 | 1.203 (3) | C8—C13 | 1.474 (4) |
O4—C9 | 1.313 (3) | C8—C9 | 1.501 (4) |
O4—C10 | 1.477 (3) | C10—C12 | 1.486 (4) |
O5—C13 | 1.203 (3) | C10—C11 | 1.488 (4) |
N1—C2 | 1.459 (4) | C10—H10 | 0.9800 |
C1—C2 | 1.360 (4) | C11—H11A | 0.9600 |
C1—C6 | 1.382 (4) | C11—H11B | 0.9600 |
C1—H1 | 0.9300 | C11—H11C | 0.9600 |
C2—C3 | 1.365 (4) | C12—H12A | 0.9600 |
C3—C4 | 1.364 (4) | C12—H12B | 0.9600 |
C3—H3 | 0.9300 | C12—H12C | 0.9600 |
C4—C5 | 1.362 (4) | C13—C14 | 1.497 (4) |
C4—H4 | 0.9300 | C14—H14A | 0.9600 |
C5—C6 | 1.391 (4) | C14—H14B | 0.9600 |
C5—H5 | 0.9300 | C14—H14C | 0.9600 |
C6—C7 | 1.453 (4) | ||
C9—O4—C10 | 118.1 (2) | O3—C9—C8 | 124.0 (2) |
O2—N1—O1 | 123.5 (3) | O4—C9—C8 | 110.4 (2) |
O2—N1—C2 | 118.4 (3) | O4—C10—C12 | 105.3 (2) |
O1—N1—C2 | 118.1 (3) | O4—C10—C11 | 108.0 (2) |
C2—C1—C6 | 119.7 (2) | C12—C10—C11 | 114.0 (3) |
C2—C1—H1 | 120.1 | O4—C10—H10 | 109.8 |
C6—C1—H1 | 120.1 | C12—C10—H10 | 109.8 |
C1—C2—C3 | 122.7 (3) | C11—C10—H10 | 109.8 |
C1—C2—N1 | 118.5 (3) | C10—C11—H11A | 109.5 |
C3—C2—N1 | 118.8 (3) | C10—C11—H11B | 109.5 |
C4—C3—C2 | 118.0 (3) | H11A—C11—H11B | 109.5 |
C4—C3—H3 | 121.0 | C10—C11—H11C | 109.5 |
C2—C3—H3 | 121.0 | H11A—C11—H11C | 109.5 |
C5—C4—C3 | 120.6 (3) | H11B—C11—H11C | 109.5 |
C5—C4—H4 | 119.7 | C10—C12—H12A | 109.5 |
C3—C4—H4 | 119.7 | C10—C12—H12B | 109.5 |
C4—C5—C6 | 121.6 (3) | H12A—C12—H12B | 109.5 |
C4—C5—H5 | 119.2 | C10—C12—H12C | 109.5 |
C6—C5—H5 | 119.2 | H12A—C12—H12C | 109.5 |
C1—C6—C5 | 117.4 (3) | H12B—C12—H12C | 109.5 |
C1—C6—C7 | 124.4 (2) | O5—C13—C8 | 119.3 (3) |
C5—C6—C7 | 118.2 (2) | O5—C13—C14 | 121.1 (3) |
C8—C7—C6 | 130.5 (2) | C8—C13—C14 | 119.6 (3) |
C8—C7—H7 | 114.8 | C13—C14—H14A | 109.5 |
C6—C7—H7 | 114.8 | C13—C14—H14B | 109.5 |
C7—C8—C13 | 123.2 (2) | H14A—C14—H14B | 109.5 |
C7—C8—C9 | 123.9 (2) | C13—C14—H14C | 109.5 |
C13—C8—C9 | 112.9 (2) | H14A—C14—H14C | 109.5 |
O3—C9—O4 | 125.6 (2) | H14B—C14—H14C | 109.5 |
C6—C1—C2—C3 | −0.3 (4) | C5—C6—C7—C8 | 162.8 (3) |
C6—C1—C2—N1 | 179.4 (2) | C6—C7—C8—C13 | 179.7 (3) |
O2—N1—C2—C1 | 0.1 (4) | C6—C7—C8—C9 | −0.7 (4) |
O1—N1—C2—C1 | 179.3 (2) | C10—O4—C9—O3 | 2.3 (4) |
O2—N1—C2—C3 | 179.7 (3) | C10—O4—C9—C8 | −176.4 (2) |
O1—N1—C2—C3 | −1.0 (4) | C7—C8—C9—O3 | 91.8 (3) |
C1—C2—C3—C4 | 1.0 (5) | C13—C8—C9—O3 | −88.6 (3) |
N1—C2—C3—C4 | −178.7 (3) | C7—C8—C9—O4 | −89.5 (3) |
C2—C3—C4—C5 | −0.6 (5) | C13—C8—C9—O4 | 90.1 (3) |
C3—C4—C5—C6 | −0.4 (5) | C9—O4—C10—C12 | 143.2 (3) |
C2—C1—C6—C5 | −0.8 (4) | C9—O4—C10—C11 | −94.7 (3) |
C2—C1—C6—C7 | 179.7 (2) | C7—C8—C13—O5 | −174.3 (3) |
C4—C5—C6—C1 | 1.1 (4) | C9—C8—C13—O5 | 6.1 (4) |
C4—C5—C6—C7 | −179.3 (3) | C7—C8—C13—C14 | 6.6 (4) |
C1—C6—C7—C8 | −17.6 (4) | C9—C8—C13—C14 | −173.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O3 | 0.93 | 2.49 | 3.302 (4) | 147 |
C4—H4···O5i | 0.93 | 2.48 | 3.308 (5) | 150 |
Symmetry code: (i) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C14H15NO5 |
Mr | 277.27 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 7.545 (4), 9.240 (5), 11.055 (6) |
α, β, γ (°) | 103.598 (8), 101.898 (8), 105.876 (8) |
V (Å3) | 689.7 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.22 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.980, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3816, 2754, 1499 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.156, 1.02 |
No. of reflections | 2754 |
No. of parameters | 184 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.19 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O3 | 0.93 | 2.49 | 3.302 (4) | 147 |
C4—H4···O5i | 0.93 | 2.48 | 3.308 (5) | 150 |
Symmetry code: (i) x, y−1, z. |
The title compound (I) is an intermediate in a synthesis of azelnidipine, which is a calcium antagonist for the treatment of hypertension (Takashi et al., 1995) and we report its crystal structure here (Fig. 1).
C1—C6, N1 and O2—O3 are almost coplanar, with an r.m.s. deviation from the mean plane of 0.008 (8) Å. C7—C9, C13—C14 and O5 are also almost coplanar, with an r.m.s. deviation of 0.055 (4) Å, forming a dihedral angle of 15.33 (8)° with the above plane. In addition, C8—C10 and O3—O4 are almost coplanar, with an r.m.s. deviation from the mean plane of 0.018 (7) Å, which is nearly orthogonal to the second plane (C7—C9, C13—C14 and O5) with a dihedral angle of 87.27 (9)°.
In the crystal of (I), the packing is consolidated by weak C—H···O interactions (Table 1).