The title compound, C9H15NO4, a Mannich base of Meldrum's acid, proves to be an inner salt.
Supporting information
CCDC reference: 285513
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.039
- wR factor = 0.102
- Data-to-parameter ratio = 9.5
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.99 Deg.
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT088_ALERT_3_C Poor Data / Parameter Ratio .................... 9.55
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem
1 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
0 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
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: RAPID-AUTO (Rigaku Corporation, 2001); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC & Rigaku Corporation, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: CrystalStructure.
5-(
N,
N-Dimethylammoniomethyl)-2,2-dimethyl-4-oxido-6-oxo-6
H-1,3-dioxine
top
Crystal data top
C9H15NO4 | Z = 2 |
Mr = 201.22 | F(000) = 216.0 |
Triclinic, P1 | Dx = 1.317 Mg m−3 |
Hall symbol: -P 1 | Melting point = 433–434 K |
a = 6.7922 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.4862 (8) Å | Cell parameters from 2555 reflections |
c = 9.1518 (8) Å | θ = 3.0–27.3° |
α = 99.810 (6)° | µ = 0.10 mm−1 |
β = 101.532 (3)° | T = 293 K |
γ = 92.919 (5)° | Prism, colourless |
V = 507.33 (8) Å3 | 0.50 × 0.48 × 0.42 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 1519 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
Detector resolution: 10.00 pixels mm-1 | h = −7→8 |
ω scans | k = −10→10 |
2699 measured reflections | l = −10→10 |
1785 independent 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | All H-atom parameters refined |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0603P)2 + 0.079P] where P = (Fo2 + 2Fc2)/3 |
1785 reflections | (Δ/σ)max < 0.001 |
187 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.25 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 | |
C1 | 0.6812 (2) | 0.94008 (16) | 0.29665 (16) | 0.0375 (3) | |
C2 | 0.7220 (3) | 1.1080 (2) | 0.3905 (2) | 0.0548 (5) | |
C3 | 0.8242 (3) | 0.90536 (19) | 0.19055 (19) | 0.0451 (4) | |
C4 | 0.3872 (2) | 0.77380 (17) | 0.14777 (16) | 0.0395 (3) | |
C5 | 0.6148 (2) | 0.67516 (15) | 0.34926 (14) | 0.0325 (3) | |
C6 | 0.4676 (2) | 0.64525 (16) | 0.21519 (15) | 0.0338 (3) | |
C7 | 0.3766 (2) | 0.47664 (16) | 0.15857 (15) | 0.0357 (3) | |
C8 | 0.0699 (3) | 0.5110 (2) | 0.2689 (2) | 0.0482 (4) | |
C9 | 0.1868 (3) | 0.24183 (18) | 0.21733 (19) | 0.0448 (4) | |
O1 | 0.47762 (15) | 0.92680 (11) | 0.21273 (12) | 0.0452 (3) | |
O2 | 0.70212 (15) | 0.82985 (11) | 0.40314 (10) | 0.0394 (3) | |
O3 | 0.67002 (16) | 0.57220 (12) | 0.42798 (11) | 0.0430 (3) | |
O4 | 0.24329 (18) | 0.76470 (14) | 0.04196 (14) | 0.0608 (4) | |
N1 | 0.24865 (16) | 0.41819 (12) | 0.26113 (12) | 0.0316 (3) | |
H1 | 0.320 (3) | 0.4334 (19) | 0.352 (2) | 0.044 (4)* | |
H2 | 0.631 (3) | 1.120 (2) | 0.456 (2) | 0.071 (6)* | |
H3 | 0.860 (3) | 1.119 (2) | 0.450 (2) | 0.060 (5)* | |
H4 | 0.705 (3) | 1.188 (3) | 0.321 (2) | 0.072 (6)* | |
H5 | 0.810 (3) | 0.982 (2) | 0.124 (2) | 0.063 (5)* | |
H6 | 0.963 (3) | 0.918 (2) | 0.247 (2) | 0.060 (5)* | |
H7 | 0.798 (3) | 0.793 (2) | 0.137 (2) | 0.056 (5)* | |
H8 | 0.476 (3) | 0.399 (2) | 0.1508 (18) | 0.044 (4)* | |
H9 | 0.287 (2) | 0.4616 (18) | 0.0538 (19) | 0.042 (4)* | |
H10 | 0.111 (3) | 0.625 (2) | 0.290 (2) | 0.062 (5)* | |
H11 | −0.021 (4) | 0.485 (3) | 0.169 (3) | 0.081 (6)* | |
H12 | 0.004 (3) | 0.475 (2) | 0.343 (2) | 0.058 (5)* | |
H13 | 0.088 (3) | 0.222 (2) | 0.124 (2) | 0.056 (5)* | |
H14 | 0.302 (3) | 0.184 (2) | 0.205 (2) | 0.064 (5)* | |
H15 | 0.134 (3) | 0.207 (2) | 0.294 (2) | 0.059 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0387 (8) | 0.0329 (7) | 0.0390 (7) | 0.0002 (5) | 0.0063 (6) | 0.0049 (6) |
C2 | 0.0551 (11) | 0.0387 (9) | 0.0651 (11) | −0.0039 (7) | 0.0159 (9) | −0.0069 (8) |
C3 | 0.0516 (10) | 0.0372 (8) | 0.0483 (9) | −0.0012 (6) | 0.0174 (7) | 0.0066 (7) |
C4 | 0.0365 (8) | 0.0385 (8) | 0.0411 (8) | 0.0003 (6) | 0.0016 (6) | 0.0095 (6) |
C5 | 0.0323 (7) | 0.0373 (7) | 0.0304 (6) | 0.0028 (5) | 0.0118 (5) | 0.0070 (5) |
C6 | 0.0352 (7) | 0.0326 (7) | 0.0325 (7) | 0.0007 (5) | 0.0051 (6) | 0.0064 (5) |
C7 | 0.0411 (8) | 0.0350 (7) | 0.0308 (7) | 0.0017 (6) | 0.0087 (6) | 0.0045 (5) |
C8 | 0.0406 (9) | 0.0526 (10) | 0.0537 (10) | 0.0111 (7) | 0.0123 (8) | 0.0111 (8) |
C9 | 0.0518 (10) | 0.0352 (8) | 0.0439 (9) | −0.0065 (7) | 0.0046 (7) | 0.0075 (6) |
O1 | 0.0411 (6) | 0.0319 (5) | 0.0588 (6) | 0.0036 (4) | 0.0008 (5) | 0.0095 (4) |
O2 | 0.0414 (6) | 0.0414 (6) | 0.0312 (5) | −0.0052 (4) | 0.0029 (4) | 0.0035 (4) |
O3 | 0.0478 (6) | 0.0505 (6) | 0.0335 (5) | 0.0071 (4) | 0.0063 (4) | 0.0170 (4) |
O4 | 0.0534 (7) | 0.0567 (7) | 0.0620 (7) | −0.0019 (5) | −0.0195 (6) | 0.0217 (6) |
N1 | 0.0329 (6) | 0.0318 (6) | 0.0273 (6) | 0.0012 (4) | 0.0004 (5) | 0.0054 (4) |
Geometric parameters (Å, º) top
C3—C1 | 1.510 (2) | C6—C5 | 1.3952 (19) |
C3—H7 | 0.985 (18) | C4—O1 | 1.3879 (17) |
C3—H5 | 0.96 (2) | C5—O2 | 1.3790 (16) |
C3—H6 | 0.97 (2) | C1—O1 | 1.4299 (17) |
C7—C6 | 1.4923 (18) | C1—O2 | 1.4539 (17) |
C7—N1 | 1.5243 (18) | C1—C2 | 1.514 (2) |
C7—H8 | 0.974 (17) | N1—C8 | 1.4876 (19) |
C7—H9 | 1.010 (17) | N1—H1 | 0.859 (18) |
C9—N1 | 1.4971 (17) | C2—H4 | 1.00 (2) |
C9—H14 | 0.96 (2) | C2—H3 | 0.97 (2) |
C9—H13 | 0.96 (2) | C2—H2 | 0.94 (2) |
C9—H15 | 0.93 (2) | C8—H11 | 0.98 (2) |
O3—C5 | 1.2503 (16) | C8—H10 | 0.97 (2) |
O4—C4 | 1.2196 (18) | C8—H12 | 0.96 (2) |
C6—C4 | 1.423 (2) | | |
| | | |
C1—C3—H7 | 109.7 (11) | O2—C5—C6 | 118.47 (11) |
C1—C3—H5 | 108.2 (11) | O1—C1—O2 | 110.17 (11) |
H7—C3—H5 | 113.9 (16) | O1—C1—C3 | 110.48 (12) |
C1—C3—H6 | 110.8 (11) | O2—C1—C3 | 110.02 (12) |
H7—C3—H6 | 106.6 (15) | O1—C1—C2 | 106.61 (12) |
H5—C3—H6 | 107.7 (16) | O2—C1—C2 | 106.68 (12) |
C6—C7—N1 | 113.10 (10) | C3—C1—C2 | 112.76 (13) |
C6—C7—H8 | 113.5 (10) | C8—N1—C9 | 110.84 (12) |
N1—C7—H8 | 104.8 (10) | C8—N1—C7 | 112.17 (11) |
C6—C7—H9 | 112.6 (9) | C9—N1—C7 | 112.39 (11) |
N1—C7—H9 | 106.8 (9) | C8—N1—H1 | 106.4 (11) |
H8—C7—H9 | 105.4 (13) | C9—N1—H1 | 106.4 (11) |
N1—C9—H14 | 110.0 (11) | C4—O1—C1 | 117.53 (10) |
N1—C9—H13 | 108.7 (10) | C5—O2—C1 | 117.10 (10) |
H14—C9—H13 | 110.1 (16) | C1—C2—H4 | 109.1 (12) |
N1—C9—H15 | 109.4 (11) | C1—C2—H3 | 107.9 (11) |
H14—C9—H15 | 107.9 (16) | H4—C2—H3 | 110.5 (17) |
H13—C9—H15 | 110.6 (16) | C1—C2—H2 | 108.1 (12) |
C4—C6—C7 | 121.08 (12) | H4—C2—H2 | 111.3 (17) |
C5—C6—C4 | 120.87 (12) | H3—C2—H2 | 109.8 (17) |
C5—C6—C7 | 117.43 (12) | N1—C8—H11 | 107.4 (13) |
C7—N1—H1 | 108.3 (12) | N1—C8—H10 | 109.8 (12) |
O4—C4—O1 | 116.38 (12) | H11—C8—H10 | 108.4 (17) |
O3—C5—C6 | 124.68 (12) | N1—C8—H12 | 107.5 (11) |
O4—C4—C6 | 127.02 (13) | H11—C8—H12 | 108.9 (17) |
O1—C4—C6 | 116.56 (12) | H10—C8—H12 | 114.7 (15) |
O3—C5—O2 | 116.82 (12) | | |
| | | |
N1—C7—C6—C5 | 67.43 (16) | C6—C7—N1—C9 | −170.56 (12) |
N1—C7—C6—C4 | −103.66 (15) | O4—C4—O1—C1 | −158.43 (14) |
C5—C6—C4—O4 | −170.81 (15) | C6—C4—O1—C1 | 23.80 (19) |
C7—C6—C4—O4 | 0.0 (2) | O2—C1—O1—C4 | −48.77 (16) |
C5—C6—C4—O1 | 6.7 (2) | C3—C1—O1—C4 | 73.00 (15) |
C7—C6—C4—O1 | 177.47 (12) | C2—C1—O1—C4 | −164.15 (13) |
C4—C6—C5—O3 | 168.26 (13) | O3—C5—O2—C1 | 164.22 (11) |
C7—C6—C5—O3 | −2.8 (2) | C6—C5—O2—C1 | −17.94 (17) |
C4—C6—C5—O2 | −9.4 (2) | O1—C1—O2—C5 | 45.62 (15) |
C7—C6—C5—O2 | 179.50 (11) | C3—C1—O2—C5 | −76.43 (15) |
C6—C7—N1—C8 | 63.74 (15) | C2—C1—O2—C5 | 160.96 (12) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3 | 0.859 (18) | 2.507 (18) | 3.0696 (16) | 124.4 (14) |
N1—H1···O3i | 0.859 (18) | 2.013 (18) | 2.7740 (15) | 147.6 (19) |
Symmetry code: (i) −x+1, −y+1, −z+1. |