5-(Anilinomethyl­ene)-2,2-dimethyl-1,3-dioxane-4,6-dione

In the title enaminone, C₁₃H₁₃NO₄, the 1,3-dioxane-4,6-dione ring exhibits a distorted boat conformation. The amino H atom has one intra­molecular contact to a carbonyl O atom, forming a six-membered ring. Mol­ecules related by an inversion center are linked into dimers by N—H...O and C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.076
• wR factor = 0.204
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97

Author Response: The number of measured intensities was 2344 reflections. Due to scintillator-collimator collision predicted 68 could not be measured and 186 were rejected after data reduction and refinement.

PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C17
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.55
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.
PLAT430_ALERT_2_C Short Inter D...A Contact  O9     ..  O9      ..       2.86 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 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

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Computing details

Data collection: CAD-4-PC (Enraf–Nonius, 1993); cell refinement: CAD-4-PC; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

5-(Anilinomethylene)-2,2-dimethyl-1,3-dioxane-4,6-dione

Crystal data

C13H13NO4	Z = 2
Mr = 247.24	F(000) = 260
Triclinic, P1	Dx = 1.325 Mg m^−3
Hall symbol: -P 1	Melting point: 424 K
a = 5.495 (1) Å	Cu Kα radiation, λ = 1.54180 Å
b = 10.594 (2) Å	Cell parameters from 25 reflections
c = 11.589 (3) Å	θ = 13.1–41.4°
α = 71.42 (2)°	µ = 0.83 mm^−1
β = 82.24 (2)°	T = 297 K
γ = 76.10 (2)°	Block, light yellow
V = 619.5 (2) Å^3	0.33 × 0.28 × 0.28 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.018
Radiation source: fine-focus sealed tube	θmax = 67.0°, θmin = 4.0°
Graphite monochromator	h = −6→6
non–profiled ω/2θ scans	k = −11→12
2268 measured reflections	l = 0→13
2158 independent reflections	2 standard reflections every 120 min
1893 reflections with I > 2σ(I)	intensity decay: 1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.076	H-atom parameters constrained
wR(F^2) = 0.204	w = 1/[σ^2(Fo^2) + (0.1162P)^2 + 0.1316P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
2158 reflections	Δρmax = 0.39 e Å^−3
167 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.217 (16)

Special details

Experimental. IR (KBr) (ν_max cm^-1): 3215, 1731, 1683, 1634. ¹H NMR (CDCl₃): δ 1.75 (6H, s); 7.39–7.65 (5H, m); 8.84 (1H, d, J = 14.4 Hz); 11.41 (1H, d, J = 14.4 Hz). ¹³C NMR (CDCl₃): δ 26.9 (2CH₃); 87.2 (C); 105.1 (C); 117.9 2CH); 126.9 (CH); 130.0 (2CH); 137.7 (C); 152.5 (CH); 163.5 (C); 165.5 (C).

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.6861 (3)	0.71225 (15)	0.49340 (14)	0.0635 (5)
H1	0.6178	0.6498	0.4872	0.076*
C2	0.8394 (4)	0.6787 (2)	0.58083 (18)	0.0646 (6)
H2	0.9148	0.7468	0.5849	0.078*
C3	0.9010 (4)	0.55444 (19)	0.66695 (17)	0.0592 (5)
C4	0.8092 (4)	0.43971 (19)	0.66580 (17)	0.0625 (6)
O5	0.8766 (4)	0.32319 (14)	0.75686 (13)	0.0807 (6)
C6	0.9515 (5)	0.3342 (2)	0.86631 (19)	0.0740 (7)
O7	1.1334 (3)	0.41693 (16)	0.83805 (13)	0.0755 (6)
C8	1.0836 (5)	0.5393 (2)	0.7518 (2)	0.0727 (7)
O9	0.6854 (4)	0.43799 (14)	0.58786 (14)	0.0823 (6)
C11	1.0850 (8)	0.1932 (3)	0.9339 (3)	0.1259 (13)
H11A	1.1111	0.1905	1.0150	0.189*
H11B	1.2443	0.1702	0.8918	0.189*
H11C	0.9847	0.1289	0.9381	0.189*
C12	0.7269 (6)	0.3941 (4)	0.9356 (2)	0.1044 (10)
H12A	0.7783	0.4005	1.0091	0.157*
H12B	0.6065	0.3367	0.9559	0.157*
H12C	0.6521	0.4832	0.8862	0.157*
C13	0.6241 (4)	0.84367 (19)	0.40819 (18)	0.0633 (6)
C14	0.7429 (6)	0.9463 (3)	0.3965 (3)	0.0981 (10)
H14	0.8751	0.9312	0.4449	0.118*
C15	0.6691 (7)	1.0728 (3)	0.3134 (3)	0.1037 (10)
H15	0.7514	1.1420	0.3073	0.124*
C16	0.4829 (6)	1.0974 (3)	0.2420 (3)	0.0956 (9)
H16	0.4373	1.1821	0.1849	0.115*
C17	0.3604 (7)	0.9963 (3)	0.2542 (3)	0.1209 (13)
H17	0.2274	1.0126	0.2059	0.145*
C18	0.4310 (7)	0.8693 (3)	0.3374 (3)	0.1034 (11)
H18	0.3451	0.8012	0.3447	0.124*
O10	1.199 (2)	0.6214 (11)	0.7597 (5)	0.1026 (16)	0.70
O10'	1.203 (6)	0.625 (3)	0.7262 (17)	0.1026 (16)	0.30

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0842 (12)	0.0467 (9)	0.0576 (9)	−0.0155 (8)	−0.0178 (8)	−0.0062 (7)
C2	0.0797 (14)	0.0528 (11)	0.0609 (11)	−0.0160 (9)	−0.0169 (10)	−0.0098 (9)
C3	0.0699 (12)	0.0516 (10)	0.0545 (11)	−0.0112 (8)	−0.0139 (9)	−0.0106 (8)
C4	0.0827 (14)	0.0498 (10)	0.0531 (10)	−0.0085 (9)	−0.0198 (9)	−0.0105 (8)
O5	0.1267 (14)	0.0486 (8)	0.0679 (9)	−0.0172 (8)	−0.0430 (9)	−0.0046 (7)
C6	0.0952 (16)	0.0670 (13)	0.0593 (12)	−0.0268 (12)	−0.0307 (11)	−0.0004 (9)
O7	0.0773 (10)	0.0714 (10)	0.0710 (9)	−0.0184 (8)	−0.0304 (7)	0.0008 (7)
C8	0.0822 (15)	0.0633 (12)	0.0714 (13)	−0.0205 (11)	−0.0251 (11)	−0.0065 (10)
O9	0.1244 (14)	0.0601 (9)	0.0690 (9)	−0.0236 (8)	−0.0442 (9)	−0.0100 (7)
C11	0.179 (3)	0.0768 (18)	0.109 (2)	−0.030 (2)	−0.083 (2)	0.0218 (16)
C12	0.105 (2)	0.145 (3)	0.0626 (14)	−0.0447 (19)	−0.0121 (13)	−0.0144 (16)
C13	0.0832 (14)	0.0453 (10)	0.0572 (11)	−0.0146 (9)	−0.0121 (9)	−0.0054 (8)
C14	0.130 (2)	0.0695 (15)	0.0947 (18)	−0.0412 (15)	−0.0443 (16)	0.0051 (13)
C15	0.148 (3)	0.0611 (14)	0.1000 (19)	−0.0454 (16)	−0.0233 (19)	0.0022 (13)
C16	0.126 (2)	0.0548 (13)	0.0834 (17)	−0.0123 (13)	−0.0153 (16)	0.0093 (11)
C17	0.155 (3)	0.0777 (17)	0.115 (2)	−0.0335 (19)	−0.073 (2)	0.0258 (16)
C18	0.141 (3)	0.0641 (14)	0.1019 (19)	−0.0396 (15)	−0.0613 (18)	0.0141 (13)
O10	0.1378 (18)	0.0920 (15)	0.087 (4)	−0.0606 (13)	−0.060 (4)	0.009 (3)
O10'	0.1378 (18)	0.0920 (15)	0.087 (4)	−0.0606 (13)	−0.060 (4)	0.009 (3)

Geometric parameters (Å, º)

N1—C2	1.311 (3)	C11—H11A	0.9600
N1—C13	1.420 (2)	C11—H11B	0.9600
N1—H1	0.8600	C11—H11C	0.9600
C2—C3	1.373 (3)	C12—H12A	0.9600
C2—H2	0.9300	C12—H12B	0.9600
C3—C4	1.428 (3)	C12—H12C	0.9600
C3—C8	1.445 (3)	C13—C18	1.352 (3)
C4—O9	1.209 (2)	C13—C14	1.360 (3)
C4—O5	1.353 (2)	C14—C15	1.382 (3)
O5—C6	1.432 (3)	C14—H14	0.9300
C6—O7	1.423 (3)	C15—C16	1.327 (4)
C6—C12	1.500 (4)	C15—H15	0.9300
C6—C11	1.505 (3)	C16—C17	1.358 (4)
O7—C8	1.354 (2)	C16—H16	0.9300
C8—O10'	1.18 (3)	C17—C18	1.383 (3)
C8—O10	1.224 (10)	C17—H17	0.9300
O9—O9^i	2.856 (3)	C18—H18	0.9300
C2—N1—C13	125.03 (17)	C6—C11—H11C	109.5
C2—N1—H1	117.5	H11A—C11—H11C	109.5
C13—N1—H1	117.5	H11B—C11—H11C	109.5
N1—C2—C3	127.30 (19)	C6—C12—H12A	109.5
N1—C2—H2	116.3	C6—C12—H12B	109.5
C3—C2—H2	116.3	H12A—C12—H12B	109.5
C2—C3—C4	121.61 (18)	C6—C12—H12C	109.5
C2—C3—C8	117.61 (18)	H12A—C12—H12C	109.5
C4—C3—C8	120.47 (18)	H12B—C12—H12C	109.5
O9—C4—O5	118.31 (18)	C18—C13—C14	118.3 (2)
O9—C4—C3	125.03 (18)	C18—C13—N1	118.03 (19)
O5—C4—C3	116.60 (17)	C14—C13—N1	123.7 (2)
C4—O5—C6	117.61 (16)	C13—C14—C15	120.6 (3)
O7—C6—O5	110.33 (17)	C13—C14—H14	119.7
O7—C6—C12	109.9 (2)	C15—C14—H14	119.7
O5—C6—C12	109.9 (2)	C16—C15—C14	121.3 (3)
O7—C6—C11	105.9 (2)	C16—C15—H15	119.4
O5—C6—C11	105.9 (2)	C14—C15—H15	119.4
C12—C6—C11	114.7 (2)	C15—C16—C17	118.6 (2)
C8—O7—C6	118.05 (16)	C15—C16—H16	120.7
O10'—C8—O7	126.3 (11)	C17—C16—H16	120.7
O10—C8—O7	114.0 (4)	C16—C17—C18	120.9 (3)
O10'—C8—C3	116.4 (9)	C16—C17—H17	119.6
O10—C8—C3	129.9 (4)	C18—C17—H17	119.6
O7—C8—C3	116.02 (19)	C13—C18—C17	120.4 (2)
C6—C11—H11A	109.5	C13—C18—H18	119.8
C6—C11—H11B	109.5	C17—C18—H18	119.8
H11A—C11—H11B	109.5
C13—N1—C2—C3	178.4 (2)	C6—O7—C8—C3	−21.5 (3)
N1—C2—C3—C4	3.7 (4)	C2—C3—C8—O10'	−15 (2)
N1—C2—C3—C8	177.4 (2)	C4—C3—C8—O10'	159.2 (19)
C2—C3—C4—O9	4.6 (4)	C2—C3—C8—O10	−0.6 (9)
C8—C3—C4—O9	−168.9 (2)	C4—C3—C8—O10	173.1 (8)
C2—C3—C4—O5	−178.34 (18)	C2—C3—C8—O7	177.79 (19)
C8—C3—C4—O5	8.2 (3)	C4—C3—C8—O7	−8.5 (3)
O9—C4—O5—C6	−160.9 (2)	C2—N1—C13—C18	−168.5 (3)
C3—C4—O5—C6	21.8 (3)	C2—N1—C13—C14	9.3 (4)
C4—O5—C6—O7	−49.6 (3)	C18—C13—C14—C15	−0.7 (5)
C4—O5—C6—C12	71.8 (3)	N1—C13—C14—C15	−178.6 (2)
C4—O5—C6—C11	−163.8 (2)	C13—C14—C15—C16	−0.7 (5)
O5—C6—O7—C8	49.5 (3)	C14—C15—C16—C17	1.6 (5)
C12—C6—O7—C8	−71.9 (2)	C15—C16—C17—C18	−1.3 (6)
C11—C6—O7—C8	163.6 (2)	C14—C13—C18—C17	1.0 (5)
C6—O7—C8—O10'	172 (2)	N1—C13—C18—C17	179.0 (3)
C6—O7—C8—O10	157.1 (7)	C16—C17—C18—C13	−0.1 (6)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O9	0.86	2.14	2.760 (2)	129
N1—H1···O9^i	0.86	2.46	3.259 (2)	155
C18—H18···O5^i	0.93	2.60	3.432 (3)	150
C18—H18···O9^i	0.93	2.44	3.288 (3)	151
C15—H15···O10^ii	0.93	2.45	3.310 (10)	154

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+2, −z+1.