5-[(3,4-Dimethoxy-benzyl)-aminomethyl-ene]-2,2-dimethyl-1,3-dioxane-4,6-dione.

The title compound, C(15)H(17)NO(6), is approximately planar, with dihedral angles of 3.11 (4) and 2.12 (4)° between the connecting amino-methyl-ene unit and the planar part of the dioxane ring, and between the dimethoxy-benzyl ring and the amino-methyl-ene group, respectively. The dioxane ring exhibits a half-boat conformation, in which the C atom between the dioxane O atoms is 0.5471 (8) Å out of the plane. The mol-ecule has an intra-molecular N-H⋯O hydrogen bond which may stabilize the planar conformation. In the crystal, weak inter-molecular C-H⋯O hydrogen-bonding contacts, result in the formation of sheets parallel to the ab plane.

Related literature

For the synthesis of related compounds, see: Cassis et al. (1985 ▶). For the synthesis of related anti­tumor precursors, see Ruchelman et al. (2003 ▶). For the structure of 5-(amino­methyl­ene)-2,2-dimethyl-1,3-dioxane-4,6-dione, see: da Silva et al. (2006 ▶). For Meldrum’s acid, see: Meldrum (1908 ▶).

Experimental

Crystal data

C15H17NO6

M = 307.30

Monoclinic,

a = 6.270 (4) Å

b = 12.486 (4) Å

c = 19.529 (5) Å

β = 106.31 (3)°

V = 1467.3 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 292 K

0.44 × 0.38 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: none

2852 measured reflections

2657 independent reflections

1675 reflections with I > 2σ(I)

R int = 0.008

3 standard reflections every 150 reflections intensity decay: 1.8%

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.160

S = 1.03

2657 reflections

207 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.21 e Å−3

Δρmin = −0.26 e Å−3

Data collection: DIFRAC (Gabe & White, 1993 ▶); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017413/si2171sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017413/si2171Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H17NO6	F(000) = 648
Mr = 307.30	Dx = 1.391 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.270 (4) Å	Cell parameters from 29 reflections
b = 12.486 (4) Å	θ = 4.4–7.7°
c = 19.529 (5) Å	µ = 0.11 mm−1
β = 106.31 (3)°	T = 292 K
V = 1467.3 (11) Å3	Block, yellow
Z = 4	0.44 × 0.38 × 0.18 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.008
Radiation source: fine-focus sealed tube	θmax = 25.4°, θmin = 2.0°
graphite	h = −7→7
ω/2θ scans	k = −15→0
2852 measured reflections	l = −23→8
2657 independent reflections	3 standard reflections every 150 reflections
1675 reflections with I > 2σ(I)	intensity decay: 1.8%

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)] = 0.056	Hydrogen site location: mixed
wR(F2) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0954P)2] where P = (Fo2 + 2Fc2)/3
2657 reflections	(Δ/σ)max < 0.001
207 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.26 e Å−3

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	0.0589 (3)	0.78796 (12)	0.14968 (8)	0.0456 (5)
O2	−0.0296 (3)	0.60397 (13)	0.13307 (9)	0.0489 (5)
O3	0.3798 (3)	0.84242 (14)	0.22145 (9)	0.0522 (5)
O4	0.2084 (3)	0.47579 (14)	0.18214 (10)	0.0623 (6)
O5	1.4467 (3)	0.80170 (14)	0.40934 (10)	0.0544 (5)
O6	1.5852 (3)	0.60587 (14)	0.42558 (9)	0.0503 (5)
N1	0.7059 (3)	0.69339 (19)	0.27469 (10)	0.0403 (5)
H1N	0.677 (4)	0.761 (2)	0.2721 (13)	0.046 (8)*
C1	−0.2969 (4)	0.7333 (2)	0.08019 (14)	0.0523 (7)
H1A	−0.3797	0.6767	0.0513	0.078*
H1B	−0.3242	0.7994	0.0540	0.078*
H1C	−0.3427	0.7404	0.1229	0.078*
C2	0.0406 (5)	0.7062 (3)	0.03595 (15)	0.0674 (9)
H2A	0.1966	0.6903	0.0517	0.101*
H2B	0.0187	0.7749	0.0131	0.101*
H2C	−0.0343	0.6523	0.0027	0.101*
C3	−0.0529 (4)	0.70753 (19)	0.09947 (12)	0.0411 (6)
C4	0.2670 (4)	0.7662 (2)	0.19222 (12)	0.0389 (6)
C5	0.3347 (4)	0.65633 (19)	0.20110 (11)	0.0374 (6)
C6	0.1782 (4)	0.5710 (2)	0.17241 (13)	0.0422 (6)
C7	0.5461 (4)	0.6272 (2)	0.24184 (12)	0.0398 (6)
H7	0.5778	0.5544	0.2464	0.048*
C8	0.9280 (4)	0.66471 (19)	0.31291 (11)	0.0374 (6)
C9	1.0729 (4)	0.74811 (19)	0.34299 (11)	0.0388 (6)
H9	1.0219	0.8184	0.3384	0.047*
C10	1.2914 (4)	0.72663 (18)	0.37956 (11)	0.0392 (6)
C11	1.3659 (4)	0.61937 (18)	0.38805 (11)	0.0370 (6)
C12	1.2204 (4)	0.5382 (2)	0.35779 (12)	0.0442 (6)
H12	1.2696	0.4676	0.3626	0.053*
C13	1.0014 (4)	0.5605 (2)	0.32015 (12)	0.0445 (6)
H13	0.9050	0.5051	0.3000	0.053*
C14	1.3812 (5)	0.9112 (2)	0.39922 (15)	0.0588 (8)
H14A	1.3307	0.9266	0.3491	0.088*
H14B	1.5056	0.9562	0.4212	0.088*
H14C	1.2631	0.9245	0.4205	0.088*
C15	1.6708 (4)	0.4995 (2)	0.43247 (14)	0.0535 (7)
H15A	1.5973	0.4577	0.4603	0.080*
H15B	1.8275	0.5012	0.4557	0.080*
H15C	1.6451	0.4681	0.3860	0.080*

	U11	U22	U33	U12	U13	U23
O1	0.0390 (10)	0.0379 (10)	0.0492 (10)	0.0012 (8)	−0.0054 (8)	−0.0002 (7)
O2	0.0380 (10)	0.0398 (10)	0.0585 (11)	−0.0059 (8)	−0.0036 (8)	0.0011 (8)
O3	0.0468 (11)	0.0371 (10)	0.0602 (11)	−0.0067 (8)	−0.0054 (9)	−0.0021 (8)
O4	0.0517 (12)	0.0318 (11)	0.0890 (14)	−0.0007 (8)	−0.0040 (10)	0.0002 (9)
O5	0.0456 (11)	0.0377 (10)	0.0634 (11)	−0.0014 (8)	−0.0120 (8)	−0.0020 (8)
O6	0.0388 (10)	0.0459 (11)	0.0550 (10)	0.0053 (8)	−0.0052 (8)	−0.0005 (8)
N1	0.0345 (12)	0.0390 (13)	0.0417 (11)	0.0005 (9)	0.0012 (9)	0.0041 (9)
C1	0.0384 (15)	0.0603 (18)	0.0493 (15)	−0.0006 (13)	−0.0025 (12)	0.0020 (13)
C2	0.0541 (18)	0.097 (2)	0.0504 (15)	−0.0023 (17)	0.0130 (13)	−0.0022 (16)
C3	0.0356 (13)	0.0432 (14)	0.0392 (12)	−0.0032 (11)	0.0017 (10)	0.0001 (11)
C4	0.0371 (13)	0.0408 (14)	0.0357 (12)	−0.0019 (11)	0.0050 (10)	0.0021 (10)
C5	0.0334 (13)	0.0383 (13)	0.0366 (12)	−0.0023 (10)	0.0034 (10)	0.0010 (10)
C6	0.0338 (14)	0.0417 (15)	0.0471 (14)	−0.0016 (11)	0.0045 (11)	−0.0025 (11)
C7	0.0364 (14)	0.0424 (14)	0.0382 (12)	−0.0001 (11)	0.0063 (11)	0.0013 (10)
C8	0.0329 (13)	0.0404 (14)	0.0346 (12)	0.0006 (11)	0.0024 (9)	0.0052 (10)
C9	0.0410 (14)	0.0334 (13)	0.0377 (12)	0.0042 (11)	0.0038 (10)	0.0017 (10)
C10	0.0413 (14)	0.0378 (14)	0.0329 (11)	−0.0028 (11)	0.0011 (10)	−0.0024 (10)
C11	0.0335 (13)	0.0419 (14)	0.0320 (11)	0.0059 (11)	0.0031 (10)	0.0034 (10)
C12	0.0432 (15)	0.0351 (14)	0.0492 (14)	0.0050 (11)	0.0045 (11)	0.0021 (11)
C13	0.0425 (15)	0.0371 (14)	0.0468 (14)	−0.0042 (11)	0.0011 (11)	0.0043 (11)
C14	0.0604 (18)	0.0389 (15)	0.0644 (17)	−0.0048 (13)	−0.0030 (14)	−0.0025 (13)
C15	0.0455 (16)	0.0508 (16)	0.0572 (15)	0.0149 (13)	0.0030 (12)	0.0028 (13)

O1—C4	1.363 (3)	C2—H2C	0.9600
O1—C3	1.441 (3)	C4—C5	1.432 (3)
O2—C6	1.376 (3)	C5—C7	1.389 (3)
O2—C3	1.439 (3)	C5—C6	1.450 (3)
O3—C4	1.227 (3)	C7—H7	0.9300
O4—C6	1.211 (3)	C8—C13	1.374 (4)
O5—C10	1.359 (3)	C8—C9	1.398 (3)
O5—C14	1.425 (3)	C9—C10	1.382 (3)
O6—C11	1.375 (3)	C9—H9	0.9300
O6—C15	1.424 (3)	C10—C11	1.413 (3)
N1—C7	1.318 (3)	C11—C12	1.380 (3)
N1—C8	1.428 (3)	C12—C13	1.392 (4)
N1—H1N	0.86 (3)	C12—H12	0.9300
C1—C3	1.504 (4)	C13—H13	0.9300
C1—H1A	0.9600	C14—H14A	0.9600
C1—H1B	0.9600	C14—H14B	0.9600
C1—H1C	0.9600	C14—H14C	0.9600
C2—C3	1.513 (4)	C15—H15A	0.9600
C2—H2A	0.9600	C15—H15B	0.9600
C2—H2B	0.9600	C15—H15C	0.9600
C4—O1—C3	118.37 (18)	N1—C7—C5	126.0 (2)
C6—O2—C3	118.82 (19)	N1—C7—H7	117.0
C10—O5—C14	117.26 (19)	C5—C7—H7	117.0
C11—O6—C15	117.28 (19)	C13—C8—C9	120.2 (2)
C7—N1—C8	126.4 (2)	C13—C8—N1	122.7 (2)
C7—N1—H1N	117.7 (17)	C9—C8—N1	117.1 (2)
C8—N1—H1N	115.9 (17)	C10—C9—C8	120.4 (2)
C3—C1—H1A	109.5	C10—C9—H9	119.8
C3—C1—H1B	109.5	C8—C9—H9	119.8
H1A—C1—H1B	109.5	O5—C10—C9	125.1 (2)
C3—C1—H1C	109.5	O5—C10—C11	115.5 (2)
H1A—C1—H1C	109.5	C9—C10—C11	119.5 (2)
H1B—C1—H1C	109.5	O6—C11—C12	125.4 (2)
C3—C2—H2A	109.5	O6—C11—C10	115.3 (2)
C3—C2—H2B	109.5	C12—C11—C10	119.3 (2)
H2A—C2—H2B	109.5	C11—C12—C13	121.0 (2)
C3—C2—H2C	109.5	C11—C12—H12	119.5
H2A—C2—H2C	109.5	C13—C12—H12	119.5
H2B—C2—H2C	109.5	C8—C13—C12	119.7 (2)
O2—C3—O1	110.38 (17)	C8—C13—H13	120.1
O2—C3—C1	105.8 (2)	C12—C13—H13	120.1
O1—C3—C1	106.7 (2)	O5—C14—H14A	109.5
O2—C3—C2	110.5 (2)	O5—C14—H14B	109.5
O1—C3—C2	109.8 (2)	H14A—C14—H14B	109.5
C1—C3—C2	113.5 (2)	O5—C14—H14C	109.5
O3—C4—O1	117.1 (2)	H14A—C14—H14C	109.5
O3—C4—C5	125.1 (2)	H14B—C14—H14C	109.5
O1—C4—C5	117.8 (2)	O6—C15—H15A	109.5
C7—C5—C4	121.5 (2)	O6—C15—H15B	109.5
C7—C5—C6	117.6 (2)	H15A—C15—H15B	109.5
C4—C5—C6	120.7 (2)	O6—C15—H15C	109.5
O4—C6—O2	117.6 (2)	H15A—C15—H15C	109.5
O4—C6—C5	127.0 (2)	H15B—C15—H15C	109.5
O2—C6—C5	115.4 (2)
C6—O2—C3—O1	−48.6 (3)	C6—C5—C7—N1	−176.7 (2)
C6—O2—C3—C1	−163.7 (2)	C7—N1—C8—C13	−0.4 (4)
C6—O2—C3—C2	73.1 (3)	C7—N1—C8—C9	179.0 (2)
C4—O1—C3—O2	45.3 (3)	C13—C8—C9—C10	0.7 (4)
C4—O1—C3—C1	159.8 (2)	N1—C8—C9—C10	−178.8 (2)
C4—O1—C3—C2	−76.8 (3)	C14—O5—C10—C9	−2.9 (4)
C3—O1—C4—O3	162.7 (2)	C14—O5—C10—C11	177.2 (2)
C3—O1—C4—C5	−19.1 (3)	C8—C9—C10—O5	178.4 (2)
O3—C4—C5—C7	−3.9 (4)	C8—C9—C10—C11	−1.7 (3)
O1—C4—C5—C7	178.1 (2)	C15—O6—C11—C12	1.5 (3)
O3—C4—C5—C6	171.1 (2)	C15—O6—C11—C10	−177.0 (2)
O1—C4—C5—C6	−6.9 (3)	O5—C10—C11—O6	0.3 (3)
C3—O2—C6—O4	−158.5 (2)	C9—C10—C11—O6	−179.6 (2)
C3—O2—C6—C5	24.7 (3)	O5—C10—C11—C12	−178.3 (2)
C7—C5—C6—O4	2.9 (4)	C9—C10—C11—C12	1.9 (4)
C4—C5—C6—O4	−172.3 (3)	O6—C11—C12—C13	−179.4 (2)
C7—C5—C6—O2	179.3 (2)	C10—C11—C12—C13	−1.0 (4)
C4—C5—C6—O2	4.2 (3)	C9—C8—C13—C12	0.2 (4)
C8—N1—C7—C5	−175.7 (2)	N1—C8—C13—C12	179.6 (2)
C4—C5—C7—N1	−1.6 (4)	C11—C12—C13—C8	0.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3	0.86 (3)	2.11 (3)	2.744 (3)	130 (2)
C9—H9···O4i	0.93	2.40	3.309 (4)	164
C15—H15C···O3ii	0.96	2.59	3.528 (4)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3	0.86 (3)	2.11 (3)	2.744 (3)	130 (2)
C9—H9⋯O4i	0.93	2.40	3.309 (4)	164
C15—H15C⋯O3ii	0.96	2.59	3.528 (4)	166

Symmetry codes: (i) ; (ii) .