Methyl 2,6-bis-[(5-chloro-4,6-dimeth-oxy-pyrimidin-2-yl)-oxy]benzoate.

In the title compound, C(20)H(18)Cl(2)N(4)O(8), the two pyrimidine rings are inclined at dihedral angles of 66.68 (5) and 71.91 (6)° with respect to the central benzene ring. In the crystal structure, inter-molecular C-H⋯N hydrogen bonds link neighbouring mol-ecules into a ribbon-like structure along the b axis. The ribbons are inter-connected into a two-dimensional network parallel to the bc plane by short inter-molecular Cl⋯Cl [3.4427 (6) Å] and Cl⋯O [3.1420 (9) and 3.1750 (11) Å] inter-actions. The crystal structure is further stabilized by inter-molecular π-π inter-actions [centroid-centroid distance 3.4552 (8) Å] involving the pyrimidine rings.

Related literature

For general background to and applications of the title compound, see: Koichiro et al. (1988 ▶, 1998 ▶); He et al. (2007 ▶); Li et al. (2006 ▶); Gerorge (1983 ▶). For graph-set descriptions of hydrogen-bonded ring motifs, see: Bernstein et al. (1995 ▶). For a closely related structure, see: Li & Luo (2006 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C20H18Cl2N4O8

M = 513.28

Monoclinic,

a = 29.354 (3) Å

b = 8.0485 (8) Å

c = 22.5923 (19) Å

β = 123.014 (2)°

V = 4475.7 (7) Å3

Z = 8

Mo Kα radiation

μ = 0.35 mm−1

T = 100 K

0.58 × 0.31 × 0.16 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.825, T max = 0.948

22170 measured reflections

8040 independent reflections

6824 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.129

S = 1.08

8040 reflections

312 parameters

H-atom parameters constrained

Δρmax = 0.71 e Å−3

Δρmin = −0.55 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810024785/ci5115sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810024785/ci5115Isup2.hkl

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

C20H18Cl2N4O8	F(000) = 2112
Mr = 513.28	Dx = 1.523 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9948 reflections
a = 29.354 (3) Å	θ = 2.7–32.6°
b = 8.0485 (8) Å	µ = 0.35 mm−1
c = 22.5923 (19) Å	T = 100 K
β = 123.014 (2)°	Block, colourless
V = 4475.7 (7) Å3	0.58 × 0.31 × 0.16 mm
Z = 8

Bruker APEXII DUO CCD area-detector diffractometer	8040 independent reflections
Radiation source: fine-focus sealed tube	6824 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 32.6°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −44→43
Tmin = 0.825, Tmax = 0.948	k = −12→12
22170 measured reflections	l = −34→34

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0781P)2 + 1.9869P] where P = (Fo2 + 2Fc2)/3
8040 reflections	(Δ/σ)max = 0.001
312 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.55 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	0.307309 (11)	0.57598 (4)	0.096234 (18)	0.02454 (8)
Cl2	0.082300 (12)	0.91419 (4)	0.399331 (14)	0.01982 (8)
O1	0.11797 (3)	0.91625 (11)	0.04367 (4)	0.01529 (16)
O2	0.04987 (3)	0.57525 (11)	0.15715 (4)	0.01615 (16)
O3	0.28912 (4)	0.93539 (12)	0.08837 (5)	0.02288 (19)
O4	0.20796 (3)	0.42435 (11)	0.07368 (5)	0.01987 (17)
O5	0.16660 (4)	0.88991 (14)	0.18631 (5)	0.0263 (2)
O6	0.16179 (4)	0.62171 (15)	0.20959 (5)	0.0296 (2)
O7	0.07442 (4)	0.55550 (12)	0.37357 (4)	0.01848 (17)
O8	0.07019 (4)	1.06655 (11)	0.27317 (4)	0.01907 (17)
N1	0.20277 (4)	0.92889 (13)	0.06785 (5)	0.01634 (18)
N2	0.16079 (4)	0.66706 (13)	0.05757 (5)	0.01477 (17)
N3	0.06228 (4)	0.56256 (13)	0.26376 (5)	0.01535 (18)
N4	0.06122 (4)	0.82430 (13)	0.21320 (5)	0.01471 (17)
C1	0.24667 (4)	0.84915 (16)	0.07879 (6)	0.0167 (2)
C2	0.25047 (4)	0.67647 (16)	0.08112 (6)	0.0171 (2)
C3	0.20559 (4)	0.58939 (15)	0.07043 (5)	0.0152 (2)
C4	0.16281 (4)	0.83107 (15)	0.05732 (5)	0.01390 (19)
C5	0.07753 (4)	0.82779 (14)	0.04464 (5)	0.01343 (18)
C6	0.02637 (4)	0.83115 (16)	−0.01690 (5)	0.0172 (2)
H6A	0.0207	0.8867	−0.0565	0.021*
C7	−0.01650 (4)	0.75105 (17)	−0.01925 (6)	0.0206 (2)
H7A	−0.0510	0.7533	−0.0605	0.025*
C8	−0.00804 (4)	0.66766 (16)	0.03972 (6)	0.0179 (2)
H8A	−0.0366	0.6133	0.0382	0.022*
C9	0.04341 (4)	0.66658 (15)	0.10068 (5)	0.01393 (18)
C10	0.08739 (4)	0.74658 (14)	0.10524 (5)	0.01335 (18)
C11	0.05844 (4)	0.66055 (15)	0.21417 (5)	0.01376 (18)
C12	0.06937 (4)	0.64190 (16)	0.32011 (5)	0.01463 (19)
C13	0.07199 (4)	0.81463 (15)	0.32568 (5)	0.01496 (19)
C14	0.06775 (4)	0.90169 (15)	0.26965 (5)	0.01476 (19)
C15	0.28520 (6)	1.11370 (19)	0.08786 (9)	0.0296 (3)
H15A	0.3151	1.1619	0.0877	0.044*
H15B	0.2863	1.1497	0.1291	0.044*
H15C	0.2516	1.1484	0.0464	0.044*
C16	0.16177 (5)	0.33858 (18)	0.06581 (8)	0.0262 (3)
H16A	0.1695	0.2218	0.0735	0.039*
H16B	0.1306	0.3562	0.0190	0.039*
H16C	0.1545	0.3807	0.0997	0.039*
C17	0.14212 (4)	0.74193 (17)	0.17246 (6)	0.0187 (2)
C18	0.22073 (7)	0.8981 (3)	0.24900 (9)	0.0473 (5)
H18A	0.2353	1.0076	0.2534	0.071*
H18B	0.2435	0.8182	0.2456	0.071*
H18C	0.2194	0.8740	0.2897	0.071*
C19	0.07186 (6)	0.37652 (18)	0.36714 (6)	0.0226 (2)
H19A	0.0735	0.3285	0.4072	0.034*
H19B	0.1019	0.3373	0.3653	0.034*
H19C	0.0384	0.3449	0.3247	0.034*
C20	0.07386 (7)	1.15252 (18)	0.21994 (7)	0.0286 (3)
H20A	0.0771	1.2698	0.2292	0.043*
H20B	0.0418	1.1311	0.1743	0.043*
H20C	0.1052	1.1140	0.2209	0.043*

	U11	U22	U33	U12	U13	U23
Cl1	0.01660 (12)	0.02313 (16)	0.03475 (16)	0.00517 (10)	0.01454 (11)	0.00213 (12)
Cl2	0.02636 (14)	0.02056 (15)	0.01647 (12)	−0.00313 (10)	0.01420 (10)	−0.00502 (9)
O1	0.0144 (3)	0.0143 (4)	0.0208 (3)	0.0030 (3)	0.0119 (3)	0.0037 (3)
O2	0.0246 (4)	0.0139 (4)	0.0150 (3)	−0.0023 (3)	0.0141 (3)	−0.0023 (3)
O3	0.0179 (4)	0.0186 (4)	0.0352 (5)	0.0000 (3)	0.0164 (3)	0.0014 (4)
O4	0.0170 (3)	0.0131 (4)	0.0280 (4)	0.0012 (3)	0.0113 (3)	−0.0011 (3)
O5	0.0220 (4)	0.0305 (5)	0.0185 (4)	−0.0102 (4)	0.0060 (3)	−0.0027 (4)
O6	0.0222 (4)	0.0338 (6)	0.0234 (4)	0.0043 (4)	0.0064 (3)	0.0104 (4)
O7	0.0266 (4)	0.0176 (4)	0.0158 (3)	−0.0012 (3)	0.0144 (3)	0.0008 (3)
O8	0.0267 (4)	0.0131 (4)	0.0175 (3)	0.0004 (3)	0.0121 (3)	−0.0015 (3)
N1	0.0160 (4)	0.0151 (5)	0.0205 (4)	0.0010 (3)	0.0116 (3)	0.0012 (3)
N2	0.0148 (4)	0.0142 (4)	0.0162 (3)	0.0020 (3)	0.0090 (3)	0.0003 (3)
N3	0.0185 (4)	0.0154 (5)	0.0155 (4)	−0.0007 (3)	0.0114 (3)	−0.0009 (3)
N4	0.0179 (4)	0.0139 (4)	0.0139 (3)	0.0006 (3)	0.0097 (3)	−0.0008 (3)
C1	0.0146 (4)	0.0176 (5)	0.0190 (4)	−0.0001 (4)	0.0100 (3)	0.0005 (4)
C2	0.0141 (4)	0.0174 (5)	0.0206 (4)	0.0033 (4)	0.0100 (3)	0.0008 (4)
C3	0.0153 (4)	0.0142 (5)	0.0156 (4)	0.0023 (4)	0.0081 (3)	0.0002 (4)
C4	0.0135 (4)	0.0156 (5)	0.0140 (4)	0.0023 (4)	0.0083 (3)	0.0011 (4)
C5	0.0142 (4)	0.0135 (5)	0.0155 (4)	0.0013 (4)	0.0100 (3)	−0.0001 (4)
C6	0.0165 (4)	0.0212 (6)	0.0144 (4)	0.0016 (4)	0.0088 (3)	0.0019 (4)
C7	0.0154 (4)	0.0270 (7)	0.0167 (4)	−0.0003 (4)	0.0071 (3)	0.0010 (4)
C8	0.0162 (4)	0.0211 (6)	0.0182 (4)	−0.0024 (4)	0.0105 (4)	−0.0020 (4)
C9	0.0178 (4)	0.0133 (5)	0.0137 (4)	−0.0001 (4)	0.0105 (3)	−0.0011 (4)
C10	0.0144 (4)	0.0136 (5)	0.0130 (4)	0.0007 (3)	0.0081 (3)	−0.0009 (3)
C11	0.0146 (4)	0.0154 (5)	0.0136 (4)	−0.0007 (4)	0.0092 (3)	−0.0020 (4)
C12	0.0146 (4)	0.0177 (5)	0.0135 (4)	−0.0005 (4)	0.0089 (3)	0.0000 (4)
C13	0.0171 (4)	0.0161 (5)	0.0139 (4)	−0.0004 (4)	0.0099 (3)	−0.0025 (4)
C14	0.0153 (4)	0.0142 (5)	0.0149 (4)	0.0006 (4)	0.0083 (3)	−0.0013 (4)
C15	0.0243 (6)	0.0186 (6)	0.0490 (8)	−0.0024 (5)	0.0220 (6)	0.0008 (6)
C16	0.0207 (5)	0.0153 (6)	0.0407 (7)	−0.0013 (4)	0.0155 (5)	−0.0015 (5)
C17	0.0161 (4)	0.0242 (6)	0.0156 (4)	−0.0012 (4)	0.0085 (3)	0.0002 (4)
C18	0.0290 (7)	0.0602 (13)	0.0281 (7)	−0.0201 (8)	−0.0003 (6)	−0.0017 (7)
C19	0.0323 (6)	0.0183 (6)	0.0214 (5)	−0.0017 (5)	0.0173 (4)	0.0016 (5)
C20	0.0497 (8)	0.0162 (6)	0.0220 (5)	0.0018 (6)	0.0209 (5)	0.0020 (5)

Cl1—C2	1.7126 (11)	C5—C6	1.3834 (14)
Cl2—C13	1.7187 (11)	C5—C10	1.3978 (14)
O1—C4	1.3621 (12)	C6—C7	1.3889 (16)
O1—C5	1.3944 (13)	C6—H6A	0.93
O2—C11	1.3569 (12)	C7—C8	1.3881 (16)
O2—C9	1.3929 (13)	C7—H7A	0.93
O3—C1	1.3370 (14)	C8—C9	1.3824 (14)
O3—C15	1.4393 (18)	C8—H8A	0.93
O4—C3	1.3301 (14)	C9—C10	1.3952 (14)
O4—C16	1.4436 (15)	C10—C17	1.4934 (15)
O5—C17	1.3370 (16)	C12—C13	1.3943 (17)
O5—C18	1.4432 (17)	C13—C14	1.3918 (15)
O6—C17	1.2023 (16)	C15—H15A	0.96
O7—C12	1.3301 (13)	C15—H15B	0.96
O7—C19	1.4457 (16)	C15—H15C	0.96
O8—C14	1.3288 (14)	C16—H16A	0.96
O8—C20	1.4415 (15)	C16—H16B	0.96
N1—C4	1.3224 (14)	C16—H16C	0.96
N1—C1	1.3365 (14)	C18—H18A	0.96
N2—C4	1.3215 (16)	C18—H18B	0.96
N2—C3	1.3372 (14)	C18—H18C	0.96
N3—C11	1.3238 (14)	C19—H19A	0.96
N3—C12	1.3353 (13)	C19—H19B	0.96
N4—C11	1.3214 (16)	C19—H19C	0.96
N4—C14	1.3360 (13)	C20—H20A	0.96
C1—C2	1.3930 (18)	C20—H20B	0.96
C2—C3	1.3923 (15)	C20—H20C	0.96
C4—O1—C5	117.72 (9)	N3—C11—O2	112.86 (10)
C11—O2—C9	117.70 (9)	O7—C12—N3	119.87 (11)
C1—O3—C15	116.92 (10)	O7—C12—C13	117.78 (9)
C3—O4—C16	116.97 (9)	N3—C12—C13	122.35 (10)
C17—O5—C18	115.74 (13)	C14—C13—C12	116.54 (9)
C12—O7—C19	117.10 (9)	C14—C13—Cl2	121.81 (9)
C14—O8—C20	117.10 (9)	C12—C13—Cl2	121.61 (8)
C4—N1—C1	114.76 (11)	O8—C14—N4	119.85 (10)
C4—N2—C3	115.27 (9)	O8—C14—C13	118.24 (10)
C11—N3—C12	114.78 (10)	N4—C14—C13	121.92 (11)
C11—N4—C14	115.29 (9)	O3—C15—H15A	109.5
N1—C1—O3	120.02 (11)	O3—C15—H15B	109.5
N1—C1—C2	122.37 (10)	H15A—C15—H15B	109.5
O3—C1—C2	117.60 (10)	O3—C15—H15C	109.5
C3—C2—C1	116.54 (10)	H15A—C15—H15C	109.5
C3—C2—Cl1	121.59 (10)	H15B—C15—H15C	109.5
C1—C2—Cl1	121.87 (9)	O4—C16—H16A	109.5
O4—C3—N2	119.63 (10)	O4—C16—H16B	109.5
O4—C3—C2	118.50 (10)	H16A—C16—H16B	109.5
N2—C3—C2	121.87 (11)	O4—C16—H16C	109.5
N2—C4—N1	129.15 (10)	H16A—C16—H16C	109.5
N2—C4—O1	117.63 (9)	H16B—C16—H16C	109.5
N1—C4—O1	113.22 (10)	O6—C17—O5	124.13 (11)
C6—C5—O1	116.19 (9)	O6—C17—C10	124.84 (12)
C6—C5—C10	121.70 (9)	O5—C17—C10	111.03 (10)
O1—C5—C10	122.04 (9)	O5—C18—H18A	109.5
C5—C6—C7	119.62 (10)	O5—C18—H18B	109.5
C5—C6—H6A	120.2	H18A—C18—H18B	109.5
C7—C6—H6A	120.2	O5—C18—H18C	109.5
C8—C7—C6	120.21 (10)	H18A—C18—H18C	109.5
C8—C7—H7A	119.9	H18B—C18—H18C	109.5
C6—C7—H7A	119.9	O7—C19—H19A	109.5
C9—C8—C7	119.10 (10)	O7—C19—H19B	109.5
C9—C8—H8A	120.4	H19A—C19—H19B	109.5
C7—C8—H8A	120.4	O7—C19—H19C	109.5
C8—C9—O2	116.45 (9)	H19A—C19—H19C	109.5
C8—C9—C10	122.36 (10)	H19B—C19—H19C	109.5
O2—C9—C10	121.14 (9)	O8—C20—H20A	109.5
C9—C10—C5	117.01 (9)	O8—C20—H20B	109.5
C9—C10—C17	120.20 (9)	H20A—C20—H20B	109.5
C5—C10—C17	122.79 (9)	O8—C20—H20C	109.5
N4—C11—N3	129.10 (10)	H20A—C20—H20C	109.5
N4—C11—O2	118.04 (9)	H20B—C20—H20C	109.5
C4—N1—C1—O3	178.40 (10)	C8—C9—C10—C17	179.84 (11)
C4—N1—C1—C2	−1.96 (15)	O2—C9—C10—C17	−2.78 (16)
C15—O3—C1—N1	1.42 (16)	C6—C5—C10—C9	0.94 (16)
C15—O3—C1—C2	−178.24 (11)	O1—C5—C10—C9	177.93 (10)
N1—C1—C2—C3	0.85 (16)	C6—C5—C10—C17	−179.62 (11)
O3—C1—C2—C3	−179.50 (10)	O1—C5—C10—C17	−2.62 (17)
N1—C1—C2—Cl1	−179.21 (8)	C14—N4—C11—N3	−1.47 (16)
O3—C1—C2—Cl1	0.44 (15)	C14—N4—C11—O2	177.68 (9)
C16—O4—C3—N2	−2.55 (15)	C12—N3—C11—N4	0.79 (16)
C16—O4—C3—C2	177.03 (10)	C12—N3—C11—O2	−178.39 (9)
C4—N2—C3—O4	178.15 (10)	C9—O2—C11—N4	−1.34 (13)
C4—N2—C3—C2	−1.42 (14)	C9—O2—C11—N3	177.94 (9)
C1—C2—C3—O4	−178.62 (10)	C19—O7—C12—N3	0.01 (14)
Cl1—C2—C3—O4	1.43 (14)	C19—O7—C12—C13	−179.72 (10)
C1—C2—C3—N2	0.95 (15)	C11—N3—C12—O7	−179.16 (9)
Cl1—C2—C3—N2	−178.99 (8)	C11—N3—C12—C13	0.55 (14)
C3—N2—C4—N1	0.15 (16)	O7—C12—C13—C14	178.67 (9)
C3—N2—C4—O1	179.26 (9)	N3—C12—C13—C14	−1.04 (15)
C1—N1—C4—N2	1.52 (16)	O7—C12—C13—Cl2	0.85 (14)
C1—N1—C4—O1	−177.62 (9)	N3—C12—C13—Cl2	−178.87 (8)
C5—O1—C4—N2	12.29 (13)	C20—O8—C14—N4	−9.19 (15)
C5—O1—C4—N1	−168.46 (9)	C20—O8—C14—C13	170.99 (11)
C4—O1—C5—C6	−121.76 (11)	C11—N4—C14—O8	−179.01 (10)
C4—O1—C5—C10	61.09 (13)	C11—N4—C14—C13	0.81 (14)
O1—C5—C6—C7	−177.67 (11)	C12—C13—C14—O8	−179.86 (10)
C10—C5—C6—C7	−0.51 (18)	Cl2—C13—C14—O8	−2.04 (14)
C5—C6—C7—C8	−0.20 (19)	C12—C13—C14—N4	0.31 (15)
C6—C7—C8—C9	0.43 (19)	Cl2—C13—C14—N4	178.14 (8)
C7—C8—C9—O2	−177.46 (11)	C18—O5—C17—O6	2.3 (2)
C7—C8—C9—C10	0.03 (18)	C18—O5—C17—C10	−177.92 (13)
C11—O2—C9—C8	−110.10 (11)	C9—C10—C17—O6	41.16 (17)
C11—O2—C9—C10	72.38 (13)	C5—C10—C17—O6	−138.26 (13)
C8—C9—C10—C5	−0.70 (16)	C9—C10—C17—O5	−138.63 (11)
O2—C9—C10—C5	176.68 (10)	C5—C10—C17—O5	41.94 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···N1i	0.96	2.58	3.5018 (19)	161
C20—H20A···N3ii	0.96	2.59	3.5148 (19)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16A⋯N1i	0.96	2.58	3.5018 (19)	161
C20—H20A⋯N3ii	0.96	2.59	3.5148 (19)	161

Symmetry codes: (i) ; (ii) .