Methyl 2-(4-methoxy­pyrimidin-2-yl­carbamoyl­sulfamoyl)­benzoate

The title compound, C₁₄H₁₄N₄O₆S, has a basal plane which contains a urea group, a pyrimidine ring and the S atom. The overall conformation is V-shaped. There exists a pseudo-six-membered ring involving the pyrimidine ring and the urea moiety as a result of an intramolecular N—H...N hydrogen bond. The mol­ecules form dimers via an intermolecular N—H...N hydrogen bond and π–π interactions stabilize the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.056
• wR factor = 0.119
• Data-to-parameter ratio = 14.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Sulfonylureas are a successful class of herbicides used worldwide (Levitt, 1991). As part of a study devoted to understand the reaction mechanism of sulfonylureas, we have determined the crystal structures of a number of such compounds (Li et al., 1992, 1993, 1994, 1997; Jiang et al., 2000). We have also recently reported the structure of 1-(4-methoxypyrimidin-2-yl)-3-(2-nitrophenylsulfonyl)urea (Ma et al., 2003).

The title compound, (I), has a basal plane involving the pyrimidine ring, the urea group and the S atom, with a mean deviation of 0.02 Å. The phenyl ring is twisted out of the basal plane, with a dihedral angle of 82.6 (4)°. The orientation of the phenyl ring is defined by the torsion angles N1—S1—C7—C8 of −80.1 (2)° and C7—S1—N1—C1 of −64.0 (3)° (Table 1), hence the overall conformation of (I) is V-shaped. This is similar to the so-called conformer ε of the sulfonylureas, thromboxane synthase inhibitor (TXSI) and thromboxane receptor antagonist (TXRA), propossed by Michaux et al. (2001, 2002). The plane containing atoms C13, O5, O6 and C14 is inclined at 65.1 (5)° to the phenyl-ring plane, and at 17.7 (3)° to the basal plane. The presence of the intramolecular hydrogen bond N1—H1A···N3 means that atoms N3, C2, N2, C1, N1 and H1A form a pseudo-six-membered ring (Table 2), which results in the coplanarity of the pyrimidine ring and the urea moiety.

In the crystal, the molecules form dimers via N2—H2a···N4ⁱ intermolecular hydrogen bonds [Table 2, symmetry code: (i) 1 − x, 1 − y, −z]. Each dimer has π–π interactions between phenyl rings with a second dimer [distance 3.764 (3) Å], and π–π interactions between pyrimidine rings with a third dimer [distance 3.747 (4) Å], see Fig. 2. The crystal structure is stabilized by all of these intermolecular hydrogen bonds and the π–π-stacking interactions.

S2. Experimental

The title compound was synthesized by condensation of 2-methoxycarbonylbenzenesulfonyl isocyanate and 2-amino-4-methoxypyrimidine (Li et al., 1993). Single crystals suitable for crystallographic analysis were obtained by slow evaporation of a 1:1 methanol/acetone solution at room temperature over a period of 15 d.

S3. Refinement

All H atoms were placed at calculated positions and treated as riding atoms (C—H = 0.93–0.96 Å and N—H = 0.86 Å), with U_iso equal to 1.2 times of U_eq of the parent N or C atoms.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); 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.

Figures

	Fig. 1. The molecular structure of (I), showing all non-H atoms, with displacement ellipsoids at the 30% probability level.
	Fig. 2. Molecular packing diagram, showing the intermolecular hydrogen bonds (dashed lines) and π–π-stacking interactions.

(I)

Crystal data

C14H14N4O6S	Z = 2
Mr = 366.35	F(000) = 380
Triclinic, P1	Dx = 1.448 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.129 (2) Å	Cell parameters from 960 reflections
b = 7.529 (2) Å	θ = 2.8–21.6°
c = 16.371 (5) Å	µ = 0.23 mm^−1
α = 94.350 (5)°	T = 293 K
β = 101.426 (5)°	Prism, colourless
γ = 100.753 (5)°	0.36 × 0.32 × 0.20 mm
V = 840.3 (4) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	3413 independent reflections
Radiation source: fine-focus sealed tube	1931 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ and ω scans	θmax = 26.4°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→6
Tmin = 0.918, Tmax = 0.955	k = −9→9
4849 measured reflections	l = −18→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0327P)^2 + 0.2733P] where P = (Fo^2 + 2Fc^2)/3
3413 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

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
S1	0.22580 (13)	0.54385 (11)	0.31053 (5)	0.0454 (3)
N1	0.2280 (4)	0.4999 (3)	0.21079 (15)	0.0435 (7)
H1	0.1242	0.4363	0.1777	0.052*
N2	0.3720 (4)	0.4994 (3)	0.09462 (15)	0.0458 (7)
H2	0.4737	0.5389	0.0752	0.055*
N3	0.0552 (4)	0.3155 (3)	0.05916 (15)	0.0417 (6)
N4	0.2604 (4)	0.3600 (4)	−0.03992 (16)	0.0465 (7)
O1	0.0363 (3)	0.4544 (3)	0.31769 (13)	0.0564 (6)
O2	0.2894 (4)	0.7347 (3)	0.33491 (14)	0.0665 (7)
O3	0.5367 (3)	0.6614 (3)	0.21730 (14)	0.0683 (7)
O4	−0.2533 (3)	0.1355 (3)	0.01748 (15)	0.0618 (7)
O5	0.1109 (4)	0.0924 (3)	0.25425 (15)	0.0653 (7)
O6	0.0779 (3)	0.0551 (3)	0.38590 (14)	0.0588 (7)
C1	0.3894 (5)	0.5606 (4)	0.1778 (2)	0.0472 (8)
C2	0.2210 (4)	0.3859 (4)	0.03626 (19)	0.0386 (7)
C3	−0.0838 (5)	0.2107 (4)	−0.0001 (2)	0.0459 (8)
C4	−0.0599 (5)	0.1743 (4)	−0.0818 (2)	0.0548 (9)
H4	−0.1583	0.1008	−0.1230	0.066*
C5	0.1151 (5)	0.2523 (5)	−0.0978 (2)	0.0547 (9)
H5	0.1354	0.2299	−0.1517	0.066*
C6	−0.2818 (5)	0.1725 (5)	0.1016 (2)	0.0703 (11)
H6A	−0.1828	0.1338	0.1408	0.105*
H6B	−0.4085	0.1075	0.1055	0.105*
H6C	−0.2731	0.3007	0.1143	0.105*
C7	0.4021 (4)	0.4333 (4)	0.36434 (17)	0.0367 (7)
C8	0.3617 (4)	0.2466 (4)	0.37072 (17)	0.0373 (7)
C9	0.5049 (5)	0.1713 (4)	0.41629 (19)	0.0514 (9)
H9	0.4799	0.0474	0.4214	0.062*
C10	0.6854 (5)	0.2781 (5)	0.4545 (2)	0.0589 (10)
H10	0.7812	0.2252	0.4845	0.071*
C11	0.7240 (5)	0.4608 (5)	0.4484 (2)	0.0590 (10)
H11	0.8454	0.5321	0.4745	0.071*
C12	0.5824 (5)	0.5394 (5)	0.40337 (19)	0.0502 (9)
H12	0.6083	0.6638	0.3993	0.060*
C13	0.1691 (5)	0.1247 (4)	0.3287 (2)	0.0453 (8)
C14	−0.1069 (5)	−0.0704 (5)	0.3537 (3)	0.0858 (13)
H14A	−0.1900	−0.0147	0.3145	0.129*
H14B	−0.1688	−0.1008	0.3992	0.129*
H14C	−0.0845	−0.1791	0.3259	0.129*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0531 (6)	0.0419 (5)	0.0439 (5)	0.0115 (4)	0.0157 (4)	0.0042 (4)
N1	0.0395 (15)	0.0499 (16)	0.0370 (15)	0.0004 (12)	0.0068 (12)	0.0048 (12)
N2	0.0375 (15)	0.0580 (18)	0.0386 (16)	−0.0009 (13)	0.0107 (12)	0.0044 (13)
N3	0.0376 (15)	0.0460 (16)	0.0415 (15)	0.0067 (13)	0.0089 (13)	0.0090 (13)
N4	0.0473 (17)	0.0513 (17)	0.0400 (16)	0.0080 (13)	0.0099 (13)	0.0048 (13)
O1	0.0436 (14)	0.0711 (16)	0.0621 (15)	0.0155 (12)	0.0238 (12)	0.0122 (12)
O2	0.096 (2)	0.0394 (14)	0.0643 (16)	0.0166 (13)	0.0186 (14)	0.0002 (11)
O3	0.0566 (16)	0.0836 (19)	0.0486 (15)	−0.0205 (14)	0.0095 (13)	−0.0019 (13)
O4	0.0419 (14)	0.0736 (17)	0.0617 (16)	−0.0044 (12)	0.0062 (12)	0.0116 (13)
O5	0.0669 (17)	0.0620 (16)	0.0510 (15)	−0.0045 (13)	−0.0043 (13)	−0.0048 (12)
O6	0.0554 (15)	0.0471 (14)	0.0688 (16)	−0.0086 (11)	0.0203 (13)	0.0037 (12)
C1	0.047 (2)	0.048 (2)	0.046 (2)	0.0018 (17)	0.0119 (17)	0.0124 (16)
C2	0.0376 (19)	0.0378 (18)	0.0427 (19)	0.0111 (15)	0.0092 (15)	0.0090 (14)
C3	0.041 (2)	0.0404 (19)	0.056 (2)	0.0085 (16)	0.0066 (17)	0.0133 (16)
C4	0.054 (2)	0.052 (2)	0.048 (2)	0.0040 (18)	−0.0036 (18)	−0.0009 (17)
C5	0.061 (2)	0.057 (2)	0.044 (2)	0.0128 (19)	0.0068 (19)	0.0018 (17)
C6	0.049 (2)	0.084 (3)	0.080 (3)	0.007 (2)	0.023 (2)	0.019 (2)
C7	0.0402 (18)	0.0388 (18)	0.0305 (16)	0.0016 (14)	0.0128 (14)	0.0021 (13)
C8	0.0378 (18)	0.0396 (19)	0.0339 (16)	0.0060 (14)	0.0099 (14)	0.0002 (14)
C9	0.059 (2)	0.044 (2)	0.049 (2)	0.0112 (18)	0.0067 (18)	0.0024 (16)
C10	0.049 (2)	0.073 (3)	0.053 (2)	0.020 (2)	0.0018 (18)	0.0016 (19)
C11	0.036 (2)	0.071 (3)	0.060 (2)	−0.0038 (18)	0.0059 (18)	−0.0041 (19)
C12	0.047 (2)	0.050 (2)	0.050 (2)	−0.0037 (17)	0.0160 (17)	0.0018 (16)
C13	0.047 (2)	0.0336 (18)	0.051 (2)	0.0033 (15)	0.0053 (18)	−0.0004 (16)
C14	0.061 (3)	0.060 (3)	0.124 (4)	−0.021 (2)	0.030 (3)	−0.007 (2)

Geometric parameters (Å, º)

S1—O2	1.424 (2)	C4—C5	1.360 (4)
S1—O1	1.424 (2)	C4—H4	0.9300
S1—N1	1.645 (2)	C5—H5	0.9300
S1—C7	1.764 (3)	C6—H6A	0.9600
N1—C1	1.382 (4)	C6—H6B	0.9600
N1—H1	0.8600	C6—H6C	0.9600
N2—C1	1.378 (4)	C7—C12	1.383 (4)
N2—C2	1.388 (4)	C7—C8	1.398 (4)
N2—H2	0.8600	C8—C9	1.378 (4)
N3—C3	1.325 (4)	C8—C13	1.503 (4)
N3—C2	1.338 (4)	C9—C10	1.383 (4)
N4—C2	1.340 (4)	C9—H9	0.9300
N4—C5	1.346 (4)	C10—C11	1.367 (5)
O3—C1	1.207 (4)	C10—H10	0.9300
O4—C3	1.330 (4)	C11—C12	1.380 (5)
O4—C6	1.445 (4)	C11—H11	0.9300
O5—C13	1.197 (4)	C12—H12	0.9300
O6—C13	1.329 (4)	C14—H14A	0.9600
O6—C14	1.446 (4)	C14—H14B	0.9600
C3—C4	1.395 (4)	C14—H14C	0.9600
O2—S1—O1	119.87 (14)	O4—C6—H6B	109.5
O2—S1—N1	109.02 (13)	H6A—C6—H6B	109.5
O1—S1—N1	104.57 (13)	O4—C6—H6C	109.5
O2—S1—C7	108.33 (15)	H6A—C6—H6C	109.5
O1—S1—C7	109.24 (13)	H6B—C6—H6C	109.5
N1—S1—C7	104.77 (13)	C12—C7—C8	120.3 (3)
C1—N1—S1	122.9 (2)	C12—C7—S1	117.6 (2)
C1—N1—H1	118.6	C8—C7—S1	122.1 (2)
S1—N1—H1	118.6	C9—C8—C7	118.6 (3)
C1—N2—C2	132.0 (3)	C9—C8—C13	118.9 (3)
C1—N2—H2	114.0	C7—C8—C13	122.4 (3)
C2—N2—H2	114.0	C8—C9—C10	120.7 (3)
C3—N3—C2	116.2 (3)	C8—C9—H9	119.6
C2—N4—C5	114.9 (3)	C10—C9—H9	119.6
C3—O4—C6	118.6 (3)	C11—C10—C9	120.4 (3)
C13—O6—C14	115.8 (3)	C11—C10—H10	119.8
O3—C1—N2	120.8 (3)	C9—C10—H10	119.8
O3—C1—N1	123.8 (3)	C10—C11—C12	119.9 (3)
N2—C1—N1	115.4 (3)	C10—C11—H11	120.1
N3—C2—N4	126.6 (3)	C12—C11—H11	120.1
N3—C2—N2	119.5 (3)	C11—C12—C7	120.0 (3)
N4—C2—N2	113.9 (3)	C11—C12—H12	120.0
N3—C3—O4	120.0 (3)	C7—C12—H12	120.0
N3—C3—C4	122.3 (3)	O5—C13—O6	125.6 (3)
O4—C3—C4	117.6 (3)	O5—C13—C8	124.3 (3)
C5—C4—C3	116.3 (3)	O6—C13—C8	110.1 (3)
C5—C4—H4	121.8	O6—C14—H14A	109.5
C3—C4—H4	121.8	O6—C14—H14B	109.5
N4—C5—C4	123.5 (3)	H14A—C14—H14B	109.5
N4—C5—H5	118.2	O6—C14—H14C	109.5
C4—C5—H5	118.2	H14A—C14—H14C	109.5
O4—C6—H6A	109.5	H14B—C14—H14C	109.5
O2—S1—N1—C1	51.8 (3)	O1—S1—C7—C12	−146.2 (2)
O1—S1—N1—C1	−178.9 (2)	N1—S1—C7—C12	102.2 (2)
C7—S1—N1—C1	−64.0 (3)	O2—S1—C7—C8	163.6 (2)
C2—N2—C1—O3	−179.6 (3)	O1—S1—C7—C8	31.4 (3)
C2—N2—C1—N1	−0.2 (5)	N1—S1—C7—C8	−80.1 (2)
S1—N1—C1—O3	−5.6 (5)	C12—C7—C8—C9	−0.2 (4)
S1—N1—C1—N2	175.0 (2)	S1—C7—C8—C9	−177.8 (2)
C3—N3—C2—N4	−0.6 (4)	C12—C7—C8—C13	−179.2 (3)
C3—N3—C2—N2	179.0 (3)	S1—C7—C8—C13	3.2 (4)
C5—N4—C2—N3	0.4 (4)	C7—C8—C9—C10	−0.4 (4)
C5—N4—C2—N2	−179.2 (3)	C13—C8—C9—C10	178.7 (3)
C1—N2—C2—N3	−0.2 (5)	C8—C9—C10—C11	0.7 (5)
C1—N2—C2—N4	179.4 (3)	C9—C10—C11—C12	−0.4 (5)
C2—N3—C3—O4	−179.9 (3)	C10—C11—C12—C7	−0.2 (5)
C2—N3—C3—C4	0.3 (4)	C8—C7—C12—C11	0.5 (4)
C6—O4—C3—N3	0.7 (4)	S1—C7—C12—C11	178.2 (2)
C6—O4—C3—C4	−179.5 (3)	C14—O6—C13—O5	0.2 (5)
N3—C3—C4—C5	0.1 (5)	C14—O6—C13—C8	−177.8 (3)
O4—C3—C4—C5	−179.7 (3)	C9—C8—C13—O5	−113.4 (4)
C2—N4—C5—C4	0.1 (5)	C7—C8—C13—O5	65.6 (4)
C3—C4—C5—N4	−0.3 (5)	C9—C8—C13—O6	64.7 (3)
O2—S1—C7—C12	−14.0 (3)	C7—C8—C13—O6	−116.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3	0.86	2.01	2.690 (6)	136
N2—H2···N4^i	0.86	2.11	2.971 (7)	174

Symmetry code: (i) −x+1, −y+1, −z.