Crystal structure of oryzalin.

The title compound, C12H18N4O6S (systematic name: 4-di-propyl-amino-3,5-di-nitro-benzene-sulfonamide), is a sulfonamide with herbicidal properties marketed as oryzalin. The dihedral angles between the benzene ring and the mean planes of the nitro groups are 26.15 (11) and 54.80 (9)°. The propyl arms of the di-propyl-amino substituent lie on opposite sides of this ring plane. In the crystal, N-H⋯O and C-H⋯O hydrogen bonds generate a three-dimensional network.

Related literature

For information on the toxicity and herbicidal properties of the title compound, see: Naqvi & Leung (1983 ▸). For related crystal structures, see: O’Connell & Maslen (1967 ▸); Tremayne et al. (2002 ▸).

Experimental

Crystal data

C12H18N4O6S

M = 346.36

Triclinic,

a = 7.6057 (2) Å

b = 8.2463 (2) Å

c = 12.8657 (2) Å

α = 73.901 (1)°

β = 86.059 (1)°

γ = 83.549 (1)°

V = 769.77 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.25 mm−1

T = 173 K

0.49 × 0.17 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.888, T max = 0.988

14199 measured reflections

3778 independent reflections

3506 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.090

S = 1.05

3778 reflections

218 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.42 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: DIAMOND (Brandenburg, 2010 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S205698901500955X/sj5462sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500955X/sj5462Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901500955X/sj5462Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S205698901500955X/sj5462fig1.tif

The asymmetric unit of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

Click here for additional data file.

a . DOI: 10.1107/S205698901500955X/sj5462fig2.tif

Crystal packing viewed along the a axis. The inter­molecular N—H⋯O and C—H⋯O hydrogen bonds are shown as dashed lines.

CCDC reference: 1401628

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H18N4O6S	Z = 2
Mr = 346.36	F(000) = 364
Triclinic, P1	Dx = 1.494 Mg m−3
a = 7.6057 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2463 (2) Å	Cell parameters from 9733 reflections
c = 12.8657 (2) Å	θ = 2.6–28.3°
α = 73.901 (1)°	µ = 0.25 mm−1
β = 86.059 (1)°	T = 173 K
γ = 83.549 (1)°	Block, red
V = 769.77 (3) Å3	0.49 × 0.17 × 0.05 mm

Bruker APEXII CCD diffractometer	3778 independent reflections
Radiation source: fine-focus sealed tube	3506 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→8
Tmin = 0.888, Tmax = 0.988	k = −10→10
14199 measured reflections	l = −17→17

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0441P)2 + 0.3414P] where P = (Fo2 + 2Fc2)/3
3778 reflections	(Δ/σ)max = 0.002
218 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.42 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
S1	0.29089 (4)	−0.28775 (4)	1.01726 (2)	0.02217 (9)
O6	0.21891 (13)	0.38350 (13)	0.79517 (9)	0.0345 (2)
O5	0.27982 (13)	0.32749 (13)	0.64100 (8)	0.0310 (2)
O4	0.94829 (12)	0.02295 (14)	0.76530 (8)	0.0328 (2)
O3	0.91096 (14)	−0.24191 (14)	0.83339 (10)	0.0413 (3)
O2	0.42149 (13)	−0.38814 (12)	1.09026 (7)	0.0293 (2)
O1	0.13725 (14)	−0.20406 (13)	1.05726 (8)	0.0337 (2)
N1	0.22714 (17)	−0.41143 (15)	0.95364 (10)	0.0268 (2)
N3	0.65122 (14)	0.20712 (13)	0.66209 (8)	0.0207 (2)
N4	0.29355 (13)	0.29708 (13)	0.73912 (9)	0.0221 (2)
N2	0.85394 (14)	−0.09134 (15)	0.80100 (8)	0.0252 (2)
C1	0.40261 (16)	−0.13002 (15)	0.92262 (9)	0.0209 (2)
C6	0.31660 (16)	0.03024 (15)	0.87675 (9)	0.0201 (2)
H6	0.2012	0.0621	0.9021	0.024*
C5	0.40260 (15)	0.14133 (14)	0.79389 (9)	0.0189 (2)
C4	0.57601 (15)	0.10563 (14)	0.75238 (9)	0.0184 (2)
C10	0.64961 (16)	0.39061 (15)	0.64526 (10)	0.0210 (2)
H10A	0.5757	0.4247	0.7035	0.025*
H10B	0.5958	0.4507	0.5753	0.025*
C11	0.83533 (18)	0.44270 (17)	0.64495 (12)	0.0298 (3)
H11A	0.8881	0.3855	0.7156	0.036*
H11B	0.9104	0.4062	0.5880	0.036*
C12	0.8312 (2)	0.63353 (19)	0.62429 (14)	0.0386 (3)
H12A	0.7900	0.6898	0.5514	0.058*
H12B	0.9506	0.6633	0.6304	0.058*
H12C	0.7506	0.6707	0.6778	0.058*
C7	0.74354 (17)	0.13316 (16)	0.57981 (10)	0.0235 (2)
H7A	0.7354	0.0092	0.6013	0.028*
H7B	0.8704	0.1524	0.5751	0.028*
C8	0.66410 (19)	0.21110 (18)	0.46926 (10)	0.0298 (3)
H8A	0.5335	0.2132	0.4772	0.036*
H8B	0.6939	0.3296	0.4412	0.036*
C9	0.7322 (2)	0.1124 (2)	0.38841 (12)	0.0384 (3)
H9A	0.8618	0.1057	0.3828	0.058*
H9B	0.6843	0.1703	0.3174	0.058*
H9C	0.6943	−0.0023	0.4130	0.058*
C3	0.66129 (15)	−0.05195 (15)	0.81163 (9)	0.0207 (2)
C2	0.57619 (16)	−0.16972 (16)	0.89134 (10)	0.0227 (2)
H2	0.6365	−0.2771	0.9244	0.027*
H2N	0.312 (3)	−0.469 (2)	0.9280 (15)	0.040 (5)*
H1N	0.145 (3)	−0.371 (3)	0.9149 (16)	0.044 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.02480 (16)	0.02270 (15)	0.01851 (14)	−0.00303 (11)	0.00036 (11)	−0.00479 (11)
O6	0.0289 (5)	0.0317 (5)	0.0472 (6)	0.0089 (4)	−0.0057 (4)	−0.0212 (5)
O5	0.0278 (5)	0.0336 (5)	0.0268 (5)	0.0022 (4)	−0.0057 (4)	−0.0013 (4)
O4	0.0195 (4)	0.0433 (6)	0.0375 (5)	−0.0035 (4)	0.0010 (4)	−0.0147 (4)
O3	0.0284 (5)	0.0378 (6)	0.0472 (6)	0.0141 (4)	−0.0041 (5)	−0.0002 (5)
O2	0.0337 (5)	0.0318 (5)	0.0202 (4)	−0.0041 (4)	−0.0062 (4)	−0.0021 (4)
O1	0.0338 (5)	0.0322 (5)	0.0332 (5)	−0.0025 (4)	0.0117 (4)	−0.0093 (4)
N1	0.0269 (6)	0.0247 (5)	0.0297 (6)	−0.0011 (5)	−0.0079 (5)	−0.0078 (4)
N3	0.0221 (5)	0.0188 (5)	0.0212 (5)	−0.0008 (4)	0.0033 (4)	−0.0067 (4)
N4	0.0164 (5)	0.0198 (5)	0.0300 (5)	−0.0005 (4)	−0.0028 (4)	−0.0065 (4)
N2	0.0197 (5)	0.0344 (6)	0.0208 (5)	0.0053 (4)	−0.0031 (4)	−0.0087 (4)
C1	0.0230 (6)	0.0219 (5)	0.0182 (5)	−0.0033 (4)	−0.0005 (4)	−0.0058 (4)
C6	0.0186 (5)	0.0225 (5)	0.0213 (5)	−0.0017 (4)	−0.0008 (4)	−0.0095 (4)
C5	0.0177 (5)	0.0185 (5)	0.0213 (5)	0.0006 (4)	−0.0036 (4)	−0.0068 (4)
C4	0.0181 (5)	0.0195 (5)	0.0190 (5)	−0.0011 (4)	−0.0022 (4)	−0.0075 (4)
C10	0.0220 (6)	0.0183 (5)	0.0232 (5)	−0.0013 (4)	−0.0008 (4)	−0.0069 (4)
C11	0.0233 (6)	0.0284 (6)	0.0372 (7)	−0.0062 (5)	−0.0001 (5)	−0.0069 (5)
C12	0.0386 (8)	0.0320 (7)	0.0487 (9)	−0.0143 (6)	−0.0012 (7)	−0.0127 (6)
C7	0.0244 (6)	0.0233 (6)	0.0229 (6)	0.0007 (5)	0.0038 (4)	−0.0090 (5)
C8	0.0343 (7)	0.0312 (7)	0.0231 (6)	0.0029 (6)	0.0011 (5)	−0.0088 (5)
C9	0.0531 (9)	0.0376 (8)	0.0278 (7)	−0.0050 (7)	0.0051 (6)	−0.0155 (6)
C3	0.0169 (5)	0.0247 (6)	0.0204 (5)	0.0023 (4)	−0.0015 (4)	−0.0077 (4)
C2	0.0238 (6)	0.0221 (5)	0.0207 (5)	0.0023 (5)	−0.0034 (4)	−0.0046 (4)

S1—O1	1.4282 (10)	C10—C11	1.5213 (17)
S1—O2	1.4375 (10)	C10—H10A	0.9900
S1—N1	1.6043 (12)	C10—H10B	0.9900
S1—C1	1.7675 (12)	C11—C12	1.519 (2)
O6—N4	1.2199 (14)	C11—H11A	0.9900
O5—N4	1.2264 (14)	C11—H11B	0.9900
O4—N2	1.2168 (16)	C12—H12A	0.9800
O3—N2	1.2330 (15)	C12—H12B	0.9800
N1—H2N	0.86 (2)	C12—H12C	0.9800
N1—H1N	0.81 (2)	C7—C8	1.5248 (18)
N3—C4	1.3617 (15)	C7—H7A	0.9900
N3—C7	1.4648 (14)	C7—H7B	0.9900
N3—C10	1.4666 (15)	C8—C9	1.5208 (19)
N4—C5	1.4741 (15)	C8—H8A	0.9900
N2—C3	1.4701 (15)	C8—H8B	0.9900
C1—C2	1.3838 (17)	C9—H9A	0.9800
C1—C6	1.3961 (17)	C9—H9B	0.9800
C6—C5	1.3786 (17)	C9—H9C	0.9800
C6—H6	0.9500	C3—C2	1.3826 (17)
C5—C4	1.4193 (16)	C2—H2	0.9500
C4—C3	1.4211 (16)
O1—S1—O2	120.49 (6)	C12—C11—C10	110.85 (11)
O1—S1—N1	108.20 (7)	C12—C11—H11A	109.5
O2—S1—N1	106.10 (6)	C10—C11—H11A	109.5
O1—S1—C1	107.20 (6)	C12—C11—H11B	109.5
O2—S1—C1	106.46 (6)	C10—C11—H11B	109.5
N1—S1—C1	107.83 (6)	H11A—C11—H11B	108.1
S1—N1—H2N	114.6 (13)	C11—C12—H12A	109.5
S1—N1—H1N	114.7 (14)	C11—C12—H12B	109.5
H2N—N1—H1N	116.7 (19)	H12A—C12—H12B	109.5
C4—N3—C7	120.12 (10)	C11—C12—H12C	109.5
C4—N3—C10	122.12 (10)	H12A—C12—H12C	109.5
C7—N3—C10	117.72 (10)	H12B—C12—H12C	109.5
O6—N4—O5	124.71 (11)	N3—C7—C8	111.23 (10)
O6—N4—C5	117.62 (10)	N3—C7—H7A	109.4
O5—N4—C5	117.63 (10)	C8—C7—H7A	109.4
O4—N2—O3	123.62 (11)	N3—C7—H7B	109.4
O4—N2—C3	119.83 (11)	C8—C7—H7B	109.4
O3—N2—C3	116.50 (11)	H7A—C7—H7B	108.0
C2—C1—C6	120.07 (11)	C9—C8—C7	111.89 (12)
C2—C1—S1	118.82 (9)	C9—C8—H8A	109.2
C6—C1—S1	121.07 (9)	C7—C8—H8A	109.2
C5—C6—C1	118.64 (11)	C9—C8—H8B	109.2
C5—C6—H6	120.7	C7—C8—H8B	109.2
C1—C6—H6	120.7	H8A—C8—H8B	107.9
C6—C5—C4	124.46 (11)	C8—C9—H9A	109.5
C6—C5—N4	115.18 (10)	C8—C9—H9B	109.5
C4—C5—N4	119.93 (10)	H9A—C9—H9B	109.5
N3—C4—C5	123.91 (10)	C8—C9—H9C	109.5
N3—C4—C3	122.89 (10)	H9A—C9—H9C	109.5
C5—C4—C3	113.13 (10)	H9B—C9—H9C	109.5
N3—C10—C11	111.69 (10)	C2—C3—C4	123.50 (11)
N3—C10—H10A	109.3	C2—C3—N2	114.89 (10)
C11—C10—H10A	109.3	C4—C3—N2	121.19 (11)
N3—C10—H10B	109.3	C3—C2—C1	119.54 (11)
C11—C10—H10B	109.3	C3—C2—H2	120.2
H10A—C10—H10B	107.9	C1—C2—H2	120.2
O1—S1—C1—C2	164.43 (10)	C6—C5—C4—C3	−5.59 (16)
O2—S1—C1—C2	34.23 (11)	N4—C5—C4—C3	−177.72 (10)
N1—S1—C1—C2	−79.27 (11)	C4—N3—C10—C11	114.40 (13)
O1—S1—C1—C6	−17.88 (12)	C7—N3—C10—C11	−63.22 (14)
O2—S1—C1—C6	−148.07 (10)	N3—C10—C11—C12	178.41 (11)
N1—S1—C1—C6	98.42 (11)	C4—N3—C7—C8	122.80 (12)
C2—C1—C6—C5	5.48 (17)	C10—N3—C7—C8	−59.53 (14)
S1—C1—C6—C5	−172.19 (9)	N3—C7—C8—C9	−168.42 (12)
C1—C6—C5—C4	−1.23 (17)	N3—C4—C3—C2	−168.24 (11)
C1—C6—C5—N4	171.23 (10)	C5—C4—C3—C2	8.86 (17)
O6—N4—C5—C6	54.74 (15)	N3—C4—C3—N2	19.50 (17)
O5—N4—C5—C6	−122.95 (12)	C5—C4—C3—N2	−163.40 (10)
O6—N4—C5—C4	−132.43 (12)	O4—N2—C3—C2	−153.30 (11)
O5—N4—C5—C4	49.88 (15)	O3—N2—C3—C2	24.18 (16)
C7—N3—C4—C5	−133.66 (12)	O4—N2—C3—C4	19.59 (17)
C10—N3—C4—C5	48.78 (16)	O3—N2—C3—C4	−162.93 (12)
C7—N3—C4—C3	43.12 (16)	C4—C3—C2—C1	−5.24 (18)
C10—N3—C4—C3	−134.44 (12)	N2—C3—C2—C1	167.46 (11)
C6—C5—C4—N3	171.47 (11)	C6—C1—C2—C3	−2.40 (18)
N4—C5—C4—N3	−0.66 (17)	S1—C1—C2—C3	175.32 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N···O6i	0.86 (2)	2.529 (19)	2.9956 (15)	114.9 (15)
N1—H2N···O2ii	0.86 (2)	2.26 (2)	3.0839 (16)	160.5 (17)
N1—H1N···O3iii	0.81 (2)	2.15 (2)	2.9474 (16)	170.0 (19)
C2—H2···N1ii	0.95	2.74	3.6843 (17)	171
C9—H9A···O4iv	0.98	2.69	3.3192 (18)	122
C10—H10A···O2v	0.99	2.59	3.4033 (15)	140
C12—H12C···O3vi	0.98	2.71	3.249 (2)	115
C12—H12A···O5vii	0.98	2.61	3.492 (2)	150

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H2NO6i	0.86(2)	2.529(19)	2.9956(15)	114.9(15)
N1H2NO2ii	0.86(2)	2.26(2)	3.0839(16)	160.5(17)
N1H1NO3iii	0.81(2)	2.15(2)	2.9474(16)	170.0(19)
C2H2N1ii	0.95	2.74	3.6843(17)	171
C9H9AO4iv	0.98	2.69	3.3192(18)	122
C10H10AO2v	0.99	2.59	3.4033(15)	140
C12H12CO3vi	0.98	2.71	3.249(2)	115
C12H12AO5vii	0.98	2.61	3.492(2)	150

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .