2,4-Dinitrophenyl 3-nitrobenzenesulfonate

In the title mol­ecule, C₁₂H₇N₃O₉S, there are weak C-H...O interactions which generate rings of motifs S(5), R₁²(8) and R₁²(4).

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.059
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O8     ..  N1       =       2.82 Ang.

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   N1       =       6.79 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O8     -   N3       =       5.12 su
PLAT350_ALERT_3_C Short   C-H Bond (0.96A)   C8     -   H8       =       0.81 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O4     ..  C8       =       3.01 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.11
           From the CIF: _reflns_number_total               2952
           Count of symmetry unique reflns         1644
           Completeness (_total/calc)            179.56%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1308
           Fraction of Friedel pairs measured     0.796
           Are heavy atom types Z>Si present          yes

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Aromatic sulfonates are used in monitoring the merging of lipids (Yachi et al., 1989) and in many other fields (Spungin et al., 1992; Tharakan et al., 1992; Alford et al., 1991; Jiang et al., 1990; Narayanan & Krakow, 1983). The molecular and crystal structures of 3-nitrobenzenesulfonyl chloride have been recently reported (Vembu Nallu Spencer & Howard, 2003c). An X-ray study of the title compound, (I), was undertaken in view of the biological importance of its analogues and also to compare its structural parameters with those of its precursor, 3-nitrobenzenesulfonyl chloride.

The molecular structure of (I) is shown in Fig. 1 and selected geometric parameters are given in Table 1. Atoms N1, O1 and O2 deviate from the mean plane formed by atoms C1—C6 by 0.005 (3), −0.248 (4) and 0.267 (4) Å, respectively. Atoms N2, O6, O7, N3, O8 and O9 deviate from the mean plane formed by atoms C7—C12 by 0.069 (3), −0.849 (3), 1.051 (3), 0.026 (3), 0.341 (4) and −0.277 (4) Å, respectively. The dihedral angle between the above-mentioned planes is 36.10 (7)°. This shows their non-coplanar orientation, similar to that reported for some aromatic sulfonates (Vembu Nallu Garrison & Youngs, 2003b-e; Vembu Nallu Spencer & Howard, 2003a,b,d,e), and in contrast with the near-coplanar orientation found in 2,4-dinitrophenyl 4-toluenesulfonate (Vembu Nallu Garrison & Youngs, 2003a) and 4-methoxyphenyl 4-toluenesulfonate (Vembu et al., 2003).

The crystal structure of (I) is stabilized by weak C—H···O interactions (Table 2). The range of H···O distances found in (I) agrees with that found for weak C—H···O bonds (Desiraju & Steiner, 1999). As shown in Fig. 2, each C2—H2···O1, C4—H4···O3, C6—H6···O2, C6—H6···O4, C9—H9···O8 and C11—H11···O9 interaction generates an S(5) graph-set motif (Bernstein et al., 1995; Etter, 1990). The C6—H6···O2 and C6—H6···O4 interactions constitute a pair of bifurcated donor bonds. As can be seen in Fig. 3, the C3—H3···O3ⁱⁱ and C3—H3···O6ⁱⁱ interactions constitute a pair of bifurcated donor bonds generating an R₁²(8) motif. The C6—H6···N3^iv, C6—H6···O8^iv and C6—H6···O9^iv interactions together constitute a set of trifurcated donor bonds. The C6—H6···O8^iv and C6—H6···O9^iv interactions generate a symmetrical three-centred hydrogen-bonded chelate motif of graph set R₁²(4). There are several other weak C—H···O interactions which contribute to the supramolecular aggregation of (I) (Table 2). Other short intermolecular contacts are C9···O9(1 − x, 1 − y, z − 1/2) 3.130 (3) Å, N1···O8(1 − x, 2 − y, z − 1/2) 2.818 (2) Å and N1···O7(x, y, z − 1) 3.037 (2) Å. A view of the molecular packing down the b axis is shown in Fig. 4.

S2. Experimental

2,4-Dinitrophenol (5 mmol) and triethylamine (5 mmol) were dissolved in acetone (20 ml). To this solution, 3-nitrobenzenesulfonyl chloride (5 mmol) in acetone (20 ml) was added. The resulting solution was allowed to evaporate. The residue was washed several times with aqueous triethylamine solution. The crude product of the title compound, (I), was recrystallized from a 1:1 mixture of petroleum ether and ethanol.

S3. Refinement

All H atoms were located from difference Fourier maps and their positional parameters were refined, with U_iso = 1.2U_eq(parent atom). The C—H bond lengths are in the range 0.81 (2)–0.97 (2) Å.

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids.
	Fig. 2. Diagram showing hydrogen bonds 1–3, 5 and 6 (the numbers correspond to the sequence of entries in Table 2).
	Fig. 3. Diagram showing hydrogen bonds 7–18 (the numbers correspond to the sequence of entries in Table 2). Symmetry codes are as in Table 2.
	Fig. 4. Packing of the molecules in the unit cell of (I), viewed along the b axis, showing the network of hydrogen bonds.

2,4-Dinitrophenyl 3-nitrobenzenesulfonate

Crystal data

C12H7N3O9S	Dx = 1.732 Mg m^−3
Mr = 369.27	Melting point = 377–379 K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 3073 reflections
a = 27.730 (2) Å	θ = 2.4–27.1°
b = 4.7374 (3) Å	µ = 0.29 mm^−1
c = 10.7800 (8) Å	T = 120 K
V = 1416.16 (17) Å^3	Block, colourless
Z = 4	0.28 × 0.25 × 0.11 mm
F(000) = 752

Data collection

Bruker SMART CCD 6K area-detector diffractometer	2619 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 27.1°, θmin = 2.9°
Detector resolution: 8 pixels mm^-1	h = −35→27
ω scans	k = −6→5
8989 measured reflections	l = −13→12
2952 independent reflections

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)] = 0.030	Only H-atom coordinates refined
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0274P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.001
2952 reflections	Δρmax = 0.34 e Å^−3
247 parameters	Δρmin = −0.33 e Å^−3
1 restraint	Absolute structure: (Flack, 1983); 1310 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (6)

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
C1	0.63940 (7)	0.8435 (4)	0.11796 (18)	0.0177 (4)
C2	0.67868 (8)	1.0065 (4)	0.0840 (2)	0.0219 (5)
H2	0.6760 (7)	1.124 (5)	0.013 (2)	0.026*
C3	0.71927 (8)	1.0039 (5)	0.1583 (2)	0.0242 (5)
H3	0.7474 (9)	1.113 (4)	0.134 (2)	0.029*
C4	0.72028 (7)	0.8437 (4)	0.2661 (2)	0.0194 (4)
H4	0.7483 (9)	0.842 (4)	0.315 (2)	0.023*
C5	0.67987 (7)	0.6855 (4)	0.29759 (19)	0.0146 (4)
C6	0.63895 (8)	0.6804 (4)	0.22407 (19)	0.0175 (4)
H6	0.6131 (8)	0.564 (4)	0.250 (2)	0.021*
C7	0.61813 (7)	0.6853 (4)	0.58859 (19)	0.0154 (4)
C8	0.58006 (8)	0.8235 (4)	0.5321 (2)	0.0179 (4)
H8	0.5841 (7)	0.913 (4)	0.469 (2)	0.021*
C9	0.53528 (8)	0.8283 (4)	0.5895 (2)	0.0188 (5)
H9	0.5118 (8)	0.909 (4)	0.551 (2)	0.023*
C10	0.52982 (7)	0.6906 (4)	0.70080 (19)	0.0166 (4)
C11	0.56676 (7)	0.5508 (4)	0.7602 (2)	0.0181 (4)
H11	0.5631 (8)	0.453 (4)	0.831 (2)	0.022*
C12	0.61079 (7)	0.5526 (4)	0.70134 (18)	0.0155 (4)
S1	0.680852 (17)	0.47848 (9)	0.43241 (5)	0.01655 (11)
N1	0.59615 (6)	0.8425 (4)	0.03865 (17)	0.0234 (4)
N2	0.65165 (6)	0.4156 (4)	0.76543 (17)	0.0200 (4)
N3	0.48240 (6)	0.6976 (4)	0.76390 (18)	0.0238 (4)
O1	0.59276 (5)	1.0242 (3)	−0.04173 (15)	0.0303 (4)
O2	0.56581 (5)	0.6588 (4)	0.05693 (15)	0.0279 (4)
O3	0.72932 (5)	0.4132 (3)	0.46165 (14)	0.0247 (4)
O4	0.64466 (5)	0.2683 (3)	0.42225 (15)	0.0211 (3)
O5	0.66457 (5)	0.6961 (3)	0.54078 (13)	0.0179 (3)
O6	0.67106 (6)	0.2177 (3)	0.71487 (15)	0.0339 (4)
O7	0.66216 (6)	0.5114 (3)	0.86734 (14)	0.0299 (4)
O8	0.45300 (5)	0.8714 (3)	0.72981 (15)	0.0321 (4)
O9	0.47545 (6)	0.5267 (4)	0.84620 (17)	0.0437 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0152 (11)	0.0196 (11)	0.0182 (11)	0.0031 (9)	−0.0017 (8)	−0.0035 (8)
C2	0.0258 (12)	0.0228 (11)	0.0170 (11)	0.0027 (10)	0.0024 (9)	0.0049 (9)
C3	0.0216 (12)	0.0256 (12)	0.0255 (12)	−0.0049 (10)	0.0046 (9)	0.0056 (10)
C4	0.0159 (11)	0.0235 (11)	0.0189 (11)	−0.0006 (9)	0.0020 (9)	0.0021 (10)
C5	0.0151 (10)	0.0144 (10)	0.0142 (10)	0.0048 (9)	0.0024 (8)	0.0031 (8)
C6	0.0178 (10)	0.0152 (10)	0.0194 (12)	0.0017 (9)	0.0024 (9)	−0.0006 (8)
C7	0.0152 (10)	0.0149 (10)	0.0160 (11)	−0.0028 (8)	0.0035 (8)	−0.0025 (8)
C8	0.0221 (11)	0.0182 (11)	0.0133 (11)	−0.0030 (9)	−0.0007 (9)	0.0055 (8)
C9	0.0163 (11)	0.0203 (11)	0.0197 (11)	0.0007 (9)	−0.0049 (8)	0.0009 (9)
C10	0.0125 (10)	0.0209 (11)	0.0164 (11)	−0.0009 (8)	−0.0004 (8)	−0.0015 (8)
C11	0.0194 (11)	0.0215 (11)	0.0134 (11)	−0.0022 (9)	0.0007 (9)	0.0019 (9)
C12	0.0146 (10)	0.0169 (10)	0.0150 (11)	0.0014 (8)	−0.0021 (8)	−0.0007 (8)
S1	0.0162 (2)	0.0174 (2)	0.0160 (2)	0.0025 (2)	0.0025 (2)	0.0041 (2)
N1	0.0247 (10)	0.0262 (10)	0.0194 (10)	0.0058 (9)	−0.0012 (8)	−0.0043 (8)
N2	0.0179 (9)	0.0263 (9)	0.0159 (9)	−0.0004 (8)	0.0014 (8)	0.0062 (8)
N3	0.0162 (9)	0.0344 (11)	0.0207 (10)	−0.0018 (8)	0.0008 (8)	0.0011 (9)
O1	0.0361 (9)	0.0296 (8)	0.0253 (10)	0.0083 (7)	−0.0088 (7)	0.0082 (7)
O2	0.0244 (8)	0.0335 (9)	0.0259 (9)	−0.0030 (8)	−0.0049 (7)	−0.0019 (7)
O3	0.0200 (8)	0.0312 (8)	0.0230 (9)	0.0079 (6)	0.0020 (6)	0.0093 (6)
O4	0.0256 (8)	0.0152 (6)	0.0227 (8)	−0.0018 (6)	0.0045 (7)	0.0025 (6)
O5	0.0136 (7)	0.0221 (8)	0.0181 (8)	−0.0027 (6)	0.0023 (6)	0.0015 (6)
O6	0.0330 (9)	0.0402 (10)	0.0286 (10)	0.0214 (8)	−0.0008 (8)	−0.0027 (8)
O7	0.0291 (8)	0.0388 (9)	0.0218 (9)	0.0056 (7)	−0.0101 (7)	0.0005 (7)
O8	0.0187 (8)	0.0411 (9)	0.0364 (11)	0.0112 (7)	0.0041 (7)	0.0068 (8)
O9	0.0219 (9)	0.0711 (13)	0.0382 (12)	0.0029 (9)	0.0073 (8)	0.0315 (10)

Geometric parameters (Å, º)

C1—C6	1.380 (3)	C9—C10	1.374 (3)
C1—C2	1.385 (3)	C9—H9	0.86 (2)
C1—N1	1.473 (3)	C10—C11	1.378 (3)
C2—C3	1.382 (3)	C10—N3	1.481 (2)
C2—H2	0.95 (2)	C11—C12	1.376 (3)
C3—C4	1.388 (3)	C11—H11	0.90 (2)
C3—H3	0.97 (2)	C12—N2	1.477 (2)
C4—C5	1.390 (3)	S1—O3	1.4147 (15)
C4—H4	0.94 (2)	S1—O4	1.4182 (13)
C5—C6	1.384 (3)	S1—O5	1.6222 (15)
C5—S1	1.753 (2)	N1—O1	1.225 (2)
C6—H6	0.95 (2)	N1—O2	1.227 (2)
C7—C8	1.383 (3)	N2—O6	1.211 (2)
C7—C12	1.384 (3)	N2—O7	1.224 (2)
C7—O5	1.388 (2)	N3—O8	1.216 (2)
C8—C9	1.387 (3)	N3—O9	1.216 (2)
C8—H8	0.81 (2)
C6—C1—C2	122.58 (19)	C8—C9—H9	117.8 (16)
C6—C1—N1	118.16 (18)	C9—C10—C11	123.52 (18)
C2—C1—N1	119.27 (18)	C9—C10—N3	119.23 (17)
C3—C2—C1	118.8 (2)	C11—C10—N3	117.22 (18)
C3—C2—H2	122.4 (13)	C12—C11—C10	116.26 (19)
C1—C2—H2	118.6 (13)	C12—C11—H11	119.6 (15)
C2—C3—C4	120.5 (2)	C10—C11—H11	124.0 (15)
C2—C3—H3	119.5 (14)	C11—C12—C7	122.58 (18)
C4—C3—H3	120.0 (14)	C11—C12—N2	117.53 (17)
C3—C4—C5	118.9 (2)	C7—C12—N2	119.85 (17)
C3—C4—H4	119.5 (14)	O3—S1—O4	122.42 (8)
C5—C4—H4	121.6 (14)	O3—S1—O5	104.06 (8)
C6—C5—C4	122.03 (19)	O4—S1—O5	107.75 (8)
C6—C5—S1	118.52 (16)	O3—S1—C5	108.77 (9)
C4—C5—S1	119.43 (16)	O4—S1—C5	108.53 (10)
C1—C6—C5	117.21 (19)	O5—S1—C5	103.71 (8)
C1—C6—H6	125.3 (14)	O1—N1—O2	124.03 (18)
C5—C6—H6	117.5 (14)	O1—N1—C1	118.10 (18)
C8—C7—C12	119.30 (18)	O2—N1—C1	117.88 (17)
C8—C7—O5	121.82 (18)	O6—N2—O7	125.83 (17)
C12—C7—O5	118.65 (18)	O6—N2—C12	118.07 (17)
C7—C8—C9	119.66 (19)	O7—N2—C12	116.08 (17)
C7—C8—H8	120.9 (15)	O8—N3—O9	124.40 (18)
C9—C8—H8	119.2 (15)	O8—N3—C10	118.16 (17)
C10—C9—C8	118.7 (2)	O9—N3—C10	117.44 (17)
C10—C9—H9	123.4 (16)	C7—O5—S1	120.15 (12)
C6—C1—C2—C3	0.7 (3)	C6—C5—S1—O3	154.18 (15)
N1—C1—C2—C3	−179.36 (19)	C4—C5—S1—O3	−24.31 (19)
C1—C2—C3—C4	−1.0 (3)	C6—C5—S1—O4	18.87 (18)
C2—C3—C4—C5	0.3 (3)	C4—C5—S1—O4	−159.63 (15)
C3—C4—C5—C6	0.7 (3)	C6—C5—S1—O5	−95.51 (16)
C3—C4—C5—S1	179.18 (16)	C4—C5—S1—O5	86.00 (17)
C2—C1—C6—C5	0.2 (3)	C6—C1—N1—O1	166.58 (18)
N1—C1—C6—C5	−179.69 (17)	C2—C1—N1—O1	−13.3 (3)
C4—C5—C6—C1	−1.0 (3)	C6—C1—N1—O2	−13.7 (3)
S1—C5—C6—C1	−179.42 (15)	C2—C1—N1—O2	166.39 (18)
C12—C7—C8—C9	0.3 (3)	C11—C12—N2—O6	119.0 (2)
O5—C7—C8—C9	−174.04 (19)	C7—C12—N2—O6	−63.4 (2)
C7—C8—C9—C10	−1.0 (3)	C11—C12—N2—O7	−59.6 (2)
C8—C9—C10—C11	1.1 (3)	C7—C12—N2—O7	118.1 (2)
C8—C9—C10—N3	179.11 (18)	C9—C10—N3—O8	−15.3 (3)
C9—C10—C11—C12	−0.5 (3)	C11—C10—N3—O8	162.79 (19)
N3—C10—C11—C12	−178.51 (17)	C9—C10—N3—O9	164.2 (2)
C10—C11—C12—C7	−0.3 (3)	C11—C10—N3—O9	−17.7 (3)
C10—C11—C12—N2	177.28 (17)	C8—C7—O5—S1	−84.7 (2)
C8—C7—C12—C11	0.3 (3)	C12—C7—O5—S1	100.94 (19)
O5—C7—C12—C11	174.87 (18)	O3—S1—O5—C7	−142.85 (14)
C8—C7—C12—N2	−177.16 (17)	O4—S1—O5—C7	−11.52 (16)
O5—C7—C12—N2	−2.6 (3)	C5—S1—O5—C7	103.41 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1	0.95 (2)	2.43 (2)	2.742 (3)	99.0 (15)
C4—H4···O3	0.94 (2)	2.63 (2)	2.944 (3)	100.4 (15)
C6—H6···O2	0.95 (2)	2.50 (2)	2.715 (3)	92.7 (15)
C6—H6···O4	0.95 (2)	2.49 (2)	2.898 (2)	106.4 (16)
C9—H9···O8	0.86 (2)	2.53 (2)	2.745 (3)	94.9 (18)
C11—H11···O9	0.90 (2)	2.46 (2)	2.699 (3)	95.3 (16)
C2—H2···O7^i	0.95 (2)	2.45 (2)	3.374 (3)	166.2 (19)
C3—H3···O3^ii	0.97 (2)	2.43 (2)	3.208 (3)	137.0 (18)
C3—H3···O6^ii	0.97 (2)	2.47 (2)	3.263 (3)	138.2 (18)
C4—H4···O7^iii	0.94 (2)	2.99 (2)	3.781 (3)	142.9 (17)
C6—H6···N3^iv	0.95 (2)	2.93 (2)	3.836 (3)	161.2 (18)
C6—H6···O8^iv	0.95 (2)	2.77 (2)	3.652 (3)	155.7 (19)
C6—H6···O9^iv	0.95 (2)	2.70 (2)	3.572 (3)	153.6 (17)
C8—H8···O4^v	0.81 (2)	2.43 (2)	3.008 (2)	129.2 (19)
C8—H8···O8^vi	0.81 (2)	2.96 (2)	3.681 (3)	150.0 (18)
C9—H9···O2^vii	0.86 (2)	2.97 (2)	3.726 (3)	147 (2)
C11—H11···O1^viii	0.90 (2)	2.58 (2)	3.362 (3)	145.1 (18)
C11—H11···O2^ix	0.90 (2)	2.62 (2)	3.240 (3)	126.4 (17)

Symmetry codes: (i) x, y+1, z−1; (ii) −x+3/2, y+1, z−1/2; (iii) −x+3/2, y, z−1/2; (iv) −x+1, −y+1, z−1/2; (v) x, y+1, z; (vi) −x+1, −y+2, z−1/2; (vii) −x+1, −y+2, z+1/2; (viii) x, y−1, z+1; (ix) x, y, z+1.