A second polymorph of bis(o-nitro­phenyl) carbonate

The title compound, C₁₃H₈N₂O₇, displays s-cis-s-cis conform­ation of the carbonate group. Bond lengths and angles (Å and °) involving this group are: C=O 1.1839 (13), C-O 1.3462 (13) and 1.3483 (13), O-C_arom 1.3947 (13) and 1.3994 (13); O=C-O 127.21 (10) and 127.02 (10), O-C-O 105.77 (9). The aromatic rings are perpendicular to the carbonate plane.

Key indicators

• Single-crystal X-ray study
• T = 133 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.034
• wR factor = 0.097
• Data-to-parameter ratio = 16.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Bis(o-nitrophenyl) carbonate, (I), was synthesized some 50 years ago (Deutsch & Fernö, 1950), but has not been widely used in synthesis, in contrast to its p-isomer, which was used for activating the carboxylate group in peptide synthesis (Glatthard & Matter, 1963) and as a carbonylation reagent (Nesynov & Pel'kis, 1962; Izdebsky & Pawlok, 1989; Takata et al., 1991; Enders et al., 1999). Recently we noticed that the o-isomer is more reactive than the p-isomer in reactions with N-nucleophiles in organic solvents (Simon et al., 2002), a property that might be extended to other reactions.

As part of our investigations of the structure and reactivity of organic carbonates, we have begun to study the solid state structures of some organic carbonates. Here we present the structure of (I). This had already been determined by King & Bryant (1990) in space group Pc (with Z=2) after recrystallization from dichloromethane/hexane; our structure, recrystallized from benzene, represents a new polymorph.

In principle, the s-cis–s-trans and s-trans–s-trans conformations are both possible for organic carbonates; early studies of dimethyl and diphenyl carbonate by IR spectroscopy (Oki & Nakanishi, 1971) or by dipole moments and Molar Kerr constants (Chia et al., 1981) showed that the probable conformations were s-cis–s-cis or s-cis–s-trans. However, molecular polarization measurements of various diaryl carbonates by Exner & Jehlicka (1981) established that all investigated organic carbonates adopted only the s-cis–s-cis conformation. Finally, X-ray investigations of diphenyl (King & Bryant, 1993), bis(o-nitrophenyl) and bis(2,4-dinitrophenyl) carbonates (King & Bryant, 1990) unambiguously demonstrated s-cis-s-cis conformations.

The molecule of (I) is shown in Fig. 1. The carbonate moiety displays the s-cis–s-cis conformation (cf. torsion angles in Table 1); atoms C11 and C21 lie 0.186 (2) and 0.155 (2) Å, respectively, on opposite sides of the plane defined by C1, O1, O2 and O3. The aromatic rings are perpendicular to this plane [interplanar angles 86.41 (3) and 86.86 (3)°]. In the previous modification (King & Bryant, 1990), only one aromatic ring was perpendicular to the carbonate group; corresponding angles were 89.9 and 54.6°.

Bond lengths and angles of the carbonate moiety (Table 1) may be considered normal. A search of the Cambridge database (Allen, 2002) for the diaryl carbonate moiety revealed 15 hits, with mean values of 105.7° for the O—C—O and 127.1° for the O═C—O angles, 1.175 Å for the C═O and 1.342 Å for the C—O bonds of 21 carbonate groups. Some of the structures involved cyclic carbonate oligomers (Nagahata et al., 2000).

Short intramolecular contacts C1···O5, 2.7829 (14), and C1···O7, 2.7228 (13) Å, are observed, as are intramolecular contacts O2···C23, 2.9642 (14), and O3···N2, 3.0143 (13) Å (operator for second atoms: x, 0.5 − y, 0.5 + z). The molecular packing is further determined by four weak C—H···O hydrogen bonds (Table 2).

The structure of the corresponding para derivative is described in the following paper (Simon et al., 2003).

S2. Experimental

Triphosgene (bis(trichloromethyl) carbonate) was treated with six equivalents of o-nitrophenol and six equivalents of triethylamine in dichloromethane and recrystallized from benzene (Simon et al., 2001).

S3. Refinement

Hydrogen atoms were included using a riding model with fixed C—H bond lengths of 0.95 Å; U(H) values were fixed at 1.2 times the U(eq) of the parent atom.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998)'; data reduction: SAINT (Bruker, 1998)'; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecule of the title compound in the crystal. Ellipsoids represent 50% probability levels; H atom radii are arbitrary.

Bis(o-nitrophenyl) carbonate

Crystal data

C13H8N2O7	F(000) = 624
Mr = 304.21	Dx = 1.549 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9789 (12) Å	Cell parameters from 4316 reflections
b = 11.9076 (12) Å	θ = 2.4–27.0°
c = 9.1495 (11) Å	µ = 0.13 mm^−1
β = 92.128 (3)°	T = 133 K
V = 1304.2 (2) Å^3	Prism, colourless
Z = 4	0.55 × 0.27 × 0.17 mm

Data collection

Bruker SMART 1000 CCD diffractometer	2594 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 28.5°, θmin = 1.7°
Detector resolution: 8.192 pixels mm^-1	h = −16→15
ω–scans	k = −11→15
9339 measured reflections	l = −12→12
3286 independent reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0503P)^2 + 0.1183P] where P = (Fo^2 + 2Fc^2)/3
3286 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.25 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

− 6.1038 (0.0053) x − 6.5075 (0.0051) y + 6.2498 (0.0035) z = 1.9257 (0.0032)

* 0.0024 (0.0008) C11 * −0.0132 (0.0008) C12 * 0.0106 (0.0009) C13 * 0.0027 (0.0009) C14 * −0.0134 (0.0009) C15 * 0.0109 (0.0009) C16

Rms deviation of fitted atoms = 0.0100

8.7528 (0.0042) x + 2.6147 (0.0062) y + 5.6622 (0.0036) z = 5.4181 (0.0013)

Angle to previous plane (with approximate e.s.d.) = 86.41 (0.03)

* 0.0021 (0.0008) C1 * −0.0009 (0.0003) O1 * −0.0006 (0.0002) O2 * −0.0006 (0.0002) O3 0.1864 (0.0017) C11 − 0.1551 (0.0017) C21

Rms deviation of fitted atoms = 0.0012

− 8.6451 (0.0040) x + 2.7044 (0.0055) y + 6.2238 (0.0032) z = 2.8009 (0.0030)

Angle to previous plane (with approximate e.s.d.) = 86.86 (0.03)

* −0.0028 (0.0008) C21 * −0.0036 (0.0008) C22 * 0.0058 (0.0008) C23 * −0.0016 (0.0008) C24 * −0.0048 (0.0008) C25 * 0.0070 (0.0008) C26

Rms deviation of fitted atoms = 0.0046

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
O1	0.29019 (6)	0.17099 (7)	0.42919 (9)	0.0307 (2)
O2	0.21681 (6)	0.05444 (7)	0.59648 (9)	0.03015 (19)
O3	0.16596 (6)	0.22750 (6)	0.59518 (8)	0.02762 (19)
O4	0.50500 (10)	−0.00622 (11)	0.83351 (13)	0.0684 (4)
O5	0.39845 (9)	0.12506 (8)	0.74522 (11)	0.0464 (3)
O6	−0.07112 (8)	0.29780 (8)	0.27643 (12)	0.0465 (3)
O7	0.03683 (7)	0.16887 (7)	0.36686 (11)	0.0400 (2)
C1	0.23182 (9)	0.15314 (9)	0.52819 (12)	0.0246 (2)
C11	0.28894 (9)	−0.03163 (9)	0.55776 (12)	0.0263 (2)
C12	0.38995 (9)	−0.05030 (10)	0.63448 (12)	0.0278 (2)
C13	0.45412 (10)	−0.14359 (10)	0.60383 (14)	0.0338 (3)
H13	0.5216	−0.1577	0.6586	0.041*
C14	0.41949 (11)	−0.21607 (10)	0.49325 (15)	0.0382 (3)
H14	0.4636	−0.2797	0.4710	0.046*
C15	0.32031 (11)	−0.19585 (11)	0.41487 (15)	0.0393 (3)
H15	0.2975	−0.2447	0.3373	0.047*
C16	0.25427 (10)	−0.10472 (10)	0.44916 (14)	0.0344 (3)
H16	0.1850	−0.0928	0.3975	0.041*
C21	0.16043 (9)	0.33294 (9)	0.52775 (12)	0.0244 (2)
C22	0.08447 (9)	0.35544 (9)	0.41232 (12)	0.0246 (2)
C23	0.07547 (9)	0.46284 (9)	0.35468 (12)	0.0273 (2)
H23	0.0230	0.4783	0.2769	0.033*
C24	0.14357 (10)	0.54725 (10)	0.41140 (13)	0.0299 (3)
H24	0.1385	0.6209	0.3718	0.036*
C25	0.21931 (10)	0.52451 (10)	0.52598 (13)	0.0326 (3)
H25	0.2662	0.5827	0.5642	0.039*
C26	0.22705 (10)	0.41741 (10)	0.58515 (13)	0.0303 (3)
H26	0.2780	0.4025	0.6648	0.036*
N1	0.43350 (9)	0.02891 (10)	0.74587 (12)	0.0368 (3)
N2	0.01200 (8)	0.26778 (8)	0.34831 (11)	0.0295 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0303 (4)	0.0299 (4)	0.0324 (4)	0.0044 (3)	0.0060 (3)	0.0056 (3)
O2	0.0308 (4)	0.0246 (4)	0.0356 (4)	0.0055 (3)	0.0072 (3)	0.0066 (3)
O3	0.0326 (4)	0.0238 (4)	0.0266 (4)	0.0052 (3)	0.0042 (3)	0.0040 (3)
O4	0.0670 (7)	0.0797 (9)	0.0559 (7)	0.0188 (6)	−0.0329 (6)	−0.0114 (6)
O5	0.0606 (6)	0.0333 (5)	0.0444 (6)	−0.0041 (4)	−0.0078 (5)	−0.0041 (4)
O6	0.0409 (5)	0.0377 (5)	0.0591 (6)	0.0067 (4)	−0.0230 (5)	−0.0078 (4)
O7	0.0409 (5)	0.0233 (4)	0.0549 (6)	0.0000 (4)	−0.0103 (4)	−0.0023 (4)
C1	0.0241 (5)	0.0242 (5)	0.0253 (5)	0.0024 (4)	−0.0026 (4)	0.0025 (4)
C11	0.0269 (5)	0.0214 (5)	0.0306 (6)	0.0013 (4)	0.0033 (4)	0.0051 (4)
C12	0.0275 (5)	0.0272 (6)	0.0286 (6)	−0.0009 (4)	0.0024 (4)	0.0051 (4)
C13	0.0272 (5)	0.0339 (6)	0.0405 (7)	0.0043 (5)	0.0039 (5)	0.0094 (5)
C14	0.0377 (6)	0.0253 (6)	0.0523 (8)	0.0054 (5)	0.0123 (6)	0.0025 (5)
C15	0.0434 (7)	0.0280 (6)	0.0467 (8)	−0.0046 (5)	0.0048 (6)	−0.0062 (5)
C16	0.0303 (6)	0.0299 (6)	0.0427 (7)	−0.0013 (5)	−0.0038 (5)	0.0001 (5)
C21	0.0272 (5)	0.0218 (5)	0.0244 (5)	0.0037 (4)	0.0036 (4)	0.0018 (4)
C22	0.0246 (5)	0.0237 (5)	0.0256 (5)	0.0012 (4)	0.0015 (4)	−0.0026 (4)
C23	0.0297 (5)	0.0268 (6)	0.0254 (5)	0.0063 (4)	0.0013 (4)	0.0008 (4)
C24	0.0355 (6)	0.0229 (5)	0.0316 (6)	0.0035 (4)	0.0061 (5)	0.0022 (4)
C25	0.0361 (6)	0.0278 (6)	0.0339 (6)	−0.0041 (5)	0.0007 (5)	−0.0034 (5)
C26	0.0319 (6)	0.0319 (6)	0.0269 (6)	0.0003 (5)	−0.0026 (5)	0.0000 (5)
N1	0.0353 (5)	0.0435 (6)	0.0313 (6)	−0.0024 (5)	−0.0036 (4)	0.0000 (4)
N2	0.0282 (5)	0.0273 (5)	0.0326 (5)	0.0020 (4)	−0.0024 (4)	−0.0040 (4)

Geometric parameters (Å, º)

O1—C1	1.1839 (13)	C14—H14	0.9500
O2—C1	1.3462 (13)	C15—C16	1.3858 (18)
O2—C11	1.3947 (13)	C15—H15	0.9500
O3—C1	1.3483 (13)	C16—H16	0.9500
O3—C21	1.3994 (13)	C21—C26	1.3760 (16)
O4—N1	1.2250 (14)	C21—C22	1.3942 (15)
O5—N1	1.2194 (14)	C22—C23	1.3860 (15)
O6—N2	1.2260 (12)	C22—N2	1.4658 (14)
O7—N2	1.2250 (13)	C23—C24	1.3833 (16)
C11—C16	1.3736 (17)	C23—H23	0.9500
C11—C12	1.3939 (15)	C24—C25	1.3875 (16)
C12—C13	1.3855 (16)	C24—H24	0.9500
C12—N1	1.4700 (15)	C25—C26	1.3871 (17)
C13—C14	1.3819 (19)	C25—H25	0.9500
C13—H13	0.9500	C26—H26	0.9500
C14—C15	1.3858 (18)
C1—O2—C11	115.40 (8)	C26—C21—O3	118.06 (9)
C1—O3—C21	114.06 (8)	C22—C21—O3	121.68 (9)
O1—C1—O2	127.21 (10)	C23—C22—C21	120.32 (10)
O1—C1—O3	127.02 (10)	C23—C22—N2	117.94 (10)
O2—C1—O3	105.77 (9)	C21—C22—N2	121.74 (10)
C16—C11—C12	119.78 (10)	C24—C23—C22	119.42 (10)
C16—C11—O2	118.41 (10)	C24—C23—H23	120.3
C12—C11—O2	121.58 (10)	C22—C23—H23	120.3
C13—C12—C11	120.25 (11)	C23—C24—C25	120.11 (11)
C13—C12—N1	118.00 (10)	C23—C24—H24	119.9
C11—C12—N1	121.73 (10)	C25—C24—H24	119.9
C14—C13—C12	119.68 (11)	C26—C25—C24	120.44 (11)
C14—C13—H13	120.2	C26—C25—H25	119.8
C12—C13—H13	120.2	C24—C25—H25	119.8
C13—C14—C15	119.91 (11)	C21—C26—C25	119.58 (10)
C13—C14—H14	120.0	C21—C26—H26	120.2
C15—C14—H14	120.0	C25—C26—H26	120.2
C14—C15—C16	120.30 (12)	O5—N1—O4	123.79 (12)
C14—C15—H15	119.8	O5—N1—C12	119.06 (10)
C16—C15—H15	119.8	O4—N1—C12	117.14 (11)
C11—C16—C15	120.01 (11)	O7—N2—O6	122.88 (10)
C11—C16—H16	120.0	O7—N2—C22	119.48 (9)
C15—C16—H16	120.0	O6—N2—C22	117.63 (9)
C26—C21—C22	120.11 (10)
C11—O2—C1—O1	8.87 (16)	C26—C21—C22—C23	−0.02 (16)
C11—O2—C1—O3	−171.56 (8)	O3—C21—C22—C23	175.37 (10)
C21—O3—C1—O1	6.62 (15)	C26—C21—C22—N2	−179.94 (10)
C21—O3—C1—O2	−172.96 (8)	O3—C21—C22—N2	−4.55 (16)
C1—O2—C11—C16	−93.99 (12)	C21—C22—C23—C24	0.84 (16)
C1—O2—C11—C12	91.49 (13)	N2—C22—C23—C24	−179.24 (9)
C16—C11—C12—C13	−1.47 (17)	C22—C23—C24—C25	−0.65 (17)
O2—C11—C12—C13	172.98 (10)	C23—C24—C25—C26	−0.36 (18)
C16—C11—C12—N1	176.54 (11)	C22—C21—C26—C25	−0.99 (17)
O2—C11—C12—N1	−9.02 (17)	O3—C21—C26—C25	−176.55 (10)
C11—C12—C13—C14	2.25 (18)	C24—C25—C26—C21	1.18 (18)
N1—C12—C13—C14	−175.82 (11)	C13—C12—N1—O5	158.34 (12)
C12—C13—C14—C15	−0.74 (19)	C11—C12—N1—O5	−19.71 (17)
C13—C14—C15—C16	−1.6 (2)	C13—C12—N1—O4	−20.65 (17)
C12—C11—C16—C15	−0.84 (18)	C11—C12—N1—O4	161.30 (12)
O2—C11—C16—C15	−175.46 (11)	C23—C22—N2—O7	160.35 (11)
C14—C15—C16—C11	2.4 (2)	C21—C22—N2—O7	−19.73 (16)
C1—O3—C21—C26	−98.63 (12)	C23—C22—N2—O6	−18.87 (15)
C1—O3—C21—C22	85.88 (12)	C21—C22—N2—O6	161.05 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1^i	0.95	2.43	3.1060 (14)	128
C26—H26···O1^ii	0.95	2.57	3.3782 (15)	143
C16—H16···O6^iii	0.95	2.44	3.1756 (15)	135
C24—H24···O6^iv	0.95	2.62	3.5351 (15)	163

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x, y+1/2, −z+1/2.