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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 8| August 2011| Pages o288-o293
doi:10.1107/S0108270111024140

Extensive hydrogen and halogen bonding, and absence of intra­molecular hydrogen bonding between alcohol and nitro groups in a series of endo-nitro­norbornanol compounds

CROSSMARK_Color_square_no_text.svg
Andreas Lemmerera* and Joseph P. Michaela

aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, PO Wits 2050, South Africa
*Correspondence e-mail: andreas.lemmerer@wits.ac.za

(Received 28 April 2011; accepted 20 June 2011; online 5 July 2011)

The influence of the substituent at the C2 position on the hydrogen-bonding patterns is compared for a series of five related compounds, namely (±)-3-exo,6-exo-dibromo-5-endo-hy­droxy-3-endo-nitro­bicyclo­[2.2.1]heptane-2-exo-carbonitrile, C8H8Br2N2O3, (II), (±)-3-exo,6-exo-dibromo-6-endo-nitro-5-exo-phenyl­bicyclo­[2.2.1]heptan-2-endo-ol, C13H13Br2NO3, (III), (±)-methyl 3-exo,6-exo-dibromo-5-endo-hy­droxy-3-endo-nitro­bicyclo­[2.2.1]heptane-2-exo-carboxyl­ate, C9H11Br2NO5, (IV), (±)-methyl 3-exo,6-exo-dibromo-7-diphenyl­methyl­idene-5-endo-hy­droxy-3-endo-nitro­bicyclo­[2.2.1]heptane-2-exo-car­box­yl­ate, C22H19Br2NO5, (V), and (±)-methyl 3-exo,6-exo-dibromo-5-endo-hy­droxy-3-endo-nitro-7-oxabicyclo­[2.2.1]hep­tane-2-exo-carboxyl­ate, C8H9Br2NO6, (VI). The hydrogen-bonding motif in all five compounds is a chain, formed by O—H⋯O hydrogen bonds in (III), (IV), (V) and (VI), and by O—H⋯N hydrogen bonds in (II). All compounds except (III) contain a number of Br⋯Br and Br⋯O halogen bonds that connect the chains to each other to form two-dimensional sheets or three-dimensional networks. None of the compounds features intra­molecular hydrogen bonding between the alcohol and nitro functional groups, as was found in the related com­pound (±)-methyl 3-exo,6-exo-dichloro-5-endo-hy­droxy-3-endo-nitro­bicyclo­[2.2.1]heptane-2-exo-carboxyl­ate, (I) [Boeyens, Denner & Michael (1984b). J. Chem. Soc. Perkin Trans. 2, pp. 767–770]. The crystal structure of (V) exhibits whole-mol­ecule disorder.

Comment

Although hydrogen bonding between hy­droxy and nitro groups is not uncommon (Desiraju, 2002[Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565-573.]), intra­molecular hydrogen bonding between these groups is largely confined to systems in which they find themselves in enforced proximity, as in 2-nitro­phenols (Baitinger et al., 1964[Baitinger, W. F., Schleyer, P. R., Murty, T. S. S. R. & Robinson, L. (1964). Tetrahedron, 20, 1635-1647.]; Heintz et al., 2007[Heintz, A., Kapteina, S. & Verevkin, S. P. (2007). J. Phys. Chem. A, 111, 6552-6562.]; Litwinienko et al., 2009[Litwinienko, G., DiLabio, G. A., Mulder, P., Korth, H.-G. & Ingold, K. U. (2009). J. Phys. Chem. A, 113, 6275-6288.]). We have been inter­ested in hydrogen bonding in nitro­norbornanol systems for several years (Boeyens et al., 1984a[Boeyens, J. C. A., Denner, L. & Michael, J. P. (1984a). J. Chem. Soc. Perkin Trans. 2, pp. 1569-1573.]; Michael et al., 1994[Michael, J. P., Billing, D. G. & Maqutu, T. L. (1994). J. Chem. Crystallogr. 24, 311-314.]). In particular, when both groups are constrained to occupy the endo cavity of the norbornane skeleton, the likelihood of intra­molecular hy­dro­gen bonding is high, as we have found, for example, in 3-exo,6-exo-dichloro-5-endo-hy­droxy-3-endo-nitro­bicyclo­[2.2.1]heptane-2-exo-carbonitrile, (I) (Boeyens et al., 1984b[Boeyens, J. C. A., Denner, L. & Michael, J. P. (1984b). J. Chem. Soc. Perkin Trans. 2, pp. 767-770.]). We previously determined the room-temperature crystal structure of the corresponding dibromo compound 3-exo,6-exo-di­bromo-5-endo-hy­droxy-3-endo-nitro­bicyclo­[2.2.1]heptane-2-exo-carbonitrile, (II)[link] (Blom et al., 1980[Blom, N. F., Edwards, D. M. F., Field, J. S. & Michael, J. P. (1980). J. Chem. Soc. Chem. Commun. pp. 1240-1241.]), but owing to the limitations of the techniques available at the time, we were unable to locate H atoms and to establish unambiguously whether or not the hydrogen bonding was intra­molecular. We report here a redetermination of the crystal structure of compound (II)[link] at low temperature, as well as the structures of three analogous dibrominated endo-nitro­norbornanols, (III)–(V), and the related 7-oxanorbornanol, (VI)[link], in order to elucidate their hydrogen-bonding patterns and to establish whether there is any intra- or inter­molecular hydrogen bonding between the alcohol and nitro functionalities.

[Scheme 1]

The distances and angles within the five compounds reported (Fig. 1[link]) are generally as expected (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). In all five structures, hydrogen bonds play a part in controlling the supra­molecular assembly of the mol­ecules (Desiraju, [Desiraju, G. R. (1996). Acc. Chem. Res. 29, 441-449.], 2002[Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565-573.]). All five compounds contain an alcohol group and a number of good hydrogen-bonding acceptor functional groups including nitro, ester and ether units as well as Br atoms. Furthermore, a number of halogen-type C—Br⋯A (A = Br or O; Metrangelo et al., 2005[Metrangelo, P., Neukirch, H., Pilati, T. & Resnati, G. (2005). Acc. Chem. Res. 38, 386-395.]) inter­actions are also present (Fig. 2[link]).

Compound (II)[link] crystallizes in the polar space group Cc. The O1—H1⋯N2 hydrogen bond forms a C(8) (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) chain along the [010] direction. Adjacent chains of this type are connected by a Br2⋯O2 halogen inter­action along the [001] direction (Fig. 3[link]) and by a Br1⋯Br2 halogen inter­action (Table 6[link]) along the [100] direction to form a three-dimensional network.

In compound (III)[link], the O1—H1⋯O2 hydrogen bond forms C(7) chains along the [010] direction, containing mol­ecules related by the twofold screw axis along (0.5, y, 0.75) (Fig. 4[link]). Compound (III)[link] has no short Br⋯Br contacts and does not form a higher-dimensional network.

In the crystal structure of compound (IV)[link], C(8) chains are formed along the [1[\overline{1}]0] direction, utilizing the O1—H1⋯O4 hydrogen bond (Fig. 5[link]a). Adjacent chains of this type are connected to form a three-dimensional network by Br2⋯Br2 inter­actions along the [001] direction and by Br1⋯O1 inter­actions along the [010] direction (Table 6[link], and Figs. 5[link]a and 5b).

The entire mol­ecule of compound (V)[link] is disordered over two sets of atomic positions and the two parts, labelled A and B (Fig. 1[link]), have equal site-occupancy factors. The only substantial conformational difference between the two disorder components is the orientations of the aromatic rings relative to the nitro­norbornanol unit. Mol­ecule A has torsion angles of −46.9 (15)° (C7A—C10A—C17A—C22A) and 120.9 (12)° (C7A—C10A—C11A—C16A), as compared to angles of −61.3 (14)° (C7B—C10B—C17B—C22B) and 139.4 (12)° (C7B—C10B—C11B—C16B) in mol­ecule B. Nonetheless, the inter­molecular hydrogen and halogen bonding is similar between the two mol­ecules (Tables 4[link] and 6[link]). The O1A—H1A⋯O3A hydrogen bond in mol­ecule A forms C(7) chains from alcohol atom O1A to nitro atom O3A. The chains run along the [010] direction (Fig. 6[link]), generated by the twofold screw axis in the space group P21/c. The mol­ecules within the chains are further connected by Br2A⋯O3A halogen bonds (Table 6[link] and Fig. 6[link]). (V)[link] contains no Br⋯Br halogen bonds. The hydrogen bonding of mol­ecule B is not shown in Fig. 6[link].

In the crystal structure of compound (VI)[link], the O1—H1⋯O4 hydrogen bond forms C(8) chains along the [[\overline 1]01] direction (Fig. 7[link]a). Adjacent hydrogen-bonded chains are connected by Br1⋯O1 inter­actions along the [100] direction to form sheets (Fig. 7[link]a). Two adjacent sheets are then connected by Br2⋯Br2 halogen bonds along [010] (Table 6[link]) to form bilayers of sheets (Fig. 7[link]b).

Compound (II)[link], which is the dibromo analogue of (I), does not contain an intra­molecular O—H⋯O(nitro) hydrogen bond as observed in (I). Instead, it forms a C(8) hydrogen-bonded chain with the nitrile N atom as acceptor on a neighbouring mol­ecule. Nonetheless, the O atoms of the nitro group are utilized in inter­molecular inter­actions, in this case halogen bonding with the Br atoms to form two-dimensional sheets which are further linked into a three-dimensional network via Br⋯Br inter­actions. Compound (III)[link] has the nitrile group replaced by a phenyl group, and this seems to have an influence on the lack of any halogen bonding observed in (III)[link] because of the steric increase of the phenyl group next to one of the Br atoms. The absence of any good hydrogen-bonding acceptor at the 2-position leaves only the nitro group or the alcohol O atom as candidates and, indeed, in (III)[link], there is an inter­molecular O—H⋯O(nitro) hydrogen bond forming C(7) chains. Similar chains are formed by (V)[link], which at the same time uses the second O atom of the nitro group in halogen bonding to strengthen the chain motif. Compounds (IV)[link] and (VI)[link] have the same inter­molecular hydrogen bonding from the alcohol to the ester carbonyl group, and similar packing of the chains into larger architectures. (IV)[link] has chains connected in three dimensions by the halogen-bond inter­actions, whereas (VI)[link] has bilayers of hydrogen-bonded sheets using similar Br⋯Br and Br⋯O inter­actions. The halogen bonds observed in these compounds all have X⋯A distances less than the van der Waals radii sum (3.70 Å for Br⋯Br contacts and 3.37 Å for Br⋯O contacts).

[Figure 1]
Figure 1
The mol­ecular structures and atom-labelling schemes for (a) (II)[link], (b) (III)[link], (c) (IV)[link], (d) mol­ecule A of (V)[link], (e) mol­ecule B of (V)[link] and (f) (VI)[link]. Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii.
[Figure 2]
Figure 2
The three types of halogen bonding observed in this study of nitro­nor­bor­nan­ols.
[Figure 3]
Figure 3
The C(8) hydrogen-bonded chain of (II)[link], showing the Br⋯O halogen-bonded inter­actions along the [001] direction. The Br⋯Br halogen bonds along the [100] direction are not shown. Atoms marked with the superscripts `i' and `ii' are at the symmetry positions (x − [{1\over 2}], y + [{1\over 2}], z) and (x + 1, −y + 1, z + [{1\over 2}]), respectively. H atoms not involved in hydrogen-bonding inter­actions have been omitted for clarity.
[Figure 4]
Figure 4
The C(7) hydrogen-bonded chain of (III)[link]. Atoms marked with the superscript `i' are at the symmetry position (−x + 1, y + [{1\over 2}], −z + [{3\over 2}]). H atoms not involved in hydrogen-bonding inter­actions have been omitted for clarity.
[Figure 5]
Figure 5
(a) The C(8) hydrogen-bonded chain of (IV)[link], as well as the Br⋯O halogen bonds forming a two-dimensional sheet. (b) The sheets are then connected into a three-dimensional network by Br⋯Br halogen bonds. Atoms marked with the superscripts `i', `ii' and `iii' are at the symmetry positions (x − 1, y + 1, z), (x, y − 1, z) and (−x + 1, −y + 2, −z + 1), respectively. H atoms not involved in hydrogen-bonding inter­actions have been omitted for clarity.
[Figure 6]
Figure 6
The C(7) hydrogen-bonded chain of (V)[link]. Note how the halogen bonding connects every second mol­ecule involved in hydrogen-bonded inter­actions within the chain (by translation only). Only the hydrogen bonding of mol­ecule A is shown. Mol­ecule B has similar inter­actions but is not shown in the figure. Atoms marked with the superscripts `i' and `ii' are at the symmetry positions (−x + 1, y + [{1\over 2}], −z + [{1\over 2}]) and (x, y + 1, z), respectively. H atoms not involved in hydrogen-bonding inter­actions have been omitted for clarity.
[Figure 7]
Figure 7
(a) The C(8) hydrogen-bonded chains of (VI)[link] connected by Br⋯O halogen bonds to form two-dimensional sheets. (b) The sheets form bilayers through further Br⋯Br halogen bonding. Atoms marked with the superscripts `i', `ii' and `iii' are at the symmetry positions (x − 1, y, z − 1), (x + 1, y, z) and (−x + 2, −y, −z + 2), respectively. H atoms not involved in hydrogen-bonding inter­actions have been omitted for clarity.

Experimental

The syntheses and spectroscopic characterization of the five compounds (II)–(VI) by bromination of the corresponding endo-nitro­norbonenes have been reported previously (Michael et al., 1991[Michael, J. P., Blom, N. F. & Glintenkamp, L. A. (1991). J. Chem. Soc. Perkin Trans. 1, pp. 1855-1862.]). In these syntheses, transannular neighbouring group participation by the nitro group during bromination of the alkene bond is responsible for the introduction of the endo-hydroxy group in a regiospecific and totally stereoselective manner. Crystals of (II)[link] were grown from methanol, (III)[link] from benzene, (IV)[link] from benzene, (V)[link] from ethyl ­acetate/hexane (1:1 v/v) and (VI)[link] from acetone, all by slow evaporation.

Compound (II)[link]

Crystal data

  • C8H8Br2N2O3

  • Mr = 339.98

  • Monoclinic, C c

  • a = 6.6517 (8) Å

  • b = 16.084 (2) Å

  • c = 9.8254 (14) Å

  • β = 91.825 (6)°

  • V = 1050.6 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 7.70 mm−1

  • T = 173 K

  • 0.6 × 0.2 × 0.2 mm
Data collection

  • Bruker SMART 1K CCD area-detector diffractometer

  • Absorption correction: integration (XPREP; Bruker, 1999[Bruker (1999). SAINT-Plus (including XPREP). Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.075, Tmax = 0.301

  • 3346 measured reflections

  • 2038 independent reflections

  • 1945 reflections with I > 2σ(I)

  • Rint = 0.067
Refinement

  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.116

  • S = 1.04

  • 2038 reflections

  • 139 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 1.20 e Å−3

  • Δρmin = −0.94 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 765 Friedel pairs

  • Flack parameter: 0.003 (19)

Table 1
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1⋯N2i 0.86 (12) 2.01 (12) 2.858 (8) 169 (10)
Symmetry code: (i) [x-{\script{1\over 2}}, y+{\script{1\over 2}}, z].

Compound (III)[link]

Crystal data

  • C13H13Br2NO3

  • Mr = 391.06

  • Monoclinic, P 21 /c

  • a = 15.945 (2) Å

  • b = 6.7578 (10) Å

  • c = 13.194 (2) Å

  • β = 107.655 (9)°

  • V = 1354.7 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 5.99 mm−1

  • T = 173 K

  • 0.4 × 0.3 × 0.14 mm
Data collection

  • Bruker SMART 1K CCD area-detector diffractometer

  • Absorption correction: integration (XPREP; Bruker, 1999[Bruker (1999). SAINT-Plus (including XPREP). Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.110, Tmax = 0.467

  • 18725 measured reflections

  • 3256 independent reflections

  • 2786 reflections with I > 2σ(I)

  • Rint = 0.042
Refinement

  • R[F2 > 2σ(F2)] = 0.022

  • wR(F2) = 0.052

  • S = 1.04

  • 3256 reflections

  • 175 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.34 e Å−3

  • Δρmin = −0.64 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1⋯O2i 0.76 (3) 2.17 (3) 2.927 (2) 171 (3)
Symmetry code: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Compound (IV)[link]

Crystal data

  • C9H11Br2NO5

  • Mr = 373.01

  • Triclinic, [P \overline 1]

  • a = 6.7221 (2) Å

  • b = 7.7353 (3) Å

  • c = 12.1546 (5) Å

  • α = 88.296 (3)°

  • β = 80.595 (3)°

  • γ = 69.323 (3)°

  • V = 583.08 (4) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 6.96 mm−1

  • T = 173 K

  • 0.28 × 0.12 × 0.04 mm
Data collection

  • Bruker SMART 1K CCD area-detector diffractometer

  • Absorption correction: integration (XPREP; Bruker, 1999[Bruker (1999). SAINT-Plus (including XPREP). Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.318, Tmax = 0.770

  • 7104 measured reflections

  • 2805 independent reflections

  • 2244 reflections with I > 2σ(I)

  • Rint = 0.083
Refinement

  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.07

  • S = 0.96

  • 2805 reflections

  • 155 parameters

  • H-atom parameters constrained

  • Δρmax = 1.44 e Å−3

  • Δρmin = −1.41 e Å−3

Table 3
Hydrogen-bond geometry (Å, °) for (IV)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1⋯O4i 0.84 1.96 2.752 (3) 157
Symmetry code: (i) x-1, y+1, z.

Compound (V)[link]

Crystal data

  • C22H19Br2NO5

  • Mr = 537.2

  • Monoclinic, P 21 /c

  • a = 15.8724 (8) Å

  • b = 9.0341 (4) Å

  • c = 15.0064 (7) Å

  • β = 98.219 (2)°

  • V = 2129.71 (17) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.84 mm−1

  • T = 173 K

  • 0.3 × 0.1 × 0.06 mm
Data collection

  • Bruker SMART 1K CCD area-detector diffractometer

  • Absorption correction: integration (XPREP; Bruker, 1999[Bruker (1999). SAINT-Plus (including XPREP). Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.509, Tmax = 0.817

  • 17671 measured reflections

  • 5119 independent reflections

  • 3059 reflections with I > 2σ(I)

  • Rint = 0.078
Refinement

  • R[F2 > 2σ(F2)] = 0.033

  • wR(F2) = 0.057

  • S = 0.82

  • 5119 reflections

  • 467 parameters

  • 83 restraints

  • H-atom parameters constrained

  • Δρmax = 0.45 e Å−3

  • Δρmin = −0.43 e Å−3

Table 4
Hydrogen-bond geometry (Å, °) for (V)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1A—H1A⋯O3Ai 0.84 2.24 3.03 (2) 157
O1B—H1B⋯O3Bi 0.84 2.14 2.90 (3) 151
Symmetry code: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Compound (VI)[link]

Crystal data

  • C8H9Br2NO6

  • Mr = 374.98

  • Monoclinic, P 21 /c

  • a = 7.8071 (13) Å

  • b = 22.760 (4) Å

  • c = 6.7673 (10) Å

  • β = 110.32 (1)°

  • V = 1127.7 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 7.21 mm−1

  • T = 173 K

  • 0.42 × 0.4 × 0.2 mm
Data collection

  • Bruker SMART 1K CCD area-detector diffractometer

  • Absorption correction: integration (XPREP; Bruker, 1999[Bruker (1999). SAINT-Plus (including XPREP). Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.092, Tmax = 0.290

  • 12168 measured reflections

  • 2715 independent reflections

  • 2453 reflections with I > 2σ(I)

  • Rint = 0.085
Refinement

  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 0.076

  • S = 1.22

  • 2715 reflections

  • 158 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.47 e Å−3

  • Δρmin = −0.92 e Å−3

Table 5
Hydrogen-bond geometry (Å, °) for (VI)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1⋯O4i 0.89 (4) 1.94 (4) 2.774 (3) 156 (4)
Symmetry code: (i) x-1, y, z-1.

Table 6
Br⋯Br and Br⋯O geometries in four of the five title compounds (Å, °)

Compound Inter­action X⋯X θ1 θ2 Type
(II) C3—Br1⋯Br2i 3.663 (2) 138 99 II
  C6—Br2⋯O2ii 3.205 (2) 155   III
(IV) C6—Br2⋯Br2iii 3.453 (4) 155 155 I
  C3—Br1⋯O1iv 3.017 (3) 176   III
(V) C6A—Br2A⋯O3Av 3.159 (2) 158   III
  C6B—Br2B⋯O3Bv 3.258 (2) 152   III
(VI) C6—Br2⋯Br2vi 3.608 (10) 149 149 I
  C3—Br1⋯O1vii 3.097 (5) 168   III
Symmetry codes: (i) x − [{1\over 2}], y − [{1\over 2}], z; (ii) x + 1, −y + 1, z + [{1\over 2}]; (iii) −x + 1, −y + 2, −z + 1; (iv) x, y − 1, z; (v) x, y + 1, z; (vi) −x + 2, −y, −z + 2; (vii) x + 1, y, z.

The whole-mol­ecule disorder of (V)[link] was modelled by finding alternative positions for all the atoms in the mol­ecule. The corresponding bonded distance and the one-angle nonbonded distances in the two disorder components were restrained to have the same values, subject to s.u. values of 0.005 and 0.01 Å, respectively. The atomic displacement parameters were restrained to be equal for each of the atom pairs C1A/C1B, C2A/C2B, C3A/C3B, C5A/C5B, O1A/O1B, C6A/C6B, C7A/C7B, C8A/C8B, C9A/C9B, O2A/O2B, O3A/O3B, C10A/C10B and C11A/C11B. Refinement of the site occupancies gave values of 0.501 (8) and 0.499 (8): the occupancies were thereafter both fixed at 0.50. For all compounds, all C—H atoms were refined using a riding model, with distances of 0.95 (aromatic), 1.00 (aliphatic CH), 0.99 (CH2) and 0.98 Å (CH3), and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C). H atoms on O atoms which are involved in hydrogen-bonding inter­actions were located in difference maps for all compounds except (IV)[link] and (V)[link] (which were refined using a riding model) and their positions allowed to refine freely, with Uiso(H) = 1.5Ueq(O) for all compounds. The value of the Flack x parameter (Flack, 1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) for (II)[link], viz. 0.003 (19), confirms the correct orientation of the structure with respect to the two polar-axis directions in the space group Cc.

For all compounds, data collection: SMART-NT (Bruker, 1998[Bruker (1998). SMART-NT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 1999[Bruker (1999). SAINT-Plus (including XPREP). Version 6.02. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

Crystal structure: contains datablocks global, II, III, IV, V, VI. DOI: 10.1107/S0108270111024140/gd3390sup1.cif

Structure factors: contains datablock II. DOI: 10.1107/S0108270111024140/gd3390IIsup2.hkl

Structure factors: contains datablock III. DOI: 10.1107/S0108270111024140/gd3390IIIsup3.hkl

Structure factors: contains datablock IV. DOI: 10.1107/S0108270111024140/gd3390IVsup4.hkl

Structure factors: contains datablock V. DOI: 10.1107/S0108270111024140/gd3390Vsup5.hkl

Structure factors: contains datablock VI. DOI: 10.1107/S0108270111024140/gd3390VIsup6.hkl

Supporting information file. DOI: 10.1107/S0108270111024140/gd3390IIsup7.mol

Supporting information file. DOI: 10.1107/S0108270111024140/gd3390IIIsup8.mol

Supporting information file. DOI: 10.1107/S0108270111024140/gd3390IVsup9.mol

Supporting information file. DOI: 10.1107/S0108270111024140/gd3390Vsup10.mol

Supporting information file. DOI: 10.1107/S0108270111024140/gd3390VIsup11.mol


Comment top

Although hydrogen bonding between hydroxy and nitro groups is not uncommon (Desiraju, 2002), intramolecular hydrogen bonding between these groups is largely confined to systems in which they find themselves in enforced proximity, as in 2-nitrophenols (Baitinger et al., 1964; Heintz et al., 2007; Litwinienko et al., 2009). We have been interested in hydrogen bonding in nitronorbornanol systems for several years (Boeyens et al., 1984a; Michael et al., 1994). In particular, when both groups are constrained to occupy the endo cavity of the norbornane skeleton, the likelihood of intramolecular hydrogen bonding is high, as we have found, for example, in 3-exo,6-exo-dichloro-5-endo-hydroxy-3-endo-nitrobicyclo[2.2.1]heptane-2-exo-carbonitrile, (I) (Boeyens et al., 1984b). We previously determined the room-temperature crystal structure of the corresponding dibromo compound 3-exo,6-exo-dibromo-5-endo-hydroxy-3-endo-nitrobicyclo[2.2.1]heptane-2-exo-carbonitrile, (II) (Blom et al., 1980), but owing to the limitations of the techniques available at the time, we were unable to locate hydrogen atoms and to establish unambiguously whether or not the hydrogen bonding was intramolecular. Here we report a redetermination of the crystal structure of compound (II) at low temperature, as well as the structures of three analogous dibrominated endo-nitronorbornanols (III)–(V) and the related 7-oxanorbornanol, (VI), in order to elucidate their hydrogen-bonding patterns and to establish whether there is any intramolecular or intermolecular hydrogen bonding between the alcohol and nitro functionalities.

The distances and angles within the five compounds reported (Fig. 1) are generally as expected (Allen et al., 1987). In all five structures, hydrogen bonds play a part in controlling the supramolecular assembly of the molecules (Desiraju, 1996, 2002). All five compounds contain an alcohol group and a number of good hydrogen-bonding acceptor functional groups including nitro, ester and ether units as well as Br atoms. Furthermore, a number of halogen-type C—Br···A (A = Br or O; Metrangelo et al., 2005) interactions are also present (Fig. 2).

Compound (II) crystallizes in the polar space group Cc. The O1—H1···N2 hydrogen bond forms a C(8) (Bernstein et al., 1995) chain along the [010] direction. Adjacent chains of this type are connected by a Br2···O2 halogen interaction along the [001]direction (Fig. 3) and by a Br1···Br2 halogen interaction (Table 6) along the [100] direction to form a three-dimensional network.

In compound (III) the O1—H1···O2 hydrogen bond forms C(7) chains along the [010] direction, containing molecules related by the twofold screw axis along (0.5, y, 0.75) (Fig. 4). Compound (III) has no short Br···Br contacts and does not form a higher-dimensional network.

In the crystal structure of compound (IV), C(8) chains are formed along the [110] direction, utilizing the O1—H1···O4 hydrogen bond (Fig. 5a). Adjacent chains of this type are connected to form a three-dimensional network by Br2···Br2 interactions along the [001] direction and by Br1···O1 interactions along the [010] direction (Table 6) (Figs. 5a and 5b).

The entire molecule of compound (V) is disordered over two sets of atomic positions and the two parts, labelled A and B (Fig. 1), have equal site-occupancy factors. The only substantial conformational difference between the two disorder components is the orientations of the aromatic rings relative to the nitronorbornanol unit. Molecule A has torsion angles of -46.9 (15)° (C7A—C10A—C17A—C22A) and 120.9 (12)° (C7A—C10A—C11A—C16A), as compared to angles of -61.3 (14)° (C7B—C10B—C17B—C22B) and 139.4 (12)° (C7B—C10B—C11B—C16B) in molecule B. Nonetheless, the intermolecular hydrogen and halogen bonding is similar between the two molecules (Tables 4 and 6). The O1A—H1A···O3A hydrogen bond in molecule A forms C(7) chains from the alcohol O1A to the nitro oxygen O3A. The chains run along the [010] direction (Fig. 6), generated by the twofold screw axis in the space group P21/c. The molecules within the chains are further connected by Br2A···O3A halogen bonds (Table 6 and Fig. 6). (V) contains no Br···Br halogen bonds. The hydrogen bonding of molecule B is not shown in Fig. 6.

In the crystal structure of compound (VI) the O1—H1···O4 hydrogen bond forms C(8) chains along the [101] direction (Fig. 7a). Adjacent hydrogen-bonded chains are connected by Br1···O1 interactions along the [100] direction to form sheets (Fig. 7a). Two adjacent sheets are then connected by Br2···Br2 halogen bonds along [010] (Table 6) to form bilayers of sheets (Fig. 7b).

Compound (II), which is the dibromo analogue of (I), does not contain an intramolecular O—H···O(nitro) hydrogen bond as observed in (I). Instead, it forms a C(8) hydrogen-bonded chain with the nitrile N as acceptor atom on a neighbouring molecule. Nonetheless, the O atoms of the nitro group are utilized in intermolecular interactions, in this case halogen bonding with the bromine atoms to form two-dimensional sheets which are further linked into a three-dimensional network via Br···Br interactions. Compound (III) has the nitrile group replaced by a phenyl group, and this seems to have an influence on the lack of any halogen bonding observed in (III) due to the steric increase of the phenyl group next to one of the bromine atoms. The absence of any good hydrogen-bonding acceptor at the 2-position leaves only the nitro group or the alcohol O as candidates, and indeed, in (III) there is an intermolecular O—H···O(nitro) hydrogen bond forming C(7) chains. Similar chains are formed by (V), which at the same time uses the second O atom of the nitro group in halogen bonding to strengthen the chain motif. Compounds (IV) and (VI) have the same intermolecular hydrogen bonding from the alcohol to the ester carbonyl, and similar packing of the chains into larger architectures. (IV) has chains connected in three dimensions by the halogen-bond interactions, whereas (VI) has bilayers of hydrogenbonded sheets using similar Br···Br and Br···O interactions. The halogen bonds observed in these compounds all have X···A distances less than the van der Waals radii sum (3.70 Å for Br···Br contacts and 3.37 Å for Br···O contacts).

Related literature top

For related literature, see: Baitinger et al., 1964; Blom et al., 1980; Boeyens et al., 1984a; Boeyens et al., 1984b; Heintz et al., 2007; Litwinienko et al., 2009; Michael et al., 1991; Michael et al., 1994.

Experimental top

The syntheses and spectroscopic characterization of the five compounds (II)–(VI) by bromination of the corresponding endo-nitronorbonenes have been reported previously (Michael et al., 1991). In these syntheses, transannular neighbouring group participation by the nitro group during bromination of the alkene bond is responsible for the introduction of the endo hydroxyl group in a regiospecific and totally stereoselective manner. Crystals of (II) were grown from methanol, (III) from benzene, (IV) from benzene, (V) from 1:1 ethylacetate/hexane and (VI) from acetone, by slow evaporation.

Refinement top

The whole-molecule disorder of (V) was modelled by finding alternative positions for all the atoms in the molecule. The corresponding bonded distance and the one-angle non-bonded distances in the two disorder components were restrained to have the same values, subject to s.u.s of 0.005 and 0.01 Å, respectively. The atomic displacement parameters were restrained to be equal for each of the atom pairs C1A/C1B, C2A/C2B, C3A/C3B, C5A/C5B, O1A/O1B, C6A/C6B, C7A/C7B, C8A/C8B, C9A/C9B, O2A/O2B, O3A/O3B, C10A/C10B and C11A/C11B. Refinement of the site occupancies gave values of 0.501 (8) and 0.499 (8): the occupancies were thereafter both fixed at 0.50. For all compounds, all C—H atoms were refined using a riding model, with distances of 0.95 Å (aromatic), 1.00 Å (aliphatic CH) and 0.99 Å (CH2), 0.98 Å (CH3) and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C). H atoms on O atoms which are involved in hydrogen-bonding interactions were located in difference maps for all compounds except (IV) and (V) (which where refined using a riding model) and their positions allowed to refine freely, with Uiso(H) = 1.5Ueq(O) for all compounds. The value of the Flack x parameter (Flack, 1983) for (II), 0.003 (19), confirms the correct orientation of the structure with respect to the two polar axis directions in space group Cc.

Computing details top

For all compounds, data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structures and atom-labelling schemes for (a) (II), (b) (III), (c) (IV), (d) and (e) respectively, for molecules A and B of (V), and (f) (VI). Displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms are drawn as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The three types of halogen bonding observed in this study of nitronorbornanols.
[Figure 3] Fig. 3. The C(8) hydrogen-bonded chain of (II), showing the Br···O halogen-bonded interactions along the [001] direction. The Br···Br halogen bonds along the [100] direction are not shown. Atoms marked with the superscripts (i) and (ii) are at the symmetry positions (x - 1/2, y + 1/2, z) and (x + 1, -y + 1, z + 1/2), respectively. H atoms not involved in hydrogen-bonding interactions are omitted for clarity.
[Figure 4] Fig. 4. The C(7) hydrogen-bonded chain of (III). Atoms marked with the superscript (i) are at the symmetry position (-x + 1, y + 1/2, -z + 3/2). H atoms not involved in hydrogen-bonding interactions are omitted for clarity.
[Figure 5] Fig. 5. (a) The C(8) hydrogen-bonded chain of (IV) as well as the Br···O halogen bonds [resulting in the formation of?] to form a two-dimensional sheet. (b) The sheets are then connected to a three-dimensional network by Br···Br halogen bonds. Atoms marked with the superscripts (i), (ii) and (iii) are at the symmetry positions (x - 1, y + 1, z), (x, y - 1, z), (-x + 1, -y + 2, -z + 1), respectively. H atoms not involved in hydrogen-bonding interactions are omitted for clarity.
[Figure 6] Fig. 6. The C(7) hydrogen-bonded chain of (V). Note how the halogen bonding connects every second molecule involved in hydrogen-bonded interactions within the chain (by translation only). Only the hydrogen bonding of molecule A is shown. Molecule B has similar interactions but [these?] are not shown in the figure. Atoms marked with the superscripts (i) and (ii) are at the symmetry positions (-x + 1, y + 1/2, -z + 1/2) and (x, y + 1, z), respectively. H atoms not involved in hydrogen-bonding interactions are omitted for clarity.
[Figure 7] Fig. 7. (a) The C(8) hydrogen-bonded chains of (VI) connected by Br···O halogen bonds to form two-dimensional sheets. (b) The sheets form bilayers through further Br···Br halogen bonding. Atoms marked with the superscripts (i), (ii) and (iii) are at the symmetry positions (x - 1, y, z - 1), (x + 1, y, z) and (-x + 2, -y, -z + 2), respectively. H atoms not involved in hydrogenbonding interactions are omitted for clarity.
(II) (±)-3-exo,6-exo-dibromo-5-endo-hydroxy-3-endo- nitrobicyclo[2.2.1]heptane-2-exo-carbonitrile top
Crystal data top
C8H8Br2N2O3F(000) = 656
Mr = 339.98Dx = 2.149 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 850 reflections
a = 6.6517 (8) Åθ = 2.5–28.2°
b = 16.084 (2) ŵ = 7.70 mm−1
c = 9.8254 (14) ÅT = 173 K
β = 91.825 (6)°Block, yellow
V = 1050.6 (2) Å30.6 × 0.2 × 0.2 mm
Z = 4
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1945 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.067
ω scansθmax = 28.0°, θmin = 2.5°
Absorption correction: integration
(XPREP; Bruker, 1999)		h = −8→8
Tmin = 0.075, Tmax = 0.301k = −21→17
3346 measured reflectionsl = −10→12
2038 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116 w = 1/[σ2(Fo2) + (0.0914P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2038 reflectionsΔρmax = 1.20 e Å−3
139 parametersΔρmin = −0.94 e Å−3
2 restraintsAbsolute structure: Flack (1983), 765 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.003 (19)
Crystal data top
C8H8Br2N2O3V = 1050.6 (2) Å3
Mr = 339.98Z = 4
Monoclinic, CcMo Kα radiation
a = 6.6517 (8) ŵ = 7.70 mm−1
b = 16.084 (2) ÅT = 173 K
c = 9.8254 (14) Å0.6 × 0.2 × 0.2 mm
β = 91.825 (6)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2038 independent reflections
Absorption correction: integration
(XPREP; Bruker, 1999)		1945 reflections with I > 2σ(I)
Tmin = 0.075, Tmax = 0.301Rint = 0.067
3346 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116Δρmax = 1.20 e Å−3
S = 1.04Δρmin = −0.94 e Å−3
2038 reflectionsAbsolute structure: Flack (1983), 765 Friedel pairs
139 parametersAbsolute structure parameter: 0.003 (19)
2 restraints
Special details top

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 1999)

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 (Å2) top
xyzUiso*/Ueq
C10.5593 (9)0.3530 (4)0.5982 (6)0.0187 (11)
H1A0.69520.33060.62470.022*
C20.4484 (9)0.3079 (4)0.4748 (6)0.0195 (11)
H20.4790.33850.38920.023*
C30.2221 (8)0.3221 (3)0.5061 (6)0.0176 (11)
C40.2295 (9)0.3867 (4)0.6192 (6)0.0197 (11)
H40.10010.39430.66660.024*
C50.3266 (10)0.4690 (4)0.5676 (7)0.0218 (11)
H50.31060.51430.63620.026*
C60.5531 (9)0.4451 (3)0.5579 (7)0.0212 (12)
H60.59680.45180.46210.025*
C70.4034 (8)0.3507 (4)0.7097 (6)0.0200 (11)
H7A0.43990.3870.7880.024*
H7B0.37570.29350.74160.024*
C80.5089 (10)0.2208 (4)0.4591 (7)0.0218 (12)
N10.0955 (8)0.3456 (3)0.3808 (6)0.0238 (11)
N20.5591 (10)0.1542 (4)0.4456 (7)0.0319 (13)
O10.2507 (9)0.4953 (3)0.4383 (6)0.0294 (11)
H10.185 (17)0.541 (7)0.449 (11)0.044*
O2−0.0749 (8)0.3697 (4)0.3984 (6)0.0370 (12)
O30.1674 (8)0.3368 (4)0.2676 (5)0.0363 (12)
Br10.08836 (7)0.22101 (4)0.56746 (6)0.02728 (18)
Br20.72707 (9)0.51130 (4)0.68145 (7)0.03009 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.022 (3)0.019 (2)0.015 (3)0.003 (2)0.001 (2)0.002 (2)
C20.021 (2)0.020 (3)0.018 (3)0.005 (2)0.003 (2)0.000 (2)
C30.019 (2)0.021 (2)0.013 (3)0.002 (2)0.003 (2)0.000 (2)
C40.023 (2)0.024 (3)0.012 (3)0.005 (2)0.005 (2)0.000 (2)
C50.028 (3)0.020 (2)0.018 (3)0.002 (2)0.003 (2)−0.004 (2)
C60.025 (3)0.019 (2)0.020 (3)0.000 (2)0.005 (2)−0.001 (2)
C70.023 (3)0.020 (3)0.017 (3)0.001 (2)0.000 (2)0.002 (2)
C80.024 (3)0.027 (3)0.015 (3)0.006 (2)0.003 (2)−0.004 (2)
N10.027 (2)0.027 (3)0.018 (3)0.006 (2)−0.004 (2)0.0000 (19)
N20.037 (3)0.025 (3)0.034 (4)0.007 (2)0.010 (3)−0.002 (2)
O10.043 (3)0.025 (2)0.020 (2)0.012 (2)0.002 (2)0.0058 (17)
O20.023 (2)0.052 (3)0.036 (3)0.012 (2)−0.002 (2)0.005 (2)
O30.042 (3)0.056 (3)0.011 (2)0.010 (3)0.000 (2)−0.004 (2)
Br10.0276 (3)0.0262 (3)0.0282 (3)−0.0045 (2)0.0032 (2)0.0022 (2)
Br20.0306 (3)0.0264 (3)0.0334 (4)−0.0056 (3)0.0014 (2)−0.0062 (3)
Geometric parameters (Å, º) top
C1—C61.533 (8)C4—H41
C1—C71.533 (8)C5—O11.416 (9)
C1—C21.576 (9)C5—C61.561 (8)
C1—H1A1C5—H51
C2—C81.468 (8)C6—Br21.964 (6)
C2—C31.562 (7)C6—H61
C2—H21C7—H7A0.99
C3—N11.516 (8)C7—H7B0.99
C3—C41.521 (8)C8—N21.131 (9)
C3—Br11.957 (6)N1—O21.215 (7)
C4—C71.548 (8)N1—O31.233 (7)
C4—C51.565 (9)O1—H10.86 (12)
C6—C1—C7101.3 (4)O1—C5—C6109.6 (5)
C6—C1—C2103.8 (5)O1—C5—C4113.8 (5)
C7—C1—C2103.2 (5)C6—C5—C4102.7 (5)
C6—C1—H1A115.6O1—C5—H5110.2
C7—C1—H1A115.6C6—C5—H5110.2
C2—C1—H1A115.6C4—C5—H5110.2
C8—C2—C3115.4 (5)C1—C6—C5103.9 (5)
C8—C2—C1113.4 (5)C1—C6—Br2110.7 (4)
C3—C2—C1102.2 (4)C5—C6—Br2112.3 (4)
C8—C2—H2108.5C1—C6—H6109.9
C3—C2—H2108.5C5—C6—H6109.9
C1—C2—H2108.5Br2—C6—H6109.9
N1—C3—C4115.3 (5)C1—C7—C495.2 (5)
N1—C3—C2113.0 (5)C1—C7—H7A112.7
C4—C3—C2103.6 (5)C4—C7—H7A112.7
N1—C3—Br1102.2 (4)C1—C7—H7B112.7
C4—C3—Br1110.3 (4)C4—C7—H7B112.7
C2—C3—Br1112.9 (4)H7A—C7—H7B110.2
C3—C4—C799.8 (5)N2—C8—C2178.5 (7)
C3—C4—C5110.2 (4)O2—N1—O3123.7 (6)
C7—C4—C5101.2 (5)O2—N1—C3117.4 (5)
C3—C4—H4114.6O3—N1—C3118.9 (5)
C7—C4—H4114.6C5—O1—H1108 (7)
C5—C4—H4114.6
C6—C1—C2—C8154.7 (5)C7—C4—C5—C632.8 (6)
C7—C1—C2—C8−100.0 (5)C7—C1—C6—C5−36.9 (6)
C6—C1—C2—C3−80.4 (5)C2—C1—C6—C569.8 (6)
C7—C1—C2—C324.9 (5)C7—C1—C6—Br283.8 (5)
C8—C2—C3—N1−99.2 (6)C2—C1—C6—Br2−169.5 (3)
C1—C2—C3—N1137.3 (5)O1—C5—C6—C1−119.1 (6)
C8—C2—C3—C4135.5 (5)C4—C5—C6—C12.2 (6)
C1—C2—C3—C411.9 (5)O1—C5—C6—Br2121.2 (5)
C8—C2—C3—Br116.2 (7)C4—C5—C6—Br2−117.5 (4)
C1—C2—C3—Br1−107.4 (4)C6—C1—C7—C456.4 (5)
N1—C3—C4—C7−168.0 (5)C2—C1—C7—C4−50.8 (5)
C2—C3—C4—C7−44.1 (5)C3—C4—C7—C158.4 (5)
Br1—C3—C4—C777.0 (5)C5—C4—C7—C1−54.6 (5)
N1—C3—C4—C5−62.1 (6)C4—C3—N1—O2−50.6 (8)
C2—C3—C4—C561.8 (6)C2—C3—N1—O2−169.4 (6)
Br1—C3—C4—C5−177.1 (4)Br1—C3—N1—O269.0 (6)
C3—C4—C5—O146.3 (6)C4—C3—N1—O3131.7 (6)
C7—C4—C5—O1151.2 (5)C2—C3—N1—O312.9 (8)
C3—C4—C5—C6−72.2 (6)Br1—C3—N1—O3−108.7 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N2i0.86 (12)2.01 (12)2.858 (8)169 (10)
Symmetry code: (i) x−1/2, y+1/2, z.
(III) (±)-3-exo,6-exo-dibromo-6-endo-nitro-5-exo- phenylbicyclo[2.2.1]heptan-2-endo-ol top
Crystal data top
C13H13Br2NO3F(000) = 768
Mr = 391.06Dx = 1.917 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1017 reflections
a = 15.945 (2) Åθ = 3.1–28.3°
b = 6.7578 (10) ŵ = 5.99 mm−1
c = 13.194 (2) ÅT = 173 K
β = 107.655 (9)°Block, colourless
V = 1354.7 (4) Å30.4 × 0.3 × 0.14 mm
Z = 4
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2786 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ω scansθmax = 28°, θmin = 2.7°
Absorption correction: integration
(XPREP; Bruker, 1999)		h = −21→21
Tmin = 0.110, Tmax = 0.467k = −8→8
18725 measured reflectionsl = −17→17
3256 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.052H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0279P)2 + 0.2753P]
where P = (Fo2 + 2Fc2)/3
3256 reflections(Δ/σ)max = 0.001
175 parametersΔρmax = 0.34 e Å−3
0 restraintsΔρmin = −0.64 e Å−3
Crystal data top
C13H13Br2NO3V = 1354.7 (4) Å3
Mr = 391.06Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.945 (2) ŵ = 5.99 mm−1
b = 6.7578 (10) ÅT = 173 K
c = 13.194 (2) Å0.4 × 0.3 × 0.14 mm
β = 107.655 (9)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		3256 independent reflections
Absorption correction: integration
(XPREP; Bruker, 1999)		2786 reflections with I > 2σ(I)
Tmin = 0.110, Tmax = 0.467Rint = 0.042
18725 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0220 restraints
wR(F2) = 0.052H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.34 e Å−3
3256 reflectionsΔρmin = −0.64 e Å−3
175 parameters
Special details top

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 1999)

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 (Å2) top
xyzUiso*/Ueq
C10.27775 (12)0.6233 (3)0.57508 (14)0.0177 (4)
H1A0.24640.7520.55360.021*
C20.26315 (12)0.5247 (3)0.67562 (14)0.0162 (3)
H20.31260.56770.73870.019*
C30.27825 (12)0.3023 (3)0.65528 (14)0.0170 (4)
C40.31402 (12)0.3024 (3)0.55985 (14)0.0175 (4)
H40.31330.17050.52520.021*
C50.40313 (12)0.4131 (3)0.58711 (14)0.0184 (4)
H50.42870.39920.5270.022*
C60.37772 (12)0.6322 (3)0.59711 (15)0.0185 (4)
H60.40650.68070.67110.022*
C70.25286 (12)0.4594 (3)0.48955 (14)0.0190 (4)
H7A0.26940.49280.42510.023*
H7B0.18990.42230.470.023*
C80.17800 (12)0.5797 (3)0.69702 (15)0.0183 (4)
C90.10191 (13)0.6295 (3)0.61630 (16)0.0231 (4)
H90.10180.62430.54430.028*
C100.02572 (14)0.6869 (3)0.63967 (19)0.0300 (5)
H10−0.02540.72250.58370.036*
C110.02444 (15)0.6920 (3)0.7441 (2)0.0315 (5)
H11−0.02730.73180.76010.038*
C120.09923 (15)0.6388 (3)0.82525 (18)0.0311 (5)
H120.09820.63930.89690.037*
C130.17549 (14)0.5849 (3)0.80255 (16)0.0255 (4)
H130.22660.55110.8590.031*
N10.33908 (11)0.1948 (2)0.75250 (13)0.0215 (3)
O10.46362 (9)0.3399 (2)0.68204 (12)0.0265 (3)
H10.5070 (18)0.397 (4)0.697 (2)0.04*
O20.36379 (9)0.0287 (2)0.73598 (12)0.0284 (3)
O30.35737 (11)0.2750 (2)0.83909 (11)0.0316 (3)
Br10.171486 (13)0.13845 (3)0.624805 (16)0.02452 (6)
Br20.410813 (13)0.80248 (3)0.494432 (17)0.02799 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0166 (9)0.0155 (9)0.0211 (9)0.0021 (7)0.0060 (7)0.0008 (7)
C20.0148 (8)0.0156 (9)0.0178 (8)0.0002 (7)0.0044 (7)−0.0019 (7)
C30.0152 (9)0.0161 (9)0.0183 (9)−0.0003 (7)0.0028 (7)−0.0001 (7)
C40.0176 (9)0.0168 (9)0.0179 (9)0.0015 (7)0.0051 (7)−0.0032 (7)
C50.0162 (9)0.0201 (10)0.0192 (9)0.0037 (7)0.0058 (7)0.0019 (7)
C60.0180 (9)0.0195 (10)0.0195 (9)−0.0004 (7)0.0080 (7)0.0013 (7)
C70.0180 (9)0.0212 (10)0.0162 (9)0.0017 (7)0.0029 (7)−0.0005 (7)
C80.0188 (9)0.0133 (9)0.0240 (9)−0.0006 (7)0.0082 (7)−0.0017 (7)
C90.0210 (10)0.0241 (10)0.0255 (10)0.0024 (8)0.0092 (8)0.0032 (8)
C100.0192 (10)0.0283 (12)0.0426 (13)0.0042 (8)0.0093 (9)0.0061 (9)
C110.0256 (11)0.0255 (11)0.0518 (14)0.0016 (9)0.0243 (10)−0.0019 (10)
C120.0334 (12)0.0353 (13)0.0308 (11)−0.0033 (10)0.0188 (10)−0.0080 (9)
C130.0240 (10)0.0276 (11)0.0252 (10)−0.0011 (8)0.0078 (8)−0.0056 (8)
N10.0187 (8)0.0223 (9)0.0239 (8)0.0019 (7)0.0072 (7)0.0052 (7)
O10.0144 (7)0.0310 (8)0.0290 (8)−0.0004 (6)−0.0011 (6)0.0094 (6)
O20.0258 (8)0.0197 (7)0.0380 (8)0.0073 (6)0.0071 (6)0.0047 (6)
O30.0399 (9)0.0345 (9)0.0175 (7)0.0037 (7)0.0041 (6)0.0018 (6)
Br10.01824 (10)0.01887 (11)0.03580 (12)−0.00312 (7)0.00719 (8)−0.00286 (8)
Br20.02564 (11)0.02399 (12)0.03997 (13)0.00349 (8)0.01839 (9)0.00903 (9)
Geometric parameters (Å, º) top
C1—C61.532 (2)C6—H61
C1—C71.545 (3)C7—H7A0.99
C1—C21.564 (2)C7—H7B0.99
C1—H1A1C8—C91.391 (3)
C2—C81.515 (2)C8—C131.405 (3)
C2—C31.558 (2)C9—C101.396 (3)
C2—H21C9—H90.95
C3—C41.532 (2)C10—C111.385 (3)
C3—N11.536 (2)C10—H100.95
C3—Br11.9676 (18)C11—C121.387 (3)
C4—C71.546 (3)C11—H110.95
C4—C51.549 (3)C12—C131.386 (3)
C4—H41C12—H120.95
C5—O11.418 (2)C13—H130.95
C5—C61.551 (3)N1—O31.217 (2)
C5—H51N1—O21.231 (2)
C6—Br21.9675 (18)O1—H10.76 (3)
C6—C1—C7100.87 (14)C5—C6—Br2111.61 (12)
C6—C1—C2105.65 (14)C1—C6—H6110
C7—C1—C2104.04 (14)C5—C6—H6110
C6—C1—H1A114.9Br2—C6—H6110
C7—C1—H1A114.9C1—C7—C494.51 (13)
C2—C1—H1A114.9C1—C7—H7A112.8
C8—C2—C3117.58 (15)C4—C7—H7A112.8
C8—C2—C1115.21 (15)C1—C7—H7B112.8
C3—C2—C1101.22 (13)C4—C7—H7B112.8
C8—C2—H2107.4H7A—C7—H7B110.3
C3—C2—H2107.4C9—C8—C13118.17 (18)
C1—C2—H2107.4C9—C8—C2122.65 (17)
C4—C3—N1112.85 (14)C13—C8—C2119.16 (17)
C4—C3—C2104.89 (14)C8—C9—C10120.89 (19)
N1—C3—C2113.81 (14)C8—C9—H9119.6
C4—C3—Br1110.30 (12)C10—C9—H9119.6
N1—C3—Br1101.10 (11)C11—C10—C9120.2 (2)
C2—C3—Br1114.13 (12)C11—C10—H10119.9
C3—C4—C799.72 (14)C9—C10—H10119.9
C3—C4—C5110.68 (15)C10—C11—C12119.53 (19)
C7—C4—C5100.08 (15)C10—C11—H11120.2
C3—C4—H4114.8C12—C11—H11120.2
C7—C4—H4114.8C13—C12—C11120.4 (2)
C5—C4—H4114.8C13—C12—H12119.8
O1—C5—C4111.54 (15)C11—C12—H12119.8
O1—C5—C6112.53 (16)C12—C13—C8120.7 (2)
C4—C5—C6103.66 (14)C12—C13—H13119.6
O1—C5—H5109.7C8—C13—H13119.6
C4—C5—H5109.7O3—N1—O2124.99 (17)
C6—C5—H5109.7O3—N1—C3118.98 (16)
C1—C6—C5103.30 (14)O2—N1—C3116.00 (15)
C1—C6—Br2111.91 (12)C5—O1—H1112 (2)
C6—C1—C2—C8153.54 (15)C4—C5—C6—C10.19 (17)
C7—C1—C2—C8−100.68 (17)O1—C5—C6—Br2119.16 (14)
C6—C1—C2—C3−78.50 (16)C4—C5—C6—Br2−120.20 (13)
C7—C1—C2—C327.28 (17)C6—C1—C7—C457.05 (16)
C8—C2—C3—C4135.65 (16)C2—C1—C7—C4−52.28 (16)
C1—C2—C3—C49.25 (17)C3—C4—C7—C156.91 (15)
C8—C2—C3—N1−100.53 (18)C5—C4—C7—C1−56.32 (15)
C1—C2—C3—N1133.06 (15)C3—C2—C8—C9−89.7 (2)
C8—C2—C3—Br114.8 (2)C1—C2—C8—C929.6 (3)
C1—C2—C3—Br1−111.58 (13)C3—C2—C8—C1391.6 (2)
N1—C3—C4—C7−166.71 (15)C1—C2—C8—C13−149.18 (18)
C2—C3—C4—C7−42.28 (17)C13—C8—C9—C101.3 (3)
Br1—C3—C4—C781.04 (15)C2—C8—C9—C10−177.45 (19)
N1—C3—C4—C5−61.97 (19)C8—C9—C10—C11−1.0 (3)
C2—C3—C4—C562.46 (18)C9—C10—C11—C12−0.3 (3)
Br1—C3—C4—C5−174.21 (12)C10—C11—C12—C131.4 (3)
C3—C4—C5—O152.3 (2)C11—C12—C13—C8−1.2 (3)
C7—C4—C5—O1156.77 (15)C9—C8—C13—C12−0.2 (3)
C3—C4—C5—C6−69.04 (18)C2—C8—C13—C12178.59 (19)
C7—C4—C5—C635.46 (16)C4—C3—N1—O3132.10 (18)
C7—C1—C6—C5−35.91 (17)C2—C3—N1—O312.7 (2)
C2—C1—C6—C572.17 (17)Br1—C3—N1—O3−110.11 (16)
C7—C1—C6—Br284.28 (15)C4—C3—N1—O2−49.8 (2)
C2—C1—C6—Br2−167.64 (12)C2—C3—N1—O2−169.18 (15)
O1—C5—C6—C1−120.45 (16)Br1—C3—N1—O268.00 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.76 (3)2.17 (3)2.927 (2)171 (3)
Symmetry code: (i) −x+1, y+1/2, −z+3/2.
(IV) (±)-methyl 3-exo,6-exo-dibromo-5-endo-hydroxy-3-endo- nitrobicyclo[2.2.1]heptane-2-exo-carboxylate top
Crystal data top
C9H11Br2NO5Z = 2
Mr = 373.01F(000) = 364
Triclinic, P1Dx = 2.125 Mg m−3
Dm = 0 Mg m−3
Dm measured by not measured
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7221 (2) ÅCell parameters from 3264 reflections
b = 7.7353 (3) Åθ = 2.8–28.1°
c = 12.1546 (5) ŵ = 6.96 mm−1
α = 88.296 (3)°T = 173 K
β = 80.595 (3)°Plate, colourless
γ = 69.323 (3)°0.28 × 0.12 × 0.04 mm
V = 583.08 (4) Å3
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2244 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.083
ω scansθmax = 28°, θmin = 1.7°
Absorption correction: integration
(XPREP; Bruker, 1999)		h = −8→8
Tmin = 0.318, Tmax = 0.770k = −10→10
7104 measured reflectionsl = −16→16
2805 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.07H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0307P)2]
where P = (Fo2 + 2Fc2)/3
2805 reflections(Δ/σ)max = 0.001
155 parametersΔρmax = 1.44 e Å−3
0 restraintsΔρmin = −1.41 e Å−3
Crystal data top
C9H11Br2NO5γ = 69.323 (3)°
Mr = 373.01V = 583.08 (4) Å3
Triclinic, P1Z = 2
a = 6.7221 (2) ÅMo Kα radiation
b = 7.7353 (3) ŵ = 6.96 mm−1
c = 12.1546 (5) ÅT = 173 K
α = 88.296 (3)°0.28 × 0.12 × 0.04 mm
β = 80.595 (3)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2805 independent reflections
Absorption correction: integration
(XPREP; Bruker, 1999)		2244 reflections with I > 2σ(I)
Tmin = 0.318, Tmax = 0.770Rint = 0.083
7104 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.07H-atom parameters constrained
S = 0.96Δρmax = 1.44 e Å−3
2805 reflectionsΔρmin = −1.41 e Å−3
155 parameters
Special details top

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 1999)

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 (Å2) top
xyzUiso*/Ueq
C10.3951 (5)0.5479 (4)0.3174 (2)0.0160 (6)
H1A0.54460.49040.33470.019*
C20.3608 (4)0.4824 (4)0.2044 (2)0.0134 (5)
H20.38880.56540.14390.016*
C30.1156 (4)0.5112 (4)0.2278 (2)0.0148 (6)
C40.0339 (5)0.6194 (4)0.3391 (2)0.0159 (6)
H4−0.11220.6240.37590.019*
C50.0621 (5)0.8099 (4)0.3296 (2)0.0166 (6)
H5−0.00980.88510.40.02*
C60.3099 (5)0.7587 (4)0.3168 (2)0.0159 (6)
H60.36620.80230.24410.019*
C70.2179 (5)0.5129 (4)0.4032 (2)0.0187 (6)
H7A0.23780.38020.40960.022*
H7B0.20190.56930.47770.022*
C80.5091 (5)0.2857 (4)0.1755 (2)0.0167 (6)
C90.6991 (6)0.0704 (4)0.0305 (3)0.0297 (7)
H9A0.71420.0555−0.05060.044*
H9B0.6508−0.02580.06710.044*
H9C0.83840.05940.05040.044*
N1−0.0081 (4)0.6094 (3)0.1355 (2)0.0171 (5)
O1−0.0071 (3)0.9136 (3)0.23726 (18)0.0201 (4)
H1−0.13910.97640.2530.03*
O2−0.2044 (3)0.6620 (3)0.15927 (19)0.0247 (5)
O30.0929 (4)0.6255 (3)0.04607 (18)0.0252 (5)
O40.5898 (4)0.1785 (3)0.24275 (19)0.0243 (5)
O50.5423 (3)0.2503 (3)0.06654 (17)0.0214 (5)
Br10.05890 (5)0.27961 (4)0.23778 (3)0.02055 (9)
Br20.39158 (5)0.86070 (5)0.44082 (3)0.02960 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0126 (14)0.0165 (14)0.0170 (14)−0.0015 (12)−0.0048 (11)0.0001 (11)
C20.0122 (13)0.0117 (13)0.0154 (14)−0.0031 (11)−0.0022 (10)0.0002 (11)
C30.0147 (14)0.0124 (13)0.0180 (14)−0.0051 (12)−0.0044 (11)0.0022 (11)
C40.0156 (14)0.0170 (14)0.0158 (14)−0.0063 (12)−0.0034 (11)0.0017 (11)
C50.0174 (15)0.0124 (13)0.0164 (14)−0.0010 (12)−0.0016 (11)−0.0047 (11)
C60.0160 (14)0.0150 (14)0.0174 (14)−0.0042 (12)−0.0071 (11)−0.0034 (11)
C70.0204 (15)0.0200 (15)0.0157 (14)−0.0059 (13)−0.0052 (11)0.0017 (12)
C80.0142 (14)0.0153 (14)0.0203 (15)−0.0057 (12)−0.0002 (11)−0.0033 (12)
C90.0285 (18)0.0214 (17)0.0286 (19)0.0024 (15)0.0001 (14)−0.0070 (14)
N10.0215 (14)0.0106 (12)0.0215 (14)−0.0068 (11)−0.0076 (10)0.0004 (10)
O10.0192 (11)0.0146 (10)0.0270 (12)−0.0046 (9)−0.0089 (9)0.0036 (9)
O20.0151 (12)0.0245 (12)0.0342 (13)−0.0039 (10)−0.0101 (9)0.0009 (10)
O30.0317 (13)0.0302 (13)0.0182 (11)−0.0150 (11)−0.0084 (9)0.0047 (10)
O40.0239 (12)0.0170 (11)0.0265 (12)0.0008 (10)−0.0067 (9)0.0003 (9)
O50.0244 (12)0.0153 (11)0.0190 (11)−0.0016 (9)−0.0002 (9)−0.0033 (9)
Br10.02076 (16)0.01412 (15)0.02957 (18)−0.00897 (12)−0.00580 (12)0.00232 (12)
Br20.02740 (19)0.02775 (19)0.0349 (2)−0.00640 (15)−0.01387 (14)−0.01265 (15)
Geometric parameters (Å, º) top
C1—C61.526 (4)C5—H51
C1—C71.544 (4)C6—Br21.961 (3)
C1—C21.556 (4)C6—H61
C1—H1A1C7—H7A0.99
C2—C81.509 (4)C7—H7B0.99
C2—C31.562 (4)C8—O41.199 (4)
C2—H21C8—O51.327 (4)
C3—C41.527 (4)C9—O51.446 (4)
C3—N11.528 (4)C9—H9A0.98
C3—Br11.955 (3)C9—H9B0.98
C4—C71.540 (4)C9—H9C0.98
C4—C51.549 (4)N1—O31.212 (3)
C4—H41N1—O21.222 (3)
C5—O11.405 (4)O1—H10.84
C5—C61.552 (4)
C6—C1—C7100.8 (2)C4—C5—H5109.8
C6—C1—C2106.0 (2)C6—C5—H5109.8
C7—C1—C2103.5 (2)C1—C6—C5103.5 (2)
C6—C1—H1A115C1—C6—Br2110.54 (19)
C7—C1—H1A115C5—C6—Br2111.78 (19)
C2—C1—H1A115C1—C6—H6110.3
C8—C2—C1110.6 (2)C5—C6—H6110.3
C8—C2—C3114.9 (2)Br2—C6—H6110.3
C1—C2—C3101.8 (2)C4—C7—C194.4 (2)
C8—C2—H2109.7C4—C7—H7A112.9
C1—C2—H2109.7C1—C7—H7A112.9
C3—C2—H2109.7C4—C7—H7B112.9
C4—C3—N1112.7 (2)C1—C7—H7B112.9
C4—C3—C2103.9 (2)H7A—C7—H7B110.3
N1—C3—C2114.1 (2)O4—C8—O5125.1 (3)
C4—C3—Br1110.72 (17)O4—C8—C2123.8 (3)
N1—C3—Br1102.39 (16)O5—C8—C2111.1 (3)
C2—C3—Br1113.37 (19)O5—C9—H9A109.5
C3—C4—C799.8 (2)O5—C9—H9B109.5
C3—C4—C5111.1 (2)H9A—C9—H9B109.5
C7—C4—C5100.7 (2)O5—C9—H9C109.5
C3—C4—H4114.5H9A—C9—H9C109.5
C7—C4—H4114.5H9B—C9—H9C109.5
C5—C4—H4114.5O3—N1—O2125.7 (3)
O1—C5—C4116.1 (2)O3—N1—C3118.7 (2)
O1—C5—C6107.8 (2)O2—N1—C3115.5 (2)
C4—C5—C6103.2 (2)C5—O1—H1109.5
O1—C5—H5109.8C8—O5—C9114.6 (2)
C6—C1—C2—C8158.6 (2)C7—C1—C6—Br283.1 (2)
C7—C1—C2—C8−95.7 (3)C2—C1—C6—Br2−169.26 (16)
C6—C1—C2—C3−78.8 (2)O1—C5—C6—C1−121.9 (2)
C7—C1—C2—C326.8 (3)C4—C5—C6—C11.4 (3)
C8—C2—C3—C4129.5 (2)O1—C5—C6—Br2119.1 (2)
C1—C2—C3—C410.0 (3)C4—C5—C6—Br2−117.6 (2)
C8—C2—C3—N1−107.4 (3)C3—C4—C7—C158.0 (2)
C1—C2—C3—N1133.0 (2)C5—C4—C7—C1−55.9 (2)
C8—C2—C3—Br19.3 (3)C6—C1—C7—C457.2 (2)
C1—C2—C3—Br1−110.3 (2)C2—C1—C7—C4−52.4 (3)
N1—C3—C4—C7−167.3 (2)C1—C2—C8—O421.4 (4)
C2—C3—C4—C7−43.2 (2)C3—C2—C8—O4−93.2 (3)
Br1—C3—C4—C778.8 (2)C1—C2—C8—O5−156.8 (2)
N1—C3—C4—C5−61.7 (3)C3—C2—C8—O588.6 (3)
C2—C3—C4—C562.3 (3)C4—C3—N1—O3131.6 (2)
Br1—C3—C4—C5−175.64 (18)C2—C3—N1—O313.5 (3)
C3—C4—C5—O147.2 (3)Br1—C3—N1—O3−109.5 (2)
C7—C4—C5—O1152.2 (3)C4—C3—N1—O2−49.8 (3)
C3—C4—C5—C6−70.5 (3)C2—C3—N1—O2−168.0 (2)
C7—C4—C5—C634.5 (3)Br1—C3—N1—O269.1 (2)
C7—C1—C6—C5−36.7 (3)O4—C8—O5—C9−3.8 (4)
C2—C1—C6—C570.9 (3)C2—C8—O5—C9174.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.841.962.752 (3)157
Symmetry code: (i) x−1, y+1, z.
(V) (±)-methyl 3-exo,6-exo-dibromo-7-(diphenylmethylidene)-5-endo- hydroxy-3-endo-nitrobicyclo[2.2.1]heptane-2-exo-carboxylate top
Crystal data top
C22H19Br2NO5F(000) = 1072
Mr = 537.2Dx = 1.675 Mg m−3
Dm = 0 Mg m−3
Dm measured by not measured
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3493 reflections
a = 15.8724 (8) Åθ = 2.6–26.1°
b = 9.0341 (4) ŵ = 3.84 mm−1
c = 15.0064 (7) ÅT = 173 K
β = 98.219 (2)°Needle, brown
V = 2129.71 (17) Å30.3 × 0.1 × 0.06 mm
Z = 4
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		3059 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.078
ω scansθmax = 28°, θmin = 1.3°
Absorption correction: integration
(XPREP; Bruker, 1999)		h = −20→15
Tmin = 0.509, Tmax = 0.817k = −11→11
17671 measured reflectionsl = −19→19
5119 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.057H-atom parameters constrained
S = 0.82 w = 1/[σ2(Fo2) + (0.0158P)2]
where P = (Fo2 + 2Fc2)/3
5119 reflections(Δ/σ)max = 0.001
467 parametersΔρmax = 0.45 e Å−3
83 restraintsΔρmin = −0.43 e Å−3
Crystal data top
C22H19Br2NO5V = 2129.71 (17) Å3
Mr = 537.2Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.8724 (8) ŵ = 3.84 mm−1
b = 9.0341 (4) ÅT = 173 K
c = 15.0064 (7) Å0.3 × 0.1 × 0.06 mm
β = 98.219 (2)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		5119 independent reflections
Absorption correction: integration
(XPREP; Bruker, 1999)		3059 reflections with I > 2σ(I)
Tmin = 0.509, Tmax = 0.817Rint = 0.078
17671 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03383 restraints
wR(F2) = 0.057H-atom parameters constrained
S = 0.82Δρmax = 0.45 e Å−3
5119 reflectionsΔρmin = −0.43 e Å−3
467 parameters
Special details top

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 1999)

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
C1A0.3573 (4)0.3060 (6)0.4454 (5)0.0254 (6)0.5
H1A10.35350.35160.50540.03*0.5
C2A0.3783 (5)0.1379 (6)0.4466 (5)0.0221 (7)0.5
H2A0.4410.12620.4470.027*0.5
C3A0.3324 (3)0.0877 (6)0.3539 (5)0.0226 (8)0.5
C4A0.3119 (5)0.2321 (7)0.3025 (5)0.019 (3)0.5
H4A0.27180.22250.24490.023*0.5
C5A0.3951 (7)0.3174 (8)0.2950 (6)0.0247 (8)0.5
H5A0.38330.40180.25190.03*0.5
C6A0.4217 (5)0.3767 (5)0.3921 (6)0.0269 (6)0.5
H6A0.48060.34270.41590.032*0.5
C7A0.2779 (4)0.3197 (9)0.3760 (4)0.0225 (7)0.5
C8A0.3536 (12)0.0554 (9)0.5266 (6)0.0281 (11)0.5
C9A0.351 (2)−0.1792 (17)0.5958 (18)0.0427 (8)0.5
H9A10.2952−0.14840.61060.064*0.5
H9A20.3941−0.16640.64870.064*0.5
H9A30.3483−0.28350.57770.064*0.5
C10A0.2049 (5)0.3894 (13)0.3769 (4)0.0273 (7)0.5
C11A0.1804 (8)0.4544 (10)0.4609 (4)0.0365 (9)0.5
C12A0.1677 (6)0.3657 (8)0.5332 (5)0.049 (3)0.5
H12A0.17760.26210.53130.059*0.5
C13A0.1404 (6)0.4292 (10)0.6084 (5)0.069 (3)0.5
H13A0.1360.36950.65970.083*0.5
C14A0.1203 (8)0.5733 (12)0.6100 (6)0.072 (4)0.5
H14A0.09460.61250.65830.086*0.5
C15A0.1375 (6)0.6655 (10)0.5396 (5)0.079 (5)0.5
H15A0.1310.76970.54370.095*0.5
C16A0.1638 (6)0.6039 (10)0.4651 (4)0.059 (3)0.5
H16A0.17070.66520.41520.07*0.5
C17A0.1434 (4)0.4138 (9)0.2933 (4)0.024 (2)0.5
C18A0.0572 (4)0.3908 (9)0.2938 (4)0.047 (2)0.5
H18A0.03740.35960.34760.056*0.5
C19A−0.0002 (4)0.4130 (10)0.2163 (4)0.062 (2)0.5
H19A−0.05910.39450.21660.075*0.5
C20A0.0278 (4)0.4620 (9)0.1388 (4)0.053 (2)0.5
H20A−0.01190.47990.08630.063*0.5
C21A0.1124 (4)0.4847 (9)0.1370 (4)0.041 (2)0.5
H21A0.13210.51280.08260.049*0.5
C22A0.1695 (4)0.4664 (11)0.2154 (5)0.033 (3)0.5
H22A0.22770.49070.21540.039*0.5
N1A0.3830 (5)−0.0234 (9)0.3053 (6)0.022 (2)0.5
O1A0.4573 (8)0.2237 (18)0.2677 (14)0.0325 (10)0.5
H1A0.49490.27490.24810.049*0.5
O2A0.3551 (8)−0.049 (2)0.2269 (8)0.036 (2)0.5
O3A0.4484 (8)−0.075 (2)0.3461 (10)0.028 (2)0.5
O4A0.3141 (16)0.1077 (19)0.5811 (11)0.034 (4)0.5
O5A0.3729 (16)−0.0882 (12)0.5217 (13)0.028 (4)0.5
Br1A0.22575 (17)−0.0178 (4)0.3625 (3)0.0363 (5)0.5
Br2A0.4151 (2)0.5928 (3)0.39687 (10)0.0300 (7)0.5
C1B0.3620 (4)0.3021 (6)0.4479 (5)0.0254 (6)0.5
H1B10.35520.34890.50690.03*0.5
C2B0.3892 (5)0.1363 (6)0.4527 (5)0.0221 (7)0.5
H2B0.45250.13090.45670.027*0.5
C3B0.3491 (3)0.0794 (6)0.3592 (5)0.0226 (8)0.5
C4B0.3227 (5)0.2199 (7)0.3058 (4)0.026 (4)0.5
H4B0.28410.20390.24790.032*0.5
C5B0.4021 (7)0.3157 (8)0.2985 (6)0.0247 (8)0.5
H5B0.3870.39830.25480.03*0.5
C6B0.4250 (5)0.3783 (5)0.3953 (6)0.0269 (6)0.5
H6B0.48470.35070.42050.032*0.5
C7B0.2834 (4)0.3044 (9)0.3773 (4)0.0225 (7)0.5
C8B0.3626 (12)0.0548 (9)0.5322 (6)0.0281 (11)0.5
C9B0.351 (2)−0.1818 (17)0.5959 (18)0.0427 (8)0.5
H9B10.2887−0.18140.57980.064*0.5
H9B20.3659−0.14510.65760.064*0.5
H9B30.3722−0.2830.59180.064*0.5
C10B0.2090 (5)0.3729 (13)0.3713 (4)0.0273 (7)0.5
C11B0.1810 (9)0.4593 (10)0.4464 (4)0.0365 (9)0.5
C12B0.1977 (6)0.4121 (8)0.5352 (5)0.045 (3)0.5
H12B0.22750.3220.5490.054*0.5
C13B0.1713 (5)0.4952 (9)0.6041 (5)0.051 (3)0.5
H13B0.1790.45650.66360.062*0.5
C14B0.1353 (7)0.6289 (9)0.5883 (6)0.050 (3)0.5
H14B0.12690.69310.63640.06*0.5
C15B0.1106 (6)0.6704 (9)0.4984 (5)0.069 (3)0.5
H15B0.07430.75330.48470.083*0.5
C16B0.1384 (5)0.5920 (9)0.4304 (5)0.047 (2)0.5
H16B0.12820.62970.37080.057*0.5
C17B0.1479 (4)0.3639 (9)0.2859 (4)0.026 (2)0.5
C18B0.0679 (4)0.3028 (9)0.2855 (4)0.052 (2)0.5
H18B0.05140.26680.33990.062*0.5
C19B0.0117 (4)0.2940 (10)0.2059 (5)0.076 (3)0.5
H19B−0.04210.2480.20560.091*0.5
C20B0.0335 (4)0.3516 (11)0.1275 (4)0.069 (2)0.5
H20B−0.00630.34910.07380.082*0.5
C21B0.1119 (5)0.4121 (10)0.1266 (5)0.058 (3)0.5
H21B0.12750.45010.07220.07*0.5
C22B0.1689 (4)0.4178 (11)0.2060 (5)0.030 (3)0.5
H22B0.22360.45980.20510.037*0.5
N1B0.4068 (5)−0.0233 (10)0.3133 (6)0.024 (2)0.5
O1B0.4686 (8)0.2307 (18)0.2723 (15)0.0325 (10)0.5
H1B0.48020.26180.22280.049*0.5
O2B0.3822 (8)−0.052 (2)0.2345 (8)0.036 (2)0.5
O3B0.4723 (8)−0.069 (2)0.3570 (10)0.028 (2)0.5
O4B0.3321 (16)0.1131 (18)0.5917 (11)0.032 (4)0.5
O5B0.3889 (16)−0.0859 (11)0.5337 (13)0.026 (3)0.5
Br1B0.24718 (18)−0.0420 (4)0.3638 (3)0.0327 (4)0.5
Br2B0.4108 (2)0.5935 (3)0.39699 (15)0.0510 (9)0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0311 (16)0.0237 (14)0.0206 (12)0.0090 (12)0.0012 (12)−0.0045 (11)
C2A0.025 (2)0.0225 (13)0.0173 (14)0.0043 (12)−0.0011 (13)−0.0016 (11)
C3A0.024 (2)0.0248 (14)0.0193 (13)−0.0001 (15)0.0050 (16)−0.0013 (12)
C4A0.018 (5)0.014 (5)0.024 (6)−0.002 (4)−0.003 (4)0.010 (4)
C5A0.029 (2)0.0201 (13)0.0258 (14)0.0041 (12)0.0065 (14)−0.0003 (11)
C6A0.0317 (17)0.0179 (13)0.0295 (14)0.0062 (11)−0.0009 (12)−0.0033 (11)
C7A0.0261 (16)0.0224 (18)0.0184 (12)0.0007 (12)0.0016 (12)0.0014 (12)
C8A0.029 (3)0.0330 (17)0.0192 (16)0.0079 (14)−0.0063 (18)0.0014 (12)
C9A0.055 (2)0.0391 (19)0.0351 (16)0.0090 (15)0.0090 (16)0.0158 (15)
C10A0.0262 (16)0.034 (2)0.0217 (14)0.0008 (13)0.0016 (12)0.0038 (12)
C11A0.0218 (16)0.058 (2)0.029 (2)0.0145 (15)0.002 (2)−0.0001 (19)
C12A0.039 (6)0.087 (7)0.020 (4)0.019 (5)0.005 (3)0.003 (4)
C13A0.043 (6)0.133 (10)0.033 (4)0.043 (7)0.007 (4)0.006 (5)
C14A0.044 (7)0.134 (12)0.040 (5)0.046 (8)0.014 (4)−0.003 (6)
C15A0.070 (8)0.126 (11)0.034 (6)0.070 (7)−0.017 (6)−0.037 (7)
C16A0.056 (6)0.089 (7)0.027 (4)0.024 (5)−0.010 (4)−0.007 (4)
C17A0.027 (4)0.024 (6)0.021 (3)0.008 (3)0.002 (3)−0.002 (3)
C18A0.033 (4)0.079 (6)0.029 (3)−0.001 (4)0.004 (3)0.006 (4)
C19A0.021 (4)0.114 (7)0.047 (4)−0.010 (4)−0.008 (3)−0.004 (5)
C20A0.052 (5)0.078 (5)0.023 (3)0.012 (4)−0.012 (3)−0.003 (4)
C21A0.037 (5)0.058 (6)0.025 (3)0.002 (4)0.000 (3)0.002 (3)
C22A0.036 (4)0.025 (7)0.036 (4)0.005 (3)0.001 (3)−0.001 (3)
N1A0.029 (4)0.017 (3)0.019 (4)−0.003 (3)−0.003 (3)0.000 (3)
O1A0.035 (3)0.0252 (15)0.040 (2)0.0010 (17)0.016 (2)−0.0019 (10)
O2A0.043 (7)0.0382 (14)0.0228 (19)0.001 (5)−0.007 (3)−0.0133 (17)
O3A0.028 (6)0.0259 (16)0.027 (3)0.008 (5)−0.006 (3)−0.0022 (19)
O4A0.034 (8)0.044 (5)0.023 (6)0.016 (4)0.003 (6)0.004 (4)
O5A0.037 (8)0.028 (4)0.018 (5)−0.001 (3)−0.001 (6)0.007 (3)
Br1A0.0378 (13)0.0390 (11)0.0306 (5)−0.0126 (8)−0.0002 (9)0.0037 (7)
Br2A0.0443 (13)0.0242 (13)0.0187 (6)−0.0016 (10)−0.0050 (7)−0.0064 (7)
C1B0.0311 (16)0.0237 (14)0.0206 (12)0.0090 (12)0.0012 (12)−0.0045 (11)
C2B0.025 (2)0.0225 (13)0.0173 (14)0.0043 (12)−0.0011 (13)−0.0016 (11)
C3B0.024 (2)0.0248 (14)0.0193 (13)−0.0001 (15)0.0050 (16)−0.0013 (12)
C4B0.032 (6)0.033 (7)0.012 (6)0.000 (5)−0.004 (4)−0.008 (4)
C5B0.029 (2)0.0201 (13)0.0258 (14)0.0041 (12)0.0065 (14)−0.0003 (11)
C6B0.0317 (17)0.0179 (13)0.0295 (14)0.0062 (11)−0.0009 (12)−0.0033 (11)
C7B0.0261 (16)0.0224 (18)0.0184 (12)0.0007 (12)0.0016 (12)0.0014 (12)
C8B0.029 (3)0.0330 (17)0.0192 (16)0.0079 (14)−0.0063 (18)0.0014 (12)
C9B0.055 (2)0.0391 (19)0.0351 (16)0.0090 (15)0.0090 (16)0.0158 (15)
C10B0.0262 (16)0.034 (2)0.0217 (14)0.0008 (13)0.0016 (12)0.0038 (12)
C11B0.0218 (16)0.058 (2)0.029 (2)0.0145 (15)0.002 (2)−0.0001 (19)
C12B0.046 (7)0.048 (4)0.041 (5)0.024 (5)0.009 (4)0.008 (4)
C13B0.055 (7)0.068 (6)0.032 (4)0.018 (5)0.010 (4)0.006 (4)
C14B0.057 (7)0.046 (5)0.059 (8)0.009 (4)0.044 (6)−0.001 (6)
C15B0.082 (8)0.080 (6)0.050 (6)0.048 (5)0.028 (5)0.013 (5)
C16B0.051 (6)0.057 (5)0.038 (4)0.030 (4)0.018 (4)0.010 (4)
C17B0.026 (4)0.015 (5)0.036 (4)0.007 (3)0.002 (3)0.002 (3)
C18B0.033 (5)0.074 (6)0.047 (4)−0.017 (4)−0.003 (3)0.008 (4)
C19B0.042 (5)0.110 (8)0.070 (6)−0.023 (5)−0.008 (4)−0.010 (6)
C20B0.051 (6)0.099 (7)0.047 (5)0.001 (5)−0.022 (4)0.011 (5)
C21B0.070 (7)0.064 (7)0.036 (4)−0.003 (5)−0.009 (4)0.009 (4)
C22B0.033 (4)0.023 (6)0.034 (4)0.000 (3)0.002 (3)0.003 (4)
N1B0.021 (4)0.025 (4)0.026 (4)−0.006 (3)0.003 (4)−0.010 (3)
O1B0.035 (3)0.0252 (15)0.040 (2)0.0010 (17)0.016 (2)−0.0019 (10)
O2B0.043 (7)0.0382 (14)0.0228 (19)0.001 (5)−0.007 (3)−0.0133 (17)
O3B0.028 (6)0.0259 (16)0.027 (3)0.008 (5)−0.006 (3)−0.0022 (19)
O4B0.042 (10)0.042 (4)0.010 (3)0.013 (4)−0.001 (5)−0.001 (3)
O5B0.036 (8)0.028 (4)0.012 (4)0.013 (4)−0.005 (5)0.002 (2)
Br1B0.0307 (11)0.0349 (9)0.0315 (5)−0.0055 (6)0.0011 (8)0.0044 (6)
Br2B0.0619 (18)0.0167 (13)0.0736 (13)0.0005 (12)0.0067 (10)−0.0048 (10)
Geometric parameters (Å, º) top
C1A—C7A1.520 (4)C1B—C7B1.518 (4)
C1A—C6A1.525 (4)C1B—C6B1.524 (4)
C1A—C2A1.555 (4)C1B—C2B1.557 (4)
C1A—H1A11C1B—H1B11
C2A—C8A1.511 (4)C2B—C8B1.512 (4)
C2A—C3A1.544 (4)C2B—C3B1.543 (4)
C2A—H2A1C2B—H2B1
C3A—C4A1.527 (5)C3B—C4B1.527 (5)
C3A—N1A1.534 (4)C3B—N1B1.535 (4)
C3A—Br1A1.963 (3)C3B—Br1B1.963 (3)
C4A—C7A1.518 (4)C4B—C7B1.522 (4)
C4A—C5A1.546 (4)C4B—C5B1.545 (4)
C4A—H4A1C4B—H4B1
C5A—O1A1.406 (4)C5B—O1B1.406 (4)
C5A—C6A1.553 (4)C5B—C6B1.553 (4)
C5A—H5A1C5B—H5B1
C6A—Br2A1.957 (3)C6B—Br2B1.957 (3)
C6A—H6A1C6B—H6B1
C7A—C10A1.321 (4)C7B—C10B1.325 (4)
C8A—O4A1.197 (4)C8B—O4B1.197 (4)
C8A—O5A1.338 (4)C8B—O5B1.337 (4)
C9A—O5A1.465 (6)C9B—O5B1.466 (6)
C9A—H9A10.98C9B—H9B10.98
C9A—H9A20.98C9B—H9B20.98
C9A—H9A30.98C9B—H9B30.98
C10A—C17A1.492 (4)C10B—C11B1.490 (4)
C10A—C11A1.492 (4)C10B—C17B1.495 (4)
C11A—C16A1.379 (6)C11B—C16B1.381 (6)
C11A—C12A1.387 (6)C11B—C12B1.387 (6)
C12A—C13A1.390 (5)C12B—C13B1.390 (5)
C12A—H12A0.95C12B—H12B0.95
C13A—C14A1.341 (9)C13B—C14B1.343 (9)
C13A—H13A0.95C13B—H13B0.95
C14A—C15A1.403 (9)C14B—C15B1.401 (9)
C14A—H14A0.95C14B—H14B0.95
C15A—C16A1.366 (7)C15B—C16B1.366 (7)
C15A—H15A0.95C15B—H15B0.95
C16A—H16A0.95C16B—H16B0.95
C17A—C22A1.378 (5)C17B—C22B1.379 (5)
C17A—C18A1.384 (5)C17B—C18B1.384 (5)
C18A—C19A1.387 (6)C18B—C19B1.387 (6)
C18A—H18A0.95C18B—H18B0.95
C19A—C20A1.376 (6)C19B—C20B1.376 (6)
C19A—H19A0.95C19B—H19B0.95
C20A—C21A1.361 (6)C20B—C21B1.361 (6)
C20A—H20A0.95C20B—H20B0.95
C21A—C22A1.389 (5)C21B—C22B1.390 (5)
C21A—H21A0.95C21B—H21B0.95
C22A—H22A0.95C22B—H22B0.95
N1A—O2A1.219 (4)N1B—O2B1.220 (4)
N1A—O3A1.221 (5)N1B—O3B1.221 (5)
O1A—H1A0.84O1B—H1B0.84
C7A—C1A—C6A99.2 (3)C6B—C1B—H1B1115.4
C7A—C1A—C2A104.1 (3)C2B—C1B—H1B1115.4
C6A—C1A—C2A104.9 (3)C8B—C2B—C3B115.4 (5)
C7A—C1A—H1A1115.6C8B—C2B—C1B113.5 (4)
C6A—C1A—H1A1115.6C3B—C2B—C1B101.7 (3)
C2A—C1A—H1A1115.6C8B—C2B—H2B108.6
C8A—C2A—C3A115.4 (5)C3B—C2B—H2B108.6
C8A—C2A—C1A114.4 (4)C1B—C2B—H2B108.6
C3A—C2A—C1A101.7 (3)C4B—C3B—N1B113.8 (4)
C8A—C2A—H2A108.3C4B—C3B—C2B104.3 (3)
C3A—C2A—H2A108.3N1B—C3B—C2B114.5 (4)
C1A—C2A—H2A108.3C4B—C3B—Br1B108.5 (4)
C4A—C3A—N1A114.0 (4)N1B—C3B—Br1B103.0 (3)
C4A—C3A—C2A104.1 (3)C2B—C3B—Br1B112.9 (3)
N1A—C3A—C2A114.1 (4)C7B—C4B—C3B99.0 (3)
C4A—C3A—Br1A109.0 (3)C7B—C4B—C5B101.0 (3)
N1A—C3A—Br1A103.2 (3)C3B—C4B—C5B109.8 (4)
C2A—C3A—Br1A112.6 (3)C7B—C4B—H4B115
C7A—C4A—C3A98.6 (3)C3B—C4B—H4B115
C7A—C4A—C5A100.9 (3)C5B—C4B—H4B115
C3A—C4A—C5A109.9 (4)O1B—C5B—C4B111.5 (5)
C7A—C4A—H4A115.1O1B—C5B—C6B112.0 (5)
C3A—C4A—H4A115.1C4B—C5B—C6B102.8 (3)
C5A—C4A—H4A115.1O1B—C5B—H5B110.1
O1A—C5A—C4A111.3 (5)C4B—C5B—H5B110.1
O1A—C5A—C6A111.9 (5)C6B—C5B—H5B110.1
C4A—C5A—C6A103.0 (3)C1B—C6B—C5B103.7 (3)
O1A—C5A—H5A110.1C1B—C6B—Br2B110.9 (3)
C4A—C5A—H5A110.1C5B—C6B—Br2B111.2 (3)
C6A—C5A—H5A110.1C1B—C6B—H6B110.3
C1A—C6A—C5A103.5 (3)C5B—C6B—H6B110.3
C1A—C6A—Br2A110.8 (4)Br2B—C6B—H6B110.3
C5A—C6A—Br2A111.7 (3)C10B—C7B—C1B133.6 (4)
C1A—C6A—H6A110.2C10B—C7B—C4B129.7 (4)
C5A—C6A—H6A110.2C1B—C7B—C4B96.1 (3)
Br2A—C6A—H6A110.2O4B—C8B—O5B124.3 (5)
C10A—C7A—C4A131.2 (4)O4B—C8B—C2B124.3 (5)
C10A—C7A—C1A132.4 (4)O5B—C8B—C2B110.8 (4)
C4A—C7A—C1A96.3 (3)O5B—C9B—H9B1109.5
O4A—C8A—O5A124.5 (6)O5B—C9B—H9B2109.5
O4A—C8A—C2A124.7 (5)H9B1—C9B—H9B2109.5
O5A—C8A—C2A110.4 (4)O5B—C9B—H9B3109.5
C7A—C10A—C17A122.1 (4)H9B1—C9B—H9B3109.5
C7A—C10A—C11A122.1 (4)H9B2—C9B—H9B3109.5
C17A—C10A—C11A115.8 (4)C7B—C10B—C11B123.6 (4)
C16A—C11A—C12A118.7 (4)C7B—C10B—C17B119.7 (4)
C16A—C11A—C10A119.9 (5)C11B—C10B—C17B116.8 (4)
C12A—C11A—C10A121.2 (5)C16B—C11B—C12B117.1 (4)
C11A—C12A—C13A119.6 (5)C16B—C11B—C10B121.0 (4)
C11A—C12A—H12A120.2C12B—C11B—C10B121.9 (4)
C13A—C12A—H12A120.2C11B—C12B—C13B120.8 (5)
C14A—C13A—C12A121.2 (6)C11B—C12B—H12B119.6
C14A—C13A—H13A119.4C13B—C12B—H12B119.6
C12A—C13A—H13A119.4C14B—C13B—C12B121.3 (6)
C13A—C14A—C15A119.4 (7)C14B—C13B—H13B119.3
C13A—C14A—H14A120.3C12B—C13B—H13B119.3
C15A—C14A—H14A120.3C13B—C14B—C15B117.6 (6)
C16A—C15A—C14A119.3 (7)C13B—C14B—H14B121.2
C16A—C15A—H15A120.3C15B—C14B—H14B121.2
C14A—C15A—H15A120.3C16B—C15B—C14B120.3 (7)
C15A—C16A—C11A121.2 (6)C16B—C15B—H15B119.8
C15A—C16A—H16A119.4C14B—C15B—H15B119.8
C11A—C16A—H16A119.4C15B—C16B—C11B121.5 (6)
C22A—C17A—C18A118.3 (4)C15B—C16B—H16B119.2
C22A—C17A—C10A121.6 (4)C11B—C16B—H16B119.2
C18A—C17A—C10A120.1 (4)C22B—C17B—C18B118.2 (4)
C17A—C18A—C19A120.3 (4)C22B—C17B—C10B121.3 (5)
C17A—C18A—H18A119.8C18B—C17B—C10B120.5 (4)
C19A—C18A—H18A119.8C17B—C18B—C19B120.2 (5)
C20A—C19A—C18A120.1 (5)C17B—C18B—H18B119.9
C20A—C19A—H19A119.9C19B—C18B—H18B119.9
C18A—C19A—H19A119.9C20B—C19B—C18B120.4 (5)
C21A—C20A—C19A120.3 (5)C20B—C19B—H19B119.8
C21A—C20A—H20A119.9C18B—C19B—H19B119.8
C19A—C20A—H20A119.9C21B—C20B—C19B120.1 (5)
C20A—C21A—C22A119.4 (5)C21B—C20B—H20B119.9
C20A—C21A—H21A120.3C19B—C20B—H20B119.9
C22A—C21A—H21A120.3C20B—C21B—C22B119.4 (5)
C17A—C22A—C21A121.3 (5)C20B—C21B—H21B120.3
C17A—C22A—H22A119.3C22B—C21B—H21B120.3
C21A—C22A—H22A119.3C17B—C22B—C21B121.6 (5)
O2A—N1A—O3A125.2 (5)C17B—C22B—H22B119.2
O2A—N1A—C3A116.2 (5)C21B—C22B—H22B119.2
O3A—N1A—C3A118.5 (5)O2B—N1B—O3B125.3 (5)
C8A—O5A—C9A114.9 (6)O2B—N1B—C3B115.8 (5)
C7B—C1B—C6B99.6 (3)O3B—N1B—C3B118.9 (5)
C7B—C1B—C2B103.8 (3)C5B—O1B—H1B109.5
C6B—C1B—C2B105.1 (3)C8B—O5B—C9B114.6 (6)
C7B—C1B—H1B1115.4
C7A—C1A—C2A—C8A−103.1 (7)C7B—C1B—C2B—C8B−100.9 (7)
C6A—C1A—C2A—C8A153.3 (7)C6B—C1B—C2B—C8B155.0 (7)
C7A—C1A—C2A—C3A22.0 (5)C7B—C1B—C2B—C3B23.8 (5)
C6A—C1A—C2A—C3A−81.7 (4)C6B—C1B—C2B—C3B−80.4 (4)
C8A—C2A—C3A—C4A138.6 (6)C8B—C2B—C3B—C4B135.7 (6)
C1A—C2A—C3A—C4A14.3 (5)C1B—C2B—C3B—C4B12.4 (5)
C8A—C2A—C3A—N1A−96.4 (6)C8B—C2B—C3B—N1B−99.3 (7)
C1A—C2A—C3A—N1A139.2 (5)C1B—C2B—C3B—N1B137.3 (5)
C8A—C2A—C3A—Br1A20.8 (6)C8B—C2B—C3B—Br1B18.1 (7)
C1A—C2A—C3A—Br1A−103.6 (4)C1B—C2B—C3B—Br1B−105.2 (4)
N1A—C3A—C4A—C7A−170.4 (4)N1B—C3B—C4B—C7B−169.4 (5)
C2A—C3A—C4A—C7A−45.4 (4)C2B—C3B—C4B—C7B−44.0 (4)
Br1A—C3A—C4A—C7A75.0 (4)Br1B—C3B—C4B—C7B76.6 (4)
N1A—C3A—C4A—C5A−65.4 (5)N1B—C3B—C4B—C5B−64.2 (5)
C2A—C3A—C4A—C5A59.6 (4)C2B—C3B—C4B—C5B61.2 (4)
Br1A—C3A—C4A—C5A179.9 (4)Br1B—C3B—C4B—C5B−178.2 (3)
C7A—C4A—C5A—O1A150.3 (7)C7B—C4B—C5B—O1B151.3 (7)
C3A—C4A—C5A—O1A46.9 (8)C3B—C4B—C5B—O1B47.5 (8)
C7A—C4A—C5A—C6A30.3 (5)C7B—C4B—C5B—C6B31.1 (5)
C3A—C4A—C5A—C6A−73.1 (5)C3B—C4B—C5B—C6B−72.7 (5)
C7A—C1A—C6A—C5A−39.6 (5)C7B—C1B—C6B—C5B−38.7 (5)
C2A—C1A—C6A—C5A67.7 (5)C2B—C1B—C6B—C5B68.5 (5)
C7A—C1A—C6A—Br2A80.3 (5)C7B—C1B—C6B—Br2B80.7 (5)
C2A—C1A—C6A—Br2A−172.4 (4)C2B—C1B—C6B—Br2B−172.0 (4)
O1A—C5A—C6A—C1A−113.9 (8)O1B—C5B—C6B—C1B−115.2 (8)
C4A—C5A—C6A—C1A5.8 (5)C4B—C5B—C6B—C1B4.6 (6)
O1A—C5A—C6A—Br2A126.9 (7)O1B—C5B—C6B—Br2B125.6 (7)
C4A—C5A—C6A—Br2A−113.5 (5)C4B—C5B—C6B—Br2B−114.6 (5)
C3A—C4A—C7A—C10A−125.1 (11)C6B—C1B—C7B—C10B−113.3 (12)
C5A—C4A—C7A—C10A122.6 (12)C2B—C1B—C7B—C10B138.4 (11)
C3A—C4A—C7A—C1A57.5 (4)C6B—C1B—C7B—C4B57.8 (4)
C5A—C4A—C7A—C1A−54.8 (4)C2B—C1B—C7B—C4B−50.5 (4)
C6A—C1A—C7A—C10A−119.0 (11)C3B—C4B—C7B—C10B−131.0 (11)
C2A—C1A—C7A—C10A133.0 (11)C5B—C4B—C7B—C10B116.7 (11)
C6A—C1A—C7A—C4A58.4 (4)C3B—C4B—C7B—C1B57.4 (4)
C2A—C1A—C7A—C4A−49.6 (4)C5B—C4B—C7B—C1B−55.0 (4)
C3A—C2A—C8A—O4A−111 (2)C3B—C2B—C8B—O4B−125 (2)
C1A—C2A—C8A—O4A7 (2)C1B—C2B—C8B—O4B−8 (2)
C3A—C2A—C8A—O5A61.7 (17)C3B—C2B—C8B—O5B64.3 (17)
C1A—C2A—C8A—O5A179.2 (15)C1B—C2B—C8B—O5B−178.9 (15)
C4A—C7A—C10A—C17A−10.1 (16)C1B—C7B—C10B—C11B−7.8 (18)
C1A—C7A—C10A—C17A166.4 (7)C4B—C7B—C10B—C11B−176.2 (7)
C4A—C7A—C10A—C11A172.6 (7)C1B—C7B—C10B—C17B173.0 (7)
C1A—C7A—C10A—C11A−10.9 (17)C4B—C7B—C10B—C17B4.5 (15)
C7A—C10A—C11A—C16A120.9 (12)C7B—C10B—C11B—C16B139.4 (12)
C17A—C10A—C11A—C16A−56.6 (14)C17B—C10B—C11B—C16B−41.3 (15)
C7A—C10A—C11A—C12A−64.1 (17)C7B—C10B—C11B—C12B−39.3 (18)
C17A—C10A—C11A—C12A118.5 (11)C17B—C10B—C11B—C12B139.9 (11)
C16A—C11A—C12A—C13A−1.4 (17)C16B—C11B—C12B—C13B0.8 (17)
C10A—C11A—C12A—C13A−176.5 (9)C10B—C11B—C12B—C13B179.6 (10)
C11A—C12A—C13A—C14A4.8 (17)C11B—C12B—C13B—C14B−5.5 (16)
C12A—C13A—C14A—C15A−8.4 (18)C12B—C13B—C14B—C15B11.7 (15)
C13A—C14A—C15A—C16A8.7 (17)C13B—C14B—C15B—C16B−13.5 (15)
C14A—C15A—C16A—C11A−5.5 (15)C14B—C15B—C16B—C11B9.3 (16)
C12A—C11A—C16A—C15A1.8 (16)C12B—C11B—C16B—C15B−2.8 (17)
C10A—C11A—C16A—C15A177.0 (8)C10B—C11B—C16B—C15B178.4 (10)
C7A—C10A—C17A—C22A−46.9 (15)C7B—C10B—C17B—C22B−61.3 (14)
C11A—C10A—C17A—C22A130.6 (9)C11B—C10B—C17B—C22B119.4 (9)
C7A—C10A—C17A—C18A136.4 (10)C7B—C10B—C17B—C18B119.7 (11)
C11A—C10A—C17A—C18A−46.1 (12)C11B—C10B—C17B—C18B−59.6 (12)
C22A—C17A—C18A—C19A3.3 (13)C22B—C17B—C18B—C19B1.3 (14)
C10A—C17A—C18A—C19A−179.9 (8)C10B—C17B—C18B—C19B−179.7 (8)
C17A—C18A—C19A—C20A−1.7 (14)C17B—C18B—C19B—C20B−2.8 (15)
C18A—C19A—C20A—C21A1.9 (14)C18B—C19B—C20B—C21B2.8 (16)
C19A—C20A—C21A—C22A−3.7 (14)C19B—C20B—C21B—C22B−1.3 (16)
C18A—C17A—C22A—C21A−5.2 (14)C18B—C17B—C22B—C21B0.2 (15)
C10A—C17A—C22A—C21A178.0 (8)C10B—C17B—C22B—C21B−178.9 (8)
C20A—C21A—C22A—C17A5.5 (14)C20B—C21B—C22B—C17B−0.2 (16)
C4A—C3A—N1A—O2A−50.0 (14)C4B—C3B—N1B—O2B−49.7 (14)
C2A—C3A—N1A—O2A−169.5 (13)C2B—C3B—N1B—O2B−169.5 (13)
Br1A—C3A—N1A—O2A68.0 (14)Br1B—C3B—N1B—O2B67.6 (14)
C4A—C3A—N1A—O3A127.7 (14)C4B—C3B—N1B—O3B130.4 (14)
C2A—C3A—N1A—O3A8.2 (15)C2B—C3B—N1B—O3B10.7 (15)
Br1A—C3A—N1A—O3A−114.2 (14)Br1B—C3B—N1B—O3B−112.3 (15)
O4A—C8A—O5A—C9A−7 (4)O4B—C8B—O5B—C9B22 (4)
C2A—C8A—O5A—C9A−179 (2)C2B—C8B—O5B—C9B−167 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O3Ai0.842.243.03 (2)157
O1B—H1B···O3Bi0.842.142.90 (3)151
Symmetry code: (i) −x+1, y+1/2, −z+1/2.
(VI) (±)-methyl 3-exo,6-exo-dibromo-5-endo-hydroxy-3-endo-nitro- 7-oxabicyclo[2.2.1]heptane-2-exo-carboxylate top
Crystal data top
C8H9Br2NO6F(000) = 728
Mr = 374.98Dx = 2.209 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 921 reflections
a = 7.8071 (13) Åθ = 3.2–28.4°
b = 22.760 (4) ŵ = 7.21 mm−1
c = 6.7673 (10) ÅT = 173 K
β = 110.32 (1)°Block, colourless
V = 1127.7 (3) Å30.42 × 0.4 × 0.2 mm
Z = 4
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2453 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
ω scansθmax = 28°, θmin = 2.8°
Absorption correction: integration
(XPREP; Bruker, 1999)		h = −10→9
Tmin = 0.092, Tmax = 0.290k = −30→30
12168 measured reflectionsl = −8→8
2715 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.22 w = 1/[σ2(Fo2) + 1.494P]
where P = (Fo2 + 2Fc2)/3
2715 reflections(Δ/σ)max = 0.001
158 parametersΔρmax = 0.47 e Å−3
0 restraintsΔρmin = −0.92 e Å−3
Crystal data top
C8H9Br2NO6V = 1127.7 (3) Å3
Mr = 374.98Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.8071 (13) ŵ = 7.21 mm−1
b = 22.760 (4) ÅT = 173 K
c = 6.7673 (10) Å0.42 × 0.4 × 0.2 mm
β = 110.32 (1)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2715 independent reflections
Absorption correction: integration
(XPREP; Bruker, 1999)		2453 reflections with I > 2σ(I)
Tmin = 0.092, Tmax = 0.290Rint = 0.085
12168 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.22Δρmax = 0.47 e Å−3
2715 reflectionsΔρmin = −0.92 e Å−3
158 parameters
Special details top

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 1999)

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 (Å2) top
xyzUiso*/Ueq
C10.4596 (4)0.08700 (13)0.8249 (4)0.0151 (5)
H1A0.51910.0780.97820.018*
C20.5255 (4)0.14527 (13)0.7547 (4)0.0149 (5)
H20.44420.17850.76180.018*
C30.4978 (4)0.13033 (13)0.5217 (4)0.0157 (5)
C40.3934 (4)0.07166 (13)0.4912 (4)0.0165 (6)
H40.39310.04910.36430.02*
C50.2012 (4)0.07874 (14)0.5083 (4)0.0178 (6)
H50.13020.04150.46420.021*
C60.2510 (4)0.08814 (13)0.7492 (4)0.0171 (5)
H60.20610.12710.77880.02*
C70.7230 (4)0.15867 (13)0.8883 (4)0.0177 (6)
C80.9566 (4)0.22856 (17)0.9698 (6)0.0302 (7)
H8A0.99120.21711.11810.045*
H8B0.97350.2710.96030.045*
H8C1.03340.20760.90520.045*
N10.3988 (3)0.17724 (11)0.3625 (4)0.0180 (5)
O10.0960 (3)0.12686 (10)0.4001 (4)0.0221 (5)
H10.029 (6)0.1174 (19)0.269 (7)0.033*
O20.3489 (3)0.16231 (11)0.1774 (3)0.0270 (5)
O30.3757 (3)0.22552 (10)0.4268 (4)0.0286 (5)
O40.8248 (3)0.12368 (10)1.0054 (4)0.0251 (5)
O50.7660 (3)0.21368 (10)0.8594 (3)0.0229 (5)
O60.4935 (3)0.04365 (9)0.6866 (3)0.0183 (4)
Br10.72464 (4)0.118459 (15)0.46861 (5)0.02389 (10)
Br20.16270 (4)0.025117 (16)0.88365 (5)0.02651 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0163 (13)0.0148 (13)0.0129 (12)−0.0008 (10)0.0035 (10)−0.0011 (10)
C20.0173 (13)0.0132 (13)0.0138 (12)0.0008 (10)0.0049 (10)−0.0008 (10)
C30.0156 (13)0.0179 (14)0.0136 (12)0.0022 (10)0.0049 (10)0.0002 (11)
C40.0185 (13)0.0152 (14)0.0148 (12)0.0007 (11)0.0043 (11)−0.0025 (11)
C50.0132 (12)0.0198 (14)0.0170 (13)−0.0006 (11)0.0011 (10)0.0019 (11)
C60.0193 (13)0.0156 (14)0.0165 (12)−0.0021 (11)0.0064 (11)0.0010 (11)
C70.0200 (14)0.0182 (14)0.0149 (12)−0.0021 (11)0.0061 (11)−0.0023 (11)
C80.0223 (15)0.0312 (18)0.0323 (17)−0.0119 (14)0.0037 (13)−0.0040 (15)
N10.0182 (11)0.0177 (12)0.0183 (11)−0.0012 (10)0.0065 (10)0.0031 (10)
O10.0178 (10)0.0269 (12)0.0182 (10)0.0058 (9)0.0019 (8)0.0042 (9)
O20.0322 (12)0.0320 (13)0.0139 (10)0.0021 (10)0.0043 (9)0.0024 (9)
O30.0377 (13)0.0173 (11)0.0289 (12)0.0041 (10)0.0091 (10)0.0018 (10)
O40.0201 (11)0.0254 (12)0.0229 (11)−0.0031 (9)−0.0012 (9)0.0047 (9)
O50.0202 (10)0.0196 (11)0.0251 (11)−0.0041 (9)0.0033 (9)−0.0005 (9)
O60.0220 (10)0.0151 (10)0.0158 (9)0.0046 (8)0.0039 (8)−0.0002 (8)
Br10.01801 (14)0.03388 (19)0.02190 (16)0.00381 (12)0.00963 (12)−0.00164 (13)
Br20.02506 (16)0.03039 (18)0.02249 (16)−0.00843 (13)0.00624 (12)0.00615 (13)
Geometric parameters (Å, º) top
C1—O61.446 (3)C5—C61.554 (4)
C1—C61.528 (4)C5—H51
C1—C21.555 (4)C6—Br21.948 (3)
C1—H1A1C6—H61
C2—C71.523 (4)C7—O41.207 (4)
C2—C31.553 (4)C7—O51.328 (4)
C2—H21C8—O51.454 (4)
C3—N11.523 (4)C8—H8A0.98
C3—C41.540 (4)C8—H8B0.98
C3—Br11.944 (3)C8—H8C0.98
C4—O61.431 (3)N1—O31.218 (4)
C4—C51.553 (4)N1—O21.223 (3)
C4—H41O1—H10.89 (4)
C5—O11.411 (4)
O6—C1—C6102.0 (2)C4—C5—C6101.3 (2)
O6—C1—C2103.3 (2)O1—C5—H5109.9
C6—C1—C2108.1 (2)C4—C5—H5109.9
O6—C1—H1A114.1C6—C5—H5109.9
C6—C1—H1A114.1C1—C6—C5101.4 (2)
C2—C1—H1A114.1C1—C6—Br2109.9 (2)
C7—C2—C3113.7 (2)C5—C6—Br2112.9 (2)
C7—C2—C1111.3 (2)C1—C6—H6110.8
C3—C2—C1100.3 (2)C5—C6—H6110.8
C7—C2—H2110.4Br2—C6—H6110.8
C3—C2—H2110.4O4—C7—O5125.2 (3)
C1—C2—H2110.4O4—C7—C2123.9 (3)
N1—C3—C4113.5 (2)O5—C7—C2110.9 (2)
N1—C3—C2115.0 (2)O5—C8—H8A109.5
C4—C3—C2101.9 (2)O5—C8—H8B109.5
N1—C3—Br1103.75 (18)H8A—C8—H8B109.5
C4—C3—Br1109.16 (19)O5—C8—H8C109.5
C2—C3—Br1113.77 (19)H8A—C8—H8C109.5
O6—C4—C399.7 (2)H8B—C8—H8C109.5
O6—C4—C5102.1 (2)O3—N1—O2125.6 (3)
C3—C4—C5112.3 (2)O3—N1—C3118.8 (2)
O6—C4—H4113.8O2—N1—C3115.6 (2)
C3—C4—H4113.8C5—O1—H1111 (3)
C5—C4—H4113.8C7—O5—C8114.2 (3)
O1—C5—C4116.4 (2)C4—O6—C197.5 (2)
O1—C5—C6109.0 (2)
O6—C1—C2—C7−93.9 (3)O6—C1—C6—Br284.0 (2)
C6—C1—C2—C7158.5 (2)C2—C1—C6—Br2−167.60 (18)
O6—C1—C2—C326.7 (2)O1—C5—C6—C1−121.4 (2)
C6—C1—C2—C3−80.8 (3)C4—C5—C6—C11.9 (3)
C7—C2—C3—N1−109.0 (3)O1—C5—C6—Br2121.1 (2)
C1—C2—C3—N1132.1 (2)C4—C5—C6—Br2−115.6 (2)
C7—C2—C3—C4127.8 (2)C3—C2—C7—O4−99.5 (3)
C1—C2—C3—C48.9 (3)C1—C2—C7—O412.9 (4)
C7—C2—C3—Br110.5 (3)C3—C2—C7—O581.0 (3)
C1—C2—C3—Br1−108.5 (2)C1—C2—C7—O5−166.5 (2)
N1—C3—C4—O6−166.4 (2)C4—C3—N1—O3128.5 (3)
C2—C3—C4—O6−42.2 (2)C2—C3—N1—O311.8 (4)
Br1—C3—C4—O678.4 (2)Br1—C3—N1—O3−113.1 (2)
N1—C3—C4—C5−59.0 (3)C4—C3—N1—O2−51.5 (3)
C2—C3—C4—C565.2 (3)C2—C3—N1—O2−168.2 (2)
Br1—C3—C4—C5−174.12 (18)Br1—C3—N1—O266.9 (3)
O6—C4—C5—O1150.8 (2)O4—C7—O5—C84.9 (4)
C3—C4—C5—O144.9 (3)C2—C7—O5—C8−175.6 (3)
O6—C4—C5—C632.7 (3)C3—C4—O6—C159.7 (2)
C3—C4—C5—C6−73.2 (3)C5—C4—O6—C1−55.8 (2)
O6—C1—C6—C5−35.7 (3)C6—C1—O6—C457.5 (2)
C2—C1—C6—C572.8 (3)C2—C1—O6—C4−54.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.89 (4)1.94 (4)2.774 (3)156 (4)
Symmetry code: (i) x−1, y, z−1.

Experimental details

(II)(III)(IV)(V)
Crystal data
Chemical formulaC8H8Br2N2O3C13H13Br2NO3C9H11Br2NO5C22H19Br2NO5
Mr339.98391.06373.01537.2
Crystal system, space groupMonoclinic, CcMonoclinic, P21/cTriclinic, P1Monoclinic, P21/c
Temperature (K)173173173173
a, b, c (Å)6.6517 (8), 16.084 (2), 9.8254 (14)15.945 (2), 6.7578 (10), 13.194 (2)6.7221 (2), 7.7353 (3), 12.1546 (5)15.8724 (8), 9.0341 (4), 15.0064 (7)
α, β, γ (°)90, 91.825 (6), 9090, 107.655 (9), 9088.296 (3), 80.595 (3), 69.323 (3)90, 98.219 (2), 90
V (Å3)1050.6 (2)1354.7 (4)583.08 (4)2129.71 (17)
Z4424
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm−1)7.705.996.963.84
Crystal size (mm)0.6 × 0.2 × 0.20.4 × 0.3 × 0.140.28 × 0.12 × 0.040.3 × 0.1 × 0.06
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer		Bruker SMART 1K CCD area-detector
diffractometer		Bruker SMART 1K CCD area-detector
diffractometer		Bruker SMART 1K CCD area-detector
diffractometer
Absorption correctionIntegration
(XPREP; Bruker, 1999)		Integration
(XPREP; Bruker, 1999)		Integration
(XPREP; Bruker, 1999)		Integration
(XPREP; Bruker, 1999)
Tmin, Tmax0.075, 0.3010.110, 0.4670.318, 0.7700.509, 0.817
No. of measured, independent and
observed [I > 2σ(I)] reflections		3346, 2038, 1945 18725, 3256, 2786 7104, 2805, 2244 17671, 5119, 3059
Rint0.0670.0420.0830.078
(sin θ/λ)max (Å−1)0.6600.6610.6610.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.116, 1.04 0.022, 0.052, 1.04 0.039, 0.07, 0.96 0.033, 0.057, 0.82
No. of reflections2038325628055119
No. of parameters139175155467
No. of restraints20083
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)1.20, −0.940.34, −0.641.44, −1.410.45, −0.43
Absolute structureFlack (1983), 765 Friedel pairs???
Absolute structure parameter0.003 (19)???


(VI)
Crystal data
Chemical formulaC8H9Br2NO6
Mr374.98
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)7.8071 (13), 22.760 (4), 6.7673 (10)
α, β, γ (°)90, 110.32 (1), 90
V (Å3)1127.7 (3)
Z4
Radiation typeMo Kα
µ (mm−1)7.21
Crystal size (mm)0.42 × 0.4 × 0.2
Data collection
DiffractometerBruker SMART 1K CCD area-detector
diffractometer
Absorption correctionIntegration
(XPREP; Bruker, 1999)
Tmin, Tmax0.092, 0.290
No. of measured, independent and
observed [I > 2σ(I)] reflections		12168, 2715, 2453
Rint0.085
(sin θ/λ)max (Å−1)0.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.076, 1.22
No. of reflections2715
No. of parameters158
No. of restraints0
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.47, −0.92
Absolute structure?
Absolute structure parameter?

Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N2i0.86 (12)2.01 (12)2.858 (8)169 (10)
Symmetry code: (i) x−1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.76 (3)2.17 (3)2.927 (2)171 (3)
Symmetry code: (i) −x+1, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.841.962.752 (3)157
Symmetry code: (i) x−1, y+1, z.
Hydrogen-bond geometry (Å, º) for (V) top
D—H···AD—HH···AD···AD—H···A
O1A—H1A···O3Ai0.842.243.03 (2)157
O1B—H1B···O3Bi0.842.142.90 (3)151
Symmetry code: (i) −x+1, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) for (VI) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.89 (4)1.94 (4)2.774 (3)156 (4)
Symmetry code: (i) x−1, y, z−1.
Table 6. Br···Br and Br···O geometries in all compounds (Å, °). top
CompoundInteractionX···Xθ1θ2Type
(II)C3—Br1···Br2i3.663 (2)13899II
C6—Br2···O2ii3.205 (2)155III
(IV)C6—Br2···Br2iii3.453 (4)155155I
C3—Br1···O1iv3.017 (3)176III
(V)C6A—Br2A···O3Av3.159 (2)158III
C6B—Br2B···O3Bv3.258 (2)152III
(VI)C6—Br2···Br2vi3.608 (10)149149I
C3—Br1···O1vii3.097 (5)168III
Symmetry codes: (i) x-1/2, y-1/2, z; (ii) x+1, -y+1, z+1/2; (iii) -x+1, -y+2, -z+1; (iv) x, y-1, z; (v) x, y+1, z; (vi) -x+2, -y, -z+2; (vii) x+1, y, z.
 

Acknowledgements

This material is based upon work supported financially by the National Research Foundation, Pretoria (GUN 65559). Any opinions, findings and conclusions or recommendations expressed in this material are those of the authors and therefore the NRF does not accept any liability in regard thereto. This work was also supported by the University of the Witwatersrand, which is thanked for providing the infrastructure required to do this work.

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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296
Volume 67| Part 8| August 2011| Pages o288-o293
doi:10.1107/S0108270111024140
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