Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055493/kp2145sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055493/kp2145Isup2.hkl |
CCDC reference: 672883
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.034
- wR factor = 0.091
- Data-to-parameter ratio = 14.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.93 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C20 H24 N2 O6 Se2 Atom count from _chemical_formula_moiety:C17 H17 N1 O5 Se22 ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.931 Tmax scaled 0.530 Tmin scaled 0.418 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Absolute ethanol (30 ml), dried by distillation over sodium, was added with magnetic stirring to 1.0 g (12.6 mmol) of selenium and 0.35 g (9.3 mmol) of sodium borohydride cooled on an ice bath. After the initial reaction had subsided, the mixture was stirred and heated at reflux for 1.5 h with N2 introduced into the liquid in order to dissolve the selenium and expel H2Se. Cooled on an ice bath again, diazonium salt (8.4 mmol) prepared from anthranilic acid was added and the solution was refluxed for 3 h. O2 was passed through the mixture slowly for 1.5 h to remove any H2Se. After acidification with hydrochloric acid, the filter cake was dissolved in sodium acid carbonate solution and reflux for 1 h, then acidified with hydrochloric acid again. The pale-yellow solid product was collected by filtration and recrystallized from DMF-methanol (2: 1). Yield: 85%, 1H NMR (DMSO-d6) δ: 8.20 (d, 2 H), 7.64 (d, 2 H), 7.50 (t, 2 H), 7.38 (t, 2 H); 13C NMR (DMSO-d6) δ:123.2, 124.8, 127.0, 128.5, 131.3, 131.9, 166.9 (C=O); 77Se NMR (DMSO-d6) δ: 439.2. Anal. Calcd. for: C14H10O4Se2, C, 42.02; H, 2.52% Found: C, 41.58; H, 2.49%.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. The molecular structure of the title compound. The solvent molecules have been omitted. |
C14H10O4Se2·2C3H7NO | F(000) = 1096 |
Mr = 546.34 | Dx = 1.541 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C2yc | Cell parameters from 1983 reflections |
a = 8.202 (2) Å | θ = 2.9–27.3° |
b = 13.223 (4) Å | µ = 3.18 mm−1 |
c = 21.849 (6) Å | T = 293 K |
β = 96.425 (4)° | Block, yellow |
V = 2354.6 (11) Å3 | 0.30 × 0.20 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2072 independent reflections |
Radiation source: fine-focus sealed tube | 1607 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.449, Tmax = 0.569 | k = −14→15 |
4745 measured reflections | l = −25→25 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0388P)2 + 1.4577P] where P = (Fo2 + 2Fc2)/3 |
2072 reflections | (Δ/σ)max = 0.002 |
139 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C14H10O4Se2·2C3H7NO | V = 2354.6 (11) Å3 |
Mr = 546.34 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 8.202 (2) Å | µ = 3.18 mm−1 |
b = 13.223 (4) Å | T = 293 K |
c = 21.849 (6) Å | 0.30 × 0.20 × 0.20 mm |
β = 96.425 (4)° |
Bruker SMART CCD area-detector diffractometer | 2072 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1607 reflections with I > 2σ(I) |
Tmin = 0.449, Tmax = 0.569 | Rint = 0.025 |
4745 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.41 e Å−3 |
2072 reflections | Δρmin = −0.32 e Å−3 |
139 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Se | 1.03742 (4) | 0.89916 (3) | 0.303005 (16) | 0.06579 (17) | |
N | 0.3833 (4) | 0.0067 (3) | 0.60861 (14) | 0.0774 (9) | |
O1 | 1.0166 (5) | 0.7946 (3) | 0.49575 (13) | 0.1180 (12) | |
H1 | 1.0792 | 0.8286 | 0.5193 | 0.177* | |
O2 | 1.1015 (3) | 0.89762 (19) | 0.42617 (12) | 0.0793 (7) | |
O3 | 0.2003 (5) | −0.1147 (3) | 0.57969 (15) | 0.1173 (12) | |
C1 | 0.9004 (4) | 0.7933 (2) | 0.33137 (16) | 0.0568 (8) | |
C2 | 0.9069 (4) | 0.7714 (2) | 0.39329 (16) | 0.0591 (8) | |
C3 | 0.8061 (4) | 0.6957 (3) | 0.41283 (18) | 0.0735 (10) | |
H3 | 0.8099 | 0.6813 | 0.4546 | 0.088* | |
C4 | 0.7014 (5) | 0.6421 (3) | 0.3715 (2) | 0.0815 (11) | |
H4 | 0.6346 | 0.5918 | 0.3849 | 0.098* | |
C5 | 0.6972 (5) | 0.6636 (3) | 0.3109 (2) | 0.0829 (12) | |
H5 | 0.6268 | 0.6272 | 0.2827 | 0.099* | |
C6 | 0.7950 (4) | 0.7384 (3) | 0.28949 (18) | 0.0719 (10) | |
H6 | 0.7901 | 0.7518 | 0.2475 | 0.086* | |
C7 | 1.0173 (5) | 0.8280 (3) | 0.44022 (17) | 0.0698 (10) | |
C8 | 0.2838 (5) | −0.0414 (4) | 0.5669 (2) | 0.0895 (12) | |
H8 | 0.2762 | −0.0195 | 0.5262 | 0.107* | |
C9 | 0.3944 (6) | −0.0226 (4) | 0.67189 (18) | 0.1087 (17) | |
H9A | 0.3579 | 0.0321 | 0.6958 | 0.163* | |
H9B | 0.5062 | −0.0388 | 0.6863 | 0.163* | |
H9C | 0.3265 | −0.0808 | 0.6760 | 0.163* | |
C10 | 0.4853 (6) | 0.0882 (4) | 0.5917 (2) | 0.1167 (17) | |
H10A | 0.5978 | 0.0666 | 0.5958 | 0.175* | |
H10B | 0.4740 | 0.1451 | 0.6182 | 0.175* | |
H10C | 0.4523 | 0.1074 | 0.5498 | 0.175* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Se | 0.0719 (3) | 0.0463 (2) | 0.0776 (3) | −0.01384 (16) | 0.00154 (18) | −0.00285 (16) |
N | 0.0660 (19) | 0.084 (2) | 0.080 (2) | 0.0075 (17) | 0.0005 (17) | −0.0035 (18) |
O1 | 0.139 (3) | 0.143 (3) | 0.0727 (18) | −0.073 (2) | 0.0137 (18) | −0.0099 (19) |
O2 | 0.0797 (17) | 0.0727 (18) | 0.0833 (17) | −0.0342 (14) | −0.0008 (14) | −0.0056 (13) |
O3 | 0.124 (3) | 0.134 (3) | 0.093 (2) | −0.037 (2) | 0.012 (2) | −0.016 (2) |
C1 | 0.0492 (17) | 0.0408 (17) | 0.079 (2) | −0.0040 (14) | 0.0027 (15) | −0.0056 (15) |
C2 | 0.0502 (18) | 0.052 (2) | 0.076 (2) | −0.0037 (15) | 0.0092 (16) | −0.0096 (16) |
C3 | 0.071 (2) | 0.066 (2) | 0.086 (2) | −0.0155 (19) | 0.0219 (19) | −0.005 (2) |
C4 | 0.071 (2) | 0.065 (2) | 0.111 (3) | −0.024 (2) | 0.021 (2) | −0.012 (2) |
C5 | 0.071 (2) | 0.066 (3) | 0.108 (3) | −0.022 (2) | −0.007 (2) | −0.014 (2) |
C6 | 0.071 (2) | 0.057 (2) | 0.085 (2) | −0.0136 (18) | −0.0061 (19) | −0.0070 (18) |
C7 | 0.067 (2) | 0.070 (3) | 0.073 (2) | −0.0101 (19) | 0.0106 (18) | −0.0080 (19) |
C8 | 0.083 (3) | 0.108 (4) | 0.078 (3) | −0.010 (3) | 0.008 (2) | −0.002 (3) |
C9 | 0.117 (4) | 0.139 (5) | 0.067 (3) | 0.033 (3) | −0.008 (2) | −0.010 (3) |
C10 | 0.087 (3) | 0.106 (4) | 0.153 (5) | −0.011 (3) | −0.001 (3) | 0.008 (3) |
Se—C1 | 1.940 (3) | C3—H3 | 0.9300 |
Se—Sei | 2.3288 (9) | C4—C5 | 1.350 (5) |
N—C8 | 1.317 (5) | C4—H4 | 0.9300 |
N—C9 | 1.429 (5) | C5—C6 | 1.388 (5) |
N—C10 | 1.438 (5) | C5—H5 | 0.9300 |
O1—C7 | 1.292 (4) | C6—H6 | 0.9300 |
O1—H1 | 0.8200 | C8—H8 | 0.9300 |
O2—C7 | 1.211 (4) | C9—H9A | 0.9600 |
O3—C8 | 1.236 (5) | C9—H9B | 0.9600 |
C1—C2 | 1.379 (5) | C9—H9C | 0.9600 |
C1—C6 | 1.391 (4) | C10—H10A | 0.9600 |
C2—C3 | 1.396 (5) | C10—H10B | 0.9600 |
C2—C7 | 1.491 (5) | C10—H10C | 0.9600 |
C3—C4 | 1.372 (5) | ||
C1—Se—Sei | 102.72 (10) | C5—C6—H6 | 120.3 |
C8—N—C9 | 120.4 (4) | C1—C6—H6 | 120.3 |
C8—N—C10 | 121.2 (4) | O2—C7—O1 | 124.1 (4) |
C9—N—C10 | 118.4 (4) | O2—C7—C2 | 121.8 (3) |
C7—O1—H1 | 109.5 | O1—C7—C2 | 114.1 (3) |
C2—C1—C6 | 119.3 (3) | O3—C8—N | 122.5 (4) |
C2—C1—Se | 120.3 (2) | O3—C8—H8 | 118.7 |
C6—C1—Se | 120.4 (3) | N—C8—H8 | 118.7 |
C1—C2—C3 | 119.5 (3) | N—C9—H9A | 109.5 |
C1—C2—C7 | 121.6 (3) | N—C9—H9B | 109.5 |
C3—C2—C7 | 119.0 (3) | H9A—C9—H9B | 109.5 |
C4—C3—C2 | 121.2 (4) | N—C9—H9C | 109.5 |
C4—C3—H3 | 119.4 | H9A—C9—H9C | 109.5 |
C2—C3—H3 | 119.4 | H9B—C9—H9C | 109.5 |
C5—C4—C3 | 118.8 (4) | N—C10—H10A | 109.5 |
C5—C4—H4 | 120.6 | N—C10—H10B | 109.5 |
C3—C4—H4 | 120.6 | H10A—C10—H10B | 109.5 |
C4—C5—C6 | 121.9 (4) | N—C10—H10C | 109.5 |
C4—C5—H5 | 119.0 | H10A—C10—H10C | 109.5 |
C6—C5—H5 | 119.0 | H10B—C10—H10C | 109.5 |
C5—C6—C1 | 119.3 (4) |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3ii | 0.82 | 1.73 | 2.541 (4) | 169 |
Symmetry code: (ii) x+1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C14H10O4Se2·2C3H7NO |
Mr | 546.34 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.202 (2), 13.223 (4), 21.849 (6) |
β (°) | 96.425 (4) |
V (Å3) | 2354.6 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.18 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.449, 0.569 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4745, 2072, 1607 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.091, 1.08 |
No. of reflections | 2072 |
No. of parameters | 139 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.32 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.82 | 1.73 | 2.541 (4) | 169.1 |
Symmetry code: (i) x+1, y+1, z. |
During the past decade the non-bonded interactions (Mugesh et al., 2001) and their role in molecular recognition, conformational transformation, and molecular packing in crystals were studied (Israelachvili,1991). In particular, for organoselenium derivatives have been frequently discovered that the divalent selenium interacts with a nearby hetero-atom (O, N, Se) generating a pseudo-high-valent selenium species. The weak actions have been successfully applied not only to asymmetric synthesis (Fujita et al., 1997) but also to enzyme-mimetic catalytic reactions. Moreover, previous experiments indicated that a pseudo-multivalent state of Se might be related to biological activities of Se compounds (Iwaoka & Tomoda, 1994). The seleno compounds can serve as oxidoreductants with the methionine sufoxide reductase enzymes (Sagher et al., 2006) and as reducing agents for lipid hydroperoxides (Björnstedt et al., 1995). This phenomenon attracts considerable attention (Nagao et al., 1998).
Many kinds of diselenide compounds and their derivatives have been synthesized and fully characterized successfully, but the structure of the title compound (I) has not been investigated thoroughly. In this paper, the titled compound was synthesized and characterized by NMR spectra. In the title molecule, the Se—Se bond distance is 2.287 Å, and the distance (2.703 Å) of Se and nearby O atom of carbonyl are significantly shorter than the sum of their vander waals radii (3.40 Å) (Zade et al., 2005). The crystal structure involves hydrogen bond O—H···O beween the carboxyl group and carbonyl moiety of a solvate (Table 1). distance 2.541 (4) Å and angle is 169°. The asymmetric unit is planar with r.m.s. deviation of 0.030 Å. The dihedral angle between these symmetry related planar moieties is 83.60°.