2,2′-Diseleno­dibenzoic acid N,N-dimethyl­formamide disolvate

The mol­ecular structure of the title compound, C₁₄H₁₀O₄Se₂·2C₃H₇NO, reveals C_i symmetry, with the inversion centre located at the mid-point of the Se—Se bond. Diselenide derivatives are important in the synthesis of ebselen and other organoselenium compounds. These derivatives are of inter­est owing to their biological activity as oxidoreductans. The structure displays an O—H...O hydrogen bond between the carboxyl group and the carbonyl unit of the dimethyl­formamide solvent mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

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S1. Comment

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°.

Related literature

For related literature, see: Israelachvili (1991); Iwaoka & Tomoda (1994); Mugesh et al. (2001); Nagao et al. (1998); Zade et al. (2005); Fujita et al. (1997); Björnstedt et al. (1995); Sagher et al. (2006).

S2. Experimental

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%.

S3. Refinement

(type here to add refinement details)

Computing details

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).

Figures

Fig. 1. The molecular structure of the title compound. The solvent molecules have been omitted.

2,2'-Diselenodibenzoic acid N,N-dimethylformamide disolvate

Crystal data

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) Å^3	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0388P)^2 + 1.4577P] where P = (Fo^2 + 2Fc^2)/3
2072 reflections	(Δ/σ)max = 0.002
139 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Se—C1	1.940 (3)	C3—H3	0.9300
Se—Se^i	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—Se^i	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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^ii	0.82	1.73	2.541 (4)	169

Symmetry code: (ii) x+1, y+1, z.