3,4-Dibromo-2,5-bis­[(dieth­oxy­phosphor­yl)meth­yl]-1-phenyl­sulfonyl-1H-pyrrole

Karthikeyan, S.; Sethusankar, K.; Rajeswaran, G.G.; Mohanakrishnan, A.K.

doi:10.1107/S1600536811030273

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages o2212-o2213

doi:10.1107/S1600536811030273

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3,4-Dibromo-2,5-bis[(diethoxyphosphoryl)methyl]-1-phenylsulfonyl-1H-pyrrole

S. Karthikeyan,^a K. Sethusankar,^a ^* Ganesan Gobi Rajeswaran ^b and Arasambattu K. Mohanakrishnan ^b

^aDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India, and ^bDepartment of Organic Chemistry, University of Madras, Maraimalai Campus, Chennai 600 025, India
^*Correspondence e-mail: ksethusankar@yahoo.co.in

(Received 5 July 2011; accepted 27 July 2011; online 2 August 2011)

In the title compound, C₂₀H₂₉Br₂NO₈P₂S, the pyrrole ring is essentially planar, with a maximum deviation of 0.013 (3) Å for a C atom. The pyrrole ring is almost orthogonal to the sulfonyl-bound phenyl ring, with a dihedral angle 88.5 (2)°. Both P atoms exhibit distorted tetrahedral configurations with O—P—O angles widened and O—P—C angles narrowed from the ideal tetrahedral value. In the crystal, molecules are linked into centrosymmetric dimers via C—H⋯O interactions, resulting in R₂²(10) graph-set motifs which are further consolidated by R₂²(13) graph-set ring motifs via C—H⋯O interactions, further resulting in chains of molecules running parallel to the c axis; a phosphono O atom is involved in bifurcated hydrogen bonding. All the ethoxy groups are disordered over two positions each with unequal site-occupancy factors.

Related literature

For a related structure, see: Seshadri et al. (2009 ). For applications of pyrrole derivatives, see: Faulkner (2002 ); Banwell et al. (2006 ); Fabio et al. (2007 ). For comparison of molecular dimensions, see: Bassindale (1984 ). For graph-set motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₀H₂₉Br₂NO₈P₂S
M_r = 665.26
Monoclinic, P 2₁ /n
a = 9.6524 (2) Å
b = 17.5137 (5) Å
c = 15.8965 (4) Å
β = 95.506 (1)°
V = 2674.89 (12) Å³
Z = 4
Mo Kα radiation
μ = 3.27 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.440, T_max = 0.561
34672 measured reflections
8138 independent reflections
4819 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.121
S = 1.00
8138 reflections
355 parameters
20 restraints
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O6ⁱ	0.97	2.34	3.272 (4)	162
C16—H16⋯O3ⁱⁱ	0.93	2.44	3.162 (5)	134
C11—H11B⋯O6ⁱⁱⁱ	0.97	2.62	3.592 (19)	179
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811030273/pv2427sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030273/pv2427Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030273/pv2427Isup3.cml

checkCIF report

Comment top

Pyrrole derivatives are known to occur in many marine organisms (Faulkner, 2002). Pyrrole and its derivatives have shown to possess biological activities such as antibacterial, antiallergic, antitumor (Banwell, et al., 2006), and some of them are well known as metabotropic receptor antagonists (Fabio, et al.., 2007).

In the title compound (Fig. 1), the pyrrole ring is essentially planar with a maximum deviation of 0.013 (3)Å for atom C9. The methyl carbon atoms C5 and C10 and S1 atom lie -0.078 (3), 0.034 (3) and 0.5396 (8) Å, respectively, from the pyrrole plane. The pyrrole ring is almost orthogonal to the sulfonyl bound phenyl ring, with a dihedral angle 88.5 (2)°.

Atoms P1 and P2 have distorted tetrahedral configurations. The widening of angles O3—P1—O4 [114.4 (13)°] and O6—P2—O7 [120.0 (7)°] and narrowing of angles O5—P1—C5 [95.0 (9)°] and O8—P2—C10 [107.4 (9)°] from the ideal tetrahedral value are attributed to the Thrope-Ingold effect (Bassindale, 1984). The ethoxy side chains were disordered with un-equal site occupancy factors.

The crystal packing is stabilized by C—H···O intermolecular interactions. The molecules are linked into centrosymmetric dimers via C11—H11B···O6 interactions resulting in R²₂(10) graph set motif (Bernstein, et al., 1995). The dimers are further consolidated by R²₂(13) graph-set ring motif via C5—H5A···O6 and C16—H16···O3 interactions resulting in chains of molecules running parallel to the c-axis (Tab. 1 & Fig. 2); the phosphono O atom (O6) is involved in bifurcated hydrogen bonding.

Related literature top

For a related structure, see: Seshadri et al. (2009). For applications of pyrrole derivatives, see: Faulkner et al. (2002); Banwell et al. (2006); Fabio et al. (2007). For comparison of molecular dimensions, see: Bassindale (1984). For graph-set motifs, see: Bernstein et al. (1995).

Experimental top

To a solution of 3,4-dibromo-2,5-bis(bromomethyl)-1-phenylsulfonyl- pyrrole (1 mmol) and triethylphosphite (2.5 mmol) in dry dichloromethane at room temperature, ZnBr₂ (0.4 mmol) was added and allowed to stir for 4 h under N₂. After consumption of the 3,4-dibromo-2,5-bis (bromomethyl)-1-phenylsulfonyl-pyrrole (monitored by TLC) volatile components were removed under vacuo. The residual mass was poured over crushed ice containing conc. HCl. The precipitated solid was filtered, washed with water and dried to give crude phosphonate ester which was crystallized from CHCl₃.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing only the atoms representing major fractions of the disordered ethoxy groups, with the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. The crystal packing of the title compound viewed down a axis, showing the hydrogen bonds resulting in R²₂(10) and R²₂(13) graph-set ring motifs; H-atoms not involved in H-bonds have been excluded for clarity.

diethyl {[1-(benzenesulfonyl)-3,4-dibromo-5- [(diethoxyphosphoryl)methyl]-1H-pyrrol-2-yl]methyl}phosphonate top

Crystal data top

C₂₀H₂₉Br₂NO₈P₂S	F(000) = 1344
M_r = 665.26	D_x = 1.652 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8138 reflections
a = 9.6524 (2) Å	θ = 2.3–30.5°
b = 17.5137 (5) Å	µ = 3.27 mm⁻¹
c = 15.8965 (4) Å	T = 293 K
β = 95.506 (1)°	Block, colourless
V = 2674.89 (12) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	8138 independent reflections
Radiation source: fine-focus sealed tube	4819 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 30.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.440, T_max = 0.561	k = −24→24
34672 measured reflections	l = −22→22

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0558P)² + 1.4803P] where P = (F_o² + 2F_c²)/3
8138 reflections	(Δ/σ)_max = 0.002
355 parameters	Δρ_max = 0.79 e Å⁻³
20 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

C₂₀H₂₉Br₂NO₈P₂S	V = 2674.89 (12) Å³
M_r = 665.26	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6524 (2) Å	µ = 3.27 mm⁻¹
b = 17.5137 (5) Å	T = 293 K
c = 15.8965 (4) Å	0.30 × 0.25 × 0.20 mm
β = 95.506 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	8138 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4819 reflections with I > 2σ(I)
T_min = 0.440, T_max = 0.561	R_int = 0.039
34672 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	20 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.00	Δρ_max = 0.79 e Å⁻³
8138 reflections	Δρ_min = −0.76 e Å⁻³
355 parameters

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C5	0.0820 (3)	0.13111 (17)	0.74030 (19)	0.0400 (7)
H5A	0.0917	0.0934	0.6965	0.048*
H5B	−0.0043	0.1585	0.7257	0.048*
C6	0.2004 (3)	0.18591 (16)	0.74214 (17)	0.0335 (6)
C7	0.3347 (3)	0.16883 (16)	0.73313 (17)	0.0357 (6)
C8	0.4160 (3)	0.23518 (17)	0.74534 (18)	0.0359 (6)
C9	0.3326 (3)	0.29465 (16)	0.76079 (17)	0.0337 (6)
C10	0.3748 (3)	0.37604 (17)	0.77607 (18)	0.0372 (6)
H10A	0.2975	0.4082	0.7546	0.045*
H10B	0.4514	0.3869	0.7426	0.045*
C15	0.0367 (3)	0.33865 (18)	0.6355 (2)	0.0452 (7)
C16	0.1028 (4)	0.4005 (2)	0.6062 (2)	0.0591 (9)
H16	0.1580	0.4316	0.6432	0.071*
C17	0.0868 (5)	0.4165 (3)	0.5209 (3)	0.0812 (13)
H17	0.1331	0.4580	0.5000	0.097*
C18	0.0039 (7)	0.3722 (3)	0.4671 (3)	0.0974 (18)
H18	−0.0063	0.3835	0.4097	0.117*
C19	−0.0652 (7)	0.3108 (3)	0.4970 (3)	0.106 (2)
H19	−0.1228	0.2811	0.4599	0.127*
C20	−0.0490 (5)	0.2931 (2)	0.5821 (3)	0.0767 (13)
H20	−0.0948	0.2515	0.6029	0.092*
N1	0.1966 (2)	0.26458 (13)	0.76122 (15)	0.0329 (5)
O1	−0.0609 (2)	0.27254 (14)	0.76316 (18)	0.0588 (6)
O2	0.0806 (2)	0.38764 (13)	0.78932 (14)	0.0492 (5)
O3	0.2002 (3)	0.04497 (19)	0.8743 (2)	0.0855 (9)
O6	0.4468 (3)	0.48635 (13)	0.89029 (15)	0.0642 (7)
P1	0.07187 (10)	0.08262 (5)	0.83967 (6)	0.0522 (2)
P2	0.42646 (9)	0.40435 (5)	0.88263 (5)	0.0430 (2)
S1	0.05156 (8)	0.31902 (4)	0.74386 (5)	0.03984 (18)
Br1	0.40069 (4)	0.071636 (19)	0.71196 (2)	0.05379 (12)
Br2	0.60841 (3)	0.23995 (2)	0.74283 (3)	0.05732 (12)
O5	−0.0926 (10)	0.0770 (13)	0.8306 (16)	0.0668 (9)	0.121 (5)
C1	−0.248 (5)	−0.029 (3)	0.741 (3)	0.124 (3)	0.121 (5)
H1A	−0.3481	−0.0284	0.7344	0.186*	0.121 (5)
H1B	−0.2161	−0.0809	0.7469	0.186*	0.121 (5)
H1C	−0.2134	−0.0066	0.6921	0.186*	0.121 (5)
C2	−0.195 (5)	0.017 (3)	0.820 (4)	0.098 (2)	0.121 (5)
H2A	−0.2785	0.0386	0.8403	0.117*	0.121 (5)
H2B	−0.1631	−0.0216	0.8616	0.117*	0.121 (5)
O5'	−0.0402 (3)	0.01914 (17)	0.8237 (2)	0.0668 (9)	0.879 (5)
C1'	−0.2651 (6)	−0.0326 (4)	0.8086 (7)	0.124 (3)	0.879 (5)
H1'1	−0.2206	−0.0769	0.7880	0.186*	0.879 (5)
H1'2	−0.3563	−0.0272	0.7794	0.186*	0.879 (5)
H1'3	−0.2727	−0.0381	0.8681	0.186*	0.879 (5)
C2'	−0.1804 (6)	0.0369 (4)	0.7937 (5)	0.098 (2)	0.879 (5)
H2'1	−0.1871	0.0491	0.7339	0.117*	0.879 (5)
H2'2	−0.2131	0.0803	0.8240	0.117*	0.879 (5)
O4	0.009 (5)	0.1382 (13)	0.9016 (12)	0.078 (4)	0.411 (10)
C4	−0.007 (3)	0.1903 (13)	1.0324 (17)	0.173 (7)	0.411 (10)
H4A	0.0866	0.2090	1.0441	0.260*	0.411 (10)
H4B	−0.0482	0.1842	1.0845	0.260*	0.411 (10)
H4C	−0.0603	0.2260	0.9970	0.260*	0.411 (10)
C3	−0.004 (2)	0.1141 (11)	0.9879 (11)	0.125 (4)	0.411 (10)
H3A	0.0749	0.0835	1.0101	0.150*	0.411 (10)
H3B	−0.0892	0.0857	0.9923	0.150*	0.411 (10)
O4'	0.028 (3)	0.1505 (8)	0.8938 (8)	0.078 (4)	0.589 (10)
C3'	0.0613 (13)	0.1538 (9)	0.9850 (7)	0.125 (4)	0.589 (10)
H3'1	0.1069	0.2019	0.9999	0.150*	0.589 (10)
H3'2	0.1257	0.1130	1.0025	0.150*	0.589 (10)
C4'	−0.0661 (17)	0.1464 (14)	1.0318 (11)	0.173 (7)	0.589 (10)
H4'1	−0.1202	0.1035	1.0101	0.260*	0.589 (10)
H4'2	−0.1208	0.1921	1.0242	0.260*	0.589 (10)
H4'3	−0.0386	0.1389	1.0908	0.260*	0.589 (10)
O8	0.318 (2)	0.3710 (6)	0.9390 (13)	0.0637 (10)	0.719 (8)
C13	0.2084 (9)	0.4151 (5)	0.9727 (4)	0.078 (2)	0.719 (8)
H13A	0.1178	0.3962	0.9503	0.094*	0.719 (8)
H13B	0.2155	0.4684	0.9569	0.094*	0.719 (8)
C14	0.2251 (11)	0.4074 (6)	1.0654 (4)	0.115 (3)	0.719 (8)
H14A	0.2137	0.3548	1.0804	0.173*	0.719 (8)
H14B	0.1561	0.4378	1.0894	0.173*	0.719 (8)
H14C	0.3162	0.4244	1.0868	0.173*	0.719 (8)
O8'	0.322 (6)	0.3676 (15)	0.940 (3)	0.0637 (10)	0.281 (8)
C13'	0.278 (2)	0.4208 (13)	1.0017 (14)	0.078 (2)	0.281 (8)
H13C	0.2589	0.4709	0.9772	0.094*	0.281 (8)
H13D	0.3467	0.4254	1.0499	0.094*	0.281 (8)
C14'	0.145 (2)	0.3836 (16)	1.0264 (14)	0.115 (3)	0.281 (8)
H14D	0.0802	0.4224	1.0392	0.173*	0.281 (8)
H14E	0.1668	0.3519	1.0752	0.173*	0.281 (8)
H14F	0.1048	0.3529	0.9803	0.173*	0.281 (8)
O7	0.5503 (12)	0.3488 (9)	0.9077 (17)	0.054 (3)	0.609 (13)
C12	0.7959 (11)	0.3707 (10)	0.9575 (9)	0.120 (4)	0.609 (13)
H12A	0.8302	0.3249	0.9335	0.180*	0.609 (13)
H12B	0.8557	0.3845	1.0069	0.180*	0.609 (13)
H12C	0.7943	0.4112	0.9168	0.180*	0.609 (13)
C11	0.6496 (16)	0.3569 (8)	0.9817 (15)	0.079 (3)	0.609 (13)
H11A	0.6488	0.3110	1.0158	0.095*	0.609 (13)
H11B	0.6221	0.3994	1.0156	0.095*	0.609 (13)
O7'	0.569 (2)	0.3624 (16)	0.900 (3)	0.054 (3)	0.391 (13)
C11'	0.648 (3)	0.3788 (13)	0.980 (2)	0.079 (3)	0.391 (13)
H11C	0.5906	0.3750	1.0269	0.095*	0.391 (13)
H11D	0.6889	0.4295	0.9803	0.095*	0.391 (13)
C12'	0.7607 (19)	0.3174 (15)	0.9864 (14)	0.120 (4)	0.391 (13)
H12D	0.7218	0.2700	1.0031	0.180*	0.391 (13)
H12E	0.8352	0.3323	1.0275	0.180*	0.391 (13)
H12F	0.7959	0.3114	0.9323	0.180*	0.391 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C5	0.0387 (16)	0.0307 (15)	0.0499 (17)	−0.0039 (12)	−0.0003 (13)	−0.0013 (13)
C6	0.0332 (14)	0.0281 (14)	0.0393 (15)	0.0000 (11)	0.0035 (11)	−0.0014 (11)
C7	0.0373 (15)	0.0300 (14)	0.0400 (15)	0.0027 (12)	0.0052 (12)	−0.0054 (12)
C8	0.0257 (13)	0.0400 (16)	0.0430 (15)	−0.0003 (12)	0.0082 (11)	−0.0025 (13)
C9	0.0332 (14)	0.0296 (14)	0.0384 (15)	−0.0031 (12)	0.0031 (11)	−0.0008 (11)
C10	0.0357 (15)	0.0328 (15)	0.0423 (16)	−0.0052 (12)	−0.0002 (12)	0.0007 (12)
C15	0.0425 (17)	0.0370 (17)	0.0534 (18)	0.0123 (14)	−0.0096 (14)	−0.0056 (14)
C16	0.059 (2)	0.061 (2)	0.055 (2)	−0.0022 (19)	−0.0081 (17)	0.0075 (18)
C17	0.090 (3)	0.087 (3)	0.063 (3)	0.004 (3)	−0.006 (2)	0.017 (2)
C18	0.151 (5)	0.077 (3)	0.057 (3)	0.033 (4)	−0.025 (3)	−0.001 (2)
C19	0.158 (6)	0.071 (3)	0.075 (3)	0.020 (3)	−0.058 (3)	−0.020 (3)
C20	0.094 (3)	0.042 (2)	0.086 (3)	−0.001 (2)	−0.029 (2)	−0.006 (2)
N1	0.0310 (11)	0.0248 (11)	0.0426 (13)	0.0023 (9)	0.0013 (10)	−0.0015 (10)
O1	0.0335 (11)	0.0501 (14)	0.0946 (19)	0.0041 (10)	0.0150 (12)	0.0046 (13)
O2	0.0519 (13)	0.0376 (12)	0.0579 (14)	0.0112 (10)	0.0040 (11)	−0.0096 (10)
O3	0.079 (2)	0.086 (2)	0.091 (2)	0.0235 (17)	0.0097 (17)	0.0353 (18)
O6	0.098 (2)	0.0348 (13)	0.0568 (14)	−0.0080 (13)	−0.0081 (14)	−0.0076 (11)
P1	0.0545 (5)	0.0449 (5)	0.0587 (5)	−0.0079 (4)	0.0124 (4)	0.0034 (4)
P2	0.0529 (5)	0.0307 (4)	0.0442 (4)	−0.0004 (4)	−0.0008 (4)	−0.0029 (3)
S1	0.0312 (4)	0.0324 (4)	0.0559 (4)	0.0053 (3)	0.0039 (3)	−0.0020 (3)
Br1	0.0543 (2)	0.03644 (18)	0.0716 (2)	0.01011 (15)	0.01144 (17)	−0.01260 (15)
Br2	0.03251 (17)	0.0609 (2)	0.0805 (3)	−0.00089 (15)	0.01528 (16)	−0.01378 (18)
O5	0.0502 (17)	0.0469 (18)	0.105 (2)	−0.0058 (13)	0.0133 (16)	0.0164 (16)
C1	0.058 (3)	0.078 (4)	0.233 (10)	−0.026 (3)	−0.005 (5)	0.030 (6)
C2	0.052 (3)	0.081 (4)	0.158 (7)	0.003 (3)	0.001 (4)	0.042 (4)
O5'	0.0502 (17)	0.0469 (18)	0.105 (2)	−0.0058 (13)	0.0133 (16)	0.0164 (16)
C1'	0.058 (3)	0.078 (4)	0.233 (10)	−0.026 (3)	−0.005 (5)	0.030 (6)
C2'	0.052 (3)	0.081 (4)	0.158 (7)	0.003 (3)	0.001 (4)	0.042 (4)
O4	0.118 (8)	0.067 (5)	0.053 (3)	0.015 (6)	0.031 (3)	0.006 (3)
C4	0.176 (17)	0.26 (2)	0.088 (5)	−0.056 (11)	0.057 (9)	−0.045 (12)
C3	0.134 (11)	0.149 (13)	0.093 (5)	−0.023 (7)	0.014 (7)	−0.046 (7)
O4'	0.118 (8)	0.067 (5)	0.053 (3)	0.015 (6)	0.031 (3)	0.006 (3)
C3'	0.134 (11)	0.149 (13)	0.093 (5)	−0.023 (7)	0.014 (7)	−0.046 (7)
C4'	0.176 (17)	0.26 (2)	0.088 (5)	−0.056 (11)	0.057 (9)	−0.045 (12)
O8	0.083 (2)	0.0512 (18)	0.0605 (15)	0.0023 (17)	0.0247 (16)	0.0014 (15)
C13	0.075 (5)	0.096 (4)	0.066 (4)	0.012 (5)	0.020 (3)	−0.005 (4)
C14	0.125 (8)	0.159 (8)	0.065 (5)	0.005 (6)	0.026 (4)	0.001 (5)
O8'	0.083 (2)	0.0512 (18)	0.0605 (15)	0.0023 (17)	0.0247 (16)	0.0014 (15)
C13'	0.075 (5)	0.096 (4)	0.066 (4)	0.012 (5)	0.020 (3)	−0.005 (4)
C14'	0.125 (8)	0.159 (8)	0.065 (5)	0.005 (6)	0.026 (4)	0.001 (5)
O7	0.053 (3)	0.047 (6)	0.057 (4)	0.001 (4)	−0.015 (4)	−0.008 (4)
C12	0.067 (6)	0.157 (13)	0.130 (9)	0.014 (7)	−0.024 (5)	−0.033 (9)
C11	0.089 (4)	0.058 (8)	0.084 (3)	0.011 (5)	−0.028 (3)	−0.021 (7)
O7'	0.053 (3)	0.047 (6)	0.057 (4)	0.001 (4)	−0.015 (4)	−0.008 (4)
C11'	0.089 (4)	0.058 (8)	0.084 (3)	0.011 (5)	−0.028 (3)	−0.021 (7)
C12'	0.067 (6)	0.157 (13)	0.130 (9)	0.014 (7)	−0.024 (5)	−0.033 (9)

Geometric parameters (Å, º) top

C5—C6	1.491 (4)	C1'—C2'	1.497 (6)
C5—P1	1.804 (3)	C1'—H1'1	0.9600
C5—H5A	0.9700	C1'—H1'2	0.9600
C5—H5B	0.9700	C1'—H1'3	0.9600
C6—C7	1.351 (4)	C2'—H2'1	0.9700
C6—N1	1.412 (3)	C2'—H2'2	0.9700
C7—C8	1.405 (4)	O4—C3	1.453 (10)
C7—Br1	1.860 (3)	C4—C3	1.511 (10)
C8—C9	1.353 (4)	C4—H4A	0.9600
C8—Br2	1.863 (3)	C4—H4B	0.9600
C9—N1	1.415 (4)	C4—H4C	0.9600
C9—C10	1.496 (4)	C3—H3A	0.9700
C10—P2	1.789 (3)	C3—H3B	0.9700
C10—H10A	0.9700	O4'—C3'	1.456 (10)
C10—H10B	0.9700	C3'—C4'	1.502 (9)
C15—C16	1.363 (5)	C3'—H3'1	0.9700
C15—C20	1.381 (5)	C3'—H3'2	0.9700
C15—S1	1.748 (3)	C4'—H4'1	0.9600
C16—C17	1.379 (6)	C4'—H4'2	0.9600
C16—H16	0.9300	C4'—H4'3	0.9600
C17—C18	1.357 (7)	O8—C13	1.451 (10)
C17—H17	0.9300	C13—C14	1.473 (7)
C18—C19	1.374 (8)	C13—H13A	0.9700
C18—H18	0.9300	C13—H13B	0.9700
C19—C20	1.382 (7)	C14—H14A	0.9600
C19—H19	0.9300	C14—H14B	0.9600
C20—H20	0.9300	C14—H14C	0.9600
N1—S1	1.694 (2)	O8'—C13'	1.450 (10)
O1—S1	1.414 (3)	C13'—C14'	1.519 (10)
O2—S1	1.416 (2)	C13'—H13C	0.9700
O3—P1	1.463 (3)	C13'—H13D	0.9700
O6—P2	1.453 (2)	C14'—H14D	0.9600
P1—O4	1.548 (7)	C14'—H14E	0.9600
P1—O4'	1.549 (6)	C14'—H14F	0.9600
P1—O5'	1.555 (3)	O7—C11	1.452 (7)
P1—O5	1.583 (10)	C12—C11	1.518 (10)
P2—O8'	1.558 (8)	C12—H12A	0.9600
P2—O8	1.558 (4)	C12—H12B	0.9600
P2—O7'	1.561 (7)	C12—H12C	0.9600
P2—O7	1.563 (5)	C11—H11A	0.9700
O5—C2	1.447 (10)	C11—H11B	0.9700
O5—O4	1.78 (4)	O7'—C11'	1.448 (9)
C1—C2	1.539 (10)	C11'—C12'	1.524 (10)
C1—H1A	0.9600	C11'—H11C	0.9700
C1—H1B	0.9600	C11'—H11D	0.9700
C1—H1C	0.9600	C12'—H12D	0.9600
C2—H2A	0.9700	C12'—H12E	0.9600
C2—H2B	0.9700	C12'—H12F	0.9600
O5'—C2'	1.425 (6)

C6—C5—P1	113.1 (2)	O5—C2—H2A	104.8
C6—C5—H5A	109.0	C1—C2—H2A	104.8
P1—C5—H5A	109.0	O5—C2—H2B	104.8
C6—C5—H5B	109.0	C1—C2—H2B	104.8
P1—C5—H5B	109.0	H2A—C2—H2B	105.8
H5A—C5—H5B	107.8	C2'—O5'—P1	121.5 (3)
C7—C6—N1	106.5 (2)	C2'—C1'—H1'1	109.5
C7—C6—C5	126.7 (3)	C2'—C1'—H1'2	109.5
N1—C6—C5	126.6 (2)	H1'1—C1'—H1'2	109.5
C6—C7—C8	109.3 (2)	C2'—C1'—H1'3	109.5
C6—C7—Br1	124.8 (2)	H1'1—C1'—H1'3	109.5
C8—C7—Br1	125.8 (2)	H1'2—C1'—H1'3	109.5
C9—C8—C7	109.1 (2)	O5'—C2'—C1'	106.6 (5)
C9—C8—Br2	125.5 (2)	O5'—C2'—H2'1	110.4
C7—C8—Br2	125.4 (2)	C1'—C2'—H2'1	110.4
C8—C9—N1	106.4 (2)	O5'—C2'—H2'2	110.4
C8—C9—C10	127.3 (3)	C1'—C2'—H2'2	110.4
N1—C9—C10	126.3 (3)	H2'1—C2'—H2'2	108.6
C9—C10—P2	117.7 (2)	C3—O4—P1	119.6 (13)
C9—C10—H10A	107.9	C3—O4—O5	109 (2)
P2—C10—H10A	107.9	P1—O4—O5	56.3 (10)
C9—C10—H10B	107.9	O4—C3—C4	101.2 (16)
P2—C10—H10B	107.9	O4—C3—H3A	111.5
H10A—C10—H10B	107.2	C4—C3—H3A	111.5
C16—C15—C20	121.4 (4)	O4—C3—H3B	111.5
C16—C15—S1	119.8 (3)	C4—C3—H3B	111.5
C20—C15—S1	118.7 (3)	H3A—C3—H3B	109.3
C15—C16—C17	119.1 (4)	C3'—O4'—P1	122.6 (11)
C15—C16—H16	120.5	O4'—C3'—C4'	112.3 (14)
C17—C16—H16	120.5	O4'—C3'—H3'1	109.1
C18—C17—C16	120.4 (5)	C4'—C3'—H3'1	109.1
C18—C17—H17	119.8	O4'—C3'—H3'2	109.1
C16—C17—H17	119.8	C4'—C3'—H3'2	109.1
C17—C18—C19	120.4 (4)	H3'1—C3'—H3'2	107.9
C17—C18—H18	119.8	C3'—C4'—H4'1	109.5
C19—C18—H18	119.8	C3'—C4'—H4'2	109.5
C18—C19—C20	120.0 (4)	H4'1—C4'—H4'2	109.5
C18—C19—H19	120.0	C3'—C4'—H4'3	109.5
C20—C19—H19	120.0	H4'1—C4'—H4'3	109.5
C15—C20—C19	118.5 (5)	H4'2—C4'—H4'3	109.5
C15—C20—H20	120.7	C13—O8—P2	124.5 (9)
C19—C20—H20	120.7	O8—C13—C14	107.8 (11)
C6—N1—C9	108.6 (2)	O8—C13—H13A	110.1
C6—N1—S1	123.55 (19)	C14—C13—H13A	110.1
C9—N1—S1	122.83 (19)	O8—C13—H13B	110.1
O3—P1—O4	114.4 (13)	C14—C13—H13B	110.1
O3—P1—O4'	113.7 (10)	H13A—C13—H13B	108.5
O3—P1—O5'	106.83 (19)	C13'—O8'—P2	112.4 (14)
O4—P1—O5'	104.2 (17)	O8'—C13'—C14'	102.2 (17)
O4'—P1—O5'	114.7 (11)	O8'—C13'—H13C	111.3
O3—P1—O5	144.2 (8)	C14'—C13'—H13C	111.3
O4—P1—O5	69 (2)	O8'—C13'—H13D	111.3
O4'—P1—O5	77.1 (15)	C14'—C13'—H13D	111.3
O3—P1—C5	115.23 (17)	H13C—C13'—H13D	109.2
O4—P1—C5	108.5 (8)	C13'—C14'—H14D	109.5
O4'—P1—C5	99.5 (5)	C13'—C14'—H14E	109.5
O5'—P1—C5	106.80 (16)	H14D—C14'—H14E	109.5
O5—P1—C5	95.0 (9)	C13'—C14'—H14F	109.5
O6—P2—O8'	116.7 (9)	H14D—C14'—H14F	109.5
O6—P2—O8	114.5 (4)	H14E—C14'—H14F	109.5
O6—P2—O7'	109.9 (13)	C11—O7—P2	125.1 (15)
O8'—P2—O7'	108 (3)	O7—C11—C12	111.6 (13)
O8—P2—O7'	110.5 (17)	O7—C11—H11A	109.3
O6—P2—O7	120.0 (7)	C12—C11—H11A	109.3
O8'—P2—O7	97 (2)	O7—C11—H11B	109.3
O8—P2—O7	99.3 (12)	C12—C11—H11B	109.3
O6—P2—C10	112.10 (15)	H11A—C11—H11B	108.0
O8'—P2—C10	107 (2)	C11'—O7'—P2	117 (2)
O8—P2—C10	107.4 (9)	O7'—C11'—C12'	103.2 (16)
O7'—P2—C10	101.7 (16)	O7'—C11'—H11C	111.1
O7—P2—C10	101.9 (10)	C12'—C11'—H11C	111.1
O1—S1—O2	119.75 (15)	O7'—C11'—H11D	111.1
O1—S1—N1	106.26 (13)	C12'—C11'—H11D	111.1
O2—S1—N1	105.94 (13)	H11C—C11'—H11D	109.1
O1—S1—C15	109.56 (16)	C11'—C12'—H12D	109.5
O2—S1—C15	109.22 (15)	C11'—C12'—H12E	109.5
N1—S1—C15	105.04 (13)	H12D—C12'—H12E	109.5
C2—O5—P1	137 (3)	C11'—C12'—H12F	109.5
C2—O5—O4	147 (3)	H12D—C12'—H12F	109.5
P1—O5—O4	54.4 (11)	H12E—C12'—H12F	109.5
O5—C2—C1	130 (4)

P1—C5—C6—C7	81.3 (3)	C5—P1—O5—C2	114 (4)
P1—C5—C6—N1	−92.5 (3)	O3—P1—O5—O4	103.4 (16)
N1—C6—C7—C8	−0.5 (3)	O4'—P1—O5—O4	−9.3 (14)
C5—C6—C7—C8	−175.4 (3)	O5'—P1—O5—O4	142.6 (16)
N1—C6—C7—Br1	177.33 (19)	C5—P1—O5—O4	−107.9 (10)
C5—C6—C7—Br1	2.5 (4)	P1—O5—C2—C1	−78 (7)
C6—C7—C8—C9	−1.0 (3)	O4—O5—C2—C1	−172 (4)
Br1—C7—C8—C9	−178.8 (2)	O3—P1—O5'—C2'	176.9 (5)
C6—C7—C8—Br2	177.9 (2)	O4—P1—O5'—C2'	55.5 (11)
Br1—C7—C8—Br2	0.0 (4)	O4'—P1—O5'—C2'	50.0 (8)
C7—C8—C9—N1	2.0 (3)	O5—P1—O5'—C2'	19.6 (14)
Br2—C8—C9—N1	−176.8 (2)	C5—P1—O5'—C2'	−59.3 (5)
C7—C8—C9—C10	−179.0 (3)	P1—O5'—C2'—C1'	−164.6 (5)
Br2—C8—C9—C10	2.2 (4)	O3—P1—O4—C3	−47 (4)
C8—C9—C10—P2	−89.0 (3)	O4'—P1—O4—C3	−136 (13)
N1—C9—C10—P2	89.8 (3)	O5'—P1—O4—C3	69 (3)
C20—C15—C16—C17	−1.9 (6)	O5—P1—O4—C3	95 (3)
S1—C15—C16—C17	−178.1 (3)	C5—P1—O4—C3	−177 (3)
C15—C16—C17—C18	1.4 (7)	O3—P1—O4—O5	−141.4 (10)
C16—C17—C18—C19	0.0 (8)	O4'—P1—O4—O5	130 (11)
C17—C18—C19—C20	−0.9 (9)	O5'—P1—O4—O5	−25.1 (10)
C16—C15—C20—C19	1.0 (6)	C5—P1—O4—O5	88.4 (11)
S1—C15—C20—C19	177.3 (4)	C2—O5—O4—C3	9 (6)
C18—C19—C20—C15	0.4 (8)	P1—O5—O4—C3	−113.2 (18)
C7—C6—N1—C9	1.8 (3)	C2—O5—O4—P1	123 (6)
C5—C6—N1—C9	176.6 (3)	P1—O4—C3—C4	156 (3)
C7—C6—N1—S1	157.1 (2)	O5—O4—C3—C4	−142.1 (19)
C5—C6—N1—S1	−28.1 (4)	O3—P1—O4'—C3'	−30 (2)
C8—C9—N1—C6	−2.4 (3)	O4—P1—O4'—C3'	66 (9)
C10—C9—N1—C6	178.6 (3)	O5'—P1—O4'—C3'	93 (2)
C8—C9—N1—S1	−157.9 (2)	O5—P1—O4'—C3'	114 (2)
C10—C9—N1—S1	23.1 (4)	C5—P1—O4'—C3'	−153 (2)
C6—C5—P1—O3	−52.7 (3)	P1—O4'—C3'—C4'	−111 (2)
C6—C5—P1—O4	77.1 (18)	O6—P2—O8—C13	22 (2)
C6—C5—P1—O4'	69.2 (12)	O8'—P2—O8—C13	165 (65)
C6—C5—P1—O5'	−171.2 (2)	O7'—P2—O8—C13	147 (2)
C6—C5—P1—O5	146.9 (9)	O7—P2—O8—C13	151 (2)
C9—C10—P2—O6	−172.3 (2)	C10—P2—O8—C13	−103.3 (18)
C9—C10—P2—O8'	−42.9 (19)	P2—O8—C13—C14	−122.5 (19)
C9—C10—P2—O8	−45.7 (8)	O6—P2—O8'—C13'	−9 (6)
C9—C10—P2—O7'	70.4 (13)	O8—P2—O8'—C13'	−47 (58)
C9—C10—P2—O7	58.1 (8)	O7'—P2—O8'—C13'	115 (4)
C6—N1—S1—O1	37.7 (3)	O7—P2—O8'—C13'	119 (4)
C9—N1—S1—O1	−170.4 (2)	C10—P2—O8'—C13'	−136 (4)
C6—N1—S1—O2	166.1 (2)	P2—O8'—C13'—C14'	161 (4)
C9—N1—S1—O2	−42.0 (3)	O6—P2—O7—C11	42 (2)
C6—N1—S1—C15	−78.4 (3)	O8'—P2—O7—C11	−84 (2)
C9—N1—S1—C15	73.5 (2)	O8—P2—O7—C11	−83.4 (18)
C16—C15—S1—O1	158.4 (3)	O7'—P2—O7—C11	76 (12)
C20—C15—S1—O1	−17.9 (3)	C10—P2—O7—C11	166.5 (16)
C16—C15—S1—O2	25.5 (3)	P2—O7—C11—C12	−116 (2)
C20—C15—S1—O2	−150.8 (3)	O6—P2—O7'—C11'	55 (3)
C16—C15—S1—N1	−87.8 (3)	O8'—P2—O7'—C11'	−73 (3)
C20—C15—S1—N1	95.9 (3)	O8—P2—O7'—C11'	−72 (3)
O3—P1—O5—C2	−35 (5)	O7—P2—O7'—C11'	−94 (13)
O4—P1—O5—C2	−138 (4)	C10—P2—O7'—C11'	174 (2)
O4'—P1—O5—C2	−148 (4)	P2—O7'—C11'—C12'	168 (3)
O5'—P1—O5—C2	4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O6ⁱ	0.97	2.34	3.272 (4)	162
C16—H16···O3ⁱⁱ	0.93	2.44	3.162 (5)	134
C11—H11B···O6ⁱⁱⁱ	0.97	2.62	3.592 (19)	179

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₉Br₂NO₈P₂S
M_r	665.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.6524 (2), 17.5137 (5), 15.8965 (4)
β (°)	95.506 (1)
V (Å³)	2674.89 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.27
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.440, 0.561
No. of measured, independent and observed [I > 2σ(I)] reflections	34672, 8138, 4819
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.121, 1.00
No. of reflections	8138
No. of parameters	355
No. of restraints	20
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.76

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O6ⁱ	0.97	2.34	3.272 (4)	162
C16—H16···O3ⁱⁱ	0.93	2.44	3.162 (5)	134
C11—H11B···O6ⁱⁱⁱ	0.97	2.62	3.592 (19)	178.6

Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1, −y+1, −z+2.

Acknowledgements

SK and KS thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray intensity data collection and Dr V. Murugan, Head of the Department of Physics, RKM Vivekananda College, for providing facilities in the department to carry out this work.

References

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Volume 67| Part 9| September 2011| Pages o2212-o2213

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

3,4-Di­bromo-2,5-bis­­[(dieth­­oxy­phosphor­yl)meth­yl]-1-phenyl­sulfonyl-1H-pyrrole

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

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organic compounds

3,4-Dibromo-2,5-bis[(diethoxyphosphoryl)methyl]-1-phenylsulfonyl-1H-pyrrole