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The thienyl and pyrrole rings in the mol­ecule of the title compound, C9H7NOS, are not coplanar, their planes forming a dihedral angle of 14.7 (3)°; the C—C bond linking the rings almost coincides with the line of inter­section of the planes of the rings. The mol­ecules in the crystal structure form centrosymmetric dimeric aggregates, held together by means of N—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029636/ya6265sup1.cif
Contains datablocks general, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029636/ya6265Isup2.hkl
Contains datablock I

CCDC reference: 287768

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.036
  • wR factor = 0.112
  • Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT773_ALERT_2_A Suspect C-C Bond in CIF: C43 -C42 .. 1.72 Ang.
Author Response: The thienyl ring was found to be disordered over two positions and modelled as per "_publ_section_exptl_refinement"

Alert level B PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for S45 PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for C42
Alert level C PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.51 Ratio
Author Response: The thienyl ring was found to be disordered over two positions and modelled as per "_publ_section_exptl_refinement"
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C41
Author Response: The thienyl ring was found to be disordered over two positions and modelled as per "_publ_section_exptl_refinement"
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C45
Author Response: The thienyl ring was found to be disordered over two positions and modelled as per "_publ_section_exptl_refinement"
PLAT301_ALERT_3_C Main Residue  Disorder .........................      14.00 Perc.
PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond  C43    -   C44    ...       1.33 Ang.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       2.30 Deg.
              C45  -C41  -S45     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.70 Deg.
              C42  -C41  -S42     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      11.60 Deg.
              S42  -C43  -C42     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       4.10 Deg.
              S45  -C44  -C45     1.555   1.555   1.555

1 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 11 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 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The title compound has been utilized as a template in the synthesis of combinatorial libraries (Davis et al., 2002). The molecular structure (Fig. 1) shows that while both pyrrole and thienyl rings are essentially planar (r.m.s. deviations = 0.002 Å for each), there is a twist in the molecule about the C4—C41 bond, as evidenced by the C3—C4—C41—S42 torsion angle of −13.8 (4)°; the dihedral angle formed by the planes of the two rings is 14.7 (3)°. The molecules are linked into centrosymmetric pairs via N—H···O hydrogen bonds [H1···O21i = 2.03 Å, N1···O21i = 2.861 (3) Å and N1—H1···O21i = 163°; symmetry code: (i) −x, −y, 2 − z; Fig. 1].

Experimental top

The compound was prepared by the Suzuki–Miyaura coupling reaction as reported by Davis et al. (2002). Crystals suitable for X-ray diffraction studies were obtained by the slow evaporation of a dichloromethane solution of the compound; m.p. 456–458 K.

Refinement top

The H atoms were included in the riding-model approximation, with distances N—H = 0.86 Å and C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(N,C). The thienyl ring is disordered over two positions related by a 180° rotation around the C4—C41 bond. This disorder gives rise to two positions for each of the S42 and C45 atoms; the refinement of their occupancies showed that one of these positions is predominant, with an occupancy of 0.795 (3). The positions of C43 and C44 are effectively not affected by the disorder.

Computing details top

Data collection: MSC/AFC Diffractometer Control (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN for Windows.

Figures top
[Figure 1] Fig. 1. The structure of the centrosymmetric dimer formed via N—H···O hydrogen bonds, showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 35% probability level. Minor components of the disordered atoms have been omitted. The symmetry-related molecule is derived using the (−x, −y, 2 − z) transformation.
(I) top
Crystal data top
C9H7NOSF(000) = 368
Mr = 177.22Dx = 1.393 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 6.303 (2) Åθ = 11.4–18.5°
b = 7.745 (3) ŵ = 0.33 mm1
c = 17.424 (1) ÅT = 293 K
β = 96.64 (1)°Block, orange
V = 844.9 (4) Å30.50 × 0.20 × 0.10 mm
Z = 4
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.020
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.9°
Graphite monochromatorh = 07
ω–2θ scansk = 09
1641 measured reflectionsl = 2020
1496 independent reflections3 standard reflections every 150 reflections
883 reflections with I > 2σ(I) intensity decay: none
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0512P)2 + 0.0355P]
where P = (Fo2 + 2Fc2)/3
1496 reflections(Δ/σ)max < 0.001
117 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.23 e Å3
Crystal data top
C9H7NOSV = 844.9 (4) Å3
Mr = 177.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.303 (2) ŵ = 0.33 mm1
b = 7.745 (3) ÅT = 293 K
c = 17.424 (1) Å0.50 × 0.20 × 0.10 mm
β = 96.64 (1)°
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.020
1641 measured reflections3 standard reflections every 150 reflections
1496 independent reflections intensity decay: none
883 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.01Δρmax = 0.14 e Å3
1496 reflectionsΔρmin = 0.23 e Å3
117 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
xyzUiso*/UeqOcc. (<1)
O210.2026 (3)0.1625 (3)0.97144 (11)0.0770 (7)
N10.1619 (3)0.0592 (3)0.89633 (11)0.0535 (6)
H10.17280.01290.94150.064*
C20.0042 (4)0.1706 (3)0.86715 (14)0.0478 (6)
C30.0459 (4)0.2162 (3)0.79381 (14)0.0513 (6)
H30.03500.29140.76060.062*
C40.2314 (3)0.1296 (3)0.77791 (13)0.0445 (6)
C50.2970 (4)0.0339 (3)0.84300 (14)0.0519 (6)
H50.41650.03740.84910.062*
C210.1710 (5)0.2165 (3)0.90849 (17)0.0627 (7)
H210.26960.29480.88490.075*
C410.3319 (4)0.1321 (3)0.70659 (14)0.0475 (6)
C430.4045 (6)0.1631 (4)0.57259 (17)0.0738 (9)
H430.40150.18610.52010.089*
C440.5702 (5)0.0897 (4)0.61421 (18)0.0711 (9)
H440.69190.05760.59220.085*
S420.2045 (2)0.2100 (2)0.62231 (7)0.0596 (4)0.795 (3)
C450.5520 (16)0.0616 (12)0.6966 (6)0.040 (2)0.795 (3)
H450.65160.01240.73380.048*0.795 (3)
S450.537 (3)0.068 (2)0.6940 (11)0.101 (6)*0.205 (3)
C420.229 (6)0.195 (5)0.640 (2)0.101 (6)*0.205 (3)
H420.09380.24450.63250.121*0.205 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O210.0865 (15)0.0901 (14)0.0591 (12)0.0290 (12)0.0291 (11)0.0184 (10)
N10.0550 (12)0.0577 (13)0.0474 (12)0.0030 (11)0.0046 (10)0.0079 (9)
C20.0487 (14)0.0433 (13)0.0515 (14)0.0045 (11)0.0061 (11)0.0037 (11)
C30.0524 (15)0.0475 (14)0.0541 (15)0.0031 (12)0.0065 (12)0.0089 (12)
C40.0435 (14)0.0392 (12)0.0507 (14)0.0006 (11)0.0050 (11)0.0010 (11)
C50.0492 (14)0.0487 (14)0.0582 (15)0.0068 (12)0.0084 (12)0.0037 (12)
C210.0675 (18)0.0623 (16)0.0603 (17)0.0145 (14)0.0158 (14)0.0094 (14)
C410.0478 (14)0.0408 (13)0.0544 (15)0.0037 (11)0.0083 (12)0.0021 (11)
C430.099 (2)0.0683 (19)0.0571 (17)0.0184 (18)0.0237 (17)0.0038 (15)
C440.0665 (19)0.0673 (19)0.085 (2)0.0102 (16)0.0328 (17)0.0183 (16)
S420.0601 (7)0.0676 (6)0.0519 (7)0.0052 (5)0.0094 (5)0.0081 (5)
C450.035 (2)0.038 (3)0.049 (3)0.0019 (15)0.0111 (15)0.0053 (13)
Geometric parameters (Å, º) top
O21—C211.212 (3)C41—C451.519 (11)
N1—C51.346 (3)C41—S451.428 (19)
N1—C21.368 (3)C41—S421.701 (3)
N1—H10.8600C43—C441.328 (4)
C2—C31.380 (3)C43—S421.651 (4)
C2—C211.431 (4)C43—C421.72 (3)
C3—C41.403 (3)C43—H430.9300
C3—H30.9300C44—S451.438 (19)
C4—C51.378 (3)C44—C451.469 (11)
C4—C411.459 (3)C44—H440.9300
C5—H50.9300C45—H450.9300
C21—H210.9300C42—H420.9300
C41—C421.35 (4)
C5—N1—C2109.0 (2)C42—C41—S420.7 (16)
C5—N1—H1125.5C45—C41—S42112.0 (4)
C2—N1—H1125.5C4—C41—S42122.12 (19)
N1—C2—C3107.3 (2)S45—C41—S42109.7 (8)
N1—C2—C21122.6 (2)C44—C43—S42114.1 (2)
C3—C2—C21130.0 (2)C44—C43—C42102.4 (12)
C2—C3—C4108.2 (2)S42—C43—C4211.6 (13)
C2—C3—H3125.9C44—C43—H43123.0
C4—C3—H3125.9S42—C43—H43123.0
C5—C4—C3105.8 (2)C42—C43—H43134.6
C5—C4—C41126.1 (2)C43—C44—S45112.7 (8)
C3—C4—C41128.0 (2)C43—C44—C45116.8 (5)
N1—C5—C4109.6 (2)S45—C44—C454.1 (11)
N1—C5—H5125.2C43—C44—H44121.6
C4—C5—H5125.2S45—C44—H44125.7
O21—C21—C2126.0 (3)C45—C44—H44121.6
O21—C21—H21117.0C43—S42—C4193.55 (16)
C2—C21—H21117.0C41—C45—C44103.6 (7)
C42—C41—C45112.6 (16)C41—C45—H45128.2
C42—C41—C4121.5 (15)C44—C45—H45128.2
C45—C41—C4125.8 (4)C44—S45—C41110.0 (12)
C42—C41—S45110.3 (17)C41—C42—C43105 (2)
C45—C41—S452.3 (12)C41—C42—H42127.7
C4—C41—S45128.2 (8)C43—C42—H42127.7

Experimental details

Crystal data
Chemical formulaC9H7NOS
Mr177.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)6.303 (2), 7.745 (3), 17.424 (1)
β (°) 96.64 (1)
V3)844.9 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.50 × 0.20 × 0.10
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1641, 1496, 883
Rint0.020
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.112, 1.01
No. of reflections1496
No. of parameters117
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.23

Computer programs: MSC/AFC Diffractometer Control (Molecular Structure Corporation, 1996), MSC/AFC Diffractometer Control, TEXSAN for Windows (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN for Windows.

 

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