Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029636/ya6265sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029636/ya6265Isup2.hkl |
CCDC reference: 287768
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
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.
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.
C9H7NOS | F(000) = 368 |
Mr = 177.22 | Dx = 1.393 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 6.303 (2) Å | θ = 11.4–18.5° |
b = 7.745 (3) Å | µ = 0.33 mm−1 |
c = 17.424 (1) Å | T = 293 K |
β = 96.64 (1)° | Block, orange |
V = 844.9 (4) Å3 | 0.50 × 0.20 × 0.10 mm |
Z = 4 |
Rigaku AFC-7R diffractometer | Rint = 0.020 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.9° |
Graphite monochromator | h = 0→7 |
ω–2θ scans | k = 0→9 |
1641 measured reflections | l = −20→20 |
1496 independent reflections | 3 standard reflections every 150 reflections |
883 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-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 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C9H7NOS | V = 844.9 (4) Å3 |
Mr = 177.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.303 (2) Å | µ = 0.33 mm−1 |
b = 7.745 (3) Å | T = 293 K |
c = 17.424 (1) Å | 0.50 × 0.20 × 0.10 mm |
β = 96.64 (1)° |
Rigaku AFC-7R diffractometer | Rint = 0.020 |
1641 measured reflections | 3 standard reflections every 150 reflections |
1496 independent reflections | intensity decay: none |
883 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.14 e Å−3 |
1496 reflections | Δρmin = −0.23 e Å−3 |
117 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 | Occ. (<1) | |
O21 | −0.2026 (3) | 0.1625 (3) | 0.97144 (11) | 0.0770 (7) | |
N1 | 0.1619 (3) | 0.0592 (3) | 0.89633 (11) | 0.0535 (6) | |
H1 | 0.1728 | 0.0129 | 0.9415 | 0.064* | |
C2 | 0.0042 (4) | 0.1706 (3) | 0.86715 (14) | 0.0478 (6) | |
C3 | 0.0459 (4) | 0.2162 (3) | 0.79381 (14) | 0.0513 (6) | |
H3 | −0.0350 | 0.2914 | 0.7606 | 0.062* | |
C4 | 0.2314 (3) | 0.1296 (3) | 0.77791 (13) | 0.0445 (6) | |
C5 | 0.2970 (4) | 0.0339 (3) | 0.84300 (14) | 0.0519 (6) | |
H5 | 0.4165 | −0.0374 | 0.8491 | 0.062* | |
C21 | −0.1710 (5) | 0.2165 (3) | 0.90849 (17) | 0.0627 (7) | |
H21 | −0.2696 | 0.2948 | 0.8849 | 0.075* | |
C41 | 0.3319 (4) | 0.1321 (3) | 0.70659 (14) | 0.0475 (6) | |
C43 | 0.4045 (6) | 0.1631 (4) | 0.57259 (17) | 0.0738 (9) | |
H43 | 0.4015 | 0.1861 | 0.5201 | 0.089* | |
C44 | 0.5702 (5) | 0.0897 (4) | 0.61421 (18) | 0.0711 (9) | |
H44 | 0.6919 | 0.0576 | 0.5922 | 0.085* | |
S42 | 0.2045 (2) | 0.2100 (2) | 0.62231 (7) | 0.0596 (4) | 0.795 (3) |
C45 | 0.5520 (16) | 0.0616 (12) | 0.6966 (6) | 0.040 (2) | 0.795 (3) |
H45 | 0.6516 | 0.0124 | 0.7338 | 0.048* | 0.795 (3) |
S45 | 0.537 (3) | 0.068 (2) | 0.6940 (11) | 0.101 (6)* | 0.205 (3) |
C42 | 0.229 (6) | 0.195 (5) | 0.640 (2) | 0.101 (6)* | 0.205 (3) |
H42 | 0.0938 | 0.2445 | 0.6325 | 0.121* | 0.205 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O21 | 0.0865 (15) | 0.0901 (14) | 0.0591 (12) | 0.0290 (12) | 0.0291 (11) | 0.0184 (10) |
N1 | 0.0550 (12) | 0.0577 (13) | 0.0474 (12) | 0.0030 (11) | 0.0046 (10) | 0.0079 (9) |
C2 | 0.0487 (14) | 0.0433 (13) | 0.0515 (14) | 0.0045 (11) | 0.0061 (11) | 0.0037 (11) |
C3 | 0.0524 (15) | 0.0475 (14) | 0.0541 (15) | 0.0031 (12) | 0.0065 (12) | 0.0089 (12) |
C4 | 0.0435 (14) | 0.0392 (12) | 0.0507 (14) | −0.0006 (11) | 0.0050 (11) | −0.0010 (11) |
C5 | 0.0492 (14) | 0.0487 (14) | 0.0582 (15) | 0.0068 (12) | 0.0084 (12) | 0.0037 (12) |
C21 | 0.0675 (18) | 0.0623 (16) | 0.0603 (17) | 0.0145 (14) | 0.0158 (14) | 0.0094 (14) |
C41 | 0.0478 (14) | 0.0408 (13) | 0.0544 (15) | −0.0037 (11) | 0.0083 (12) | −0.0021 (11) |
C43 | 0.099 (2) | 0.0683 (19) | 0.0571 (17) | −0.0184 (18) | 0.0237 (17) | −0.0038 (15) |
C44 | 0.0665 (19) | 0.0673 (19) | 0.085 (2) | −0.0102 (16) | 0.0328 (17) | −0.0183 (16) |
S42 | 0.0601 (7) | 0.0676 (6) | 0.0519 (7) | 0.0052 (5) | 0.0094 (5) | 0.0081 (5) |
C45 | 0.035 (2) | 0.038 (3) | 0.049 (3) | −0.0019 (15) | 0.0111 (15) | −0.0053 (13) |
O21—C21 | 1.212 (3) | C41—C45 | 1.519 (11) |
N1—C5 | 1.346 (3) | C41—S45 | 1.428 (19) |
N1—C2 | 1.368 (3) | C41—S42 | 1.701 (3) |
N1—H1 | 0.8600 | C43—C44 | 1.328 (4) |
C2—C3 | 1.380 (3) | C43—S42 | 1.651 (4) |
C2—C21 | 1.431 (4) | C43—C42 | 1.72 (3) |
C3—C4 | 1.403 (3) | C43—H43 | 0.9300 |
C3—H3 | 0.9300 | C44—S45 | 1.438 (19) |
C4—C5 | 1.378 (3) | C44—C45 | 1.469 (11) |
C4—C41 | 1.459 (3) | C44—H44 | 0.9300 |
C5—H5 | 0.9300 | C45—H45 | 0.9300 |
C21—H21 | 0.9300 | C42—H42 | 0.9300 |
C41—C42 | 1.35 (4) | ||
C5—N1—C2 | 109.0 (2) | C42—C41—S42 | 0.7 (16) |
C5—N1—H1 | 125.5 | C45—C41—S42 | 112.0 (4) |
C2—N1—H1 | 125.5 | C4—C41—S42 | 122.12 (19) |
N1—C2—C3 | 107.3 (2) | S45—C41—S42 | 109.7 (8) |
N1—C2—C21 | 122.6 (2) | C44—C43—S42 | 114.1 (2) |
C3—C2—C21 | 130.0 (2) | C44—C43—C42 | 102.4 (12) |
C2—C3—C4 | 108.2 (2) | S42—C43—C42 | 11.6 (13) |
C2—C3—H3 | 125.9 | C44—C43—H43 | 123.0 |
C4—C3—H3 | 125.9 | S42—C43—H43 | 123.0 |
C5—C4—C3 | 105.8 (2) | C42—C43—H43 | 134.6 |
C5—C4—C41 | 126.1 (2) | C43—C44—S45 | 112.7 (8) |
C3—C4—C41 | 128.0 (2) | C43—C44—C45 | 116.8 (5) |
N1—C5—C4 | 109.6 (2) | S45—C44—C45 | 4.1 (11) |
N1—C5—H5 | 125.2 | C43—C44—H44 | 121.6 |
C4—C5—H5 | 125.2 | S45—C44—H44 | 125.7 |
O21—C21—C2 | 126.0 (3) | C45—C44—H44 | 121.6 |
O21—C21—H21 | 117.0 | C43—S42—C41 | 93.55 (16) |
C2—C21—H21 | 117.0 | C41—C45—C44 | 103.6 (7) |
C42—C41—C45 | 112.6 (16) | C41—C45—H45 | 128.2 |
C42—C41—C4 | 121.5 (15) | C44—C45—H45 | 128.2 |
C45—C41—C4 | 125.8 (4) | C44—S45—C41 | 110.0 (12) |
C42—C41—S45 | 110.3 (17) | C41—C42—C43 | 105 (2) |
C45—C41—S45 | 2.3 (12) | C41—C42—H42 | 127.7 |
C4—C41—S45 | 128.2 (8) | C43—C42—H42 | 127.7 |
Experimental details
Crystal data | |
Chemical formula | C9H7NOS |
Mr | 177.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.303 (2), 7.745 (3), 17.424 (1) |
β (°) | 96.64 (1) |
V (Å3) | 844.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.50 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1641, 1496, 883 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.112, 1.01 |
No. of reflections | 1496 |
No. of parameters | 117 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
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].