Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029910/bh6030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029910/bh6030Isup2.hkl |
CCDC reference: 287447
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.004 Å
- R factor = 0.052
- wR factor = 0.148
- Data-to-parameter ratio = 19.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT230_ALERT_2_C Hirshfeld Test Diff for C5 - C7 .. 6.64 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C6 - C10 .. 6.68 su PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
The title compound was synthesized by dissolving 2,3-dimethyl-2,3-bis(hydroxylamino)butane (1.48 g, 10 mmol) in an alcoholic (Ethanolic?) solution (Volume?) of 2-thiazolecarboxaldehyde (1.07 g, 10 mmol), following the method of Ullman et al. (1970). The resulting solution was refluxed for 5 h and then stirred for 24 h at 298 K. The mixture was then filtered to remove an amount of white precipitate and the clear filtrate was allowed to stand at 298 K in the dark for three weeks. Yellow crystals of (I) suitable for X-ray diffraction were obtained. Analysis, found: C 49.43, H 7.12, N 17.18%; calculated for C10H17N3O2S: C 49.36, H 7.04, N 17.27%.
H atoms were placed in calculated positions and refined using a riding-model approximation, with C—H bond lengths and Uiso(H) values as follows: 0.93 Å and 1.2Ueq(C) for Csp2H; 0.96 Å and 1.5Ueq(C) for methyl CH3; 0.98 Å and 1.2Ueq(C) for methine CH; 0.82 Å and 1.5Ueq(O) for hydroxyl OH.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.
C10H17N3O2S | F(000) = 520 |
Mr = 243.33 | Dx = 1.281 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9785 (5) Å | Cell parameters from 4327 reflections |
b = 18.7982 (13) Å | θ = 3.0–27.6° |
c = 10.0764 (7) Å | µ = 0.25 mm−1 |
β = 107.367 (1)° | T = 273 K |
V = 1261.59 (15) Å3 | Prism, yellow |
Z = 4 | 0.39 × 0.29 × 0.28 mm |
Bruker SMART CCD area-detector diffractometer | 2886 independent reflections |
Radiation source: fine-focus sealed tube | 2326 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −8→9 |
Tmin = 0.909, Tmax = 0.934 | k = −24→24 |
10799 measured reflections | l = −13→12 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0644P)2 + 0.6505P] where P = (Fo2 + 2Fc2)/3 |
2886 reflections | (Δ/σ)max < 0.001 |
151 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C10H17N3O2S | V = 1261.59 (15) Å3 |
Mr = 243.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.9785 (5) Å | µ = 0.25 mm−1 |
b = 18.7982 (13) Å | T = 273 K |
c = 10.0764 (7) Å | 0.39 × 0.29 × 0.28 mm |
β = 107.367 (1)° |
Bruker SMART CCD area-detector diffractometer | 2886 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2326 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 0.934 | Rint = 0.015 |
10799 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.49 e Å−3 |
2886 reflections | Δρmin = −0.33 e Å−3 |
151 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 | ||
S1 | 0.08575 (9) | 0.63584 (5) | 0.48980 (7) | 0.0742 (3) | |
O1 | 0.5623 (2) | 0.74143 (7) | 0.72796 (16) | 0.0547 (4) | |
H1 | 0.4925 | 0.7654 | 0.7635 | 0.082* | |
O2 | 0.7023 (2) | 0.54614 (9) | 0.55417 (17) | 0.0579 (4) | |
H2 | 0.6727 | 0.5109 | 0.5043 | 0.087* | |
N1 | 0.3076 (3) | 0.68503 (10) | 0.35203 (18) | 0.0564 (5) | |
N2 | 0.4980 (3) | 0.66873 (8) | 0.71949 (15) | 0.0416 (4) | |
N3 | 0.5373 (2) | 0.56442 (8) | 0.60613 (15) | 0.0395 (4) | |
C1 | −0.0274 (4) | 0.66449 (16) | 0.3255 (3) | 0.0759 (8) | |
H1A | −0.1650 | 0.6634 | 0.2812 | 0.091* | |
C2 | 0.1094 (5) | 0.68864 (15) | 0.2694 (3) | 0.0754 (8) | |
H2A | 0.0744 | 0.7070 | 0.1797 | 0.091* | |
C3 | 0.3157 (3) | 0.65796 (10) | 0.47212 (19) | 0.0418 (4) | |
C4 | 0.5066 (3) | 0.64225 (9) | 0.58516 (17) | 0.0377 (4) | |
H4 | 0.6211 | 0.6635 | 0.5622 | 0.045* | |
C5 | 0.5835 (4) | 0.55112 (11) | 0.7620 (2) | 0.0547 (6) | |
C6 | 0.6467 (4) | 0.62476 (11) | 0.8261 (2) | 0.0537 (5) | |
C7 | 0.3797 (5) | 0.52849 (15) | 0.7822 (3) | 0.0742 (8) | |
H7A | 0.3266 | 0.4885 | 0.7236 | 0.111* | |
H7B | 0.2867 | 0.5674 | 0.7580 | 0.111* | |
H7C | 0.4000 | 0.5156 | 0.8777 | 0.111* | |
C8 | 0.7338 (5) | 0.49203 (13) | 0.8116 (3) | 0.0736 (8) | |
H8A | 0.6788 | 0.4484 | 0.7668 | 0.110* | |
H8B | 0.7635 | 0.4868 | 0.9105 | 0.110* | |
H8C | 0.8547 | 0.5032 | 0.7892 | 0.110* | |
C9 | 0.6168 (5) | 0.63854 (13) | 0.9663 (2) | 0.0689 (7) | |
H9A | 0.6683 | 0.6848 | 0.9990 | 0.103* | |
H9B | 0.6869 | 0.6030 | 1.0312 | 0.103* | |
H9C | 0.4762 | 0.6366 | 0.9579 | 0.103* | |
C10 | 0.8690 (4) | 0.64071 (15) | 0.8348 (3) | 0.0728 (7) | |
H10A | 0.8951 | 0.6241 | 0.7517 | 0.109* | |
H10B | 0.9567 | 0.6169 | 0.9140 | 0.109* | |
H10C | 0.8924 | 0.6911 | 0.8438 | 0.109* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0440 (3) | 0.1121 (6) | 0.0640 (4) | 0.0035 (3) | 0.0121 (3) | 0.0014 (4) |
O1 | 0.0654 (10) | 0.0340 (7) | 0.0605 (9) | −0.0081 (6) | 0.0124 (7) | −0.0061 (6) |
O2 | 0.0459 (8) | 0.0671 (10) | 0.0639 (10) | 0.0002 (7) | 0.0214 (7) | −0.0231 (8) |
N1 | 0.0729 (12) | 0.0464 (9) | 0.0412 (9) | 0.0012 (9) | 0.0035 (8) | 0.0095 (7) |
N2 | 0.0585 (10) | 0.0317 (7) | 0.0327 (8) | −0.0056 (7) | 0.0106 (7) | −0.0034 (6) |
N3 | 0.0445 (8) | 0.0435 (8) | 0.0301 (7) | 0.0045 (6) | 0.0108 (6) | −0.0031 (6) |
C1 | 0.0584 (15) | 0.0778 (17) | 0.0724 (17) | 0.0214 (13) | −0.0097 (13) | −0.0113 (14) |
C2 | 0.0865 (19) | 0.0641 (15) | 0.0529 (14) | 0.0170 (14) | −0.0139 (13) | 0.0081 (12) |
C3 | 0.0475 (10) | 0.0381 (9) | 0.0367 (9) | 0.0025 (7) | 0.0080 (8) | −0.0011 (7) |
C4 | 0.0412 (9) | 0.0409 (9) | 0.0306 (8) | −0.0042 (7) | 0.0102 (7) | 0.0004 (7) |
C5 | 0.0834 (16) | 0.0424 (10) | 0.0327 (9) | 0.0050 (10) | 0.0088 (9) | −0.0002 (8) |
C6 | 0.0786 (15) | 0.0433 (10) | 0.0328 (10) | 0.0035 (10) | 0.0070 (9) | −0.0006 (8) |
C7 | 0.105 (2) | 0.0705 (16) | 0.0530 (14) | −0.0303 (15) | 0.0326 (14) | 0.0048 (12) |
C8 | 0.110 (2) | 0.0477 (12) | 0.0493 (13) | 0.0195 (13) | 0.0031 (13) | 0.0029 (10) |
C9 | 0.111 (2) | 0.0579 (14) | 0.0324 (11) | 0.0008 (13) | 0.0131 (12) | −0.0047 (9) |
C10 | 0.0594 (14) | 0.0714 (16) | 0.0691 (16) | −0.0052 (12) | −0.0089 (12) | 0.0058 (12) |
S1—C1 | 1.696 (3) | C5—C8 | 1.507 (3) |
S1—C3 | 1.718 (2) | C5—C6 | 1.536 (3) |
O1—N2 | 1.4330 (19) | C5—C7 | 1.555 (4) |
O1—H1 | 0.8200 | C6—C9 | 1.511 (3) |
O2—N3 | 1.4415 (19) | C6—C10 | 1.557 (4) |
O2—H2 | 0.8200 | C7—H7A | 0.9600 |
N1—C3 | 1.298 (3) | C7—H7B | 0.9600 |
N1—C2 | 1.387 (3) | C7—H7C | 0.9600 |
N2—C4 | 1.460 (2) | C8—H8A | 0.9600 |
N2—C6 | 1.500 (3) | C8—H8B | 0.9600 |
N3—C4 | 1.484 (2) | C8—H8C | 0.9600 |
N3—C5 | 1.526 (2) | C9—H9A | 0.9600 |
C1—C2 | 1.326 (4) | C9—H9B | 0.9600 |
C1—H1A | 0.9300 | C9—H9C | 0.9600 |
C2—H2A | 0.9300 | C10—H10A | 0.9600 |
C3—C4 | 1.501 (3) | C10—H10B | 0.9600 |
C4—H4 | 0.9800 | C10—H10C | 0.9600 |
C1—S1—C3 | 89.95 (13) | N2—C6—C9 | 108.42 (19) |
N2—O1—H1 | 109.5 | N2—C6—C5 | 98.34 (16) |
N3—O2—H2 | 109.5 | C9—C6—C5 | 116.5 (2) |
C3—N1—C2 | 109.7 (2) | N2—C6—C10 | 113.51 (18) |
O1—N2—C4 | 106.35 (13) | C9—C6—C10 | 109.2 (2) |
O1—N2—C6 | 110.21 (15) | C5—C6—C10 | 110.7 (2) |
C4—N2—C6 | 105.36 (15) | C5—C7—H7A | 109.5 |
O2—N3—C4 | 106.26 (14) | C5—C7—H7B | 109.5 |
O2—N3—C5 | 112.83 (15) | H7A—C7—H7B | 109.5 |
C4—N3—C5 | 106.57 (13) | C5—C7—H7C | 109.5 |
C2—C1—S1 | 109.9 (2) | H7A—C7—H7C | 109.5 |
C2—C1—H1A | 125.1 | H7B—C7—H7C | 109.5 |
S1—C1—H1A | 125.1 | C5—C8—H8A | 109.5 |
C1—C2—N1 | 116.3 (2) | C5—C8—H8B | 109.5 |
C1—C2—H2A | 121.8 | H8A—C8—H8B | 109.5 |
N1—C2—H2A | 121.8 | C5—C8—H8C | 109.5 |
N1—C3—C4 | 124.49 (18) | H8A—C8—H8C | 109.5 |
N1—C3—S1 | 114.17 (16) | H8B—C8—H8C | 109.5 |
C4—C3—S1 | 121.24 (14) | C6—C9—H9A | 109.5 |
N2—C4—N3 | 104.37 (13) | C6—C9—H9B | 109.5 |
N2—C4—C3 | 111.31 (16) | H9A—C9—H9B | 109.5 |
N3—C4—C3 | 111.07 (14) | C6—C9—H9C | 109.5 |
N2—C4—H4 | 110.0 | H9A—C9—H9C | 109.5 |
N3—C4—H4 | 110.0 | H9B—C9—H9C | 109.5 |
C3—C4—H4 | 110.0 | C6—C10—H10A | 109.5 |
C8—C5—N3 | 112.03 (18) | C6—C10—H10B | 109.5 |
C8—C5—C6 | 116.1 (2) | H10A—C10—H10B | 109.5 |
N3—C5—C6 | 103.36 (15) | C6—C10—H10C | 109.5 |
C8—C5—C7 | 109.1 (2) | H10A—C10—H10C | 109.5 |
N3—C5—C7 | 105.03 (18) | H10B—C10—H10C | 109.5 |
C6—C5—C7 | 110.5 (2) | ||
C3—S1—C1—C2 | −0.5 (2) | C4—N3—C5—C8 | −144.5 (2) |
S1—C1—C2—N1 | 0.6 (3) | O2—N3—C5—C6 | 97.55 (19) |
C3—N1—C2—C1 | −0.5 (3) | C4—N3—C5—C6 | −18.7 (2) |
C2—N1—C3—C4 | 176.40 (19) | O2—N3—C5—C7 | −146.56 (17) |
C2—N1—C3—S1 | 0.1 (2) | C4—N3—C5—C7 | 97.19 (19) |
C1—S1—C3—N1 | 0.22 (18) | O1—N2—C6—C9 | 77.0 (2) |
C1—S1—C3—C4 | −176.23 (17) | C4—N2—C6—C9 | −168.64 (18) |
O1—N2—C4—N3 | 153.55 (14) | O1—N2—C6—C5 | −161.42 (16) |
C6—N2—C4—N3 | 36.55 (18) | C4—N2—C6—C5 | −47.08 (19) |
O1—N2—C4—C3 | −86.57 (17) | O1—N2—C6—C10 | −44.5 (2) |
C6—N2—C4—C3 | 156.43 (16) | C4—N2—C6—C10 | 69.9 (2) |
O2—N3—C4—N2 | −130.74 (14) | C8—C5—C6—N2 | 162.0 (2) |
C5—N3—C4—N2 | −10.17 (19) | N3—C5—C6—N2 | 38.9 (2) |
O2—N3—C4—C3 | 109.22 (16) | C7—C5—C6—N2 | −73.0 (2) |
C5—N3—C4—C3 | −130.22 (17) | C8—C5—C6—C9 | −82.6 (3) |
N1—C3—C4—N2 | 132.84 (19) | N3—C5—C6—C9 | 154.3 (2) |
S1—C3—C4—N2 | −51.1 (2) | C7—C5—C6—C9 | 42.4 (3) |
N1—C3—C4—N3 | −111.3 (2) | C8—C5—C6—C10 | 42.9 (3) |
S1—C3—C4—N3 | 64.75 (19) | N3—C5—C6—C10 | −80.2 (2) |
O2—N3—C5—C8 | −28.2 (3) | C7—C5—C6—C10 | 167.85 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.82 | 2.00 | 2.821 (3) | 174 |
O2—H2···N3ii | 0.82 | 2.10 | 2.848 (2) | 151 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H17N3O2S |
Mr | 243.33 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 6.9785 (5), 18.7982 (13), 10.0764 (7) |
β (°) | 107.367 (1) |
V (Å3) | 1261.59 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.39 × 0.29 × 0.28 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.909, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10799, 2886, 2326 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.148, 1.06 |
No. of reflections | 2886 |
No. of parameters | 151 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.49, −0.33 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.
S1—C1 | 1.696 (3) | N2—C4 | 1.460 (2) |
S1—C3 | 1.718 (2) | N2—C6 | 1.500 (3) |
O1—N2 | 1.4330 (19) | N3—C4 | 1.484 (2) |
O2—N3 | 1.4415 (19) | N3—C5 | 1.526 (2) |
N1—C3 | 1.298 (3) | C1—C2 | 1.326 (4) |
N1—C2 | 1.387 (3) | C5—C6 | 1.536 (3) |
C1—S1—C3 | 89.95 (13) | C4—N2—C6 | 105.36 (15) |
C3—N1—C2 | 109.7 (2) | O2—N3—C4 | 106.26 (14) |
O1—N2—C4 | 106.35 (13) | O2—N3—C5 | 112.83 (15) |
O1—N2—C6 | 110.21 (15) | C4—N3—C5 | 106.57 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1i | 0.82 | 2.00 | 2.821 (3) | 174 |
O2—H2···N3ii | 0.82 | 2.10 | 2.848 (2) | 151 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, −y+1, −z+1. |
The design and synthesis of multidimensional molecule-based magnetic materials is one of the major challenges in molecular materials research (Kahn 1993; Laget et al., 1998; Vaz et al., 1999; Yamamoto et al., 2001). Nitronyl nitroxide radicals, due to their intriguing structural diversity and potential applications, have played a prominent role in the design and construction of molecular magnetic materials (Vasilevsky et al., 1998; Marvilliers et al., 1999; Hirel et al., 2001; Li et al., 2003). However, problems associated with the preparation of key intermediates of nitronyl nitroxides are probably the reason for the limited number of developments reported so far concerning structural variations in nitronyl nitroxides (Lin et al., 2003; Wang et al., 2004). During the course of synthesizing a novel thiazolyl-substituted nitronyl nitroxide radical, we simultaneously obtained the title compound, (I), as an intermediate, and we now report its synthesis and X-ray structure.
The molecular structure of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1. The dihedral angle between the thiazole and imidazolidine rings is 92.79 (9)°.
There are two types of intermolecular O—H···N hydrogen-bonding interactions in the crystal structure of (I). One type of hydrogen bond occurs between one N atom of the thiazole ring and one O atom of a symmetry-related imidazolidine ring (Table 2). The other type of hydrogen bond exists between two adjacent imidazolidine rings: one O atom of one imidazolidine ring and one N atom of a neighbouring molecule form double hydrogen bonds (Table 2). In the crystal structure, single and double hydrogen bonds are alternately arranged in such a way that six adjacent molecules form a ring. Thus, the molecules of (I) are linked via intermolecular O—H···N hydrogen bonds, resulting in a two-dimensional network arrangement (Fig. 2).