4,4,5,5-Tetra­methyl-2-(thia­zol-2-yl)imidazolidine-1,3-diol

In the crystal structure of the title compound, C₁₀H₁₇N₃O₂S, the packing of the mol­ecules is mainly a result of two types of O—H...N hydrogen-bonding inter­actions, forming a two-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](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

---

S1. Comment

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).

S2. Experimental

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%.

S3. Refinement

H atoms were placed in calculated positions and refined using a riding-model approximation, with C—H bond lengths and U_iso(H) values as follows: 0.93 Å and 1.2U_eq(C) for Csp²H; 0.96 Å and 1.5U_eq(C) for methyl CH₃; 0.98 Å and 1.2U_eq(C) for methine CH; 0.82 Å and 1.5U_eq(O) for hydroxyl OH.

Computing details

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.

Figures

	Fig. 1. A drawing of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The two-dimensional network arrangement of the crystal structure of (I), viewed along the [100] axis.

4,4,5,5-Tetramethyl-2-thiazol-2-ylimidazolidine-1,3-diol

Crystal data

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) Å^3	Prism, yellow
Z = 4	0.39 × 0.29 × 0.28 mm

Data collection

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

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0644P)^2 + 0.6505P] where P = (Fo^2 + 2Fc^2)/3
2886 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.33 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
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*

Atomic displacement parameters (Ų)

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

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1^i	0.82	2.00	2.821 (3)	174
O2—H2···N3^ii	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.