5-(4-Chloro­phen­yl)-3-hydr­oxy-4-methylthia­zole-2(3H)-thione: an instance of bifurcated hydrogen bonding

The asymmetric unit of the title compound, C₁₀H₈ClNOS₂, comprises two unique mol­ecules. Aggregation occurs via inter­molecular bifurcated hydrogen bonding between the thio­hydroxamate H atom and the thio­carbonyl S atoms of the same and of an adjacent mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.082
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............      24.11 Deg.

Author Response: The compound was prepared in a project that ended a few years ago. The meassurement was performed using the theta range that was routinely applied at that time. In view of the fact that the structure is an organic compound, which scatters with minor intensity at high theta values we feel that the presented structural information on this compound is reliable enough in order to unambigiously solve the structure and refine the structure model reliably

Alert level B
THETM01_ALERT_3_B  The value of sine(theta_max)/wavelength is less than 0.575
            Calculated sin(theta_max)/wavelength =    0.5747

Alert level C
PLAT023_ALERT_3_C Resolution (too) Low [sin(th)/Lambda < 0.6].....      24.11 Deg.
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....        H1'
PLAT166_ALERT_4_C S.U's Given on Coordinates for calc-flagged ....         H1
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          3

   1 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: EXPOSE in IPDS Software (Stoe & Cie, 1998); cell refinement: CELL in IPDS Software; data reduction: INTEGRATE in IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1994); software used to prepare material for publication: SHELXTL-Plus.

5-(4-Chlorophenyl)-3-hydroxy-4-methylthiazole-2(3H)-thione:

Crystal data

C10H8ClNOS2	F(000) = 1056
Mr = 257.74	Dx = 1.546 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8000 reflections
a = 9.843 (2) Å	θ = 1.9–24.1°
b = 14.707 (3) Å	µ = 0.69 mm^−1
c = 15.312 (3) Å	T = 291 K
β = 92.34 (3)°	Prism, yellow
V = 2214.7 (8) Å^3	0.30 × 0.25 × 0.20 mm
Z = 8

Data collection

Stoe IPDS diffractometer	3008 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
Graphite monochromator	θmax = 24.1°, θmin = 1.9°
φ scans	h = −11→11
25254 measured reflections	k = −16→16
3499 independent reflections	l = −17→17

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 0.4154P] where P = (Fo^2 + 2Fc^2)/3
3499 reflections	(Δ/σ)max = 0.001
275 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. Analysis calculated for C₁₀H₈ClNOS₂ (257.76 g mol^-1): C 46.60, H 3.13, N 5.43%; found C 46.82, H 3.10, N 5.40%. ¹H NMR (400 MHz, CDCl₃, δ, p.p.m.): 2.44 (s, 3H), 7.28–7.30 (m_c, 2H), 7.41–7.43 (m_c, 2H); ¹³C NMR (100 MHz, CDCl₃, δ, p.p.m.): 12.3, 118.3, 128.6, 129.6, 130.0, 131.3, 135.2, 170.2; UV-VIS (EtOH): λmax (ε, m² mol^-1) = 334 nm (1024).

For cell measurement 8000 reflections selected from the whole data set were selected with the program SELECT 2.87 (Stoe, 1998) For data collection 225 exposures were taken in the 0–360.0 phi range with a crystal to detector distance of 80 mm and an exposure time of 3.00 minutes. Dynamic profiles (15–21 pixels) were used for integration. At least 50 reflections with I/s(I) > 6 taken from each frame were used to calculate the decay

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
C2'	0.9308 (2)	0.60197 (14)	0.40065 (12)	0.0445 (5)
C2	0.45265 (19)	0.67331 (13)	0.25501 (12)	0.0419 (4)
C4'	0.92944 (19)	0.63026 (13)	0.55209 (12)	0.0425 (4)
C4	0.44585 (19)	0.63862 (14)	0.10445 (12)	0.0428 (4)
C5'	0.7990 (2)	0.60281 (13)	0.53784 (12)	0.0423 (4)
C5	0.58170 (19)	0.65126 (13)	0.11789 (12)	0.0399 (4)
C6'	1.0020 (2)	0.66381 (17)	0.63306 (13)	0.0570 (6)
H17'A	0.9368	0.6839	0.6738	0.085*
H17'B	1.0602	0.7136	0.6188	0.085*
H17'C	1.0557	0.6155	0.6587	0.085*
C6	0.3645 (2)	0.61025 (19)	0.02501 (14)	0.0645 (6)
H17A	0.3122	0.6610	0.0029	0.097*
H17B	0.3043	0.5617	0.0397	0.097*
H17C	0.4244	0.5897	−0.0188	0.097*
C51	0.69215 (19)	0.64507 (13)	0.05669 (12)	0.0399 (4)
C51'	0.6866 (2)	0.59617 (13)	0.59779 (12)	0.0420 (4)
C52	0.8189 (2)	0.61156 (15)	0.08553 (12)	0.0475 (5)
H18	0.8311	0.5915	0.1429	0.057*
C52'	0.5542 (2)	0.61610 (14)	0.56718 (13)	0.0488 (5)
H18'	0.5390	0.6340	0.5094	0.059*
C53'	0.4455 (2)	0.60974 (15)	0.62104 (14)	0.0516 (5)
H23'	0.3581	0.6235	0.5997	0.062*
C53	0.9262 (2)	0.60763 (16)	0.03086 (13)	0.0528 (5)
H23	1.0099	0.5851	0.0512	0.063*
C54'	0.4675 (2)	0.58286 (13)	0.70652 (13)	0.0462 (5)
C54	0.9086 (2)	0.63740 (14)	−0.05454 (13)	0.0476 (5)
C55'	0.5972 (2)	0.56279 (14)	0.73884 (13)	0.0489 (5)
H10'	0.6112	0.5449	0.7968	0.059*
C55	0.7851 (2)	0.67061 (15)	−0.08499 (12)	0.0491 (5)
H10	0.7739	0.6903	−0.1426	0.059*
C56	0.6773 (2)	0.67478 (14)	−0.02975 (12)	0.0476 (5)
H9	0.5940	0.6977	−0.0505	0.057*
C56'	0.7063 (2)	0.56930 (14)	0.68487 (13)	0.0467 (5)
H9'	0.7934	0.5557	0.7068	0.056*
N3	0.37983 (15)	0.65263 (11)	0.18184 (10)	0.0433 (4)
N3'	0.99787 (15)	0.62739 (12)	0.47443 (10)	0.0449 (4)
Cl1	1.04344 (6)	0.63260 (5)	−0.12435 (4)	0.0741 (2)
Cl1'	0.33059 (6)	0.57221 (4)	0.77373 (4)	0.06810 (19)
O1'	1.13351 (14)	0.65224 (12)	0.47449 (10)	0.0622 (4)
H1'	1.1591 (10)	0.64975 (16)	0.4267 (18)	0.093*
O1	0.24051 (14)	0.64225 (12)	0.18253 (10)	0.0624 (4)
H1	0.2138 (10)	0.6523 (4)	0.2336 (18)	0.094*
S1'	0.76744 (5)	0.57572 (4)	0.42756 (3)	0.04812 (15)
S1	0.62032 (5)	0.67879 (4)	0.22697 (3)	0.04540 (15)
S2'	0.99656 (5)	0.59761 (5)	0.30185 (3)	0.05829 (17)
S2	0.38791 (5)	0.68903 (4)	0.35287 (3)	0.05618 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2'	0.0416 (10)	0.0526 (12)	0.0389 (10)	−0.0003 (9)	−0.0017 (8)	−0.0004 (8)
C2	0.0409 (10)	0.0429 (10)	0.0418 (10)	−0.0006 (8)	−0.0019 (8)	−0.0017 (8)
C4'	0.0423 (10)	0.0498 (11)	0.0354 (9)	−0.0023 (9)	−0.0003 (8)	0.0039 (8)
C4	0.0421 (11)	0.0496 (12)	0.0366 (10)	−0.0028 (9)	−0.0010 (8)	0.0026 (8)
C5'	0.0440 (11)	0.0472 (11)	0.0355 (9)	−0.0014 (9)	−0.0003 (8)	0.0023 (8)
C5	0.0423 (10)	0.0417 (10)	0.0353 (9)	0.0007 (8)	−0.0029 (8)	0.0017 (8)
C6'	0.0537 (13)	0.0752 (15)	0.0415 (11)	−0.0108 (11)	−0.0050 (9)	−0.0014 (10)
C6	0.0529 (13)	0.0963 (19)	0.0434 (12)	−0.0132 (12)	−0.0076 (10)	−0.0006 (11)
C51	0.0399 (10)	0.0421 (10)	0.0374 (10)	−0.0002 (8)	−0.0031 (8)	−0.0005 (8)
C51'	0.0425 (10)	0.0421 (10)	0.0414 (10)	−0.0038 (8)	0.0011 (8)	0.0016 (8)
C52	0.0451 (11)	0.0609 (13)	0.0360 (10)	0.0046 (9)	−0.0039 (8)	0.0055 (9)
C52'	0.0448 (11)	0.0586 (13)	0.0427 (11)	−0.0063 (9)	−0.0014 (9)	0.0066 (9)
C53'	0.0411 (11)	0.0549 (13)	0.0586 (13)	−0.0063 (9)	−0.0001 (9)	0.0018 (10)
C53	0.0411 (11)	0.0708 (15)	0.0459 (11)	0.0088 (10)	−0.0029 (9)	0.0039 (10)
C54'	0.0483 (11)	0.0398 (11)	0.0514 (12)	−0.0055 (9)	0.0117 (9)	−0.0024 (8)
C54	0.0483 (11)	0.0554 (12)	0.0392 (10)	0.0029 (9)	0.0045 (9)	−0.0003 (9)
C55'	0.0603 (13)	0.0472 (11)	0.0396 (11)	−0.0011 (10)	0.0066 (9)	0.0034 (8)
C55	0.0545 (12)	0.0591 (13)	0.0336 (10)	0.0044 (10)	0.0001 (9)	0.0063 (9)
C56	0.0450 (11)	0.0559 (12)	0.0413 (10)	0.0076 (9)	−0.0053 (8)	0.0059 (9)
C56'	0.0453 (11)	0.0501 (12)	0.0447 (11)	0.0039 (9)	0.0001 (9)	0.0048 (9)
N3	0.0339 (8)	0.0549 (10)	0.0408 (9)	−0.0026 (7)	−0.0026 (7)	0.0030 (7)
N3'	0.0358 (8)	0.0585 (10)	0.0401 (9)	−0.0060 (7)	−0.0017 (7)	0.0036 (7)
Cl1	0.0610 (4)	0.1081 (5)	0.0546 (3)	0.0146 (3)	0.0189 (3)	0.0090 (3)
Cl1'	0.0622 (4)	0.0716 (4)	0.0726 (4)	−0.0054 (3)	0.0290 (3)	−0.0025 (3)
O1'	0.0381 (8)	0.1023 (13)	0.0462 (8)	−0.0160 (8)	0.0012 (6)	0.0040 (8)
O1	0.0360 (7)	0.1054 (13)	0.0456 (8)	−0.0066 (8)	0.0008 (6)	0.0005 (8)
S1'	0.0422 (3)	0.0631 (3)	0.0390 (3)	−0.0094 (2)	0.0003 (2)	−0.0048 (2)
S1	0.0394 (3)	0.0578 (3)	0.0387 (3)	−0.0029 (2)	−0.0024 (2)	−0.0072 (2)
S2'	0.0457 (3)	0.0904 (4)	0.0390 (3)	−0.0043 (3)	0.0040 (2)	−0.0030 (3)
S2	0.0480 (3)	0.0782 (4)	0.0427 (3)	−0.0058 (3)	0.0048 (2)	−0.0123 (3)

Geometric parameters (Å, º)

C2'—N3'	1.338 (2)	C51'—C56'	1.397 (3)
C2'—S2'	1.671 (2)	C51'—C52'	1.398 (3)
C2'—S1'	1.720 (2)	C52—C53	1.375 (3)
C2—N3	1.340 (2)	C52—H18	0.9300
C2—S2	1.668 (2)	C52'—C53'	1.380 (3)
C2—S1	1.724 (2)	C52'—H18'	0.9300
C4'—C5'	1.355 (3)	C53'—C54'	1.376 (3)
C4'—N3'	1.391 (2)	C53'—H23'	0.9300
C4'—C6'	1.489 (3)	C53—C54	1.383 (3)
C4—C5	1.357 (3)	C53—H23	0.9300
C4—N3	1.390 (2)	C54'—C55'	1.382 (3)
C4—C6	1.488 (3)	C54'—Cl1'	1.736 (2)
C5'—C51'	1.470 (3)	C54—C55	1.373 (3)
C5'—S1'	1.7505 (19)	C54—Cl1	1.739 (2)
C5—C51	1.467 (3)	C55'—C56'	1.384 (3)
C5—S1	1.7453 (19)	C55'—H10'	0.9300
C6'—H17'A	0.9600	C55—C56	1.385 (3)
C6'—H17'B	0.9600	C55—H10	0.9300
C6'—H17'C	0.9600	C56—H9	0.9300
C6—H17A	0.9600	C56'—H9'	0.9300
C6—H17B	0.9600	N3—O1	1.380 (2)
C6—H17C	0.9600	N3'—O1'	1.384 (2)
C51—C56	1.396 (3)	O1'—H1'	0.7841
C51—C52	1.396 (3)	O1—H1	0.8476
N3'—C2'—S2'	125.40 (15)	C51—C52—H18	119.3
N3'—C2'—S1'	107.11 (14)	C53'—C52'—C51'	121.34 (19)
S2'—C2'—S1'	127.49 (12)	C53'—C52'—H18'	119.3
N3—C2—S2	124.86 (15)	C51'—C52'—H18'	119.3
N3—C2—S1	106.69 (13)	C54'—C53'—C52'	119.47 (19)
S2—C2—S1	128.45 (12)	C54'—C53'—H23'	120.3
C5'—C4'—N3'	110.00 (17)	C52'—C53'—H23'	120.3
C5'—C4'—C6'	130.67 (18)	C52—C53—C54	119.51 (19)
N3'—C4'—C6'	119.29 (17)	C52—C53—H23	120.2
C5—C4—N3	110.02 (17)	C54—C53—H23	120.2
C5—C4—C6	131.02 (19)	C53'—C54'—C55'	120.63 (19)
N3—C4—C6	118.91 (17)	C53'—C54'—Cl1'	119.59 (16)
C4'—C5'—C51'	130.69 (18)	C55'—C54'—Cl1'	119.78 (16)
C4'—C5'—S1'	110.67 (15)	C55—C54—C53	120.57 (19)
C51'—C5'—S1'	118.60 (14)	C55—C54—Cl1	119.52 (15)
C4—C5—C51	130.23 (17)	C53—C54—Cl1	119.92 (16)
C4—C5—S1	110.59 (14)	C54'—C55'—C56'	119.92 (19)
C51—C5—S1	119.18 (13)	C54'—C55'—H10'	120.0
C4'—C6'—H17'A	109.5	C56'—C55'—H10'	120.0
C4'—C6'—H17'B	109.5	C54—C55—C56	119.84 (18)
H17'A—C6'—H17'B	109.5	C54—C55—H10	120.1
C4'—C6'—H17'C	109.5	C56—C55—H10	120.1
H17'A—C6'—H17'C	109.5	C55—C56—C51	120.81 (18)
H17'B—C6'—H17'C	109.5	C55—C56—H9	119.6
C4—C6—H17A	109.5	C51—C56—H9	119.6
C4—C6—H17B	109.5	C55'—C56'—C51'	120.57 (19)
H17A—C6—H17B	109.5	C55'—C56'—H9'	119.7
C4—C6—H17C	109.5	C51'—C56'—H9'	119.7
H17A—C6—H17C	109.5	C2—N3—O1	121.09 (16)
H17B—C6—H17C	109.5	C2—N3—C4	119.58 (16)
C56—C51—C52	117.90 (18)	O1—N3—C4	119.30 (15)
C56—C51—C5	122.32 (17)	C2'—N3'—O1'	121.12 (16)
C52—C51—C5	119.74 (17)	C2'—N3'—C4'	119.40 (16)
C56'—C51'—C52'	118.07 (19)	O1'—N3'—C4'	119.48 (15)
C56'—C51'—C5'	122.44 (18)	N3'—O1'—H1'	109.5
C52'—C51'—C5'	119.49 (18)	N3—O1—H1	109.5
C53—C52—C51	121.38 (18)	C2'—S1'—C5'	92.81 (9)
C53—C52—H18	119.3	C2—S1—C5	93.10 (9)
N3'—C4'—C5'—C51'	−178.31 (19)	C52—C51—C56—C55	0.3 (3)
C6'—C4'—C5'—C51'	−0.7 (4)	C5—C51—C56—C55	177.91 (19)
N3'—C4'—C5'—S1'	−0.6 (2)	C54'—C55'—C56'—C51'	0.1 (3)
C6'—C4'—C5'—S1'	176.96 (19)	C52'—C51'—C56'—C55'	0.0 (3)
N3—C4—C5—C51	−179.38 (18)	C5'—C51'—C56'—C55'	−179.14 (19)
C6—C4—C5—C51	3.3 (4)	S2—C2—N3—O1	−0.2 (3)
N3—C4—C5—S1	0.7 (2)	S1—C2—N3—O1	179.32 (15)
C6—C4—C5—S1	−176.7 (2)	S2—C2—N3—C4	−178.18 (15)
C4—C5—C51—C56	37.7 (3)	S1—C2—N3—C4	1.3 (2)
S1—C5—C51—C56	−142.38 (17)	C5—C4—N3—C2	−1.4 (3)
C4—C5—C51—C52	−144.7 (2)	C6—C4—N3—C2	176.36 (19)
S1—C5—C51—C52	35.2 (2)	C5—C4—N3—O1	−179.40 (17)
C4'—C5'—C51'—C56'	−36.8 (3)	C6—C4—N3—O1	−1.7 (3)
S1'—C5'—C51'—C56'	145.69 (17)	S2'—C2'—N3'—O1'	−0.7 (3)
C4'—C5'—C51'—C52'	144.1 (2)	S1'—C2'—N3'—O1'	179.45 (14)
S1'—C5'—C51'—C52'	−33.4 (2)	S2'—C2'—N3'—C4'	178.25 (16)
C56—C51—C52—C53	−0.1 (3)	S1'—C2'—N3'—C4'	−1.6 (2)
C5—C51—C52—C53	−177.8 (2)	C5'—C4'—N3'—C2'	1.5 (3)
C56'—C51'—C52'—C53'	0.1 (3)	C6'—C4'—N3'—C2'	−176.40 (19)
C5'—C51'—C52'—C53'	179.27 (19)	C5'—C4'—N3'—O1'	−179.53 (17)
C51'—C52'—C53'—C54'	−0.3 (3)	C6'—C4'—N3'—O1'	2.6 (3)
C51—C52—C53—C54	0.0 (3)	N3'—C2'—S1'—C5'	0.94 (16)
C52'—C53'—C54'—C55'	0.4 (3)	S2'—C2'—S1'—C5'	−178.88 (16)
C52'—C53'—C54'—Cl1'	−178.50 (16)	C4'—C5'—S1'—C2'	−0.20 (17)
C52—C53—C54—C55	−0.1 (3)	C51'—C5'—S1'—C2'	177.83 (16)
C52—C53—C54—Cl1	−179.91 (18)	N3—C2—S1—C5	−0.70 (15)
C53'—C54'—C55'—C56'	−0.3 (3)	S2—C2—S1—C5	178.77 (15)
Cl1'—C54'—C55'—C56'	178.60 (16)	C4—C5—S1—C2	0.01 (16)
C53—C54—C55—C56	0.3 (3)	C51—C5—S1—C2	−179.95 (16)
Cl1—C54—C55—C56	−179.89 (17)	H1—O1—N3—C2	1.5
C54—C55—C56—C51	−0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1′—H1′···S2^i	0.78	2.63	3.2266 (18)	135
O1—H1···S2′^ii	0.85	2.55	3.1452 (18)	128
C52—H18···S2′	0.93	2.87	3.688 (2)	147
C52′—H18′···S2	0.93	2.88	3.763 (2)	158

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