2,3-Dihydroxy­benzaldehyde thio­semicarbazone hemihydrate

The mol­ecule of the Schiff base in the crystal structure of the title compound, C₈H₉N₃O₂S·0.5H₂O, inter­acts with symmetry-equivalent molecules and with the water mol­ecule, which lies on a twofold rotation axis, to give a three-dimensional hydrogen-bonded network structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.057
• wR factor = 0.129
• Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.04
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Ra
              O1   -H1O     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              O2   -H2O     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              O1W  -H1W     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              N1   -H1N1    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              N1   -H1N2    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.840(10) ......       3.00 su-Ra
              O1   -H1O     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              O2   -H2O     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              N1   -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              N1   -H2#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.85(3), Rep   0.850(10) ......       3.00 su-Ra
              O1W  -H1W     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.94(3), Rep   1.950(10) ......       3.00 su-Ra
              H2O  -O1W     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.56(3), Rep   2.560(10) ......       3.00 su-Ra
              H1#  -S1      1.555   5.565
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H2 O

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K

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

  16 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97.

2,3-Dihydroxybenzaldehyde thiosemicarbazone hemihydrate

Crystal data

C8H9N3O2S·0.5H2O	F(000) = 920
Mr = 220.25	Dx = 1.479 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 870 reflections
a = 21.546 (2) Å	θ = 3.0–26.5°
b = 11.658 (1) Å	µ = 0.31 mm^−1
c = 8.190 (1) Å	T = 293 K
β = 105.923 (1)°	Needle, yellow
V = 1978.3 (3) Å^3	0.50 × 0.20 × 0.10 mm
Z = 8

Data collection

Bruker APEX CCD area-detector diffractometer	1510 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
ω and φ scans	h = −20→25
5025 measured reflections	k = −11→13
1740 independent reflections	l = −9→9

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0539P)^2 + 2.2284P] where P = (Fo^2 + 2Fc^2)/3
1740 reflections	(Δ/σ)max = 0.001
150 parameters	Δρmax = 0.24 e Å^−3
7 restraints	Δρmin = −0.20 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.05404 (4)	0.66980 (7)	0.05330 (10)	0.0400 (3)
O1	0.33493 (11)	0.65271 (18)	0.7870 (3)	0.0437 (6)
H1O	0.3647 (12)	0.673 (3)	0.872 (3)	0.052*
O2	0.42287 (11)	0.52486 (19)	1.0011 (3)	0.0447 (6)
H2O	0.4441 (15)	0.477 (2)	1.074 (3)	0.054*
O1W	0.5000	0.3835 (3)	1.2500	0.0460 (8)
H1W	0.5190 (15)	0.3410 (15)	1.194 (4)	0.055*
N1	0.07603 (14)	0.4660 (2)	0.2009 (4)	0.0468 (8)
H1N1	0.0429 (11)	0.442 (3)	0.127 (3)	0.056*
H1N2	0.0936 (16)	0.425 (3)	0.287 (3)	0.056*
N2	0.14665 (12)	0.6054 (2)	0.3211 (3)	0.0365 (6)
H2N	0.1620 (16)	0.6719 (14)	0.317 (4)	0.044*
N3	0.18247 (12)	0.5253 (2)	0.4308 (3)	0.0334 (6)
C1	0.09380 (14)	0.5736 (3)	0.1997 (4)	0.0316 (7)
C2	0.23371 (14)	0.5627 (3)	0.5353 (3)	0.0312 (7)
H2	0.2428	0.6407	0.5357	0.037*
C3	0.27822 (14)	0.4890 (2)	0.6533 (4)	0.0291 (7)
C4	0.32941 (14)	0.5363 (2)	0.7768 (4)	0.0290 (7)
C5	0.37463 (14)	0.4673 (3)	0.8885 (4)	0.0338 (7)
C6	0.36873 (15)	0.3497 (3)	0.8757 (4)	0.0391 (8)
H6	0.3990	0.3029	0.9484	0.047*
C7	0.31737 (17)	0.3014 (3)	0.7537 (4)	0.0436 (8)
H7	0.3133	0.2220	0.7456	0.052*
C8	0.27283 (15)	0.3693 (3)	0.6458 (4)	0.0370 (7)
H8	0.2384	0.3355	0.5661	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0375 (5)	0.0327 (5)	0.0385 (5)	−0.0004 (3)	−0.0088 (3)	−0.0010 (4)
O1	0.0407 (13)	0.0297 (12)	0.0457 (14)	−0.0065 (9)	−0.0135 (10)	0.0013 (10)
O2	0.0384 (13)	0.0425 (14)	0.0393 (13)	−0.0032 (10)	−0.0126 (10)	0.0057 (10)
O1W	0.043 (2)	0.051 (2)	0.041 (2)	0.000	0.0071 (15)	0.000
N1	0.0411 (16)	0.0375 (17)	0.0461 (18)	−0.0126 (13)	−0.0148 (13)	0.0064 (13)
N2	0.0321 (14)	0.0292 (14)	0.0380 (14)	−0.0060 (11)	−0.0078 (11)	0.0025 (12)
N3	0.0314 (14)	0.0310 (14)	0.0311 (14)	−0.0033 (11)	−0.0025 (11)	0.0013 (11)
C1	0.0282 (15)	0.0343 (17)	0.0288 (15)	−0.0033 (13)	0.0022 (12)	−0.0052 (13)
C2	0.0318 (16)	0.0276 (16)	0.0310 (16)	−0.0051 (13)	0.0030 (13)	−0.0018 (13)
C3	0.0290 (15)	0.0307 (16)	0.0262 (15)	−0.0031 (12)	0.0053 (12)	0.0010 (12)
C4	0.0307 (16)	0.0278 (16)	0.0279 (16)	−0.0026 (12)	0.0069 (12)	−0.0003 (12)
C5	0.0303 (16)	0.0385 (18)	0.0294 (16)	−0.0013 (13)	0.0026 (13)	0.0022 (14)
C6	0.0391 (18)	0.0360 (19)	0.0367 (18)	0.0090 (14)	0.0014 (14)	0.0085 (14)
C7	0.053 (2)	0.0288 (17)	0.045 (2)	0.0000 (15)	0.0053 (16)	0.0011 (15)
C8	0.0386 (17)	0.0336 (17)	0.0335 (17)	−0.0055 (14)	0.0008 (14)	−0.0049 (14)

Geometric parameters (Å, º)

S1—C1	1.693 (3)	N3—C2	1.274 (4)
O1—C4	1.363 (4)	C2—C3	1.443 (4)
O1—H1O	0.84 (1)	C2—H2	0.930
O2—C5	1.362 (3)	C3—C4	1.390 (4)
O2—H2O	0.85 (1)	C3—C8	1.400 (4)
O1W—H1W	0.85 (1)	C4—C5	1.394 (4)
N1—C1	1.313 (4)	C5—C6	1.378 (4)
N1—H1N1	0.85 (1)	C6—C7	1.390 (4)
N1—H1N2	0.85 (1)	C6—H6	0.930
N2—C1	1.342 (4)	C7—C8	1.365 (4)
N2—N3	1.376 (3)	C7—H7	0.930
N2—H2N	0.85 (1)	C8—H8	0.930
C4—O1—H1O	111 (2)	C8—C3—C2	122.2 (3)
C5—O2—H2O	109 (2)	O1—C4—C3	118.6 (3)
C1—N1—H1N1	120 (2)	O1—C4—C5	120.0 (3)
C1—N1—H1N2	119 (2)	C3—C4—C5	121.4 (3)
H1N1—N1—H1N2	120 (3)	O2—C5—C6	125.4 (3)
C1—N2—N3	120.4 (2)	O2—C5—C4	115.3 (3)
C1—N2—H2N	119 (2)	C6—C5—C4	119.4 (3)
N3—N2—H2N	119 (2)	C5—C6—C7	119.8 (3)
C2—N3—N2	115.7 (2)	C5—C6—H6	120.1
N1—C1—N2	116.6 (3)	C7—C6—H6	120.1
N1—C1—S1	123.1 (2)	C8—C7—C6	120.7 (3)
N2—C1—S1	120.2 (2)	C8—C7—H7	119.7
N3—C2—C3	122.7 (3)	C6—C7—H7	119.7
N3—C2—H2	118.6	C7—C8—C3	121.0 (3)
C3—C2—H2	118.6	C7—C8—H8	119.5
C4—C3—C8	117.8 (3)	C3—C8—H8	119.5
C4—C3—C2	120.0 (3)
C1—N2—N3—C2	176.2 (3)	O1—C4—C5—O2	−0.9 (4)
N3—N2—C1—N1	5.2 (4)	C3—C4—C5—O2	178.9 (3)
N3—N2—C1—S1	−174.0 (2)	O1—C4—C5—C6	−179.4 (3)
N2—N3—C2—C3	−177.0 (3)	C3—C4—C5—C6	0.4 (5)
N3—C2—C3—C4	−172.8 (3)	O2—C5—C6—C7	−179.4 (3)
N3—C2—C3—C8	8.8 (5)	C4—C5—C6—C7	−1.0 (5)
C8—C3—C4—O1	−179.3 (3)	C5—C6—C7—C8	0.3 (5)
C2—C3—C4—O1	2.3 (4)	C6—C7—C8—C3	1.0 (5)
C8—C3—C4—C5	0.9 (4)	C4—C3—C8—C7	−1.6 (5)
C2—C3—C4—C5	−177.6 (3)	C2—C3—C8—C7	176.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···S1^i	0.84 (1)	2.50 (2)	3.162 (2)	137 (3)
O2—H2O···O1W	0.85 (1)	1.95 (1)	2.788 (3)	173 (4)
N1—H1N1···S1^ii	0.85 (1)	2.56 (1)	3.390 (3)	167 (3)
N1—H1N2···N3	0.85 (1)	2.28 (4)	2.629 (3)	105 (3)
N2—H2N···O1^i	0.85 (1)	2.22 (2)	3.014 (3)	155 (3)
O1W—H1W···S1^iii	0.85 (1)	2.52 (1)	3.345 (3)	163 (2)

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, −y+1, −z; (iii) x+1/2, y−1/2, z+1.