2-(3-Oxo-3,4-dihydro-2H-1,4-benzothia­zin-4-yl)acetohydrazide

In the title compound, C₁₀H₁₁N₃O₂S, the thia­zine ring exists in a conformation inter­mediate between twist-boat and half-chair. The dihedral angle between the mean plane of the thia­zine ring and the hydrazide group is 89.45 (13)°. In the crystal, N—H...O hydrogen bonds link the mol­ecules into (100) sheets and weak C—H...O inter­actions further consolidate the packing.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.027
• wR factor = 0.076
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S1
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H2N    ...          ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1
PLAT915_ALERT_3_C Low Friedel Pair Coverage ......................      56.94 Perc.
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         18

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.38
           From the CIF: _reflns_number_total               2168
           Count of symmetry unique reflns         1396
           Completeness (_total/calc)            155.30%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       772
           Fraction of Friedel pairs measured     0.553
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT850_ALERT_4_G Check Flack Parameter Exact Value 0.00 and su ..       0.07

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 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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S1. Comment

The 4H-benzo(1,4)thiazine compounds exhibit a broad spectrum of biological activitives, such as tetramic acids substituted benzothiazine derivatives are potent inhibitors of HCV polymerase (Vicente et al., 2009)and the pyrazino subsituted 1,4-benzothiazine derivatives are inhibitors of adhesion molecule-1, (Kaneko et al., 2002).They are also known to have antibacterial (Armenise et al.,1991),anticancer (Gupta et al.,1993), antifungal (Schiaffella et al., 2006) activities. The hydrazone compounds were known for their coordinating capability, pharmacological activity, antibacterial and antifungal properties (Sivasankar et al., 1995) (Satyanarayana, et al., 2008). We paid attention to the preparation of hydrazone derivatives of 2-(3-oxo-2,3-dihydro-2H-1,4-benzothiazin-3-one and we report here the structure of the title compound.

The dihedral angle between the aromatic benzene ring C1–C6 and thiazine ring C1/C6/N1/C7/C8/S1 is 16.77(0.10)° while the hydrazide group C9/C10/N2/N3 is oriented at dihedral angle of 89.45(0.13)° with respect to the thiazine ring. The symmetry related intermolecular N—H···O and C—H···O interaction form the dimer along the b axis which results in a ring motif R₂²(9) (Bernstein et al., 1995). The crystal structure is further stabilized through the N—H···O and week C—H···O interaction to form three dimentional network.

Related literature

For the biological and medicinal activity of 1,4-benzothiazine compounds, see: Armenise et al. (1991); Gupta et al. (1993); Vicente et al. (2009); Schiaffella et al. (2006); Kaneko et al. (2002). For the pharmacological properties of hydrazones and their derivatives, see: Sivasankar et al. (1995); Satyanarayana et al. (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995).

S2. Experimental

Ethyl 2-(3-oxo-2,3-dihydrobenzo[b][1,4]thiazin-4-yl)acetate (1.26 g, 5mmol) was refluxed in 50 ml ethanol with 2.0 ml of hydrazine for 5 hours. On completion the solution was evaporated under reduce pressure and solid obtained was purified from ethanol. Colourless needles of (I) were obtained by slow evaporation from methanol (m.p. 430 K).

S3. Refinement

The C-H H-atoms were positioned with idealized geometry with C—H = 0.93 Å and were refined using a riding model with U_iso(H) = 1.2 U_eq(C). The N-H H atoms were located in difference map with N—H= 0.76 (4)—0.83 (4) Å, U_iso(H) = 1.2 for N atoms.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound and Intermolecular hydrogen bonds are shown by dashed lines.

2-(3-Oxo-3,4-dihydro-2H-1,4-benzothiazin-4-yl)acetohydrazide

Crystal data

C10H11N3O2S	F(000) = 496
Mr = 237.28	Dx = 1.423 Mg m^−3
Monoclinic, Cc	Melting point: 430 K
Hall symbol: C -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 15.3744 (10) Å	Cell parameters from 4206 reflections
b = 7.5162 (5) Å	θ = 3.0–31.2°
c = 9.6256 (7) Å	µ = 0.28 mm^−1
β = 95.413 (3)°	T = 296 K
V = 1107.35 (13) Å^3	Needle, colorless
Z = 4	0.46 × 0.23 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2168 independent reflections
Radiation source: fine-focus sealed tube	2077 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 28.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −12→20
Tmin = 0.882, Tmax = 0.946	k = −8→10
6103 measured reflections	l = −12→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0437P)^2 + 0.2667P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2168 reflections	Δρmax = 0.18 e Å^−3
157 parameters	Δρmin = −0.14 e Å^−3
2 restraints	Absolute structure: Flack (1983), 792 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (7)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.81283 (13)	0.1402 (3)	0.4407 (2)	0.0444 (4)
C2	0.88393 (15)	0.1642 (4)	0.3624 (3)	0.0684 (7)
H2	0.9061	0.0674	0.3170	0.082*
C3	0.92138 (15)	0.3276 (5)	0.3514 (3)	0.0727 (7)
H3	0.9691	0.3412	0.2998	0.087*
C4	0.88855 (14)	0.4717 (4)	0.4166 (3)	0.0621 (6)
H4	0.9145	0.5827	0.4099	0.074*
C5	0.81688 (12)	0.4524 (2)	0.4924 (2)	0.0451 (4)
H5	0.7944	0.5514	0.5347	0.054*
C6	0.77806 (10)	0.2868 (2)	0.50596 (15)	0.0325 (3)
C7	0.64582 (13)	0.1320 (2)	0.56774 (18)	0.0393 (4)
C8	0.65696 (13)	−0.0005 (2)	0.4532 (2)	0.0473 (4)
H8A	0.6398	0.0537	0.3633	0.057*
H8B	0.6194	−0.1024	0.4638	0.057*
C9	0.68864 (12)	0.3985 (2)	0.69169 (16)	0.0371 (4)
H9A	0.7419	0.4638	0.7190	0.044*
H9B	0.6710	0.3388	0.7738	0.044*
C10	0.61760 (11)	0.52828 (19)	0.63748 (15)	0.0311 (3)
N1	0.70588 (9)	0.26545 (17)	0.58681 (13)	0.0328 (3)
N2	0.57596 (11)	0.60513 (19)	0.73773 (16)	0.0391 (3)
N3	0.50598 (12)	0.7263 (3)	0.70912 (19)	0.0491 (4)
O1	0.60169 (9)	0.56431 (16)	0.51324 (12)	0.0441 (3)
O2	0.58443 (11)	0.1213 (2)	0.63853 (16)	0.0602 (4)
S1	0.76839 (4)	−0.07275 (6)	0.45907 (6)	0.06435 (19)
H1N	0.5831 (14)	0.561 (3)	0.822 (3)	0.036 (5)*
H2N	0.4722 (19)	0.678 (4)	0.641 (3)	0.072 (9)*
H3N	0.5321 (18)	0.834 (4)	0.681 (3)	0.065 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0391 (9)	0.0492 (9)	0.0446 (10)	0.0071 (7)	0.0020 (8)	−0.0098 (8)
C2	0.0384 (11)	0.108 (2)	0.0598 (13)	0.0113 (12)	0.0099 (10)	−0.0256 (14)
C3	0.0360 (10)	0.126 (2)	0.0580 (14)	−0.0063 (14)	0.0133 (9)	0.0076 (15)
C4	0.0409 (10)	0.0773 (15)	0.0673 (14)	−0.0139 (10)	0.0019 (10)	0.0272 (12)
C5	0.0411 (10)	0.0407 (9)	0.0531 (12)	−0.0021 (8)	0.0022 (8)	0.0107 (8)
C6	0.0334 (8)	0.0347 (7)	0.0288 (8)	0.0042 (6)	0.0004 (6)	0.0033 (6)
C7	0.0462 (10)	0.0359 (8)	0.0360 (9)	−0.0013 (7)	0.0057 (7)	0.0027 (7)
C8	0.0532 (11)	0.0358 (9)	0.0529 (11)	−0.0081 (7)	0.0049 (8)	−0.0080 (7)
C9	0.0463 (9)	0.0382 (8)	0.0266 (8)	0.0068 (7)	0.0026 (7)	−0.0034 (6)
C10	0.0391 (8)	0.0292 (7)	0.0253 (7)	−0.0012 (6)	0.0052 (6)	−0.0015 (5)
N1	0.0393 (7)	0.0293 (6)	0.0304 (7)	0.0025 (5)	0.0068 (6)	−0.0012 (5)
N2	0.0516 (9)	0.0405 (7)	0.0261 (7)	0.0102 (6)	0.0081 (6)	0.0003 (6)
N3	0.0518 (10)	0.0517 (10)	0.0455 (9)	0.0147 (8)	0.0134 (8)	0.0016 (8)
O1	0.0585 (8)	0.0504 (7)	0.0239 (6)	0.0137 (6)	0.0059 (5)	0.0007 (5)
O2	0.0559 (9)	0.0728 (9)	0.0553 (9)	−0.0161 (7)	0.0223 (7)	−0.0008 (8)
S1	0.0661 (3)	0.0354 (2)	0.0898 (4)	0.0116 (2)	−0.0018 (3)	−0.0191 (3)

Geometric parameters (Å, º)

C1—C2	1.397 (3)	C7—C8	1.508 (3)
C1—C6	1.400 (2)	C8—S1	1.793 (2)
C1—S1	1.756 (2)	C8—H8A	0.9700
C2—C3	1.364 (4)	C8—H8B	0.9700
C2—H2	0.9300	C9—N1	1.463 (2)
C3—C4	1.372 (4)	C9—C10	1.520 (2)
C3—H3	0.9300	C9—H9A	0.9700
C4—C5	1.385 (3)	C9—H9B	0.9700
C4—H4	0.9300	C10—O1	1.228 (2)
C5—C6	1.392 (2)	C10—N2	1.338 (2)
C5—H5	0.9300	N2—N3	1.417 (2)
C6—N1	1.423 (2)	N2—H1N	0.87 (2)
C7—O2	1.218 (2)	N3—H2N	0.87 (3)
C7—N1	1.364 (2)	N3—H3N	0.96 (3)
C2—C1—C6	119.5 (2)	S1—C8—H8A	109.5
C2—C1—S1	120.28 (17)	C7—C8—H8B	109.5
C6—C1—S1	120.24 (15)	S1—C8—H8B	109.5
C3—C2—C1	121.0 (2)	H8A—C8—H8B	108.1
C3—C2—H2	119.5	N1—C9—C10	111.90 (13)
C1—C2—H2	119.5	N1—C9—H9A	109.2
C2—C3—C4	119.9 (2)	C10—C9—H9A	109.2
C2—C3—H3	120.0	N1—C9—H9B	109.2
C4—C3—H3	120.0	C10—C9—H9B	109.2
C3—C4—C5	120.3 (2)	H9A—C9—H9B	107.9
C3—C4—H4	119.9	O1—C10—N2	122.83 (15)
C5—C4—H4	119.9	O1—C10—C9	123.14 (14)
C4—C5—C6	120.8 (2)	N2—C10—C9	113.99 (13)
C4—C5—H5	119.6	C7—N1—C6	124.21 (13)
C6—C5—H5	119.6	C7—N1—C9	115.53 (14)
C5—C6—C1	118.46 (16)	C6—N1—C9	120.12 (13)
C5—C6—N1	121.03 (15)	C10—N2—N3	122.91 (15)
C1—C6—N1	120.49 (15)	C10—N2—H1N	118.4 (13)
O2—C7—N1	121.60 (17)	N3—N2—H1N	117.0 (14)
O2—C7—C8	120.86 (17)	N2—N3—H2N	105.3 (19)
N1—C7—C8	117.53 (15)	N2—N3—H3N	105.6 (16)
C7—C8—S1	110.54 (14)	H2N—N3—H3N	112 (2)
C7—C8—H8A	109.5	C1—S1—C8	95.78 (9)
C6—C1—C2—C3	1.6 (3)	O2—C7—N1—C6	−178.88 (18)
S1—C1—C2—C3	−177.5 (2)	C8—C7—N1—C6	−0.2 (2)
C1—C2—C3—C4	−0.8 (4)	O2—C7—N1—C9	−3.3 (2)
C2—C3—C4—C5	−0.7 (4)	C8—C7—N1—C9	175.45 (16)
C3—C4—C5—C6	1.2 (3)	C5—C6—N1—C7	155.73 (17)
C4—C5—C6—C1	−0.3 (3)	C1—C6—N1—C7	−25.7 (2)
C4—C5—C6—N1	178.29 (17)	C5—C6—N1—C9	−19.7 (2)
C2—C1—C6—C5	−1.1 (3)	C1—C6—N1—C9	158.89 (15)
S1—C1—C6—C5	178.02 (14)	C10—C9—N1—C7	−76.87 (18)
C2—C1—C6—N1	−179.71 (19)	C10—C9—N1—C6	98.95 (17)
S1—C1—C6—N1	−0.6 (2)	O1—C10—N2—N3	4.2 (3)
O2—C7—C8—S1	−135.26 (18)	C9—C10—N2—N3	−178.15 (17)
N1—C7—C8—S1	46.0 (2)	C2—C1—S1—C8	−143.10 (19)
N1—C9—C10—O1	−26.9 (2)	C6—C1—S1—C8	37.80 (16)
N1—C9—C10—N2	155.47 (14)	C7—C8—S1—C1	−58.15 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O2^i	0.96 (3)	2.35 (3)	3.299 (3)	171 (2)
N2—H1N···O1^ii	0.87 (2)	2.07 (2)	2.935 (2)	175.5 (18)
C3—H3···O2^iii	0.93	2.48	3.406 (3)	174
C8—H8B···O1^iv	0.97	2.57	3.442 (2)	150

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