4-Hydrazinyl­idene-1-methyl-3H-2λ6,1-benzothia­zine-2,2-dione

Shafiq, M.; Khan, I.U.; Zia-ur-Rehman, M.; Arshad, M.N.; Asiri, A.M.

doi:10.1107/S1600536811027577

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2038

doi:10.1107/S1600536811027577

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4-Hydrazinylidene-1-methyl-3H-2λ⁶,1-benzothiazine-2,2-dione

Muhammad Shafiq,^a Islam Ullah Khan,^a Muhammad Zia-ur-Rehman,^b Muhammad Nadeem Arshad ^c ^*‡ and Abdullah M. Asiri ^d

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, ^bApplied Chemistry Research Center, PCSIR Laboratories Complex, Ferozpur Road, Lahore 54600, Pakistan, ^cX-ray Diffraction and Physical Laboratory, Department of Physics, School of Physical Sciences, University of the Punjab, Quaid-e-Azam Campus, Lahore 54590, Pakistan, and ^dThe Center of Excellence for Advanced Materials Research, King Abdul Aziz University, Jeddah, PO Box 80203, Saudi Arabia
^*Correspondence e-mail: mnachemist@hotmail.com

(Received 26 June 2011; accepted 9 July 2011; online 16 July 2011)

In the title compound, C₉H₁₁N₃O₂S, the thiazine ring adopts a half-chair conformation. In the crystal structure N—H⋯N hydrogen bonds connect two molecules into a centrosymmetric dimer, forming an R₂²(6) ring motif. These dimers are further connected into chains by N—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For the synthesis of the title compound, see: Shafiq et al. (2011b ). For information on 1,2 and 2,1-benzothiazine, see: Shafiq et al. (2011a ); Arshad et al. (2011 ). For related structures, see: Tahir et al. (2008 ); Khan et al. (2010 ); Shafiq et al. (2009 ); Arshad et al. (2009 ). For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₁₁N₃O₂S
M_r = 225.27
Monoclinic, P 2₁ /n
a = 6.6643 (2) Å
b = 9.6834 (3) Å
c = 15.5890 (5) Å
β = 97.699 (1)°
V = 996.94 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.41 × 0.22 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.884, T_max = 0.947
8966 measured reflections
2426 independent reflections
2114 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.111
S = 0.93
2426 reflections
143 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N⋯O1ⁱ	0.86 (2)	2.46 (2)	3.221 (2)	147.7 (17)
N3—H2N⋯N2ⁱⁱ	0.790 (19)	2.376 (19)	3.094 (2)	151.8 (19)
C8—H8A⋯O1ⁱ	0.97	2.59	3.4178 (19)	144
Symmetry codes: (i) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+3, -y, -z.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811027577/bt5565sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027577/bt5565Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027577/bt5565Isup3.cml

checkCIF report

Comment top

We are already engaged in the synthesis (Shafiq et al., 2011a), (Arshad et al., 2011) and crystallographic studies of 1,2- & 2,1-benzothiazine molecules (Arshad et al., 2009), (Shafiq et al., 2009). Here in, we report the crystal structure of hydrazide (I), synthesized from 1-methyl-1H-2,1-benzothiazin-4(3H)-one 2,2-dioxide (II) (Tahir et al., 2008).

In the crystal structure of title compound, the bond lengths and angles are almost similar to structurally similar molecules (II) and 1-propyl-1H-2,1-benzothiazin-4(3H)-one 2,2-dioxide (III) (Khan et al., 2010). The fused aromatic and thiazine rings are twisted at dihedral angle of 11.13 (8)°. The thiazine ring (C1/C6/C7/C8/S1/N1) adopted the sofa shape with the r. m. s. deviavtion of fitted atoms of 0.2380Å showing the maximum deviation for the S1 (0.3969 (8)Å) & C8 (0.2687 (7)Å). The molecules in the crystal structure dimerized through N—H···N hydrogen bonding forming six-membered R₂²(6) ring motif (Bernstein et al., 1995). There are C—H···O and N—H···N type interactions which connect the dimers in zig-zag mode along c axis and a axis and generate another seven membered ring motif R₂¹(7).

Related literature top

For the synthesis of the title compound, see: Shafiq et al. (2011b). For information about 1,2 and 2,1-benzothiazine, see: Shafiq et al. (2011a); Arshad et al. (2011). For related structures, see: Tahir et al. (2008); Khan et al. (2010); Shafiq et al. (2009); Arshad et al. (2009). For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995).

Experimental top

The synthesis of title compound have already been reportrd (Shafiq et al., 2011b). Suitable crystals were grown in dry ethanol under slow evaporation.

Computing details top

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 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at 50% probability level.
	Fig. 2. Perspective view showing the dimers and hydrogen bonding via dashed lines, hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

4-Hydrazinylidene-1-methyl-3H-2λ⁶,1-benzothiazine-2,2-dione top

Crystal data top

C₉H₁₁N₃O₂S	F(000) = 472
M_r = 225.27	D_x = 1.501 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5698 reflections
a = 6.6643 (2) Å	θ = 3.7–28.3°
b = 9.6834 (3) Å	µ = 0.31 mm⁻¹
c = 15.5890 (5) Å	T = 296 K
β = 97.699 (1)°	Needle, yellow
V = 996.94 (5) Å³	0.41 × 0.22 × 0.18 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2426 independent reflections
Radiation source: fine-focus sealed tube	2114 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 28.3°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −6→8
T_min = 0.884, T_max = 0.947	k = −11→12
8966 measured reflections	l = −19→20

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ²(F_o²) + (0.0763P)² + 0.3098P] where P = (F_o² + 2F_c²)/3
2426 reflections	(Δ/σ)_max < 0.001
143 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₉H₁₁N₃O₂S	V = 996.94 (5) Å³
M_r = 225.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.6643 (2) Å	µ = 0.31 mm⁻¹
b = 9.6834 (3) Å	T = 296 K
c = 15.5890 (5) Å	0.41 × 0.22 × 0.18 mm
β = 97.699 (1)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2426 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2114 reflections with I > 2σ(I)
T_min = 0.884, T_max = 0.947	R_int = 0.020
8966 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.30 e Å⁻³
2426 reflections	Δρ_min = −0.29 e Å⁻³
143 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8692 (2)	0.28978 (14)	0.04960 (9)	0.0354 (3)
C2	0.7617 (2)	0.38627 (17)	−0.00433 (10)	0.0460 (4)
H2	0.6510	0.4306	0.0138	0.055*
C3	0.8167 (3)	0.41727 (17)	−0.08437 (11)	0.0491 (4)
H3	0.7420	0.4811	−0.1200	0.059*
C4	0.9815 (3)	0.35393 (17)	−0.11144 (10)	0.0468 (4)
H4	1.0209	0.3765	−0.1647	0.056*
C5	1.0884 (2)	0.25656 (16)	−0.05909 (10)	0.0409 (3)
H5	1.1990	0.2134	−0.0781	0.049*
C6	1.0349 (2)	0.22102 (13)	0.02180 (9)	0.0328 (3)
C7	1.1508 (2)	0.11464 (13)	0.07523 (8)	0.0341 (3)
C8	1.0878 (3)	0.07413 (16)	0.16103 (10)	0.0454 (4)
H8A	1.2040	0.0386	0.1987	0.054*
H8B	0.9866	0.0017	0.1524	0.054*
C9	0.6206 (3)	0.3164 (2)	0.15568 (14)	0.0609 (5)
H9A	0.6343	0.4141	0.1652	0.091*
H9B	0.5906	0.2723	0.2076	0.091*
H9C	0.5128	0.2991	0.1096	0.091*
N1	0.80990 (19)	0.26108 (15)	0.13215 (9)	0.0446 (3)
N2	1.30403 (19)	0.06040 (13)	0.04671 (8)	0.0427 (3)
N3	1.4169 (2)	−0.03646 (17)	0.09606 (11)	0.0565 (4)
O1	1.14407 (18)	0.31926 (13)	0.22310 (7)	0.0515 (3)
O2	0.8941 (2)	0.17659 (15)	0.28274 (8)	0.0587 (3)
S1	0.98824 (5)	0.21730 (4)	0.20972 (2)	0.03865 (15)
H1N	1.357 (3)	−0.087 (2)	0.1305 (13)	0.046*
H2N	1.494 (3)	−0.070 (2)	0.0678 (12)	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0314 (6)	0.0370 (7)	0.0375 (7)	0.0038 (5)	0.0035 (5)	−0.0031 (5)
C2	0.0376 (7)	0.0488 (8)	0.0501 (8)	0.0144 (6)	0.0008 (6)	−0.0016 (7)
C3	0.0513 (8)	0.0484 (8)	0.0442 (8)	0.0120 (7)	−0.0065 (6)	0.0047 (6)
C4	0.0572 (9)	0.0476 (8)	0.0345 (7)	0.0076 (7)	0.0028 (6)	0.0034 (6)
C5	0.0457 (8)	0.0419 (7)	0.0356 (7)	0.0095 (6)	0.0075 (6)	−0.0007 (6)
C6	0.0338 (6)	0.0312 (6)	0.0334 (6)	0.0043 (5)	0.0040 (5)	−0.0026 (5)
C7	0.0363 (6)	0.0317 (6)	0.0350 (6)	0.0052 (5)	0.0076 (5)	−0.0005 (5)
C8	0.0563 (9)	0.0386 (7)	0.0445 (8)	0.0131 (6)	0.0188 (7)	0.0076 (6)
C9	0.0404 (8)	0.0763 (12)	0.0702 (12)	0.0155 (8)	0.0231 (8)	0.0002 (10)
N1	0.0331 (6)	0.0560 (7)	0.0470 (7)	0.0112 (5)	0.0137 (5)	0.0033 (6)
N2	0.0440 (6)	0.0422 (6)	0.0437 (6)	0.0151 (5)	0.0122 (5)	0.0063 (5)
N3	0.0554 (8)	0.0581 (9)	0.0595 (9)	0.0307 (7)	0.0210 (7)	0.0176 (7)
O1	0.0558 (7)	0.0577 (7)	0.0402 (6)	−0.0082 (5)	0.0041 (5)	−0.0058 (5)
O2	0.0627 (7)	0.0715 (8)	0.0479 (7)	0.0109 (6)	0.0288 (6)	0.0109 (6)
S1	0.0408 (2)	0.0428 (2)	0.0345 (2)	0.00504 (13)	0.01310 (14)	0.00140 (12)

Geometric parameters (Å, º) top

C1—C2	1.390 (2)	C8—S1	1.7532 (15)
C1—C6	1.4068 (19)	C8—H8A	0.9700
C1—N1	1.4234 (19)	C8—H8B	0.9700
C2—C3	1.380 (2)	C9—N1	1.4616 (19)
C2—H2	0.9300	C9—H9A	0.9600
C3—C4	1.373 (2)	C9—H9B	0.9600
C3—H3	0.9300	C9—H9C	0.9600
C4—C5	1.381 (2)	N1—S1	1.6338 (14)
C4—H4	0.9300	N2—N3	1.3721 (18)
C5—C6	1.398 (2)	N3—H1N	0.86 (2)
C5—H5	0.9300	N3—H2N	0.790 (19)
C6—C7	1.4761 (18)	O1—S1	1.4278 (12)
C7—N2	1.2801 (17)	O2—S1	1.4270 (12)
C7—C8	1.5063 (19)

C2—C1—C6	119.61 (14)	S1—C8—H8A	109.6
C2—C1—N1	119.68 (13)	C7—C8—H8B	109.6
C6—C1—N1	120.71 (13)	S1—C8—H8B	109.6
C3—C2—C1	121.03 (14)	H8A—C8—H8B	108.1
C3—C2—H2	119.5	N1—C9—H9A	109.5
C1—C2—H2	119.5	N1—C9—H9B	109.5
C4—C3—C2	120.07 (14)	H9A—C9—H9B	109.5
C4—C3—H3	120.0	N1—C9—H9C	109.5
C2—C3—H3	120.0	H9A—C9—H9C	109.5
C3—C4—C5	119.60 (15)	H9B—C9—H9C	109.5
C3—C4—H4	120.2	C1—N1—C9	120.59 (14)
C5—C4—H4	120.2	C1—N1—S1	117.21 (10)
C4—C5—C6	121.84 (14)	C9—N1—S1	118.42 (13)
C4—C5—H5	119.1	C7—N2—N3	119.27 (13)
C6—C5—H5	119.1	N2—N3—H1N	118.0 (13)
C5—C6—C1	117.81 (13)	N2—N3—H2N	108.4 (14)
C5—C6—C7	120.23 (12)	H1N—N3—H2N	121 (2)
C1—C6—C7	121.95 (13)	O2—S1—O1	117.61 (8)
N2—C7—C6	118.14 (12)	O2—S1—N1	107.94 (8)
N2—C7—C8	122.12 (12)	O1—S1—N1	111.81 (8)
C6—C7—C8	119.74 (11)	O2—S1—C8	111.06 (8)
C7—C8—S1	110.19 (10)	O1—S1—C8	107.46 (8)
C7—C8—H8A	109.6	N1—S1—C8	99.48 (8)

C6—C1—C2—C3	−0.9 (2)	C6—C7—C8—S1	−33.65 (17)
N1—C1—C2—C3	179.38 (15)	C2—C1—N1—C9	9.0 (2)
C1—C2—C3—C4	−0.9 (3)	C6—C1—N1—C9	−170.69 (15)
C2—C3—C4—C5	1.7 (3)	C2—C1—N1—S1	−148.76 (13)
C3—C4—C5—C6	−0.7 (3)	C6—C1—N1—S1	31.55 (18)
C4—C5—C6—C1	−1.1 (2)	C6—C7—N2—N3	178.54 (14)
C4—C5—C6—C7	178.92 (14)	C8—C7—N2—N3	−0.9 (2)
C2—C1—C6—C5	1.9 (2)	C1—N1—S1—O2	−172.78 (11)
N1—C1—C6—C5	−178.42 (13)	C9—N1—S1—O2	28.97 (17)
C2—C1—C6—C7	−178.15 (13)	C1—N1—S1—O1	56.36 (14)
N1—C1—C6—C7	1.5 (2)	C9—N1—S1—O1	−101.89 (15)
C5—C6—C7—N2	2.4 (2)	C1—N1—S1—C8	−56.87 (13)
C1—C6—C7—N2	−177.54 (13)	C9—N1—S1—C8	144.88 (15)
C5—C6—C7—C8	−178.13 (13)	C7—C8—S1—O2	169.33 (11)
C1—C6—C7—C8	1.9 (2)	C7—C8—S1—O1	−60.75 (13)
N2—C7—C8—S1	145.78 (13)	C7—C8—S1—N1	55.82 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N···O1ⁱ	0.86 (2)	2.46 (2)	3.221 (2)	147.7 (17)
N3—H2N···N2ⁱⁱ	0.790 (19)	2.376 (19)	3.094 (2)	151.8 (19)
C8—H8A···O1ⁱ	0.97	2.59	3.4178 (19)	144

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) −x+3, −y, −z.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂S
M_r	225.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	6.6643 (2), 9.6834 (3), 15.5890 (5)
β (°)	97.699 (1)
V (Å³)	996.94 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.41 × 0.22 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.884, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	8966, 2426, 2114
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.111, 0.93
No. of reflections	2426
No. of parameters	143
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N···O1ⁱ	0.86 (2)	2.46 (2)	3.221 (2)	147.7 (17)
N3—H2N···N2ⁱⁱ	0.790 (19)	2.376 (19)	3.094 (2)	151.8 (19)
C8—H8A···O1ⁱ	0.97	2.59	3.4178 (19)	143.8

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) −x+3, −y, −z.

Footnotes

‡Materials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan.

Acknowledgements

The authors acknowledge the Higher Education Commission of Pakistan for providing a grant for the project to strengthen the Materials Chemistry Laboratory at GC University Lahore, Pakistan.

References

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