Ethyl 6-amino-8-(4-chloro-phen-yl)-9-nitro-2,3,4,8-tetra-hydro-pyrido[2,1-b][1,3]thia-zine-7-carboxyl-ate.

In the structure of the title compound, C(17)H(18)ClN(3)O(4)S, the thia-zinane ring displays a twist-boat conformation. The 1,4-dihydro-pyridine ring is approximately perpendicular to the benzene ring [dihedral angle = 88.3 (1)°]. The mol-ecular conformation is stabilized by an intra-molecular N-H⋯O hydrogen bond. In the crystal, mol-ecules are linked by N-H⋯O inter-actions into a C(8) chain along [100].

Related literature

For a related structure, see: Tian et al. (2009 ▶). For puckering parameters, see: Cremer & Pople 1(975). For background to neonicotinoid insecticides, see: Mori et al. (2001 ▶); Kagabu (1997 ▶); Tian et al. (2007 ▶); Jeschke & Nauen (2008 ▶); Tomizawa & Casida (2005 ▶). For set-graph notation, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶);

Experimental

Crystal data

C17H18ClN3O4S

M = 395.85

Triclinic,

a = 8.6376 (8) Å

b = 9.9719 (8) Å

c = 12.0616 (11) Å

α = 110.970 (8)°

β = 103.252 (8)°

γ = 99.663 (7)°

V = 907.88 (16) Å3

Z = 2

Mo Kα radiation

μ = 0.35 mm−1

T = 298 K

0.58 × 0.28 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.821, T max = 0.946

7457 measured reflections

3692 independent reflections

2856 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.119

S = 1.03

3692 reflections

242 parameters

4 restraints

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811032193/bx2362sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032193/bx2362Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811032193/bx2362Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H18ClN3O4S	Z = 2
Mr = 395.85	F(000) = 412
Triclinic, P1	Dx = 1.448 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6376 (8) Å	Cell parameters from 4541 reflections
b = 9.9719 (8) Å	θ = 2.4–27.7°
c = 12.0616 (11) Å	µ = 0.35 mm−1
α = 110.970 (8)°	T = 298 K
β = 103.252 (8)°	Prism, colourless
γ = 99.663 (7)°	0.58 × 0.28 × 0.16 mm
V = 907.88 (16) Å3

Bruker APEXII CCD area-detector diffractometer	3692 independent reflections
Radiation source: fine-focus sealed tube	2856 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 26.4°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.821, Tmax = 0.946	k = −12→12
7457 measured reflections	l = −15→14

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0499P)2 + 0.3496P] where P = (Fo2 + 2Fc2)/3
3692 reflections	(Δ/σ)max < 0.001
242 parameters	Δρmax = 0.30 e Å−3
4 restraints	Δρmin = −0.38 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.55649 (9)	0.69346 (7)	1.02703 (6)	0.0526 (2)
Cl1	−0.06895 (8)	0.51657 (8)	0.27303 (6)	0.0582 (2)
O1	0.7918 (2)	1.0629 (2)	0.70241 (19)	0.0661 (6)
C12	0.0733 (3)	0.6242 (3)	0.4217 (2)	0.0402 (5)
C13	0.1908 (3)	0.5640 (2)	0.4697 (2)	0.0426 (5)
H13	0.1918	0.4665	0.4251	0.051*
C10	0.1846 (3)	0.8525 (3)	0.6042 (2)	0.0415 (5)
H10	0.1810	0.9488	0.6496	0.050*
C15	0.6594 (3)	1.0300 (3)	0.7201 (2)	0.0440 (5)
C14	0.3069 (3)	0.6519 (2)	0.5857 (2)	0.0385 (5)
H14	0.3874	0.6128	0.6183	0.046*
C11	0.0684 (3)	0.7665 (3)	0.4875 (2)	0.0478 (6)
H11	−0.0120	0.8051	0.4543	0.057*
C16	0.5733 (4)	1.1999 (3)	0.6395 (3)	0.0589 (7)
H16A	0.6017	1.1547	0.5639	0.071*
H16B	0.6655	1.2843	0.6994	0.071*
C6	0.7619 (4)	0.6382 (3)	0.8644 (3)	0.0706 (8)
H6A	0.8354	0.6341	0.8141	0.085*
H6B	0.6767	0.5437	0.8247	0.085*
C5	0.7196 (3)	0.8499 (3)	0.8047 (2)	0.0405 (5)
O2	0.53736 (19)	1.09179 (17)	0.69114 (15)	0.0449 (4)
O3	0.2722 (2)	0.75602 (19)	0.98083 (15)	0.0513 (4)
O4	0.21057 (18)	0.91022 (19)	0.89999 (15)	0.0484 (4)
C3	0.4386 (2)	0.8934 (2)	0.78073 (18)	0.0317 (4)
H3	0.4147	0.9901	0.8135	0.038*
N3	0.3003 (2)	0.8315 (2)	0.92150 (16)	0.0373 (4)
C9	0.3064 (2)	0.7963 (2)	0.65422 (18)	0.0312 (4)
C1	0.5529 (3)	0.7644 (2)	0.91386 (19)	0.0347 (5)
N1	0.6833 (2)	0.7590 (2)	0.86615 (17)	0.0422 (4)
C4	0.6108 (2)	0.9223 (2)	0.76932 (19)	0.0354 (5)
C2	0.4350 (2)	0.8266 (2)	0.87397 (18)	0.0311 (4)
C8	0.7765 (4)	0.7224 (4)	1.0854 (3)	0.0815 (10)
H8A	0.8287	0.8291	1.1280	0.098*
H8B	0.7976	0.6811	1.1472	0.098*
N2	0.8663 (3)	0.8554 (3)	0.7814 (2)	0.0656 (7)
H2A	0.943 (3)	0.848 (4)	0.8361	0.068*
H2B	0.895 (4)	0.923 (4)	0.756	0.068*
C17	0.4207 (4)	1.2497 (4)	0.6110 (3)	0.0777 (9)
H17A	0.3289	1.1643	0.5560	0.117*
H17B	0.4372	1.3166	0.5713	0.117*
H17C	0.3982	1.3001	0.6873	0.117*
C7	0.8573 (5)	0.6566 (5)	0.9903 (4)	0.0968 (12)
H7A	0.9679	0.7208	1.0146	0.116*
H7B	0.8672	0.5600	0.9875	0.116*

	U11	U22	U33	U12	U13	U23
S1	0.0649 (4)	0.0527 (4)	0.0599 (4)	0.0256 (3)	0.0266 (3)	0.0369 (3)
Cl1	0.0493 (4)	0.0660 (4)	0.0387 (3)	0.0006 (3)	−0.0040 (3)	0.0164 (3)
O1	0.0412 (10)	0.0883 (14)	0.0853 (14)	0.0094 (9)	0.0283 (10)	0.0529 (12)
C12	0.0315 (11)	0.0478 (13)	0.0337 (11)	−0.0002 (9)	0.0041 (9)	0.0173 (10)
C13	0.0494 (13)	0.0377 (11)	0.0354 (12)	0.0073 (10)	0.0095 (10)	0.0139 (10)
C10	0.0344 (12)	0.0419 (12)	0.0434 (12)	0.0143 (9)	0.0070 (10)	0.0138 (10)
C15	0.0362 (12)	0.0493 (13)	0.0399 (12)	0.0006 (10)	0.0100 (10)	0.0172 (10)
C14	0.0364 (11)	0.0411 (12)	0.0380 (12)	0.0132 (9)	0.0067 (10)	0.0184 (10)
C11	0.0335 (12)	0.0581 (15)	0.0487 (14)	0.0150 (11)	0.0029 (11)	0.0238 (12)
C16	0.0721 (18)	0.0534 (15)	0.0672 (17)	0.0148 (13)	0.0333 (15)	0.0368 (14)
C6	0.087 (2)	0.0748 (19)	0.076 (2)	0.0578 (17)	0.0406 (18)	0.0346 (16)
C5	0.0283 (11)	0.0528 (13)	0.0365 (11)	0.0099 (10)	0.0089 (9)	0.0153 (10)
O2	0.0443 (9)	0.0480 (9)	0.0495 (9)	0.0093 (7)	0.0181 (8)	0.0274 (8)
O3	0.0466 (10)	0.0598 (10)	0.0512 (10)	0.0043 (8)	0.0218 (8)	0.0277 (9)
O4	0.0303 (8)	0.0637 (10)	0.0541 (10)	0.0190 (8)	0.0145 (8)	0.0241 (9)
C3	0.0271 (10)	0.0319 (10)	0.0333 (10)	0.0069 (8)	0.0085 (9)	0.0114 (8)
N3	0.0285 (9)	0.0408 (10)	0.0320 (9)	0.0012 (8)	0.0060 (8)	0.0091 (8)
C9	0.0250 (10)	0.0370 (11)	0.0313 (10)	0.0058 (8)	0.0086 (8)	0.0151 (9)
C1	0.0381 (11)	0.0283 (10)	0.0327 (11)	0.0073 (9)	0.0098 (9)	0.0085 (8)
N1	0.0406 (10)	0.0479 (11)	0.0440 (11)	0.0222 (9)	0.0157 (9)	0.0196 (9)
C4	0.0256 (10)	0.0430 (11)	0.0332 (11)	0.0049 (9)	0.0076 (9)	0.0141 (9)
C2	0.0262 (10)	0.0330 (10)	0.0294 (10)	0.0050 (8)	0.0082 (8)	0.0096 (8)
C8	0.079 (2)	0.125 (3)	0.073 (2)	0.060 (2)	0.0246 (18)	0.062 (2)
N2	0.0324 (11)	0.106 (2)	0.0749 (17)	0.0273 (12)	0.0228 (11)	0.0482 (15)
C17	0.092 (2)	0.082 (2)	0.093 (2)	0.0385 (19)	0.039 (2)	0.059 (2)
C7	0.095 (3)	0.154 (4)	0.104 (3)	0.088 (3)	0.049 (2)	0.088 (3)

S1—C1	1.744 (2)	C6—H6B	0.9700
S1—C8	1.802 (3)	C5—N2	1.356 (3)
Cl1—C12	1.745 (2)	C5—C4	1.361 (3)
O1—C15	1.224 (3)	C5—N1	1.400 (3)
C12—C11	1.369 (3)	O3—N3	1.242 (2)
C12—C13	1.382 (3)	O4—N3	1.242 (2)
C13—C14	1.384 (3)	C3—C2	1.502 (3)
C13—H13	0.9300	C3—C4	1.514 (3)
C10—C11	1.387 (3)	C3—C9	1.531 (3)
C10—C9	1.390 (3)	C3—H3	0.9800
C10—H10	0.9300	N3—C2	1.410 (3)
C15—O2	1.347 (3)	C1—C2	1.362 (3)
C15—C4	1.449 (3)	C1—N1	1.378 (3)
C14—C9	1.382 (3)	C8—C7	1.488 (5)
C14—H14	0.9300	C8—H8A	0.9700
C11—H11	0.9300	C8—H8B	0.9700
C16—O2	1.450 (3)	N2—H2A	0.855 (17)
C16—C17	1.495 (4)	N2—H2B	0.859 (17)
C16—H16A	0.9700	C17—H17A	0.9600
C16—H16B	0.9700	C17—H17B	0.9600
C6—N1	1.475 (3)	C17—H17C	0.9600
C6—C7	1.482 (4)	C7—H7A	0.9700
C6—H6A	0.9700	C7—H7B	0.9700
C1—S1—C8	98.75 (13)	C9—C3—H3	107.7
C11—C12—C13	121.3 (2)	O4—N3—O3	121.78 (18)
C11—C12—Cl1	119.83 (18)	O4—N3—C2	118.18 (17)
C13—C12—Cl1	118.85 (18)	O3—N3—C2	120.02 (18)
C12—C13—C14	118.5 (2)	C14—C9—C10	118.33 (19)
C12—C13—H13	120.7	C14—C9—C3	120.93 (18)
C14—C13—H13	120.7	C10—C9—C3	120.73 (19)
C11—C10—C9	120.8 (2)	C2—C1—N1	119.40 (19)
C11—C10—H10	119.6	C2—C1—S1	124.77 (16)
C9—C10—H10	119.6	N1—C1—S1	115.80 (16)
O1—C15—O2	121.5 (2)	C1—N1—C5	120.12 (18)
O1—C15—C4	126.6 (2)	C1—N1—C6	116.9 (2)
O2—C15—C4	111.94 (18)	C5—N1—C6	122.2 (2)
C9—C14—C13	121.7 (2)	C5—C4—C15	119.96 (19)
C9—C14—H14	119.2	C5—C4—C3	121.27 (19)
C13—C14—H14	119.2	C15—C4—C3	118.76 (19)
C12—C11—C10	119.4 (2)	C1—C2—N3	119.81 (18)
C12—C11—H11	120.3	C1—C2—C3	123.84 (18)
C10—C11—H11	120.3	N3—C2—C3	116.35 (18)
O2—C16—C17	107.0 (2)	C7—C8—S1	116.0 (3)
O2—C16—H16A	110.3	C7—C8—H8A	108.3
C17—C16—H16A	110.3	S1—C8—H8A	108.3
O2—C16—H16B	110.3	C7—C8—H8B	108.3
C17—C16—H16B	110.3	S1—C8—H8B	108.3
H16A—C16—H16B	108.6	H8A—C8—H8B	107.4
N1—C6—C7	113.6 (3)	C5—N2—H2A	115 (2)
N1—C6—H6A	108.8	C5—N2—H2B	114 (2)
C7—C6—H6A	108.8	H2A—N2—H2B	116 (3)
N1—C6—H6B	108.8	C16—C17—H17A	109.5
C7—C6—H6B	108.8	C16—C17—H17B	109.5
H6A—C6—H6B	107.7	H17A—C17—H17B	109.5
N2—C5—C4	124.0 (2)	C16—C17—H17C	109.5
N2—C5—N1	115.0 (2)	H17A—C17—H17C	109.5
C4—C5—N1	121.05 (19)	H17B—C17—H17C	109.5
C15—O2—C16	116.12 (18)	C6—C7—C8	111.6 (3)
C2—C3—C4	109.50 (16)	C6—C7—H7A	109.3
C2—C3—C9	111.93 (15)	C8—C7—H7A	109.3
C4—C3—C9	112.25 (16)	C6—C7—H7B	109.3
C2—C3—H3	107.7	C8—C7—H7B	109.3
C4—C3—H3	107.7	H7A—C7—H7B	108.0
C11—C12—C13—C14	−1.3 (3)	C7—C6—N1—C5	120.1 (3)
Cl1—C12—C13—C14	177.68 (16)	N2—C5—C4—C15	−9.6 (4)
C12—C13—C14—C9	0.8 (3)	N1—C5—C4—C15	172.29 (19)
C13—C12—C11—C10	0.6 (3)	N2—C5—C4—C3	170.7 (2)
Cl1—C12—C11—C10	−178.39 (17)	N1—C5—C4—C3	−7.4 (3)
C9—C10—C11—C12	0.6 (3)	O1—C15—C4—C5	2.2 (4)
O1—C15—O2—C16	−0.7 (3)	O2—C15—C4—C5	−179.4 (2)
C4—C15—O2—C16	−179.22 (19)	O1—C15—C4—C3	−178.1 (2)
C17—C16—O2—C15	178.3 (2)	O2—C15—C4—C3	0.3 (3)
C13—C14—C9—C10	0.4 (3)	C2—C3—C4—C5	20.6 (3)
C13—C14—C9—C3	−178.31 (18)	C9—C3—C4—C5	−104.3 (2)
C11—C10—C9—C14	−1.1 (3)	C2—C3—C4—C15	−159.09 (18)
C11—C10—C9—C3	177.56 (19)	C9—C3—C4—C15	76.0 (2)
C2—C3—C9—C14	−61.2 (2)	N1—C1—C2—N3	179.49 (17)
C4—C3—C9—C14	62.4 (2)	S1—C1—C2—N3	−2.5 (3)
C2—C3—C9—C10	120.2 (2)	N1—C1—C2—C3	−0.9 (3)
C4—C3—C9—C10	−116.2 (2)	S1—C1—C2—C3	177.04 (15)
C8—S1—C1—C2	−152.2 (2)	O4—N3—C2—C1	168.14 (18)
C8—S1—C1—N1	25.8 (2)	O3—N3—C2—C1	−13.3 (3)
C2—C1—N1—C5	17.0 (3)	O4—N3—C2—C3	−11.5 (3)
S1—C1—N1—C5	−161.12 (16)	O3—N3—C2—C3	167.08 (17)
C2—C1—N1—C6	−153.1 (2)	C4—C3—C2—C1	−16.8 (3)
S1—C1—N1—C6	28.7 (3)	C9—C3—C2—C1	108.4 (2)
N2—C5—N1—C1	168.8 (2)	C4—C3—C2—N3	162.84 (16)
C4—C5—N1—C1	−12.9 (3)	C9—C3—C2—N3	−72.0 (2)
N2—C5—N1—C6	−21.6 (3)	C1—S1—C8—C7	−54.3 (3)
C4—C5—N1—C6	156.7 (2)	N1—C6—C7—C8	36.1 (5)
C7—C6—N1—C1	−70.0 (3)	S1—C8—C7—C6	25.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1	0.89 (4)	1.95 (5)	2.680 (4)	138 (4)
N2—H2A···O4i	0.87 (4)	2.16 (4)	2.850 (3)	137 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O1	0.89 (4)	1.95 (5)	2.680 (4)	138 (4)
N2—H2A⋯O4i	0.87 (4)	2.16 (4)	2.850 (3)	137 (4)

Symmetry code: (i) .