A concise and versatile route to tetra­hydro-1-benzazepines carrying [a]-fused heterocyclic units: synthetic sequence and spectroscopic characterization, and the mol­ecular and supra­molecular structures of one inter­mediate and two products

A concise, efficient and versatile route from simple starting materials to tricyclic tetra­hydro-1-benzazepines carrying [a]-fused heterocyclic units is reported. Thus, the easily accessible methyl 2-[(2-allyl-4-chloro­phen­yl)amino]­acetate, (I), was converted, via (2RS,4SR)-7-chloro-2,3,4,5-tetra­hydro-1,4-ep­oxy-1-benzo[b]azepine-2-carboxyl­ate, (II), to the key inter­mediate methyl (2RS,4SR)-7-chloro-4-hy­droxy-2,3,4,5-tetra­hydro-1H-benzo[b]azepine-2-carboxyl­ate, (III). Chloro­acetyl­ation of (III) provided the two regioisomers methyl (2RS,4SR)-7-chloro-1-(2-chloro­acet­yl)-4-hy­droxy-2,3,4,5-tetra­hydro-1H-benzo[b]azepine-2-carboxyl­ate, (IVa), and methyl (2RS,4SR)-7-chloro-4-(2-chloro­acet­oxy)-2,3,4,5-tetra­hydro-1H-benzo[b]azepine-2-carboxyl­ate, C₁₄H₁₅Cl₂NO₄, (IVb), as the major and minor products, respectively, and further reaction of (IVa) with amino­ethanol gave the tricyclic target compound (4aRS,6SR)-9-chloro-6-hy­droxy-3-(2-hy­droxy­eth­yl)-2,3,4a,5,6,7-hexa­hydro­benzo[f]pyrazino­[1,2-a]azepine-1,4-dione, C₁₅H₁₇ClN₂O₄, (V). Reaction of ester (III) with hydrazine hydrate gave the cor­responding carbohydrazide (VI), which, with tri­meth­oxy­methane, gave a second tricyclic target product, (4aRS,6SR)-9-chloro-6-hy­droxy-4a,5,6,7-tetra­hydro­benzo[f][1,2,4]triazino[4,5-a]azepin-4(3H)-one, C₁₂H₁₂ClN₃O₂, (VII). Full spectroscopic characterization (IR, ¹H and ¹³C NMR, and mass spectrometry) is reported for each of compounds (I)–(III), (IVa), (IVb) and (V)–(VII), along with the mol­ecular and supra­molecular structures of (IVb), (V) and (VII). In each of (IVb), (V) and (VII), the azepine ring adopts a chair conformation and the six-membered heterocyclic rings in (V) and (VII) adopt approximate boat forms. The mol­ecules in (IVb), (V) and (VII) are linked, in each case, into complex hydrogen-bonded sheets, but these sheets all contain a different range of hydrogen-bond types: N—H...O, C—H...O, C—H...N and C—H...π(arene) in (IVb), multiple C—H...O hydrogen bonds in (V), and N—H...N, O—H...O, C—H...N, C—H...O and C—H...π(arene) in (VII).

Computing details

For all structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

Methyl (2RS,4SR)-7-chloro-4-(2-chloroacetoxy)-2,3,4,5-tetrahydro-1H-benzo[b]azepine-2-carboxylate (IVb)

Crystal data

C14H15Cl2NO4	Z = 2
Mr = 332.17	F(000) = 344
Triclinic, P1	Dx = 1.507 Mg m^−3
a = 8.858 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.328 (5) Å	Cell parameters from 3362 reflections
c = 10.526 (6) Å	θ = 2.4–27.6°
α = 96.039 (18)°	µ = 0.46 mm^−1
β = 112.651 (19)°	T = 100 K
γ = 108.99 (3)°	Plate, colourless
V = 732.0 (8) Å^3	0.41 × 0.31 × 0.16 mm

Data collection

Bruker D8 Venture diffractometer	3362 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3121 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.038
φ and ω scans	θmax = 27.6°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −11→11
Tmin = 0.901, Tmax = 0.929	k = −12→12
35772 measured reflections	l = −13→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0312P)^2 + 0.4351P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.002
3362 reflections	Δρmax = 0.34 e Å^−3
194 parameters	Δρmin = −0.41 e Å^−3

Special details

Experimental. Spectroscopic characterisation of compounds (I)–(III), (IVa), (IVb) and (V)–(VII)

Compound (I). IR (ATR, cm^-1) 3420 (N-H), 1743 (C═O), 1637 [C═C (allyl)], 908 (═C-H). NMR (CDCl₃) δ(¹H) 3.31 (dt, J = 6.2, 1.6 Hz, 2H, -CH₂-), 3.79 (s, 3H, OCH₃), 3.90 (d, J = 5.2 Hz, 2H, N-CH₂-), 4.39 (t, J = 5.2 Hz, 1H, NH), 5.15–5.20 (m, 2H, ═CH₂), 5.92 (ddt, J = 16.8, 10.7, 6.2 Hz, 1H, ═CH-), 6.40 (d, J = 8.5 Hz, 1H, H-6), 7.05 (d, J = 2.5 Hz, 1H, H-3), 7.10 (dd, J = 8.5, 2.5 Hz, 1H, H-5); δ(¹³C) 36.1 (-CH₂-), 45.6 (N-CH₂-), 52.4 (OCH₃), 111.5 (C-6), 117.3 (═CH₂), 122.7 (C-4), 125.9 (C-2), 127.3 (C-5), 129.7 (C-3), 134.8 (-CH═), 143.7 (C-1), 171.4 (C═O). CG-MS (70 eV) m/z (%) 239 (M⁺, ³⁵Cl, 52), 182 (32, ³⁷Cl), 180 (100), 165 (8), 164 (27), 152 (20), 145 (58), 144 (48).

Compound (II). IR (ATR, cm^-1) 1740 (C═O), 1277 (C-N), 1055 (C-O), 951 (N-O). NMR (CDCl₃) δ(¹H) 2.26 (ddd, J = 12.8, 9.0, 1.7 Hz, 1H, 3-H_B), 2.48 (d, J = 16.9 Hz, 1H, 5-H_B), 2.95 (dddd, J = 12.8, 7.8, 2.6, 1.1 Hz, 1H, 3-H_A), 3.34 (dd, J = 16.9, 5.3 Hz, 1H, 5-H_A), 3.81 (s, 3H, OCH₃), 4.09 (dd, J = 9.0, 2.6 Hz, 1H, 2-H), 4.87-4.91 (m, 1 H, 4-H), 7.05 (d, J = 8.4 Hz, 1H, 9-H), 7.09 (d, J = 2.2 Hz, 1H, 6-H), 7.13 (dd, J = 8.4, 2.2 Hz, 1H, 8-H); δ(¹³C) 34.2 (5-C), 36.9 (3-C), 52.9 (OCH₃), 73.0 (2-C), 74.2 (4-C), 123.3 (9-C), 127.0 (8-C), 127.1 (5a-C), 129.7 (6-C), 131.7 (7-C), 147.7 (9a-C), 171.1 (C═O). CG-MS (70 eV) m/z (%) 253 (M⁺, ³⁵Cl, 100), 235 (4), 194 (70), 177 (14), 166 (41), 164 (47), 152 (18), 138 (37); HRMS (EI-MS) m/z found 253.0511, C₁₂H₁₂ClNO₃ requires 253.0506.

Compound (III). IR (ATR, cm^-1) 3278 (N-H/O-H), 1744 (C═O), 1028 (C-O). NMR (CDCl₃) δ⁽¹H) 1.90 (ddd, J = 13.1, 11.2, 9.0 Hz, 1H, 3-H_ax), 2.21 (d, J = 4.1 Hz, 1H, 4-OH), 2.54 (dt, J = 13.1, 3.3 Hz, 1H, 3-H_eq), 2.93-2.97 (m, 2H, 5-H_ax, 5-H_eq), 3.65 (dd, J = 11.2, 2.5 Hz, 1H, 2-H_ax), 3.79 (s, 3H, OCH₃), 3.87-3.92 (m, 1H, 4-H_ax), 4.51 (br s, 1H, NH), 6.73 (d, J = 8.3 Hz, 1H, 9-H), 7.04 (dd, J = 8.3, 2.5 Hz, 1H, 8-H), 7.09 (d, J = 2.5 Hz, 1H, 6-H); δ(¹³C) 41.7 (3-C), 43.1 (5-C), 52.9 (OCH₃), 57.4 (2-C), 68.8 (4-C), 121.4 (9-C), 126.7 (7-C), 127.3 (8-C), 129.8 (5a-C), 131.2 (6-C), 146.2 (9a-C), 173.3 (C═O). CG-MS (70 eV) m/z (%) 255 (M⁺, ³⁵Cl, 25), 196 (100), 178 (29), 152 (33); HRMS (Q-TOF-ESI) m/z found 256.0734, for C₁₂H₁₅³⁵ClNO₃ [M + H]⁺ requires 256.0740.

Compound (IVa). IR (ATR, cm^-1) 3434 (O-H), 1741 [C═O (ester)], 1660 [C═O (amide)], 1382 (CH₂-Cl), 1035 (C-O), 830 (C-Cl). NMR (CDCl₃) δ(¹H) 1.44 (ddd, J = 14.5, 11.4, 9.0 Hz, 1H, 3-H_ax), 2.04 (br s, 1H, 4-OH), 2.32 (ddd, J = 14.5, 4.8, 3.7 Hz, 1H, 3-H_eq), 2.74 (dd, J = 14.5, 2.0 Hz, 1H, 5-H_eq), 3.07 (dd, J = 14.5, 5.0 Hz, 1H, 5-H_ax), 3.71 (s, 3H, OCH₃), 3.88 (d, J = 13.0 Hz, 1H, N-COCH_AH_B), 3.95 (d, J = 13.0 Hz, 1H, N-COCH_AH_B), 4.22-4.28 (m, 1 H, 4-H_ax), 4.98 (dd, J = 11.4, 3.5 Hz, 1H, 2-H_ax), 7.33-7.36 (m, 3H, 6-H, 8-H, 9-H); δ(¹³C) 34.2 (3-C), 39.3 (5-C), 41.4 (-COCH₂-), 52.7 (OCH₃), 55.1 (2-C), 65.3 (4-C), 128.4 (8-C), 129.9 (9-C), 130.9 (6-C), 135.1 (9a-C), 135.4 (7-C), 136.8 (5a-C), 166.8 (N-C═O), 171.3 (COOCH₃). CG-MS (70 eV) m/z (%) 331 (M⁺, ³⁵Cl, 9), 282 (27), 272 (51), 254 (4), 226 (3), 222 (4), 196 (100), 178 (86), 152 (77).

Compound (IVb). IR (ATR, cm^-1) 3346 (N-H), 1730 [C═O (ester)], 1378 (CH₂-Cl), 1045 (C-O), 777 (C-Cl). NMR (CDCl₃) δ(¹H) 1.93-1.99 (m, 1H, 3-H_ax), 2.63 (dt, J = 12.6, 1.9 Hz, 1H, 3-H_eq), 2.91(dt, J = 13.6, 1.8 Hz, 1H, 5-H_eq), 3.02 (dd, J = 13.6, 10.1 Hz, 1H, 5-H_ax), 3.61 (dd, J = 11.5, 1.9 Hz, 1H, 2-H_ax), 3.80 (s, 3H, OCH₃), 4.06 (d, J = 15.6 Hz, 1H, O-COCH_AH_B), 4.09 (d, J = 15.6 Hz, 1H, O-COCH_AH), 4.53 (s, 1H, NH), 4.98-4.92 (m, 1H, 4-H_ax), 6.78 (d, J = 8.2 Hz, 1H, 9-H), 7.07 (dd, J = 8.2, 2.2 Hz, 1H, 8-H),7.10 (d, J = 2.2 Hz, 1H, 6-H); δ(¹³C) 38.1 (3-C), 39.8 (5-C), 41.1 (-COCH₂-), 53.0 (OCH₃), 57.0 (2-C), 73.0 (4-C), 121.8 (9-C), 127.0 (7-C), 127.8 (8-C), 128.9 (5a-C), 131.1 (6-C), 146.2 (9a-C), 166.6 (O-C═O), 172.6 (COOCH₃). CG-MS (70 eV) m/z (%) 331 (M⁺, ³⁵Cl, 14), 272 (1), 178 (100), 143 (55), 117 (6); HRMS (Q-TOF-ESI) m/z found 332.0450, for C₁₄H₁₆³⁵Cl₂NO₄ [M + H]⁺ requires 332.0451.

Compound (V). IR (ATR, cm^-1) 3400 (O-H), 1640 [C═O (amide)], 1248 (N-C), 1035 (C-O). NMR (DMSO-d₆) δ(¹H) 1.93-2.02 (m, 1H, 5-H_ax), 2.24 (br d, J = 13.0 Hz, 1H, 5-H_eq), 2.72 (dd, J = 13.8, 10.8 Hz, 1H, 7-H_ax), 2.84 (d, J = 13.8 Hz, 1H, 7-H_eq), 3.29-3. 37 (m, 1H, 1'-H_B), 3.50-3.58 (m, 3H, 1'-H_A, 2'-H_A, 2'-H_B), 3.61-3.68 (m, 1H, 6-H_ax), 3.84 (d, J = 12.5 Hz, 1H, 4a-H_ax), 4.06 (d, J = 17.6 Hz, 1H, 2-H_B), 4.48 (d, J = 17.6 Hz, 1H, 2-H_A), 4.83 (t, J = 5.3 Hz, 1H, 2'-OH), 5.19 (d, J = 3.9 Hz, 1H, 6-OH), 7.18 (d, J = 8.4 Hz, 1H, 11-H), 7.32 (dd, J = 8.4, 2.4 Hz, 1H, 10-H), 7.44 (s, 1H, 8-H); δ(¹³C) 43.1 (7-C), 43.2 (5-C), 48.7 (1'-C), 51.0 (2-C), 58.7 (2'-C), 60.7 (4a-C), 67.8 (6-C), 127.6 (10-C), 130.6 (11-C), 131.0 (8-C), 132.6 (9-C), 138.0 (7a-C), 139.7 (11a-C), 164.5 (1-C═O), 166.6 (4-C═O). HRMS (Q-TOF-ESI) m/z found 325.0947, for C₁₅H₁₈³⁵ClN₂O₄ [M + H]⁺ requires 325.0955.

Compound (VI). IR (ATR, cm^-1) 3370 [O-H, N-H (azepine)], 3315 [NH-H (asymmetric)], 3228 [N-H (hydrazide)], 3190 [NH-H (symmetric)], 1665 (C═O), 1532 (C═C), 1252 (C-N), 1116 (N-N), 1045 (C-O). NMR (DMSO-d₆) δ(¹H) 1.65 (dt, J = 12.6, 10.9 Hz, 1H, 3-H_ax), 2.06 (dd, J = 12.6, 3.1 Hz, 1H, 3-H_eq), 2.62 (dd, J = 13.4, 9.4 Hz, 1H, 5-H_ax), 2.83 (br d, J = 13.4 Hz, 1H, 5-H_eq), 3.31 (br d, J = 10.9 Hz, 1H, 2-H_ax), 3.51-3.59 (m, 1H, 4-H_ax), 4.25 (s, 2H, 2-CONH-NH₂), 4.92 (d, J = 4.6 Hz, 1H, 4-OH), 5.05 (s, 1H, 1-NH), 6.91 (d, J = 8.4 Hz, 1H, 9-H), 7.01 (dd, J = 8.4, 2.4 Hz, 1H, 8-H), 7.07 (d, J = 2.4 Hz, 1H, 6-H), 9.18 (s, 1H, 2-CONH-); δ(¹³C) 43.2 (3-C), 43.6 (5-C), 57.0 (2-C), 67.6 (4-C), 121.4 (9-C), 123.7 (7-C), 126.4 (8-C), 130.1 (6-C), 130.6 (5a-C), 148.2 (9a-C), 171.5 (2-C═O). HRMS (Q-TOF-ESI) m/z found 256.0852, for C₁₁H₁₅³⁵ClN₃O₂ [M + H]⁺ requires 256.0847.

Compound (VII). IR (ATR, cm^-1) 3390 (O-H), 3306 (N-H), 1644 (C═O, C═N), 1479 (C═C), 1244 (C-N), 1189 (N-N), 1044 (C—O). NMR (DMSO-d₆) δ(¹H) 1.60-1.71 (m, 1H, 5-H_ax), 2.34-2.38 (m, 1H, 5-H_eq), 2.76 (dd, J = 13.8, 9.8 Hz, 1H, 7-H_ax), 2.95 (br d, J =13.8 Hz, 1H, 7-H_eq), 3.62-3.71 (m, 1H, 6-H_ax), 3.94 (br d, J = 11.4 Hz, 1H, 4a-H_ax), 5.09 (d, J = 4.4 Hz, 1H, 6-OH), 6.92 (s, 1H, 1-H), 7.12 (d, J = 8.4 Hz, 1H, 11-H), 7.31 (dd, J = 8.4, 2.5 Hz, 1H, 10-H), 7.39 (d, J = 2.5 Hz, 1H, 8-H), 10.54 (s, 1H, 3-NH); δ(¹³C) 41.4 (5-C), 43.4 (7-C), 57.0 (4a-C), 67.0 (6-C), 127.9 (10-C), 128.3 (11-C), 133.3 (8-C), 133.5 (9-C), 136.5 (1-C), 137.0 (7a-C), 142.0 (11a-C), 161.5 (4-C═O). HRMS (Q-TOF-ESI) m/z found 266.0687, for C₁₂H₁₃³⁵ClN₃O₂ [M + H]⁺ requires 266.0691.

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.

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

	x	y	z	Uiso*/Ueq
N1	0.44762 (14)	0.56160 (12)	0.28278 (10)	0.0116 (2)
H1	0.505 (2)	0.5620 (18)	0.3733 (18)	0.014*
C2	0.38259 (15)	0.40475 (13)	0.18878 (12)	0.0104 (2)
H2	0.4731	0.4022	0.1550	0.012*
C3	0.20228 (15)	0.36071 (14)	0.05747 (12)	0.0112 (2)
H3A	0.1554	0.2486	0.0069	0.013*
H3B	0.1154	0.3751	0.0895	0.013*
C4	0.22174 (15)	0.46129 (13)	−0.04432 (12)	0.0104 (2)
H4	0.3084	0.4466	−0.0779	0.012*
C5	0.27825 (15)	0.63579 (14)	0.01909 (12)	0.0121 (2)
H5A	0.2472	0.6862	−0.0600	0.014*
H5B	0.2089	0.6465	0.0714	0.014*
C5A	0.47441 (15)	0.72309 (13)	0.11919 (12)	0.0108 (2)
C6	0.57917 (16)	0.84550 (14)	0.08498 (12)	0.0125 (2)
H6	0.5292	0.8687	−0.0038	0.015*
C7	0.75652 (16)	0.93315 (14)	0.18095 (13)	0.0132 (2)
Cl7	0.88752 (4)	1.08441 (3)	0.13695 (3)	0.01900 (9)
C8	0.83340 (16)	0.90270 (14)	0.31181 (13)	0.0141 (2)
H8	0.9545	0.9648	0.3771	0.017*
C9	0.73041 (16)	0.77998 (14)	0.34551 (12)	0.0132 (2)
H9	0.7815	0.7581	0.4348	0.016*
C9A	0.55202 (15)	0.68796 (13)	0.24954 (12)	0.0108 (2)
C21	0.36412 (15)	0.28579 (14)	0.27607 (13)	0.0127 (2)
O21	0.37808 (15)	0.31486 (11)	0.39519 (10)	0.0253 (2)
O22	0.33143 (13)	0.14524 (10)	0.20271 (10)	0.01758 (19)
C22	0.30469 (19)	0.01898 (15)	0.27159 (15)	0.0214 (3)
H22A	0.4032	0.0520	0.3678	0.032*
H22B	0.3010	−0.0741	0.2157	0.032*
H22C	0.1918	−0.0063	0.2779	0.032*
O41	0.04395 (11)	0.40450 (10)	−0.16560 (9)	0.01230 (17)
C42	0.04097 (16)	0.44151 (14)	−0.28694 (12)	0.0130 (2)
O42	0.17192 (12)	0.50990 (11)	−0.30148 (9)	0.01741 (19)
C43	−0.14867 (17)	0.38657 (16)	−0.40294 (13)	0.0166 (2)
H43A	−0.1583	0.4647	−0.4591	0.020*
H43B	−0.2320	0.3747	−0.3597	0.020*
Cl43	−0.20377 (4)	0.20199 (4)	−0.51611 (4)	0.02496 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0139 (5)	0.0120 (5)	0.0075 (4)	0.0034 (4)	0.0049 (4)	0.0026 (4)
C2	0.0110 (5)	0.0109 (5)	0.0091 (5)	0.0035 (4)	0.0049 (4)	0.0031 (4)
C3	0.0097 (5)	0.0133 (5)	0.0092 (5)	0.0032 (4)	0.0038 (4)	0.0035 (4)
C4	0.0073 (5)	0.0145 (5)	0.0078 (5)	0.0040 (4)	0.0021 (4)	0.0029 (4)
C5	0.0108 (5)	0.0140 (5)	0.0118 (5)	0.0061 (4)	0.0042 (4)	0.0044 (4)
C5A	0.0115 (5)	0.0107 (5)	0.0107 (5)	0.0055 (4)	0.0049 (4)	0.0018 (4)
C6	0.0151 (6)	0.0128 (5)	0.0124 (5)	0.0076 (5)	0.0068 (5)	0.0050 (4)
C7	0.0148 (6)	0.0097 (5)	0.0167 (6)	0.0043 (4)	0.0087 (5)	0.0044 (4)
Cl7	0.01637 (15)	0.01494 (15)	0.02314 (16)	0.00258 (11)	0.00805 (12)	0.01001 (12)
C8	0.0127 (5)	0.0127 (5)	0.0135 (5)	0.0033 (4)	0.0044 (5)	0.0015 (4)
C9	0.0144 (6)	0.0140 (5)	0.0098 (5)	0.0053 (5)	0.0046 (4)	0.0029 (4)
C9A	0.0123 (5)	0.0108 (5)	0.0108 (5)	0.0048 (4)	0.0067 (4)	0.0025 (4)
C21	0.0093 (5)	0.0136 (5)	0.0123 (5)	0.0023 (4)	0.0034 (4)	0.0045 (4)
O21	0.0396 (6)	0.0174 (5)	0.0116 (4)	0.0025 (4)	0.0113 (4)	0.0045 (4)
O22	0.0255 (5)	0.0135 (4)	0.0184 (4)	0.0089 (4)	0.0124 (4)	0.0082 (3)
C22	0.0253 (7)	0.0160 (6)	0.0251 (7)	0.0086 (5)	0.0112 (6)	0.0128 (5)
O41	0.0093 (4)	0.0179 (4)	0.0078 (4)	0.0044 (3)	0.0027 (3)	0.0041 (3)
C42	0.0151 (6)	0.0160 (5)	0.0097 (5)	0.0084 (5)	0.0053 (4)	0.0045 (4)
O42	0.0165 (4)	0.0230 (5)	0.0149 (4)	0.0076 (4)	0.0083 (4)	0.0089 (4)
C43	0.0152 (6)	0.0249 (6)	0.0103 (5)	0.0104 (5)	0.0042 (5)	0.0042 (5)
Cl43	0.02001 (16)	0.02011 (16)	0.02154 (17)	0.00626 (13)	−0.00085 (13)	0.00004 (12)

Geometric parameters (Å, º)

N1—C9A	1.4120 (16)	C7—C8	1.3883 (18)
N1—C2	1.4695 (16)	C7—Cl7	1.7429 (14)
N1—H1	0.889 (16)	C8—C9	1.3869 (18)
C2—C21	1.5213 (17)	C8—H8	0.9500
C2—C3	1.5438 (18)	C9—C9A	1.3998 (19)
C2—H2	1.0000	C9—H9	0.9500
C3—C4	1.5187 (17)	C21—O21	1.2034 (17)
C3—H3A	0.9900	C21—O22	1.3292 (16)
C3—H3B	0.9900	O22—C22	1.4489 (16)
C4—O41	1.4686 (16)	C22—H22A	0.9800
C4—C5	1.5262 (18)	C22—H22B	0.9800
C4—H4	1.0000	C22—H22C	0.9800
C5—C5A	1.5103 (19)	O41—C42	1.3505 (16)
C5—H5A	0.9900	C42—O42	1.2048 (17)
C5—H5B	0.9900	C42—C43	1.5178 (19)
C5A—C6	1.3960 (17)	C43—Cl43	1.7875 (16)
C5A—C9A	1.4062 (17)	C43—H43A	0.9900
C6—C7	1.3874 (19)	C43—H43B	0.9900
C6—H6	0.9500
C9A—N1—C2	115.90 (10)	C6—C7—C8	121.50 (11)
C9A—N1—H1	110.8 (10)	C6—C7—Cl7	119.68 (10)
C2—N1—H1	110.0 (10)	C8—C7—Cl7	118.82 (10)
N1—C2—C21	107.98 (10)	C9—C8—C7	118.86 (12)
N1—C2—C3	112.84 (10)	C9—C8—H8	120.6
C21—C2—C3	109.78 (10)	C7—C8—H8	120.6
N1—C2—H2	108.7	C8—C9—C9A	120.79 (12)
C21—C2—H2	108.7	C8—C9—H9	119.6
C3—C2—H2	108.7	C9A—C9—H9	119.6
C4—C3—C2	111.35 (10)	C9—C9A—C5A	119.73 (11)
C4—C3—H3A	109.4	C9—C9A—N1	120.89 (11)
C2—C3—H3A	109.4	C5A—C9A—N1	119.38 (11)
C4—C3—H3B	109.4	O21—C21—O22	124.66 (11)
C2—C3—H3B	109.4	O21—C21—C2	124.82 (12)
H3A—C3—H3B	108.0	O22—C21—C2	110.52 (11)
O41—C4—C3	105.90 (10)	C21—O22—C22	116.37 (11)
O41—C4—C5	107.54 (10)	O22—C22—H22A	109.5
C3—C4—C5	113.76 (10)	O22—C22—H22B	109.5
O41—C4—H4	109.8	H22A—C22—H22B	109.5
C3—C4—H4	109.8	O22—C22—H22C	109.5
C5—C4—H4	109.8	H22A—C22—H22C	109.5
C5A—C5—C4	114.57 (10)	H22B—C22—H22C	109.5
C5A—C5—H5A	108.6	C42—O41—C4	115.35 (10)
C4—C5—H5A	108.6	O42—C42—O41	124.46 (11)
C5A—C5—H5B	108.6	O42—C42—C43	124.14 (12)
C4—C5—H5B	108.6	O41—C42—C43	111.40 (11)
H5A—C5—H5B	107.6	C42—C43—Cl43	108.23 (9)
C6—C5A—C9A	119.24 (11)	C42—C43—H43A	110.1
C6—C5A—C5	119.56 (11)	Cl43—C43—H43A	110.1
C9A—C5A—C5	121.13 (11)	C42—C43—H43B	110.1
C7—C6—C5A	119.84 (11)	Cl43—C43—H43B	110.1
C7—C6—H6	120.1	H43A—C43—H43B	108.4
C5A—C6—H6	120.1
C9A—N1—C2—C21	150.43 (10)	C6—C5A—C9A—C9	2.69 (16)
C9A—N1—C2—C3	−88.05 (13)	C5—C5A—C9A—C9	−174.45 (10)
N1—C2—C3—C4	68.29 (13)	C6—C5A—C9A—N1	−178.36 (10)
C21—C2—C3—C4	−171.21 (9)	C5—C5A—C9A—N1	4.50 (16)
C2—C3—C4—O41	178.13 (9)	C2—N1—C9A—C9	−116.96 (13)
C2—C3—C4—C5	−63.98 (13)	C2—N1—C9A—C5A	64.10 (14)
O41—C4—C5—C5A	−164.87 (9)	N1—C2—C21—O21	8.91 (17)
C3—C4—C5—C5A	78.19 (13)	C3—C2—C21—O21	−114.49 (14)
C4—C5—C5A—C6	117.59 (12)	N1—C2—C21—O22	−170.71 (9)
C4—C5—C5A—C9A	−65.28 (14)	C3—C2—C21—O22	65.90 (13)
C9A—C5A—C6—C7	−1.58 (17)	O21—C21—O22—C22	2.41 (18)
C5—C5A—C6—C7	175.60 (11)	C2—C21—O22—C22	−177.97 (10)
C5A—C6—C7—C8	−0.31 (18)	C3—C4—O41—C42	−159.97 (10)
C5A—C6—C7—Cl7	179.27 (9)	C5—C4—O41—C42	78.06 (12)
C6—C7—C8—C9	1.08 (18)	C4—O41—C42—O42	3.24 (17)
Cl7—C7—C8—C9	−178.50 (9)	C4—O41—C42—C43	−176.53 (9)
C7—C8—C9—C9A	0.06 (18)	O42—C42—C43—Cl43	83.12 (14)
C8—C9—C9A—C5A	−1.95 (17)	O41—C42—C43—Cl43	−97.11 (11)
C8—C9—C9A—N1	179.12 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21	0.890 (17)	2.293 (17)	2.700 (2)	107.7 (13)
N1—H1···O21^i	0.890 (17)	2.241 (17)	3.032 (2)	147.9 (15)
C43—H43A···O42^ii	0.99	2.52	3.305 (3)	136
C43—H43B···N1^iii	0.99	2.55	3.483 (3)	158
C4—H4···Cg1^iv	1.00	2.86	3.650 (3)	137

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

(4aRS,6SR)-9-chloro-6-hydroxy-3-(2-hydroxyethyl)-2,3,4a,5,6,7-hexahydrobenzo[f]pyrazino[1,2-a]azepine-1,4-dione (V)

Crystal data

C15H17ClN2O4	F(000) = 680
Mr = 324.76	Dx = 1.511 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.198 (6) Å	Cell parameters from 3278 reflections
b = 10.586 (7) Å	θ = 2.3–27.5°
c = 15.223 (11) Å	µ = 0.29 mm^−1
β = 105.56 (2)°	T = 100 K
V = 1428.0 (17) Å^3	Block, colourless
Z = 4	0.21 × 0.20 × 0.15 mm

Data collection

Bruker D8 Venture diffractometer	3278 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	3013 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.026
φ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −11→11
Tmin = 0.929, Tmax = 0.958	k = −13→13
21974 measured reflections	l = −19→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.0338P)^2 + 1.0495P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3278 reflections	Δρmax = 0.33 e Å^−3
205 parameters	Δρmin = −0.27 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
C1	0.30345 (13)	0.42642 (12)	0.21947 (8)	0.0089 (2)
O1	0.35892 (10)	0.44094 (9)	0.15460 (6)	0.01210 (19)
C2	0.30775 (15)	0.29799 (12)	0.26223 (9)	0.0117 (2)
H2A	0.2897	0.2339	0.2131	0.014*
H2B	0.4107	0.2838	0.3021	0.014*
N3	0.20027 (12)	0.27639 (10)	0.31584 (7)	0.0095 (2)
C4	0.12956 (14)	0.37040 (12)	0.34697 (8)	0.0086 (2)
O4	0.03211 (10)	0.35457 (9)	0.38804 (6)	0.01219 (19)
C4A	0.18065 (14)	0.50472 (12)	0.33529 (8)	0.0083 (2)
H4A	0.0897	0.5602	0.3250	0.010*
C5	0.28939 (15)	0.54458 (12)	0.42629 (8)	0.0118 (2)
H5A	0.2452	0.5205	0.4764	0.014*
H5B	0.3852	0.4975	0.4349	0.014*
C6	0.32398 (15)	0.68571 (12)	0.43298 (8)	0.0118 (2)
H6A	0.2366	0.7372	0.4329	0.014*
C7	0.41043 (14)	0.73055 (12)	0.36543 (8)	0.0101 (2)
H7A	0.4597	0.8122	0.3868	0.012*
H7B	0.4908	0.6686	0.3648	0.012*
C7A	0.31062 (13)	0.74667 (12)	0.26903 (8)	0.0086 (2)
C8	0.29423 (14)	0.86622 (12)	0.22896 (8)	0.0098 (2)
H8	0.3452	0.9366	0.2620	0.012*
C9	0.20319 (14)	0.88239 (12)	0.14055 (8)	0.0101 (2)
Cl9	0.18123 (4)	1.03400 (3)	0.09380 (2)	0.01329 (9)
C10	0.13006 (14)	0.78209 (12)	0.08833 (8)	0.0110 (2)
H10	0.0702	0.7948	0.0276	0.013*
C11	0.14701 (14)	0.66250 (12)	0.12742 (8)	0.0097 (2)
H11	0.0991	0.5919	0.0931	0.012*
C11A	0.23446 (14)	0.64603 (11)	0.21710 (8)	0.0084 (2)
N12	0.24386 (12)	0.52184 (10)	0.25662 (7)	0.0081 (2)
C31	0.17095 (14)	0.14464 (12)	0.33517 (9)	0.0111 (2)
H31A	0.1594	0.0941	0.2790	0.013*
H31B	0.0745	0.1402	0.3523	0.013*
C32	0.29544 (15)	0.08677 (13)	0.41134 (9)	0.0143 (3)
H32A	0.3115	0.1400	0.4666	0.017*
H32B	0.2631	0.0021	0.4262	0.017*
O33	0.43442 (11)	0.07536 (10)	0.38713 (7)	0.0159 (2)
H33	0.494 (2)	0.1266 (19)	0.4166 (13)	0.024*
O6	0.41672 (12)	0.71383 (9)	0.52259 (6)	0.0164 (2)
H6	0.384 (2)	0.6649 (18)	0.5653 (13)	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0077 (5)	0.0106 (6)	0.0075 (5)	−0.0010 (4)	0.0004 (4)	−0.0014 (4)
O1	0.0152 (4)	0.0139 (4)	0.0090 (4)	0.0013 (4)	0.0062 (3)	0.0002 (3)
C2	0.0135 (6)	0.0100 (6)	0.0143 (6)	0.0005 (5)	0.0083 (5)	−0.0001 (5)
N3	0.0107 (5)	0.0081 (5)	0.0108 (5)	−0.0008 (4)	0.0048 (4)	0.0003 (4)
C4	0.0083 (5)	0.0104 (6)	0.0057 (5)	−0.0006 (4)	−0.0008 (4)	0.0002 (4)
O4	0.0124 (4)	0.0136 (4)	0.0123 (4)	−0.0005 (3)	0.0062 (4)	0.0008 (3)
C4A	0.0102 (5)	0.0093 (5)	0.0061 (5)	−0.0002 (4)	0.0035 (4)	−0.0004 (4)
C5	0.0165 (6)	0.0120 (6)	0.0062 (5)	−0.0031 (5)	0.0018 (5)	−0.0005 (4)
C6	0.0161 (6)	0.0121 (6)	0.0070 (5)	−0.0030 (5)	0.0024 (5)	−0.0023 (4)
C7	0.0111 (6)	0.0112 (6)	0.0068 (5)	−0.0019 (5)	0.0002 (5)	0.0003 (4)
C7A	0.0085 (5)	0.0110 (6)	0.0068 (5)	0.0006 (4)	0.0029 (4)	−0.0004 (4)
C8	0.0115 (6)	0.0096 (6)	0.0090 (6)	0.0002 (4)	0.0040 (5)	−0.0016 (4)
C9	0.0121 (6)	0.0092 (6)	0.0101 (6)	0.0022 (4)	0.0051 (5)	0.0019 (4)
Cl9	0.01935 (16)	0.00930 (15)	0.01079 (15)	0.00271 (11)	0.00332 (12)	0.00236 (10)
C10	0.0107 (6)	0.0143 (6)	0.0077 (5)	0.0011 (5)	0.0020 (4)	0.0006 (5)
C11	0.0097 (5)	0.0116 (6)	0.0078 (5)	−0.0012 (5)	0.0024 (4)	−0.0015 (4)
C11A	0.0097 (6)	0.0084 (6)	0.0081 (5)	0.0010 (4)	0.0044 (4)	0.0008 (4)
N12	0.0113 (5)	0.0077 (5)	0.0060 (5)	−0.0006 (4)	0.0034 (4)	0.0002 (4)
C31	0.0126 (6)	0.0081 (6)	0.0132 (6)	−0.0024 (5)	0.0046 (5)	−0.0007 (5)
C32	0.0180 (6)	0.0128 (6)	0.0126 (6)	0.0001 (5)	0.0052 (5)	0.0010 (5)
O33	0.0133 (5)	0.0143 (5)	0.0185 (5)	0.0000 (4)	0.0014 (4)	−0.0033 (4)
O6	0.0236 (5)	0.0168 (5)	0.0075 (4)	−0.0079 (4)	0.0018 (4)	−0.0018 (4)

Geometric parameters (Å, º)

C1—O1	1.2367 (17)	C7—H7B	0.9900
C1—N12	1.3442 (17)	C7A—C8	1.3955 (19)
C1—C2	1.5033 (19)	C7A—C11A	1.3977 (18)
C2—N3	1.4590 (17)	C8—C9	1.3918 (19)
C2—H2A	0.9900	C8—H8	0.9500
C2—H2B	0.9900	C9—C10	1.3875 (19)
N3—C4	1.3429 (17)	C9—Cl9	1.7453 (16)
N3—C31	1.4652 (18)	C10—C11	1.3897 (19)
C4—O4	1.2341 (17)	C10—H10	0.9500
C4—C4A	1.5228 (19)	C11—C11A	1.3972 (19)
C4A—N12	1.4760 (17)	C11—H11	0.9500
C4A—C5	1.5344 (19)	C11A—N12	1.4388 (17)
C4A—H4A	1.0000	C31—C32	1.5227 (19)
C5—C6	1.525 (2)	C31—H31A	0.9900
C5—H5A	0.9900	C31—H31B	0.9900
C5—H5B	0.9900	C32—O33	1.4273 (18)
C6—O6	1.4328 (17)	C32—H32A	0.9900
C6—C7	1.5342 (19)	C32—H32B	0.9900
C6—H6A	0.9710	O33—H33	0.82 (2)
C7—C7A	1.5174 (19)	O6—H6	0.94 (2)
C7—H7A	0.9900
O1—C1—N12	123.00 (12)	C6—C7—H7B	108.9
O1—C1—C2	119.31 (11)	H7A—C7—H7B	107.7
N12—C1—C2	117.63 (11)	C8—C7A—C11A	117.71 (12)
N3—C2—C1	116.16 (10)	C8—C7A—C7	119.42 (11)
N3—C2—H2A	108.2	C11A—C7A—C7	122.87 (12)
C1—C2—H2A	108.2	C9—C8—C7A	120.05 (12)
N3—C2—H2B	108.2	C9—C8—H8	120.0
C1—C2—H2B	108.2	C7A—C8—H8	120.0
H2A—C2—H2B	107.4	C10—C9—C8	122.24 (12)
C4—N3—C2	123.11 (11)	C10—C9—Cl9	119.00 (11)
C4—N3—C31	120.13 (11)	C8—C9—Cl9	118.76 (10)
C2—N3—C31	116.77 (10)	C9—C10—C11	118.06 (12)
O4—C4—N3	124.36 (12)	C9—C10—H10	121.0
O4—C4—C4A	118.34 (11)	C11—C10—H10	121.0
N3—C4—C4A	117.20 (11)	C10—C11—C11A	120.07 (12)
N12—C4A—C4	114.23 (10)	C10—C11—H11	120.0
N12—C4A—C5	113.29 (11)	C11A—C11—H11	120.0
C4—C4A—C5	107.35 (10)	C11—C11A—C7A	121.83 (12)
N12—C4A—H4A	107.2	C11—C11A—N12	118.48 (11)
C4—C4A—H4A	107.2	C7A—C11A—N12	119.68 (12)
C5—C4A—H4A	107.2	C1—N12—C11A	119.75 (11)
C6—C5—C4A	113.80 (10)	C1—N12—C4A	122.88 (11)
C6—C5—H5A	108.8	C11A—N12—C4A	117.32 (10)
C4A—C5—H5A	108.8	N3—C31—C32	113.24 (11)
C6—C5—H5B	108.8	N3—C31—H31A	108.9
C4A—C5—H5B	108.8	C32—C31—H31A	108.9
H5A—C5—H5B	107.7	N3—C31—H31B	108.9
O6—C6—C5	109.11 (10)	C32—C31—H31B	108.9
O6—C6—C7	106.90 (11)	H31A—C31—H31B	107.7
C5—C6—C7	113.24 (11)	O33—C32—C31	112.34 (12)
O6—C6—H6A	99.5	O33—C32—H32A	109.1
C5—C6—H6A	113.1	C31—C32—H32A	109.1
C7—C6—H6A	113.8	O33—C32—H32B	109.1
C7A—C7—C6	113.27 (11)	C31—C32—H32B	109.1
C7A—C7—H7A	108.9	H32A—C32—H32B	107.9
C6—C7—H7A	108.9	C32—O33—H33	108.7 (13)
C7A—C7—H7B	108.9	C6—O6—H6	108.9 (12)
O1—C1—C2—N3	−160.31 (11)	C8—C9—C10—C11	1.38 (19)
N12—C1—C2—N3	22.25 (16)	Cl9—C9—C10—C11	−178.93 (9)
C1—C2—N3—C4	−17.45 (17)	C9—C10—C11—C11A	0.61 (18)
C1—C2—N3—C31	162.51 (11)	C10—C11—C11A—C7A	−1.98 (19)
C2—N3—C4—O4	175.79 (12)	C10—C11—C11A—N12	177.24 (11)
C31—N3—C4—O4	−4.17 (19)	C8—C7A—C11A—C11	1.30 (18)
C2—N3—C4—C4A	−7.96 (17)	C7—C7A—C11A—C11	−177.92 (11)
C31—N3—C4—C4A	172.08 (10)	C8—C7A—C11A—N12	−177.90 (11)
O4—C4—C4A—N12	−155.55 (11)	C7—C7A—C11A—N12	2.88 (18)
N3—C4—C4A—N12	27.98 (15)	O1—C1—N12—C11A	3.88 (18)
O4—C4—C4A—C5	77.95 (14)	C2—C1—N12—C11A	−178.79 (10)
N3—C4—C4A—C5	−98.53 (13)	O1—C1—N12—C4A	−178.67 (11)
N12—C4A—C5—C6	65.68 (14)	C2—C1—N12—C4A	−1.33 (17)
C4—C4A—C5—C6	−167.26 (11)	C11—C11A—N12—C1	61.75 (16)
C4A—C5—C6—O6	175.66 (10)	C7A—C11A—N12—C1	−119.02 (13)
C4A—C5—C6—C7	−65.42 (15)	C11—C11A—N12—C4A	−115.84 (13)
O6—C6—C7—C7A	−161.54 (11)	C7A—C11A—N12—C4A	63.38 (16)
C5—C6—C7—C7A	78.27 (14)	C4—C4A—N12—C1	−23.56 (16)
C6—C7—C7A—C8	117.13 (13)	C5—C4A—N12—C1	99.79 (14)
C6—C7—C7A—C11A	−63.66 (15)	C4—C4A—N12—C11A	153.95 (11)
C11A—C7A—C8—C9	0.67 (18)	C5—C4A—N12—C11A	−82.70 (13)
C7—C7A—C8—C9	179.92 (11)	C4—N3—C31—C32	−102.19 (14)
C7A—C8—C9—C10	−2.05 (19)	C2—N3—C31—C32	77.85 (15)
C7A—C8—C9—Cl9	178.26 (9)	N3—C31—C32—O33	−65.90 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O1^i	0.942 (19)	1.823 (19)	2.753 (2)	168.7 (18)
O33—H33···O6^ii	0.82 (2)	1.99 (2)	2.781 (2)	162.2 (19)
C8—H8···O33^iii	0.95	2.37	3.271 (3)	158
C10—H10···O4^iv	0.95	2.60	3.275 (3)	129

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

(4aRS,6SR)-9-Chloro-6-hydroxy-4a,5,6,7-tetrahydrobenzo[f][1,2,4]triazino[4,5-a]azepin-4(3H)-one (VII)

Crystal data

C12H12ClN3O2	Z = 2
Mr = 265.70	F(000) = 276
Triclinic, P1	Dx = 1.563 Mg m^−3
a = 5.595 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.377 (5) Å	Cell parameters from 2621 reflections
c = 12.712 (8) Å	θ = 2.5–27.7°
α = 98.10 (3)°	µ = 0.34 mm^−1
β = 100.10 (2)°	T = 100 K
γ = 101.76 (3)°	Block, colourless
V = 564.5 (6) Å^3	0.42 × 0.28 × 0.14 mm

Data collection

Bruker D8 Venture diffractometer	2621 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	2324 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.091
φ and ω scans	θmax = 27.7°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −7→7
Tmin = 0.710, Tmax = 0.954	k = −10→10
32796 measured reflections	l = −16→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0598P)^2 + 0.5564P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2621 reflections	Δρmax = 1.09 e Å^−3
169 parameters	Δρmin = −0.47 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
C1	−0.1025 (3)	0.1380 (2)	0.67888 (14)	0.0113 (3)
H1	−0.1400	0.1088	0.7447	0.014*
N2	−0.2845 (3)	0.0994 (2)	0.59607 (13)	0.0133 (3)
N3	−0.2149 (3)	0.13368 (19)	0.49910 (13)	0.0120 (3)
H3	−0.332 (4)	0.098 (3)	0.443 (2)	0.014*
C4	0.0097 (3)	0.2105 (2)	0.48798 (14)	0.0102 (3)
O4	0.0539 (2)	0.22764 (16)	0.39827 (10)	0.0141 (3)
C4A	0.2115 (3)	0.2817 (2)	0.58964 (14)	0.0096 (3)
H4A	0.3658	0.2454	0.5778	0.012*
C5	0.2700 (3)	0.4718 (2)	0.60567 (15)	0.0127 (4)
H5A	0.3058	0.5057	0.5375	0.015*
H5B	0.1197	0.5094	0.6193	0.015*
C6	0.4902 (3)	0.5597 (2)	0.69886 (15)	0.0123 (4)
H6A	0.6401	0.5173	0.6875	0.015*
C7	0.4366 (3)	0.5304 (2)	0.80897 (15)	0.0125 (4)
H7A	0.5466	0.6207	0.8663	0.015*
H7B	0.2616	0.5351	0.8100	0.015*
C7A	0.4758 (3)	0.3662 (2)	0.83493 (14)	0.0105 (3)
C8	0.6642 (3)	0.3614 (2)	0.92073 (14)	0.0121 (3)
H8	0.7679	0.4619	0.9634	0.015*
C9	0.7019 (3)	0.2107 (2)	0.94440 (14)	0.0109 (3)
Cl9	0.94256 (8)	0.20966 (5)	1.05161 (4)	0.01508 (14)
C10	0.5540 (3)	0.0610 (2)	0.88454 (14)	0.0112 (3)
H10	0.5815	−0.0414	0.9018	0.013*
C11	0.3651 (3)	0.0645 (2)	0.79890 (14)	0.0110 (3)
H11	0.2607	−0.0365	0.7571	0.013*
C11A	0.3276 (3)	0.2149 (2)	0.77381 (14)	0.0097 (3)
N12	0.1370 (3)	0.21567 (18)	0.68314 (12)	0.0100 (3)
O6	0.5424 (3)	0.73324 (17)	0.69910 (12)	0.0195 (3)
H6	0.683 (5)	0.759 (3)	0.665 (2)	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0098 (8)	0.0127 (8)	0.0117 (8)	0.0021 (6)	0.0042 (6)	0.0016 (6)
N2	0.0106 (7)	0.0179 (8)	0.0116 (7)	0.0022 (6)	0.0044 (6)	0.0028 (6)
N3	0.0097 (7)	0.0165 (8)	0.0083 (7)	0.0016 (6)	−0.0003 (6)	0.0019 (6)
C4	0.0127 (8)	0.0090 (8)	0.0101 (8)	0.0054 (6)	0.0013 (6)	0.0025 (6)
O4	0.0171 (6)	0.0167 (6)	0.0091 (6)	0.0038 (5)	0.0035 (5)	0.0039 (5)
C4A	0.0091 (7)	0.0109 (8)	0.0090 (8)	0.0010 (6)	0.0022 (6)	0.0036 (6)
C5	0.0158 (8)	0.0107 (8)	0.0115 (8)	0.0027 (7)	0.0016 (7)	0.0042 (6)
C6	0.0134 (8)	0.0075 (8)	0.0149 (9)	0.0007 (6)	0.0011 (7)	0.0031 (6)
C7	0.0141 (8)	0.0089 (8)	0.0124 (8)	0.0026 (6)	−0.0009 (6)	−0.0002 (6)
C7A	0.0107 (8)	0.0105 (8)	0.0104 (8)	0.0010 (6)	0.0036 (6)	0.0024 (6)
C8	0.0123 (8)	0.0106 (8)	0.0118 (8)	−0.0003 (6)	0.0023 (7)	0.0016 (6)
C9	0.0093 (8)	0.0150 (8)	0.0085 (8)	0.0021 (6)	0.0014 (6)	0.0047 (6)
Cl9	0.0130 (2)	0.0149 (2)	0.0150 (2)	0.00107 (16)	−0.00297 (16)	0.00561 (16)
C10	0.0140 (8)	0.0110 (8)	0.0092 (8)	0.0019 (6)	0.0037 (6)	0.0036 (6)
C11	0.0131 (8)	0.0099 (8)	0.0089 (8)	−0.0014 (6)	0.0038 (6)	0.0019 (6)
C11A	0.0088 (7)	0.0131 (8)	0.0075 (8)	0.0015 (6)	0.0027 (6)	0.0029 (6)
N12	0.0088 (7)	0.0114 (7)	0.0086 (7)	−0.0009 (5)	0.0014 (5)	0.0036 (5)
O6	0.0204 (7)	0.0122 (7)	0.0264 (8)	0.0023 (5)	0.0071 (6)	0.0046 (5)

Geometric parameters (Å, º)

C1—N2	1.282 (2)	C6—H6A	1.0000
C1—N12	1.353 (2)	C7—C7A	1.508 (2)
C1—H1	0.9500	C7—H7A	0.9900
N2—N3	1.406 (2)	C7—H7B	0.9900
N3—C4	1.331 (2)	C7A—C8	1.389 (3)
N3—H3	0.85 (2)	C7A—C11A	1.402 (3)
C4—O4	1.230 (2)	C8—C9	1.386 (3)
C4—C4A	1.516 (3)	C8—H8	0.9500
C4A—N12	1.469 (2)	C9—C10	1.387 (3)
C4A—C5	1.535 (3)	C9—Cl9	1.742 (2)
C4A—H4A	1.0000	C10—C11	1.386 (3)
C5—C6	1.528 (3)	C10—H10	0.9500
C5—H5A	0.9900	C11—C11A	1.389 (3)
C5—H5B	0.9900	C11—H11	0.9500
C6—O6	1.423 (2)	C11A—N12	1.428 (2)
C6—C7	1.524 (3)	O6—H6	0.96 (3)
N2—C1—N12	127.35 (17)	C7A—C7—C6	113.22 (15)
N2—C1—H1	116.3	C7A—C7—H7A	108.9
N12—C1—H1	116.3	C6—C7—H7A	108.9
C1—N2—N3	113.96 (15)	C7A—C7—H7B	108.9
C4—N3—N2	126.86 (15)	C6—C7—H7B	108.9
C4—N3—H3	119.4 (16)	H7A—C7—H7B	107.7
N2—N3—H3	113.7 (16)	C8—C7A—C11A	117.93 (16)
O4—C4—N3	121.63 (17)	C8—C7A—C7	120.23 (16)
O4—C4—C4A	120.03 (16)	C11A—C7A—C7	121.84 (16)
N3—C4—C4A	118.32 (16)	C9—C8—C7A	120.39 (17)
N12—C4A—C4	110.34 (14)	C9—C8—H8	119.8
N12—C4A—C5	113.71 (15)	C7A—C8—H8	119.8
C4—C4A—C5	108.90 (14)	C8—C9—C10	121.72 (17)
N12—C4A—H4A	107.9	C8—C9—Cl9	119.07 (14)
C4—C4A—H4A	107.9	C10—C9—Cl9	119.21 (14)
C5—C4A—H4A	107.9	C11—C10—C9	118.33 (17)
C6—C5—C4A	114.38 (15)	C11—C10—H10	120.8
C6—C5—H5A	108.7	C9—C10—H10	120.8
C4A—C5—H5A	108.7	C10—C11—C11A	120.39 (16)
C6—C5—H5B	108.7	C10—C11—H11	119.8
C4A—C5—H5B	108.7	C11A—C11—H11	119.8
H5A—C5—H5B	107.6	C11—C11A—C7A	121.24 (17)
O6—C6—C7	108.68 (15)	C11—C11A—N12	119.49 (16)
O6—C6—C5	109.35 (15)	C7A—C11A—N12	119.26 (16)
C7—C6—C5	111.94 (15)	C1—N12—C11A	119.82 (15)
O6—C6—H6A	108.9	C1—N12—C4A	121.14 (15)
C7—C6—H6A	108.9	C11A—N12—C4A	118.51 (14)
C5—C6—H6A	108.9	C6—O6—H6	107.3 (16)
N12—C1—N2—N3	4.7 (3)	C8—C9—C10—C11	0.2 (3)
C1—N2—N3—C4	−5.2 (3)	Cl9—C9—C10—C11	−179.35 (13)
N2—N3—C4—O4	176.61 (16)	C9—C10—C11—C11A	0.5 (3)
N2—N3—C4—C4A	−5.0 (3)	C10—C11—C11A—C7A	−1.0 (3)
O4—C4—C4A—N12	−167.42 (15)	C10—C11—C11A—N12	178.07 (15)
N3—C4—C4A—N12	14.1 (2)	C8—C7A—C11A—C11	0.9 (3)
O4—C4—C4A—C5	67.1 (2)	C7—C7A—C11A—C11	−179.72 (16)
N3—C4—C4A—C5	−111.33 (18)	C8—C7A—C11A—N12	−178.23 (15)
N12—C4A—C5—C6	62.6 (2)	C7—C7A—C11A—N12	1.2 (2)
C4—C4A—C5—C6	−173.87 (14)	N2—C1—N12—C11A	−165.33 (17)
C4A—C5—C6—O6	174.25 (14)	N2—C1—N12—C4A	6.2 (3)
C4A—C5—C6—C7	−65.3 (2)	C11—C11A—N12—C1	57.6 (2)
O6—C6—C7—C7A	−157.89 (15)	C7A—C11A—N12—C1	−123.34 (18)
C5—C6—C7—C7A	81.23 (19)	C11—C11A—N12—C4A	−114.23 (18)
C6—C7—C7A—C8	114.41 (19)	C7A—C11A—N12—C4A	64.9 (2)
C6—C7—C7A—C11A	−65.0 (2)	C4—C4A—N12—C1	−15.1 (2)
C11A—C7A—C8—C9	−0.2 (3)	C5—C4A—N12—C1	107.64 (18)
C7—C7A—C8—C9	−179.61 (16)	C4—C4A—N12—C11A	156.62 (15)
C7A—C8—C9—C10	−0.4 (3)	C5—C4A—N12—C11A	−80.68 (19)
C7A—C8—C9—Cl9	179.21 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N2^i	0.85 (2)	2.35 (2)	3.006 (3)	134 (2)
O6—H6···O4^ii	0.96 (2)	1.79 (3)	2.745 (3)	171 (2)
C4A—H4A···N2^iii	1.00	2.50	3.464 (3)	161
C11—H11···O4^iv	0.95	2.51	3.412 (3)	158
C1—H1···Cg2^v	0.95	2.82	3.482 (3)	128

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