Crystal structure of 3-hy­droxy­methyl-1,2,3,4-tetra­hydro­isoquinolin-1-one

In the title compound, C₁₀H₁₁NO₂, two independent but virtually superimposable mol­ecules, A and B, comprise the asymmetric unit. The heterocyclic ring in each mol­ecule has a screw-boat conformation, and the methyl­hydroxyl group occupies a position to one side of this ring with N—C—C—O torsion angles of −55.30 (15) (mol­ecule A) and −55.94 (16)° (mol­ecule B). In the crystal, O—H...O and N—H...O hydrogen bonding leads to 11-membered {...HNCO...HO...HNC₂O} heterosynthons, involving three different mol­ecules, which are edge-shared to generate a supra­molecular chain along the a axis. Inter­actions of the type C—H...O provide additional stability to the chains, and link these into a three-dimensional architecture.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.026
• wR factor = 0.070
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

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Alert level C
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT918_ALERT_3_C Reflection(s) with I(obs) much smaller I(calc) .          1 Check

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          8 Note
PLAT142_ALERT_4_G su on b - Axis Small or Missing ................    0.00010 Ang.
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT791_ALERT_4_G The Model has Chirality at C9      (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G The Model has Chirality at C19     (Chiral SPGR)          S Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          4 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         33 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   0 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
   3 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Structural commentary

Referring to Fig. 1, the treatment of la­ctam carbonate (1) with sodium hydride to form compound (2) was unsuccessful and led only to the la­ctam alcohol product (3). Compound (3) might be used as an inter­mediate in organic synthesis. The heterocyclic ring has a screw-boat conformation with puckering parameters (Cremer & Pople, 1975): Puckering Amplitude (Q) = 0.4213 (14) Å, θ = 64.15 (19)° and φ = 271.6 (2)° (molecule A), and Q = 0.4050 (15) Å, θ = 64.9 (2)° and φ = 269.3 (2)° (molecule B).

S2. Synthesis and crystallization

A 60% suspension of sodium hydride in mineral oil (22 mg, 1.55 mmol) was suspended in dry tetra­hydro­furan (10 mL; THF) under argon. La­ctam carbonate (1) (250 mg, 1.0 mmol) dissolved in THF (7 mL) was added drop-wise over 5 mins. The resulting reaction mixture was stirred at room temperature for 6 h. The solvent was removed with a rotary evaporator, and the resulting mixture was poured into saturated ammonium hydroxide (10 mL) and extracted with three 20 mL portions of chloro­form. The chloro­form extracts were combined and washed with saturated NaCl solution (20 mL), and dried over anhydrous Mg₂SO₄. The solvent was removed and the residue was purified by flash column chromatography (silica gel) with EtOAc as the eluent to yield la­ctam alcohol (3) as a white solid (0.12g, 67%), which was slowly recrystallised from its chloro­form solution (ca 7 days). M.pt: 140-142 °C. ¹H NMR (300 MHz, CDCl₃): δ 7.20-8.00 (m, 4H, ArH), 7.70 (s, 1H, NH), 2.0-5.0 (m, 5H), 2.02 (s, 1H, OH). ¹³C NMR (300 MHz): δ 167.0, 137.9, 132.3, 126.0, 127.0, 128.0, 129.0, 65.0, 53.0, 30.0. IR (KBr, cm^-1): ν 3684 (OH), 3399, (NH), 1667 (C═O).

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93 to 0.99 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2–1.5U_eq(C). The O-and N-bound H-atoms were refined with O—H = 0.84±0.01 Å and N—H = 0.86±0.01 Å, and with U_iso(H) = 1.5U_eq(O) or 1.2U_eq(N).

Related literature

For background, including medicinal potential, to compounds related to the title compound, see: Biaggio et al. (2007); Grunewald et al. (1999); Zoretic & Soja (1977). For additional conformational analysis, see: Cremer & Pople (1975).

Structure description

Referring to Fig. 1, the treatment of la­ctam carbonate (1) with sodium hydride to form compound (2) was unsuccessful and led only to the la­ctam alcohol product (3). Compound (3) might be used as an inter­mediate in organic synthesis. The heterocyclic ring has a screw-boat conformation with puckering parameters (Cremer & Pople, 1975): Puckering Amplitude (Q) = 0.4213 (14) Å, θ = 64.15 (19)° and φ = 271.6 (2)° (molecule A), and Q = 0.4050 (15) Å, θ = 64.9 (2)° and φ = 269.3 (2)° (molecule B).

For background, including medicinal potential, to compounds related to the title compound, see: Biaggio et al. (2007); Grunewald et al. (1999); Zoretic & Soja (1977). For additional conformational analysis, see: Cremer & Pople (1975).

Synthesis and crystallization

A 60% suspension of sodium hydride in mineral oil (22 mg, 1.55 mmol) was suspended in dry tetra­hydro­furan (10 mL; THF) under argon. La­ctam carbonate (1) (250 mg, 1.0 mmol) dissolved in THF (7 mL) was added drop-wise over 5 mins. The resulting reaction mixture was stirred at room temperature for 6 h. The solvent was removed with a rotary evaporator, and the resulting mixture was poured into saturated ammonium hydroxide (10 mL) and extracted with three 20 mL portions of chloro­form. The chloro­form extracts were combined and washed with saturated NaCl solution (20 mL), and dried over anhydrous Mg₂SO₄. The solvent was removed and the residue was purified by flash column chromatography (silica gel) with EtOAc as the eluent to yield la­ctam alcohol (3) as a white solid (0.12g, 67%), which was slowly recrystallised from its chloro­form solution (ca 7 days). M.pt: 140-142 °C. ¹H NMR (300 MHz, CDCl₃): δ 7.20-8.00 (m, 4H, ArH), 7.70 (s, 1H, NH), 2.0-5.0 (m, 5H), 2.02 (s, 1H, OH). ¹³C NMR (300 MHz): δ 167.0, 137.9, 132.3, 126.0, 127.0, 128.0, 129.0, 65.0, 53.0, 30.0. IR (KBr, cm^-1): ν 3684 (OH), 3399, (NH), 1667 (C═O).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93 to 0.99 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2–1.5U_eq(C). The O-and N-bound H-atoms were refined with O—H = 0.84±0.01 Å and N—H = 0.86±0.01 Å, and with U_iso(H) = 1.5U_eq(O) or 1.2U_eq(N).

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMOL (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010) and publCIF (Westrip, 2010).

Figures

	Fig. 1. Reaction scheme for the preparation of the title compound.
	Fig. 2. The molecular structures of the two independent molecules in the title compound showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.
	Fig. 3. Superimposition of the two independent molecules. Molecule A is shown in blue and B in red. The molecules have been superimposed such that the benzene rings are overlapped.
	Fig. 4. A view of the supramolecular chain sustained by O—H···O and N—H···O hydrogen bonds (orange and blue dashed lines, respectively) and aligned along the a axis in the crystal packing.
	Fig. 5. A view in projection down the a axis of the unit-cell contents. The O—H···O, N—H···O and C—H···O interactions are shown as orange, blue and purple dashed lines, respectively.

3-Hydroxymethyl-1,2,3,4-tetrahydroisoquinolin-1-one

Crystal data

C10H11NO2	Dx = 1.379 Mg m^−3
Mr = 177.20	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 5937 reflections
a = 6.2846 (1) Å	θ = 3.2–74.2°
b = 13.8914 (1) Å	µ = 0.79 mm^−1
c = 19.5592 (2) Å	T = 100 K
V = 1707.56 (3) Å^3	Prism, colourless
Z = 8	0.35 × 0.25 × 0.15 mm
F(000) = 752

Data collection

Agilent SuperNova CCD diffractometer	3336 reflections with I > 2σ(I)
Radiation source: SuperNova (Cu) X-ray Source	Rint = 0.011
ω scans	θmax = 74.3°, θmin = 3.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	h = −7→7
Tmin = 0.882, Tmax = 1.000	k = −17→17
6258 measured reflections	l = −14→24
3358 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.026	w = 1/[σ^2(Fo^2) + (0.0483P)^2 + 0.1971P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.070	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.15 e Å^−3
3358 reflections	Δρmin = −0.29 e Å^−3
251 parameters	Absolute structure: Flack x determined using 1359 quotients [(I^+)-(I^-)]/[(I^+)+(I^-)] (Parsons et al., 2013)
4 restraints	Absolute structure parameter: −0.05 (6)

Special details

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.

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

	x	y	z	Uiso*/Ueq
O1	0.62669 (16)	0.73762 (7)	0.18705 (5)	0.0180 (2)
O2	1.32523 (16)	0.66602 (7)	0.10231 (5)	0.0168 (2)
H2O	1.424 (3)	0.6888 (18)	0.1273 (11)	0.049 (7)*
N1	0.91512 (19)	0.75379 (8)	0.11906 (6)	0.0150 (2)
H1N	0.887 (3)	0.6996 (10)	0.0994 (9)	0.021 (5)*
C1	0.7850 (2)	0.78505 (10)	0.16823 (6)	0.0144 (3)
C2	0.8387 (2)	0.87911 (10)	0.20099 (7)	0.0156 (3)
C3	0.6905 (2)	0.92359 (11)	0.24371 (7)	0.0195 (3)
H3	0.5548	0.8950	0.2507	0.023*
C4	0.7411 (3)	1.00942 (11)	0.27601 (8)	0.0228 (3)
H4	0.6397	1.0401	0.3047	0.027*
C5	0.9411 (3)	1.05064 (11)	0.26623 (8)	0.0212 (3)
H5	0.9764	1.1091	0.2887	0.025*
C6	1.0884 (2)	1.00671 (10)	0.22384 (7)	0.0187 (3)
H6	1.2240	1.0355	0.2172	0.022*
C7	1.0392 (2)	0.92024 (10)	0.19065 (7)	0.0158 (3)
C8	1.1995 (2)	0.86671 (10)	0.14844 (7)	0.0169 (3)
H8A	1.2810	0.8226	0.1784	0.020*
H8B	1.3008	0.9132	0.1282	0.020*
C9	1.0952 (2)	0.80877 (10)	0.09148 (7)	0.0153 (3)
H9	1.0405	0.8544	0.0561	0.018*
C10	1.2538 (2)	0.74041 (10)	0.05779 (7)	0.0163 (3)
H10A	1.1863	0.7108	0.0172	0.020*
H10B	1.3783	0.7779	0.0419	0.020*
O3	0.10908 (16)	0.52866 (7)	−0.04188 (5)	0.0200 (2)
O4	0.80454 (17)	0.57641 (7)	0.04790 (5)	0.0183 (2)
H4O	0.904 (3)	0.5612 (18)	0.0200 (11)	0.050 (7)*
N2	0.3944 (2)	0.49397 (8)	0.02382 (6)	0.0165 (2)
H2N	0.373 (4)	0.5458 (11)	0.0481 (9)	0.028 (5)*
C11	0.2649 (2)	0.47641 (10)	−0.02887 (7)	0.0160 (3)
C12	0.3141 (2)	0.39062 (10)	−0.07222 (7)	0.0174 (3)
C13	0.1653 (2)	0.35932 (11)	−0.12001 (7)	0.0217 (3)
H13	0.0327	0.3916	−0.1242	0.026*
C14	0.2107 (3)	0.28085 (12)	−0.16165 (7)	0.0241 (3)
H14	0.1092	0.2591	−0.1941	0.029*
C15	0.4058 (3)	0.23446 (11)	−0.15537 (8)	0.0249 (3)
H15	0.4370	0.1805	−0.1835	0.030*
C16	0.5553 (3)	0.26632 (11)	−0.10831 (8)	0.0230 (3)
H16	0.6883	0.2342	−0.1047	0.028*
C17	0.5124 (2)	0.34507 (10)	−0.06620 (7)	0.0188 (3)
C18	0.6750 (2)	0.38637 (10)	−0.01815 (8)	0.0208 (3)
H18A	0.7610	0.4350	−0.0428	0.025*
H18B	0.7720	0.3344	−0.0031	0.025*
C19	0.5744 (2)	0.43317 (10)	0.04445 (7)	0.0179 (3)
H19	0.5197	0.3811	0.0751	0.022*
C20	0.7337 (2)	0.49417 (10)	0.08474 (7)	0.0194 (3)
H20A	0.6665	0.5155	0.1279	0.023*
H20B	0.8583	0.4539	0.0966	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0137 (5)	0.0198 (5)	0.0204 (5)	−0.0022 (4)	0.0008 (4)	−0.0006 (4)
O2	0.0153 (5)	0.0148 (5)	0.0203 (5)	0.0004 (4)	−0.0012 (4)	−0.0004 (4)
N1	0.0141 (5)	0.0138 (5)	0.0171 (5)	−0.0010 (4)	−0.0001 (4)	−0.0022 (4)
C1	0.0131 (6)	0.0157 (6)	0.0145 (6)	0.0020 (5)	−0.0029 (5)	0.0016 (5)
C2	0.0162 (7)	0.0161 (6)	0.0146 (6)	0.0009 (5)	−0.0017 (5)	0.0005 (5)
C3	0.0163 (7)	0.0229 (7)	0.0193 (6)	0.0007 (6)	0.0009 (6)	−0.0021 (5)
C4	0.0222 (7)	0.0242 (7)	0.0219 (7)	0.0035 (6)	0.0021 (6)	−0.0061 (6)
C5	0.0247 (8)	0.0180 (7)	0.0210 (7)	−0.0005 (6)	−0.0045 (6)	−0.0050 (5)
C6	0.0193 (7)	0.0172 (6)	0.0196 (7)	−0.0026 (6)	−0.0027 (5)	−0.0004 (5)
C7	0.0170 (7)	0.0154 (6)	0.0152 (6)	0.0011 (5)	−0.0021 (5)	0.0015 (5)
C8	0.0131 (6)	0.0162 (6)	0.0216 (7)	−0.0017 (5)	0.0005 (6)	−0.0017 (5)
C9	0.0137 (6)	0.0153 (6)	0.0167 (6)	0.0003 (5)	0.0015 (5)	0.0009 (5)
C10	0.0158 (6)	0.0179 (6)	0.0152 (6)	0.0013 (5)	0.0013 (5)	0.0013 (5)
O3	0.0151 (5)	0.0225 (5)	0.0225 (5)	0.0022 (4)	−0.0001 (4)	−0.0020 (4)
O4	0.0162 (5)	0.0161 (5)	0.0227 (5)	−0.0004 (4)	0.0016 (4)	−0.0021 (4)
N2	0.0163 (6)	0.0150 (5)	0.0183 (5)	0.0013 (5)	0.0003 (5)	−0.0032 (4)
C11	0.0143 (6)	0.0167 (6)	0.0172 (6)	−0.0033 (5)	0.0034 (5)	0.0004 (5)
C12	0.0179 (7)	0.0169 (6)	0.0174 (6)	−0.0030 (5)	0.0034 (5)	−0.0017 (5)
C13	0.0191 (7)	0.0253 (7)	0.0206 (7)	−0.0040 (6)	0.0026 (6)	−0.0014 (6)
C14	0.0275 (8)	0.0260 (7)	0.0187 (7)	−0.0089 (6)	0.0018 (6)	−0.0036 (6)
C15	0.0348 (9)	0.0187 (6)	0.0212 (7)	−0.0057 (7)	0.0083 (6)	−0.0046 (6)
C16	0.0250 (7)	0.0173 (7)	0.0267 (7)	0.0007 (6)	0.0057 (6)	−0.0022 (6)
C17	0.0195 (7)	0.0159 (6)	0.0210 (6)	−0.0020 (5)	0.0034 (5)	−0.0006 (5)
C18	0.0156 (7)	0.0180 (6)	0.0288 (7)	0.0018 (5)	−0.0001 (6)	−0.0040 (6)
C19	0.0169 (6)	0.0153 (6)	0.0215 (7)	0.0011 (5)	−0.0018 (5)	0.0019 (5)
C20	0.0185 (7)	0.0200 (6)	0.0198 (6)	−0.0005 (6)	−0.0026 (5)	0.0005 (5)

Geometric parameters (Å, º)

O1—C1	1.2486 (17)	O3—C11	1.2454 (18)
O2—C10	1.4239 (16)	O4—C20	1.4220 (17)
O2—H2O	0.849 (13)	O4—H4O	0.855 (13)
N1—C1	1.3351 (18)	N2—C11	1.3356 (18)
N1—C9	1.4680 (17)	N2—C19	1.4682 (18)
N1—H1N	0.863 (12)	N2—H2N	0.872 (12)
C1—C2	1.4939 (18)	C11—C12	1.4949 (18)
C2—C3	1.396 (2)	C12—C13	1.392 (2)
C2—C7	1.398 (2)	C12—C17	1.402 (2)
C3—C4	1.386 (2)	C13—C14	1.390 (2)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.395 (2)	C14—C15	1.391 (2)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.385 (2)	C15—C16	1.388 (2)
C5—H5	0.9500	C15—H15	0.9500
C6—C7	1.400 (2)	C16—C17	1.396 (2)
C6—H6	0.9500	C16—H16	0.9500
C7—C8	1.4997 (19)	C17—C18	1.502 (2)
C8—C9	1.5227 (18)	C18—C19	1.524 (2)
C8—H8A	0.9900	C18—H18A	0.9900
C8—H8B	0.9900	C18—H18B	0.9900
C9—C10	1.5263 (19)	C19—C20	1.5303 (19)
C9—H9	1.0000	C19—H19	1.0000
C10—H10A	0.9900	C20—H20A	0.9900
C10—H10B	0.9900	C20—H20B	0.9900
C10—O2—H2O	108.1 (18)	C20—O4—H4O	110.7 (17)
C1—N1—C9	124.60 (12)	C11—N2—C19	125.20 (12)
C1—N1—H1N	118.7 (14)	C11—N2—H2N	118.6 (14)
C9—N1—H1N	116.5 (14)	C19—N2—H2N	116.2 (14)
O1—C1—N1	121.92 (13)	O3—C11—N2	122.02 (13)
O1—C1—C2	121.01 (12)	O3—C11—C12	120.76 (12)
N1—C1—C2	117.06 (12)	N2—C11—C12	117.21 (12)
C3—C2—C7	120.47 (13)	C13—C12—C17	120.82 (13)
C3—C2—C1	119.55 (13)	C13—C12—C11	119.41 (13)
C7—C2—C1	119.94 (12)	C17—C12—C11	119.73 (13)
C4—C3—C2	120.03 (14)	C14—C13—C12	120.04 (15)
C4—C3—H3	120.0	C14—C13—H13	120.0
C2—C3—H3	120.0	C12—C13—H13	120.0
C3—C4—C5	119.83 (14)	C13—C14—C15	119.50 (14)
C3—C4—H4	120.1	C13—C14—H14	120.3
C5—C4—H4	120.1	C15—C14—H14	120.3
C6—C5—C4	120.26 (13)	C16—C15—C14	120.51 (14)
C6—C5—H5	119.9	C16—C15—H15	119.7
C4—C5—H5	119.9	C14—C15—H15	119.7
C5—C6—C7	120.54 (14)	C15—C16—C17	120.70 (15)
C5—C6—H6	119.7	C15—C16—H16	119.7
C7—C6—H6	119.7	C17—C16—H16	119.7
C2—C7—C6	118.86 (13)	C16—C17—C12	118.42 (14)
C2—C7—C8	118.83 (12)	C16—C17—C18	122.47 (14)
C6—C7—C8	122.17 (13)	C12—C17—C18	119.00 (12)
C7—C8—C9	112.08 (12)	C17—C18—C19	112.53 (12)
C7—C8—H8A	109.2	C17—C18—H18A	109.1
C9—C8—H8A	109.2	C19—C18—H18A	109.1
C7—C8—H8B	109.2	C17—C18—H18B	109.1
C9—C8—H8B	109.2	C19—C18—H18B	109.1
H8A—C8—H8B	107.9	H18A—C18—H18B	107.8
N1—C9—C8	109.74 (11)	N2—C19—C18	110.14 (11)
N1—C9—C10	109.78 (11)	N2—C19—C20	109.10 (11)
C8—C9—C10	111.33 (11)	C18—C19—C20	112.23 (12)
N1—C9—H9	108.6	N2—C19—H19	108.4
C8—C9—H9	108.6	C18—C19—H19	108.4
C10—C9—H9	108.6	C20—C19—H19	108.4
O2—C10—C9	113.17 (11)	O4—C20—C19	112.88 (11)
O2—C10—H10A	108.9	O4—C20—H20A	109.0
C9—C10—H10A	108.9	C19—C20—H20A	109.0
O2—C10—H10B	108.9	O4—C20—H20B	109.0
C9—C10—H10B	108.9	C19—C20—H20B	109.0
H10A—C10—H10B	107.8	H20A—C20—H20B	107.8
C9—N1—C1—O1	175.75 (12)	C19—N2—C11—O3	176.74 (13)
C9—N1—C1—C2	−5.26 (19)	C19—N2—C11—C12	−3.2 (2)
O1—C1—C2—C3	−12.24 (19)	O3—C11—C12—C13	−11.1 (2)
N1—C1—C2—C3	168.76 (13)	N2—C11—C12—C13	168.84 (13)
O1—C1—C2—C7	165.51 (12)	O3—C11—C12—C17	166.40 (13)
N1—C1—C2—C7	−13.49 (18)	N2—C11—C12—C17	−13.68 (19)
C7—C2—C3—C4	0.3 (2)	C17—C12—C13—C14	1.2 (2)
C1—C2—C3—C4	178.05 (13)	C11—C12—C13—C14	178.68 (13)
C2—C3—C4—C5	−0.6 (2)	C12—C13—C14—C15	−0.4 (2)
C3—C4—C5—C6	0.7 (2)	C13—C14—C15—C16	−0.4 (2)
C4—C5—C6—C7	−0.4 (2)	C14—C15—C16—C17	0.3 (2)
C3—C2—C7—C6	0.0 (2)	C15—C16—C17—C12	0.5 (2)
C1—C2—C7—C6	−177.76 (12)	C15—C16—C17—C18	−175.52 (14)
C3—C2—C7—C8	175.65 (13)	C13—C12—C17—C16	−1.3 (2)
C1—C2—C7—C8	−2.08 (18)	C11—C12—C17—C16	−178.75 (13)
C5—C6—C7—C2	0.1 (2)	C13—C12—C17—C18	174.88 (13)
C5—C6—C7—C8	−175.46 (13)	C11—C12—C17—C18	−2.57 (19)
C2—C7—C8—C9	33.21 (17)	C16—C17—C18—C19	−151.24 (14)
C6—C7—C8—C9	−151.25 (13)	C12—C17—C18—C19	32.74 (18)
C1—N1—C9—C8	35.96 (18)	C11—N2—C19—C18	32.98 (18)
C1—N1—C9—C10	158.62 (12)	C11—N2—C19—C20	156.58 (12)
C7—C8—C9—N1	−47.52 (15)	C17—C18—C19—N2	−45.45 (16)
C7—C8—C9—C10	−169.26 (11)	C17—C18—C19—C20	−167.21 (12)
N1—C9—C10—O2	−55.30 (15)	N2—C19—C20—O4	−55.94 (16)
C8—C9—C10—O2	66.42 (15)	C18—C19—C20—O4	66.41 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1^i	0.85 (1)	1.86 (1)	2.7066 (14)	176 (3)
O4—H4O···O3^i	0.86 (1)	1.83 (1)	2.6808 (15)	178 (3)
N1—H1N···O4	0.86 (1)	2.05 (1)	2.9141 (15)	176 (2)
N2—H2N···O2^ii	0.87 (1)	2.00 (1)	2.8737 (15)	179 (2)
C4—H4···O2^iii	0.95	2.53	3.2512 (18)	132
C8—H8A···O1^i	0.99	2.48	3.3157 (16)	142
C18—H18A···O3^i	0.99	2.55	3.4007 (16)	145

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