A purple odyssey: synthesis and structure of 3-amino-4-hy­droxy-6-oxo­cyclo­hexa-2,4-dien-1-iminium chloride monohydrate

The unequal C—C bond lengths in the six-membered ring of the C₆H₇N₂O₂⁺ cation of the title compound can be understood in terms of two separate delocalized systems.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.072
• wR factor = 0.159
• Data-to-parameter ratio = 23.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00433 Ang.
PLAT369_ALERT_2_C Long    C(sp2)-C(sp2) Bond  C2     -   C3     ..       1.53 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H1O    ..  H1W     ..       2.12 Ang.
PLAT417_ALERT_2_C Short Inter D-H..H-D       H1O    ..  H2W     ..       2.11 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      9.622 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.157 Check

Alert level G
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C1     -C6            1.44 Ang.
PLAT335_ALERT_2_G Check Large C6 Ring    C-C Range C1     -C6            0.18 Ang.
PLAT432_ALERT_2_G Short Inter X...Y Contact  C2     ..  C4      ..       3.16 Ang.
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          ! Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          5 Note
PLAT931_ALERT_5_G Found Twin Law ( 0 0  1)[       ] Estimated BASF       0.48 Check
PLAT996_ALERT_1_G Non-Standard SHELXL LIST 4 Style FCF Supplied ..          ! Check

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Chemical context

In the course of our ongoing studies (Plater & Harrison, 2013, 2014a,b; Plater & Jackson, 2014) on new conjugated products obtained from the oxidation of aromatic amines, we attempted the oxidation of 1,2,4,5-tetra­amino­benzene, 1. As long ago as 1887, it was demonstrated (Nietzki & Hagenbach, 1887) that this compound undergoes aerial oxidation to form 2,5-di­amino-1,4-benzo­quinonedi­imine, 2. More recently, Braunstein et al. (2003) have studied the oxidation of compound 1 and the related compound 2,4-di­amino­resorcinol, 3, to synthesize (1E)-N-(2,2-di­methyl­propyl)-5-[(2,2-di­methyl­propyl)­amino]-2-hy­droxy-4-oxo­cyclo­hexa-2,5-dien-1-iminium chloride, 4, which generates the zwitterion 5 when treated with base.

By careful oxidation of the tetra­hydro­chloride salt of amine 1 with potassium dichromate, we isolated and crystallized the chloride salt of the parent 5-amino-2-hy­droxy-4-oxo­cyclo­hexa-2,5-dien-1-iminium cation, 8, as a monohydrate [C₆H₇N₂O₂⁺.Cl^-.H₂O, (I)] in the form of purple needles. This reaction must proceed via the elusive inter­mediate 6 which spontaneously hydrolyses. The first hydrolysis product should be inter­mediate 7. This contains a conjugated iminium salt and a vinyl­ogous amide, which must hydrolyse rapidly, possibly because of the stability of the acidic enol formed. It appears to be a rapid hydrolysis for an amide under mild conditions and so stabilization of a tetra­hedral inter­mediate by the positive iminium salt might occur.

S2. Structural commentary

The asymmetric unit of (I) consists of one essentially planar C₆H₇N₂O₂⁺ cation (r.m.s. deviation for the non-hydrogen atoms = 0.028 Å), a chloride counter-ion and a water molecule of crystallization (Fig. 1). Despite being a nominal 6π aromatic system, the bond lengths of the C1–C6 ring in (I) are far from equal and are split into three groups of two: the shortest are C1—C6 [1.354 (5)] and C3—C4 [1.381 (5)], followed by C4—C5 [1.406 (5)] and C1—C2 [1.436 (5) Å]. Finally, the C2—C3 [1.532 (4)] and C5—C6 [1.500 (5) Å] lengths are those expected for a C—C σ bond.

The short C3—C4 and C4—C5 bonds correlate with the approximately equal C3—N1 [1.320 (4)] and C5—N2 [1.306 (4) Å] bond lengths, which imply equal delocalization of the positive charge of the cation over atoms N1 and N2, mediated via the C—N and C—C bonds between them. In terms of the `oxygen side' of the cation, the C6—O2 bond [1.320 (4) Å] is short for a C—O single bond whereas C2—O1 [1.227 (4) Å] is slightly lengthened for a nominal C═O double bond. This in combination with the C1—C2 and C1—C6 bond lengths again implies a degree of delocalization over these five atoms. However, the long C2—C3 and C5—C6 bonds imply little, if any, conjugation between the two delocalized components (O2/C6/C1/C2/O1 and N2/C5/C4/C3/N1) of the cation.

The cation features two intra­molecular N—H···O hydrogen bonds, viz. N1—H2n···O1 and N2—H4n···O2 (Table 1), which both close S(5) rings.

S3. Supra­molecular features

In the crystal, the components are linked by N—H···Cl, N—H···O, O—H···Cl and O—H···O hydrogen bonds (Table 1). If the cation and chloride anion are considered together, then [001] chains arise (Fig. 2) in which adjacent cations are related to each other by c-glide symmetry. Each link in the chain comprises two cations and two anions and R²₄(12) loops are apparent.

When the cation and water molecule are considered together, an [001] chain also arises (Fig. 3). The water molecule plays a key role in terms of both accepting hydrogen bonds from O2 and N1 and donating a hydrogen bond to O1 (it also acts as a donor to the chloride ion). The end result is a chain featuring R⁴₄(12) loops (counted via the intra­molecular N1—H2n···O1 hydrogen bond).

When all components are considered together, (100) double sheets result (Fig. 4), with the water-O3—H2w···Cl1 hydrogen bond providing the key link between the sheets. Overall, the chloride ion accepts four hydrogen bonds (three N—H···Cl and one O—H···Cl inter­actions) in an irregular geometry.

S4. Database survey

The compound (1E)-N-(2,2-di­methyl­propyl)-5-[(2,2-di­methyl­propyl)­amino]-2-hy­droxy-4-οxo­cyclo­hexa-2,5-dien-1-iminium chloride chloro­form monosolvate (CCDC refcode: VASVER; Braunstein et al., 2003) was noted in the chemical context section above: these authors discuss its electronic structure in detail including its potentially anti-aromatic character. The crystal structure of the parent unprotonated zwitterion 3-oxo-4-amino-6-iminiophenolate monohydrate (HAZQUV; Yang et al., 2005) is known as are those of a number of its alkyl­ated/functionalized derivatives (Braunstein et al., 2009; Tamboura et al., 2009; Kauf & Braunstein, 2011) and metal complexes (Paretzki et al., 2010). The carbon–carbon bond lengths in the six-membered ring in all these compounds are similar to those seen in (I).

S5. Synthesis and crystallization

1,2,4,5-Benzene­tetra­amine tetra­hydro­chloride (200 mg, 0.7 mmol) in distilled water (75 ml) was treated with an excess of K₂Cr₂O₇ (140 mg, 0.48 mmol, 0.6 eq) and stirred at room temperature for 24 h. The brown mixture was neutralized with NaHCO₃ giving a brown or red precipitate, which was then extracted with CH₂Cl₂ (10 × 50 ml). The yellow extracts were combined, decanted, then stirred with methanol (50 ml) containing five drops of conc. HCl(aq). The yellow solution turned purple. This was evaporated to dryness, then the product was dissolved in methanol (50 ml) to yield a red solution and recrystallized by slow evaporation to leave the title compound (15 mg, 8%) as purple needles: m.p. > 473 K; λ_max (ethanol)/nm 503 (log ε 2.90) and 325(3.99); ν (diamond anvil)/cm^-1 2953br, 1688s, 1547vs, 1401vs, 1310vs, 1251vs, 1141vs, 871vs, 853s, 711vs, 654vs, 579vs, 454s and 420s; m/z (orbitrap ASAP) 139.0498 (M⁺, 100%), C₆H₇N₂O₂ requires 139.0502. The UV/visible spectrum of (I) is shown in Fig. 5.

S6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were geometrically placed (C—H = 0.95 Å) and refined as riding atoms. The N- and O-bound H atoms were located in difference maps and their positions were freely refined. The constraint U_iso(H) = 1.2U_eq(carrier) was applied in all cases. The crystal studied was found to be a twin with the components related by a 180° rotation about [001].

Structure description

In the course of our ongoing studies (Plater & Harrison, 2013, 2014a,b; Plater & Jackson, 2014) on new conjugated products obtained from the oxidation of aromatic amines, we attempted the oxidation of 1,2,4,5-tetra­amino­benzene, 1. As long ago as 1887, it was demonstrated (Nietzki & Hagenbach, 1887) that this compound undergoes aerial oxidation to form 2,5-di­amino-1,4-benzo­quinonedi­imine, 2. More recently, Braunstein et al. (2003) have studied the oxidation of compound 1 and the related compound 2,4-di­amino­resorcinol, 3, to synthesize (1E)-N-(2,2-di­methyl­propyl)-5-[(2,2-di­methyl­propyl)­amino]-2-hy­droxy-4-oxo­cyclo­hexa-2,5-dien-1-iminium chloride, 4, which generates the zwitterion 5 when treated with base.

By careful oxidation of the tetra­hydro­chloride salt of amine 1 with potassium dichromate, we isolated and crystallized the chloride salt of the parent 5-amino-2-hy­droxy-4-oxo­cyclo­hexa-2,5-dien-1-iminium cation, 8, as a monohydrate [C₆H₇N₂O₂⁺.Cl^-.H₂O, (I)] in the form of purple needles. This reaction must proceed via the elusive inter­mediate 6 which spontaneously hydrolyses. The first hydrolysis product should be inter­mediate 7. This contains a conjugated iminium salt and a vinyl­ogous amide, which must hydrolyse rapidly, possibly because of the stability of the acidic enol formed. It appears to be a rapid hydrolysis for an amide under mild conditions and so stabilization of a tetra­hedral inter­mediate by the positive iminium salt might occur.

The asymmetric unit of (I) consists of one essentially planar C₆H₇N₂O₂⁺ cation (r.m.s. deviation for the non-hydrogen atoms = 0.028 Å), a chloride counter-ion and a water molecule of crystallization (Fig. 1). Despite being a nominal 6π aromatic system, the bond lengths of the C1–C6 ring in (I) are far from equal and are split into three groups of two: the shortest are C1—C6 [1.354 (5)] and C3—C4 [1.381 (5)], followed by C4—C5 [1.406 (5)] and C1—C2 [1.436 (5) Å]. Finally, the C2—C3 [1.532 (4)] and C5—C6 [1.500 (5) Å] lengths are those expected for a C—C σ bond.

The short C3—C4 and C4—C5 bonds correlate with the approximately equal C3—N1 [1.320 (4)] and C5—N2 [1.306 (4) Å] bond lengths, which imply equal delocalization of the positive charge of the cation over atoms N1 and N2, mediated via the C—N and C—C bonds between them. In terms of the `oxygen side' of the cation, the C6—O2 bond [1.320 (4) Å] is short for a C—O single bond whereas C2—O1 [1.227 (4) Å] is slightly lengthened for a nominal C═O double bond. This in combination with the C1—C2 and C1—C6 bond lengths again implies a degree of delocalization over these five atoms. However, the long C2—C3 and C5—C6 bonds imply little, if any, conjugation between the two delocalized components (O2/C6/C1/C2/O1 and N2/C5/C4/C3/N1) of the cation.

The cation features two intra­molecular N—H···O hydrogen bonds, viz. N1—H2n···O1 and N2—H4n···O2 (Table 1), which both close S(5) rings.

In the crystal, the components are linked by N—H···Cl, N—H···O, O—H···Cl and O—H···O hydrogen bonds (Table 1). If the cation and chloride anion are considered together, then [001] chains arise (Fig. 2) in which adjacent cations are related to each other by c-glide symmetry. Each link in the chain comprises two cations and two anions and R²₄(12) loops are apparent.

When the cation and water molecule are considered together, an [001] chain also arises (Fig. 3). The water molecule plays a key role in terms of both accepting hydrogen bonds from O2 and N1 and donating a hydrogen bond to O1 (it also acts as a donor to the chloride ion). The end result is a chain featuring R⁴₄(12) loops (counted via the intra­molecular N1—H2n···O1 hydrogen bond).

When all components are considered together, (100) double sheets result (Fig. 4), with the water-O3—H2w···Cl1 hydrogen bond providing the key link between the sheets. Overall, the chloride ion accepts four hydrogen bonds (three N—H···Cl and one O—H···Cl inter­actions) in an irregular geometry.

The compound (1E)-N-(2,2-di­methyl­propyl)-5-[(2,2-di­methyl­propyl)­amino]-2-hy­droxy-4-οxo­cyclo­hexa-2,5-dien-1-iminium chloride chloro­form monosolvate (CCDC refcode: VASVER; Braunstein et al., 2003) was noted in the chemical context section above: these authors discuss its electronic structure in detail including its potentially anti-aromatic character. The crystal structure of the parent unprotonated zwitterion 3-oxo-4-amino-6-iminiophenolate monohydrate (HAZQUV; Yang et al., 2005) is known as are those of a number of its alkyl­ated/functionalized derivatives (Braunstein et al., 2009; Tamboura et al., 2009; Kauf & Braunstein, 2011) and metal complexes (Paretzki et al., 2010). The carbon–carbon bond lengths in the six-membered ring in all these compounds are similar to those seen in (I).

Synthesis and crystallization

1,2,4,5-Benzene­tetra­amine tetra­hydro­chloride (200 mg, 0.7 mmol) in distilled water (75 ml) was treated with an excess of K₂Cr₂O₇ (140 mg, 0.48 mmol, 0.6 eq) and stirred at room temperature for 24 h. The brown mixture was neutralized with NaHCO₃ giving a brown or red precipitate, which was then extracted with CH₂Cl₂ (10 × 50 ml). The yellow extracts were combined, decanted, then stirred with methanol (50 ml) containing five drops of conc. HCl(aq). The yellow solution turned purple. This was evaporated to dryness, then the product was dissolved in methanol (50 ml) to yield a red solution and recrystallized by slow evaporation to leave the title compound (15 mg, 8%) as purple needles: m.p. > 473 K; λ_max (ethanol)/nm 503 (log ε 2.90) and 325(3.99); ν (diamond anvil)/cm^-1 2953br, 1688s, 1547vs, 1401vs, 1310vs, 1251vs, 1141vs, 871vs, 853s, 711vs, 654vs, 579vs, 454s and 420s; m/z (orbitrap ASAP) 139.0498 (M⁺, 100%), C₆H₇N₂O₂ requires 139.0502. The UV/visible spectrum of (I) is shown in Fig. 5.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were geometrically placed (C—H = 0.95 Å) and refined as riding atoms. The N- and O-bound H atoms were located in difference maps and their positions were freely refined. The constraint U_iso(H) = 1.2U_eq(carrier) was applied in all cases. The crystal studied was found to be a twin with the components related by a 180° rotation about [001].

Computing details

Data collection: CrysAlis PRO (Rigaku, 2015); cell refinement: CrysAlis PRO (Rigaku, 2015); data reduction: CrysAlis PRO (Rigaku, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids. Hydrogen bonds are shown as double-dashed lines.
	Fig. 2. Detail of the crystal structure of (I) showing the formation of [001] chains of cations and chloride ions linked by N—H···Cl hydrogen bonds. Symmetry codes as in Table 1.
	Fig. 3. Detail of the crystal structure of (I) showing the formation of [001] chains of cations and water molecules linked by O—H···O and N—H···O hydrogen bonds. Symmetry codes as in Table 1.
	Fig. 4. The packing in (I) viewed along [001] showing the formation of (100) double layers.
	Fig. 5. UV/visible spectrum of (I) (2.3 × 10^-4 M solution in ethanol).

3-Amino-4-hydroxy-6-oxocyclohexa-2,4-dien-1-iminium chloride monohydrate

Crystal data

C6H7N2O2·Cl·H2O	F(000) = 400
Mr = 192.60	Dx = 1.523 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.3070 (7) Å	Cell parameters from 1747 reflections
b = 14.9614 (18) Å	θ = 3.2–27.5°
c = 8.9198 (11) Å	µ = 0.42 mm^−1
β = 93.457 (1)°	T = 100 K
V = 840.15 (17) Å^3	Rod, purple
Z = 4	0.11 × 0.04 × 0.03 mm

Data collection

Rigaku Mercury CCD diffractometer	θmax = 27.6°, θmin = 2.7°
ω scans	h = −8→8
3102 measured reflections	k = −19→19
3102 independent reflections	l = −7→11
2789 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.072	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.159	w = 1/[σ^2(Fo^2) + (0.0472P)^2 + 1.7994P] where P = (Fo^2 + 2Fc^2)/3
S = 1.22	(Δ/σ)max < 0.001
3102 reflections	Δρmax = 0.56 e Å^−3
131 parameters	Δρmin = −0.39 e Å^−3
0 restraints

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. Refined as a 2-component twin (180° rotation about [001])

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

	x	y	z	Uiso*/Ueq
C1	0.2403 (6)	0.3972 (2)	0.3386 (4)	0.0152 (7)
H1	0.2413	0.3419	0.2865	0.018*
C2	0.2473 (6)	0.3979 (2)	0.4998 (4)	0.0132 (7)
C3	0.2536 (6)	0.4888 (2)	0.5792 (4)	0.0120 (7)
C4	0.2459 (6)	0.5671 (2)	0.4970 (4)	0.0155 (7)
H4	0.2493	0.6233	0.5468	0.019*
C5	0.2332 (6)	0.5632 (2)	0.3392 (4)	0.0133 (7)
C6	0.2324 (6)	0.4747 (2)	0.2601 (4)	0.0133 (7)
N1	0.2648 (6)	0.4838 (2)	0.7271 (3)	0.0165 (7)
H1n	0.265 (7)	0.527 (3)	0.779 (5)	0.020*
H2n	0.270 (7)	0.436 (3)	0.770 (5)	0.020*
N2	0.2212 (6)	0.6344 (2)	0.2543 (4)	0.0162 (7)
H3n	0.227 (7)	0.690 (3)	0.300 (5)	0.019*
H4n	0.216 (7)	0.629 (3)	0.161 (5)	0.019*
O1	0.2459 (4)	0.33037 (17)	0.5778 (3)	0.0184 (6)
O2	0.2219 (5)	0.48297 (18)	0.1125 (3)	0.0201 (6)
H1o	0.230 (7)	0.430 (3)	0.063 (5)	0.024*
Cl1	0.22638 (16)	0.67344 (6)	0.89828 (10)	0.0208 (3)
O3	0.3077 (5)	0.34226 (17)	−0.0329 (3)	0.0223 (6)
H1w	0.247 (8)	0.294 (3)	−0.001 (5)	0.027*
H2w	0.458 (8)	0.334 (3)	0.008 (6)	0.027*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.019 (2)	0.0121 (15)	0.0149 (17)	0.0016 (14)	0.0001 (14)	−0.0023 (13)
C2	0.0134 (18)	0.0119 (15)	0.0146 (17)	−0.0007 (14)	0.0013 (14)	−0.0015 (13)
C3	0.0101 (17)	0.0119 (15)	0.0137 (16)	0.0012 (13)	−0.0030 (13)	−0.0036 (12)
C4	0.0170 (19)	0.0134 (16)	0.0161 (17)	−0.0001 (15)	0.0001 (14)	−0.0038 (13)
C5	0.0118 (18)	0.0113 (15)	0.0168 (17)	−0.0006 (14)	0.0005 (14)	0.0021 (13)
C6	0.0105 (18)	0.0179 (16)	0.0112 (16)	0.0006 (14)	−0.0014 (13)	−0.0031 (13)
N1	0.0243 (19)	0.0150 (14)	0.0101 (15)	0.0015 (14)	−0.0005 (13)	−0.0001 (12)
N2	0.0246 (19)	0.0122 (13)	0.0120 (15)	−0.0015 (13)	0.0038 (13)	−0.0003 (12)
O1	0.0271 (15)	0.0137 (11)	0.0143 (12)	0.0001 (12)	0.0017 (11)	0.0015 (10)
O2	0.0335 (18)	0.0165 (13)	0.0103 (12)	0.0016 (12)	0.0008 (11)	−0.0001 (10)
Cl1	0.0343 (5)	0.0136 (4)	0.0144 (4)	−0.0010 (4)	−0.0010 (4)	0.0012 (3)
O3	0.0368 (18)	0.0133 (13)	0.0170 (14)	−0.0015 (12)	0.0034 (12)	0.0015 (10)

Geometric parameters (Å, º)

C1—C6	1.354 (5)	C5—C6	1.500 (5)
C1—C2	1.436 (5)	C6—O2	1.320 (4)
C1—H1	0.9500	N1—H1n	0.80 (5)
C2—O1	1.227 (4)	N1—H2n	0.81 (5)
C2—C3	1.532 (4)	N2—H3n	0.93 (4)
C3—N1	1.320 (4)	N2—H4n	0.83 (5)
C3—C4	1.381 (5)	O2—H1o	0.92 (5)
C4—C5	1.406 (5)	O3—H1w	0.88 (5)
C4—H4	0.9500	O3—H2w	1.00 (5)
C5—N2	1.306 (4)
C6—C1—C2	120.6 (3)	N2—C5—C6	116.6 (3)
C6—C1—H1	119.7	C4—C5—C6	120.4 (3)
C2—C1—H1	119.7	O2—C6—C1	126.4 (3)
O1—C2—C1	124.1 (3)	O2—C6—C5	112.6 (3)
O1—C2—C3	118.0 (3)	C1—C6—C5	120.9 (3)
C1—C2—C3	117.9 (3)	C3—N1—H1n	122 (3)
N1—C3—C4	125.2 (3)	C3—N1—H2n	121 (3)
N1—C3—C2	114.2 (3)	H1n—N1—H2n	117 (4)
C4—C3—C2	120.6 (3)	C5—N2—H3n	119 (3)
C3—C4—C5	119.6 (3)	C5—N2—H4n	120 (3)
C3—C4—H4	120.2	H3n—N2—H4n	121 (4)
C5—C4—H4	120.2	C6—O2—H1o	114 (3)
N2—C5—C4	123.0 (3)	H1w—O3—H2w	102 (4)
C6—C1—C2—O1	176.9 (4)	C3—C4—C5—N2	178.6 (4)
C6—C1—C2—C3	−2.2 (5)	C3—C4—C5—C6	−1.3 (6)
O1—C2—C3—N1	2.4 (5)	C2—C1—C6—O2	−178.8 (4)
C1—C2—C3—N1	−178.5 (3)	C2—C1—C6—C5	0.7 (6)
O1—C2—C3—C4	−177.1 (4)	N2—C5—C6—O2	0.8 (5)
C1—C2—C3—C4	2.0 (5)	C4—C5—C6—O2	−179.3 (3)
N1—C3—C4—C5	−179.7 (4)	N2—C5—C6—C1	−178.8 (4)
C2—C3—C4—C5	−0.3 (5)	C4—C5—C6—C1	1.1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2n···O1	0.81 (5)	2.33 (5)	2.653 (4)	105 (4)
N2—H4n···O2	0.84 (4)	2.23 (5)	2.595 (4)	107 (4)
N1—H1n···Cl1	0.80 (5)	2.45 (5)	3.238 (3)	169 (4)
N1—H2n···O3^i	0.81 (5)	2.25 (5)	3.011 (4)	156 (4)
N2—H3n···Cl1^ii	0.93 (4)	2.22 (4)	3.149 (3)	177 (4)
N2—H4n···Cl1^iii	0.83 (5)	2.44 (5)	3.231 (3)	158 (4)
O2—H1o···O3	0.92 (5)	1.65 (5)	2.548 (4)	165 (4)
O3—H1w···O1^iv	0.88 (5)	1.98 (5)	2.801 (4)	154 (4)
O3—H2w···Cl1^v	1.00 (5)	2.11 (5)	3.116 (3)	176 (4)

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