3,7-Bis­(di­methyl­amino)­pheno­thia­zin-5-ium nitrate dihydrate

Kavitha, S.J.; Raj, M.M.; Panchanatheswaran, K.; Lynch, D.E.

doi:10.1107/S1600536804017222

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 60| Part 8| August 2004| Pages o1367-o1369

https://doi.org/10.1107/S1600536804017222

3,7-Bis(dimethylamino)phenothiazin-5-ium nitrate dihydrate

Savaridasson Jose Kavitha,^a Mani Mohan Raj,^a Krishnaswamy Panchanatheswaran ^a and Daniel E. Lynch ^b ^*

^aDepartment of Chemistry, Bharathidasan University, Tiruchirappalli 24, India, and ^bSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, England
^*Correspondence e-mail: apx106@coventry.ac.uk

(Received 24 June 2004; accepted 14 July 2004; online 24 July 2004)

The reaction of 3,7-bis(dimethylamino)phenothiazin-5-ium chloride pentahydrate (methylene blue) with silver nitrate in a 1:2 molar ratio in water yielded the title compound, C₁₆H₁₈N₃S⁺·NO₃⁻·2H₂O, as one of the products. The cationic dye molecules are planar and stacked in an antiparallel fashion, exhibiting π–π associations at a distance of 3.7040 (18) Å. The nitrate anion and the two water molecules are involved in a hydrogen-bonding network that also includes the phenothiazinium N atom.

Comment

Methylene blue (MB) is an important cationic dye with various colorimetric uses (Tuite & Kelly, 1993 ). It is marketed as its chloride salt. Other forms, such as the cyanide and nitrate [the title compound, (I)] salts exhibit antimethemoglobinemic, antiseptic and disinfectant properties (The Merck Index, 2001 ). The Cambridge Structural Database (Version 5.25, April 2004 update; Allen, 2002 ) includes four MB crystal structures containing the phenothiazinium moiety, as chloride pentahydrate (Marr et al., 1973 ), triiodide (Endres et al., 1977 ), thiocyanate (Kahn-Harari et al., 1973 ), urate hexahydrate (Sours et al., 2002 ) and bis(maleonitriledithiolato)cuprate(II) (Snaathorst et al., 1981 ) salts. In each case, the bond distances in the MB cations indicate a resonance structure in which the positive charge is delocalized over the two dimethylamine N atoms, with conjugation through the phenothiazinium N atom, although the MB cation is sometimes represented as aromatic with a positive S atom. The addition of AgNO₃ to aqueous MB chloride solution does not precipitate silver chloride, yet the IR spectrum of the product shows features very different from that of the starting materials. Further investigations are currently underway to determine the nature of the resultant soluble silver product but here we report the structure of the precipitated product.

The asymmetric unit of (I) consists of an MB cation, a nitrate anion and two water molecules (Fig. 1). The MB cation displays a typical MB resonance structure, as evident from the pronounced shortening of the C1—C2, C4—C12, C8—C9 and C6—C13 bonds compared with other C—C bonds (Table 1). The two C—S bonds are equal in length, indicating that conjugation occurs via N10. The MB cation is thus planar and the cations are stacked in an antiparallel fashion, exhibiting π–π associations at a distance of 3.7040 (18) Å. In contrast to MB chloride, which crystallizes with five lattice water molecules, the degree of hydration of the MB nitrate is lower. This difference may be due in part to the hydrogen-bonding network and the fact that more hydrogen-bond acceptor atoms are available on the nitrate ion than for a chloride anion. Hydrogen-bonding associations are listed in Table 2 and indicate that all of the strong hydrogen-bond donor atoms are utilized, although this is not the case for the strong hydrogen-bond acceptor atoms. Only one hydrogen-bond acceptor atom from the phenothiazinium moiety, N10, is involved in the hydrogen-bond network, along with two nitrate O atoms and one water O atom. The nitrate ion and the water molecules form a one-dimensional hydrogen-bonded chain in the a cell direction (Fig. 2). There are close contacts between the S atom and the nitrate N atom [3.369 (4) Å] and also between atom O3 and both N3 [2.906 (4) Å; symmetry code: (1 − x, −y, 2 − z)] and C32 [2.962 (4) Å; symmetry code: (1 − x, −y, 2 − z)], although for the latter there is no appropriate H atom to construct a C—H⋯O association. These close contacts for O3 may explain why there is no strong hydrogen-bonding interaction with this atom. Two unassigned areas of electron density, 0.64 and 0.59 e Å⁻³, exist approximately equidistant, 1.94 and 1.96 Å, respectively, from atom S5, which may be the cause of the higher than expected R values.

Figure 1
Molecular structure and atom-numbering scheme for (I

). Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Packing diagram for (I

). For clarity, the non-essential H atoms have been omitted. [Symmetry codes: (i) −1 + x, y, z; (ii) −x, −y + 1, −z + 2.]

Experimental

Methylene blue (1 mmol) was dissolved with silver nitrate (2 mmol) in water (10 ml). Crystals of the title compound were obtained by the slow evaporation of this reaction mixture.

Crystal data

C₁₆H₁₈N₃S⁺·NO₃⁻·2H₂O
M_r = 382.44
Triclinic, $[P\overline 1]$
a = 7.6985 (3) Å
b = 10.9638 (3) Å
c = 11.3244 (4) Å
α = 87.081 (2)°
β = 76.032 (2)°
γ = 73.524 (2)°
V = 889.33 (5) Å³
Z = 2
D_x = 1.428 Mg m⁻³
Mo Kα radiation
Cell parameters from 12 187 reflections
θ = 2.9–27.5°
μ = 0.22 mm⁻¹
T = 120 (2) K
Prism, red
0.42 × 0.36 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.836, T_max = 0.952
17 489 measured reflections
4077 independent reflections
3225 reflections with I > 2σ(I)
R_int = 0.068
θ_max = 27.6°
h = −9 → 9
k = −14 → 14
l = −14 → 14

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.206
S = 1.13
4077 reflections
255 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0821P)² + 1.7607P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected bond lengths (Å)

C1—C2	1.359 (4)
C1—C11	1.430 (4)
C2—C3	1.439 (4)
C3—N3	1.335 (4)
C3—C4	1.416 (4)
C4—C12	1.373 (4)
S5—C13	1.728 (3)
S5—C12	1.728 (3)
C6—C13	1.376 (4)
C6—C7	1.415 (4)
C7—N7	1.340 (4)
C7—C8	1.436 (4)
C8—C9	1.361 (4)
C9—C14	1.424 (4)
N10—C11	1.335 (4)
N10—C14	1.344 (4)
C11—C12	1.438 (4)
C13—C14	1.432 (4)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11W⋯O2ⁱ	0.88 (5)	1.91 (5)	2.789 (4)	174 (4)
O1W—H12W⋯N10ⁱⁱ	0.84 (5)	2.10 (5)	2.929 (4)	172 (4)
O2W—H21W⋯O1	0.81 (6)	2.14 (6)	2.886 (5)	154 (5)
O2W—H22W⋯O1W	0.75 (5)	2.05 (5)	2.792 (4)	171 (5)
Symmetry codes: (i) x-1,y,z; (ii) -x,1-y,2-z.

All H atoms, except the water H atoms, were included in the refinement at calculated positions, in the riding-model approximation, with C—H distances of 0.95 (aromatic H atoms) and 0.98 Å (CH₃ H atoms). The isotropic displacement parameters were set equal to 1.25U_eq of the carrier atom. The water H atoms were located in difference syntheses and both positional and displacement parameters were refined.

Data collection: DENZO (Otwinowski & Minor, 1997 ) and COLLECT (Hooft, 1998 ); cell refinement: DENZO and COLLECT; data reduction: DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536804017222/ww6237sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804017222/ww6237Isup2.hkl

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.

3,7-Bis(dimethylamino)phenothiazin-5-ium nitrate dihydrate top

Crystal data top

C₁₆H₁₈N₃S⁺·NO₃⁻·2H₂O	Z = 2
M_r = 382.44	F(000) = 404
Triclinic, P1	D_x = 1.428 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6985 (3) Å	Cell parameters from 12187 reflections
b = 10.9638 (3) Å	θ = 2.9–27.5°
c = 11.3244 (4) Å	µ = 0.22 mm⁻¹
α = 87.081 (2)°	T = 120 K
β = 76.032 (2)°	Prism, red
γ = 73.524 (2)°	0.42 × 0.36 × 0.20 mm
V = 889.33 (5) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	4077 independent reflections
Radiation source: Nonius FR591 rotating anode	3225 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.6°, θ_min = 3.0°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −14→14
T_min = 0.836, T_max = 0.952	l = −14→14
17489 measured reflections

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.206	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ²(F_o²) + (0.0821P)² + 1.7607P] where P = (F_o² + 2F_c²)/3
4077 reflections	(Δ/σ)_max < 0.001
255 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3039 (4)	0.4163 (3)	1.2264 (3)	0.0253 (6)
H1	0.2291	0.4793	1.2864	0.032*
C2	0.4150 (4)	0.3079 (3)	1.2620 (3)	0.0256 (6)
H2	0.4170	0.2967	1.3455	0.032*
C3	0.5295 (4)	0.2101 (3)	1.1740 (3)	0.0244 (6)
N3	0.6397 (4)	0.1028 (3)	1.2068 (2)	0.0272 (6)
C31	0.6448 (5)	0.0733 (3)	1.3341 (3)	0.0345 (8)
H311	0.6506	0.1483	1.3749	0.043*
H312	0.7550	0.0025	1.3368	0.043*
H313	0.5321	0.0495	1.3756	0.043*
C32	0.7498 (5)	0.0020 (3)	1.1173 (3)	0.0356 (8)
H321	0.6679	−0.0213	1.0738	0.045*
H322	0.8106	−0.0726	1.1590	0.045*
H323	0.8448	0.0322	1.0592	0.045*
C4	0.5233 (4)	0.2303 (3)	1.0504 (3)	0.0245 (6)
H4	0.5982	0.1670	0.9908	0.031*
S5	0.40954 (11)	0.35433 (7)	0.86311 (7)	0.0265 (2)
C6	0.2292 (4)	0.5433 (3)	0.7434 (3)	0.0241 (6)
H6	0.2934	0.4895	0.6741	0.030*
C7	0.1059 (4)	0.6632 (3)	0.7289 (3)	0.0239 (6)
N7	0.0768 (4)	0.6987 (3)	0.6188 (2)	0.0278 (6)
C71	0.1732 (6)	0.6157 (3)	0.5125 (3)	0.0372 (8)
H711	0.3070	0.6078	0.4951	0.046*
H712	0.1244	0.6520	0.4422	0.046*
H713	0.1531	0.5315	0.5287	0.046*
C72	−0.0522 (5)	0.8200 (3)	0.5977 (3)	0.0343 (8)
H721	−0.1634	0.8390	0.6653	0.043*
H722	−0.0887	0.8143	0.5215	0.043*
H723	0.0091	0.8879	0.5923	0.043*
C8	0.0147 (4)	0.7430 (3)	0.8354 (3)	0.0258 (7)
H8	−0.0662	0.8250	0.8282	0.032*
C9	0.0430 (5)	0.7022 (3)	0.9465 (3)	0.0263 (7)
H9	−0.0202	0.7566	1.0155	0.033*
N10	0.1816 (4)	0.5488 (2)	1.0768 (2)	0.0232 (5)
C11	0.2953 (4)	0.4392 (3)	1.1023 (3)	0.0226 (6)
C12	0.4104 (4)	0.3402 (3)	1.0157 (3)	0.0231 (6)
C13	0.2576 (4)	0.5031 (3)	0.8561 (3)	0.0216 (6)
C14	0.1637 (4)	0.5808 (3)	0.9632 (3)	0.0223 (6)
N1	0.7431 (4)	0.0916 (3)	0.7386 (3)	0.0341 (7)
O1	0.7351 (4)	0.1430 (3)	0.6394 (3)	0.0543 (8)
O2	0.8749 (4)	0.0886 (3)	0.7856 (3)	0.0531 (8)
O3	0.6206 (5)	0.0440 (3)	0.7940 (3)	0.0568 (9)
O1W	0.0499 (4)	0.2807 (3)	0.7190 (2)	0.0354 (6)
H11W	−0.012 (6)	0.223 (5)	0.738 (4)	0.043 (12)*
H12W	−0.022 (7)	0.334 (5)	0.772 (5)	0.049 (13)*
O2W	0.3966 (5)	0.2779 (3)	0.5684 (2)	0.0390 (6)
H21W	0.471 (8)	0.225 (5)	0.597 (5)	0.058 (16)*
H22W	0.306 (7)	0.271 (5)	0.606 (5)	0.044 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0292 (16)	0.0240 (15)	0.0211 (14)	−0.0060 (13)	−0.0038 (12)	−0.0036 (11)
C2	0.0275 (16)	0.0290 (16)	0.0206 (14)	−0.0081 (13)	−0.0058 (12)	0.0002 (12)
C3	0.0210 (15)	0.0255 (15)	0.0258 (15)	−0.0064 (12)	−0.0042 (12)	0.0019 (12)
N3	0.0273 (14)	0.0271 (14)	0.0242 (13)	−0.0021 (11)	−0.0071 (11)	0.0013 (10)
C31	0.0397 (19)	0.0335 (18)	0.0248 (16)	−0.0006 (15)	−0.0098 (14)	0.0040 (13)
C32	0.0344 (19)	0.0325 (18)	0.0309 (17)	0.0059 (14)	−0.0084 (14)	−0.0015 (14)
C4	0.0225 (15)	0.0238 (15)	0.0235 (15)	−0.0022 (12)	−0.0028 (12)	−0.0022 (11)
S5	0.0305 (4)	0.0231 (4)	0.0199 (4)	0.0013 (3)	−0.0048 (3)	−0.0022 (3)
C6	0.0260 (15)	0.0231 (15)	0.0222 (14)	−0.0063 (12)	−0.0041 (12)	−0.0016 (11)
C7	0.0243 (15)	0.0243 (15)	0.0246 (15)	−0.0089 (12)	−0.0064 (12)	0.0022 (12)
N7	0.0320 (15)	0.0231 (13)	0.0250 (13)	−0.0012 (11)	−0.0080 (11)	0.0003 (10)
C71	0.054 (2)	0.0296 (17)	0.0205 (15)	0.0014 (16)	−0.0101 (15)	−0.0008 (13)
C72	0.0382 (19)	0.0294 (17)	0.0303 (17)	−0.0006 (14)	−0.0100 (14)	0.0032 (13)
C8	0.0260 (16)	0.0210 (15)	0.0286 (16)	−0.0036 (12)	−0.0065 (12)	0.0001 (12)
C9	0.0283 (16)	0.0228 (15)	0.0255 (15)	−0.0047 (12)	−0.0040 (12)	−0.0049 (12)
N10	0.0253 (13)	0.0215 (12)	0.0224 (12)	−0.0059 (10)	−0.0052 (10)	−0.0023 (10)
C11	0.0229 (15)	0.0217 (14)	0.0234 (14)	−0.0072 (12)	−0.0040 (11)	−0.0015 (11)
C12	0.0233 (15)	0.0249 (15)	0.0212 (14)	−0.0088 (12)	−0.0028 (11)	−0.0013 (11)
C13	0.0221 (14)	0.0200 (14)	0.0223 (14)	−0.0054 (11)	−0.0049 (11)	−0.0010 (11)
C14	0.0231 (15)	0.0211 (14)	0.0228 (14)	−0.0062 (12)	−0.0053 (11)	−0.0006 (11)
N1	0.0309 (15)	0.0285 (15)	0.0371 (16)	−0.0040 (12)	−0.0014 (13)	−0.0032 (12)
O1	0.0538 (18)	0.0563 (19)	0.0371 (15)	0.0022 (15)	−0.0042 (13)	0.0103 (13)
O2	0.0501 (18)	0.0491 (18)	0.064 (2)	−0.0109 (14)	−0.0253 (15)	0.0024 (15)
O3	0.0553 (19)	0.0553 (19)	0.0579 (19)	−0.0301 (16)	0.0095 (15)	−0.0096 (15)
O1W	0.0364 (14)	0.0331 (14)	0.0320 (13)	−0.0022 (12)	−0.0066 (11)	−0.0059 (11)
O2W	0.0415 (17)	0.0415 (16)	0.0281 (13)	−0.0048 (13)	−0.0054 (13)	0.0017 (11)

Geometric parameters (Å, º) top

C1—C2	1.359 (4)	N7—C71	1.458 (4)
C1—C11	1.430 (4)	N7—C72	1.464 (4)
C1—H1	0.95	C71—H711	0.98
C2—C3	1.439 (4)	C71—H712	0.98
C2—H2	0.95	C71—H713	0.98
C3—N3	1.335 (4)	C72—H721	0.98
C3—C4	1.416 (4)	C72—H722	0.98
N3—C32	1.461 (4)	C72—H723	0.98
N3—C31	1.469 (4)	C8—C9	1.361 (4)
C31—H311	0.98	C8—H8	0.95
C31—H312	0.98	C9—C14	1.424 (4)
C31—H313	0.98	C9—H9	0.95
C32—H321	0.98	N10—C11	1.335 (4)
C32—H322	0.98	N10—C14	1.344 (4)
C32—H323	0.98	C11—C12	1.438 (4)
C4—C12	1.373 (4)	C13—C14	1.432 (4)
C4—H4	0.95	N1—O3	1.231 (4)
S5—C13	1.728 (3)	N1—O1	1.238 (4)
S5—C12	1.728 (3)	N1—O2	1.246 (4)
C6—C13	1.376 (4)	O1W—H11W	0.88 (5)
C6—C7	1.415 (4)	O1W—H12W	0.84 (5)
C6—H6	0.95	O2W—H21W	0.81 (6)
C7—N7	1.340 (4)	O2W—H22W	0.75 (5)
C7—C8	1.436 (4)

C2—C1—C11	122.5 (3)	C71—H711—109.5
C2—C1—H1	118.7	C71—H712—109.5
C11—C1—H1	118.7	C71—H712—109.5
C1—C2—C3	120.3 (3)	C71—H713—109.5
C1—C2—H2	119.8	C71—H713—109.5
C3—C2—H2	119.8	C71—H713—109.5
N3—C3—C4	120.3 (3)	C72—H721—109.5
N3—C3—C2	121.4 (3)	C72—H722—109.5
C4—C3—C2	118.3 (3)	C72—H722—109.5
C3—N3—C32	120.9 (3)	C72—H723—109.5
C3—N3—C31	122.9 (3)	C72—H723—109.5
C32—N3—C31	115.9 (3)	C72—H723—109.5
N3—C31—H311	109.5	C8—C7—120.6 (3)
N3—C31—H312	109.5	C8—H8—119.7
H311—C31—H312	109.5	C8—H8—119.7
N3—C31—H313	109.5	C9—C14—122.4 (3)
H311—C31—H313	109.5	C9—H9—118.8
H312—C31—H313	109.5	C9—H9—118.8
N3—C32—H321	109.5	N10—C14—123.0 (3)
N3—C32—H322	109.5	C11—C1—117.9 (3)
H321—C32—H322	109.5	C11—C12—125.8 (3)
N3—C32—H323	109.5	C11—C12—116.3 (3)
H321—C32—H323	109.5	C12—C11—121.7 (3)
H322—C32—H323	109.5	C12—S5—117.2 (2)
C12—C4—C3	120.8 (3)	C12—S5—121.0 (2)
C12—C4—H4	119.6	C13—C14—121.4 (3)
C3—C4—H4	119.6	C13—S5—117.1 (2)
C13—S5—C12	103.28 (15)	C13—S5—121.4 (2)
C13—C6—C7	121.2 (3)	C14—C9—118.0 (3)
C13—C6—H6	119.4	C14—C13—125.4 (3)
C7—C6—H6	119.4	C14—C13—116.6 (3)
N7—C7—C6	120.0 (3)	N1—O1—121.1 (4)
N7—C7—C8	122.2 (3)	N1—O2—118.4 (3)
C6—C7—C8	117.8 (3)	N1—O2—120.5 (3)
C7—N7—C71	120.7 (3)	O1W—H12W—95 (4)
C7—N7—C72	122.9 (3)	O2W—H22W—102 (5)
N7—C72—116.4 (3)

C11—C1—C2—C3	−0.3 (5)	C2—C1—C11—C12	0.4 (5)
C1—C2—C3—N3	−180.0 (3)	C3—C4—C12—C11	0.4 (5)
C1—C2—C3—C4	0.2 (5)	C3—C4—C12—S5	−178.8 (2)
C4—C3—N3—C32	−2.6 (5)	N10—C11—C12—C4	−180.0 (3)
C2—C3—N3—C32	177.6 (3)	C1—C11—C12—C4	−0.5 (4)
C4—C3—N3—C31	−176.6 (3)	N10—C11—C12—S5	−0.8 (4)
C2—C3—N3—C31	3.5 (5)	C1—C11—C12—S5	178.7 (2)
N3—C3—C4—C12	179.9 (3)	C13—S5—C12—C4	−178.9 (2)
C2—C3—C4—C12	−0.2 (5)	C13—S5—C12—C11	1.9 (3)
C13—C6—C7—N7	−178.2 (3)	C7—C6—C13—C14	0.1 (5)
C13—C6—C7—C8	1.4 (5)	C7—C6—C13—S5	179.4 (2)
C6—C7—N7—C71	−1.0 (5)	C12—S5—C13—C6	179.2 (2)
C8—C7—N7—C71	179.4 (3)	C12—S5—C13—C14	−1.5 (3)
C6—C7—N7—C72	178.5 (3)	C11—N10—C14—C9	−177.9 (3)
C8—C7—N7—C72	−1.2 (5)	C11—N10—C14—C13	1.6 (5)
N7—C7—C8—C9	177.9 (3)	C8—C9—C14—N10	−179.6 (3)
C6—C7—C8—C9	−1.8 (5)	C8—C9—C14—C13	0.9 (5)
C7—C8—C9—C14	0.6 (5)	C6—C13—C14—N10	179.3 (3)
C14—N10—C11—C1	179.3 (3)	S5—C13—C14—N10	0.0 (4)
C14—N10—C11—C12	−1.2 (5)	C6—C13—C14—C9	−1.2 (4)
C2—C1—C11—N10	180.0 (3)	S5—C13—C14—C9	179.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11W···O2ⁱ	0.88 (5)	1.91 (5)	2.789 (4)	174 (4)
O1W—H12W···N10ⁱⁱ	0.84 (5)	2.10 (5)	2.929 (4)	172 (4)
O2W—H21W···O1	0.81 (6)	2.14 (6)	2.886 (5)	154 (5)
O2W—H22W···O1W	0.75 (5)	2.05 (5)	2.792 (4)	171 (5)

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

Acknowledgements

The authors thank the EPSRC National Crystallography Service (Southampton, England).

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