Two rhod­amine derivatives: 9-[2-(ethoxycarbonyl)phenyl]-3,6-bis(ethyl­amino)-2,7-di­methyl­xanthyl­ium chloride monohydrate and 3,6-di­amino-9-[2-(methoxy­carbonyl)­phenyl]xanthyl­ium chloride trihydrate

The title compounds, C₂₈H₃₁N₂O₃⁺·Cl⁻·H₂O (common name rhod­amine-6g), (I), and C₂₁H₁₇N₂O₃⁺·Cl⁻·3H₂O (common name rhod­amine-123), (II), both have planar xanthene skeletons with a formal +1 charge on the amino N atoms delocalized through the π-electron system so that the N—Csp² bond distances indicate significant double-bond character. The substituted planar phenyl groups make angles of 63.29 (8) and 87.96 (11)° with the xanthene planes in (I) and (II), respectively. In both mol­ecules, the carbonyl bond vectors point toward the xanthene rings. The ethyl­amine groups in (I) are oriented similarly with their CH₂–CH₃ bond vectors pointing nearly perpendicular to the xanthene plane. The chloride ions and water mol­ecules are disordered in both structures. In (I), the chloride ion and water mol­ecule are disordered between two sites. One water and chloride alternately occupy the same site with occupancy factors of 0.5. The other 0.5-chloride and 0.5-water occupy two distinct positions separated by 0.747 (8) Å. In (II), the chloride ion is disordered between three sites and one of the waters is disordered about two other sites. Both crystal structures are stabilized by hydrogen bonds involving the chloride ions, amino groups and water mol­ecules, as well as by π–π stacking between xanthene planes.

S1. Comment

Rhodamine derivatives are lipophilic cationic dyes that have found wide use in tunable lasers and other electro-optical devices (Wittman et al., 1992; Johnson & McGrane, 1993). Our interest in these compounds, however, is in their use and development as potential anticancer agents. Rhodamine-123 has been shown to be selectively taken up by mitochondria of tumor cells (Summerhayes et al., 1982) and to suppress the growth of rat prostate tumor cells (Arcadi, 1998). These compounds are also substrates for P-glycoprotein, a membrane-bound protein that expels cytotoxic drugs from cells making them resistant to chemotherapy (Eytan et al., 1997). The rhodamine molecules' interactions with the different cellular components are dependent on the three-dimensional stereochemistries of both ligands and receptors. The two rhodamine structures are presented here to provide accurate three-dimensional data that may contribute to elucidating the stereochemical bases of their biological activity. \sch

The conformations of (I) and (II) are shown in the displacement ellipsoid plot in Figure 1. The fourteen atoms of the xanthene rings define planes with r.m.s. deviations of the fitted atoms from the planes equal to 0.048 Å for (I) and 0.015 Å for (II). The dihedral angles between the xanthene planes and substituent phenyl ring planes are 63.29 (8) and 87.96 (11)° in (I) and (II), respectively. These compare with values that range from 76.2 to 88.1° for reported structures of metal complexes of rhodamine-6 g (Wang et al., 1997; Liu et al., 1998) and a value of 78.6° for an iodide hydrate of rhodamine-6 g (Fun et al., 1997). The ethylamine groups in (I) have similar orientations with C2—N5—C23—C24 and C10—N16—C27—C28 torsion angles of 84.0 (5) and -76.7 (5)°, respectively. The C17—C18—C29—O30 torsion angle [35.3 (4)°] in (I) and the C17—C18—C23—O24 torsion angle [-2.8 (6)°] in (II) places the phenylcarbonyl groups pointing toward the xanthene rings. This contrasts with the opposite conformation for the phenylcarbonyl group found in the rhodamine-Cu complex (Liu et al., 1998) and in the iodide hydrate (Fun et al., 1997). Delocalization of the positive charge between the N atoms is indicated by the C2—N15 and C10—N16 distances, which show significant double-bond character. In (I) the C2—N15 and C10—N16 bond distances are 1.324 (3) and 1.339 (4) Å, respectively, and in (II) they are 1.343 (5) and 1.341 (5) Å. The short C2—N15 distance observed in (I) is also significantly shorter than equivalent partial double-bond distances found in the other rhodamine derivatives referenced above.

In (I) both amino N atoms are involved in hydrogen bonds to disordered chlorine and water O atoms (Table 1). The disorder is unique in that 0.5 chlorine (Cl1) and 0.5 oxygen (O1W) share the same position. This position is hydrogen bonded to N16. The other 0.5 chlorine and 0.5 water oxygen started out sharing a common second position but converged to two distinct sites (O2w, Cl2) during refinement. The site assigned to 0.5 water (O2w) makes contacts of 2.13 (1) Å and 2.798 (8) Å to center of symmetry related atoms O2wⁱ and Cl2ⁱ [symmetry code: (i) 1 - x, -y, 1 - z], respectively. The site occupied by Cl1 or O1W makes contacts of 2.814 (6) Å with Cl2ⁱⁱ and 3.276 (7) Å with O2Wⁱⁱ [symmetry code: (ii) x, 1 + y, 1 + z]. Because of the possible short Cl1—Cl2ⁱⁱ and O2W—O2Wⁱ contacts, it is proposed that when N16 is hydrogen bonded to Cl1, N15 is hydrogen bonded to O2W and the center of symmetry related Rhodamine-6 g would have N16ⁱ hydrogen bonded to O1Wⁱ and N15ⁱ hydrogen bonded to Cl2ⁱ. An equally probable opposite arrangement would occur in other unit cells, i.e., N16 hydrogen bonded to O1W, N15 hydrogen bonded to Cl2, N16ⁱ hydrogen bonded to Cl1ⁱ and N15ⁱ hydrogen bonded to O2Wⁱ. In this way the charge balance is maintained and all contacts between disordered sites are of the water oxygen-chloride ion hydrogen-bonded type. In addition, the average of the two possible arrangements of the disorded atoms taken over all unit cells preserves the centrosymmetric distribution of atoms.

In (II), the chloride ion is disordered about one major site and two minor sites. The major site (occupancy factor = 0.68) is hydrogen bonded to N15 and one of the minor sites is hydrogen bonded to a water molecule. N15 is also hydrogen bonded to a disordered water oxygen (occupancy 1/2). N16 is hydrogen bonded to two water molecules and a symmetry-related water is hydrogen bonded to the phenylcarbonyl oxygen (see Table 2).

The crystal lattices in these structures are also stabilized by π-π stacking interactions of their xanthene rings. The perpendicular separations between their planes are 3.457 (4) Å in (I) and 3.445 (5) Å in (II).

Related literature

For related literature, see: Arcadi (1998); Eytan et al. (1997); Fun et al. (1997); Johnson & McGrane (1993); Liu et al. (1998); Summerhayes et al. (1982); Wang et al. (1997); Wittman et al. (1992).

S2. Experimental

Compounds (I) and (II) were supplied by Eastman-Kodak Company. Orange crystals of both compounds were obtained by slow evaporation of a methanol, ethanol, water mixture maintained at room temperature. Crystals of (II) were unstable in air and for data collection were sealed in capillary tubes with some mother liquor.

S3. Refinement

Methyl group H positions were located form difference Fourier maps, idealized and refined as riding atoms using SHELXL97 instructions which also allowed for rotation about the C—C bonds. Isotropic displacement parameters for these atoms were assigned to a free variable which was refined. All other rhodamine H atoms were fixed geometrically and treated as riding atoms using SHELXL97 defaults. A second free variable was assigned to the displacement parameters for the amino and aromatic H atoms, a third for methylene H atoms and all were refined isotropically. O1W and O2W H atoms in (II) were positioned based on hydrogen-bond geometry and restrained with SHELXL97 instructions DFIX and DANG [O—H 0.95 (2) and H—H 1.52 (4) Å]. H atoms on the disordered water molecules in (I) and (II) were not located. Occupancy factors for disordered atoms were estimated from electron-density maps and consideration of the refined displacement parameters.

Computing details

For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software. Data reduction: DATRDN Xray76 (Stewart, 1976) for (I); Xray76 (Stewart, 1976) for (II). For both compounds, program(s) used to solve structure: MULTAN80 (Main et al., 1980); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEP-3 (Farrugia, 1997) view of (I) (top) and (II) (bottom) showing 40% probability displacement ellipsoids along with the numbering schemes. Hydrogen bonds to the rhodamine derivatives are represented by dashed bonds.

(I) 9-[2-(ethoxycarbonyl)phenyl]-3,6-bis(ethylamino)- 2,7-dimethylxanthylium chloride monohydrate

Crystal data

C28H31N2O3^+·Cl^−·H2O	Z = 2
Mr = 496.46	F(000) = 528
Triclinic, P1	Dx = 1.243 Mg m^−3
a = 9.1947 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.240 (3) Å	Cell parameters from 25 reflections
c = 13.1995 (13) Å	θ = 8–15°
α = 95.874 (13)°	µ = 0.18 mm^−1
β = 91.525 (10)°	T = 293 K
γ = 102.63 (2)°	Plate, orange
V = 1322.6 (4) Å^3	0.60 × 0.40 × 0.40 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.6°
Graphite monochromator	h = −10→10
θ/2θ scans	k = −13→13
4642 measured reflections	l = 0→15
4642 independent reflections	3 standard reflections every 120 min
3182 reflections with I > 2σ(I)	intensity decay: no decay

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.217	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.116P)^2 + 0.4678P] where P = (Fo^2 + 2Fc^2)/3
4642 reflections	(Δ/σ)max = 0.001
333 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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.

Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

7.5735 (0.0042) x + 4.0918 (0.0061) y - 2.4571 (0.0078) z = 1.3181 (0.0068)

* 0.0411 (0.0024) C1 * 0.0766 (0.0025) C2 * 0.0336 (0.0026) C3 * -0.0222 (0.0025) C4 * -0.0321 (0.0026) C5 * -0.0585 (0.0024) C6 * -0.0265 (0.0026) C7 * 0.0484 (0.0025) C8 * 0.0706 (0.0026) C9 * 0.0335 (0.0024) C10 * -0.0180 (0.0024) C11 * -0.0451 (0.0025) C12 * -0.0790 (0.0019) O13 * -0.0224 (0.0026) C14 0.1521 (0.0033) N15 0.0596 (0.0033) N16 - 0.0247 (0.0036) C17 0.0217 (0.0046) C25 0.1568 (0.0045) C26

Rms deviation of fitted atoms = 0.0477

0.7746 (0.0120) x + 8.4932 (0.0097) y + 6.7195 (0.0147) z = 10.7398 (0.0160)

Angle to previous plane (with approximate e.s.d.) = 63.29 (0.08)

* 0.0076 (0.0019) C17 * -0.0104 (0.0019) C18 * 0.0064 (0.0021) C19 * 0.0005 (0.0023) C20 * -0.0033 (0.0024) C21 * -0.0009 (0.0022) C22 - 0.1062 (0.0048) C29

Rms deviation of fitted atoms = 0.0060

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.2386 (3)	0.3742 (2)	0.8054 (2)	0.0622 (7)
H1	0.2015	0.4214	0.7615	0.087 (3)*
C2	0.2871 (3)	0.2692 (3)	0.7657 (2)	0.0610 (7)
C3	0.3429 (4)	0.1978 (2)	0.8362 (2)	0.0637 (7)
C4	0.3486 (3)	0.2338 (2)	0.9365 (2)	0.0616 (7)
H4	0.3841	0.1861	0.9807	0.087 (3)*
C5	0.3033 (3)	0.3411 (2)	0.9796 (2)	0.0572 (7)
C6	0.3110 (3)	0.3823 (2)	1.08276 (19)	0.0573 (7)
C7	0.2665 (3)	0.4918 (2)	1.1146 (2)	0.0593 (7)
C8	0.2788 (4)	0.5482 (2)	1.2161 (2)	0.0656 (7)
H8	0.3198	0.5113	1.2663	0.087 (3)*
C9	0.2335 (4)	0.6543 (3)	1.2442 (2)	0.0670 (8)
C10	0.1718 (3)	0.7129 (2)	1.1668 (2)	0.0635 (7)
C11	0.1606 (3)	0.6602 (2)	1.0653 (2)	0.0634 (7)
H11	0.1219	0.6974	1.0143	0.087 (3)*
C12	0.2072 (3)	0.5531 (2)	1.0415 (2)	0.0571 (7)
O13	0.1938 (2)	0.50885 (16)	0.94044 (13)	0.0607 (5)
C14	0.2457 (3)	0.4070 (2)	0.9079 (2)	0.0577 (7)
N15	0.2834 (3)	0.2350 (2)	0.66645 (17)	0.0730 (7)
H15	0.3150	0.1700	0.6474	0.087 (3)*
N16	0.1275 (3)	0.8172 (2)	1.1932 (2)	0.0750 (7)
H16	0.1327	0.8439	1.2569	0.087 (3)*
C17	0.3761 (3)	0.3152 (2)	1.15768 (19)	0.0573 (7)
C18	0.2952 (3)	0.2592 (2)	1.23509 (19)	0.0571 (7)
C19	0.3660 (4)	0.2009 (3)	1.3031 (2)	0.0680 (8)
H19	0.3134	0.1658	1.3559	0.087 (3)*
C20	0.5112 (4)	0.1945 (3)	1.2936 (2)	0.0785 (9)
H20	0.5566	0.1542	1.3391	0.087 (3)*
C21	0.5908 (4)	0.2473 (3)	1.2172 (3)	0.0830 (9)
H21	0.6900	0.2429	1.2106	0.087 (3)*
C22	0.5231 (4)	0.3067 (3)	1.1502 (2)	0.0714 (8)
H22	0.5778	0.3422	1.0985	0.087 (3)*
C23	0.2304 (4)	0.2978 (3)	0.5868 (2)	0.0779 (9)
H23A	0.1458	0.3296	0.6103	0.099 (5)*
H23B	0.1963	0.2392	0.5272	0.099 (5)*
C24	0.3475 (5)	0.4011 (4)	0.5571 (3)	0.0983 (12)
H24A	0.3792	0.4608	0.6152	0.126 (4)*
H24B	0.3074	0.4386	0.5039	0.126 (4)*
H24C	0.4313	0.3702	0.5331	0.126 (4)*
C25	0.3906 (5)	0.0828 (3)	0.7967 (2)	0.0859 (10)
H25A	0.4169	0.0428	0.8531	0.126 (4)*
H25B	0.4754	0.1034	0.7558	0.126 (4)*
H25C	0.3101	0.0288	0.7560	0.126 (4)*
C26	0.2502 (5)	0.7098 (3)	1.3529 (3)	0.0870 (10)
H26A	0.2947	0.6599	1.3936	0.126 (4)*
H26B	0.1538	0.7143	1.3771	0.126 (4)*
H26C	0.3128	0.7908	1.3577	0.126 (4)*
C27	0.0711 (4)	0.8882 (3)	1.1212 (3)	0.0836 (10)
H27A	0.0180	0.9435	1.1577	0.099 (5)*
H27B	0.0007	0.8329	1.0724	0.099 (5)*
C28	0.1927 (5)	0.9614 (3)	1.0650 (3)	0.0939 (11)
H28A	0.2630	1.0161	1.1129	0.126 (4)*
H28B	0.1503	1.0081	1.0199	0.126 (4)*
H28C	0.2426	0.9069	1.0260	0.126 (4)*
C29	0.1343 (4)	0.2567 (3)	1.2425 (2)	0.0653 (7)
O30	0.0473 (3)	0.2469 (2)	1.17170 (17)	0.0832 (7)
O31	0.1005 (3)	0.2663 (3)	1.34014 (16)	0.0891 (7)
C32	−0.0565 (4)	0.2560 (5)	1.3622 (3)	0.1059 (13)
H32A	−0.0783	0.2166	1.4237	0.099 (5)*
H32B	−0.1199	0.2070	1.3063	0.099 (5)*
C33	−0.0846 (6)	0.3803 (6)	1.3756 (5)	0.148 (2)
H33A	−0.0194	0.4288	1.4297	0.126 (4)*
H33B	−0.1865	0.3759	1.3923	0.126 (4)*
H33C	−0.0663	0.4175	1.3135	0.126 (4)*
Cl1	0.0737 (2)	0.96327 (16)	1.39878 (15)	0.1320 (7)	0.50
O1W	0.0737 (2)	0.96327 (16)	1.39878 (15)	0.1320 (7)	0.50
Cl2	0.3220 (7)	0.0100 (5)	0.5379 (3)	0.171 (2)	0.50
O2W	0.4004 (7)	0.0273 (8)	0.5229 (4)	0.0667 (15)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.086 (2)	0.0564 (15)	0.0485 (15)	0.0214 (14)	0.0063 (13)	0.0111 (12)
C2	0.0768 (18)	0.0581 (16)	0.0487 (15)	0.0150 (13)	0.0073 (13)	0.0076 (12)
C3	0.090 (2)	0.0539 (15)	0.0510 (15)	0.0224 (14)	0.0103 (14)	0.0074 (12)
C4	0.087 (2)	0.0521 (15)	0.0507 (15)	0.0229 (14)	0.0084 (13)	0.0110 (12)
C5	0.0774 (18)	0.0472 (14)	0.0493 (14)	0.0156 (12)	0.0098 (12)	0.0107 (11)
C6	0.0752 (18)	0.0485 (14)	0.0501 (14)	0.0138 (12)	0.0109 (12)	0.0122 (11)
C7	0.0811 (19)	0.0496 (14)	0.0499 (14)	0.0164 (13)	0.0137 (13)	0.0111 (11)
C8	0.091 (2)	0.0535 (15)	0.0538 (15)	0.0180 (14)	0.0092 (14)	0.0076 (12)
C9	0.088 (2)	0.0549 (16)	0.0604 (17)	0.0200 (14)	0.0194 (15)	0.0067 (13)
C10	0.0756 (19)	0.0474 (14)	0.0688 (18)	0.0150 (13)	0.0203 (14)	0.0057 (12)
C11	0.0798 (19)	0.0505 (15)	0.0648 (17)	0.0218 (13)	0.0145 (14)	0.0113 (13)
C12	0.0704 (17)	0.0509 (14)	0.0513 (15)	0.0140 (12)	0.0124 (12)	0.0081 (11)
O13	0.0844 (13)	0.0518 (10)	0.0515 (10)	0.0247 (9)	0.0100 (9)	0.0093 (8)
C14	0.0745 (18)	0.0473 (14)	0.0541 (15)	0.0162 (12)	0.0120 (12)	0.0108 (11)
N15	0.105 (2)	0.0713 (15)	0.0473 (13)	0.0301 (14)	0.0036 (12)	0.0040 (11)
N16	0.100 (2)	0.0582 (14)	0.0735 (16)	0.0319 (13)	0.0202 (14)	0.0067 (12)
C17	0.0792 (19)	0.0457 (14)	0.0478 (14)	0.0162 (12)	0.0035 (12)	0.0036 (11)
C18	0.0774 (18)	0.0524 (14)	0.0458 (14)	0.0222 (13)	0.0093 (12)	0.0079 (11)
C19	0.101 (2)	0.0629 (17)	0.0482 (15)	0.0312 (16)	0.0083 (14)	0.0132 (12)
C20	0.099 (3)	0.080 (2)	0.0679 (19)	0.0460 (18)	−0.0069 (17)	0.0081 (16)
C21	0.080 (2)	0.090 (2)	0.085 (2)	0.0338 (18)	−0.0023 (18)	0.0062 (18)
C22	0.077 (2)	0.0705 (19)	0.0671 (18)	0.0152 (15)	0.0063 (15)	0.0100 (15)
C23	0.100 (2)	0.087 (2)	0.0483 (16)	0.0276 (18)	−0.0041 (15)	0.0034 (15)
C24	0.117 (3)	0.105 (3)	0.078 (2)	0.026 (2)	0.009 (2)	0.030 (2)
C25	0.137 (3)	0.074 (2)	0.0574 (18)	0.048 (2)	0.0109 (18)	0.0048 (15)
C26	0.130 (3)	0.072 (2)	0.0660 (19)	0.039 (2)	0.0154 (19)	−0.0009 (15)
C27	0.100 (2)	0.0586 (18)	0.102 (3)	0.0374 (17)	0.016 (2)	0.0072 (17)
C28	0.122 (3)	0.0595 (19)	0.104 (3)	0.0217 (19)	0.006 (2)	0.0211 (18)
C29	0.085 (2)	0.0645 (17)	0.0511 (16)	0.0221 (15)	0.0059 (15)	0.0151 (13)
O30	0.0801 (15)	0.1048 (17)	0.0637 (13)	0.0176 (12)	−0.0010 (11)	0.0129 (12)
O31	0.0853 (16)	0.130 (2)	0.0604 (13)	0.0386 (14)	0.0127 (11)	0.0149 (12)
C32	0.087 (3)	0.159 (4)	0.082 (3)	0.046 (3)	0.015 (2)	0.020 (3)
C33	0.119 (4)	0.173 (5)	0.153 (5)	0.067 (4)	−0.001 (3)	−0.047 (4)
Cl1	0.1636 (17)	0.1009 (12)	0.1281 (14)	0.0226 (11)	0.0547 (12)	−0.0003 (10)
O1W	0.1636 (17)	0.1009 (12)	0.1281 (14)	0.0226 (11)	0.0547 (12)	−0.0003 (10)
Cl2	0.284 (6)	0.134 (3)	0.110 (3)	0.093 (4)	0.005 (3)	−0.012 (2)
O2W	0.088 (3)	0.101 (4)	0.0245 (19)	0.051 (3)	0.006 (2)	0.004 (2)

Geometric parameters (Å, º)

C1—C14	1.361 (4)	O31—C32	1.462 (4)
C1—C2	1.409 (4)	C32—C33	1.470 (7)
C2—N15	1.324 (3)	Cl2—O2W	0.747 (8)
C2—C3	1.442 (4)	C1—H1	0.9300
C3—C4	1.341 (4)	C4—H4	0.9300
C3—C25	1.502 (4)	C8—H8	0.9300
C4—C5	1.429 (4)	C11—H11	0.9300
C5—C6	1.387 (4)	N15—H15	0.8600
C5—C14	1.419 (4)	N16—H16	0.8600
C6—C7	1.408 (4)	C19—H19	0.9300
C6—C17	1.491 (4)	C20—H20	0.9300
C7—C12	1.406 (4)	C21—H21	0.9300
C7—C8	1.413 (4)	C22—H22	0.9300
C8—C9	1.366 (4)	C23—H23A	0.9700
C9—C10	1.439 (4)	C23—H23B	0.9700
C9—C26	1.495 (4)	C24—H24A	0.9600
C10—N16	1.339 (4)	C24—H24B	0.9600
C10—C11	1.400 (4)	C24—H24C	0.9600
C11—C12	1.373 (4)	C25—H25A	0.9600
C12—O13	1.368 (3)	C25—H25B	0.9600
O13—C14	1.369 (3)	C25—H25C	0.9600
N15—C23	1.455 (4)	C26—H26A	0.9600
N16—C27	1.457 (4)	C26—H26B	0.9600
C17—C22	1.381 (4)	C26—H26C	0.9600
C17—C18	1.400 (4)	C27—H27A	0.9700
C18—C19	1.392 (4)	C27—H27B	0.9700
C18—C29	1.479 (4)	C28—H28A	0.9600
C19—C20	1.361 (4)	C28—H28B	0.9600
C20—C21	1.370 (5)	C28—H28C	0.9600
C21—C22	1.374 (4)	C32—H32A	0.9700
C23—C24	1.493 (5)	C32—H32B	0.9700
C27—C28	1.498 (5)	C33—H33A	0.9600
C29—O30	1.195 (3)	C33—H33B	0.9600
C29—O31	1.333 (3)	C33—H33C	0.9600
C14—C1—C2	120.3 (2)	C10—C11—H11	120.2
N15—C2—C1	122.1 (2)	C2—N15—H15	117.2
N15—C2—C3	119.6 (3)	C23—N15—H15	117.2
C1—C2—C3	118.3 (2)	C10—N16—H16	117.9
C4—C3—C2	119.3 (2)	C27—N16—H16	117.9
C4—C3—C25	120.9 (3)	C20—C19—H19	119.5
C2—C3—C25	119.8 (2)	C18—C19—H19	119.5
C3—C4—C5	124.0 (2)	C19—C20—H20	119.9
C6—C5—C14	119.8 (2)	C21—C20—H20	119.9
C6—C5—C4	125.4 (2)	C20—C21—H21	120.2
C14—C5—C4	114.8 (2)	C22—C21—H21	120.2
C5—C6—C7	119.4 (2)	C21—C22—H22	119.1
C5—C6—C17	119.7 (2)	C17—C22—H22	119.1
C7—C6—C17	120.8 (2)	N15—C23—H23A	109.0
C12—C7—C6	119.1 (2)	C24—C23—H23A	109.0
C12—C7—C8	115.9 (2)	N15—C23—H23B	109.0
C6—C7—C8	125.0 (2)	C24—C23—H23B	109.0
C9—C8—C7	123.3 (3)	H23A—C23—H23B	107.8
C8—C9—C10	118.7 (3)	C23—C24—H24A	109.5
C8—C9—C26	120.7 (3)	C23—C24—H24B	109.5
C10—C9—C26	120.5 (3)	H24A—C24—H24B	109.5
N16—C10—C11	121.5 (3)	C23—C24—H24C	109.5
N16—C10—C9	119.3 (3)	H24A—C24—H24C	109.5
C11—C10—C9	119.2 (2)	H24B—C24—H24C	109.5
C12—C11—C10	119.6 (3)	C3—C25—H25A	109.5
O13—C12—C11	115.7 (2)	C3—C25—H25B	109.5
O13—C12—C7	121.1 (2)	H25A—C25—H25B	109.5
C11—C12—C7	123.2 (3)	C3—C25—H25C	109.5
C12—O13—C14	120.2 (2)	H25A—C25—H25C	109.5
C1—C14—O13	116.6 (2)	H25B—C25—H25C	109.5
C1—C14—C5	123.2 (2)	C9—C26—H26A	109.5
O13—C14—C5	120.2 (2)	C9—C26—H26B	109.5
C2—N15—C23	125.6 (3)	H26A—C26—H26B	109.5
C10—N16—C27	124.3 (3)	C9—C26—H26C	109.5
C22—C17—C18	118.1 (2)	H26A—C26—H26C	109.5
C22—C17—C6	118.6 (2)	H26B—C26—H26C	109.5
C18—C17—C6	123.3 (3)	N16—C27—H27A	109.1
C19—C18—C17	119.4 (3)	C28—C27—H27A	109.1
C19—C18—C29	119.8 (2)	N16—C27—H27B	109.1
C17—C18—C29	120.8 (2)	C28—C27—H27B	109.1
C20—C19—C18	121.0 (3)	H27A—C27—H27B	107.8
C19—C20—C21	120.2 (3)	C27—C28—H28A	109.5
C20—C21—C22	119.6 (3)	C27—C28—H28B	109.5
C21—C22—C17	121.8 (3)	H28A—C28—H28B	109.5
N15—C23—C24	112.8 (3)	C27—C28—H28C	109.5
N16—C27—C28	112.6 (3)	H28A—C28—H28C	109.5
O30—C29—O31	124.9 (3)	H28B—C28—H28C	109.5
O30—C29—C18	125.2 (3)	O31—C32—H32A	110.1
O31—C29—C18	109.9 (2)	C33—C32—H32A	110.1
C29—O31—C32	117.5 (3)	O31—C32—H32B	110.1
O31—C32—C33	108.1 (4)	C33—C32—H32B	110.1
C14—C1—H1	119.9	H32A—C32—H32B	108.4
C2—C1—H1	119.9	C32—C33—H33A	109.5
C3—C4—H4	118.0	C32—C33—H33B	109.5
C5—C4—H4	118.0	H33A—C33—H33B	109.5
C9—C8—H8	118.3	C32—C33—H33C	109.5
C7—C8—H8	118.3	H33A—C33—H33C	109.5
C12—C11—H11	120.2	H33B—C33—H33C	109.5
C14—C1—C2—N15	−179.3 (3)	C2—C1—C14—O13	−178.8 (2)
C14—C1—C2—C3	0.5 (4)	C2—C1—C14—C5	1.2 (5)
N15—C2—C3—C4	179.0 (3)	C12—O13—C14—C1	−175.2 (2)
C1—C2—C3—C4	−0.8 (4)	C12—O13—C14—C5	4.9 (4)
N15—C2—C3—C25	−2.3 (5)	C6—C5—C14—C1	178.1 (3)
C1—C2—C3—C25	177.9 (3)	C4—C5—C14—C1	−2.3 (4)
C2—C3—C4—C5	−0.5 (5)	C6—C5—C14—O13	−1.9 (4)
C25—C3—C4—C5	−179.2 (3)	C4—C5—C14—O13	177.6 (2)
C3—C4—C5—C6	−178.4 (3)	C1—C2—N15—C23	−0.2 (5)
C3—C4—C5—C14	2.0 (4)	C3—C2—N15—C23	−180.0 (3)
C14—C5—C6—C7	−2.3 (4)	C11—C10—N16—C27	−3.0 (5)
C4—C5—C6—C7	178.2 (3)	C9—C10—N16—C27	176.5 (3)
C14—C5—C6—C17	−178.1 (2)	C5—C6—C17—C22	61.2 (4)
C4—C5—C6—C17	2.4 (4)	C7—C6—C17—C22	−114.5 (3)
C5—C6—C7—C12	3.6 (4)	C5—C6—C17—C18	−118.3 (3)
C17—C6—C7—C12	179.3 (2)	C7—C6—C17—C18	66.0 (4)
C5—C6—C7—C8	−175.2 (3)	C22—C17—C18—C19	2.0 (4)
C17—C6—C7—C8	0.5 (4)	C6—C17—C18—C19	−178.5 (2)
C12—C7—C8—C9	1.5 (4)	C22—C17—C18—C29	−175.3 (3)
C6—C7—C8—C9	−179.7 (3)	C6—C17—C18—C29	4.1 (4)
C7—C8—C9—C10	−0.8 (5)	C17—C18—C19—C20	−1.9 (4)
C7—C8—C9—C26	−179.7 (3)	C29—C18—C19—C20	175.4 (3)
C8—C9—C10—N16	−179.8 (3)	C18—C19—C20—C21	0.9 (5)
C26—C9—C10—N16	−0.9 (5)	C19—C20—C21—C22	0.0 (5)
C8—C9—C10—C11	−0.3 (4)	C20—C21—C22—C17	0.1 (5)
C26—C9—C10—C11	178.6 (3)	C18—C17—C22—C21	−1.1 (4)
N16—C10—C11—C12	−179.9 (3)	C6—C17—C22—C21	179.4 (3)
C9—C10—C11—C12	0.6 (4)	C2—N15—C23—C24	84.6 (4)
C10—C11—C12—O13	−179.3 (2)	C10—N16—C27—C28	−76.5 (4)
C10—C11—C12—C7	0.1 (4)	C19—C18—C29—O30	−142.0 (3)
C6—C7—C12—O13	−0.7 (4)	C17—C18—C29—O30	35.3 (4)
C8—C7—C12—O13	178.2 (2)	C19—C18—C29—O31	37.6 (4)
C6—C7—C12—C11	179.9 (3)	C17—C18—C29—O31	−145.1 (3)
C8—C7—C12—C11	−1.2 (4)	O30—C29—O31—C32	4.2 (5)
C11—C12—O13—C14	175.9 (2)	C18—C29—O31—C32	−175.4 (3)
C7—C12—O13—C14	−3.5 (4)	C29—O31—C32—C33	−93.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15···Cl2	0.86	2.20	2.992 (5)	152
N15—H15···O2W	0.86	2.45	3.247 (7)	154
N16—H16···Cl1	0.86	2.34	3.133 (3)	154
N16—H16···O1W	0.86	2.34	3.133 (3)	154

(II) 9-[2-(methoxycarbonyl)phenyl]-3,6-diamio- xanthylium chloride trihydrate

Crystal data

C21H17N2O3^+·Cl^−·3H2O	F(000) = 1808
Mr = 434.88	Dx = 1.286 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.5624 (14) Å	Cell parameters from 21 reflections
b = 21.468 (3) Å	θ = 6–14°
c = 15.427 (3) Å	µ = 0.21 mm^−1
β = 95.409 (12)°	T = 293 K
V = 4471.5 (11) Å^3	Plate, orange
Z = 8	0.4 × 0.3 × 0.2 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.8°
Graphite monochromator	h = 0→16
θ/2θ scans	k = 0→25
3924 measured reflections	l = −18→18
3924 independent reflections	3 standard reflections every 180 min
2256 reflections with I > 2σ(I)	intensity decay: <1%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.072	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.268	w = 1/[σ^2(Fo^2) + (0.1558P)^2 + 2.1805P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.005
3924 reflections	Δρmax = 0.41 e Å^−3
314 parameters	Δρmin = −0.20 e Å^−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0030 (8)

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.

Mean plane data from final SHELX refinement run

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

13.4409 (0.0028) x + 0.9635 (0.0190) y + 0.4870 (0.0072) z = 2.1230 (0.0063)

* -0.0130 (0.0031) C1 * 0.0099 (0.0031) C2 * 0.0154 (0.0031) C3 * 0.0141 (0.0031) C4 * -0.0019 (0.0031) C5 * 0.0015 (0.0030) C6 * -0.0135 (0.0032) C7 * -0.0174 (0.0032) C8 * 0.0016 (0.0034) C9 * 0.0367 (0.0031) C10 * 0.0094 (0.0030) C11 * -0.0177 (0.0031) C12 * -0.0117 (0.0024) O13 * -0.0135 (0.0031) C14 0.0197 (0.0043) N15 0.1017 (0.0040) N16 0.1625 (0.0046) C17

Rms deviation of fitted atoms = 0.0153

- 1.9736 (0.0246) x - 5.4817 (0.0387) y + 14.8917 (0.0081) z = 5.5157 (0.0067)

Angle to previous plane (with approximate e.s.d.) = 87.96 (0.11)

* 0.0040 (0.0029) C17 * -0.0053 (0.0028) C18 * -0.0001 (0.0032) C19 * 0.0070 (0.0036) C20 * -0.0083 (0.0036) C21 * 0.0028 (0.0033) C22 0.0049 (0.0063) C23

Rms deviation of fitted atoms = 0.0053

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.1218 (3)	0.31515 (17)	0.3483 (3)	0.0639 (10)
H1	0.1171	0.3561	0.3669	0.084 (3)*
C2	0.1276 (3)	0.30185 (17)	0.2600 (3)	0.0647 (10)
C3	0.1335 (3)	0.23964 (18)	0.2334 (2)	0.0678 (10)
H3	0.1366	0.2306	0.1748	0.084 (3)*
C4	0.1346 (3)	0.19253 (17)	0.2918 (2)	0.0640 (10)
H4	0.1390	0.1517	0.2724	0.084 (3)*
C5	0.1293 (2)	0.20394 (15)	0.3822 (2)	0.0558 (9)
C6	0.1306 (2)	0.15796 (16)	0.4465 (2)	0.0582 (9)
C7	0.1250 (3)	0.17561 (16)	0.5331 (2)	0.0574 (9)
C8	0.1252 (3)	0.13368 (18)	0.6037 (3)	0.0685 (10)
H8	0.1275	0.0911	0.5931	0.084 (3)*
C9	0.1221 (3)	0.1543 (2)	0.6872 (3)	0.0750 (11)
H9	0.1218	0.1254	0.7322	0.084 (3)*
C10	0.1195 (3)	0.2176 (2)	0.7063 (2)	0.0678 (10)
C11	0.1168 (3)	0.26110 (19)	0.6380 (2)	0.0661 (10)
H11	0.1134	0.3036	0.6490	0.084 (3)*
C12	0.1194 (2)	0.23922 (16)	0.5548 (2)	0.0570 (9)
O13	0.11894 (18)	0.28359 (11)	0.49163 (15)	0.0632 (7)
C14	0.1231 (2)	0.26735 (15)	0.4064 (2)	0.0554 (9)
N15	0.1271 (3)	0.34833 (17)	0.2017 (2)	0.0835 (11)
H15A	0.1232	0.3864	0.2185	0.084 (3)*
H15B	0.1307	0.3400	0.1475	0.084 (3)*
N16	0.1199 (3)	0.2381 (2)	0.7884 (2)	0.0861 (11)
H16A	0.1218	0.2119	0.8308	0.084 (3)*
H16B	0.1182	0.2774	0.7988	0.084 (3)*
C17	0.1481 (3)	0.09132 (16)	0.4239 (2)	0.0619 (9)
C18	0.0741 (3)	0.04864 (16)	0.3978 (2)	0.0614 (9)
C19	0.0999 (3)	−0.01293 (18)	0.3789 (3)	0.0791 (12)
H19	0.0506	−0.0417	0.3617	0.084 (3)*
C20	0.1967 (4)	−0.0308 (2)	0.3856 (3)	0.0917 (14)
H20	0.2131	−0.0718	0.3737	0.084 (3)*
C21	0.2697 (4)	0.0112 (2)	0.4097 (3)	0.0945 (15)
H21	0.3357	−0.0010	0.4127	0.084 (3)*
C22	0.2458 (3)	0.07223 (19)	0.4297 (3)	0.0813 (12)
H22	0.2959	0.1004	0.4472	0.084 (3)*
C23	−0.0308 (3)	0.06757 (17)	0.3915 (2)	0.0653 (10)
O24	−0.0592 (2)	0.11815 (13)	0.4107 (2)	0.0883 (9)
O25	−0.0921 (2)	0.02381 (13)	0.3605 (2)	0.0969 (11)
C26	−0.1973 (4)	0.0383 (3)	0.3526 (4)	0.1085 (17)
H26A	−0.2341	0.0029	0.3291	0.202 (19)*
H26B	−0.2098	0.0733	0.3146	0.202 (19)*
H26C	−0.2175	0.0481	0.4091	0.202 (19)*
Cl	0.3640 (2)	0.17706 (16)	−0.00454 (19)	0.1557 (11)	0.68
Cl2A	0.4815 (9)	0.0827 (5)	0.0290 (10)	0.142 (4)	0.16
Cl2B	0.5172 (9)	0.0593 (6)	−0.0342 (11)	0.151 (5)	0.16
O1W	0.3501 (4)	0.3135 (2)	0.0367 (3)	0.1255 (14)
H1WA	0.397 (4)	0.341 (2)	0.015 (4)	0.181 (16)*
H1WB	0.367 (5)	0.2715 (13)	0.019 (4)	0.181 (16)*
O2W	0.4059 (5)	0.1202 (3)	0.1879 (6)	0.199 (3)
H2WA	0.435 (6)	0.103 (4)	0.136 (3)	0.181 (16)*
H2WB	0.437 (5)	0.099 (3)	0.237 (2)	0.181 (16)*
O3WB	0.0691 (7)	0.4775 (4)	0.3592 (11)	0.168 (5)	0.50
O3W	0.0561 (11)	0.4702 (4)	0.2896 (6)	0.151 (5)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.060 (2)	0.055 (2)	0.076 (3)	0.0002 (16)	0.0073 (18)	0.0024 (18)
C2	0.056 (2)	0.067 (2)	0.071 (2)	−0.0044 (17)	0.0049 (17)	0.0131 (19)
C3	0.065 (2)	0.079 (3)	0.060 (2)	−0.0022 (19)	0.0048 (17)	−0.005 (2)
C4	0.066 (2)	0.059 (2)	0.067 (2)	−0.0053 (17)	0.0059 (18)	−0.0077 (18)
C5	0.0536 (19)	0.0498 (19)	0.064 (2)	−0.0009 (15)	0.0065 (15)	−0.0017 (16)
C6	0.051 (2)	0.053 (2)	0.069 (2)	−0.0028 (15)	0.0012 (16)	−0.0052 (17)
C7	0.054 (2)	0.055 (2)	0.062 (2)	−0.0042 (15)	0.0044 (16)	−0.0007 (17)
C8	0.067 (2)	0.061 (2)	0.076 (3)	−0.0076 (18)	0.0026 (19)	0.0047 (19)
C9	0.072 (3)	0.081 (3)	0.071 (3)	−0.010 (2)	0.004 (2)	0.014 (2)
C10	0.056 (2)	0.091 (3)	0.057 (2)	−0.0093 (19)	0.0086 (16)	−0.001 (2)
C11	0.063 (2)	0.073 (2)	0.063 (2)	−0.0085 (18)	0.0087 (17)	−0.0128 (19)
C12	0.0490 (19)	0.058 (2)	0.065 (2)	−0.0051 (15)	0.0070 (15)	−0.0003 (17)
O13	0.0738 (16)	0.0525 (14)	0.0642 (16)	−0.0019 (11)	0.0110 (12)	−0.0041 (11)
C14	0.0506 (19)	0.055 (2)	0.061 (2)	−0.0025 (15)	0.0065 (15)	−0.0031 (16)
N15	0.092 (3)	0.078 (2)	0.080 (2)	−0.0059 (19)	0.0067 (19)	0.0135 (19)
N16	0.082 (2)	0.113 (3)	0.064 (2)	−0.009 (2)	0.0118 (17)	−0.005 (2)
C17	0.067 (2)	0.0504 (19)	0.068 (2)	0.0027 (17)	0.0032 (17)	−0.0010 (17)
C18	0.066 (2)	0.050 (2)	0.067 (2)	−0.0016 (16)	0.0025 (17)	−0.0046 (16)
C19	0.088 (3)	0.055 (2)	0.093 (3)	−0.005 (2)	0.002 (2)	−0.012 (2)
C20	0.091 (3)	0.063 (3)	0.118 (4)	0.017 (2)	−0.007 (3)	−0.021 (2)
C21	0.077 (3)	0.078 (3)	0.126 (4)	0.022 (2)	−0.002 (3)	−0.019 (3)
C22	0.066 (3)	0.066 (2)	0.110 (3)	0.004 (2)	−0.003 (2)	−0.013 (2)
C23	0.072 (2)	0.054 (2)	0.070 (2)	−0.0067 (19)	0.0030 (18)	−0.0003 (18)
O24	0.0678 (18)	0.0681 (18)	0.129 (3)	−0.0003 (14)	0.0097 (16)	−0.0209 (17)
O25	0.0701 (19)	0.0706 (18)	0.146 (3)	−0.0122 (15)	−0.0080 (18)	−0.0146 (18)
C26	0.076 (3)	0.101 (4)	0.145 (5)	−0.023 (3)	−0.008 (3)	0.005 (3)
Cl	0.147 (2)	0.181 (3)	0.141 (2)	−0.021 (2)	0.0258 (17)	−0.0309 (19)
Cl2A	0.118 (8)	0.107 (8)	0.198 (13)	0.007 (6)	−0.004 (8)	−0.011 (8)
Cl2B	0.115 (8)	0.107 (8)	0.222 (15)	−0.011 (7)	−0.037 (9)	0.044 (9)
O1W	0.140 (4)	0.122 (3)	0.116 (3)	−0.020 (3)	0.022 (2)	0.032 (3)
O2W	0.167 (5)	0.123 (4)	0.291 (8)	−0.036 (4)	−0.052 (5)	0.018 (4)
O3WB	0.107 (6)	0.067 (5)	0.322 (17)	0.013 (4)	−0.020 (10)	−0.012 (9)
O3W	0.276 (15)	0.043 (4)	0.135 (8)	−0.015 (5)	0.031 (7)	−0.002 (4)

Geometric parameters (Å, º)

C1—C14	1.362 (5)	C23—O25	1.315 (4)
C1—C2	1.401 (5)	O25—C26	1.454 (6)
C2—N15	1.343 (5)	Cl2A—Cl2B	1.236 (19)
C2—C3	1.402 (5)	Cl2B—O3WB^i	2.01 (2)
C3—C4	1.354 (5)	O3WB—O3W	1.083 (15)
C4—C5	1.425 (5)	O3WB—Cl2B^ii	2.01 (2)
C5—C6	1.398 (5)	C1—H1	0.9300
C5—C14	1.416 (5)	C3—H3	0.9300
C6—C7	1.397 (5)	C4—H4	0.9300
C6—C17	1.497 (5)	C8—H8	0.9300
C7—C12	1.410 (5)	C9—H9	0.9300
C7—C8	1.413 (5)	C11—H11	0.9300
C8—C9	1.367 (6)	N15—H15A	0.8600
C9—C10	1.392 (6)	N15—H15B	0.8600
C10—N16	1.341 (5)	N16—H16A	0.8600
C10—C11	1.406 (5)	N16—H16B	0.8600
C11—C12	1.369 (5)	C19—H19	0.9300
C12—O13	1.363 (4)	C20—H20	0.9300
O13—C14	1.367 (4)	C21—H21	0.9300
C17—C22	1.381 (5)	C22—H22	0.9300
C17—C18	1.391 (5)	C26—H26A	0.9600
C18—C19	1.405 (5)	C26—H26B	0.9600
C18—C23	1.473 (5)	C26—H26C	0.9600
C19—C20	1.363 (6)	O1W—H1WA	0.95 (2)
C20—C21	1.364 (6)	O1W—H1WB	0.98 (2)
C21—C22	1.392 (6)	O2W—H2WA	0.99 (2)
C23—O24	1.199 (4)	O2W—H2WB	0.95 (2)
C14—C1—C2	119.2 (3)	O24—C23—C18	124.4 (3)
N15—C2—C1	120.2 (4)	O25—C23—C18	113.6 (3)
N15—C2—C3	120.6 (4)	C23—O25—C26	117.4 (4)
C1—C2—C3	119.3 (3)	Cl2A—Cl2B—O3WB^i	177.0 (12)
C4—C3—C2	121.0 (4)	O3W—O3WB—Cl2B^ii	135.8 (12)
C3—C4—C5	121.6 (3)	C14—C1—H1	120.4
C6—C5—C14	119.3 (3)	C2—C1—H1	120.4
C6—C5—C4	125.1 (3)	C4—C3—H3	119.5
C14—C5—C4	115.7 (3)	C2—C3—H3	119.5
C7—C6—C5	119.2 (3)	C3—C4—H4	119.2
C7—C6—C17	120.4 (3)	C5—C4—H4	119.2
C5—C6—C17	120.1 (3)	C9—C8—H8	119.2
C6—C7—C12	119.9 (3)	C7—C8—H8	119.2
C6—C7—C8	124.6 (3)	C8—C9—H9	119.4
C12—C7—C8	115.5 (3)	C10—C9—H9	119.4
C9—C8—C7	121.5 (4)	C12—C11—H11	120.9
C8—C9—C10	121.2 (4)	C10—C11—H11	120.9
N16—C10—C9	121.5 (4)	C2—N15—H15A	120.0
N16—C10—C11	119.2 (4)	C2—N15—H15B	120.0
C9—C10—C11	119.3 (4)	H15A—N15—H15B	120.0
C12—C11—C10	118.2 (4)	C10—N16—H16A	120.0
O13—C12—C11	115.6 (3)	C10—N16—H16B	120.0
O13—C12—C7	120.2 (3)	H16A—N16—H16B	120.0
C11—C12—C7	124.2 (3)	C20—C19—H19	119.8
C12—O13—C14	120.8 (3)	C18—C19—H19	119.8
C1—C14—O13	116.2 (3)	C19—C20—H20	119.9
C1—C14—C5	123.3 (3)	C21—C20—H20	119.9
O13—C14—C5	120.5 (3)	C20—C21—H21	119.8
C22—C17—C18	119.0 (3)	C22—C21—H21	119.8
C22—C17—C6	116.2 (3)	C17—C22—H22	119.8
C18—C17—C6	124.8 (3)	C21—C22—H22	119.8
C17—C18—C19	119.5 (4)	O25—C26—H26A	109.5
C17—C18—C23	120.2 (3)	O25—C26—H26B	109.5
C19—C18—C23	120.3 (3)	H26A—C26—H26B	109.5
C20—C19—C18	120.4 (4)	O25—C26—H26C	109.5
C19—C20—C21	120.2 (4)	H26A—C26—H26C	109.5
C20—C21—C22	120.3 (4)	H26B—C26—H26C	109.5
C17—C22—C21	120.5 (4)	H1WA—O1W—H1WB	107 (4)
O24—C23—O25	122.0 (4)	H2WA—O2W—H2WB	107 (4)
C14—C1—C2—N15	−179.6 (3)	C2—C1—C14—O13	178.8 (3)
C14—C1—C2—C3	0.8 (5)	C2—C1—C14—C5	−0.5 (5)
N15—C2—C3—C4	179.6 (3)	C12—O13—C14—C1	179.7 (3)
C1—C2—C3—C4	−0.7 (5)	C12—O13—C14—C5	−0.9 (5)
C2—C3—C4—C5	0.4 (6)	C6—C5—C14—C1	179.8 (3)
C3—C4—C5—C6	−179.7 (3)	C4—C5—C14—C1	0.2 (5)
C3—C4—C5—C14	−0.1 (5)	C6—C5—C14—O13	0.5 (5)
C14—C5—C6—C7	0.3 (5)	C4—C5—C14—O13	−179.1 (3)
C4—C5—C6—C7	179.9 (3)	C7—C6—C17—C22	−85.0 (5)
C14—C5—C6—C17	−173.4 (3)	C5—C6—C17—C22	88.7 (4)
C4—C5—C6—C17	6.2 (5)	C7—C6—C17—C18	95.3 (4)
C5—C6—C7—C12	−0.7 (5)	C5—C6—C17—C18	−91.1 (5)
C17—C6—C7—C12	173.0 (3)	C22—C17—C18—C19	0.7 (6)
C5—C6—C7—C8	179.7 (3)	C6—C17—C18—C19	−179.5 (4)
C17—C6—C7—C8	−6.6 (5)	C22—C17—C18—C23	179.6 (4)
C6—C7—C8—C9	178.3 (4)	C6—C17—C18—C23	−0.7 (6)
C12—C7—C8—C9	−1.3 (5)	C17—C18—C19—C20	−0.3 (6)
C7—C8—C9—C10	−0.5 (6)	C23—C18—C19—C20	−179.2 (4)
C8—C9—C10—N16	−177.7 (4)	C18—C19—C20—C21	−0.8 (7)
C8—C9—C10—C11	2.0 (6)	C19—C20—C21—C22	1.6 (8)
N16—C10—C11—C12	178.1 (3)	C18—C17—C22—C21	0.0 (7)
C9—C10—C11—C12	−1.6 (5)	C6—C17—C22—C21	−179.7 (4)
C10—C11—C12—O13	−178.5 (3)	C20—C21—C22—C17	−1.2 (8)
C10—C11—C12—C7	−0.3 (5)	C17—C18—C23—O24	−2.8 (6)
C6—C7—C12—O13	0.2 (5)	C19—C18—C23—O24	176.1 (4)
C8—C7—C12—O13	179.9 (3)	C17—C18—C23—O25	175.7 (3)
C6—C7—C12—C11	−177.9 (3)	C19—C18—C23—O25	−5.5 (5)
C8—C7—C12—C11	1.7 (5)	O24—C23—O25—C26	−2.0 (6)
C11—C12—O13—C14	178.9 (3)	C18—C23—O25—C26	179.5 (4)
C7—C12—O13—C14	0.6 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15A···O3W	0.86	2.34	3.140 (10)	156
N15—H15B···Cl^iii	0.86	2.24	3.103 (5)	177
N16—H16A···O1W^iv	0.86	2.12	2.909 (5)	153
N16—H16B···O2W^iv	0.86	2.23	3.086 (7)	172
O1W—H1WA···O24^i	0.95 (2)	1.97 (5)	2.810 (5)	146 (6)
O1W—H1WB···Cl	0.98 (2)	2.06 (2)	3.008 (5)	163 (5)
O2W—H2WA···Cl2A	0.99 (2)	1.88 (3)	2.861 (18)	170 (7)
O2W—H2WB···O2W^v	0.95 (2)	2.38 (6)	3.043 (13)	127 (5)

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