Thia­mine tetra­phenyl­borate monohydrate: a two-dimensional hydrogen-bonded network with (4,4)-topology

The title compound, 3-[(4-amino-2-methyl­pyrimidin-5-yl)­meth­yl]-5-(2-hydroxy­eth­yl)-4-methyl­thia­zolium tetra­phenyl­borate monohydrate, C₁₂H₁₇N₄OS⁺·C₂₄H₂₀B⁻·H₂O, is a salt in which the thiamine cations are linked by hydrogen bonds into a two-dimensional network having (4,4)-topology. The stacked sheets form channels, which are occupied by the anions; the cations and anions are linked by C—H...π(arene) hydrogen bonds.

S1. Comment

The construction of hydrogen-bonded networks is one of the goals of organic crystal engineering (Etter, 1991; Desiraju, 1995). In the development of new materials for storage, sensors and catalysis, one target is a host framework that traps anionic or neutral guests (Videnova-Adrabińska, 1996; Beatty, 2003; Biradha, 2003). Thiamine (vitamin B₁), as a naturally occurring cationic host, provides multiple sites that serve as donors or acceptors to form various supramolecular arrays by hydrogen bonding (Aoki et al., 1993; Hu et al., 2001b). Structural studies have revealed that the packing features in thiamine–anion systems are closely related to the nature of the anions and the conformation of the thiamine moiety.

It was found that, for example, ClO₄⁻ (Kozioł et al., 1987; Aoki et al., 1988), BF₄⁻ (Aoki et al., 1990; Hu et al., 2001a) and PF₆⁻ (Aoki et al., 1988) anions facilitate the formation of a one-dimensional helical chain, while a molecular column consisting of stacks of alternating cyclic thiamine dimers and anions is commonly observed in the PtCl₄²⁻ (Cramer et al., 1988), PtCl₆²⁻ (Aoki et al., 1993) and Pt(NO₂)₄²⁻ (Hu et al., 2001b) salts. In these structures, the thiamine molecule adopts the usual F conformation (torsion angles ϕ_T = C10—C7—N1—C1 ≈ 0° and ϕ_P = N1—C7—C10—C9 ≈ ± 90 ° for the F conformation; refer to Fig. 1 for atom labels) (Pletcher et al., 1977). A sole example of a two-dimensional network occurs in the structure of HET·HgI₄·H₂O [HET is 2-(α-hydroxyethyl)thiamine; Hu et al., 2003), where the substituent at atom C1 imposes the S conformation on the HET molecule (ϕ_T ≈ ±100° and ϕ_P ≈ ±150° for the S conformation). In this regard, we were interested as to whether a two-dimensional network can be constructed when thiamine is in the F conformation and how the anion influences the supramolecular assembly. We report here an example, thiaminH.[B(phenyl)₄]·H₂O, (I), where the thiamine molecules in the F conformation form a two-dimensional cationic network in the presence of B(phenyl)₄⁻ anions, rather than helical chains as in the BF₄⁻ salt. The tetraphenylborate anions are linked to the network by electrostatic forces and by O—H..π(arene) and C—H..π(arene) hydrogen bonds.

In the structure of (I), thiamine occurs as a monovalent cation with N2 unprotonated. The dimensions of the pyrimidine moiety are in agreement with those found in N2-unprotonated thiamine; the C9—N4 bond length and the C8—N2—C11 bond angle are 1.338 (2) Å and 116.10 (16)° in (I), and 1.337 (4) Å and 115.0 (3)° in thiamine(BF₄)·H₂O (Aoki et al., 1990), but the bond length decreases [1.318 (5) Å] and the angle increases [119.9 (4)°] in thiamine(BF₄)₂, which has an N2-protonated pyrimidine ring (Hu et al., 2001a). The thiamine molecule adopts an F conformation in terms of the torsion angles ϕ_T = 11.9 (2)° and ϕ_P = 79.4 (2)°, which are comparable to the BF₄⁻ salts. Each thiamine molecule coordinates with a water molecule by N4—H···O2—H···O1 hydrogen bonds and an O2–thiazolium-ring close contact [Fig. 1; the closest contact distance O2···C4 = 3.132 (2) Å]. The other H atom of the water molecule forms an O—H..π(arene) hydrogen bonds (Table 1).

As shown in Table 1, a two-dimensional supramolecular network is constructed using two types of hydrogen bond. First, the base-pairing dimer is formed through a self-complementary pyrimidine–pyrimidine interaction involving a pair of N—H···N hydrogen bonds (Fig. 2), which is a supramolecular synthon frequently observed in thiamine structures. Second, an O—H···N hydrogen bond is utilized in the assembly of the dimers to complete the two-dimensional sheet parallel to (100) having (4,4) topology (Batten & Robson, 1998) (Fig. 3). The sheet undulates with a wavelength of ca 10.7 Å and wave height of ca 11.5 Å. The thiazolium rings are located in the ridges and troughs of the wave, and the pyrimidine base-pairs were located in between the ridges and troughs of the wave. Interestingly, the puckered sheets, which are perpendicular to the a axis, are eclipsed such that channels exist along the [−101] direction. The tetraphenylborate anions occupy the channels and are linked to the cationic network via O—H···π(arene) and C—H···π(arene) hydrogen bonds. The C—H···π interaction is typical of host–guest interactions found in thiamine compounds with the F conformation (Aoki et al., 1988).

It was shown in our previous study (Hu et al., 2003) that there are three types of base-paring dimers of thiamine depending on the molecular conformation, that is, U form and Z form for the dimers in the F conformation and linear form for the dimer in the S conformation (Fig. 4). The two-dimensional hydrogen-bonded motif has been observed for the linear-form dimer in the structure of HET·HgI₄·H₂O and for the Z-form dimer in (I), but not for the U form. The difference between HET·HgI₄·H₂O and (I) is that an N—H···O1 hydrogen bond is used to propagate the network in the former whereas an O—H···N hydrogen bond is used in the latter. Both types of hydrogen bond involve hydroxy O1 atoms. We note that the C3-hydroxyethyl side chain is trans with respect to the base-pair plane in both the Z form and the linear form but it is cis in the U form. Thus the formation of the two-dimensional network is closely related to the conformation of the base-paring dimers of thiamine.

Moreover, the ability of anions in accepting hydrogen bonds is also a factor that affects the formation of the two-dimensional network. When the anion is strongly electronegative, it competes for the acceptor sites on thiamine, and thus precludes self-assembly of thiamine molecules in multi-dimensional arrays. In contrast, the existence of weakly electronegative anions, such as HgI₄²⁻ and B(phenyl)₄⁻, allows facile associations between thiamine molecules leading to two-dimensional structures.

In summary, we have synthesized the first cationic two-dimensional network of thiamine in the F conformation utilizing pyrimidine base-pairs as the network nodes. The nature of the anion and molecular conformation of the cation play important roles in determining the self-assembly of thiamine cations.

S2. Experimental

Equimolar quantities of thiamine chloride hydrochloride and sodium tetraphenylborate (purchased from Aldrich) were dissolved in water and acetone, respectively. The solutions were mixed, and the mixture was set aside to afford crystals of (I) suitable for single-crystal X-ray diffraction. Analysis found: C 72.2, H 6.0, N 9.1%; C₃₆H₃₉BN₄O₂S requires: C 71.8, H 6.5, N 9.3%.

S3. Refinement

H atoms of the hydroxy group of the C5-hydroxyethyl side chain and the water molecule were located from difference Fourier maps and were fixed in the refinements. All other H atoms were treated as riding atoms, with C—H distances of 0.98 (CH₃), 0.99 (CH₂) or 0.95 Å (CH), and N—H distances of 0.88 Å, All H atoms were assigned isotropic displacement parameters the same as the U_eq value of the non-H atoms to which they are bonded.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Broken lines denote hydrogen bonds.
	Fig. 2. A view of the base-pairing dimer in (I). H atoms, except those taking part in hydrogen bonds, have been omitted for clarity. [Symmetry code: (i) 1 − x, 1 − y, 1 − z.]
	Fig. 3. A stereoview of the two-dimensional network consisting of hydrogen-bonded thiamine cations, showing the intermolecular connections (dashed lines) and cavities. The anions and H atoms have been omitted.
	Fig. 4. Base-pairing dimers of thiamine derivatives in different forms. (a) The U form and (b) the Z form for thiamine in the F conformation, and (c) the linear form for HET in the S conformation (N atoms: right hatched; other atoms: circles).

3-[(4-amino-2-methylpyrimidin-5-yl)methyl]-5-(2-hydroxyethyl)-4-methylthiazolium tetraphenylborate monohydrate

Crystal data

C24H20B^−·C12H17N4OS^+·H2O	F(000) = 1280
Mr = 602.58	Dx = 1.259 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5012 reflections
a = 14.6464 (6) Å	θ = 2.4–26.0°
b = 10.6667 (4) Å	µ = 0.14 mm^−1
c = 20.4459 (8) Å	T = 187 K
β = 95.523 (1)°	Tablet, colourless
V = 3179.4 (2) Å^3	0.30 × 0.24 × 0.12 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	6251 independent reflections
Radiation source: fine-focus sealed tube	5011 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 26.0°, θmin = 1.4°
Absorption correction: multi-scan (SAINT; Bruker, 2003)	h = −17→18
Tmin = 0.962, Tmax = 0.986	k = −13→13
17468 measured reflections	l = −19→25

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 1.2737P] where P = (Fo^2 + 2Fc^2)/3
6251 reflections	(Δ/σ)max = 0.004
399 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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

	x	y	z	Uiso*/Ueq
S1	0.29451 (3)	−0.03968 (5)	0.46066 (2)	0.03145 (14)
N1	0.22862 (10)	0.17438 (14)	0.46865 (7)	0.0249 (3)
N2	0.32011 (11)	0.42606 (15)	0.65068 (8)	0.0332 (4)
N3	0.42585 (11)	0.46379 (15)	0.57161 (7)	0.0310 (4)
N4	0.40371 (11)	0.38414 (16)	0.46710 (7)	0.0333 (4)
H4A	0.4582	0.4134	0.4604	0.033*
H4B	0.3707	0.3439	0.4355	0.033*
O1	0.26526 (11)	0.08000 (13)	0.27484 (6)	0.0415 (4)
H1	0.2851	0.0862	0.2353	0.042*
O2	0.31515 (11)	0.29804 (14)	0.34436 (7)	0.0445 (4)
H2A	0.3027	0.2311	0.3214	0.044*
H2B	0.3051	0.3636	0.3183	0.044*
C1	0.28942 (12)	0.09837 (17)	0.49929 (9)	0.0279 (4)
H1A	0.3261	0.1193	0.5387	0.028*
C2	0.18078 (12)	0.12337 (17)	0.41241 (9)	0.0268 (4)
C3	0.21091 (12)	0.00691 (17)	0.40012 (9)	0.0272 (4)
C4	0.10609 (14)	0.1953 (2)	0.37483 (10)	0.0373 (5)
H4C	0.0776	0.1432	0.3390	0.037*
H4D	0.1317	0.2711	0.3566	0.037*
H4E	0.0599	0.2189	0.4042	0.037*
C5	0.19123 (13)	−0.07100 (18)	0.33918 (9)	0.0316 (4)
H5A	0.1304	−0.0483	0.3170	0.032*
H5B	0.1899	−0.1608	0.3512	0.032*
C6	0.26470 (14)	−0.04902 (17)	0.29274 (9)	0.0320 (4)
H6A	0.3255	−0.0731	0.3145	0.032*
H6B	0.2520	−0.1014	0.2529	0.032*
C7	0.21286 (13)	0.30585 (17)	0.48943 (9)	0.0292 (4)
H7A	0.1524	0.3104	0.5071	0.029*
H7B	0.2103	0.3606	0.4502	0.029*
C8	0.39803 (13)	0.47419 (18)	0.63163 (9)	0.0318 (4)
C9	0.37099 (13)	0.40084 (17)	0.52538 (9)	0.0275 (4)
C10	0.28416 (12)	0.35582 (16)	0.54005 (9)	0.0269 (4)
C11	0.26413 (13)	0.37049 (18)	0.60373 (9)	0.0315 (4)
H11	0.2071	0.3393	0.6153	0.031*
C12	0.45790 (15)	0.5448 (2)	0.68217 (10)	0.0423 (5)
H12A	0.4254	0.6194	0.6955	0.042*
H12B	0.5144	0.5702	0.6637	0.042*
H12C	0.4733	0.4910	0.7205	0.042*
B	0.21305 (14)	0.57783 (19)	0.18076 (10)	0.0265 (4)
C13	0.23119 (12)	0.58899 (16)	0.26148 (9)	0.0269 (4)
C14	0.16434 (14)	0.56452 (17)	0.30437 (9)	0.0323 (4)
H14	0.1049	0.5397	0.2863	0.032*
C15	0.18122 (15)	0.57506 (18)	0.37231 (10)	0.0369 (5)
H15	0.1340	0.5558	0.3994	0.037*
C16	0.26602 (15)	0.61321 (19)	0.40064 (10)	0.0392 (5)
H16	0.2777	0.6206	0.4470	0.039*
C17	0.33357 (15)	0.64046 (19)	0.36008 (10)	0.0381 (5)
H17	0.3922	0.6678	0.3786	0.038*
C18	0.31616 (13)	0.62805 (18)	0.29234 (9)	0.0317 (4)
H18	0.3640	0.6469	0.2657	0.032*
C19	0.13886 (12)	0.46577 (17)	0.15669 (9)	0.0275 (4)
C20	0.12048 (13)	0.36083 (18)	0.19427 (10)	0.0344 (4)
H20	0.1512	0.3528	0.2372	0.034*
C21	0.05888 (15)	0.2676 (2)	0.17128 (12)	0.0443 (5)
H21	0.0474	0.1987	0.1988	0.044*
C22	0.01474 (14)	0.2749 (2)	0.10896 (13)	0.0479 (6)
H22	−0.0278	0.2119	0.0933	0.048*
C23	0.03284 (15)	0.3744 (2)	0.06949 (12)	0.0461 (6)
H23	0.0039	0.3795	0.0260	0.046*
C24	0.09336 (14)	0.46749 (19)	0.09320 (10)	0.0368 (5)
H24	0.1045	0.5356	0.0651	0.037*
C25	0.31209 (12)	0.53770 (18)	0.15468 (9)	0.0281 (4)
C26	0.34524 (13)	0.41625 (19)	0.16709 (9)	0.0314 (4)
H26	0.3084	0.3592	0.1887	0.031*
C27	0.42946 (14)	0.3748 (2)	0.14944 (10)	0.0395 (5)
H27	0.4495	0.2917	0.1596	0.039*
C28	0.48353 (14)	0.4547 (3)	0.11717 (11)	0.0490 (6)
H28	0.5401	0.4262	0.1034	0.049*
C29	0.45531 (15)	0.5757 (3)	0.10489 (12)	0.0529 (6)
H29	0.4931	0.6316	0.0834	0.053*
C30	0.37072 (14)	0.6173 (2)	0.12388 (10)	0.0396 (5)
H30	0.3528	0.7019	0.1156	0.040*
C31	0.16942 (12)	0.71057 (17)	0.15058 (9)	0.0272 (4)
C32	0.11504 (12)	0.78701 (18)	0.18651 (9)	0.0305 (4)
H32	0.1075	0.7645	0.2306	0.031*
C33	0.07152 (13)	0.89418 (19)	0.16092 (11)	0.0383 (5)
H33	0.0362	0.9436	0.1878	0.038*
C34	0.07905 (15)	0.92939 (19)	0.09708 (11)	0.0412 (5)
H34	0.0488	1.0023	0.0793	0.041*
C35	0.13144 (16)	0.8567 (2)	0.05939 (11)	0.0422 (5)
H35	0.1373	0.8792	0.0150	0.042*
C36	0.17565 (15)	0.75087 (19)	0.08582 (10)	0.0369 (5)
H36	0.2120	0.7033	0.0588	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0368 (3)	0.0313 (3)	0.0259 (3)	0.0061 (2)	0.00114 (19)	0.00246 (19)
N1	0.0238 (8)	0.0280 (8)	0.0229 (8)	−0.0004 (6)	0.0031 (6)	0.0024 (6)
N2	0.0375 (9)	0.0383 (9)	0.0246 (8)	0.0012 (7)	0.0072 (7)	−0.0010 (7)
N3	0.0317 (8)	0.0363 (9)	0.0251 (8)	−0.0020 (7)	0.0025 (6)	−0.0020 (7)
N4	0.0319 (9)	0.0438 (10)	0.0247 (8)	−0.0076 (7)	0.0053 (7)	−0.0046 (7)
O1	0.0673 (10)	0.0334 (8)	0.0261 (7)	−0.0092 (7)	0.0162 (7)	−0.0018 (6)
O2	0.0633 (10)	0.0375 (8)	0.0314 (8)	−0.0088 (7)	−0.0022 (7)	−0.0013 (6)
C1	0.0290 (10)	0.0323 (10)	0.0222 (9)	0.0012 (8)	0.0005 (7)	0.0026 (8)
C2	0.0252 (9)	0.0329 (10)	0.0224 (9)	−0.0038 (8)	0.0021 (7)	0.0031 (7)
C3	0.0274 (9)	0.0305 (10)	0.0237 (9)	−0.0039 (8)	0.0029 (7)	0.0047 (8)
C4	0.0330 (11)	0.0405 (12)	0.0366 (11)	0.0025 (9)	−0.0062 (9)	−0.0001 (9)
C5	0.0371 (11)	0.0306 (10)	0.0265 (10)	−0.0049 (8)	0.0006 (8)	−0.0016 (8)
C6	0.0376 (11)	0.0314 (10)	0.0269 (10)	−0.0035 (8)	0.0020 (8)	−0.0038 (8)
C7	0.0289 (10)	0.0283 (9)	0.0305 (10)	0.0023 (8)	0.0026 (8)	0.0005 (8)
C8	0.0359 (11)	0.0335 (10)	0.0261 (10)	0.0041 (8)	0.0035 (8)	−0.0012 (8)
C9	0.0312 (10)	0.0270 (9)	0.0242 (9)	0.0017 (8)	0.0025 (7)	0.0017 (7)
C10	0.0288 (9)	0.0247 (9)	0.0273 (10)	0.0022 (7)	0.0033 (7)	0.0003 (7)
C11	0.0318 (10)	0.0324 (10)	0.0310 (10)	0.0007 (8)	0.0070 (8)	0.0018 (8)
C12	0.0427 (12)	0.0535 (14)	0.0303 (11)	−0.0042 (10)	0.0016 (9)	−0.0094 (10)
B	0.0274 (10)	0.0274 (10)	0.0252 (10)	−0.0017 (8)	0.0050 (8)	−0.0030 (8)
C13	0.0321 (10)	0.0224 (9)	0.0264 (10)	0.0020 (7)	0.0044 (8)	−0.0002 (7)
C14	0.0349 (10)	0.0292 (10)	0.0337 (11)	0.0030 (8)	0.0085 (8)	−0.0011 (8)
C15	0.0514 (13)	0.0293 (10)	0.0324 (11)	0.0086 (9)	0.0169 (9)	0.0045 (8)
C16	0.0554 (14)	0.0370 (11)	0.0255 (10)	0.0118 (10)	0.0051 (9)	0.0010 (9)
C17	0.0410 (12)	0.0389 (11)	0.0330 (11)	0.0049 (9)	−0.0039 (9)	−0.0036 (9)
C18	0.0337 (10)	0.0321 (10)	0.0296 (10)	0.0006 (8)	0.0047 (8)	−0.0008 (8)
C19	0.0240 (9)	0.0264 (9)	0.0327 (10)	0.0026 (7)	0.0056 (7)	−0.0047 (8)
C20	0.0337 (11)	0.0313 (10)	0.0392 (11)	−0.0019 (8)	0.0085 (9)	−0.0029 (9)
C21	0.0415 (12)	0.0314 (11)	0.0628 (15)	−0.0079 (9)	0.0202 (11)	−0.0050 (10)
C22	0.0291 (11)	0.0364 (12)	0.0781 (18)	−0.0066 (9)	0.0040 (11)	−0.0206 (12)
C23	0.0375 (12)	0.0428 (13)	0.0547 (14)	0.0026 (10)	−0.0116 (10)	−0.0135 (11)
C24	0.0376 (11)	0.0315 (10)	0.0400 (12)	0.0005 (8)	−0.0027 (9)	−0.0029 (9)
C25	0.0269 (9)	0.0362 (10)	0.0210 (9)	−0.0051 (8)	0.0013 (7)	−0.0082 (8)
C26	0.0286 (10)	0.0408 (11)	0.0245 (9)	−0.0011 (8)	0.0017 (7)	−0.0059 (8)
C27	0.0314 (11)	0.0530 (13)	0.0329 (11)	0.0076 (10)	−0.0022 (9)	−0.0090 (10)
C28	0.0254 (11)	0.0765 (18)	0.0454 (13)	0.0046 (11)	0.0055 (9)	−0.0097 (12)
C29	0.0340 (12)	0.0760 (18)	0.0501 (14)	−0.0190 (12)	0.0115 (10)	−0.0013 (13)
C30	0.0366 (11)	0.0443 (12)	0.0386 (12)	−0.0112 (9)	0.0065 (9)	−0.0037 (10)
C31	0.0280 (9)	0.0251 (9)	0.0285 (10)	−0.0047 (7)	0.0028 (7)	−0.0051 (8)
C32	0.0282 (10)	0.0333 (10)	0.0298 (10)	−0.0030 (8)	0.0010 (8)	−0.0059 (8)
C33	0.0306 (11)	0.0344 (11)	0.0501 (13)	0.0020 (9)	0.0044 (9)	−0.0089 (10)
C34	0.0406 (12)	0.0270 (10)	0.0549 (14)	0.0006 (9)	−0.0018 (10)	0.0054 (10)
C35	0.0548 (14)	0.0371 (11)	0.0349 (12)	−0.0036 (10)	0.0048 (10)	0.0089 (9)
C36	0.0472 (12)	0.0315 (10)	0.0332 (11)	0.0021 (9)	0.0100 (9)	−0.0019 (9)

Geometric parameters (Å, º)

S1—C1	1.6760 (19)	C13—C18	1.403 (3)
S1—C3	1.7282 (18)	C14—C15	1.392 (3)
N1—C1	1.317 (2)	C14—H14	0.95
N1—C2	1.398 (2)	C15—C16	1.380 (3)
N1—C7	1.490 (2)	C15—H15	0.95
N2—C11	1.339 (2)	C16—C17	1.382 (3)
N2—C8	1.343 (2)	C16—H16	0.95
N3—C8	1.334 (2)	C17—C18	1.390 (3)
N3—C9	1.358 (2)	C17—H17	0.95
N4—C9	1.338 (2)	C18—H18	0.95
N4—H4A	0.88	C19—C20	1.399 (3)
N4—H4B	0.88	C19—C24	1.401 (3)
O1—C6	1.424 (2)	C20—C21	1.394 (3)
O1—H1	0.89	C20—H20	0.95
O2—H2A	0.86	C21—C22	1.374 (3)
O2—H2B	0.88	C21—H21	0.95
C1—H1A	0.95	C22—C23	1.375 (3)
C2—C3	1.350 (3)	C22—H22	0.95
C2—C4	1.488 (3)	C23—C24	1.387 (3)
C3—C5	1.502 (3)	C23—H23	0.95
C4—H4C	0.98	C24—H24	0.95
C4—H4D	0.98	C25—C26	1.398 (3)
C4—H4E	0.98	C25—C30	1.400 (3)
C5—C6	1.520 (3)	C26—C27	1.390 (3)
C5—H5A	0.99	C26—H26	0.95
C5—H5B	0.99	C27—C28	1.375 (3)
C6—H6A	0.99	C27—H27	0.95
C6—H6B	0.99	C28—C29	1.371 (4)
C7—C10	1.496 (3)	C28—H28	0.95
C7—H7A	0.99	C29—C30	1.406 (3)
C7—H7B	0.99	C29—H29	0.95
C8—C12	1.493 (3)	C30—H30	0.95
C9—C10	1.418 (3)	C31—C32	1.397 (3)
C10—C11	1.371 (3)	C31—C36	1.403 (3)
C11—H11	0.95	C32—C33	1.387 (3)
C12—H12A	0.98	C32—H32	0.95
C12—H12B	0.98	C33—C34	1.373 (3)
C12—H12C	0.98	C33—H33	0.95
B—C31	1.649 (3)	C34—C35	1.378 (3)
B—C25	1.649 (3)	C34—H34	0.95
B—C13	1.651 (3)	C35—C36	1.385 (3)
B—C19	1.658 (3)	C35—H35	0.95
C13—C14	1.400 (3)	C36—H36	0.95
C1—S1—C3	91.40 (9)	C18—C13—B	121.43 (16)
C1—N1—C2	114.46 (15)	C15—C14—C13	122.84 (19)
C1—N1—C7	124.04 (15)	C15—C14—H14	119
C2—N1—C7	121.47 (15)	C13—C14—H14	119
C11—N2—C8	116.10 (16)	C16—C15—C14	120.59 (19)
C8—N3—C9	117.94 (16)	C16—C15—H15	120
C9—N4—H4A	120	C14—C15—H15	120
C9—N4—H4B	120	C15—C16—C17	118.52 (19)
H4A—N4—H4B	120	C15—C16—H16	121
C6—O1—H1	108	C17—C16—H16	121
H2A—O2—H2B	108	C16—C17—C18	120.30 (19)
N1—C1—S1	112.04 (14)	C16—C17—H17	120
N1—C1—H1A	124	C18—C17—H17	120
S1—C1—H1A	124	C17—C18—C13	123.09 (18)
C3—C2—N1	111.37 (16)	C17—C18—H18	118
C3—C2—C4	127.99 (17)	C13—C18—H18	118
N1—C2—C4	120.63 (16)	C20—C19—C24	114.83 (18)
C2—C3—C5	128.56 (17)	C20—C19—B	124.70 (17)
C2—C3—S1	110.67 (14)	C24—C19—B	120.36 (17)
C5—C3—S1	120.07 (14)	C21—C20—C19	122.6 (2)
C2—C4—H4C	109	C21—C20—H20	119
C2—C4—H4D	109	C19—C20—H20	119
H4C—C4—H4D	109	C22—C21—C20	120.2 (2)
C2—C4—H4E	109	C22—C21—H21	120
H4C—C4—H4E	109	C20—C21—H21	120
H4D—C4—H4E	109	C23—C22—C21	119.2 (2)
C3—C5—C6	109.99 (15)	C23—C22—H22	120
C3—C5—H5A	110	C21—C22—H22	120
C6—C5—H5A	110	C22—C23—C24	120.0 (2)
C3—C5—H5B	110	C22—C23—H23	120
C6—C5—H5B	110	C24—C23—H23	120
H5A—C5—H5B	108	C23—C24—C19	123.1 (2)
O1—C6—C5	109.36 (15)	C23—C24—H24	118
O1—C6—H6A	110	C19—C24—H24	118
C5—C6—H6A	110	C26—C25—C30	115.26 (18)
O1—C6—H6B	110	C26—C25—B	118.86 (16)
C5—C6—H6B	110	C30—C25—B	125.77 (18)
H6A—C6—H6B	108	C27—C26—C25	123.29 (19)
N1—C7—C10	114.57 (15)	C27—C26—H26	118
N1—C7—H7A	109	C25—C26—H26	118
C10—C7—H7A	109	C28—C27—C26	119.6 (2)
N1—C7—H7B	109	C28—C27—H27	120
C10—C7—H7B	109	C26—C27—H27	120
H7A—C7—H7B	108	C29—C28—C27	119.6 (2)
N3—C8—N2	125.33 (18)	C29—C28—H28	120
N3—C8—C12	117.87 (18)	C27—C28—H28	120
N2—C8—C12	116.80 (17)	C28—C29—C30	120.4 (2)
N4—C9—N3	116.55 (17)	C28—C29—H29	120
N4—C9—C10	123.26 (17)	C30—C29—H29	120
N3—C9—C10	120.19 (16)	C25—C30—C29	121.8 (2)
C11—C10—C9	116.13 (17)	C25—C30—H30	119
C11—C10—C7	119.92 (17)	C29—C30—H30	119
C9—C10—C7	123.70 (16)	C32—C31—C36	114.17 (17)
N2—C11—C10	124.00 (18)	C32—C31—B	121.64 (16)
N2—C11—H11	118	C36—C31—B	123.93 (16)
C10—C11—H11	118	C33—C32—C31	123.20 (19)
C8—C12—H12A	109	C33—C32—H32	118
C8—C12—H12B	109	C31—C32—H32	118
H12A—C12—H12B	109	C34—C33—C32	120.55 (19)
C8—C12—H12C	109	C34—C33—H33	120
H12A—C12—H12C	109	C32—C33—H33	120
H12B—C12—H12C	109	C33—C34—C35	118.54 (19)
C31—B—C25	115.03 (15)	C33—C34—H34	121
C31—B—C13	109.36 (14)	C35—C34—H34	121
C25—B—C13	106.27 (15)	C34—C35—C36	120.3 (2)
C31—B—C19	106.78 (15)	C34—C35—H35	120
C25—B—C19	106.77 (14)	C36—C35—H35	120
C13—B—C19	112.75 (15)	C35—C36—C31	123.19 (19)
C14—C13—C18	114.65 (17)	C35—C36—H36	118
C14—C13—B	123.91 (16)	C31—C36—H36	118
C2—N1—C1—S1	1.42 (19)	C2—N1—C7—C10	−165.79 (15)
C7—N1—C1—S1	−176.39 (13)	C9—N3—C8—N2	0.8 (3)
C3—S1—C1—N1	0.11 (14)	C9—N3—C8—C12	−179.27 (18)
C1—N1—C2—C3	−2.7 (2)	C11—N2—C8—N3	−4.5 (3)
C7—N1—C2—C3	175.18 (15)	C11—N2—C8—C12	175.58 (18)
C1—N1—C2—C4	176.40 (17)	C8—N3—C9—N4	−175.34 (17)
C7—N1—C2—C4	−5.7 (2)	C8—N3—C9—C10	4.3 (3)
N1—C2—C3—C5	−167.66 (17)	N4—C9—C10—C11	174.26 (18)
C4—C2—C3—C5	13.3 (3)	N3—C9—C10—C11	−5.3 (3)
N1—C2—C3—S1	2.66 (19)	N4—C9—C10—C7	−11.5 (3)
C4—C2—C3—S1	−176.35 (16)	N3—C9—C10—C7	168.93 (17)
C1—S1—C3—C2	−1.64 (14)	N1—C7—C10—C11	−106.53 (19)
C1—S1—C3—C5	169.62 (15)	N1—C7—C10—C9	79.4 (2)
C2—C3—C5—C6	91.9 (2)	C8—N2—C11—C10	3.1 (3)
S1—C3—C5—C6	−77.58 (19)	C9—C10—C11—N2	1.5 (3)
C3—C5—C6—O1	−60.2 (2)	C7—C10—C11—N2	−172.97 (17)
C1—N1—C7—C10	11.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N3^i	0.88	2.29	3.142 (2)	163
N4—H4B···O2	0.88	2.02	2.863 (2)	160
O1—H1···N2^ii	0.89	1.86	2.736 (2)	171
O2—H2A···O1	0.86	1.92	2.786 (2)	175
O2—H2B···Cg1	0.88	2.69	3.385 (2)	136
C1—H1A···Cg2^iii	0.95	2.50	3.252 (2)	137

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