The salt–cocrystal spectrum in salicylic acid–adenine: the influence of crystal structure on proton-transfer balance

At one extreme of the proton-transfer spectrum in cocrystals, proton transfer is absent, whilst at the opposite extreme, in salts, the proton-transfer process is complete. However, for acid–base pairs with a small ΔpK_a (pK_a of base − pK_a of acid), prediction of the extent of proton transfer is not possible as there is a continuum between the salt and cocrystal ends. In this context, we attempt to illustrate that in these systems, in addition to ΔpK_a, the crystalline environment could change the extent of proton transfer. To this end, two compounds of salicylic acid (SaH) and adenine (Ad) have been prepared. Despite the same small ΔpK_a value (≈1.2), different ionization states are found. Both crystals, namely adeninium salicylate monohydrate, C₅H₆N₅⁺·C₇H₅O₃⁻·H₂O, I, and adeninium salicylate–adenine–salicylic acid–water (1/2/1/2), C₅H₆N₅⁺·C₇H₅O₃⁻·2C₅H₅N₅·C₇H₆O₃·2H₂O, II, have been characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis (C, H and N) techniques. In addition, the inter­molecular hydrogen-bonding inter­actions of compounds I and II have been investigated and qu­anti­fied in detail on the basis of Hirshfeld surface analysis and fingerprint plots. Throughout the study, we use crystal engineering, which is based on modifications of the inter­molecular inter­actions, thus offering a more comprehensive screening of the salt–cocrystal continuum in comparison with pure pK_a analysis.

Computing details

Data collection: CrysAlis CCD (Rigaku OD, 2015 for COMP_I; CrysAlis CCD (Rigaku OD, 2015) for COMP_II. For both structures, cell refinement: CrysAlis RED (Rigaku OD, 2015); data reduction: CrysAlis RED (Rigaku OD, 2015). Program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a) for COMP_I; SHELXT (Sheldrick, 2015a) for COMP_II. For both structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

Adeninium salicylate monohydrate (COMP_I)

Crystal data

C5H6N5^+·C7H5O3^−·H2O	Z = 4
Mr = 291.27	F(000) = 608
Triclinic, P1	Dx = 1.497 Mg m^−3
a = 7.2329 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.4405 (7) Å	Cell parameters from 2470 reflections
c = 14.7468 (8) Å	θ = 3.3–26.1°
α = 82.507 (4)°	µ = 0.12 mm^−1
β = 79.385 (6)°	T = 100 K
γ = 86.828 (5)°	Needle, colourless
V = 1292.42 (14) Å^3	0.23 × 0.11 × 0.08 mm

Data collection

Kuma KM-4 with CCD detector diffractometer	5357 independent reflections
Radiation source: fine-focus sealed X-ray tube	2777 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.091
ω–scan	θmax = 26.5°, θmin = 2.8°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −9→9
Tmin = 0.982, Tmax = 1.000	k = −15→15
27185 measured reflections	l = −18→18

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)] = 0.066	Hydrogen site location: mixed
wR(F^2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0282P)^2] where P = (Fo^2 + 2Fc^2)/3
5357 reflections	(Δ/σ)max = 0.001
415 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

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. 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 > 2sigma(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
C1	0.0998 (4)	0.7395 (2)	−0.07331 (19)	0.0179 (7)
C2	0.0963 (4)	0.8214 (2)	−0.1473 (2)	0.0237 (7)
C3	0.0646 (4)	0.7957 (2)	−0.2338 (2)	0.0278 (8)
H3	0.060306	0.851171	−0.284200	0.033*
C4	0.0399 (4)	0.6889 (2)	−0.2441 (2)	0.0268 (8)
H4	0.020921	0.671305	−0.302370	0.032*
C5	0.0423 (4)	0.6063 (2)	−0.1702 (2)	0.0266 (8)
H5	0.023052	0.533454	−0.178096	0.032*
C6	0.0731 (4)	0.6315 (2)	−0.0857 (2)	0.0246 (7)
H6	0.076148	0.575483	−0.035565	0.030*
C7	0.1389 (4)	0.7641 (2)	0.0173 (2)	0.0219 (7)
O1	0.1677 (3)	0.86069 (15)	0.02821 (14)	0.0286 (5)
O2	0.1440 (3)	0.68351 (15)	0.08059 (14)	0.0263 (5)
O3	0.1224 (3)	0.92645 (16)	−0.13982 (16)	0.0401 (6)
H3O	0.159 (4)	0.924 (3)	−0.073 (2)	0.060*
C11	0.1972 (4)	0.2541 (2)	0.6302 (2)	0.0200 (7)
C12	0.1721 (4)	0.1472 (2)	0.6135 (2)	0.0193 (7)
C13	0.1539 (4)	0.1258 (2)	0.5259 (2)	0.0222 (7)
H13	0.140833	0.053246	0.514886	0.027*
C14	0.1546 (4)	0.2088 (2)	0.4549 (2)	0.0248 (7)
H14	0.143371	0.193229	0.394790	0.030*
C15	0.1717 (4)	0.3161 (2)	0.4700 (2)	0.0256 (7)
H15	0.169445	0.373706	0.421071	0.031*
C16	0.1918 (4)	0.3369 (2)	0.5567 (2)	0.0238 (7)
H16	0.202458	0.409836	0.567112	0.029*
C17	0.2299 (4)	0.2771 (2)	0.7231 (2)	0.0208 (7)
O11	0.2580 (3)	0.37330 (15)	0.73554 (13)	0.0263 (5)
O12	0.2266 (3)	0.19721 (15)	0.78684 (13)	0.0247 (5)
O13	0.1652 (3)	0.06232 (16)	0.68184 (15)	0.0276 (5)
H13O	0.185 (4)	0.090 (2)	0.736 (2)	0.041*
C21	0.2635 (4)	0.8034 (2)	0.2634 (2)	0.0199 (7)
N22	0.2284 (3)	0.70744 (19)	0.23615 (17)	0.0226 (6)
H22	0.209 (4)	0.706 (2)	0.170 (2)	0.027*
C23	0.2343 (4)	0.6131 (2)	0.2921 (2)	0.0228 (7)
H23	0.211383	0.549597	0.267038	0.027*
N24	0.2683 (3)	0.59907 (18)	0.37781 (17)	0.0213 (6)
C25	0.2988 (4)	0.6959 (2)	0.4056 (2)	0.0201 (7)
N26	0.3370 (3)	0.71268 (19)	0.48976 (17)	0.0209 (6)
H26	0.352 (4)	0.667 (2)	0.5398 (19)	0.025*
C27	0.3585 (4)	0.8212 (2)	0.4849 (2)	0.0221 (7)
H27	0.386767	0.854246	0.535114	0.027*
N28	0.3370 (3)	0.87668 (18)	0.40549 (17)	0.0233 (6)
C29	0.2992 (4)	0.7970 (2)	0.3537 (2)	0.0199 (7)
N30	0.2614 (4)	0.8925 (2)	0.20328 (19)	0.0273 (7)
H30A	0.230 (4)	0.886 (2)	0.151 (2)	0.033*
H30B	0.286 (4)	0.955 (2)	0.218 (2)	0.033*
C31	0.3747 (4)	0.3116 (2)	0.9692 (2)	0.0197 (7)
N32	0.3301 (3)	0.21236 (18)	0.94933 (17)	0.0196 (6)
H32	0.300 (3)	0.211 (2)	0.8875 (19)	0.023*
C33	0.3297 (4)	0.1199 (2)	1.0092 (2)	0.0234 (7)
H33	0.299093	0.055115	0.988259	0.028*
N34	0.3673 (3)	0.11196 (17)	1.09251 (17)	0.0225 (6)
C35	0.4076 (4)	0.2091 (2)	1.11553 (19)	0.0167 (7)
N36	0.4489 (3)	0.22995 (19)	1.19730 (18)	0.0228 (6)
H36	0.465 (4)	0.181 (2)	1.242 (2)	0.027*
C37	0.4802 (4)	0.3380 (2)	1.1888 (2)	0.0215 (7)
H37	0.512706	0.372796	1.237099	0.026*
N38	0.4607 (3)	0.38987 (17)	1.10652 (16)	0.0203 (6)
C39	0.4148 (4)	0.3085 (2)	1.0592 (2)	0.0195 (7)
N40	0.3718 (3)	0.39732 (19)	0.90723 (18)	0.0211 (6)
H40A	0.339 (4)	0.393 (2)	0.848 (2)	0.025*
H40B	0.419 (4)	0.458 (2)	0.9200 (18)	0.025*
O1W	0.4158 (3)	0.55525 (14)	0.62864 (15)	0.0272 (5)
H1W1	0.521711	0.525156	0.616369	0.041*
H2W1	0.345274	0.503857	0.654402	0.041*
O2W	0.5113 (3)	0.07390 (14)	1.33830 (16)	0.0282 (5)
H1W2	0.609376	0.041407	1.315705	0.042*
H2W2	0.435551	0.023731	1.359483	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0194 (17)	0.0189 (16)	0.0149 (16)	−0.0014 (12)	−0.0001 (13)	−0.0043 (13)
C2	0.0232 (18)	0.0180 (17)	0.032 (2)	−0.0054 (13)	−0.0042 (15)	−0.0082 (14)
C3	0.0270 (19)	0.0321 (19)	0.0258 (19)	−0.0041 (14)	−0.0097 (15)	−0.0010 (15)
C4	0.0263 (19)	0.0315 (19)	0.0279 (19)	0.0001 (14)	−0.0113 (15)	−0.0140 (16)
C5	0.0224 (18)	0.0249 (18)	0.036 (2)	0.0008 (13)	−0.0096 (15)	−0.0094 (15)
C6	0.0226 (18)	0.0248 (18)	0.0279 (19)	−0.0032 (13)	−0.0023 (15)	−0.0105 (14)
C7	0.0193 (17)	0.0224 (18)	0.0234 (18)	−0.0054 (13)	−0.0004 (14)	−0.0037 (15)
O1	0.0398 (14)	0.0199 (12)	0.0281 (13)	−0.0050 (10)	−0.0100 (11)	−0.0033 (10)
O2	0.0359 (13)	0.0221 (12)	0.0220 (12)	−0.0036 (9)	−0.0075 (10)	−0.0023 (10)
O3	0.0602 (17)	0.0259 (13)	0.0387 (15)	−0.0135 (11)	−0.0209 (13)	0.0013 (11)
C11	0.0174 (17)	0.0198 (17)	0.0236 (18)	−0.0023 (13)	−0.0028 (14)	−0.0065 (14)
C12	0.0195 (17)	0.0156 (16)	0.0229 (17)	0.0025 (12)	−0.0069 (14)	0.0009 (14)
C13	0.0189 (17)	0.0230 (17)	0.0270 (19)	−0.0008 (13)	−0.0047 (14)	−0.0106 (14)
C14	0.0234 (18)	0.0302 (19)	0.0230 (18)	−0.0027 (14)	−0.0077 (14)	−0.0056 (15)
C15	0.0247 (18)	0.0291 (18)	0.0248 (18)	−0.0063 (14)	−0.0102 (15)	0.0007 (14)
C16	0.0195 (17)	0.0219 (17)	0.0307 (19)	−0.0023 (13)	−0.0054 (15)	−0.0037 (15)
C17	0.0151 (16)	0.0258 (18)	0.0216 (18)	−0.0032 (13)	−0.0011 (13)	−0.0061 (15)
O11	0.0358 (13)	0.0192 (12)	0.0253 (13)	−0.0073 (9)	−0.0052 (10)	−0.0052 (9)
O12	0.0324 (13)	0.0224 (12)	0.0212 (12)	−0.0043 (9)	−0.0079 (10)	−0.0037 (10)
O13	0.0387 (13)	0.0215 (12)	0.0239 (13)	−0.0031 (9)	−0.0052 (11)	−0.0071 (10)
C21	0.0177 (17)	0.0167 (17)	0.0233 (18)	−0.0006 (12)	−0.0003 (14)	0.0004 (14)
N22	0.0307 (16)	0.0182 (14)	0.0206 (15)	−0.0008 (11)	−0.0060 (12)	−0.0062 (12)
C23	0.0247 (18)	0.0183 (17)	0.0270 (19)	0.0007 (13)	−0.0030 (15)	−0.0113 (14)
N24	0.0234 (15)	0.0195 (14)	0.0228 (15)	−0.0003 (11)	−0.0066 (12)	−0.0057 (11)
C25	0.0145 (16)	0.0225 (17)	0.0236 (18)	−0.0007 (12)	−0.0045 (14)	−0.0025 (14)
N26	0.0246 (15)	0.0185 (14)	0.0207 (15)	0.0003 (11)	−0.0101 (12)	0.0018 (11)
C27	0.0184 (17)	0.0219 (18)	0.0289 (19)	−0.0003 (13)	−0.0048 (14)	−0.0134 (15)
N28	0.0263 (15)	0.0211 (14)	0.0241 (15)	−0.0050 (11)	−0.0059 (12)	−0.0051 (12)
C29	0.0146 (16)	0.0188 (17)	0.0254 (18)	−0.0011 (12)	−0.0013 (14)	−0.0031 (14)
N30	0.0403 (18)	0.0198 (15)	0.0236 (16)	−0.0036 (12)	−0.0096 (14)	−0.0026 (13)
C31	0.0149 (16)	0.0210 (17)	0.0243 (18)	−0.0009 (12)	−0.0022 (14)	−0.0081 (14)
N32	0.0243 (15)	0.0170 (14)	0.0205 (15)	−0.0032 (10)	−0.0095 (12)	−0.0049 (12)
C33	0.0286 (19)	0.0138 (16)	0.0299 (19)	−0.0060 (13)	−0.0066 (15)	−0.0056 (14)
N34	0.0263 (15)	0.0155 (14)	0.0266 (16)	−0.0039 (11)	−0.0065 (12)	−0.0022 (12)
C35	0.0178 (16)	0.0175 (16)	0.0144 (16)	−0.0032 (12)	−0.0005 (13)	−0.0034 (13)
N36	0.0249 (15)	0.0205 (15)	0.0230 (16)	−0.0036 (11)	−0.0061 (12)	0.0013 (11)
C37	0.0228 (18)	0.0197 (17)	0.0238 (18)	−0.0004 (13)	−0.0052 (14)	−0.0083 (14)
N38	0.0263 (15)	0.0181 (14)	0.0187 (14)	−0.0017 (11)	−0.0077 (12)	−0.0045 (11)
C39	0.0171 (16)	0.0153 (16)	0.0272 (18)	−0.0036 (12)	−0.0025 (14)	−0.0077 (13)
N40	0.0333 (16)	0.0126 (14)	0.0194 (15)	−0.0075 (11)	−0.0085 (12)	−0.0011 (12)
O1W	0.0314 (13)	0.0194 (12)	0.0314 (14)	−0.0025 (9)	−0.0076 (11)	−0.0011 (10)
O2W	0.0317 (13)	0.0179 (12)	0.0325 (14)	−0.0006 (9)	−0.0015 (11)	0.0000 (10)

Geometric parameters (Å, º)

C1—C2	1.396 (4)	N22—H22	1.02 (3)
C1—C6	1.407 (4)	C23—N24	1.319 (3)
C1—C7	1.488 (4)	C23—H23	0.9500
C2—O3	1.352 (3)	N24—C25	1.363 (3)
C2—C3	1.416 (4)	C25—N26	1.364 (3)
C3—C4	1.380 (4)	C25—C29	1.384 (4)
C3—H3	0.9500	N26—C27	1.359 (3)
C4—C5	1.398 (4)	N26—H26	0.89 (3)
C4—H4	0.9500	C27—N28	1.310 (3)
C5—C6	1.384 (4)	C27—H27	0.9500
C5—H5	0.9500	N28—C29	1.395 (3)
C6—H6	0.9500	N30—H30A	0.85 (3)
C7—O1	1.266 (3)	N30—H30B	0.87 (3)
C7—O2	1.282 (3)	C31—N40	1.313 (3)
O3—H3O	1.06 (3)	C31—N32	1.373 (3)
C11—C16	1.399 (4)	C31—C39	1.405 (4)
C11—C12	1.411 (4)	N32—C33	1.356 (3)
C11—C17	1.498 (4)	N32—H32	0.98 (3)
C12—O13	1.357 (3)	C33—N34	1.297 (3)
C12—C13	1.384 (4)	C33—H33	0.9500
C13—C14	1.371 (4)	N34—C35	1.358 (3)
C13—H13	0.9500	C35—N36	1.354 (3)
C14—C15	1.398 (4)	C35—C39	1.395 (4)
C14—H14	0.9500	N36—C37	1.361 (3)
C15—C16	1.371 (4)	N36—H36	0.86 (3)
C15—H15	0.9500	C37—N38	1.326 (3)
C16—H16	0.9500	C37—H37	0.9500
C17—O11	1.267 (3)	N38—C39	1.388 (3)
C17—O12	1.274 (3)	N40—H40A	0.96 (3)
O13—H13O	0.94 (3)	N40—H40B	0.90 (3)
C21—N30	1.327 (4)	O1W—H1W1	0.8334
C21—N22	1.360 (3)	O1W—H2W1	0.8455
C21—C29	1.394 (4)	O2W—H1W2	0.8333
N22—C23	1.347 (3)	O2W—H2W2	0.8432
C2—C1—C6	119.5 (3)	C21—N22—H22	119.3 (15)
C2—C1—C7	120.9 (2)	N24—C23—N22	127.3 (3)
C6—C1—C7	119.5 (3)	N24—C23—H23	116.3
O3—C2—C1	122.2 (3)	N22—C23—H23	116.3
O3—C2—C3	117.8 (3)	C23—N24—C25	110.7 (2)
C1—C2—C3	120.0 (3)	N24—C25—N26	127.0 (3)
C4—C3—C2	119.2 (3)	N24—C25—C29	126.9 (3)
C4—C3—H3	120.4	N26—C25—C29	106.1 (2)
C2—C3—H3	120.4	C27—N26—C25	105.9 (2)
C3—C4—C5	121.2 (3)	C27—N26—H26	121.9 (17)
C3—C4—H4	119.4	C25—N26—H26	132.2 (17)
C5—C4—H4	119.4	N28—C27—N26	114.6 (3)
C6—C5—C4	119.5 (3)	N28—C27—H27	122.7
C6—C5—H5	120.2	N26—C27—H27	122.7
C4—C5—H5	120.2	C27—N28—C29	103.1 (2)
C5—C6—C1	120.5 (3)	C25—C29—N28	110.3 (2)
C5—C6—H6	119.7	C25—C29—C21	118.1 (3)
C1—C6—H6	119.7	N28—C29—C21	131.5 (3)
O1—C7—O2	123.4 (3)	C21—N30—H30A	117 (2)
O1—C7—C1	119.9 (3)	C21—N30—H30B	120.6 (19)
O2—C7—C1	116.7 (2)	H30A—N30—H30B	122 (3)
C2—O3—H3O	103.8 (17)	N40—C31—N32	119.8 (3)
C16—C11—C12	117.4 (3)	N40—C31—C39	126.9 (3)
C16—C11—C17	121.7 (3)	N32—C31—C39	113.3 (3)
C12—C11—C17	120.9 (3)	C33—N32—C31	123.7 (3)
O13—C12—C13	117.8 (2)	C33—N32—H32	120.4 (15)
O13—C12—C11	121.7 (3)	C31—N32—H32	115.9 (15)
C13—C12—C11	120.5 (3)	N34—C33—N32	125.7 (3)
C14—C13—C12	120.3 (3)	N34—C33—H33	117.1
C14—C13—H13	119.9	N32—C33—H33	117.1
C12—C13—H13	119.9	C33—N34—C35	112.2 (2)
C13—C14—C15	120.7 (3)	N36—C35—N34	127.5 (3)
C13—C14—H14	119.7	N36—C35—C39	105.7 (2)
C15—C14—H14	119.7	N34—C35—C39	126.8 (3)
C16—C15—C14	118.9 (3)	C35—N36—C37	107.1 (2)
C16—C15—H15	120.6	C35—N36—H36	124.4 (19)
C14—C15—H15	120.6	C37—N36—H36	128.1 (19)
C15—C16—C11	122.2 (3)	N38—C37—N36	113.3 (2)
C15—C16—H16	118.9	N38—C37—H37	123.4
C11—C16—H16	118.9	N36—C37—H37	123.4
O11—C17—O12	123.0 (3)	C37—N38—C39	103.5 (2)
O11—C17—C11	119.7 (3)	N38—C39—C35	110.4 (2)
O12—C17—C11	117.3 (3)	N38—C39—C31	131.4 (3)
C12—O13—H13O	107.3 (18)	C35—C39—C31	118.2 (2)
N30—C21—N22	118.3 (3)	C31—N40—H40A	121.5 (15)
N30—C21—C29	126.5 (3)	C31—N40—H40B	116.4 (17)
N22—C21—C29	115.2 (3)	H40A—N40—H40B	121 (2)
C23—N22—C21	121.7 (3)	H1W1—O1W—H2W1	103.9
C23—N22—H22	118.8 (15)	H1W2—O2W—H2W2	103.8
C6—C1—C2—O3	−179.5 (3)	C23—N24—C25—C29	−1.1 (4)
C7—C1—C2—O3	−2.0 (4)	N24—C25—N26—C27	179.3 (3)
C6—C1—C2—C3	0.5 (4)	C29—C25—N26—C27	−0.1 (3)
C7—C1—C2—C3	178.0 (3)	C25—N26—C27—N28	0.3 (3)
O3—C2—C3—C4	179.1 (3)	N26—C27—N28—C29	−0.4 (3)
C1—C2—C3—C4	−0.9 (4)	N24—C25—C29—N28	−179.6 (3)
C2—C3—C4—C5	1.2 (4)	N26—C25—C29—N28	−0.1 (3)
C3—C4—C5—C6	−1.1 (4)	N24—C25—C29—C21	0.6 (4)
C4—C5—C6—C1	0.7 (4)	N26—C25—C29—C21	180.0 (3)
C2—C1—C6—C5	−0.4 (4)	C27—N28—C29—C25	0.3 (3)
C7—C1—C6—C5	−178.0 (3)	C27—N28—C29—C21	−179.9 (3)
C2—C1—C7—O1	0.8 (4)	N30—C21—C29—C25	−178.7 (3)
C6—C1—C7—O1	178.3 (3)	N22—C21—C29—C25	1.1 (4)
C2—C1—C7—O2	−178.3 (3)	N30—C21—C29—N28	1.4 (5)
C6—C1—C7—O2	−0.8 (4)	N22—C21—C29—N28	−178.8 (3)
C16—C11—C12—O13	−176.5 (3)	N40—C31—N32—C33	179.9 (3)
C17—C11—C12—O13	4.1 (4)	C39—C31—N32—C33	−1.7 (4)
C16—C11—C12—C13	3.6 (4)	C31—N32—C33—N34	1.2 (5)
C17—C11—C12—C13	−175.9 (3)	N32—C33—N34—C35	0.5 (4)
O13—C12—C13—C14	178.2 (2)	C33—N34—C35—N36	178.5 (3)
C11—C12—C13—C14	−1.9 (4)	C33—N34—C35—C39	−1.5 (4)
C12—C13—C14—C15	−0.7 (4)	N34—C35—N36—C37	179.7 (3)
C13—C14—C15—C16	1.4 (4)	C39—C35—N36—C37	−0.3 (3)
C14—C15—C16—C11	0.5 (4)	C35—N36—C37—N38	0.4 (3)
C12—C11—C16—C15	−2.9 (4)	N36—C37—N38—C39	−0.4 (3)
C17—C11—C16—C15	176.6 (3)	C37—N38—C39—C35	0.2 (3)
C16—C11—C17—O11	−1.7 (4)	C37—N38—C39—C31	179.2 (3)
C12—C11—C17—O11	177.7 (2)	N36—C35—C39—N38	0.1 (3)
C16—C11—C17—O12	177.9 (3)	N34—C35—C39—N38	−179.9 (3)
C12—C11—C17—O12	−2.7 (4)	N36—C35—C39—C31	−179.1 (3)
N30—C21—N22—C23	177.7 (3)	N34—C35—C39—C31	0.9 (4)
C29—C21—N22—C23	−2.1 (4)	N40—C31—C39—N38	−0.1 (5)
C21—N22—C23—N24	1.7 (5)	N32—C31—C39—N38	−178.3 (3)
N22—C23—N24—C25	0.0 (4)	N40—C31—C39—C35	179.0 (3)
C23—N24—C25—N26	179.6 (3)	N32—C31—C39—C35	0.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1	1.06 (3)	1.61 (3)	2.580 (3)	150 (3)
O13—H13O···O12	0.94 (3)	1.68 (3)	2.535 (3)	148 (3)
N22—H22···O2	1.02 (3)	1.53 (3)	2.537 (3)	166 (2)
N26—H26···O1W	0.89 (3)	1.88 (3)	2.760 (3)	169 (3)
C27—H27···O2W^i	0.95	2.42	3.363 (4)	174
N30—H30A···O1	0.85 (3)	2.02 (3)	2.867 (3)	176 (3)
N30—H30B···N34^ii	0.87 (3)	2.52 (3)	3.052 (3)	120 (2)
N32—H32···O12	0.98 (3)	1.70 (3)	2.670 (3)	173 (2)
C33—H33···O1^iii	0.95	2.60	3.451 (3)	149
N36—H36···O2W	0.86 (3)	1.88 (3)	2.737 (3)	178 (3)
C37—H37···O1W^i	0.95	2.42	3.371 (4)	174
N40—H40A···O11	0.96 (3)	1.90 (3)	2.858 (3)	175 (2)
N40—H40B···N38^i	0.90 (3)	2.09 (3)	2.940 (3)	158 (2)
O1W—H1W1···N24^iv	0.83	2.11	2.898 (3)	157
O1W—H2W1···O11	0.85	1.95	2.758 (3)	160
O2W—H1W2···O13^v	0.83	2.03	2.806 (3)	156
O2W—H2W2···N28^iii	0.84	1.99	2.800 (3)	161

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

Adeninium salicylate–adenine–salicylic acid–water (1/2/1/2) (COMP_II)

Crystal data

C5H6N5^+·C7H5O3^−·2C5H5N5·C7H6O3·2H2O	F(000) = 1496
Mr = 717.69	Dx = 1.483 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 22.335 (2) Å	Cell parameters from 1871 reflections
b = 4.8497 (4) Å	θ = 2.8–26.2°
c = 31.567 (3) Å	µ = 0.11 mm^−1
β = 109.936 (9)°	T = 100 K
V = 3214.4 (6) Å^3	Needle, colourless
Z = 4	0.26 × 0.18 × 0.12 mm

Data collection

Kuma KM-4 with CCD detector diffractometer	6457 independent reflections
Radiation source: fine-focus sealed X-ray tube	3318 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.063
ω–scan	θmax = 26.5°, θmin = 2.6°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −27→28
Tmin = 0.981, Tmax = 1.000	k = −6→6
31280 measured reflections	l = −39→39

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)] = 0.075	Hydrogen site location: mixed
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0152P)^2] where P = (Fo^2 + 2Fc^2)/3
6457 reflections	(Δ/σ)max = 0.001
514 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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. 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 > 2sigma(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
C1	0.20080 (16)	−1.2519 (6)	0.43125 (11)	0.0193 (8)
C2	0.14835 (17)	−1.2842 (6)	0.39250 (12)	0.0217 (8)
C3	0.10092 (17)	−1.4761 (7)	0.39024 (13)	0.0286 (9)
H3	0.064878	−1.494351	0.363562	0.034*
C4	0.10701 (18)	−1.6385 (7)	0.42711 (14)	0.0316 (10)
H4	0.074409	−1.767432	0.425820	0.038*
C5	0.15971 (18)	−1.6188 (7)	0.46626 (13)	0.0288 (10)
H5	0.163698	−1.734683	0.491337	0.035*
C6	0.20647 (17)	−1.4257 (6)	0.46796 (12)	0.0251 (9)
H6	0.242920	−1.411211	0.494437	0.030*
C7	0.25128 (17)	−1.0450 (7)	0.43405 (13)	0.0206 (8)
O1	0.24216 (10)	−0.8907 (4)	0.39927 (8)	0.0216 (6)
O2	0.29970 (11)	−1.0290 (4)	0.46885 (8)	0.0247 (6)
O3	0.13995 (11)	−1.1335 (5)	0.35403 (9)	0.0292 (7)
H3A	0.1693 (17)	−1.002 (7)	0.3613 (12)	0.044*
C11	0.61234 (16)	2.3071 (6)	0.11017 (11)	0.0192 (8)
C12	0.66820 (17)	2.3781 (7)	0.10148 (12)	0.0238 (9)
C13	0.66538 (18)	2.5738 (7)	0.06838 (12)	0.0286 (9)
H13	0.703026	2.621978	0.062488	0.034*
C14	0.60919 (19)	2.6959 (7)	0.04453 (12)	0.0331 (10)
H14	0.607975	2.829965	0.022308	0.040*
C15	0.55309 (18)	2.6259 (7)	0.05242 (12)	0.0329 (10)
H15	0.513941	2.711435	0.035555	0.039*
C16	0.55503 (17)	2.4326 (7)	0.08474 (12)	0.0273 (9)
H16	0.516866	2.383680	0.089853	0.033*
C17	0.61545 (18)	2.1071 (7)	0.14615 (12)	0.0231 (9)
O11	0.56015 (11)	2.0284 (4)	0.14773 (8)	0.0238 (6)
H11	0.5657 (16)	1.892 (6)	0.1676 (11)	0.036*
O12	0.66655 (12)	2.0247 (5)	0.17261 (8)	0.0311 (7)
O13	0.72574 (12)	2.2583 (5)	0.12319 (8)	0.0304 (7)
H13A	0.7288 (17)	2.138 (7)	0.1460 (12)	0.046*
C21	0.42850 (16)	−0.3061 (6)	0.42841 (11)	0.0192 (8)
N22	0.49074 (14)	−0.2542 (5)	0.45400 (9)	0.0254 (7)
C23	0.50670 (18)	−0.0528 (7)	0.43125 (12)	0.0264 (9)
H23	0.547708	0.029942	0.440625	0.032*
N24	0.45854 (14)	0.0229 (6)	0.39325 (10)	0.0217 (7)
H24	0.4598 (14)	0.164 (6)	0.3722 (10)	0.026*
C25	0.40816 (17)	−0.1383 (6)	0.39060 (11)	0.0182 (8)
N26	0.35023 (14)	−0.1313 (5)	0.35784 (9)	0.0218 (7)
C27	0.31162 (17)	−0.3180 (7)	0.36474 (12)	0.0228 (9)
H27	0.269782	−0.328545	0.343305	0.027*
N28	0.32678 (14)	−0.4964 (6)	0.39999 (10)	0.0190 (7)
H28	0.2980 (14)	−0.629 (6)	0.3996 (10)	0.023*
C29	0.38464 (17)	−0.4969 (7)	0.43391 (12)	0.0211 (8)
N30	0.39555 (14)	−0.6706 (6)	0.46788 (10)	0.0225 (8)
H30A	0.3643 (15)	−0.787 (6)	0.4680 (10)	0.027*
H30B	0.4324 (15)	−0.663 (6)	0.4901 (11)	0.027*
C31	0.60073 (17)	1.4984 (7)	0.24087 (12)	0.0226 (9)
N32	0.55973 (13)	1.6262 (5)	0.20248 (9)	0.0205 (7)
C33	0.50459 (17)	1.4972 (6)	0.19494 (12)	0.0224 (9)
H33	0.466820	1.540998	0.170690	0.027*
N34	0.50796 (14)	1.2965 (5)	0.22553 (10)	0.0200 (7)
H34	0.4705 (14)	1.193 (6)	0.2230 (10)	0.024*
C35	0.56832 (17)	1.2942 (6)	0.25515 (12)	0.0191 (8)
N36	0.59293 (13)	1.1347 (5)	0.29232 (10)	0.0217 (7)
C37	0.65379 (17)	1.1989 (7)	0.31469 (12)	0.0261 (9)
H37	0.673644	1.095191	0.341330	0.031*
N38	0.69040 (13)	1.3863 (6)	0.30507 (9)	0.0237 (7)
C39	0.66427 (17)	1.5398 (7)	0.26633 (13)	0.0246 (9)
N40	0.70192 (15)	1.7232 (6)	0.25521 (11)	0.0255 (8)
H40A	0.7420 (15)	1.739 (7)	0.2732 (11)	0.031*
H40B	0.6869 (16)	1.812 (7)	0.2298 (11)	0.031*
C41	0.41770 (17)	0.5401 (6)	0.29382 (12)	0.0207 (8)
N42	0.46068 (14)	0.4170 (5)	0.33163 (9)	0.0221 (7)
C43	0.51471 (17)	0.5525 (7)	0.33720 (12)	0.0250 (9)
H43	0.553560	0.513972	0.360808	0.030*
N44	0.50863 (14)	0.7522 (6)	0.30559 (9)	0.0210 (7)
H44	0.5426 (14)	0.874 (6)	0.3016 (10)	0.025*
C45	0.44727 (17)	0.7472 (6)	0.27787 (12)	0.0191 (8)
N46	0.42015 (13)	0.9092 (5)	0.24124 (10)	0.0234 (7)
C47	0.35805 (18)	0.8503 (7)	0.22242 (12)	0.0290 (10)
H47	0.335728	0.957093	0.196643	0.035*
N48	0.32276 (13)	0.6636 (6)	0.23448 (9)	0.0246 (7)
C49	0.35297 (18)	0.5011 (7)	0.27141 (12)	0.0274 (9)
N50	0.31804 (15)	0.3103 (6)	0.28373 (11)	0.0259 (8)
H50A	0.2728 (15)	0.300 (6)	0.2687 (11)	0.031*
H50B	0.3333 (16)	0.188 (7)	0.3048 (11)	0.031*
O1W	0.33544 (12)	−0.6390 (5)	0.59644 (9)	0.0344 (7)
H1WA	0.299361	−0.641388	0.601298	0.052*
H1WB	0.342410	−0.800211	0.586976	0.052*
O2W	0.35024 (13)	−1.1365 (5)	0.55945 (8)	0.0334 (7)
H2WA	0.342899	−1.300961	0.567556	0.050*
H2WB	0.331270	−1.133914	0.530377	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.022 (2)	0.0164 (19)	0.024 (2)	0.0016 (16)	0.0137 (19)	−0.0032 (17)
C2	0.025 (2)	0.0157 (19)	0.027 (2)	−0.0014 (17)	0.013 (2)	−0.0024 (18)
C3	0.024 (2)	0.022 (2)	0.040 (3)	−0.0011 (18)	0.012 (2)	−0.0014 (19)
C4	0.031 (3)	0.018 (2)	0.058 (3)	−0.0062 (18)	0.032 (2)	−0.011 (2)
C5	0.044 (3)	0.022 (2)	0.034 (2)	−0.0008 (19)	0.032 (2)	−0.0007 (19)
C6	0.028 (2)	0.024 (2)	0.027 (2)	−0.0021 (18)	0.014 (2)	−0.0075 (18)
C7	0.018 (2)	0.020 (2)	0.028 (2)	0.0004 (17)	0.014 (2)	−0.0047 (18)
O1	0.0247 (15)	0.0207 (13)	0.0225 (14)	−0.0043 (11)	0.0121 (12)	−0.0001 (12)
O2	0.0245 (15)	0.0263 (14)	0.0231 (15)	−0.0051 (12)	0.0078 (13)	0.0011 (12)
O3	0.0272 (17)	0.0222 (14)	0.0361 (17)	−0.0073 (12)	0.0082 (14)	−0.0032 (13)
C11	0.024 (2)	0.0162 (19)	0.020 (2)	0.0002 (17)	0.0109 (18)	−0.0006 (16)
C12	0.026 (2)	0.024 (2)	0.023 (2)	−0.0032 (18)	0.011 (2)	−0.0084 (18)
C13	0.036 (3)	0.029 (2)	0.028 (2)	−0.005 (2)	0.021 (2)	−0.0002 (19)
C14	0.049 (3)	0.026 (2)	0.032 (2)	−0.002 (2)	0.023 (2)	0.0050 (19)
C15	0.044 (3)	0.029 (2)	0.031 (2)	0.010 (2)	0.020 (2)	0.009 (2)
C16	0.029 (2)	0.026 (2)	0.033 (2)	0.0037 (18)	0.019 (2)	0.0034 (19)
C17	0.029 (3)	0.0174 (19)	0.027 (2)	0.0027 (18)	0.015 (2)	−0.0058 (18)
O11	0.0225 (15)	0.0222 (14)	0.0303 (16)	0.0023 (12)	0.0136 (13)	0.0109 (12)
O12	0.0237 (16)	0.0387 (16)	0.0327 (16)	0.0073 (13)	0.0120 (14)	0.0138 (13)
O13	0.0255 (16)	0.0445 (17)	0.0248 (16)	0.0016 (14)	0.0135 (14)	0.0066 (13)
C21	0.020 (2)	0.0172 (19)	0.019 (2)	−0.0012 (16)	0.0050 (19)	−0.0021 (17)
N22	0.030 (2)	0.0235 (17)	0.0232 (18)	−0.0043 (15)	0.0102 (17)	0.0028 (15)
C23	0.024 (2)	0.027 (2)	0.029 (2)	−0.0030 (18)	0.010 (2)	−0.0024 (19)
N24	0.0218 (19)	0.0213 (17)	0.0235 (19)	0.0015 (15)	0.0095 (16)	0.0039 (15)
C25	0.020 (2)	0.0157 (19)	0.022 (2)	0.0006 (17)	0.0115 (19)	−0.0041 (17)
N26	0.026 (2)	0.0193 (16)	0.0273 (19)	−0.0045 (14)	0.0180 (17)	−0.0029 (14)
C27	0.022 (2)	0.027 (2)	0.022 (2)	0.0080 (18)	0.0108 (19)	−0.0083 (18)
N28	0.0164 (19)	0.0202 (17)	0.0213 (18)	−0.0034 (13)	0.0075 (16)	−0.0039 (15)
C29	0.025 (2)	0.0183 (19)	0.022 (2)	0.0010 (17)	0.011 (2)	−0.0052 (18)
N30	0.021 (2)	0.0227 (18)	0.0226 (19)	−0.0054 (15)	0.0059 (16)	−0.0010 (16)
C31	0.026 (2)	0.0191 (19)	0.025 (2)	0.0045 (17)	0.012 (2)	−0.0036 (18)
N32	0.0240 (19)	0.0187 (16)	0.0206 (18)	0.0026 (14)	0.0099 (16)	−0.0009 (14)
C33	0.029 (2)	0.0157 (18)	0.024 (2)	0.0037 (17)	0.0115 (19)	−0.0002 (17)
N34	0.019 (2)	0.0172 (16)	0.0265 (18)	−0.0002 (14)	0.0118 (17)	0.0006 (15)
C35	0.025 (2)	0.0140 (18)	0.024 (2)	−0.0031 (17)	0.016 (2)	−0.0039 (17)
N36	0.0187 (19)	0.0209 (16)	0.0273 (18)	0.0003 (14)	0.0100 (16)	−0.0005 (15)
C37	0.026 (2)	0.026 (2)	0.028 (2)	−0.0014 (18)	0.012 (2)	−0.0030 (18)
N38	0.0212 (19)	0.0241 (17)	0.0249 (18)	0.0017 (14)	0.0065 (16)	0.0040 (15)
C39	0.023 (2)	0.022 (2)	0.035 (3)	−0.0028 (17)	0.014 (2)	−0.0119 (19)
N40	0.0187 (19)	0.0296 (19)	0.029 (2)	−0.0100 (16)	0.0096 (17)	0.0000 (16)
C41	0.022 (2)	0.021 (2)	0.022 (2)	0.0002 (17)	0.011 (2)	−0.0074 (17)
N42	0.0262 (19)	0.0214 (16)	0.0224 (18)	0.0051 (15)	0.0131 (16)	0.0041 (15)
C43	0.027 (2)	0.025 (2)	0.027 (2)	0.0015 (18)	0.014 (2)	−0.0029 (18)
N44	0.024 (2)	0.0185 (16)	0.0248 (18)	−0.0023 (14)	0.0133 (17)	0.0036 (15)
C45	0.025 (2)	0.0152 (19)	0.023 (2)	−0.0002 (17)	0.015 (2)	−0.0007 (17)
N46	0.0144 (18)	0.0263 (17)	0.029 (2)	0.0022 (14)	0.0071 (16)	−0.0058 (16)
C47	0.033 (3)	0.025 (2)	0.032 (2)	0.0093 (19)	0.014 (2)	−0.0016 (19)
N48	0.0231 (19)	0.0261 (17)	0.0259 (19)	0.0006 (15)	0.0101 (16)	0.0001 (15)
C49	0.033 (3)	0.024 (2)	0.030 (2)	−0.0047 (19)	0.017 (2)	−0.017 (2)
N50	0.0227 (19)	0.0220 (18)	0.034 (2)	−0.0059 (16)	0.0114 (18)	−0.0021 (15)
O1W	0.0331 (18)	0.0332 (15)	0.0432 (18)	−0.0024 (13)	0.0213 (15)	−0.0044 (14)
O2W	0.0399 (18)	0.0342 (15)	0.0256 (15)	−0.0075 (14)	0.0105 (15)	0.0024 (13)

Geometric parameters (Å, º)

C1—C2	1.384 (4)	C27—H27	0.9500
C1—C6	1.403 (4)	N28—C29	1.369 (4)
C1—C7	1.489 (4)	N28—H28	0.91 (3)
C2—O3	1.374 (4)	C29—N30	1.320 (4)
C2—C3	1.394 (4)	N30—H30A	0.90 (3)
C3—C4	1.373 (5)	N30—H30B	0.88 (3)
C3—H3	0.9500	C31—C39	1.386 (5)
C4—C5	1.389 (5)	C31—C35	1.389 (4)
C4—H4	0.9500	C31—N32	1.391 (4)
C5—C6	1.390 (4)	N32—C33	1.328 (4)
C5—H5	0.9500	C33—N34	1.355 (4)
C6—H6	0.9500	C33—H33	0.9500
C7—O2	1.254 (4)	N34—C35	1.354 (4)
C7—O1	1.286 (4)	N34—H34	0.95 (3)
O3—H3A	0.89 (3)	C35—N36	1.356 (4)
C11—C16	1.397 (4)	N36—C37	1.337 (4)
C11—C12	1.408 (4)	C37—N38	1.325 (4)
C11—C17	1.477 (4)	C37—H37	0.9500
C12—O13	1.363 (4)	N38—C39	1.380 (4)
C12—C13	1.397 (4)	C39—N40	1.350 (4)
C13—C14	1.360 (5)	N40—H40A	0.88 (3)
C13—H13	0.9500	N40—H40B	0.87 (3)
C14—C15	1.400 (4)	C41—N42	1.386 (4)
C14—H14	0.9500	C41—C45	1.388 (4)
C15—C16	1.376 (4)	C41—C49	1.389 (5)
C15—H15	0.9500	N42—C43	1.332 (4)
C16—H16	0.9500	C43—N44	1.363 (4)
C17—O12	1.229 (4)	C43—H43	0.9500
C17—O11	1.310 (4)	N44—C45	1.351 (4)
O11—H11	0.89 (3)	N44—H44	1.00 (3)
O13—H13A	0.91 (3)	C45—N46	1.358 (4)
C21—N22	1.372 (4)	N46—C47	1.340 (4)
C21—C25	1.387 (4)	C47—N48	1.338 (4)
C21—C29	1.401 (4)	C47—H47	0.9500
N22—C23	1.331 (4)	N48—C49	1.378 (4)
C23—N24	1.361 (4)	C49—N50	1.350 (4)
C23—H23	0.9500	N50—H50A	0.96 (3)
N24—C25	1.349 (4)	N50—H50B	0.87 (3)
N24—H24	0.96 (3)	O1W—H1WA	0.8701
C25—N26	1.354 (4)	O1W—H1WB	0.8700
N26—C27	1.319 (4)	O2W—H2WA	0.8701
C27—N28	1.358 (4)	O2W—H2WB	0.8701
C2—C1—C6	118.2 (3)	N28—C27—H27	117.3
C2—C1—C7	121.6 (3)	C27—N28—C29	123.2 (3)
C6—C1—C7	120.1 (3)	C27—N28—H28	118 (2)
O3—C2—C1	122.7 (3)	C29—N28—H28	119 (2)
O3—C2—C3	115.9 (3)	N30—C29—N28	120.0 (3)
C1—C2—C3	121.4 (3)	N30—C29—C21	125.4 (3)
C4—C3—C2	119.1 (4)	N28—C29—C21	114.6 (3)
C4—C3—H3	120.5	C29—N30—H30A	118 (2)
C2—C3—H3	120.5	C29—N30—H30B	119 (2)
C3—C4—C5	121.6 (3)	H30A—N30—H30B	123 (3)
C3—C4—H4	119.2	C39—C31—C35	117.3 (3)
C5—C4—H4	119.2	C39—C31—N32	132.9 (3)
C4—C5—C6	118.6 (3)	C35—C31—N32	109.8 (3)
C4—C5—H5	120.7	C33—N32—C31	103.9 (3)
C6—C5—H5	120.7	N32—C33—N34	112.8 (3)
C5—C6—C1	121.2 (4)	N32—C33—H33	123.6
C5—C6—H6	119.4	N34—C33—H33	123.6
C1—C6—H6	119.4	C33—N34—C35	107.4 (3)
O2—C7—O1	123.4 (3)	C33—N34—H34	118.9 (19)
O2—C7—C1	120.2 (3)	C35—N34—H34	133.7 (19)
O1—C7—C1	116.4 (3)	N34—C35—N36	128.1 (3)
C2—O3—H3A	107 (2)	N34—C35—C31	106.0 (3)
C16—C11—C12	118.7 (3)	N36—C35—C31	125.8 (3)
C16—C11—C17	121.4 (3)	C37—N36—C35	111.3 (3)
C12—C11—C17	119.8 (3)	N38—C37—N36	129.4 (3)
O13—C12—C13	117.4 (3)	N38—C37—H37	115.3
O13—C12—C11	123.0 (3)	N36—C37—H37	115.3
C13—C12—C11	119.6 (3)	C37—N38—C39	117.7 (3)
C14—C13—C12	120.5 (3)	N40—C39—N38	118.2 (3)
C14—C13—H13	119.7	N40—C39—C31	123.3 (4)
C12—C13—H13	119.7	N38—C39—C31	118.4 (3)
C13—C14—C15	120.6 (3)	C39—N40—H40A	118 (2)
C13—C14—H14	119.7	C39—N40—H40B	119 (2)
C15—C14—H14	119.7	H40A—N40—H40B	122 (3)
C16—C15—C14	119.6 (4)	N42—C41—C45	110.4 (3)
C16—C15—H15	120.2	N42—C41—C49	132.5 (3)
C14—C15—H15	120.2	C45—C41—C49	117.1 (3)
C15—C16—C11	120.9 (3)	C43—N42—C41	103.4 (3)
C15—C16—H16	119.5	N42—C43—N44	113.2 (3)
C11—C16—H16	119.5	N42—C43—H43	123.4
O12—C17—O11	123.3 (3)	N44—C43—H43	123.4
O12—C17—C11	121.7 (3)	C45—N44—C43	106.7 (3)
O11—C17—C11	115.0 (3)	C45—N44—H44	124.9 (17)
C17—O11—H11	110 (2)	C43—N44—H44	128.3 (18)
C12—O13—H13A	118 (2)	N44—C45—N46	126.9 (3)
N22—C21—C25	111.6 (3)	N44—C45—C41	106.3 (3)
N22—C21—C29	131.2 (3)	N46—C45—C41	126.8 (3)
C25—C21—C29	117.2 (3)	C47—N46—C45	110.4 (3)
C23—N22—C21	102.8 (3)	N48—C47—N46	129.7 (3)
N22—C23—N24	113.4 (3)	N48—C47—H47	115.1
N22—C23—H23	123.3	N46—C47—H47	115.1
N24—C23—H23	123.3	C47—N48—C49	117.5 (3)
C25—N24—C23	106.9 (3)	N50—C49—N48	118.1 (3)
C25—N24—H24	126.2 (19)	N50—C49—C41	123.4 (4)
C23—N24—H24	126.9 (19)	N48—C49—C41	118.5 (3)
N24—C25—N26	126.3 (3)	C49—N50—H50A	120.6 (19)
N24—C25—C21	105.4 (3)	C49—N50—H50B	125 (2)
N26—C25—C21	128.3 (3)	H50A—N50—H50B	114 (3)
C27—N26—C25	111.4 (3)	H1WA—O1W—H1WB	109.5
N26—C27—N28	125.3 (3)	H2WA—O2W—H2WB	104.5
N26—C27—H27	117.3
C6—C1—C2—O3	−176.8 (3)	C27—N28—C29—C21	−2.8 (4)
C7—C1—C2—O3	1.4 (5)	N22—C21—C29—N30	1.8 (6)
C6—C1—C2—C3	2.5 (5)	C25—C21—C29—N30	−179.4 (3)
C7—C1—C2—C3	−179.3 (3)	N22—C21—C29—N28	−177.4 (3)
O3—C2—C3—C4	178.5 (3)	C25—C21—C29—N28	1.4 (4)
C1—C2—C3—C4	−0.9 (5)	C39—C31—N32—C33	−178.7 (4)
C2—C3—C4—C5	−1.0 (5)	C35—C31—N32—C33	0.1 (3)
C3—C4—C5—C6	1.2 (5)	C31—N32—C33—N34	−0.4 (3)
C4—C5—C6—C1	0.5 (5)	N32—C33—N34—C35	0.6 (4)
C2—C1—C6—C5	−2.3 (5)	C33—N34—C35—N36	177.4 (3)
C7—C1—C6—C5	179.5 (3)	C33—N34—C35—C31	−0.5 (3)
C2—C1—C7—O2	−176.7 (3)	C39—C31—C35—N34	179.3 (3)
C6—C1—C7—O2	1.5 (5)	N32—C31—C35—N34	0.3 (4)
C2—C1—C7—O1	2.8 (4)	C39—C31—C35—N36	1.3 (5)
C6—C1—C7—O1	−179.0 (3)	N32—C31—C35—N36	−177.7 (3)
C16—C11—C12—O13	−177.2 (3)	N34—C35—N36—C37	−177.0 (3)
C17—C11—C12—O13	3.9 (5)	C31—C35—N36—C37	0.5 (4)
C16—C11—C12—C13	1.0 (5)	C35—N36—C37—N38	−0.6 (5)
C17—C11—C12—C13	−178.0 (3)	N36—C37—N38—C39	−1.1 (5)
O13—C12—C13—C14	178.2 (3)	C37—N38—C39—N40	−177.3 (3)
C11—C12—C13—C14	0.0 (5)	C37—N38—C39—C31	2.9 (4)
C12—C13—C14—C15	−0.6 (5)	C35—C31—C39—N40	177.2 (3)
C13—C14—C15—C16	0.3 (5)	N32—C31—C39—N40	−4.1 (6)
C14—C15—C16—C11	0.7 (5)	C35—C31—C39—N38	−3.0 (4)
C12—C11—C16—C15	−1.3 (5)	N32—C31—C39—N38	175.7 (3)
C17—C11—C16—C15	177.7 (3)	C45—C41—N42—C43	−0.2 (3)
C16—C11—C17—O12	−169.9 (3)	C49—C41—N42—C43	−177.4 (3)
C12—C11—C17—O12	9.0 (5)	C41—N42—C43—N44	0.1 (3)
C16—C11—C17—O11	9.5 (5)	N42—C43—N44—C45	0.1 (4)
C12—C11—C17—O11	−171.6 (3)	C43—N44—C45—N46	−179.2 (3)
C25—C21—N22—C23	0.6 (4)	C43—N44—C45—C41	−0.2 (3)
C29—C21—N22—C23	179.4 (3)	N42—C41—C45—N44	0.3 (3)
C21—N22—C23—N24	−0.1 (4)	C49—C41—C45—N44	177.9 (3)
N22—C23—N24—C25	−0.4 (4)	N42—C41—C45—N46	179.2 (3)
C23—N24—C25—N26	−180.0 (3)	C49—C41—C45—N46	−3.1 (5)
C23—N24—C25—C21	0.7 (3)	N44—C45—N46—C47	−178.8 (3)
N22—C21—C25—N24	−0.9 (4)	C41—C45—N46—C47	2.5 (4)
C29—C21—C25—N24	−179.9 (3)	C45—N46—C47—N48	−0.5 (5)
N22—C21—C25—N26	179.9 (3)	N46—C47—N48—C49	−0.6 (5)
C29—C21—C25—N26	0.9 (5)	C47—N48—C49—N50	−179.4 (3)
N24—C25—N26—C27	179.2 (3)	C47—N48—C49—C41	0.0 (4)
C21—C25—N26—C27	−1.7 (5)	N42—C41—C49—N50	−1.9 (6)
C25—N26—C27—N28	0.2 (4)	C45—C41—C49—N50	−178.9 (3)
N26—C27—N28—C29	2.1 (5)	N42—C41—C49—N48	178.6 (3)
C27—N28—C29—N30	178.0 (3)	C45—C41—C49—N48	1.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O1	0.89 (3)	1.74 (4)	2.533 (3)	146 (3)
O11—H11···N32	0.89 (3)	1.73 (3)	2.608 (3)	168 (3)
O13—H13A···O12	0.91 (3)	1.93 (3)	2.621 (3)	131 (3)
O13—H13A···N38^i	0.91 (3)	2.29 (4)	3.000 (4)	135 (3)
C23—H23···O2W^ii	0.95	2.34	3.240 (4)	158
N24—H24···N42	0.96 (3)	1.78 (3)	2.739 (4)	178 (3)
N28—H28···O1	0.91 (3)	1.78 (3)	2.683 (3)	180 (4)
N30—H30A···O2	0.90 (3)	1.87 (3)	2.766 (4)	179 (3)
N30—H30B···N22^ii	0.88 (3)	2.04 (3)	2.897 (4)	164 (3)
C33—H33···O3^iii	0.95	2.40	3.132 (4)	134
N34—H34···N46	0.95 (3)	1.98 (3)	2.879 (4)	155 (3)
N40—H40A···O12^iv	0.88 (3)	2.41 (3)	3.191 (4)	148 (3)
N40—H40B···O12	0.87 (3)	1.99 (3)	2.856 (4)	171 (3)
C43—H43···O1W^v	0.95	2.46	3.314 (5)	150
N44—H44···N36	1.00 (3)	1.78 (3)	2.775 (4)	170 (3)
N50—H50A···N48^vi	0.96 (3)	2.20 (3)	3.081 (4)	152 (3)
N50—H50B···N26	0.87 (3)	2.22 (3)	3.071 (4)	167 (3)
O1W—H1WA···O13^vii	0.87	2.07	2.909 (3)	162
O1W—H1WB···O2W	0.87	1.88	2.749 (3)	173
O2W—H2WA···O1W^viii	0.87	1.91	2.770 (3)	169
O2W—H2WB···O2	0.87	1.90	2.743 (3)	164

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) −x+1, −y−1, −z+1; (iii) −x+1/2, y+5/2, −z+1/2; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+1, −y, −z+1; (vi) −x+1/2, y−1/2, −z+1/2; (vii) x−1/2, −y+3/2, z+1/2; (viii) x, y−1, z.