Crystal engineering of an adenine–decavanadate molecular device towards label-free chemical sensing and biological screening

Due to the inherent geometrical interdependencies of nucleic acid structures, the ability to engineer biosensors that rely on the specific interactions of these compounds is of considerable importance. Additionally, sensing or screening in a label-free fashion is a capability of these structures that can be readily achieved by exploiting the fluorescent component. In this work, the [AdH]₆[V₁₀O₂₈].4(H₂O) (1) supramolecular structure is introduced using adenine and decavanadate moieties that allow probing of selectivity to specific nucleic acid binding events by optical changes. The structure of (1) is an alternating organic–inorganic hybrid architecture of cationic adeninium (AdH⁺) ribbons and anionic decavanadate (DV)–water sheets. The luminescent screening and anticancer activity of compound (1) on the two human mammary carcinoma cell lines MDA-MB-231 and MCF7 were investigated using fluorescent microscopy and MTT assays, respectively. It was found that compound (1) is cell permeable with no toxicity below 12.5 µM concentration and moderate cytotoxicity at concentrations as high as 200 µM in human breast cancer cell lines, making it a useful tool to study the cell nucleus in real time.

Computing details

Data collection: CrysAlis CCD 1.171.38.41 (Rigaku Oxford Diffraction, 2015; cell refinement: CrysAlis RED 1.171.38.41 (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis RED 1.171.38.41 (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2014); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2018); molecular graphics: Brandenburg & Putz (2006). Diamond 3.0. Crystal and Molecular Structure Visualisation, University of Bonn, Germany; software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2018).

(I)

Crystal data

O28V10·6(C5H6N5)·4(H2O)	Z = 1
Mr = 1846.35	F(000) = 920
Triclinic, P1	Dx = 2.070 Mg m^−3
a = 11.3756 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5611 (3) Å	Cell parameters from 15803 reflections
c = 14.0894 (4) Å	θ = 3.0–29.3°
α = 73.533 (2)°	µ = 1.62 mm^−1
β = 67.176 (3)°	T = 100 K
γ = 60.845 (3)°	Parallelepiped, yellow
V = 1481.18 (9) Å^3	0.14 × 0.12 × 0.07 mm

Data collection

KUMA KM-4 with CCD detector diffractometer	7654 independent reflections
Radiation source: fine-focus sealed X-ray tube	5898 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.039
ω–scan	θmax = 29.5°, θmin = 2.4°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −15→15
Tmin = 0.897, Tmax = 1.000	k = −15→15
48373 measured reflections	l = −19→19

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)] = 0.039	Hydrogen site location: mixed
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0457P)^2 + 1.4419P] where P = (Fo^2 + 2Fc^2)/3
7654 reflections	(Δ/σ)max = 0.001
460 parameters	Δρmax = 1.42 e Å^−3
0 restraints	Δρmin = −0.53 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
V1	1.01943 (4)	0.47426 (4)	0.38479 (3)	0.01774 (10)
V2	0.75387 (4)	0.47450 (4)	0.57856 (3)	0.01838 (10)
V3	0.69263 (5)	0.75569 (4)	0.60968 (3)	0.02034 (10)
V4	0.95368 (5)	0.75566 (4)	0.42078 (3)	0.01902 (10)
V5	0.72245 (5)	0.70485 (4)	0.39759 (3)	0.02039 (10)
O1	0.93212 (18)	0.35794 (15)	0.47808 (12)	0.0193 (3)
O2	1.16007 (18)	0.35347 (16)	0.31411 (12)	0.0202 (3)
O3	1.09951 (18)	0.59900 (15)	0.34858 (12)	0.0192 (3)
O4	0.87397 (18)	0.59893 (15)	0.50036 (12)	0.0193 (3)
O5	0.68471 (19)	0.36891 (16)	0.63157 (13)	0.0228 (4)
O6	0.64651 (18)	0.60822 (16)	0.65738 (12)	0.0208 (3)
O7	0.57573 (19)	0.85740 (17)	0.69275 (13)	0.0245 (4)
O8	0.80903 (18)	0.84110 (15)	0.53320 (12)	0.0204 (3)
O9	1.02660 (19)	0.85762 (16)	0.36718 (12)	0.0218 (4)
O10	0.90196 (18)	0.55684 (15)	0.31664 (12)	0.0203 (3)
O11	0.67744 (18)	0.56156 (16)	0.47033 (12)	0.0213 (4)
O12	0.61171 (18)	0.80470 (16)	0.50419 (13)	0.0219 (4)
O13	0.83868 (19)	0.79814 (16)	0.34624 (12)	0.0215 (4)
O14	0.63272 (19)	0.76768 (16)	0.31643 (13)	0.0247 (4)
C1	0.3475 (2)	0.5426 (2)	0.94107 (18)	0.0165 (4)
N2	0.33193 (19)	0.56925 (18)	1.03605 (15)	0.0175 (4)
C3	0.3258 (2)	0.4621 (2)	1.09959 (19)	0.0194 (5)
H3	0.315929	0.450896	1.171319	0.023*
N4	0.3353 (2)	0.36916 (19)	1.05160 (16)	0.0213 (4)
H4	0.332565	0.292005	1.080717	0.026*
C5	0.3496 (2)	0.4191 (2)	0.95025 (19)	0.0195 (5)
N6	0.3611 (2)	0.36092 (19)	0.87352 (17)	0.0224 (4)
C7	0.3726 (3)	0.4351 (2)	0.7835 (2)	0.0237 (5)
H7	0.382949	0.400795	0.725548	0.028*
N8	0.3708 (2)	0.5584 (2)	0.76725 (16)	0.0213 (4)
H8	0.378387	0.600830	0.704078	0.026*
C9	0.3581 (2)	0.6196 (2)	0.84274 (18)	0.0170 (4)
N10	0.3541 (2)	0.73872 (19)	0.82210 (15)	0.0190 (4)
H10A	0.359676	0.780541	0.758815	0.023*
H10B	0.345918	0.777166	0.871463	0.023*
C11	0.3241 (2)	0.9367 (2)	1.03888 (18)	0.0175 (5)
N12	0.3366 (2)	0.91061 (18)	0.94480 (15)	0.0178 (4)
C13	0.3480 (2)	1.0144 (2)	0.8799 (2)	0.0212 (5)
H13	0.358090	1.024472	0.808269	0.025*
N14	0.3438 (2)	1.10636 (18)	0.92609 (16)	0.0212 (4)
H14	0.349920	1.181872	0.895763	0.025*
C15	0.3283 (2)	1.0583 (2)	1.0277 (2)	0.0200 (5)
N16	0.3180 (2)	1.1157 (2)	1.10425 (18)	0.0246 (5)
C17	0.3007 (3)	1.0437 (2)	1.1949 (2)	0.0249 (5)
H17	0.292555	1.077961	1.252068	0.030*
N18	0.2932 (2)	0.92530 (19)	1.21491 (16)	0.0217 (4)
H18	0.281301	0.885380	1.278902	0.026*
C19	0.3036 (2)	0.8657 (2)	1.13908 (18)	0.0184 (5)
N20	0.2930 (2)	0.75192 (18)	1.16150 (16)	0.0210 (4)
H20A	0.279074	0.713379	1.225867	0.025*
H20B	0.299824	0.714435	1.112104	0.025*
C21	0.9884 (2)	0.1981 (2)	0.04875 (17)	0.0154 (4)
N22	0.9991 (2)	0.17174 (18)	−0.04524 (14)	0.0164 (4)
C23	1.0092 (2)	0.2759 (2)	−0.11035 (19)	0.0188 (5)
H23	1.017509	0.286225	−0.181687	0.023*
N24	1.0065 (2)	0.36801 (18)	−0.06514 (16)	0.0199 (4)
H24	1.012613	0.443451	−0.095842	0.024*
C25	0.9926 (2)	0.3197 (2)	0.03639 (19)	0.0180 (5)
N26	0.9839 (2)	0.37757 (19)	0.11230 (17)	0.0220 (4)
C27	0.9709 (3)	0.3035 (2)	0.2022 (2)	0.0240 (5)
H27	0.964169	0.337723	0.258914	0.029*
N28	0.9662 (2)	0.18378 (19)	0.22311 (15)	0.0194 (4)
H28	0.957257	0.142999	0.286824	0.023*
C29	0.9750 (2)	0.1248 (2)	0.14763 (18)	0.0165 (4)
N30	0.9707 (2)	0.00817 (18)	0.16995 (15)	0.0185 (4)
H30A	0.962105	−0.032284	0.233749	0.022*
H30B	0.976380	−0.029384	0.121066	0.022*
O1W	0.3885 (2)	0.6393 (2)	0.56410 (16)	0.0380 (5)
H1WA	0.339507	0.668319	0.524831	0.057*
H1WB	0.473777	0.617405	0.527186	0.057*
O2W	0.32070 (19)	0.91226 (18)	0.63433 (14)	0.0306 (4)
H2WA	0.396295	0.896485	0.585078	0.046*
H2WB	0.290252	0.993573	0.640940	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0329 (2)	0.01253 (18)	0.01039 (19)	−0.01026 (17)	−0.00896 (16)	−0.00043 (14)
V2	0.0290 (2)	0.01462 (19)	0.0137 (2)	−0.01139 (17)	−0.00732 (16)	0.00048 (14)
V3	0.0293 (2)	0.0176 (2)	0.0147 (2)	−0.00965 (17)	−0.00489 (17)	−0.00560 (15)
V4	0.0333 (2)	0.01293 (19)	0.01222 (19)	−0.01138 (17)	−0.00618 (17)	−0.00138 (14)
V5	0.0338 (2)	0.01505 (19)	0.0138 (2)	−0.01072 (17)	−0.00912 (17)	−0.00039 (14)
O1	0.0317 (9)	0.0175 (8)	0.0118 (8)	−0.0126 (7)	−0.0080 (7)	−0.0002 (6)
O2	0.0340 (10)	0.0181 (8)	0.0122 (8)	−0.0140 (7)	−0.0066 (7)	−0.0018 (6)
O3	0.0335 (9)	0.0151 (8)	0.0129 (8)	−0.0124 (7)	−0.0094 (7)	0.0003 (6)
O4	0.0315 (9)	0.0173 (8)	0.0125 (8)	−0.0122 (7)	−0.0081 (7)	−0.0009 (6)
O5	0.0355 (10)	0.0192 (8)	0.0187 (9)	−0.0152 (8)	−0.0095 (7)	−0.0004 (7)
O6	0.0294 (9)	0.0185 (8)	0.0147 (8)	−0.0114 (7)	−0.0046 (7)	−0.0030 (6)
O7	0.0319 (10)	0.0226 (9)	0.0200 (9)	−0.0115 (8)	−0.0048 (7)	−0.0085 (7)
O8	0.0327 (9)	0.0151 (8)	0.0143 (8)	−0.0108 (7)	−0.0063 (7)	−0.0029 (6)
O9	0.0372 (10)	0.0159 (8)	0.0150 (8)	−0.0134 (7)	−0.0087 (7)	−0.0004 (6)
O10	0.0356 (10)	0.0172 (8)	0.0135 (8)	−0.0141 (7)	−0.0099 (7)	−0.0004 (6)
O11	0.0335 (10)	0.0166 (8)	0.0159 (8)	−0.0113 (7)	−0.0095 (7)	−0.0006 (6)
O12	0.0314 (9)	0.0157 (8)	0.0184 (8)	−0.0081 (7)	−0.0090 (7)	−0.0031 (6)
O13	0.0363 (10)	0.0169 (8)	0.0145 (8)	−0.0131 (7)	−0.0084 (7)	−0.0017 (6)
O14	0.0399 (11)	0.0175 (8)	0.0198 (9)	−0.0121 (8)	−0.0135 (8)	−0.0001 (7)
C1	0.0114 (10)	0.0139 (10)	0.0230 (12)	−0.0052 (8)	−0.0046 (9)	−0.0016 (9)
N2	0.0145 (9)	0.0161 (9)	0.0180 (10)	−0.0072 (8)	−0.0010 (8)	−0.0008 (7)
C3	0.0148 (11)	0.0157 (11)	0.0229 (12)	−0.0059 (9)	−0.0038 (9)	0.0007 (9)
N4	0.0206 (10)	0.0139 (9)	0.0284 (11)	−0.0090 (8)	−0.0075 (9)	0.0024 (8)
C5	0.0118 (10)	0.0138 (10)	0.0299 (13)	−0.0042 (9)	−0.0039 (9)	−0.0040 (9)
N6	0.0198 (10)	0.0174 (10)	0.0308 (12)	−0.0084 (8)	−0.0055 (9)	−0.0059 (8)
C7	0.0216 (12)	0.0205 (12)	0.0324 (14)	−0.0112 (10)	−0.0057 (10)	−0.0070 (10)
N8	0.0239 (11)	0.0228 (10)	0.0214 (10)	−0.0149 (9)	−0.0027 (8)	−0.0050 (8)
C9	0.0123 (10)	0.0190 (11)	0.0203 (12)	−0.0084 (9)	−0.0025 (9)	−0.0034 (9)
N10	0.0233 (10)	0.0193 (10)	0.0159 (10)	−0.0130 (8)	−0.0033 (8)	−0.0004 (7)
C11	0.0129 (10)	0.0143 (10)	0.0241 (12)	−0.0047 (9)	−0.0045 (9)	−0.0043 (9)
N12	0.0157 (9)	0.0146 (9)	0.0213 (10)	−0.0070 (8)	−0.0034 (8)	−0.0013 (7)
C13	0.0180 (11)	0.0147 (11)	0.0255 (13)	−0.0063 (9)	−0.0031 (10)	−0.0012 (9)
N14	0.0149 (9)	0.0115 (9)	0.0318 (12)	−0.0059 (8)	−0.0022 (8)	−0.0014 (8)
C15	0.0115 (10)	0.0131 (10)	0.0332 (14)	−0.0028 (9)	−0.0064 (10)	−0.0042 (9)
N16	0.0177 (10)	0.0175 (10)	0.0400 (13)	−0.0063 (8)	−0.0091 (9)	−0.0069 (9)
C17	0.0214 (12)	0.0193 (12)	0.0377 (15)	−0.0065 (10)	−0.0118 (11)	−0.0084 (11)
N18	0.0261 (11)	0.0182 (10)	0.0217 (10)	−0.0081 (8)	−0.0104 (9)	−0.0014 (8)
C19	0.0165 (11)	0.0153 (11)	0.0224 (12)	−0.0047 (9)	−0.0063 (9)	−0.0040 (9)
N20	0.0282 (11)	0.0137 (9)	0.0197 (10)	−0.0080 (8)	−0.0092 (9)	0.0011 (8)
C21	0.0129 (10)	0.0140 (10)	0.0179 (11)	−0.0053 (8)	−0.0017 (8)	−0.0049 (8)
N22	0.0170 (9)	0.0136 (9)	0.0163 (9)	−0.0072 (8)	−0.0012 (8)	−0.0027 (7)
C23	0.0171 (11)	0.0129 (10)	0.0222 (12)	−0.0066 (9)	−0.0011 (9)	−0.0024 (9)
N24	0.0179 (10)	0.0108 (9)	0.0292 (11)	−0.0077 (8)	−0.0047 (8)	−0.0001 (8)
C25	0.0120 (10)	0.0135 (10)	0.0273 (13)	−0.0035 (9)	−0.0040 (9)	−0.0069 (9)
N26	0.0181 (10)	0.0147 (9)	0.0348 (12)	−0.0059 (8)	−0.0081 (9)	−0.0070 (8)
C27	0.0278 (13)	0.0187 (12)	0.0288 (13)	−0.0096 (10)	−0.0092 (11)	−0.0069 (10)
N28	0.0269 (11)	0.0177 (9)	0.0159 (10)	−0.0097 (8)	−0.0068 (8)	−0.0042 (7)
C29	0.0154 (11)	0.0164 (11)	0.0190 (11)	−0.0050 (9)	−0.0060 (9)	−0.0059 (9)
N30	0.0246 (10)	0.0169 (9)	0.0150 (9)	−0.0109 (8)	−0.0039 (8)	−0.0022 (7)
O1W	0.0386 (12)	0.0442 (12)	0.0334 (11)	−0.0154 (10)	−0.0142 (9)	−0.0068 (9)
O2W	0.0304 (10)	0.0229 (9)	0.0295 (10)	−0.0049 (8)	−0.0093 (8)	−0.0022 (8)

Geometric parameters (Å, º)

V1—O10	1.6887 (17)	N6—C7	1.313 (3)
V1—O2	1.6962 (17)	C7—N8	1.369 (3)
V1—O3	1.9163 (16)	C7—H7	0.9500
V1—O1	1.9517 (16)	N8—C9	1.364 (3)
V1—O4	2.0936 (16)	N8—H8	0.8800
V1—O4^i	2.1334 (16)	C9—N10	1.306 (3)
V1—V3^i	3.0657 (6)	N10—H10A	0.8800
V1—V5	3.0947 (6)	N10—H10B	0.8800
V1—V4	3.1098 (5)	C11—N12	1.381 (3)
V2—O5	1.6217 (17)	C11—C15	1.392 (3)
V2—O6	1.7878 (16)	C11—C19	1.412 (3)
V2—O11	1.8440 (16)	N12—C13	1.315 (3)
V2—O3^i	2.0025 (17)	C13—N14	1.369 (3)
V2—O1	2.0307 (17)	C13—H13	0.9500
V2—O4	2.2357 (16)	N14—C15	1.356 (3)
V2—V4^i	3.0875 (6)	N14—H14	0.8800
V2—V3	3.1000 (5)	C15—N16	1.360 (3)
V2—V5	3.1066 (5)	N16—C17	1.313 (3)
V3—O7	1.6031 (17)	C17—N18	1.355 (3)
V3—O12	1.8581 (17)	C17—H17	0.9500
V3—O8	1.8583 (17)	N18—C19	1.368 (3)
V3—O6	1.8926 (17)	N18—H18	0.8800
V3—O2^i	2.0300 (17)	C19—N20	1.317 (3)
V3—O4	2.3211 (16)	N20—H20A	0.8800
V3—V5	3.0668 (6)	N20—H20B	0.8800
V4—O9	1.6155 (17)	C21—C25	1.389 (3)
V4—O13	1.7897 (17)	C21—N22	1.389 (3)
V4—O8	1.8637 (16)	C21—C29	1.405 (3)
V4—O3	1.9685 (16)	N22—C23	1.316 (3)
V4—O1^i	2.0385 (16)	C23—N24	1.371 (3)
V4—O4	2.2412 (16)	C23—H23	0.9500
V4—V5	3.1068 (6)	N24—C25	1.357 (3)
V5—O14	1.6091 (17)	N24—H24	0.8800
V5—O12	1.8094 (16)	C25—N26	1.364 (3)
V5—O11	1.8744 (16)	N26—C27	1.312 (3)
V5—O13	1.9079 (17)	C27—N28	1.355 (3)
V5—O10	2.0721 (17)	C27—H27	0.9500
V5—O4	2.3327 (16)	N28—C29	1.367 (3)
C1—N2	1.383 (3)	N28—H28	0.8800
C1—C5	1.386 (3)	C29—N30	1.316 (3)
C1—C9	1.415 (3)	N30—H30A	0.8800
N2—C3	1.322 (3)	N30—H30B	0.8800
C3—N4	1.366 (3)	O1W—H1WA	0.8256
C3—H3	0.9500	O1W—H1WB	0.8479
N4—C5	1.357 (3)	O2W—H2WA	0.8427
N4—H4	0.8800	O2W—H2WB	0.8484
C5—N6	1.362 (3)
O10—V1—O2	106.86 (8)	O11—V5—O13	154.17 (8)
O10—V1—O3	98.37 (7)	O14—V5—O10	100.09 (8)
O2—V1—O3	97.39 (8)	O12—V5—O10	155.69 (7)
O10—V1—O1	96.88 (8)	O11—V5—O10	82.96 (7)
O2—V1—O1	95.79 (7)	O13—V5—O10	82.81 (7)
O3—V1—O1	155.99 (7)	O14—V5—O4	173.37 (8)
O10—V1—O4	87.79 (7)	O12—V5—O4	82.37 (7)
O2—V1—O4	165.26 (7)	O11—V5—O4	78.04 (6)
O3—V1—O4	81.72 (7)	O13—V5—O4	77.27 (6)
O1—V1—O4	80.46 (6)	O10—V5—O4	73.33 (6)
O10—V1—O4^i	165.59 (7)	O14—V5—V3	137.94 (6)
O2—V1—O4^i	87.47 (7)	O12—V5—V3	33.76 (5)
O3—V1—O4^i	80.84 (6)	O11—V5—V3	85.72 (5)
O1—V1—O4^i	79.79 (6)	O13—V5—V3	83.67 (5)
O4—V1—O4^i	77.85 (7)	O10—V5—V3	121.94 (5)
O10—V1—V3^i	145.21 (6)	O4—V5—V3	48.61 (4)
O2—V1—V3^i	38.36 (6)	O14—V5—V1	130.86 (6)
O3—V1—V3^i	89.73 (5)	O12—V5—V1	124.92 (6)
O1—V1—V3^i	88.23 (5)	O11—V5—V1	78.77 (5)
O4—V1—V3^i	126.95 (5)	O13—V5—V1	77.97 (5)
O4^i—V1—V3^i	49.11 (4)	O10—V5—V1	30.78 (4)
O10—V1—V5	38.89 (6)	O4—V5—V1	42.55 (4)
O2—V1—V5	145.73 (6)	V3—V5—V1	91.161 (15)
O3—V1—V5	90.92 (5)	O14—V5—V2	135.15 (6)
O1—V1—V5	89.40 (5)	O12—V5—V2	81.78 (5)
O4—V1—V5	48.90 (4)	O11—V5—V2	33.03 (5)
O4^i—V1—V5	126.74 (5)	O13—V5—V2	123.12 (5)
V3^i—V1—V5	175.589 (16)	O10—V5—V2	81.81 (5)
O10—V1—V4	85.41 (5)	O4—V5—V2	45.86 (4)
O2—V1—V4	134.78 (6)	V3—V5—V2	60.280 (12)
O3—V1—V4	37.40 (5)	V1—V5—V2	61.918 (13)
O1—V1—V4	126.47 (5)	O14—V5—V4	133.05 (7)
O4—V1—V4	46.09 (4)	O12—V5—V4	82.80 (6)
O4^i—V1—V4	85.41 (4)	O11—V5—V4	124.00 (5)
V3^i—V1—V4	118.764 (17)	O13—V5—V4	31.67 (5)
V5—V1—V4	60.097 (13)	O10—V5—V4	79.87 (5)
O5—V2—O6	104.23 (8)	O4—V5—V4	45.99 (4)
O5—V2—O11	101.53 (8)	V3—V5—V4	60.831 (13)
O6—V2—O11	95.79 (7)	V1—V5—V4	60.193 (13)
O5—V2—O3^i	99.57 (8)	V2—V5—V4	91.641 (15)
O6—V2—O3^i	90.55 (7)	V1—O1—V2	106.45 (7)
O11—V2—O3^i	155.70 (8)	V1—O1—V4^i	107.77 (8)
O5—V2—O1	98.25 (8)	V2—O1—V4^i	98.70 (7)
O6—V2—O1	155.49 (7)	V1—O2—V3^i	110.40 (8)
O11—V2—O1	89.06 (7)	V1—O3—V4	106.35 (8)
O3^i—V2—O1	76.06 (7)	V1—O3—V2^i	107.28 (7)
O5—V2—O4	173.15 (8)	V4—O3—V2^i	102.06 (7)
O6—V2—O4	81.58 (7)	V1—O4—V1^i	102.15 (7)
O11—V2—O4	81.24 (7)	V1—O4—V2	94.87 (6)
O3^i—V2—O4	76.52 (6)	V1^i—O4—V2	92.48 (6)
O1—V2—O4	75.43 (6)	V1—O4—V4	91.62 (6)
O5—V2—V4^i	89.16 (6)	V1^i—O4—V4	94.91 (6)
O6—V2—V4^i	129.12 (6)	V2—O4—V4	168.93 (8)
O11—V2—V4^i	129.80 (6)	V1—O4—V3	170.91 (8)
O3^i—V2—V4^i	38.57 (5)	V1^i—O4—V3	86.88 (5)
O1—V2—V4^i	40.74 (4)	V2—O4—V3	85.71 (6)
O4—V2—V4^i	84.30 (4)	V4—O4—V3	86.47 (5)
O5—V2—V3	137.79 (6)	V1—O4—V5	88.55 (6)
O6—V2—V3	33.68 (5)	V1^i—O4—V5	169.26 (8)
O11—V2—V3	85.24 (5)	V2—O4—V5	85.66 (6)
O3^i—V2—V3	87.21 (5)	V4—O4—V5	85.54 (5)
O1—V2—V3	123.67 (5)	V3—O4—V5	82.44 (5)
O4—V2—V3	48.30 (4)	V2—O6—V3	114.74 (9)
V4^i—V2—V3	118.392 (17)	V3—O8—V4	114.24 (8)
O5—V2—V5	134.98 (6)	V1—O10—V5	110.33 (8)
O6—V2—V5	83.35 (5)	V2—O11—V5	113.33 (9)
O11—V2—V5	33.64 (5)	V5—O12—V3	113.47 (9)
O3^i—V2—V5	124.99 (5)	V4—O13—V5	114.29 (8)
O1—V2—V5	87.66 (5)	N2—C1—C5	110.5 (2)
O4—V2—V5	48.48 (4)	N2—C1—C9	131.1 (2)
V4^i—V2—V5	120.589 (17)	C5—C1—C9	118.4 (2)
V3—V2—V5	59.223 (12)	C3—N2—C1	103.81 (19)
O7—V3—O12	103.63 (8)	N2—C3—N4	113.2 (2)
O7—V3—O8	101.95 (8)	N2—C3—H3	123.4
O12—V3—O8	91.70 (7)	N4—C3—H3	123.4
O7—V3—O6	102.24 (8)	C5—N4—C3	106.59 (19)
O12—V3—O6	89.57 (7)	C5—N4—H4	126.7
O8—V3—O6	154.76 (7)	C3—N4—H4	126.7
O7—V3—O2^i	99.40 (8)	N4—C5—N6	127.1 (2)
O12—V3—O2^i	156.92 (7)	N4—C5—C1	106.0 (2)
O8—V3—O2^i	84.76 (7)	N6—C5—C1	126.9 (2)
O6—V3—O2^i	84.27 (7)	C7—N6—C5	112.4 (2)
O7—V3—O4	174.65 (8)	N6—C7—N8	124.7 (2)
O12—V3—O4	81.70 (6)	N6—C7—H7	117.6
O8—V3—O4	78.04 (6)	N8—C7—H7	117.6
O6—V3—O4	77.21 (6)	C9—N8—C7	124.2 (2)
O2^i—V3—O4	75.25 (6)	C9—N8—H8	117.9
O7—V3—V1^i	130.64 (7)	C7—N8—H8	117.9
O12—V3—V1^i	125.70 (5)	N10—C9—N8	120.9 (2)
O8—V3—V1^i	79.96 (5)	N10—C9—C1	125.8 (2)
O6—V3—V1^i	78.88 (5)	N8—C9—C1	113.3 (2)
O2^i—V3—V1^i	31.24 (5)	C9—N10—H10A	120.0
O4—V3—V1^i	44.01 (4)	C9—N10—H10B	120.0
O7—V3—V5	136.40 (7)	H10A—N10—H10B	120.0
O12—V3—V5	32.76 (5)	N12—C11—C15	110.3 (2)
O8—V3—V5	84.57 (5)	N12—C11—C19	131.6 (2)
O6—V3—V5	82.94 (5)	C15—C11—C19	118.1 (2)
O2^i—V3—V5	124.19 (5)	C13—N12—C11	104.13 (19)
O4—V3—V5	48.94 (4)	N12—C13—N14	113.2 (2)
V1^i—V3—V5	92.951 (15)	N12—C13—H13	123.4
O7—V3—V2	133.79 (7)	N14—C13—H13	123.4
O12—V3—V2	81.29 (5)	C15—N14—C13	106.52 (19)
O8—V3—V2	124.02 (5)	C15—N14—H14	126.7
O6—V3—V2	31.59 (5)	C13—N14—H14	126.7
O2^i—V3—V2	81.87 (5)	N14—C15—N16	127.8 (2)
O4—V3—V2	45.99 (4)	N14—C15—C11	105.9 (2)
V1^i—V3—V2	61.581 (13)	N16—C15—C11	126.3 (2)
V5—V3—V2	60.497 (12)	C17—N16—C15	112.3 (2)
O9—V4—O13	103.54 (8)	N16—C17—N18	126.4 (2)
O9—V4—O8	102.14 (8)	N16—C17—H17	116.8
O13—V4—O8	94.40 (8)	N18—C17—H17	116.8
O9—V4—O3	99.69 (8)	C17—N18—C19	122.2 (2)
O13—V4—O3	93.29 (7)	C17—N18—H18	118.9
O8—V4—O3	154.42 (7)	C19—N18—H18	118.9
O9—V4—O1^i	98.67 (8)	N20—C19—N18	120.7 (2)
O13—V4—O1^i	156.90 (7)	N20—C19—C11	124.6 (2)
O8—V4—O1^i	87.02 (7)	N18—C19—C11	114.7 (2)
O3—V4—O1^i	76.63 (7)	C19—N20—H20A	120.0
O9—V4—O4	173.70 (8)	C19—N20—H20B	120.0
O13—V4—O4	82.08 (7)	H20A—N20—H20B	120.0
O8—V4—O4	80.05 (6)	C25—C21—N22	110.1 (2)
O3—V4—O4	76.91 (6)	C25—C21—C29	118.5 (2)
O1^i—V4—O4	75.45 (6)	N22—C21—C29	131.4 (2)
O9—V4—V2^i	89.40 (6)	C23—N22—C21	103.96 (18)
O13—V4—V2^i	132.64 (5)	N22—C23—N24	113.4 (2)
O8—V4—V2^i	127.56 (5)	N22—C23—H23	123.3
O3—V4—V2^i	39.37 (5)	N24—C23—H23	123.3
O1^i—V4—V2^i	40.55 (5)	C25—N24—C23	106.31 (19)
O4—V4—V2^i	84.63 (4)	C25—N24—H24	126.8
O9—V4—V5	137.38 (6)	C23—N24—H24	126.8
O13—V4—V5	34.04 (5)	N24—C25—N26	127.6 (2)
O8—V4—V5	83.33 (5)	N24—C25—C21	106.3 (2)
O3—V4—V5	89.59 (5)	N26—C25—C21	126.1 (2)
O1^i—V4—V5	123.92 (5)	C27—N26—C25	111.7 (2)
O4—V4—V5	48.47 (4)	N26—C27—N28	127.2 (2)
V2^i—V4—V5	120.850 (16)	N26—C27—H27	116.4
O9—V4—V1	135.32 (6)	N28—C27—H27	116.4
O13—V4—V1	79.03 (5)	C27—N28—C29	121.6 (2)
O8—V4—V1	122.32 (5)	C27—N28—H28	119.2
O3—V4—V1	36.25 (5)	C29—N28—H28	119.2
O1^i—V4—V1	80.77 (5)	N30—C29—N28	120.4 (2)
O4—V4—V1	42.30 (4)	N30—C29—C21	124.8 (2)
V2^i—V4—V1	61.235 (13)	N28—C29—C21	114.8 (2)
V5—V4—V1	59.711 (13)	C29—N30—H30A	120.0
O14—V5—O12	104.19 (8)	C29—N30—H30B	120.0
O14—V5—O11	102.27 (8)	H30A—N30—H30B	120.0
O12—V5—O11	92.85 (7)	H1WA—O1W—H1WB	108.0
O14—V5—O13	101.38 (8)	H2WA—O2W—H2WB	104.2
O12—V5—O13	91.31 (7)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2^ii	0.95	2.52	3.163 (3)	125
C3—H3···O6^iii	0.95	2.46	3.390 (3)	166
N4—H4···N16^iv	0.88	2.05	2.897 (3)	162
C7—H7···O14^v	0.95	2.29	3.092 (3)	142
N8—H8···O1W	0.88	1.86	2.707 (3)	160
N10—H10A···O2W	0.88	2.01	2.863 (3)	164
N10—H10B···N12	0.88	2.03	2.876 (3)	161
C13—H13···O7	0.95	2.55	3.129 (3)	120
C13—H13···O14^vi	0.95	2.57	3.189 (3)	123
N14—H14···N6^vii	0.88	2.06	2.909 (3)	161
C17—H17···O7^viii	0.95	2.39	3.180 (3)	140
N20—H20A···O5^iii	0.88	2.07	2.904 (3)	158
N20—H20B···N2	0.88	2.05	2.894 (3)	160
C23—H23···O10^ix	0.95	2.46	3.106 (3)	125
C23—H23···O13^ix	0.95	2.41	3.237 (3)	146
N24—H24···N26^ix	0.88	2.03	2.873 (3)	159
C27—H27···O10	0.95	2.56	3.354 (3)	141
N30—H30A···O9^iv	0.88	2.12	2.951 (3)	157
N30—H30B···N22^x	0.88	2.06	2.905 (3)	160
O1W—H1WA···O5^v	0.83	2.50	3.211 (2)	145.2
O1W—H1WB···O11	0.85	1.96	2.789 (3)	167.7
O2W—H2WA···O12	0.84	2.10	2.905 (3)	159.4
O2W—H2WB···O13^vi	0.85	2.14	2.965 (2)	163.9

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