6-Benzyl­amino-2-(2-hydroxy­ethyl­amino)-9-methyl­purine-1,7-diium bis(perchlorate) monohydrate

The title compound, C₁₅H₂₀N₆O²⁺·2ClO₄⁻·H₂O, belongs to a group of cytokinin-derived compounds. It has been found that some cytokinin derivatives, e.g. 2,6,9-trisubstituted purine derivatives, behave as potent inhibitors of cyclin-dependent kinases (CDKs) and show anticancer activity. Olomoucine, i.e. the title cation in its neutral form, represents one of the first CDK specific inhibitors that selectively blocks CDK1, CDK2 and CDK5 kinases at micromolar concentrations. The asymmetric unit of the title compound consists of the diprotonated cation, two perchlorate anions and a water mol­ecule of crystallization. The cation contains nearly planar benzene and purine ring systems, the dihedral angle between them being 46.77 (6)°. The crystal structure is stabilized by N_purine—H...O_water/O_hydroxy, N_amine—H...O_water/O_hydroxy, O_water—H...O_perchlorate and O_hydroxy—H...O_perchlorate hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.046
• wR factor = 0.120
• Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT244_ALERT_4_C Low  Solvent U(eq) as Compared to Neighbors  for        Cl1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2004); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

6-Benzylamino-2-(2-hydroxyethylamino)-9-methylpurin-1,7-ium diperchlorate monohydrate

Crystal data

C15H20N6O^2+·2ClO4^−·H2O	F(000) = 1072
Mr = 517.29	Dx = 1.584 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12391 reflections
a = 17.8770 (7) Å	θ = 1.8–31.8°
b = 7.4072 (3) Å	µ = 0.37 mm^−1
c = 16.4214 (6) Å	T = 100 K
β = 94.187 (4)°	Cube, colorless
V = 2168.69 (15) Å^3	0.40 × 0.40 × 0.40 mm
Z = 4

Data collection

Xcalibur2 (Sapphire2 CCD) diffractometer	3569 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Enhance (Oxford Diffraction) monochromator	θmax = 25.0°, θmin = 3.3°
Detector resolution: 16.3 pixels mm^-1	h = −21→21
rotation method via ω scans	k = −8→7
13724 measured reflections	l = −19→19
3802 independent reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.06P)^2 + 4.28P] where P = (Fo^2 + 2Fc^2)/3
3802 reflections	(Δ/σ)max = 0.001
311 parameters	Δρmax = 0.94 e Å^−3
3 restraints	Δρmin = −0.63 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.

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
O1	0.92285 (10)	0.4568 (3)	0.67233 (11)	0.0256 (4)
Cl1	0.94730 (3)	0.97020 (8)	0.64423 (3)	0.01851 (17)
O2	0.87567 (11)	0.8872 (3)	0.64721 (14)	0.0405 (5)
O3	0.95922 (11)	1.0902 (3)	0.71416 (12)	0.0328 (5)
O4	1.00550 (11)	0.8369 (3)	0.64940 (12)	0.0347 (5)
O5	0.95054 (11)	1.0763 (3)	0.57151 (11)	0.0316 (5)
Cl2	0.63155 (3)	0.32984 (8)	0.13018 (3)	0.01946 (17)
O6	0.70636 (12)	0.3885 (3)	0.11614 (13)	0.0404 (5)
O7	0.59219 (13)	0.4729 (3)	0.16858 (12)	0.0379 (5)
O8	0.59156 (10)	0.2802 (3)	0.05357 (11)	0.0254 (4)
O9	0.63657 (10)	0.1786 (2)	0.18465 (11)	0.0233 (4)
H1W	0.938 (2)	0.352 (4)	0.695 (2)	0.061 (12)*
H1V	0.9580 (19)	0.535 (5)	0.692 (2)	0.058 (12)*
N1	0.66952 (10)	0.5842 (3)	0.53987 (11)	0.0124 (4)
H1	0.6380	0.6350	0.5716	0.015*
N2	0.57211 (10)	0.5794 (3)	0.43875 (11)	0.0138 (4)
H2	0.5443	0.6317	0.4740	0.017*
C2	0.64358 (12)	0.5422 (3)	0.46001 (13)	0.0120 (4)
N3	0.68667 (10)	0.4709 (3)	0.40590 (11)	0.0134 (4)
C4	0.75663 (12)	0.4403 (3)	0.43714 (14)	0.0129 (5)
C5	0.78664 (12)	0.4726 (3)	0.51548 (14)	0.0139 (5)
N6	0.76308 (10)	0.5912 (3)	0.64801 (11)	0.0139 (4)
H6	0.8076	0.5522	0.6667	0.017*
C6	0.74088 (12)	0.5512 (3)	0.57188 (14)	0.0129 (5)
N7	0.86101 (10)	0.4181 (3)	0.51913 (12)	0.0174 (4)
H7	0.8932	0.4248	0.5622	0.021*
C8	0.87511 (13)	0.3543 (3)	0.44674 (15)	0.0180 (5)
H8	0.9219	0.3062	0.4332	0.022*
N9	0.81344 (11)	0.3675 (3)	0.39494 (12)	0.0146 (4)
C9	0.71963 (13)	0.6958 (3)	0.70444 (14)	0.0173 (5)
H9B	0.6655	0.6701	0.6930	0.021*
H9A	0.7276	0.8263	0.6955	0.021*
O10	0.46250 (9)	0.2882 (2)	0.39930 (10)	0.0181 (4)
C10	0.74273 (13)	0.6492 (3)	0.79247 (14)	0.0163 (5)
C11	0.69016 (14)	0.5765 (3)	0.84138 (15)	0.0202 (5)
H11	0.6403	0.5556	0.8194	0.024*
C12	0.71056 (16)	0.5340 (3)	0.92286 (16)	0.0245 (6)
H12	0.6743	0.4854	0.9563	0.029*
C13	0.78324 (16)	0.5624 (3)	0.95507 (15)	0.0253 (6)
H13	0.7969	0.5331	1.0105	0.030*
C14	0.83636 (15)	0.6340 (4)	0.90620 (15)	0.0234 (6)
H14	0.8865	0.6521	0.9281	0.028*
C15	0.81605 (14)	0.6789 (3)	0.82538 (15)	0.0200 (5)
H15	0.8521	0.7299	0.7924	0.024*
C16	0.80574 (14)	0.3138 (3)	0.30852 (14)	0.0182 (5)
H16C	0.8424	0.2193	0.2988	0.027*
H16B	0.8147	0.4186	0.2742	0.027*
H16A	0.7550	0.2676	0.2950	0.027*
C17	0.53948 (13)	0.5339 (3)	0.35683 (14)	0.0171 (5)
H17B	0.5754	0.5677	0.3163	0.020*
H17A	0.4933	0.6058	0.3451	0.020*
C18	0.52057 (13)	0.3361 (3)	0.34692 (15)	0.0201 (5)
H18B	0.5034	0.3110	0.2894	0.024*
H18A	0.5659	0.2624	0.3611	0.024*
H10	0.4508 (19)	0.1678 (19)	0.387 (2)	0.043 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0238 (10)	0.0259 (10)	0.0256 (10)	0.0007 (8)	−0.0079 (8)	−0.0049 (8)
Cl1	0.0158 (3)	0.0234 (3)	0.0162 (3)	0.0034 (2)	0.0009 (2)	−0.0007 (2)
O2	0.0258 (11)	0.0499 (14)	0.0451 (13)	−0.0120 (10)	−0.0018 (9)	0.0091 (11)
O3	0.0416 (12)	0.0300 (11)	0.0256 (10)	0.0115 (9)	−0.0060 (8)	−0.0058 (8)
O4	0.0369 (11)	0.0374 (12)	0.0295 (11)	0.0178 (9)	0.0011 (8)	−0.0016 (9)
O5	0.0399 (11)	0.0326 (11)	0.0225 (10)	0.0045 (9)	0.0038 (8)	0.0079 (8)
Cl2	0.0271 (3)	0.0140 (3)	0.0181 (3)	−0.0031 (2)	0.0079 (2)	−0.0029 (2)
O6	0.0378 (12)	0.0521 (14)	0.0325 (11)	−0.0219 (10)	0.0116 (9)	−0.0061 (10)
O7	0.0667 (15)	0.0238 (10)	0.0251 (10)	0.0185 (10)	0.0164 (10)	0.0026 (8)
O8	0.0300 (10)	0.0240 (10)	0.0219 (9)	0.0002 (8)	−0.0006 (7)	0.0009 (7)
O9	0.0248 (9)	0.0194 (9)	0.0249 (9)	0.0020 (7)	−0.0031 (7)	0.0018 (7)
N1	0.0125 (9)	0.0124 (9)	0.0124 (9)	0.0005 (7)	0.0023 (7)	−0.0005 (7)
N2	0.0137 (9)	0.0162 (10)	0.0117 (9)	0.0012 (8)	0.0013 (7)	−0.0027 (7)
C2	0.0140 (11)	0.0085 (10)	0.0135 (11)	−0.0021 (8)	0.0017 (8)	0.0014 (8)
N3	0.0143 (9)	0.0128 (10)	0.0133 (9)	−0.0001 (7)	0.0017 (7)	0.0007 (7)
C4	0.0137 (11)	0.0097 (10)	0.0155 (11)	−0.0013 (8)	0.0040 (8)	0.0017 (8)
C5	0.0127 (11)	0.0134 (11)	0.0157 (11)	−0.0005 (9)	0.0015 (9)	0.0011 (9)
N6	0.0139 (9)	0.0136 (9)	0.0137 (9)	0.0005 (8)	−0.0019 (7)	0.0002 (8)
C6	0.0131 (11)	0.0095 (10)	0.0162 (11)	−0.0025 (8)	0.0018 (8)	0.0029 (8)
N7	0.0114 (9)	0.0207 (11)	0.0197 (10)	0.0032 (8)	−0.0006 (8)	−0.0002 (8)
C8	0.0136 (11)	0.0189 (12)	0.0217 (12)	0.0024 (9)	0.0031 (9)	−0.0005 (10)
N9	0.0150 (9)	0.0135 (9)	0.0158 (10)	0.0006 (8)	0.0040 (7)	0.0004 (8)
C9	0.0208 (12)	0.0155 (12)	0.0153 (11)	0.0040 (9)	−0.0005 (9)	−0.0019 (9)
O10	0.0151 (8)	0.0196 (9)	0.0200 (8)	−0.0013 (7)	0.0039 (6)	−0.0067 (7)
C10	0.0223 (12)	0.0113 (11)	0.0150 (12)	0.0040 (9)	−0.0002 (9)	−0.0032 (9)
C11	0.0240 (12)	0.0156 (12)	0.0209 (12)	0.0039 (10)	0.0027 (10)	−0.0046 (10)
C12	0.0365 (15)	0.0178 (13)	0.0204 (13)	0.0046 (11)	0.0098 (11)	−0.0012 (10)
C13	0.0405 (15)	0.0197 (13)	0.0154 (12)	0.0092 (11)	0.0004 (11)	−0.0026 (10)
C14	0.0278 (14)	0.0221 (13)	0.0190 (12)	0.0067 (11)	−0.0057 (10)	−0.0057 (10)
C15	0.0258 (13)	0.0158 (12)	0.0184 (12)	0.0021 (10)	0.0014 (10)	−0.0033 (9)
C16	0.0214 (12)	0.0187 (12)	0.0151 (11)	0.0014 (10)	0.0065 (9)	−0.0023 (9)
C17	0.0144 (11)	0.0244 (13)	0.0122 (11)	0.0008 (9)	0.0000 (9)	−0.0002 (9)
C18	0.0141 (11)	0.0279 (14)	0.0187 (12)	−0.0021 (10)	0.0042 (9)	−0.0096 (10)

Geometric parameters (Å, º)

O1—H1W	0.90 (3)	C8—N9	1.346 (3)
O1—H1V	0.90 (3)	C8—H8	0.9500
Cl1—O2	1.425 (2)	N9—C16	1.471 (3)
Cl1—O4	1.433 (2)	C9—C10	1.514 (3)
Cl1—O5	1.4343 (19)	C9—H9B	0.9900
Cl1—O3	1.455 (2)	C9—H9A	0.9900
Cl2—O9	1.4321 (18)	O10—C18	1.440 (3)
Cl2—O6	1.441 (2)	O10—H10	0.936 (10)
Cl2—O7	1.442 (2)	C10—C11	1.389 (3)
Cl2—O8	1.4485 (18)	C10—C15	1.398 (3)
N1—C6	1.366 (3)	C11—C12	1.397 (4)
N1—C2	1.394 (3)	C11—H11	0.9500
N1—H1	0.8800	C12—C13	1.383 (4)
N2—C2	1.329 (3)	C12—H12	0.9500
N2—C17	1.466 (3)	C13—C14	1.392 (4)
N2—H2	0.8800	C13—H13	0.9500
C2—N3	1.327 (3)	C14—C15	1.391 (3)
N3—C4	1.336 (3)	C14—H14	0.9500
C4—C5	1.378 (3)	C15—H15	0.9500
C4—N9	1.380 (3)	C16—H16C	0.9800
C5—N7	1.387 (3)	C16—H16B	0.9800
C5—C6	1.406 (3)	C16—H16A	0.9800
N6—C6	1.317 (3)	C17—C18	1.509 (3)
N6—C9	1.472 (3)	C17—H17B	0.9900
N6—H6	0.8800	C17—H17A	0.9900
N7—C8	1.320 (3)	C18—H18B	0.9900
N7—H7	0.8800	C18—H18A	0.9900
H1W—O1—H1V	103 (4)	N6—C9—C10	111.20 (18)
O2—Cl1—O4	110.56 (14)	N6—C9—H9B	109.4
O2—Cl1—O5	110.87 (13)	C10—C9—H9B	109.4
O4—Cl1—O5	110.72 (12)	N6—C9—H9A	109.4
O2—Cl1—O3	108.47 (13)	C10—C9—H9A	109.4
O4—Cl1—O3	108.07 (12)	H9B—C9—H9A	108.0
O5—Cl1—O3	108.05 (13)	C18—O10—H10	105 (2)
O9—Cl2—O6	108.62 (13)	C11—C10—C15	119.5 (2)
O9—Cl2—O7	108.17 (11)	C11—C10—C9	119.4 (2)
O6—Cl2—O7	109.67 (14)	C15—C10—C9	121.1 (2)
O9—Cl2—O8	110.38 (11)	C10—C11—C12	120.1 (2)
O6—Cl2—O8	110.04 (11)	C10—C11—H11	120.0
O7—Cl2—O8	109.92 (12)	C12—C11—H11	120.0
C6—N1—C2	124.03 (19)	C13—C12—C11	120.3 (2)
C6—N1—H1	118.0	C13—C12—H12	119.8
C2—N1—H1	118.0	C11—C12—H12	119.8
C2—N2—C17	120.26 (19)	C12—C13—C14	119.9 (2)
C2—N2—H2	119.9	C12—C13—H13	120.0
C17—N2—H2	119.9	C14—C13—H13	120.0
N3—C2—N2	120.0 (2)	C15—C14—C13	120.0 (2)
N3—C2—N1	123.3 (2)	C15—C14—H14	120.0
N2—C2—N1	116.65 (19)	C13—C14—H14	120.0
C2—N3—C4	112.54 (19)	C14—C15—C10	120.2 (2)
N3—C4—C5	128.2 (2)	C14—C15—H15	119.9
N3—C4—N9	125.2 (2)	C10—C15—H15	119.9
C5—C4—N9	106.61 (19)	N9—C16—H16C	109.5
C4—C5—N7	107.25 (19)	N9—C16—H16B	109.5
C4—C5—C6	118.8 (2)	H16C—C16—H16B	109.5
N7—C5—C6	134.0 (2)	N9—C16—H16A	109.5
C6—N6—C9	125.41 (19)	H16C—C16—H16A	109.5
C6—N6—H6	117.3	H16B—C16—H16A	109.5
C9—N6—H6	117.3	N2—C17—C18	113.2 (2)
N6—C6—N1	122.2 (2)	N2—C17—H17B	108.9
N6—C6—C5	124.7 (2)	C18—C17—H17B	108.9
N1—C6—C5	113.1 (2)	N2—C17—H17A	108.9
C8—N7—C5	108.10 (19)	C18—C17—H17A	108.9
C8—N7—H7	125.9	H17B—C17—H17A	107.8
C5—N7—H7	125.9	O10—C18—C17	109.89 (19)
N7—C8—N9	110.0 (2)	O10—C18—H18B	109.7
N7—C8—H8	125.0	C17—C18—H18B	109.7
N9—C8—H8	125.0	O10—C18—H18A	109.7
C8—N9—C4	108.05 (19)	C17—C18—H18A	109.7
C8—N9—C16	127.2 (2)	H18B—C18—H18A	108.2
C4—N9—C16	124.73 (19)
C17—N2—C2—N3	3.1 (3)	C6—C5—N7—C8	−179.1 (2)
C17—N2—C2—N1	−177.86 (19)	C5—N7—C8—N9	1.1 (3)
C6—N1—C2—N3	−2.3 (3)	N7—C8—N9—C4	−1.2 (3)
C6—N1—C2—N2	178.6 (2)	N7—C8—N9—C16	179.2 (2)
N2—C2—N3—C4	−179.4 (2)	N3—C4—N9—C8	−179.0 (2)
N1—C2—N3—C4	1.6 (3)	C5—C4—N9—C8	0.9 (3)
C2—N3—C4—C5	0.3 (3)	N3—C4—N9—C16	0.5 (3)
C2—N3—C4—N9	−179.9 (2)	C5—C4—N9—C16	−179.6 (2)
N3—C4—C5—N7	179.6 (2)	C6—N6—C9—C10	154.8 (2)
N9—C4—C5—N7	−0.2 (2)	N6—C9—C10—C11	−118.9 (2)
N3—C4—C5—C6	−1.5 (4)	N6—C9—C10—C15	61.3 (3)
N9—C4—C5—C6	178.65 (19)	C15—C10—C11—C12	0.2 (3)
C9—N6—C6—N1	−8.7 (3)	C9—C10—C11—C12	−179.6 (2)
C9—N6—C6—C5	171.0 (2)	C10—C11—C12—C13	−0.6 (4)
C2—N1—C6—N6	−179.3 (2)	C11—C12—C13—C14	0.1 (4)
C2—N1—C6—C5	1.0 (3)	C12—C13—C14—C15	0.8 (4)
C4—C5—C6—N6	−179.0 (2)	C13—C14—C15—C10	−1.2 (4)
N7—C5—C6—N6	−0.5 (4)	C11—C10—C15—C14	0.7 (4)
C4—C5—C6—N1	0.8 (3)	C9—C10—C15—C14	−179.5 (2)
N7—C5—C6—N1	179.2 (2)	C2—N2—C17—C18	77.8 (3)
C4—C5—N7—C8	−0.6 (3)	N2—C17—C18—O10	64.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···O3^i	0.90 (3)	1.99 (3)	2.865 (3)	163 (4)
O1—H1V···O3^ii	0.90 (3)	2.10 (3)	2.885 (3)	146 (4)
O1—H1V···O4	0.90 (3)	2.51 (3)	3.214 (3)	136 (3)
N1—H1···O10^iii	0.88	1.98	2.794 (2)	154
N2—H2···O10^iii	0.88	2.18	2.942 (2)	145
N6—H6···O1	0.88	2.17	3.024 (3)	162
N7—H7···O1	0.88	1.86	2.688 (3)	156
O10—H10···O7^iv	0.94 (1)	1.84 (2)	2.738 (3)	159 (3)

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