Diisopropyl {[(R)-2-(2-amino-6-chloro-9H-purin-9-yl)-1-methyl-eth-oxy]meth-yl}-phospho-nate.

In the title compound, C(15)H(25)ClN(5)O(4)P, the r.m.s. deviation for the purine ring system is 0.0165 Å. The coordination about the P atom is a distorted tetrahedron [O=P-O angles = 116.70 (6) and 109.87 (6)°]. In the crystal, molecules are linked by N-H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For details of the synthesis, see: Yu et al. (1992 ▶). For the bioactivity of nucleoside analogues, see: Martin (1989 ▶). For reference bond lengths, see: Allen et al. (1987 ▶). For a related structure, see: Baszczyňski et al. (2011 ▶).

Experimental

Crystal data

C15H25ClN5O4P

M = 405.82

Orthorhombic,

a = 7.7991 (12) Å

b = 13.950 (2) Å

c = 18.053 (3) Å

V = 1964.0 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 113 K

0.22 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.936, T max = 0.947

24716 measured reflections

4669 independent reflections

4468 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.066

S = 1.05

4669 reflections

240 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.31 e Å−3

Absolute structure: Flack (1983 ▶), 2007 Friedel pairs

Flack parameter: 0.02 (4)

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2005 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812006757/fk2051sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006757/fk2051Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812006757/fk2051Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H25ClN5O4P	Dx = 1.372 Mg m−3
Mr = 405.82	Melting point: 404 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7255 reflections
a = 7.7991 (12) Å	θ = 1.8–27.9°
b = 13.950 (2) Å	µ = 0.31 mm−1
c = 18.053 (3) Å	T = 113 K
V = 1964.0 (6) Å3	Block, colourless
Z = 4	0.22 × 0.20 × 0.18 mm
F(000) = 856

Rigaku Saturn CCD area-detector diffractometer	4669 independent reflections
Radiation source: rotating anode	4468 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.039
Detector resolution: 7.31 pixels mm-1	θmax = 27.9°, θmin = 1.8°
ω and φ scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
Tmin = 0.936, Tmax = 0.947	l = −21→23
24716 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028	H-atom parameters constrained
wR(F2) = 0.066	w = 1/[σ2(Fo2) + (0.0412P)2 + 0.0557P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
4669 reflections	Δρmax = 0.21 e Å−3
240 parameters	Δρmin = −0.31 e Å−3
0 restraints	Absolute structure: Flack (1983), 2007 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.02 (4)

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.

	x	y	z	Uiso*/Ueq
Cl1	0.70932 (5)	0.28859 (3)	0.167353 (19)	0.02209 (9)
P1	−0.06920 (4)	−0.07232 (3)	0.118252 (19)	0.01452 (8)
O1	−0.02385 (12)	0.01978 (7)	0.24534 (5)	0.0159 (2)
O2	−0.01664 (13)	−0.15893 (7)	0.07748 (5)	0.0181 (2)
O3	−0.27016 (12)	−0.06894 (7)	0.12487 (6)	0.0235 (2)
O4	−0.00844 (13)	0.02658 (7)	0.08574 (5)	0.0196 (2)
N1	0.18098 (14)	0.18007 (8)	0.28806 (6)	0.0161 (2)
N2	0.30287 (16)	0.23315 (8)	0.18180 (6)	0.0194 (3)
N3	0.42068 (14)	0.19898 (8)	0.37275 (6)	0.0160 (2)
N4	0.67530 (15)	0.25616 (9)	0.30921 (6)	0.0175 (2)
N5	0.67325 (16)	0.23154 (9)	0.43524 (6)	0.0239 (3)
H5A	0.6250	0.2149	0.4780	0.029*
H5B	0.7770	0.2581	0.4341	0.029*
C1	0.16466 (18)	0.19896 (10)	0.21332 (8)	0.0192 (3)
H1	0.0612	0.1880	0.1868	0.023*
C2	0.41989 (18)	0.23658 (9)	0.23985 (7)	0.0162 (3)
C3	0.34601 (17)	0.20501 (9)	0.30642 (7)	0.0152 (3)
C4	0.58455 (17)	0.22921 (10)	0.37114 (7)	0.0168 (3)
C5	0.59151 (18)	0.25824 (9)	0.24618 (7)	0.0167 (3)
C6	0.05519 (17)	0.13378 (10)	0.33578 (8)	0.0175 (3)
H6A	−0.0582	0.1641	0.3282	0.021*
H6B	0.0882	0.1433	0.3882	0.021*
C7	0.04188 (18)	0.02758 (10)	0.31995 (7)	0.0176 (3)
H7	0.1582	−0.0023	0.3227	0.021*
C8	−0.0777 (2)	−0.02117 (12)	0.37504 (8)	0.0301 (4)
H8B	−0.1886	0.0119	0.3753	0.045*
H8C	−0.0270	−0.0185	0.4247	0.045*
H8A	−0.0944	−0.0882	0.3606	0.045*
C9	0.02123 (19)	−0.06768 (11)	0.20997 (7)	0.0187 (3)
H9B	−0.0218	−0.1224	0.2396	0.022*
H9A	0.1476	−0.0730	0.2069	0.022*
C10	−0.36850 (19)	0.01452 (11)	0.15103 (8)	0.0212 (3)
H10	−0.2899	0.0705	0.1578	0.025*
C11	−0.4980 (3)	0.03695 (17)	0.09230 (11)	0.0483 (6)
H11A	−0.4388	0.0548	0.0464	0.072*
H11C	−0.5704	0.0903	0.1087	0.072*
H11B	−0.5696	−0.0196	0.0833	0.072*
C12	−0.4493 (2)	−0.01170 (11)	0.22435 (9)	0.0287 (4)
H12B	−0.5299	−0.0648	0.2171	0.043*
H12C	−0.5107	0.0439	0.2443	0.043*
H12A	−0.3596	−0.0312	0.2593	0.043*
C13	−0.0413 (2)	0.05138 (11)	0.00761 (8)	0.0237 (3)
H13	−0.1452	0.0161	−0.0101	0.028*
C14	0.1104 (2)	0.02249 (12)	−0.03813 (9)	0.0306 (4)
H14C	0.2119	0.0579	−0.0215	0.046*
H14B	0.0881	0.0372	−0.0903	0.046*
H14A	0.1305	−0.0465	−0.0325	0.046*
C15	−0.0760 (3)	0.15761 (14)	0.00579 (10)	0.0476 (6)
H15C	−0.1792	0.1717	0.0348	0.071*
H15A	−0.0933	0.1782	−0.0456	0.071*
H15B	0.0220	0.1920	0.0270	0.071*

	U11	U22	U33	U12	U13	U23
Cl1	0.02487 (18)	0.02488 (17)	0.01653 (16)	−0.00578 (14)	0.00178 (13)	0.00367 (14)
P1	0.01522 (16)	0.01520 (16)	0.01314 (16)	0.00033 (13)	−0.00102 (14)	−0.00204 (13)
O1	0.0198 (5)	0.0169 (5)	0.0112 (4)	0.0001 (4)	−0.0030 (4)	−0.0028 (4)
O2	0.0199 (5)	0.0185 (5)	0.0160 (5)	0.0024 (4)	−0.0008 (4)	−0.0038 (4)
O3	0.0156 (5)	0.0207 (5)	0.0341 (6)	0.0004 (4)	−0.0005 (4)	−0.0124 (5)
O4	0.0278 (5)	0.0184 (5)	0.0126 (5)	−0.0008 (4)	−0.0008 (4)	0.0019 (4)
N1	0.0153 (6)	0.0163 (5)	0.0165 (6)	−0.0005 (5)	−0.0027 (5)	−0.0019 (4)
N2	0.0219 (6)	0.0180 (6)	0.0183 (6)	−0.0012 (5)	−0.0055 (5)	0.0011 (4)
N3	0.0155 (5)	0.0169 (6)	0.0155 (6)	−0.0012 (5)	−0.0009 (5)	−0.0006 (4)
N4	0.0168 (6)	0.0190 (6)	0.0168 (5)	−0.0013 (5)	0.0003 (5)	0.0033 (5)
N5	0.0177 (6)	0.0374 (7)	0.0166 (6)	−0.0083 (5)	−0.0022 (5)	0.0061 (5)
C1	0.0197 (7)	0.0174 (7)	0.0204 (7)	−0.0005 (6)	−0.0063 (6)	−0.0020 (5)
C2	0.0197 (7)	0.0139 (6)	0.0151 (6)	0.0001 (5)	−0.0020 (6)	0.0003 (5)
C3	0.0166 (6)	0.0110 (6)	0.0182 (6)	0.0009 (5)	−0.0011 (5)	−0.0012 (5)
C4	0.0171 (7)	0.0185 (7)	0.0148 (6)	0.0006 (5)	−0.0002 (6)	0.0004 (5)
C5	0.0218 (7)	0.0120 (6)	0.0162 (6)	0.0002 (5)	0.0013 (6)	0.0021 (5)
C6	0.0141 (6)	0.0228 (7)	0.0157 (6)	−0.0016 (5)	0.0003 (6)	−0.0043 (5)
C7	0.0186 (7)	0.0226 (7)	0.0116 (6)	−0.0020 (6)	−0.0030 (5)	−0.0016 (5)
C8	0.0366 (9)	0.0367 (9)	0.0168 (7)	−0.0163 (8)	0.0018 (7)	−0.0008 (7)
C9	0.0255 (7)	0.0153 (7)	0.0154 (7)	0.0006 (6)	−0.0012 (5)	0.0000 (6)
C10	0.0180 (7)	0.0207 (7)	0.0250 (8)	0.0058 (6)	0.0001 (6)	−0.0067 (6)
C11	0.0364 (10)	0.0772 (16)	0.0314 (10)	0.0307 (10)	−0.0098 (8)	−0.0162 (10)
C12	0.0283 (8)	0.0192 (8)	0.0385 (9)	0.0006 (6)	0.0108 (7)	0.0004 (7)
C13	0.0300 (8)	0.0298 (8)	0.0114 (7)	0.0036 (6)	−0.0026 (6)	0.0024 (6)
C14	0.0405 (10)	0.0264 (8)	0.0250 (8)	0.0026 (7)	0.0116 (7)	0.0028 (7)
C15	0.0765 (15)	0.0412 (11)	0.0250 (9)	0.0284 (11)	0.0135 (10)	0.0143 (8)

Cl1—C5	1.7460 (14)	C6—H6B	0.9900
P1—O2	1.4729 (10)	C7—C8	1.523 (2)
P1—O4	1.5724 (11)	C7—H7	1.0000
P1—O3	1.5726 (10)	C8—H8B	0.9800
P1—C9	1.8009 (14)	C8—H8C	0.9800
O1—C9	1.4213 (17)	C8—H8A	0.9800
O1—C7	1.4453 (16)	C9—H9B	0.9900
O3—C10	1.4720 (16)	C9—H9A	0.9900
O4—C13	1.4748 (17)	C10—C11	1.498 (2)
N1—C3	1.3738 (17)	C10—C12	1.511 (2)
N1—C1	1.3806 (18)	C10—H10	1.0000
N1—C6	1.4566 (18)	C11—H11A	0.9800
N2—C1	1.3088 (19)	C11—H11C	0.9800
N2—C2	1.3904 (17)	C11—H11B	0.9800
N3—C3	1.3341 (17)	C12—H12B	0.9800
N3—C4	1.3462 (17)	C12—H12C	0.9800
N4—C5	1.3124 (17)	C12—H12A	0.9800
N4—C4	1.3756 (17)	C13—C14	1.498 (2)
N5—C4	1.3486 (17)	C13—C15	1.507 (2)
N5—H5A	0.8900	C13—H13	1.0000
N5—H5B	0.8901	C14—H14C	0.9800
C1—H1	0.9500	C14—H14B	0.9800
C2—C5	1.377 (2)	C14—H14A	0.9800
C2—C3	1.4038 (19)	C15—H15C	0.9800
C6—C7	1.5123 (19)	C15—H15A	0.9800
C6—H6A	0.9900	C15—H15B	0.9800
O2—P1—O4	116.70 (6)	H8B—C8—H8C	109.5
O2—P1—O3	109.87 (6)	C7—C8—H8A	109.5
O4—P1—O3	107.60 (6)	H8B—C8—H8A	109.5
O2—P1—C9	112.33 (6)	H8C—C8—H8A	109.5
O4—P1—C9	101.17 (6)	O1—C9—P1	110.30 (9)
O3—P1—C9	108.63 (6)	O1—C9—H9B	109.6
C9—O1—C7	113.30 (10)	P1—C9—H9B	109.6
C10—O3—P1	124.57 (9)	O1—C9—H9A	109.6
C13—O4—P1	120.69 (9)	P1—C9—H9A	109.6
C3—N1—C1	105.90 (11)	H9B—C9—H9A	108.1
C3—N1—C6	126.91 (12)	O3—C10—C11	106.83 (12)
C1—N1—C6	126.91 (11)	O3—C10—C12	107.87 (12)
C1—N2—C2	103.04 (11)	C11—C10—C12	112.93 (15)
C3—N3—C4	112.04 (11)	O3—C10—H10	109.7
C5—N4—C4	117.03 (12)	C11—C10—H10	109.7
C4—N5—H5A	121.4	C12—C10—H10	109.7
C4—N5—H5B	117.2	C10—C11—H11A	109.5
H5A—N5—H5B	120.9	C10—C11—H11C	109.5
N2—C1—N1	114.73 (12)	H11A—C11—H11C	109.5
N2—C1—H1	122.6	C10—C11—H11B	109.5
N1—C1—H1	122.6	H11A—C11—H11B	109.5
C5—C2—N2	135.10 (12)	H11C—C11—H11B	109.5
C5—C2—C3	113.37 (12)	C10—C12—H12B	109.5
N2—C2—C3	111.41 (12)	C10—C12—H12C	109.5
N3—C3—N1	127.56 (13)	H12B—C12—H12C	109.5
N3—C3—C2	127.52 (13)	C10—C12—H12A	109.5
N1—C3—C2	104.91 (12)	H12B—C12—H12A	109.5
N3—C4—N5	118.43 (12)	H12C—C12—H12A	109.5
N3—C4—N4	126.27 (12)	O4—C13—C14	109.06 (12)
N5—C4—N4	115.27 (12)	O4—C13—C15	106.42 (13)
N4—C5—C2	123.45 (12)	C14—C13—C15	113.22 (14)
N4—C5—Cl1	116.74 (10)	O4—C13—H13	109.4
C2—C5—Cl1	119.80 (10)	C14—C13—H13	109.4
N1—C6—C7	111.64 (11)	C15—C13—H13	109.4
N1—C6—H6A	109.3	C13—C14—H14C	109.5
C7—C6—H6A	109.3	C13—C14—H14B	109.5
N1—C6—H6B	109.3	H14C—C14—H14B	109.5
C7—C6—H6B	109.3	C13—C14—H14A	109.5
H6A—C6—H6B	108.0	H14C—C14—H14A	109.5
O1—C7—C6	105.91 (11)	H14B—C14—H14A	109.5
O1—C7—C8	110.96 (11)	C13—C15—H15C	109.5
C6—C7—C8	110.85 (12)	C13—C15—H15A	109.5
O1—C7—H7	109.7	H15C—C15—H15A	109.5
C6—C7—H7	109.7	C13—C15—H15B	109.5
C8—C7—H7	109.7	H15C—C15—H15B	109.5
C7—C8—H8B	109.5	H15A—C15—H15B	109.5
C7—C8—H8C	109.5
O2—P1—O3—C10	−169.42 (10)	C5—N4—C4—N3	4.4 (2)
O4—P1—O3—C10	−41.40 (12)	C5—N4—C4—N5	−177.53 (13)
C9—P1—O3—C10	67.35 (12)	C4—N4—C5—C2	1.1 (2)
O2—P1—O4—C13	52.62 (12)	C4—N4—C5—Cl1	−177.90 (10)
O3—P1—O4—C13	−71.35 (11)	N2—C2—C5—N4	−179.99 (14)
C9—P1—O4—C13	174.81 (10)	C3—C2—C5—N4	−4.5 (2)
C2—N2—C1—N1	0.42 (16)	N2—C2—C5—Cl1	−1.0 (2)
C3—N1—C1—N2	0.27 (16)	C3—C2—C5—Cl1	174.40 (10)
C6—N1—C1—N2	−173.85 (13)	C3—N1—C6—C7	−100.58 (15)
C1—N2—C2—C5	174.56 (15)	C1—N1—C6—C7	72.34 (17)
C1—N2—C2—C3	−0.96 (15)	C9—O1—C7—C6	154.99 (11)
C4—N3—C3—N1	179.73 (13)	C9—O1—C7—C8	−84.65 (15)
C4—N3—C3—C2	1.00 (19)	N1—C6—C7—O1	−64.84 (14)
C1—N1—C3—N3	−179.77 (13)	N1—C6—C7—C8	174.73 (12)
C6—N1—C3—N3	−5.7 (2)	C7—O1—C9—P1	178.87 (9)
C1—N1—C3—C2	−0.82 (14)	O2—P1—C9—O1	176.25 (9)
C6—N1—C3—C2	173.30 (12)	O4—P1—C9—O1	51.07 (10)
C5—C2—C3—N3	3.5 (2)	O3—P1—C9—O1	−62.00 (11)
N2—C2—C3—N3	−179.91 (13)	P1—O3—C10—C11	125.75 (14)
C5—C2—C3—N1	−175.42 (11)	P1—O3—C10—C12	−112.57 (13)
N2—C2—C3—N1	1.13 (15)	P1—O4—C13—C14	−92.90 (14)
C3—N3—C4—N5	176.77 (12)	P1—O4—C13—C15	144.64 (13)
C3—N3—C4—N4	−5.24 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O2i	0.89	2.13	3.0185 (16)	174
N5—H5B···O2ii	0.89	2.21	3.0920 (16)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O2i	0.89	2.13	3.0185 (16)	174
N5—H5B⋯O2ii	0.89	2.21	3.0920 (16)	172

Symmetry codes: (i) ; (ii) .