2-Amino-4,6-dimethyl-pyrimidin-1-ium 1-oxo-2,6,7-trioxa-1λ-phosphabicyclo-[2.2.2]octane-4-carboxyl-ate.

In the title compound, C(6)H(10)N(3) (+)·C(5)H(6)O(6)P(-), the cation and anion are linked by pairs of N-H⋯O hydrogen bonds. There are additional inter-molecular N-H⋯N hydrogen bonds, which generate centrosymmetric tetramers of two cations and two anions.

Related literature

For the applications of caged bicyclic phosphates, see: Li et al. (2000 ▶). For related structures, see: Meng et al. (2009 ▶); Guo & Zang (2008 ▶); Thakur & Desiraju (2008 ▶); Wang et al. (2007 ▶).

Experimental

Crystal data

C6H10N3 +·C5H6O6P−

M = 317.24

Monoclinic,

a = 9.5080 (13) Å

b = 6.1870 (8) Å

c = 23.974 (2) Å

β = 99.611 (5)°

V = 1390.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 113 K

0.24 × 0.22 × 0.14 mm

Data collection

Rigaku Saturn724 CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009 ▶) T min = 0.947, T max = 0.969

23989 measured reflections

6532 independent reflections

4883 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.107

S = 1.01

6532 reflections

204 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.38 e Å−3

Data collection: CrystalClear-SM Expert (Rigaku/MSC, 2009 ▶); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku/MSC, 2009 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810019896/fj2308sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810019896/fj2308Isup2.hkl

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

C6H10N3+·C5H6O6P−	F(000) = 664
Mr = 317.24	Dx = 1.515 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 5985 reflections
a = 9.5080 (13) Å	θ = 2.2–36.3°
b = 6.1870 (8) Å	µ = 0.23 mm−1
c = 23.974 (2) Å	T = 113 K
β = 99.611 (5)°	Prism, colorless
V = 1390.5 (3) Å3	0.24 × 0.22 × 0.14 mm
Z = 4

Rigaku Saturn724 CCD diffractometer	6532 independent reflections
Radiation source: rotating anode	4883 reflections with I > 2σ(I)
multilayer	Rint = 0.035
Detector resolution: 14.222 pixels mm-1	θmax = 36.5°, θmin = 1.7°
ω scans	h = −15→14
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009)	k = −10→10
Tmin = 0.947, Tmax = 0.969	l = −36→39
23989 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0615P)2] where P = (Fo2 + 2Fc2)/3
6532 reflections	(Δ/σ)max = 0.001
204 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

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
P1	0.14090 (2)	0.74372 (4)	0.157866 (9)	0.01584 (6)
O1	0.32415 (8)	0.33013 (12)	0.32735 (3)	0.02813 (17)
O2	0.46621 (8)	0.62093 (12)	0.33500 (3)	0.02544 (16)
O3	0.29862 (7)	0.67033 (12)	0.15596 (3)	0.02097 (14)
O4	0.15812 (7)	0.91396 (11)	0.20765 (3)	0.02023 (13)
O5	0.06923 (7)	0.54214 (12)	0.18168 (3)	0.02421 (15)
O6	0.06557 (8)	0.82445 (13)	0.10419 (3)	0.02619 (16)
N1	0.45629 (9)	0.17785 (15)	0.43177 (4)	0.02312 (17)
N2	0.61028 (8)	0.46847 (12)	0.43466 (3)	0.01702 (14)
N3	0.63811 (8)	0.21010 (14)	0.50821 (3)	0.01949 (15)
C1	0.36366 (9)	0.50774 (14)	0.31115 (4)	0.01674 (15)
C2	0.27993 (8)	0.59650 (13)	0.25498 (3)	0.01332 (14)
C3	0.37600 (9)	0.58891 (16)	0.20974 (4)	0.01990 (17)
H3A	0.4621	0.6782	0.2219	0.024*
H3B	0.4070	0.4383	0.2049	0.024*
C4	0.23414 (10)	0.83103 (15)	0.26188 (4)	0.02018 (17)
H4A	0.1711	0.8386	0.2908	0.024*
H4B	0.3193	0.9214	0.2749	0.024*
C5	0.14789 (10)	0.45860 (16)	0.23533 (4)	0.02254 (19)
H5A	0.1769	0.3072	0.2302	0.027*
H5B	0.0854	0.4605	0.2645	0.027*
C6	0.56840 (9)	0.28450 (15)	0.45830 (4)	0.01698 (15)
C7	0.72567 (10)	0.58213 (15)	0.45997 (4)	0.01896 (16)
C8	0.79892 (10)	0.51036 (16)	0.51086 (4)	0.02109 (17)
H8	0.8792	0.5871	0.5300	0.025*
C9	0.75166 (10)	0.32090 (16)	0.53356 (4)	0.01951 (17)
C10	0.76334 (12)	0.77807 (16)	0.42947 (5)	0.0264 (2)
H10A	0.8040	0.7342	0.3962	0.032*
H10B	0.8334	0.8642	0.4547	0.032*
H10C	0.6774	0.8647	0.4173	0.032*
C11	0.82793 (13)	0.22887 (19)	0.58813 (4)	0.0295 (2)
H11A	0.7581	0.1869	0.6120	0.035*
H11B	0.8927	0.3379	0.6079	0.035*
H11C	0.8828	0.1016	0.5803	0.035*
H1	0.4144 (16)	0.231 (2)	0.3998 (7)	0.033 (4)*
H2	0.4287 (15)	0.065 (2)	0.4512 (6)	0.039 (4)*
H3	0.5623 (16)	0.511 (3)	0.3965 (6)	0.052 (4)*

	U11	U22	U33	U12	U13	U23
P1	0.01665 (11)	0.01722 (10)	0.01235 (10)	0.00168 (8)	−0.00133 (7)	0.00215 (7)
O1	0.0314 (4)	0.0245 (3)	0.0237 (3)	−0.0074 (3)	−0.0093 (3)	0.0116 (3)
O2	0.0232 (3)	0.0255 (3)	0.0229 (3)	−0.0060 (3)	−0.0101 (3)	0.0070 (3)
O3	0.0215 (3)	0.0277 (3)	0.0142 (3)	0.0069 (3)	0.0043 (2)	0.0034 (2)
O4	0.0265 (3)	0.0171 (3)	0.0155 (3)	0.0085 (2)	−0.0013 (2)	0.0013 (2)
O5	0.0211 (3)	0.0261 (3)	0.0213 (3)	−0.0082 (3)	−0.0087 (2)	0.0080 (3)
O6	0.0282 (4)	0.0310 (4)	0.0167 (3)	0.0031 (3)	−0.0042 (3)	0.0060 (3)
N1	0.0190 (4)	0.0305 (4)	0.0177 (4)	−0.0039 (3)	−0.0029 (3)	0.0094 (3)
N2	0.0183 (3)	0.0190 (3)	0.0127 (3)	0.0026 (3)	−0.0005 (2)	0.0021 (2)
N3	0.0171 (3)	0.0277 (4)	0.0127 (3)	0.0015 (3)	−0.0002 (3)	0.0054 (3)
C1	0.0161 (4)	0.0180 (4)	0.0149 (4)	0.0020 (3)	−0.0012 (3)	0.0028 (3)
C2	0.0126 (3)	0.0130 (3)	0.0134 (3)	0.0002 (3)	−0.0007 (3)	0.0011 (3)
C3	0.0157 (4)	0.0266 (4)	0.0171 (4)	0.0057 (3)	0.0018 (3)	0.0032 (3)
C4	0.0240 (4)	0.0190 (4)	0.0151 (4)	0.0073 (3)	−0.0040 (3)	−0.0018 (3)
C5	0.0200 (4)	0.0239 (4)	0.0203 (4)	−0.0077 (3)	−0.0065 (3)	0.0090 (3)
C6	0.0151 (4)	0.0231 (4)	0.0125 (3)	0.0028 (3)	0.0016 (3)	0.0034 (3)
C7	0.0219 (4)	0.0185 (4)	0.0157 (4)	0.0021 (3)	0.0009 (3)	−0.0016 (3)
C8	0.0231 (4)	0.0231 (4)	0.0154 (4)	0.0002 (3)	−0.0018 (3)	−0.0015 (3)
C9	0.0187 (4)	0.0273 (4)	0.0116 (3)	0.0031 (3)	−0.0002 (3)	0.0010 (3)
C10	0.0334 (5)	0.0182 (4)	0.0247 (5)	−0.0026 (4)	−0.0033 (4)	0.0018 (3)
C11	0.0280 (5)	0.0417 (6)	0.0151 (4)	−0.0023 (4)	−0.0070 (4)	0.0075 (4)

P1—O6	1.4529 (7)	C2—C3	1.5310 (12)
P1—O5	1.5734 (7)	C2—C4	1.5318 (12)
P1—O3	1.5748 (7)	C3—H3A	0.9900
P1—O4	1.5798 (7)	C3—H3B	0.9900
O1—C1	1.2443 (11)	C4—H4A	0.9900
O2—C1	1.2578 (11)	C4—H4B	0.9900
O3—C3	1.4631 (11)	C5—H5A	0.9900
O4—C4	1.4703 (10)	C5—H5B	0.9900
O5—C5	1.4694 (11)	C7—C8	1.3737 (12)
N1—C6	1.3227 (12)	C7—C10	1.4901 (14)
N1—H1	0.866 (15)	C8—C9	1.3977 (14)
N1—H2	0.900 (14)	C8—H8	0.9500
N2—C7	1.3580 (12)	C9—C11	1.4983 (13)
N2—C6	1.3603 (12)	C10—H10A	0.9800
N2—H3	0.988 (15)	C10—H10B	0.9800
N3—C9	1.3363 (12)	C10—H10C	0.9800
N3—C6	1.3484 (11)	C11—H11A	0.9800
C1—C2	1.5460 (11)	C11—H11B	0.9800
C2—C5	1.5260 (12)	C11—H11C	0.9800
O6—P1—O5	114.50 (4)	O4—C4—H4B	109.7
O6—P1—O3	113.86 (4)	C2—C4—H4B	109.7
O5—P1—O3	104.73 (4)	H4A—C4—H4B	108.2
O6—P1—O4	114.43 (4)	O5—C5—C2	110.24 (7)
O5—P1—O4	104.52 (4)	O5—C5—H5A	109.6
O3—P1—O4	103.59 (4)	C2—C5—H5A	109.6
C3—O3—P1	114.52 (5)	O5—C5—H5B	109.6
C4—O4—P1	114.14 (5)	C2—C5—H5B	109.6
C5—O5—P1	114.11 (5)	H5A—C5—H5B	108.1
C6—N1—H1	116.8 (10)	N1—C6—N3	119.58 (8)
C6—N1—H2	114.7 (9)	N1—C6—N2	119.05 (8)
H1—N1—H2	128.2 (13)	N3—C6—N2	121.37 (8)
C7—N2—C6	121.20 (7)	N2—C7—C8	118.78 (8)
C7—N2—H3	119.3 (10)	N2—C7—C10	116.39 (8)
C6—N2—H3	119.1 (10)	C8—C7—C10	124.83 (9)
C9—N3—C6	117.95 (8)	C7—C8—C9	117.94 (8)
O1—C1—O2	126.96 (8)	C7—C8—H8	121.0
O1—C1—C2	116.56 (7)	C9—C8—H8	121.0
O2—C1—C2	116.46 (7)	N3—C9—C8	122.75 (8)
C5—C2—C3	108.75 (7)	N3—C9—C11	116.02 (9)
C5—C2—C4	109.20 (7)	C8—C9—C11	121.23 (9)
C3—C2—C4	108.63 (7)	C7—C10—H10A	109.5
C5—C2—C1	110.36 (7)	C7—C10—H10B	109.5
C3—C2—C1	108.95 (7)	H10A—C10—H10B	109.5
C4—C2—C1	110.90 (7)	C7—C10—H10C	109.5
O3—C3—C2	110.00 (7)	H10A—C10—H10C	109.5
O3—C3—H3A	109.7	H10B—C10—H10C	109.5
C2—C3—H3A	109.7	C9—C11—H11A	109.5
O3—C3—H3B	109.7	C9—C11—H11B	109.5
C2—C3—H3B	109.7	H11A—C11—H11B	109.5
H3A—C3—H3B	108.2	C9—C11—H11C	109.5
O4—C4—C2	109.99 (7)	H11A—C11—H11C	109.5
O4—C4—H4A	109.7	H11B—C11—H11C	109.5
C2—C4—H4A	109.7
O6—P1—O3—C3	179.91 (6)	C5—C2—C4—O4	−59.68 (9)
O5—P1—O3—C3	−54.29 (7)	C3—C2—C4—O4	58.79 (9)
O4—P1—O3—C3	55.00 (7)	C1—C2—C4—O4	178.50 (7)
O6—P1—O4—C4	179.86 (6)	P1—O5—C5—C2	1.39 (11)
O5—P1—O4—C4	53.84 (7)	C3—C2—C5—O5	−60.03 (10)
O3—P1—O4—C4	−55.60 (7)	C4—C2—C5—O5	58.35 (10)
O6—P1—O5—C5	178.68 (7)	C1—C2—C5—O5	−179.49 (7)
O3—P1—O5—C5	53.28 (8)	C9—N3—C6—N1	179.42 (9)
O4—P1—O5—C5	−55.34 (8)	C9—N3—C6—N2	−1.06 (13)
O1—C1—C2—C5	8.87 (11)	C7—N2—C6—N1	−179.24 (9)
O2—C1—C2—C5	−172.46 (9)	C7—N2—C6—N3	1.24 (13)
O1—C1—C2—C3	−110.46 (9)	C6—N2—C7—C8	−1.19 (13)
O2—C1—C2—C3	68.20 (10)	C6—N2—C7—C10	178.60 (8)
O1—C1—C2—C4	130.02 (9)	N2—C7—C8—C9	0.99 (13)
O2—C1—C2—C4	−51.31 (11)	C10—C7—C8—C9	−178.78 (9)
P1—O3—C3—C2	0.12 (9)	C6—N3—C9—C8	0.90 (14)
C5—C2—C3—O3	59.14 (9)	C6—N3—C9—C11	−178.44 (9)
C4—C2—C3—O3	−59.61 (9)	C7—C8—C9—N3	−0.89 (14)
C1—C2—C3—O3	179.47 (7)	C7—C8—C9—C11	178.42 (9)
P1—O4—C4—C2	1.10 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.866 (15)	1.907 (15)	2.7719 (11)	176.4 (14)
N1—H2···N3i	0.900 (14)	2.113 (15)	3.0114 (12)	176.3 (12)
N2—H3···O2	0.988 (15)	1.738 (16)	2.7170 (10)	170.4 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.866 (15)	1.907 (15)	2.7719 (11)	176.4 (14)
N1—H2⋯N3i	0.900 (14)	2.113 (15)	3.0114 (12)	176.3 (12)
N2—H3⋯O2	0.988 (15)	1.738 (16)	2.7170 (10)	170.4 (15)

Symmetry code: (i) .