Bis[2-(pyrimidin-2-ylamino)pyrimidin-ium] hexa-molybdate.

The title compound, (C(8)H(8)N(5))(2)[Mo(6)O(19)], was prepared by reaction of Mo(CO)(6) and dipyrimidylamine in refluxing toluene. The hexa-nuclear polyoxomolybdate anions lie on centres of inversion. Each 2-(pyrimidin-2-ylamino)pyrimidinium cation forms an intra-molecular N-H⋯N hydrogen bond and the cations are linked through self-complementary pairs of N-H⋯N hydrogen bonds into dimers across centres of inversion. The cations and anions are inter-linked through C-H⋯O contacts.

Related literature

For related literature, see: Shivaiah (2006 ▶); Bridgeman & Cavigliasso (2002 ▶); Shi et al. (2006 ▶); Wang et al. (2004 ▶); Guo et al. (2004 ▶); Burkholder & Zubieta (2004 ▶); Hagrman et al. (1999 ▶).

Experimental

Crystal data

(C8H8N5)2[Mo6O19]

M = 1228.03

Monoclinic,

a = 10.4338 (19) Å

b = 13.7437 (19) Å

c = 11.0792 (17) Å

β = 105.471 (13)°

V = 1531.2 (4) Å3

Z = 2

Mo Kα radiation

μ = 2.48 mm−1

T = 295 (2) K

0.40 × 0.20 × 0.05 mm

Data collection

Bruker P4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.578, T max = 0.883

3399 measured reflections

2660 independent reflections

1833 reflections with I > 2σ(I)

R int = 0.082

3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.146

S = 1.02

2660 reflections

232 parameters

H-atom parameters constrained

Δρmax = 0.91 e Å−3

Δρmin = −1.78 e Å−3

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 1997 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062897/bi2259sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062897/bi2259Isup2.hkl

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

(C8H8N5)2[Mo6O19]	F000 = 1172
Mr = 1228.03	Dx = 2.664 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 31 reflections
a = 10.4338 (19) Å	θ = 4.8–12.5º
b = 13.7437 (19) Å	µ = 2.48 mm−1
c = 11.0792 (17) Å	T = 295 (2) K
β = 105.471 (13)º	Plate, green
V = 1531.2 (4) Å3	0.40 × 0.20 × 0.05 mm
Z = 2

Bruker P4 diffractometer	Rint = 0.082
Radiation source: fine-focus sealed tube	θmax = 25.0º
Monochromator: graphite	θmin = 2.4º
T = 295(2) K	h = −1→12
ω scans	k = −1→16
Absorption correction: ψ scan(North et al., 1968)	l = −13→12
Tmin = 0.578, Tmax = 0.883	3 standard reflections
3399 measured reflections	every 97 reflections
2660 independent reflections	intensity decay: none
1833 reflections with I > 2σ(I)

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)] = 0.057	H-atom parameters constrained
wR(F2) = 0.146	w = 1/[σ2(Fo2) + (0.0858P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2660 reflections	Δρmax = 0.91 e Å−3
232 parameters	Δρmin = −1.78 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
Mo1	0.06601 (9)	0.95848 (7)	0.32376 (8)	0.0380 (3)
Mo2	−0.15184 (9)	0.87281 (7)	0.46013 (9)	0.0418 (3)
Mo3	0.16049 (9)	0.89727 (7)	0.61876 (9)	0.0434 (3)
N1	0.4384 (8)	0.9695 (6)	0.3239 (8)	0.040 (2)
H1N	0.4607	1.0166	0.3764	0.048*
N2	0.4053 (10)	1.0908 (7)	0.1792 (9)	0.052 (2)
N3	0.3659 (9)	0.9281 (7)	0.1128 (8)	0.043 (2)
H3N	0.3676	0.8676	0.1331	0.052*
N4	0.4025 (9)	0.8036 (6)	0.2961 (9)	0.046 (2)
N5	0.4845 (8)	0.8709 (6)	0.4968 (9)	0.040 (2)
O1	0.1142 (7)	0.9318 (7)	0.1952 (7)	0.065 (2)
O2	−0.2622 (8)	0.7811 (6)	0.4336 (9)	0.072 (3)
O3	0.2743 (9)	0.8222 (7)	0.7019 (9)	0.076 (3)
O4	0.0000	1.0000	0.5000	0.0286 (19)
O5	−0.0732 (7)	0.8658 (5)	0.3211 (7)	0.052 (2)
O6	0.1775 (7)	1.0683 (5)	0.3902 (7)	0.0414 (17)
O7	0.1797 (7)	0.8825 (5)	0.4514 (7)	0.0446 (18)
O8	0.0033 (7)	0.8138 (5)	0.5623 (8)	0.056 (2)
O9	−0.0736 (7)	1.0520 (6)	0.2626 (6)	0.052 (2)
O10	−0.2525 (6)	0.9816 (6)	0.3719 (6)	0.0465 (19)
C1	0.4034 (10)	0.9955 (8)	0.1993 (9)	0.041 (3)
C2	0.3673 (12)	1.1171 (10)	0.0578 (12)	0.060 (3)
H2	0.3699	1.1827	0.0376	0.072*
C3	0.3249 (13)	1.0509 (11)	−0.0372 (12)	0.064 (4)
H3	0.2968	1.0711	−0.1202	0.077*
C4	0.3252 (12)	0.9553 (10)	−0.0069 (11)	0.055 (3)
H4	0.2971	0.9089	−0.0694	0.066*
C5	0.4425 (9)	0.8789 (7)	0.3750 (10)	0.037 (2)
C6	0.4060 (12)	0.7135 (9)	0.3495 (12)	0.054 (3)
H6	0.3774	0.6596	0.2987	0.064*
C7	0.4491 (11)	0.7019 (8)	0.4714 (11)	0.048 (3)
H7	0.4537	0.6402	0.5068	0.057*
C8	0.4876 (10)	0.7831 (8)	0.5462 (10)	0.046 (3)
H8	0.5161	0.7758	0.6327	0.055*

	U11	U22	U33	U12	U13	U23
Mo1	0.0374 (5)	0.0496 (6)	0.0324 (5)	−0.0021 (4)	0.0188 (4)	−0.0061 (4)
Mo2	0.0393 (5)	0.0414 (5)	0.0508 (6)	−0.0114 (4)	0.0228 (4)	−0.0095 (4)
Mo3	0.0400 (5)	0.0502 (6)	0.0424 (6)	0.0122 (4)	0.0151 (4)	0.0098 (5)
N1	0.043 (5)	0.041 (5)	0.035 (5)	−0.002 (4)	0.009 (4)	−0.005 (4)
N2	0.059 (6)	0.049 (6)	0.048 (6)	−0.006 (5)	0.016 (5)	0.000 (5)
N3	0.053 (5)	0.046 (5)	0.034 (5)	0.004 (4)	0.016 (4)	−0.005 (4)
N4	0.047 (5)	0.042 (5)	0.051 (6)	0.003 (4)	0.018 (4)	−0.007 (5)
N5	0.036 (5)	0.045 (5)	0.038 (5)	0.004 (4)	0.009 (4)	0.001 (4)
O1	0.046 (4)	0.120 (7)	0.036 (4)	−0.014 (5)	0.023 (4)	−0.025 (5)
O2	0.069 (6)	0.067 (6)	0.100 (7)	−0.029 (5)	0.054 (5)	−0.034 (5)
O3	0.067 (6)	0.088 (7)	0.075 (6)	0.035 (5)	0.026 (5)	0.038 (5)
O4	0.024 (4)	0.037 (5)	0.029 (5)	−0.002 (4)	0.014 (4)	−0.009 (4)
O5	0.047 (4)	0.055 (5)	0.061 (5)	−0.024 (4)	0.029 (4)	−0.029 (4)
O6	0.040 (4)	0.042 (4)	0.049 (4)	0.004 (3)	0.025 (3)	0.003 (3)
O7	0.042 (4)	0.042 (4)	0.058 (5)	0.012 (3)	0.028 (4)	0.003 (4)
O8	0.062 (5)	0.032 (4)	0.085 (6)	0.012 (4)	0.037 (5)	0.014 (4)
O9	0.042 (4)	0.083 (6)	0.034 (4)	0.013 (4)	0.017 (3)	0.016 (4)
O10	0.028 (3)	0.077 (5)	0.035 (4)	−0.003 (4)	0.009 (3)	−0.002 (4)
C1	0.046 (6)	0.047 (7)	0.034 (6)	−0.002 (5)	0.018 (5)	0.004 (5)
C2	0.063 (8)	0.066 (8)	0.053 (8)	0.001 (7)	0.021 (7)	0.007 (7)
C3	0.067 (8)	0.085 (10)	0.039 (7)	−0.007 (7)	0.011 (6)	0.010 (7)
C4	0.055 (7)	0.066 (8)	0.046 (8)	0.004 (6)	0.017 (6)	−0.005 (6)
C5	0.025 (5)	0.047 (6)	0.038 (6)	−0.001 (4)	0.008 (4)	−0.012 (5)
C6	0.061 (7)	0.044 (7)	0.060 (9)	0.002 (6)	0.023 (6)	−0.012 (6)
C7	0.058 (7)	0.035 (6)	0.048 (8)	0.000 (5)	0.011 (6)	−0.002 (5)
C8	0.051 (7)	0.052 (7)	0.041 (7)	0.007 (5)	0.023 (5)	0.008 (6)

Mo1—O1	1.673 (7)	N3—C1	1.315 (13)
Mo1—O7	1.897 (7)	N3—C4	1.333 (14)
Mo1—O9	1.926 (7)	N3—H3N	0.860
Mo1—O5	1.926 (7)	N4—C5	1.347 (13)
Mo1—O6	1.927 (7)	N4—C6	1.369 (15)
Mo1—O4	2.3087 (9)	N5—C5	1.308 (13)
Mo2—O2	1.680 (8)	N5—C8	1.321 (13)
Mo2—O8	1.892 (8)	O4—Mo1i	2.3087 (9)
Mo2—O6i	1.927 (7)	O4—Mo3i	2.3137 (9)
Mo2—O5	1.931 (8)	O4—Mo2i	2.3210 (9)
Mo2—O10	1.935 (7)	O6—Mo2i	1.927 (7)
Mo2—O4	2.3210 (9)	O9—Mo3i	1.916 (7)
Mo3—O3	1.655 (8)	O10—Mo3i	1.911 (8)
Mo3—O10i	1.911 (8)	C2—C3	1.372 (18)
Mo3—O9i	1.916 (7)	C2—H2	0.930
Mo3—O7	1.928 (8)	C3—C4	1.356 (19)
Mo3—O8	1.963 (8)	C3—H3	0.930
Mo3—O4	2.3137 (9)	C4—H4	0.930
N1—C5	1.364 (13)	C6—C7	1.314 (16)
N1—C1	1.378 (13)	C6—H6	0.930
N1—H1N	0.860	C7—C8	1.384 (15)
N2—C1	1.329 (14)	C7—H7	0.930
N2—C2	1.347 (15)	C8—H8	0.930
O1—Mo1—O7	104.1 (4)	C1—N3—H3N	120.6
O1—Mo1—O9	102.6 (4)	C4—N3—H3N	120.6
O7—Mo1—O9	153.3 (3)	C5—N4—C6	116.5 (10)
O1—Mo1—O5	103.8 (4)	C5—N5—C8	117.9 (9)
O7—Mo1—O5	88.1 (3)	Mo1i—O4—Mo1	180.0
O9—Mo1—O5	86.5 (4)	Mo1i—O4—Mo3	90.22 (4)
O1—Mo1—O6	102.0 (4)	Mo1—O4—Mo3	89.78 (4)
O7—Mo1—O6	87.3 (3)	Mo1i—O4—Mo3i	89.78 (4)
O9—Mo1—O6	86.2 (3)	Mo1—O4—Mo3i	90.22 (4)
O5—Mo1—O6	154.1 (3)	Mo3—O4—Mo3i	180.0
O1—Mo1—O4	178.3 (4)	Mo1i—O4—Mo2	90.27 (3)
O7—Mo1—O4	76.9 (2)	Mo1—O4—Mo2	89.73 (3)
O9—Mo1—O4	76.4 (2)	Mo3—O4—Mo2	90.14 (4)
O5—Mo1—O4	77.4 (2)	Mo3i—O4—Mo2	89.86 (4)
O6—Mo1—O4	76.7 (2)	Mo1i—O4—Mo2i	89.73 (3)
O2—Mo2—O8	102.7 (4)	Mo1—O4—Mo2i	90.27 (3)
O2—Mo2—O6i	102.7 (4)	Mo3—O4—Mo2i	89.86 (4)
O8—Mo2—O6i	87.6 (3)	Mo3i—O4—Mo2i	90.14 (4)
O2—Mo2—O5	103.9 (3)	Mo2—O4—Mo2i	180.0
O8—Mo2—O5	88.8 (4)	Mo1—O5—Mo2	115.7 (3)
O6i—Mo2—O5	153.3 (3)	Mo2i—O6—Mo1	116.7 (3)
O2—Mo2—O10	103.7 (4)	Mo1—O7—Mo3	117.0 (3)
O8—Mo2—O10	153.6 (3)	Mo2—O8—Mo3	116.7 (3)
O6i—Mo2—O10	85.9 (3)	Mo3i—O9—Mo1	116.9 (3)
O5—Mo2—O10	85.6 (3)	Mo3i—O10—Mo2	116.6 (3)
O2—Mo2—O4	179.1 (3)	N3—C1—N2	125.9 (10)
O8—Mo2—O4	77.2 (2)	N3—C1—N1	119.6 (10)
O6i—Mo2—O4	76.4 (2)	N2—C1—N1	114.3 (10)
O5—Mo2—O4	77.0 (2)	N2—C2—C3	122.4 (13)
O10—Mo2—O4	76.4 (2)	N2—C2—H2	118.8
O3—Mo3—O10i	103.7 (4)	C3—C2—H2	118.8
O3—Mo3—O9i	104.2 (4)	C4—C3—C2	118.3 (12)
O10i—Mo3—O9i	88.2 (3)	C4—C3—H3	120.9
O3—Mo3—O7	103.1 (4)	C2—C3—H3	120.9
O10i—Mo3—O7	88.0 (3)	N3—C4—C3	119.8 (12)
O9i—Mo3—O7	152.6 (3)	N3—C4—H4	120.1
O3—Mo3—O8	103.1 (4)	C3—C4—H4	120.1
O10i—Mo3—O8	153.1 (3)	N5—C5—N4	124.5 (10)
O9i—Mo3—O8	85.6 (3)	N5—C5—N1	118.0 (9)
O7—Mo3—O8	85.7 (3)	N4—C5—N1	117.5 (9)
O3—Mo3—O4	179.0 (4)	C7—C6—N4	121.1 (11)
O10i—Mo3—O4	77.1 (2)	C7—C6—H6	119.5
O9i—Mo3—O4	76.4 (2)	N4—C6—H6	119.5
O7—Mo3—O4	76.2 (2)	C6—C7—C8	118.8 (11)
O8—Mo3—O4	76.0 (2)	C6—C7—H7	120.6
C5—N1—C1	128.6 (9)	C8—C7—H7	120.6
C5—N1—H1N	115.7	N5—C8—C7	121.2 (10)
C1—N1—H1N	115.7	N5—C8—H8	119.4
C1—N2—C2	114.8 (10)	C7—C8—H8	119.4
C1—N3—C4	118.7 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N4	0.86	1.95	2.605 (12)	132
N1—H1N···N5ii	0.86	2.07	2.924 (13)	180
C2—H2···O8iii	0.93	2.65	3.444 (14)	144
C4—H4···O2iv	0.93	2.69	3.391 (14)	133
C6—H6···O6v	0.93	2.38	3.250 (15)	157
C7—H7···O1vi	0.93	2.51	3.196 (14)	131

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N4	0.86	1.95	2.605 (12)	132
N1—H1N⋯N5i	0.86	2.07	2.924 (13)	180
C2—H2⋯O8ii	0.93	2.65	3.444 (14)	144
C4—H4⋯O2iii	0.93	2.69	3.391 (14)	133
C6—H6⋯O6iv	0.93	2.38	3.250 (15)	157
C7—H7⋯O1v	0.93	2.51	3.196 (14)	131

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .