Bis{4,4'-[oxalylbis(aza-nedi-yl)]dipyridinium} octa-molybdate.

In the crystal structure of the title compound, (C(12)H(12)N(4)O(2))(2)[Mo(8)O(26)], the amino and pyridinium groups of the N(1),N(2)-di(pyridinium-4-yl)oxalamide cations are hydrogen bonded to the O atoms of the centrosymmetric isopolyoxometalate β-[Mo(8)O(26)](4-) anions, forming a three-dimensional supra-molecular architecture.

Related literature

For polyoxometalates (POMs), see: Cronin et al. (2002 ▶); Fukaya & Yamase (2003 ▶); Katsoulis (1988 ▶); Pope & Müller (1991 ▶). For the applications of POMs in biology and materials sciences, see: Cui et al. (2003 ▶); Luan et al. (2002 ▶); Wang et al. (2003 ▶). For the structure of N 1,N 2-di(pyridin-4-yl)oxalamide, see: Tzeng et al. (2007 ▶). For details of the geometrical parameters in the same isopolyoxometalate anion, see: Gong et al. (2007 ▶).

Experimental

Crystal data

(C12H12N4O2)2[Mo8O26]

M = 1672.03

Monoclinic,

a = 10.633 (2) Å

b = 11.552 (2) Å

c = 17.240 (4) Å

β = 101.553 (3)°

V = 2074.7 (8) Å3

Z = 2

Mo Kα radiation

μ = 2.45 mm−1

T = 293 K

0.23 × 0.22 × 0.05 mm

Data collection

Siemens SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.829, T max = 1.000

14669 measured reflections

4534 independent reflections

4215 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.098

S = 1.40

4534 reflections

316 parameters

H-atom parameters constrained

Δρmax = 1.40 e Å−3

Δρmin = −2.27 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAIn class="Chemical">NT; 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: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020714/su2182sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020714/su2182Isup2.hkl

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

(C12H12N4O2)2[Mo8O26]	F(000) = 1592
Mr = 1672.03	Dx = 2.670 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5569 reflections
a = 10.633 (2) Å	θ = 2.1–27.5°
b = 11.552 (2) Å	µ = 2.45 mm−1
c = 17.240 (4) Å	T = 293 K
β = 101.553 (3)°	Prism, colorless
V = 2074.7 (8) Å3	0.23 × 0.22 × 0.05 mm
Z = 2

Siemens CCD area-detector diffractometer	4534 independent reflections
Radiation source: fine-focus sealed tube	4215 reflections with I > 2σ(I)
graphite	Rint = 0.021
φ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.829, Tmax = 1.000	k = −13→14
14669 measured reflections	l = −22→17

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.40	w = 1/[σ2(Fo2) + (0.054P)2 + 0.4946P] where P = (Fo2 + 2Fc2)/3
4534 reflections	(Δ/σ)max = 0.001
316 parameters	Δρmax = 1.40 e Å−3
0 restraints	Δρmin = −2.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
Mo1	0.08119 (2)	0.53770 (2)	0.098624 (15)	0.01481 (10)
Mo2	0.03951 (3)	0.71904 (2)	−0.069243 (16)	0.01713 (10)
Mo3	0.25513 (2)	0.49409 (2)	−0.029720 (16)	0.01602 (10)
Mo4	−0.13294 (3)	0.77083 (2)	0.064661 (17)	0.01917 (10)
O12	0.0104 (2)	0.8099 (2)	0.01704 (14)	0.0218 (5)
O6	0.2011 (2)	0.4893 (2)	0.17096 (15)	0.0252 (5)
O15	0.1779 (2)	0.61483 (18)	0.02814 (13)	0.0168 (4)
O5	−0.0636 (2)	0.44017 (19)	0.11312 (13)	0.0165 (4)
O4	−0.2513 (2)	0.8238 (2)	−0.00841 (16)	0.0297 (6)
O7	0.3709 (2)	0.4459 (2)	0.04628 (15)	0.0275 (5)
N2	0.5229 (3)	0.1925 (2)	1.09498 (17)	0.0221 (6)
H2A	0.5102	0.2587	1.0720	0.026*
O13	0.0261 (2)	0.6628 (2)	0.13799 (13)	0.0205 (5)
C2	0.3935 (3)	0.2606 (3)	1.1832 (2)	0.0259 (7)
H2	0.3675	0.3224	1.1491	0.031*
O11	0.3343 (2)	0.5745 (2)	−0.08718 (14)	0.0242 (5)
O9	−0.0852 (3)	0.7563 (2)	−0.14308 (15)	0.0274 (5)
O10	0.1691 (3)	0.7832 (2)	−0.09476 (16)	0.0273 (5)
C5	0.4718 (4)	0.0833 (3)	1.2863 (2)	0.0301 (8)
H5	0.4985	0.0245	1.3227	0.036*
C4	0.5210 (4)	0.0892 (3)	1.2190 (2)	0.0265 (7)
H4	0.5801	0.0346	1.2091	0.032*
N1	0.3858 (3)	0.1609 (3)	1.30054 (17)	0.0280 (7)
H1	0.3545	0.1541	1.3426	0.034*
O3	−0.1253 (3)	0.8654 (2)	0.14042 (16)	0.0321 (6)
C3	0.4805 (3)	0.1793 (3)	1.16520 (18)	0.0196 (6)
C1	0.3471 (4)	0.2490 (3)	1.2508 (2)	0.0286 (8)
H1A	0.2882	0.3025	1.2626	0.034*
O14	0.0844 (2)	0.40727 (19)	0.01120 (12)	0.0173 (4)
O8	0.2273 (2)	0.3590 (2)	−0.09586 (13)	0.0205 (5)
N3	0.8440 (3)	0.0969 (3)	0.75088 (17)	0.0285 (7)
H3	0.8761	0.0988	0.7089	0.034*
O2	0.5624 (3)	0.2419 (2)	0.94778 (15)	0.0289 (6)
O1	0.6119 (3)	0.0145 (2)	1.08260 (16)	0.0334 (6)
N4	0.6865 (3)	0.0776 (3)	0.94989 (17)	0.0236 (6)
H4A	0.7065	0.0154	0.9770	0.028*
C11	0.7132 (3)	0.1824 (3)	0.8303 (2)	0.0261 (7)
H11	0.6606	0.2428	0.8399	0.031*
C10	0.7680 (4)	0.1841 (3)	0.7648 (2)	0.0298 (8)
H10	0.7525	0.2461	0.7297	0.036*
C8	0.8193 (4)	0.0012 (3)	0.8668 (2)	0.0303 (8)
H8	0.8384	−0.0609	0.9015	0.036*
C9	0.8712 (4)	0.0072 (3)	0.8005 (2)	0.0333 (9)
H9	0.9256	−0.0512	0.7898	0.040*
C12	0.7373 (3)	0.0892 (3)	0.88212 (18)	0.0204 (6)
C6	0.5830 (3)	0.1107 (3)	1.05882 (19)	0.0206 (6)
C7	0.6084 (3)	0.1539 (3)	0.97837 (19)	0.0226 (7)

	U11	U22	U33	U12	U13	U23
Mo1	0.01333 (15)	0.02061 (16)	0.01084 (15)	−0.00116 (9)	0.00325 (10)	−0.00091 (10)
Mo2	0.01807 (16)	0.01867 (16)	0.01602 (16)	0.00122 (10)	0.00673 (11)	0.00088 (10)
Mo3	0.01266 (15)	0.02166 (17)	0.01468 (16)	0.00069 (9)	0.00496 (11)	0.00006 (10)
Mo4	0.01891 (17)	0.02088 (16)	0.01936 (16)	0.00103 (10)	0.00773 (12)	−0.00038 (10)
O12	0.0232 (12)	0.0214 (11)	0.0228 (11)	−0.0027 (9)	0.0093 (10)	−0.0038 (9)
O6	0.0216 (12)	0.0342 (13)	0.0184 (12)	0.0020 (10)	0.0003 (10)	0.0029 (10)
O15	0.0156 (10)	0.0194 (10)	0.0160 (10)	−0.0018 (8)	0.0047 (8)	−0.0007 (9)
O5	0.0162 (10)	0.0199 (10)	0.0146 (10)	0.0006 (8)	0.0057 (8)	0.0005 (9)
O4	0.0250 (13)	0.0339 (14)	0.0311 (14)	0.0052 (11)	0.0073 (11)	0.0089 (11)
O7	0.0216 (12)	0.0381 (14)	0.0221 (12)	0.0048 (11)	0.0026 (10)	0.0052 (11)
N2	0.0260 (15)	0.0251 (14)	0.0176 (13)	0.0021 (12)	0.0105 (11)	0.0042 (11)
O13	0.0204 (11)	0.0226 (11)	0.0192 (11)	−0.0004 (9)	0.0059 (9)	−0.0040 (9)
C2	0.0268 (18)	0.0300 (17)	0.0226 (17)	0.0055 (14)	0.0089 (14)	0.0044 (14)
O11	0.0217 (12)	0.0292 (12)	0.0237 (12)	−0.0022 (10)	0.0091 (10)	0.0032 (10)
O9	0.0291 (13)	0.0281 (12)	0.0232 (12)	0.0072 (11)	0.0010 (11)	0.0008 (11)
O10	0.0272 (13)	0.0269 (13)	0.0305 (13)	−0.0026 (10)	0.0127 (11)	0.0019 (10)
C5	0.038 (2)	0.0303 (18)	0.0222 (17)	0.0010 (16)	0.0069 (15)	0.0068 (15)
C4	0.0269 (18)	0.0316 (18)	0.0222 (17)	0.0038 (14)	0.0074 (14)	0.0026 (15)
N1	0.0295 (16)	0.0401 (17)	0.0171 (13)	−0.0029 (13)	0.0114 (12)	−0.0004 (13)
O3	0.0354 (14)	0.0310 (13)	0.0332 (14)	0.0015 (11)	0.0146 (12)	−0.0097 (12)
C3	0.0180 (15)	0.0268 (16)	0.0148 (14)	−0.0016 (12)	0.0053 (12)	0.0005 (13)
C1	0.0263 (18)	0.0380 (19)	0.0235 (17)	0.0048 (15)	0.0097 (15)	−0.0007 (16)
O14	0.0169 (10)	0.0209 (10)	0.0153 (10)	0.0003 (8)	0.0063 (8)	0.0001 (9)
O8	0.0223 (11)	0.0228 (11)	0.0193 (11)	0.0002 (9)	0.0110 (9)	−0.0029 (9)
N3	0.0311 (16)	0.0405 (17)	0.0173 (13)	−0.0040 (14)	0.0130 (12)	−0.0015 (13)
O2	0.0333 (14)	0.0309 (13)	0.0244 (13)	0.0054 (11)	0.0104 (11)	0.0031 (11)
O1	0.0461 (17)	0.0300 (14)	0.0293 (14)	0.0072 (12)	0.0204 (13)	0.0039 (11)
N4	0.0278 (15)	0.0276 (14)	0.0188 (13)	0.0042 (12)	0.0127 (12)	0.0029 (12)
C11	0.0261 (17)	0.0322 (18)	0.0218 (16)	0.0051 (14)	0.0090 (14)	0.0019 (14)
C10	0.0299 (19)	0.040 (2)	0.0209 (17)	0.0027 (16)	0.0074 (15)	0.0061 (15)
C8	0.040 (2)	0.0269 (18)	0.0284 (19)	0.0052 (15)	0.0175 (17)	0.0041 (15)
C9	0.042 (2)	0.0317 (19)	0.032 (2)	−0.0007 (16)	0.0210 (18)	−0.0033 (16)
C12	0.0232 (16)	0.0244 (16)	0.0155 (14)	−0.0036 (13)	0.0081 (12)	−0.0026 (12)
C6	0.0195 (15)	0.0278 (16)	0.0171 (14)	−0.0042 (13)	0.0094 (12)	−0.0017 (13)
C7	0.0235 (16)	0.0286 (16)	0.0172 (15)	−0.0049 (14)	0.0076 (13)	−0.0018 (14)

Mo1—O6	1.690 (2)	C2—C3	1.395 (5)
Mo1—O13	1.747 (2)	C2—H2	0.9300
Mo1—O15	1.956 (2)	C5—N1	1.338 (5)
Mo1—O5	1.964 (2)	C5—C4	1.366 (5)
Mo1—O14	2.136 (2)	C5—H5	0.9300
Mo1—O14i	2.399 (2)	C4—C3	1.403 (5)
Mo1—Mo3	3.1951 (6)	C4—H4	0.9300
Mo2—O10	1.699 (3)	N1—C1	1.342 (5)
Mo2—O9	1.699 (3)	N1—H1	0.8600
Mo2—O12	1.896 (2)	C1—H1A	0.9300
Mo2—O5i	2.024 (2)	O14—Mo2i	2.322 (2)
Mo2—O14i	2.322 (2)	O14—Mo1i	2.399 (2)
Mo2—O15	2.333 (2)	O8—Mo4i	1.939 (2)
Mo3—O11	1.699 (2)	N3—C9	1.338 (5)
Mo3—O7	1.702 (2)	N3—C10	1.342 (5)
Mo3—O8	1.921 (2)	N3—H3	0.8600
Mo3—O15	1.986 (2)	O2—C7	1.203 (4)
Mo3—O14	2.305 (2)	O1—C6	1.203 (4)
Mo3—O5i	2.370 (2)	N4—C7	1.368 (4)
Mo4—O3	1.692 (3)	N4—C12	1.388 (4)
Mo4—O4	1.706 (3)	N4—H4A	0.8600
Mo4—O12	1.924 (2)	C11—C10	1.371 (5)
Mo4—O8i	1.939 (2)	C11—C12	1.390 (5)
Mo4—O13	2.271 (2)	C11—H11	0.9300
O5—Mo2i	2.024 (2)	C10—H10	0.9300
O5—Mo3i	2.370 (2)	C8—C9	1.368 (5)
N2—C6	1.360 (4)	C8—C12	1.398 (5)
N2—C3	1.383 (4)	C8—H8	0.9300
N2—H2A	0.8600	C9—H9	0.9300
C2—C1	1.361 (5)	C6—C7	1.548 (5)
O6—Mo1—O13	104.42 (12)	O12—Mo4—O13	78.54 (10)
O6—Mo1—O15	101.34 (11)	O8i—Mo4—O13	77.86 (9)
O13—Mo1—O15	97.08 (10)	Mo2—O12—Mo4	118.21 (12)
O6—Mo1—O5	102.18 (11)	Mo1—O15—Mo3	108.29 (10)
O13—Mo1—O5	95.32 (10)	Mo1—O15—Mo2	110.37 (10)
O15—Mo1—O5	149.67 (9)	Mo3—O15—Mo2	105.41 (9)
O6—Mo1—O14	99.85 (11)	Mo1—O5—Mo2i	108.21 (10)
O13—Mo1—O14	155.72 (10)	Mo1—O5—Mo3i	109.83 (10)
O15—Mo1—O14	78.37 (9)	Mo2i—O5—Mo3i	102.84 (9)
O5—Mo1—O14	78.98 (9)	C6—N2—C3	126.2 (3)
O6—Mo1—O14i	174.94 (10)	C6—N2—H2A	116.9
O13—Mo1—O14i	80.62 (9)	C3—N2—H2A	116.9
O15—Mo1—O14i	77.46 (8)	Mo1—O13—Mo4	120.57 (11)
O5—Mo1—O14i	77.42 (8)	C1—C2—C3	119.6 (3)
O14—Mo1—O14i	75.11 (9)	C1—C2—H2	120.2
O6—Mo1—Mo3	90.19 (9)	C3—C2—H2	120.2
O13—Mo1—Mo3	133.25 (8)	N1—C5—C4	121.0 (3)
O15—Mo1—Mo3	36.17 (6)	N1—C5—H5	119.5
O5—Mo1—Mo3	125.10 (6)	C4—C5—H5	119.5
O14—Mo1—Mo3	46.13 (6)	C5—C4—C3	118.6 (3)
O14i—Mo1—Mo3	86.01 (5)	C5—C4—H4	120.7
O10—Mo2—O9	104.31 (13)	C3—C4—H4	120.7
O10—Mo2—O12	103.29 (11)	C5—N1—C1	121.6 (3)
O9—Mo2—O12	102.84 (11)	C5—N1—H1	119.2
O10—Mo2—O5i	97.46 (11)	C1—N1—H1	119.2
O9—Mo2—O5i	95.06 (11)	N2—C3—C2	117.9 (3)
O12—Mo2—O5i	148.09 (10)	N2—C3—C4	123.3 (3)
O10—Mo2—O14i	160.99 (11)	C2—C3—C4	118.8 (3)
O9—Mo2—O14i	93.28 (11)	N1—C1—C2	120.3 (3)
O12—Mo2—O14i	79.28 (9)	N1—C1—H1A	119.8
O5i—Mo2—O14i	73.47 (8)	C2—C1—H1A	119.8
O10—Mo2—O15	89.10 (11)	Mo1—O14—Mo3	91.94 (8)
O9—Mo2—O15	162.69 (11)	Mo1—O14—Mo2i	92.79 (8)
O12—Mo2—O15	84.24 (9)	Mo3—O14—Mo2i	162.71 (11)
O5i—Mo2—O15	72.02 (8)	Mo1—O14—Mo1i	104.89 (9)
O14i—Mo2—O15	72.31 (8)	Mo3—O14—Mo1i	98.15 (8)
O11—Mo3—O7	105.16 (12)	Mo2i—O14—Mo1i	96.69 (8)
O11—Mo3—O8	97.69 (11)	Mo3—O8—Mo4i	119.38 (11)
O7—Mo3—O8	101.11 (12)	C9—N3—C10	121.9 (3)
O11—Mo3—O15	102.23 (11)	C9—N3—H3	119.1
O7—Mo3—O15	98.71 (11)	C10—N3—H3	119.1
O8—Mo3—O15	147.03 (9)	C7—N4—C12	127.3 (3)
O11—Mo3—O14	158.28 (10)	C7—N4—H4A	116.3
O7—Mo3—O14	96.57 (11)	C12—N4—H4A	116.3
O8—Mo3—O14	77.93 (9)	C10—C11—C12	119.1 (3)
O15—Mo3—O14	73.83 (8)	C10—C11—H11	120.4
O11—Mo3—O5i	86.39 (10)	C12—C11—H11	120.4
O7—Mo3—O5i	166.64 (10)	N3—C10—C11	120.4 (3)
O8—Mo3—O5i	83.62 (9)	N3—C10—H10	119.8
O15—Mo3—O5i	71.82 (8)	C11—C10—H10	119.8
O14—Mo3—O5i	72.03 (8)	C9—C8—C12	119.5 (3)
O11—Mo3—Mo1	137.78 (9)	C9—C8—H8	120.3
O7—Mo3—Mo1	87.02 (9)	C12—C8—H8	120.3
O8—Mo3—Mo1	119.84 (7)	N3—C9—C8	120.1 (4)
O15—Mo3—Mo1	35.55 (6)	N3—C9—H9	119.9
O14—Mo3—Mo1	41.93 (5)	C8—C9—H9	119.9
O5i—Mo3—Mo1	79.83 (5)	N4—C12—C11	124.3 (3)
O3—Mo4—O4	104.63 (14)	N4—C12—C8	116.8 (3)
O3—Mo4—O12	104.98 (12)	C11—C12—C8	118.9 (3)
O4—Mo4—O12	97.54 (12)	O1—C6—N2	126.7 (3)
O3—Mo4—O8i	103.44 (11)	O1—C6—C7	121.6 (3)
O4—Mo4—O8i	97.81 (12)	N2—C6—C7	111.6 (3)
O12—Mo4—O8i	142.92 (9)	O2—C7—N4	127.6 (3)
O3—Mo4—O13	90.56 (11)	O2—C7—C6	122.5 (3)
O4—Mo4—O13	164.80 (11)	N4—C7—C6	110.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O7ii	0.86	2.61	3.368 (4)	148
N1—H1···O8iii	0.86	1.89	2.699 (4)	158
N3—H3···O5iv	0.86	1.94	2.779 (4)	165
N4—H4A···O1	0.86	2.25	2.669 (4)	110
N4—H4A···O4v	0.86	2.26	3.059 (4)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O7i	0.86	2.61	3.368 (4)	148
N1—H1⋯O8ii	0.86	1.89	2.699 (4)	158
N3—H3⋯O5iii	0.86	1.94	2.779 (4)	165
N4—H4A⋯O1	0.86	2.25	2.669 (4)	110
N4—H4A⋯O4iv	0.86	2.26	3.059 (4)	154

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