Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104016944/ta1466sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104016944/ta1466Isup2.hkl |
CCDC reference: 251290
A mixture of Na2MoO4·H2O (0.24 g, 1 mmol), nicotinic acid (0.25 g, 2.0 mmol), (C2H5)4NCl·H2O (0.18 g, 1.0 mmol) and NH2OH.HCl(0.18 g, 2.5 mmol) in H2O (10 ml) was heated at 413 K for 3 d. After the reaction was cooled to room temperature over a period of 72 h, colorless crystals of (I) were produced (yield 51% based on Mo). Analysis calculated for C6NH7Mo2O9: C 16.80, H 1.64, N 3.26%; found: C 16.99, H 1.48, N 3.11%. IR (KBr, cm−1): 3541 (m), 1637 (s), 1585 (m), 1416 (s), 953 (versus), 924 (s), 544 (s).
H atoms attached to C and N atoms were positioned geometrically and included in the refinement using a riding model [C—H = 0.93 Å, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C,N)]. The water H atoms were located from difference maps and their positions were refined isotropically, with the O—H distances fixed at 0.82 (6) and 0.82 (8) Å [Uiso(H) = 1.5Ueq(O)]. The −1.119 Å−3 hole in the final difference map is 1.05 Å from atom Mo1.
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens,1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Mo2O6(C6H5NO2)]·H2O | F(000) = 824 |
Mr = 429.01 | Dx = 2.538 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1888 reflections |
a = 8.5404 (6) Å | θ = 2.3–25.1° |
b = 7.3459 (5) Å | µ = 2.28 mm−1 |
c = 18.3735 (11) Å | T = 293 K |
β = 103.045 (2)° | Prism, colorless |
V = 1122.95 (13) Å3 | 0.28 × 0.10 × 0.06 mm |
Z = 4 |
Siemens SMART CCD area detector diffractometer | 1987 independent reflections |
Radiation source: fine-focus sealed tube | 1501 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.3° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −10→6 |
Tmin = 0.761, Tmax = 0.872 | k = −8→8 |
3942 measured reflections | l = −17→21 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0683P)2 + 10.3372P] where P = (Fo2 + 2Fc2)/3 |
1987 reflections | (Δ/σ)max = 0.001 |
169 parameters | Δρmax = 0.71 e Å−3 |
2 restraints | Δρmin = −1.12 e Å−3 |
[Mo2O6(C6H5NO2)]·H2O | V = 1122.95 (13) Å3 |
Mr = 429.01 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.5404 (6) Å | µ = 2.28 mm−1 |
b = 7.3459 (5) Å | T = 293 K |
c = 18.3735 (11) Å | 0.28 × 0.10 × 0.06 mm |
β = 103.045 (2)° |
Siemens SMART CCD area detector diffractometer | 1987 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1501 reflections with I > 2σ(I) |
Tmin = 0.761, Tmax = 0.872 | Rint = 0.030 |
3942 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 2 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0683P)2 + 10.3372P] where P = (Fo2 + 2Fc2)/3 |
1987 reflections | Δρmax = 0.71 e Å−3 |
169 parameters | Δρmin = −1.12 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 | ||
Mo1 | 0.35759 (7) | 0.12365 (9) | 0.44005 (3) | 0.0160 (2) | |
Mo2 | 0.66692 (7) | 0.37571 (9) | 0.53880 (3) | 0.0155 (2) | |
O1 | 0.2951 (6) | 0.1656 (8) | 0.5503 (3) | 0.0248 (12) | |
O1W | 0.7871 (8) | 0.0687 (11) | 0.7544 (3) | 0.0383 (16) | |
H1WB | 0.809 (13) | 0.028 (14) | 0.797 (3) | 0.058* | |
H1WA | 0.737 (12) | −0.010 (11) | 0.727 (5) | 0.058* | |
O2 | 0.4387 (7) | 0.0888 (7) | 0.3639 (3) | 0.0227 (12) | |
O3 | 0.1590 (7) | 0.1258 (8) | 0.4016 (3) | 0.0291 (13) | |
O4 | 0.6083 (6) | 0.1222 (7) | 0.5183 (3) | 0.0176 (11) | |
O5 | 0.5002 (6) | 0.3275 (7) | 0.6193 (3) | 0.0226 (12) | |
O6 | 0.7675 (7) | 0.4084 (8) | 0.4706 (3) | 0.0294 (14) | |
O7 | 0.8135 (7) | 0.3678 (8) | 0.6176 (3) | 0.0281 (13) | |
O8 | 0.4215 (6) | 0.3787 (7) | 0.4564 (3) | 0.0181 (11) | |
N1 | 0.0791 (9) | 0.1644 (11) | 0.7295 (4) | 0.0329 (18) | |
H1A | −0.0226 | 0.1474 | 0.7235 | 0.039* | |
C1 | 0.3969 (10) | 0.2199 (11) | 0.7488 (4) | 0.0261 (18) | |
H1 | 0.5062 | 0.2435 | 0.7555 | 0.031* | |
C2 | 0.3018 (9) | 0.2097 (11) | 0.6776 (4) | 0.0215 (17) | |
C3 | 0.1395 (10) | 0.1846 (12) | 0.6682 (5) | 0.0278 (19) | |
H3 | 0.0725 | 0.1816 | 0.6206 | 0.033* | |
C4 | 0.3310 (11) | 0.1952 (13) | 0.8111 (5) | 0.035 (2) | |
H4 | 0.3951 | 0.1962 | 0.8593 | 0.041* | |
C5 | 0.1690 (10) | 0.1696 (12) | 0.7985 (5) | 0.0298 (19) | |
H5 | 0.1209 | 0.1555 | 0.8388 | 0.036* | |
C6 | 0.3709 (9) | 0.2375 (10) | 0.6099 (4) | 0.0201 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mo1 | 0.0198 (4) | 0.0127 (4) | 0.0133 (4) | 0.0009 (3) | −0.0010 (3) | 0.0002 (3) |
Mo2 | 0.0190 (4) | 0.0123 (4) | 0.0141 (4) | 0.0008 (3) | 0.0012 (3) | 0.0007 (3) |
O1 | 0.028 (3) | 0.027 (3) | 0.022 (3) | −0.003 (2) | 0.011 (2) | 0.000 (2) |
O1W | 0.036 (4) | 0.062 (5) | 0.017 (3) | −0.020 (3) | 0.005 (3) | −0.004 (3) |
O2 | 0.031 (3) | 0.018 (3) | 0.018 (3) | 0.000 (2) | 0.004 (2) | −0.002 (2) |
O3 | 0.025 (3) | 0.027 (3) | 0.030 (3) | 0.001 (3) | −0.004 (2) | 0.002 (3) |
O4 | 0.021 (3) | 0.013 (3) | 0.017 (2) | 0.001 (2) | 0.000 (2) | −0.002 (2) |
O5 | 0.031 (3) | 0.018 (3) | 0.018 (3) | −0.003 (2) | 0.004 (2) | −0.001 (2) |
O6 | 0.039 (3) | 0.028 (3) | 0.027 (3) | 0.000 (3) | 0.020 (3) | 0.000 (3) |
O7 | 0.029 (3) | 0.028 (3) | 0.025 (3) | 0.002 (3) | 0.001 (2) | −0.003 (3) |
O8 | 0.028 (3) | 0.009 (3) | 0.017 (3) | 0.001 (2) | 0.003 (2) | 0.002 (2) |
N1 | 0.024 (4) | 0.046 (5) | 0.030 (4) | 0.006 (3) | 0.010 (3) | 0.006 (4) |
C1 | 0.028 (4) | 0.029 (5) | 0.021 (4) | −0.006 (4) | 0.004 (3) | 0.001 (4) |
C2 | 0.024 (4) | 0.017 (4) | 0.024 (4) | 0.001 (3) | 0.006 (3) | 0.004 (3) |
C3 | 0.027 (4) | 0.034 (5) | 0.019 (4) | 0.001 (4) | 0.000 (3) | 0.003 (4) |
C4 | 0.042 (5) | 0.039 (5) | 0.022 (4) | −0.011 (4) | 0.006 (4) | −0.006 (4) |
C5 | 0.035 (5) | 0.034 (5) | 0.024 (4) | 0.001 (4) | 0.014 (4) | 0.001 (4) |
C6 | 0.031 (4) | 0.017 (4) | 0.013 (4) | 0.008 (3) | 0.008 (3) | −0.001 (3) |
Mo1—O3 | 1.683 (5) | O1W—H1WA | 0.82 (8) |
Mo1—O2 | 1.714 (5) | O5—C6 | 1.265 (9) |
Mo1—O8 | 1.956 (5) | N1—C5 | 1.327 (11) |
Mo1—O4i | 1.957 (5) | N1—C3 | 1.348 (11) |
Mo1—O1 | 2.230 (5) | N1—H1A | 0.8600 |
Mo1—O4 | 2.295 (5) | C1—C2 | 1.377 (11) |
Mo1—Mo2 | 3.3965 (9) | C1—C4 | 1.397 (12) |
Mo2—O6 | 1.688 (5) | C1—H1 | 0.9300 |
Mo2—O7 | 1.688 (5) | C2—C3 | 1.371 (11) |
Mo2—O4 | 1.943 (5) | C2—C6 | 1.507 (11) |
Mo2—O8ii | 1.965 (5) | C3—H3 | 0.9300 |
Mo2—O8 | 2.291 (5) | C4—C5 | 1.363 (12) |
Mo2—O5 | 2.300 (5) | C4—H4 | 0.9300 |
O1—C6 | 1.255 (9) | C5—H5 | 0.9300 |
O1W—H1WB | 0.82 (6) | ||
O3—Mo1—O2 | 102.3 (3) | O6—Mo2—Mo1 | 98.4 (2) |
O3—Mo1—O8 | 106.0 (2) | O7—Mo2—Mo1 | 140.9 (2) |
O2—Mo1—O8 | 96.8 (2) | O4—Mo2—Mo1 | 40.43 (14) |
O3—Mo1—O4i | 102.7 (2) | O8ii—Mo2—Mo1 | 105.29 (15) |
O2—Mo1—O4i | 97.4 (2) | O8—Mo2—Mo1 | 33.63 (12) |
O8—Mo1—O4i | 144.3 (2) | O5—Mo2—Mo1 | 74.91 (13) |
O3—Mo1—O1 | 87.4 (2) | C6—O1—Mo1 | 131.9 (5) |
O2—Mo1—O1 | 170.2 (2) | H1WB—O1W—H1WA | 107 (10) |
O8—Mo1—O1 | 81.0 (2) | C6—O5—Mo2 | 129.8 (5) |
O4i—Mo1—O1 | 79.5 (2) | Mo1—O8—Mo2ii | 142.1 (3) |
O3—Mo1—O4 | 166.5 (2) | Mo1—O8—Mo2 | 105.9 (2) |
O2—Mo1—O4 | 91.1 (2) | Mo2ii—O8—Mo2 | 106.4 (2) |
O8—Mo1—O4 | 73.70 (19) | C5—N1—C3 | 123.2 (8) |
O4i—Mo1—O4 | 73.5 (2) | C5—N1—H1A | 118.4 |
O1—Mo1—O4 | 79.16 (19) | C3—N1—H1A | 118.4 |
O3—Mo1—Mo2 | 143.9 (2) | C2—C1—C4 | 120.7 (8) |
O2—Mo1—Mo2 | 96.21 (18) | C2—C1—H1 | 119.6 |
O8—Mo1—Mo2 | 40.45 (15) | C4—C1—H1 | 119.6 |
O4i—Mo1—Mo2 | 105.38 (14) | C3—C2—C1 | 119.4 (7) |
O1—Mo1—Mo2 | 75.89 (14) | C3—C2—C6 | 119.1 (7) |
O4—Mo1—Mo2 | 33.31 (12) | C1—C2—C6 | 121.4 (7) |
O6—Mo2—O7 | 103.8 (3) | N1—C3—C2 | 118.4 (8) |
O6—Mo2—O4 | 98.3 (2) | N1—C3—H3 | 120.8 |
O7—Mo2—O4 | 104.0 (2) | C2—C3—H3 | 120.8 |
O6—Mo2—O8ii | 99.6 (2) | C5—C4—C1 | 117.4 (8) |
O7—Mo2—O8ii | 102.2 (2) | C5—C4—H4 | 121.3 |
O4—Mo2—O8ii | 143.5 (2) | C1—C4—H4 | 121.3 |
O6—Mo2—O8 | 93.0 (2) | N1—C5—C4 | 120.8 (8) |
O7—Mo2—O8 | 163.2 (2) | N1—C5—H5 | 119.6 |
O4—Mo2—O8 | 74.00 (19) | C4—C5—H5 | 119.6 |
O8ii—Mo2—O8 | 73.6 (2) | O1—C6—O5 | 127.0 (7) |
O6—Mo2—O5 | 172.5 (2) | O1—C6—C2 | 116.2 (7) |
O7—Mo2—O5 | 83.7 (2) | O5—C6—C2 | 116.8 (7) |
O4—Mo2—O5 | 78.9 (2) | Mo2—O4—Mo1i | 143.1 (3) |
O8ii—Mo2—O5 | 79.2 (2) | Mo2—O4—Mo1 | 106.3 (2) |
O8—Mo2—O5 | 79.59 (18) | Mo1i—O4—Mo1 | 106.5 (2) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O7iii | 0.82 (6) | 2.39 (7) | 3.059 (8) | 141 (10) |
O1W—H1WB···O5iii | 0.82 (6) | 2.47 (7) | 3.151 (9) | 142 (10) |
O1W—H1WA···O2i | 0.82 (8) | 2.07 (6) | 2.809 (8) | 151 (11) |
N1—H1A···O1Wiv | 0.86 | 1.93 | 2.727 (9) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Mo2O6(C6H5NO2)]·H2O |
Mr | 429.01 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 8.5404 (6), 7.3459 (5), 18.3735 (11) |
β (°) | 103.045 (2) |
V (Å3) | 1122.95 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.28 |
Crystal size (mm) | 0.28 × 0.10 × 0.06 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.761, 0.872 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3942, 1987, 1501 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.126, 0.99 |
No. of reflections | 1987 |
No. of parameters | 169 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0683P)2 + 10.3372P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.71, −1.12 |
Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens,1994), XPREP in SHELXTL (Siemens, 1994), SHELXTL.
Mo1—O3 | 1.683 (5) | Mo2—O6 | 1.688 (5) |
Mo1—O2 | 1.714 (5) | Mo2—O7 | 1.688 (5) |
Mo1—O8 | 1.956 (5) | Mo2—O4 | 1.943 (5) |
Mo1—O4i | 1.957 (5) | Mo2—O8ii | 1.965 (5) |
Mo1—O1 | 2.230 (5) | Mo2—O8 | 2.291 (5) |
Mo1—O4 | 2.295 (5) | Mo2—O5 | 2.300 (5) |
Mo1—Mo2 | 3.3965 (9) | ||
O3—Mo1—O2 | 102.3 (3) | O6—Mo2—O7 | 103.8 (3) |
O3—Mo1—O8 | 106.0 (2) | O6—Mo2—O4 | 98.3 (2) |
O2—Mo1—O8 | 96.8 (2) | O7—Mo2—O4 | 104.0 (2) |
O3—Mo1—O1 | 87.4 (2) | O6—Mo2—O8 | 93.0 (2) |
O2—Mo1—O1 | 170.2 (2) | O7—Mo2—O8 | 163.2 (2) |
O8—Mo1—O1 | 81.0 (2) | O4—Mo2—O8 | 74.00 (19) |
O3—Mo1—O4 | 166.5 (2) | O6—Mo2—O5 | 172.5 (2) |
O2—Mo1—O4 | 91.1 (2) | O7—Mo2—O5 | 83.7 (2) |
O8—Mo1—O4 | 73.70 (19) | O4—Mo2—O5 | 78.9 (2) |
O1—Mo1—O4 | 79.16 (19) | O8—Mo2—O5 | 79.59 (18) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O7iii | 0.82 (6) | 2.39 (7) | 3.059 (8) | 141 (10) |
O1W—H1WB···O5iii | 0.82 (6) | 2.47 (7) | 3.151 (9) | 142 (10) |
O1W—H1WA···O2i | 0.82 (8) | 2.07 (6) | 2.809 (8) | 151 (11) |
N1—H1A···O1Wiv | 0.86 | 1.93 | 2.727 (9) | 154.3 |
Symmetry codes: (i) −x+1, −y, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x−1, y, z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Chemists are increasingly interested in topics concerning transition metal oxides, owing mainly to their structural variety and promising potential applications in catalysis, biology, medicine and materials science (Pope & Müller, 1999). The molybdenum oxides are an important subclass and have been reported frequently (Rarig & Zubieta, 2001). It has been recognized that molybdenum in its higher oxidation states readily forms polynuclear anionic metal–oxygen clusters, and many giant polymolybdates have been reported (Müller & Kögerler, 1999). However, the number of dimeric structures of molybdenum oxides that are known is much smaller; only a few compounds, such as [Mo2O4(C2O4)2(H2O)2]2− (Strukan & Cindric, 2000) and [Mo2(iPr-O)6(Cat)2] (iPr-O is isopropoxy and Cat is tetrachloro-o-catecholato; Timothy et al., 1988), have been reported. Recently, compounds based on polyoxometalates linked by clusters, organic ligands and so on have been of a hot topic in this research area (Müller et al., 1999), but solid materials of one-dimensional structure with only molybdenum oxide frameworks have rarely been reported. On the other hand, nicotinic acid has often been used as a ligand to prepare transition-metal cation compounds. To our knowledge, only one Mo compound, [Mo2Cl2(C6H4NO2)4]Cl2·6H2O (Cotton et al., 1990), that is directly coordinated by nicotinic acid has been reported. Recently, we have launched a systematic program aimed at linking polyoxometalates by organic ligands and (or) transition-metal fragments, in order to generate distinctive architectures. We have succeeded in obtaining an infinite rail-like chain compound, [Mo2O6(nic)]n.nH2O (nic is nicotinic acid), (I), by hydrothermal reaction. The preparation, elemental analysis, IR spectrum and crystal structure of this compound are presented here.
Compound (I) consists of an infinite rail-like chain formed by molybdate oxide units linked by nicotinic acid ligands. As shown in Figs. 1 and 2, every Mo is octahedrally coordinated by six O atoms, which can be divided into three groups according to their Mo—O distances; two short terminal bonds [Mo—O = 1.685 (5) and 1.712 (5) Å], two medium-length bonds [1.958 (5) Å] and two longer bonds [2.231 (5) and 2.293 (5) Å] are observed. It is known that nicotinic acid can offer three coordination atoms, namely two O atoms and one N atom, and has several coordination modes (Chen et al., 2001). In (I), each nicotinic acid ligand bridges two Mo centers only by the two O atoms of its carboxylate group. The most interesting structural feature of (I), however, is that all nicotinic acid ligands are coordinated to Mo atoms in a bridging mode [Mo1···Mo2 = 3.3965 (9) Å].
As shown in Fig. 2, the MoO6 octahedra are linked to one another via edge sharing to produce a zigzag polymeric chain. In this one-dimensional structural motif, nicotinic acid ligands are located, alternately, on each side of the rail-like chain plane. Such a coordination mode for the nicotinic acid ligand has been reported previously but infrequently for other related compounds (Chen et al., 2001).
Fig. 3 shows the structure of (I), with the one-dimensional chains viewed end on. It can be seen that the chains are held together in two-dimensional layers by weak π–π stacking contacts between interleaved pyridine rings from adjacent chains. One pyridine ring of a chain and another pyridine ring of an adjacent chain form π–π stacks with a dihedral angle of 18.2°, and the shortest and the longest atom-to-centroid distances are 3.761 and 4.639 Å, respectively. This two-dimensional structure is further extended into a three-dimensional structure by interlayer hydrogen-bonded water molecules (Table 2).