Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title compound, [Na(NO3)(C3H7NO2)]n, was obtained unintentionally as the product of an attempted reaction of sodium molybdate in aqueous solution and the amino acid L-alanine (ala), in order to obtain a γ-type octa­molybdate, Na4[Mo8O26(ala)2].18H2O, coordinated by L-alanine. The coordination geometry around the Na atom can be considered as trigonal–bipyramidal, with three bidentate nitrate anions coordinating through their O atoms and two L-alanine mol­ecules each coordinating through one carboxylate O atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807039438/rt2007sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807039438/rt2007Isup2.hkl
Contains datablock I

CCDC reference: 660115

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.037
  • wR factor = 0.092
  • Data-to-parameter ratio = 10.2

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry ..... 81 PerFi PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem... m PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem... c PLAT112_ALERT_2_B ADDSYM Detects Additional (Pseudo) Symm. Elem... n
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 70.31 From the CIF: _reflns_number_total 1241 Count of symmetry unique reflns 766 Completeness (_total/calc) 162.01% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 475 Fraction of Friedel pairs measured 0.620 Are heavy atom types Z>Si present no PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 = . S
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Polyoxometalates (POMs) can be considered as oligomeric aggregates of metal cations, bridged by oxide anions that form by self-assembly processes (Rhule et al., 1998). There are two generic families of POMs, the isopolyoxometalates, that contain only d0 metal cations and oxide anions and the heteropolyoxometalates, that contain one or more p-, d-, or f-block heteroatoms in addition to the other ions (Pope, 1983; Rhule et al., 1998).

The medicinal features of these compounds cover a variety of important biological activities, such as the inhibition of specific enzymes or antiviral and antitumor activity (Pope and Mueller, 1994; Rhule et al., 1998). When used in combination with β-lactam antibiotics, polyoxotungstates enhance the antibiotic effectiveness against otherwise resistant strains of bacteria (Yamase et al., 1996). The heptamolybdate, [NH3Pri]6[Mo7O24].3H2O had shown a potent in vivo antitumor activity (Fujita, et al., 1992), which has been explained by repeated redox cycles of [Mo7O24]6- in the tumor cells (Yamase, 1993).

The biomedical investigations of polyoxomolybdates containing amino acids or even peptides (Yamase et al., 1999) have been focused upon finding polyoxomolybdates with both improved activity against cancer and clinical safety profiles.

The reported structure Na(NO3)C3H7NO2 was obtained unintentionally as the product of an attempted reaction of sodium molybdate in aqueous solution and the amino acid L-alanine, in order to obtain a γ type octamolybdate, coordinated by L-alanine Na4[Mo8O26(ala)2].18H2O (Cindrić et al., 2006). In contrast to Cindrić et al., L-alanine was used instead of D,L-alanine.

The asymmetric unit consists of one sodium and one nitrate ion and one L-alanine molecule.

The coordination geometry around the sodium atom can be considered as trigonal bipyramidal, with three bidentate nitrate anions coordinating through their oxygen atoms and two L-alanine molecules, each coordinating through one carboxyl oxygen atom (Figure 1,2).

Three nitrate anions are bidentate coordinating to the sodium atom (2.612 (2)–2.771 (2) Å), forming one plane, parallel with the (110) plane. The third nitrate oxygen atoms are coordinating to other symmetry equivalent sodium atoms, extending the plane formed. Almost perpendicular to this plane, two L-alanine molecules are coordinating to the sodium atom, each through one carboxyl oxygen atom (2.3651 (16) and 2.3891 (17) Å). The other carboxyl oxygen atoms are coordinated to sodium atoms in the planes above and beneath, respectively. Hence, infinite planes parallel with (110) are formed by the nitrate anions and the sodium atoms and these are perpendicularly linked to each other by L-alanine molecules (Figure 3).

Intermolecular hydrogen bonds are observed between N1(H1A)···O(1)[1/2 + x,-1/2 - y,2 - z] (1.92 (4) Å), N1(H1B)···O(5)[1/2 + x,1/2 - y,2 - z] (2.10 (3) Å) and N1(H1C)···O(2)[1 + x,y,z] (1.87 (4) Å) and an intramolecular hydrogen bond is found for N1(H1B)···O(2) (2.44 (3) Å).

Only four structures of alanine coordination complexes are found in the CSD (Version 5.28) (Allen, 2002). Only in one of them (Rajagopal et al., 2003), two alanine molecules are coordinated to the same cobalt ion. Concerning the nitrate ions, the reported structure is the first structure where three nitrate ions are coordinated to a sodium atom.

Related literature top

For related literature, see: Allen (2002); Cindrić et al. (2006); Fujita et al. (1992); Pope (1983); Pope & Mueller (1994); Rajagopal et al. (2003); Rhule et al. (1998); Yamase (1993); Yamase et al. (1996, 1999).

Experimental top

L-Alanine (0.18 g, 2 mmol) was added to an aqueous solution of Na2MoO4 (0.484 g, 2 mmol) and the solution was acidified by addition of HNO3 to pH 3.4. Colourless crystals of the title compound were obtained after standing for 5 days at room temperature 0.02 g, 10%). L-Alanine and Na2MoO4 were purchased from Acros Organics (Geel, Belgium).

Refinement top

All hydrogen atoms could be located in a difference Fourier map, and were further refined unrestrained with isotropic temperature factors fixed at 1.5 times Ueq of the parent atoms for the methyl and ammonia groups and 1.2 times Ueq of the parent atom for the H2(C2) atom.

Structure description top

Polyoxometalates (POMs) can be considered as oligomeric aggregates of metal cations, bridged by oxide anions that form by self-assembly processes (Rhule et al., 1998). There are two generic families of POMs, the isopolyoxometalates, that contain only d0 metal cations and oxide anions and the heteropolyoxometalates, that contain one or more p-, d-, or f-block heteroatoms in addition to the other ions (Pope, 1983; Rhule et al., 1998).

The medicinal features of these compounds cover a variety of important biological activities, such as the inhibition of specific enzymes or antiviral and antitumor activity (Pope and Mueller, 1994; Rhule et al., 1998). When used in combination with β-lactam antibiotics, polyoxotungstates enhance the antibiotic effectiveness against otherwise resistant strains of bacteria (Yamase et al., 1996). The heptamolybdate, [NH3Pri]6[Mo7O24].3H2O had shown a potent in vivo antitumor activity (Fujita, et al., 1992), which has been explained by repeated redox cycles of [Mo7O24]6- in the tumor cells (Yamase, 1993).

The biomedical investigations of polyoxomolybdates containing amino acids or even peptides (Yamase et al., 1999) have been focused upon finding polyoxomolybdates with both improved activity against cancer and clinical safety profiles.

The reported structure Na(NO3)C3H7NO2 was obtained unintentionally as the product of an attempted reaction of sodium molybdate in aqueous solution and the amino acid L-alanine, in order to obtain a γ type octamolybdate, coordinated by L-alanine Na4[Mo8O26(ala)2].18H2O (Cindrić et al., 2006). In contrast to Cindrić et al., L-alanine was used instead of D,L-alanine.

The asymmetric unit consists of one sodium and one nitrate ion and one L-alanine molecule.

The coordination geometry around the sodium atom can be considered as trigonal bipyramidal, with three bidentate nitrate anions coordinating through their oxygen atoms and two L-alanine molecules, each coordinating through one carboxyl oxygen atom (Figure 1,2).

Three nitrate anions are bidentate coordinating to the sodium atom (2.612 (2)–2.771 (2) Å), forming one plane, parallel with the (110) plane. The third nitrate oxygen atoms are coordinating to other symmetry equivalent sodium atoms, extending the plane formed. Almost perpendicular to this plane, two L-alanine molecules are coordinating to the sodium atom, each through one carboxyl oxygen atom (2.3651 (16) and 2.3891 (17) Å). The other carboxyl oxygen atoms are coordinated to sodium atoms in the planes above and beneath, respectively. Hence, infinite planes parallel with (110) are formed by the nitrate anions and the sodium atoms and these are perpendicularly linked to each other by L-alanine molecules (Figure 3).

Intermolecular hydrogen bonds are observed between N1(H1A)···O(1)[1/2 + x,-1/2 - y,2 - z] (1.92 (4) Å), N1(H1B)···O(5)[1/2 + x,1/2 - y,2 - z] (2.10 (3) Å) and N1(H1C)···O(2)[1 + x,y,z] (1.87 (4) Å) and an intramolecular hydrogen bond is found for N1(H1B)···O(2) (2.44 (3) Å).

Only four structures of alanine coordination complexes are found in the CSD (Version 5.28) (Allen, 2002). Only in one of them (Rajagopal et al., 2003), two alanine molecules are coordinated to the same cobalt ion. Concerning the nitrate ions, the reported structure is the first structure where three nitrate ions are coordinated to a sodium atom.

For related literature, see: Allen (2002); Cindrić et al. (2006); Fujita et al. (1992); Pope (1983); Pope & Mueller (1994); Rajagopal et al. (2003); Rhule et al. (1998); Yamase (1993); Yamase et al. (1996, 1999).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures top
[Figure 1] Fig. 1. Coordination geometry of the title compound, showing atom-labelling scheme and 50% probability displacement ellipsoids. Hydrogen atoms are drawn at arbitrary size.
[Figure 2] Fig. 2. Packing diagram of the title compound.
Poly[µ2-L-alanine-µ3-nitrato-sodium(I)] top
Crystal data top
[Na(NO3)(C3H7NO2)]F(000) = 360
Mr = 174.10Dx = 1.743 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2abCell parameters from 2690 reflections
a = 5.3477 (3) Åθ = 5.8–70.3°
b = 9.1719 (6) ŵ = 1.98 mm1
c = 13.5284 (8) ÅT = 100 K
V = 663.55 (7) Å3Rod, colourless
Z = 40.5 × 0.3 × 0.2 mm
Data collection top
Bruker SMART 6000
diffractometer
1241 independent reflections
Radiation source: fine-focus sealed tube1170 reflections with I > 2σ(I)
Crossed Göbel mirrors monochromatorRint = 0.048
ω and φ scansθmax = 70.3°, θmin = 5.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 66
Tmin = 0.431, Tmax = 0.673k = 011
6562 measured reflectionsl = 016
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullOnly H-atom coordinates refined
R[F2 > 2σ(F2)] = 0.037 w = 1/[σ2(Fo2) + (0.0662P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.092(Δ/σ)max < 0.001
S = 1.10Δρmax = 0.32 e Å3
1241 reflectionsΔρmin = 0.47 e Å3
122 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.046 (3)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack, 1983
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.10 (12)
Crystal data top
[Na(NO3)(C3H7NO2)]V = 663.55 (7) Å3
Mr = 174.10Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 5.3477 (3) ŵ = 1.98 mm1
b = 9.1719 (6) ÅT = 100 K
c = 13.5284 (8) Å0.5 × 0.3 × 0.2 mm
Data collection top
Bruker SMART 6000
diffractometer
1241 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1170 reflections with I > 2σ(I)
Tmin = 0.431, Tmax = 0.673Rint = 0.048
6562 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037Only H-atom coordinates refined
wR(F2) = 0.092Δρmax = 0.32 e Å3
S = 1.10Δρmin = 0.47 e Å3
1241 reflectionsAbsolute structure: Flack, 1983
122 parametersAbsolute structure parameter: 0.10 (12)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.6356 (4)1.05721 (19)0.00853 (15)0.0078 (4)
C20.3525 (4)1.0453 (2)0.00305 (15)0.0090 (4)
C30.2757 (4)0.8870 (2)0.02082 (14)0.0136 (4)
H20.300 (5)1.109 (3)0.0538 (19)0.016*
H1A0.247 (7)1.201 (3)0.0929 (19)0.020*
H3A0.322 (5)0.825 (3)0.033 (2)0.020*
H1B0.287 (6)1.064 (3)0.140 (2)0.020*
H3B0.095 (6)0.881 (3)0.028 (2)0.020*
H1C0.062 (6)1.080 (3)0.087 (2)0.020*
H3C0.348 (6)0.841 (3)0.082 (2)0.020*
N10.2284 (4)1.10123 (18)0.08786 (11)0.0082 (3)
N20.7554 (4)0.71413 (16)0.24472 (10)0.0087 (3)
Na10.75451 (17)1.04449 (8)0.23836 (5)0.0127 (3)
O10.7615 (3)1.09249 (14)0.06664 (8)0.0097 (3)
O20.7253 (3)1.02859 (15)0.09235 (10)0.0122 (3)
O30.5568 (3)0.7841 (2)0.24054 (13)0.0209 (4)
O40.9608 (3)0.7753 (2)0.23456 (13)0.0201 (4)
O50.7487 (4)0.57822 (15)0.26006 (9)0.0211 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0083 (9)0.0061 (9)0.0090 (9)0.0009 (7)0.0015 (8)0.0025 (7)
C20.0072 (9)0.0125 (9)0.0072 (9)0.0007 (8)0.0004 (7)0.0005 (8)
C30.0106 (10)0.0135 (9)0.0166 (10)0.0021 (10)0.0000 (9)0.0047 (7)
N10.0056 (8)0.0122 (8)0.0067 (7)0.0012 (8)0.0001 (7)0.0007 (5)
N20.0103 (8)0.0103 (7)0.0056 (7)0.0002 (8)0.0003 (8)0.0019 (5)
Na10.0135 (4)0.0164 (4)0.0084 (4)0.0005 (4)0.0010 (4)0.0027 (2)
O10.0089 (6)0.0119 (6)0.0082 (6)0.0011 (7)0.0022 (7)0.0005 (4)
O20.0086 (7)0.0214 (8)0.0067 (6)0.0002 (7)0.0014 (6)0.0014 (5)
O30.0142 (8)0.0329 (9)0.0157 (8)0.0120 (7)0.0030 (7)0.0045 (9)
O40.0142 (8)0.0264 (8)0.0197 (9)0.0095 (7)0.0053 (7)0.0051 (7)
O50.0418 (10)0.0106 (7)0.0108 (6)0.0020 (9)0.0036 (9)0.0012 (5)
Geometric parameters (Å, º) top
C1—O21.259 (3)N1—H1B0.84 (3)
C1—O11.262 (2)N1—H1C0.91 (3)
C1—C21.526 (3)N2—O41.241 (3)
C2—N11.489 (2)N2—O31.242 (3)
C2—C31.528 (3)N2—O51.264 (2)
C2—H20.94 (3)N2—Na13.0312 (17)
C3—H3A0.96 (3)Na1—O12.3647 (13)
C3—H3B0.97 (3)Na1—O32.612 (2)
C3—H3C1.00 (3)Na1—O42.705 (2)
N1—H1A0.92 (3)
O2—C1—O1125.16 (19)C2—N1—H1C110.9 (19)
O2—C1—C2117.11 (17)H1A—N1—H1C108 (3)
O1—C1—C2117.72 (17)H1B—N1—H1C106 (3)
N1—C2—C1109.44 (16)O4—N2—O3121.22 (17)
N1—C2—C3109.74 (16)O4—N2—O5119.3 (2)
C1—C2—C3110.54 (17)O3—N2—O5119.5 (2)
N1—C2—H2104.8 (17)O4—N2—Na163.02 (11)
C1—C2—H2109.2 (17)O3—N2—Na158.74 (12)
C3—C2—H2112.9 (17)O5—N2—Na1171.99 (11)
C2—C3—H3A111.7 (17)O1—Na1—O3100.82 (6)
C2—C3—H3B109.6 (18)O1—Na1—O498.33 (6)
H3A—C3—H3B108 (2)O3—Na1—O447.99 (5)
C2—C3—H3C115.1 (16)O1—Na1—N2102.35 (5)
H3A—C3—H3C106 (2)O3—Na1—N223.98 (6)
H3B—C3—H3C106 (2)O4—Na1—N224.14 (6)
C2—N1—H1A110.8 (18)C1—O1—Na1137.35 (13)
C2—N1—H1B112.4 (19)N2—O3—Na197.28 (13)
H1A—N1—H1B108 (3)N2—O4—Na192.84 (13)

Experimental details

Crystal data
Chemical formula[Na(NO3)(C3H7NO2)]
Mr174.10
Crystal system, space groupOrthorhombic, P212121
Temperature (K)100
a, b, c (Å)5.3477 (3), 9.1719 (6), 13.5284 (8)
V3)663.55 (7)
Z4
Radiation typeCu Kα
µ (mm1)1.98
Crystal size (mm)0.5 × 0.3 × 0.2
Data collection
DiffractometerBruker SMART 6000
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.431, 0.673
No. of measured, independent and
observed [I > 2σ(I)] reflections
6562, 1241, 1170
Rint0.048
(sin θ/λ)max1)0.611
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.092, 1.10
No. of reflections1241
No. of parameters122
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.32, 0.47
Absolute structureFlack, 1983
Absolute structure parameter0.10 (12)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.

 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds