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The title compound, C11H11N7O4, possesses crystallographically imposed C2 symmetry. The two side chains are twisted in opposite directions from the mean plane of the pyridine ring. C—H...O inter­actions link symmetry-related mol­ecules into two-dimensional layers perpendicular to the a axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041735/rz6152sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041735/rz6152Isup2.hkl
Contains datablock I

CCDC reference: 296643

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.048
  • wR factor = 0.137
  • Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 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 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Azides are used to synthesize triazole or tetrazole derivatives, which frequently exhibit significant biological activity and, in consequence, have found a wide variety of applications as active heterocycles in pharmacy and agriculture (Ostrovskii & Koren, 2000; Nomiya et al., 2000). In addition, photolysis of azide leads to the formation of azido radicals, which are employed in the photoinitiation of radical polymerization industrially (Endicott et al., 1970). In an attempt to synthesize new triazoles or tetrazoles, the title compound, (I), was synthesized and its structure is reported here.

The asymmetric unit of (I) contains one half-molecule, the other half being related by a crystallographic twofold axis passing through the C1···N4 line. The bond lengths and angles in (I) show normal values (Allen et al., 1987). The molecule is not planar, the two side chains twisting from the mean plane of pyridine ring in opposite directions. In the packing of the title compound, molecules are linked into two-dimensional layers perpendicular to the a axis (Fig. 2) by C6—H6A···O1 intermolecular hydrogen bonds. These interactions, together with van der Waals forces, stabilize the crystal structure.

Experimental top

A mixture of pyridine-2,6-dicarboxylic acid (1.0 g, 6.0 mmol) and thionyl chloride (3 ml) was refluxed for 3 h. To this solution, 2-azidoethanol (1.5 g, 13.2 mmol) and triethylamine (1.84 ml, 13.2 mmol) in dry CH2Cl2 (15 ml) were added. The mixture was stirred overnight at 323 K and then filtered. Evaporation of the solvent left a crude yellow solid, followed by chromatographic purification on a silica-gel column with ethyl acetate–petroleum ether (1:8 v/v) as eluants. Colorless single crystals suitable for X-ray crystallographic analysis were grown by slow evaporation of an ethyl acetate solution.

Refinement top

All H atoms were located in difference Fourier maps and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The structure of the compound (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. A view down the a axis, showing the two-dimensional layer. Hydrogen bonds are indicated by dashed lines.
Bis(2-azidoethyl) pyridine-2,6-dicarboxylate top
Crystal data top
C11H11N7O4F(000) = 632
Mr = 305.27Dx = 1.424 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1833 reflections
a = 14.407 (3) Åθ = 2.3–25.6°
b = 11.854 (3) ŵ = 0.11 mm1
c = 8.942 (2) ÅT = 293 K
β = 111.142 (3)°Needle, colorless
V = 1424.3 (6) Å30.36 × 0.14 × 0.11 mm
Z = 4
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer
1416 independent reflections
Radiation source: fine-focus sealed tube1233 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
Detector resolution: 8.33 pixels mm-1θmax = 26.1°, θmin = 2.3°
ω scansh = 1617
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 1410
Tmin = 0.961, Tmax = 0.988l = 1110
4299 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0749P)2 + 0.6085P]
where P = (Fo2 + 2Fc2)/3
1416 reflections(Δ/σ)max < 0.001
101 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C11H11N7O4V = 1424.3 (6) Å3
Mr = 305.27Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.407 (3) ŵ = 0.11 mm1
b = 11.854 (3) ÅT = 293 K
c = 8.942 (2) Å0.36 × 0.14 × 0.11 mm
β = 111.142 (3)°
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer
1416 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1233 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.988Rint = 0.017
4299 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.06Δρmax = 0.20 e Å3
1416 reflectionsΔρmin = 0.24 e Å3
101 parameters
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
O10.19434 (13)0.30279 (12)0.62244 (19)0.0888 (6)
O20.10863 (8)0.14788 (9)0.51612 (12)0.0494 (3)
N10.13452 (17)0.09088 (15)0.5125 (2)0.0800 (6)
N20.13037 (14)0.19311 (15)0.5167 (2)0.0676 (5)
N30.1290 (2)0.28773 (18)0.5058 (3)0.0996 (8)
N40.00000.25984 (14)0.25000.0425 (5)
C10.00000.4952 (2)0.25000.0713 (8)
H1A0.00000.57360.25000.086*
C20.06356 (15)0.43658 (15)0.3780 (2)0.0617 (5)
H2A0.10780.47450.46580.074*
C30.06074 (12)0.31924 (13)0.37417 (19)0.0461 (4)
C40.12839 (13)0.25668 (14)0.51653 (19)0.0503 (4)
C50.17262 (14)0.08486 (16)0.6543 (2)0.0584 (5)
H5A0.17750.12370.75230.070*
H5B0.23890.07870.65070.070*
C60.12965 (13)0.02960 (14)0.6518 (2)0.0514 (4)
H6A0.16700.06980.74960.062*
H6B0.06110.02350.64480.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0998 (12)0.0640 (9)0.0689 (10)0.0301 (8)0.0103 (9)0.0078 (7)
O20.0558 (7)0.0426 (7)0.0392 (6)0.0082 (5)0.0044 (5)0.0021 (5)
N10.1328 (17)0.0522 (10)0.0686 (11)0.0154 (10)0.0529 (12)0.0094 (8)
N20.0789 (12)0.0604 (11)0.0695 (11)0.0004 (8)0.0338 (9)0.0042 (8)
N30.133 (2)0.0617 (13)0.118 (2)0.0143 (12)0.0617 (17)0.0204 (12)
N40.0517 (10)0.0335 (9)0.0433 (10)0.0000.0182 (8)0.000
C10.100 (2)0.0307 (12)0.082 (2)0.0000.0311 (17)0.000
C20.0808 (13)0.0390 (9)0.0654 (12)0.0103 (8)0.0265 (10)0.0108 (8)
C30.0561 (9)0.0374 (8)0.0473 (9)0.0065 (6)0.0220 (8)0.0054 (6)
C40.0584 (10)0.0442 (9)0.0445 (9)0.0117 (7)0.0138 (8)0.0076 (7)
C50.0554 (10)0.0650 (12)0.0416 (9)0.0053 (8)0.0016 (7)0.0077 (8)
C60.0592 (10)0.0507 (10)0.0412 (9)0.0067 (7)0.0142 (7)0.0098 (7)
Geometric parameters (Å, º) top
O1—C41.204 (2)C1—H1A0.9300
O2—C41.321 (2)C2—C31.392 (2)
O2—C51.453 (2)C2—H2A0.9300
N1—N21.215 (2)C3—C41.492 (2)
N1—C61.465 (2)C5—C61.488 (3)
N2—N31.125 (2)C5—H5A0.9700
N4—C31.3392 (18)C5—H5B0.9700
N4—C3i1.3392 (18)C6—H6A0.9700
C1—C2i1.369 (2)C6—H6B0.9700
C1—C21.369 (2)
C4—O2—C5115.45 (12)O1—C4—C3122.21 (16)
N2—N1—C6116.77 (16)O2—C4—C3114.16 (13)
N3—N2—N1172.4 (2)O2—C5—C6108.86 (13)
C3—N4—C3i116.56 (19)O2—C5—H5A109.9
C2i—C1—C2119.0 (2)C6—C5—H5A109.9
C2i—C1—H1A120.5O2—C5—H5B109.9
C2—C1—H1A120.5C6—C5—H5B109.9
C1—C2—C3118.82 (18)H5A—C5—H5B108.3
C1—C2—H2A120.6N1—C6—C5108.50 (15)
C3—C2—H2A120.6N1—C6—H6A110.0
N4—C3—C2123.39 (16)C5—C6—H6A110.0
N4—C3—C4118.46 (14)N1—C6—H6B110.0
C2—C3—C4118.14 (15)C5—C6—H6B110.0
O1—C4—O2123.63 (17)H6A—C6—H6B108.4
C2i—C1—C2—C30.57 (11)N4—C3—C4—O1169.43 (17)
C3i—N4—C3—C20.62 (13)C2—C3—C4—O111.1 (3)
C3i—N4—C3—C4178.86 (16)N4—C3—C4—O211.3 (2)
C1—C2—C3—N41.2 (2)C2—C3—C4—O2168.23 (15)
C1—C2—C3—C4178.26 (14)C4—O2—C5—C6169.33 (14)
C5—O2—C4—O10.1 (3)N2—N1—C6—C5159.13 (19)
C5—O2—C4—C3179.33 (14)O2—C5—C6—N166.4 (2)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···O1ii0.972.443.280 (3)145
Symmetry code: (ii) x+1/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC11H11N7O4
Mr305.27
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)14.407 (3), 11.854 (3), 8.942 (2)
β (°) 111.142 (3)
V3)1424.3 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.36 × 0.14 × 0.11
Data collection
DiffractometerSiemens SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.961, 0.988
No. of measured, independent and
observed [I > 2σ(I)] reflections
4299, 1416, 1233
Rint0.017
(sin θ/λ)max1)0.619
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.137, 1.06
No. of reflections1416
No. of parameters101
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.24

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Selected bond lengths (Å) top
O1—C41.204 (2)N1—N21.215 (2)
O2—C41.321 (2)N1—C61.465 (2)
O2—C51.453 (2)N2—N31.125 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···O1i0.972.443.280 (3)145
Symmetry code: (i) x+1/2, y1/2, z+3/2.
 

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