Crystal structure of poly[di-μ-aqua-{5-[(1Z)-2-(4-chloro­phen­yl)-1-cyano­ethenyl]-1,2,3,4-tetra­zol-1-ido-κN¹}sodium]

In the title compound, [Na(C₁₀H₅ClN₅)(H₂O)₂]_n, infinite chains of [Na(H₂O)₂]⁺ cations having a diamond-shaped cross-section and running parallel to the b axis are formed. O—H...N hydrogen bonds to the anions generate layers parallel to (100) which have the chloro­benzene­cyano­ethenyl substituents protruding from both surfaces. The sodium ion makes a short contact of 2.4801 (13) Å with the N atom of the tetra­zolide ring which is syn to the cyano N atom.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.032
• wR factor = 0.086
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          6 Report

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          4 Report
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         34 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

Tetrazole compounds have been largely associated with a wide range of applications in medicine, biochemistry and agriculture (Modarresi et al., 2009; Singh et al., 1980). The medicinal activity of the tetrazole functionality is due to its ability to serve as a bioequivalent (bioisostere) of the carboxylic acid group (Smith et al., 1991; Duncia et al., 1990). They are also used as anti-hypertensive, anti-allergic, anti-biotic and anti-convulsant agents (Myznikov et al., 2007; Schocken et al., 1989; Mekni & Bakloiti, 2008; Lim et al., 2007). As part of our on-going study of bio-active molecules we herein report the synthesis and X-ray structure of the title compound as a building block precursor in the synthesis of new tetrazole scaffold compounds.

The title compound, Fig. 1, comprises infinite chains of [Na(H₂O)₂]⁺ cations having a diamond-shaped cross-section (Fig. 2) and running parallel to the b axis. These are associated on all four sides by tetrazoluide anions via O—H···N hydrogen bonds (Table 1) to generate layers parallel to (100) which have the chlorobenzenecyanoethenyl substituents protruding from both surfaces (Figs 3 and 4). Additionally, the sodium ion makes a contact of 2.4801 (13) Å with N4 of the tetrazolide ring which is significantly shorter than the sum of the ionic radius of Na⁺ and the van der Waals radius of N (2.71 Å). The C—N and N—N bond lengths in the ring (1.314 (2)–1.345 (2) Å) suggest significant delocalization of the negative charge. The hydrogen bonding interactions may restrict the cation to approach this site as opposed to the face of the ring. The tetrazolide and benzene rings, respectively, make dihedral angle of 4.8 (2) and 25.8 (2)° with the plane defined by C2–C4.

Related literature

For chemical behaviour of tetrazoles, see: Smith et al. (1991); Duncia et al. (1990). For various industrial applications of different tetrazole derivatives, see: Modarresi et al. (2009); Singh et al. (1980). For medicinal activities of compounds with a tetrazole scaffold, see: Myznikov et al. (2007); Schocken et al. (1989); Mekni & Bakloiti (2008); Lim et al. (2007).

S2. Experimental

The title compound has been obtained as an unexpected product from a multi-component reaction of 1 mmol (94 mg) of amino-pyridine, 4-chloro-benzaldehyde (1 mmol, 141.5 mg), malononitrile (1 mmol, 66 mg), sodium acetate (0.15 mmol, 12.3 mg) and sodium azide (1 mmol, 65 mg). The reaction mixture was refluxed in ethanol/water (1:1) and monitored by TLC until completion after 3 hours. On cooling, the solid precipitate was collected, dried under vacuum and recrystallized from ethanol to afford suitable crystals for X-ray diffraction.

S3. Refinement

H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 Å) while those attached to oxygen were placed in locations derived from a difference map and their parameters adjusted to give O—H = 0.84 Å. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms.

Computing details

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Title compound with numbering scheme and 50% probability ellipsoids.
	Fig. 2. A portion of the {[Na(H2O)2]^+}n chain (symmetry operations: (i) x, 1 + y, z, (ii) 2 - x, 1/2 + y, 3/2 - z, (iii) x, -1 + y, z, (iv) 2 - x, -1/2 + y, 3/2 - z, (v) 2 - x, -3/2 + y, 3/2 - z, (vi) x, -2 + y, z).
	Fig. 3. Packing viewed along the b axis.
	Fig. 4. Elevation view of the chain structure.

Poly[di-µ-aqua-{5-[(1Z)-2-(4-chlorophenyl)-1-cyanoethenyl]-1,2,3,4-tetrazol-1-ido-κN¹}sodium]

Crystal data

[Na(C10H5ClN5)(H2O)2]	F(000) = 592
Mr = 289.66	Dx = 1.517 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 22.0438 (4) Å	Cell parameters from 6311 reflections
b = 3.8343 (1) Å	θ = 4.0–74.5°
c = 15.0141 (3) Å	µ = 3.08 mm^−1
β = 92.427 (1)°	T = 150 K
V = 1267.89 (5) Å^3	Plate, colourless
Z = 4	0.29 × 0.11 × 0.04 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2560 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2249 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.026
Detector resolution: 10.4167 pixels mm^-1	θmax = 74.5°, θmin = 2.0°
ω scans	h = −27→25
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −4→4
Tmin = 0.73, Tmax = 0.89	l = −18→18
9115 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: mixed
wR(F^2) = 0.086	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0487P)^2 + 0.4982P] where P = (Fo^2 + 2Fc^2)/3
2560 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 Å) while those attached to oxygen were placed in locations derived from a difference map and their parameters adjusted to give O—H = 0.84 Å. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.49516 (2)	0.10717 (11)	0.35718 (3)	0.03137 (13)
N1	0.86367 (6)	1.0318 (4)	0.43087 (8)	0.0206 (3)
N2	0.91834 (6)	1.1473 (4)	0.46047 (8)	0.0220 (3)
N3	0.92611 (6)	1.0749 (4)	0.54572 (8)	0.0221 (3)
N4	0.87680 (6)	0.9091 (4)	0.57424 (8)	0.0209 (3)
N5	0.74923 (7)	0.5087 (5)	0.65661 (10)	0.0382 (4)
C1	0.83943 (7)	0.8871 (4)	0.50194 (9)	0.0176 (3)
C2	0.77918 (7)	0.7259 (4)	0.50140 (9)	0.0194 (3)
C3	0.76111 (7)	0.6066 (5)	0.58710 (10)	0.0242 (3)
C4	0.74473 (7)	0.6828 (4)	0.42591 (10)	0.0210 (3)
H4	0.7629	0.7579	0.3729	0.025*
C5	0.68365 (7)	0.5378 (4)	0.41324 (10)	0.0204 (3)
C6	0.66615 (7)	0.4117 (4)	0.32820 (10)	0.0240 (3)
H6	0.6941	0.4214	0.2818	0.029*
C7	0.60884 (7)	0.2734 (4)	0.31088 (10)	0.0244 (3)
H7	0.5977	0.1835	0.2535	0.029*
C8	0.56795 (7)	0.2681 (4)	0.37836 (11)	0.0232 (3)
C9	0.58373 (7)	0.3933 (5)	0.46302 (10)	0.0254 (3)
H9	0.5553	0.3870	0.5088	0.030*
C10	0.64131 (7)	0.5273 (4)	0.47993 (10)	0.0243 (3)
H10	0.6523	0.6135	0.5377	0.029*
Na1	0.92711 (3)	0.78850 (17)	0.72191 (4)	0.02362 (16)
O1	0.99226 (5)	0.9704 (3)	0.84267 (6)	0.0211 (2)
H1A	1.0146	0.8147	0.8659	0.025*
H1B	0.9717	1.0768	0.8799	0.025*
O2	0.86926 (5)	0.2859 (3)	0.75583 (7)	0.0251 (3)
H2A	0.8664	0.3340	0.8101	0.030*
H2B	0.8326	0.2395	0.7434	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0220 (2)	0.0323 (2)	0.0393 (2)	−0.00816 (16)	−0.00439 (15)	−0.00037 (17)
N1	0.0179 (6)	0.0247 (7)	0.0192 (6)	−0.0011 (5)	0.0002 (5)	0.0004 (5)
N2	0.0194 (6)	0.0248 (7)	0.0216 (6)	−0.0015 (5)	0.0001 (5)	0.0001 (5)
N3	0.0196 (6)	0.0251 (7)	0.0214 (6)	−0.0024 (5)	−0.0017 (5)	−0.0011 (5)
N4	0.0190 (6)	0.0243 (7)	0.0191 (6)	−0.0017 (5)	−0.0008 (5)	−0.0003 (5)
N5	0.0268 (8)	0.0584 (11)	0.0292 (7)	−0.0056 (8)	−0.0005 (6)	0.0161 (7)
C1	0.0171 (7)	0.0178 (7)	0.0179 (6)	0.0020 (6)	0.0007 (5)	−0.0010 (5)
C2	0.0181 (7)	0.0181 (7)	0.0221 (7)	0.0018 (6)	0.0019 (5)	0.0021 (6)
C3	0.0161 (7)	0.0301 (9)	0.0260 (8)	−0.0015 (6)	−0.0029 (6)	0.0041 (7)
C4	0.0195 (7)	0.0214 (7)	0.0222 (7)	0.0002 (6)	0.0022 (5)	0.0008 (6)
C5	0.0187 (7)	0.0187 (7)	0.0237 (7)	0.0013 (6)	−0.0009 (5)	0.0008 (6)
C6	0.0226 (8)	0.0262 (8)	0.0230 (7)	0.0024 (7)	0.0007 (6)	0.0003 (6)
C7	0.0243 (8)	0.0235 (8)	0.0250 (7)	0.0014 (7)	−0.0049 (6)	−0.0027 (6)
C8	0.0190 (7)	0.0190 (8)	0.0311 (8)	−0.0018 (6)	−0.0039 (6)	0.0020 (6)
C9	0.0201 (8)	0.0300 (9)	0.0263 (7)	0.0005 (7)	0.0028 (6)	0.0013 (7)
C10	0.0232 (8)	0.0262 (8)	0.0233 (7)	0.0001 (7)	−0.0014 (6)	−0.0028 (6)
Na1	0.0246 (3)	0.0255 (3)	0.0205 (3)	0.0022 (3)	−0.0020 (2)	−0.0011 (2)
O1	0.0211 (5)	0.0246 (6)	0.0176 (5)	0.0045 (4)	0.0001 (4)	−0.0001 (4)
O2	0.0252 (6)	0.0323 (6)	0.0175 (5)	0.0033 (5)	−0.0022 (4)	−0.0019 (5)

Geometric parameters (Å, º)

Cl1—C8	1.7359 (16)	C7—C8	1.384 (2)
N1—C1	1.3343 (19)	C7—H7	0.9500
N1—N2	1.3419 (18)	C8—C9	1.389 (2)
N2—N3	1.3138 (17)	C9—C10	1.383 (2)
N3—N4	1.3449 (18)	C9—H9	0.9500
N4—C1	1.3374 (19)	C10—H10	0.9500
N4—Na1	2.4801 (13)	Na1—O2^i	2.3619 (13)
N5—C3	1.150 (2)	Na1—O1	2.3697 (12)
C1—C2	1.465 (2)	Na1—O2	2.3780 (14)
C2—C4	1.348 (2)	Na1—O1^ii	2.3941 (12)
C2—C3	1.438 (2)	O1—Na1^iii	2.3941 (12)
C4—C5	1.462 (2)	O1—H1A	0.8399
C4—H4	0.9500	O1—H1B	0.8398
C5—C10	1.398 (2)	O2—Na1^iv	2.3619 (13)
C5—C6	1.404 (2)	O2—H2A	0.8399
C6—C7	1.385 (2)	O2—H2B	0.8401
C6—H6	0.9500
C1—N1—N2	104.89 (12)	C9—C10—C5	120.98 (15)
N3—N2—N1	109.33 (12)	C9—C10—H10	119.5
N2—N3—N4	109.65 (12)	C5—C10—H10	119.5
C1—N4—N3	104.47 (12)	O2^i—Na1—O1	84.99 (4)
C1—N4—Na1	161.92 (11)	O2^i—Na1—O2	107.99 (5)
N3—N4—Na1	92.06 (8)	O1—Na1—O2	112.82 (4)
N1—C1—N4	111.66 (13)	O2^i—Na1—O1^ii	156.29 (5)
N1—C1—C2	124.39 (13)	O1—Na1—O1^ii	91.35 (4)
N4—C1—C2	123.95 (13)	O2—Na1—O1^ii	95.05 (4)
C4—C2—C3	123.10 (14)	O2^i—Na1—N4	79.46 (4)
C4—C2—C1	122.35 (13)	O1—Na1—N4	149.61 (5)
C3—C2—C1	114.51 (13)	O2—Na1—N4	96.83 (4)
N5—C3—C2	177.07 (17)	O1^ii—Na1—N4	92.55 (4)
C2—C4—C5	129.74 (14)	O2^i—Na1—N3	84.63 (4)
C2—C4—H4	115.1	O1—Na1—N3	125.07 (5)
C5—C4—H4	115.1	O2—Na1—N3	121.70 (4)
C10—C5—C6	118.38 (14)	O1^ii—Na1—N3	78.35 (4)
C10—C5—C4	123.85 (14)	N4—Na1—N3	27.99 (4)
C6—C5—C4	117.74 (14)	Na1—O1—Na1^iii	106.04 (4)
C7—C6—C5	121.07 (14)	Na1—O1—H1A	115.7
C7—C6—H6	119.5	Na1^iii—O1—H1A	95.6
C5—C6—H6	119.5	Na1—O1—H1B	109.0
C8—C7—C6	119.03 (14)	Na1^iii—O1—H1B	116.9
C8—C7—H7	120.5	H1A—O1—H1B	113.0
C6—C7—H7	120.5	Na1^iv—O2—Na1	107.98 (5)
C7—C8—C9	121.26 (15)	Na1^iv—O2—H2A	116.7
C7—C8—Cl1	119.77 (12)	Na1—O2—H2A	95.3
C9—C8—Cl1	118.96 (12)	Na1^iv—O2—H2B	107.7
C10—C9—C8	119.26 (15)	Na1—O2—H2B	130.0
C10—C9—H9	120.4	H2A—O2—H2B	98.7
C8—C9—H9	120.4
C1—N1—N2—N3	−0.19 (17)	C3—C2—C4—C5	4.3 (3)
N1—N2—N3—N4	0.17 (17)	C1—C2—C4—C5	−178.16 (15)
N1—N2—N3—Na1	31.8 (5)	C2—C4—C5—C10	23.5 (3)
N2—N3—N4—C1	−0.08 (17)	C2—C4—C5—C6	−158.45 (17)
N2—N3—N4—Na1	172.51 (11)	C10—C5—C6—C7	−1.3 (2)
N2—N1—C1—N4	0.14 (17)	C4—C5—C6—C7	−179.43 (15)
N2—N1—C1—C2	179.72 (14)	C5—C6—C7—C8	1.5 (2)
N3—N4—C1—N1	−0.04 (17)	C6—C7—C8—C9	−1.0 (2)
Na1—N4—C1—N1	−155.5 (3)	C6—C7—C8—Cl1	178.18 (13)
N3—N4—C1—C2	−179.62 (14)	C7—C8—C9—C10	0.3 (3)
Na1—N4—C1—C2	24.9 (4)	Cl1—C8—C9—C10	−178.91 (13)
N1—C1—C2—C4	6.0 (2)	C8—C9—C10—C5	−0.1 (3)
N4—C1—C2—C4	−174.48 (15)	C6—C5—C10—C9	0.6 (2)
N1—C1—C2—C3	−176.27 (15)	C4—C5—C10—C9	178.56 (15)
N4—C1—C2—C3	3.3 (2)

Symmetry codes: (i) x, y+1, z; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+2, y+1/2, −z+3/2; (iv) x, y−1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3^ii	0.84	2.04	2.8443 (17)	160
O1—H1B···N2^v	0.84	2.02	2.8593 (17)	175
O2—H2B···N5	0.84	2.44	3.1009 (19)	136

Symmetry codes: (ii) −x+2, y−1/2, −z+3/2; (v) x, −y+5/2, z+1/2.