catena-Poly[[chloro­(pyridinium-3-carboxyl­ato-κO)zinc(II)]-μ-nicotinato-κ²O:N]

The title bis-nicotinate zinc chloride, [Zn(C₆H₄NO₂)Cl(C₆H₅NO₂)]_n, has an infinite head-to-tail one-dimensional chain structure. The compound was synthesized under mild hydro­thermal conditions. The Zn^II atom exhibits a distorted tetra­hedral coordination geometry. The structure is statistically disordered, with 0.5 site occupancy for the Zn atom and the H atom located on the pyridine N atom. As a result, Zn positions in the crystal structure alternate between two sites related by a crystallographic twofold axis and rows of mol­ecules are formed, supported by strong N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.050
• wR factor = 0.134
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT143_ALERT_4_C su on c - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Zn1
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.29 Ratio

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

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Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL.

catena-Poly[[chloro(pyridinium-3-carboxylato-κO)zinc(II)]- µ-nicotinato-κ²O:N]

Crystal data

[Zn(C6H4NO2)Cl(C6H5NO2)]	F(000) = 696
Mr = 346.03	Dx = 1.782 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4195 reflections
a = 13.0493 (2) Å	θ = 3.1–26.5°
b = 7.7050 (1) Å	µ = 2.12 mm^−1
c = 12.9115 (1) Å	T = 173 K
β = 96.439 (1)°	Plate, colourless
V = 1290.00 (3) Å^3	0.20 × 0.08 × 0.04 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	1341 independent reflections
Radiation source: fine-focus sealed tube	1104 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 26.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −16→16
Tmin = 0.676, Tmax = 0.920	k = −9→9
6430 measured reflections	l = −16→16

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0709P)^2 + 5.3068P] where P = (Fo^2 + 2Fc^2)/3
1341 reflections	(Δ/σ)max < 0.001
96 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

Special details

Experimental. Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3020 (C═C, s), 1742 (C═O, s), 1534 (C═C, m), 1395 (C—H, s), 1243 (C—N, s), 1062 (C—O, m), 764 (C—H, m).

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.45298 (6)	0.06492 (10)	0.18285 (5)	0.0256 (3)	0.50
Cl1	0.5000	−0.19001 (19)	0.2500	0.0526 (5)
O1	0.6264 (2)	0.2194 (4)	0.22467 (18)	0.0430 (7)
O2	0.5120 (2)	0.2083 (4)	0.08291 (19)	0.0392 (6)
N1	0.8221 (2)	0.5186 (4)	0.0759 (3)	0.0400 (8)
H1	0.8817	0.5500	0.1093	0.048*	0.50
C2	0.7570 (3)	0.4240 (5)	0.1242 (3)	0.0344 (8)
H2	0.7762	0.3900	0.1944	0.041*
C3	0.6626 (3)	0.3740 (4)	0.0757 (2)	0.0266 (7)
C4	0.6349 (3)	0.4246 (4)	−0.0274 (2)	0.0262 (7)
H4	0.5699	0.3921	−0.0628	0.031*
C5	0.7034 (3)	0.5228 (4)	−0.0775 (3)	0.0300 (8)
H5	0.6858	0.5591	−0.1475	0.036*
C6	0.7971 (3)	0.5672 (5)	−0.0248 (3)	0.0377 (9)
H6	0.8449	0.6326	−0.0592	0.045*
C7	0.5942 (3)	0.2583 (5)	0.1318 (3)	0.0352 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0275 (4)	0.0358 (5)	0.0142 (4)	−0.0035 (3)	0.0056 (3)	−0.0011 (3)
Cl1	0.0706 (10)	0.0382 (8)	0.0415 (8)	0.000	−0.0259 (7)	0.000
O1	0.0637 (19)	0.0511 (17)	0.0156 (12)	0.0106 (14)	0.0105 (12)	0.0068 (11)
O2	0.0452 (16)	0.0482 (16)	0.0262 (13)	−0.0042 (13)	0.0133 (12)	0.0055 (11)
N1	0.0276 (16)	0.0468 (19)	0.0444 (19)	0.0026 (14)	−0.0010 (14)	−0.0211 (16)
C2	0.0339 (19)	0.049 (2)	0.0203 (16)	0.0111 (17)	0.0001 (14)	−0.0083 (15)
C3	0.0346 (18)	0.0304 (17)	0.0157 (14)	0.0078 (14)	0.0073 (13)	−0.0017 (12)
C4	0.0302 (17)	0.0298 (17)	0.0185 (15)	0.0026 (14)	0.0023 (13)	−0.0006 (13)
C5	0.0353 (18)	0.0306 (18)	0.0253 (17)	0.0015 (15)	0.0086 (14)	0.0004 (14)
C6	0.0338 (19)	0.0302 (19)	0.051 (2)	−0.0039 (15)	0.0157 (17)	−0.0117 (17)
C7	0.055 (2)	0.0323 (19)	0.0219 (17)	0.0135 (17)	0.0202 (17)	0.0022 (14)

Geometric parameters (Å, º)

Zn1—O2	1.924 (3)	N1—Zn1^iii	2.104 (3)
Zn1—Zn1^i	2.0088 (14)	N1—H1	0.8800
Zn1—O1^i	2.048 (3)	C2—C3	1.372 (5)
Zn1—N1^ii	2.104 (3)	C2—H2	0.9500
Zn1—Cl1	2.2061 (15)	C3—C4	1.395 (4)
Zn1—C7	2.514 (4)	C3—C7	1.505 (5)
Cl1—Zn1^i	2.2061 (15)	C4—C5	1.386 (5)
O1—C7	1.261 (4)	C4—H4	0.9500
O1—Zn1^i	2.048 (3)	C5—C6	1.374 (5)
O2—C7	1.243 (5)	C5—H5	0.9500
N1—C2	1.327 (5)	C6—H6	0.9500
N1—C6	1.357 (5)
O2—Zn1—Zn1^i	109.10 (10)	C6—N1—H1	119.8
O2—Zn1—O1^i	108.91 (12)	N1—C2—C3	121.9 (3)
Zn1^i—Zn1—O1^i	78.26 (9)	N1—C2—H2	119.1
O2—Zn1—N1^ii	90.79 (14)	C3—C2—H2	119.1
Zn1^i—Zn1—N1^ii	159.94 (12)	C2—C3—C4	118.7 (3)
O1^i—Zn1—N1^ii	93.14 (12)	C2—C3—C7	119.8 (3)
O2—Zn1—Cl1	131.31 (9)	C4—C3—C7	121.4 (3)
Zn1^i—Zn1—Cl1	62.92 (3)	C5—C4—C3	119.0 (3)
O1^i—Zn1—Cl1	115.15 (8)	C5—C4—H4	120.5
N1^ii—Zn1—Cl1	106.06 (1)	C3—C4—H4	120.5
O2—Zn1—C7	28.80 (11)	C4—C5—C6	119.4 (3)
Zn1^i—Zn1—C7	80.30 (9)	C4—C5—H5	120.3
O1^i—Zn1—C7	103.99 (11)	C6—C5—H5	120.3
N1^ii—Zn1—C7	119.58 (14)	N1—C6—C5	120.7 (4)
Cl1—Zn1—C7	116.80 (9)	N1—C6—H6	119.7
Zn1^i—Cl1—Zn1	54.16 (5)	C5—C6—H6	119.7
C7—O1—Zn1^i	123.8 (3)	O2—C7—O1	125.9 (4)
C7—O2—Zn1	103.0 (2)	O2—C7—C3	117.6 (3)
C2—N1—C6	120.3 (3)	O1—C7—C3	116.5 (4)
C2—N1—Zn1^iii	107.4 (3)	O2—C7—Zn1	48.22 (18)
C6—N1—Zn1^iii	132.2 (3)	O1—C7—Zn1	77.7 (2)
C2—N1—H1	119.8	C3—C7—Zn1	165.8 (3)
O2—Zn1—Cl1—Zn1^i	92.29 (13)	Zn1^i—O1—C7—Zn1	−1.0 (2)
O1^i—Zn1—Cl1—Zn1^i	−60.50 (9)	C2—C3—C7—O2	−176.1 (3)
N1^ii—Zn1—Cl1—Zn1^i	−161.93 (11)	C4—C3—C7—O2	0.4 (5)
C7—Zn1—Cl1—Zn1^i	61.95 (10)	C2—C3—C7—O1	3.3 (5)
Zn1^i—Zn1—O2—C7	0.9 (2)	C4—C3—C7—O1	179.7 (3)
O1^i—Zn1—O2—C7	84.7 (2)	C2—C3—C7—Zn1	−173.7 (8)
N1^ii—Zn1—O2—C7	178.3 (2)	C4—C3—C7—Zn1	2.7 (12)
Cl1—Zn1—O2—C7	−69.4 (3)	Zn1^i—Zn1—C7—O2	−179.1 (2)
C6—N1—C2—C3	−0.8 (5)	O1^i—Zn1—C7—O2	−103.9 (2)
Zn1^iii—N1—C2—C3	178.9 (3)	N1^ii—Zn1—C7—O2	−2.0 (3)
N1—C2—C3—C4	0.0 (5)	Cl1—Zn1—C7—O2	128.0 (2)
N1—C2—C3—C7	176.5 (3)	O2—Zn1—C7—O1	180.0 (4)
C2—C3—C4—C5	0.3 (5)	Zn1^i—Zn1—C7—O1	0.86 (18)
C7—C3—C4—C5	−176.2 (3)	O1^i—Zn1—C7—O1	76.1 (2)
C3—C4—C5—C6	0.3 (5)	N1^ii—Zn1—C7—O1	177.98 (19)
C2—N1—C6—C5	1.5 (5)	Cl1—Zn1—C7—O1	−52.0 (2)
Zn1^iii—N1—C6—C5	−178.2 (3)	O2—Zn1—C7—C3	−2.8 (9)
C4—C5—C6—N1	−1.2 (5)	Zn1^i—Zn1—C7—C3	178.1 (10)
Zn1—O2—C7—O1	−0.1 (4)	O1^i—Zn1—C7—C3	−106.7 (10)
Zn1—O2—C7—C3	179.2 (2)	N1^ii—Zn1—C7—C3	−4.8 (10)
Zn1^i—O1—C7—O2	−1.0 (5)	Cl1—Zn1—C7—C3	125.2 (10)
Zn1^i—O1—C7—C3	179.8 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^iii	0.88	2.15	2.870 (4)	139
C5—H5···O1^iv	0.95	2.44	3.302 (4)	151

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