Poly[bis­(μ2-pyrazine-2-carboxyl­ato)-κ3N1,O:O′;κ3N1,O:O-cadmium(II)]

Liu, G.

doi:10.1107/S1600536809053525

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m93

doi:10.1107/S1600536809053525

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Poly[bis(μ₂-pyrazine-2-carboxylato)-κ³N¹,O:O′;κ³N¹,O:O-cadmium(II)]

Ge Liu ^a ^*

^aChifeng University, Chifeng 024000, People's Republic of China
^*Correspondence e-mail: liu_ge2008@mail.163.com

(Received 27 November 2009; accepted 11 December 2009; online 24 December 2009)

In the structure of the title compound, [Cd(C₅H₃N₂O₂)₂]_n, the Cd^II ion is six-coordinated by two N atoms and four O atoms from three different pyrazine-2-carboxylate ligands. One N atom and one O atom of the carboxylate group in the ligand coordinate to the metal center, forming a five-membered chelate ring. The carboxylate anion adopts two types of bridging modes, viz. μ₂-O and syn–anti. Two Cd^II ions form a centrosymmetric dimer via a μ₂-O bridge, and the dimers are linked through the syn–anti carboxylate functional group, forming a two-dimensional polymeric structure extending along (100).

Related literature

The title compound is isostructural with the Mn(II) complex, see: Cai et al. (2002 ); Devereux et al. (2002 ); Liang et al. (2002 ). For a homologous Cd(II) complex with a picolinate ligand, see: Deloume & Loiseleur (1974 ).

Experimental

Crystal data

[Cd(C₅H₃N₂O₂)₂]
M_r = 358.59
Monoclinic, P 2₁ /c
a = 10.304 (2) Å
b = 11.044 (2) Å
c = 10.274 (2) Å
β = 107.89 (3)°
V = 1112.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.98 mm⁻¹
T = 293 K
0.18 × 0.13 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
11295 measured reflections
2550 independent reflections
1943 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.065
S = 1.16
2550 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809053525/bh2262sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053525/bh2262Isup2.hkl

checkCIF report

Comment top

Pyrazine-2-carboxylate is a suitable multidentate bridging ligand to build coordination polymers and several novel structural coordination polymers containing derivatives of pyrazinecarboxylate have been obtained. Here, we report the reaction of pyrazine-2-carboxylate with a Cd^II salt, which afforded a two-dimensional Cd^II coordination polymer. The compound is isostructural with the Mn^II complex (Cai et al., 2002; Devereux et al., 2002; Liang et al., 2002). An isostructural Cd(II) complex including picolinate in place of pyrazine-2-carboxylate has also been X-ray characterized (Deloume & Loiseleur, 1974).

In the structure of the title compound, each Cd^II ion is six-coordinated by two N atoms and four O atoms from three different pyrazine-2-carboxylate ligands (Fig. 1). One N atom and one O atom of the neighboring carboxylate of the ligand coordinate to the center Cd^II ion forming a five-member chelate ring. The carboxylate of the ligand adopts two types of bridging mode: µ₂-O and syn–anti. The second N atom is not involved in bonding, so the complex is also isostructural with the Cd(II) complex with picolinate (Deloume & Loiseleur, 1974). Cd^II ion form a dimer via an µ₂-O bridge, and these dimers are linked through syn–anti carboxy O atoms, to form a two-dimensional structure.

Related literature top

The title compound is isostructural with the Mn(II) complex, see: Cai et al. (2002); Devereux et al. (2002); Liang et al. (2002). For a homologous Cd(II) complex with a picolinate ligand, see: Deloume & Loiseleur (1974).

Experimental top

A mixture of cadmium(II) nitrate (1 mmol), pyrazine-2-carboxylate (0.5 mmol), NaOH (1 mmol), tetrazolate (0.5 mmol) and water (10 ml) was sealed in a 23 ml Teflon-lined reactor, heated to 433 K at 10.8 K/h and kept at this temperature for three days, finally cooled to 303 K at 5.4 K/h (yield 20%).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound showing the coordination of Cd atom with the atom-labelling scheme. Ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) x, -y + 3/2, z + 1/2; (ii) -x, -y + 1, -z; (iii) x, -y + 3/2, z

Poly[bis(µ₂-pyrazine-2-carboxylato)- κ³N¹,O:O';κ³N¹,O:O- cadmium(II)] top

Crystal data top

[Cd(C₅H₃N₂O₂)₂]	F(000) = 696
M_r = 358.59	D_x = 2.141 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9922 reflections
a = 10.304 (2) Å	θ = 3.1–27.5°
b = 11.044 (2) Å	µ = 1.98 mm⁻¹
c = 10.274 (2) Å	T = 293 K
β = 107.89 (3)°	Block, colourless
V = 1112.7 (4) Å³	0.18 × 0.13 × 0.12 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1943 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.069
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −13→13
11295 measured reflections	k = −14→14
2550 independent reflections	l = −13→13

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.0199P)² + 0.0187P] where P = (F_o² + 2F_c²)/3
2550 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.80 e Å⁻³
0 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

[Cd(C₅H₃N₂O₂)₂]	V = 1112.7 (4) Å³
M_r = 358.59	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.304 (2) Å	µ = 1.98 mm⁻¹
b = 11.044 (2) Å	T = 293 K
c = 10.274 (2) Å	0.18 × 0.13 × 0.12 mm
β = 107.89 (3)°

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	1943 reflections with I > 2σ(I)
11295 measured reflections	R_int = 0.069
2550 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.16	Δρ_max = 0.80 e Å⁻³
2550 reflections	Δρ_min = −0.64 e Å⁻³
172 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3232 (4)	0.6168 (3)	0.1469 (4)	0.0246 (9)
C2	0.4605 (4)	0.6443 (4)	0.1809 (4)	0.0373 (10)
H2	0.5148	0.6004	0.1402	0.045*
C3	0.4363 (5)	0.7903 (4)	0.3276 (4)	0.0398 (12)
H3	0.4728	0.8507	0.3915	0.048*
C4	0.2983 (5)	0.7643 (4)	0.2953 (4)	0.0377 (11)
H4	0.2446	0.8077	0.3370	0.045*
C5	0.2594 (4)	0.5175 (4)	0.0442 (4)	0.0283 (10)
C6	−0.1395 (4)	0.8772 (4)	−0.0343 (4)	0.0294 (10)
C7	−0.2299 (5)	0.9723 (4)	−0.0745 (5)	0.0415 (12)
H7	−0.2229	1.0226	−0.1446	0.050*
C8	−0.3322 (5)	0.9200 (4)	0.0826 (5)	0.0412 (12)
H8	−0.3991	0.9315	0.1250	0.049*
C9	−0.2419 (4)	0.8262 (4)	0.1254 (4)	0.0376 (12)
H9	−0.2484	0.7770	0.1967	0.045*
C10	−0.0370 (4)	0.8481 (4)	−0.1094 (4)	0.0303 (10)
Cd1	0.00719 (3)	0.63837 (3)	0.10693 (3)	0.02760 (11)
N1	0.2415 (3)	0.6773 (3)	0.2048 (3)	0.0294 (8)
N2	0.5188 (4)	0.7323 (4)	0.2710 (4)	0.0438 (10)
N3	−0.1448 (3)	0.8035 (3)	0.0671 (3)	0.0298 (8)
N4	−0.3279 (4)	0.9948 (4)	−0.0163 (4)	0.0473 (11)
O1	0.1363 (3)	0.4919 (2)	0.0364 (3)	0.0345 (7)
O2	0.3285 (3)	0.4700 (3)	−0.0196 (3)	0.0416 (8)
O3	0.0344 (3)	0.7562 (3)	−0.0752 (3)	0.0396 (8)
O4	−0.0375 (3)	0.9214 (3)	−0.2042 (3)	0.0411 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.023 (2)	0.027 (2)	0.024 (2)	0.0016 (18)	0.0073 (17)	0.0029 (18)
C2	0.032 (2)	0.039 (3)	0.044 (3)	0.001 (2)	0.016 (2)	0.001 (2)
C3	0.042 (3)	0.044 (3)	0.033 (3)	−0.009 (2)	0.010 (2)	−0.011 (2)
C4	0.036 (3)	0.042 (3)	0.038 (3)	−0.008 (2)	0.015 (2)	−0.011 (2)
C5	0.026 (2)	0.027 (2)	0.030 (3)	0.005 (2)	0.006 (2)	0.003 (2)
C6	0.028 (2)	0.032 (3)	0.028 (2)	−0.003 (2)	0.0085 (18)	−0.003 (2)
C7	0.043 (3)	0.040 (3)	0.042 (3)	0.008 (2)	0.013 (2)	0.011 (2)
C8	0.034 (3)	0.053 (3)	0.040 (3)	0.005 (2)	0.017 (2)	−0.007 (3)
C9	0.039 (3)	0.042 (3)	0.035 (3)	0.004 (2)	0.017 (2)	−0.003 (2)
C10	0.026 (2)	0.039 (3)	0.025 (2)	−0.013 (2)	0.0066 (19)	−0.006 (2)
Cd1	0.02236 (16)	0.02999 (17)	0.03203 (18)	0.00188 (16)	0.01067 (12)	−0.00474 (17)
N1	0.029 (2)	0.029 (2)	0.029 (2)	0.0000 (16)	0.0077 (17)	−0.0018 (16)
N2	0.035 (2)	0.052 (2)	0.045 (2)	−0.008 (2)	0.013 (2)	−0.004 (2)
N3	0.026 (2)	0.034 (2)	0.032 (2)	0.0025 (16)	0.0122 (17)	−0.0026 (17)
N4	0.039 (2)	0.048 (3)	0.057 (3)	0.015 (2)	0.016 (2)	0.000 (2)
O1	0.0240 (16)	0.0357 (17)	0.045 (2)	−0.0046 (14)	0.0130 (14)	−0.0159 (15)
O2	0.0314 (18)	0.049 (2)	0.049 (2)	0.0041 (15)	0.0189 (16)	−0.0136 (16)
O3	0.0391 (19)	0.040 (2)	0.0485 (19)	0.0050 (15)	0.0268 (16)	0.0049 (16)
O4	0.048 (2)	0.0451 (19)	0.0348 (18)	−0.0053 (16)	0.0193 (16)	0.0032 (16)

Geometric parameters (Å, º) top

C1—N1	1.348 (5)	C7—H7	0.9300
C1—C2	1.383 (5)	C8—N4	1.321 (6)
C1—C5	1.523 (5)	C8—C9	1.372 (6)
C2—N2	1.350 (5)	C8—H8	0.9300
C2—H2	0.9300	C9—N3	1.339 (5)
C3—N2	1.332 (5)	C9—H9	0.9300
C3—C4	1.388 (6)	C10—O3	1.240 (5)
C3—H3	0.9300	C10—O4	1.265 (5)
C4—N1	1.341 (5)	Cd1—O4ⁱ	2.227 (3)
C4—H4	0.9300	Cd1—O1ⁱⁱ	2.256 (3)
C5—O2	1.224 (4)	Cd1—O1	2.346 (3)
C5—O1	1.277 (4)	Cd1—N1	2.352 (3)
C6—N3	1.336 (5)	Cd1—N3	2.356 (3)
C6—C7	1.380 (5)	Cd1—O3	2.366 (3)
C6—C10	1.522 (5)	O1—Cd1ⁱⁱ	2.256 (3)
C7—N4	1.346 (5)	O4—Cd1ⁱⁱⁱ	2.227 (3)

N1—C1—C2	120.6 (4)	O4—C10—C6	114.6 (4)
N1—C1—C5	117.8 (3)	O4ⁱ—Cd1—O1ⁱⁱ	96.34 (11)
C2—C1—C5	121.6 (4)	O4ⁱ—Cd1—O1	110.68 (11)
N2—C2—C1	122.5 (4)	O1ⁱⁱ—Cd1—O1	71.28 (11)
N2—C2—H2	118.8	O4ⁱ—Cd1—N1	98.14 (11)
C1—C2—H2	118.8	O1ⁱⁱ—Cd1—N1	140.96 (11)
N2—C3—C4	122.7 (4)	O1—Cd1—N1	69.70 (10)
N2—C3—H3	118.6	O4ⁱ—Cd1—N3	94.39 (11)
C4—C3—H3	118.6	O1ⁱⁱ—Cd1—N3	96.46 (11)
N1—C4—C3	120.7 (4)	O1—Cd1—N3	152.84 (11)
N1—C4—H4	119.6	N1—Cd1—N3	118.22 (11)
C3—C4—H4	119.6	O4ⁱ—Cd1—O3	163.44 (10)
O2—C5—O1	126.9 (4)	O1ⁱⁱ—Cd1—O3	92.72 (11)
O2—C5—C1	118.7 (4)	O1—Cd1—O3	85.35 (10)
O1—C5—C1	114.3 (4)	N1—Cd1—O3	83.22 (11)
N3—C6—C7	120.8 (4)	N3—Cd1—O3	70.77 (11)
N3—C6—C10	117.8 (4)	C4—N1—C1	117.6 (4)
C7—C6—C10	121.2 (4)	C4—N1—Cd1	126.8 (3)
N4—C7—C6	122.5 (4)	C1—N1—Cd1	114.8 (2)
N4—C7—H7	118.8	C3—N2—C2	115.9 (4)
C6—C7—H7	118.8	C6—N3—C9	116.7 (4)
N4—C8—C9	122.7 (4)	C6—N3—Cd1	115.1 (3)
N4—C8—H8	118.7	C9—N3—Cd1	128.0 (3)
C9—C8—H8	118.7	C8—N4—C7	115.7 (4)
N3—C9—C8	121.6 (4)	C5—O1—Cd1ⁱⁱ	128.4 (3)
N3—C9—H9	119.2	C5—O1—Cd1	118.3 (3)
C8—C9—H9	119.2	Cd1ⁱⁱ—O1—Cd1	108.72 (11)
O3—C10—O4	127.1 (4)	C10—O3—Cd1	118.1 (3)
O3—C10—C6	118.2 (4)	C10—O4—Cd1ⁱⁱⁱ	121.9 (3)

N1—C1—C2—N2	−0.7 (6)	C8—C9—N3—Cd1	−173.5 (3)
C5—C1—C2—N2	179.6 (4)	O4ⁱ—Cd1—N3—C6	172.6 (3)
N2—C3—C4—N1	0.6 (7)	O1ⁱⁱ—Cd1—N3—C6	−90.5 (3)
N1—C1—C5—O2	172.7 (4)	O1—Cd1—N3—C6	−29.6 (4)
C2—C1—C5—O2	−7.6 (6)	N1—Cd1—N3—C6	70.9 (3)
N1—C1—C5—O1	−8.3 (5)	O3—Cd1—N3—C6	0.2 (3)
C2—C1—C5—O1	171.4 (4)	O4ⁱ—Cd1—N3—C9	−13.4 (3)
N3—C6—C7—N4	−0.9 (7)	O1ⁱⁱ—Cd1—N3—C9	83.5 (3)
C10—C6—C7—N4	175.2 (4)	O1—Cd1—N3—C9	144.4 (3)
N4—C8—C9—N3	−1.2 (7)	N1—Cd1—N3—C9	−115.0 (3)
N3—C6—C10—O3	1.6 (6)	O3—Cd1—N3—C9	174.2 (4)
C7—C6—C10—O3	−174.6 (4)	C9—C8—N4—C7	0.9 (7)
N3—C6—C10—O4	179.9 (3)	C6—C7—N4—C8	0.1 (7)
C7—C6—C10—O4	3.7 (6)	O2—C5—O1—Cd1ⁱⁱ	−5.3 (6)
C3—C4—N1—C1	0.0 (6)	C1—C5—O1—Cd1ⁱⁱ	175.9 (2)
C3—C4—N1—Cd1	−169.2 (3)	O2—C5—O1—Cd1	−158.4 (3)
C2—C1—N1—C4	0.1 (6)	C1—C5—O1—Cd1	22.8 (4)
C5—C1—N1—C4	179.8 (3)	O4ⁱ—Cd1—O1—C5	−112.2 (3)
C2—C1—N1—Cd1	170.6 (3)	O1ⁱⁱ—Cd1—O1—C5	158.0 (4)
C5—C1—N1—Cd1	−9.7 (4)	N1—Cd1—O1—C5	−20.9 (3)
O4ⁱ—Cd1—N1—C4	−66.6 (3)	N3—Cd1—O1—C5	91.6 (3)
O1ⁱⁱ—Cd1—N1—C4	−177.3 (3)	O3—Cd1—O1—C5	63.6 (3)
O1—Cd1—N1—C4	−175.7 (4)	O4ⁱ—Cd1—O1—Cd1ⁱⁱ	89.81 (14)
N3—Cd1—N1—C4	32.9 (4)	O1ⁱⁱ—Cd1—O1—Cd1ⁱⁱ	0.0
O3—Cd1—N1—C4	96.7 (3)	N1—Cd1—O1—Cd1ⁱⁱ	−178.94 (15)
O4ⁱ—Cd1—N1—C1	124.0 (3)	N3—Cd1—O1—Cd1ⁱⁱ	−66.4 (3)
O1ⁱⁱ—Cd1—N1—C1	13.3 (4)	O3—Cd1—O1—Cd1ⁱⁱ	−94.46 (13)
O1—Cd1—N1—C1	14.9 (3)	O4—C10—O3—Cd1	−179.5 (3)
N3—Cd1—N1—C1	−136.6 (3)	C6—C10—O3—Cd1	−1.5 (5)
O3—Cd1—N1—C1	−72.7 (3)	O4ⁱ—Cd1—O3—C10	−26.6 (5)
C4—C3—N2—C2	−1.1 (7)	O1ⁱⁱ—Cd1—O3—C10	96.6 (3)
C1—C2—N2—C3	1.2 (6)	O1—Cd1—O3—C10	167.6 (3)
C7—C6—N3—C9	0.6 (6)	N1—Cd1—O3—C10	−122.3 (3)
C10—C6—N3—C9	−175.6 (3)	N3—Cd1—O3—C10	0.7 (3)
C7—C6—N3—Cd1	175.3 (3)	O3—C10—O4—Cd1ⁱⁱⁱ	31.3 (5)
C10—C6—N3—Cd1	−0.9 (4)	C6—C10—O4—Cd1ⁱⁱⁱ	−146.8 (3)
C8—C9—N3—C6	0.4 (6)

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

Experimental details

Crystal data
Chemical formula	[Cd(C₅H₃N₂O₂)₂]
M_r	358.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.304 (2), 11.044 (2), 10.274 (2)
β (°)	107.89 (3)
V (Å³)	1112.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.98
Crystal size (mm)	0.18 × 0.13 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11295, 2550, 1943
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.065, 1.16
No. of reflections	2550
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.64

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The project was supported by the Research Program of Natural Science at the Universities of Inner Mongolia Autonomous Region (No. NG09168).

References

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