Poly[(3-nitro­benzoato)(μ₃-1,2,4-triazolato)cobalt(II)]

Abstract

In the title compound, [Co(C₂H₂N₃)(C₇H₄NO₄)]_n, the Co^II atom is five-coordinated by three triazolate ligands and one bidentate 3-nitro­benzoate anion in a distorted trigonal-bipyramidal geometry. The triazolate ligand bridges the Co^II atoms, generating a two-dimensional net parallel to the ab plane, in which both the Co^II atom and the triazolate ligand act as three-connected nodes. Two weak inter­molecular C—H⋯O hydrogen bonds connect the nets.

Related literature

For metal–triazole complexes, see: Park et al. (2006 ▶); Yang et al. (2008 ▶); Zhai et al. (2007 ▶). For Co—O and Co—N bond lengths, see: Zhang et al. (2008 ▶).

Experimental

Crystal data

• [Co(C₂H₂N₃)(C₇H₄NO₄)]

• M _r = 293.11

• Orthorhombic,

• a = 9.2419 (18) Å

• b = 10.377 (2) Å

• c = 22.597 (5) Å

• V = 2167.1 (8) ų

• Z = 8

• Mo Kα radiation

• μ = 1.60 mm⁻¹

• T = 296 (2) K

• 0.14 × 0.12 × 0.12 mm

Data collection

• Bruker SMART 1K CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.802, T _max = 0.826

• 19233 measured reflections

• 2477 independent reflections

• 2245 reflections with I > 2σ(I)

• R _int = 0.029

Refinement

• R[F ² > 2σ(F ²)] = 0.023

• wR(F ²) = 0.059

• S = 1.04

• 2477 reflections

• 163 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Co1—O1	2.3314 (12)
Co1—O2	2.0008 (12)
Co1—N1	2.0232 (12)
Co1—N2i	2.0118 (12)
Co1—N3ii	2.0385 (12)

Symmetry codes: (i) ; (ii) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2iii	0.93	2.54	3.250 (3)	134
C8—H8⋯O4iv	0.93	2.46	3.372 (2)	169

Symmetry codes: (iii) ; (iv) .

supplementary crystallographic information

Comment

Recently, more and more attention is paid on the coordination chemistry about trz ligand or analogy ligand (Park et al., 2006; Yang et al., 2008; Zhai et al., 2007), driven by their intriguing topological matrix and potential applications.

The asymmetric unit of I is shown in Fig. 1. The Co^II atom is five-coordinated by two L (3-nitrobenzoate anion) O atoms, three trz N atoms to give rise to a distorted trigonal-bipyramidal geometry. The Co—O/N bond lengths of 2.0008 (12)–2.3314 (12)Å (Table 1) are in the normal range (Zhang et al., 2008). The trz and L ligand adopt bridging and bidentate coordinated modes, respectively. As shown in Fig. 2a, the Co^II atoms are combined together by trz ligands to generate a two-dimensional net parallel to the ab plane with the L ligands ligated on the two-dimensional net up and down. From a topological point of view, if considering the trz ligands and cobalt ions as three-connected nodes. Moreover, besides the presence of two weak intermolecular C—H···O hydrogen bonds, see Table 2, there is not other obvious supramolecular interactions between two-dimensional nets,

Experimental

CoCl₂ (1.0 mmol), 3-nitrobenzoic acid (1 mmol) and triazole (1 mmol) were dissolved in water (10 ml). The solution was heated in a 25 ml Teflonlined reaction vessel at 433 K for ca 3 days and then cooled to room temperature. Purple crystals of the title compound were obtained in a yield of 78%.

Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

An ORTEP view of the asymmetric unit with 50% thermal ellipsoids for non-H atoms [symmetry codes: (A) -x + 1/2, y - 1/2, z; (B) x + 1/2, -y + 3/2, -z + 1].

Fig. 2.

a) View of the two-dimensional net onto the ab plane, formed by cobalt ions and trz ligands; b) View of the two-dimensional net built on three-connected trz and cobalt nodes.

Crystal data

[Co(C2H2N3)(C7H4NO4)]	F(000) = 1176
Mr = 293.11	Dx = 1.797 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 15896 reflections
a = 9.2419 (18) Å	θ = 3.1–27.5°
b = 10.377 (2) Å	µ = 1.60 mm−1
c = 22.597 (5) Å	T = 296 K
V = 2167.1 (8) Å3	Block, purple
Z = 8	0.14 × 0.12 × 0.12 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer	2477 independent reflections
Radiation source: sealed tube	2245 reflections with I > 2σ(I)
graphite	Rint = 0.029
Detector resolution: 8.192 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −12→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −13→12
Tmin = 0.802, Tmax = 0.826	l = −29→29
19233 measured reflections

Refinement

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0278P)2 + 1.1998P] where P = (Fo2 + 2Fc2)/3
2477 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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

	x	y	z	Uiso*/Ueq
C1	0.0918 (2)	0.62096 (17)	0.17212 (8)	0.0358 (4)
C2	−0.0058 (2)	0.7078 (2)	0.14920 (8)	0.0470 (5)
H2	−0.0198	0.7141	0.1085	0.056*
C3	−0.0823 (3)	0.7853 (2)	0.18746 (9)	0.0522 (6)
H3	−0.1473	0.8457	0.1728	0.063*
C4	−0.0620 (2)	0.77306 (18)	0.24798 (8)	0.0406 (4)
H4	−0.1157	0.8240	0.2738	0.049*
C5	0.1165 (2)	0.60861 (16)	0.23241 (7)	0.0322 (4)
H5	0.1843	0.5503	0.2468	0.039*
C6	0.03721 (19)	0.68583 (16)	0.27043 (7)	0.0295 (3)
C7	0.05354 (18)	0.67429 (16)	0.33614 (7)	0.0290 (3)
C8	0.32376 (16)	0.75394 (14)	0.51070 (7)	0.0253 (3)
H8	0.3425	0.6826	0.5344	0.030*
C9	0.22994 (17)	0.87843 (13)	0.44808 (6)	0.0231 (3)
H9	0.1693	0.9118	0.4190	0.028*
Co1	0.08538 (2)	0.615646 (17)	0.442261 (8)	0.01829 (7)
N1	0.21652 (13)	0.75890 (11)	0.47077 (5)	0.0227 (2)
N2	0.39953 (13)	0.86141 (12)	0.51260 (5)	0.0225 (3)
N3	0.33828 (13)	0.94272 (11)	0.47154 (5)	0.0209 (2)
N4	0.1706 (2)	0.53740 (17)	0.13114 (7)	0.0459 (4)
O1	−0.00457 (13)	0.75383 (12)	0.36970 (5)	0.0367 (3)
O2	0.12664 (15)	0.58069 (12)	0.35684 (5)	0.0351 (3)
O3	0.2746 (2)	0.47839 (18)	0.14938 (7)	0.0683 (5)
O4	0.1257 (2)	0.53020 (16)	0.08006 (6)	0.0627 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0517 (11)	0.0329 (9)	0.0228 (8)	−0.0083 (7)	0.0032 (7)	−0.0016 (6)
C2	0.0745 (14)	0.0453 (11)	0.0211 (8)	−0.0027 (10)	−0.0091 (8)	0.0050 (8)
C3	0.0778 (16)	0.0444 (12)	0.0345 (10)	0.0148 (10)	−0.0150 (9)	0.0058 (9)
C4	0.0592 (11)	0.0331 (9)	0.0295 (9)	0.0079 (8)	−0.0040 (8)	0.0000 (7)
C5	0.0422 (9)	0.0299 (8)	0.0246 (8)	−0.0020 (7)	−0.0011 (7)	0.0013 (6)
C6	0.0418 (9)	0.0261 (8)	0.0208 (7)	−0.0037 (7)	−0.0026 (6)	0.0022 (6)
C7	0.0371 (8)	0.0284 (8)	0.0214 (7)	−0.0058 (6)	−0.0020 (6)	0.0014 (6)
C8	0.0290 (7)	0.0196 (7)	0.0274 (7)	−0.0033 (6)	−0.0042 (6)	0.0061 (6)
C9	0.0269 (7)	0.0190 (7)	0.0234 (7)	−0.0015 (5)	−0.0031 (5)	0.0034 (5)
Co1	0.02203 (12)	0.01445 (11)	0.01838 (11)	−0.00039 (6)	0.00086 (7)	0.00145 (7)
N1	0.0263 (6)	0.0181 (6)	0.0238 (6)	−0.0032 (5)	−0.0026 (5)	0.0025 (5)
N2	0.0247 (6)	0.0185 (6)	0.0243 (6)	−0.0015 (5)	−0.0038 (5)	0.0050 (5)
N3	0.0246 (6)	0.0163 (6)	0.0217 (6)	−0.0005 (4)	−0.0008 (4)	0.0039 (5)
N4	0.0611 (11)	0.0437 (9)	0.0330 (8)	−0.0104 (8)	0.0139 (7)	−0.0058 (7)
O1	0.0453 (7)	0.0413 (7)	0.0234 (6)	0.0066 (6)	−0.0001 (5)	−0.0033 (5)
O2	0.0541 (7)	0.0304 (6)	0.0207 (5)	0.0052 (6)	−0.0027 (5)	0.0020 (5)
O3	0.0667 (11)	0.0791 (12)	0.0590 (10)	0.0140 (10)	0.0135 (8)	−0.0168 (9)
O4	0.1046 (13)	0.0585 (10)	0.0249 (7)	−0.0100 (9)	0.0117 (8)	−0.0095 (7)

Geometric parameters (Å, °)

C1—C2	1.376 (3)	C8—N2	1.3175 (19)
C1—C5	1.388 (2)	C8—N1	1.3414 (19)
C1—N4	1.463 (2)	C8—H8	0.9300
C2—C3	1.376 (3)	C9—N3	1.3149 (19)
C2—H2	0.9300	C9—N1	1.3478 (18)
C3—C4	1.386 (3)	C9—H9	0.9300
C3—H3	0.9300	Co1—O1	2.3314 (12)
C4—C6	1.385 (2)	Co1—O2	2.0008 (12)
C4—H4	0.9300	Co1—N1	2.0232 (12)
C5—C6	1.385 (2)	Co1—N2i	2.0118 (12)
C5—H5	0.9300	Co1—N3ii	2.0385 (12)
C6—C7	1.497 (2)	N2—N3	1.3759 (16)
C7—O1	1.243 (2)	N4—O3	1.212 (2)
C7—O2	1.272 (2)	N4—O4	1.229 (2)
C2—C1—C5	122.56 (17)	N1—C9—H9	123.7
C2—C1—N4	118.45 (17)	O2—Co1—N2i	132.33 (5)
C5—C1—N4	118.98 (17)	O2—Co1—N1	109.04 (5)
C1—C2—C3	118.87 (17)	N2i—Co1—N1	105.25 (5)
C1—C2—H2	120.6	O2—Co1—N3ii	95.03 (5)
C3—C2—H2	120.6	N2i—Co1—N3ii	103.60 (5)
C2—C3—C4	119.79 (19)	N1—Co1—N3ii	109.64 (5)
C2—C3—H3	120.1	O2—Co1—O1	60.06 (5)
C4—C3—H3	120.1	N2i—Co1—O1	88.82 (5)
C6—C4—C3	120.72 (18)	N1—Co1—O1	89.18 (5)
C6—C4—H4	119.6	N3ii—Co1—O1	153.26 (5)
C3—C4—H4	119.6	C8—N1—C9	102.90 (12)
C6—C5—C1	117.93 (16)	C8—N1—Co1	128.95 (10)
C6—C5—H5	121.0	C9—N1—Co1	127.60 (10)
C1—C5—H5	121.0	C8—N2—N3	106.17 (12)
C4—C6—C5	120.10 (15)	C8—N2—Co1iii	124.78 (10)
C4—C6—C7	118.83 (15)	N3—N2—Co1iii	128.36 (9)
C5—C6—C7	121.04 (15)	C9—N3—N2	105.91 (11)
O1—C7—O2	120.80 (14)	C9—N3—Co1iv	125.40 (10)
O1—C7—C6	120.56 (15)	N2—N3—Co1iv	128.05 (9)
O2—C7—C6	118.63 (15)	O3—N4—O4	123.81 (19)
N2—C8—N1	112.47 (13)	O3—N4—C1	118.64 (17)
N2—C8—H8	123.8	O4—N4—C1	117.55 (19)
N1—C8—H8	123.8	C7—O1—Co1	82.34 (10)
N3—C9—N1	112.56 (13)	C7—O2—Co1	96.61 (10)
N3—C9—H9	123.7
C5—C1—C2—C3	−0.2 (3)	C7—Co1—N1—C9	25.56 (14)
N4—C1—C2—C3	178.90 (19)	N1—C8—N2—N3	0.24 (17)
C1—C2—C3—C4	−1.2 (3)	N1—C8—N2—Co1iii	−170.88 (10)
C2—C3—C4—C6	1.7 (3)	N1—C9—N3—N2	−0.56 (17)
C2—C1—C5—C6	1.2 (3)	N1—C9—N3—Co1iv	170.84 (10)
N4—C1—C5—C6	−177.94 (16)	C8—N2—N3—C9	0.19 (16)
C3—C4—C6—C5	−0.7 (3)	Co1iii—N2—N3—C9	170.89 (10)
C3—C4—C6—C7	−178.94 (19)	C8—N2—N3—Co1iv	−170.91 (10)
C1—C5—C6—C4	−0.7 (3)	Co1iii—N2—N3—Co1iv	−0.21 (18)
C1—C5—C6—C7	177.51 (16)	C2—C1—N4—O3	166.47 (19)
C4—C6—C7—O1	−10.4 (2)	C5—C1—N4—O3	−14.4 (3)
C5—C6—C7—O1	171.35 (16)	C2—C1—N4—O4	−14.4 (3)
C4—C6—C7—O2	168.80 (16)	C5—C1—N4—O4	164.78 (17)
C5—C6—C7—O2	−9.4 (2)	O2—C7—O1—Co1	−4.03 (15)
N2—C8—N1—C9	−0.55 (17)	C6—C7—O1—Co1	175.16 (15)
N2—C8—N1—Co1	171.29 (10)	O2—Co1—O1—C7	2.54 (10)
N3—C9—N1—C8	0.68 (17)	N2i—Co1—O1—C7	−139.56 (10)
N3—C9—N1—Co1	−171.31 (10)	N1—Co1—O1—C7	115.17 (10)
O2—Co1—N1—C8	−113.76 (13)	N3ii—Co1—O1—C7	−20.77 (16)
N2i—Co1—N1—C8	99.90 (13)	O1—C7—O2—Co1	4.68 (18)
N3ii—Co1—N1—C8	−10.96 (14)	C6—C7—O2—Co1	−174.52 (13)
O1—Co1—N1—C8	−171.55 (13)	N2i—Co1—O2—C7	53.70 (13)
O2—Co1—N1—C9	56.19 (14)	N1—Co1—O2—C7	−79.98 (11)
N2i—Co1—N1—C9	−90.15 (13)	N3ii—Co1—O2—C7	167.23 (10)
N3ii—Co1—N1—C9	158.99 (12)	O1—Co1—O2—C7	−2.47 (9)
O1—Co1—N1—C9	−1.60 (13)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2v	0.93	2.54	3.250 (3)	134
C8—H8···O4vi	0.93	2.46	3.372 (2)	169

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