Di-μ-nitrito-κ³ O:O,O′;κ³ O,O′:O-bis­{[2,6-bis­(pyrazol-1-yl-κN ²)pyridine-κN](nitrito-κ² O,O′)cadmium(II)}

Abstract

In the title centrosymmetric binuclear complex, [Cd₂(NO₂)₄(C₁₁H₉N₅)₂], the unique Cd^II ion is in a distorted dodeca­hedral CdN₃O₅ coordination environment. The two inversion-related Cd^II ions are separated by 3.9920 (6) Å and are bridged by two O atoms from two nitrite ligands. There are two types of π–π stacking inter­actions involving symmetry-related pyrazole rings, with centroid–centroid distances of 3.445 (2) and 3.431 (2) Å.

Related literature

For related structures, see: Yang & Sun (2008 ▶); Bessel et al. (1993 ▶).

Experimental

Crystal data

• [Cd₂(NO₂)₄(C₁₁H₉N₅)₂]

• M _r = 831.30

• Triclinic,

• a = 7.7618 (13) Å

• b = 9.5522 (16) Å

• c = 10.9665 (19) Å

• α = 110.285 (2)°

• β = 90.616 (2)°

• γ = 112.155 (2)°

• V = 696.9 (2) ų

• Z = 1

• Mo Kα radiation

• μ = 1.60 mm⁻¹

• T = 298 K

• 0.32 × 0.21 × 0.10 mm

Data collection

• Bruker SMART APEX CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.628, T _max = 0.856

• 3815 measured reflections

• 2666 independent reflections

• 2468 reflections with I > 2σ(I)

• R _int = 0.017

Refinement

• R[F ² > 2σ(F ²)] = 0.029

• wR(F ²) = 0.076

• S = 1.09

• 2666 reflections

• 208 parameters

• H-atom parameters constrained

• Δρ_max = 0.56 e Å⁻³

• Δρ_min = −0.53 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

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

supplementary crystallographic information

Comment

2,6-Dipyrazol-1-ylpyridine is expected be a useful tridentate ligand, but complexes with it as ligand to our knowledge are somewhat rare (e.g. Yang & Sun, 2008; Bessel et al., 1993). Our interest in complexes with 2,6-dipyrazol-1-ylpyridine as a ligand has motivated us to prepare the title complex, (I), and herein we report its crystal structure.

Fig. 1 shows the molecular structure of the title complex. Each Cd^II ion is coordinated by five O atoms and three N atoms in a distorted dodecahedral coordination environment (see Fig. 2). It is rare for Cd^II to assume this coordination mode. Fig. 1 also shows that two nitrite anions function as bridging ligands, linking two inversion related Cd^II ions with a separation of 3.9920 (6) Å leading to a binuclear Cd^II complex. In the crystal there are the strong π–π stacking interactions involving the symmetry related triazole rings, with the relevant distances being Cg1···Cg2ⁱ = 3.445 (2) Å, Cg2···Cg2ⁱⁱ = 3.431 (2) Å, Cg1···Cg2ⁱ_perp = 3.299 Å and Cg2···Cg2ⁱⁱ_perp = 3.274 Å (symmetric codes: (i) -1+x, y, z; (ii) 1-x, 1-y, 2-z; Cg1 and Cg2 are the centroids of C1-C3/N1/N2; C9-C11/N4/N5 triazole rings, respectively; Cgi···Cgj_perp is the perpendicular distance from Cgi ring to Cgj ring).

Experimental

10 ml dichloromethane solution of 2,6-Dipyrazol-1-ylpyridine (0.0692 g, 0.328 mmol) was added into 10 ml methanol solution containing Cd(ClO₄).6H₂O (0.0740 g, 0.176 mmol) and sodium nitrite (0.0138 g, 0.200 mmol) and the mixed soluton was stirred for a few minutes. The colorless single crystals were obtained after the filtrate had been allowed to stand at room temperature for about one month.

Refinement

All H atoms were placed in calculated positions and refined as riding with C—H = 0.93 Å, U_iso = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: (i) 1 - x, 2 - y, 2 - z

Fig. 2.

The coordination environment of CdII

Crystal data

[Cd2(NO2)4(C11H9N5)2]	Z = 1
Mr = 831.30	F(000) = 408
Triclinic, P1	Dx = 1.981 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7618 (13) Å	Cell parameters from 2504 reflections
b = 9.5522 (16) Å	θ = 2.5–27.8°
c = 10.9665 (19) Å	µ = 1.60 mm−1
α = 110.285 (2)°	T = 298 K
β = 90.616 (2)°	Block, colorless
γ = 112.155 (2)°	0.32 × 0.21 × 0.10 mm
V = 696.9 (2) Å3

Data collection

Bruker SMART APEX CCD diffractometer	2666 independent reflections
Radiation source: fine-focus sealed tube	2468 reflections with I > 2σ(I)
graphite	Rint = 0.017
φ and ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.628, Tmax = 0.856	k = −11→11
3815 measured reflections	l = −7→13

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.044P)2] where P = (Fo2 + 2Fc2)/3
2666 reflections	(Δ/σ)max = 0.002
208 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.53 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.

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

	x	y	z	Uiso*/Ueq
C1	−0.0700 (5)	0.7853 (5)	0.7004 (4)	0.0445 (8)
H1	−0.0364	0.8974	0.7345	0.053*
C2	−0.2364 (5)	0.6713 (5)	0.6144 (4)	0.0454 (8)
H2	−0.3315	0.6920	0.5817	0.055*
C3	−0.2301 (4)	0.5239 (5)	0.5885 (3)	0.0431 (8)
H3	−0.3207	0.4227	0.5338	0.052*
C4	0.0015 (4)	0.4386 (4)	0.6698 (3)	0.0296 (6)
C5	0.2520 (4)	0.4068 (3)	0.7464 (3)	0.0298 (6)
C6	0.1560 (4)	0.2398 (4)	0.7011 (4)	0.0405 (7)
H6	0.2125	0.1736	0.7117	0.049*
C7	−0.0287 (5)	0.1747 (4)	0.6390 (3)	0.0449 (8)
H7	−0.0984	0.0623	0.6074	0.054*
C8	−0.1103 (5)	0.2735 (4)	0.6234 (3)	0.0410 (8)
H8	−0.2350	0.2311	0.5835	0.049*
C9	0.5554 (4)	0.4211 (4)	0.8411 (3)	0.0357 (7)
H9	0.5291	0.3105	0.8142	0.043*
C10	0.7180 (4)	0.5479 (4)	0.9151 (3)	0.0373 (7)
H10	0.8247	0.5419	0.9481	0.045*
C11	0.6898 (4)	0.6888 (4)	0.9306 (3)	0.0364 (7)
H11	0.7781	0.7945	0.9778	0.044*
Cd1	0.35091 (3)	0.79984 (2)	0.84217 (2)	0.03281 (10)
N1	0.0340 (4)	0.7146 (3)	0.7277 (3)	0.0374 (6)
N2	−0.0654 (3)	0.5526 (3)	0.6580 (3)	0.0340 (6)
N3	0.1788 (3)	0.5057 (3)	0.7307 (2)	0.0290 (5)
N4	0.4388 (3)	0.4869 (3)	0.8142 (2)	0.0291 (5)
N5	0.5215 (3)	0.6530 (3)	0.8697 (2)	0.0323 (5)
N6	0.2056 (4)	0.8778 (4)	1.0874 (3)	0.0506 (7)
N7	0.4464 (4)	0.9665 (4)	0.6637 (3)	0.0485 (7)
O1	0.1706 (4)	0.7339 (3)	1.0265 (3)	0.0568 (7)
O2	0.3107 (4)	0.9700 (3)	1.0329 (3)	0.0542 (7)
O3	0.3877 (4)	1.0225 (3)	0.7663 (3)	0.0506 (6)
O4	0.4610 (4)	0.8348 (3)	0.6500 (3)	0.0491 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0479 (19)	0.048 (2)	0.054 (2)	0.0301 (17)	0.0146 (16)	0.0260 (18)
C2	0.0422 (18)	0.062 (2)	0.048 (2)	0.0337 (17)	0.0107 (15)	0.0256 (18)
C3	0.0323 (16)	0.056 (2)	0.0377 (18)	0.0187 (16)	0.0004 (14)	0.0135 (16)
C4	0.0314 (14)	0.0328 (15)	0.0262 (14)	0.0157 (13)	0.0086 (12)	0.0100 (12)
C5	0.0325 (14)	0.0285 (14)	0.0298 (14)	0.0139 (12)	0.0074 (12)	0.0110 (12)
C6	0.0434 (18)	0.0305 (15)	0.0486 (19)	0.0162 (14)	0.0023 (15)	0.0147 (14)
C7	0.0458 (19)	0.0280 (16)	0.051 (2)	0.0087 (14)	−0.0021 (16)	0.0111 (15)
C8	0.0353 (16)	0.0388 (18)	0.0395 (18)	0.0087 (14)	−0.0009 (14)	0.0112 (15)
C9	0.0379 (16)	0.0376 (16)	0.0449 (18)	0.0231 (14)	0.0152 (14)	0.0219 (15)
C10	0.0312 (15)	0.0472 (19)	0.0455 (18)	0.0210 (14)	0.0100 (14)	0.0256 (16)
C11	0.0314 (15)	0.0367 (16)	0.0412 (17)	0.0109 (13)	0.0041 (13)	0.0182 (14)
Cd1	0.03791 (15)	0.02645 (14)	0.03535 (15)	0.01474 (11)	0.00396 (10)	0.01137 (10)
N1	0.0360 (14)	0.0340 (14)	0.0457 (16)	0.0174 (12)	0.0059 (12)	0.0158 (12)
N2	0.0312 (13)	0.0396 (14)	0.0345 (14)	0.0175 (12)	0.0061 (11)	0.0144 (12)
N3	0.0303 (12)	0.0283 (12)	0.0305 (13)	0.0138 (10)	0.0043 (10)	0.0115 (10)
N4	0.0302 (12)	0.0271 (12)	0.0338 (13)	0.0136 (10)	0.0055 (10)	0.0137 (11)
N5	0.0324 (13)	0.0262 (12)	0.0396 (14)	0.0120 (11)	0.0054 (11)	0.0138 (11)
N6	0.0513 (18)	0.0524 (19)	0.0435 (17)	0.0200 (15)	0.0137 (14)	0.0140 (15)
N7	0.0554 (18)	0.0436 (17)	0.0508 (18)	0.0175 (15)	0.0031 (15)	0.0257 (15)
O1	0.0566 (16)	0.0422 (15)	0.0591 (17)	0.0080 (13)	0.0077 (13)	0.0181 (14)
O2	0.0708 (17)	0.0338 (13)	0.0464 (14)	0.0131 (12)	0.0090 (13)	0.0108 (11)
O3	0.0584 (15)	0.0340 (12)	0.0602 (17)	0.0202 (12)	0.0044 (13)	0.0171 (12)
O4	0.0610 (16)	0.0464 (14)	0.0462 (14)	0.0291 (13)	0.0099 (12)	0.0166 (12)

Geometric parameters (Å, °)

C1—N1	1.320 (4)	C9—C10	1.364 (4)
C1—C2	1.395 (5)	C9—H9	0.9300
C1—H1	0.9300	C10—C11	1.397 (5)
C2—C3	1.357 (5)	C10—H10	0.9300
C2—H2	0.9300	C11—N5	1.325 (4)
C3—N2	1.364 (4)	C11—H11	0.9300
C3—H3	0.9300	Cd1—O2	2.270 (3)
C4—N3	1.330 (4)	Cd1—N5	2.345 (2)
C4—C8	1.379 (4)	Cd1—O4	2.365 (3)
C4—N2	1.413 (4)	Cd1—N3	2.434 (2)
C5—N3	1.328 (4)	Cd1—N1	2.450 (3)
C5—C6	1.376 (4)	Cd1—O3	2.464 (2)
C5—N4	1.409 (4)	Cd1—O1	2.592 (3)
C6—C7	1.385 (4)	N1—N2	1.357 (4)
C6—H6	0.9300	N4—N5	1.361 (3)
C7—C8	1.371 (5)	N6—O1	1.220 (4)
C7—H7	0.9300	N6—O2	1.277 (4)
C8—H8	0.9300	N7—O3	1.240 (4)
C9—N4	1.361 (4)	N7—O4	1.264 (4)
N1—C1—C2	111.8 (3)	O4—Cd1—N3	93.58 (9)
N1—C1—H1	124.1	O2—Cd1—N1	94.34 (10)
C2—C1—H1	124.1	N5—Cd1—N1	132.58 (9)
C3—C2—C1	105.3 (3)	O4—Cd1—N1	86.53 (9)
C3—C2—H2	127.3	N3—Cd1—N1	65.49 (8)
C1—C2—H2	127.3	O2—Cd1—O3	83.63 (9)
C2—C3—N2	106.8 (3)	N5—Cd1—O3	139.36 (9)
C2—C3—H3	126.6	O4—Cd1—O3	51.23 (9)
N2—C3—H3	126.6	N3—Cd1—O3	130.34 (8)
N3—C4—C8	124.0 (3)	N1—Cd1—O3	77.14 (8)
N3—C4—N2	113.9 (3)	O2—Cd1—O1	50.02 (9)
C8—C4—N2	122.2 (3)	N5—Cd1—O1	87.76 (9)
N3—C5—C6	123.6 (3)	O4—Cd1—O1	169.63 (9)
N3—C5—N4	114.4 (2)	N3—Cd1—O1	80.15 (8)
C6—C5—N4	122.0 (3)	N1—Cd1—O1	83.36 (9)
C5—C6—C7	117.0 (3)	O3—Cd1—O1	127.86 (9)
C5—C6—H6	121.5	C1—N1—N2	104.8 (3)
C7—C6—H6	121.5	C1—N1—Cd1	137.4 (2)
C8—C7—C6	121.0 (3)	N2—N1—Cd1	117.31 (18)
C8—C7—H7	119.5	N1—N2—C3	111.2 (3)
C6—C7—H7	119.5	N1—N2—C4	120.0 (2)
C7—C8—C4	116.8 (3)	C3—N2—C4	128.7 (3)
C7—C8—H8	121.6	C5—N3—C4	117.6 (3)
C4—C8—H8	121.6	C5—N3—Cd1	119.45 (19)
N4—C9—C10	107.1 (3)	C4—N3—Cd1	122.21 (19)
N4—C9—H9	126.4	C9—N4—N5	111.0 (2)
C10—C9—H9	126.4	C9—N4—C5	128.9 (3)
C9—C10—C11	105.3 (3)	N5—N4—C5	120.0 (2)
C9—C10—H10	127.4	C11—N5—N4	105.1 (2)
C11—C10—H10	127.4	C11—N5—Cd1	136.3 (2)
N5—C11—C10	111.5 (3)	N4—N5—Cd1	118.55 (17)
N5—C11—H11	124.2	O1—N6—O2	112.5 (3)
C10—C11—H11	124.2	O3—N7—O4	113.2 (3)
O2—Cd1—N5	114.66 (9)	N6—O1—Cd1	91.5 (2)
O2—Cd1—O4	133.53 (9)	N6—O2—Cd1	105.9 (2)
N5—Cd1—O4	97.45 (9)	N7—O3—Cd1	95.73 (19)
O2—Cd1—N3	128.85 (8)	N7—O4—Cd1	99.9 (2)
N5—Cd1—N3	67.11 (8)
N1—C1—C2—C3	−0.3 (4)	O1—Cd1—N3—C4	83.5 (2)
C1—C2—C3—N2	0.2 (4)	C10—C9—N4—N5	−0.4 (3)
N3—C5—C6—C7	−1.7 (5)	C10—C9—N4—C5	−176.8 (3)
N4—C5—C6—C7	178.2 (3)	N3—C5—N4—C9	−176.9 (3)
C5—C6—C7—C8	0.3 (5)	C6—C5—N4—C9	3.2 (5)
C6—C7—C8—C4	1.3 (5)	N3—C5—N4—N5	7.0 (4)
N3—C4—C8—C7	−1.8 (5)	C6—C5—N4—N5	−172.9 (3)
N2—C4—C8—C7	179.1 (3)	C10—C11—N5—N4	0.2 (4)
N4—C9—C10—C11	0.5 (4)	C10—C11—N5—Cd1	179.2 (2)
C9—C10—C11—N5	−0.5 (4)	C9—N4—N5—C11	0.1 (3)
C2—C1—N1—N2	0.3 (4)	C5—N4—N5—C11	176.8 (3)
C2—C1—N1—Cd1	171.8 (2)	C9—N4—N5—Cd1	−179.10 (18)
O2—Cd1—N1—C1	55.0 (4)	C5—N4—N5—Cd1	−2.4 (3)
N5—Cd1—N1—C1	−175.4 (3)	O2—Cd1—N5—C11	−56.5 (3)
O4—Cd1—N1—C1	−78.5 (3)	O4—Cd1—N5—C11	89.0 (3)
N3—Cd1—N1—C1	−174.0 (4)	N3—Cd1—N5—C11	179.8 (3)
O3—Cd1—N1—C1	−27.5 (3)	N1—Cd1—N5—C11	−178.9 (3)
O1—Cd1—N1—C1	103.8 (3)	O3—Cd1—N5—C11	53.8 (4)
O2—Cd1—N1—N2	−134.3 (2)	O1—Cd1—N5—C11	−100.0 (3)
N5—Cd1—N1—N2	−4.7 (3)	O2—Cd1—N5—N4	122.4 (2)
O4—Cd1—N1—N2	92.3 (2)	O4—Cd1—N5—N4	−92.1 (2)
N3—Cd1—N1—N2	−3.3 (2)	N3—Cd1—N5—N4	−1.34 (19)
O3—Cd1—N1—N2	143.2 (2)	N1—Cd1—N5—N4	0.1 (3)
O1—Cd1—N1—N2	−85.4 (2)	O3—Cd1—N5—N4	−127.3 (2)
C1—N1—N2—C3	−0.1 (4)	O1—Cd1—N5—N4	78.9 (2)
Cd1—N1—N2—C3	−173.6 (2)	O2—N6—O1—Cd1	−3.4 (3)
C1—N1—N2—C4	−176.7 (3)	O2—Cd1—O1—N6	2.3 (2)
Cd1—N1—N2—C4	9.8 (3)	N5—Cd1—O1—N6	127.6 (2)
C2—C3—N2—N1	−0.1 (4)	O4—Cd1—O1—N6	−112.0 (5)
C2—C3—N2—C4	176.1 (3)	N3—Cd1—O1—N6	−165.3 (2)
N3—C4—N2—N1	−12.6 (4)	N1—Cd1—O1—N6	−99.1 (2)
C8—C4—N2—N1	166.5 (3)	O3—Cd1—O1—N6	−31.1 (3)
N3—C4—N2—C3	171.5 (3)	O1—N6—O2—Cd1	4.0 (3)
C8—C4—N2—C3	−9.4 (5)	N5—Cd1—O2—N6	−66.1 (2)
C6—C5—N3—C4	1.3 (5)	O4—Cd1—O2—N6	164.6 (2)
N4—C5—N3—C4	−178.6 (2)	N3—Cd1—O2—N6	13.5 (3)
C6—C5—N3—Cd1	171.7 (3)	N1—Cd1—O2—N6	75.3 (2)
N4—C5—N3—Cd1	−8.2 (3)	O3—Cd1—O2—N6	151.8 (2)
C8—C4—N3—C5	0.6 (4)	O1—Cd1—O2—N6	−2.3 (2)
N2—C4—N3—C5	179.7 (3)	O4—N7—O3—Cd1	−1.1 (3)
C8—C4—N3—Cd1	−169.6 (2)	O2—Cd1—O3—N7	168.8 (2)
N2—C4—N3—Cd1	9.5 (3)	N5—Cd1—O3—N7	47.8 (3)
O2—Cd1—N3—C5	−98.7 (2)	O4—Cd1—O3—N7	0.71 (19)
N5—Cd1—N3—C5	5.3 (2)	N3—Cd1—O3—N7	−54.0 (2)
O4—Cd1—N3—C5	101.9 (2)	N1—Cd1—O3—N7	−95.2 (2)
N1—Cd1—N3—C5	−173.6 (2)	O1—Cd1—O3—N7	−166.11 (18)
O3—Cd1—N3—C5	141.5 (2)	O3—N7—O4—Cd1	1.2 (3)
O1—Cd1—N3—C5	−86.4 (2)	O2—Cd1—O4—N7	−17.1 (3)
O2—Cd1—N3—C4	71.3 (2)	N5—Cd1—O4—N7	−151.9 (2)
N5—Cd1—N3—C4	175.2 (2)	N3—Cd1—O4—N7	140.7 (2)
O4—Cd1—N3—C4	−88.2 (2)	N1—Cd1—O4—N7	75.6 (2)
N1—Cd1—N3—C4	−3.6 (2)	O3—Cd1—O4—N7	−0.70 (19)
O3—Cd1—N3—C4	−48.5 (3)	O1—Cd1—O4—N7	88.4 (5)