Di-μ-sulfato-κ4O:O′-bis­{bis­[3-(2-pyrid­yl)pyrazole]cobalt(II)}

Lin, P.-X.; Yang, G.-B.; An, Z.

doi:10.1107/S160053681000797X

Di-μ-sulfato-κ⁴O:O′-bis{bis[3-(2-pyridyl)pyrazole]cobalt(II)}

In the centrosymmetric binuclear title molecule, [Co₂(SO₄)₂(C₈H₇N₃)₄], the Co^II ion is coordinated by two N,N′-bidentate 3-(2-pyridyl)pyrazole ligands and two sulfate ions, generating a distorted cis-CoO₂N₄ octahedral geometry for the metal atom. The dihedral angles between the pyridine and pyrazole rings in the two ligands are 10.5 (2) and 7.38 (19)°. The bridging sulfate ions generate an eight-membered ring and intramolecular N—H

O hydrogen bonds help to establish the molecular conformation.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053681000797X/hb5349sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S160053681000797X/hb5349Isup2.hkl Contains datablock I

CCDC reference: 774118

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.006 Å
R factor = 0.041
wR factor = 0.130
Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O1     ..  O1      ..       2.73 Ang.

Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.60 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.09 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    --  O2_a    ..       6.08 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O4
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      64.00 A   3 
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         20

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   9 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
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The tridentate ligand 3-(2-pyridyl)pyrazole and its derivatives have been used widely in the construction of supramolecular architectures by way of metal-organic coordination (Ward et al. 1998; 2001; Zhang et al. 2003).

As a continuation of these studies, we now report the crystal structure of the title complex, (I). As shown in Figure 1, two Co(II) cations chelated by two 3-(2-Pyridyl)pyrazole) are linked by two sulfate ions to form one circle in which the cobalt ion is hexacoordinated by two 3-(2-Pyridyl)pyrazole) ligands and two O from two sulfate ions (Table 1).

Related literature top

For coordination compounds with pyridyl-pyrazolide ligands, see: Ward et al. (1998, 2001); Zhang et al. (2003).

Experimental top

A mixture of cobalt sulfate heptahydrate (1 mmol, 0.25 g), sodium hydroxide (0.04 g, 1 mmol) and 3-(2-pyridyl)pyrazole (1 mmol, 0.15 g) and water (15 ml) was stirred for 30 min in air. The mixture was then transferred to a 25 ml Teflon-lined hydrothermal bomb. The bomb was kept at 433 K for 72 h under autogenous pressure. Upon cooling, red blocks of (I) were obtained from the reaction mixture.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius. Unlabelled atoms are generated by the symmetry operation (1–x, 2–y, 2–z).

Di-µ-sulfato-κ⁴O:O'-bis{bis[3-(2-pyridyl)pyrazole]cobalt(II)} top

Crystal data top

[Co₂(SO₄)₂(C₈H₇N₃)₄]	Z = 1
M_r = 890.64	F(000) = 454
Triclinic, P1	D_x = 1.599 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.318 (5) Å	Cell parameters from 3228 reflections
b = 9.879 (5) Å	θ = 2.1–25.0°
c = 11.807 (6) Å	µ = 1.08 mm⁻¹
α = 100.342 (8)°	T = 294 K
β = 98.820 (9)°	Block, red
γ = 99.302 (8)°	0.12 × 0.10 × 0.08 mm
V = 925.2 (9) Å³

Data collection top

Bruker APEXII CCD diffractometer	3228 independent reflections
Radiation source: fine-focus sealed tube	2990 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.011
phi and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.882, T_max = 0.919	k = −11→11
4790 measured reflections	l = −14→10

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters not refined
S = 1.00	w = 1/[σ²(F_o²) + (0.078P)² + 1.7757P] where P = (F_o² + 2F_c²)/3
3228 reflections	(Δ/σ)_max = 0.005
253 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Co₂(SO₄)₂(C₈H₇N₃)₄]	γ = 99.302 (8)°
M_r = 890.64	V = 925.2 (9) Å³
Triclinic, P1	Z = 1
a = 8.318 (5) Å	Mo Kα radiation
b = 9.879 (5) Å	µ = 1.08 mm⁻¹
c = 11.807 (6) Å	T = 294 K
α = 100.342 (8)°	0.12 × 0.10 × 0.08 mm
β = 98.820 (9)°

Data collection top

Bruker APEXII CCD diffractometer	3228 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2990 reflections with I > 2σ(I)
T_min = 0.882, T_max = 0.919	R_int = 0.011
4790 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.130	H-atom parameters not refined
S = 1.00	Δρ_max = 0.61 e Å⁻³
3228 reflections	Δρ_min = −0.54 e Å⁻³
253 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.42221 (5)	0.79964 (4)	0.84355 (4)	0.03040 (18)
C1	−0.0398 (5)	0.9232 (4)	0.7050 (3)	0.0420 (9)
H1	−0.1395	0.9531	0.7097	0.050*
C2	0.0198 (5)	0.8857 (4)	0.6063 (3)	0.0448 (9)
H2	−0.0302	0.8835	0.5298	0.054*
C3	0.1714 (4)	0.8511 (4)	0.6431 (3)	0.0318 (7)
C4	0.2985 (4)	0.8065 (4)	0.5790 (3)	0.0371 (8)
C5	0.2946 (6)	0.8116 (6)	0.4641 (4)	0.0636 (13)
H5	0.2092	0.8431	0.4223	0.076*
C6	0.4197 (7)	0.7690 (8)	0.4113 (4)	0.090 (2)
H6	0.4207	0.7721	0.3332	0.108*
C7	0.5414 (7)	0.7226 (7)	0.4750 (4)	0.0846 (19)
H7	0.6261	0.6922	0.4406	0.102*
C8	0.5382 (5)	0.7212 (5)	0.5893 (4)	0.0530 (11)
H8	0.6220	0.6890	0.6322	0.064*
C9	0.8750 (4)	0.6412 (4)	0.9368 (4)	0.0403 (8)
H9	0.9883	0.6490	0.9619	0.048*
C10	0.7598 (4)	0.5198 (3)	0.9034 (3)	0.0368 (8)
H10	0.7774	0.4287	0.9004	0.044*
C11	0.6107 (4)	0.5620 (3)	0.8748 (3)	0.0249 (6)
C12	0.4408 (4)	0.4824 (3)	0.8353 (3)	0.0252 (6)
C13	0.4011 (4)	0.3396 (3)	0.8316 (3)	0.0342 (7)
H13	0.4828	0.2898	0.8524	0.041*
C14	0.2386 (5)	0.2743 (4)	0.7967 (4)	0.0490 (10)
H14	0.2081	0.1786	0.7933	0.059*
C15	0.1224 (5)	0.3493 (4)	0.7670 (4)	0.0517 (10)
H15	0.0114	0.3059	0.7434	0.062*
C16	0.1705 (4)	0.4906 (4)	0.7721 (3)	0.0425 (8)
H16	0.0898	0.5414	0.7512	0.051*
N1	0.0705 (3)	0.9095 (3)	0.7943 (2)	0.0293 (6)
H1A	0.0596	0.9270	0.8664	0.035*
N2	0.2007 (3)	0.8649 (3)	0.7574 (2)	0.0283 (6)
N3	0.4193 (4)	0.7642 (3)	0.6426 (2)	0.0355 (6)
N4	0.7960 (3)	0.7468 (3)	0.9271 (2)	0.0298 (6)
H4	0.8437	0.8338	0.9435	0.036*
N5	0.6333 (3)	0.7005 (3)	0.8887 (2)	0.0249 (5)
N6	0.3280 (3)	0.5577 (3)	0.8057 (2)	0.0294 (6)
O1	0.1481 (3)	0.9642 (2)	1.03701 (19)	0.0307 (5)
O2	0.4260 (3)	1.0067 (3)	1.1403 (3)	0.0592 (9)
O3	0.2278 (3)	0.8263 (3)	1.1747 (2)	0.0411 (6)
O4	0.3184 (3)	0.7973 (3)	0.9944 (2)	0.0429 (6)
S1	0.28057 (8)	0.89939 (7)	1.08803 (6)	0.0206 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0288 (3)	0.0295 (3)	0.0343 (3)	0.00912 (19)	0.00506 (19)	0.00780 (19)
C1	0.0307 (18)	0.055 (2)	0.044 (2)	0.0196 (16)	0.0048 (15)	0.0114 (17)
C2	0.041 (2)	0.066 (3)	0.0311 (18)	0.0229 (18)	0.0006 (15)	0.0126 (17)
C3	0.0290 (17)	0.0389 (18)	0.0276 (16)	0.0088 (14)	0.0025 (13)	0.0076 (13)
C4	0.0332 (18)	0.052 (2)	0.0267 (17)	0.0145 (16)	0.0054 (14)	0.0047 (15)
C5	0.056 (3)	0.114 (4)	0.031 (2)	0.042 (3)	0.0086 (18)	0.018 (2)
C6	0.083 (4)	0.175 (7)	0.033 (2)	0.069 (4)	0.022 (2)	0.028 (3)
C7	0.071 (3)	0.158 (6)	0.045 (3)	0.066 (4)	0.029 (2)	0.019 (3)
C8	0.042 (2)	0.084 (3)	0.040 (2)	0.031 (2)	0.0119 (17)	0.012 (2)
C9	0.0263 (17)	0.0351 (19)	0.060 (2)	0.0111 (14)	0.0031 (16)	0.0110 (17)
C10	0.0328 (18)	0.0241 (16)	0.055 (2)	0.0121 (13)	0.0036 (15)	0.0092 (15)
C11	0.0291 (16)	0.0198 (14)	0.0280 (15)	0.0069 (12)	0.0082 (12)	0.0060 (11)
C12	0.0301 (16)	0.0218 (15)	0.0248 (14)	0.0052 (12)	0.0095 (12)	0.0040 (11)
C13	0.043 (2)	0.0224 (15)	0.0372 (18)	0.0033 (14)	0.0113 (15)	0.0063 (13)
C14	0.057 (3)	0.0294 (18)	0.055 (2)	−0.0076 (17)	0.0132 (19)	0.0058 (16)
C15	0.034 (2)	0.048 (2)	0.061 (3)	−0.0140 (17)	0.0075 (18)	0.0009 (19)
C16	0.0308 (18)	0.043 (2)	0.050 (2)	0.0051 (15)	0.0048 (16)	0.0058 (17)
N1	0.0252 (13)	0.0342 (14)	0.0300 (14)	0.0082 (11)	0.0074 (11)	0.0068 (11)
N2	0.0234 (13)	0.0339 (14)	0.0284 (14)	0.0061 (11)	0.0051 (10)	0.0080 (11)
N3	0.0339 (15)	0.0463 (17)	0.0280 (14)	0.0131 (13)	0.0062 (12)	0.0068 (12)
N4	0.0246 (13)	0.0223 (13)	0.0421 (15)	0.0037 (10)	0.0055 (11)	0.0075 (11)
N5	0.0231 (13)	0.0203 (12)	0.0336 (14)	0.0067 (10)	0.0072 (10)	0.0081 (10)
N6	0.0250 (13)	0.0277 (13)	0.0351 (14)	0.0048 (11)	0.0064 (11)	0.0051 (11)
O1	0.0285 (11)	0.0287 (11)	0.0361 (12)	0.0150 (9)	−0.0003 (9)	0.0068 (9)
O2	0.0386 (15)	0.0315 (13)	0.094 (2)	−0.0101 (11)	−0.0226 (15)	0.0237 (14)
O3	0.0504 (15)	0.0437 (14)	0.0438 (14)	0.0197 (12)	0.0231 (12)	0.0255 (11)
O4	0.0641 (17)	0.0460 (14)	0.0352 (13)	0.0374 (13)	0.0234 (12)	0.0156 (11)
S1	0.0194 (4)	0.0186 (4)	0.0260 (4)	0.0064 (3)	0.0043 (3)	0.0078 (3)

Geometric parameters (Å, º) top

Co1—O2ⁱ	2.074 (3)	C9—H9	0.9300
Co1—O4	2.097 (3)	C10—C11	1.384 (5)
Co1—N5	2.187 (3)	C10—H10	0.9300
Co1—N2	2.212 (3)	C11—N5	1.327 (4)
Co1—N6	2.331 (3)	C11—C12	1.463 (4)
Co1—N3	2.331 (3)	C12—N6	1.332 (4)
C1—N1	1.329 (4)	C12—C13	1.387 (4)
C1—C2	1.351 (5)	C13—C14	1.366 (5)
C1—H1	0.9300	C13—H13	0.9300
C2—C3	1.386 (5)	C14—C15	1.351 (6)
C2—H2	0.9300	C14—H14	0.9300
C3—N2	1.312 (4)	C15—C16	1.376 (6)
C3—C4	1.469 (5)	C15—H15	0.9300
C4—N3	1.328 (4)	C16—N6	1.334 (4)
C4—C5	1.362 (5)	C16—H16	0.9300
C5—C6	1.376 (6)	N1—N2	1.337 (4)
C5—H5	0.9300	N1—H1A	0.8600
C6—C7	1.357 (7)	N4—N5	1.336 (4)
C6—H6	0.9300	N4—H4	0.8600
C7—C8	1.357 (6)	O1—S1	1.466 (2)
C7—H7	0.9300	O2—S1	1.446 (3)
C8—N3	1.336 (5)	O2—Co1ⁱ	2.074 (3)
C8—H8	0.9300	O3—S1	1.436 (2)
C9—N4	1.332 (4)	O4—S1	1.466 (2)
C9—C10	1.363 (5)

O2ⁱ—Co1—O4	109.51 (13)	N5—C11—C10	110.9 (3)
O2ⁱ—Co1—N5	92.56 (11)	N5—C11—C12	117.4 (3)
O4—Co1—N5	99.64 (10)	C10—C11—C12	131.7 (3)
O2ⁱ—Co1—N2	93.38 (11)	N6—C12—C13	122.9 (3)
O4—Co1—N2	89.94 (10)	N6—C12—C11	115.1 (3)
N5—Co1—N2	166.34 (10)	C13—C12—C11	122.0 (3)
O2ⁱ—Co1—N6	161.04 (12)	C14—C13—C12	118.1 (3)
O4—Co1—N6	83.92 (10)	C14—C13—H13	121.0
N5—Co1—N6	71.51 (10)	C12—C13—H13	121.0
N2—Co1—N6	100.13 (10)	C15—C14—C13	119.7 (3)
O2ⁱ—Co1—N3	87.49 (13)	C15—C14—H14	120.1
O4—Co1—N3	155.57 (11)	C13—C14—H14	120.1
N5—Co1—N3	96.88 (10)	C14—C15—C16	119.2 (4)
N2—Co1—N3	71.12 (10)	C14—C15—H15	120.4
N6—Co1—N3	84.40 (10)	C16—C15—H15	120.4
N1—C1—C2	107.2 (3)	N6—C16—C15	122.7 (4)
N1—C1—H1	126.4	N6—C16—H16	118.7
C2—C1—H1	126.4	C15—C16—H16	118.7
C1—C2—C3	105.4 (3)	C1—N1—N2	111.2 (3)
C1—C2—H2	127.3	C1—N1—H1A	124.4
C3—C2—H2	127.3	N2—N1—H1A	124.4
N2—C3—C2	110.2 (3)	C3—N2—N1	106.0 (3)
N2—C3—C4	117.7 (3)	C3—N2—Co1	119.5 (2)
C2—C3—C4	132.1 (3)	N1—N2—Co1	134.3 (2)
N3—C4—C5	122.7 (3)	C4—N3—C8	117.8 (3)
N3—C4—C3	114.8 (3)	C4—N3—Co1	116.2 (2)
C5—C4—C3	122.5 (3)	C8—N3—Co1	125.5 (2)
C4—C5—C6	118.6 (4)	C9—N4—N5	111.4 (3)
C4—C5—H5	120.7	C9—N4—H4	124.3
C6—C5—H5	120.7	N5—N4—H4	124.3
C7—C6—C5	119.0 (4)	C11—N5—N4	105.3 (2)
C7—C6—H6	120.5	C11—N5—Co1	119.8 (2)
C5—C6—H6	120.5	N4—N5—Co1	134.78 (19)
C8—C7—C6	119.3 (4)	C16—N6—C12	117.4 (3)
C8—C7—H7	120.3	C16—N6—Co1	126.2 (2)
C6—C7—H7	120.3	C12—N6—Co1	115.8 (2)
N3—C8—C7	122.5 (4)	S1—O2—Co1ⁱ	153.33 (18)
N3—C8—H8	118.7	S1—O4—Co1	137.65 (16)
C7—C8—H8	118.7	O3—S1—O2	110.08 (18)
N4—C9—C10	107.6 (3)	O3—S1—O4	108.22 (15)
N4—C9—H9	126.2	O2—S1—O4	110.2 (2)
C10—C9—H9	126.2	O3—S1—O1	110.61 (15)
C9—C10—C11	104.7 (3)	O2—S1—O1	109.36 (15)
C9—C10—H10	127.7	O4—S1—O1	108.40 (14)
C11—C10—H10	127.7

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	1.98	2.772 (4)	152
N4—H4···O1ⁱ	0.86	1.96	2.761 (4)	155

Symmetry code: (i) −x+1, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	[Co₂(SO₄)₂(C₈H₇N₃)₄]
M_r	890.64
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	8.318 (5), 9.879 (5), 11.807 (6)
α, β, γ (°)	100.342 (8), 98.820 (9), 99.302 (8)
V (Å³)	925.2 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.882, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	4790, 3228, 2990
R_int	0.011
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.130, 1.00
No. of reflections	3228
No. of parameters	253
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.54

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Co1—O2ⁱ	2.074 (3)	Co1—N2	2.212 (3)
Co1—O4	2.097 (3)	Co1—N6	2.331 (3)
Co1—N5	2.187 (3)	Co1—N3	2.331 (3)

N5—Co1—N6	71.51 (10)	N2—Co1—N3	71.12 (10)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	1.98	2.772 (4)	152
N4—H4···O1ⁱ	0.86	1.96	2.761 (4)	155

Symmetry code: (i) −x+1, −y+2, −z+2.

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Di-μ-sulfato-κ4O:O′-bis­{bis­[3-(2-pyrid­yl)pyrazole]cobalt(II)}

Supporting information

Key indicators

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Di-μ-sulfato-κ⁴O:O′-bis{bis[3-(2-pyridyl)pyrazole]cobalt(II)}