Synthesis, crystal structure and reactivity of bis­(μ-2-methyl­pyridine N-oxide-κ2O:O)bis­[di­bromido­(2-methyl­pyridine N-oxide-κO)cobalt(II)] butanol monosolvate

Näther, C.; Jess, I.

doi:10.1107/S2056989023008228

Synthesis, crystal structure and reactivity of bis(μ-2-methylpyridine N-oxide-κ²O:O)bis[dibromido(2-methylpyridine N-oxide-κO)cobalt(II)] butanol monosolvate

The crystal structure of the title compound consists of dinuclear complexes, in which the Co^II cations are fivefold coordinated and linked by centrosymmetric pairs of μ-1,1(O,O)-bridging 2-methylpyridine N-oxide coligands.

Keywords: crystal structure; synthesis; thermoanalytical investigations; cobalt thiocyanate; 2-methylpyridine N-oxide.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989023008228/pk2697sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989023008228/pk2697Isup2.hkl Contains datablock I
	Portable Network Graphics (PNG) image https://doi.org/10.1107/S2056989023008228/pk2697sup3.png DTG, TG and DTA curve of the title compound measured with 4C/min in a nitrogen atmosphere.
	Portable Network Graphics (PNG) image https://doi.org/10.1107/S2056989023008228/pk2697sup4.png Experimental powder pattern of the residue obtained after the first mass loss in a DTA-TG measurement of the title compound.
	Portable Network Graphics (PNG) image https://doi.org/10.1107/S2056989023008228/pk2697sup5.png IR spectrum of the residue obtained after the first mass loss in a DTA-TG measurement of the title compound. The wavenumbers of the most prominent vibrations are given.
	Portable Network Graphics (PNG) image https://doi.org/10.1107/S2056989023008228/pk2697sup6.png IR spectrum of the title compound. The wavenumbers of the most prominent vibrations are given.
	Portable Network Graphics (PNG) image https://doi.org/10.1107/S2056989023008228/pk2697sup7.png Experimental powder pattern of the residue obtained after storage of the title compound for 60 h at room-temperature.

CCDC reference: 2295983

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.004 Å
Disorder in solvent or counterion
R factor = 0.024
wR factor = 0.065
Data-to-parameter ratio = 18.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         17 Report
PLAT977_ALERT_2_C Check Negative Difference Density on H21D      .      -0.61 eA-3

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2 Note
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.u. Differ by ...         -3 Units
PLAT153_ALERT_1_G The s.u.'s on the Cell Axes   are Equal ..(Note)     0.0001 Ang.
PLAT154_ALERT_1_G The s.u.'s on the Cell Angles are Equal ..(Note)      0.001 Degree
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT300_ALERT_4_G Atom Site Occupancy of O21        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H21        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H21A       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H21B       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H21C       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H21D       Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of H21E       Constrained at        0.5 Check
PLAT302_ALERT_4_G Anion/Solvent/Minor-Residue Disorder (Resd  2  )        20% Note
PLAT432_ALERT_2_G Short Inter X...Y Contact  O21      ..C15      .       2.90 Ang.
                                                 1-x,1-y,-z  =      2_665 Check
PLAT432_ALERT_2_G Short Inter X...Y Contact  O21      ..C14      .       2.99 Ang.
                                                 1-x,1-y,-z  =      2_665 Check
PLAT480_ALERT_4_G Long H...A H-Bond Reported H5       ..BR1      .       3.12 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H5       ..BR1      .       2.98 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H6C      ..BR1      .       3.02 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H12      ..BR2      .       2.99 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H14      ..BR1      .       3.11 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H16C     ..BR1      .       3.13 Ang.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         71 Note
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  26 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 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
  16 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Computing details top

Data collection: CrysAlis PRO 1.171.42.67a (Rigaku OD, 2022); cell refinement: CrysAlis PRO 1.171.42.67a (Rigaku OD, 2022); data reduction: CrysAlis PRO 1.171.42.67a (Rigaku OD, 2022); program(s) used to solve structure: SHELXT2014/4 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(µ-2-methylpyridine N-oxide-κ²O:O)bis[dibromido(2-methylpyridine N-oxide-κO)cobalt(II)] butanol monosolvate top

Crystal data top

[Co₂Br₄(C₆H₇NO)₄]·C₄H₁₀O	Z = 1
M_r = 948.12	F(000) = 468
Triclinic, P1	D_x = 1.819 Mg m⁻³
a = 8.0900 (1) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.5772 (1) Å	Cell parameters from 14929 reflections
c = 12.2400 (1) Å	θ = 3.9–79.9°
α = 70.242 (1)°	µ = 13.26 mm⁻¹
β = 76.004 (1)°	T = 100 K
γ = 83.860 (1)°	Block, dark blue
V = 865.69 (2) Å³	0.15 × 0.03 × 0.03 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3705 independent reflections
Mirror monochromator	3686 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.021
ω scans	θ_max = 80.2°, θ_min = 3.9°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	h = −10→10
T_min = 0.721, T_max = 1.000	k = −12→12
18480 measured reflections	l = −12→15

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.024	w = 1/[σ²(F_o²) + (0.0306P)² + 1.2686P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.065	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.50 e Å⁻³
3705 reflections	Δρ_min = −0.59 e Å⁻³
204 parameters	Extinction correction: SHELXL2016/6 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.00106 (14)
Primary atom site location: dual

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.52210 (5)	0.46947 (4)	0.36734 (3)	0.01558 (10)
Br1	0.24435 (3)	0.41656 (3)	0.34944 (2)	0.02233 (8)
Br2	0.71203 (4)	0.28893 (3)	0.28069 (2)	0.02820 (9)
O1	0.5761 (2)	0.38106 (17)	0.52800 (14)	0.0163 (3)
N1	0.6713 (2)	0.2555 (2)	0.56405 (17)	0.0161 (4)
C1	0.5945 (3)	0.1227 (3)	0.60505 (19)	0.0183 (4)
C2	0.6944 (3)	−0.0046 (3)	0.6432 (2)	0.0238 (5)
H2	0.644348	−0.099275	0.673735	0.029*
C3	0.8660 (4)	0.0060 (3)	0.6368 (2)	0.0279 (5)
H3	0.933382	−0.081032	0.663242	0.033*
C4	0.9388 (3)	0.1438 (3)	0.5918 (2)	0.0264 (5)
H4	1.056708	0.152377	0.586252	0.032*
C5	0.8382 (3)	0.2689 (3)	0.5550 (2)	0.0212 (5)
H5	0.886759	0.364257	0.523258	0.025*
C6	0.4125 (3)	0.1211 (3)	0.6032 (2)	0.0211 (5)
H6A	0.345495	0.183462	0.647998	0.032*
H6B	0.372568	0.019130	0.639542	0.032*
H6C	0.398996	0.159651	0.520671	0.032*
O11	0.6147 (2)	0.65388 (19)	0.24397 (14)	0.0243 (4)
N11	0.6946 (3)	0.6523 (2)	0.13423 (17)	0.0234 (4)
C11	0.8634 (3)	0.6742 (3)	0.0986 (2)	0.0254 (5)
C12	0.9411 (4)	0.6781 (3)	−0.0169 (2)	0.0318 (6)
H12	1.059812	0.694910	−0.045090	0.038*
C13	0.8485 (4)	0.6581 (3)	−0.0914 (2)	0.0346 (7)
H13	0.903094	0.660251	−0.169909	0.041*
C14	0.6774 (4)	0.6351 (3)	−0.0508 (2)	0.0369 (7)
H14	0.611936	0.621342	−0.101029	0.044*
C15	0.6004 (4)	0.6320 (3)	0.0638 (2)	0.0320 (6)
H15	0.481643	0.615737	0.092873	0.038*
C16	0.9546 (4)	0.6917 (4)	0.1847 (3)	0.0347 (6)
H16A	0.911410	0.781415	0.204957	0.052*
H16B	1.076871	0.700157	0.148968	0.052*
H16C	0.935641	0.604983	0.256956	0.052*
O21	0.6568 (6)	0.1984 (4)	0.0597 (4)	0.0427 (10)	0.5
H21	0.673583	0.200477	0.124200	0.064*	0.5
C21	0.6912 (6)	0.0492 (4)	0.0530 (3)	0.0562 (10)
H21A	0.658475	−0.023433	0.133764	0.067*	0.5
H21B	0.814941	0.035705	0.023128	0.067*	0.5
H21C	0.665943	−0.027068	0.131402	0.067*	0.5
H21D	0.656102	0.147024	0.061153	0.067*	0.5
H21E	0.813823	0.047438	0.018754	0.067*	0.5
C22	0.5932 (5)	0.0184 (4)	−0.0294 (3)	0.0485 (9)
H22A	0.598140	0.106639	−0.101445	0.058*
H22B	0.650354	−0.065663	−0.054982	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02026 (19)	0.01482 (18)	0.01137 (18)	−0.00042 (13)	−0.00241 (14)	−0.00463 (13)
Br1	0.02518 (13)	0.02280 (13)	0.02382 (14)	0.00051 (9)	−0.01136 (10)	−0.00991 (10)
Br2	0.03810 (16)	0.01941 (13)	0.02232 (14)	−0.00291 (10)	0.00953 (10)	−0.01123 (10)
O1	0.0195 (7)	0.0143 (7)	0.0161 (7)	0.0058 (6)	−0.0053 (6)	−0.0070 (6)
N1	0.0196 (9)	0.0134 (8)	0.0159 (9)	0.0051 (7)	−0.0058 (7)	−0.0061 (7)
C1	0.0250 (11)	0.0177 (10)	0.0122 (10)	−0.0007 (8)	−0.0029 (8)	−0.0057 (8)
C2	0.0314 (13)	0.0187 (11)	0.0200 (11)	0.0045 (9)	−0.0055 (10)	−0.0064 (9)
C3	0.0334 (13)	0.0264 (12)	0.0235 (12)	0.0117 (10)	−0.0107 (10)	−0.0085 (10)
C4	0.0224 (11)	0.0291 (13)	0.0305 (13)	0.0070 (10)	−0.0087 (10)	−0.0136 (11)
C5	0.0201 (11)	0.0223 (11)	0.0235 (12)	0.0013 (9)	−0.0034 (9)	−0.0119 (9)
C6	0.0247 (11)	0.0173 (11)	0.0215 (11)	−0.0026 (9)	−0.0048 (9)	−0.0062 (9)
O11	0.0383 (10)	0.0193 (8)	0.0119 (7)	−0.0059 (7)	0.0046 (7)	−0.0063 (6)
N11	0.0373 (12)	0.0158 (9)	0.0139 (9)	−0.0049 (8)	0.0030 (8)	−0.0054 (7)
C11	0.0348 (13)	0.0173 (11)	0.0199 (12)	0.0049 (9)	−0.0010 (10)	−0.0056 (9)
C12	0.0414 (15)	0.0250 (13)	0.0210 (12)	0.0047 (11)	0.0042 (11)	−0.0067 (10)
C13	0.0589 (19)	0.0239 (12)	0.0161 (11)	−0.0058 (12)	0.0055 (12)	−0.0085 (10)
C14	0.063 (2)	0.0294 (14)	0.0200 (13)	−0.0174 (13)	−0.0001 (13)	−0.0112 (11)
C15	0.0461 (16)	0.0282 (13)	0.0240 (13)	−0.0153 (12)	−0.0010 (12)	−0.0119 (11)
C16	0.0295 (13)	0.0441 (16)	0.0257 (13)	0.0102 (12)	−0.0078 (11)	−0.0072 (12)
O21	0.053 (3)	0.044 (2)	0.044 (3)	0.006 (2)	−0.027 (2)	−0.022 (2)
C21	0.079 (3)	0.053 (2)	0.0378 (18)	0.035 (2)	−0.0255 (18)	−0.0177 (16)
C22	0.081 (3)	0.0339 (16)	0.0270 (15)	0.0242 (17)	−0.0127 (15)	−0.0121 (13)

Geometric parameters (Å, º) top

Co1—Br1	2.4312 (4)	C11—C12	1.391 (3)
Co1—Br2	2.5217 (4)	C11—C16	1.485 (4)
Co1—O1	1.9964 (16)	C12—H12	0.9500
Co1—O1ⁱ	2.1968 (15)	C12—C13	1.381 (4)
Co1—O11	1.9732 (17)	C13—H13	0.9500
O1—N1	1.357 (2)	C13—C14	1.368 (5)
N1—C1	1.357 (3)	C14—H14	0.9500
N1—C5	1.344 (3)	C14—C15	1.382 (4)
C1—C2	1.394 (3)	C15—H15	0.9500
C1—C6	1.480 (3)	C16—H16A	0.9800
C2—H2	0.9500	C16—H16B	0.9800
C2—C3	1.384 (4)	C16—H16C	0.9800
C3—H3	0.9500	O21—H21	0.8400
C3—C4	1.382 (4)	O21—C21	1.4524 (10)
C4—H4	0.9500	C21—H21A	0.9900
C4—C5	1.380 (3)	C21—H21B	0.9900
C5—H5	0.9500	C21—H21C	0.9800
C6—H6A	0.9800	C21—H21D	0.9800
C6—H6B	0.9800	C21—H21E	0.9800
C6—H6C	0.9800	C21—C22	1.539 (5)
O11—N11	1.347 (2)	C22—C22ⁱⁱ	1.528 (8)
N11—C11	1.346 (4)	C22—H22A	0.9900
N11—C15	1.351 (4)	C22—H22B	0.9900

Br1—Co1—Br2	101.355 (16)	N11—C11—C12	117.5 (3)
O1—Co1—Br1	116.56 (5)	N11—C11—C16	118.2 (2)
O1ⁱ—Co1—Br1	95.39 (4)	C12—C11—C16	124.3 (3)
O1—Co1—Br2	94.52 (4)	C11—C12—H12	119.5
O1ⁱ—Co1—Br2	161.54 (4)	C13—C12—C11	121.1 (3)
O1—Co1—O1ⁱ	70.82 (7)	C13—C12—H12	119.5
O11—Co1—Br1	112.08 (6)	C12—C13—H13	120.4
O11—Co1—Br2	97.54 (5)	C14—C13—C12	119.3 (2)
O11—Co1—O1ⁱ	83.12 (6)	C14—C13—H13	120.4
O11—Co1—O1	126.08 (7)	C13—C14—H14	120.2
Co1—O1—Co1ⁱ	109.18 (7)	C13—C14—C15	119.5 (3)
N1—O1—Co1	125.78 (12)	C15—C14—H14	120.2
N1—O1—Co1ⁱ	124.80 (12)	N11—C15—C14	119.7 (3)
O1—N1—C1	118.60 (18)	N11—C15—H15	120.1
C5—N1—O1	118.18 (19)	C14—C15—H15	120.1
C5—N1—C1	123.2 (2)	C11—C16—H16A	109.5
N1—C1—C2	117.5 (2)	C11—C16—H16B	109.5
N1—C1—C6	118.4 (2)	C11—C16—H16C	109.5
C2—C1—C6	124.0 (2)	H16A—C16—H16B	109.5
C1—C2—H2	119.8	H16A—C16—H16C	109.5
C3—C2—C1	120.5 (2)	H16B—C16—H16C	109.5
C3—C2—H2	119.8	C21—O21—H21	109.5
C2—C3—H3	120.2	O21—C21—H21A	109.2
C4—C3—C2	119.7 (2)	O21—C21—H21B	109.2
C4—C3—H3	120.2	O21—C21—C22	112.1 (3)
C3—C4—H4	120.4	H21A—C21—H21B	107.9
C5—C4—C3	119.2 (2)	H21C—C21—H21D	109.5
C5—C4—H4	120.4	H21C—C21—H21E	109.5
N1—C5—C4	119.9 (2)	H21D—C21—H21E	109.5
N1—C5—H5	120.1	C22—C21—H21A	109.2
C4—C5—H5	120.1	C22—C21—H21B	109.2
C1—C6—H6A	109.5	C22—C21—H21C	109.5
C1—C6—H6B	109.5	C22—C21—H21D	109.5
C1—C6—H6C	109.5	C22—C21—H21E	109.5
H6A—C6—H6B	109.5	C21—C22—H22A	108.9
H6A—C6—H6C	109.5	C21—C22—H22B	108.9
H6B—C6—H6C	109.5	C22ⁱⁱ—C22—C21	113.3 (3)
N11—O11—Co1	120.09 (13)	C22ⁱⁱ—C22—H22A	108.9
O11—N11—C15	118.3 (2)	C22ⁱⁱ—C22—H22B	108.9
C11—N11—O11	118.8 (2)	H22A—C22—H22B	107.7
C11—N11—C15	122.9 (2)

Co1ⁱ—O1—N1—C1	102.20 (19)	C5—N1—C1—C6	−175.8 (2)
Co1—O1—N1—C1	−84.0 (2)	C6—C1—C2—C3	176.9 (2)
Co1ⁱ—O1—N1—C5	−79.2 (2)	O11—N11—C11—C12	−177.4 (2)
Co1—O1—N1—C5	94.6 (2)	O11—N11—C11—C16	3.0 (3)
Co1—O11—N11—C11	−111.6 (2)	O11—N11—C15—C14	177.7 (2)
Co1—O11—N11—C15	69.9 (3)	N11—C11—C12—C13	−0.9 (4)
O1—N1—C1—C2	−179.10 (19)	C11—N11—C15—C14	−0.7 (4)
O1—N1—C1—C6	2.8 (3)	C11—C12—C13—C14	0.5 (4)
O1—N1—C5—C4	179.4 (2)	C12—C13—C14—C15	−0.1 (4)
N1—C1—C2—C3	−1.1 (3)	C13—C14—C15—N11	0.2 (4)
C1—N1—C5—C4	−2.1 (4)	C15—N11—C11—C12	1.1 (4)
C1—C2—C3—C4	−0.3 (4)	C15—N11—C11—C16	−178.6 (2)
C2—C3—C4—C5	0.6 (4)	C16—C11—C12—C13	178.7 (3)
C3—C4—C5—N1	0.5 (4)	O21—C21—C22—C22ⁱⁱ	−79.5 (5)
C5—N1—C1—C2	2.3 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Br1ⁱⁱⁱ	0.95	3.12	3.704 (2)	121
C5—H5···Br1ⁱ	0.95	2.98	3.531 (2)	118
C6—H6A···O11ⁱ	0.98	2.45	3.259 (3)	140
C6—H6B···Br2^iv	0.98	2.88	3.852 (2)	172
C6—H6C···Br1	0.98	3.02	3.845 (2)	142
C12—H12···Br2^v	0.95	2.99	3.676 (3)	130
C12—H12···O21^v	0.95	2.55	3.441 (6)	156
C14—H14···Br1^vi	0.95	3.11	3.747 (3)	126
C16—H16C···Br1ⁱⁱⁱ	0.98	3.13	3.725 (3)	121
O21—H21···Br2	0.84	2.43	3.244 (4)	162

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

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Synthesis, crystal structure and reactivity of bis­(μ-2-methyl­pyridine N-oxide-κ2O:O)bis­[di­bromido­(2-methyl­pyridine N-oxide-κO)cobalt(II)] butanol monosolvate

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Synthesis, crystal structure and reactivity of bis(μ-2-methylpyridine N-oxide-κ²O:O)bis[dibromido(2-methylpyridine N-oxide-κO)cobalt(II)] butanol monosolvate