Synthesis, crystal structure and thermal behavior of tetra­kis­(3-cyano­pyridine N-oxide-κO)bis­(thio­cyanato-κN)cobalt(II), which shows strong pseudo­symmetry

The crystal structure of the title compound consists of discrete complexes in which the Co^II cations are octa­hedrally coordinated and show strong pseudosymmetry.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.027
• wR factor = 0.083
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT110_ALERT_2_B ADDSYM Detects Potential Lattice Translation ...          ? Check
PLAT112_ALERT_2_B ADDSYM Detects New (Pseudo) Symm. Elem         I        100 %Fit
PLAT113_ALERT_2_B ADDSYM Suggests Possible Pseudo/New  Space Group       I2/m Check
              Check Model Parameter Symmmetry for Reflection Data Support

Alert level G
PLAT116_ALERT_2_G ADDSYM Included (Pseudo) Lattice Translation ...     Please Check
PLAT143_ALERT_4_G s.u. on c - Axis Small or Missing ..............    0.00010 Ang.
PLAT230_ALERT_2_G Hirshfeld Test Diff for    S1       --C1       .        8.0 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Co1      --N1       .        5.8 s.u.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H11      ..O21      .       2.61 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H14      ..S1       .       2.91 Ang.
PLAT480_ALERT_4_G Long H...A H-Bond Reported H24      ..S1       .       2.96 Ang.
PLAT794_ALERT_5_G Tentative Bond Valency for Co1       (II)      .       2.13 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         31 Note
PLAT933_ALERT_2_G Number of HKL-OMIT Records in Embedded .res File          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          8 Info

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis PRO 1.171.42.40a (Rigaku OD, 2022); cell refinement: CrysAlis PRO 1.171.42.40a (Rigaku OD, 2022); data reduction: CrysAlis PRO 1.171.42.40a (Rigaku OD, 2022); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015b); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015a); molecular graphics: DIAMOND (Brandenburg & Putz, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Tetrakis(3-cyanopyridine N-oxide-κO)bis(thiocyanato-κN)\ cobalt(II)

Crystal data

[Co(NCS)2(C6H4N2O)4]	F(000) = 666
Mr = 655.54	Dx = 1.548 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 6.5899 (1) Å	Cell parameters from 16616 reflections
b = 17.9658 (2) Å	θ = 4.5–76.3°
c = 11.9444 (1) Å	µ = 6.63 mm^−1
β = 96.131 (1)°	T = 100 K
V = 1406.04 (3) Å^3	Needle, yellow
Z = 2	0.28 × 0.03 × 0.03 mm

Data collection

XtaLAB Synergy, Dualflex, HyPix diffractometer	2990 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2829 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.028
Detector resolution: 10.0000 pixels mm^-1	θmax = 78.3°, θmin = 4.5°
ω scans	h = −8→7
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −22→22
Tmin = 0.571, Tmax = 1.000	l = −13→15
23719 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0511P)^2 + 0.3714P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.083	(Δ/σ)max = 0.001
S = 1.11	Δρmax = 0.24 e Å^−3
2990 reflections	Δρmin = −0.34 e Å^−3
197 parameters	Extinction correction: SHELXL2016/6 (Sheldrick, 2015a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0007 (2)
Primary atom site location: dual

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.000000	0.500000	0.500000	0.01595 (11)
N1	0.1137 (2)	0.50708 (6)	0.66710 (11)	0.0204 (3)
C1	0.1405 (2)	0.50936 (7)	0.76538 (13)	0.0196 (3)
S1	0.17656 (6)	0.51232 (2)	0.90206 (3)	0.02903 (12)
O11	0.22429 (14)	0.57834 (6)	0.46915 (8)	0.0237 (2)
N11	0.23654 (17)	0.60259 (6)	0.36497 (9)	0.0198 (2)
C11	0.0786 (2)	0.64024 (8)	0.31076 (11)	0.0208 (3)
H11	−0.037683	0.652022	0.348001	0.025*
C12	0.0881 (2)	0.66154 (8)	0.19988 (11)	0.0214 (3)
C13	0.2587 (2)	0.64494 (8)	0.14458 (12)	0.0246 (3)
H13	0.264095	0.658366	0.068026	0.030*
C14	0.4198 (2)	0.60828 (9)	0.20484 (13)	0.0270 (3)
H14	0.539395	0.597242	0.170098	0.032*
C15	0.4073 (2)	0.58770 (8)	0.31525 (12)	0.0242 (3)
H15	0.518894	0.563014	0.356478	0.029*
C16	−0.0832 (2)	0.70028 (8)	0.14185 (12)	0.0246 (3)
N12	−0.2185 (2)	0.73137 (8)	0.09481 (11)	0.0324 (3)
O21	0.20988 (14)	0.41291 (6)	0.49113 (8)	0.0221 (2)
C21	0.0785 (2)	0.34632 (7)	0.33413 (12)	0.0206 (3)
H21	−0.041400	0.335659	0.368791	0.025*
C22	0.0971 (2)	0.32231 (8)	0.22576 (12)	0.0218 (3)
C23	0.2739 (2)	0.33654 (8)	0.17478 (12)	0.0263 (3)
H23	0.286155	0.320817	0.099860	0.032*
C24	0.4310 (2)	0.37428 (9)	0.23672 (13)	0.0279 (3)
H24	0.554515	0.383844	0.204898	0.034*
C25	0.4087 (2)	0.39810 (8)	0.34478 (12)	0.0239 (3)
H25	0.517252	0.423673	0.387264	0.029*
C26	−0.0726 (2)	0.28445 (8)	0.16431 (12)	0.0247 (3)
N22	−0.2080 (2)	0.25501 (8)	0.11394 (12)	0.0323 (3)
N21	0.23268 (17)	0.38504 (6)	0.39006 (9)	0.0190 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01140 (17)	0.02239 (17)	0.01407 (18)	0.00014 (9)	0.00137 (12)	−0.00016 (10)
N1	0.0170 (6)	0.0261 (6)	0.0178 (6)	0.0005 (4)	0.0010 (5)	−0.0008 (4)
C1	0.0135 (6)	0.0248 (6)	0.0207 (7)	−0.0004 (4)	0.0032 (5)	−0.0009 (5)
S1	0.0330 (2)	0.0394 (2)	0.01490 (19)	−0.00001 (15)	0.00368 (14)	−0.00104 (13)
O11	0.0188 (4)	0.0343 (5)	0.0174 (5)	−0.0063 (4)	−0.0012 (3)	0.0061 (4)
N11	0.0162 (5)	0.0236 (5)	0.0193 (5)	−0.0040 (4)	0.0009 (4)	0.0026 (4)
C11	0.0167 (6)	0.0240 (6)	0.0216 (6)	−0.0005 (5)	0.0014 (5)	0.0002 (5)
C12	0.0208 (6)	0.0205 (6)	0.0230 (7)	−0.0007 (5)	0.0016 (5)	0.0004 (5)
C13	0.0256 (7)	0.0284 (7)	0.0203 (6)	−0.0024 (5)	0.0044 (5)	0.0011 (5)
C14	0.0192 (6)	0.0348 (8)	0.0279 (7)	0.0011 (5)	0.0057 (5)	0.0002 (6)
C15	0.0172 (6)	0.0279 (7)	0.0275 (7)	−0.0008 (5)	0.0018 (5)	0.0021 (5)
C16	0.0276 (7)	0.0264 (7)	0.0202 (6)	0.0020 (5)	0.0038 (5)	0.0001 (5)
N12	0.0348 (7)	0.0369 (7)	0.0250 (6)	0.0122 (6)	0.0009 (5)	0.0006 (5)
O21	0.0200 (5)	0.0295 (5)	0.0165 (4)	0.0058 (4)	0.0000 (3)	−0.0042 (4)
C21	0.0165 (6)	0.0222 (6)	0.0230 (6)	−0.0001 (5)	0.0022 (5)	0.0011 (5)
C22	0.0214 (6)	0.0209 (6)	0.0227 (6)	0.0009 (5)	0.0003 (5)	−0.0010 (5)
C23	0.0239 (7)	0.0324 (7)	0.0232 (7)	0.0005 (6)	0.0053 (5)	−0.0035 (6)
C24	0.0197 (6)	0.0380 (8)	0.0268 (7)	−0.0013 (6)	0.0057 (5)	−0.0031 (6)
C25	0.0158 (6)	0.0294 (7)	0.0261 (7)	−0.0005 (5)	0.0010 (5)	−0.0022 (5)
C26	0.0273 (7)	0.0244 (7)	0.0226 (7)	−0.0020 (5)	0.0030 (5)	−0.0002 (5)
N22	0.0343 (7)	0.0333 (7)	0.0286 (6)	−0.0102 (6)	0.0001 (5)	−0.0022 (5)
N21	0.0168 (5)	0.0219 (5)	0.0181 (5)	0.0034 (4)	0.0010 (4)	−0.0020 (4)

Geometric parameters (Å, º)

Co1—N1^i	2.0596 (13)	C14—H14	0.9500
Co1—N1	2.0596 (13)	C14—C15	1.381 (2)
Co1—O11	2.1019 (10)	C15—H15	0.9500
Co1—O11^i	2.1019 (10)	C16—N12	1.147 (2)
Co1—O21^i	2.0985 (9)	O21—N21	1.3302 (14)
Co1—O21	2.0985 (9)	C21—H21	0.9500
N1—C1	1.169 (2)	C21—C22	1.382 (2)
C1—S1	1.6254 (16)	C21—N21	1.3480 (17)
O11—N11	1.3290 (14)	C22—C23	1.395 (2)
N11—C11	1.3478 (17)	C22—C26	1.4410 (19)
N11—C15	1.3540 (18)	C23—H23	0.9500
C11—H11	0.9500	C23—C24	1.384 (2)
C11—C12	1.3864 (18)	C24—H24	0.9500
C12—C13	1.3956 (19)	C24—C25	1.382 (2)
C12—C16	1.4398 (19)	C25—H25	0.9500
C13—H13	0.9500	C25—N21	1.3519 (18)
C13—C14	1.384 (2)	C26—N22	1.150 (2)
N1^i—Co1—N1	180.0	C14—C13—H13	121.1
N1^i—Co1—O11^i	86.48 (4)	C13—C14—H14	119.9
N1^i—Co1—O11	93.52 (4)	C15—C14—C13	120.24 (13)
N1—Co1—O11	86.48 (4)	C15—C14—H14	119.9
N1—Co1—O11^i	93.52 (4)	N11—C15—C14	120.21 (13)
N1^i—Co1—O21^i	85.49 (4)	N11—C15—H15	119.9
N1—Co1—O21	85.49 (4)	C14—C15—H15	119.9
N1^i—Co1—O21	94.51 (4)	N12—C16—C12	179.29 (17)
N1—Co1—O21^i	94.51 (4)	N21—O21—Co1	117.74 (7)
O11^i—Co1—O11	180.00 (3)	C22—C21—H21	120.4
O21—Co1—O11	90.62 (4)	N21—C21—H21	120.4
O21—Co1—O11^i	89.38 (4)	N21—C21—C22	119.20 (12)
O21^i—Co1—O11^i	90.62 (4)	C21—C22—C23	120.87 (13)
O21^i—Co1—O11	89.38 (4)	C21—C22—C26	118.88 (13)
O21^i—Co1—O21	180.0	C23—C22—C26	120.21 (13)
C1—N1—Co1	167.31 (12)	C22—C23—H23	121.0
N1—C1—S1	179.70 (15)	C24—C23—C22	117.94 (13)
N11—O11—Co1	119.86 (7)	C24—C23—H23	121.0
O11—N11—C11	119.56 (11)	C23—C24—H24	119.9
O11—N11—C15	118.84 (11)	C25—C24—C23	120.19 (13)
C11—N11—C15	121.60 (12)	C25—C24—H24	119.9
N11—C11—H11	120.5	C24—C25—H25	120.0
N11—C11—C12	119.07 (12)	N21—C25—C24	120.07 (13)
C12—C11—H11	120.5	N21—C25—H25	120.0
C11—C12—C13	120.94 (13)	N22—C26—C22	178.95 (16)
C11—C12—C16	118.69 (12)	O21—N21—C21	119.46 (11)
C13—C12—C16	120.36 (12)	O21—N21—C25	118.86 (11)
C12—C13—H13	121.1	C21—N21—C25	121.66 (12)
C14—C13—C12	117.87 (13)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O21^i	0.95	2.61	3.3295 (17)	133
C11—H11···N22^ii	0.95	2.57	3.3902 (19)	145
C14—H14···S1^iii	0.95	2.91	3.7585 (15)	149
C15—H15···O21^iii	0.95	2.45	3.2351 (16)	140
C21—H21···N12^iv	0.95	2.52	3.3233 (19)	142
C24—H24···S1^iii	0.95	2.96	3.8082 (15)	150
C25—H25···O11^iii	0.95	2.28	3.1335 (16)	148

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