Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705057X/ng2333sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680705057X/ng2333Isup2.hkl |
CCDC reference: 667172
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.011 Å
- R factor = 0.066
- wR factor = 0.168
- Data-to-parameter ratio = 17.0
checkCIF/PLATON results
No syntax errors found
Alert level A DIFF020_ALERT_1_A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards.
Author Response: CCD detector used |
PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for C33
Author Response: C33 is part of terminal isothiocyanate ligand with large S ADP, which could not be modeled successfully as a disordered position. |
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 47 Perc. PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT220_ALERT_2_C Large Non-Solvent S Ueq(max)/Ueq(min) ... 2.70 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N12 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C32
Author Response: C33 is part of terminal isothiocyanate ligand with large S ADP, which could not be modeled successfully as a disordered position. |
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C34
Author Response: C33 is part of terminal isothiocyanate ligand with large S ADP, which could not be modeled successfully as a disordered position. |
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 11 PLAT731_ALERT_1_C Bond Calc 0.89(5), Rep 0.89(2) ...... 2.50 su-Ra N2 -H2N 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.89(5), Rep 0.89(2) ...... 2.50 su-Ra N2 -H2N 1.555 1.555
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 8215 Count of symmetry unique reflns 5050 Completeness (_total/calc) 162.67% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 3165 Fraction of Friedel pairs measured 0.627 Are heavy atom types Z>Si present yes PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (2) 1.56 PLAT794_ALERT_5_G Check Predicted Bond Valency for Co2 (2) 1.79 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 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 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
For literature on complexes of 4,4'-dipyridylamine, see: Mallika Krishnan et al. (2007); Montney et al. (2007). For the synthesis of 4,4'-dipyridylamine, see Zapf et al. (1998). For the radii of cobalt ions, see: Shannon (1976).
Cobalt thiocyanate was obtained commercially. 4,4'-Dipyridylamine (dpa) was prepared via a published procedure (Zapf et al., 1998). Cobalt thiocyanate (58 mg, 0.33 mmol) and dpa (57 mg, 0.33 mmol) were added to 10 ml water in a 23 ml a Teflon-lined Parr acid digestion bomb. The mixture was then heated under autogenous pressure at 423 K for 48 h, whereupon it was cooled slowly to 293 K. Dark blue crystals (78 mg, 0.27 mmol, 82% yield base on dpa) of the title compound were produced.
All H atoms bound to C atoms were placed in calculated positions, with C—H = 0.95 (2) Å and refined in riding mode with Uiso = 1.2Ueq(C). Two of the H atoms bound to N within dpa ligands were found via Fourier difference map, restrained with N—H = 0.88 (2) Å, and refined with Uiso = 1.2Ueq(N). The third dpa amine H atom was placed in a calculated position, with N—H = 0.88 (2) Å and refined in riding mode with Uiso = 1.2Ueq(N).
One of the most common tethering ligands for the generation of functional coordination polymers is 4,4'-bipyridine. By comparison, similar materials based on 4,4'-dipyridylamine (dpa) are much less common (Montney et al., 2007). The title compound was prepared during continued attempts to investigate the effect of the counteranion on the structure of dpa-containing cobalt coordination polymers (Mallika Krishnan et al., 2007).
The title compound crystallizes in the non-centrosymmetric space group P212121 with an asymmetric unit (Fig. 1) comprised of two cobalt atoms, four ligated N-bound isothiocyanate anions and three crystallographically distinct dpa ligands. The two crystallographically distinct cobalt atoms have differing coordination geometries, with Co1 displaying an octahedral [CoN6] arrangement and Co2 possessing a tetrahedral [CoN4] coordination sphere. The longer bond distances about the octahedrally coordinated Co atom are consistent with the well known trend towards larger ionic radii for higher coordination numbers (Shannon, 1976).
Propagation of the asymmetric unit via the 21 screw axis coincident with the c crystal direction generates a 1-D coordination polymeric ribbon with a formulation of [Co2(SCN)4(dpa)3] (Fig. 2). Each octahedrally coordinated Co1 atom connects to two other neighboring Co1 atoms and two tetrahedrally coordinated Co2 atoms through tethering dpa ligands. In turn, each Co2 atom is linked to two neighboring Co1 atoms in the same fashion. The Co1–Co1 distance measures 11.409 (1) Å, while the two distinct through-ligand Co1–Co2 distances are 11.160 (1) Å and 11.234 (1) Å.
The 1-D ribbon motifs construct sinusoidal pseudo 2-D layers coincident with the ac crystal planess via N—H···S hydrogen bonding between dpa amines and S2 atoms of isothiocyanate ligands bound to Co2, within the next-nearest neighbor ribbon motif (Fig. 3). Neighboring ribbons within the pseudo 2-D layer do not engage in hydrogen bonding. The closest Co—Co distance between neighboring ribbons within the same pseudo 2-D layer is 7.924 (1) Å, defining the a lattice parameter. These layers in turn link together via three different N–H···S hydrogen bonding interactions to afford the full pseudo 3-D structure of the title compound.
For literature on complexes of 4,4'-dipyridylamine, see: Mallika Krishnan et al. (2007); Montney et al. (2007). For the synthesis of 4,4'-dipyridylamine, see Zapf et al. (1998). For the radii of cobalt ions, see: Shannon (1976).
Data collection: APEX2 (Bruker, 2001); cell refinement: APEX2 (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CrystalMaker (Palmer, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Co2(NCS)4(C10H9N3)3] | Dx = 1.462 Mg m−3 |
Mr = 863.79 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 21566 reflections |
a = 7.9245 (2) Å | θ = 1.3–27.5° |
b = 21.7051 (5) Å | µ = 1.10 mm−1 |
c = 22.8134 (5) Å | T = 173 K |
V = 3923.95 (16) Å3 | Plate, blue |
Z = 4 | 0.24 × 0.16 × 0.04 mm |
F(000) = 1760 |
Bruker APEXII diffractometer | 8215 independent reflections |
Radiation source: fine-focus sealed tube | 3888 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
ω/φ scans | θmax = 27.5°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.769, Tmax = 0.957 | k = −23→27 |
21566 measured reflections | l = −29→28 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.168 | w = 1/[σ2(Fo2) + (0.0636P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
8215 reflections | Δρmax = 0.48 e Å−3 |
484 parameters | Δρmin = −0.44 e Å−3 |
2 restraints | Absolute structure: Flack (1983), with 4324 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (3) |
[Co2(NCS)4(C10H9N3)3] | V = 3923.95 (16) Å3 |
Mr = 863.79 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.9245 (2) Å | µ = 1.10 mm−1 |
b = 21.7051 (5) Å | T = 173 K |
c = 22.8134 (5) Å | 0.24 × 0.16 × 0.04 mm |
Bruker APEXII diffractometer | 8215 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3888 reflections with I > 2σ(I) |
Tmin = 0.769, Tmax = 0.957 | Rint = 0.087 |
21566 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.168 | Δρmax = 0.48 e Å−3 |
S = 1.00 | Δρmin = −0.44 e Å−3 |
8215 reflections | Absolute structure: Flack (1983), with 4324 Friedel pairs |
484 parameters | Absolute structure parameter: 0.07 (3) |
2 restraints |
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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.72244 (11) | 0.50638 (5) | 0.98492 (4) | 0.0355 (3) | |
Co2 | −0.19707 (13) | 0.77752 (6) | 1.25735 (5) | 0.0601 (4) | |
S1 | 0.3044 (3) | 0.36061 (11) | 1.04968 (12) | 0.0650 (7) | |
S2 | −0.5888 (6) | 0.6243 (2) | 1.22905 (16) | 0.1580 (19) | |
S3 | 1.1421 (3) | 0.63571 (12) | 0.89090 (10) | 0.0585 (7) | |
S4 | −0.4974 (3) | 0.95834 (18) | 1.28237 (18) | 0.1299 (16) | |
N1 | 1.5164 (8) | 0.2278 (4) | 0.8190 (3) | 0.059 (2) | |
N2 | 1.0726 (9) | 0.2531 (3) | 0.9131 (3) | 0.0503 (19) | |
H2N | 1.023 (9) | 0.2168 (19) | 0.909 (3) | 0.060* | |
N3 | 0.8455 (7) | 0.4207 (3) | 0.9616 (2) | 0.0360 (16) | |
N4 | 0.6024 (7) | 0.5921 (3) | 1.0081 (3) | 0.0397 (16) | |
N5 | 0.3715 (8) | 0.7490 (3) | 1.0815 (3) | 0.054 (2) | |
H5A | 0.4276 | 0.7837 | 1.0770 | 0.064* | |
N6 | −0.0573 (8) | 0.7694 (4) | 1.1858 (3) | 0.0530 (19) | |
N7 | 0.5961 (6) | 0.5045 (3) | 0.8987 (2) | 0.0332 (15) | |
N8 | 0.3962 (7) | 0.4829 (4) | 0.7301 (3) | 0.057 (2) | |
H8N | 0.287 (3) | 0.491 (4) | 0.731 (3) | 0.069* | |
N9 | 0.6494 (7) | 0.4914 (3) | 0.5685 (2) | 0.0378 (16) | |
N10 | 0.9299 (8) | 0.5549 (3) | 0.9507 (3) | 0.0414 (17) | |
N11 | 0.5209 (8) | 0.4570 (3) | 1.0222 (3) | 0.0441 (17) | |
N12 | −0.3452 (10) | 0.7073 (4) | 1.2577 (4) | 0.080 (3) | |
N13 | −0.3002 (10) | 0.8556 (4) | 1.2636 (3) | 0.074 (2) | |
C1 | 1.3997 (12) | 0.1836 (5) | 0.8223 (4) | 0.066 (3) | |
H1 | 1.4220 | 0.1459 | 0.8026 | 0.080* | |
C2 | 1.2493 (11) | 0.1886 (4) | 0.8523 (3) | 0.056 (2) | |
H2 | 1.1687 | 0.1562 | 0.8527 | 0.068* | |
C3 | 1.2216 (10) | 0.2452 (4) | 0.8826 (3) | 0.047 (2) | |
C4 | 1.3462 (10) | 0.2899 (4) | 0.8809 (3) | 0.050 (2) | |
H4 | 1.3341 | 0.3273 | 0.9021 | 0.059* | |
C5 | 1.4861 (11) | 0.2789 (5) | 0.8482 (4) | 0.063 (3) | |
H5 | 1.5686 | 0.3106 | 0.8463 | 0.075* | |
C6 | 0.9431 (10) | 0.4146 (4) | 0.9130 (3) | 0.043 (2) | |
H6 | 0.9600 | 0.4506 | 0.8900 | 0.052* | |
C7 | 1.0190 (10) | 0.3622 (4) | 0.8941 (4) | 0.047 (2) | |
H7 | 1.0827 | 0.3615 | 0.8589 | 0.057* | |
C8 | 1.0000 (9) | 0.3095 (4) | 0.9282 (3) | 0.038 (2) | |
C9 | 0.8950 (9) | 0.3134 (4) | 0.9768 (3) | 0.045 (2) | |
H9 | 0.8728 | 0.2778 | 0.9997 | 0.054* | |
C10 | 0.8250 (9) | 0.3675 (4) | 0.9915 (3) | 0.048 (2) | |
H10 | 0.7558 | 0.3684 | 1.0255 | 0.058* | |
C11 | 0.6909 (10) | 0.6408 (4) | 1.0275 (3) | 0.046 (2) | |
H11 | 0.8104 | 0.6396 | 1.0243 | 0.055* | |
C12 | 0.6186 (10) | 0.6920 (4) | 1.0517 (3) | 0.051 (2) | |
H12 | 0.6877 | 0.7248 | 1.0653 | 0.061* | |
C13 | 0.4435 (10) | 0.6962 (4) | 1.0565 (3) | 0.048 (2) | |
C14 | 0.3538 (11) | 0.6476 (4) | 1.0330 (4) | 0.058 (3) | |
H14 | 0.2340 | 0.6489 | 1.0330 | 0.069* | |
C15 | 0.4360 (10) | 0.5969 (4) | 1.0094 (4) | 0.053 (2) | |
H15 | 0.3702 | 0.5644 | 0.9935 | 0.064* | |
C16 | 0.0310 (10) | 0.8176 (4) | 1.1639 (3) | 0.048 (2) | |
H16 | −0.0047 | 0.8580 | 1.1738 | 0.058* | |
C17 | 0.1659 (9) | 0.8114 (4) | 1.1290 (3) | 0.048 (2) | |
H17 | 0.2243 | 0.8469 | 1.1154 | 0.058* | |
C18 | 0.2204 (11) | 0.7526 (4) | 1.1128 (3) | 0.052 (2) | |
C19 | 0.1268 (11) | 0.7033 (4) | 1.1330 (4) | 0.069 (3) | |
H19 | 0.1571 | 0.6624 | 1.1224 | 0.082* | |
C20 | −0.0092 (12) | 0.7135 (5) | 1.1683 (4) | 0.065 (3) | |
H20 | −0.0730 | 0.6790 | 1.1811 | 0.078* | |
C21 | 0.4854 (9) | 0.5064 (4) | 0.5748 (3) | 0.042 (2) | |
H21 | 0.4260 | 0.5194 | 0.5408 | 0.051* | |
C22 | 0.3991 (9) | 0.5044 (4) | 0.6259 (3) | 0.055 (2) | |
H22 | 0.2839 | 0.5164 | 0.6272 | 0.066* | |
C23 | 0.4817 (8) | 0.4843 (4) | 0.6772 (3) | 0.042 (2) | |
C24 | 0.6493 (9) | 0.4671 (4) | 0.6714 (3) | 0.0362 (19) | |
H24 | 0.7102 | 0.4514 | 0.7040 | 0.043* | |
C25 | 0.7255 (9) | 0.4729 (3) | 0.6180 (3) | 0.041 (2) | |
H25 | 0.8421 | 0.4631 | 0.6157 | 0.049* | |
C26 | 0.4431 (9) | 0.4811 (4) | 0.8876 (3) | 0.046 (2) | |
H26 | 0.3776 | 0.4683 | 0.9202 | 0.055* | |
C27 | 0.3730 (10) | 0.4740 (4) | 0.8332 (3) | 0.055 (3) | |
H27 | 0.2634 | 0.4568 | 0.8290 | 0.066* | |
C28 | 0.4634 (9) | 0.4922 (4) | 0.7844 (3) | 0.046 (2) | |
C29 | 0.6197 (9) | 0.5176 (4) | 0.7943 (3) | 0.046 (2) | |
H29 | 0.6863 | 0.5312 | 0.7622 | 0.055* | |
C30 | 0.6785 (9) | 0.5234 (3) | 0.8494 (3) | 0.038 (2) | |
H30 | 0.7860 | 0.5421 | 0.8543 | 0.045* | |
C31 | 1.0209 (9) | 0.5889 (4) | 0.9264 (3) | 0.035 (2) | |
C32 | 0.4329 (9) | 0.4177 (4) | 1.0336 (3) | 0.039 (2) | |
C33 | −0.4444 (13) | 0.6725 (5) | 1.2456 (4) | 0.068 (3) | |
C34 | −0.3839 (11) | 0.8982 (5) | 1.2716 (4) | 0.072 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0386 (5) | 0.0427 (7) | 0.0253 (5) | 0.0015 (5) | 0.0051 (5) | −0.0005 (5) |
Co2 | 0.0419 (6) | 0.0872 (10) | 0.0514 (7) | 0.0058 (7) | −0.0016 (6) | 0.0045 (7) |
S1 | 0.0450 (11) | 0.0500 (16) | 0.1002 (18) | −0.0023 (12) | −0.0013 (14) | 0.0113 (15) |
S2 | 0.189 (4) | 0.178 (4) | 0.107 (3) | −0.109 (4) | −0.042 (3) | 0.019 (3) |
S3 | 0.0443 (11) | 0.0676 (18) | 0.0634 (15) | −0.0119 (12) | 0.0110 (12) | 0.0117 (14) |
S4 | 0.0483 (15) | 0.141 (3) | 0.200 (4) | 0.0435 (18) | −0.040 (2) | −0.094 (3) |
N1 | 0.048 (4) | 0.063 (6) | 0.066 (5) | 0.005 (4) | 0.006 (4) | −0.013 (5) |
N2 | 0.060 (4) | 0.028 (5) | 0.063 (5) | 0.000 (4) | 0.016 (4) | −0.002 (4) |
N3 | 0.038 (3) | 0.037 (4) | 0.032 (3) | 0.003 (3) | 0.002 (3) | 0.002 (3) |
N4 | 0.035 (3) | 0.052 (5) | 0.032 (4) | 0.007 (3) | 0.001 (3) | −0.006 (4) |
N5 | 0.056 (4) | 0.039 (5) | 0.065 (5) | 0.004 (4) | 0.011 (4) | −0.012 (4) |
N6 | 0.042 (4) | 0.060 (6) | 0.057 (5) | 0.002 (4) | 0.002 (4) | 0.003 (5) |
N7 | 0.037 (3) | 0.034 (4) | 0.029 (3) | 0.001 (3) | 0.003 (3) | −0.009 (3) |
N8 | 0.036 (3) | 0.105 (7) | 0.031 (4) | −0.023 (4) | 0.004 (3) | 0.001 (4) |
N9 | 0.034 (3) | 0.050 (5) | 0.029 (3) | 0.004 (3) | −0.003 (3) | −0.005 (3) |
N10 | 0.042 (4) | 0.046 (5) | 0.036 (4) | 0.001 (3) | −0.005 (3) | −0.006 (4) |
N11 | 0.045 (4) | 0.052 (5) | 0.035 (4) | 0.001 (4) | 0.001 (3) | −0.004 (4) |
N12 | 0.072 (5) | 0.097 (8) | 0.071 (6) | −0.021 (5) | 0.000 (5) | −0.001 (5) |
N13 | 0.063 (4) | 0.102 (7) | 0.057 (5) | 0.047 (5) | −0.003 (5) | −0.011 (5) |
C1 | 0.067 (6) | 0.058 (7) | 0.074 (7) | 0.003 (6) | 0.027 (6) | −0.018 (6) |
C2 | 0.069 (6) | 0.048 (6) | 0.052 (5) | 0.008 (5) | 0.015 (5) | 0.000 (5) |
C3 | 0.041 (4) | 0.057 (6) | 0.044 (5) | 0.005 (5) | 0.010 (4) | 0.006 (5) |
C4 | 0.051 (5) | 0.058 (7) | 0.039 (5) | 0.014 (5) | 0.007 (4) | −0.006 (5) |
C5 | 0.053 (5) | 0.060 (7) | 0.075 (6) | −0.014 (5) | 0.015 (5) | −0.022 (6) |
C6 | 0.053 (5) | 0.041 (6) | 0.035 (4) | 0.000 (4) | 0.011 (4) | 0.008 (4) |
C7 | 0.051 (5) | 0.037 (6) | 0.054 (5) | 0.001 (4) | 0.023 (4) | 0.001 (5) |
C8 | 0.048 (4) | 0.041 (6) | 0.026 (4) | 0.001 (4) | 0.003 (4) | −0.003 (4) |
C9 | 0.051 (4) | 0.036 (5) | 0.047 (5) | 0.008 (4) | 0.008 (4) | 0.007 (5) |
C10 | 0.049 (5) | 0.051 (6) | 0.044 (5) | 0.011 (4) | 0.017 (4) | 0.007 (5) |
C11 | 0.045 (4) | 0.053 (6) | 0.039 (5) | 0.004 (5) | 0.011 (4) | 0.003 (5) |
C12 | 0.060 (5) | 0.042 (6) | 0.051 (5) | −0.004 (5) | 0.005 (5) | 0.004 (5) |
C13 | 0.051 (5) | 0.054 (7) | 0.040 (5) | 0.012 (5) | 0.006 (4) | −0.009 (5) |
C14 | 0.048 (5) | 0.063 (7) | 0.062 (6) | 0.006 (5) | −0.018 (5) | −0.005 (5) |
C15 | 0.060 (5) | 0.053 (6) | 0.046 (5) | 0.012 (5) | −0.013 (5) | −0.006 (5) |
C16 | 0.038 (4) | 0.055 (7) | 0.051 (5) | 0.012 (5) | 0.001 (4) | −0.011 (5) |
C17 | 0.036 (4) | 0.042 (6) | 0.066 (6) | 0.004 (4) | −0.002 (4) | −0.005 (5) |
C18 | 0.054 (5) | 0.060 (7) | 0.043 (5) | 0.017 (5) | 0.000 (5) | 0.005 (5) |
C19 | 0.066 (6) | 0.037 (6) | 0.102 (8) | 0.007 (5) | 0.014 (6) | 0.012 (6) |
C20 | 0.073 (7) | 0.055 (8) | 0.068 (7) | −0.005 (6) | 0.022 (6) | 0.004 (6) |
C21 | 0.045 (4) | 0.054 (6) | 0.029 (4) | 0.007 (4) | −0.005 (4) | 0.000 (5) |
C22 | 0.035 (4) | 0.100 (8) | 0.031 (4) | 0.001 (5) | 0.000 (4) | −0.006 (5) |
C23 | 0.036 (4) | 0.063 (7) | 0.026 (4) | −0.016 (4) | 0.002 (4) | −0.007 (4) |
C24 | 0.037 (4) | 0.048 (6) | 0.024 (4) | −0.002 (4) | −0.005 (3) | 0.001 (4) |
C25 | 0.036 (4) | 0.053 (6) | 0.033 (4) | 0.008 (4) | −0.005 (4) | −0.003 (4) |
C26 | 0.043 (4) | 0.063 (7) | 0.032 (4) | −0.015 (4) | 0.012 (4) | −0.007 (5) |
C27 | 0.052 (5) | 0.092 (8) | 0.022 (4) | −0.026 (5) | 0.004 (4) | −0.004 (5) |
C28 | 0.043 (4) | 0.072 (7) | 0.023 (4) | −0.010 (5) | −0.009 (4) | −0.009 (5) |
C29 | 0.044 (4) | 0.071 (7) | 0.023 (4) | −0.009 (4) | −0.002 (4) | −0.004 (4) |
C30 | 0.036 (4) | 0.048 (6) | 0.029 (4) | −0.010 (4) | 0.008 (4) | −0.001 (4) |
C31 | 0.028 (4) | 0.052 (6) | 0.026 (4) | 0.007 (4) | −0.007 (4) | −0.009 (4) |
C32 | 0.032 (4) | 0.049 (6) | 0.036 (5) | 0.004 (4) | −0.004 (4) | 0.002 (4) |
C33 | 0.080 (7) | 0.076 (8) | 0.049 (6) | −0.011 (6) | 0.004 (6) | 0.005 (6) |
C34 | 0.050 (5) | 0.116 (10) | 0.050 (6) | 0.005 (6) | −0.011 (5) | −0.037 (7) |
Co1—N10 | 2.103 (7) | C3—C4 | 1.385 (11) |
Co1—N11 | 2.103 (7) | C4—C5 | 1.357 (10) |
Co1—N4 | 2.155 (6) | C4—H4 | 0.9500 |
Co1—N9i | 2.161 (5) | C5—H5 | 0.9500 |
Co1—N3 | 2.165 (6) | C6—C7 | 1.357 (10) |
Co1—N7 | 2.207 (5) | C6—H6 | 0.9500 |
Co2—N13 | 1.888 (8) | C7—C8 | 1.390 (10) |
Co2—N12 | 1.924 (9) | C7—H7 | 0.9500 |
Co2—N6 | 1.981 (7) | C8—C9 | 1.390 (10) |
Co2—N1i | 2.010 (7) | C9—C10 | 1.340 (10) |
S1—C32 | 1.645 (9) | C9—H9 | 0.9500 |
S2—C33 | 1.596 (12) | C10—H10 | 0.9500 |
S3—C31 | 1.615 (9) | C11—C12 | 1.366 (11) |
S4—C34 | 1.605 (11) | C11—H11 | 0.9500 |
N1—C5 | 1.317 (11) | C12—C13 | 1.394 (11) |
N1—C1 | 1.334 (11) | C12—H12 | 0.9500 |
N1—Co2ii | 2.010 (7) | C13—C14 | 1.380 (11) |
N2—C3 | 1.380 (10) | C14—C15 | 1.387 (11) |
N2—C8 | 1.396 (10) | C14—H14 | 0.9500 |
N2—H2N | 0.89 (2) | C15—H15 | 0.9500 |
N3—C10 | 1.352 (9) | C16—C17 | 1.339 (10) |
N3—C6 | 1.358 (9) | C16—H16 | 0.9500 |
N4—C15 | 1.323 (10) | C17—C18 | 1.398 (11) |
N4—C11 | 1.344 (9) | C17—H17 | 0.9500 |
N5—C18 | 1.396 (10) | C18—C19 | 1.381 (12) |
N5—C13 | 1.402 (10) | C19—C20 | 1.363 (12) |
N5—H5A | 0.8800 | C19—H19 | 0.9500 |
N6—C20 | 1.332 (11) | C20—H20 | 0.9500 |
N6—C16 | 1.354 (10) | C21—C22 | 1.353 (9) |
N7—C26 | 1.339 (9) | C21—H21 | 0.9500 |
N7—C30 | 1.365 (8) | C22—C23 | 1.409 (10) |
N8—C28 | 1.364 (9) | C22—H22 | 0.9500 |
N8—C23 | 1.383 (9) | C23—C24 | 1.387 (10) |
N8—H8N | 0.88 (2) | C24—C25 | 1.365 (9) |
N9—C25 | 1.341 (8) | C24—H24 | 0.9500 |
N9—C21 | 1.348 (8) | C25—H25 | 0.9500 |
N9—Co1ii | 2.161 (5) | C26—C27 | 1.367 (9) |
N10—C31 | 1.171 (9) | C26—H26 | 0.9500 |
N11—C32 | 1.131 (9) | C27—C28 | 1.381 (10) |
N12—C33 | 1.124 (10) | C27—H27 | 0.9500 |
N13—C34 | 1.151 (11) | C28—C29 | 1.375 (10) |
C1—C2 | 1.378 (11) | C29—C30 | 1.346 (9) |
C1—H1 | 0.9500 | C29—H29 | 0.9500 |
C2—C3 | 1.429 (11) | C30—H30 | 0.9500 |
C2—H2 | 0.9500 | ||
N10—Co1—N11 | 177.7 (2) | C9—C8—C7 | 117.4 (8) |
N10—Co1—N4 | 90.2 (2) | C9—C8—N2 | 119.9 (8) |
N11—Co1—N4 | 90.3 (2) | C7—C8—N2 | 122.5 (7) |
N10—Co1—N9i | 87.1 (2) | C10—C9—C8 | 120.1 (8) |
N11—Co1—N9i | 90.7 (2) | C10—C9—H9 | 120.0 |
N4—Co1—N9i | 88.4 (2) | C8—C9—H9 | 120.0 |
N10—Co1—N3 | 89.2 (2) | C9—C10—N3 | 124.9 (7) |
N11—Co1—N3 | 90.2 (2) | C9—C10—H10 | 117.5 |
N4—Co1—N3 | 179.4 (2) | N3—C10—H10 | 117.5 |
N9i—Co1—N3 | 91.4 (2) | N4—C11—C12 | 123.6 (8) |
N10—Co1—N7 | 91.9 (2) | N4—C11—H11 | 118.2 |
N11—Co1—N7 | 90.3 (2) | C12—C11—H11 | 118.2 |
N4—Co1—N7 | 92.0 (2) | C11—C12—C13 | 120.2 (8) |
N9i—Co1—N7 | 178.9 (2) | C11—C12—H12 | 119.9 |
N3—Co1—N7 | 88.3 (2) | C13—C12—H12 | 119.9 |
N13—Co2—N12 | 116.6 (4) | C14—C13—C12 | 115.6 (8) |
N13—Co2—N6 | 112.6 (3) | C14—C13—N5 | 125.0 (7) |
N12—Co2—N6 | 105.9 (3) | C12—C13—N5 | 119.4 (8) |
N13—Co2—N1i | 107.9 (3) | C13—C14—C15 | 121.0 (8) |
N12—Co2—N1i | 112.7 (3) | C13—C14—H14 | 119.5 |
N6—Co2—N1i | 100.0 (3) | C15—C14—H14 | 119.5 |
C5—N1—C1 | 116.8 (8) | N4—C15—C14 | 122.6 (8) |
C5—N1—Co2ii | 122.1 (7) | N4—C15—H15 | 118.7 |
C1—N1—Co2ii | 119.5 (7) | C14—C15—H15 | 118.7 |
C3—N2—C8 | 125.8 (7) | C17—C16—N6 | 123.7 (9) |
C3—N2—H2N | 103 (5) | C17—C16—H16 | 118.1 |
C8—N2—H2N | 128 (5) | N6—C16—H16 | 118.1 |
C10—N3—C6 | 113.4 (6) | C16—C17—C18 | 119.7 (9) |
C10—N3—Co1 | 123.8 (5) | C16—C17—H17 | 120.2 |
C6—N3—Co1 | 122.7 (5) | C18—C17—H17 | 120.2 |
C15—N4—C11 | 116.8 (7) | C19—C18—N5 | 126.0 (9) |
C15—N4—Co1 | 120.9 (6) | C19—C18—C17 | 117.0 (8) |
C11—N4—Co1 | 122.0 (5) | N5—C18—C17 | 116.8 (8) |
C18—N5—C13 | 127.1 (8) | C20—C19—C18 | 119.6 (9) |
C18—N5—H5A | 116.5 | C20—C19—H19 | 120.2 |
C13—N5—H5A | 116.5 | C18—C19—H19 | 120.2 |
C20—N6—C16 | 116.4 (7) | N6—C20—C19 | 123.5 (9) |
C20—N6—Co2 | 119.2 (7) | N6—C20—H20 | 118.2 |
C16—N6—Co2 | 121.6 (6) | C19—C20—H20 | 118.2 |
C26—N7—C30 | 113.0 (6) | N9—C21—C22 | 124.8 (7) |
C26—N7—Co1 | 126.0 (5) | N9—C21—H21 | 117.6 |
C30—N7—Co1 | 120.8 (4) | C22—C21—H21 | 117.6 |
C28—N8—C23 | 126.7 (6) | C21—C22—C23 | 119.4 (7) |
C28—N8—H8N | 109 (5) | C21—C22—H22 | 120.3 |
C23—N8—H8N | 121 (5) | C23—C22—H22 | 120.3 |
C25—N9—C21 | 114.6 (6) | N8—C23—C24 | 123.1 (7) |
C25—N9—Co1ii | 122.6 (4) | N8—C23—C22 | 120.2 (6) |
C21—N9—Co1ii | 122.8 (5) | C24—C23—C22 | 116.6 (6) |
C31—N10—Co1 | 166.6 (6) | C25—C24—C23 | 119.0 (7) |
C32—N11—Co1 | 161.0 (7) | C25—C24—H24 | 120.5 |
C33—N12—Co2 | 163.1 (9) | C23—C24—H24 | 120.5 |
C34—N13—Co2 | 169.0 (9) | N9—C25—C24 | 125.5 (6) |
N1—C1—C2 | 124.8 (9) | N9—C25—H25 | 117.3 |
N1—C1—H1 | 117.6 | C24—C25—H25 | 117.3 |
C2—C1—H1 | 117.6 | N7—C26—C27 | 125.6 (7) |
C1—C2—C3 | 116.2 (9) | N7—C26—H26 | 117.2 |
C1—C2—H2 | 121.9 | C27—C26—H26 | 117.2 |
C3—C2—H2 | 121.9 | C26—C27—C28 | 119.3 (7) |
N2—C3—C4 | 122.5 (8) | C26—C27—H27 | 120.4 |
N2—C3—C2 | 118.8 (8) | C28—C27—H27 | 120.4 |
C4—C3—C2 | 118.7 (8) | N8—C28—C29 | 124.1 (7) |
C5—C4—C3 | 118.4 (8) | N8—C28—C27 | 119.2 (6) |
C5—C4—H4 | 120.8 | C29—C28—C27 | 116.7 (6) |
C3—C4—H4 | 120.8 | C30—C29—C28 | 120.2 (7) |
N1—C5—C4 | 125.1 (9) | C30—C29—H29 | 119.9 |
N1—C5—H5 | 117.5 | C28—C29—H29 | 119.9 |
C4—C5—H5 | 117.5 | C29—C30—N7 | 125.2 (7) |
C7—C6—N3 | 126.4 (8) | C29—C30—H30 | 117.4 |
C7—C6—H6 | 116.8 | N7—C30—H30 | 117.4 |
N3—C6—H6 | 116.8 | N10—C31—S3 | 178.0 (6) |
C6—C7—C8 | 117.6 (7) | N11—C32—S1 | 179.5 (8) |
C6—C7—H7 | 121.2 | N12—C33—S2 | 178.6 (11) |
C8—C7—H7 | 121.2 | N13—C34—S4 | 178.9 (11) |
N10—Co1—N3—C10 | 149.6 (6) | C6—C7—C8—C9 | 4.4 (11) |
N11—Co1—N3—C10 | −28.1 (6) | C6—C7—C8—N2 | −179.9 (7) |
N9i—Co1—N3—C10 | 62.5 (6) | C3—N2—C8—C9 | −153.7 (8) |
N7—Co1—N3—C10 | −118.5 (6) | C3—N2—C8—C7 | 30.8 (12) |
N10—Co1—N3—C6 | −34.6 (6) | C7—C8—C9—C10 | −4.2 (11) |
N11—Co1—N3—C6 | 147.6 (6) | N2—C8—C9—C10 | 180.0 (7) |
N9i—Co1—N3—C6 | −121.7 (5) | C8—C9—C10—N3 | 1.2 (12) |
N7—Co1—N3—C6 | 57.3 (5) | C6—N3—C10—C9 | 1.4 (11) |
N10—Co1—N4—C15 | 150.3 (6) | Co1—N3—C10—C9 | 177.5 (6) |
N11—Co1—N4—C15 | −31.9 (6) | C15—N4—C11—C12 | 4.7 (11) |
N9i—Co1—N4—C15 | −122.6 (6) | Co1—N4—C11—C12 | −168.7 (6) |
N7—Co1—N4—C15 | 58.4 (6) | N4—C11—C12—C13 | −1.1 (12) |
N10—Co1—N4—C11 | −36.5 (6) | C11—C12—C13—C14 | −2.9 (12) |
N11—Co1—N4—C11 | 141.3 (6) | C11—C12—C13—N5 | 179.8 (7) |
N9i—Co1—N4—C11 | 50.6 (6) | C18—N5—C13—C14 | 33.3 (13) |
N7—Co1—N4—C11 | −128.4 (6) | C18—N5—C13—C12 | −149.8 (8) |
N13—Co2—N6—C20 | −164.5 (7) | C12—C13—C14—C15 | 3.4 (12) |
N12—Co2—N6—C20 | −36.0 (8) | N5—C13—C14—C15 | −179.5 (8) |
N1i—Co2—N6—C20 | 81.2 (7) | C11—N4—C15—C14 | −4.2 (12) |
N13—Co2—N6—C16 | 35.0 (7) | Co1—N4—C15—C14 | 169.3 (6) |
N12—Co2—N6—C16 | 163.6 (6) | C13—C14—C15—N4 | 0.2 (14) |
N1i—Co2—N6—C16 | −79.2 (6) | C20—N6—C16—C17 | −3.6 (12) |
N10—Co1—N7—C26 | −177.1 (6) | Co2—N6—C16—C17 | 157.4 (6) |
N11—Co1—N7—C26 | 3.6 (7) | N6—C16—C17—C18 | 1.0 (12) |
N4—Co1—N7—C26 | −86.8 (6) | C13—N5—C18—C19 | 11.1 (13) |
N3—Co1—N7—C26 | 93.8 (6) | C13—N5—C18—C17 | −174.2 (8) |
N10—Co1—N7—C30 | 8.9 (6) | C16—C17—C18—C19 | 1.7 (12) |
N11—Co1—N7—C30 | −170.5 (6) | C16—C17—C18—N5 | −173.6 (7) |
N4—Co1—N7—C30 | 99.2 (6) | N5—C18—C19—C20 | 173.2 (8) |
N4—Co1—N10—C31 | −47 (3) | C17—C18—C19—C20 | −1.6 (13) |
N9i—Co1—N10—C31 | −135 (3) | C16—N6—C20—C19 | 3.7 (14) |
N3—Co1—N10—C31 | 134 (3) | Co2—N6—C20—C19 | −157.8 (7) |
N7—Co1—N10—C31 | 45 (3) | C18—C19—C20—N6 | −1.2 (15) |
N4—Co1—N11—C32 | 165 (2) | C25—N9—C21—C22 | 0.6 (13) |
N9i—Co1—N11—C32 | −106 (2) | Co1ii—N9—C21—C22 | 178.4 (7) |
N3—Co1—N11—C32 | −15 (2) | N9—C21—C22—C23 | −1.1 (15) |
N7—Co1—N11—C32 | 73 (2) | C28—N8—C23—C24 | 31.3 (14) |
N13—Co2—N12—C33 | 65 (3) | C28—N8—C23—C22 | −148.2 (10) |
N6—Co2—N12—C33 | −61 (3) | C21—C22—C23—N8 | 179.0 (8) |
N1i—Co2—N12—C33 | −170 (3) | C21—C22—C23—C24 | −0.6 (13) |
N12—Co2—N13—C34 | 24 (4) | N8—C23—C24—C25 | −176.8 (7) |
N6—Co2—N13—C34 | 147 (4) | C22—C23—C24—C25 | 2.8 (12) |
N1i—Co2—N13—C34 | −104 (4) | C21—N9—C25—C24 | 1.9 (12) |
C5—N1—C1—C2 | 2.2 (15) | Co1ii—N9—C25—C24 | −176.0 (6) |
Co2ii—N1—C1—C2 | −163.8 (7) | C23—C24—C25—N9 | −3.6 (12) |
N1—C1—C2—C3 | −1.5 (14) | C30—N7—C26—C27 | 2.0 (12) |
C8—N2—C3—C4 | 23.3 (13) | Co1—N7—C26—C27 | −172.5 (7) |
C8—N2—C3—C2 | −157.5 (8) | N7—C26—C27—C28 | −0.2 (14) |
C1—C2—C3—N2 | 179.6 (8) | C23—N8—C28—C29 | 14.9 (15) |
C1—C2—C3—C4 | −1.2 (11) | C23—N8—C28—C27 | −163.6 (9) |
N2—C3—C4—C5 | −177.9 (8) | C26—C27—C28—N8 | 177.4 (9) |
C2—C3—C4—C5 | 3.0 (12) | C26—C27—C28—C29 | −1.2 (13) |
C1—N1—C5—C4 | −0.3 (14) | N8—C28—C29—C30 | −177.9 (8) |
Co2ii—N1—C5—C4 | 165.4 (7) | C27—C28—C29—C30 | 0.6 (13) |
C3—C4—C5—N1 | −2.3 (14) | C28—C29—C30—N7 | 1.4 (13) |
C10—N3—C6—C7 | −1.1 (11) | C26—N7—C30—C29 | −2.6 (11) |
Co1—N3—C6—C7 | −177.2 (6) | Co1—N7—C30—C29 | 172.2 (6) |
N3—C6—C7—C8 | −1.9 (12) |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+3/2, −y+1, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···S1iii | 0.89 (2) | 2.59 (5) | 3.366 (7) | 147 (7) |
N5—H5A···S3iv | 0.88 | 2.55 | 3.355 (7) | 153 |
N8—H8N···S4v | 0.88 (2) | 2.53 (3) | 3.382 (7) | 162 (7) |
Symmetry codes: (iii) x+1/2, −y+1/2, −z+2; (iv) x−1/2, −y+3/2, −z+2; (v) x+1/2, −y+3/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Co2(NCS)4(C10H9N3)3] |
Mr | 863.79 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 173 |
a, b, c (Å) | 7.9245 (2), 21.7051 (5), 22.8134 (5) |
V (Å3) | 3923.95 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.10 |
Crystal size (mm) | 0.24 × 0.16 × 0.04 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.769, 0.957 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21566, 8215, 3888 |
Rint | 0.087 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.168, 1.00 |
No. of reflections | 8215 |
No. of parameters | 484 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −0.44 |
Absolute structure | Flack (1983), with 4324 Friedel pairs |
Absolute structure parameter | 0.07 (3) |
Computer programs: APEX2 (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CrystalMaker (Palmer, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···S1i | 0.89 (2) | 2.59 (5) | 3.366 (7) | 147 (7) |
N5—H5A···S3ii | 0.88 | 2.55 | 3.355 (7) | 153.0 |
N8—H8N···S4iii | 0.88 (2) | 2.53 (3) | 3.382 (7) | 162 (7) |
Symmetry codes: (i) x+1/2, −y+1/2, −z+2; (ii) x−1/2, −y+3/2, −z+2; (iii) x+1/2, −y+3/2, −z+2. |
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One of the most common tethering ligands for the generation of functional coordination polymers is 4,4'-bipyridine. By comparison, similar materials based on 4,4'-dipyridylamine (dpa) are much less common (Montney et al., 2007). The title compound was prepared during continued attempts to investigate the effect of the counteranion on the structure of dpa-containing cobalt coordination polymers (Mallika Krishnan et al., 2007).
The title compound crystallizes in the non-centrosymmetric space group P212121 with an asymmetric unit (Fig. 1) comprised of two cobalt atoms, four ligated N-bound isothiocyanate anions and three crystallographically distinct dpa ligands. The two crystallographically distinct cobalt atoms have differing coordination geometries, with Co1 displaying an octahedral [CoN6] arrangement and Co2 possessing a tetrahedral [CoN4] coordination sphere. The longer bond distances about the octahedrally coordinated Co atom are consistent with the well known trend towards larger ionic radii for higher coordination numbers (Shannon, 1976).
Propagation of the asymmetric unit via the 21 screw axis coincident with the c crystal direction generates a 1-D coordination polymeric ribbon with a formulation of [Co2(SCN)4(dpa)3] (Fig. 2). Each octahedrally coordinated Co1 atom connects to two other neighboring Co1 atoms and two tetrahedrally coordinated Co2 atoms through tethering dpa ligands. In turn, each Co2 atom is linked to two neighboring Co1 atoms in the same fashion. The Co1–Co1 distance measures 11.409 (1) Å, while the two distinct through-ligand Co1–Co2 distances are 11.160 (1) Å and 11.234 (1) Å.
The 1-D ribbon motifs construct sinusoidal pseudo 2-D layers coincident with the ac crystal planess via N—H···S hydrogen bonding between dpa amines and S2 atoms of isothiocyanate ligands bound to Co2, within the next-nearest neighbor ribbon motif (Fig. 3). Neighboring ribbons within the pseudo 2-D layer do not engage in hydrogen bonding. The closest Co—Co distance between neighboring ribbons within the same pseudo 2-D layer is 7.924 (1) Å, defining the a lattice parameter. These layers in turn link together via three different N–H···S hydrogen bonding interactions to afford the full pseudo 3-D structure of the title compound.