research communications
Structures of dicobalt and dinickel 4,4′-biphenyldicarboxylate dihydroxide, M2(O2CC6H4C6H4CO2)(OH)2, M = Co and Ni, and diammonium 4,4′-biphenyldicarboxylate from powder diffraction data
aDepartment of Chemistry, North Central College, 131 S. Loomis St., Naperville IL 60540, USA
*Correspondence e-mail: kaduk@polycrystallography.com
The triclinic structures of poly[(μ4-4,4′-biphenyldicarboxylato)di-μ-hydroxido-dicobalt], [Co2(C14H8O4)(OH)2]n, and poly[(μ4-4,4′-biphenyldicarboxylato)di-μ-hydroxido-dinickel], [Ni2(C14H8O4)(OH)2]n, were established using laboratory X-ray powder diffraction data. These structures, as well as that of poly[(μ4-4,4′-biphenyldicarboxylato)di-μ-hydroxido-dimanganese], [Mn2(C14H8O4)(OH)2]n, were optimized using density functional techniques. The structure of diammonium 4,4′-biphenyldicarboxylate, 2NH4+·C14H8O42−, was also solved using laboratory powder data. The Mn and Co compounds are isostructural: the octahedral MO6 groups share edges to form chains running parallel to the c-axis. These chains share corners (OH groups) to link into layers lying parallel to the bc plane. The hydroxyl groups do not participate in hydrogen bonds. The structure of (NH4)2BPDC consists of alternating layers of BPDC and ammonium ions lying parallel to the ab plane. Each hydrogen atom of the ammonium ions in (NH4)2BPDC participates in a strong N—H⋯O hydrogen bond.
1. Chemical context
Metal–organic frameworks (MOFs) are a class of compounds that have both organic (linker molecule) and inorganic (metal node) components. MOFs are used in many applied areas of science, such as gas separation and catalysis, but often the crystal structures of these MOFs are not reported. Knowing the crystal structures of MOFs lets us understand them at a molecular level as well as identify them more efficiently.
From an attempt to prepare a porous Co-BPDC (BPDC = 4,4′-biphenyldicarboxylate, C14H8O42–) MOF we obtained a dense Co-BPDC phase previously synthesized by Ipadeola & Ozoemena (2020). They reported a powder pattern, but did not otherwise characterize the compound, as it was decomposed to make nano-Co3O4. Their XRD pattern was similar to ours, but they did not measure to a low-enough angle to observe the strongest peak of the pattern (Fig. 1).
The magnetic properties of Co2BPDC(OH)2 were studied by Kurmoo & Kumagai (2002) and an X-ray powder pattern was provided (Fig. 2). They stated that the compound was isostructural to the analogous terephthalate. That structure was reported to crystallize in C2/m, which we believe to be incorrect (Markun et al., 2022).
Most syntheses involving BPDC use H2BPDC and a base. We prepared diammonium 4,4-biphenyldicarboxylate as an alternative (and more soluble) reagent, characterized its and used it to prepare Ni2BPDC(OH)2.
2. Structural commentary
The X-ray powder patterns show that the M2BPDC(OH)2 phases for M = Mn, Co, and Ni are isostructural (Fig. 3). The root-mean-square Cartesian displacements between the experimental (single crystal or Rietveld-refined) and DFT-optimized structures are 0.133, 0.264, and 0.563 Å for M = Mn, Co, and Ni, respectively (Figs. 4–6). The value for nickel is outside of the normal range for correct structures (van de Streek & Neumann, 2014). The behavior of the structure during various refinements and optimizations suggests that there might be alternate orientations of the BPDC ligand and alternate coordination of the Ni cations. Sorting out these details is not supported by the relatively poor diffraction data on the Ni compound. This discussion concentrates on the DFT-optimized structures.
All of the bond distances, angles, and torsion angles in the BPDC anions fall within the normal ranges indicated by a Mercury Mogul Geometry check (Macrae et al., 2020). The O12—C11—C5—C6 torsion angles (which represent the twist of the carboxylate group out of the phenyl ring plane) of −13.1, −14.1, and −6.6° for Mn, Co, and Ni, respectively, represent increases of conformational energy of approximately 1 kcal mol−1 (Kaduk et al., 1999). These small increases can be easily overcome by energy gains in coordination to the metal ions. The C8—C10—C10—C1 torsion angles of 0.6, 0.6, and 0.1° indicate that the BPDC ligands are essentially planar. The approximate Miller planes of the benzene rings of the BPDC moieties are (238), (225) and (259) for Mn, Co, and Ni, respectively.
Unlike the metal complexes, in diammonium BPDC, the aromatic rings are nearly perpendicular (C2—C4—C11—C14 = 85.7°). One carboxylate group lies nearly in the ring plane (O25—C21—C12—C15 = 4.6°), while the other (O24—C22—C6—C3 = 85.6°) is nearly perpendicular to its ring. The r.m.s. Cartesian displacement of the non-H atoms in the BPDC anion is 0.384 Å (Fig. 7).
Analysis of the contributions to the total crystal energy of the structures using the Forcite module of Materials Studio (Dassault Systèmes, 2021) suggests that bond and angle distortion terms dominate the intramolecular deformation energy in all three metal compounds. The intermolecular energy in all three compounds is dominated by electrostatic attractions, which represent the M—O coordinate bonds.
The VASP (Kresse & Furthmüller, 1996) indicate that all three M-BPDC compounds are semiconductors, with band gaps of 1.695, 1.407 and 0.856 eV for Mn, Co and Ni respectively. Both the HOMO and LUMO consist mainly of metal d states. For Mn and Co, the DOS for the up and down spins differ, while for Ni they are very similar. Thus, the bonding in the Ni compound seems to be different than that in the other two.
(DOS) calculated byA uniaxial microstrain model (100 as the unique axis) was used to model the peak profiles. The axial and equatorial microstrains for Co are 7.4 × 104 and 5.6 × 104 ppm, while those for Ni show a greater difference, at 1.1 × 105 and 1.5 × 104 ppm, respectively. This possibly indicates that the Ni compound also contains some alternate metal-ion coordinations (different orientations of the carboxyl groups). During some refinements of the Ni compound, the orientation of the carboxyl groups changed considerably, and/or the displacement coefficients became very large. The very broad peaks of the Ni powder pattern certainly limit the structural information that can be obtained.
The Bravais–Friedel–Donnay–Harker (Bravais, 1866, Friedel, 1907; Donnay & Harker, 1937) morphology suggests that we might expect a platy (with {100} as the major faces) morphology for the compounds. No correction model was necessary in the Co and Ni refinements.
3. Supramolecular features
The Mn and Co compounds are isostructural (Fig. 8). Both M14 and M15 exhibit an octahedral coordination, and occupy centers of symmetry. For M14, the coordination consists of trans carboxylate O12 atoms and four equatorial hydroxyl groups. For M15 there are trans hydroxyl groups and four equatorial carboxylate O13 atoms. The bond-valence sums are 1.94 and 2.09 for Mn and 1.80 and 1.85 for Co, in acceptable agreement with the expected values of 2.00. The carboxylate O12 atom bonds to one M14, and O13 bridges two M15. The hydroxyl group O16 bridges two M14 and one M15.
The M14 octahedra share edges to form chains running parallel to the c-axis. The M15 octahedra also share edges to form chains parallel to the c-axis. These chains share corners (the O16 OH groups), linking into layers lying parallel to the bc plane. The hydroxyl groups do not participate in hydrogen bonds.
The coordination in the Ni compound is different from the other two (Fig. 9). Ni14 is square planar, with trans carboxylate O12 atoms and two trans hydroxyl groups. Ni15 is also square planar, with trans hydroxyl O16 and carboxylate O13 atoms. Atom O12 is bonded to Ni14 (same), and O13 is bonded to Ni15 (different). Each carboxyl group bridges two metal atoms (not three), and the hydroxyl group O16 bridges one Ni14 and one Ni15. Both Ni ions share hydroxyl corners to form chains lying parallel to the [01] axis. The result is layers, but not connected (Fig. 10).
The structure of (NH4)2BPDC consists of alternating layers of BPDC dianions and ammonium cations lying parallel to the ab plane (Fig. 11). As expected, each hydrogen atom of the ammonium ions in (NH4)2BPDC participates in a strong N—H⋯O hydrogen bond (Table 1). The energies of these hydrogen bonds were calculated using the correlation of Wheatley & Kaduk (2019).
4. Database survey
We attempted to solve the structure of Co2BPDC(OH)2 from the powder data without success. Previous searches of the Cambridge Structural Database [CSD version 5.43 June 2022 (Groom et al., 2016); ConQuest 2022.2.0 (Bruno et al., 2002)] did not yield suitable analogues, but searches of CSD release 2021.3 using a BPDC fragment and the chemistry CHO and Ni, Zn, Fe, Mn, or Mg only yielded a few hits, among which was Mn2BPDC(OH)2, refcode UBUPEQ (Sibille et al., 2021). This compound has a similar powder pattern to our Co and Ni compounds (Fig. 3), and provided a suitable starting model for Rietveld refinements.
5. Synthesis and crystallization
Cobalt(II) nitrate hexahydrate (0.4383 g, 1.5 mmol) and biphenyl-4,4′-dicarboxylic acid (0.3645 g, 1.5 mmol) were added to a flask with 1.5 ml of triethylamine and ∼60 ml of dimethylformamide (DMF). The mixture was stirred on a hot plate (343 K) until the solution appeared to be homogenous (∼15 min). A 5 ml
of this solution was transferred to a Pyrex microwave vial and heated using a CEM Discover microwave with power set to 150 W using a ramp time of 2 min to reach 423 K with a hold time of 30 min and internal stirring off. Automatic cooling was turned off and the vial was left in the microwave until it cooled to 343 K. The solution was filtered using vacuum filtration and washed with DMF (10 ml). The remaining purple solid was dried in a vacuum oven at ∼343 K.Nickel(II) acetate tetrahydrate (0.0880 g, 0.35 mmol) and diammonium biphenyl-4,4′-dicarboxylate (0.1278 g, 0.5 mmol) were added to a flask and ∼20 ml of DMF was added. The reaction was stirred on a hot plate (343 K) until solution appeared to be homogenous (∼15 min). A 5 ml
of this solution was transferred to a Pyrex microwave vial and heated using a CEM Discover microwave with power set to 200 W using a ramp time of 5 min to reach 423 K with a hold time of 30 min and internal stirring on high. Automatic cooling was turned on. The solution was filtered using vacuum filtration and washed with DMF (10 ml). The remaining green solid was dried in a vacuum oven at ∼343 K.0.8990 g (4.1 mmol) of biphenyl-4,4′-dicarboxylic acid (Aldrich Lot #BCCF5104) were placed into a 50 ml beaker. About 50 ml of 15 M aqueous ammonia were placed in a 250 ml beaker, and the 50 ml beaker placed in the larger beaker. The large beaker was covered with a Petri dish, and allowed to stand at ambient conditions overnight. The white recovered solid weighed 1.0257 g, corresponding to the expected quantitative yield for (NH4)2BPDC.
6. Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
The powder pattern of (NH4)2BPDC was indexed using DOCVOL14 (Louër & Boultif, 2014). All attempts to solve and refine the structure in P were unsuccessful, so P1 was used. The structure was solved by Monte Carlo simulated-annealing techniques as implemented in EXPO2014 (Altomare et al., 2013), using a BPDC anion and two N atoms as fragments.
Rietveld refinements (Figs. 12–14) were carried out using GSAS-II (Toby & Von Dreele, 2013). All non-H bond distances and angles in the BPDC dianion were subjected to restraints, based on a Mercury Mogul Geometry Check (Sykes et al., 2011; Bruno et al., 2004). The Mogul average and standard deviation for each quantity were used as the restraint parameters. The restraints contributed 0–2.3% to the final χ2. The Uiso parameters were grouped by chemical similarity: given the complex, low-symmetry structures and poor data quality, these values should be treated with caution. The Uiso for the H atoms were fixed at 1.3 × Uiso of the heavy atoms to which they are attached. The peak profiles were described using the generalized microstrain model and the backgrounds were modeled using a 3–12-term shifted Chebyshev polynomial. For Co, the value of μ·R used was 0.37. For the ammonium salt, no absorption correction was necessary. For Ni, the geometry was reflection, so no absorption correction was appropriate.
The structures were optimized with density functional techniques using VASP (Kresse & Furthmüller, 1996) (fixed experimental unit cells) through the MedeA graphical interface (Materials Design, 2016). The calculations were carried out on 16 2.4 GHz processors (each with 4 Gb RAM) of a 64-processor HP Proliant DL580 Generation 7 Linux cluster at North Central College. The calculations for Co and Ni were spin-polarized magnetic calculations, using the simplified LDSA+U approach, and UJ = 3.7 for Mn, Co and Ni. The calculations used the GGA-PBE functional, a plane wave cutoff energy of 400.0 eV, and a k-point spacing of 0.5 Å−1 leading to a 1 × 3 × 4 mesh.
Supporting information
Program(s) used to solve structure: DFT for Co_DFT, NH4_DFT. Program(s) used to refine structure: GSAS-II (Toby & Von Dreele, 2013) for Co_X, Ni_X, NH4_X.
[Co(C14H8O4)0.5(OH)] | β = 98.46 (7)° |
Mr = 392.09 | γ = 90.0 (3)° |
Triclinic, P1 | V = 291.6 (2) Å3 |
Hall symbol: -P 1 | Z = 1 |
a = 14.16 (5) Å | Dx = 2.233 Mg m−3 |
b = 6.269 (3) Å | Kα1,2 radiation, λ = 0.70932, 0.71361 Å |
c = 3.323 (4) Å | T = 300 K |
α = 91.43 (2)° | cylinder, 12 × 0.7 mm |
PANalytical Empyrean diffractometer | Scan method: step |
Specimen mounting: glass capillary | 2θmin = 1.002°, 2θmax = 49.991°, 2θstep = 0.008° |
Data collection mode: transmission |
Least-squares matrix: full | Profile function: Finger-Cox-Jephcoat function parameters U, V, W, X, Y, SH/L: peak variance(Gauss) = Utan(Th)2+Vtan(Th)+W: peak HW(Lorentz) = X/cos(Th)+Ytan(Th); SH/L = S/L+H/L U, V, W in (centideg)2, X & Y in centideg 30.816, 10.768, 0.000, 1.935, 0.000, 0.033, |
Rp = 0.065 | 49 parameters |
Rwp = 0.092 | H-atom parameters not defined? |
Rexp = 0.022 | (Δ/σ)max = 2.587 |
R(F2) = 0.11340 | Background function: Background function: "chebyschev-1" function with 4 terms: 1205(8), -655(9), 147(7), -88(6), Background peak parameters: pos, int, sig, gam: 11.72(4), 4.94(12)e5, 3.12(13)e4, 0.100, |
5864 data points | Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1] |
x | y | z | Uiso*/Ueq | ||
C1 | 0.613 (3) | 0.625 (7) | 0.90 (3) | 0.26 (3)* | |
C3 | 0.704 (3) | 0.560 (8) | 0.84 (3) | 0.26 (3)* | |
C5 | 0.7409 (16) | 0.364 (3) | 0.97 (2) | 0.26 (3)* | |
C6 | 0.688 (3) | 0.233 (7) | 1.18 (3) | 0.26 (3)* | |
C8 | 0.594 (3) | 0.287 (11) | 1.23 (2) | 0.26 (3)* | |
C10 | 0.5516 (10) | 0.485 (9) | 1.077 (11) | 0.26 (3)* | |
C11 | 0.8397 (9) | 0.301 (2) | 0.895 (13) | 0.026 (13)* | |
O12 | 0.8581 (8) | 0.108 (3) | 0.890 (6) | 0.026 (13)* | |
O13 | 0.9031 (7) | 0.446 (2) | 0.938 (3) | 0.026 (13)* | |
H2 | 0.58666 | 0.79555 | 0.81088 | 0.3419* | |
H4 | 0.75003 | 0.66882 | 0.67401 | 0.3419* | |
H7 | 0.72054 | 0.07982 | 1.31427 | 0.3419* | |
H9 | 0.54982 | 0.17404 | 1.38976 | 0.3419* | |
O16 | 0.9611 (9) | 0.8112 (12) | 0.471 (3) | 0.0500* | |
H17 | 0.89031 | 0.81057 | 0.42272 | 0.0650* | |
Co14 | 1.00000 | 0.00000 | 1.00000 | 0.018 (3)* | |
Co15 | 1.00000 | 0.50000 | 0.50000 | 0.018 (3)* |
C1—C3 | 1.399 (18) | O12—C11 | 1.232 (10) |
C1—C10 | 1.427 (15) | O12—Co14 | 2.105 (9) |
C3—C1 | 1.399 (18) | O13—C11 | 1.272 (11) |
C3—C5 | 1.389 (7) | O16—H17 | 0.992 (13) |
C5—C3 | 1.389 (7) | O16—Co14ii | 2.098 (8) |
C5—C6 | 1.385 (8) | O16—Co14iii | 2.121 (8) |
C5—C11 | 1.503 (8) | O16—Co15 | 2.028 (8) |
C6—C5 | 1.385 (8) | H17—O16 | 0.992 (13) |
C6—C8 | 1.41 (3) | Co14—O12 | 2.105 (9) |
C8—C6 | 1.41 (3) | Co14—O12iv | 2.105 (9) |
C8—C10 | 1.447 (15) | Co14—O16v | 2.121 (8) |
C10—C1 | 1.427 (15) | Co14—O16vi | 2.098 (8) |
C10—C8 | 1.447 (15) | Co14—O16vii | 2.098 (8) |
C10—C10i | 1.489 (5) | Co14—O16viii | 2.121 (8) |
C11—C5 | 1.503 (8) | Co15—O16 | 2.028 (8) |
C11—O12 | 1.232 (10) | Co15—O16viii | 2.028 (8) |
C11—O13 | 1.272 (11) | ||
C3—C1—C10 | 121.0 (6) | C1—C10—C8 | 116.0 (9) |
C1—C3—C5 | 121.4 (5) | C1—C10—C10i | 114 (5) |
C3—C5—C6 | 119.5 (5) | C8—C10—C10i | 124 (6) |
C3—C5—C11 | 119.9 (5) | C5—C11—O12 | 117.3 (8) |
C6—C5—C11 | 120.5 (6) | C5—C11—O13 | 117.1 (8) |
C5—C6—C8 | 120.5 (9) | O12—C11—O13 | 123.6 (10) |
C6—C8—C10 | 120.9 (10) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y+1, z; (iii) x, y+1, z−1; (iv) −x+2, −y, −z+2; (v) x, y−1, z+1; (vi) x, y−1, z; (vii) −x+2, −y+1, −z+2; (viii) −x+2, −y+1, −z+1. |
C14H10Co2O6 | α = 91.80° |
Mr = 392.09 | β = 99.44° |
Triclinic, P1 | γ = 89.98° |
a = 14.20000 Å | V = 302.23 Å3 |
b = 6.23720 Å | Z = 1 |
c = 3.46100 Å |
x | y | z | Biso*/Beq | ||
C1 | 0.61569 | 0.62016 | 0.89476 | ||
C3 | 0.70973 | 0.56535 | 0.88026 | ||
C5 | 0.74057 | 0.35498 | 0.94939 | ||
C6 | 0.67601 | 0.20338 | 1.04253 | ||
C8 | 0.58279 | 0.26043 | 1.06503 | ||
C10 | 0.54978 | 0.47000 | 0.98891 | ||
C11 | 0.84012 | 0.29062 | 0.92724 | ||
O12 | 0.85873 | 0.09206 | 0.91494 | ||
O13 | 0.90299 | 0.44077 | 0.92824 | ||
H2 | 0.59361 | 0.78413 | 0.83081 | ||
H4 | 0.76000 | 0.68483 | 0.81104 | ||
H7 | 0.70119 | 0.04101 | 1.10392 | ||
H9 | 0.53543 | 0.13971 | 1.15004 | ||
O16 | 0.95981 | −0.19591 | 0.47462 | ||
H17 | 0.89031 | −0.18943 | 0.42272 | ||
Co14 | 1.00000 | 0.00000 | 1.00000 | ||
Co15 | 1.00000 | 0.50000 | 0.50000 |
[Ni(C14H8O4)0.5(OH)] | β = 72.3 (8)° |
Mr = 391.63 | γ = 82 (2)° |
Triclinic, P1 | V = 345 (2) Å3 |
Hall symbol: -P 1 | Z = 1 |
a = 15.0 (11) Å | Dx = 1.883 Mg m−3 |
b = 6.04 (12) Å | Kα1,2 radiation, λ = 1.54059, 1.54445 Å |
c = 4.04 (9) Å | T = 300 K |
α = 82.7 (2)° | flat_sheet, 16 × 16 mm |
PANalytical X'Pert diffractometer | Scan method: step |
Specimen mounting: Si zero-background cell with well | 2θmin = 4.008°, 2θmax = 99.998°, 2θstep = 0.017° |
Data collection mode: reflection |
Least-squares matrix: full | 47 parameters |
Rp = 0.042 | 30 restraints |
Rwp = 0.059 | H-atom parameters not defined? |
Rexp = 0.011 | (Δ/σ)max = 4.433 |
R(F2) = 0.09176 | Background function: Background function: "chebyschev-1" function with 6 terms: 6.12(5)e3, -3.68(4)e3, 8.6(4)e2, 83(31), -134(21), 50(21), |
5745 data points | Preferred orientation correction: March-Dollase correction coef. = 1.000 axis = [0, 0, 1] |
Profile function: Finger-Cox-Jephcoat function parameters U, V, W, X, Y, SH/L: peak variance(Gauss) = Utan(Th)2+Vtan(Th)+W: peak HW(Lorentz) = X/cos(Th)+Ytan(Th); SH/L = S/L+H/L U, V, W in (centideg)2, X & Y in centideg 5.186, -8.449, 5.755, 3.463, 0.000, 0.021, |
x | y | z | Uiso*/Ueq | ||
C1 | 0.620 (3) | 0.56 (4) | −0.23 (3) | 0.02 (4)* | |
C3 | 0.707 (2) | 0.51 (2) | −0.21 (3) | 0.02 (4)* | |
C5 | 0.7272 (18) | 0.38 (2) | 0.07 (2) | 0.02 (4)* | |
C6 | 0.653 (4) | 0.30 (3) | 0.34 (3) | 0.02 (4)* | |
C8 | 0.568 (2) | 0.322 (18) | 0.32 (2) | 0.02 (4)* | |
C10 | 0.546 (3) | 0.46 (3) | 0.02 (4) | 0.02 (4)* | |
C11 | 0.8370 (16) | 0.350 (15) | 0.074 (19) | 0.2200* | |
O12 | 0.873 (4) | 0.147 (19) | 0.13 (5) | 0.2200* | |
O13 | 0.897 (4) | 0.50 (2) | −0.066 (13) | 0.2200* | |
H2 | 0.60369 | 0.68368 | −0.44499 | 0.0500* | |
H4 | 0.76708 | 0.58056 | −0.43809 | 0.0500* | |
H7 | 0.66673 | 0.210111 | 0.58822 | 0.0500* | |
H9 | 0.51034 | 0.233993 | 0.52487 | 0.0500* | |
Ni14 | 1.00000 | 0.00000 | 0.00000 | 0.018 (14)* | |
O16 | 1.00 (2) | −0.179 (4) | 0.43 (2) | 0.1000* | |
H17 | 0.93829 | −0.17184 | 0.50234 | 0.1300* | |
Ni15 | 1.00000 | 0.50000 | −0.50000 | 0.018 (14)* |
C1—C3 | 1.31 (2) | C11—O13 | 1.311 (16) |
C1—C10 | 1.39 (3) | O12—C11 | 1.297 (10) |
C3—C1 | 1.31 (2) | O12—Ni14 | 1.942 (14) |
C3—C5 | 1.396 (9) | O13—C11 | 1.311 (16) |
C5—C3 | 1.396 (9) | O13—Ni15 | 1.953 (12) |
C5—C6 | 1.404 (16) | Ni14—O12 | 1.942 (14) |
C5—C11 | 1.642 (12) | Ni14—O12ii | 1.942 (14) |
C6—C5 | 1.404 (16) | Ni14—O16 | 1.927 (19) |
C6—C8 | 1.31 (2) | Ni14—O16ii | 1.927 (19) |
C8—C6 | 1.31 (2) | O16—Ni14 | 1.927 (19) |
C8—C10 | 1.46 (2) | O16—Ni15ii | 1.919 (13) |
C10—C1 | 1.39 (3) | Ni15—O13 | 1.953 (12) |
C10—C8 | 1.46 (2) | Ni15—O13iii | 1.953 (12) |
C10—C10i | 1.464 (8) | Ni15—O16iv | 1.919 (13) |
C11—C5 | 1.642 (12) | Ni15—O16ii | 1.919 (13) |
C11—O12 | 1.297 (10) | ||
C3—C1—C10 | 122 (2) | C1—C10—C8 | 117.5 (18) |
C1—C3—C5 | 120.8 (6) | C1—C10—C10i | 114 (5) |
C3—C5—C6 | 119.0 (9) | C8—C10—C10i | 128 (8) |
C5—C6—C8 | 120.9 (19) | O12—C11—O13 | 115.7 (12) |
C6—C8—C10 | 119.7 (8) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y, −z; (iii) −x+2, −y+1, −z−1; (iv) x, y+1, z−1. |
C14H10Ni2O6 | α = 81.57° |
Mr = 391.63 | β = 71.90° |
Triclinic, P1 | γ = 81.90° |
a = 15.10000 Å | V = 343.52 Å3 |
b = 6.05000 Å | Z = 1 |
c = 4.02000 Å |
x | y | z | Biso*/Beq | ||
C1 | 0.61147 | 0.63610 | −0.07671 | ||
C3 | 0.70313 | 0.58310 | −0.06941 | ||
C5 | 0.73667 | 0.36292 | 0.03127 | ||
C6 | 0.67329 | 0.19956 | 0.14026 | ||
C8 | 0.58130 | 0.25374 | 0.13082 | ||
C10 | 0.54811 | 0.47197 | 0.01398 | ||
C11 | 0.83907 | 0.31116 | −0.01437 | ||
O12 | 0.87153 | 0.11194 | 0.07915 | ||
O13 | 0.88625 | 0.47867 | −0.15724 | ||
H2 | 0.58988 | 0.80914 | −0.16146 | ||
H4 | 0.75109 | 0.71275 | −0.14925 | ||
H7 | 0.69710 | 0.02821 | 0.22559 | ||
H9 | 0.53478 | 0.12063 | 0.21394 | ||
Ni14 | 1.00000 | 0.00000 | 0.00000 | ||
O16 | 0.96416 | −0.18943 | 0.44560 | ||
H17 | 0.89673 | −0.16684 | 0.55127 | ||
Ni15 | 1.00000 | 0.50000 | −0.50000 |
C14H10Mn2O6 | α = 90.09° |
Triclinic, P1 | β = 96.84° |
a = 14.20370 Å | γ = 91.71° |
b = 6.47851 Å | V = 315.35 Å3 |
c = 3.45320 Å | Z = 2 |
x | y | z | Biso*/Beq | ||
C1 | 0.62098 | 0.61370 | 0.92029 | ||
H1 | 0.60389 | 0.77429 | 0.86234 | ||
C2 | 0.71402 | 0.55707 | 0.91323 | ||
H2 | 0.76792 | 0.67253 | 0.85491 | ||
C3 | 0.73912 | 0.35104 | 0.97430 | ||
C4 | 0.66914 | 0.20599 | 0.05646 | ||
H3 | 0.68946 | 0.04707 | 0.11422 | ||
C5 | 0.57681 | 0.26460 | 0.07216 | ||
H4 | 0.52506 | 0.14840 | 0.14642 | ||
C6 | 0.54945 | 0.46945 | 0.99724 | ||
C7 | 0.83666 | 0.28496 | 0.94908 | ||
O1 | 0.85281 | 0.09402 | 0.92904 | ||
O2 | 0.90327 | 0.42816 | 0.95195 | ||
Mn1 | 1.00000 | 0.00000 | 0.00000 | ||
Mn2 | 1.00000 | 0.50000 | −0.50000 | ||
O3 | 0.95566 | −0.19618 | 0.47885 | ||
H17 | 0.886619 | −0.19037 | 0.44315 |
2NH4+·C14H8O42− | β = 91.41 (4)° |
Mr = 276.29 | γ = 92.775 (11)° |
Triclinic, P1 | V = 351.43 (17) Å3 |
Hall symbol: P 1 | Z = 1 |
a = 4.6770 (6) Å | Dx = 1.306 Mg m−3 |
b = 5.2306 (14) Å | Kα1,2 radiation, λ = 0.70932, 0.71361 Å |
c = 14.387 (6) Å | T = 300 K |
α = 90.57 (7)° | cylinder, 12 × 0.7 mm |
PANalytical Empyrean diffractometer | Scan method: step |
Specimen mounting: glass capillary | 2θmin = 1.008°, 2θmax = 49.982°, 2θstep = 0.008° |
Data collection mode: transmission |
Least-squares matrix: full | 93 parameters |
Rp = 0.033 | 55 restraints |
Rwp = 0.043 | H-atom parameters not defined? |
Rexp = 0.015 | (Δ/σ)max = 0.723 |
R(F2) = 0.09394 | Background function: Background function: "chebyschev-1" function with 4 terms: 3149(17), -491(16), 99(12), -147(15), Background peak parameters: pos, int, sig, gam: 12.38(8), 1.18(6)e6, 1.20(8)e5, 0.100, |
5862 data points | Preferred orientation correction: Simple spherical harmonic correction Order = 4 Coefficients: 0:0:C(2,-2) = 0.79(3); 0:0:C(2,-1) = 0.32(7); 0:0:C(2,0) = 0.330(31); 0:0:C(2,1) = 1.58(9); 0:0:C(2,2) = 0.88(4); 0:0:C(4,-4) = 0.33(7); 0:0:C(4,-3) = 1.02(5); 0:0:C(4,-2) = 0.65(6); 0:0:C(4,-1) = -0.39(8); 0:0:C(4,0) = -0.79(4); 0:0:C(4,1) = -0.01(9); 0:0:C(4,2) = 1.10(6); 0:0:C(4,3) = 0.79(8); 0:0:C(4,4) = -0.31(7) |
Profile function: Finger-Cox-Jephcoat function parameters U, V, W, X, Y, SH/L: peak variance(Gauss) = Utan(Th)2+Vtan(Th)+W: peak HW(Lorentz) = X/cos(Th)+Ytan(Th); SH/L = S/L+H/L U, V, W in (centideg)2, X & Y in centideg 30.816, 10.768, 0.000, 1.935, 0.000, 0.033, |
x | y | z | Uiso*/Ueq | ||
H1 | 0.56271 | 0.55748 | −0.04903 | 0.0500* | |
C2 | 0.72650 | 0.71007 | −0.07277 | 0.0042* | |
C3 | 1.092 (10) | 1.091 (7) | −0.1369 (14) | 0.0042* | |
C4 | 0.886 (5) | 0.858 (4) | −0.0073 (7) | 0.0042* | |
C5 | 0.759 (8) | 0.741 (7) | −0.1644 (4) | 0.0042* | |
C6 | 0.942 (5) | 0.928 (5) | −0.1987 (9) | 0.0042* | |
C7 | 1.068 (8) | 1.055 (6) | −0.0421 (13) | 0.0042* | |
H8 | 0.63274 | 0.60998 | −0.21606 | 0.0500* | |
H9 | 1.19666 | 1.18586 | 0.00901 | 0.0500* | |
H10 | 1.23536 | 1.25494 | −0.16391 | 0.0500* | |
C11 | 0.935 (5) | 0.754 (5) | 0.0884 (8) | 0.0042* | |
C12 | 1.040 (7) | 0.578 (6) | 0.2730 (11) | 0.0042* | |
C13 | 0.788 (12) | 0.847 (10) | 0.1638 (15) | 0.0042* | |
C14 | 1.140 (8) | 0.571 (9) | 0.1072 (12) | 0.0042* | |
C15 | 1.197 (11) | 0.490 (10) | 0.1986 (15) | 0.0042* | |
C16 | 0.833 (10) | 0.754 (9) | 0.2538 (12) | 0.0042* | |
H17 | 0.62741 | 1.00179 | 0.15295 | 0.0500* | |
H18 | 1.26305 | 0.48583 | 0.04787 | 0.0500* | |
H19 | 1.37364 | 0.35094 | 0.21156 | 0.0500* | |
H20 | 0.69528 | 0.82586 | 0.31194 | 0.0500* | |
C21 | 1.076 (7) | 0.480 (7) | 0.3737 (13) | 0.0566* | |
C22 | 0.944 (5) | 0.962 (6) | −0.3033 (10) | 0.0566* | |
O23 | 0.840 (7) | 0.413 (8) | 0.4081 (17) | 0.0566* | |
O24 | 0.969 (10) | 0.758 (7) | −0.3508 (14) | 0.0566* | |
O25 | 1.309 (7) | 0.371 (8) | 0.4015 (16) | 0.0566* | |
O26 | 0.762 (7) | 1.119 (7) | −0.3310 (18) | 0.0566* | |
N27 | 0.34475 | 1.28836 | −0.39168 | 0.0500* | |
H29 | 0.36001 | 1.43931 | −0.43695 | 0.0500* | |
H30 | 0.22878 | 1.13756 | −0.42606 | 0.0500* | |
H31 | 0.54682 | 1.23237 | −0.37405 | 0.0500* | |
H32 | 0.24338 | 1.34422 | −0.33265 | 0.0500* | |
N28 | 0.88714 | 0.85588 | −0.47716 | 0.0500* | |
H33 | 0.85037 | 0.66062 | −0.48279 | 0.0500* | |
H34 | 0.69609 | 0.94431 | −0.48449 | 0.0500* | |
H35 | 1.02320 | 0.91738 | −0.52839 | 0.0500* | |
H36 | 0.97893 | 0.90122 | −0.41298 | 0.0500* |
C2—C4 | 1.392 (7) | C16—C13 | 1.402 (7) |
C2—C5 | 1.342 (6) | C21—C12 | 1.550 (7) |
C3—C6 | 1.379 (6) | C21—O23 | 1.258 (9) |
C3—C7 | 1.385 (6) | C21—O25 | 1.310 (9) |
C4—C2 | 1.392 (7) | C22—C6 | 1.518 (7) |
C4—C7 | 1.408 (7) | C22—O24 | 1.269 (9) |
C4—C11 | 1.501 (8) | C22—O26 | 1.272 (9) |
C5—C2 | 1.342 (6) | O23—C21 | 1.258 (9) |
C5—C6 | 1.373 (6) | O24—C22 | 1.269 (9) |
C6—C3 | 1.379 (6) | O25—C21 | 1.310 (9) |
C6—C5 | 1.373 (6) | O26—C22 | 1.272 (9) |
C6—C22 | 1.518 (7) | N27—H29 | 1.0294 |
C7—C3 | 1.385 (6) | N27—H30 | 1.0294 |
C7—C4 | 1.408 (7) | N27—H31 | 1.0295 |
C11—C4 | 1.501 (8) | N27—H32 | 1.0294 |
C11—C13 | 1.394 (8) | H29—N27 | 1.0294 |
C11—C14 | 1.410 (7) | H30—N27 | 1.0294 |
C12—C15 | 1.401 (6) | H31—N27 | 1.0295 |
C12—C16 | 1.390 (6) | H32—N27 | 1.0294 |
C12—C21 | 1.550 (7) | N28—H33 | 1.0295 |
C13—C11 | 1.394 (8) | N28—H34 | 1.0295 |
C13—C16 | 1.402 (7) | N28—H35 | 1.0294 |
C14—C11 | 1.410 (7) | N28—H36 | 1.0293 |
C14—C15 | 1.408 (6) | H33—N28 | 1.0295 |
C15—C12 | 1.401 (6) | H34—N28 | 1.0295 |
C15—C14 | 1.408 (6) | H35—N28 | 1.0294 |
C16—C12 | 1.390 (6) | H36—N28 | 1.0293 |
C4—C2—C5 | 121.9 (4) | C12—C16—C13 | 121.6 (3) |
C6—C3—C7 | 119.9 (3) | C12—C21—O23 | 111.9 (7) |
C2—C4—C7 | 116.5 (4) | C12—C21—O25 | 121.5 (7) |
C2—C4—C11 | 119.4 (6) | O23—C21—O25 | 119.6 (8) |
C7—C4—C11 | 120.9 (6) | C6—C22—O24 | 115.6 (7) |
C2—C5—C6 | 121.7 (3) | C6—C22—O26 | 112.0 (7) |
C3—C6—C5 | 118.8 (4) | O24—C22—O26 | 118.2 (8) |
C3—C6—C22 | 123.5 (5) | H29—N27—H30 | 109.483 |
C5—C6—C22 | 117.4 (5) | H29—N27—H31 | 109.476 |
C3—C7—C4 | 121.0 (4) | H30—N27—H31 | 109.464 |
C4—C11—C13 | 120.6 (5) | H29—N27—H32 | 109.459 |
C4—C11—C14 | 122.2 (5) | H30—N27—H32 | 109.468 |
C13—C11—C14 | 117.1 (4) | H31—N27—H32 | 109.477 |
C15—C12—C16 | 117.7 (3) | H33—N28—H34 | 109.48 |
C15—C12—C21 | 123.1 (4) | H33—N28—H35 | 109.471 |
C16—C12—C21 | 119.1 (4) | H34—N28—H35 | 109.47 |
C11—C13—C16 | 121.4 (6) | H33—N28—H36 | 109.475 |
C11—C14—C15 | 121.2 (4) | H34—N28—H36 | 109.469 |
C12—C15—C14 | 120.8 (4) | H35—N28—H36 | 109.461 |
C14H16N2O4 | α = 90.7300° |
Mr = 276.29 | β = 91.3790° |
Triclinic, P1 | γ = 92.7400° |
a = 4.6875 Å | V = 352.86 Å3 |
b = 5.2421 Å | Z = 1 |
c = 14.3820 Å |
x | y | z | Uiso*/Ueq | ||
H1 | 0.59450 | 0.55016 | −0.04709 | 0.0500* | |
C2 | 0.72650 | 0.71007 | −0.07277 | 0.0042* | |
C3 | 1.06402 | 1.11446 | −0.14004 | 0.0042* | |
C4 | 0.92175 | 0.84164 | −0.01188 | 0.0042* | |
C5 | 0.69564 | 0.78221 | −0.16536 | 0.0042* | |
C6 | 0.86113 | 0.98774 | −0.19952 | 0.0042* | |
C7 | 1.09298 | 1.04187 | −0.04764 | 0.0042* | |
H8 | 0.54136 | 0.67676 | −0.21098 | 0.0500* | |
H9 | 1.25407 | 1.13999 | −0.00242 | 0.0500* | |
H10 | 1.20239 | 1.26916 | −0.16643 | 0.0500* | |
C11 | 0.93949 | 0.77658 | 0.08868 | 0.0042* | |
C12 | 0.94951 | 0.64759 | 0.27910 | 0.0042* | |
C13 | 0.78111 | 0.91048 | 0.15313 | 0.0042* | |
C14 | 1.10777 | 0.58142 | 0.12166 | 0.0042* | |
C15 | 1.11387 | 0.51792 | 0.21543 | 0.0042* | |
C16 | 0.78458 | 0.84572 | 0.24662 | 0.0042* | |
H17 | 0.65053 | 1.06440 | 0.12910 | 0.0500* | |
H18 | 1.23568 | 0.47852 | 0.07278 | 0.0500* | |
H19 | 1.24343 | 0.36444 | 0.24034 | 0.0500* | |
H20 | 0.65294 | 0.94638 | 0.29501 | 0.0500* | |
C21 | 0.93857 | 0.56900 | 0.37898 | 0.0566* | |
C22 | 0.83362 | 1.07341 | −0.29872 | 0.0566* | |
O23 | 0.76266 | 0.66899 | 0.43252 | 0.0566* | |
O24 | 0.99747 | 0.98318 | −0.35852 | 0.0566* | |
O25 | 1.09802 | 0.39029 | 0.40741 | 0.0566* | |
O26 | 0.65872 | 1.24648 | −0.31870 | 0.0566* | |
N27 | 0.16243 | 0.51693 | 0.60441 | 0.0400* | |
H29 | 0.16090 | 0.49359 | 0.53198 | 0.0500* | |
H30 | 0.33993 | 0.43870 | 0.63488 | 0.0500* | |
H31 | 0.13695 | 0.71068 | 0.62373 | 0.0500* | |
H32 | −0.01991 | 0.41734 | 0.62701 | 0.0500* | |
N28 | 0.59171 | 0.12978 | 0.47646 | 0.0400* | |
H33 | 0.62253 | −0.06146 | 0.45540 | 0.0500* | |
H34 | 0.58472 | 0.14431 | 0.54856 | 0.0500* | |
H35 | 0.41516 | 0.20817 | 0.44485 | 0.0500* | |
H36 | 0.77650 | 0.23333 | 0.45705 | 0.0500* |
D—H···A | D—H | H···A | D···A | D—H···A |
N27—H29···O25i | 1.05 | 1.88 | 2.907 | 167 |
N27—H30···O26ii | 1.04 | 1.95 | 2.979 | 172 |
N27—H31···O24iii | 1.06 | 1.62 | 2.650 | 162 |
N27—H32···O26iv | 1.04 | 1.90 | 2.942 | 174 |
N28—H33···O23v | 1.06 | 1.62 | 2.655 | 164 |
N28—H34···O26ii | 1.04 | 2.00 | 3.007 | 164 |
N28—H35···O25i | 1.04 | 1.88 | 2.904 | 169 |
N28—H36···O25 | 1.05 | 1.85 | 2.885 | 172 |
Symmetry codes: (i) x−1, y, z; (ii) x, y−1, z+1; (iii) x−1, y, z+1; (iv) x−1, y−1, z+1; (v) x, y−1, z. |
Acknowledgements
We thank Professors Paul F. Brandt and Jeffrey A. Bjorklund for guidance and helpful discussions.
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