research communications
trans-(1,8-dibutyl-1,3,6,8,10,13-hexaazacyclotetradecane-κ4N3,N6,N10,N13)bis(isonicotinato-κO)nickel(II) determined from synchrotron data
ofaBeamline Department, Pohang Accelerator Laboratory 80, Jigokro-127-beongil, Nam-Gu Pohang, Gyeongbuk 37673, Republic of Korea
*Correspondence e-mail: dmoon@postech.ac.kr
The title compound, [Ni(C6H4NO2)2(C16H38N6)], was prepared through self-assembly of a nickel(II) azamacrocyclic complex with isonicotinic acid. The NiII atom is located on an inversion center and exhibits a distorted octahedral N4O2 coordination environment, with the four secondary N atoms of the azamacrocyclic ligand in the equatorial plane [average Ni—Neq = 2.064 (11) Å] and two O atoms of monodentate isonicotinate anions in axial positions [Ni—Oax = 2.137 (1) Å]. Intramolecular N—H⋯O hydrogen bonds between one of the secondary amine N atoms of the azamacrocyclic ligand and the non-coordinating carboxylate O atom of the anion stabilize the molecular structure. Intermolecular N—H⋯N hydrogen bonds, as well as π–π interactions between neighbouring pyridine rings, give rise to the formations of supramolecular ribbons extending parallel to [001].
Keywords: crystal structure; azamacrocyclic ligand; isonicotinic acid; π–π interactions; synchrotron data.
CCDC reference: 1447865
1. Chemical context
The molecular design and synthesis of coordination polymers with macrocyclic ligands have attracted considerable attention because of their potential applications in chemistry, environmental chemistry, and materials science (Churchard et al., 2010; Lehn, 2015). To obtain specific molecular compounds through assembly of supramolecular building blocks with properties such as guest recognition or catalytic effects, macrocyclic complexes involving vacant sites in an axial position are good candidates. Moreover, these complexes can also be easily derivatized by carboxylic acid moieties, such as 1,3,5-BTC (1,3,5-benzenetricarboxylic acid), 2,7-NDC (2,7-naphthalenedicarboxylic acid) or 1,3,5-CTC (1,3,5-cyclohexanetricarboxylic acid), forming interesting coordination compounds with supramolecular structures ranging from chains to networks (Min & Suh, 2001; Shin et al., 2016b). For example, [Ni(LR,R)]3[BTC3–]2·12H2O·CH3CN (LR,R = 1,8-bis[(R)-α-methylbenzyl]-1,3,6,8,10,13-hexaazacyclotetradecane) displays a two-dimensional supramolecular network structure and exhibits a selective chiral recognition for racemic material (Ryoo et al., 2010). Isonicotinic acid as another building unit can easily bind or interact with transition metal ions through its possible bridging or coordination modes associated with the carboxylic group and pyridine moieties, respectively, thus allowing the assembly of compounds with supramolecular structures or the formation of heterometallic complexes (Xie et al., 2014).
Here, we report on the synthesis and II azamacrocyclic complex including isonicotinate anions, [Ni(C6H4NO2)2(C16H38N6)], (I).
of an Ni2. Structural commentary
Compound (I) is isotypic with its copper(II) analogue (Shin et al., 2015). The nickel(II) atom is located on an inversion center. The coordination environment around the nickel(II) atom is distorted octahedral with the four secondary amine N atoms of the azamacrocyclic ligand in the equatorial plane and two O atoms of two monodentate isonicotinate anions in axial positions (Fig. 1). The average Ni—Neq bond lengths is 2.064 (11) Å and the Ni—Oax bond length is 2.137 (1) Å. The longer axial bonds can be attributed to a ring contraction of the azamacrocyclic ligand (Melson, 1979). The six-membered NiC2N3 ring (Ni1–N1–C2–N3–C3–N2) adopts the expected chair conformation, whereas the five-membered NiC2N2 ring (Ni1–N1–C1–C4–N2) has a gauche conformation (Min & Suh, 2001). Since the carboxylate group is fully delocalized, the two C—O bonds and the bond angle (O1—C9—O2) are 1.267 (2), 1.248 (2) Å and 126.9 (2)°, respectively. The bond angles around the nickel(II) atom are in the normal range for an octahedral complex. Intramolecular N—H⋯O hydrogen bonds between one of the secondary amine groups of the azamacrocyclic ligand and the non-coordinating carboxylate O atom of the isonicotinate anion form six-membered rings and stabilize the molecular structure (Fig. 1, Table 1).
3. Supramolecular features
The N4 atom of the isonicotinate anion forms an intermolecular hydrogen bond with an adjacent secondary amine group of the azamacrocyclic ligand (Fig. 2, Table 1) (Steed & Atwood, 2009). In addition, parallel pyridine rings (Hunter & Sanders, 1990) of the isonicotinate anions participate in π–π interactions with a centroid-to-centroid distance of 3.741 (1) Å and an interplanar separation of 3.547 (1) Å. The interplay between hydrogen bonds and π–π interactions give rise to the formation of supramolecular ribbons extending parallel to [001].
4. Database survey
A search of the Cambridge Structural Database (Version 5.36, May 2014 with 3 updates; Groom & Allen, 2014) reveals two complexes with the same nickel(II) azamacrocyclic building block (Kim et al., 2015a,b) for which synthesis, FT–IR spectroscopic data and the have been reported.
5. Synthesis and crystallization
The starting complex, [Ni(C16H38N6)(ClO4)2], was prepared in a slightly modified procedure with respect to the reported method (Kim et al., 2015b). To an acetonitrile solution (14 mL) of [Ni(C16H38N6)(ClO4)2] (0.298 g, 0.52 mmol) was slowly added an acetonitrile solution (8 mL) containing isonicotinic acid (0.128 g, 1.04 mmol) and excess triethylamine (0.12 g, 1.20 mmol) at room temperature. The purple precipitate was filtered off, washed with acetonitrile and diethyl ether, and dried in air. Single crystals of compound (l) were obtained by layering of the acetonitrile solution of isonicotinic acid on the acetonitrile solution of [Ni(C16H38N6)(ClO4)2] for several days. Yield: 0.167 g (52%). FT–IR (ATR, cm−1): 3145, 3075, 2951, 2920, 1571, 1457, 1351, 1272, 1014, 915.
Safety note: Although we have experienced no problems with the compounds reported in this study, perchlorate salts of metal complexes are often explosive and should be handled with great caution.
6. Refinement
Crystal data, data collection and structure . All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (ring H atoms) or 0.98–0.99 Å (open-chain H atoms), and an N—H distance of 1.0 Å, with Uiso(H) values of 1.2 or 1.5Ueq of the parent atoms.
details are summarized in Table 2Supporting information
CCDC reference: 1447865
10.1107/S2056989016001031/wm5263sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989016001031/wm5263Isup2.hkl
The α-methylbenzyl]-1,3,6,8,10,13-hexaazacyclotetradecane) displays a two-dimensional supramolecular network structure and exhibits a selective chiral recognition for racemic material (Ryoo et al., 2010). Isonicotinic acid as another building unit can easily bind or interact with transition metal ions through its possible bridging or coordination modes associated with the carboxylic group and pyridine moieties, respectively, thus allowing the assembly of compounds with supramolecular structures or the formation of heterometallic complexes (Xie et al., 2014).
and synthesis of coordination polymers with macrocyclic ligands have attracted considerable attention because of their potential applications in chemistry, environmental chemistry, and materials science (Churchard et al., 2010; Lehn, 2015). To obtain specific molecular compounds through assembly of supramolecular building blocks with properties such as guest recognition or catalytic effects, macrocyclic complexes involving vacant sites in an axial position are good candidates. Moreover, these complexes can also be easily derivatized by carboxylic acid moieties, such as 1,3,5-BTC (1,3,5-benzenetricarboxylic acid), 2,7-NDC (2,7-naphthalenedicarboxylic acid) or 1,3,5-CTC (1,3,5-cyclohexanetricarboxylic acid), forming interesting coordination compounds with supramolecular structures ranging from chains to networks (Min & Suh, 2001; Shin et al., 2016b). For example, [Ni(LR,R)]3[BTC3–]2·12H2O·CH3CN (LR,R = 1,8-bis[(R)-Here, we report on the synthesis and
of an NiII azamacrocyclic complex including isonicotinate anions, [Ni(C6H4NO2)2(C16H38N6)], (I).Compound (I) is isotypic with its copper(II) analogue (Shin et al., 2015). The nickel(II) atom is located on an inversion centre. The coordination environment around the nickel(II) atom is distorted octahedral with the four secondary amine N atoms of the azamacrocyclic ligand in the equatorial plane and two O atoms of two monodentate isonicotinate anions in axial positions (Fig. 1). The average Ni—Neq bond lengths is 2.064 (11) Å and the Ni—Oax bond length is 2.137 (1) Å. The longer axial bonds can be attributed to a ring contraction of the azamacrocyclic ligand (Melson, 1979). The six-membered NiC2N3 ring (Ni1–N1–C2–N3–C3–N2) adopts the expected chair conformation, whereas the five-membered NiC2N2 ring (Ni1–N1–C1–C4–N2) has a
conformation (Min & Suh, 2001). Since the carboxylate group is fully delocalized, the two C—O bonds and the bond angle (O1—C9—O2) are 1.267 (2), 1.248 (2) Å and 126.9 (2)°, respectively. The bond angles around the nickel(II) atom are in the normal range for an octahedral complex. Intramolecular N—H···O hydrogen bonds between one of the secondary amine groups of the azamacrocyclic ligand and the non-coordinating carboxylate O atom of the isonicotinate anion form six-membered rings and stabilize the molecular structure (Fig. 1, Table 1).The N4 atom of the isonicotinate anion forms an intermolecular hydrogen bond with an adjacent secondary amine group of the azamacrocyclic ligand (Fig. 2, Table 1) (Steed & Atwood, 2009). In addition, parallel pyridine rings (Hunter & Sanders, 1990) of the isonicotinate anions participate in π–π interactions with a centroid-to-centroid distance of 3.741 (1) Å and an interplanar separation of 3.547 (1) Å. The interplay between hydrogen bonds and π—π interactions give rise to the formation of supramolecular ribbons extending parallel to [001].
A search of the Cambridge Structural Database (Version 5.36, May 2014 with 3 updates; Groom & Allen, 2014) reveals two complexes with the same nickel(II) azamacrocyclic building block (Kim et al., 2015a,b) for which synthesis, FT–IR spectroscopic data and the
have been reported.The starting complex, [Ni(C16H38N6)(ClO4)2], was prepared in a slightly modified procedure with respect to the reported method (Kim et al., 2015b). To an acetonitrile solution (14 ml) of [Ni(C16H38N6)(ClO4)2] (0.298 g, 0.52 mmol) was slowly added an acetonitrile solution (8 ml) containing isonicotinic acid (0.128 g, 1.04 mmol) and excess triethylamine (0.12 g, 1.20 mmol) at room temperature. The purple precipitate was filtered off, washed with acetonitrile and diethyl ether, and dried in air. Single crystals of compound (I) were obtained by layering of the acetonitrile solution of isonicotinic acid on the acetonitrile solution of [Ni(C16H38N6)(ClO4)2] for several days. Yield: 0.167 g (52%). FT–IR (ATR, cm−1): 3145, 3075, 2951, 2920, 1571, 1457, 1351, 1272, 1014, 915.
Safety note: Although we have experienced no problems with the compounds reported in this study, perchlorate salts of metal complexes are often explosive and should be handled with great caution.
Crystal data, data collection and structure
details are summarized in Table 2. A l l H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (ring H atoms) or 0.98–0.99 Å (open-chain H atoms), and an N—H distance of 1.0 Å, with Uiso(H) values of 1.2 or 1.5Ueq of the parent atoms.The α-methylbenzyl]-1,3,6,8,10,13-hexaazacyclotetradecane) displays a two-dimensional supramolecular network structure and exhibits a selective chiral recognition for racemic material (Ryoo et al., 2010). Isonicotinic acid as another building unit can easily bind or interact with transition metal ions through its possible bridging or coordination modes associated with the carboxylic group and pyridine moieties, respectively, thus allowing the assembly of compounds with supramolecular structures or the formation of heterometallic complexes (Xie et al., 2014).
and synthesis of coordination polymers with macrocyclic ligands have attracted considerable attention because of their potential applications in chemistry, environmental chemistry, and materials science (Churchard et al., 2010; Lehn, 2015). To obtain specific molecular compounds through assembly of supramolecular building blocks with properties such as guest recognition or catalytic effects, macrocyclic complexes involving vacant sites in an axial position are good candidates. Moreover, these complexes can also be easily derivatized by carboxylic acid moieties, such as 1,3,5-BTC (1,3,5-benzenetricarboxylic acid), 2,7-NDC (2,7-naphthalenedicarboxylic acid) or 1,3,5-CTC (1,3,5-cyclohexanetricarboxylic acid), forming interesting coordination compounds with supramolecular structures ranging from chains to networks (Min & Suh, 2001; Shin et al., 2016b). For example, [Ni(LR,R)]3[BTC3–]2·12H2O·CH3CN (LR,R = 1,8-bis[(R)-Here, we report on the synthesis and
of an NiII azamacrocyclic complex including isonicotinate anions, [Ni(C6H4NO2)2(C16H38N6)], (I).Compound (I) is isotypic with its copper(II) analogue (Shin et al., 2015). The nickel(II) atom is located on an inversion centre. The coordination environment around the nickel(II) atom is distorted octahedral with the four secondary amine N atoms of the azamacrocyclic ligand in the equatorial plane and two O atoms of two monodentate isonicotinate anions in axial positions (Fig. 1). The average Ni—Neq bond lengths is 2.064 (11) Å and the Ni—Oax bond length is 2.137 (1) Å. The longer axial bonds can be attributed to a ring contraction of the azamacrocyclic ligand (Melson, 1979). The six-membered NiC2N3 ring (Ni1–N1–C2–N3–C3–N2) adopts the expected chair conformation, whereas the five-membered NiC2N2 ring (Ni1–N1–C1–C4–N2) has a
conformation (Min & Suh, 2001). Since the carboxylate group is fully delocalized, the two C—O bonds and the bond angle (O1—C9—O2) are 1.267 (2), 1.248 (2) Å and 126.9 (2)°, respectively. The bond angles around the nickel(II) atom are in the normal range for an octahedral complex. Intramolecular N—H···O hydrogen bonds between one of the secondary amine groups of the azamacrocyclic ligand and the non-coordinating carboxylate O atom of the isonicotinate anion form six-membered rings and stabilize the molecular structure (Fig. 1, Table 1).The N4 atom of the isonicotinate anion forms an intermolecular hydrogen bond with an adjacent secondary amine group of the azamacrocyclic ligand (Fig. 2, Table 1) (Steed & Atwood, 2009). In addition, parallel pyridine rings (Hunter & Sanders, 1990) of the isonicotinate anions participate in π–π interactions with a centroid-to-centroid distance of 3.741 (1) Å and an interplanar separation of 3.547 (1) Å. The interplay between hydrogen bonds and π—π interactions give rise to the formation of supramolecular ribbons extending parallel to [001].
A search of the Cambridge Structural Database (Version 5.36, May 2014 with 3 updates; Groom & Allen, 2014) reveals two complexes with the same nickel(II) azamacrocyclic building block (Kim et al., 2015a,b) for which synthesis, FT–IR spectroscopic data and the
have been reported.The starting complex, [Ni(C16H38N6)(ClO4)2], was prepared in a slightly modified procedure with respect to the reported method (Kim et al., 2015b). To an acetonitrile solution (14 ml) of [Ni(C16H38N6)(ClO4)2] (0.298 g, 0.52 mmol) was slowly added an acetonitrile solution (8 ml) containing isonicotinic acid (0.128 g, 1.04 mmol) and excess triethylamine (0.12 g, 1.20 mmol) at room temperature. The purple precipitate was filtered off, washed with acetonitrile and diethyl ether, and dried in air. Single crystals of compound (I) were obtained by layering of the acetonitrile solution of isonicotinic acid on the acetonitrile solution of [Ni(C16H38N6)(ClO4)2] for several days. Yield: 0.167 g (52%). FT–IR (ATR, cm−1): 3145, 3075, 2951, 2920, 1571, 1457, 1351, 1272, 1014, 915.
Safety note: Although we have experienced no problems with the compounds reported in this study, perchlorate salts of metal complexes are often explosive and should be handled with great caution.
detailsCrystal data, data collection and structure
details are summarized in Table 2. A l l H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (ring H atoms) or 0.98–0.99 Å (open-chain H atoms), and an N—H distance of 1.0 Å, with Uiso(H) values of 1.2 or 1.5Ueq of the parent atoms.Data collection: PAL BL2D-SMDC (Shin et al., 2016a); cell
HKL-3000SM (Otwinowski & Minor, 1997); data reduction: HKL-3000SM (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. View of the molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 30% probability level. H atoms bonded to C atoms have been omitted for clarity. Intramolecular N—H···O hydrogen bonds are shown as red dashed lines. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.] | |
Fig. 2. View of the crystal packing of the title compound, showing hydrogen bonds and π–π interactions (red: intramolecular N—H···O hydrogen bonds, green: intermolecular N—H···N hydrogen bonds, black: π–π interactions). |
[Ni(C6H4NO2)2(C16H38N6)] | Z = 1 |
Mr = 617.44 | F(000) = 330 |
Triclinic, P1 | Dx = 1.389 Mg m−3 |
a = 8.0630 (16) Å | Synchrotron radiation, λ = 0.62998 Å |
b = 8.5110 (17) Å | Cell parameters from 20128 reflections |
c = 10.927 (2) Å | θ = 0.4–33.6° |
α = 80.52 (3)° | µ = 0.51 mm−1 |
β = 88.26 (3)° | T = 100 K |
γ = 86.44 (3)° | Needle, pale pink |
V = 738.0 (3) Å3 | 0.01 × 0.004 × 0.004 mm |
ADSC Q210 CCD area-detector diffractometer | 3326 reflections with I > 2σ(I) |
Radiation source: PLSII 2D bending magnet | Rint = 0.023 |
ω scan | θmax = 26.0°, θmin = 2.5° |
Absorption correction: empirical (using intensity measurements) (HKL-3000SM SCALEPACK; Otwinowski & Minor, 1997) | h = −11→11 |
Tmin = 0.995, Tmax = 0.998 | k = −11→11 |
7634 measured reflections | l = −15→15 |
3879 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0649P)2 + 0.1918P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3879 reflections | Δρmax = 1.12 e Å−3 |
188 parameters | Δρmin = −0.95 e Å−3 |
[Ni(C6H4NO2)2(C16H38N6)] | γ = 86.44 (3)° |
Mr = 617.44 | V = 738.0 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.0630 (16) Å | Synchrotron radiation, λ = 0.62998 Å |
b = 8.5110 (17) Å | µ = 0.51 mm−1 |
c = 10.927 (2) Å | T = 100 K |
α = 80.52 (3)° | 0.01 × 0.004 × 0.004 mm |
β = 88.26 (3)° |
ADSC Q210 CCD area-detector diffractometer | 3879 independent reflections |
Absorption correction: empirical (using intensity measurements) (HKL-3000SM SCALEPACK; Otwinowski & Minor, 1997) | 3326 reflections with I > 2σ(I) |
Tmin = 0.995, Tmax = 0.998 | Rint = 0.023 |
7634 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.110 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.12 e Å−3 |
3879 reflections | Δρmin = −0.95 e Å−3 |
188 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.5000 | 0.5000 | 0.5000 | 0.02066 (10) | |
O1 | 0.43513 (15) | 0.41029 (17) | 0.33736 (11) | 0.0257 (3) | |
O2 | 0.18613 (16) | 0.52908 (19) | 0.28022 (12) | 0.0322 (3) | |
N1 | 0.27809 (18) | 0.6311 (2) | 0.50735 (13) | 0.0244 (3) | |
H1 | 0.2171 | 0.6276 | 0.4296 | 0.029* | |
N2 | 0.61452 (18) | 0.67953 (19) | 0.38249 (13) | 0.0241 (3) | |
H2 | 0.5798 | 0.6766 | 0.2959 | 0.029* | |
N3 | 0.3946 (2) | 0.8835 (2) | 0.41256 (14) | 0.0304 (3) | |
N4 | 0.3686 (2) | 0.2837 (2) | −0.09149 (14) | 0.0335 (4) | |
C1 | 0.1835 (2) | 0.5457 (3) | 0.61221 (15) | 0.0276 (4) | |
H1A | 0.0642 | 0.5807 | 0.6057 | 0.033* | |
H1B | 0.2242 | 0.5692 | 0.6915 | 0.033* | |
C2 | 0.3004 (2) | 0.8006 (2) | 0.51521 (16) | 0.0296 (4) | |
H2A | 0.1895 | 0.8566 | 0.5192 | 0.036* | |
H2B | 0.3574 | 0.8058 | 0.5933 | 0.036* | |
C3 | 0.5703 (2) | 0.8414 (2) | 0.41070 (18) | 0.0308 (4) | |
H3A | 0.6153 | 0.8493 | 0.4926 | 0.037* | |
H3B | 0.6249 | 0.9202 | 0.3480 | 0.037* | |
C4 | 0.7938 (2) | 0.6330 (3) | 0.39084 (16) | 0.0280 (4) | |
H4A | 0.8376 | 0.6572 | 0.4689 | 0.034* | |
H4B | 0.8552 | 0.6932 | 0.3203 | 0.034* | |
C5 | 0.3160 (2) | 0.9034 (2) | 0.29077 (17) | 0.0310 (4) | |
H5A | 0.2983 | 0.7968 | 0.2700 | 0.037* | |
H5B | 0.3922 | 0.9575 | 0.2269 | 0.037* | |
C6 | 0.1502 (3) | 0.9999 (3) | 0.28701 (18) | 0.0341 (4) | |
H6A | 0.0727 | 0.9447 | 0.3493 | 0.041* | |
H6B | 0.1671 | 1.1058 | 0.3093 | 0.041* | |
C7 | 0.0730 (3) | 1.0223 (3) | 0.15954 (19) | 0.0390 (5) | |
H7A | 0.1527 | 1.0726 | 0.0966 | 0.047* | |
H7B | 0.0507 | 0.9166 | 0.1390 | 0.047* | |
C8 | −0.0882 (3) | 1.1257 (4) | 0.1543 (2) | 0.0502 (6) | |
H8A | −0.1692 | 1.0739 | 0.2140 | 0.075* | |
H8B | −0.1328 | 1.1395 | 0.0705 | 0.075* | |
H8C | −0.0667 | 1.2302 | 0.1750 | 0.075* | |
C9 | 0.3163 (2) | 0.4477 (2) | 0.26295 (15) | 0.0235 (3) | |
C10 | 0.4760 (2) | 0.2978 (3) | 0.10910 (16) | 0.0294 (4) | |
H10 | 0.5631 | 0.2691 | 0.1666 | 0.035* | |
C11 | 0.3367 (2) | 0.3884 (2) | 0.13963 (14) | 0.0234 (3) | |
C12 | 0.2134 (2) | 0.4252 (3) | 0.05120 (16) | 0.0300 (4) | |
H12 | 0.1158 | 0.4874 | 0.0676 | 0.036* | |
C13 | 0.2347 (2) | 0.3703 (3) | −0.06044 (17) | 0.0339 (4) | |
H13 | 0.1486 | 0.3957 | −0.1191 | 0.041* | |
C14 | 0.4868 (2) | 0.2496 (3) | −0.00601 (17) | 0.0340 (4) | |
H14 | 0.5838 | 0.1887 | −0.0256 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01767 (15) | 0.03464 (19) | 0.00987 (14) | 0.00142 (11) | −0.00201 (9) | −0.00504 (11) |
O1 | 0.0246 (6) | 0.0412 (7) | 0.0122 (5) | 0.0012 (5) | −0.0054 (4) | −0.0073 (5) |
O2 | 0.0235 (6) | 0.0543 (9) | 0.0207 (6) | 0.0047 (6) | −0.0043 (5) | −0.0139 (6) |
N1 | 0.0225 (7) | 0.0384 (8) | 0.0122 (6) | 0.0027 (6) | −0.0022 (5) | −0.0048 (6) |
N2 | 0.0227 (7) | 0.0355 (8) | 0.0142 (6) | 0.0007 (6) | −0.0016 (5) | −0.0049 (6) |
N3 | 0.0338 (8) | 0.0354 (9) | 0.0209 (7) | 0.0055 (7) | −0.0018 (6) | −0.0041 (7) |
N4 | 0.0344 (8) | 0.0525 (11) | 0.0148 (6) | 0.0002 (7) | −0.0027 (6) | −0.0091 (7) |
C1 | 0.0186 (7) | 0.0485 (11) | 0.0149 (7) | 0.0026 (7) | 0.0012 (5) | −0.0052 (7) |
C2 | 0.0331 (9) | 0.0384 (10) | 0.0169 (8) | 0.0078 (8) | −0.0008 (6) | −0.0068 (7) |
C3 | 0.0339 (9) | 0.0350 (10) | 0.0240 (8) | −0.0011 (7) | −0.0018 (7) | −0.0063 (8) |
C4 | 0.0205 (8) | 0.0460 (11) | 0.0173 (7) | −0.0038 (7) | 0.0002 (6) | −0.0043 (7) |
C5 | 0.0376 (10) | 0.0345 (10) | 0.0188 (8) | 0.0059 (8) | −0.0014 (7) | −0.0011 (7) |
C6 | 0.0356 (10) | 0.0414 (11) | 0.0227 (9) | 0.0064 (8) | −0.0008 (7) | −0.0009 (8) |
C7 | 0.0394 (11) | 0.0506 (13) | 0.0243 (9) | 0.0048 (9) | −0.0033 (7) | −0.0006 (9) |
C8 | 0.0400 (12) | 0.0733 (18) | 0.0320 (11) | 0.0119 (11) | −0.0033 (9) | 0.0018 (11) |
C9 | 0.0213 (7) | 0.0366 (9) | 0.0128 (7) | −0.0044 (6) | −0.0018 (5) | −0.0040 (6) |
C10 | 0.0258 (8) | 0.0468 (11) | 0.0160 (7) | 0.0028 (7) | −0.0044 (6) | −0.0071 (7) |
C11 | 0.0222 (7) | 0.0365 (9) | 0.0119 (7) | −0.0038 (7) | −0.0016 (5) | −0.0047 (7) |
C12 | 0.0257 (8) | 0.0484 (11) | 0.0158 (7) | 0.0020 (8) | −0.0044 (6) | −0.0062 (8) |
C13 | 0.0307 (9) | 0.0562 (13) | 0.0157 (8) | 0.0009 (8) | −0.0073 (6) | −0.0085 (8) |
C14 | 0.0306 (9) | 0.0534 (12) | 0.0186 (8) | 0.0056 (8) | −0.0017 (7) | −0.0106 (8) |
Ni1—N1i | 2.0559 (16) | C3—H3B | 0.9900 |
Ni1—N1 | 2.0559 (16) | C4—C1i | 1.526 (3) |
Ni1—N2 | 2.0720 (17) | C4—H4A | 0.9900 |
Ni1—N2i | 2.0720 (17) | C4—H4B | 0.9900 |
Ni1—O1i | 2.1371 (13) | C5—C6 | 1.523 (3) |
Ni1—O1 | 2.1372 (13) | C5—H5A | 0.9900 |
O1—C9 | 1.2669 (19) | C5—H5B | 0.9900 |
O2—C9 | 1.248 (2) | C6—C7 | 1.521 (3) |
N1—C1 | 1.471 (2) | C6—H6A | 0.9900 |
N1—C2 | 1.481 (3) | C6—H6B | 0.9900 |
N1—H1 | 1.0000 | C7—C8 | 1.521 (3) |
N2—C4 | 1.477 (2) | C7—H7A | 0.9900 |
N2—C3 | 1.481 (3) | C7—H7B | 0.9900 |
N2—H2 | 1.0000 | C8—H8A | 0.9800 |
N3—C3 | 1.440 (3) | C8—H8B | 0.9800 |
N3—C2 | 1.444 (2) | C8—H8C | 0.9800 |
N3—C5 | 1.471 (2) | C9—C11 | 1.516 (2) |
N4—C13 | 1.336 (3) | C10—C14 | 1.384 (3) |
N4—C14 | 1.340 (2) | C10—C11 | 1.386 (3) |
C1—C4i | 1.526 (3) | C10—H10 | 0.9500 |
C1—H1A | 0.9900 | C11—C12 | 1.393 (2) |
C1—H1B | 0.9900 | C12—C13 | 1.379 (3) |
C2—H2A | 0.9900 | C12—H12 | 0.9500 |
C2—H2B | 0.9900 | C13—H13 | 0.9500 |
C3—H3A | 0.9900 | C14—H14 | 0.9500 |
N1i—Ni1—N1 | 180.0 | H3A—C3—H3B | 107.6 |
N1i—Ni1—N2 | 85.97 (6) | N2—C4—C1i | 108.14 (15) |
N1—Ni1—N2 | 94.03 (6) | N2—C4—H4A | 110.1 |
N1i—Ni1—N2i | 94.03 (6) | C1i—C4—H4A | 110.1 |
N1—Ni1—N2i | 85.97 (6) | N2—C4—H4B | 110.1 |
N2—Ni1—N2i | 180.0 | C1i—C4—H4B | 110.1 |
N1i—Ni1—O1i | 93.29 (6) | H4A—C4—H4B | 108.4 |
N1—Ni1—O1i | 86.71 (6) | N3—C5—C6 | 112.79 (16) |
N2—Ni1—O1i | 92.90 (6) | N3—C5—H5A | 109.0 |
N2i—Ni1—O1i | 87.10 (6) | C6—C5—H5A | 109.0 |
N1i—Ni1—O1 | 86.71 (6) | N3—C5—H5B | 109.0 |
N1—Ni1—O1 | 93.29 (6) | C6—C5—H5B | 109.0 |
N2—Ni1—O1 | 87.10 (6) | H5A—C5—H5B | 107.8 |
N2i—Ni1—O1 | 92.90 (6) | C7—C6—C5 | 111.93 (17) |
O1i—Ni1—O1 | 180.0 | C7—C6—H6A | 109.2 |
C9—O1—Ni1 | 131.99 (12) | C5—C6—H6A | 109.2 |
C1—N1—C2 | 114.34 (14) | C7—C6—H6B | 109.2 |
C1—N1—Ni1 | 105.52 (11) | C5—C6—H6B | 109.2 |
C2—N1—Ni1 | 112.75 (11) | H6A—C6—H6B | 107.9 |
C1—N1—H1 | 108.0 | C8—C7—C6 | 111.81 (19) |
C2—N1—H1 | 108.0 | C8—C7—H7A | 109.3 |
Ni1—N1—H1 | 108.0 | C6—C7—H7A | 109.3 |
C4—N2—C3 | 113.96 (15) | C8—C7—H7B | 109.3 |
C4—N2—Ni1 | 104.76 (11) | C6—C7—H7B | 109.3 |
C3—N2—Ni1 | 113.72 (11) | H7A—C7—H7B | 107.9 |
C4—N2—H2 | 108.0 | C7—C8—H8A | 109.5 |
C3—N2—H2 | 108.0 | C7—C8—H8B | 109.5 |
Ni1—N2—H2 | 108.0 | H8A—C8—H8B | 109.5 |
C3—N3—C2 | 115.84 (15) | C7—C8—H8C | 109.5 |
C3—N3—C5 | 114.58 (15) | H8A—C8—H8C | 109.5 |
C2—N3—C5 | 115.55 (16) | H8B—C8—H8C | 109.5 |
C13—N4—C14 | 116.05 (17) | O2—C9—O1 | 126.88 (16) |
N1—C1—C4i | 108.60 (14) | O2—C9—C11 | 117.12 (15) |
N1—C1—H1A | 110.0 | O1—C9—C11 | 115.99 (16) |
C4i—C1—H1A | 110.0 | C14—C10—C11 | 119.30 (17) |
N1—C1—H1B | 110.0 | C14—C10—H10 | 120.4 |
C4i—C1—H1B | 110.0 | C11—C10—H10 | 120.4 |
H1A—C1—H1B | 108.4 | C10—C11—C12 | 117.25 (16) |
N3—C2—N1 | 114.07 (15) | C10—C11—C9 | 122.61 (15) |
N3—C2—H2A | 108.7 | C12—C11—C9 | 120.14 (16) |
N1—C2—H2A | 108.7 | C13—C12—C11 | 119.15 (18) |
N3—C2—H2B | 108.7 | C13—C12—H12 | 120.4 |
N1—C2—H2B | 108.7 | C11—C12—H12 | 120.4 |
H2A—C2—H2B | 107.6 | N4—C13—C12 | 124.30 (17) |
N3—C3—N2 | 114.51 (16) | N4—C13—H13 | 117.8 |
N3—C3—H3A | 108.6 | C12—C13—H13 | 117.8 |
N2—C3—H3A | 108.6 | N4—C14—C10 | 123.94 (18) |
N3—C3—H3B | 108.6 | N4—C14—H14 | 118.0 |
N2—C3—H3B | 108.6 | C10—C14—H14 | 118.0 |
C2—N1—C1—C4i | −166.23 (14) | C5—C6—C7—C8 | −177.2 (2) |
Ni1—N1—C1—C4i | −41.74 (15) | Ni1—O1—C9—O2 | −15.1 (3) |
C3—N3—C2—N1 | −72.6 (2) | Ni1—O1—C9—C11 | 164.15 (12) |
C5—N3—C2—N1 | 65.5 (2) | C14—C10—C11—C12 | 0.4 (3) |
C1—N1—C2—N3 | 179.49 (14) | C14—C10—C11—C9 | −179.18 (18) |
Ni1—N1—C2—N3 | 58.94 (17) | O2—C9—C11—C10 | 179.64 (18) |
C2—N3—C3—N2 | 70.3 (2) | O1—C9—C11—C10 | 0.3 (3) |
C5—N3—C3—N2 | −68.2 (2) | O2—C9—C11—C12 | 0.1 (3) |
C4—N2—C3—N3 | −175.30 (14) | O1—C9—C11—C12 | −179.24 (17) |
Ni1—N2—C3—N3 | −55.32 (18) | C10—C11—C12—C13 | 0.3 (3) |
C3—N2—C4—C1i | 167.84 (13) | C9—C11—C12—C13 | 179.86 (18) |
Ni1—N2—C4—C1i | 42.93 (14) | C14—N4—C13—C12 | 0.4 (3) |
C3—N3—C5—C6 | −160.49 (18) | C11—C12—C13—N4 | −0.7 (3) |
C2—N3—C5—C6 | 60.9 (2) | C13—N4—C14—C10 | 0.4 (3) |
N3—C5—C6—C7 | 178.71 (18) | C11—C10—C14—N4 | −0.8 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 1.00 | 1.98 | 2.892 (2) | 150 |
N2—H2···N4ii | 1.00 | 2.23 | 3.143 (2) | 151 |
Symmetry code: (ii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 1.00 | 1.98 | 2.892 (2) | 150.0 |
N2—H2···N4i | 1.00 | 2.23 | 3.143 (2) | 150.6 |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C6H4NO2)2(C16H38N6)] |
Mr | 617.44 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 8.0630 (16), 8.5110 (17), 10.927 (2) |
α, β, γ (°) | 80.52 (3), 88.26 (3), 86.44 (3) |
V (Å3) | 738.0 (3) |
Z | 1 |
Radiation type | Synchrotron, λ = 0.62998 Å |
µ (mm−1) | 0.51 |
Crystal size (mm) | 0.01 × 0.004 × 0.004 |
Data collection | |
Diffractometer | ADSC Q210 CCD area-detector |
Absorption correction | Empirical (using intensity measurements) (HKL-3000SM SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.995, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7634, 3879, 3326 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.696 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.110, 1.04 |
No. of reflections | 3879 |
No. of parameters | 188 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.12, −0.95 |
Computer programs: PAL BL2D-SMDC (Shin et al., 2016a), HKL-3000SM (Otwinowski & Minor, 1997), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Putz & Brandenburg, 2014), publCIF (Westrip, 2010).
Acknowledgements
This work was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2014R1A1A2058815) and supported by the Institute for Basic Science (IBS-R007-D1–2016–a01). The X-ray crystallography BL2D–SMC beamline and FT–IR experiment at the PLS-II are supported in part by MSIP and POSTECH.
References
Churchard, A. J., Cyranski, M. K., Dobrzycki, Ł., Budzianowski, A. & Grochala, W. (2010). Energ. Environ. Sci. 3, 1973–1978. CSD CrossRef CAS Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Hunter, C. A. & Sanders, K. M. (1990). J. Am. Chem. Soc. 112, 5525–5534. CrossRef CAS Web of Science Google Scholar
Kim, D.-W., Kim, J. J., Shin, J. W., Kim, J. H. & Moon, D. (2015a). Acta Cryst. E71, 779–782. CSD CrossRef IUCr Journals Google Scholar
Kim, D.-W., Shin, J. W. & Moon, D. (2015b). Acta Cryst. E71, 136–138. CSD CrossRef IUCr Journals Google Scholar
Lehn, J.-M. (2015). Angew. Chem. Int. Ed. 54, 3276–3289. Web of Science CrossRef CAS Google Scholar
Melson, G. A. (1979). In Coordination Chemistry of Macrocyclic Compounds, 1st ed. New York: Plenum Press. Google Scholar
Min, K. S. & Suh, M. P. (2001). Chem. Eur. J. 7, 303–313. Web of Science CSD CrossRef PubMed CAS Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Putz, H. & Brandenburg, K. (2014). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Ryoo, J. J., Shin, J. W., Dho, H.-S. & Min, K. S. (2010). Inorg. Chem. 49, 7232–7234. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shin, J. W., Eom, K. & Moon, D. (2016a). J. Synchrotron Rad. 23, 369–373. CrossRef IUCr Journals Google Scholar
Shin, J. W., Kim, D.-W., Kim, J. H. & Moon, D. (2015). Acta Cryst. E71, 203–205. CSD CrossRef IUCr Journals Google Scholar
Shin, J. W., Kim, D.-W. & Moon, D. (2016b). Polyhedron, 105, 62–70. CSD CrossRef CAS Google Scholar
Steed, J. W. & Atwood, J. L. (2009). Supramol. Chem. 2nd ed. Chichester: John Wiley & Sons Ltd. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, W.-P., Wang, N., Long, Y., Ran, X.-R., Gao, J.-Y., Chen, C.-J., Yue, S.-T. & Cai, Y.-P. (2014). Inorg. Chem. Commun. 40, 151–156. CSD CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.