catena-Poly[[bis(di-4-pyridylamine-κN)(terephthalato-κ2O,O′)nickel(II)]-μ-di-4-pyridylamine-κ2N:N′]
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051112/hg2318sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051112/hg2318Isup2.hkl |
CCDC reference: 667196
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.006 Å
- R factor = 0.068
- wR factor = 0.168
- Data-to-parameter ratio = 16.8
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.58 Ratio PLAT220_ALERT_2_B Large Non-Solvent N Ueq(max)/Ueq(min) ... 4.04 Ratio
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.118 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.12 PLAT048_ALERT_1_C MoietyFormula Not Given ........................ ? PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.28 Ratio PLAT320_ALERT_2_C Check Hybridisation of C35 in Main Residue . ? PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C34 - C35 ... 1.38 Ang. PLAT410_ALERT_2_C Short Intra H...H Contact H32 .. H37 .. 1.91 Ang.
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Nickel chloride hexahydrate and terephthalic acid were obtained commercially. Di-4-pyridylamine (dpa) was prepared via a published procedure (Zapf et al., 1998). Nickel chloride hexahydrate (88 mg, 0.37 mmol), terephthalic acid (62 mg, 0.37 mmol) and dpa (127 mg, 0.74 mmol) were added to 10 ml H2O in a 23 ml a Teflon-lined Parr acid digestion bomb. The pH was adjusted with 0.75 ml of 0.1 M NaOH and the bomb was sealed. The mixture was then heated under autogenous pressure at 393 K for 48 h., whereupon it was cooled slowly to 293 K. Small dark blue plates (76 mg, 42% yield based on dpa) of the title compound were produced.
All H atoms bound to C atoms were placed in calculated positions, with C—H = 0.93 (2) Å and refined in riding mode with Uiso = 1.2Ueq(C). The H atoms bound to N within the dpa ligands were found via Fourier difference map and refined with Uiso =1.2Ueq(N). The largest difference peak of 1.117 e-/Å3 was located 0.77 Å from H17.
In comparison to the large number of coordination polymers constructed from the rigid rod tethering ligand 4,4'-bipyridine, metal-organic materials based on 4,4'-dipyridylamine (dpa) are much rarer (Montney et al., 2007). Prepared during continued attempts to develop this chemistry, the title compound possesses an asymmetric unit (Fig. 1) consisting of one nickel atom, one terephthalate (tp) dianion, and three crystallographically distinct dpa moieties. The nickel atom displays a [NiN4O2] octahedral coordination sphere, with the cis O donor atoms belonging to a chelating carboxylate terminus of the tp ligand. Two of the N atom donors, disposed in a cis fashion, belong to different bridging dpa ligands. The other two N donors belong to crystallographically independent monodentate dpa lignds.
Extension of the structure along the b crystal direction reveals an 1-D chain coordination polymer of formulation [Ni(tp)(dpa)3]n, constructed by the linkage of adjacent Ni atoms through exobidentate dpa ligands (Fig. 2). Within the 1-D chain motif, the Ni–Ni through-ligand distance is 11.048 (2) Å, marking the b lattice parameter.
Each [Ni(tp)(dpa)3]n chain is interwoven by another identical chain, related by the crystallographic 21 screw axis along b (Fig. 3). The double chain motifs are stabilized through N—H···O hydrogen bonding promoted by the central amine groups of the bridging dpa ligands. These one-dimensional subunits further aggregate into three dimensions via additional N—H···O hydrogen bonding patterns mediated by the pendant dpa ligands (Fig. 4).
For related literature, see: Montney et al. (2007); Zapf et al. (1998).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); 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 (CrystalMaker Software, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Ni(C8H4O4)(C10H9N3)3] | F(000) = 1524 |
Mr = 735.42 | Dx = 1.478 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 39515 reflections |
a = 17.025 (3) Å | θ = 1.4–28.5° |
b = 11.048 (2) Å | µ = 0.65 mm−1 |
c = 18.736 (4) Å | T = 173 K |
β = 110.281 (3)° | Plate, blue |
V = 3305.7 (11) Å3 | 0.38 × 0.14 × 0.08 mm |
Z = 4 |
Bruker SMART 1K diffractometer | 8097 independent reflections |
Radiation source: fine-focus sealed tube | 4711 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.118 |
ω scans | θmax = 28.5°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −22→21 |
Tmin = 0.834, Tmax = 0.950 | k = −14→14 |
39515 measured reflections | l = −24→24 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0719P)2 + 3.6742P] where P = (Fo2 + 2Fc2)/3 |
8097 reflections | (Δ/σ)max < 0.001 |
481 parameters | Δρmax = 1.12 e Å−3 |
0 restraints | Δρmin = −0.84 e Å−3 |
[Ni(C8H4O4)(C10H9N3)3] | V = 3305.7 (11) Å3 |
Mr = 735.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 17.025 (3) Å | µ = 0.65 mm−1 |
b = 11.048 (2) Å | T = 173 K |
c = 18.736 (4) Å | 0.38 × 0.14 × 0.08 mm |
β = 110.281 (3)° |
Bruker SMART 1K diffractometer | 8097 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4711 reflections with I > 2σ(I) |
Tmin = 0.834, Tmax = 0.950 | Rint = 0.118 |
39515 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.168 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 1.12 e Å−3 |
8097 reflections | Δρmin = −0.84 e Å−3 |
481 parameters |
Experimental. The small crystal width resulted in relatively weak diffraction and an Rint value in excess of 0.10 despite collection of 30 second frames. Nevertheless, refinement was satisfactory. |
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 > σ(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 | ||
Ni1 | 0.89296 (3) | 0.64879 (4) | 0.19611 (3) | 0.01181 (14) | |
O1 | 0.90765 (17) | 0.5489 (2) | 0.29935 (15) | 0.0182 (6) | |
O2 | 0.90374 (17) | 0.7477 (2) | 0.29665 (15) | 0.0187 (6) | |
O3 | 0.78211 (18) | 0.6437 (3) | 0.61865 (15) | 0.0265 (7) | |
O4 | 0.91737 (18) | 0.6727 (3) | 0.68384 (15) | 0.0232 (7) | |
N1 | 0.7629 (2) | 0.6457 (3) | 0.17926 (18) | 0.0170 (7) | |
N2 | 0.5155 (2) | 0.6293 (3) | 0.17493 (19) | 0.0187 (8) | |
H2N | 0.490 (3) | 0.704 (5) | 0.186 (3) | 0.044 (15)* | |
N3 | 0.3284 (2) | 0.3713 (4) | 0.0703 (2) | 0.0387 (11) | |
N4 | 1.0226 (2) | 0.6513 (3) | 0.21577 (18) | 0.0153 (7) | |
N5 | 1.2732 (2) | 0.7399 (4) | 0.2528 (2) | 0.0234 (8) | |
H5N | 1.278 (3) | 0.781 (4) | 0.210 (3) | 0.033 (13)* | |
N6 | 1.4651 (3) | 0.7791 (6) | 0.4648 (2) | 0.0549 (15) | |
N7 | 0.8835 (2) | 0.4967 (3) | 0.12859 (18) | 0.0142 (7) | |
N8 | 0.8390 (2) | 0.1492 (3) | 0.03052 (19) | 0.0169 (7) | |
H8N | 0.801 (3) | 0.148 (4) | −0.017 (3) | 0.026 (12)* | |
N9 | 0.8784 (2) | −0.1977 (3) | 0.12899 (18) | 0.0136 (7) | |
C1 | 0.7255 (2) | 0.5395 (4) | 0.1831 (2) | 0.0176 (9) | |
H1 | 0.7564 | 0.4690 | 0.1864 | 0.021* | |
C2 | 0.6448 (2) | 0.5283 (3) | 0.1824 (2) | 0.0166 (9) | |
H2 | 0.6227 | 0.4526 | 0.1862 | 0.020* | |
C3 | 0.5969 (2) | 0.6323 (3) | 0.1759 (2) | 0.0150 (8) | |
C4 | 0.6360 (2) | 0.7443 (4) | 0.1748 (2) | 0.0166 (9) | |
H4 | 0.6070 | 0.8163 | 0.1725 | 0.020* | |
C5 | 0.7172 (2) | 0.7456 (3) | 0.1770 (2) | 0.0178 (9) | |
H5 | 0.7422 | 0.8204 | 0.1769 | 0.021* | |
C6 | 0.3238 (3) | 0.4470 (5) | 0.1237 (3) | 0.0344 (12) | |
H6 | 0.2760 | 0.4440 | 0.1370 | 0.041* | |
C7 | 0.3849 (3) | 0.5299 (4) | 0.1610 (3) | 0.0247 (10) | |
H7 | 0.3779 | 0.5804 | 0.1980 | 0.030* | |
C8 | 0.4569 (3) | 0.5369 (4) | 0.1424 (2) | 0.0205 (9) | |
C9 | 0.4629 (3) | 0.4571 (4) | 0.0871 (2) | 0.0284 (11) | |
H9 | 0.5101 | 0.4571 | 0.0729 | 0.034* | |
C10 | 0.3983 (3) | 0.3783 (4) | 0.0536 (3) | 0.0345 (12) | |
H10 | 0.4036 | 0.3261 | 0.0166 | 0.041* | |
C11 | 1.0816 (2) | 0.6437 (4) | 0.2848 (2) | 0.0202 (9) | |
H11 | 1.0646 | 0.6216 | 0.3251 | 0.024* | |
C12 | 1.1652 (3) | 0.6660 (4) | 0.3008 (2) | 0.0223 (10) | |
H12 | 1.2031 | 0.6564 | 0.3500 | 0.027* | |
C13 | 1.1925 (2) | 0.7032 (4) | 0.2422 (2) | 0.0170 (9) | |
C14 | 1.1316 (3) | 0.7071 (4) | 0.1691 (2) | 0.0196 (9) | |
H14 | 1.1466 | 0.7277 | 0.1275 | 0.024* | |
C15 | 1.0502 (3) | 0.6805 (3) | 0.1592 (2) | 0.0160 (9) | |
H15 | 1.0114 | 0.6828 | 0.1099 | 0.019* | |
C16 | 1.4283 (3) | 0.6742 (6) | 0.4430 (3) | 0.0472 (16) | |
H16 | 1.4462 | 0.6090 | 0.4761 | 0.057* | |
C17 | 1.3634 (3) | 0.6534 (5) | 0.3728 (3) | 0.0376 (12) | |
H17 | 1.3389 | 0.5774 | 0.3603 | 0.045* | |
C18 | 1.3377 (3) | 0.7499 (4) | 0.3236 (2) | 0.0238 (10) | |
C19 | 1.3794 (3) | 0.8621 (5) | 0.3451 (3) | 0.0342 (12) | |
H19 | 1.3654 | 0.9286 | 0.3128 | 0.041* | |
C20 | 1.4403 (3) | 0.8694 (6) | 0.4146 (3) | 0.0489 (16) | |
H20 | 1.4671 | 0.9436 | 0.4285 | 0.059* | |
C21 | 0.8941 (2) | 0.6499 (4) | 0.4072 (2) | 0.0157 (8) | |
C22 | 0.8732 (3) | 0.7556 (4) | 0.4357 (2) | 0.0218 (9) | |
H22 | 0.8664 | 0.8268 | 0.4077 | 0.026* | |
C23 | 0.8625 (3) | 0.7565 (4) | 0.5055 (2) | 0.0217 (9) | |
H23 | 0.8475 | 0.8282 | 0.5235 | 0.026* | |
C24 | 0.8736 (2) | 0.6528 (4) | 0.5489 (2) | 0.0164 (8) | |
C25 | 0.8957 (3) | 0.5464 (4) | 0.5212 (2) | 0.0233 (10) | |
H25 | 0.9048 | 0.4761 | 0.5502 | 0.028* | |
C26 | 0.9042 (3) | 0.5447 (4) | 0.4500 (2) | 0.0207 (9) | |
H26 | 0.9169 | 0.4724 | 0.4309 | 0.025* | |
C27 | 0.9029 (2) | 0.6480 (4) | 0.3309 (2) | 0.0138 (8) | |
C28 | 0.8570 (2) | 0.6560 (4) | 0.6235 (2) | 0.0162 (8) | |
C31 | 0.9124 (3) | 0.3975 (4) | 0.1706 (2) | 0.0192 (9) | |
H31 | 0.9433 | 0.4073 | 0.2220 | 0.023* | |
C32 | 0.8987 (3) | 0.2815 (4) | 0.1417 (2) | 0.0200 (9) | |
H32 | 0.9175 | 0.2159 | 0.1743 | 0.024* | |
C33 | 0.8576 (2) | 0.2617 (3) | 0.0654 (2) | 0.0154 (8) | |
C34 | 0.8301 (2) | 0.3659 (3) | 0.0207 (2) | 0.0171 (9) | |
H34 | 0.8032 | 0.3584 | −0.0316 | 0.020* | |
C35 | 0.8425 (3) | 0.4797 (3) | 0.0536 (2) | 0.0157 (9) | |
C36 | 0.9312 (2) | −0.1059 (3) | 0.1603 (2) | 0.0163 (8) | |
H36 | 0.9755 | −0.1210 | 0.2052 | 0.020* | |
C37 | 0.9237 (2) | 0.0090 (3) | 0.1299 (2) | 0.0178 (9) | |
H37 | 0.9634 | 0.0679 | 0.1531 | 0.021* | |
C38 | 0.8561 (2) | 0.0363 (3) | 0.0640 (2) | 0.0148 (8) | |
C39 | 0.8039 (2) | −0.0605 (4) | 0.0296 (2) | 0.0156 (8) | |
H39 | 0.7600 | −0.0487 | −0.0161 | 0.019* | |
C40 | 0.8171 (2) | −0.1734 (3) | 0.0629 (2) | 0.0151 (8) | |
H40 | 0.7816 | −0.2362 | 0.0383 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0145 (3) | 0.0100 (2) | 0.0120 (2) | −0.0003 (2) | 0.00601 (19) | −0.0002 (2) |
O1 | 0.0243 (16) | 0.0161 (15) | 0.0179 (15) | 0.0015 (12) | 0.0118 (13) | −0.0024 (12) |
O2 | 0.0253 (16) | 0.0154 (15) | 0.0184 (15) | −0.0014 (12) | 0.0115 (13) | 0.0008 (12) |
O3 | 0.0186 (16) | 0.0465 (19) | 0.0155 (15) | −0.0040 (15) | 0.0072 (12) | −0.0053 (14) |
O4 | 0.0215 (16) | 0.0316 (18) | 0.0144 (15) | −0.0036 (13) | 0.0036 (13) | 0.0033 (12) |
N1 | 0.0184 (18) | 0.0145 (16) | 0.0196 (18) | 0.0000 (15) | 0.0086 (15) | 0.0005 (14) |
N2 | 0.0139 (17) | 0.021 (2) | 0.0227 (19) | −0.0001 (14) | 0.0087 (15) | −0.0023 (15) |
N3 | 0.026 (2) | 0.034 (3) | 0.045 (3) | −0.0097 (19) | −0.002 (2) | 0.007 (2) |
N4 | 0.0202 (18) | 0.0108 (15) | 0.0146 (16) | 0.0015 (14) | 0.0057 (14) | 0.0004 (14) |
N5 | 0.0161 (19) | 0.041 (2) | 0.0141 (18) | −0.0029 (16) | 0.0062 (16) | 0.0051 (17) |
N6 | 0.026 (3) | 0.117 (5) | 0.022 (2) | −0.021 (3) | 0.010 (2) | 0.005 (3) |
N7 | 0.0145 (17) | 0.0139 (17) | 0.0146 (17) | 0.0015 (13) | 0.0058 (14) | −0.0001 (13) |
N8 | 0.0219 (18) | 0.0119 (16) | 0.0141 (17) | −0.0014 (15) | 0.0029 (15) | −0.0012 (15) |
N9 | 0.0160 (18) | 0.0104 (16) | 0.0146 (17) | 0.0006 (13) | 0.0056 (14) | 0.0013 (13) |
C1 | 0.016 (2) | 0.014 (2) | 0.023 (2) | 0.0036 (16) | 0.0073 (18) | −0.0012 (17) |
C2 | 0.017 (2) | 0.012 (2) | 0.022 (2) | −0.0012 (16) | 0.0085 (18) | −0.0025 (16) |
C3 | 0.015 (2) | 0.019 (2) | 0.0123 (19) | 0.0008 (17) | 0.0055 (16) | 0.0020 (16) |
C4 | 0.017 (2) | 0.015 (2) | 0.019 (2) | 0.0069 (17) | 0.0077 (18) | 0.0011 (16) |
C5 | 0.020 (2) | 0.012 (2) | 0.025 (2) | 0.0002 (16) | 0.0114 (19) | −0.0003 (17) |
C6 | 0.019 (2) | 0.040 (3) | 0.041 (3) | −0.006 (2) | 0.006 (2) | 0.016 (3) |
C7 | 0.014 (2) | 0.030 (3) | 0.030 (2) | 0.0020 (18) | 0.0075 (19) | 0.009 (2) |
C8 | 0.017 (2) | 0.021 (2) | 0.020 (2) | −0.0024 (17) | 0.0013 (18) | 0.0026 (17) |
C9 | 0.022 (2) | 0.034 (3) | 0.025 (2) | −0.002 (2) | 0.003 (2) | −0.001 (2) |
C10 | 0.035 (3) | 0.034 (3) | 0.025 (3) | −0.002 (2) | −0.002 (2) | −0.001 (2) |
C11 | 0.017 (2) | 0.026 (2) | 0.016 (2) | −0.0007 (19) | 0.0054 (17) | 0.0091 (18) |
C12 | 0.017 (2) | 0.034 (3) | 0.015 (2) | −0.0015 (19) | 0.0050 (18) | 0.0043 (18) |
C13 | 0.014 (2) | 0.021 (2) | 0.017 (2) | 0.0014 (17) | 0.0059 (17) | 0.0039 (17) |
C14 | 0.021 (2) | 0.026 (2) | 0.014 (2) | 0.0011 (18) | 0.0096 (18) | 0.0007 (17) |
C15 | 0.020 (2) | 0.018 (2) | 0.0088 (19) | 0.0036 (16) | 0.0032 (17) | −0.0012 (15) |
C16 | 0.028 (3) | 0.084 (5) | 0.035 (3) | 0.014 (3) | 0.017 (3) | 0.027 (3) |
C17 | 0.025 (3) | 0.059 (3) | 0.032 (3) | 0.006 (3) | 0.014 (2) | 0.020 (3) |
C18 | 0.012 (2) | 0.046 (3) | 0.016 (2) | 0.000 (2) | 0.0077 (18) | 0.002 (2) |
C19 | 0.022 (2) | 0.059 (3) | 0.025 (2) | −0.002 (2) | 0.013 (2) | 0.004 (2) |
C20 | 0.035 (3) | 0.086 (5) | 0.027 (3) | −0.024 (3) | 0.012 (2) | −0.015 (3) |
C21 | 0.016 (2) | 0.021 (2) | 0.0129 (19) | −0.0013 (18) | 0.0088 (16) | −0.0002 (17) |
C22 | 0.029 (2) | 0.018 (2) | 0.020 (2) | −0.0030 (19) | 0.0115 (19) | 0.0008 (17) |
C23 | 0.031 (3) | 0.016 (2) | 0.025 (2) | −0.0008 (18) | 0.017 (2) | −0.0022 (17) |
C24 | 0.0128 (19) | 0.026 (2) | 0.0113 (19) | 0.0012 (18) | 0.0048 (16) | −0.0006 (17) |
C25 | 0.033 (3) | 0.022 (2) | 0.016 (2) | 0.0079 (19) | 0.0102 (19) | 0.0033 (18) |
C26 | 0.030 (2) | 0.020 (2) | 0.016 (2) | 0.0067 (19) | 0.0119 (19) | 0.0014 (17) |
C27 | 0.0129 (19) | 0.0157 (19) | 0.0136 (19) | −0.0024 (17) | 0.0059 (15) | −0.0004 (17) |
C28 | 0.018 (2) | 0.0130 (19) | 0.017 (2) | 0.0000 (17) | 0.0054 (17) | 0.0000 (17) |
C31 | 0.027 (2) | 0.019 (2) | 0.011 (2) | 0.0086 (18) | 0.0068 (18) | −0.0002 (17) |
C32 | 0.032 (3) | 0.0091 (19) | 0.016 (2) | 0.0035 (17) | 0.0051 (19) | 0.0006 (16) |
C33 | 0.017 (2) | 0.013 (2) | 0.017 (2) | −0.0007 (16) | 0.0071 (18) | −0.0017 (16) |
C34 | 0.023 (2) | 0.015 (2) | 0.0122 (19) | 0.0026 (17) | 0.0044 (17) | 0.0016 (16) |
C35 | 0.022 (2) | 0.015 (2) | 0.011 (2) | 0.0010 (17) | 0.0067 (17) | 0.0003 (15) |
C36 | 0.014 (2) | 0.0149 (19) | 0.017 (2) | 0.0009 (16) | 0.0016 (17) | 0.0009 (16) |
C37 | 0.014 (2) | 0.014 (2) | 0.023 (2) | −0.0025 (16) | 0.0030 (18) | −0.0040 (17) |
C38 | 0.020 (2) | 0.012 (2) | 0.015 (2) | 0.0018 (16) | 0.0091 (17) | −0.0012 (16) |
C39 | 0.014 (2) | 0.020 (2) | 0.0107 (19) | −0.0014 (17) | 0.0019 (16) | −0.0012 (16) |
C40 | 0.014 (2) | 0.012 (2) | 0.019 (2) | −0.0020 (15) | 0.0057 (17) | −0.0051 (15) |
Ni1—N9i | 2.075 (3) | C9—C10 | 1.372 (6) |
Ni1—N7 | 2.075 (3) | C9—H9 | 0.9300 |
Ni1—N4 | 2.108 (3) | C10—H10 | 0.9300 |
Ni1—N1 | 2.125 (3) | C11—C12 | 1.372 (6) |
Ni1—O2 | 2.130 (3) | C11—H11 | 0.9300 |
Ni1—O1 | 2.165 (3) | C12—C13 | 1.395 (5) |
Ni1—C27 | 2.472 (4) | C12—H12 | 0.9300 |
O1—C27 | 1.261 (4) | C13—C14 | 1.403 (5) |
O2—C27 | 1.277 (4) | C14—C15 | 1.365 (5) |
O3—C28 | 1.253 (5) | C14—H14 | 0.9300 |
O4—C28 | 1.250 (5) | C15—H15 | 0.9300 |
N1—C5 | 1.343 (5) | C16—C17 | 1.412 (7) |
N1—C1 | 1.349 (5) | C16—H16 | 0.9300 |
N2—C3 | 1.379 (5) | C17—C18 | 1.378 (6) |
N2—C8 | 1.410 (5) | C17—H17 | 0.9300 |
N2—H2N | 0.99 (5) | C18—C19 | 1.416 (7) |
N3—C6 | 1.327 (6) | C19—C20 | 1.357 (7) |
N3—C10 | 1.334 (6) | C19—H19 | 0.9300 |
N4—C11 | 1.337 (5) | C20—H20 | 0.9300 |
N4—C15 | 1.340 (5) | C21—C22 | 1.382 (6) |
N5—C13 | 1.379 (5) | C21—C26 | 1.389 (5) |
N5—C18 | 1.403 (5) | C21—C27 | 1.487 (5) |
N5—H5N | 0.94 (5) | C22—C23 | 1.383 (6) |
N6—C16 | 1.314 (8) | C22—H22 | 0.9300 |
N6—C20 | 1.334 (7) | C23—C24 | 1.379 (6) |
N7—C31 | 1.341 (5) | C23—H23 | 0.9300 |
N7—C35 | 1.348 (5) | C24—C25 | 1.389 (6) |
N8—C38 | 1.381 (5) | C24—C28 | 1.520 (5) |
N8—C33 | 1.389 (5) | C25—C26 | 1.391 (5) |
N8—H8N | 0.91 (4) | C25—H25 | 0.9300 |
N9—C40 | 1.340 (5) | C26—H26 | 0.9300 |
N9—C36 | 1.348 (5) | C31—C32 | 1.379 (5) |
N9—Ni1ii | 2.075 (3) | C31—H31 | 0.9300 |
C1—C2 | 1.375 (5) | C32—C33 | 1.374 (5) |
C1—H1 | 0.9300 | C32—H32 | 0.9300 |
C2—C3 | 1.390 (5) | C33—C34 | 1.406 (5) |
C2—H2 | 0.9300 | C34—C35 | 1.384 (5) |
C3—C4 | 1.409 (5) | C34—H34 | 0.9300 |
C4—C5 | 1.368 (5) | C36—C37 | 1.378 (5) |
C4—H4 | 0.9300 | C36—H36 | 0.9300 |
C5—H5 | 0.9300 | C37—C38 | 1.399 (5) |
C6—C7 | 1.380 (6) | C37—H37 | 0.9300 |
C6—H6 | 0.9300 | C38—C39 | 1.397 (5) |
C7—C8 | 1.388 (6) | C39—C40 | 1.379 (5) |
C7—H7 | 0.9300 | C39—H39 | 0.9300 |
C8—C9 | 1.391 (6) | C40—H40 | 0.9300 |
N9i—Ni1—N7 | 108.93 (12) | C13—C12—H12 | 120.5 |
N9i—Ni1—N4 | 89.61 (13) | N5—C13—C12 | 124.1 (4) |
N7—Ni1—N4 | 88.43 (12) | N5—C13—C14 | 119.6 (4) |
N9i—Ni1—N1 | 91.35 (13) | C12—C13—C14 | 116.3 (4) |
N7—Ni1—N1 | 92.26 (13) | C15—C14—C13 | 119.9 (4) |
N4—Ni1—N1 | 178.57 (13) | C15—C14—H14 | 120.1 |
N9i—Ni1—O2 | 94.13 (11) | C13—C14—H14 | 120.1 |
N7—Ni1—O2 | 156.80 (11) | N4—C15—C14 | 124.2 (4) |
N4—Ni1—O2 | 94.28 (11) | N4—C15—H15 | 117.9 |
N1—Ni1—O2 | 84.59 (12) | C14—C15—H15 | 117.9 |
N9i—Ni1—O1 | 155.65 (11) | N6—C16—C17 | 124.6 (5) |
N7—Ni1—O1 | 95.30 (11) | N6—C16—H16 | 117.7 |
N4—Ni1—O1 | 93.49 (11) | C17—C16—H16 | 117.7 |
N1—Ni1—O1 | 85.20 (11) | C18—C17—C16 | 117.5 (5) |
O2—Ni1—O1 | 61.56 (10) | C18—C17—H17 | 121.3 |
N9i—Ni1—C27 | 125.00 (13) | C16—C17—H17 | 121.3 |
N7—Ni1—C27 | 125.69 (13) | C17—C18—N5 | 122.3 (4) |
N4—Ni1—C27 | 97.17 (12) | C17—C18—C19 | 118.4 (4) |
N1—Ni1—C27 | 81.41 (12) | N5—C18—C19 | 119.3 (4) |
O2—Ni1—C27 | 31.11 (11) | C20—C19—C18 | 117.8 (5) |
O1—Ni1—C27 | 30.65 (11) | C20—C19—H19 | 121.1 |
C27—O1—Ni1 | 88.2 (2) | C18—C19—H19 | 121.1 |
C27—O2—Ni1 | 89.4 (2) | N6—C20—C19 | 125.6 (6) |
C5—N1—C1 | 115.9 (3) | N6—C20—H20 | 117.2 |
C5—N1—Ni1 | 123.7 (3) | C19—C20—H20 | 117.2 |
C1—N1—Ni1 | 119.5 (3) | C22—C21—C26 | 118.8 (3) |
C3—N2—C8 | 125.5 (3) | C22—C21—C27 | 120.5 (4) |
C3—N2—H2N | 119 (3) | C26—C21—C27 | 120.7 (4) |
C8—N2—H2N | 114 (3) | C21—C22—C23 | 120.6 (4) |
C6—N3—C10 | 115.6 (4) | C21—C22—H22 | 119.7 |
C11—N4—C15 | 115.4 (3) | C23—C22—H22 | 119.7 |
C11—N4—Ni1 | 123.9 (3) | C24—C23—C22 | 121.0 (4) |
C15—N4—Ni1 | 119.9 (3) | C24—C23—H23 | 119.5 |
C13—N5—C18 | 125.0 (3) | C22—C23—H23 | 119.5 |
C13—N5—H5N | 113 (3) | C23—C24—C25 | 118.9 (4) |
C18—N5—H5N | 120 (3) | C23—C24—C28 | 119.4 (4) |
C16—N6—C20 | 116.1 (5) | C25—C24—C28 | 121.6 (4) |
C31—N7—C35 | 116.8 (3) | C24—C25—C26 | 120.1 (4) |
C31—N7—Ni1 | 111.7 (2) | C24—C25—H25 | 119.9 |
C35—N7—Ni1 | 130.6 (3) | C26—C25—H25 | 119.9 |
C38—N8—C33 | 128.0 (3) | C21—C26—C25 | 120.6 (4) |
C38—N8—H8N | 114 (3) | C21—C26—H26 | 119.7 |
C33—N8—H8N | 116 (3) | C25—C26—H26 | 119.7 |
C40—N9—C36 | 116.1 (3) | O1—C27—O2 | 120.0 (3) |
C40—N9—Ni1ii | 127.9 (3) | O1—C27—C21 | 120.4 (3) |
C36—N9—Ni1ii | 115.5 (3) | O2—C27—C21 | 119.6 (3) |
N1—C1—C2 | 124.5 (4) | O1—C27—Ni1 | 61.11 (19) |
N1—C1—H1 | 117.8 | O2—C27—Ni1 | 59.51 (18) |
C2—C1—H1 | 117.8 | C21—C27—Ni1 | 170.9 (3) |
C1—C2—C3 | 118.8 (4) | O4—C28—O3 | 125.4 (4) |
C1—C2—H2 | 120.6 | O4—C28—C24 | 118.5 (3) |
C3—C2—H2 | 120.6 | O3—C28—C24 | 116.1 (3) |
N2—C3—C2 | 122.6 (4) | N7—C31—C32 | 123.5 (4) |
N2—C3—C4 | 119.9 (3) | N7—C31—H31 | 118.3 |
C2—C3—C4 | 117.4 (3) | C32—C31—H31 | 118.3 |
C5—C4—C3 | 119.1 (4) | C33—C32—C31 | 120.8 (4) |
C5—C4—H4 | 120.4 | C33—C32—H32 | 119.6 |
C3—C4—H4 | 120.4 | C31—C32—H32 | 119.6 |
N1—C5—C4 | 124.1 (4) | C32—C33—N8 | 125.7 (4) |
N1—C5—H5 | 117.9 | C32—C33—C34 | 115.7 (3) |
C4—C5—H5 | 117.9 | N8—C33—C34 | 118.5 (3) |
N3—C6—C7 | 124.6 (5) | C35—C34—C33 | 120.7 (4) |
N3—C6—H6 | 117.7 | C35—C34—H34 | 119.7 |
C7—C6—H6 | 117.7 | C33—C34—H34 | 119.7 |
C6—C7—C8 | 119.1 (5) | N7—C35—C34 | 122.4 (3) |
C6—C7—H7 | 120.4 | N9—C36—C37 | 124.2 (4) |
C8—C7—H7 | 120.4 | N9—C36—H36 | 117.9 |
C7—C8—C9 | 116.8 (4) | C37—C36—H36 | 117.9 |
C7—C8—N2 | 119.1 (4) | C36—C37—C38 | 119.5 (4) |
C9—C8—N2 | 123.9 (4) | C36—C37—H37 | 120.2 |
C10—C9—C8 | 119.2 (4) | C38—C37—H37 | 120.2 |
C10—C9—H9 | 120.4 | N8—C38—C39 | 118.8 (4) |
C8—C9—H9 | 120.4 | N8—C38—C37 | 125.1 (4) |
N3—C10—C9 | 124.7 (5) | C39—C38—C37 | 116.1 (3) |
N3—C10—H10 | 117.7 | C40—C39—C38 | 120.4 (4) |
C9—C10—H10 | 117.7 | C40—C39—H39 | 119.8 |
N4—C11—C12 | 125.1 (4) | C38—C39—H39 | 119.8 |
N4—C11—H11 | 117.5 | N9—C40—C39 | 123.5 (4) |
C12—C11—H11 | 117.5 | N9—C40—H40 | 118.2 |
C11—C12—C13 | 119.0 (4) | C39—C40—H40 | 118.2 |
C11—C12—H12 | 120.5 | ||
N9i—Ni1—O1—C27 | 1.4 (4) | N5—C13—C14—C15 | −174.7 (4) |
N7—Ni1—O1—C27 | −173.1 (2) | C12—C13—C14—C15 | 2.9 (6) |
N4—Ni1—O1—C27 | 98.2 (2) | C11—N4—C15—C14 | −3.1 (6) |
N1—Ni1—O1—C27 | −81.2 (2) | Ni1—N4—C15—C14 | 167.0 (3) |
O2—Ni1—O1—C27 | 5.2 (2) | C13—C14—C15—N4 | 0.8 (6) |
N9i—Ni1—O2—C27 | 173.3 (2) | C20—N6—C16—C17 | −2.7 (8) |
N7—Ni1—O2—C27 | −0.8 (4) | N6—C16—C17—C18 | 0.7 (8) |
N4—Ni1—O2—C27 | −96.8 (2) | C16—C17—C18—N5 | −179.3 (4) |
N1—Ni1—O2—C27 | 82.3 (2) | C16—C17—C18—C19 | 1.9 (6) |
O1—Ni1—O2—C27 | −5.1 (2) | C13—N5—C18—C17 | 57.8 (6) |
N9i—Ni1—N1—C5 | −38.6 (3) | C13—N5—C18—C19 | −123.4 (5) |
N7—Ni1—N1—C5 | −147.6 (3) | C17—C18—C19—C20 | −2.5 (6) |
O2—Ni1—N1—C5 | 55.4 (3) | N5—C18—C19—C20 | 178.7 (4) |
O1—Ni1—N1—C5 | 117.3 (3) | C16—N6—C20—C19 | 2.1 (8) |
C27—Ni1—N1—C5 | 86.6 (3) | C18—C19—C20—N6 | 0.5 (8) |
N9i—Ni1—N1—C1 | 152.6 (3) | C26—C21—C22—C23 | −0.1 (6) |
N7—Ni1—N1—C1 | 43.6 (3) | C27—C21—C22—C23 | 177.9 (4) |
O2—Ni1—N1—C1 | −113.4 (3) | C21—C22—C23—C24 | 1.1 (7) |
O1—Ni1—N1—C1 | −51.6 (3) | C22—C23—C24—C25 | −0.3 (6) |
C27—Ni1—N1—C1 | −82.2 (3) | C22—C23—C24—C28 | −177.0 (4) |
N9i—Ni1—N4—C11 | 130.0 (3) | C23—C24—C25—C26 | −1.5 (6) |
N7—Ni1—N4—C11 | −121.0 (3) | C28—C24—C25—C26 | 175.1 (4) |
O2—Ni1—N4—C11 | 35.9 (3) | C22—C21—C26—C25 | −1.7 (6) |
O1—Ni1—N4—C11 | −25.8 (3) | C27—C21—C26—C25 | −179.7 (4) |
C27—Ni1—N4—C11 | 4.7 (3) | C24—C25—C26—C21 | 2.5 (7) |
N9i—Ni1—N4—C15 | −39.2 (3) | Ni1—O1—C27—O2 | −8.8 (3) |
N7—Ni1—N4—C15 | 69.8 (3) | Ni1—O1—C27—C21 | 169.6 (3) |
O2—Ni1—N4—C15 | −133.3 (3) | Ni1—O2—C27—O1 | 9.0 (4) |
O1—Ni1—N4—C15 | 165.0 (3) | Ni1—O2—C27—C21 | −169.5 (3) |
C27—Ni1—N4—C15 | −164.4 (3) | C22—C21—C27—O1 | −167.8 (4) |
N9i—Ni1—N7—C31 | 164.7 (3) | C26—C21—C27—O1 | 10.2 (6) |
N4—Ni1—N7—C31 | 75.6 (3) | C22—C21—C27—O2 | 10.7 (6) |
N1—Ni1—N7—C31 | −103.1 (3) | C26—C21—C27—O2 | −171.3 (4) |
O2—Ni1—N7—C31 | −21.6 (5) | N9i—Ni1—C27—O1 | −179.3 (2) |
O1—Ni1—N7—C31 | −17.7 (3) | N7—Ni1—C27—O1 | 8.5 (3) |
C27—Ni1—N7—C31 | −22.1 (3) | N4—Ni1—C27—O1 | −84.7 (2) |
N9i—Ni1—N7—C35 | −27.1 (4) | N1—Ni1—C27—O1 | 95.1 (2) |
N4—Ni1—N7—C35 | −116.1 (3) | O2—Ni1—C27—O1 | −171.1 (4) |
N1—Ni1—N7—C35 | 65.1 (3) | N9i—Ni1—C27—O2 | −8.2 (3) |
O2—Ni1—N7—C35 | 146.7 (3) | N7—Ni1—C27—O2 | 179.6 (2) |
O1—Ni1—N7—C35 | 150.5 (3) | N4—Ni1—C27—O2 | 86.4 (2) |
C27—Ni1—N7—C35 | 146.2 (3) | N1—Ni1—C27—O2 | −93.8 (2) |
C5—N1—C1—C2 | 2.1 (6) | O1—Ni1—C27—O2 | 171.1 (4) |
Ni1—N1—C1—C2 | 171.7 (3) | C23—C24—C28—O4 | −95.8 (5) |
N1—C1—C2—C3 | 1.3 (6) | C25—C24—C28—O4 | 87.6 (5) |
C8—N2—C3—C2 | −34.4 (6) | C23—C24—C28—O3 | 82.8 (5) |
C8—N2—C3—C4 | 149.3 (4) | C25—C24—C28—O3 | −93.8 (5) |
C1—C2—C3—N2 | −179.9 (4) | C35—N7—C31—C32 | −3.2 (6) |
C1—C2—C3—C4 | −3.5 (6) | Ni1—N7—C31—C32 | 166.8 (3) |
N2—C3—C4—C5 | 179.0 (4) | N7—C31—C32—C33 | 3.7 (7) |
C2—C3—C4—C5 | 2.5 (6) | C31—C32—C33—N8 | −178.6 (4) |
C1—N1—C5—C4 | −3.2 (6) | C31—C32—C33—C34 | −1.1 (6) |
Ni1—N1—C5—C4 | −172.3 (3) | C38—N8—C33—C32 | 1.0 (7) |
C3—C4—C5—N1 | 0.9 (6) | C38—N8—C33—C34 | −176.5 (4) |
C10—N3—C6—C7 | 0.5 (7) | C32—C33—C34—C35 | −1.8 (6) |
N3—C6—C7—C8 | 0.1 (7) | N8—C33—C34—C35 | 176.0 (4) |
C6—C7—C8—C9 | −0.8 (6) | C31—N7—C35—C34 | 0.2 (6) |
C6—C7—C8—N2 | 173.9 (4) | Ni1—N7—C35—C34 | −167.5 (3) |
C3—N2—C8—C7 | 164.6 (4) | C33—C34—C35—N7 | 2.3 (6) |
C3—N2—C8—C9 | −21.1 (6) | C40—N9—C36—C37 | 2.3 (6) |
C7—C8—C9—C10 | 0.9 (6) | Ni1ii—N9—C36—C37 | −170.0 (3) |
N2—C8—C9—C10 | −173.5 (4) | N9—C36—C37—C38 | 2.4 (6) |
C6—N3—C10—C9 | −0.4 (7) | C33—N8—C38—C39 | 152.2 (4) |
C8—C9—C10—N3 | −0.3 (7) | C33—N8—C38—C37 | −29.4 (6) |
C15—N4—C11—C12 | 1.6 (6) | C36—C37—C38—N8 | 176.2 (4) |
Ni1—N4—C11—C12 | −168.0 (3) | C36—C37—C38—C39 | −5.4 (6) |
N4—C11—C12—C13 | 2.1 (7) | N8—C38—C39—C40 | −177.5 (3) |
C18—N5—C13—C12 | −2.9 (7) | C37—C38—C39—C40 | 4.0 (6) |
C18—N5—C13—C14 | 174.4 (4) | C36—N9—C40—C39 | −3.8 (6) |
C11—C12—C13—N5 | 173.2 (4) | Ni1ii—N9—C40—C39 | 167.4 (3) |
C11—C12—C13—C14 | −4.2 (6) | C38—C39—C40—N9 | 0.7 (6) |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O4iii | 0.99 (5) | 1.83 (5) | 2.793 (4) | 164 (4) |
N5—H5N···O3iv | 0.94 (5) | 1.93 (5) | 2.874 (5) | 177 (4) |
N8—H8N···O3v | 0.91 (4) | 1.93 (5) | 2.841 (4) | 179 (4) |
Symmetry codes: (iii) x−1/2, −y+3/2, z−1/2; (iv) x+1/2, −y+3/2, z−1/2; (v) −x+3/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C8H4O4)(C10H9N3)3] |
Mr | 735.42 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 17.025 (3), 11.048 (2), 18.736 (4) |
β (°) | 110.281 (3) |
V (Å3) | 3305.7 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.65 |
Crystal size (mm) | 0.38 × 0.14 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART 1K |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.834, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39515, 8097, 4711 |
Rint | 0.118 |
(sin θ/λ)max (Å−1) | 0.670 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.168, 1.02 |
No. of reflections | 8097 |
No. of parameters | 481 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.12, −0.84 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CrystalMaker (CrystalMaker Software, 2005).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O4i | 0.99 (5) | 1.83 (5) | 2.793 (4) | 164 (4) |
N5—H5N···O3ii | 0.94 (5) | 1.93 (5) | 2.874 (5) | 177 (4) |
N8—H8N···O3iii | 0.91 (4) | 1.93 (5) | 2.841 (4) | 179 (4) |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z−1/2; (iii) −x+3/2, y−1/2, −z+1/2. |
In comparison to the large number of coordination polymers constructed from the rigid rod tethering ligand 4,4'-bipyridine, metal-organic materials based on 4,4'-dipyridylamine (dpa) are much rarer (Montney et al., 2007). Prepared during continued attempts to develop this chemistry, the title compound possesses an asymmetric unit (Fig. 1) consisting of one nickel atom, one terephthalate (tp) dianion, and three crystallographically distinct dpa moieties. The nickel atom displays a [NiN4O2] octahedral coordination sphere, with the cis O donor atoms belonging to a chelating carboxylate terminus of the tp ligand. Two of the N atom donors, disposed in a cis fashion, belong to different bridging dpa ligands. The other two N donors belong to crystallographically independent monodentate dpa lignds.
Extension of the structure along the b crystal direction reveals an 1-D chain coordination polymer of formulation [Ni(tp)(dpa)3]n, constructed by the linkage of adjacent Ni atoms through exobidentate dpa ligands (Fig. 2). Within the 1-D chain motif, the Ni–Ni through-ligand distance is 11.048 (2) Å, marking the b lattice parameter.
Each [Ni(tp)(dpa)3]n chain is interwoven by another identical chain, related by the crystallographic 21 screw axis along b (Fig. 3). The double chain motifs are stabilized through N—H···O hydrogen bonding promoted by the central amine groups of the bridging dpa ligands. These one-dimensional subunits further aggregate into three dimensions via additional N—H···O hydrogen bonding patterns mediated by the pendant dpa ligands (Fig. 4).