A new gadolinium(III)–pyridine-2,5-dicarboxylic acid (GdIII–2,5-H2pdc)-based three-dimensional coordination polymer, namely, poly[dimethylazanium [bis(μ-pyridine-2,5-dicarboxylato)gadolinium(III)]], {[(CH3)2NH2][Gd(C7H3NO4)2]}n, CP-1, has been synthesized via a typical solvothermal method. The as-synthesized material was characterized in the solid state using single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis and FT–IR spectroscopy. During the synthesis of CP-1, the in situ dimethylformamide (DMF) promotes the formation of a dimeric unit and these act as secondary building blocks in the assembly of a three-dimensional anionic {[Gd(pdc)2]−}∞ framework. The framework has channels along the c axis which are filled by dimethylazanium cations. Interestingly, the framework shows a helical-type assembly running down the a axis. A Hirshfeld surface analysis of CP-1 suggests that extra stability is provided by hydrogen-bonding interactions. The magnetic properties of CP-1 showed weak antiferromagnetic couplings between adjacent Gd3+ ions.
Supporting information
CCDC reference: 1990670
Data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009),
DIAMOND (Pennington, 1999) and ORTEP-3 for Windows
(Farrugia, 2012); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
Poly[dimethylazanium [bis(µ-pyridine-2,5-dicarboxylato)gadolinium(III)]]
top
Crystal data top
(C2H7N)[Gd(C7H3NO4)2] | Dx = 1.646 Mg m−3 |
Mr = 532.54 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Fddd | Cell parameters from 10910 reflections |
a = 17.9185 (7) Å | θ = 3.5–30.4° |
b = 18.0874 (8) Å | µ = 3.13 mm−1 |
c = 26.5146 (11) Å | T = 296 K |
V = 8593.4 (6) Å3 | Plate, clear light colourless |
Z = 16 | 0.24 × 0.22 × 0.19 mm |
F(000) = 4128 | |
Data collection top
Rigaku OD SuperNova Dual source diffractometer with a Pilatus 200K detector | 2173 independent reflections |
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source | 2015 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.019 |
ω scans | θmax = 30.5°, θmin = 3.6° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018) | h = −21→23 |
Tmin = 0.686, Tmax = 1.000 | k = −24→21 |
13872 measured reflections | l = −31→32 |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.018 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.045 | w = 1/[σ2(Fo2) + (0.0211P)2 + 40.8363P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.003 |
2173 reflections | Δρmax = 0.51 e Å−3 |
133 parameters | Δρmin = −0.52 e Å−3 |
1 restraint | |
Special details top
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. Single-crystal structure determination of CP-1 was executed on a
SuperNova, Dual, Mo at home/near, Pilatus 200 K diffractometer equipped with a
microfocus, 2.4 kW sealed-tube X-ray source (Mo—Kα radiation,
wavelength = 0.71073 Å) operating at 40 kV and 40 mA. Under OLEX2
software, the structure was solved by the direct method using SHELXT-2014 and
refined on F2 by a full-matrix least-squares technique using the
SHELXL2014 program package. ?(Sheldrick, 2014)? An empirical absorption
correction based on symmetry-equivalent reflections was applied using
SADABS. ?(Sheldrick, 2014)? The graphics programs DIAMOND
(Pennington, 1999) and ORTEP-3 for Windows (Farrugia, 2012) were used
to draw the structures. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Gd1 | 0.50093 (2) | 0.875000 | 0.375000 | 0.01937 (6) | |
O4 | 0.31052 (11) | 0.78977 (12) | 0.43005 (8) | 0.0491 (5) | |
O1 | 0.33860 (11) | 0.52839 (10) | 0.61310 (7) | 0.0418 (4) | |
O3 | 0.43328 (11) | 0.79673 (12) | 0.42726 (8) | 0.0527 (5) | |
N1 | 0.33178 (11) | 0.63435 (11) | 0.54518 (7) | 0.0295 (4) | |
C7 | 0.37391 (13) | 0.76847 (14) | 0.44120 (9) | 0.0295 (5) | |
C5 | 0.33041 (14) | 0.69163 (14) | 0.51301 (10) | 0.0329 (5) | |
C4 | 0.38030 (14) | 0.70176 (15) | 0.47455 (10) | 0.0344 (5) | |
C1 | 0.38371 (19) | 0.58430 (18) | 0.53825 (12) | 0.0532 (9) | |
O2 | 0.4217 (2) | 0.46732 (19) | 0.56820 (13) | 0.1366 (19) | |
C6 | 0.3818 (2) | 0.52096 (19) | 0.57581 (13) | 0.0613 (10) | |
N2 | 0.375000 | 0.375000 | 0.64885 (18) | 0.098 (2) | |
H2A | 0.381700 | 0.342040 | 0.625919 | 0.117* | 0.5 |
C2 | 0.4356 (3) | 0.5905 (3) | 0.50064 (17) | 0.109 (2) | |
H2 | 0.471236 | 0.553617 | 0.496400 | 0.131* | |
C3 | 0.4353 (2) | 0.6504 (2) | 0.46922 (16) | 0.0865 (16) | |
H3 | 0.472046 | 0.656070 | 0.444717 | 0.104* | |
C8 | 0.4413 (4) | 0.3878 (3) | 0.6772 (2) | 0.1093 (19) | |
H8A | 0.476246 | 0.348612 | 0.671027 | 0.164* | |
H8B | 0.429428 | 0.389495 | 0.712463 | 0.164* | |
H8C | 0.463015 | 0.434097 | 0.667133 | 0.164* | |
H5 | 0.2940 (14) | 0.7261 (14) | 0.5166 (11) | 0.044 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Gd1 | 0.02181 (9) | 0.01815 (9) | 0.01814 (9) | 0.000 | 0.000 | −0.00319 (5) |
O4 | 0.0424 (11) | 0.0550 (13) | 0.0500 (12) | 0.0142 (9) | 0.0044 (9) | 0.0296 (10) |
O1 | 0.0507 (11) | 0.0358 (10) | 0.0389 (10) | 0.0183 (9) | 0.0096 (8) | 0.0126 (8) |
O3 | 0.0452 (11) | 0.0555 (13) | 0.0575 (13) | −0.0112 (10) | 0.0114 (10) | 0.0231 (11) |
N1 | 0.0315 (10) | 0.0309 (10) | 0.0261 (10) | 0.0056 (8) | 0.0043 (8) | 0.0060 (8) |
C7 | 0.0373 (13) | 0.0288 (12) | 0.0224 (11) | 0.0012 (10) | 0.0046 (9) | 0.0083 (9) |
C5 | 0.0336 (13) | 0.0320 (13) | 0.0331 (13) | 0.0071 (10) | 0.0041 (10) | 0.0115 (10) |
C4 | 0.0365 (13) | 0.0360 (14) | 0.0306 (12) | 0.0063 (10) | 0.0049 (10) | 0.0102 (11) |
C1 | 0.067 (2) | 0.0455 (17) | 0.0468 (17) | 0.0291 (15) | 0.0230 (15) | 0.0190 (14) |
O2 | 0.203 (4) | 0.095 (2) | 0.112 (3) | 0.112 (3) | 0.105 (3) | 0.069 (2) |
C6 | 0.084 (2) | 0.0460 (18) | 0.0538 (19) | 0.0351 (17) | 0.0310 (17) | 0.0236 (15) |
N2 | 0.196 (7) | 0.053 (3) | 0.044 (3) | −0.026 (3) | 0.000 | 0.000 |
C2 | 0.125 (4) | 0.103 (3) | 0.099 (3) | 0.089 (3) | 0.082 (3) | 0.068 (3) |
C3 | 0.091 (3) | 0.088 (3) | 0.080 (3) | 0.056 (2) | 0.060 (2) | 0.053 (2) |
C8 | 0.133 (5) | 0.096 (4) | 0.100 (4) | 0.035 (3) | −0.007 (4) | 0.024 (3) |
Geometric parameters (Å, º) top
Gd1—O4i | 2.3915 (18) | C5—H5 | 0.908 (17) |
Gd1—O4ii | 2.3915 (18) | C4—C3 | 1.362 (4) |
Gd1—O1iii | 2.3709 (18) | C1—C6 | 1.518 (4) |
Gd1—O1iv | 2.3709 (17) | C1—C2 | 1.368 (4) |
Gd1—O3v | 2.3224 (18) | O2—C6 | 1.222 (4) |
Gd1—O3 | 2.3223 (18) | N2—H2Avi | 0.8598 |
Gd1—N1iii | 2.5704 (19) | N2—H2A | 0.8599 |
Gd1—N1iv | 2.5704 (19) | N2—C8vi | 1.425 (6) |
O4—C7 | 1.235 (3) | N2—C8 | 1.425 (6) |
O1—C6 | 1.263 (3) | C2—H2 | 0.9300 |
O3—C7 | 1.237 (3) | C2—C3 | 1.368 (5) |
N1—C5 | 1.342 (3) | C3—H3 | 0.9300 |
N1—C1 | 1.311 (3) | C8—H8A | 0.9600 |
C7—C4 | 1.500 (3) | C8—H8B | 0.9600 |
C5—C4 | 1.368 (4) | C8—H8C | 0.9600 |
| | | |
O4ii—Gd1—O4i | 125.18 (10) | O4—C7—O3 | 126.2 (2) |
O4i—Gd1—N1iii | 143.56 (7) | O4—C7—C4 | 117.5 (2) |
O4ii—Gd1—N1iv | 143.56 (7) | O3—C7—C4 | 116.3 (2) |
O4i—Gd1—N1iv | 73.41 (7) | N1—C5—C4 | 124.4 (2) |
O4ii—Gd1—N1iii | 73.41 (7) | N1—C5—H5 | 119 (2) |
O1iv—Gd1—O4ii | 84.90 (7) | C4—C5—H5 | 117 (2) |
O1iii—Gd1—O4ii | 134.34 (7) | C5—C4—C7 | 119.8 (2) |
O1iv—Gd1—O4i | 134.34 (7) | C3—C4—C7 | 122.8 (2) |
O1iii—Gd1—O4i | 84.90 (7) | C3—C4—C5 | 117.3 (3) |
O1iii—Gd1—O1iv | 97.00 (10) | N1—C1—C6 | 114.4 (2) |
O1iv—Gd1—N1iii | 71.80 (7) | N1—C1—C2 | 121.9 (3) |
O1iii—Gd1—N1iv | 71.80 (7) | C2—C1—C6 | 123.7 (3) |
O1iii—Gd1—N1iii | 64.24 (6) | O1—C6—C1 | 116.6 (2) |
O1iv—Gd1—N1iv | 64.24 (6) | O2—C6—O1 | 124.9 (3) |
O3—Gd1—O4i | 77.79 (9) | O2—C6—C1 | 118.5 (3) |
O3v—Gd1—O4ii | 77.79 (9) | H2A—N2—H2Avi | 90.0 |
O3v—Gd1—O4i | 74.39 (8) | C8vi—N2—H2Avi | 111.7 (3) |
O3—Gd1—O4ii | 74.39 (8) | C8—N2—H2A | 111.7 |
O3v—Gd1—O1iv | 150.99 (8) | C8—N2—H2Avi | 112.1 (3) |
O3v—Gd1—O1iii | 79.46 (8) | C8vi—N2—H2A | 112.1 |
O3—Gd1—O1iv | 79.46 (8) | C8vi—N2—C8 | 116.4 (6) |
O3—Gd1—O1iii | 150.99 (8) | C1—C2—H2 | 119.8 |
O3—Gd1—O3v | 117.07 (11) | C1—C2—C3 | 120.4 (3) |
O3v—Gd1—N1iv | 138.19 (7) | C3—C2—H2 | 119.8 |
O3—Gd1—N1iii | 138.19 (7) | C4—C3—C2 | 118.7 (3) |
O3v—Gd1—N1iii | 80.97 (7) | C4—C3—H3 | 120.7 |
O3—Gd1—N1iv | 80.97 (7) | C2—C3—H3 | 120.7 |
N1iv—Gd1—N1iii | 111.39 (9) | N2—C8—H8A | 109.5 |
C7—O4—Gd1i | 140.40 (17) | N2—C8—H8B | 109.5 |
C6—O1—Gd1vii | 126.06 (17) | N2—C8—H8C | 109.5 |
C7—O3—Gd1 | 151.55 (19) | H8A—C8—H8B | 109.5 |
C5—N1—Gd1vii | 124.31 (16) | H8A—C8—H8C | 109.5 |
C1—N1—Gd1vii | 118.03 (17) | H8B—C8—H8C | 109.5 |
C1—N1—C5 | 117.2 (2) | | |
| | | |
Gd1i—O4—C7—O3 | 9.3 (5) | N1—C5—C4—C3 | −0.8 (5) |
Gd1i—O4—C7—C4 | −170.3 (2) | N1—C1—C6—O1 | −9.8 (5) |
Gd1vii—O1—C6—C1 | 7.4 (5) | N1—C1—C6—O2 | 170.6 (5) |
Gd1vii—O1—C6—O2 | −173.0 (4) | N1—C1—C2—C3 | 1.0 (9) |
Gd1—O3—C7—O4 | −14.6 (6) | C7—C4—C3—C2 | −178.4 (5) |
Gd1—O3—C7—C4 | 165.0 (3) | C5—N1—C1—C6 | −179.7 (3) |
Gd1vii—N1—C5—C4 | 170.5 (2) | C5—N1—C1—C2 | 1.4 (6) |
Gd1vii—N1—C1—C6 | 7.8 (4) | C5—C4—C3—C2 | 3.1 (7) |
Gd1vii—N1—C1—C2 | −171.1 (4) | C1—N1—C5—C4 | −1.5 (4) |
O4—C7—C4—C5 | −37.5 (4) | C1—C2—C3—C4 | −3.3 (9) |
O4—C7—C4—C3 | 144.1 (4) | C6—C1—C2—C3 | −177.8 (5) |
O3—C7—C4—C5 | 142.8 (3) | C2—C1—C6—O1 | 169.0 (5) |
O3—C7—C4—C3 | −35.6 (5) | C2—C1—C6—O2 | −10.6 (8) |
N1—C5—C4—C7 | −179.3 (2) | | |
Symmetry codes: (i) −x+3/4, −y+7/4, z; (ii) −x+3/4, y, −z+3/4; (iii) x+1/4, −y+3/2, z−1/4; (iv) x+1/4, y+1/4, −z+1; (v) x, −y+7/4, −z+3/4; (vi) −x+3/4, −y+3/4, z; (vii) x−1/4, y−1/4, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1vi | 0.86 | 2.27 | 3.004 (2) | 144 |
N2—H2A···O2vi | 0.86 | 2.10 | 2.839 (5) | 144 |
C2—H2···O2viii | 0.93 | 2.60 | 3.311 (6) | 134 |
C5—H5···O4ix | 0.91 (3) | 2.37 (3) | 2.961 (3) | 123 (2) |
Symmetry codes: (vi) −x+3/4, −y+3/4, z; (viii) −x+1, −y+1, −z+1; (ix) −x+1/2, −y+3/2, −z+1. |