A three-dimensional gadolinium organic framework based on a pyridinedi­carb­oxy­lic acid organic linker with a paddle-wheel-type network structure

A new gadolinium(III)–pyridine-2,5-di­carb­oxy­lic acid (Gd^III–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.

Computing details

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)]]

Crystal data

(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) Å^3	Plate, clear light colourless
Z = 16	0.24 × 0.22 × 0.19 mm
F(000) = 4128

Data collection

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

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.045	w = 1/[σ^2(Fo^2) + (0.0211P)^2 + 40.8363P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Gd1—O4^i	2.3915 (18)	C5—H5	0.908 (17)
Gd1—O4^ii	2.3915 (18)	C4—C3	1.362 (4)
Gd1—O1^iii	2.3709 (18)	C1—C6	1.518 (4)
Gd1—O1^iv	2.3709 (17)	C1—C2	1.368 (4)
Gd1—O3^v	2.3224 (18)	O2—C6	1.222 (4)
Gd1—O3	2.3223 (18)	N2—H2A^vi	0.8598
Gd1—N1^iii	2.5704 (19)	N2—H2A	0.8599
Gd1—N1^iv	2.5704 (19)	N2—C8^vi	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
O4^ii—Gd1—O4^i	125.18 (10)	O4—C7—O3	126.2 (2)
O4^i—Gd1—N1^iii	143.56 (7)	O4—C7—C4	117.5 (2)
O4^ii—Gd1—N1^iv	143.56 (7)	O3—C7—C4	116.3 (2)
O4^i—Gd1—N1^iv	73.41 (7)	N1—C5—C4	124.4 (2)
O4^ii—Gd1—N1^iii	73.41 (7)	N1—C5—H5	119 (2)
O1^iv—Gd1—O4^ii	84.90 (7)	C4—C5—H5	117 (2)
O1^iii—Gd1—O4^ii	134.34 (7)	C5—C4—C7	119.8 (2)
O1^iv—Gd1—O4^i	134.34 (7)	C3—C4—C7	122.8 (2)
O1^iii—Gd1—O4^i	84.90 (7)	C3—C4—C5	117.3 (3)
O1^iii—Gd1—O1^iv	97.00 (10)	N1—C1—C6	114.4 (2)
O1^iv—Gd1—N1^iii	71.80 (7)	N1—C1—C2	121.9 (3)
O1^iii—Gd1—N1^iv	71.80 (7)	C2—C1—C6	123.7 (3)
O1^iii—Gd1—N1^iii	64.24 (6)	O1—C6—C1	116.6 (2)
O1^iv—Gd1—N1^iv	64.24 (6)	O2—C6—O1	124.9 (3)
O3—Gd1—O4^i	77.79 (9)	O2—C6—C1	118.5 (3)
O3^v—Gd1—O4^ii	77.79 (9)	H2A—N2—H2A^vi	90.0
O3^v—Gd1—O4^i	74.39 (8)	C8^vi—N2—H2A^vi	111.7 (3)
O3—Gd1—O4^ii	74.39 (8)	C8—N2—H2A	111.7
O3^v—Gd1—O1^iv	150.99 (8)	C8—N2—H2A^vi	112.1 (3)
O3^v—Gd1—O1^iii	79.46 (8)	C8^vi—N2—H2A	112.1
O3—Gd1—O1^iv	79.46 (8)	C8^vi—N2—C8	116.4 (6)
O3—Gd1—O1^iii	150.99 (8)	C1—C2—H2	119.8
O3—Gd1—O3^v	117.07 (11)	C1—C2—C3	120.4 (3)
O3^v—Gd1—N1^iv	138.19 (7)	C3—C2—H2	119.8
O3—Gd1—N1^iii	138.19 (7)	C4—C3—C2	118.7 (3)
O3^v—Gd1—N1^iii	80.97 (7)	C4—C3—H3	120.7
O3—Gd1—N1^iv	80.97 (7)	C2—C3—H3	120.7
N1^iv—Gd1—N1^iii	111.39 (9)	N2—C8—H8A	109.5
C7—O4—Gd1^i	140.40 (17)	N2—C8—H8B	109.5
C6—O1—Gd1^vii	126.06 (17)	N2—C8—H8C	109.5
C7—O3—Gd1	151.55 (19)	H8A—C8—H8B	109.5
C5—N1—Gd1^vii	124.31 (16)	H8A—C8—H8C	109.5
C1—N1—Gd1^vii	118.03 (17)	H8B—C8—H8C	109.5
C1—N1—C5	117.2 (2)
Gd1^i—O4—C7—O3	9.3 (5)	N1—C5—C4—C3	−0.8 (5)
Gd1^i—O4—C7—C4	−170.3 (2)	N1—C1—C6—O1	−9.8 (5)
Gd1^vii—O1—C6—C1	7.4 (5)	N1—C1—C6—O2	170.6 (5)
Gd1^vii—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)
Gd1^vii—N1—C5—C4	170.5 (2)	C5—N1—C1—C2	1.4 (6)
Gd1^vii—N1—C1—C6	7.8 (4)	C5—C4—C3—C2	3.1 (7)
Gd1^vii—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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1^vi	0.86	2.27	3.004 (2)	144
N2—H2A···O2^vi	0.86	2.10	2.839 (5)	144
C2—H2···O2^viii	0.93	2.60	3.311 (6)	134
C5—H5···O4^ix	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.