A novel three-dimensional hetero­metallic coordination polymer: poly[[diaqua­di-μ₃-chlorido-μ₂-chlorido-tri-μ₃-nicotinato-tricopper(I)gadolinium(III)] hemihydrate]

In the title polymeric heterometallic compound, {[Cu₃Gd(C₆H₄NO₂)₃Cl₃(H₂O)₂]·0.5H₂O}_n, comprising copper(I) and gadolinium(III) cations bridged by nicotinate (nic) ligands and chloride anions, the Gd^III centers display a bicapped trigonal prismatic geometry, defined by six carboxyl­ate O atoms and two water mol­ecules. For copper(I), one Cu center is three-coordinated by three chloride ions and displays a trigonal–planar geometry; the other two Cu centers are four-coordinated and display a very distorted tetrahedral geometry. The chloride anions act in μ₂- and μ₃-bridging modes, linking the Cu^I ions into an infinite chain. The nic ligand exhibits a tridentate coordination mode, with the carboxyl­ate O atoms linking to two Gd^III ions and the N atom linking to one Cu^I ion. Thus, a novel three-dimensional heterometallic coordination polymer is constructed from Gd–carboxyl­ate subunits and Cu—Cl chains. In addition, intra- and inter­molecular O—H...O and O—H...Cl hydrogen bonds are also observed within the three-dimensional structure. Topologically, the framework represents an unusual 3,6-connected (4.8²)₃(4¹⁰.6⁵) net.

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

poly[[diaquatri-µ₂-chlorido-tri-µ₃-nicotinato- tricopper(I)gadolinium(III)] hemiydrate]

Crystal data

[Cu3Gd(C6H4NO2)3Cl3(H2O)2]·0.5H2O	F(000) = 1664
Mr = 865.52	Dx = 2.250 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1702 reflections
a = 9.5388 (11) Å	θ = 2.5–25.9°
b = 12.6589 (14) Å	µ = 5.40 mm^−1
c = 21.400 (2) Å	T = 110 K
β = 98.539 (1)°	Block, yellow
V = 2555.4 (5) Å^3	0.30 × 0.25 × 0.21 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	4591 independent reflections
Radiation source: fine-focus sealed tube	3561 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
φ and ω scans	θmax = 25.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→7
Tmin = 0.228, Tmax = 0.334	k = −15→13
12988 measured reflections	l = −25→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0474P)^2 + 7.0683P] where P = (Fo^2 + 2Fc^2)/3
4591 reflections	(Δ/σ)max = 0.001
334 parameters	Δρmax = 1.64 e Å^−3
0 restraints	Δρmin = −1.41 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Gd1	0.23187 (3)	0.47896 (3)	0.495689 (16)	0.01964 (12)
Cu1	0.48905 (12)	0.83009 (10)	0.73655 (6)	0.0596 (4)
Cu2	0.36048 (10)	−0.05740 (8)	0.37544 (5)	0.0406 (3)
Cu3	0.49387 (13)	−0.10681 (11)	0.26759 (6)	0.0635 (4)
Cl1	0.5019 (2)	−0.21584 (15)	0.35562 (10)	0.0390 (5)
Cl2	0.3585 (2)	0.03707 (17)	0.24938 (10)	0.0466 (5)
Cl3	0.6236 (3)	−0.18044 (19)	0.19970 (12)	0.0587 (7)
O1	0.1562 (5)	0.5733 (4)	0.5810 (2)	0.0341 (12)
O1W	0.3980 (5)	0.4442 (4)	0.5979 (2)	0.0270 (11)
H1W	0.3645	0.4696	0.6294	0.041*
H2W	0.4078	0.3800	0.6094	0.041*
O2	−0.0710 (5)	0.6146 (4)	0.5804 (2)	0.0352 (13)
O2W	0.3096 (6)	0.5051 (4)	0.3910 (2)	0.0372 (13)
H3W	0.3906	0.5332	0.4016	0.056*
H4W	0.3179	0.4415	0.3793	0.056*
O3	0.3759 (5)	0.3303 (4)	0.4794 (2)	0.0280 (11)
O4	0.5974 (5)	0.3886 (4)	0.4942 (2)	0.0329 (12)
O5	0.0849 (5)	−0.3872 (4)	0.4496 (2)	0.0350 (13)
O6	−0.1421 (5)	−0.3439 (4)	0.4438 (2)	0.0356 (13)
N1	0.2850 (7)	0.7934 (5)	0.7181 (3)	0.0324 (15)
N2	0.4971 (7)	0.0403 (5)	0.4192 (3)	0.0309 (15)
N3	0.1693 (6)	−0.1110 (5)	0.3604 (3)	0.0322 (15)
C1	0.1004 (7)	0.6971 (5)	0.6551 (3)	0.0250 (16)
C2	0.2414 (7)	0.7264 (6)	0.6718 (3)	0.0286 (17)
H2	0.3099	0.6969	0.6489	0.034*
C3	0.1882 (9)	0.8330 (6)	0.7516 (4)	0.038 (2)
H3	0.2188	0.8791	0.7860	0.046*
C4	0.0476 (10)	0.8088 (6)	0.7378 (4)	0.042 (2)
H4	−0.0182	0.8390	0.7620	0.050*
C5	0.0009 (8)	0.7408 (6)	0.6889 (3)	0.0311 (17)
H5	−0.0969	0.7241	0.6785	0.037*
C6	0.0579 (8)	0.6211 (6)	0.6007 (3)	0.0266 (16)
C7	0.5555 (7)	0.2112 (5)	0.4614 (3)	0.0219 (15)
C8	0.4598 (7)	0.1365 (6)	0.4368 (3)	0.0290 (17)
H8	0.3618	0.1537	0.4320	0.035*
C9	0.6366 (8)	0.0164 (6)	0.4279 (4)	0.0368 (19)
H9	0.6650	−0.0525	0.4174	0.044*
C10	0.7393 (8)	0.0885 (6)	0.4515 (4)	0.040 (2)
H10	0.8367	0.0695	0.4570	0.048*
C11	0.6988 (8)	0.1886 (6)	0.4671 (3)	0.0289 (17)
H11	0.7677	0.2407	0.4815	0.035*
C12	0.5067 (7)	0.3192 (5)	0.4799 (3)	0.0211 (15)
C13	0.0037 (7)	−0.2349 (5)	0.3934 (3)	0.0240 (15)
C14	0.1402 (7)	−0.2016 (6)	0.3888 (3)	0.0269 (16)
H14	0.2172	−0.2449	0.4067	0.032*
C15	0.0580 (9)	−0.0562 (6)	0.3317 (4)	0.043 (2)
H15	0.0759	0.0070	0.3103	0.052*
C16	−0.0804 (9)	−0.0858 (7)	0.3314 (5)	0.055 (3)
H16	−0.1557	−0.0456	0.3090	0.065*
C17	−0.1078 (8)	−0.1750 (6)	0.3642 (4)	0.039 (2)
H17	−0.2027	−0.1951	0.3667	0.047*
C18	−0.0190 (8)	−0.3303 (5)	0.4317 (3)	0.0249 (16)
O3W	0.1089 (12)	0.1450 (9)	0.4653 (6)	0.055 (3)	0.50
H5W	0.1054	0.1867	0.4962	0.082*	0.50
H6W	0.0727	0.1870	0.4363	0.082*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Gd1	0.01189 (17)	0.01873 (19)	0.0281 (2)	−0.00065 (14)	0.00240 (13)	−0.00094 (14)
Cu1	0.0410 (7)	0.0665 (8)	0.0668 (8)	−0.0195 (6)	−0.0069 (6)	−0.0158 (6)
Cu2	0.0281 (5)	0.0316 (5)	0.0619 (7)	−0.0130 (4)	0.0065 (5)	−0.0090 (5)
Cu3	0.0443 (7)	0.0732 (9)	0.0713 (9)	−0.0073 (6)	0.0026 (6)	−0.0160 (7)
Cl1	0.0344 (11)	0.0310 (11)	0.0497 (12)	0.0055 (9)	0.0004 (10)	−0.0011 (9)
Cl2	0.0477 (13)	0.0439 (13)	0.0473 (12)	−0.0133 (10)	0.0042 (10)	0.0002 (9)
Cl3	0.0519 (14)	0.0589 (15)	0.0709 (16)	0.0057 (12)	0.0274 (13)	0.0161 (12)
O1	0.025 (3)	0.039 (3)	0.038 (3)	0.005 (2)	0.006 (2)	−0.015 (2)
O1W	0.021 (3)	0.030 (3)	0.030 (3)	0.006 (2)	0.003 (2)	0.000 (2)
O2	0.017 (3)	0.042 (3)	0.044 (3)	−0.003 (2)	−0.003 (2)	−0.011 (3)
O2W	0.029 (3)	0.047 (3)	0.037 (3)	−0.009 (3)	0.007 (2)	−0.003 (2)
O3	0.016 (2)	0.023 (3)	0.045 (3)	0.004 (2)	0.003 (2)	−0.005 (2)
O4	0.023 (3)	0.023 (3)	0.052 (3)	−0.010 (2)	0.004 (2)	−0.008 (2)
O5	0.025 (3)	0.028 (3)	0.050 (3)	0.010 (2)	0.001 (3)	0.012 (2)
O6	0.023 (3)	0.035 (3)	0.050 (3)	−0.003 (2)	0.010 (3)	0.012 (2)
N1	0.028 (4)	0.030 (4)	0.036 (4)	−0.009 (3)	−0.006 (3)	−0.001 (3)
N2	0.026 (3)	0.026 (4)	0.042 (4)	−0.007 (3)	0.008 (3)	−0.006 (3)
N3	0.024 (3)	0.027 (4)	0.046 (4)	−0.006 (3)	0.006 (3)	0.003 (3)
C1	0.023 (4)	0.019 (4)	0.033 (4)	0.002 (3)	0.002 (3)	0.000 (3)
C2	0.018 (4)	0.032 (4)	0.034 (4)	−0.005 (3)	−0.002 (3)	0.000 (3)
C3	0.051 (6)	0.032 (4)	0.030 (4)	−0.002 (4)	−0.003 (4)	−0.009 (3)
C4	0.057 (6)	0.032 (5)	0.036 (5)	0.011 (4)	0.008 (4)	−0.004 (4)
C5	0.021 (4)	0.029 (4)	0.043 (5)	0.001 (3)	0.004 (3)	0.002 (3)
C6	0.022 (4)	0.028 (4)	0.030 (4)	0.000 (3)	0.003 (3)	−0.003 (3)
C7	0.019 (4)	0.019 (4)	0.028 (4)	−0.004 (3)	0.004 (3)	0.003 (3)
C8	0.016 (4)	0.028 (4)	0.044 (5)	0.002 (3)	0.006 (3)	−0.002 (3)
C9	0.021 (4)	0.030 (4)	0.059 (5)	0.005 (3)	0.005 (4)	−0.017 (4)
C10	0.020 (4)	0.044 (5)	0.055 (5)	0.011 (4)	0.003 (4)	−0.016 (4)
C11	0.021 (4)	0.029 (4)	0.036 (4)	0.000 (3)	0.002 (3)	−0.006 (3)
C12	0.020 (4)	0.021 (4)	0.021 (4)	−0.004 (3)	0.000 (3)	0.001 (3)
C13	0.017 (4)	0.024 (4)	0.031 (4)	−0.001 (3)	0.003 (3)	0.000 (3)
C14	0.014 (3)	0.027 (4)	0.038 (4)	0.000 (3)	0.001 (3)	0.001 (3)
C15	0.035 (5)	0.024 (4)	0.072 (6)	0.000 (4)	0.013 (5)	0.021 (4)
C16	0.029 (5)	0.045 (5)	0.089 (7)	0.016 (4)	0.008 (5)	0.041 (5)
C17	0.021 (4)	0.036 (5)	0.061 (6)	0.005 (4)	0.009 (4)	0.014 (4)
C18	0.026 (4)	0.024 (4)	0.023 (4)	0.000 (3)	−0.004 (3)	0.004 (3)
O3W	0.039 (7)	0.044 (7)	0.085 (9)	0.008 (6)	0.018 (7)	−0.007 (6)

Geometric parameters (Å, º)

Gd1—O5^i	2.324 (5)	N1—C2	1.323 (9)
Gd1—O4^ii	2.325 (5)	N1—C3	1.348 (10)
Gd1—O6^iii	2.380 (5)	N2—C8	1.339 (9)
Gd1—O2^iv	2.380 (5)	N2—C9	1.350 (9)
Gd1—O1	2.381 (5)	N3—C15	1.338 (10)
Gd1—O3	2.386 (4)	N3—C14	1.347 (9)
Gd1—O2W	2.485 (5)	C1—C2	1.390 (9)
Gd1—O1W	2.542 (4)	C1—C5	1.391 (10)
Cu1—N1	1.982 (6)	C1—C6	1.518 (9)
Cu1—Cl2^ii	2.215 (2)	C2—H2	0.9500
Cu1—Cl3^v	2.482 (3)	C3—C4	1.364 (12)
Cu1—Cu3^v	2.9022 (19)	C3—H3	0.9500
Cu2—N3	1.928 (6)	C4—C5	1.378 (10)
Cu2—N2	1.934 (6)	C4—H4	0.9500
Cu2—Cl1	2.488 (2)	C5—H5	0.9500
Cu2—Cu3	2.8652 (17)	C7—C8	1.364 (9)
Cu3—Cl2	2.233 (3)	C7—C11	1.384 (9)
Cu3—Cl3	2.246 (3)	C7—C12	1.515 (9)
Cu3—Cl1	2.327 (2)	C8—H8	0.9500
Cu3—Cu1^vi	2.9022 (19)	C9—C10	1.379 (11)
Cl2—Cu1^ii	2.215 (2)	C9—H9	0.9500
Cl3—Cu1^vi	2.482 (3)	C10—C11	1.380 (10)
O1—C6	1.241 (8)	C10—H10	0.9500
O1W—H1W	0.8500	C11—H11	0.9500
O1W—H2W	0.8501	C13—C17	1.378 (10)
O2—C6	1.245 (8)	C13—C14	1.385 (9)
O2—Gd1^iv	2.380 (5)	C13—C18	1.494 (9)
O2W—H3W	0.8501	C14—H14	0.9500
O2W—H4W	0.8500	C15—C16	1.371 (11)
O3—C12	1.254 (8)	C15—H15	0.9500
O4—C12	1.239 (8)	C16—C17	1.374 (11)
O4—Gd1^ii	2.325 (5)	C16—H16	0.9500
O5—C18	1.239 (8)	C17—H17	0.9500
O5—Gd1^vii	2.324 (5)	O3W—H5W	0.8500
O6—C18	1.251 (8)	O3W—H6W	0.8500
O6—Gd1^iii	2.380 (5)
O5^i—Gd1—O4^ii	83.34 (18)	C2—N1—C3	118.2 (6)
O5^i—Gd1—O6^iii	120.80 (18)	C2—N1—Cu1	119.3 (5)
O4^ii—Gd1—O6^iii	140.44 (18)	C3—N1—Cu1	122.5 (5)
O5^i—Gd1—O2^iv	77.61 (18)	C8—N2—C9	117.6 (6)
O4^ii—Gd1—O2^iv	142.59 (18)	C8—N2—Cu2	122.0 (5)
O6^iii—Gd1—O2^iv	76.52 (18)	C9—N2—Cu2	120.2 (5)
O5^i—Gd1—O1	74.19 (18)	C15—N3—C14	116.5 (6)
O4^ii—Gd1—O1	81.66 (18)	C15—N3—Cu2	124.1 (5)
O6^iii—Gd1—O1	76.61 (19)	C14—N3—Cu2	118.5 (5)
O2^iv—Gd1—O1	122.38 (17)	C2—C1—C5	117.9 (7)
O5^i—Gd1—O3	146.85 (18)	C2—C1—C6	120.3 (6)
O4^ii—Gd1—O3	99.89 (17)	C5—C1—C6	121.7 (6)
O6^iii—Gd1—O3	76.95 (17)	N1—C2—C1	123.3 (7)
O2^iv—Gd1—O3	80.46 (16)	N1—C2—H2	118.4
O1—Gd1—O3	138.95 (17)	C1—C2—H2	118.4
O5^i—Gd1—O2W	76.22 (18)	N1—C3—C4	122.1 (7)
O4^ii—Gd1—O2W	71.91 (18)	N1—C3—H3	119.0
O6^iii—Gd1—O2W	140.00 (18)	C4—C3—H3	119.0
O2^iv—Gd1—O2W	72.42 (17)	C3—C4—C5	120.0 (8)
O1—Gd1—O2W	142.16 (18)	C3—C4—H4	120.0
O3—Gd1—O2W	73.62 (17)	C5—C4—H4	120.0
O5^i—Gd1—O1W	138.72 (17)	C4—C5—C1	118.4 (7)
O4^ii—Gd1—O1W	72.91 (17)	C4—C5—H5	120.8
O6^iii—Gd1—O1W	68.64 (16)	C1—C5—H5	120.8
O2^iv—Gd1—O1W	139.33 (17)	O1—C6—O2	127.3 (7)
O1—Gd1—O1W	69.40 (16)	O1—C6—C1	116.2 (6)
O3—Gd1—O1W	71.96 (16)	O2—C6—C1	116.6 (6)
O2W—Gd1—O1W	124.62 (16)	C8—C7—C11	119.1 (6)
N1—Cu1—Cl2^ii	144.1 (2)	C8—C7—C12	120.8 (6)
N1—Cu1—Cl3^v	107.3 (2)	C11—C7—C12	120.1 (6)
Cl2^ii—Cu1—Cl3^v	105.23 (10)	N2—C8—C7	123.3 (7)
N1—Cu1—Cu3^v	78.43 (18)	N2—C8—H8	118.4
Cl2^ii—Cu1—Cu3^v	136.11 (8)	C7—C8—H8	118.4
Cl3^v—Cu1—Cu3^v	48.54 (7)	N2—C9—C10	122.3 (7)
N3—Cu2—N2	149.2 (3)	N2—C9—H9	118.8
N3—Cu2—Cl1	102.19 (19)	C10—C9—H9	118.8
N2—Cu2—Cl1	104.75 (19)	C9—C10—C11	119.1 (7)
N3—Cu2—Cu3	108.09 (19)	C9—C10—H10	120.4
N2—Cu2—Cu3	100.45 (19)	C11—C10—H10	120.4
Cl1—Cu2—Cu3	50.95 (6)	C10—C11—C7	118.5 (7)
Cl2—Cu3—Cl3	125.84 (10)	C10—C11—H11	120.7
Cl2—Cu3—Cl1	124.99 (9)	C7—C11—H11	120.7
Cl3—Cu3—Cl1	108.81 (10)	O4—C12—O3	125.4 (6)
Cl2—Cu3—Cu2	69.39 (7)	O4—C12—C7	118.3 (6)
Cl3—Cu3—Cu2	164.77 (9)	O3—C12—C7	116.2 (6)
Cl1—Cu3—Cu2	56.12 (6)	C17—C13—C14	118.1 (7)
Cl2—Cu3—Cu1^vi	139.92 (8)	C17—C13—C18	121.9 (6)
Cl3—Cu3—Cu1^vi	55.90 (7)	C14—C13—C18	119.9 (6)
Cl1—Cu3—Cu1^vi	66.75 (6)	N3—C14—C13	123.3 (7)
Cu2—Cu3—Cu1^vi	113.77 (6)	N3—C14—H14	118.3
Cu3—Cl1—Cu2	72.93 (7)	C13—C14—H14	118.3
Cu1^ii—Cl2—Cu3	104.15 (11)	N3—C15—C16	123.9 (7)
Cu3—Cl3—Cu1^vi	75.56 (8)	N3—C15—H15	118.0
C6—O1—Gd1	146.7 (5)	C16—C15—H15	118.0
Gd1—O1W—H1W	110.9	C15—C16—C17	118.5 (7)
Gd1—O1W—H2W	116.2	C15—C16—H16	120.7
H1W—O1W—H2W	99.9	C17—C16—H16	120.7
C6—O2—Gd1^iv	140.8 (5)	C16—C17—C13	119.4 (7)
Gd1—O2W—H3W	101.3	C16—C17—H17	120.3
Gd1—O2W—H4W	101.2	C13—C17—H17	120.3
H3W—O2W—H4W	110.7	O5—C18—O6	126.1 (7)
C12—O3—Gd1	132.9 (4)	O5—C18—C13	117.6 (6)
C12—O4—Gd1^ii	171.2 (5)	O6—C18—C13	116.2 (6)
C18—O5—Gd1^vii	163.6 (5)	H5W—O3W—H6W	97.0
C18—O6—Gd1^iii	129.5 (5)

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1; (v) x, −y+1/2, z+1/2; (vi) x, −y+1/2, z−1/2; (vii) x, y−1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···Cl2^v	0.85	2.58	3.326 (5)	148
O1W—H2W···Cl1^viii	0.85	2.33	3.158 (5)	165
O2W—H3W···O1W^ii	0.85	2.04	2.838 (7)	157
O2W—H4W···Cl3^ix	0.85	2.41	3.171 (6)	149
O3W—H5W···O6^iii	0.85	2.37	3.168 (13)	158
O3W—H6W···O2^iv	0.85	2.54	3.200 (13)	136

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1; (v) x, −y+1/2, z+1/2; (viii) −x+1, −y, −z+1; (ix) −x+1, y+1/2, −z+1/2.