A one-dimensional copper(II) coordination polymer incorporating succinate and N,N-di­ethyl­ethyl­ene­di­amine ligands: crystallographic analysis, vibrational and surface features, and DFT analysis

Transition metal atoms can be bridged by aliphatic di­carboxyl­ate ligands to pro­duce chains, layers and frameworks. The reaction of copper sulfate with succinic acid (H₂succ) and N,N-di­ethyl­ethylenedi­amine (deed) in basic solution produces the complex catena-poly[[[(N,N-di­ethyl­ethylenedi­amine-κ²N,N′)copper(II)]-μ-succinato-κ²O¹:O⁴] tetra­hydrate], {[Cu(C₄H₄O₄)(C₆H₁₆N₂)]·4H₂O}_n or {[Cu(succ)(deed)]·4H₂O}_n. Each carboxyl­ate group of the succinate ligand coordinates to a Cu^II atom in a monodentate fashion, giving rise to a square-planar coordination envir­onment. The succinate ligands bridge the Cu^II centres to form one-dimensional polymeric chains. Hydrogen bonds between the ligands and water mol­ecules link these chains into sheets that lie in the ab plane. Density functional theory (DFT) calculations were used to support the experimental data. From these calculations, a good linear correlation was observed between the experimental and theoretically predicted structural and spectroscopic parameters (R² ∼ 0.97).

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012).

catena-poly[[[(N,N'-diethylethylenediamine-κ²N,N')copper(II)]-µ-succinato-κ²O¹:O⁴] tetrahydrate]

Crystal data

[Cu(C4H4O4)(C6H16N2)]·4H2O	F(000) = 780
Mr = 367.88	Dx = 1.480 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.7523 (8) Å	Cell parameters from 4139 reflections
b = 7.1201 (3) Å	θ = 2.6–28.4°
c = 15.9540 (8) Å	µ = 1.36 mm^−1
β = 112.709 (4)°	T = 296 K
V = 1650.65 (14) Å^3	Prism, colourless
Z = 4	0.59 × 0.28 × 0.22 mm

Data collection

Stoe IPDS 2 diffractometer	4139 independent reflections
Radiation source: fine-focus sealed tube	3319 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
rotation method scans	θmax = 28.4°, θmin = 2.6°
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	h = −21→19
Tmin = 0.706, Tmax = 0.746	k = −9→9
14320 measured reflections	l = −21→21

Refinement

Refinement on F^2	8 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.0463P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.003
4139 reflections	Δρmax = 0.31 e Å^−3
230 parameters	Δρmin = −0.39 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.67131 (2)	0.18512 (3)	0.01348 (2)	0.03201 (7)
O2	0.57540 (9)	−0.10373 (19)	−0.06668 (9)	0.0420 (3)
O1	0.69858 (8)	0.02860 (17)	−0.07478 (8)	0.0370 (3)
O4	0.58542 (9)	−0.66700 (17)	−0.08988 (9)	0.0406 (3)
O3	0.71163 (9)	−0.4996 (2)	−0.05059 (10)	0.0509 (4)
O8	1.03765 (13)	−0.3245 (3)	0.10053 (12)	0.0609 (4)
O6	0.84947 (12)	0.0078 (2)	−0.13168 (12)	0.0585 (4)
N2	0.77661 (9)	0.0890 (2)	0.12811 (9)	0.0341 (3)
O7	0.87644 (11)	−0.3607 (2)	−0.05928 (13)	0.0593 (4)
N1	0.61688 (11)	0.2886 (3)	0.09755 (11)	0.0405 (3)
O5	0.40918 (11)	−0.6981 (3)	−0.09353 (12)	0.0555 (4)
C8	0.62893 (12)	−0.2168 (2)	−0.17965 (11)	0.0346 (4)
H8A	0.690903	−0.242006	−0.175631	0.042*
H8B	0.596571	−0.150742	−0.236230	0.042*
C10	0.63105 (12)	−0.5279 (2)	−0.10114 (12)	0.0338 (3)
C7	0.63387 (11)	−0.0920 (2)	−0.10136 (11)	0.0317 (3)
C9	0.58072 (12)	−0.4019 (2)	−0.18145 (12)	0.0347 (3)
H9A	0.519677	−0.376373	−0.182916	0.042*
H9B	0.573513	−0.468278	−0.236896	0.042*
C3	0.85343 (13)	0.2279 (3)	0.15207 (13)	0.0456 (4)
H3A	0.898168	0.199061	0.212368	0.055*
H3B	0.829092	0.352101	0.154316	0.055*
C2	0.73707 (13)	0.0909 (3)	0.19961 (12)	0.0426 (4)
H2A	0.786433	0.084256	0.259245	0.051*
H2B	0.697829	−0.018002	0.192329	0.051*
C5	0.80721 (13)	−0.1044 (3)	0.11766 (14)	0.0433 (4)
H5A	0.828946	−0.103754	0.068463	0.052*
H5B	0.754329	−0.187371	0.100051	0.052*
C4	0.90179 (15)	0.2320 (4)	0.08705 (16)	0.0562 (5)
H4A	0.950012	0.324078	0.106826	0.084*
H4B	0.927679	0.110593	0.085503	0.084*
H4C	0.858510	0.263838	0.027373	0.084*
C1	0.68198 (14)	0.2672 (3)	0.19240 (13)	0.0432 (4)
H1A	0.648690	0.259110	0.232283	0.052*
H1B	0.722698	0.375030	0.210470	0.052*
C6	0.88274 (19)	−0.1852 (4)	0.20193 (17)	0.0661 (6)
H6A	0.897986	−0.309480	0.188980	0.099*
H6B	0.936313	−0.106635	0.219133	0.099*
H6C	0.861539	−0.190427	0.250788	0.099*
H7A	0.5710 (16)	0.221 (3)	0.0898 (15)	0.048 (6)*
H7B	0.6036 (17)	0.407 (4)	0.0821 (16)	0.055 (7)*
H8WA	1.041 (3)	−0.218 (3)	0.075 (3)	0.146 (17)*
H8WB	1.066 (3)	−0.424 (4)	0.087 (3)	0.125 (14)*
H7WB	0.914 (4)	−0.337 (10)	−0.001 (2)	0.26 (3)*
H7WA	0.8247 (16)	−0.388 (4)	−0.052 (2)	0.082 (9)*
H6WA	0.8053 (16)	0.027 (4)	−0.115 (2)	0.082 (9)*
H6WB	0.867 (2)	−0.104 (3)	−0.111 (3)	0.129 (15)*
H5WA	0.414 (2)	−0.756 (4)	−0.049 (2)	0.069 (9)*
H5WB	0.463 (2)	−0.697 (4)	−0.0933 (18)	0.069 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03143 (11)	0.03345 (11)	0.03124 (11)	−0.00226 (8)	0.01220 (8)	−0.00288 (9)
O2	0.0469 (7)	0.0427 (7)	0.0445 (7)	−0.0045 (6)	0.0265 (6)	−0.0034 (6)
O1	0.0368 (6)	0.0377 (6)	0.0375 (6)	−0.0063 (5)	0.0155 (5)	−0.0076 (5)
O4	0.0393 (6)	0.0376 (7)	0.0444 (7)	−0.0048 (5)	0.0157 (6)	0.0039 (6)
O3	0.0337 (7)	0.0524 (8)	0.0551 (8)	−0.0042 (6)	0.0043 (6)	0.0130 (7)
O8	0.0618 (10)	0.0614 (10)	0.0625 (10)	−0.0038 (8)	0.0273 (8)	−0.0019 (9)
O6	0.0581 (10)	0.0569 (10)	0.0688 (11)	−0.0002 (8)	0.0335 (9)	0.0013 (8)
N2	0.0326 (7)	0.0370 (8)	0.0317 (7)	−0.0027 (6)	0.0113 (6)	−0.0006 (6)
O7	0.0437 (8)	0.0585 (9)	0.0745 (11)	0.0010 (7)	0.0215 (8)	0.0102 (8)
N1	0.0391 (8)	0.0442 (10)	0.0406 (8)	−0.0005 (7)	0.0181 (7)	−0.0047 (7)
O5	0.0440 (8)	0.0715 (11)	0.0532 (9)	0.0052 (7)	0.0213 (7)	0.0143 (8)
C8	0.0422 (9)	0.0320 (9)	0.0301 (8)	0.0000 (7)	0.0145 (7)	0.0000 (6)
C10	0.0355 (8)	0.0319 (8)	0.0368 (9)	0.0002 (7)	0.0170 (7)	−0.0029 (7)
C7	0.0353 (8)	0.0293 (8)	0.0287 (8)	0.0027 (6)	0.0106 (6)	0.0039 (6)
C9	0.0350 (8)	0.0332 (9)	0.0330 (8)	0.0003 (7)	0.0101 (7)	−0.0031 (7)
C3	0.0394 (9)	0.0533 (12)	0.0408 (10)	−0.0119 (8)	0.0118 (8)	−0.0048 (9)
C2	0.0443 (10)	0.0517 (11)	0.0339 (9)	−0.0013 (8)	0.0173 (8)	0.0018 (8)
C5	0.0421 (10)	0.0407 (10)	0.0456 (10)	0.0045 (8)	0.0152 (8)	0.0011 (8)
C4	0.0419 (11)	0.0728 (15)	0.0560 (13)	−0.0124 (10)	0.0214 (10)	0.0061 (11)
C1	0.0465 (10)	0.0507 (11)	0.0355 (9)	−0.0027 (8)	0.0191 (8)	−0.0075 (8)
C6	0.0683 (15)	0.0681 (15)	0.0568 (13)	0.0273 (12)	0.0186 (12)	0.0178 (12)

Geometric parameters (Å, º)

Cu1—O1	1.9689 (12)	C8—C9	1.516 (2)
Cu1—O4^i	1.9839 (13)	C8—H8A	0.9700
Cu1—N1	1.9914 (16)	C8—H8B	0.9700
Cu1—N2	2.0547 (14)	C10—C9	1.513 (2)
O2—C7	1.247 (2)	C9—H9A	0.9700
O1—C7	1.274 (2)	C9—H9B	0.9700
O4—C10	1.277 (2)	C3—C4	1.506 (3)
O3—C10	1.229 (2)	C3—H3A	0.9700
O8—H8WA	0.877 (18)	C3—H3B	0.9700
O8—H8WB	0.902 (17)	C2—C1	1.505 (3)
O6—H6WA	0.847 (17)	C2—H2A	0.9700
O6—H6WB	0.865 (18)	C2—H2B	0.9700
N2—C5	1.490 (2)	C5—C6	1.523 (3)
N2—C3	1.494 (2)	C5—H5A	0.9700
N2—C2	1.496 (2)	C5—H5B	0.9700
O7—H7WB	0.91 (2)	C4—H4A	0.9600
O7—H7WA	0.885 (18)	C4—H4B	0.9600
N1—C1	1.472 (2)	C4—H4C	0.9600
N1—H7A	0.84 (2)	C1—H1A	0.9700
N1—H7B	0.88 (3)	C1—H1B	0.9700
O5—H5WA	0.79 (3)	C6—H6A	0.9600
O5—H5WB	0.85 (3)	C6—H6B	0.9600
C8—C7	1.510 (2)	C6—H6C	0.9600
O1—Cu1—O4^i	88.45 (5)	C10—C9—H9B	108.8
O1—Cu1—N1	163.90 (6)	C8—C9—H9B	108.8
O4^i—Cu1—N1	91.76 (6)	H9A—C9—H9B	107.7
O1—Cu1—N2	97.13 (5)	N2—C3—C4	114.32 (17)
O4^i—Cu1—N2	166.84 (6)	N2—C3—H3A	108.7
N1—Cu1—N2	86.18 (6)	C4—C3—H3A	108.7
C7—O1—Cu1	104.60 (10)	N2—C3—H3B	108.7
C10—O4—Cu1^ii	106.76 (11)	C4—C3—H3B	108.7
H8WA—O8—H8WB	116 (3)	H3A—C3—H3B	107.6
H6WA—O6—H6WB	102 (2)	N2—C2—C1	110.27 (15)
C5—N2—C3	112.06 (15)	N2—C2—H2A	109.6
C5—N2—C2	109.96 (14)	C1—C2—H2A	109.6
C3—N2—C2	109.50 (14)	N2—C2—H2B	109.6
C5—N2—Cu1	113.15 (11)	C1—C2—H2B	109.6
C3—N2—Cu1	107.65 (11)	H2A—C2—H2B	108.1
C2—N2—Cu1	104.19 (10)	N2—C5—C6	115.26 (17)
H7WB—O7—H7WA	101 (5)	N2—C5—H5A	108.5
C1—N1—Cu1	110.11 (12)	C6—C5—H5A	108.5
C1—N1—H7A	108.2 (16)	N2—C5—H5B	108.5
Cu1—N1—H7A	105.0 (16)	C6—C5—H5B	108.5
C1—N1—H7B	112.5 (16)	H5A—C5—H5B	107.5
Cu1—N1—H7B	106.4 (15)	C3—C4—H4A	109.5
H7A—N1—H7B	114 (2)	C3—C4—H4B	109.5
H5WA—O5—H5WB	105 (3)	H4A—C4—H4B	109.5
C7—C8—C9	113.13 (14)	C3—C4—H4C	109.5
C7—C8—H8A	109.0	H4A—C4—H4C	109.5
C9—C8—H8A	109.0	H4B—C4—H4C	109.5
C7—C8—H8B	109.0	N1—C1—C2	108.50 (15)
C9—C8—H8B	109.0	N1—C1—H1A	110.0
H8A—C8—H8B	107.8	C2—C1—H1A	110.0
O3—C10—O4	121.96 (17)	N1—C1—H1B	110.0
O3—C10—C9	121.95 (16)	C2—C1—H1B	110.0
O4—C10—C9	116.07 (15)	H1A—C1—H1B	108.4
O2—C7—O1	122.06 (15)	C5—C6—H6A	109.5
O2—C7—C8	121.10 (15)	C5—C6—H6B	109.5
O1—C7—C8	116.81 (14)	H6A—C6—H6B	109.5
C10—C9—C8	113.84 (14)	C5—C6—H6C	109.5
C10—C9—H9A	108.8	H6A—C6—H6C	109.5
C8—C9—H9A	108.8	H6B—C6—H6C	109.5
Cu1^ii—O4—C10—O3	−3.0 (2)	C2—N2—C3—C4	177.19 (18)
Cu1^ii—O4—C10—C9	175.82 (11)	Cu1—N2—C3—C4	−70.13 (19)
Cu1—O1—C7—O2	−5.97 (19)	C5—N2—C2—C1	−163.71 (16)
Cu1—O1—C7—C8	171.91 (12)	C3—N2—C2—C1	72.75 (19)
C9—C8—C7—O2	−26.7 (2)	Cu1—N2—C2—C1	−42.16 (17)
C9—C8—C7—O1	155.35 (15)	C3—N2—C5—C6	60.3 (2)
O3—C10—C9—C8	−14.5 (2)	C2—N2—C5—C6	−61.8 (2)
O4—C10—C9—C8	166.67 (14)	Cu1—N2—C5—C6	−177.80 (15)
C7—C8—C9—C10	−65.18 (19)	Cu1—N1—C1—C2	−32.42 (19)
C5—N2—C3—C4	54.9 (2)	N2—C2—C1—N1	50.7 (2)

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6WA···O1	0.85 (2)	2.02 (2)	2.857 (2)	171 (3)
O6—H6WB···O7	0.87 (2)	1.99 (2)	2.832 (2)	166 (3)
O7—H7WB···O8	0.91 (2)	1.99 (4)	2.831 (3)	153 (7)
O7—H7WA···O3	0.89 (2)	1.96 (2)	2.831 (2)	167 (3)
O5—H5WB···O4	0.85 (3)	1.91 (3)	2.763 (2)	174 (3)
C8—H8A···O6	0.97	2.92	3.628 (2)	130
C8—H8A···O7	0.97	2.92	3.763 (2)	146
C5—H5A···O1	0.97	2.59	3.032 (2)	108
C4—H4C···O1	0.96	2.94	3.554 (3)	123
C8—H8B···O5^iii	0.97	2.70	3.434 (2)	133
C3—H3A···O8^iv	0.97	2.76	3.665 (3)	155
C2—H2A···O8^iv	0.97	2.88	3.793 (3)	156
O5—H5WA···O2^v	0.79 (3)	2.05 (3)	2.847 (2)	178 (3)
C5—H5B···O5^v	0.97	2.67	3.568 (3)	155
C2—H2B···O5^v	0.97	2.71	3.603 (3)	153
C4—H4A···O8^i	0.96	2.88	3.774 (3)	156
C4—H4C···O3^i	0.96	2.74	3.517 (3)	138
C1—H1B···O6^vi	0.97	2.67	3.418 (3)	134
C6—H6C···O6^vii	0.96	2.99	3.698 (3)	132
C6—H6C···O7^vii	0.96	2.97	3.863 (3)	155
N1—H7A···O2^viii	0.84 (2)	2.34 (3)	3.162 (2)	166 (2)
N1—H7B···O5^viii	0.88 (3)	2.10 (3)	2.941 (3)	160 (2)
O8—H8WA···O6^ix	0.88 (2)	2.19 (4)	2.795 (2)	125 (4)
O8—H8WB···O7^x	0.90 (2)	1.92 (2)	2.824 (3)	178 (3)

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