Bis(μ-naphthalene-1,8-dicarboxyl-ato-κO:O)bis-[aqua-bis-(N,N'-dimethyl-formamide-κO)copper(II)].

In the centrosymmetric dinuclear title complex, [Cu(2)(C(12)H(6)O(4))(2)(C(3)H(7)NO)(4)(H(2)O)(2)], the coordination environment of each Cu(II) atom displays a distorted CuO(5) square-pyramidal geometry, which is formed by two carboxyl-ate O atoms of two μ-1,8-nap ligands (1,8-nap is naphthalene-1,8-dicarboxyl-ate), two O atoms of two DMF (DMF is N,N'-dimethyl-formamide) and one coordinated water mol-ecule. The Cu-O distances involving the four O atoms in the square plane are in the range 1.9501 (11)-1.9677 (11) Å, with the Cu atom lying nearly in the plane [deviation = 0.0726 (2) Å]. The axial O atom occupies the peak position with a Cu-O distance of 2.885 (12) Å, which is significantly longer than the rest of the Cu-O distances. Each 1,8-nap ligand acts as bridge, linking two Cu(II) atoms into a dinuclear structure. Inter-molecular O-H⋯O and C-H⋯O hydrogen-bonding inter-actions consolidate the structure.

Related literature

For the coordination modes of the 1,8-nap ligand, see: Wen et al. (2007 ▶, 2008 ▶). For related complexes, see: Abourahma et al. (2002 ▶); Bencini et al. (2003 ▶); Fokin et al. (2004 ▶); Sun et al. (2009 ▶).

Experimental

Crystal data

[Cu2(C12H6O4)2(C3H7NO)4(H2O)2]

M = 883.83

Monoclinic,

a = 17.7078 (4) Å

b = 9.9025 (1) Å

c = 23.0393 (5) Å

β = 102.249 (2)°

V = 3948.00 (13) Å3

Z = 4

Mo Kα radiation

μ = 1.15 mm−1

T = 296 K

0.40 × 0.26 × 0.13 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.71, T max = 0.86

29673 measured reflections

4625 independent reflections

4076 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.076

S = 1.04

4625 reflections

259 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028497/pv2300sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028497/pv2300Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu2(C12H6O4)2(C3H7NO)4(H2O)2]	F(000) = 1832
Mr = 883.83	Dx = 1.487 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9928 reflections
a = 17.7078 (4) Å	θ = 2.4–27.7°
b = 9.9025 (1) Å	µ = 1.15 mm−1
c = 23.0393 (5) Å	T = 296 K
β = 102.249 (2)°	Block, blue
V = 3948.00 (13) Å3	0.40 × 0.26 × 0.13 mm
Z = 4

Bruker APEXII area-detector diffractometer	4625 independent reflections
Radiation source: fine-focus sealed tube	4076 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω scans	θmax = 27.7°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→23
Tmin = 0.71, Tmax = 0.86	k = −12→12
29673 measured reflections	l = −28→30

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0415P)2 + 2.4079P] where P = (Fo2 + 2Fc2)/3
4625 reflections	(Δ/σ)max = 0.002
259 parameters	Δρmax = 0.28 e Å−3
5 restraints	Δρmin = −0.27 e Å−3

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
Cu1	0.124473 (10)	0.670966 (18)	0.464441 (8)	0.03052 (7)
C1	0.33281 (9)	0.85492 (16)	0.40975 (7)	0.0341 (3)
C2	0.31963 (10)	0.94374 (17)	0.35537 (7)	0.0395 (4)
C3	0.38265 (12)	1.0098 (2)	0.34354 (9)	0.0543 (5)
H3A	0.4291	1.0076	0.3714	0.065*
C4	0.37868 (14)	1.0808 (2)	0.29013 (11)	0.0684 (6)
H4A	0.4219	1.1266	0.2834	0.082*
C5	0.31253 (14)	1.0826 (2)	0.24877 (10)	0.0627 (6)
H5A	0.3110	1.1271	0.2130	0.075*
C6	0.24541 (13)	1.01821 (18)	0.25878 (8)	0.0485 (4)
C7	0.24722 (10)	0.95047 (16)	0.31396 (7)	0.0381 (3)
C8	0.17617 (14)	1.0204 (2)	0.21466 (8)	0.0568 (5)
H8A	0.1752	1.0654	0.1791	0.068*
C9	0.11186 (13)	0.9584 (2)	0.22331 (8)	0.0571 (5)
H9A	0.0680	0.9554	0.1929	0.069*
C10	0.11117 (11)	0.89818 (19)	0.27848 (8)	0.0460 (4)
H10A	0.0660	0.8583	0.2846	0.055*
C11	0.17582 (10)	0.89708 (16)	0.32346 (7)	0.0367 (3)
C12	0.16459 (9)	0.85435 (16)	0.38382 (7)	0.0334 (3)
C13	0.09853 (12)	0.4309 (2)	0.38365 (9)	0.0543 (5)
H13A	0.1348	0.4846	0.3707	0.065*
C14	0.1278 (3)	0.2623 (3)	0.31590 (17)	0.1263 (15)
H14A	0.1622	0.3321	0.3085	0.189*
H14B	0.0923	0.2401	0.2796	0.189*
H14C	0.1572	0.1836	0.3310	0.189*
C15	0.02931 (19)	0.2191 (3)	0.37687 (13)	0.0902 (9)
H15A	0.0055	0.2632	0.4055	0.135*
H15B	0.0551	0.1388	0.3940	0.135*
H15C	−0.0096	0.1955	0.3426	0.135*
C16	−0.03349 (10)	0.72571 (17)	0.46612 (8)	0.0418 (4)
H16A	−0.0370	0.6338	0.4735	0.050*
C17	−0.16911 (14)	0.7426 (3)	0.46719 (17)	0.0956 (10)
H17A	−0.1636	0.6470	0.4735	0.143*
H17B	−0.2080	0.7597	0.4320	0.143*
H17C	−0.1841	0.7838	0.5007	0.143*
C18	−0.09461 (13)	0.9433 (2)	0.44989 (12)	0.0661 (6)
H18A	−0.0439	0.9698	0.4457	0.099*
H18B	−0.1075	0.9902	0.4829	0.099*
H18C	−0.1315	0.9656	0.4143	0.099*
O1W	0.22801 (6)	0.59540 (12)	0.46744 (5)	0.0358 (2)
H1WA	0.2520 (12)	0.641 (2)	0.4477 (8)	0.054*
H1WB	0.2520 (12)	0.589 (2)	0.5009 (7)	0.054*
O1	0.06739 (7)	0.47781 (13)	0.42143 (6)	0.0511 (3)
O2	0.02961 (7)	0.77247 (12)	0.46251 (6)	0.0434 (3)
O3	0.13036 (6)	0.74302 (12)	0.38655 (5)	0.0389 (2)
O4	0.18619 (7)	0.93436 (12)	0.42557 (5)	0.0407 (3)
O5	0.30792 (7)	0.73769 (11)	0.40428 (5)	0.0389 (3)
O6	0.37233 (6)	0.90670 (12)	0.45727 (5)	0.0395 (3)
N1	0.08503 (14)	0.30962 (18)	0.35940 (9)	0.0687 (5)
N2	−0.09595 (8)	0.79924 (16)	0.46006 (7)	0.0458 (3)

	U11	U22	U33	U12	U13	U23
Cu1	0.02809 (11)	0.02933 (11)	0.03456 (11)	0.00029 (7)	0.00758 (7)	−0.00087 (7)
C1	0.0308 (7)	0.0369 (8)	0.0381 (8)	0.0040 (6)	0.0154 (6)	0.0037 (6)
C2	0.0456 (9)	0.0357 (8)	0.0405 (8)	0.0005 (7)	0.0167 (7)	0.0047 (7)
C3	0.0534 (11)	0.0562 (12)	0.0563 (11)	−0.0080 (9)	0.0181 (9)	0.0110 (9)
C4	0.0724 (15)	0.0669 (14)	0.0723 (15)	−0.0164 (12)	0.0299 (12)	0.0220 (12)
C5	0.0888 (16)	0.0545 (12)	0.0502 (11)	−0.0057 (11)	0.0271 (11)	0.0172 (9)
C6	0.0709 (12)	0.0388 (9)	0.0386 (9)	0.0042 (8)	0.0179 (8)	0.0068 (7)
C7	0.0525 (10)	0.0301 (7)	0.0338 (8)	0.0041 (7)	0.0137 (7)	0.0039 (6)
C8	0.0837 (15)	0.0503 (11)	0.0345 (9)	0.0080 (10)	0.0086 (9)	0.0115 (8)
C9	0.0696 (13)	0.0567 (11)	0.0391 (10)	0.0086 (10)	−0.0020 (9)	0.0083 (9)
C10	0.0512 (10)	0.0445 (10)	0.0388 (9)	0.0060 (8)	0.0018 (7)	0.0035 (7)
C11	0.0460 (9)	0.0296 (8)	0.0339 (8)	0.0074 (6)	0.0075 (7)	0.0016 (6)
C12	0.0294 (7)	0.0356 (7)	0.0348 (8)	0.0099 (5)	0.0057 (6)	0.0046 (6)
C13	0.0593 (12)	0.0406 (10)	0.0641 (12)	−0.0089 (9)	0.0157 (10)	−0.0125 (9)
C14	0.204 (4)	0.0723 (19)	0.129 (3)	−0.004 (2)	0.093 (3)	−0.0396 (19)
C15	0.120 (2)	0.0554 (14)	0.094 (2)	−0.0337 (16)	0.0198 (17)	−0.0182 (14)
C16	0.0412 (9)	0.0345 (8)	0.0528 (10)	0.0041 (7)	0.0171 (8)	0.0013 (7)
C17	0.0436 (12)	0.0725 (17)	0.180 (3)	0.0018 (12)	0.0436 (16)	0.0084 (19)
C18	0.0562 (12)	0.0503 (12)	0.0948 (17)	0.0194 (10)	0.0228 (12)	0.0182 (11)
O1W	0.0315 (5)	0.0401 (6)	0.0366 (6)	0.0036 (4)	0.0088 (4)	0.0051 (5)
O1	0.0484 (7)	0.0433 (7)	0.0632 (8)	−0.0096 (6)	0.0151 (6)	−0.0163 (6)
O2	0.0338 (6)	0.0384 (6)	0.0601 (8)	0.0058 (5)	0.0147 (5)	0.0016 (6)
O3	0.0368 (6)	0.0414 (6)	0.0378 (6)	0.0003 (5)	0.0067 (5)	0.0057 (5)
O4	0.0430 (6)	0.0438 (6)	0.0348 (6)	0.0076 (5)	0.0069 (5)	−0.0017 (5)
O5	0.0431 (6)	0.0337 (6)	0.0427 (6)	0.0024 (5)	0.0156 (5)	0.0040 (5)
O6	0.0365 (6)	0.0442 (6)	0.0388 (6)	−0.0036 (5)	0.0103 (5)	0.0041 (5)
N1	0.0966 (15)	0.0409 (9)	0.0714 (12)	−0.0079 (9)	0.0241 (11)	−0.0189 (8)
N2	0.0344 (7)	0.0431 (8)	0.0626 (10)	0.0063 (6)	0.0166 (7)	0.0011 (7)

Cu1—O2	1.9500 (11)	C12—O3	1.266 (2)
Cu1—O6i	1.9505 (11)	C13—O1	1.217 (2)
Cu1—O3	1.9544 (11)	C13—N1	1.324 (2)
Cu1—O1W	1.9678 (11)	C13—H13A	0.9300
Cu1—O1	2.2885 (12)	C14—N1	1.456 (3)
C1—O5	1.2386 (19)	C14—H14A	0.9600
C1—O6	1.275 (2)	C14—H14B	0.9600
C1—C2	1.508 (2)	C14—H14C	0.9600
C2—C3	1.370 (2)	C15—N1	1.452 (3)
C2—C7	1.428 (2)	C15—H15A	0.9600
C3—C4	1.406 (3)	C15—H15B	0.9600
C3—H3A	0.9300	C15—H15C	0.9600
C4—C5	1.344 (3)	C16—O2	1.228 (2)
C4—H4A	0.9300	C16—N2	1.307 (2)
C5—C6	1.410 (3)	C16—H16A	0.9300
C5—H5A	0.9300	C17—N2	1.453 (3)
C6—C8	1.417 (3)	C17—H17A	0.9600
C6—C7	1.432 (2)	C17—H17B	0.9600
C7—C11	1.430 (2)	C17—H17C	0.9600
C8—C9	1.345 (3)	C18—N2	1.447 (3)
C8—H8A	0.9300	C18—H18A	0.9600
C9—C10	1.406 (3)	C18—H18B	0.9600
C9—H9A	0.9300	C18—H18C	0.9600
C10—C11	1.371 (2)	O1W—H1WA	0.82 (2)
C10—H10A	0.9300	O1W—H1WB	0.80 (1)
C11—C12	1.507 (2)	O6—Cu1i	1.9505 (11)
C12—O4	1.242 (2)
O2—Cu1—O6i	94.60 (5)	O3—C12—C11	116.67 (14)
O2—Cu1—O3	90.25 (5)	O1—C13—N1	125.4 (2)
O6i—Cu1—O3	175.05 (5)	O1—C13—H13A	117.3
O2—Cu1—O1W	171.31 (5)	N1—C13—H13A	117.3
O6i—Cu1—O1W	88.48 (5)	N1—C14—H14A	109.5
O3—Cu1—O1W	86.58 (5)	N1—C14—H14B	109.5
O2—Cu1—O1	96.99 (5)	H14A—C14—H14B	109.5
O6i—Cu1—O1	89.67 (5)	N1—C14—H14C	109.5
O3—Cu1—O1	90.71 (5)	H14A—C14—H14C	109.5
O1W—Cu1—O1	91.15 (5)	H14B—C14—H14C	109.5
O5—C1—O6	125.65 (15)	N1—C15—H15A	109.5
O5—C1—C2	118.24 (15)	N1—C15—H15B	109.5
O6—C1—C2	116.03 (14)	H15A—C15—H15B	109.5
C3—C2—C7	119.91 (16)	N1—C15—H15C	109.5
C3—C2—C1	117.06 (16)	H15A—C15—H15C	109.5
C7—C2—C1	122.75 (14)	H15B—C15—H15C	109.5
C2—C3—C4	121.4 (2)	O2—C16—N2	122.97 (16)
C2—C3—H3A	119.3	O2—C16—H16A	118.5
C4—C3—H3A	119.3	N2—C16—H16A	118.5
C5—C4—C3	120.1 (2)	N2—C17—H17A	109.5
C5—C4—H4A	120.0	N2—C17—H17B	109.5
C3—C4—H4A	120.0	H17A—C17—H17B	109.5
C4—C5—C6	121.06 (18)	N2—C17—H17C	109.5
C4—C5—H5A	119.5	H17A—C17—H17C	109.5
C6—C5—H5A	119.5	H17B—C17—H17C	109.5
C5—C6—C8	120.45 (17)	N2—C18—H18A	109.5
C5—C6—C7	119.75 (19)	N2—C18—H18B	109.5
C8—C6—C7	119.79 (18)	H18A—C18—H18B	109.5
C2—C7—C11	125.34 (14)	N2—C18—H18C	109.5
C2—C7—C6	117.57 (16)	H18A—C18—H18C	109.5
C11—C7—C6	117.08 (16)	H18B—C18—H18C	109.5
C9—C8—C6	121.18 (17)	Cu1—O1W—H1WA	110.9 (15)
C9—C8—H8A	119.4	Cu1—O1W—H1WB	111.5 (16)
C6—C8—H8A	119.4	H1WA—O1W—H1WB	110.4 (19)
C8—C9—C10	119.82 (18)	C13—O1—Cu1	113.79 (12)
C8—C9—H9A	120.1	C16—O2—Cu1	126.56 (11)
C10—C9—H9A	120.1	C12—O3—Cu1	118.88 (10)
C11—C10—C9	121.36 (19)	C1—O6—Cu1i	122.57 (10)
C11—C10—H10A	119.3	C13—N1—C15	121.0 (2)
C9—C10—H10A	119.3	C13—N1—C14	120.5 (2)
C10—C11—C7	120.33 (15)	C15—N1—C14	118.4 (2)
C10—C11—C12	116.57 (15)	C16—N2—C18	121.61 (16)
C7—C11—C12	122.64 (14)	C16—N2—C17	121.86 (18)
O4—C12—O3	126.08 (15)	C18—N2—C17	116.40 (17)
O4—C12—C11	117.15 (14)
O5—C1—C2—C3	−129.54 (18)	C2—C7—C11—C12	14.1 (2)
O6—C1—C2—C3	47.3 (2)	C6—C7—C11—C12	−164.70 (15)
O5—C1—C2—C7	44.3 (2)	C10—C11—C12—O4	−124.12 (16)
O6—C1—C2—C7	−138.81 (16)	C7—C11—C12—O4	48.1 (2)
C7—C2—C3—C4	−2.4 (3)	C10—C11—C12—O3	52.4 (2)
C1—C2—C3—C4	171.7 (2)	C7—C11—C12—O3	−135.41 (15)
C2—C3—C4—C5	−1.4 (4)	N1—C13—O1—Cu1	168.26 (19)
C3—C4—C5—C6	2.4 (4)	O2—Cu1—O1—C13	135.72 (15)
C4—C5—C6—C8	−179.7 (2)	O6i—Cu1—O1—C13	−129.68 (15)
C4—C5—C6—C7	0.5 (3)	O3—Cu1—O1—C13	45.38 (15)
C3—C2—C7—C11	−173.81 (17)	O1W—Cu1—O1—C13	−41.21 (15)
C1—C2—C7—C11	12.5 (3)	N2—C16—O2—Cu1	−174.76 (13)
C3—C2—C7—C6	5.0 (2)	O6i—Cu1—O2—C16	−59.16 (15)
C1—C2—C7—C6	−168.68 (15)	O3—Cu1—O2—C16	121.82 (15)
C5—C6—C7—C2	−4.1 (3)	O1—Cu1—O2—C16	31.08 (15)
C8—C6—C7—C2	176.05 (17)	O4—C12—O3—Cu1	−10.9 (2)
C5—C6—C7—C11	174.82 (17)	C11—C12—O3—Cu1	172.91 (10)
C8—C6—C7—C11	−5.0 (2)	O2—Cu1—O3—C12	87.85 (11)
C5—C6—C8—C9	179.4 (2)	O1W—Cu1—O3—C12	−84.05 (11)
C7—C6—C8—C9	−0.8 (3)	O1—Cu1—O3—C12	−175.16 (11)
C6—C8—C9—C10	4.5 (3)	O5—C1—O6—Cu1i	−18.5 (2)
C8—C9—C10—C11	−2.2 (3)	C2—C1—O6—Cu1i	164.90 (10)
C9—C10—C11—C7	−3.8 (3)	O1—C13—N1—C15	0.0 (4)
C9—C10—C11—C12	168.60 (17)	O1—C13—N1—C14	−177.9 (3)
C2—C7—C11—C10	−173.94 (16)	O2—C16—N2—C18	−1.4 (3)
C6—C7—C11—C10	7.2 (2)	O2—C16—N2—C17	−177.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O5	0.82 (2)	1.82 (2)	2.642 (2)	178 (2)
O1W—H1WB···O4i	0.80 (1)	1.82 (2)	2.623 (2)	175 (2)
C3—H3A···O1ii	0.93	2.49	3.396 (3)	164
C13—H13A···O3	0.93	2.59	3.140 (2)	119
C17—H17A···O6iii	0.96	2.51	3.424 (3)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O5	0.82 (2)	1.82 (2)	2.642 (2)	178 (2)
O1W—H1WB⋯O4i	0.80 (1)	1.82 (2)	2.623 (2)	175 (2)
C3—H3A⋯O1ii	0.93	2.49	3.396 (3)	164
C13—H13A⋯O3	0.93	2.59	3.140 (2)	119
C17—H17A⋯O6iii	0.96	2.51	3.424 (3)	159

Symmetry codes: (i) ; (ii) ; (iii) .