Tetrakis(μ-2-nitrobenzoato-κ²O:O′)­bis­[aqua­copper(II)] ethanol disolvate

The title complex, [Cu₂(C₇H₄NO₄)₄(H₂O)₂]·2C₂H₆O, forms a dimer of the paddle-wheel type located on a crystallographic inversion center. The two Cu²⁺ cations [Cu...Cu = 2.6543 (10) Å] are connected by four 2-nitro­benzoate ligands. The apical positions of the square-pyramidal copper coordination polyhedra are occupied by the water O atoms. The two ethanol solvent mol­ecules are linked to complex mol­ecules via O—H...O hydrogen bonds, which create one-dimensional chains of R₂³(13) and R₄⁴(12) rings. A π–π stacking inter­action is observed between symmetry-related benzene rings of the 2-nitro­benzoate anions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.081
• Data-to-parameter ratio = 19.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.65 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu     -   O1W     ..       6.49 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1998); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Tetrakis(µ-2-nitrobenzoato-κ²O:O')bis[aquacopper(II)] ethanol solvate

Crystal data

[Cu2(C7H4NO4)4(H2O)2]·2C2H6O	F(000) = 940
Mr = 919.72	Dx = 1.711 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 8.326 (3) Å	Cell parameters from 21708 reflections
b = 20.028 (6) Å	θ = 3.2–30.0°
c = 10.803 (3) Å	µ = 1.29 mm^−1
β = 97.77 (3)°	T = 100 K
V = 1784.9 (10) Å^3	Block, green-blue
Z = 2	0.59 × 0.55 × 0.48 mm

Data collection

Kuma KM-4 CCD diffractometer	5144 independent reflections
Radiation source: medium-focus sealed tube	4424 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 30.0°, θmin = 3.2°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003)	h = −11→11
Tmin = 0.494, Tmax = 0.636	k = −25→28
22049 measured reflections	l = −14→15

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 1.2345P] where P = (Fo^2 + 2Fc^2)/3
5144 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.62 e Å^−3
3 restraints	Δρmin = −0.39 e Å^−3

Special details

Experimental. IR (cm^-1, KBr): 3610 (sh,ν(OH)), 3491 (s,ν(OH)), 1625 (s,ν_a(COO), 1577 (w), 1530 (s,ν_a(NOO), 1487 (w), 1413 (s,ν_s(COO)), 1348 (s,ν_s(NOO)), 1306 (w), 1267 (w), 1159 (w), 1078 (w), 1039 (w), 864 (w), 839 (w), 793 (w), 783 (w), 743 (w), 703 (w), 652 (w), 492 (s); UV-VIS (nm): 716 (λ(d–d)).

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.

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

	x	y	z	Uiso*/Ueq
Cu	0.64057 (2)	0.499545 (8)	0.454909 (15)	0.01055 (6)
N1	0.28053 (16)	0.68053 (7)	0.22338 (12)	0.0178 (3)
N2	0.09068 (18)	0.38054 (7)	0.25129 (13)	0.0228 (3)
O1	0.58936 (13)	0.59556 (5)	0.43561 (10)	0.0155 (2)
O2	0.34781 (13)	0.59799 (5)	0.50880 (10)	0.0143 (2)
O1W	0.86484 (15)	0.51320 (6)	0.38329 (12)	0.0225 (2)
O3	0.31691 (16)	0.62119 (6)	0.22755 (11)	0.0228 (2)
O4	0.18168 (16)	0.70557 (6)	0.14186 (12)	0.0284 (3)
O5	0.50660 (13)	0.48074 (6)	0.29450 (10)	0.0156 (2)
O6	0.26610 (14)	0.48510 (5)	0.37038 (10)	0.0161 (2)
O7	0.19917 (18)	0.35025 (6)	0.31637 (12)	0.0308 (3)
O8	−0.05209 (18)	0.38324 (8)	0.27126 (14)	0.0379 (3)
O9	1.02981 (15)	0.63037 (7)	0.39121 (13)	0.0296 (3)
H9O	1.1051	0.6243	0.4501	0.044*
C1	0.46225 (18)	0.62388 (7)	0.45797 (13)	0.0133 (3)
C2	0.44859 (17)	0.69775 (7)	0.42914 (13)	0.0135 (3)
C3	0.36281 (18)	0.72476 (7)	0.32081 (14)	0.0152 (3)
C4	0.35452 (19)	0.79303 (8)	0.29764 (15)	0.0179 (3)
H4	0.2949	0.8098	0.2229	0.021*
C5	0.4349 (2)	0.83628 (8)	0.38555 (16)	0.0206 (3)
H5	0.4309	0.8831	0.3713	0.025*
C6	0.5215 (2)	0.81086 (8)	0.49449 (15)	0.0200 (3)
H6	0.5764	0.8405	0.5546	0.024*
C7	0.52815 (19)	0.74219 (8)	0.51624 (14)	0.0176 (3)
H7	0.5875	0.7255	0.5911	0.021*
C8	0.35381 (18)	0.47656 (7)	0.28482 (13)	0.0137 (3)
C9	0.26630 (18)	0.45987 (7)	0.15736 (13)	0.0150 (3)
C10	0.1349 (2)	0.41613 (8)	0.14181 (14)	0.0187 (3)
C11	0.0473 (2)	0.40171 (8)	0.02658 (16)	0.0223 (3)
H11	−0.0424	0.3720	0.0196	0.027*
C12	0.0944 (2)	0.43207 (9)	−0.07882 (15)	0.0233 (3)
H12	0.0372	0.4227	−0.1591	0.028*
C13	0.2251 (2)	0.47603 (9)	−0.06686 (15)	0.0224 (3)
H13	0.2569	0.4964	−0.1392	0.027*
C14	0.3098 (2)	0.49043 (8)	0.05091 (14)	0.0186 (3)
H14	0.3974	0.5212	0.0583	0.022*
C15	0.9511 (3)	0.69339 (11)	0.40860 (18)	0.0331 (4)
H15A	1.0314	0.7301	0.4148	0.040*
H15B	0.9010	0.6924	0.4866	0.040*
C16	0.8237 (2)	0.70436 (11)	0.29851 (19)	0.0334 (4)
H16A	0.8753	0.7081	0.2225	0.050*
H16B	0.7643	0.7456	0.3106	0.050*
H16C	0.7483	0.6665	0.2905	0.050*
H1W	0.915 (2)	0.5497 (6)	0.387 (2)	0.040*
H2W	0.933 (2)	0.4844 (9)	0.369 (2)	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.01289 (9)	0.00924 (9)	0.00887 (9)	−0.00110 (6)	−0.00095 (6)	−0.00018 (6)
N1	0.0197 (6)	0.0180 (6)	0.0151 (6)	−0.0021 (5)	−0.0002 (5)	0.0010 (5)
N2	0.0284 (7)	0.0190 (6)	0.0202 (6)	−0.0064 (5)	0.0002 (5)	−0.0026 (5)
O1	0.0183 (5)	0.0104 (5)	0.0172 (5)	0.0009 (4)	0.0010 (4)	0.0006 (4)
O2	0.0169 (5)	0.0106 (4)	0.0150 (5)	−0.0005 (4)	0.0005 (4)	0.0010 (4)
O1W	0.0194 (6)	0.0249 (6)	0.0240 (6)	0.0016 (4)	0.0056 (5)	0.0023 (5)
O3	0.0327 (7)	0.0146 (5)	0.0198 (5)	−0.0005 (4)	−0.0014 (5)	−0.0012 (4)
O4	0.0315 (7)	0.0256 (6)	0.0238 (6)	0.0015 (5)	−0.0114 (5)	0.0020 (5)
O5	0.0181 (5)	0.0153 (5)	0.0122 (5)	−0.0004 (4)	−0.0024 (4)	−0.0013 (4)
O6	0.0195 (5)	0.0168 (5)	0.0110 (5)	−0.0018 (4)	−0.0023 (4)	−0.0021 (4)
O7	0.0427 (8)	0.0220 (6)	0.0258 (6)	0.0012 (5)	−0.0020 (6)	0.0046 (5)
O8	0.0278 (7)	0.0483 (9)	0.0384 (8)	−0.0107 (6)	0.0076 (6)	0.0031 (7)
O9	0.0182 (6)	0.0387 (7)	0.0302 (7)	−0.0008 (5)	−0.0026 (5)	0.0065 (6)
C1	0.0175 (7)	0.0109 (6)	0.0101 (6)	−0.0009 (5)	−0.0028 (5)	−0.0009 (5)
C2	0.0147 (6)	0.0105 (6)	0.0156 (6)	−0.0002 (5)	0.0026 (5)	0.0010 (5)
C3	0.0158 (7)	0.0141 (6)	0.0153 (6)	−0.0004 (5)	0.0006 (5)	−0.0002 (5)
C4	0.0193 (7)	0.0152 (7)	0.0189 (7)	0.0019 (5)	0.0022 (6)	0.0035 (5)
C5	0.0242 (8)	0.0119 (6)	0.0260 (8)	0.0008 (6)	0.0047 (6)	0.0018 (6)
C6	0.0238 (8)	0.0128 (7)	0.0228 (8)	−0.0023 (5)	0.0012 (6)	−0.0030 (5)
C7	0.0208 (7)	0.0141 (7)	0.0172 (7)	−0.0006 (5)	0.0002 (5)	−0.0001 (5)
C8	0.0198 (7)	0.0088 (6)	0.0109 (6)	−0.0007 (5)	−0.0031 (5)	0.0004 (5)
C9	0.0172 (7)	0.0144 (6)	0.0121 (6)	0.0022 (5)	−0.0029 (5)	−0.0023 (5)
C10	0.0216 (8)	0.0172 (7)	0.0166 (7)	0.0005 (5)	0.0007 (6)	−0.0018 (5)
C11	0.0230 (8)	0.0214 (7)	0.0208 (7)	−0.0015 (6)	−0.0037 (6)	−0.0048 (6)
C12	0.0254 (8)	0.0260 (8)	0.0163 (7)	0.0042 (6)	−0.0049 (6)	−0.0053 (6)
C13	0.0271 (8)	0.0254 (8)	0.0141 (7)	0.0038 (6)	0.0009 (6)	−0.0005 (6)
C14	0.0200 (7)	0.0204 (7)	0.0147 (7)	0.0007 (6)	0.0004 (5)	−0.0006 (5)
C15	0.0324 (10)	0.0405 (11)	0.0277 (9)	−0.0038 (8)	0.0089 (8)	−0.0033 (8)
C16	0.0316 (10)	0.0351 (10)	0.0353 (10)	0.0068 (8)	0.0111 (8)	0.0120 (8)

Geometric parameters (Å, º)

Cu—O1W	2.1331 (15)	C3—C4	1.390 (2)
Cu—O1	1.9746 (12)	C4—C5	1.389 (2)
Cu—O2^i	1.9922 (12)	C4—H4	0.9500
Cu—O5	1.9664 (12)	C5—C6	1.391 (2)
Cu—O6^i	1.9657 (12)	C5—H5	0.9500
Cu—Cu^i	2.6543 (10)	C6—C7	1.395 (2)
N1—O3	1.2259 (18)	C6—H6	0.9500
N1—O4	1.2281 (18)	C7—H7	0.9500
N1—C3	1.4720 (19)	C8—C9	1.5058 (19)
N2—O7	1.227 (2)	C9—C14	1.393 (2)
N2—O8	1.238 (2)	C9—C10	1.394 (2)
N2—C10	1.470 (2)	C10—C11	1.386 (2)
O1—C1	1.2527 (19)	C11—C12	1.393 (3)
O2—C1	1.2726 (19)	C11—H11	0.9500
O2—Cu^i	1.9922 (12)	C12—C13	1.392 (3)
O1W—H1W	0.84 (1)	C12—H12	0.9500
O1W—H2W	0.84 (1)	C13—C14	1.399 (2)
O5—C8	1.2651 (19)	C13—H13	0.9500
O6—C8	1.2647 (19)	C14—H14	0.9500
O6—Cu^i	1.9657 (12)	C15—C16	1.499 (3)
O9—C15	1.446 (3)	C15—H15A	0.9900
O9—H9O	0.8400	C15—H15B	0.9900
C1—C2	1.513 (2)	C16—H16A	0.9800
C2—C3	1.395 (2)	C16—H16B	0.9800
C2—C7	1.396 (2)	C16—H16C	0.9800
O1—Cu—O1W	91.37 (5)	C4—C5—H5	120.1
O2^i—Cu—O1W	100.11 (5)	C6—C5—H5	120.1
O5—Cu—O1W	97.18 (6)	C5—C6—C7	120.51 (14)
O6^i—Cu—O1W	94.38 (6)	C5—C6—H6	119.7
O1—Cu—O2^i	168.45 (5)	C7—C6—H6	119.7
O1—Cu—O5	90.28 (5)	C6—C7—C2	120.71 (14)
O1—Cu—O6^i	90.04 (5)	C6—C7—H7	119.6
O2^i—Cu—O5	89.56 (5)	C2—C7—H7	119.6
O2^i—Cu—O6^i	87.82 (5)	O6—C8—O5	127.17 (13)
O5—Cu—O6^i	168.42 (5)	O6—C8—C9	116.27 (13)
O6^i—Cu—Cu^i	84.28 (4)	O5—C8—C9	116.56 (13)
O5—Cu—Cu^i	84.34 (4)	C14—C9—C10	117.64 (14)
O1—Cu—Cu^i	81.00 (3)	C14—C9—C8	120.65 (14)
O2^i—Cu—Cu^i	87.49 (3)	C10—C9—C8	121.64 (14)
O1W—Cu—Cu^i	172.24 (4)	C11—C10—C9	123.29 (15)
O3—N1—O4	124.09 (13)	C11—C10—N2	117.58 (15)
O3—N1—C3	117.93 (13)	C9—C10—N2	119.06 (14)
O4—N1—C3	117.97 (13)	C10—C11—C12	118.08 (16)
O7—N2—O8	124.85 (16)	C10—C11—H11	121.0
O7—N2—C10	117.10 (15)	C12—C11—H11	121.0
O8—N2—C10	118.04 (15)	C13—C12—C11	120.22 (15)
C1—O1—Cu	126.63 (10)	C13—C12—H12	119.9
C1—O2—Cu^i	117.72 (9)	C11—C12—H12	119.9
Cu—O1W—H1W	123.2 (16)	C12—C13—C14	120.43 (16)
Cu—O1W—H2W	128.9 (17)	C12—C13—H13	119.8
H1W—O1W—H2W	105.3 (17)	C14—C13—H13	119.8
C8—O5—Cu	122.00 (10)	C9—C14—C13	120.32 (15)
C8—O6—Cu^i	122.04 (10)	C9—C14—H14	119.8
C15—O9—H9O	109.5	C13—C14—H14	119.8
O1—C1—O2	126.87 (13)	O9—C15—C16	108.01 (16)
O1—C1—C2	116.43 (13)	O9—C15—H15A	110.1
O2—C1—C2	116.57 (13)	C16—C15—H15A	110.1
C3—C2—C7	117.44 (13)	O9—C15—H15B	110.1
C3—C2—C1	124.58 (13)	C16—C15—H15B	110.1
C7—C2—C1	117.98 (13)	H15A—C15—H15B	108.4
C4—C3—C2	122.67 (14)	C15—C16—H16A	109.5
C4—C3—N1	117.14 (13)	C15—C16—H16B	109.5
C2—C3—N1	120.17 (13)	H16A—C16—H16B	109.5
C5—C4—C3	118.86 (14)	C15—C16—H16C	109.5
C5—C4—H4	120.6	H16A—C16—H16C	109.5
C3—C4—H4	120.6	H16B—C16—H16C	109.5
C4—C5—C6	119.81 (14)
O6^i—Cu—O1—C1	−88.45 (12)	C3—C4—C5—C6	−0.1 (2)
O5—Cu—O1—C1	79.98 (12)	C4—C5—C6—C7	0.0 (3)
O2^i—Cu—O1—C1	−9.2 (3)	C5—C6—C7—C2	0.1 (2)
O1W—Cu—O1—C1	177.17 (12)	C3—C2—C7—C6	−0.1 (2)
Cu^i—Cu—O1—C1	−4.25 (11)	C1—C2—C7—C6	179.38 (14)
O6^i—Cu—O5—C8	11.6 (3)	Cu^i—O6—C8—O5	−5.0 (2)
O1—Cu—O5—C8	−80.00 (11)	Cu^i—O6—C8—C9	175.27 (9)
O2^i—Cu—O5—C8	88.45 (11)	Cu—O5—C8—O6	2.1 (2)
O1W—Cu—O5—C8	−171.42 (11)	Cu—O5—C8—C9	−178.21 (9)
Cu^i—Cu—O5—C8	0.92 (11)	O6—C8—C9—C14	136.38 (15)
Cu—O1—C1—O2	7.4 (2)	O5—C8—C9—C14	−43.4 (2)
Cu—O1—C1—C2	−176.92 (9)	O6—C8—C9—C10	−40.5 (2)
Cu^i—O2—C1—O1	−5.47 (19)	O5—C8—C9—C10	139.73 (15)
Cu^i—O2—C1—C2	178.82 (9)	C14—C9—C10—C11	0.3 (2)
O1—C1—C2—C3	98.68 (18)	C8—C9—C10—C11	177.26 (15)
O2—C1—C2—C3	−85.15 (18)	C14—C9—C10—N2	177.06 (14)
O1—C1—C2—C7	−80.80 (18)	C8—C9—C10—N2	−5.9 (2)
O2—C1—C2—C7	95.37 (17)	O7—N2—C10—C11	125.48 (17)
C7—C2—C3—C4	0.0 (2)	O8—N2—C10—C11	−54.6 (2)
C1—C2—C3—C4	−179.47 (15)	O7—N2—C10—C9	−51.5 (2)
C7—C2—C3—N1	178.05 (14)	O8—N2—C10—C9	128.45 (17)
C1—C2—C3—N1	−1.4 (2)	C9—C10—C11—C12	0.7 (3)
O3—N1—C3—C4	163.19 (15)	N2—C10—C11—C12	−176.16 (15)
O4—N1—C3—C4	−15.7 (2)	C10—C11—C12—C13	−0.7 (3)
O3—N1—C3—C2	−14.9 (2)	C11—C12—C13—C14	−0.3 (3)
O4—N1—C3—C2	166.20 (15)	C10—C9—C14—C13	−1.2 (2)
C2—C3—C4—C5	0.1 (2)	C8—C9—C14—C13	−178.26 (14)
N1—C3—C4—C5	−177.97 (14)	C12—C13—C14—C9	1.3 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9O···O2^ii	0.84	2.10	2.852 (2)	149
O1W—H1W···O9	0.84 (1)	1.88 (1)	2.715 (2)	178 (2)
O1W—H2W···O8^ii	0.84 (1)	2.29 (1)	2.991 (2)	141 (2)

Symmetry code: (ii) x+1, y, z.