Structural and Magnetic Characterization of a Tetranuclear Copper(II

Supporting information for

Structural and magnetic characterization of a tetranuclear copper(II) cubane stabilized by intramolecular metal cation-π interactions. Distribution of Cu-O distances in cubane complexes DIST1 Plot Data File=cq_temp0 Test=1 Tot.Obs.=336 Obs.=336 Supp.=0

N 70

60 X-axis Min.=1.912 Max.=2.436 Range=0.524 Mean=2.095 Mean SE=0.010 Sample SD=0.184

50

40

Histogram Median=1.974 Skew=0.715 Quantile=10.000 LQ=1.942 HQ=2.359 Bin Width=0.015 Max. Bin =70.000

30

20

10

0 1.90

2.00

2.10

2.20

2.30

2.40

2.50 DIST1

Figure S1. Distribution of Cu-O distances in Cu4(OH)4 cubane complexes

1

Crystal structure of 1: representation of the unit cell

Figure S2. Representation of the unit cell of 1

2

Crystallographic data Complex 1: CCDC 915281 Crystal data C26H28Cl2Cu2N4O11

F(000) = 3136

Mr = 770.5

Dx = 1.436 Mg m-3

Monoclinic, C2/c

Mo Kα radiation, λ = 0.71073 Å

Hall symbol: -C 2yc

Cell parameters from 34076 reflections

a = 22.9841 (4) Å

θ = 2.6–28.5°

b = 13.3899 (2) Å

µ = 1.40 mm-1

c = 23.2330 (5) Å

T = 293 K

β = 94.514 (1)°

Prism, green

V = 7127.9 (2) Å3

0.3 × 0.16 × 0.1 mm

Z=8

Data collection KappaCCD diffractometer

Rint = 0.056

graphite

θmax = 28.5°, θmin = 2.6°

ω + Phi scan

h = 0→30

34076 measured reflections

k = 0→17

8758 independent reflections

l = -31→30

6094 reflections with I > 2σ(I)

Refinement 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)] = 0.066

Hydrogen site location: difference Fourier map

2

wR(F ) = 0.193

H-atom parameters constrained

S = 1.07

w = 1/[σ2(Fo2) + (0.0839P)2 + 26.2725P] where P = (Fo2 + 2Fc2)/3

8758 reflections

(Δ/σ)max < 0.001

424 parameters

Δ〉max = 0.79 e Å-3

0 restraints

Δ〉min = -0.58 e Å-3

3

Geometric parameters (Å, °) C1—N1

1.259 (6)

C20—N4

1.468 (7)

C1—C2

1.463 (7)

C20—C21

1.501 (9)

C1—H1

0.93

C20—H20A

0.97

C2—N2

1.337 (6)

C20—H20B

0.97

C2—C3

1.374 (7)

C21—C22

1.379 (8)

C3—C4

1.366 (9)

C21—C26

1.388 (8)

C3—H3

0.93

C22—C23

1.387 (10)

C4—C5

1.359 (10)

C22—H22

0.93

C4—H4

0.93

C23—C24

1.376 (10)

C5—C6

1.387 (7)

C23—H23

0.93

C5—H5

0.93

C24—C25

1.369 (11)

C6—N2

1.327 (6)

C24—H24

0.93

C6—H6

0.93

C25—C26

1.373 (10)

C7—N1

1.468 (6)

C25—H25

0.93

C7—C8

1.508 (8)

C26—H26

0.93

C7—H7A

0.97

N1—Cu1

2.016 (4)

C7—H7B

0.97

N2—Cu1

2.004 (3)

C8—C13

1.372 (8)

N3—Cu2

1.997 (4)

C8—C9

1.391 (8)

N4—Cu2

2.004 (4)

C9—C10

1.385 (10)

O1—Cu1

1.953 (3)

C9—H9

0.93

O1—Cu2

1.975 (3) i

C10—C11

1.339 (11)

O1—Cu2

C10—H10

0.93

O1—H1H

C11—C12

1.363 (11)

O2—Cu2

C11—H11

0.93

O2—Cu1

i

2.315 (3) 0.8671 1.950 (3) 1.984 (3)

i

C12—C13

1.390 (9)

O2—Cu1

C12—H12

0.93

O2—H2H

0.9585

C13—H13

0.93

O3—Cl1

1.345 (7)

C14—N4

1.278 (6)

O4—Cl1

1.371 (6)

C14—C15

1.451 (8)

O5—Cl1

1.356 (8)

C14—H14

0.93

O6—Cl1

1.389 (7)

C15—N3

1.339 (7)

O7—Cl2

1.419 (5)

C15—C16

1.382 (7)

O8—Cl2

1.405 (6)

C16—C17

1.362 (11)

O9—Cl2

1.390 (5)

C16—H16

0.93

O10—Cl2

1.426 (5)

Cu1—O2

i

2.326 (3)

Cu2—O2

i

1.950 (3)

Cu2—O1

i

2.315 (3)

C17—C18 C17—H17 C18—C19

1.360 (11) 0.93 1.385 (8)

2.326 (3)

4

C18—H18

0.93

O2W—O1W

1.42 (6)

C19—N3

1.333 (7)

O1W—O3W

1.61 (5)

C19—H19

0.93

N1—C1—C2

118.5 (5)

C23—C22—H22

119.6

N1—C1—H1

120.8

C24—C23—C22

119.5 (7)

C2—C1—H1

120.8

C24—C23—H23

120.2

N2—C2—C3

122.5 (5)

C22—C23—H23

120.2

N2—C2—C1

114.4 (4)

C25—C24—C23

119.9 (7)

C3—C2—C1

123.0 (5)

C25—C24—H24

120.1

C4—C3—C2

118.8 (6)

C23—C24—H24

120.1

C4—C3—H3

120.6

C24—C25—C26

120.9 (7)

C2—C3—H3

120.6

C24—C25—H25

119.5

C5—C4—C3

118.8 (5)

C26—C25—H25

119.5

C5—C4—H4

120.6

C25—C26—C21

119.9 (7)

C3—C4—H4

120.6

C25—C26—H26

120

C4—C5—C6

120.2 (6)

C21—C26—H26

120

C4—C5—H5

119.9

C1—N1—C7

118.5 (5)

C6—C5—H5

119.9

C1—N1—Cu1

113.1 (3)

N2—C6—C5

120.9 (6)

C7—N1—Cu1

128.2 (3)

N2—C6—H6

119.6

C6—N2—C2

118.8 (4)

C5—C6—H6

119.6

C6—N2—Cu1

128.5 (4)

N1—C7—C8

113.7 (4)

C2—N2—Cu1

112.7 (3)

N1—C7—H7A

108.8

C19—N3—C15

118.4 (5)

C8—C7—H7A

108.8

C19—N3—Cu2

128.7 (4)

N1—C7—H7B

108.8

C15—N3—Cu2

112.8 (4)

C8—C7—H7B

108.8

C14—N4—C20

118.2 (5)

H7A—C7—H7B

107.7

C14—N4—Cu2

112.9 (4)

C13—C8—C9

117.8 (6)

C20—N4—Cu2

128.7 (3)

C13—C8—C7

122.0 (5)

Cu1—O1—Cu2

103.30 (13)

C9—C8—C7

120.1 (5)

Cu1—O1—Cu2i

C10—C9—C8

120.7 (7)

Cu2—O1—Cu2

i

C10—C9—H9

119.7

Cu1—O1—H1H

95.4

C8—C9—H9

119.7

Cu2—O1—H1H

145.9

C11—C10—C9 C11—C10—H10 C9—C10—H10 C10—C11—C12

120.4 (7) 119.8 119.8 120.3 (7)

92.39 (11) 100.82 (13)

i

Cu2 —O1—H1H i

Cu2 —O2—Cu1 i

Cu2 —O2—Cu1 Cu1—O2—Cu1

106.7 103.53 (13)

i

i

i

91.75 (11) 101.52 (12)

C10—C11—H11

119.9

Cu2 —O2—H2H

115.2

C12—C11—H11

119.9

Cu1—O2—H2H

129.2

5

C11—C12—C13

120.2 (7)

Cu1i—O2—H2H

108.4

C11—C12—H12

119.9

O3—Cl1—O5

101.7 (7)

C13—C12—H12

119.9

O3—Cl1—O4

107.5 (6)

C8—C13—C12

120.6 (6)

O5—Cl1—O4

111.2 (7)

C8—C13—H13

119.7

O3—Cl1—O6

110.9 (6)

C12—C13—H13

119.7

O5—Cl1—O6

113.2 (5)

N4—C14—C15

118.2 (5)

O4—Cl1—O6

111.7 (5)

N4—C14—H14

120.9

O9—Cl2—O8

107.8 (5)

C15—C14—H14

120.9

O9—Cl2—O7

111.0 (4)

N3—C15—C16

122.0 (6)

O8—Cl2—O7

110.0 (4)

N3—C15—C14

114.5 (4)

O9—Cl2—O10

106.7 (4)

C16—C15—C14

123.5 (6)

O8—Cl2—O10

111.9 (5)

C17—C16—C15

119.2 (6)

O7—Cl2—O10

109.4 (4)

C17—C16—H16

120.4

O1—Cu1—O2

85.05 (12)

C15—C16—H16

120.4

O1—Cu1—N2

175.75 (15)

C18—C17—C16

119.2 (6)

O2—Cu1—N2

98.64 (14)

C18—C17—H17

120.4

O1—Cu1—N1

94.80 (14)

C16—C17—H17

120.4

O2—Cu1—N1

172.47 (14)

C17—C18—C19

119.4 (7)

N2—Cu1—N1

C17—C18—H18 C19—C18—H18 N3—C19—C18 N3—C19—H19 C18—C19—H19

120.3 120.3 121.8 (7) 119.1 119.1

81.27 (16)

O1—Cu1—O2

i

76.66 (11)

O2—Cu1—O2

i

78.31 (12)

N2—Cu1—O2

i

106.08 (13)

N1—Cu1—O2

i

109.01 (14)

i

85.74 (11)

i

O2 —Cu2—O1

N4—C20—C21

114.5 (4)

O2 —Cu2—N3

176.81 (15)

N4—C20—H20A

108.6

O1—Cu2—N3

97.33 (15)

i

C21—C20—H20A

108.6

O2 —Cu2—N4

95.33 (14)

N4—C20—H20B

108.6

O1—Cu2—N4

171.20 (16)

C21—C20—H20B

108.6

N3—Cu2—N4

81.51 (17)

i

i

H20A—C20—H20B

107.6

O2 —Cu2—O1

C22—C21—C26

119.0 (6)

O1—Cu2—O1i

123.4 (5)

N3—Cu2—O1

i

104.69 (14)

i

109.75 (16)

C22—C21—C20 C26—C21—C20

117.6 (6)

N4—Cu2—O1

C21—C22—C23

120.7 (6)

O2W—O1W—O3W

C21—C22—H22

119.6

76.71 (11) 79.02 (13)

75 (3)

Symmetry code: (i) -x, y, -z+1/2.

6

complex 2: CCDC 915280 Crystal data C14H17ClCuN2O6

Z=2

Mr = 408.29

F(000) = 418

Triclinic, P¯1

Dx = 1.647 Mg m-3

Hall symbol: -P 1


a = 9.0049 (3) Å


b = 9.0910 (2) Å

θ = 3.2–29.0°

c = 10.3035 (3) Å

µ = 1.52 mm-1

α = 94.190 (1)°

T = 293 K

β = 98.429 (1)°

Prism, blue 0.3 × 0.3 × 0.08 mm

γ = 97.648 (3)° V = 823.25 (4) Å

3


Rint = 0.028

graphite

θmax = 29.0°, θmin = 3.2°

ω + Phi scan

h = 0→11


k = -12→12


l = -13→13






R[F2 > 2σ(F2)] = 0.046


2

wR(F ) = 0.136

H atoms treated by a mixture of independent and constrained refinement

S = 1.06


4133 reflections

(Δ/σ)max < 0.001

226 parameters

Δ〉max = 0.46 e Å-3

3 restraints

Δ〉min = -0.76 e Å-3

7

Geometric parameters (Å, º) C1—N2

1.326 (3)

C10—C11

1.386 (5)

C1—C2

1.389 (4)

C10—H10

0.93

C1—H1

0.93

C11—C12

1.354 (6)

C2—C3

1.373 (5)

C11—H11

0.93

C2—H2

0.93

C12—C13

1.379 (7)

C3—C4

1.381 (5)

C12—H12

0.93

C3—H3

0.93

C13—C14

1.409 (6)

C4—C5

1.382 (4)

C13—H13

0.93

C4—H4

0.93

C14—H14

0.93

C5—N2

1.345 (3)

N1—Cu1

1.993 (2)

C5—C6

1.460 (4)

N2—Cu1

2.004 (2)

C6—N1

1.270 (4)

O1—Cu1

1.910 (2) i

C6—H6

0.93

O1—Cu1

C7—N1

1.467 (3)

O1—H1O

0.898 (5)

C7—C8

1.530 (4)

O2—Cl1

1.408 (4)

C7—H7A

0.97

O3—Cl1

1.422 (3)

C7—H7B

0.97

O4—Cl1

1.424 (3)

C8—C9

1.508 (4)

O5—Cl1

1.381 (4)

C8—H8A

0.97

O6—H1W

0.905 (5)

C8—H8B

0.97

O6—H2W

0.906 (5)

C9—C10

1.380 (5)

Cu1—O1

1.9162 (19)

i

1.916 (2) i

C9—C14

1.384 (4)

Cu1—Cu1

2.9186 (6)

N2—C1—C2

121.9 (3)

C12—C11—H11

119.8

N2—C1—H1

119.1

C10—C11—H11

119.8

C2—C1—H1

119.1

C11—C12—C13

119.9 (3)

C3—C2—C1

119.4 (3)

C11—C12—H12

120

C3—C2—H2

120.3

C13—C12—H12

120

C1—C2—H2

120.3

C12—C13—C14

119.8 (4)

C2—C3—C4

118.9 (3)

C12—C13—H13

120.1

C2—C3—H3

120.6

C14—C13—H13

120.1

C4—C3—H3

120.6

C9—C14—C13

120.2 (4)

C3—C4—C5

118.7 (3)

C9—C14—H14

119.9

C3—C4—H4

120.7

C13—C14—H14

119.9

C5—C4—H4

120.7

C6—N1—C7

120.0 (2)

N2—C5—C4

122.3 (3)

C6—N1—Cu1

113.05 (18)

N2—C5—C6

114.2 (2)

C7—N1—Cu1

126.87 (17)

C4—C5—C6

123.5 (3)

C1—N2—C5

118.8 (2)

8

N1—C6—C5

118.5 (2)

C1—N2—Cu1

N1—C6—H6

120.7

C5—N2—Cu1

129.0 (2) 112.17 (17) i

C5—C6—H6

120.7

Cu1—O1—Cu1

99.43 (9)

N1—C7—C8

109.8 (2)

Cu1—O1—H1O i

119 (2)

N1—C7—H7A

109.7

Cu1 —O1—H1O

118 (2)

C8—C7—H7A

109.7

H1W—O6—H2W

126 (7)

N1—C7—H7B

109.7

O5—Cl1—O2

110.3 (4)

C8—C7—H7B

109.7

O5—Cl1—O3

108.4 (3)

H7A—C7—H7B

108.2

O2—Cl1—O3

108.8 (3)

C9—C8—C7

111.6 (2)

O5—Cl1—O4

111.4 (3)

C9—C8—H8A

109.3

O2—Cl1—O4

107.7 (2)

C7—C8—H8A

109.3

O3—Cl1—O4

110.20 (19) i

C9—C8—H8B

109.3

O1—Cu1—O1

C7—C8—H8B

109.3

O1—Cu1—N1

179.04 (9)

H8A—C8—H8B

108

O1i—Cu1—N1

98.81 (9)

C10—C9—C14

118.2 (3)

O1—Cu1—N2

98.74 (9)

i

C10—C9—C8

120.7 (3)

O1 —Cu1—N2

C14—C9—C8

121.1 (3)

N1—Cu1—N2

C9—C10—C11 C9—C10—H10 C11—C10—H10 C12—C11—C10

121.4 (3)

80.57 (9)

O1—Cu1—Cu1

175.15 (10) 81.94 (9) i

i

40.36 (6) i

119.3

O1 —Cu1—Cu1

119.3

N1—Cu1—Cu1

i

139.01 (7)

N2—Cu1—Cu1

i

138.90 (7)

120.4 (4)

40.20 (6)

Symmetry code: (i) -x+2, -y+1, -z+2.

9

complex 3: CCDC 915279 Crystal data C28H30Cl2CuN4O9

F(000) = 1444

Mr = 701.01

Dx = 1.502 Mg m-3

Orthorhombic, Pbcn


Hall symbol: -P 2n 2ab


a = 20.8464 (5) Å

θ = 2.3–28.3°

b = 8.4305 (2) Å

µ = 0.94 mm-1

c = 17.6443 (4) Å V = 3100.91 (13) Å

T = 293 K 3

Prism, blue

Z=4

0.3 × 0.2 × 0.16 mm


Rint = 0.07

graphite

θmax = 28.3°, θmin = 2.3°

ω + Phi scan

h = 0→27


k = 0→10


l = 0→23






R[F2 > 2σ(F2)] = 0.061


2

wR(F ) = 0.231

H-atom parameters constrained

S = 1.07


3475 reflections

(Δ/σ)max < 0.001

218 parameters

Δ〉max = 0.59 e Å-3

0 restraints

Δ〉min = -0.90 e Å-3

Geometric parameters (Å, º) C1—N1

1.325 (6)

C12—C13

1.377 (9)

C1—C2

1.379 (7)

C12—H12

0.93

C1—H1

0.93

C13—C14

1.357 (9)

10

C2—C3

1.357 (9)

C13—H13

0.93

C2—H2

0.93

C14—C16

1.384 (7)

C3—C4

1.364 (8)

C14—H14

0.93

C3—H3

0.93

C16—H16

0.93

C4—C5

1.380 (6)

N1—Cu1

1.975 (4)

C4—H4

0.93

N2—Cu1

2.090 (3)

C5—N1

1.345 (6)

O1—Cu1

2.037 (5)

C5—C6

1.473 (6)

O1—H1w

0.8496

C6—N2

1.261 (6)

O2—Cl2

1.414 (15)

C6—H6

0.93

O2—Cl1

1.423 (6)

C7—N2

1.464 (5)

O3—Cl1

1.424 (7)

C7—C9

1.524 (6)

O3—Cl2

2.033 (13)

C7—H7A

0.97

O4—Cl1

1.392 (6)

C7—H7B

0.97

O4—Cl2

1.447 (15)

C9—C10

1.501 (6)

O5—Cl2

1.327 (17)

C9—H9A

0.97

O5—Cl1

1.365 (7)

C9—H9B

0.97

O6—Cl2

1.22 (2)

C10—C11

1.376 (7)

O6—Cl1

1.824 (18)

C10—C16

1.385 (7)

Cl1—Cl2

C11—C12

1.395 (7)

0.612 (11)

Cu1—N1

i

1.975 (4)

i

2.090 (3)

C11—H11

0.93

Cu1—N2

N1—C1—C2

121.8 (5)

C5—N1—Cu1

114.7 (3)

N1—C1—H1

119.1

C6—N2—C7

118.8 (4)

C2—C1—H1

119.1

C6—N2—Cu1

111.4 (3)

C3—C2—C1

119.2 (5)

C7—N2—Cu1

129.5 (3)

C3—C2—H2

120.4

Cu1—O1—H1w

126.1

C1—C2—H2

120.4

Cl2—O2—Cl1

24.9 (4)

C2—C3—C4

119.7 (5)

Cl1—O3—Cl2

2.0 (6)

C2—C3—H3

120.2

Cl1—O4—Cl2

24.8 (4)

C4—C3—H3

120.2

Cl2—O5—Cl1

26.2 (5)

C3—C4—C5

118.9 (5)

Cl2—O6—Cl1

3.1 (8)

C3—C4—H4

120.5

Cl2—Cl1—O5

73.4 (18)

C5—C4—H4

120.5

Cl2—Cl1—O4

82.7 (16)

N1—C5—C4

121.4 (4)

O5—Cl1—O4

120.1 (5)

N1—C5—C6

114.0 (4)

Cl2—Cl1—O2

76.7 (16)

C4—C5—C6

124.5 (4)

O5—Cl1—O2

115.4 (5)

N2—C6—C5

119.0 (4)

O4—Cl1—O2

110.8 (4)

N2—C6—H6

120.5

Cl2—Cl1—O3

173.3 (19)

C5—C6—H6

120.5

O5—Cl1—O3

101.2 (6)

11

N2—C7—C9

110.4 (3)

O4—Cl1—O3

103.6 (4)

N2—C7—H7A

109.6

O2—Cl1—O3

102.8 (5)

C9—C7—H7A

109.6

Cl2—Cl1—O6

6.2 (16)

N2—C7—H7B

109.6

O5—Cl1—O6

69.1 (7)

C9—C7—H7B

109.6

O4—Cl1—O6

81.5 (6)

H7A—C7—H7B

108.1

O2—Cl1—O6

82.8 (6)

C10—C9—C7

113.1 (4)

O3—Cl1—O6

170.3 (7)

C10—C9—H9A

109

Cl1—Cl2—O6

171 (2)

C7—C9—H9A

109

Cl1—Cl2—O5

80.4 (18)

C10—C9—H9B

109

O6—Cl2—O5

93.1 (13)

C7—C9—H9B

109

Cl1—Cl2—O2

78.3 (16)

H9A—C9—H9B

107.8

O6—Cl2—O2

110.7 (13)

C11—C10—C16

117.8 (4)

O5—Cl2—O2

118.6 (11)

C11—C10—C9

120.4 (4)

Cl1—Cl2—O4

72.5 (15)

C16—C10—C9

121.8 (5)

O6—Cl2—O4

105.4 (12)

C10—C11—C12

121.3 (5)

O5—Cl2—O4

118.9 (11)

C10—C11—H11

119.4

O2—Cl2—O4

108.1 (10)

C12—C11—H11

119.4

Cl1—Cl2—O3

4.7 (13)

C13—C12—C11

119.7 (5)

O6—Cl2—O3

169.0 (14)

C13—C12—H12

120.2

O5—Cl2—O3

76.6 (8)

C11—C12—H12

120.2

O2—Cl2—O3

78.1 (6)

C14—C13—C12

119.5 (5)

O4—Cl2—O3

C14—C13—H13

120.2

N1—Cu1—N1

C12—C13—H13

120.2

N1—Cu1—O1

76.9 (6) i

179.9 (2) 90.06 (10)

i

C13—C14—C16

120.9 (6)

N1 —Cu1—O1

90.06 (10)

C13—C14—H14

119.5

N1—Cu1—N2

80.77 (14)

i

C16—C14—H14

119.5

N1 —Cu1—N2

99.16 (14)

C14—C16—C10

120.8 (5)

O1—Cu1—N2

124.24 (9)

C14—C16—H16

119.6

N1—Cu1—N2

i

i

C10—C16—H16

119.6

N1 —Cu1—N2

C1—N1—C5

118.9 (4)

O1—Cu1—N2i

126.4 (3)

i

C1—N1—Cu1

N2—Cu1—N2

99.16 (14) i

80.77 (14) 124.24 (9) 111.52 (18)

Symmetry code: (i) -x+2, y, -z+3/2.

12

Structural and Magnetic Characterization of a Tetranuclear Copper(II

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