Controllable assembly of Cu(II) coordination compounds based on a
flexible zwitterionic benzimidazole-dicarboxylate ligand: Synthesis,
structural diversity, reversible SCSC transformations
and magnetic properties Yan-Fang Feng, Qi Tang, Kai-Liang Luo, Ji-Qing Wu, Zhong Zhang*, Yu-Ning Liang and
Fu-Pei Liang*
School of Chemistry and Pharmacy of Guangxi Normal University, Key Laboratory for the
Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China),
Guilin 541004, P. R. China
Corresponding authors
Zhong Zhang and Fu-Pei Liang
E-mail address, telephone and fax numbers of the corresponding authors
e-mail: [email protected]
telephone: +86-773-5854878
fax: +86-773-5832294
† Electronic supplementary information (ESI) available: PXRD patterns (Fig. S1–S4),
IR spectra (Fig. S5), images of single crystals (Fig. S6), selected bond distances
(Table S1) and selected hydrogen bond parameters (Table S2) for complexes 1–9.
CCDC reference numbers 1551820–1551828 for 1–9. For ESI and crystallographic
data in CIF or other electronic format see
Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2017
Fig. S1 Powder X-ray diffraction patterns of (a) 3 obtained by recrystallizing 2 in
water at room temperature; (b) as-synthesized 3; (c) simulated 3 from single-crystal
data.
Fig. S2 Powder X-ray diffraction patterns of (a) 4 obtained by 4 obtained by
recrystallizing 2 in a mixture solution of H2O–CH3CN with its pH value being
adjusted to 5 by aqueous NaOH; (b) as-synthesized 4; (c) simulated 4 from single-
crystal data; (d) 2 obtained by recrystallizing 4 in a mixture solution of H2O–CH3OH
with its pH value being adjusted to 3 by aqueous HNO3; (d) as-synthesized 2; (e)
simulated 2 from single-crystal data.
Fig. S3 Powder X-ray diffraction patterns of (a) 4 obtained by recrystallizing 3 in a
mixture solution of H2O–CH3CN with its pH value being adjusted to 5 by aqueous
NaOH; (b) as-synthesized 4; (c) simulated 4 from single-crystal data.
Fig. S4 Powder X-ray diffraction patterns of (a) 6 obtained by dispersing the crystals
of 2 in a mixed solvent of H2O–CH3OH at 80 °C in the presence of SO42–; (b) as-
synthesized 6; (c) simulated 6 from single-crystal data.
Fig. S5 FT-IR spectra of compounds 1–9.
Fig. S6 Photograph of the single crystals of compounds 1 and 3 and the single crystal
image of 1 after exposure to water vapor for ten minutes.
1 3 3 from 1
Table S1. Selected bond lengths (Å) and angles (º) for compounds 1–9.Compound 1Cu1–O1#1 1.972(3) Cu1–O2 1.970(3)Cu1–O3 1.969(3) Cu1–O4#1 1.987(3)Cu1–O5 2.146(3)O1#1–Cu1–O2 167.15(13) O1#1–Cu1–O3 88.93(14)O1#1–Cu1–O4#1 88.54(14) O1#1–Cu1–O5 97.07(14)O2–Cu1–O3 90.44(14) O2–Cu1–O4#1 89.26(14)O2–Cu1–O5 95.58(14) O3–Cu1–O4#1 167.27(13)O3–Cu1–O5 103.06(14) O4#1–Cu1–O5 89.64(14)
Compound 2Cu1–O1 1.969(4) Cu1–O2 1.969(3)Cu1–O3 2.149(6)O1–Cu1–O1#1 89.1(2) O1–Cu1–O2 89.69(15)O1–Cu1–O2#2 168.76(16) O1–Cu1–O3 98.50(18)O2–Cu1–O2#2 89.3(2) O2–Cu1–O3 92.73(18)
Compound 3Cu1–O2 1.968(2) Cu1–O3 1.952(2)Cu1–O5 2.491(2) Cu2–O2#1 2.564(2)Cu2–O4 1.946(2) Cu2–O5 1.932(2)O2–Cu1–O3 89.97(8) O2–Cu1–O5 95.63(8)O2–Cu1–O3#1 90.03(8) O2–Cu1–O5#1 84.37(8)O3–Cu1–O5 92.73(8) O3–Cu1–O5#1 87.27(8)O2#1–Cu1–O4 89.90(8) O2#1–Cu1–O5 83.11(8)O2#2–Cu1–O4 90.10(8) O2#1–Cu1–O5 96.89(8)O4–Cu1–O5 93.16(8) O4–Cu1–O5#3 86.84(8)
Compound 4Cu1–O2 1.954(3) Cu1–O3 2.312(4)Cu1–O7 1.983(4) Cu1–O9 1.972(4)Cu1–O10 1.928(3) Cu2–O4#1 1.973(4)Cu2–O6#1 1.932(3) Cu2–O8 2.282(4)Cu2–O10 1.987(3) Cu2–O10#1 1.973(3)O2–Cu1–O3 91.69(15) O2–Cu1–O7 172.08(14)O2–Cu1–O9 86.30(15) O2–Cu1–O10 94.65(14)O3–Cu1–O7 84.38(15) O3–Cu1–O9 87.65(14)O3–Cu1–O10 97.60(13) O7–Cu1–O9 86.67(16)O7–Cu1–O10 92.69(14) O9–Cu1–O10 174.63(13)
O4#1–Cu2–O6#1 86.44(15) O4#1–Cu2–O8 84.64(15)O4#1–Cu2–O10 177.02(14) O4#1–Cu2–O10#1 99.69(14)O6#1–Cu2–O8 106.91(15) O6#1–Cu2–O10 93.75(14)O6#1–Cu2–O10#1 156.70(14) O8–Cu2–O10 98.14(13)O8–Cu2–O10#1 96.07(14) O10–Cu2–O10#1 78.99(14)
Compound 5Cu1–O1 1.959(2) Cu1–O2#1 1.968(2)Cu1–O3#1 1.971(2) Cu1–O4 1.972(2)Cu1–O5 2.197(3)O1–Cu1–O2#1 169.02(10) O1–Cu1–O3#1 89.16(11)O1–Cu1–O4 89.73(11) O1–Cu1–O5 98.17(11)O2#1–Cu1–O3#1 89.49(11) O2#1–Cu1–O4 89.55(11)O2#1–Cu1–O5 92.78(11) O3#1–Cu1–O4 169.19(10)O3#1–Cu1–O5 93.13(10) O4–Cu1–O5 97.67(10)
Compound 6Cu1–O2 1.941(2) Cu1–O3 1.958(2)Cu1–O9 1.958(2) Cu1–O10 1.958(2)Cu1–O11 2.407(2) Cu2–O6 1.954(2)Cu2–O7 1.949(2) Cu2–O12 1.954(2)Cu2–O13 1.959(2) Cu2–O14 2.268(2)O2–Cu1–O3 88.36(8) O2–Cu1–O9 87.09(8)O2–Cu1–O10 178.24(8) O2–Cu1–O11 93.25(8)O3–Cu1–O9 175.30(8) O3–Cu1–O10 92.49(8)O3–Cu1–O11 86.73(8) O9–Cu1–O10 92.02(8)O9–Cu1–O11 94.71(8) O10–Cu1–O11 88.33(8)O6–Cu2–O7 88.65(9) O6–Cu2–O12 87.99(8)O6–Cu2–O13 176.05(9) O6–Cu2–O14 90.97(9)O7–Cu2–O12 176.49(9) O7–Cu2–O13 93.45(9)O7–Cu2–O14 90.25(9) O12–Cu2–O13 89.84(9)O12–Cu2–O14 90.83(9) O13–Cu2–O14 92.36(9)
Compound 7Cu1–O1 2.722(2) Cu1–O2 1.971(2)Cu1–Cl1 2.284(1)O1–Cu1–O2 53.39(6) O1–Cu1–Cl 84.19(4)O1–Cu1–O2#1 126.61(6) O1–Cu1–Cl#1 95.81(4)O2–Cu1–Cl1 90.55(6) O2–Cu1–Cl1#1 89.45(6)
Compound 8Cu1–O1 1.990(1) Cu1–O2#1 1.980(2)Cu1–O3#1 1.981(1) Cu1–O4 1.983(1)Cu1–Cl1 2.450(1)O1–Cu1–O2#1 165.72(6) O1–Cu1–O3#1 89.53(7)O1–Cu1–O4 89.13(6) O2#1–Cu1–O3#1 89.69(7)O2#1–Cu1–O4 88.14(7) O3#1–Cu1–O4 165.82(6)O1–Cu1–Cl1 97.34(4) O2#1–Cu1–Cl1 96.94(5)O3#1–Cu1–Cl1 94.18(5) O4–Cu1–Cl1 100.00(5)
Compound 9Cu1–O1 1.962(3) Cu1–O2#1 1.967(4)Cu1–O3#2 1.966(4) Cu1–O4#3 1.976(3)Cu1–Cl1 2.418(2)O1–Cu1–O2#1 166.26(12) O1–Cu1–O3#2 87.87(17)O1–Cu1–O4#3 89.39(15) O2#1–Cu1–O3#2 89.70(20)O2#1–Cu1–O4#3 87.77(18) O3#2–Cu1–O4#3 166.33(13)O1–Cu1–Cl1 99.85(10) O2#1–Cu1–Cl1 93.88(11)O3#2–Cu1–Cl1 93.55(11) O4#3–Cu1–Cl1 100.03(11)
Symmetry codes for 1: #1 2 −x, 2 − y, 1 − z. for 2: #1 x, y, 1 – z; #1 −x, −y, 1 – z. for 3: #1 1 − x, 1 − y, −z; #2 −x, 1 − y, −z; #3 −1 + x, y, z. for 4: #1 2 − x, 1 − y, 2 − z. for 5: #1 1 − x, 2 − y, 2 − z. for 7: #1 −1 − x, 2 − y, −z. for 8: #1 −x, −y + 1, −z + 1. for 9: #1 −x, 1 − y, 1 − z; #2 x, 1 + y, z; #3 1 − x, −y, 2 − z.
Table S2. Hydrogen bond distances (Å) and angles (º) for compounds 1–9.D–H∙∙∙A d(D–H) d(H∙∙∙A) d(D∙∙∙A) D–H∙∙∙A
Compound 2
O3–H3A∙∙∙O5#1 0.85 2.40 2.832(17) 112
O6–H6C∙∙∙O7 0.85 2.60 3.03(2) 113
Compound 3
O5–H5C∙∙∙O6#1 0.85 2.22 3.033(5) 159
O5–H5C∙∙∙O8#1 0.85 2.05 2.780(4) 143
O5–H5D∙∙∙O1 0.85 1.73 2.565(3) 167
Compound 4
O9–H9C∙∙∙O8#1 0.85 2.11 2.776(6) 135
O9–H9D∙∙∙O5#2 0.85 1.80 2.633(6) 165
O10–H10∙∙∙O1 0.85 1.78 2.611(6) 164
O15–H15C∙∙∙O17 0.85 2.53 2.611(6) 164
O15–H15D∙∙∙O16#3 0.85 2.11 2.782(18) 136
O17–H17C∙∙∙O12#4 0.85 2.24 3.06(3) 163
O17–H17D∙∙∙O18#3 0.85 2.54 3.22(4) 138
Compound 5
O5–H5C∙∙∙O6#1 0.85 2.00 2.840(6) 171
O5–H5D∙∙∙O9#2 0.85 2.09 2.908(6) 162
Compound 6
O9–H9C∙∙∙O1#1 0.85 2.02 2.844(3) 164
O9–H9D∙∙∙O24#2 0.85 1.79 2.613(3) 162
O10–H10C∙∙∙O19#1 0.85 1.95 2.728(3) 151
O10–H10D∙∙∙O22#2 0.85 1.78 2.623(3) 171
O11–H11C∙∙∙O20 0.85 2.05 2.891(3) 168
O11–H11D∙∙∙O17#2 0.85 2.09 2.765(3) 136
O12–H12C∙∙∙O5#3 0.85 1.89 2.735(3) 176
O12–H12D∙∙∙O21#4 0.85 1.82 2.667(3) 170
O13–H13C∙∙∙O15#4 0.85 1.95 2.698(3) 147
O13–H13D∙∙∙O25#4 0.85 1.85 2.672(3) 163
O14–H14C∙∙∙O16#5 0.85 2.10 2.841(3) 145
O14–H14D∙∙∙O23#4 0.85 1.93 2.775(3) 174
O15–H15C∙∙∙O8 0.85 2.06 2.912(3) 176
O15–H15D∙∙∙O23#6 0.85 2.11 2.926(3) 162
O17–H17C∙∙∙O23#6 0.85 2.59 3.314(3) 144
O17–H17C∙∙∙O24#6 0.85 2.34 3.109(3) 152
O17–H17D∙∙∙O25 0.85 2.21 2.991(3) 152
O18–H18C∙∙∙O23#6 0.85 2.45 3.029(4) 126
O18–H18D∙∙∙O19 0.85 2.30 2.934(4) 132
O19–H19C∙∙∙O11#2 0.85 2.11 2.894(3) 154
O21–H21C∙∙∙O18 0.85 1.95 2.765(4) 160
O21–H21D∙∙∙O22 0.85 1.95 2.794(3) 174
Compound 7
O3–H3∙∙∙O1#1 0.85 1.76 2.574(2) 160
Compound 8
O5–H5C∙∙∙Cl1#1 0.85 2.38 3.2206(18) 169
O5–H5D∙∙∙Cl1#2 0.85 2.56 3.382(2) 163
Compound 9
O5–H5C∙∙∙O4#1 0.85 2.33 3.036(8) 141
O5–H5D∙∙∙Cl1#2 0.85 2.43 3.008(7) 126
Symmetry codes for 2: #1 y, – x, 1/2 – z. for 3: #1 x, y, –1 + z. for 4: #1 1 – x, 1 – y, 2 – z; #2 – 1 + x, y,
z; #3 x, 1 + y, z; #4 1 – x, 1 – y, 1 – z. for 5: #1 –1 + x, 2/3 – y, 1/2 + z; #2 –1 + x, 1 + y, z. for 6: #1 –x,
1 – y, –z; #2 1 – x, 1 – y, –z; #3 1 – x, 2 – y, 1 – z; #4 1 – x, 1 – y, 1 – z; #5 –x, 1 – y, 1 – z; #6 –1 + x, y,
z. for 7: #1 1 + x, 1 + y, z. for 8: #1 1 – x, – y, 1 – z; #2 1 + x, y, z. for 9: #1 x, 1 + y, z; #2 1 + x, –1 +
y, z.