Analyzing Coordination Preferences of Mg2+Complexes: Insights from Computational and Database Study
Y. Indra Neela, A. Subha Mahadevi and G. Narahari Sastry *
Molecular Modeling Group, Organic Chemical Sciences, Indian Institute of Chemical Technology, Tarnaka, Hyderabad 500 607, AP, India
E-mail:
Supporting Information
(9 pages including this page)
Fig. S1 Variation in interaction energy (kcal/mol) with the increase in size of water cluster [Mg2+(H2O)1–6] around magnesium ion calculated at MP2/cc–pVTZ//B3LYP/6–31G(d,p) level of theory.
Fig. S2 Variation in charge on Mg2+ ion with the increase in size of water cluster [Mg2+(H2O)1–20] calculatedat B3LYP/6–311++G(2d,2p)//B3LYP/6–31G(d,p) level of theory.
Table S1: The cif codes of crystal structures representing coordination of magnesium ion with water and various metal atoms obtained from CSD.
Table S2: The interaction energy (IE in kcal/mol) of Mg2+(H2O)1–6 complexes optimized at B3LYP/6–31G(d,p) level of theory.
Table S3: The interaction energy (IE in kcal/mol) of Mg2+(H2O)7–12complexes optimized at B3LYP/6–31G(d,p) level of theory.
Table S4: The interaction energy (IE in kcal/mol) of Mg2+(H2O)13–18complexes optimized at B3LYP/6–31G(d,p) level of theory.
Table S5: The interaction energy (IE in kcal/mol) of Mg2+(H2O)19–20complexes optimized at B3LYP/6–31G(d,p) level of theory.
Table S6:Summed up NPA charge at B3LYP/6-311++G(2d,2p) and Mulliken charges at B3LYP/6-31G(d,p) level in a. u. on all waters in first, second and third solvation shell of representative Mg2+(H2O)ncomplexes.
Fig. S1 Variation in interaction energy (kcal/mol) with the increase in size of water cluster [Mg2+(H2O)1–6] around magnesium ion calculated at MP2/cc–pVTZ//B3LYP/6–31G(d,p) level of theory.
Fig. S2 Variation in charge on Mg2+ ion with the increase in size of water cluster [Mg2+(H2O)1–20] calculated at B3LYP/6–311++G(2d,2p)//B3LYP/6–31G(d,p) level of theory.
Table S1:The cif codes of crystal structures representing coordination of magnesium ion with water and various metal atoms obtained from CSD.
cif CODE / CN / cif CODE / CN / cif CODE / CN / cif CODE / CN / cif CODE / CNAJIDUT / 6 / FAPFOR10 / 5 / KEQRAZ / 6 / POZHUI / 6 / WIKXAP / 6
ANAPHS / 6 / FAPFOR / 6 / KIDLUF / 6 / PUFYOF / 6 / XECJIY / 6
AQMEDA / 6 / FEDQUA01 / 6 / KIMNID / 6 / QERJIH / 6 / XEZCIP / 6
ASABAX / 6 / FEDQUA / 6 / KURWOK / 6 / QEZKEM / 6 / XITDUZ / 6
AXIMOJ / 6 / FETHAO / 6 / KUZJEU / 6 / RAKYOR / 6 / XOSPOL / 6
BADTEX01 / 6 / FOJWOQ / 6 / LAFYIB / 6 / RAMXOS / 6 / XUXLUX / 6
BADTEX10 / 6 / FUGCAM / 6 / LIFHEO / 6 / RATRIN01 / 6 / YAQVUI / 6
BAWGOV / 6 / FURWIZ / 5 / LIWJUW01 / 6 / RATRIN / 6 / YIBROR / 6
BEJYIZ / 6 / GAKPOY / 6 / LIWJUW / 6 / REFTEC / 6 / YIDVIR / 6
BEKCID / 6 / GATLUI / 6 / LONQIP / 6 / RIRGEF / 6 / YIGCOH / 6
BIHLIO / 6 / GAYLUN / 6 / MAVDOD / 6 / RIVCAA / 6 / YIQGOU / 6
BIHNEM / 6 / GELTEX / 6 / MAZLOO / 6 / RUMQUL / 6 / YIZWUZ / 6
BIKPUG / 6 / GIJVEA / 6 / MGABES / 6 / SEKKEZ / 6 / YODWUK / 6
CAWTID / 6 / GIYCAT / 6 / MGCITD / 6 / SIMZUJ / 6 / YORYOU / 7
CDEDTA11 / 6 / GIYCEX / 6 / MGEDTA01 / 7 / TAHKUJ / 6 / ZARMEK / 6
CIPGIS / 6 / GIYCIB / 6 / MGEDTA10 / 7 / TAKZEK / 6 / ZEQWEX / 6
CIRVAA01 / 6 / GIYCOH / 6 / MGHBZA10 / 6 / TEKBIU / 6 / ZURWIS01 / 6
CIRVAA / 6 / GOBSIA / 6 / MGHBZA20 / 6 / THIAMG10 / 6 / ZURWIS / 6
CUPRUB / 6 / GOLPIG / 6 / MGNTSP / 6 / TIZTIG / 6 / ZZZNLI01 / 6
CUPSIQ / 6 / GUHHOG / 6 / MGPICD / 6 / TOXDMG / 6
CUPVEP / 6 / GUMPEJ / 6 / MINKOJ / 6 / TUCGII / 6
DABDEQ / 6 / HAGVOA / 6 / MISXER / 6 / TUHMIT / 6
DAMZAT / 6 / HAHWAO / 6 / MODFAN / 6 / TUHMOZ / 6
DANFUU / 6 / HETZUB / 6 / MOYTAV / 6 / TUWXIT / 6
DAWVED / 6 / HMTMGC10 / 6 / MOYVOM / 6 / TUXYOA / 6
DAWVON01 / 6 / HONGOH / 6 / NIMXOX / 6 / UDIVIN / 6
DAWVON / 6 / IBEMIM / 6 / NIMXUD / 6 / UFAPEX / 6
DECDIY / 6 / IDIFEG / 6 / NIQLIJ / 6 / UMANEB / 6
DEHMIN / 6 / IFOYAE / 6 / NOGLAW / 6 / UMANOL / 6
DERJOZ / 6 / ILUXAO / 6 / NOPPUE / 6 / UNATEI / 6
DIPNUL / 6 / IMAFOR / 6 / NUHROY / 6 / UNEVUE / 6
DOFXAY / 6 / IWOYEY / 6 / OCEQIW / 6 / UNEWEP / 6
DOFXIG / 6 / JAMQAQ / 6 / OHUCEZ / 6 / VAFKET / 6
DXMGHC10 / 6 / JAPFOV / 6 / OHUCID / 6 / VILLAE / 6
EMEZAX / 6 / JAPFUB / 6 / OMARID / 6 / VILLEI / 6
ERUPAI / 6 / JEJTEY / 6 / POHGIC01 / 6 / VILLIM / 6
EXUBOO / 6 / JEYCEW / 6 / POHGIC / 6 / VOPCEI / 6
FADPEG / 6 / JOKQOQ / 6 / PONGIJ / 6 / VUKMIX / 6
FAHSAI / 6 / KAVBUE / 6 / PONGUV / 6 / VUYJIJ / 6
Table S2: The interaction energy (IE in kcal/mol) of Mg2+(H2O)1–6 complexes optimized at B3LYP/6–31G(d,p) level of theory.
Structure / m+n / PG / OPT / SP / QB3LYP/6–31G(d,p) / B3LYP/6–311++G(2d,2p) / MP2/cc–pVTZ
IE / IE / IE
1a / 1+0 / C2v / –91.38 / –82.91 / –82.28 / 1.957
2a / 2+0 / D2d / –174.20 / –157.56 / –156.96 / 1.869
2b / 1+1 / Cs / –175.14 / –158.42 / –160.36 / 1.915
3a / 3+0 / D3 / –244.04 / –219.13 / –220.1 / 1.755
3b / 2+1 / Cs / –229.30 / –201.68 / –207.47 / 1.862
3c / 2+1 / C1 / –207.33 / –138.98 / –186.69 / 1.862
3d / 1+2 / C1 / –188.02 / –168.01 / –168.58 / 1.905
4a / 4+0 / S4 / –303.11 / –270.96 / –273.79 / 1.632
4b / 3+1 / C1 / –285.77 / –255.93 / –258.08 / 1.738
4c / 3+1 / C2 / –278.13 / –249.14 / –250.70 / 1.744
4d / 2+2 / C1 / –271.75 / –244.06 / –245.99 / 1.825
4e / 2+2 / C1 / –256.64 / –228.98 / –230.78 / 1.830
5a / 5+0 / C2 / –345.93 / –308.75 / –313.38 / 1.538
5b / 4+1 / C2 / –335.03 / –298.73 / –302.28 / 1.622
5c / 3+2 / C1 / –311.92 / –279.00 / –281.46 / 1.729
5d / 2+3 / Cs / –298.88 / –266.69 / –269.39 / 1.814
6a / 6+0 / Th / –385.73 / –343.40 / –350.07 / 1.420
6b / 6+0 / D3 / –380.79 / –338.58 / –345.37 / 1.422
6c / 5+1 / C1 / –377.04 / –335.39 / –341.14 / 1.528
6d / 4+2 / D2d / –366.53 / –326.20 / –330.51 / 1.614
6e / 3+3 / Cs / –354.11 / –309.29 / –302.04 / 1.708
6f / 2+4 / S4 / –326.63 / –290.19 / –293.63 / 1.804
m = # water molecules in 1st solvation shell
n = # water molecules in 2nd solvation shell
o = # water molecules in 3rd solvation shell
PG = Point group symmetry
SP = Single point calculations performed on B3LYP/6–31G(d,p) optimized geometries
Q = Charge on Mg2+ ion in complex at B3LYP/6–311++G(2d,2p) level of theory
Table S3: The interaction energy (IE in kcal/mol) of Mg2+(H2O)7–12complexes optimized at B3LYP/6–31G(d,p) level of theory.
Structure / m+n+o / PG / OPT / SP / QB3LYP/6–31G(d,p) / B3LYP/6–311++G(2d,2p) / MP2/cc–pVTZ
IE / IE / IE
7a / 6+1 / C1 / –412.10 / –365.56 / –373.34 / 1.419
7b / 5+2 / C1 / –406.90 / –361.45 / –367.74 / 1.520
7c / 4+3 / C2 / –389.13 / –345.80 / –350.66 / 1.610
7d / 4+3 / C1 / –381.43 / –337.40 / –342.40 / 1.598
7e / 4+3 / C1 / –371.40 / –329.94 / –334.77 / 1.613
7f / 3+4 / C1 / –365.07 / –325.09 / –328.76 / 1.709
7g / 3+2+2 / Cs / –352.55 / –315.02 / –318.43 / 1.722
7h / 2+2+3 / C1 / –344.35 / –308.75 / –316.71 / 1.788
8a / 6+2 / C1 / –437.21 / –386.45 / –395.20 / 1.413
8b / 6+2 / C1 / –429.07 / –380.48 / –388.25 / 1.408
8c / 5+3 / C1 / –431.79 / –382.14 / –389.54 / 1.511
8d / 4+4 / C1 / –424.73 / –376.43 / –383.07 / 1.599
8e / 4+4 / S4 / –414.53 / –367.45 / –373.44 / 1.612
8f / 4+3+1 / C1 / –386.73 / –343.59 / –347.88 / 1.605
8g / 3+2+3 / C1 / –393.29 / –351.44 / –360.29 / 1.695
8h / 2+2+4 / C1 / –356.17 / –319.22 / –327.36 / 1.782
9a / 6+3 / C1 / –465.27 / –410.1 / –419.98 / 1.410
9b / 6+3 / C1 / –458.48 / –404.22 / –413.70 / 1.404
9c / 6+3 / C1 / –454.8 / –401.17 / –410.28 / 1.400
9d / 6+3 / C1 / –453.52 / –400.53 / –409.70 / 1.407
9e / 5+4 / C1 / –456.22 / –402.29 / –410.77 / 1.496
9f / 5+4 / C1 / –449.29 / –396.81 / –404.99 / 1.508
9g / 4+5 / C1 / –436.26 / –383.98 / –391.14 / 1.589
9h / 4+4+1 / C1 / –394.11 / –349.42 / –353.35 / 1.594
9i / 4+3+2 / C1 / –416.45 / –369.69 / –375.31 / 1.599
9j / 3+6 / C1 / –428.43 / –379.32 / –385.31 / 1.691
9k / 3+6 / C1 / –405.59 / –359.37 / –364.30 / 1.688
9l / 2+2+5 / C1 / –358.83 / –322.65 / –330.68 / 1.777
10a / 6+4 / C1 / –480.81 / –423.06 / –433.21 / 1.437
10b / 6+4 / C1 / –473.02 / –416.59 / –426.28 / 1.395
10c / 6+3+1 / C1 / –480.74 / –423.93 / –434.15 / 1.407
10d / 5+5 / C1 / –437.43 / –388.11 / –393.99 / 1.505
10e / 4+6 / C1 / –462.16 / –407.69 / –415.52 / 1.586
10f / 4+5+1 / C1 / –412.30 / –365.17 / –369.77 / 1.596
10g / 4+4+2 / C2 / –444.76 / –394.96 / –401.83 / 1.594
10h / 3+3+4 / C1 / –360.03 / –322.32 / –324.86 / 1.701
10i / 2+2+6 / C1 / –356.98 / –325.67 / –332.19 / 1.760
11a / 6+5 / C1 / –496.13 / –434.93 / –446.10 / 1.390
11b / 6+4+1 / C1 / –494.23 / –434.89 / –444.95 / 1.400
11c / 6+4+1 / C1 / –485.60 / –426.91 / –437.17 / 1.391
11d / 5+6 / C1 / –454.60 / –402.89 / –409.52 / 1.503
11e / 5+6 / C1 / –454.28 / –401.14 / –408.62 / 1.504
11f / 4+6+1 / C1 / –431.94 / –382.55 / –387.40 / 1.586
11g / 3+3+5 / C1 / –419.72 / –377.05 / –384.62 / 1.678
11h / 2+3+6 / C1 / –360.82 / –330.03 / –334.61 / 1.776
12a / 6+6 / C1 / –513.82 / –448.23 / –460.19 / 1.376
12b / 6+6 / C1 / –492.81 / –433.95 / –443.29 / 1.393
12c / 6+6 / C1 / –480.00 / –422.98 / –431.64 / 1.391
12d / 6+5+1 / C2 / –502.30 / –440.32 / –451.44 / 1.389
12e / 6+4+2 / C1 / –505.78 / –444.47 / –454.82 / 1.393
12f / 6+4+2 / C2 / –494.81 / –436.54 / –446.14 / 1.397
12g / 5+7 / C1 / –470.26 / –416.41 / –423.32 / 1.497
12h / 5+7 / C1 / –467.39 / –413.04 / –420.10 / 1.502
12i / 4+6+2 / C1 / –452.75 / –399.35 / –404.99 / 1.583
12j / 4+6+2 / C1 / –430.79 / –380.25 / –385.76 / 1.590
12k / 3+3+6 / Cs / –429.39 / –389.48 / –393.56 / 1.676
12l / 2+4+6 / C1 / –384.30 / –345.81 / –349.51 / 1.779
Table S4: The interaction energy (IE in kcal/mol) of Mg2+(H2O)13–18complexes optimized at B3LYP/6–31G(d,p) level of theory.
Structure / m+n+o / PG / OPT / SP / QB3LYP/6–31G(d,p) / B3LYP/6–311++G(2d,2p) / MP2/cc–pVTZ
IE / IE / IE
13a / 6+7 / C1 / –495.29 / –435.62 / –444.94 / 1.387
13b / 6+6+1 / Cs / –501.89 / –442.32 / –452.00 / 1.387
13c / 6+5+2 / C1 / –489.96 / –429.88 / –439.79 / 1.414
13d / 5+8 / C1 / –479.64 / –423.15 / –430.04 / 1.492
13e / 5+8 / C1 / –471.42 / –418.58 / –425.33 / 1.516
13f / 5+7+1 / C1 / –464.93 / –411.38 / –417.48 / 1.498
13g / 4+6+3 / C1 / –470.24 / –415.02 / –421.42 / 1.579
13h / 4+5+4 / C1 / –444.06 / –400.65 / –407.45 / 1.588
13i / 4+4+5 / C1 / –466.43 / –416.66 / –426.80 / 1.566
13j / 3+6+4 / C1 / –465.15 / –411.22 / –418.59 / 1.674
13k / 2+4+7 / C1 / –420.36 / –378.4 / –385.86 / 1.767
14a / 6+8 / C1 / –520.51 / –456.37 / –467.31 / 1.388
14b / 6+8 / C1 / –503.08 / –442.44 / –452.06 / 1.397
14c / 6+8 / C1 / –489.33 / –431.19 / –438.60 / 1.383
14d / 6+7+1 / C1 / –506.28 / –445.58 / –454.86 / 1.386
14e / 6+4+4 / C1 / –531.69 / –467.43 / –478.43 / 1.389
14f / 5+8+1 / C1 / –485.39 / –429.93 / –435.86 / 1.497
14g / 4+6+4 / C1 / –482.03 / –425.13 / –432.17 / 1.577
14h / 4+5+5 / C1 / –458.59 / –414.32 / –421.70 / 1.586
14i / 4+4+6 / C1 / –498.16 / –448.48 / –460.42 / 1.564
14j / 3+6+5 / C1 / –479.10 / –423.10 / –431.19 / 1.670
14k / 2+4+8 / C1 / –431.13 / –387.00 / –394.86 / 1.764
15a / 6+9 / C1 / –504.21 / –443.80 / –452.80 / 1.394
15b / 6+8+1 / C1 / –516.49 / –454.59 / –463.90 / 1.394
15c / 6+8+1 / C1 / –465.51 / –413.30 / –421.12 / 1.395
15d / 6+7+2 / C1 / –517.69 / –454.83 / –465.07 / 1.384
15e / 5+10 / C1 / –459.07 / –404.98 / –412.63 / 1.491
15f / 5+9+1 / C1 / –504.07 / –443.75 / –451.72 / 1.495
15g / 5+8+2 / C1 / –501.73 / –442.33 / –450.08 / 1.491
15h / 5+7+3 / C1 / –475.10 / –420.70 / –427.22 / 1.498
15i / 4+8+3 / C1 / –463.74 / –409.94 / –414.09 / 1.575
15j / 4+6+5 / C1 / –486.02 / –427.86 / –435.55 / 1.577
15k / 2+4+9 / C1 / –432.9 / –388.87 / –396.42 / 1.764
16a / 6+10 / C1 / –508.92 / –449.51 / –457.56 / 1.397
16b / 6+8+2 / C1 / –527.63 / –463.88 / –473.98 / 1.393
16c / 6+8+2 / C1 / –469.53 / –417.40 / –425.34 / 1.395
16d / 5+6+5 / C1 / –504.48 / –444.59 / –453.73 / 1.477
16e / 4+8+4 / C1 / –471.41 / –416.23 / –420.78 / 1.572
16f / 4+8+4 / C1 / –458.17 / –402.75 / –407.57 / 1.576
16g / 2+4+10 / C1 / –475.58 / –427.58 / –441.34 / 1.741
17a / 6+11 / C1 / –527.01 / –464.12 / –472.88 / 1.396
17b / 5+9+3 / C1 / –481.52 / –425.80 / –432.52 / 1.495
17c / 4+9+4 / C1 / –455.16 / –404.86 / –408.73 / 1.570
17d / 4+8+5 / C1 / –456.87 / –401.87 / –407.11 / 1.573
17e / 3+5+9 / C1 / –420.49 / –376.79 / –379.61 / 1.685
17f / 2+4+11 / C1 / –442.15 / –410.37 / –407.51 / 1.755
18a / 6+12 / C1 / –545.82 / –480.20 / –489.65 / 1.396
18b / 5+9+4 / C1 / –483.41 / –427.85 / –434.31 / 1.497
18c / 4+9+5 / C1 / –467.54 / –415.79 / –419.99 / 1.568
18d / 3+6+9 / C1 / –448.38 / –408.29 / –412.77 / 1.671
18e / 2+5+11 / C1 / –461.21 / –462.38 / –431.51 / 1.742
Table S5: The interaction energy (IE in kcal/mol) of Mg2+(H2O)19–20complexes optimized at B3LYP/6–31G(d,p) level of theory.
Structure / m+n+o / PG / OPT / SP / QB3LYP/6–31G(d,p) / B3LYP/6–311++G(2d,2p) / MP2/cc–pVTZ
IE / IE / IE
19a / 6+12+1 / C1 / –556.39 / –489.04 / –499.18 / 1.394
19b / 5+9+5 / C1 / –501.27 / –442.60 / –449.81 / 1.497
19c / 4+8+7 / C1 / –493.87 / –436.71 / –441.91 / 1.567
19d / 4+8+7 / C1 / –480.57 / –422.67 / –427.96 / 1.558
19e / 3+6+10 / C1 / –498.00 / –463.74 / –462.98 / 1.657
19f / 2+5+12 / C1 / –470.18 / –432.60 / –444.56 / 1.740
20a / 6+12+2 / C1 / –566.29 / –498.8 / –508.34 / 1.393
20b / 5+9+6 / C1 / –512.10 / –451.89 / –459.60 / 1.495
20c / 4+9+7 / C1 / –464.94 / –415.05 / –420.68 / 1.576
20d / 4+8+8 / C1 / –502.48 / –444.23 / –449.99 / 1.566
20e / 4+8+8 / C1 / –484.30 / –425.06 / –431.08 / 1.558
20f / 3+6+11 / C1 / –510.90 / –464.42 / –475.57 / 1.656
20g / 2+6+12 / C1 / –444.31 / –408.00 / –414.29 / 1.745
Table S6: Summed up NPA charge at B3LYP/6-311++G(2d,2p) and Mulliken charges at B3LYP/6-31G(d,p) level in a. u. on all waters in first, second and third solvation shell of representative Mg2+(H2O)ncomplexes.
m+n+o / Total NPA chargetransferred from
Mg2+ / Summed up NPA charge on
all waters / Total Mulliken charge
transferred from
Mg2+ / Summed up Mulliken charge on all waters
1st Shell / 2nd Shell / 3rd Shell / 1st Shell / 2nd Shell / 3rd Shell
1+0 / 0.043 / 0.043 / - / - / 0.272 / 0.272 / - / -
1+1 / 0.085 / -0.216 / 0.301 / - / 0.423 / 0.086 / 0.337 / -
2+0 / 0.131 / 0.131 / - / - / 0.487 / 0.487 / - / -
2+2 / 0.175 / -0.144 / 0.319 / - / 0.624 / 0.259 / 0.364 / -
3+0 / 0.245 / 0.245 / - / - / 0.683 / 0.683 / - / -
3+3 / 0.292 / 0.206 / 0.086 / - / 0.804 / 0.388 / 0.416 / -
3+6 / 0.312 / -0.056 / 0.368 / - / 0.880 / 0.284 / 0.596 / -
4+0 / 0.368 / 0.368 / - / - / 0.825 / 0.825 / - / -
4+4 / 0.388 / 0.186 / 0.202 / - / 0.912 / 0.400 / 0.512 / -
5+0 / 0.462 / 0.462 / - / - / 0.896 / 0.896 / - / -
6+0+0 / 0.581 / 0.581 / - / - / 0.963 / 0.963 / - / -
6+6+0 / 0.625 / 0.376 / 0.249 / - / 1.253 / 0.567 / 0.686 / -
6+12+0 / 0.604 / 0.285 / 0.320 / - / 1.086 / 0.276 / 0.810 / -
1