Hydrothermal syntheses and structural chemistry of Mn(II), Co(II) and Ni(II) coordination polymers with xylyl-diphosphonate ligands

Inorganica Chimica Acta 402 (2013) 46–59

Contents lists available at SciVerse ScienceDirect

Inorganica Chimica Acta journal homepage: www.elsevier.com/locate/ica

Hydrothermal syntheses and structural chemistry of Mn(II), Co(II) and Ni(II) coordination polymers with xylyl-diphosphonate ligands Tiffany M. Smith a, Diona Symester a, Kathryn Perrin a, Jose Vargas b, Michael Tichenor a, Charles J. O’Connor b, Jon Zubieta a,⇑ a b

Department of Chemistry, Syracuse University, Syracuse, NY 13244, United States Advances Materials Research Institute, College of Sciences, University of New Orleans, New Orleans, LA 70148, United States

a r t i c l e

i n f o

Article history: Received 9 January 2013 Accepted 3 March 2013 Available online 20 March 2013 Keywords: Coordination polymers of Mn(II) Co(II) and Ni(II) Metal-xylyldiphosphonate compounds Hydrogen-bonded coordination polymers Magnetic properties of Mn(II) Co(II) and Ni(II) coordination polymers

a b s t r a c t The hydrothermal reactions of the appropriate metal salt, a xylyldiphosphonic acid and a secondary organonitrogen chelating ligand yielded a series of coordination polymers of the M(II)/xylyldiphosphonate/ (organoimine chelate family) with M(II) represented by Mn(II), Co(II) and Ni(II); the 1,2-, 1,3- and 1,4-isomers of xylyldiphosphonate; and the organoimine chelate present as 2,20 -bipyridine (bpy), o-phenanthroline (o-phen) or tetra-2-pyridinylpyrazine (tpyprz). Several representative structural types were observed related to the constraints imposed by the xylyldiphosphonate ligand: the two-dimensional materials [Mn(bpy)(1,2-HO3PC8H8PO3H)] (1), [Mn(o-phen)(1,2-HO3PC8H8PO3H)] (4) and [Co(ophen)(1,2-HO3PC8H8PO3H)] (7) constructed from {M2(N^N)2(HO3PR)2} clusters linked through the xylyl backbone of the ligands; the network structures of the series [M(bpy)(1,3-HO3PC8H8PO3H)] (M@Mn (2), Co (6), Ni (12) and [M(o-phen)(1,3-HO3PC8H8PO3H)] (M@Mn (5) and Co (8)) which consists of {M2(N^N)2(HO3PR)2}n chains linked through the xylyl tethers; and the virtual two-dimensional series [M(N^N)2(1,4-H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (M@Mn, N^N@bpy (3); M@Co, N^N@o-phen (10); and M@Ni, N^N@o-phen (14)) which contain one-dimensional {M(N^N)2(1,4-H2O3PC8H8PO3H2)}n2n+ chains hydrogen-bonded to (HO3PC8H8PO3H)2 anions to provide expansion in two dimensions. The unique example of a three-dimensional material is [Co(o-phen)(1,4-HO3PC8H8PO3H)] (9). The tpyprz containing compounds [M(tpyprz)(1,2-HO3PC8H8PO3H)] (M@Co (11), Ni (15)) and [Ni2(tpyprz)(1,4-HO3PC8H8PO3H)]4H2O (16) are one-dimensional. Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction Organic–inorganic hybrid materials, including the more specific classes of coordination polymers and metal organic frameworks, have witnessed considerable contemporary development for the rational design of functional materials for technological applications [1]. The synthetic strategy is based on the design of complex structures [2–7] constructed from molecular scale composites of inorganic and organic components. In this approach, the inorganic component is a source of magnetic or optical properties, mechanical hardness, thermal stability and potentially reactive sites, while the organic subunits may provide processability, structural diversification and a range of polarizabilities and luminescence properties [8]. Furthermore, metal sites offer variable coordination polyhedra, as well as differences in covalent radii, ligand preferences and crystal field energies, factors which introduce considerable synthetic and structural versatility. By combining the distinct characteristics

⇑ Corresponding author. Tel.: +1 315 443 2547; fax: +1 315 443 4070. E-mail address: [email protected] (J. Zubieta). 0020-1693/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.ica.2013.03.003

of the organic and inorganic components, the composite materials provide access to a vast domain of complex, multifunctional structures [9] with applications ranging from heavy construction to molecular electronics [10]. Organic–inorganic materials of this type include metal–organic frameworks (MOFs) constructed from metal or metal cluster nodes linked through polyfunctional carboxylate, polypyridyl or polyazaheterocyclic ligands. Such materials have been extensively studied by Yaghi and co-workers [11–18], Féréy and co-workers [19–23], Kitagawa and co-workers [24–29] and Long and co-workers [30– 34] among others [35–64]. However, metal-organophosphonates represent the prototypical organic–inorganic hybrid materials, whose earliest representatives are the layered materials first reported in the 1970s by Alberti and Clearfield [65,66]. Since that time, there has been a remarkable growth in the field [67–79]. Phosphonates are ligands that typically form layered and ‘‘pillared layer’’ materials. ‘‘Pillared layer’’ materials constructed from organodiphosphonate ligands are three-dimensional frameworks with alternating organic and inorganic domains (Scheme 1), whose interlamellar separations may be varied by modification of the tether lengths and whose

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59

V–P–O

V–P–O

= Organic Tether

47

(99%), tetra-2-pyridinylpyrazine (97%), and hydrofluoric acid (48 wt.% in H2O) were all purchased from Sigma–Aldrich. All syntheses were carried out in 23-mL poly(tetrafluoroethylene)-lined stainless steel containers under autogeneous pressure. The pH of the solutions were measured prior to and after heating using pHydrion vivid 1–11Ò pH paper. Water was distilled above 3.0 MO in-house using a Barnstead Model 525 Biopure Distilled Water Center. 2.2. Synthesis of [Mn(bpy)(1,2-HO3PC8H8PO3H)] (1)

V–P–O Scheme 1. A typical example of the pillared layer motif in the vanadyl diphosphonate system.

interlamellar structure may be sculpted by appropriate functionalization of the organic tethers [80,81]. While a,x-alkyldiphosphonates have been extensively studied, the coordination chemistry of the corresponding xylyldiphosphonates, that is, 1,2-, 1,3- and 1–4-(H2O3PCH2)2C6H4 (Scheme 2), remains relatively unexplored [82–88]. In the course of our systematic investigations of metal-organodiphosphonate chemistry [89–110], we have also noted that the introduction of ancillary ligands such as bipyridine (bpy), o-phenanthroline (o-phen) or tetra-2-pyridinylpyrazine (tpyprz) can have dramatic structural consequences, most commonly resulting in lower dimensionality rather than the prototypical three-dimensional ‘‘pillared layer’’ motif. In this contribution, we present the syntheses and structures of a series of Mn(II), Co(II) and Ni(II) complexes of xylyldiphosphonate ligands with ancillary bipyridyl, o-phenanthroline and tetrapyridylpyrazine ligands: [Mn(bpy)(1,2-HO3PC8H8PO3H)] (1), [Mn(bpy)(1,3-HO3PC8H8PO3H)] (2), [Mn(bpy)2(1,4-HO3PC8H8PO3H)(H2O3PC8H8PO3H2)] (3), [Mn(o-phen)(1,2-HO3PC8H8PO3H)] (4), [Mn(o-phen)(1,3-HO3PC8H8PO3H)] (5), [Co(bpy)(1,3-HO3PC8H8PO3H)] (6), [Co(o-phen)(1,2-HO3PC8H8PO3H)] (7), [Co(ophen)(1,3-HOPC8H8PO3H)] (8), [Co(o-phen)(1,4-HO3PC8H8PO3H)] (9), [Co(o-phen)2(1,4-HO3PC8H8PO3H)(1,4-H2O3PC8H8PO3H2)] (10), [Co(tpyprz)(1,2-HO3PC8H8PO3H)] (11), [Ni(bpy)(1,3-HO3PC8H8PO3H)] (12), [Ni(o-phen)(1,3-HO3PC8H8PO3H)] (13), [Ni(ophen)2(1,4-HO3PC8H8PO3H2)(1,4-H2O3PC8H8PO3H2)] (14), [Ni(tpyprz)(1,2-HO3PC8H8PO3H)] (15) and [Ni2(tpyprz)(1,4-HO3PC8H8PO3H)2]4H2O (164H2O).

2. Experimental 2.1. General procedures All chemicals were used as obtained without further purification with the exception of para-xylenediphosphonic acid, orthoxylenediphosphonic acid and meta-xylenediphosphonic acid which were synthesized in a similar fashion to the literature method [111] using the respective dibromide starting materials. Nickel(II) acetate tetrahydrate (99.9%) and cobalt(II) acetate tetrahydrate (99.9%) were purchased from VWR. Manganese(II) acetate tetrahydrate (99.99%), 2,20 -bipyridine (99%), 1,10 phenanthroline (o-phen)

Scheme 2. The xylyldiphosphonic acids of this study.

A solution of manganese(II) acetate tetrahydrate (0.103 g, 0.420 mmol), 2,20 bipyridine (0.040 g, 0.256 mmol), o-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.61:0.714:1323 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 6 and 4, respectively. Yellow rods suitable for X-ray diffraction were isolated in 70% yield. IR (KBr pellet, cm1): 3405(w), 3058(w), 2927(w), 1595(m), 1573(w), 1490(w), 1438(m), 1241(m), 1111(m), 1081(m), 1064(m), 1036(s), 997(w), 978(w), 917(s), 553(w), 528(w). Anal. Calc. for C18H18MnN2O6P2: C, 45.5; H, 3.79; N, 5.89. Found: C, 45.4; H, 3.88; N, 5.76%. 2.3. Synthesis of [Mn(bpy)(1,3-HO3PC8H8PO3H)] (2) A solution of manganese(II) acetate tetrahydrate (0.103 g, 0.420 mmol), 2,20 bipyridine (0.040 g, 0.256 mmol), m-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.61:0.714:1323 was stirred briefly before heating to 120 °C for 48 h. The initial and final pH values were 5 and 4, respectively. Yellow rods suitable for X-ray diffraction were isolated in 50% yield. IR (KBr pellet, cm1): IR (KBr pellet, cm1): 3006(m), 3005(m), 1596(m), 1475(m), 1438(m), 1247(s), 1172(s), 1058(s), 1043(s), 1013(m), 912(s), 894(m), 805(w), 760(m), 737(m), 701(m), 521(s). Anal. Calc. for C18H18MnN2O6P2: C, 45.5; H, 3.79; N, 5.89. Found: C, 45.1; H, 3.56; N, 5.95%. 2.4. Synthesis of [Mn(bpy)2(1,4-H2O3PC8H8PO3H2)(1,4HO3PC8H8PO3H)] (3) A solution of manganese(II) acetate tetrahydrate (0.103 g, 0.420 mmol), 2,20 bipyridine (0.039 g, 0.250 mmol), p-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.6:0.714:1323 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 4 and 3, respectively. Yellow blocks suitable for X-ray diffraction were isolated in 5% yield. IR (KBr pellet, cm1): 3497(m), 3053(w), 3025(w), 2917(w), 1599(m), 1514(m), 1439(w), 1259(m), 1100(s), 1086(s), 989(s), 854(m), 600(m), 542(m). Anal. Calc. for C36H38MnN4O12P4: C, 48.1; H, 4.23; N, 6.24. Found: C, 48.3; H, 3.98; N, 6.20%. 2.5. Synthesis of [Mn(o-phen)(1,2-HO3PC8H8PO3H)] (4) A solution of manganese(II) acetate tetrahydrate (0.103 g, 0.420 mmol), 1,10 phenanthroline (0.040 g, 0.223 mmol), o-xylene-diphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.53:0.714:1323 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 6 and 5, respectively. Yellow rods suitable for X-ray diffraction were isolated in 60% yield. IR (KBr pellet, cm1): 3056(w), 2933(w), 2343(w), 1625(w), 1577(m), 1518(m), 1492(m), 1421(s), 1234(s), 1212(s), 1165(s), 1136(s), 1103(s), 1079(m), 1038(s), 941(m), 888(m), 791(m), 730(m), 542(s). Anal. Calc. for C20H18MnN2O6P2: C, 48.0; H, 3.61; N, 5.61. Found: C, 48.3; H, 3.49; N, 5.33%.

48

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59

2.6. Synthesis of [Mn(o-phen)(1,3-HO3PC8H8PO3H)] (5) A solution of manganese(II) acetate tetrahydrate (0.103 g, 0.420 mmol), 1,10 phenanthroline (0.040 g, 0.223 mmol), m-xylene-diphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.53:0.714:1323 was stirred briefly before heating to 120 °C for 48 h. The initial and final pH values were 5 and 4, respectively. Yellow rods suitable for X-ray diffraction were isolated in 60% yield. IR (KBr pellet, cm1): 3480(w), 3006(w), 2948(w), 2914(w), 1513(m), 1486(w), 1426(m), 1411(w), 1251(s), 1171(s), 1057(m), 1039(s), 923(m), 908(m), 847(w), 730(m), 698(m), 636(w), 522(s). Anal. Calc. for C20H18MnN2O6P2: C, 48.0; H, 3.61; N, 5.61. Found: C, 47.6; H, 3.55; N, 5.49%. 2.7. Synthesis of [Co(bpy)(1,3-HO3PC8H8PO3H)] (6) A solution of cobalt(II) acetate tetrahydrate (0.074 g, 0.30 mmol), 2,20 bipyridine (0.078 g, 0.50 mmol), m-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:1.7:1:1853 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 2 and 4, respectively. Purple blocks suitable for X-ray diffraction were isolated in 80% yield. (KBr pellet, cm1): 3071(s), 3006(s), 2941(s), 1600(s), 1563(m), 1439(s), 1250(s), 1171(s), 1132(s), 1059(s), 919(s), 893(s), 804(m), 761(s), 737(s), 700(s), 651(s), 626(w), 585(w), 482(s). Anal. Calc. for C18H18CoN2O6P2: C, 45.1; H, 3.76; N, 5.84. Found: C, 45.4; H, 3.22; N, 5.76%. 2.8. Synthesis of [Co(o-phen)(1,2-HO3PC8H8PO3H)] (7) A solution of cobalt(II) acetate tetrahydrate (0.074 g, 0.30 mmol), 1,10 phenanthroline (0.039 g, 0.22 mmol), o-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.73:1:1853 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 6 and 3, respectively. Blue rods suitable for X-ray diffraction were isolated in 90% yield. IR (KBr pellet, cm1): 3055(m), 2984(w), 2933(w), 2266(w), 1685(m), 1626(w), 1603(w), 1579(m), 1450(m), 1421(m), 1303(w), 1212(s), 1163(s), 1134(s), 1040(m), 938(s), 885(s), 790(s), 725(s), 640(m), 541(s). Anal. Calc. for C20H18CoN2O6P2: C, 47.7; H, 3.58; N, 5.56. Found: C, 48.0; H, 3.75; N, 5.41%. 2.9. Synthesis of [Co(o-phen)(1,3-HO3PC8H8PO3H)] (8) A solution of cobalt(II) acetate tetrahydrate (0.074 g, 0.30 mmol), 1,10 phenanthroline (0.078 g, 0.43 mmol), m-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:1.43:1:1853 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 2 and 4, respectively. Purple rods suitable for X-ray diffraction were isolated in 85% yield. IR (KBr pellet, cm1): 3448(s), 3005(w), 2948(s), 1560(w), 1421(m), 1254(m), 1228(m), 1206(m), 1168(s), 1132(w), 1081(w), 1057(s), 925(m), 698(m), 522(s). Anal. Calc. for C20H18CoN2O6P2: C, 47.7; H, 3.58; N, 5.56. Found: C, 47.5; H, 3.48; N, 5.66%. 2.10. Synthesis of [Co(o-phen)(1,4-HO3PC8H8PO3H)] (9) and [Co(ophen)2(1,4-H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (10) A solution of cobalt(II) acetate tetrahydrate (0.074 g, 0.30 mmol), 1,10 phenanthroline (0.0784 g, 0.44 mmol), p-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:1.5:1:1853 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 4 and 4, respectively. Orange and purple rods suitable for X-ray diffraction were isolated in 15% and 10% yield, respectively.

IR (KBr pellet, cm1): (9) 3471(s), 3055(w), 2919(w), 2344(w), 1609(m), 1514(s), 1422(s), 1262(m), 1172(m), 1143(m), 1104(s), 972(s), 853(m), 727(m), 671(w), 550(s0, 502(m); (10) 3422(m), 2766(m), 2344(m), 1624(w), 1577(w), 1514(s), 1423(s), 1259(m), 1102(s), 1050(s), 1027(s), 988(s), 970(s), 849(s), 726(s), 688(w), 564(w), 512(m). Anal. Calc. for C20H18CoN2O6P2 (9): C, 47.7; H, 3.58; N, 5.56. Found: C, 47.3; H, 3.29; N, 5.63%. Anal. Calc. for C40H38CoN4O12P4 (10): C, 50.6; H, 4.00; N, 5.90. Found: C, 51.0; H, 4.51; N, 5.76%. 2.11. Synthesis of [Co(tpypyz)(1,2-HO3PC8H8PO3H)] (11) A solution of cobalt(II) acetate tetrahydrate (0.074 g, 0.30 mmol), tetra-2-pyridinylpyrazine (0.085 g, 0.219 mmol), o-xylene-diphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.73:1:1853 was stirred briefly before heating to 120 °C for 48 h. The initial and final pH values were 4 and 3, respectively. Orange rods suitable for X-ray diffraction were isolated in 90% yield. IR (KBr pellet, cm1): 2880(w), 2344(w), 1570(m), 1587(w), 1399(s), 1307(w), 1274(w), 1250(m), 1180(m), 1161(s), 1136(s), 1076(w), 1057(s), 991(w), 793(m), 753(s), 738(m), 530(m), 505(w), 482(w). Anal. Calc. for C32H26CoN6O6P2: C, 54.0; H, 3.65; N, 11.8. Found: C, 53.5; H, 3.24; N, 11.7%. 2.12. Synthesis of [Ni(bpy)(1,3-HO3PC8H8PO3H)] (12) A solution of nickel(II) acetate tetrahydrate (0.074 g, 0.30 mmol), 2,20 -bipyridine (0.068 g, 0.44 mmol), m-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (5 mL, 278 mmol) with the mole ratio of 1:1.5:1:927 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 4 and 3, respectively. Green blocks suitable for X-ray diffraction were isolated in 10% yield. IR (KBr pellet, cm1): 3073(m), 3005(m), 2948(m), 2916(m), 2362(w), 1601(s), 1474(m), 1440(s), 1289(w), 1268(w), 1251(s), 1227(s), 1132(s), 1117(w), 1061(s), 1022(w), 919(m), 910(m), 803(w), 737(m), 700(m), 522(s). Anal. Calc. for C18H18NiN2O6P2: C, 45.1; H, 3.76; N, 5.85. Found: C, 45.2; H, 3.82; N, 5.68%. 2.13. Synthesis of [Ni(o-phen)(1,3-HO3PC8HPO3H)] (13) A solution of nickel(II) acetate tetrahydrate (0.074 g, 0.30 mmol), 1,10 phenanthroline (0.068 g, 0.38 mmol), m-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (5 mL, 278 mmol) with the mole ratio of 1:1.23:1:927 was stirred briefly before heating to 120 °C for 48 h. The initial and final pH values were 4 and 3, respectively. Green rods suitable for X-ray diffraction were isolated in 10% yield. IR (KBr pellet, cm1): 3004(m), 2947(m), 2914(m), 1625(m), 1513(m), 1468(m), 1421(s), 1255(s), 1226(s), 1139(s), 1059(s), 927(s), 908(s), 843(s), 867(m), 802(w), 729(s), 698(s), 585(w), 524(m). Anal. Calc. for C20H18NiN2O6P2: C, 47.7; H, 3.58; N, 5.57. Found: C, 48.1; H, 3.66; N, 5.72%. 2.14. Synthesis of [Ni(o-phen)2(1,4-H2O3PC8H8PO3H2)(1,4HO3PC8H8PO3H)] (14) A solution of nickel(II) acetate tetrahydrate (0.074 g, 0.30 mmol), 1,10 phenanthroline (0.068 g, 0.38 mmol), p-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (5 mL, 278 mmol) with the mole ratio of 1:1.23:1:927 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 4 and 4, respectively. Blue blocks suitable for X-ray diffraction were isolated in 90% yield. IR (KBr pellet, cm1): 3078(w), 3043(w), 3002(w), 2750(w), 2344(w), 1514(s), 1423(s), 1340(m), 1258(m), 1200(s), 1190(s), 1141(s), 1001(s), 923(s), 849(s), 726(s), 564(s), 512(m). Anal. Calc. for C40H38NiN4O12P4: C, 50.6; H, 4.00; N, 5.90. Found: C, 50.6; H, 4.11; N, 5.62%.

49

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59 Table 1 Summary of crystallographic data for structures 1 through 16.

Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z Dcalc (g cm3) l (mm1) T (K) k R1a wR2b

Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z Dcalc (g cm3) l (mm1) T (K) k R1a wR2b

Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z Dcalc (g cm3) l (mm1) T (K) k R1a wR2b

Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z

[Mn(bpy)(1,2-HO3PC8H8PO3H)] (1)

[Mn(bpy)(1,3-HO3PC8H8PO3H)] (2)

[Mn(bpy)2(1,4-H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (3)

C18H18MnN2O6P2 475.22 monoclinic P2(1)/n 10.4041(15) 14.670(2) 12.4281(19) 90.00 103.314(2) 90.00 1845.9(5) 4 1.710 0.930 90(2) 0.71073 0.0212 0.0611

C18H18MnN2O6P2 475.22 triclinic  P1

C36H38MnN4O12P4 897.52 monoclinic C2/c 18.035(3) 24.643(4) 8.7660(13) 90.00 102.609(2) 90.00 3801.8(10) 4 1.568 0.586 90(2) 0.71073 0.0261 0.0729

7.6596(14) 10.843(2) 11.025(2) 96.309(4) 91.689(4) 94.815(4) 906.2(3) 2 1.742 0.947 90(2) 0.71073 0.0349 0.0839

[Mn(o-phen)(1,2-HO3PC8H8PO3H)] (4)

[Mn(o-phen)(1,3-HO3PC8H8PO3H)] (5)

[Co(bpy)(1,3-HO3PC8H8PO3H)] (6)

C20H18MnN2O6P2 499.24 monoclinic P2(1)/n 10.5123(7) 14.6743(9) 12.6219(8) 90.00 104.6010(10) 90.00 1884.2(2) 4 1.760 0.916 90 0.71073 0.0253 0.0982

C20H18MnN2O6P2 499.24 monoclinic P21/c 10.8871(11) 23.673(3) 7.6062(8) 90 95.014(2) 90 1952.8(4) 4 1.698 0.884 90 0.71073 0.0287 0.0777

C18H18CoN2O6P2 479.21 Triclinic P-1 7.6118(4) 10.8203(6) 10.8610(6) 95.9570(10) 92.4070(10) 94.2100(10) 886.19(8) 2 1.796 1.192 90 0.71073 0.0199 0.0533

[Co(o-phen)(1,2-HO3PC8H8PO3H)] (7)

[Co(o-phen)(1,3-HO3PC8H8PO3H)] (8)

[Co(o-phen)(1,4-HO3PC8H8PO3H)] (9)

C20H18CoN2O6P2 503.23 monoclinic P2(1)/n 10.3139(8) 14.5501(11) 12.6700(9) 90 104.161(2) 90 1843.6(2) 4 1.813 1.151 90 0.71073 0.0270 0.0708

C20H18CoN2O6P2 503.23 monoclinic P2(1)/c 10.8283(8) 23.3785(18) 7.5532(6) 90 94.518(2) 90 1906.1(3) 4 1.754 1.113 90 0.71073 0.0400 0.1087

C20H18CoN2O6P2 503.23 monoclinic C2/c 21.099(2) 12.0022(12) 7.5739(8) 90 98.0770(10) 90 1899.0(3) 4 1.760 1.118 90 0.71073 0.0250 0.0681

[Co(o-phen)2(1,4-H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (10)

[Co(tpypyz)(1,2-HO3PC8H8PO3H)] (11)

[Ni(bpy)(1,3-HO3PC8H8PO3H)] (12)

C40H38CoN4O12P4 949.55 monoclinic C2/c 18.2825(11) 25.5632(16) 8.5534(5) 90 96.5220(10) 90 3971.6(4) 4

C32H26CoN6O6P2 711.46 triclinic  P1

C18H18N2NiO6P2 478.99 triclinic  P1

10.1252(9) 10.7137(10) 15.4619(14) 72.6270(10) 72.5630(10) 76.6930(10) 1508.9(2) 2

7.6024(8) 10.8033(11) 10.8232(11) 95.760(2) 94.041(2) 92.794(2) 880.84(16) 2 (continued on next page)

50

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59

Table 1 (continued)

Dcalc (g cm3) l (mm1) T (K) k R1a wR2b

[Co(o-phen)2(1,4-H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (10)

[Co(tpypyz)(1,2-HO3PC8H8PO3H)] (11)

[Ni(bpy)(1,3-HO3PC8H8PO3H)] (12)

1.588 0.665 90 0.71073 0.0288 0.0775

1.566 0.733 90 0.71073 0.0354 0.1031

1.806 1.327 90 0.71073 0.0199 0.0552

Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z Dcalc (g cm3) l (mm1) T (K) k R1a wR2b

Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z Dcalc (g cm3) l (mm1) T (K) k R1a wR2b a b

[Ni(o-phen)(1,3HO3PC8HPO3H)] (13)

[Ni(o-phen)2(1,4-H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (14)

C20H18N2NiO6P2 503.01 triclinic  P1 7.5380(18) 10.783(3) 11.934(3) 82.441(6) 88.115(6) 85.638(6) 958.6(4) 2 1.743 1.224 90 0.71073 0.0435 0.1242

C40H38N4NiO12P4 949.33 monoclinic C2/c 18.2692(16) 25.477(2) 8.5637(8) 90 96.733(2) 90 3958.5(6) 4 1.593 0.724 90 0.71073 0.0263 0.0765

[Ni(tpypyz)(1,2-HO3PC8H8PO3H)] (15)

[Ni2(tpyprz)(1,4-HO3PC8H8PO3H)2]4H2O (164H2O)

C32H26N6NiO6P2 711.24 triclinic  P1 10.0453(9) 10.7094(10) 15.4596(14) 72.1320(10) 72.7960(10) 76.9610(10) 1495.4(2) 2 1.580 0.814 90 0.71073 0.0299 0.0758

C20H22N3NiO8P2 553.06 triclinic  P1 10.8732(5) 11.0085(5) 11.2619(5) 63.681(2) 66.155(2) 72.920(2) 1094.32(9) 2 1.678 1.088 90 0.71073 0.0305 0.0896

R1 = R|Fo|  |Fc|/R|Fo|. wR2 = {R[w(Fo2  Fc2)2]/R[w(Fo2)2]}1/2.

2.15. Synthesis of [Ni(tpypyz)(1,2-HO3PC8H8PO3H)] (15) A solution of nickel(II) acetate tetrahydrate (0.074 g, 0.30 mmol), tetra-2-pyridinylpyrazine (0.085 g, 0.22 mmol), o-xylene-diphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.73:1:1853 was stirred briefly before heating to 120 °C for 48 h. The initial and final pH values were 3 and 3, respectively. Green blocks suitable for X-ray diffraction were isolated in 90% yield. IR (KBr pellet, cm1): 3064(m), 2879(m), 2342(m), 1587(m), 1570(w), 1401(m), 1137(s), 1090(s), 1058(s), 923(s), 865(s), 805(s), 769(w), 754(w), 738(m), 655(w), 598(w), 482(w), 467(w). Anal. Calc. for C32H26NiN6O6P2: C, 54.0; H, 3.66; N, 11.8. Found: C, 54.2; H, 3.83; N, 11.5%. 2.16. Synthesis of [Ni2(tpyprz)(1,4-HO3PC8H8PO3H)2]4H2O (164H2O) A solution of nickel(II) acetate 0.30 mmol), tetra-2-pyridinylpyrazine

tetrahydrate (0.074 g, (0.085 g, 0.22 mmol),

p-xylenediphosphonic acid (0.080 g, 0.30 mmol), and H2O (10 mL, 556 mmol) with the mole ratio of 1:0.73:1:1853 was stirred briefly before heating to 120 °C for 72 h. The initial and final pH values were 3 and 3, respectively. Green blocks suitable for X-ray diffraction were isolated in 90% yield. IR (KBr pellet, cm1): 3434(s), 3100(s), 2912(s), 2343(s), 1647(m), 1610(s), 1513(m), 1497(s), 1127(s), 1080(s), 1048(s), 1014(w), 907(s), 864(w), 779(s), 752(m), 580(m), 540(m), 523(s), 482(m), 441(w). Anal. Calc. for C20H22NiN3O8P4: C, 43.4; H, 3.98; N, 7.59. Found: C, 43.0; H, 4.31; N, 7.33%. 2.17. X-ray crystallography Structural measurements were performed on a Bruker KAPPA APEX DUO diffractometer containing a APEX II CCD system at low temperature (90 K) using graphite-monochromated Mo Ka radiation (Mo Ka = 0.71073Å) [112]. The data were corrected for Lorentz and polarization effects and absorption using SADABS

51

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59 Table 2 Selected bond lengths (Å) and angles (°) for the compounds of this study. [Mn(bpy)(1,2-HO3PC8H8PO3H)] (1) Mn1 O2 Mn1 O6 Mn1 O1 Mn1 N2 Mn1 N1 P1 O3 P1 O2 P1 O4(H) P2 O6 P2 O1 P2 O5(H)

2.0412(8) 2.0625(8) 2.1207(8) 2.2565(9) 2.2662(9) 1.5030(8) 1.5116(8) 1.5889(9) 1.5056(8) 1.5284(8) 1.5711(8)

O2 O2 O2 O6 O2 O1

Mn1 Mn1 Mn1 Mn1 Mn1 Mn1

O6 O1 N2 N2 N1 N1

101.08(3) 103.45(3) 108.76(3) 147.31(3) 106.93(3) 148.13(3)

[Mn(bpy)(1,3-HO3PC8H8PO3H)] (2) Mn1 O4 Mn1 O1 Mn1 O3 Mn1 O2 Mn1 N1 Mn1 N2 P1 O4 P1 O2 P1 O5(H) P2 O3 P2 O1 P2 O6(H)

2.0973(12) 2.1474(11) 2.1566(12) 2.2108(12) 2.2848(14) 2.2947(14) 1.4950(12) 1.5071(12) 1.5842(12) 1.4952(12) 1.5190(12) 1.5755(12)

O4 O3 O4 O1

Mn1 Mn1 Mn1 Mn1

O1 O2 N1 N2

106.45(5) 171.93(4) 162.62(5) 161.49(5)

O1 O1 O1 O1 N1

Mn1 Mn1 Mn1 Mn1 Mn1

N2 N2 N1 N1 N1

159.33(4) 159.33(4) 103.33(4) 103.33(4) 163.00(6)

[Mn(bpy)2(1,4-H2O3PC8H8PO3H2) (HO3PC8H8PO3H)] (3) Mn1 O1 2.0916(10) Mn1 O1 2.0916(10) Mn1 N2 2.2688(12) Mn1 N2 2.2688(12) Mn1 N1 2.2768(11) Mn1 N1 2.2768(11) P1 O5 1.5107(10) P1 O6 1.5240(10) P1 O4(H) 1.5635(10) P2 O1 1.4871(10) P2 O3 1.5499(10) P2 O2(H) 1.5623(10) [Mn(o-phen)(1,2-HO3PC8H8PO3H)] (4) Mn1 O2 Mn1 O1 Mn1 O3 Mn1 N2 Mn1 N1 P1 O1 P1 O3 P1 O6(H) P2 O4 P2 O2 P2 O5(H)

2.0372(13) 2.0591(14) 2.1126(14) 2.2603(16) 2.2698(16) 1.5013(15) 1.5264(14) 1.5704(15) 1.5005(14) 1.5082(14) 1.5881(15)

O2 O2 O2 O1 O2 O3

Mn1 Mn1 Mn1 Mn1 Mn1 Mn1

O1 O3 N2 N2 N1 N1

101.25(6) 103.25(5) 108.30(6) 147.51(6) 107.67(6) 147.74(5)

[Mn(o-phen)(1,3-HO3PC8H8PO3H)] (5) Mn1 O4 Mn1 O3 Mn1 O1 Mn1 O2 Mn1 N1 Mn1 N2 P1 O3 P1 O1 P1 O5(H) P2 O4 P2 O2 P2 O6(H)

2.1077(14) 2.1422(14) 2.1630(14) 2.2102(14) 2.2977(17) 2.3232(17) 1.4997(14) 1.5270(14) 1.5747(15) 1.4966(14) 1.5123(14) 1.5805(14)

O4 O3 O4 O1 O2

Mn1 Mn1 Mn1 Mn1 Mn1

O1 O2 N1 N2 N2

106.92(5) 173.32(5) 162.23(6) 162.58(6)

[Co(bpy)(1,3-HO3PC8H8PO3H)] (6) Co1 O2 Co1 O5 Co1 O1 Co1 N1 Co1 N2 Co1 O3 P1 O2 P1 O3 P1 O4(H)

2.0419(9) 2.0879(9) 2.1095(9) 2.1464(11) 2.1540(12) 2.1602(9) 1.4986(10) 1.5083(10) 1.5867(10)

O2 O2 O1 O5

Co1 Co1 Co1 Co1

O1 N1 N2 O3

102.73(4) 166.53(4) 165.52(4) 173.48(4)

(continued on next page)

52

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59 P2 O5 P2 O1 P2 O6(H)

1.5022(10) 1.5194(10) 1.5782(10)

[Co(o-phen)(1,2-HO3PC8H8PO3H)] (7) Co1 O3 Co1 O2 Co1 O1 Co1 N1 Co1 N2 P1 O3 P1 O1 P1 O4(H) P2 O5 P2 O2 P2 O6(H)

1.9921(12) 1.9983(13) 2.0597(12) 2.1323(14) 2.1412(15) 1.5041(13) 1.5216(13) 1.5678(13) 1.5038(13) 1.5090(13) 1.5870(13)

O3 O2 O3 O2 O2 O1

Co1 Co1 Co1 Co1 Co1 Co1

O2 O1 N1 N1 N2 N2

102.31(5) 103.85(5) 152.56(6) 103.03(5) 101.39(5) 153.76(5)

[Co(o-phen)(1,3-HO3PC8H8PO3H)] (8) Co1 O2 Co1 O3 Co1 O1 Co1 O6 Co1 N2 Co1 N1 P1 O3 P1 O1 P1 O4(H) P2 O2 P2 O6 P2 O5(H)

2.046(2) 2.071(2) 2.128(2) 2.152(2) 2.157(3) 2.181(3) 1.502(2) 1.522(2) 1.575(2) 1.499(2) 1.510(2) 1.588(2)

O2 O3 O2 O1

Co1 Co1 Co1 Co1

O1 O6 N2 N1

103.57(8) 174.35(8) 165.91(10) 166.20(9)

[Co(o-phen)(1,4-HO3PC8H8PO3H)] (9) Co1 O3 Co1 O3 Co1 O1 Co1 O1 Co1 N1 Co1 N1 P1 O1 P1 O3 P1 O2(H)

2.0994(12) 2.0994(12) 2.1046(12) 2.1046(12) 2.1559(15) 2.1559(15) 1.4992(12) 1.5172(13) 1.5717(12)

O1 Co1 O1 O3 Co1 N1 O3 Co1 N1

177.38(7) 165.28(5) 165.28(5)

N1 Co1 N1 O1 Co1 N2 O1 Co1 N2

169.04(6) 165.09(4) 165.09(4)

[Co(o-phen)2(1,4-H2O3PC8H8PO3H2) (1,4-HO3PC8H8PO3H)] (10) Co1 O1 2.0521(10) Co1 O1 2.0521(10) Co1 N1 2.1320(11) Co1 N1 2.1320(11) Co1 N2 2.1643(12) Co1 N2 2.1643(12) P1 O1 1.4885(10) P1 O3(H) 1.5565(10) P1 O2(H) 1.5582(10) P2 O4 1.5111(10) P2 O5 1.5309(9) P2 O6(H) 1.5739(10) [Co(tpypyz)(1,2-HO3PC8H8PO3H)] (11) Co1 O1 Co1 O3 Co1 N2 Co1 O2 Co1 N3 Co1 N1 P1 O3 P1 O1 P1 O4(H) P2 O2 P2 O6 P2 O5(H)

1.997(2) 2.0708(19) 2.092(2) 2.1191(19) 2.147(2) 2.153(2) 1.5010(19) 1.511(2) 1.575(2) 1.5008(19) 1.517(2) 1.575(2)

O1 O3 O1 N3

Co1 Co1 Co1 Co1

N2 O2 N3 N1

174.71(8) 170.96(8) 108.62(9) 151.76(9)

[Ni(bpy)(1,3-HO3PC8H8PO3H)] (12) Ni1 O2 Ni1 O1 Ni1 O3 Ni1 N1 Ni1 N2 Ni1 O4 P1 O2 P1 O4 P1 O5(H) P2 O3

2.0234(11) 2.0777(11) 2.0750(11) 2.0978(14) 2.1058(14) 2.1411(11) 1.4998(12) 1.5110(11) 1.5918(12) 1.5057(12)

O2 O2 O1 O3

Ni1 Ni1 Ni1 Ni1

O1 N1 N2 O4

101.96(4) 167.81(5) 166.62(5) 174.13(4)

53

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59 P2 O1 P2 O6(H)

1.5214(11) 1.5811(11)

[Ni(o-phen)(1,3HO3PC8HPO3H)] (13) Ni1 O1 Ni1 O2 Ni1 O4 Ni1 N1 Ni1 N2 Ni1 O3 P1 O2 P1 O4 P1 O5(H) P2 O1 P2 O3 P2 O6(H)

2.028(3) 2.056(3) 2.087(3) 2.107(4) 2.111(4) 2.128(3) 1.504(3) 1.524(3) 1.574(3) 1.502(3) 1.513(3) 1.585(3)

[Ni(o-phen)2(1,4-H2O3PC8H8PO3H2) (1,4-HO3PC8H8PO3H)] (14) Ni1 O1 2.0460(9) Ni1 O1 2.0460(9) Ni1 N2 2.0791(10) Ni1 N2 2.0791(10) Ni1 N1 2.1122(10) Ni1 N1 2.1122(10) P1 O1 1.4868(9) P1 O2(H) 1.5571(9) P1 O3(H) 1.5610(9) P2 O4 1.5106(9) P2 O6 1.5306(8) P2 O5(H) 1.5754(9) [Ni(tpypyz)(1,2-HO3PC8H8PO3H)] (15) Ni1 O2 Ni1 N2 Ni1 O1 Ni1 O3 Ni1 N3 Ni1 N1 P1 O3 P1 O4 P1 O5(H) P2 O1 P2 O2 P2 O6(H)

1.9920(15) 2.0142(18) 2.0534(14) 2.0891(14) 2.0894(18) 2.0983(18) 1.5003(15) 1.5181(15) 1.5769(15) 1.4975(15) 1.5080(15) 1.5813(15)

[Ni2(tpyprz)(1,4-HO3PC8H8PO3H)2]4H2O Ni1 O2 Ni1 O3 Ni1 N2 Ni1 O1 Ni1 N3 Ni1 N1 P1 O1 P1 O5 P1 O4(H) P2 O3 P2 O2 P2 O6(H)

(164H2O) 1.9807(18) 2.0157(19) 2.044(2) 2.0819(18) 2.096(2) 2.113(2) 1.4991(19) 1.5288(19) 1.5737(19) 1.4917(19) 1.5042(19) 1.5858(19)

[113,114]. The structures were solved by direct methods. All nonhydrogen atoms were refined anisotropically. After all of the nonhydrogen atoms had been located, the model was refined against F2, initially using isotropic and later anisotropic thermal displacement parameters. Hydrogen atoms were introduced in calculated positions and refined isotropically. Neutral atom scattering coefficients and anomalous dispersion corrections were taken from the International Tables, Vol. C. All calculations were performed using SHELXTL crystallographic software packages [115]. Crystallographic details have been summarized in Table 1. Selected bond lengths and angles are given in Table 2. Full tables of crystal parameters and experimental conditions, atomic positional parameters and isotropic temperature factors, bond lengths and angles, anisotropic temperature factors, hydrogen atom coordinates, and torsion angles for 1–16 are available as Supplementary

O1 O4 O1 O2

Ni1 Ni1 Ni1 Ni1

O4 N1 N2 O3

103.30(13) 167.21(14) 167.29(14) 174.40(12)

N2 Ni1 N2 O1 Ni1 N1 O1 Ni1 N1

170.72(5) 167.17(4) 167.17(4)

O2 Ni1 N2 O1 Ni1 O3 O2 Ni1 N3 N3 Ni1 N1

174.66(7) 172.34(6) 106.87(7) 155.97(7)

O2 Ni1 N2 O3 Ni1 O1 O2 Ni1 N3 N3 Ni1 N1

171.88(8) 174.63(7) 107.90(8) 154.24(8)

materials (Tables S1–S96). ORTEP plots of the metal coordination spheres and ligand atoms are also available (Figs. S1–S16). 2.18. Thermogravimetric analyses TGA data were collected on a TA instruments Q500 v6.7 Thermogravimetric Analyzer. Data was collected on samples that ranged between 4 and 10 mg, ramping the temperature at 10 °C/min (with the exception of compound 6 which was ramped at 5 °C/ min) between 25 and 800 °C. 2.19. Magnetic susceptibility studies The temperature dependent magnetic data were recorded at magnetic field of H = 1000 Oe in the temperature range of T = 2–

54

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59

300 K, in field cooling mode (FC) on samples weighing 20–50 mg, using a Quantum Design MPMS-XL-7 SQUID magnetometer.

3. Results and discussion 3.1. Syntheses and infrared spectroscopy Hydrothermal syntheses, conventionally carried out in water at 120–250 °C at autogenous pressure, have been extended to the routine synthesis of metal oxides and organic–inorganic composite materials [116–119]. Product composition depends on a number of critical conditions, including pH of the medium, temperature and hence pressure, the presence of structure-directing cations, and the use of mineralizers. Since a variety of cationic and anionic components may be present in solution, those of appropriate size, geometry and charge to fulfill crystal packing requirements may be selected from the mixture in the crystallization process. The technique thus exploits ‘‘self-assembly’’ of a solid phase from soluble precursors at moderate temperatures. Hydrothermal methods have been exploited for decades in the preparation of metal-diphosphonate materials with pillared layer structures, such as that of the recently described [Cu2(H2O)2(1,4O3PC8H8PO3)] [120]. The introduction of auxiliary ligands, such as o-phenanthroline or 2,20 -bipyridyl, provides a method for reducing the overall dimensionality of the phase by blocking coordination sites at the metal and preventing structural expansion in one or more dimensions. The layers associated with compounds 1, 2–8, 12 and 13 and the two-dimensional hydrogen-bonded assemblies of 3, 10 and 14 are characteristic examples of the use of simple auxiliary chelates in the design of lower dimensional materials. It is noteworthy that only in the case of compound 9 is a threedimensional structure encountered. Curiously, our naïve design principles did not extend to the chemistry of the M(II)/tpyprz/xylyldiphosphonate system. Our expectation was that the dipodal tpyprz would bridge metal sites of metal-diphosphonate chains or networks to provide two- or three-dimensional materials, or would decorate the surfaces of chains or networks. Rather unexpectedly, compounds 11 and 15 exhibited one-dimensional structures with one terminus of the tpyprz ligand pendant and uncoordinated. The tpyprz derivative 16 is also one-dimensional, despite the tpyprz adopting the common bridging coordination to provide a {M2(tpyprz)} structural rod. It is also noteworthy that the structures of this study are generally quite distinct from those of the copper(II)/xylyldiphosphonate/bpy and ophen system where numerous molecular species are encountered as well as one- and two-dimensional structures, as described below. Under the mildly acidic conditions of synthesis, the xylyldiphosphonate ligands may adopt a variety of protonated forms, rather than the more common fully deprotonated tetranegative anion {O3P-R-PO3}4 with dramatic consequences to the product composition and structure. Furthermore, as noted previously [120], changes in the identity of the organic tether of the diphosphonate ligand also result in profound structural consequences. In contrasting the chemistries of metal/xylyldiphosphonates and metal/phenyldiphosphonates for example, the compositional and structural variations may reflect simply the different pK values of the parent acids, as well as the geometric consequences of the increased flexibility of the xylyl tether compared to the phenyl spacer. The infrared spectra of compounds 1–16 exhibit a pattern of two or three medium to strong bands in the 1000–1200 cm1 range attributed to m(P–O) of the phosphonate ligands [121]. In addition, compound 16 uniquely exhibits an intense broad band at ca. 3100 cm1 assigned to m(O–H) of the coordinated water molecules.

3.2. Descriptions of the structures of this study The use of 1,2-xylyldiphosphonate as the ligand provides the series of isomorphous materials [Mn(bpy)(1,2-HO3PC8H8PO3H)] (1), [Mn(o-phen)(1,2-HO3PC8H8PO3H)] (4), and [Co(o-phen)(1,2HO3PC8H8PO3H)] (7). As shown in Fig. 1, the structures are twodimensional with the secondary, capping ligands bpy and o-phen projecting above and below the planes to limit spatial expansion to two dimensions. The structures exhibit the characteristic di-l (O,O0 ) phosphonate bridge of two metal square pyramids bridged through phosphonate tetrahedra in a {M2P2O4} ring [78]. The basal plane of each metal site is defined by the oxygen donors of the two bridging diphosphonate tetrahedra and the nitrogen donors of the organonitrogen chelate, bpy or o-phen. The apical site is occupied by an oxygen donor from one terminus of a diphosphonate ligand linking to an adjacent {M2P2O4} unit of the layer. Consequently, each diphosphonate ligand uses one terminus in the l-O,O0 bridging mode while the second bonds to a single metal site of an adjacent {M2(bpy)2(HO3PR)2} or {M2(o-phen)2(HO3PR)2} cluster. In this fashion each {M2(N^N)2(HO3PR)2} cluster is linked to four adjacent clusters to provide the two-dimensional connectivity. The linkage pattern provides intralamellar cavities of approximate dimensions 13.5 Å  9.0 Å whose perimeters are defined by four {M2(N^N)2(HO3PR)2} clusters and four xylyl groups. In each case, the distances from the metal to the basal oxygen donors are considerably shorter than those to the apical site: M– Obasal (ave): 2.0519(9) Å (1), 2.048(1) Å (4), 1.995(1) Å (7) and M– Oapical: 2.1207(8) Å (1), 2.113(1) Å (4) and 2.060(1) Å (7). The bond lengths for the Co analogue are significantly shorter than those for the Mn derivative as expected from the decrease in the covalent

Fig. 1. (a) Mixed polyhedral and ball-and-stick representation of the network structure of [Mn(bpy)(1,2-HO3PC8H8PO3H)] (1), in the ac plane. (b) A view along the edge of plane 1, parallel to the b-axis. Color scheme: Mn, maroon polyhedra; P, yellow tetrahedra; oxygen, red spheres; nitrogen, light blue spheres; carbon, black spheres. Color scheme used throughout except where otherwise stated. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59

radius of the transition metal on moving from left to right across the series. The phosphonate protonation sites are also apparent from the P–O and P–O(H) bond distances. For example, for compound 1, the average for the unprotonated P–O distances is 1.5122(9) Å, while the P–O(H) distances are 1.5889(9) Å and 1.5711(8) Å. With 1,3-xylyldiphosphonate as the bridging ligand, six isostructural compounds are obtained: the isomorphous series [M(bpy)(1,3-HO3PC8H8PO3H)] (M@Mn (2), Co (6), Ni (12)) and [Ni(o-phen)(1,3-HO3PC8H8PO3H)] (13) and the isomorphous pair [M(o-phen)(1,3-HO3PC8H8PO3H)] (M@Mn (5) and Co (8)). While the structures are again two-dimensional, the juxtaposition of the {M2(N^N)2(l-O,O0 -phosphonate)2} secondary building units is distinct from that observed for 1, 4 and 7. Rather than isolated {M2(N^N)2(HO3PR)2} clusters as observed previously, this second series of compounds exhibits chains of {M2(N^N)2(HO3PR)2} clusters running parallel to the a-axis (Fig. 2). Adjacent chains are linked through the xylyl tethers of the diphosphonate ligands to provide expansion into two dimensions. The metal sites of compound 2, 5, 6, 8, 12 and 13 exhibit trigonally distorted {MO4N2} octahedral geometries. As illustrated by compound 2, the {MO3} face of the polyhedron provides an average bond distance of 2.134(1) Å, while the {MO2N} face exhibits an average bond distance of 2.263(1) Å, with the M–O distance expanded to 2.211(1) Å. The series also exhibits the anticipated contraction in metal donor bond distances upon moving from Mn to Co to Ni: M–O(ave): 2.153(1) Å (2, M@Mn), 2.156(1) Å (5, M@Mn), 2.100(1) Å (6, M@Co), 2.099(2) Å (8, M@Co), 2.079(1) Å (12, M@Ni) and 2.075(3) Å (13, M@Ni); M–N(ave): 2.290(1) Å (2, M@Mn), 2.310(2) Å (5, M@Mn), 2.150(1) Å (6, M@Co), 2.169(2) Å (8, M@Co), 2.102(1) Å (2, M@Ni) and 2.109(3) Å (13, M@Ni). Once again, the protonation sites are revealed by the P–O and P–O(H) distances; for example, for compound 2, the average P–O distance is 1.504(1) Å, while the P–O(H) distances are 1.584(1)Å and 1.576(1)Å. The most unusual structures are those of the isomorphous series of virtual two-dimensional networks observed for [Mn(bpy)2(1,4H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (3), [Co(o-phen)2(1,4-H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (10) and [Ni(o-phen)2(1,4H2O3PC8H8PO3H2)(1,4-HO3PC8H8PO3H)] (14). As shown in Fig. 3, the structure of 3 is constructed from one-dimensional {Mn(bpy)2(1,4-H2O3PC8H8PO3H2)}n2n+ chains. The building motif departs from the conventional {M2(N^N)2(HO3PR)2} unit of the previously discussed examples. In these instances, each metal bonds to

Fig. 2. Mixed polyhedral and ball-and-stick representation of the layered structure of [Mn(bpy)(1,3-HO3PC8H8PO3H)] (2) in the ab plane.

55

Fig. 3. (a) Mixed polyhedral and ball-and-stick representation of the one-dimensional substructure of [Mn(bpy)2(1,4-H2O3PC8H8PO3H)(1,4-HO3PC8H8PO3H)] (3). (b) A view of the structure of 3 showing the hydrogen bonding network and the expansion of the structure into two-dimensions. The layer is viewed in the ab plane and parallel to the chain axes of part (a) of this figure. Color scheme: as above with hydrogen as pink spheres.

two bpy or o-phen ligands and to two H2O3PR groups from two diphosphonic acid ligands to provide cis-{MO2N4} coordination. Adjacent metal octahedra of the chain are linked through the 1,4diphosphonic acid ligands, each bonding to one metal site through one oxygen of each terminus. The remaining oxygen atoms are protonated. The structure achieves virtual two-dimensional expansion through strong hydrogen bonding between the P–O(H) groups of the chain and the unprotonated oxygen atoms of the associated but uncoordinated {HO3PC8H8PO3H}2 anions. As shown in Fig. 3b, the hydrogen bonding interactions result in two-dimensional network of cationic {Mn(bpy)2(H2O3PC8H8PO3H2}n2n+ chains linked through charge-compensating {HO3PC8H8PO3H}2 anions. The {Mn(bpy)2}2+ groups of the layer project above and below the plane into the interlamellar domain. The {Mn(bpy)2}2+ groups from adjacent layers interdigitate to produce a dense structure with minimal void space. The protonation sites are revealed by the appearance of peaks at locations consistent with P–O(H) hydrogens and by comparisons of the P–O and P–O(H) bond distances in compounds 3, 10 and 14. The hydrogen bonding distances and O–H  O angles are provided in Table 3. The usual trends in M–O and M–N distances are observed: M–O(ave): 2.092(1) Å (3, M@Mn), 2.052(1) Å (10, M@Co), and 2.0460(9) Å (14, M@Ni); M-N(ave): 2.273(1) Å (3, M@Mn), 2.148(1) Å (10, M@Co), and 2.096(1) Å (14, M@Ni). The unique example of a three-dimensional structure is provided by compound 9, [Co(o-phen)(1,4-HO3PC8H8PO3H)]. Once again, the common {M2(N^N)2(HO3PR)2} secondary building unit is encountered. As shown in Fig. 4, these clusters fuse into chains in a fashion reminiscent of structures 2, 5, 6, 8, 12 and 13. However, in this case, each chain is linked through the 1,4-diphosphonate ligand to four adjacent chains, rather than two, to provide expansion into three dimensions. An unusual feature of the structure is the large cavities running parallel to the c-axis, formed by four {M2(HO3PR)2} clusters and the four bridging 1,4-xylyl groups, which are occupied by the o-phen ligands. Consequently, the o-phen groups, which decorate the surfaces of the layers in the previously described two-dimensional series, are incorporated into organic capsules within the three-dimensional framework of 9. The ligand tpyprz was introduced in the naïve expectation that this bridging, binucleating group would provide expansion into three-dimensional structures. However, as shown in Fig. 5, the structures of [Co(tpyprz)(1,2-HO3PC8H8PO3H)] (11) and [Ni(tpyprz)(1,2-HO3PC8H8PO3H)] (15) are one-dimensional. The

56

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59

Table 3 Hydrogen bond distance and angles for compounds 3, 10 and 14. Compound [Mn(bpy)2(1,4H2O3PC8H8PO3H2) (1,4-HO3PC8H8PO3H)] (3)

[Co(o-phen)2(1,4-H2O3PC8H8PO3H2) (1,4-HO3PC8H8PO3H)] (10)

[Ni(o-phen)2(1,4-H2O3PC8H8PO3H2) (1,4-HO3PC8H8PO3H)] (14)

H–O bond distance (Å) 0

H3 –O5 H20 –O6 H40 –O6 H20 –O4 H30 –O5 H60 –O5 H20 –O6 H30 –O4 H50 –O6

H–O–H bond angle (°) 1.657 1.718 1.806 1.690 1.709 1.829 1.708 1.700 1.826

O3–H30 –O5 O2–H20 –O6 O4–H40 –O6 O2–H20 –O4 O3–H30 –O5 O6–H60 –O5 O2-H20 –O6 O3-H30 –O4 O5-H50 –O6

175.5 173.5 155.8 175.1 165.8 163.0 166.8 172.9 163.1

Fig. 5. A view of the one-dimensional structure of [Co(tpyprz)(1,2-HO3PC8H8PO3H)] (11) viewed in the [111] plane.

Fig. 6. (a) A representation of the one-dimensional structure of [Ni2(tpyprz)(1,4HO3PC8H8PO3H)2]4H2O (164H2O). (b) A view of the structure of 164H2O showing the water molecules of crystallization. Color scheme: as about with nickel shown as green polyhedra. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 4. (a) Mixed polyhedral and ball-and-stick representation of the threedimensional structure of [Co(o-phen)(1,4-HO3PC8H8PO3H)] (9) in the ab plane, viewed parallel to the {Co(o-phen)(HO3PR)}n chains. (b) A view of the structure in the ac plane showing the pillared layer profile. Color scheme: as above with purple polyhedra for Co.

structure of 11 is constructed from the {Co2(tpyprz)2(HO3PR)2} clusters, linked through the xylyl tethers of the ligand. The coordination geometry at each Co(II) site is {CoN3O3} distorted octahedral. Each cobalt site coordinates to two oxygen donors of the {M2(di-l-O,O0 -phosphonate)2} unit, an oxygen donor from a third diphosphonate ligand and the three nitrogen donors of the tpyprz ligand. Each diphosphonate ligand directs one terminus to the dil-O,O0 bridging mode, while the second terminus bonds through a single oxygen donor to a cobalt site of an adjacent cluster. The protonation sites of the phosphonate oxygen atoms are clearly revealed by the P–O(H) distances. An unusual feature of the structures of 11 and 15 is the coordination geometry of the tpyprz ligand which coordinates to a single metal site. This observation may reflect the reaction conditions: metal to ligand ratio and the acidity of the reaction medium. Since catenation of {M(tpyprz)} groups is not uncommon, as in [{Co4(tpyprz)3{Mo5O15)O3P(CH2)2PO3}] [122], it is also likely that 11

and 15 may serve as building blocks for bimetallic materials with two- or three-dimensional structures. The structure of [Ni2(tpyprz)(1,4-HO3PC8H8PO3H)]4H2O (164H2O) is also one-dimensional (Fig. 6). In this case, the tpyprz ligand adopts the more common bridging mode between two coordinated metal sites. Once again, the {M2(di-l-O,O0 -phosphonate)2} cluster building unit is observed. The clusters are linked through the xylyl tethers of the diphosphonate ligands and the tpyprz ligands. Each Ni(II) adopts distorted octahedral {NiO3N3} geometry with a meridional configuration of donor groups. Each nickel site bonds to two oxygen donors from two diphosphonate ligands in the {Ni2(di-l-O,O0 -phosphonate)2} unit and a third oxygen donor from a diphosphonate ligand bridging to an adjacent cluster. The remaining coordination sites are occupied by the nitrogen donors of one terminus of the tpyprz ligand. The 1,4-xylyl geometry provides sufficient spacing between the –PO3H termini of the ligand to allow the tpyprz ligand to bridge adjacent {Ni2(HO3PR)2} clusters and nestle between xylyl tethers linking these clusters. 3.3. Structural trends and generalizations The structures of this study exhibit the influences of incorporation of a secondary chelating ligand which serves to occupy coordination sites on the metal with the effect of reducing the overall dimensionality of the materials. This observation is quite evident in comparing the one- and two-dimensional structures of this

57

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59

Scheme 3. The syn and anti configuration of the methylenephosphonate groups with respect to the phenyl rings of the xylyldiphosphonate ligands.

study with the conventional pillared layer structure of [Cu2(H2O)2(1,4-O3PC8H8PO3)] in the absence of a secondary ligand [123]. It is instructive to compare the structures of this study with those of the previously reported copper series [123]. In addition to the secondary ligand, the coordination preferences of the metal also provide a significant structural determinant. Thus, while the structure of [Cu(o-phen)(1,2-HO3PC8H8PO3H)] is similar to those of compounds 1, 4, and 7, [Cu(bpy)(1,3-HO3PC8H8PO3H)] and [Cu(o-phen)(1,3-HO3PC8H8PO3)] are one-dimensional with structures most similar to that of [Ni(tpyprz)(1,2-HO3PC8H8PO3H)] rather than those of 1,3-xylyl diphosphonate series. Furthermore, the copper sites are five coordinate rather than six coordinate. With 1,4-xylyldiphosphonate, the copper series includes the molecular species [Cu2(H2O)2(bpy)2(1,4-HO3PC8H8PO3H2)2(1,4HO3PC8H8PO3H)] and [Cu(H2O)(o-phen)(1,4-HO3PC8H8PO3H)] and the one-dimensional [Cu2(o-phen)(H2O)2(1,4-O3PC8H8PO3)], as well as the two-dimensional materials [Cu(o-phen)(1,4-HO3PC8H8PO3H)] and [Cu(bpy)(1,4-HO3PC8H8PO3H)]. These layered structures share common features with [Co(o-phen)(1,2-HO3PC8H8PO3H)] and compounds 1, 4 ad 7 of this study. In all cases, the network is constructed from {M2(di-l-O,O0 -phosphonate)2} clusters linked through the xylyl tethers. Five coordination of the metal centers is also observed for these structures. A rather obvious structural determinant is the relative locations of the methylenephosphonate groups on the ligand phenyl rings, whether 1,2-, 1,3- or 1,4-substituted. Thus, the two-dimensional structures incorporating (1,2-HO3PC8H8PO3H)2, 1, 4 and 7 are distinct from the network structures adopted by the (1,3-HO3PC8H8PO3H)2 series, 2, 5, 6, 8, 12 and 13, while the (1,4-HO3PC8H8PO3H)2 series 3, 10 and 14 adopts a one-dimensional chain structure, expanded to two-dimensions through hydrogen-bonding. The structures of these series also reflect the free rotation of the HnPO3 groups about the methylene carbon atoms. For example, in the virtual two-dimensional series 3, 10 and 14, the HnPO3 groups are disposed in the syn configuration with respect to the phenyl rings while in the three-dimensional material 9, the substituents adopt the anti limiting geometry (Scheme 3). This rotational versatility is also apparent in the previously reported copper series of xylyldiphosphonates. Structural variability is additionally enhanced by accessibility of different coordination polyhedra for the metals, variable coordination of aqua ligands and the flexibility of the M–O–P angle. In addition, variable protonation of the phosphonate ligands is also encountered. Under the acidic condition of this study, the ligands are generally observed in the symmetrically protonated form (HO3PC8H8PO3H)2. Under neutral or basic conditions, the fully deprotonated (O3PC8H8PO3)4 is expected to exhibit different coordination requirements, a hypothesis which we will address in future work. 3.4. Thermal analyses The thermal gravimetric analysis (TGA) plots of the metal(II) compounds of this study (M(II)@Mn, Co, Ni) exhibit four common motifs in the analysis of decomposition products. For many compounds, the decomposition process does not appear to be complete at a temperature of 800 °C, as evidenced by the gradual loss continuing at the limiting temperature of the instrument. All TGA profiles can be found in the ESI. . The TGA for compound 1 exhibits stability up to about 280 °C followed by a weight loss of about 40% at 400 °C, attributed to

the loss of the 2,20 -bipyridine ligand (32.8%, theoretical). The compound then has a stable plateau from around 400 °C to 510 °C, followed by an additional weight loss of about 20% at 600 °C. Over this range the diphosphonate ligand is decomposing resulting in the condensation of the hydrogen phosphonate groups and the oxidation and loss of P2O5 [83,124]. The residue, which is most likely a manganese oxide is stable from 600 °C to 800 °C. Compounds 4, 5, and 11 exhibit similar features in their respective TGA plots. The TGA for compound 3 exhibits a loss of about 20% (17.4%, calculated) at about 290 °C attributed to the pyrolysis of one of the organonitrogen ligands. The second organo-nitrogen ligand then is slowly lost from about 290 °C to about 660 °C. The total weight loss, including that attributed to first organonitrogen ligand, is about 30% (34.8%, calculated). The compound is then stable from around 660 °C to 800 °C. It is interesting to note that the hydrogen-bonded {1,4-HO3PC8H8PO3H}2 is so integral to the complex that even at 800 °C there is no evidence of its loss. The resultant amorphous residue is most likely the metal diphosphonate complex. Similar behavior is exhibited in compounds 10 and 14. The TGA of compound 12 is consistent with unusual thermal stability, with a single major weight loss observed. The compound is thermally stable up to ca. 475 °C, whereupon there is a weight loss of about 30% between 475 °C and 600 °C, corresponding to the loss of the 2,20 -bipyridine ligand (32.6%,theoretical). Between 600 °C and 800 °C there is a gradual weight loss of <10%, mostly likely corresponding to the gradual decomposition of the diphosphonate ligand. Compounds 6, 7, 8, 9, 13 and 15 exhibit similar behavior to compound 12. The TGA for compound 164H2O exhibits a loss of about 8% (7.6%, calculated) from around 25 °C to 200 °C attributed to the loss of the two of the waters of crystallization. The compound is then stable from ca. 200 °C to 440 °C. The next weight loss occurs between 440 °C to about 510 °C, where the compound loses the remaining waters of crystallization. The total weight loss over these two ranges is about 15% (13%, calculated). From 510 °C to 800 °C the compound continues to gradually loose mass, most likely due to the decomposition of the organonitrogen ligands. 3.5. Magnetism The temperature dependent magnetic susceptibilities of the majority of the compounds of this study were investigated. Compounds 3, 12 and 13 were not included in the study due to the presence of paramagnetic impurities which precluded meaningful interpretations of the magnetic properties. In all cases, the magnetic data were analyzed using the Curie– Weiss law with a temperature-independent paramagnetism term (TIP) added to account for the baseline correction. The final expression used in the susceptibility fittings is the following:

v ¼ vh þ TIP ¼

Ng 2 l2B SðS þ 1Þ þ TIP 3kB ½T  h

ð1Þ

As a function of the magnetic moment, the expression is:

v ¼ vh þ TIP ¼

l2eff 8½T  h

þ TIP;

where

l2eff ¼ g 2 SðS þ 1Þ

ð2Þ

The results for the Curie–Weiss analyses are given in Table 4 (see Supplementary materials Figs. S49–S61 for plots of the temperature dependence of the magnetic susceptibilities and of the effective magnetic moments). The Mn2+ compounds 1, 2, 4 and 5 exhibit leff values in the range 5.98–6.38 lB, consistent with the S = 5/2 ground state (5.9 ± lB, calculated). The Co2+ compounds

58

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59

Table 4 Summary of magnetic susceptibility properties of the compounds of this study: best fit parameters to the Curie–Weiss law (Eqs. (1) and (2)). Compound

leff (BM)

H (K)

g

1 2 4 5 6 7 8 9 10 11 14 15 16

6.12 ± 0.9 6.10 ± 0.9 6.38 ± 0.64 5.98 ± 0.60 4.54 ± 0.8 4.11 ± 0.42 3.94 ± 0.59 4.57 ± 0.8 3.90 ± 0.58 4.46 ± 0.7 3.23 ± 0.48 2.89 ± 0.44 3.28 ± 0.49

5.7 ± 0.8 3.0 ± 0.5 1.81 ± 0.20 0.77 ± 0.09 10.5 ± 1.8 0.70 ± 0.10 0.41 ± 0.06 17.8 ± 2.6 0.19 ± 0.03 9.5 ± 1.7 1.31 ± 0.19 1.59 ± 0.24 1.47 ± 0.22

2.06 2.06 2.10 2.02 2.32 2.12 2.03 2.60 2.01 2.30 2.28 2.04 2.32

6–11 show leff values in the 3.90–4.57 lB range, consistent with the S = 3/2 ground state. The deviations from the spin only value of 3.87 lB reflects the contributions of spin–orbit coupling. The Ni2+ compounds 14–16 with leff values in the 2.89–3.28 lB range, are consistent with an S = 1 ground state (2.83 lB, calculated) with contributions from spin–orbit coupling. These results suggest negligible magnetic exchange through the {M2(di-l-O,O0 -phosphonate)2} bridges exhibited by many of the compounds of this study.

4. Conclusions Hydrothermal methods have been used to prepare a series of coordination polymers of the general type M(II)/xylyldiphosphonate/organoimine chelate. Several recurrent structural prototypes were observed reflecting the identity of the xylyldiphosphonate ligand. The materials [M(N^N)(1,2-HO3PC8H8PO3H)] with M@Mn(II), N^N@bpy (1), o-phen (4) and M@Co(II), N^N@o-phen (7) exhibit a two-dimensional structure constructed from the ubiquitous {M2(di-l-O,O0 -phosphonate)2} rings linked through the xylyl backbones of the ligands. While the series [M(bpy)(1,3HO3PC8H8PO3H)] (M@Mn (2), Co (6), Ni (12) and [M(o-phen)(1,3HO3PC8H8PO3H)] (M@Mn (5), Co (8)) are also two-dimensional, the networks are constructed from {M2(N^N)2(HO3PR)2}n chains linked through the xylyl tethers of the diphosphonate ligands. The layered structures of [M(N^N)2(1,4-H2O3PC8H8PO3H2)(1,4HO3PC8H8PO3H)] (M@Mn, N^N@bpy (3); M@Co, N^N@o-phen (10); M@Ni, N^N@o-phen (14)) exhibit {M(N^N)2(1,4-H2O3PC8H8PO3H2)}n2n+ chains linked through hydrogen-bonded (HO3PC8H8PO3H)2 anions to provide the dimensional expansion. Although tpyprz was introduced in the naïve expectation that this rigid binucleating ligand would favor two- or three-dimensional structures, the compounds [M(tpyprz)(1,2-HO3PC8H8PO3H)] (M@Co (11), Ni (15)) and [Ni2(tpyprz)(1,4-HO3PC8H8PO3H)]4H2O (164H2O) are one-dimensional. In the case of 11 and 15, one terminus of the tpyprz ligand is pendant and uncoordinated, and the structures are similar to those of 1, 4 and 7 but with the metals in a six coordinate {MO3N3} environment rather than the square pyramidal {MO3N2} coordination of the latter series. While the tpyprz ligand of 16 is present as a binucleating rod linking two M(II) sites, this does not accomplish expansion into two-dimensions, as the 1,4-xylyldiphosphonate ligand can effectively span the distance between {Ni2(tpyprz)(di-l-O,O0 -diphosphonate)2} secondary building units. The only example of a three-dimensional structure is [Co(ophen)(1,4-HO3PC8H8PO3H)] (9) where the common {Co2(ophen)2(di-l-O,O0 -phosphonate)2} building blocks are linked into {Co(o-phen)(HO3PR)}n chains which are in turn linked to four adjacent chains through the 1,4-xylyl framework of the ligands. Spatial

expansion is accomplished in this instance as a consequence of the para-xylyl geometry and the anti-configuration of the (HO3P–) substituents to provide cavities, defined by four {Co2(HO3PR)4} clusters linked through four –C8H8-tethers, sufficiently spacious to accommodate the o-phen ligands within the framework. The structural systematics of these series of compounds demonstrate the general principle of designing lower dimensional polymers (1-D and 2-D) by occupying metal coordination sites with secondary chelating ligands. However, the interplay of relative ligand sizes and geometries also plays a role in the ultimate structure, as noted for compound 9. Of course, other structural determinants, such as accessibility of different coordination polyhedra, variable aqua coordination, variable protonation and coordination of phosphonate oxygen atoms, and the flexibility of the M–O–P valence angle also contribute as structural determinants. Reaction conditions such as stoichiometry, temperature and pH in particular also play significant roles in determining the product composition and structure. Acknowledgement This work was funded by a grant from the National Science Foundation (CHE-0907787). Appendix A. Supplementary material CCDC 881705–881717 contain the supplementary crystallographic data for Compounds 1–16. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif. The supplementary data consists of tables of atomic positional parameters, bond lengths, bond angles, anisotropic temperature factors, and calculated hydrogen atom positions for 1–16 (Supplementary Tables S1–S78). In addition, ORTEP views of the structures are provided in Supplementary Figs. S1–S16, infrared spectra in Figs. S17–S32, TGA profiles in Figs. S33–S48 and magnetic susceptibility plots in Figs. S49–S61. Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/ j.ica.2013.03.003. References [1] [2] [3] [4] [5] [6] [7] [8] [9]

[10]

[11] [12] [13] [14] [15] [16] [17]

C. Janiak, Dalton Trans. (2003) 2781. and references therein. G.M. Whitesides, R.F. Ismagilov, Science 284 (1999) 89. I.Z. Kiss, J.L. Hudson, AIChE J. 49 (2003) 2234. J.M. Lehn, Proc. Natl. Acad. Sci. USA 99 (2002) 4763. J.M. Lehn, Science 295 (2002) 2400. S. Forster, T. Plantenberg, Angew. Chem., Int. Ed. 41 (2002) 688. A.D. Miller, ChemBioChem 3 (2002) 45. D.B. Mitzi, J. Chem. Soc., Dalton Trans. 1 (2001). For example: (a) B. Chen, N.W. Ockwig, A.R. Millward, D.S. Contreras, O.M. Yaghi, Angew. Chem., Int. Ed. 44 (2005) 4745; (b) D. Bradshaw, J.B. Claridge, E.J. Cussen, T.J. Prior, M.J. Rosseinsky, Acc. Chem. Res. 38 (2005) 273. (a) H.L. Ngo, A. Hu, W. Lin, J. Mol. Catal. A: Chem. 215 (2004) 177; (b) C. Sanchez, B. Lebeau, F. Chaput, J.P. Boilet, Adv. Mater. 2003 (1969) 15; (c) P. Jannasch, Curr. Opin. Colloid Interface Sci. 8 (2003) 96; (d) J.L.C. Rowsell, A.R. Millward, K.S. Park, O.M. Yaghi, J. Am. Chem. Soc. 126 (2004) 5666. D.J. Tranchemontagne, K.S. Park, H. Furukawa, J. Eckert, C. Knobler, O.M. Yaghi, J. Phys. Chem. C 116 (2012) 13143. M. Hmadeh, Z. Lu, Z. Liu, F. Gandara, H. Furukawa, S. Wan, V. Agustyn, Veronica, R. Chang, L. Liao, F. Zhou, O.M. Yaghi, Chem. Mater. 24 (2012) 3511. D.J. Tranchemontagne, Z. Ni, M. O0 Keefe, O.M. Yaghi, Angew. Chem., Int. Ed. 47 (2008) 5136. E.D. Bloch, D. Britt, C. Lee, C.J. Doonan, F.J. Uribe-Romo, H. Furukawa, J.R. Long, O.M. Yaghi, J. Am. Chem. Soc. 132 (2010) 14382. W. Morris, C.J. Doonan, H. Furukawa, R. Banerjee, O.M. Yaghi, J. Am. Chem. Soc. 130 (2008) 12626. Q. Li, C.-H. Sue, S. Basu, A.K. Shveyd, W. Zhang, G. Barin, L. Fang, A.A. Sarjeant, J.F. Stoddart, O.M. Yaghi, Angew. Chem., Int. Ed. 49 (2010) 6751. B. Wang, A.P. Côté, H. Furukawa, M. O’Keeffe, O.M. Yaghi, Nature 453 (2008) 207.

T.M. Smith et al. / Inorganica Chimica Acta 402 (2013) 46–59 [18] K.S. Park, Z. Ni, A.P. Côté, J.Y. Choi, R. Huang, F.J. Uribe-Romo, H.K. Chae, M. O’Keeffe, O.M. Yaghi, Proc. Natl. Acad. Sci. USA 103 (2006) 10186. [19] P. Horcajada, R. Gref, T. Baati, P.K. Allan, G. Maurin, P. Couvreur, G. Ferey, Gerard, R.E. Morris, C. Serre, Chem. Rev. 112 (2012) 1232. [20] P. Horcajada, F. Salles, S. Wuttke, T. Devic, D. Heurtaux, G. Maurin, A. Vimont, M. Daturi, O. David, E. Magnier, N. Stock, Y. Filinchuk, D. Popov, C. Riekel, G. Férey, C. Serre, J. Am. Chem. Soc. 133 (2011) 17839. [21] G. De Weireld, A. Vimont, M. Daturi, J.-S. Chang, Chem. Soc. Rev. 40 (2011) 550. [22] G. Férey, Stud. Surf. Sci. Catal. 170A (2007) 66. [23] G. Ferey, Chem. Soc. Rev. 37 (2008) 191. [24] E. Procopio, T. Fukushima, E. Barea, J.A.R. Navarro, S. Horike, S. Kitagawa, Chem. Eur. J. 18 (41) (2012) 13117. [25] T. Fukushima, S. Horike, H. Kobayashi, M. Tsujimoto, S. Isoda, M.L. Foo, Y. Kubota, M. Takata, S. Kitagawa, Susumu, J. Am. Chem. Soc. 134 (32) (2012) 13341. [26] Y. Hijikata, S. Horike, M. Sugimoto, H. Sato, R. Matsuda, S. Kitagawa, Chem. Eur. J. 17 (2011) 5138. [27] S. Noro, S. Kitagawa, in: K. Rurack, R. Martinez-Manez (Eds.), Supramolecular Chemistry of Organic–Inorganic Hybrid Materials, 2010, p. 235. [28] Y. Kubota, M. Takata, T.C. Kobayashi, S. Kitagawa, Coord. Chem. Rev. 251 (2007) 2510. [29] S. Kitagawa, R. Matsuda, Coord. Chem. Rev. 251 (2007) 2490. [30] X. Kong, E. Scott, W. Ding, J.A. Mason, J.R. Long, J.A. Reimer, J. Am. Chem. Soc. 134 (2012) 14341. [31] E.D. Bloch, W.L. Queen, R. Krishna, J.M. Zadrozny, C.M. Brown, J.R. Long, Science 335 (2012) 1606. [32] L.J. Murray, M. Dinca, J.R. Long, Chem. Soc. Rev. 38 (2009) 1294. [33] M. Dinca, J.R. Long, Angew. Chem., Int. Ed. 47 (2008) 6766. [34] H.J. Choi, M. Dinca, J.R. Long, J. Am. Chem. Soc. 130 (2008) 7848. [35] B. Moulton, M.J. Zaworotko, Curr. Opin. Solid State Mater. Sci. 6 (2002) 117. [36] C. Wang, W. Lin, J. Am. Chem. Soc. 133 (2011) 4232. [37] L. Ma, J.-Y. Lee, J. Li, W. Lin, Inorg. Chem. 47 (2008) 3955. [38] W.J. Rieter, K.M.L. Taylor, W. Lin, J. Am. Chem. Soc. 129 (2007) 9852. [39] M. Eddaoudi, J.F. Eubank, Org. Nanostruct. (2008) 251. [40] D.F. Sava, V.Ch. Kravtsov, F. Nouar, L. Wojtas, J.F. Eubank, M. Eddaoudi, J. Am. Chem. Soc. 130 (2008) 3768. [41] A. Schoedel, L. Wojtas, M. Eddaoudi, M.J. Zaworotko, Preprints of Symposia – American Chemical Society, Division of Fuel Chemistry, vol. 57, 2012, p. 299. [42] U. Beckmann, S. Brooker, Coord. Chem. Rev. 245 (2003) 17. [43] J.G. Haasnoot, Coord. Chem. Rev. 200 (2000) 131. [44] R.M. Hellyer, D.S. Larsen, S. Brooker, Eur. J. Inorg. Chem. (2009) 1162. [45] J.-P. Zhang, X.-M. Chen, Chem. Commun. (2006) 1689. [46] L.N. Dawe, L.K. Thompson, Dalton Trans. (2008) 3610. [47] J.-P. Zhang, Y.-Y. Lin, X.-C. Huang, X.-M. Chen, J. Am. Chem. Soc. 127 (2005) 5495. [48] J.-P. Zhang, S.-L. Zheng, X.-C. Huang, X.-M. Chen, Angew. Chem., Int. Ed. 43 (2004) 206. [49] S. Ferrer, F. Lloret, I. Bertomeu, G. Alzuet, J. Borras, S. Garcia-Granda, M. LiuGonzález, J.G. Haasnoot, Inorg. Chem. 41 (2002) 5821. [50] J.-H. Zhou, R.-M. Cheng, Y. Song, Y.-Z. Li, Z. Yu, X.-T. Chen, Z.-L. Xue, X.-Z. You, Inorg. Chem. 44 (2005) 8011. and references therein. [51] J.-P. Zhang, Y.-Y. Lin, W.-X. Zhang, X.-M. Chen, J. Am. Chem. Soc. 127 (2005) 14162. [52] Z. Li, M. Li, S.-Z. Zhan, X.-C. Huang, S.W. Ng, D. Li, CrystEngComm 10 (2008) 978. [53] W. Ouellette, M.H. Yu, C.J. O’Connor, D. Hagrman, J. Zubieta, Angew. Chem., Int. Ed. 45 (2006) 3497. [54] W. Ouellette, A.V. Prosvirin, J. Valeich, K.R. Dunbar, J. Zubieta, Inorg. Chem. 46 (2007) 9067. [55] W. Ouellette, J.R. Galán-Mascarós, K.R. Dunbar, J. Zubieta, Inorg. Chem. 45 (2006) 1909. [56] W. Ouellette, A.V. Prosvirin, V. Chieffo, K.R. Dunbar, B. Hudson, J. Zubieta, Inorg. Chem. 45 (2006) 9346. [57] D.J. Chesnut, A. Kusnetzow, R. Birge, J. Zubieta, Inorg. Chem. 38 (1999) 5484. [58] W. Ouellette, B.S. Hudson, J. Zubieta, Inorg. Chem. 46 (2007) 4887. [59] W. Ouellette, H. Liu, C.J. O’Connor, J. Zubieta, Inorg. Chem. 48 (2009) 4655. [60] W. Ouellette, J. Zubieta, Chem. Commun. (2009) 4533. [61] W. Ouellette, A.V. Prosvirin, K. Whitenack, K.R. Dunbar, J. Zubieta, Angew. Chem., Int. Ed. 48 (2009) 2140. [62] W. Ouellette, S. Jones, J. Zubieta, CrystEngComm 13 (2011) 4457. [63] W. Ouellette, K. Darling, A. Prosvirin, K. Whitenac, K.R. Dunbar, J. Zubieta, Dalton Trans. 40 (2011) 12288. [64] W. Ouellette, S. Jones, J. Zubieta, CrystChemComm 13 (2011) 4457. [65] G. Alberti, U. Costantino, S. Alluli, N. Tomassini, J. Inorg. Nucl. Chem. 40 (1978) 1113. [66] A. Clearfield, Prog. Inorg. Chem. 47 (1998) 371. [67] A. Clearfield, Dalton Trans. (2008) 6089. [68] A. Vioux, J. LeBideau, P.H. Mutin, D. Leclercq, Top. Curr. Chem. 232 (2004) 145. [69] A. Clearfield, Curr. Opin. Solid State Mater. Sci. 6 (2002) 495.

59

[70] A. Clearfield, in: J.L. Atwood, J.E.D. Davies, F. Vogel (Eds.), Comprehensive Supramolecular Chemistry, vol. 9, in: G. Alberti, T. Bein, (Eds.), Pergamon Press, New York, 1996, p. 107. [71] A. Clearfield, Chem. Mater. 10 (1998) 2801. [72] S. Konar, A.V. Prosvirin, K.R. Dunbar, A. Clearfield, Inorg. Chem. 46 (2007) 5229. and references therein. [73] J.W. Johnson, A.J. Jacobson, W.M. Butler, S.E. Rosenthal, J.F. Brody, J.T. Lewandowsky, J. Am. Chem. Soc. 111 (1989) 381. [74] K. Maeda, Micropor. Mesopor. Mater. 73 (2004) 47. [75] G. Alberti, M. Casiola, U. Costantino, R. Vivani, Adv. Mater. 8 (1996) 291. [76] L.A. Vermeulen, Prog. Inorg. Chem. 44 (1997) 143. [77] G. Alberti, in: J.L. Atwood, J.E.D. Davies, F. Vogel (Eds.), Comprehensive Supramolecular Chemistry, Pergamon Press, New York, 1996. [78] R.C. Finn, J. Zubieta, R.C. Haushalter, Prog. Inorg. Chem. 51 (2003) 451. [79] A. Clearfield, K.D. Demadis (Eds.), Metal Phosphonate Chemistry from Synthesis to Applications, Royal Society of Chemistry, Cambridge, UK, 2012. [80] V. Soghomonian, Q. Chen, R.C. Haushalter, J. Zubieta, Angew. Chem., Int. Ed. 34 (1995) 4460. [81] D. Riou, O. Roubeau, G. Ferey, Micropor. Mesopor. Mater. 23 (1998) 23. [82] D.M. Poojary, B. Zhang, A. Clearfield, Chem. Mater. 11 (1999) 421. [83] D.I. Arnold, X. Ouyang, A. Clearfield, Chem. Mater. 14 (2002) 2020. [84] D.M. Poorjary, B. Zhang, A. Clearfield, J. Am. Chem. Soc. 119 (1997) 12550. [85] D.M. Poorjary, B. Zhang, P. Bellinghausen, A. Clearfield, Inorg. Chem. 35 (1996) 4942. [86] D. Knog, J. Zn, J. McBee, A. Clearfield, Inorg. Chem. 45 (2006) 977. [87] D. Kong, Y. Li, J.H. Ross, R.A. Clearfield, Chem. Commun. (2003) 1720. [88] M.M. Gomez-Alcantura, A. Cabeza, M. Martinez-Lara, M.A.G. Aranda, R. Suau, N. Bhuvanesh, A. Clearfield, Inorg. Chem. 43 (2004) 5283. [89] P. DeBurgomaster, W. Ouellette, H. Liu, C.J. O’Connor, J. Zubieta, Cryst. Eng. Commun. 12 (2010) 446. [90] R. Finn, J. Zubieta, Chem. Comm. (2000) 1821. [91] P.J. Hagrman, R.C. Finn, J. Zubieta, Solid State Sci. 3 (2001) 745. [92] R.C. Finn, J. Zubieta, J. Phys. Chem. Solids 62 (2001) 1513. [93] R.C. Finn, J. Zubieta, J. Chem. Soc., Dalton Trans. (2002) 856. [94] R.C. Finn, R. Lam, J.E. Greedan, J. Zubieta, Inorg. Chem. 40 (2001) 3745. [95] W. Ouellette, B.-K. Koo, E. Burkholder, V. Golub, C.J. O’Connor, J. Zubieta, Dalton Trans. (2004) 1527. [96] G. Yucesan, V. Golub, C.J. O’Connor, J. Zubieta, Dalton Trans. (2005) 2241. [97] G. Yucesan, N.G. Armatas, J. Zubieta, Inorg. Chim. Acta 359 (2006) 4557. [98] G. Yucesan, M.H. Yu, C.J. O’Connor, J. Zubieta, Cryst. Eng. Comm. 7 (2005) 711. [99] G. Yucesan, M.H. Yu, C.J. O’Connor, J. Zubieta, Cryst. Eng. Comm. 7 (2005) 480. [100] G. Yucesan, V. Golub, C.J. O’Connor, J. Zubieta, Dalton Trans. (2005) 7241. [101] G. Yucesan, W. Ouellette, V. Golub, C.J. O’Connor, J. Zubieta, Solid State Sci. 7 (2005) 445. [102] G. Yucesan, V. Golub, C.J. O’Connor, J. Zubieta, Sold State Sci. 7 (2005) 133. [103] G. Yucesan, J.E. Valeich, H. Liu, W. Ouellette, C.J. O’Connor, J. Zubieta, Inorg. Chim. Acta 362 (2010) 1831. [104] W. Ouellette, G. Wang, H. Liu, G.T. Lee, C.J. O’Connor, J. Zubieta, Inorg. Chem. 48 (2009) 953. [105] W. Ouellette, V. Golub, C.J. O’Connor, J. Zubieta, Dalton Trans. (2005) 291. [106] W. Ouellette, V. Golub, C.J. O’Connor, J. Zubieta, J. Solid State Chem. 180 (2007) 2500. [107] W. Ouellette, M.H. Yu, C.J. O’Connor, J. Zubieta, Inorg. Chem. 45 (2006) 7628. [108] N.G. Armatas, W. Ouellette, K. Whitenack, J. Pelcher, H. Liu, E. Romaine, C.J. O’Connor, J. Zubieta, Inorg. Chem. 48 (2009) 8897. [109] P. DeBurgomaster, A. Aldous, H. Liu, C.J. O’Connor, J. Zubieta, Cryst. Growth Des. (2010) 2209. [110] M. Bartholomae, H. Chueng, S. Pellizzeri, K. Ellis-Guardiola, S. Jones, J. Zubieta, Inorg. Chim. Acta (2012) 90. [111] D.I. Arnold, X. Ouyang, A. Clearfield, Chem. Mater. 14 (2002) 20. [112] SMART, Data Collection Software, Version 5.630, Bruker-AXS Inc., Madison, WI, 1997–2002. [113] SAINT Plus, Date Reduction Software, Version 6.45A, Bruker-AXS Inc., Madison, WI, 1997–2002. [114] G.M. Sheldrick, SADABS, University of Göttingen, Göttingen, Germany, 1996. [115] SHELXTL PC, version 6.12, Bruker-AXS Inc., Madison, WI, 2002. [116] M.S. Whittingham, Curr. Opin. Solid State Mater. Sci. 1 (1996) 227. [117] R.A. Laudise, Chem. Eng. News 65 (1987) 30. [118] J. Gopalakrishnan, Chem. Mater. 7 (1995) 1265. [119] J. Zubieta, Solid-State Methods, Hydrothermal, in: J.A. McCleverty, T.J. Meyer (Eds.), Comprehensive Coordination Chemistry II, Elsevier Science, New York, vol. 1, 2004, pp. 697. [120] W. Ouellette, M.H. Yu, C.J. O’Connor, J. Zubieta, Inorg. Chem. 45 (2006) 3224. [121] C.Y. Ortiz-Avila, C. Bhardwaj, A. Clearfield, Inor. Chem. 33 (1994) 2499. [122] N.G. Armatas, D.G. Allis, A. Prosvirin, G. Carnutu, C.J. O’Connor, K. Dunbar, J. Zubieta, Inorg. Chem. 47 (2008) 832. [123] T.M. Smith, J. Vargas, D. Symester, M. Tichenor, C.J. O’Connor, J. Zubieta, Inorg. Chim. Acta. http://dx.doi.org/10.1016/j.ica.2013.01.001. [124] A. Cabeza, X. Ouyang, C.V.K. Sharma, M.A.G. Avanda, S. Bruque, A. Clearfield, Inorg. Chem. 41 (2002) 2325.