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A new coordination polymer, catena-poly[[(dipyrido[3,2-a:2′,3′-c]phenazine-κ2N,N′)nickel(II)]-μ-2,6-dipicolinato-κ4O2,N,O6:O2′], [Ni(C7H3NO4)(C18H10N4)]n, exhibits a one-dimensional structure in which 2,6-dipicolinate acts as a bridging ligand interconnecting adjacent nickel(II) centers to form a chain structure. The asymmetric unit contains one NiII center, one dipyrido[3,2-a:2′,3′-c]phenazine ligand and one 2,6-dipicolinate ligand. Each NiII center is six-coordinated and surrounded by three N atoms and three O atoms from one dipyrido[3,2-a:2′,3′-c]phenazine ligand and two different 2,6-dipicolinate ligands, leading to a distorted octahedral geometry. Adjacent chains are linked by π–π stacking interactions and weak interactions to form a three-dimensional supramolecular network.
Supporting information
CCDC reference: 672402
DPPZ was prepared according to the method reported by Dickeson & Summers (1970).
A mixture of Ni(NO3)2.6H2O (0.145 g, 0.5 mmol), H2pydc (0.084 g, 0.5 mmol), DPPZ (0.141 g, 0.5 mmol), NaOH (0.04 g, 1 mmol) and water (10 ml) was
mixed in a 23 ml Teflon reactor and stirred for 20 min in air. It was then
heated at 433 K for five days, followed by cooling to room temperature at a
rate of 5 K h-1. Green block crystals of (I) were isolated.
The H atoms were placed at calculated positions in the riding model
approximation (C—H = 0.93 Å), with their Uiso(H) parameters set
to 1.2Ueq of the parent atoms. Standard DFIX restraints
(SHELXL97; Sheldrick, 1997) were used for the atoms C11 and C25
[C11—C25 = 1.395 (5) Å].
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia,
1997)
and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2001).
catena-poly[(dipyrido[3,2 -
a:2',3'-c]phenazine-
κ2N,
N')nickel(II)]-µ-2,6-dipicolinato-
κ3O2,
O6:
O2']
top
Crystal data top
[Ni(C7H3NO4)(C18H10N4)] | F(000) = 1032 |
Mr = 506.11 | Dx = 1.690 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3623 reflections |
a = 7.3482 (11) Å | θ = 2.4–26.3° |
b = 35.825 (4) Å | µ = 1.02 mm−1 |
c = 7.8986 (12) Å | T = 293 K |
β = 106.906 (12)° | Block, green |
V = 1989.4 (5) Å3 | 0.37 × 0.32 × 0.26 mm |
Z = 4 | |
Data collection top
Bruker APEX area-detector diffractometer | 3504 independent reflections |
Radiation source: fine-focus sealed tube | 2860 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scan | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan '(SADABS; Sheldrick, 1996)' | h = −8→8 |
Tmin = 0.704, Tmax = 0.780 | k = −1→42 |
4459 measured reflections | l = −9→1 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0536P)2 + 1.7276P] where P = (Fo2 + 2Fc2)/3 |
3504 reflections | (Δ/σ)max < 0.001 |
316 parameters | Δρmax = 0.64 e Å−3 |
2 restraints | Δρmin = −0.60 e Å−3 |
Crystal data top
[Ni(C7H3NO4)(C18H10N4)] | V = 1989.4 (5) Å3 |
Mr = 506.11 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3482 (11) Å | µ = 1.02 mm−1 |
b = 35.825 (4) Å | T = 293 K |
c = 7.8986 (12) Å | 0.37 × 0.32 × 0.26 mm |
β = 106.906 (12)° | |
Data collection top
Bruker APEX area-detector diffractometer | 3504 independent reflections |
Absorption correction: multi-scan '(SADABS; Sheldrick, 1996)' | 2860 reflections with I > 2σ(I) |
Tmin = 0.704, Tmax = 0.780 | Rint = 0.021 |
4459 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 2 restraints |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.64 e Å−3 |
3504 reflections | Δρmin = −0.60 e Å−3 |
316 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 0.82244 (5) | 0.185119 (10) | 0.64973 (5) | 0.02248 (15) | |
C1 | 0.8131 (4) | 0.25886 (9) | 0.4786 (4) | 0.0245 (7) | |
C2 | 0.6213 (4) | 0.24791 (9) | 0.4585 (4) | 0.0244 (7) | |
C3 | 0.4735 (5) | 0.27022 (10) | 0.3964 (5) | 0.0311 (8) | |
H3A | 0.4856 | 0.2952 | 0.3690 | 0.037* | |
C4 | 0.3081 (5) | 0.25400 (11) | 0.3767 (5) | 0.0386 (9) | |
H4A | 0.1971 | 0.2678 | 0.3336 | 0.046* | |
C5 | 0.2962 (5) | 0.21686 (11) | 0.4191 (5) | 0.0361 (9) | |
H5A | 0.1771 | 0.2058 | 0.3971 | 0.043* | |
C6 | 0.4508 (4) | 0.19662 (9) | 0.4903 (4) | 0.0255 (7) | |
C7 | 0.4676 (5) | 0.15682 (9) | 0.5624 (4) | 0.0278 (7) | |
C8 | 1.1226 (5) | 0.15194 (10) | 0.9717 (5) | 0.0320 (8) | |
H8A | 1.1054 | 0.1726 | 1.0368 | 0.038* | |
C9 | 1.2380 (5) | 0.12336 (11) | 1.0570 (5) | 0.0399 (9) | |
H9A | 1.3003 | 0.1241 | 1.1777 | 0.048* | |
C10 | 1.2557 (5) | 0.09312 (10) | 0.9510 (5) | 0.0368 (9) | |
H10A | 1.3311 | 0.0731 | 1.0051 | 0.044* | |
C11 | 1.1607 (4) | 0.09087 (8) | 0.7554 (4) | 0.0271 (7) | |
C12 | 1.1744 (4) | 0.06117 (9) | 0.6383 (5) | 0.0284 (7) | |
C13 | 1.2856 (5) | 0.00363 (9) | 0.5917 (6) | 0.0360 (9) | |
C14 | 1.3943 (5) | −0.02765 (10) | 0.6627 (6) | 0.0451 (10) | |
H14A | 1.4562 | −0.0296 | 0.7831 | 0.054* | |
C15 | 1.4053 (6) | −0.05583 (11) | 0.5437 (7) | 0.0518 (12) | |
H15A | 1.4778 | −0.0768 | 0.5897 | 0.062* | |
C16 | 1.3118 (6) | −0.05511 (11) | 0.3517 (7) | 0.0515 (11) | |
H16A | 1.3262 | −0.0751 | 0.2818 | 0.062* | |
C17 | 1.2049 (6) | −0.02541 (11) | 0.2768 (7) | 0.0490 (11) | |
H17A | 1.1439 | −0.0243 | 0.1559 | 0.059* | |
C18 | 1.1903 (5) | 0.00476 (10) | 0.3955 (6) | 0.0376 (9) | |
C19 | 1.0778 (4) | 0.06153 (9) | 0.4384 (5) | 0.0281 (7) | |
C20 | 0.9642 (4) | 0.09347 (9) | 0.3624 (5) | 0.0264 (7) | |
C21 | 0.8637 (5) | 0.09625 (11) | 0.1724 (5) | 0.0352 (8) | |
H21A | 0.8718 | 0.0771 | 0.0955 | 0.042* | |
C22 | 0.7602 (5) | 0.12692 (11) | 0.1118 (5) | 0.0374 (9) | |
H22A | 0.6959 | 0.1302 | −0.0075 | 0.045* | |
C23 | 0.7549 (5) | 0.15433 (10) | 0.2423 (5) | 0.0335 (8) | |
H23A | 0.6824 | 0.1755 | 0.2018 | 0.040* | |
C24 | 0.9509 (4) | 0.12229 (9) | 0.4840 (4) | 0.0225 (7) | |
C25 | 1.0507 (4) | 0.12140 (8) | 0.6841 (4) | 0.0231 (7) | |
N1 | 0.6076 (3) | 0.21282 (7) | 0.5092 (4) | 0.0223 (6) | |
N2 | 1.0299 (4) | 0.15092 (7) | 0.7891 (4) | 0.0249 (6) | |
N3 | 0.8472 (4) | 0.15269 (7) | 0.4247 (4) | 0.0257 (6) | |
N4 | 1.2762 (4) | 0.03168 (8) | 0.7101 (4) | 0.0336 (7) | |
N5 | 1.0869 (4) | 0.03420 (8) | 0.3203 (4) | 0.0346 (7) | |
O1 | 0.8402 (3) | 0.28967 (6) | 0.4126 (3) | 0.0339 (6) | |
O2 | 0.9272 (3) | 0.23526 (6) | 0.5597 (3) | 0.0331 (6) | |
O3 | 0.3351 (3) | 0.13674 (7) | 0.5182 (4) | 0.0450 (7) | |
O4 | 0.6220 (3) | 0.14774 (6) | 0.6653 (3) | 0.0308 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0147 (2) | 0.0195 (2) | 0.0307 (3) | 0.00195 (15) | 0.00253 (16) | 0.00072 (17) |
C1 | 0.0215 (15) | 0.0237 (17) | 0.0265 (17) | −0.0029 (13) | 0.0040 (13) | −0.0010 (13) |
C2 | 0.0216 (15) | 0.0234 (16) | 0.0258 (17) | 0.0004 (13) | 0.0032 (13) | 0.0015 (13) |
C3 | 0.0294 (18) | 0.0303 (18) | 0.0299 (18) | 0.0087 (14) | 0.0028 (14) | 0.0055 (15) |
C4 | 0.0206 (17) | 0.049 (2) | 0.041 (2) | 0.0121 (16) | 0.0011 (15) | 0.0025 (18) |
C5 | 0.0156 (15) | 0.049 (2) | 0.039 (2) | 0.0011 (15) | 0.0012 (15) | 0.0007 (18) |
C6 | 0.0182 (15) | 0.0328 (18) | 0.0248 (17) | −0.0023 (13) | 0.0054 (13) | −0.0031 (14) |
C7 | 0.0259 (17) | 0.0322 (18) | 0.0265 (18) | −0.0075 (14) | 0.0097 (14) | −0.0044 (14) |
C8 | 0.0229 (16) | 0.0341 (19) | 0.035 (2) | 0.0070 (14) | 0.0029 (15) | −0.0046 (16) |
C9 | 0.0320 (19) | 0.045 (2) | 0.035 (2) | 0.0091 (17) | −0.0030 (16) | −0.0031 (17) |
C10 | 0.0288 (18) | 0.036 (2) | 0.040 (2) | 0.0139 (15) | 0.0003 (16) | 0.0025 (16) |
C11 | 0.0179 (15) | 0.0280 (17) | 0.0350 (19) | 0.0009 (13) | 0.0071 (13) | 0.0033 (14) |
C12 | 0.0200 (15) | 0.0248 (17) | 0.041 (2) | 0.0000 (13) | 0.0092 (14) | 0.0021 (15) |
C13 | 0.0250 (17) | 0.0231 (17) | 0.063 (3) | 0.0018 (14) | 0.0173 (17) | 0.0001 (17) |
C14 | 0.033 (2) | 0.029 (2) | 0.073 (3) | 0.0073 (16) | 0.015 (2) | 0.0070 (19) |
C15 | 0.035 (2) | 0.024 (2) | 0.100 (4) | 0.0088 (16) | 0.026 (2) | 0.000 (2) |
C16 | 0.041 (2) | 0.027 (2) | 0.091 (4) | 0.0011 (17) | 0.027 (2) | −0.016 (2) |
C17 | 0.038 (2) | 0.037 (2) | 0.072 (3) | 0.0016 (17) | 0.015 (2) | −0.015 (2) |
C18 | 0.0255 (17) | 0.0250 (18) | 0.065 (3) | −0.0012 (14) | 0.0174 (18) | −0.0056 (17) |
C19 | 0.0210 (15) | 0.0222 (16) | 0.041 (2) | −0.0030 (13) | 0.0092 (14) | −0.0017 (15) |
C20 | 0.0195 (15) | 0.0252 (17) | 0.0338 (19) | −0.0013 (13) | 0.0067 (13) | −0.0005 (14) |
C21 | 0.0327 (18) | 0.038 (2) | 0.034 (2) | 0.0022 (15) | 0.0085 (16) | −0.0046 (16) |
C22 | 0.0350 (19) | 0.045 (2) | 0.0269 (19) | 0.0051 (17) | 0.0006 (15) | 0.0015 (16) |
C23 | 0.0302 (18) | 0.034 (2) | 0.034 (2) | 0.0076 (15) | 0.0051 (15) | 0.0085 (16) |
C24 | 0.0148 (14) | 0.0227 (16) | 0.0306 (18) | −0.0001 (12) | 0.0076 (13) | 0.0012 (13) |
C25 | 0.0137 (14) | 0.0232 (16) | 0.0321 (18) | 0.0009 (12) | 0.0060 (13) | −0.0002 (13) |
N1 | 0.0142 (12) | 0.0208 (13) | 0.0304 (14) | −0.0003 (10) | 0.0042 (11) | 0.0006 (11) |
N2 | 0.0178 (13) | 0.0240 (14) | 0.0321 (15) | 0.0012 (10) | 0.0061 (11) | −0.0016 (12) |
N3 | 0.0183 (13) | 0.0247 (14) | 0.0325 (16) | 0.0040 (10) | 0.0049 (11) | 0.0025 (12) |
N4 | 0.0239 (14) | 0.0223 (15) | 0.0536 (19) | 0.0054 (12) | 0.0097 (13) | 0.0025 (13) |
N5 | 0.0265 (15) | 0.0290 (16) | 0.0476 (19) | −0.0003 (12) | 0.0095 (13) | −0.0073 (14) |
O1 | 0.0341 (13) | 0.0257 (12) | 0.0398 (14) | −0.0088 (10) | 0.0074 (11) | 0.0047 (11) |
O2 | 0.0154 (11) | 0.0291 (13) | 0.0519 (16) | −0.0022 (9) | 0.0051 (10) | 0.0078 (11) |
O3 | 0.0286 (13) | 0.0459 (16) | 0.0589 (18) | −0.0196 (12) | 0.0100 (12) | −0.0036 (14) |
O4 | 0.0234 (12) | 0.0260 (12) | 0.0398 (14) | −0.0035 (9) | 0.0043 (11) | 0.0031 (10) |
Geometric parameters (Å, º) top
Ni1—N1 | 1.921 (3) | C11—C12 | 1.432 (4) |
Ni1—N2 | 2.015 (3) | C12—N4 | 1.323 (4) |
Ni1—O4 | 2.021 (2) | C12—C19 | 1.532 (5) |
Ni1—O2 | 2.155 (2) | C13—N4 | 1.388 (5) |
Ni1—N3 | 2.175 (3) | C13—C14 | 1.395 (5) |
Ni1—O1i | 2.233 (2) | C13—C18 | 1.504 (6) |
C1—O2 | 1.231 (4) | C14—C15 | 1.397 (6) |
C1—O1 | 1.261 (4) | C14—H14A | 0.9300 |
C1—C2 | 1.426 (4) | C15—C16 | 1.472 (7) |
C2—C3 | 1.322 (5) | C15—H15A | 0.9300 |
C2—N1 | 1.332 (4) | C16—C17 | 1.352 (6) |
C3—C4 | 1.315 (5) | C16—H16A | 0.9300 |
C3—H3A | 0.9300 | C17—C18 | 1.455 (5) |
C4—C5 | 1.381 (5) | C17—H17A | 0.9300 |
C4—H4A | 0.9300 | C18—N5 | 1.334 (5) |
C5—C6 | 1.327 (5) | C19—N5 | 1.367 (4) |
C5—H5A | 0.9300 | C19—C20 | 1.441 (5) |
C6—N1 | 1.260 (4) | C20—C24 | 1.432 (5) |
C6—C7 | 1.527 (5) | C20—C21 | 1.471 (5) |
C7—O3 | 1.179 (4) | C21—C22 | 1.343 (5) |
C7—O4 | 1.232 (4) | C21—H21A | 0.9300 |
C8—C9 | 1.374 (5) | C22—C23 | 1.432 (5) |
C8—N2 | 1.405 (4) | C22—H22A | 0.9300 |
C8—H8A | 0.9300 | C23—N3 | 1.403 (4) |
C9—C10 | 1.398 (5) | C23—H23A | 0.9300 |
C9—H9A | 0.9300 | C24—N3 | 1.333 (4) |
C10—C11 | 1.501 (5) | C24—C25 | 1.537 (4) |
C10—H10A | 0.9300 | C25—N2 | 1.380 (4) |
C11—C25 | 1.379 (3) | O1—Ni1ii | 2.233 (2) |
| | | |
N1—Ni1—N2 | 173.60 (11) | N4—C13—C18 | 125.1 (3) |
N1—Ni1—O4 | 83.48 (10) | C14—C13—C18 | 118.4 (3) |
N2—Ni1—O4 | 90.72 (10) | C13—C14—C15 | 116.7 (4) |
N1—Ni1—O2 | 72.01 (9) | C13—C14—H14A | 121.7 |
N2—Ni1—O2 | 113.65 (10) | C15—C14—H14A | 121.7 |
O4—Ni1—O2 | 155.40 (9) | C14—C15—C16 | 125.4 (4) |
N1—Ni1—N3 | 93.08 (11) | C14—C15—H15A | 117.3 |
N2—Ni1—N3 | 83.80 (10) | C16—C15—H15A | 117.3 |
O4—Ni1—N3 | 86.07 (10) | C17—C16—C15 | 120.2 (4) |
O2—Ni1—N3 | 93.01 (10) | C17—C16—H16A | 119.9 |
N1—Ni1—O1i | 98.30 (10) | C15—C16—H16A | 119.9 |
N2—Ni1—O1i | 84.69 (10) | C16—C17—C18 | 116.4 (4) |
O4—Ni1—O1i | 93.33 (10) | C16—C17—H17A | 121.8 |
O2—Ni1—O1i | 92.29 (9) | C18—C17—H17A | 121.8 |
N3—Ni1—O1i | 168.47 (9) | N5—C18—C17 | 116.1 (4) |
O2—C1—O1 | 130.6 (3) | N5—C18—C13 | 120.9 (3) |
O2—C1—C2 | 111.8 (3) | C17—C18—C13 | 123.0 (3) |
O1—C1—C2 | 117.7 (3) | N5—C19—C20 | 115.0 (3) |
C3—C2—N1 | 123.8 (3) | N5—C19—C12 | 126.7 (3) |
C3—C2—C1 | 123.6 (3) | C20—C19—C12 | 118.3 (3) |
N1—C2—C1 | 112.6 (3) | C24—C20—C19 | 116.0 (3) |
C4—C3—C2 | 114.1 (3) | C24—C20—C21 | 121.6 (3) |
C4—C3—H3A | 123.0 | C19—C20—C21 | 122.5 (3) |
C2—C3—H3A | 123.0 | C22—C21—C20 | 118.9 (3) |
C3—C4—C5 | 121.2 (3) | C22—C21—H21A | 120.5 |
C3—C4—H4A | 119.4 | C20—C21—H21A | 120.5 |
C5—C4—H4A | 119.4 | C21—C22—C23 | 115.8 (3) |
C6—C5—C4 | 121.5 (3) | C21—C22—H22A | 122.1 |
C6—C5—H5A | 119.3 | C23—C22—H22A | 122.1 |
C4—C5—H5A | 119.3 | N3—C23—C22 | 127.2 (3) |
N1—C6—C5 | 116.0 (3) | N3—C23—H23A | 116.4 |
N1—C6—C7 | 114.5 (3) | C22—C23—H23A | 116.4 |
C5—C6—C7 | 129.4 (3) | N3—C24—C20 | 119.8 (3) |
O3—C7—O4 | 123.9 (3) | N3—C24—C25 | 115.5 (3) |
O3—C7—C6 | 119.3 (3) | C20—C24—C25 | 124.7 (3) |
O4—C7—C6 | 116.9 (3) | C11—C25—N2 | 121.1 (3) |
C9—C8—N2 | 122.0 (3) | C11—C25—C24 | 118.9 (3) |
C9—C8—H8A | 119.0 | N2—C25—C24 | 120.0 (2) |
N2—C8—H8A | 119.0 | C6—N1—C2 | 123.1 (3) |
C8—C9—C10 | 115.8 (3) | C6—N1—Ni1 | 113.6 (2) |
C8—C9—H9A | 122.1 | C2—N1—Ni1 | 122.7 (2) |
C10—C9—H9A | 122.1 | C25—N2—C8 | 122.1 (3) |
C9—C10—C11 | 124.2 (3) | C25—N2—Ni1 | 109.6 (2) |
C9—C10—H10A | 117.9 | C8—N2—Ni1 | 127.5 (2) |
C11—C10—H10A | 117.9 | C24—N3—C23 | 116.8 (3) |
C25—C11—C10 | 114.8 (3) | C24—N3—Ni1 | 108.9 (2) |
C25—C11—C12 | 118.0 (3) | C23—N3—Ni1 | 133.3 (2) |
C10—C11—C12 | 127.3 (3) | C12—N4—C13 | 115.0 (3) |
N4—C12—C11 | 117.0 (3) | C18—N5—C19 | 113.4 (3) |
N4—C12—C19 | 118.9 (3) | C1—O1—Ni1ii | 139.9 (2) |
C11—C12—C19 | 124.1 (3) | C1—O2—Ni1 | 119.3 (2) |
N4—C13—C14 | 116.5 (4) | C7—O4—Ni1 | 109.4 (2) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O2iii | 0.93 | 2.48 | 3.190 (4) | 134 |
C22—H22A···O4iv | 0.93 | 2.56 | 3.456 (4) | 162 |
Symmetry codes: (iii) x−1, −y+1/2, z−1/2; (iv) x, y, z−1. |
Experimental details
Crystal data |
Chemical formula | [Ni(C7H3NO4)(C18H10N4)] |
Mr | 506.11 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.3482 (11), 35.825 (4), 7.8986 (12) |
β (°) | 106.906 (12) |
V (Å3) | 1989.4 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.37 × 0.32 × 0.26 |
|
Data collection |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan '(SADABS; Sheldrick, 1996)' |
Tmin, Tmax | 0.704, 0.780 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4459, 3504, 2860 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.111, 1.08 |
No. of reflections | 3504 |
No. of parameters | 316 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.64, −0.60 |
Selected geometric parameters (Å, º) topNi1—N1 | 1.921 (3) | Ni1—O2 | 2.155 (2) |
Ni1—N2 | 2.015 (3) | Ni1—N3 | 2.175 (3) |
Ni1—O4 | 2.021 (2) | Ni1—O1i | 2.233 (2) |
| | | |
N1—Ni1—N2 | 173.60 (11) | N2—Ni1—O2 | 113.65 (10) |
N1—Ni1—O4 | 83.48 (10) | O4—Ni1—O2 | 155.40 (9) |
N2—Ni1—O4 | 90.72 (10) | O2—Ni1—O1i | 92.29 (9) |
N1—Ni1—O2 | 72.01 (9) | | |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O2ii | 0.9300 | 2.4800 | 3.190 (4) | 134.00 |
C22—H22A···O4iii | 0.9300 | 2.5600 | 3.456 (4) | 162.00 |
Symmetry codes: (ii) x−1, −y+1/2, z−1/2; (iii) x, y, z−1. |
π-π stacking parameters for the title compound topCg···Cg is the distance between ring centroids (Å);
CgI_Perp is the perpendicular distance of CgI from ring J (Å);
CgJ_Perp is the perpendicular distance of CgJ on ring I (Å);
Slippage is the distance between CgI and the erpendicular projection of CgJ on
ring I (Å).
Cg7 is the centroid of the N4/C12/C19/N5/C18/C13 plane,
Cg8 is the centroid of the C11/C12/C19/C20/C24/C25 plane
and
Cg9 is the centroid of the C13–C18 plane. |
CgI, CgJ | CgI···CgJ | CgI_Perp | CgJ_Perp | Slippage |
Cg7, Cg7iv | 3.5102 (18) | 3.294 | 3.294 | 1.14 |
Cg7, Cg9iv | 3.574 (2) | 3.290 | 3.304 | 1.29 |
Cg8, Cg9iv | 3.509 (2) | 3.294 | 3.298 | 1.14 |
Cg9, Cg9v | 3.410 (2) | 3.256 | 3.256 | 0.97 |
Symmetry codes: (iv) 2-x, -y, 1-z; (v) 3-x, -y, 1-z. |
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In the past decade, the technology of design and synthesis of inorganic-organic coordination polymers has been developed very quickly because there has been much interest in their intriguing topologies and fascinating applications as functional materials (Moulton & Zaworotko, 2001; Eddaoudi et al., 2001; Tong et al., 2003; Zhang et al., 2004; Seo et al., 2000; Tao et al., 2000). Many networks with various structural motifs, including honeycomb, brick wall, rectangular grid, bilayer, ladder, herringbone, diamondoid and octahedral geometries, have been documented (Hayashi et al., 1991; Gable et al., 1990; Fujita et al.,1994; Kondo et al., 1997; Losier & Zaworotko, 1996; Withersby et al., 1999; Yaghi & Li, 1995; Soma et al., 1994). Recently, building blocks with heterocyclic carboxylic acids such as pyridine-, pyrazole- and imidazolecarboxylic acids have been used in the construction of coordination polymers (Tong et al., 2005; Zhao et al., 2005; Pan et al., 2001; Lu et al., 2006; Han et al., 2006). Among them, 2,6-dipicolinate is an important ligand for transition metal complexes owing to its having versatile bidentate, tridentate or bridging coordination modes, applications to diverse areas of technology, and the capacity to stabilize unusual oxidation states (Ma et al., 2003; Scapin et al., 1997; Pocker & Fong, 1980).
With the intention of studying the influences of the size of the aromatic chelate ligands on the framework structure of the [M/pydc/L] system (M is a transition metal, pydc is 2,6-dipicolinate and L is a chelating ligand), we choose the planar aromatic chelate dipyrido[3,2 - a:2',3'-c]phenazine as a second ligand (Han, Cheng & Chen, 2005), and a new coordination polymer, [Ni(pydc)(DPPZ)]n, (I) (DPPZ is dipyrido[3,2 - a:2',3'-c]phenazine) was successfully synthesized. The coordination environment of the nickel center in complex (I) is shown in Fig. 1. The six atoms around the nickel center form a distorted octahedron. The O,N,O-tridentate chelation of the pydc ligand and the bidentate chelation of the DPPZ ligand have an important effect on the distorted octahedron. Each NiII ion is six-coordinated by three N atoms and three O atoms from a chelating DPPZ ligand and two different pydc ligands (Table 1), so the Ni center is octahedral with a mer arrangement (three N and three O atoms in two perpendicular planes).
The pydc ligand adopts O,N,O-tridentate chelating and monodentate bridging coordination modes to link two adjacent NiII centers to form a one-dimensional chain, in which the 2-carboxyl group of the pydc ligand bridges two adjacent NiII centers in an anti–anti coordination mode, with the DPPZ ligands pointing away from the chain like wings, as shown in Fig. 2, forming a roof-like arrangement. The conformation of the chain is severely puckered, with an Ni···Ni···Ni angle between adjacent metal centres of 80.72 (7)°. The pydc ligands within the chain give a dihedral angle of 32.8 (3)° and the minimum distance observed between two adjacent pyridine rings centroids is 4.131 (2) Å (Streb et al., 2007).
The lateral DPPZ ligands from adjacent chains are paired to furnish π–π stacking interactions (Han, Cheng, Li & Chen, 2005; Han et al., 2007) and the data are listed in Table 3. π–π stacking is observed between two phenazine rings of the DPPZ ligands with perpendicular separation of 3.338 Å, a centroid-to-centroid distance of 3.510 Å and a slip angle (the angle between the centroid vector normal to the plane) of 18.38° [are s.u. values available?]. These values are typical for aromatic π–π stacking interactions (Hunter, 1994). Atom O3 of the pydc ligand also has weak interactions with a DPPZ aromatic ring [C11/C12/C19/C20/C24/C25 at (x - 1, y, z)] of an adjacent chain [the O3 atom–ring centroid distance is ca 2.662 (2) Å]. Adjacent chains are further linked via hydrogen bonds and π–π stacking interactions to construct a three-dimensional supramolecular network (Tables 2 and 3). These weak interactions enhance the stability of the complex.
In the [M/pydc/L] system, the similar complexes [Cu(pydc)(2,2'-bipyridine)] (Bresciain-Pahor et al., 1985), [Mn(pydc)(1,10-phenanthroline)] (Ma et al., 2002) and [Co(pydc)(1,10-phenanthroline)] (Yin & Jiang, 2001) have been reported before. These complexes have simple discrete structures. In this paper, the remarked feature of (I) is that the title complex has a rooflike chain. To the best of our knowledge, this type of rooflike chain has not been reported so far.