Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112006051/em3046sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112006051/em3046Isup2.hkl |
CCDC reference: 879429
A mixture of Zn(NO3)2.6H2O (60 mg, 0.2 mmol), H2mspda (59 mg, 0.2 mmol), imidazole (14 mg, 0.2 mmol), Et3N (0.02 ml) and dimethylformamide (10 ml) was sealed in a 25 ml Teflon-lined stainless steel reactor and directly heated to 413 K for 2 d, then cooled to room temperature. The crystals were washed with methanol to yield 20 mg of (I) (yield ~25% based on the H2mspda ligand).
The methyl H atoms were constrained to an ideal geometry, with C—H = 0.96 Å and with Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely. Other H atoms attached to C atoms were refined using a riding model, with C—H = 0.93 Å (CH) and Uiso(H) = 1.2Ueq(parent atom). The N-bound H atom was freely refined.
Data collection: APEX2 (Bruker, 2010); cell refinement: APEX2 (Bruker, 2010); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).
[Zn(C17H13NO4)(C2H7N)] | Z = 2 |
Mr = 405.76 | F(000) = 420 |
Triclinic, P1 | Dx = 1.434 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.134 (2) Å | Cell parameters from 1490 reflections |
b = 9.694 (2) Å | θ = 2.7–23.1° |
c = 11.735 (3) Å | µ = 1.33 mm−1 |
α = 80.602 (4)° | T = 298 K |
β = 87.611 (4)° | Block, orange |
γ = 66.518 (4)° | 0.28 × 0.25 × 0.22 mm |
V = 939.9 (4) Å3 |
Bruker APEXII CCD area-detector diffractometer | 3295 independent reflections |
Radiation source: fine-focus sealed tube | 2691 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→10 |
Tmin = 0.707, Tmax = 0.758 | k = −9→11 |
5025 measured reflections | l = −13→12 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.0029P] where P = (Fo2 + 2Fc2)/3 |
3295 reflections | (Δ/σ)max = 0.002 |
243 parameters | Δρmax = 0.32 e Å−3 |
1 restraint | Δρmin = −0.31 e Å−3 |
[Zn(C17H13NO4)(C2H7N)] | γ = 66.518 (4)° |
Mr = 405.76 | V = 939.9 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.134 (2) Å | Mo Kα radiation |
b = 9.694 (2) Å | µ = 1.33 mm−1 |
c = 11.735 (3) Å | T = 298 K |
α = 80.602 (4)° | 0.28 × 0.25 × 0.22 mm |
β = 87.611 (4)° |
Bruker APEXII CCD area-detector diffractometer | 3295 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2691 reflections with I > 2σ(I) |
Tmin = 0.707, Tmax = 0.758 | Rint = 0.021 |
5025 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 1 restraint |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.32 e Å−3 |
3295 reflections | Δρmin = −0.31 e Å−3 |
243 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.18549 (4) | 0.30228 (4) | 0.53051 (3) | 0.03462 (14) | |
O1 | 0.3329 (2) | 0.3717 (2) | 0.4424 (2) | 0.0469 (6) | |
O2 | 0.4374 (3) | 0.1398 (2) | 0.3973 (2) | 0.0484 (6) | |
O3 | 0.0213 (2) | 0.2818 (2) | 0.44043 (19) | 0.0428 (5) | |
O4 | 0.0823 (2) | 0.4697 (2) | 0.62438 (18) | 0.0395 (5) | |
N1 | 0.6595 (3) | 0.3871 (3) | 0.1472 (2) | 0.0404 (6) | |
N2 | 0.2617 (3) | 0.1183 (3) | 0.6545 (2) | 0.0424 (7) | |
H2 | 0.340 (3) | 0.051 (3) | 0.628 (3) | 0.056 (11)* | |
C1 | 0.4359 (3) | 0.2687 (3) | 0.3939 (3) | 0.0347 (7) | |
C2 | 0.5617 (3) | 0.3120 (3) | 0.3293 (3) | 0.0309 (7) | |
C3 | 0.5544 (4) | 0.3429 (3) | 0.2087 (3) | 0.0356 (7) | |
C4 | 0.4256 (4) | 0.3313 (4) | 0.1402 (3) | 0.0557 (10) | |
H4A | 0.4263 | 0.3773 | 0.0614 | 0.084* | |
H4B | 0.3237 | 0.3833 | 0.1723 | 0.084* | |
H4C | 0.4445 | 0.2260 | 0.1431 | 0.084* | |
C5 | 0.7741 (4) | 0.4051 (3) | 0.2036 (3) | 0.0349 (7) | |
C6 | 0.8874 (4) | 0.4544 (4) | 0.1275 (3) | 0.0568 (10) | |
H6A | 0.9094 | 0.4044 | 0.0607 | 0.085* | |
H6B | 0.9852 | 0.4273 | 0.1699 | 0.085* | |
H6C | 0.8398 | 0.5627 | 0.1035 | 0.085* | |
C7 | 0.7876 (3) | 0.3787 (3) | 0.3238 (2) | 0.0290 (6) | |
C8 | 0.6815 (3) | 0.3277 (3) | 0.3890 (3) | 0.0308 (7) | |
C9 | 0.6987 (3) | 0.2934 (3) | 0.5161 (3) | 0.0371 (7) | |
H9 | 0.7097 | 0.3673 | 0.5524 | 0.045* | |
C10 | 0.7005 (4) | 0.1702 (4) | 0.5844 (3) | 0.0427 (8) | |
H10 | 0.6852 | 0.0968 | 0.5501 | 0.051* | |
C11 | 0.7248 (4) | 0.1402 (4) | 0.7107 (3) | 0.0436 (8) | |
C12 | 0.6999 (5) | 0.2556 (4) | 0.7737 (3) | 0.0614 (11) | |
H12 | 0.6629 | 0.3559 | 0.7362 | 0.074* | |
C13 | 0.7288 (6) | 0.2248 (6) | 0.8909 (4) | 0.0839 (14) | |
H13 | 0.7136 | 0.3037 | 0.9318 | 0.101* | |
C14 | 0.7795 (6) | 0.0797 (6) | 0.9468 (4) | 0.0905 (15) | |
H14 | 0.7988 | 0.0594 | 1.0262 | 0.109* | |
C15 | 0.8026 (6) | −0.0374 (6) | 0.8876 (4) | 0.0916 (16) | |
H15 | 0.8371 | −0.1371 | 0.9263 | 0.110* | |
C16 | 0.7739 (5) | −0.0056 (4) | 0.7694 (3) | 0.0645 (11) | |
H16 | 0.7884 | −0.0848 | 0.7290 | 0.077* | |
C17 | −0.0831 (3) | 0.3990 (3) | 0.3845 (3) | 0.0331 (7) | |
C18 | 0.3220 (5) | 0.1458 (5) | 0.7596 (4) | 0.0737 (12) | |
H18A | 0.2358 | 0.2189 | 0.7952 | 0.111* | |
H18B | 0.4031 | 0.1844 | 0.7393 | 0.111* | |
H18C | 0.3664 | 0.0520 | 0.8127 | 0.111* | |
C19 | 0.1382 (4) | 0.0566 (4) | 0.6850 (4) | 0.0647 (11) | |
H19A | 0.1822 | −0.0350 | 0.7404 | 0.097* | |
H19B | 0.1033 | 0.0343 | 0.6168 | 0.097* | |
H19C | 0.0490 | 0.1305 | 0.7176 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0309 (2) | 0.0362 (2) | 0.0394 (2) | −0.01660 (15) | −0.00111 (15) | −0.00423 (16) |
O1 | 0.0388 (13) | 0.0425 (13) | 0.0642 (16) | −0.0209 (10) | 0.0182 (12) | −0.0139 (12) |
O2 | 0.0492 (14) | 0.0432 (13) | 0.0621 (16) | −0.0276 (11) | 0.0091 (12) | −0.0112 (12) |
O3 | 0.0377 (12) | 0.0412 (12) | 0.0512 (14) | −0.0180 (10) | −0.0115 (11) | −0.0021 (11) |
O4 | 0.0475 (13) | 0.0400 (12) | 0.0403 (13) | −0.0264 (10) | 0.0059 (10) | −0.0094 (10) |
N1 | 0.0432 (16) | 0.0530 (16) | 0.0279 (15) | −0.0228 (13) | −0.0016 (12) | −0.0037 (13) |
N2 | 0.0341 (15) | 0.0390 (16) | 0.0481 (18) | −0.0093 (12) | 0.0034 (13) | −0.0049 (14) |
C1 | 0.0292 (16) | 0.0431 (18) | 0.0331 (18) | −0.0165 (14) | −0.0057 (14) | −0.0026 (15) |
C2 | 0.0307 (16) | 0.0320 (15) | 0.0316 (17) | −0.0133 (13) | 0.0018 (13) | −0.0074 (13) |
C3 | 0.0381 (17) | 0.0391 (17) | 0.0294 (17) | −0.0155 (14) | −0.0062 (14) | −0.0025 (14) |
C4 | 0.056 (2) | 0.078 (3) | 0.044 (2) | −0.039 (2) | −0.0114 (18) | −0.0007 (19) |
C5 | 0.0359 (17) | 0.0399 (17) | 0.0304 (18) | −0.0167 (14) | 0.0044 (14) | −0.0064 (14) |
C6 | 0.060 (2) | 0.088 (3) | 0.036 (2) | −0.045 (2) | 0.0130 (18) | −0.010 (2) |
C7 | 0.0284 (15) | 0.0328 (15) | 0.0263 (16) | −0.0123 (12) | 0.0013 (12) | −0.0056 (13) |
C8 | 0.0337 (16) | 0.0304 (15) | 0.0302 (17) | −0.0142 (13) | 0.0024 (13) | −0.0065 (13) |
C9 | 0.0433 (18) | 0.0432 (18) | 0.0326 (18) | −0.0242 (15) | 0.0058 (14) | −0.0099 (15) |
C10 | 0.048 (2) | 0.047 (2) | 0.0386 (19) | −0.0232 (16) | −0.0001 (16) | −0.0095 (16) |
C11 | 0.049 (2) | 0.050 (2) | 0.037 (2) | −0.0255 (16) | 0.0025 (16) | −0.0047 (16) |
C12 | 0.084 (3) | 0.057 (2) | 0.041 (2) | −0.025 (2) | 0.006 (2) | −0.0125 (19) |
C13 | 0.132 (4) | 0.087 (3) | 0.041 (3) | −0.050 (3) | 0.008 (3) | −0.017 (2) |
C14 | 0.124 (4) | 0.104 (4) | 0.040 (3) | −0.044 (3) | −0.005 (3) | −0.004 (3) |
C15 | 0.137 (5) | 0.078 (3) | 0.051 (3) | −0.038 (3) | −0.016 (3) | 0.007 (3) |
C16 | 0.092 (3) | 0.054 (2) | 0.049 (2) | −0.032 (2) | −0.004 (2) | −0.002 (2) |
C17 | 0.0299 (16) | 0.0465 (19) | 0.0275 (17) | −0.0197 (15) | 0.0109 (13) | −0.0092 (15) |
C18 | 0.075 (3) | 0.077 (3) | 0.060 (3) | −0.025 (2) | −0.021 (2) | 0.005 (2) |
C19 | 0.061 (2) | 0.059 (2) | 0.074 (3) | −0.030 (2) | 0.007 (2) | 0.004 (2) |
Zn1—O1 | 1.927 (2) | C10—H10 | 0.9300 |
Zn1—O3 | 1.961 (2) | C11—C16 | 1.369 (4) |
Zn1—O4 | 2.004 (2) | C11—C12 | 1.379 (4) |
Zn1—N2 | 2.008 (3) | C9—H9 | 0.9300 |
O2—C1 | 1.238 (3) | C16—C15 | 1.383 (6) |
O3—C17 | 1.255 (4) | C16—H16 | 0.9300 |
O4—C17i | 1.263 (3) | C6—H6A | 0.9600 |
O1—C1 | 1.265 (3) | C6—H6B | 0.9600 |
N1—C3 | 1.340 (4) | C6—H6C | 0.9600 |
N1—C5 | 1.344 (4) | C14—C15 | 1.367 (6) |
C1—C2 | 1.509 (4) | C14—H14 | 0.9300 |
C2—C8 | 1.394 (4) | C15—H15 | 0.9300 |
C2—C3 | 1.396 (4) | C4—H4A | 0.9600 |
C8—C7 | 1.402 (4) | C4—H4B | 0.9600 |
C8—C9 | 1.475 (4) | C4—H4C | 0.9600 |
C17—O4i | 1.263 (3) | C12—H12 | 0.9300 |
C17—C7ii | 1.497 (4) | N2—C18 | 1.476 (5) |
C7—C5 | 1.394 (4) | N2—C19 | 1.480 (4) |
C7—C17iii | 1.497 (4) | N2—H2 | 0.841 (18) |
C5—C6 | 1.508 (4) | C19—H19A | 0.9600 |
C3—C4 | 1.502 (4) | C19—H19B | 0.9600 |
C13—C14 | 1.352 (6) | C19—H19C | 0.9600 |
C13—C12 | 1.372 (6) | C18—H18A | 0.9600 |
C13—H13 | 0.9300 | C18—H18B | 0.9600 |
C10—C9 | 1.320 (4) | C18—H18C | 0.9600 |
C10—C11 | 1.472 (5) | ||
O1—Zn1—O3 | 115.82 (10) | C11—C16—C15 | 121.3 (4) |
O1—Zn1—O4 | 101.18 (8) | C11—C16—H16 | 119.3 |
O3—Zn1—O4 | 109.50 (9) | C15—C16—H16 | 119.3 |
O1—Zn1—N2 | 121.58 (10) | C5—C6—H6A | 109.5 |
O3—Zn1—N2 | 105.88 (10) | C5—C6—H6B | 109.5 |
O4—Zn1—N2 | 101.31 (10) | H6A—C6—H6B | 109.5 |
C17—O3—Zn1 | 119.2 (2) | C5—C6—H6C | 109.5 |
C17i—O4—Zn1 | 131.48 (18) | H6A—C6—H6C | 109.5 |
C1—O1—Zn1 | 112.53 (18) | H6B—C6—H6C | 109.5 |
C3—N1—C5 | 118.8 (3) | C13—C14—C15 | 120.6 (4) |
O2—C1—O1 | 124.0 (3) | C13—C14—H14 | 119.7 |
O2—C1—C2 | 120.6 (3) | C15—C14—H14 | 119.7 |
O1—C1—C2 | 115.5 (2) | C14—C15—C16 | 119.1 (4) |
C8—C2—C3 | 119.6 (3) | C14—C15—H15 | 120.5 |
C8—C2—C1 | 120.6 (3) | C16—C15—H15 | 120.5 |
C3—C2—C1 | 119.8 (3) | C3—C4—H4A | 109.5 |
C2—C8—C7 | 117.5 (3) | C3—C4—H4B | 109.5 |
C2—C8—C9 | 122.5 (3) | H4A—C4—H4B | 109.5 |
C7—C8—C9 | 120.0 (3) | C3—C4—H4C | 109.5 |
O3—C17—O4i | 123.5 (3) | H4A—C4—H4C | 109.5 |
O3—C17—C7ii | 117.2 (3) | H4B—C4—H4C | 109.5 |
O4i—C17—C7ii | 119.3 (3) | C13—C12—C11 | 121.1 (4) |
C5—C7—C8 | 119.5 (3) | C13—C12—H12 | 119.4 |
C5—C7—C17iii | 121.1 (2) | C11—C12—H12 | 119.4 |
C8—C7—C17iii | 119.3 (3) | C18—N2—C19 | 109.9 (3) |
N1—C5—C7 | 122.2 (3) | C18—N2—Zn1 | 113.0 (2) |
N1—C5—C6 | 115.2 (3) | C19—N2—Zn1 | 112.4 (2) |
C7—C5—C6 | 122.6 (3) | C18—N2—H2 | 106 (2) |
N1—C3—C2 | 122.3 (3) | C19—N2—H2 | 108 (2) |
N1—C3—C4 | 115.9 (3) | Zn1—N2—H2 | 107 (2) |
C2—C3—C4 | 121.8 (3) | N2—C19—H19A | 109.5 |
C14—C13—C12 | 120.0 (4) | N2—C19—H19B | 109.5 |
C14—C13—H13 | 120.0 | H19A—C19—H19B | 109.5 |
C12—C13—H13 | 120.0 | N2—C19—H19C | 109.5 |
C9—C10—C11 | 125.0 (3) | H19A—C19—H19C | 109.5 |
C9—C10—H10 | 117.5 | H19B—C19—H19C | 109.5 |
C11—C10—H10 | 117.5 | N2—C18—H18A | 109.5 |
C16—C11—C12 | 117.8 (3) | N2—C18—H18B | 109.5 |
C16—C11—C10 | 120.2 (3) | H18A—C18—H18B | 109.5 |
C12—C11—C10 | 121.9 (3) | N2—C18—H18C | 109.5 |
C10—C9—C8 | 127.7 (3) | H18A—C18—H18C | 109.5 |
C10—C9—H9 | 116.2 | H18B—C18—H18C | 109.5 |
C8—C9—H9 | 116.2 | ||
O1—Zn1—O3—C17 | −66.1 (2) | C17iii—C7—C5—N1 | 179.7 (3) |
O4—Zn1—O3—C17 | 47.4 (2) | C8—C7—C5—C6 | −177.6 (3) |
N2—Zn1—O3—C17 | 155.9 (2) | C17iii—C7—C5—C6 | 0.3 (4) |
O1—Zn1—O4—C17i | 13.4 (3) | C5—N1—C3—C2 | −1.3 (4) |
O3—Zn1—O4—C17i | −109.3 (3) | C5—N1—C3—C4 | 177.5 (3) |
N2—Zn1—O4—C17i | 139.2 (3) | C8—C2—C3—N1 | 0.2 (4) |
O3—Zn1—O1—C1 | −75.7 (2) | C1—C2—C3—N1 | 177.6 (3) |
O4—Zn1—O1—C1 | 166.0 (2) | C8—C2—C3—C4 | −178.6 (3) |
N2—Zn1—O1—C1 | 55.2 (2) | C1—C2—C3—C4 | −1.2 (4) |
Zn1—O1—C1—O2 | 3.6 (4) | C9—C10—C11—C16 | −159.5 (3) |
Zn1—O1—C1—C2 | −176.4 (2) | C9—C10—C11—C12 | 20.3 (5) |
O2—C1—C2—C8 | −107.5 (3) | C11—C10—C9—C8 | 177.3 (3) |
O1—C1—C2—C8 | 72.5 (4) | C2—C8—C9—C10 | 49.1 (5) |
O2—C1—C2—C3 | 75.2 (4) | C7—C8—C9—C10 | −131.2 (3) |
O1—C1—C2—C3 | −104.8 (3) | C12—C11—C16—C15 | −1.9 (6) |
C3—C2—C8—C7 | 1.8 (4) | C10—C11—C16—C15 | 177.9 (4) |
C1—C2—C8—C7 | −175.5 (2) | C12—C13—C14—C15 | 0.1 (8) |
C3—C2—C8—C9 | −178.5 (3) | C13—C14—C15—C16 | 0.2 (8) |
C1—C2—C8—C9 | 4.2 (4) | C11—C16—C15—C14 | 0.7 (8) |
Zn1—O3—C17—O4i | 5.4 (4) | C14—C13—C12—C11 | −1.4 (7) |
Zn1—O3—C17—C7ii | −175.88 (17) | C16—C11—C12—C13 | 2.2 (6) |
C2—C8—C7—C5 | −2.8 (4) | C10—C11—C12—C13 | −177.6 (4) |
C9—C8—C7—C5 | 177.5 (3) | O1—Zn1—N2—C18 | 72.9 (3) |
C2—C8—C7—C17iii | 179.3 (2) | O3—Zn1—N2—C18 | −152.1 (2) |
C9—C8—C7—C17iii | −0.5 (4) | O4—Zn1—N2—C18 | −37.9 (3) |
C3—N1—C5—C7 | 0.3 (4) | O1—Zn1—N2—C19 | −161.9 (2) |
C3—N1—C5—C6 | 179.7 (3) | O3—Zn1—N2—C19 | −26.9 (3) |
C8—C7—C5—N1 | 1.8 (4) | O4—Zn1—N2—C19 | 87.3 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y, z; (iii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2iv | 0.84 (2) | 2.19 (2) | 3.010 (3) | 167 (3) |
C9—H9···O1v | 0.93 | 2.41 | 3.258 (4) | 151 |
Symmetry codes: (iv) −x+1, −y, −z+1; (v) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C17H13NO4)(C2H7N)] |
Mr | 405.76 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 9.134 (2), 9.694 (2), 11.735 (3) |
α, β, γ (°) | 80.602 (4), 87.611 (4), 66.518 (4) |
V (Å3) | 939.9 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.33 |
Crystal size (mm) | 0.28 × 0.25 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.707, 0.758 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5025, 3295, 2691 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.091, 1.07 |
No. of reflections | 3295 |
No. of parameters | 243 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.31 |
Computer programs: APEX2 (Bruker, 2010), SAINT-Plus (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2008) and ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).
Zn1—O1 | 1.927 (2) | Zn1—O4 | 2.004 (2) |
Zn1—O3 | 1.961 (2) | Zn1—N2 | 2.008 (3) |
C2—C8—C9—C10 | 49.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2i | 0.841 (18) | 2.19 (2) | 3.010 (3) | 167 (3) |
C9—H9···O1ii | 0.93 | 2.41 | 3.258 (4) | 151.2 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
The construction of metal–organic coordination polymers has attracted intense attention, owing to their intriguing network topologies and useful properties (gas storage, catalysis, photosensitivity, molecular recognition etc.), which are intimately related to their structures (Yaghi et al., 2003; O'Keeffe et al., 2008; Ockwig et al., 2005). Helices and atropisomeric units in metal complexes are two of the main aspects in the study of structural isomerism and, compared with the former, the latter has not been well explored (Kesanli & Lin, 2003; Han & Hong, 2005). For the structural construction of metal complexes, besides coordination bonds, secondary forces such as hydrogen-bonding and π–π stacking must also be considered.
Compared with common pyridine dicarboxylic acids (PDAs), highly substituted PDAs have not been effectively utilized in the construction of supramolecular polymers (Huang, He, Liang et al., 2007). In our previous work, 2,6-dimethyl-4-(2-thiophenyl)pyridine-3,5-dicarboxylate, 2,6-dimethyl-4-phenylpyridine-3,5-dicarboxylate and 2,6-dimethyl-4-(4-pyridinyl)pyridine-3,5-dicarboxylate were employed in the construction of luminescent metal compounds (Huang, He, Wang et al., 2007). Only a few reports exist of coordination polymers related to (E)-2,6-dimethyl-4-styrylpyridine-3,5-dicarboxylic acid (H2mspda) (Zhang et al., 2011; Huang et al., 2010). In this work, we report a new photoluminescent complex, poly[(dimethylamine-κN)[µ3-(E)-2,6-dimethyl-4-styrylpyridine-3,5-dicarboxylato]zinc(II)], (I), with a helical motif, assembled by distinct chiral units from an axially prochiral ligand through C—H···O hydrogen bonds.
The asymmetric unit of (I) contains one crystallographically independent ZnII cation, one mspda2- ligand and one coordinated dimethylamine molecule (Fig. 1). The N—H bond of the dimethylamine is confirmed by a characteristic peak (3176 cm-1) in the FT–IR spectrum of (I). It should be noted that the hydrolysis of dimethylformamide is observed in the formation of (I). Similar cases have also been discovered in some anionic metal–organic frameworks with aromatic polycarboxylates (Rosi et al., 2005; Chen et al., 2003). The geometry around atom Zn1 is a distorted tetrahedron (ZnNO3), with the four binding sites occupied by three O atoms (O1, O3 and O4) from three equivalent mspda2- ligands and one N atom (N2) from the coordinated dimethylamine molecule. All the Zn—O and Zn—N bond lengths are in agreement with those reported in other ZnII complexes of N,O-mixed ligands (Wang et al., 2007).
As shown in Fig. 1, the mspda2- anion serves as an exo-tridenate ligand and bridges three Zn atoms through atoms O1, O3 and O4, leaving the uncoordinated carboxylate O atom involved in an N2—H···O2i hydrogen bond [symmetry code: (i) x + 1, y, z]. The Zn···Zn separations over the mspda2- bridge are 8.0331 (14) and 9.134 (2) Å. The C9—C10 bond of 1.320 (4) Å is assigned as a C═C double bond, with the mspda2- ligand displaying a trans conformation (E). The C6H5—CH═CH dihedral angle in mspda2- is 19.76 (14)°, and that between the pyridine and phenyl rings is 68.03 (14)°. Thus, the pyridine and phenyl rings in the mspda2- ligand are not coplanar, with the major twist occuring about the C8—C9 bond (Table 1).
It is interesting that S- and R-type chiral units co-exist in the structure of (I) (Fig. 2). In the mspda2- ligand, according to the Cahn–Ingold–Prelog sequence rule (Cahn et al., 1966), atom C10 has priority over atom H9, and the two carboxylate (CO2-) groups may exist in different chemical environments within the metal complex. Thus, the mspda2- ligand is an axially prochiral ligand. In the structure of (I), one CO2- group (denoted as C17i) of the mspda2- anion is coordinated to two Zn2+ centres while the other (C1) is coordinated to only one Zn2+ centre, and thus atom C17i has priority over atom C1. In crystal engineering, C—H···O contacts are electrostatic and they occur within certain distance (C—H···O = 3.0–4.0 Å) and angle (C—H···O = 90–180°) ranges (Desiraju, 1991; Taylor & Kennard, 1982). Therefore, we believe that there are reliable C—H···O in (I) interactions because of the C9—H9···O1ii angle and the short C9···O1ii distance [Table 1; symmetry code: (ii) -x + 1, -y + 1, -z + 1]. The rotation of C6H5—CH═CH around the aryl-carbon bond (C8—C9) controls the C—H···O hydrogen bonds to a certain degree. Thus, there are two types of chiral units (S and R) that co-exist in the same crystal lattice (Fig. 3).
Another interesting feature is the presence of P- and M-type helical chains comprising the S- and R-chiral units separately. It should be emphasized that the R-chiral units assemble a left-handed (M) Zn–mspda2- helical chain with a helical pitch of 9.134 Å, while the right-handed (P) Zn–mspda2- helical chain is constructed from the connection of neighbouring S-chiral units (Fig. 3). Thus, the P- and M-type helices assembled by distinct separate S- and R-chiral units are interlinked by atoms O4 to form a one-dimensional ladder. To our knowledge, such an arrangement of helical chains has rarely been reported among Zn frameworks (Yashima et al., 2008; Bishop, 2008).
The configuration of the chiral units in (I) is similar to those of atropisomeric [M(Hsmpdc)2(H2O)4].6H2O, (II) [smpdc is 2,6-dimethyl-4-(thiophen-2-yl)pyridine-3,5-dicarboxylate, M = ?; Huang, He, Liang et al., 2007), [M(H-mpypdc)(Cl)(H2O)3]n, (III) [mpypdc is 2,6-dimethyl-4-(pyridin-4-yl)pyridine-3,5-dicarboxylate, M = ?; Huang & Hu, 2007] and {Cd3(phen)3(HL)2(H2O)2.4.25H2O}n, (IV) [H4L = p-terphenyl-type 4,4'-(1,4-phenylene)bis(2,6-dimethyl-3,5-pyridine-dicarboxylic acid); Huang et al., 2009]. However, the structure of (I) is quite different from these structures. For example, (II) has an interesting hydrogen-bonded M2+(H2O)8 ionic cluster, which links the Hsmpdc ligands into a one-dimensional supramolecular motif. Compound (III) displays wave-like motifs generated from the Hmpypdc ligands. The R- and S-components composed of [M(Hmpypdc)] are arranged alternately [Please check rephrasing] in the one-dimensional coordination polymer. In complex (IV), the T-type secondary building units construct independent one-dimensional metal–organic nanotubes (MONTs) with 63 topology, containing distinct axially asymmetric [R-Cd3(HL) and S-Cd3(HL)] subunits. In (I), the construction of atropisomeric type units from axially prochiral ligands through hydrogen bonds is the major feature of interest.
Interchain hydrogen bonds between the coordinated dimethylamine molecules and mspda2- ligands [N2···O2iii; symmetry code: (i) -x + 1, -y, -z + 1] extend the one-dimensional ladders of (I) into a two-dimensional supramolecular architecture (Fig. 4).
The photoluminescent emission maximum of free H2mspda was observed at 496 nm (em). The emission spectra of (I) in the solid state at room temperature are shown in Fig. 5. Excitation at 365 nm leads to a broad fluorescent emission band at 432 nm. The distinct maximum emission wavelength indicates that the mechanism of photoluminescence can be assigned to ligand–metal charge transfer (LMCT) (Hu et al., 2010; Zhou et al., 2008).