Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110009121/dn3139sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110009121/dn31391sup2.hkl |
CCDC reference: 774917
A solution of benzene-1,4-diboronic acid (0.250 g, 1.50 mmol) and 4,4'-bipyridine (0.470 g,3.01 mmol) in 20 ml of methanol was refluxed for 1 h. A precipitate formed upon cooling that was recrystallized from 25 ml of a solvent mixture of methanol and water (10:1) to give crystals suitable for X-ray diffraction analysis (m.p. 573 K).
H atoms were positioned geometrically and constrained using the riding-model approximation [C—Haryl= 0.93 Å, Uiso(Haryl) = 1.2Ueq(C)]. H atoms bonded to O (H1', H2', H3', H4', H5A, H5B, H6A and H6B) were located in difference Fourier maps. Their coordinates were refined with a distance restraint: O—H = 0.84 Å and [Uiso(H) = 1.5Ueq(O)].
Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus NT (Bruker, 2001); data reduction: SAINT-Plus NT (Bruker, 2001); program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-NT (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009) and and publCIF (Westrip, 2010).
C6H8B2O4·2C10H8N2·2H2O | Z = 2 |
Mr = 514.14 | F(000) = 540 |
Triclinic, P1 | Dx = 1.333 Mg m−3 |
Hall symbol: -P 1 | Melting point: 573 K |
a = 6.8262 (9) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.1914 (13) Å | Cell parameters from 3439 reflections |
c = 18.834 (2) Å | θ = 2.2–28.2° |
α = 98.825 (2)° | µ = 0.09 mm−1 |
β = 90.804 (2)° | T = 100 K |
γ = 98.000 (2)° | Rectangular prism, light brown |
V = 1281.3 (3) Å3 | 0.44 × 0.41 × 0.34 mm |
Bruker SMART APEX CCD area-detector diffractometer | 4495 independent reflections |
Radiation source: fine-focus sealed tube | 3542 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 1.1° |
ϕ and ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −12→12 |
Tmin = 0.960, Tmax = 0.969 | l = −22→22 |
12443 measured reflections |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.063P)2 + 0.356P] where P = (Fo2 + 2Fc2)/3 |
4495 reflections | (Δ/σ)max < 0.001 |
343 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C6H8B2O4·2C10H8N2·2H2O | γ = 98.000 (2)° |
Mr = 514.14 | V = 1281.3 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.8262 (9) Å | Mo Kα radiation |
b = 10.1914 (13) Å | µ = 0.09 mm−1 |
c = 18.834 (2) Å | T = 100 K |
α = 98.825 (2)° | 0.44 × 0.41 × 0.34 mm |
β = 90.804 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 4495 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3542 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.969 | Rint = 0.029 |
12443 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.29 e Å−3 |
4495 reflections | Δρmin = −0.23 e Å−3 |
343 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
O1 | 1.00366 (17) | 0.36258 (11) | 0.09145 (7) | 0.0243 (3) | |
H1' | 0.9670 | 0.4355 | 0.1092 | 0.036* | |
O2 | 0.66707 (17) | 0.26441 (11) | 0.05601 (6) | 0.0210 (3) | |
H2' | 0.6160 | 0.3320 | 0.0738 | 0.031* | |
C1 | 0.9372 (2) | 0.12387 (16) | 0.02925 (9) | 0.0161 (4) | |
C2 | 1.1378 (2) | 0.10909 (17) | 0.02768 (9) | 0.0163 (4) | |
H2 | 1.2344 | 0.1831 | 0.0465 | 0.020* | |
C3 | 1.1974 (2) | −0.01181 (17) | −0.00092 (9) | 0.0164 (4) | |
H3 | 1.3348 | −0.0186 | −0.0012 | 0.020* | |
B1 | 0.8643 (3) | 0.2613 (2) | 0.06120 (10) | 0.0174 (4) | |
O3 | 0.52342 (17) | 0.64073 (11) | 0.41006 (7) | 0.0241 (3) | |
H3' | 0.5620 | 0.5694 | 0.3909 | 0.036* | |
O4 | 0.85741 (17) | 0.75050 (11) | 0.44009 (6) | 0.0211 (3) | |
H4' | 0.9070 | 0.6810 | 0.4249 | 0.032* | |
C14 | 0.5747 (2) | 0.88023 (16) | 0.47058 (9) | 0.0158 (4) | |
C15 | 0.7004 (2) | 0.99541 (16) | 0.50211 (9) | 0.0158 (4) | |
H15 | 0.8391 | 0.9936 | 0.5040 | 0.019* | |
C16 | 0.6283 (3) | 1.11195 (16) | 0.53061 (9) | 0.0164 (4) | |
H16 | 0.7185 | 1.1882 | 0.5514 | 0.020* | |
B2 | 0.6583 (3) | 0.74744 (19) | 0.43810 (10) | 0.0157 (4) | |
N1 | 0.9408 (2) | 0.60492 (14) | 0.15777 (8) | 0.0205 (4) | |
N2 | 1.0640 (2) | 1.28044 (14) | 0.33608 (8) | 0.0209 (4) | |
C4 | 0.9229 (3) | 0.70721 (17) | 0.12212 (10) | 0.0204 (4) | |
H4 | 0.8899 | 0.6874 | 0.0721 | 0.024* | |
C5 | 0.9499 (2) | 0.84017 (17) | 0.15457 (9) | 0.0176 (4) | |
H5 | 0.9357 | 0.9092 | 0.1270 | 0.021* | |
C6 | 0.9981 (2) | 0.87203 (16) | 0.22768 (9) | 0.0157 (4) | |
C7 | 1.0187 (2) | 0.76538 (17) | 0.26469 (9) | 0.0182 (4) | |
H7 | 1.0525 | 0.7820 | 0.3147 | 0.022* | |
C8 | 0.9894 (3) | 0.63609 (17) | 0.22799 (10) | 0.0206 (4) | |
H8 | 1.0044 | 0.5651 | 0.2540 | 0.025* | |
C9 | 1.0831 (3) | 1.25078 (17) | 0.26506 (10) | 0.0203 (4) | |
H9 | 1.1108 | 1.3229 | 0.2385 | 0.024* | |
C10 | 1.0648 (2) | 1.12159 (16) | 0.22799 (9) | 0.0177 (4) | |
H10 | 1.0804 | 1.1066 | 0.1775 | 0.021* | |
C11 | 1.0233 (2) | 1.01304 (16) | 0.26529 (9) | 0.0154 (4) | |
C12 | 1.0045 (2) | 1.04365 (17) | 0.33932 (9) | 0.0182 (4) | |
H12 | 0.9775 | 0.9737 | 0.3674 | 0.022* | |
C13 | 1.0253 (3) | 1.17622 (17) | 0.37173 (10) | 0.0208 (4) | |
H13 | 1.0114 | 1.1945 | 0.4223 | 0.025* | |
N3 | 0.5964 (2) | 0.40286 (14) | 0.34234 (8) | 0.0204 (3) | |
N4 | 0.4626 (2) | −0.27539 (14) | 0.16698 (8) | 0.0215 (4) | |
C17 | 0.6045 (3) | 0.37180 (17) | 0.27103 (10) | 0.0207 (4) | |
H17 | 0.6261 | 0.4431 | 0.2437 | 0.025* | |
C18 | 0.5833 (3) | 0.24262 (17) | 0.23503 (9) | 0.0192 (4) | |
H18 | 0.5926 | 0.2264 | 0.1842 | 0.023* | |
C19 | 0.5481 (2) | 0.13497 (16) | 0.27332 (9) | 0.0158 (4) | |
C20 | 0.5374 (3) | 0.16714 (17) | 0.34747 (9) | 0.0190 (4) | |
H20 | 0.5128 | 0.0980 | 0.3761 | 0.023* | |
C21 | 0.5629 (3) | 0.30013 (17) | 0.37928 (10) | 0.0206 (4) | |
H21 | 0.5563 | 0.3198 | 0.4301 | 0.025* | |
C22 | 0.4563 (3) | −0.17298 (17) | 0.13038 (10) | 0.0208 (4) | |
H22 | 0.4322 | −0.1929 | 0.0798 | 0.025* | |
C23 | 0.4830 (2) | −0.03972 (17) | 0.16235 (9) | 0.0190 (4) | |
H23 | 0.4765 | 0.0290 | 0.1339 | 0.023* | |
C24 | 0.5194 (2) | −0.00657 (16) | 0.23635 (9) | 0.0159 (4) | |
C25 | 0.5261 (2) | −0.11381 (17) | 0.27413 (9) | 0.0181 (4) | |
H25 | 0.5509 | −0.0973 | 0.3247 | 0.022* | |
C26 | 0.4967 (2) | −0.24348 (17) | 0.23794 (10) | 0.0195 (4) | |
H26 | 0.5008 | −0.3144 | 0.2651 | 0.023* | |
O5 | 0.43577 (19) | 0.44785 (12) | 0.11056 (7) | 0.0319 (4) | |
H5A | 0.3139 | 0.4230 | 0.1027 | 0.048* | |
H5B | 0.4470 | 0.5316 | 0.1219 | 0.048* | |
O6 | 1.09092 (18) | 0.55994 (12) | 0.39151 (7) | 0.0281 (3) | |
H6A | 1.2139 | 0.5790 | 0.3990 | 0.042* | |
H6B | 1.0770 | 0.4757 | 0.3833 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0221 (7) | 0.0134 (7) | 0.0347 (8) | 0.0052 (5) | −0.0003 (6) | −0.0069 (6) |
O2 | 0.0227 (7) | 0.0153 (6) | 0.0243 (7) | 0.0072 (5) | 0.0008 (5) | −0.0031 (5) |
C1 | 0.0219 (9) | 0.0153 (9) | 0.0116 (9) | 0.0040 (7) | 0.0012 (7) | 0.0024 (7) |
C2 | 0.0195 (9) | 0.0130 (9) | 0.0145 (9) | −0.0006 (7) | −0.0012 (7) | −0.0003 (7) |
C3 | 0.0157 (9) | 0.0190 (9) | 0.0152 (9) | 0.0052 (7) | 0.0010 (7) | 0.0025 (7) |
B1 | 0.0223 (11) | 0.0174 (11) | 0.0130 (10) | 0.0030 (8) | 0.0025 (8) | 0.0042 (8) |
O3 | 0.0224 (7) | 0.0134 (7) | 0.0339 (8) | 0.0045 (5) | 0.0021 (6) | −0.0061 (6) |
O4 | 0.0212 (7) | 0.0134 (6) | 0.0275 (7) | 0.0058 (5) | 0.0026 (5) | −0.0032 (5) |
C14 | 0.0213 (9) | 0.0150 (9) | 0.0113 (9) | 0.0030 (7) | 0.0012 (7) | 0.0021 (7) |
C15 | 0.0153 (9) | 0.0177 (9) | 0.0144 (9) | 0.0024 (7) | 0.0016 (7) | 0.0026 (7) |
C16 | 0.0218 (9) | 0.0114 (9) | 0.0141 (9) | −0.0002 (7) | 0.0010 (7) | −0.0015 (7) |
B2 | 0.0205 (10) | 0.0151 (10) | 0.0122 (10) | 0.0032 (8) | 0.0012 (8) | 0.0040 (8) |
N1 | 0.0168 (8) | 0.0165 (8) | 0.0269 (9) | 0.0026 (6) | 0.0036 (6) | −0.0012 (7) |
N2 | 0.0165 (8) | 0.0167 (8) | 0.0277 (9) | 0.0045 (6) | −0.0031 (6) | −0.0036 (7) |
C4 | 0.0198 (9) | 0.0198 (10) | 0.0206 (10) | 0.0021 (7) | 0.0022 (7) | 0.0006 (8) |
C5 | 0.0173 (9) | 0.0148 (9) | 0.0205 (10) | 0.0012 (7) | 0.0024 (7) | 0.0031 (7) |
C6 | 0.0102 (8) | 0.0154 (9) | 0.0205 (9) | 0.0019 (7) | 0.0030 (7) | −0.0002 (7) |
C7 | 0.0175 (9) | 0.0180 (9) | 0.0187 (9) | 0.0037 (7) | 0.0005 (7) | 0.0005 (7) |
C8 | 0.0187 (9) | 0.0175 (9) | 0.0261 (10) | 0.0035 (7) | 0.0004 (7) | 0.0041 (8) |
C9 | 0.0181 (9) | 0.0155 (9) | 0.0274 (11) | 0.0021 (7) | −0.0025 (7) | 0.0038 (8) |
C10 | 0.0176 (9) | 0.0165 (9) | 0.0186 (9) | 0.0029 (7) | 0.0005 (7) | 0.0011 (7) |
C11 | 0.0108 (8) | 0.0155 (9) | 0.0199 (9) | 0.0038 (7) | −0.0009 (7) | 0.0011 (7) |
C12 | 0.0170 (9) | 0.0163 (9) | 0.0211 (10) | 0.0015 (7) | 0.0000 (7) | 0.0027 (7) |
C13 | 0.0203 (10) | 0.0196 (10) | 0.0205 (10) | 0.0036 (7) | −0.0009 (7) | −0.0032 (8) |
N3 | 0.0168 (8) | 0.0157 (8) | 0.0280 (9) | 0.0030 (6) | 0.0018 (6) | 0.0001 (7) |
N4 | 0.0172 (8) | 0.0178 (8) | 0.0275 (9) | 0.0024 (6) | 0.0006 (6) | −0.0031 (7) |
C17 | 0.0208 (9) | 0.0152 (9) | 0.0264 (10) | 0.0015 (7) | 0.0032 (7) | 0.0046 (8) |
C18 | 0.0203 (9) | 0.0185 (9) | 0.0187 (10) | 0.0023 (7) | 0.0025 (7) | 0.0027 (8) |
C19 | 0.0112 (8) | 0.0159 (9) | 0.0202 (10) | 0.0038 (7) | 0.0013 (7) | 0.0010 (7) |
C20 | 0.0199 (9) | 0.0158 (9) | 0.0209 (10) | 0.0023 (7) | 0.0008 (7) | 0.0022 (7) |
C21 | 0.0245 (10) | 0.0177 (10) | 0.0188 (10) | 0.0053 (7) | 0.0024 (7) | −0.0022 (8) |
C22 | 0.0182 (9) | 0.0224 (10) | 0.0202 (10) | 0.0046 (7) | −0.0012 (7) | −0.0035 (8) |
C23 | 0.0186 (9) | 0.0181 (9) | 0.0203 (10) | 0.0044 (7) | −0.0010 (7) | 0.0015 (8) |
C24 | 0.0097 (8) | 0.0163 (9) | 0.0211 (10) | 0.0019 (7) | 0.0025 (7) | 0.0007 (7) |
C25 | 0.0179 (9) | 0.0175 (9) | 0.0180 (9) | 0.0016 (7) | 0.0014 (7) | 0.0009 (7) |
C26 | 0.0185 (9) | 0.0158 (9) | 0.0246 (10) | 0.0033 (7) | 0.0041 (7) | 0.0037 (8) |
O5 | 0.0229 (7) | 0.0170 (7) | 0.0517 (10) | 0.0048 (5) | −0.0013 (6) | −0.0084 (6) |
O6 | 0.0219 (7) | 0.0146 (7) | 0.0452 (9) | 0.0044 (5) | −0.0014 (6) | −0.0051 (6) |
O1—B1 | 1.351 (2) | C8—H8 | 0.9500 |
O1—H1' | 0.8393 | C9—C10 | 1.381 (2) |
O2—B1 | 1.354 (2) | C9—H9 | 0.9500 |
O2—H2' | 0.8412 | C10—C11 | 1.398 (2) |
C1—C3i | 1.393 (2) | C10—H10 | 0.9500 |
C1—C2 | 1.398 (2) | C11—C12 | 1.393 (2) |
C1—B1 | 1.586 (3) | C12—C13 | 1.382 (2) |
C2—C3 | 1.384 (2) | C12—H12 | 0.9500 |
C2—H2 | 0.9500 | C13—H13 | 0.9500 |
C3—C1i | 1.393 (2) | N3—C17 | 1.335 (2) |
C3—H3 | 0.9500 | N3—C21 | 1.339 (2) |
O3—B2 | 1.357 (2) | N4—C26 | 1.335 (2) |
O3—H3' | 0.8388 | N4—C22 | 1.341 (2) |
O4—B2 | 1.355 (2) | C17—C18 | 1.373 (2) |
O4—H4' | 0.8399 | C17—H17 | 0.9500 |
C14—C15 | 1.399 (2) | C18—C19 | 1.398 (2) |
C14—C16ii | 1.399 (2) | C18—H18 | 0.9500 |
C14—B2 | 1.582 (2) | C19—C20 | 1.390 (2) |
C15—C16 | 1.384 (2) | C19—C24 | 1.488 (2) |
C15—H15 | 0.9500 | C20—C21 | 1.381 (2) |
C16—C14ii | 1.399 (2) | C20—H20 | 0.9500 |
C16—H16 | 0.9500 | C21—H21 | 0.9500 |
N1—C8 | 1.338 (2) | C22—C23 | 1.385 (2) |
N1—C4 | 1.342 (2) | C22—H22 | 0.9500 |
N2—C9 | 1.338 (2) | C23—C24 | 1.393 (2) |
N2—C13 | 1.340 (2) | C23—H23 | 0.9500 |
C4—C5 | 1.385 (2) | C24—C25 | 1.398 (2) |
C4—H4 | 0.9500 | C25—C26 | 1.377 (2) |
C5—C6 | 1.389 (2) | C25—H25 | 0.9500 |
C5—H5 | 0.9500 | C26—H26 | 0.9500 |
C6—C7 | 1.400 (2) | O5—H5A | 0.8396 |
C6—C11 | 1.487 (2) | O5—H5B | 0.8398 |
C7—C8 | 1.377 (2) | O6—H6A | 0.8397 |
C7—H7 | 0.9500 | O6—H6B | 0.8401 |
B1—O1—H1' | 118.2 | C10—C9—H9 | 118.0 |
B1—O2—H2' | 122.0 | C9—C10—C11 | 119.55 (16) |
C3i—C1—C2 | 116.85 (15) | C9—C10—H10 | 120.2 |
C3i—C1—B1 | 121.04 (16) | C11—C10—H10 | 120.2 |
C2—C1—B1 | 122.11 (15) | C12—C11—C10 | 116.64 (15) |
C3—C2—C1 | 120.94 (15) | C12—C11—C6 | 121.70 (15) |
C3—C2—H2 | 119.5 | C10—C11—C6 | 121.66 (16) |
C1—C2—H2 | 119.5 | C13—C12—C11 | 119.66 (16) |
C2—C3—C1i | 122.21 (16) | C13—C12—H12 | 120.2 |
C2—C3—H3 | 118.9 | C11—C12—H12 | 120.2 |
C1i—C3—H3 | 118.9 | N2—C13—C12 | 123.84 (17) |
O1—B1—O2 | 126.57 (17) | N2—C13—H13 | 118.1 |
O1—B1—C1 | 117.19 (16) | C12—C13—H13 | 118.1 |
O2—B1—C1 | 116.24 (15) | C17—N3—C21 | 116.73 (15) |
B2—O3—H3' | 119.7 | C26—N4—C22 | 116.54 (15) |
B2—O4—H4' | 120.1 | N3—C17—C18 | 123.68 (16) |
C15—C14—C16ii | 116.81 (15) | N3—C17—H17 | 118.2 |
C15—C14—B2 | 121.57 (15) | C18—C17—H17 | 118.2 |
C16ii—C14—B2 | 121.63 (15) | C17—C18—C19 | 119.84 (16) |
C16—C15—C14 | 121.88 (16) | C17—C18—H18 | 120.1 |
C16—C15—H15 | 119.1 | C19—C18—H18 | 120.1 |
C14—C15—H15 | 119.1 | C20—C19—C18 | 116.55 (16) |
C15—C16—C14ii | 121.31 (15) | C20—C19—C24 | 121.79 (16) |
C15—C16—H16 | 119.3 | C18—C19—C24 | 121.64 (16) |
C14ii—C16—H16 | 119.3 | C21—C20—C19 | 119.68 (16) |
O4—B2—O3 | 125.82 (16) | C21—C20—H20 | 120.2 |
O4—B2—C14 | 117.38 (15) | C19—C20—H20 | 120.2 |
O3—B2—C14 | 116.80 (15) | N3—C21—C20 | 123.51 (17) |
C8—N1—C4 | 116.95 (15) | N3—C21—H21 | 118.2 |
C9—N2—C13 | 116.38 (15) | C20—C21—H21 | 118.2 |
N1—C4—C5 | 123.32 (17) | N4—C22—C23 | 123.53 (17) |
N1—C4—H4 | 118.3 | N4—C22—H22 | 118.2 |
C5—C4—H4 | 118.3 | C23—C22—H22 | 118.2 |
C4—C5—C6 | 119.56 (16) | C22—C23—C24 | 119.86 (17) |
C4—C5—H5 | 120.2 | C22—C23—H23 | 120.1 |
C6—C5—H5 | 120.2 | C24—C23—H23 | 120.1 |
C5—C6—C7 | 117.08 (15) | C23—C24—C25 | 116.30 (16) |
C5—C6—C11 | 121.50 (16) | C23—C24—C19 | 121.94 (16) |
C7—C6—C11 | 121.41 (16) | C25—C24—C19 | 121.76 (16) |
C8—C7—C6 | 119.41 (16) | C26—C25—C24 | 119.92 (16) |
C8—C7—H7 | 120.3 | C26—C25—H25 | 120.0 |
C6—C7—H7 | 120.3 | C24—C25—H25 | 120.0 |
N1—C8—C7 | 123.67 (16) | N4—C26—C25 | 123.86 (17) |
N1—C8—H8 | 118.2 | N4—C26—H26 | 118.1 |
C7—C8—H8 | 118.2 | C25—C26—H26 | 118.1 |
N2—C9—C10 | 123.92 (16) | H5A—O5—H5B | 104.8 |
N2—C9—H9 | 118.0 | H6A—O6—H6B | 101.5 |
C3i—C1—C2—C3 | 0.1 (3) | C7—C6—C11—C12 | −21.1 (2) |
B1—C1—C2—C3 | −179.60 (15) | C5—C6—C11—C10 | −21.4 (2) |
C1—C2—C3—C1i | −0.1 (3) | C7—C6—C11—C10 | 159.62 (16) |
C3i—C1—B1—O1 | 176.17 (15) | C10—C11—C12—C13 | 0.6 (2) |
C2—C1—B1—O1 | −4.2 (2) | C6—C11—C12—C13 | −178.72 (16) |
C3i—C1—B1—O2 | −3.1 (2) | C9—N2—C13—C12 | −0.2 (2) |
C2—C1—B1—O2 | 176.57 (15) | C11—C12—C13—N2 | −0.2 (3) |
C16ii—C14—C15—C16 | −0.2 (3) | C21—N3—C17—C18 | −0.9 (3) |
B2—C14—C15—C16 | 179.98 (15) | N3—C17—C18—C19 | 1.0 (3) |
C14—C15—C16—C14ii | 0.2 (3) | C17—C18—C19—C20 | −0.3 (2) |
C15—C14—B2—O4 | −1.8 (2) | C17—C18—C19—C24 | 178.51 (15) |
C16ii—C14—B2—O4 | 178.37 (15) | C18—C19—C20—C21 | −0.5 (2) |
C15—C14—B2—O3 | 178.74 (15) | C24—C19—C20—C21 | −179.27 (16) |
C16ii—C14—B2—O3 | −1.0 (2) | C17—N3—C21—C20 | 0.1 (3) |
C8—N1—C4—C5 | −0.7 (2) | C19—C20—C21—N3 | 0.6 (3) |
N1—C4—C5—C6 | −0.1 (3) | C26—N4—C22—C23 | 0.1 (2) |
C4—C5—C6—C7 | 0.6 (2) | N4—C22—C23—C24 | 0.2 (3) |
C4—C5—C6—C11 | −178.34 (15) | C22—C23—C24—C25 | −0.1 (2) |
C5—C6—C7—C8 | −0.5 (2) | C22—C23—C24—C19 | −179.67 (15) |
C11—C6—C7—C8 | 178.46 (15) | C20—C19—C24—C23 | 164.43 (16) |
C4—N1—C8—C7 | 0.8 (2) | C18—C19—C24—C23 | −14.3 (2) |
C6—C7—C8—N1 | −0.2 (3) | C20—C19—C24—C25 | −15.1 (2) |
C13—N2—C9—C10 | 0.2 (2) | C18—C19—C24—C25 | 166.21 (16) |
N2—C9—C10—C11 | 0.2 (3) | C23—C24—C25—C26 | −0.2 (2) |
C9—C10—C11—C12 | −0.6 (2) | C19—C24—C25—C26 | 179.29 (15) |
C9—C10—C11—C6 | 178.71 (15) | C22—N4—C26—C25 | −0.5 (2) |
C5—C6—C11—C12 | 157.82 (16) | C24—C25—C26—N4 | 0.6 (3) |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1′···N1 | 0.84 | 1.86 | 2.6846 (18) | 168 |
O2—H2′···O5 | 0.84 | 1.89 | 2.7058 (17) | 164 |
O3—H3′···N3 | 0.84 | 1.85 | 2.6753 (18) | 169 |
O4—H4′···O6 | 0.84 | 1.93 | 2.7398 (16) | 163 |
O5—H5A···O1iii | 0.84 | 2.12 | 2.9574 (18) | 176 |
O5—H5B···N4iv | 0.84 | 2.01 | 2.8371 (19) | 170 |
O6—H6A···O3v | 0.84 | 2.12 | 2.9533 (17) | 174 |
O6—H6B···N2vi | 0.84 | 2.04 | 2.8591 (19) | 164 |
Symmetry codes: (iii) x−1, y, z; (iv) x, y+1, z; (v) x+1, y, z; (vi) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C6H8B2O4·2C10H8N2·2H2O |
Mr | 514.14 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 6.8262 (9), 10.1914 (13), 18.834 (2) |
α, β, γ (°) | 98.825 (2), 90.804 (2), 98.000 (2) |
V (Å3) | 1281.3 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.44 × 0.41 × 0.34 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.960, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12443, 4495, 3542 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.129, 1.04 |
No. of reflections | 4495 |
No. of parameters | 343 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.23 |
Computer programs: SMART (Bruker, 2000), SAINT-Plus NT (Bruker, 2001), SHELXTL-NT (Sheldrick, 2008), PLATON (Spek, 2009) and and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1'···N1 | 0.84 | 1.86 | 2.6846 (18) | 167.5 |
O2—H2'···O5 | 0.84 | 1.89 | 2.7058 (17) | 163.8 |
O3—H3'···N3 | 0.84 | 1.85 | 2.6753 (18) | 168.8 |
O4—H4'···O6 | 0.84 | 1.93 | 2.7398 (16) | 162.9 |
O5—H5A···O1i | 0.84 | 2.12 | 2.9574 (18) | 175.6 |
O5—H5B···N4ii | 0.84 | 2.01 | 2.8371 (19) | 169.6 |
O6—H6A···O3iii | 0.84 | 2.12 | 2.9533 (17) | 174.1 |
O6—H6B···N2iv | 0.84 | 2.04 | 2.8591 (19) | 164.4 |
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z; (iii) x+1, y, z; (iv) x, y−1, z. |
Cg1···Cg2 (Å) | Dihedral angle (°) | Cg1 to plane (Å) | Cg2 to plane (Å) | |
Cg1···Cg2 i | 3.6479 (11) | 4.43 (8) | 3.3379 (7) | -3.2566 (7) |
Cg1···Cg2ii | 3.5880 (11) | 4.43 (8) | -3.4065 (7) | 3.3863 (7) |
Cg3···Cg4 i | 3.6103 (11) | 2.69 (8) | 3.3948 (7) | -3.3756 (8) |
Cg3···Cg4 ii | 3.6392 (11) | 2.69 (8) | -3.3976 (7) | 3.3776 (8) |
Cg1, Cg2, Cg3 and Cg4 are the centroids of rings N1/C4–C8, N4/C22–C26,
N2/C9–C13 and N3/C17–C21, respectively. Symmetry codes: (i) -1+x, 1+y, z; (ii) x, 1+y, z. |
Boronic acids form dimeric synthons of the composition PhB(OH)2···(HO)2BPh, which are structurally related to the well known carboxylic acid and carboxamide homodimeric motifs (Rodríguez-Cuamatzi, Vargas-Díaz & Höpfl, 2004; Rodríguez-Cuamatzi, Vargas-Díaz, Maris et al., 2004). Since the –B(OH)2 function can also be integrated into neutral and charged heterodimeric motifs, boronic acids have become interesting building blocks for crystal engineering (Filthaus et al., 2008; Fournier et al., 2003; Kara et al., 2006; Maly et al., 2006; Rodríguez-Cuamatzi et al., 2005; Rogowska et al., 2006; SeethaLekshmi et al., 2006, 2007; Shimpi et al., 2007). In contrast to carboxylic acids, pyridine adducts of boronic acids show a larger structural variety of hydrogen-bonding motifs, which have been studied systematically during the last few years by different research groups (Aakeröy et al., 2004, 2005; Braga et al., 2003). It has been shown that the co-crystallization of boric and boronic acids with 4,4'-bpy gives one-dimensional or two-dimensional hydrogen-bonded supramolecular structures, in which frequently water molecules are incorporated to allow for an optimization of π–π interactions between the 4,4'-bpy molecules (Pedireddi et al., 2004; Rodríguez-Cuamatzi et al., 2009). When combining benzene-1,4-diboronic acid (1,4-bdba) with 4,4'-bipyridine (4,4'-bpy) in benzene, co-crystals of the composition [(1,4-bdba)(4,4'-bpy)2] have been obtained (Rodríguez-Cuamatzi et al., 2009), in which the –B(OH)2 groups are hydrogen-bonded to two pyridyl fragments of the 4,4'-bpy molecules to give one-dimensional chains containing hydrogen-bonded cyclophane-type macrocycles (motif I in the scheme).
We report herein on the single-crystal X-ray diffraction analysis of the corresponding dihydrate, (1). Co-crystals of the composition [(1,4-bdba)(4,4'-bpy)2(H2O)2], (1), were obtained by a self-assembly reaction of 1,4-bdba and 4,4'-bpy in a 1:2 stoichiometric ratio in methanol containing small quantities of water. The unit cell of the title compound contains four 4,4'-bpy and four water molecules, of which two are independent in each case. Further, there are two independent 1,4-bdba molecules, which are both located at crystallographic inversion centers. In the crystal structure, each –B(OH)2 group is involved in one (B)O—H···Npyr and one (B)O—H···Ow hydrogen-bonding interaction, thus showing an asymmetric hydrogen-bonding behaviour. Similarly, each 4,4'-bpy molecule participates in two different types of O—H···N interactions, of which the first is formed with a BOH group and the second with a water molecule, which is further connected to a –B(OH)2 moiety.
In the hydrogen-bonding pattern (Table 1) a cyclophane-type macrocycle with the graph set R66(30) (Bernstein et al., 1995) can be distinguished, involving two 4,4'-bpy molecules, two –B(OH)2 moieties and two water molecules (motif IV in the scheme) (Fig. 1). Although structurally related, this arrangement is different from all motifs observed so far for boric and boronic acid adducts with 4,4'-bpy (see Scheme) (Pedireddi et al., 2004; Rodríguez-Cuamatzi et al., 2009). In contrast, in motif III one –B(OH)2 group interacts only with one of its two OH groups in the hydrogen-bonding pattern. In motif V each –B(OH)2 group participates also with both hydroxyl functions; however, at the same time the configuration of the –B(OH)2 group changes, one has syn–anti and the other one syn–syn orientation. In the present case (Fig. 1) (motif IV), both –B(OH)2 functions have syn–syn orientation, with the consequence that both water molecules act as simultaneous hydrogen-bonding donor and acceptor within the macrocycle. In the crystal structure, these cyclophane-type macrocycles are connected further through additional Ow—H···O(H)B interactions to give a two-dimensional hydrogen-bonded layer structure (Fig. 2). Interestingly, this association generates an additional, novel hydrogen-bonded macrocyclic motif that can be described by the graph set R66(26), in which two 4,4'-bpy and two water molecules, but only two BOH hydroxyl groups are involved (Fig. 1, motif II. This motif completes therefore a series of cyclophane-type hydrogen-bonding motifs I–V (Scheme) containing a varying number of BOH hydroxyl groups (n = 2, 3 and 4) and water molecules (n = 0 and 2). Analogous patterns containing only one water molecule have not been described so far. As described previously (Rodríguez-Cuamatzi et al., 2009), it is probable that the differences in the supramolecular structure of motifs I–V result from the optimization of π–π interactions between the 4,4'-bpy molecules within the crystal structure. Indeed, in the two-dimensional layers of the title compound the 4,4'-bpy are stacked along axis a (Fig. 2). Thereby, the pyridine rings of opposite 4,4'-bpy molecules have slightly displaced parallel-sandwich geometries and are almost coplanar to each other, having perpendicular distances varying from 3.26 to 3.40 Å, centroid–centroid distances from 3.59 to 3.65 Å, N···N distances from 3.59 to 3.67 Å and interplanar angles of 2.7 and 4.4 Å. Within the 4,4'-bpy molecules, the pyridine rings are twisted about the central C—C bonds by angles of 14.3 (2) and 21.4 (2) °.