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The structures of the Mg, Ca, Sr and Ba salts of 1-naphthoic acid are examined and compared with analogous structures of salts of benzoate derivatives. It is shown that
catena-poly[[[diaquabis(1-naphthoato-κ
O)magnesium(II)]-μ-aqua] dihydrate], {[Mg(C
11H
7O
2)
2(H
2O)
3]·2H
2O}
n, exists as a one-dimensional coordination polymer that propagates only through Mg—OH
2—Mg interactions along the crystallographic
b direction. In contrast with related benzoate salts, the naphthalene systems are large enough to prevent inorganic chain-to-chain interactions, and thus species with inorganic channels rather than layers are formed. The Ca, Sr and Ba salts all have metal centres that lie on a twofold axis (
Z′ =
) and all have the common name
catena-poly[[diaquametal(II)]-bis(μ-1-naphthoato)-κ
3O,
O′:
O;κ
3O:
O,
O′], [
M(C
11H
7O
2)
2(H
2O)
2]
n, where
M = Ca, Sr or Ba. The Ca and Sr salts are essentially isostructural, and all three species form one-dimensional coordination polymers through a carboxylate group that forms three
M—O bonds. The polymeric chains propagate
via c-glide planes and through
MO
MO four-membered rings. Again, inorganic channel structures are formed rather than layered structures, and the three structures are similar to those found for Ca and Sr salicylates and other substituted benzoates.
Supporting information
CCDC references: 899055; 899056; 899057; 899058
All samples were prepared by slowly adding a slight excess of an aqueous
solution of the appropriate metal carbonate to a stirred aqueous slurry of
1-naphthoic acid. The solutions were gently heated to give complete
dissolution of the solids. The volumes of the resulting clear solutions were
reduced until white precipitates were deposited; these were collected by
filtration. Colourless crystals suitable for single-crystal diffraction
studies were obtained by recrystallization of the samples from warm water.
Water H atoms were positioned as found by difference syntheses and were refined
with restraints such that the O—H and H···H distances approximated 0.88 and
1.33 Å, respectively; Uiso(H) vales were set at 1.5Ueq(O).
This introduced 15 restraints for the Mg salt and three restraints for each of
the other salts. H atoms bonded to C atoms were positioned geometrically and
refined in riding mode, with C—H = 0.95 Å and with Uiso(H) =
1.2Ueq(C).
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for MgNPH, CaNPH, SrNPH; APEX2 (Bruker, 2007) for BaNPH. Cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998) for MgNPH, CaNPH, SrNPH; SAINT (Bruker, 2007) for BaNPH. Data reduction: DENZO (Otwinowski & Minor, 1997) for MgNPH, CaNPH, SrNPH; SAINT (Bruker, 2007) for BaNPH. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEP-3 (Farrugia, 1997) and X-SEED (Barbour, 2001) for MgNPH, CaNPH; ORTEP-3 (Farrugia, 1997) for SrNPH, BaNPH. For all compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(MgNPH)
catena-poly[[[diaquabis(1-naphthoato-
κO)magnesium(II)]-µ-aqua]
dihydrate]
top
Crystal data top
[Mg(C11H7O2)2(H2O)3]·2H2O | F(000) = 960 |
Mr = 456.72 | Dx = 1.401 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5287 reflections |
a = 12.8896 (4) Å | θ = 1.0–27.5° |
b = 8.0048 (2) Å | µ = 0.13 mm−1 |
c = 24.5300 (5) Å | T = 123 K |
β = 121.190 (1)° | Plate, colourless |
V = 2165.13 (10) Å3 | 0.15 × 0.13 × 0.03 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2744 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.078 |
Graphite monochromator | θmax = 27.5°, θmin = 2.7° |
ϕ and ω scans | h = −16→16 |
8977 measured reflections | k = −10→10 |
4968 independent reflections | l = −31→31 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0616P)2 + 1.1013P] where P = (Fo2 + 2Fc2)/3 |
4968 reflections | (Δ/σ)max < 0.001 |
319 parameters | Δρmax = 0.31 e Å−3 |
15 restraints | Δρmin = −0.43 e Å−3 |
Crystal data top
[Mg(C11H7O2)2(H2O)3]·2H2O | V = 2165.13 (10) Å3 |
Mr = 456.72 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.8896 (4) Å | µ = 0.13 mm−1 |
b = 8.0048 (2) Å | T = 123 K |
c = 24.5300 (5) Å | 0.15 × 0.13 × 0.03 mm |
β = 121.190 (1)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2744 reflections with I > 2σ(I) |
8977 measured reflections | Rint = 0.078 |
4968 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.059 | 15 restraints |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.31 e Å−3 |
4968 reflections | Δρmin = −0.43 e Å−3 |
319 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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mg1 | 0.00172 (8) | 0.76819 (11) | 0.24870 (4) | 0.0177 (2) | |
O1 | 0.10496 (17) | 0.6870 (2) | 0.34203 (8) | 0.0231 (5) | |
O2 | 0.20189 (19) | 0.9184 (2) | 0.39368 (9) | 0.0316 (5) | |
O1W | 0.08195 (16) | 1.0194 (2) | 0.27487 (8) | 0.0182 (4) | |
H1W | 0.1309 (19) | 1.001 (4) | 0.3160 (5) | 0.027* | |
H2W | 0.1338 (18) | 1.036 (4) | 0.2627 (11) | 0.027* | |
O3 | −0.12473 (17) | 0.8492 (2) | 0.27004 (9) | 0.0232 (5) | |
O2W | 0.13182 (19) | 0.6868 (2) | 0.23202 (9) | 0.0241 (5) | |
H3W | 0.134 (3) | 0.718 (3) | 0.1986 (10) | 0.036* | |
H4W | 0.136 (3) | 0.5784 (12) | 0.2308 (13) | 0.036* | |
O4 | −0.21291 (17) | 0.6144 (2) | 0.27392 (9) | 0.0268 (5) | |
O3W | −0.09957 (19) | 0.8507 (2) | 0.15824 (9) | 0.0256 (5) | |
H5W | −0.105 (3) | 0.9587 (13) | 0.1520 (13) | 0.038* | |
H6W | −0.116 (3) | 0.813 (3) | 0.1212 (8) | 0.038* | |
O4W | −0.1462 (2) | 0.3629 (3) | 0.35837 (11) | 0.0382 (6) | |
H7W | −0.191 (3) | 0.443 (3) | 0.3324 (14) | 0.057* | |
H8W | −0.192 (3) | 0.332 (4) | 0.3731 (15) | 0.057* | |
O5W | 0.1341 (2) | 1.1675 (3) | 0.44229 (11) | 0.0499 (7) | |
H9W | 0.177 (3) | 1.088 (4) | 0.4373 (16) | 0.075* | |
H10W | 0.187 (3) | 1.190 (5) | 0.4833 (7) | 0.075* | |
C1 | 0.1754 (3) | 0.7674 (4) | 0.39284 (13) | 0.0230 (7) | |
C2 | 0.2250 (3) | 0.6739 (3) | 0.45441 (12) | 0.0216 (7) | |
C3 | 0.3512 (3) | 0.6791 (3) | 0.50196 (13) | 0.0228 (7) | |
C4 | 0.4398 (3) | 0.7619 (4) | 0.49337 (15) | 0.0324 (8) | |
H4 | 0.4158 | 0.8176 | 0.4544 | 0.039* | |
C5 | 0.5587 (3) | 0.7612 (5) | 0.54091 (17) | 0.0438 (9) | |
H5 | 0.6166 | 0.8177 | 0.5347 | 0.053* | |
C6 | 0.5974 (3) | 0.6789 (5) | 0.59874 (17) | 0.0473 (10) | |
H6 | 0.6808 | 0.6800 | 0.6312 | 0.057* | |
C7 | 0.5165 (3) | 0.5982 (4) | 0.60841 (15) | 0.0394 (9) | |
H7 | 0.5435 | 0.5432 | 0.6479 | 0.047* | |
C8 | 0.3909 (3) | 0.5941 (4) | 0.56028 (14) | 0.0290 (7) | |
C9 | 0.3053 (3) | 0.5072 (4) | 0.56976 (14) | 0.0336 (8) | |
H9 | 0.3320 | 0.4502 | 0.6088 | 0.040* | |
C10 | 0.1856 (3) | 0.5048 (4) | 0.52358 (14) | 0.0322 (8) | |
H10 | 0.1291 | 0.4477 | 0.5307 | 0.039* | |
C11 | 0.1456 (3) | 0.5872 (4) | 0.46524 (14) | 0.0269 (7) | |
H11 | 0.0622 | 0.5827 | 0.4329 | 0.032* | |
C12 | −0.1851 (2) | 0.7647 (4) | 0.28802 (13) | 0.0214 (6) | |
C13 | −0.2203 (3) | 0.8519 (3) | 0.33046 (13) | 0.0206 (6) | |
C14 | −0.3384 (3) | 0.8366 (3) | 0.32240 (13) | 0.0212 (7) | |
C15 | −0.4348 (3) | 0.7466 (4) | 0.27194 (14) | 0.0260 (7) | |
H15 | −0.4221 | 0.6897 | 0.2419 | 0.031* | |
C16 | −0.5468 (3) | 0.7411 (4) | 0.26617 (15) | 0.0319 (8) | |
H16 | −0.6107 | 0.6801 | 0.2321 | 0.038* | |
C17 | −0.5680 (3) | 0.8241 (4) | 0.30977 (16) | 0.0338 (8) | |
H17 | −0.6457 | 0.8188 | 0.3052 | 0.041* | |
C18 | −0.4776 (3) | 0.9120 (4) | 0.35840 (15) | 0.0300 (8) | |
H18 | −0.4929 | 0.9679 | 0.3877 | 0.036* | |
C19 | −0.3605 (3) | 0.9224 (4) | 0.36655 (14) | 0.0244 (7) | |
C20 | −0.2664 (3) | 1.0156 (4) | 0.41677 (14) | 0.0284 (7) | |
H20 | −0.2814 | 1.0719 | 0.4461 | 0.034* | |
C21 | −0.1550 (3) | 1.0261 (4) | 0.42391 (13) | 0.0281 (7) | |
H21 | −0.0924 | 1.0880 | 0.4583 | 0.034* | |
C22 | −0.1322 (3) | 0.9453 (4) | 0.38020 (13) | 0.0259 (7) | |
H22 | −0.0544 | 0.9553 | 0.3851 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mg1 | 0.0203 (5) | 0.0143 (5) | 0.0192 (5) | −0.0003 (4) | 0.0107 (4) | −0.0008 (4) |
O1 | 0.0292 (12) | 0.0185 (11) | 0.0170 (10) | −0.0034 (9) | 0.0087 (9) | −0.0018 (8) |
O2 | 0.0417 (13) | 0.0176 (11) | 0.0245 (11) | −0.0063 (10) | 0.0094 (10) | 0.0007 (9) |
O1W | 0.0193 (10) | 0.0178 (10) | 0.0188 (10) | 0.0003 (9) | 0.0107 (8) | 0.0014 (9) |
O3 | 0.0274 (11) | 0.0171 (11) | 0.0339 (12) | −0.0018 (9) | 0.0222 (10) | −0.0006 (9) |
O2W | 0.0330 (12) | 0.0139 (10) | 0.0333 (12) | 0.0006 (10) | 0.0228 (10) | 0.0009 (9) |
O4 | 0.0321 (12) | 0.0161 (11) | 0.0414 (13) | −0.0043 (9) | 0.0257 (10) | −0.0042 (9) |
O3W | 0.0363 (12) | 0.0165 (11) | 0.0185 (10) | 0.0011 (10) | 0.0102 (10) | −0.0011 (9) |
O4W | 0.0580 (16) | 0.0289 (13) | 0.0409 (14) | 0.0016 (12) | 0.0350 (13) | 0.0022 (11) |
O5W | 0.0619 (18) | 0.0432 (16) | 0.0392 (14) | 0.0042 (13) | 0.0223 (13) | 0.0046 (13) |
C1 | 0.0250 (16) | 0.0202 (16) | 0.0222 (16) | −0.0020 (13) | 0.0112 (13) | −0.0025 (13) |
C2 | 0.0286 (17) | 0.0168 (15) | 0.0189 (15) | −0.0020 (13) | 0.0120 (13) | −0.0021 (12) |
C3 | 0.0298 (17) | 0.0177 (15) | 0.0197 (15) | 0.0019 (13) | 0.0119 (13) | −0.0036 (13) |
C4 | 0.0322 (19) | 0.0306 (18) | 0.0330 (18) | −0.0011 (15) | 0.0159 (15) | 0.0002 (15) |
C5 | 0.0290 (19) | 0.050 (2) | 0.049 (2) | −0.0036 (18) | 0.0174 (18) | −0.0054 (19) |
C6 | 0.031 (2) | 0.052 (2) | 0.041 (2) | 0.0093 (19) | 0.0063 (17) | −0.0065 (19) |
C7 | 0.044 (2) | 0.037 (2) | 0.0249 (18) | 0.0118 (18) | 0.0088 (16) | 0.0004 (15) |
C8 | 0.0401 (19) | 0.0206 (16) | 0.0209 (16) | 0.0083 (15) | 0.0120 (15) | 0.0007 (13) |
C9 | 0.057 (2) | 0.0211 (17) | 0.0224 (16) | 0.0061 (16) | 0.0206 (17) | 0.0056 (14) |
C10 | 0.053 (2) | 0.0233 (18) | 0.0324 (18) | −0.0064 (16) | 0.0305 (17) | −0.0035 (15) |
C11 | 0.0323 (17) | 0.0231 (16) | 0.0243 (16) | −0.0015 (14) | 0.0140 (14) | −0.0034 (13) |
C12 | 0.0193 (15) | 0.0197 (16) | 0.0247 (16) | 0.0009 (13) | 0.0111 (13) | 0.0011 (13) |
C13 | 0.0267 (16) | 0.0130 (14) | 0.0249 (16) | 0.0026 (13) | 0.0154 (13) | 0.0042 (12) |
C14 | 0.0261 (16) | 0.0153 (15) | 0.0245 (16) | 0.0008 (13) | 0.0146 (13) | 0.0029 (12) |
C15 | 0.0298 (18) | 0.0186 (16) | 0.0325 (17) | 0.0033 (14) | 0.0182 (15) | 0.0020 (13) |
C16 | 0.0282 (18) | 0.0235 (17) | 0.0404 (19) | 0.0010 (14) | 0.0152 (16) | 0.0034 (15) |
C17 | 0.0315 (18) | 0.0296 (18) | 0.052 (2) | 0.0057 (16) | 0.0297 (18) | 0.0042 (17) |
C18 | 0.0390 (19) | 0.0247 (17) | 0.0393 (19) | 0.0082 (15) | 0.0295 (17) | 0.0042 (15) |
C19 | 0.0328 (17) | 0.0171 (15) | 0.0317 (17) | 0.0070 (14) | 0.0226 (15) | 0.0064 (13) |
C20 | 0.043 (2) | 0.0211 (16) | 0.0267 (16) | 0.0041 (15) | 0.0223 (15) | 0.0023 (14) |
C21 | 0.0386 (19) | 0.0206 (16) | 0.0215 (15) | −0.0015 (14) | 0.0130 (14) | −0.0032 (13) |
C22 | 0.0268 (17) | 0.0226 (16) | 0.0288 (17) | 0.0005 (14) | 0.0149 (14) | 0.0033 (14) |
Geometric parameters (Å, º) top
Mg1—O3W | 2.016 (2) | C6—C7 | 1.349 (5) |
Mg1—O2W | 2.028 (2) | C6—H6 | 0.9500 |
Mg1—O3 | 2.058 (2) | C7—C8 | 1.427 (4) |
Mg1—O1 | 2.069 (2) | C7—H7 | 0.9500 |
Mg1—O1Wi | 2.195 (2) | C8—C9 | 1.421 (5) |
Mg1—O1W | 2.200 (2) | C9—C10 | 1.362 (4) |
O1—C1 | 1.273 (3) | C9—H9 | 0.9500 |
O2—C1 | 1.253 (3) | C10—C11 | 1.409 (4) |
O1W—Mg1ii | 2.195 (2) | C10—H10 | 0.9500 |
O1W—H1W | 0.881 (10) | C11—H11 | 0.9500 |
O1W—H2W | 0.873 (10) | C12—C13 | 1.505 (4) |
O3—C12 | 1.270 (3) | C13—C22 | 1.379 (4) |
O2W—H3W | 0.871 (10) | C13—C14 | 1.435 (4) |
O2W—H4W | 0.872 (10) | C14—C15 | 1.415 (4) |
O4—C12 | 1.252 (3) | C14—C19 | 1.430 (4) |
O3W—H5W | 0.874 (10) | C15—C16 | 1.377 (4) |
O3W—H6W | 0.874 (10) | C15—H15 | 0.9500 |
O4W—H7W | 0.876 (10) | C16—C17 | 1.401 (4) |
O4W—H8W | 0.873 (10) | C16—H16 | 0.9500 |
O5W—H9W | 0.896 (10) | C17—C18 | 1.355 (4) |
O5W—H10W | 0.894 (10) | C17—H17 | 0.9500 |
C1—C2 | 1.500 (4) | C18—C19 | 1.418 (4) |
C2—C11 | 1.371 (4) | C18—H18 | 0.9500 |
C2—C3 | 1.430 (4) | C19—C20 | 1.414 (4) |
C3—C8 | 1.419 (4) | C20—C21 | 1.356 (4) |
C3—C4 | 1.427 (4) | C20—H20 | 0.9500 |
C4—C5 | 1.364 (4) | C21—C22 | 1.407 (4) |
C4—H4 | 0.9500 | C21—H21 | 0.9500 |
C5—C6 | 1.401 (5) | C22—H22 | 0.9500 |
C5—H5 | 0.9500 | | |
| | | |
O3W—Mg1—O2W | 90.86 (9) | C6—C7—C8 | 121.0 (3) |
O3W—Mg1—O3 | 91.72 (9) | C6—C7—H7 | 119.5 |
O2W—Mg1—O3 | 177.36 (10) | C8—C7—H7 | 119.5 |
O3W—Mg1—O1 | 179.08 (9) | C3—C8—C9 | 119.7 (3) |
O2W—Mg1—O1 | 89.84 (8) | C3—C8—C7 | 119.0 (3) |
O3—Mg1—O1 | 87.58 (8) | C9—C8—C7 | 121.3 (3) |
O3W—Mg1—O1Wi | 93.30 (8) | C10—C9—C8 | 120.8 (3) |
O2W—Mg1—O1Wi | 90.03 (8) | C10—C9—H9 | 119.6 |
O3—Mg1—O1Wi | 90.40 (8) | C8—C9—H9 | 119.6 |
O1—Mg1—O1Wi | 87.31 (8) | C9—C10—C11 | 120.0 (3) |
O3W—Mg1—O1W | 87.73 (8) | C9—C10—H10 | 120.0 |
O2W—Mg1—O1W | 92.27 (8) | C11—C10—H10 | 120.0 |
O3—Mg1—O1W | 87.27 (8) | C2—C11—C10 | 121.1 (3) |
O1—Mg1—O1W | 91.64 (8) | C2—C11—H11 | 119.5 |
O1Wi—Mg1—O1W | 177.47 (5) | C10—C11—H11 | 119.5 |
C1—O1—Mg1 | 130.42 (18) | O4—C12—O3 | 123.7 (3) |
Mg1ii—O1W—Mg1 | 131.30 (8) | O4—C12—C13 | 119.4 (2) |
Mg1ii—O1W—H1W | 114.4 (19) | O3—C12—C13 | 116.8 (2) |
Mg1—O1W—H1W | 97.7 (18) | C22—C13—C14 | 119.8 (3) |
Mg1ii—O1W—H2W | 97.5 (19) | C22—C13—C12 | 117.3 (2) |
Mg1—O1W—H2W | 112 (2) | C14—C13—C12 | 122.9 (2) |
H1W—O1W—H2W | 101.2 (18) | C15—C14—C19 | 118.5 (3) |
C12—O3—Mg1 | 129.00 (17) | C15—C14—C13 | 123.5 (3) |
Mg1—O2W—H3W | 122 (2) | C19—C14—C13 | 117.9 (3) |
Mg1—O2W—H4W | 113.7 (19) | C16—C15—C14 | 120.4 (3) |
H3W—O2W—H4W | 102.7 (19) | C16—C15—H15 | 119.8 |
Mg1—O3W—H5W | 117.7 (18) | C14—C15—H15 | 119.8 |
Mg1—O3W—H6W | 134.4 (19) | C15—C16—C17 | 121.0 (3) |
H5W—O3W—H6W | 101.9 (19) | C15—C16—H16 | 119.5 |
H7W—O4W—H8W | 100.0 (19) | C17—C16—H16 | 119.5 |
H9W—O5W—H10W | 97.4 (19) | C18—C17—C16 | 120.0 (3) |
O2—C1—O1 | 123.6 (3) | C18—C17—H17 | 120.0 |
O2—C1—C2 | 119.6 (2) | C16—C17—H17 | 120.0 |
O1—C1—C2 | 116.7 (2) | C17—C18—C19 | 121.4 (3) |
C11—C2—C3 | 120.3 (3) | C17—C18—H18 | 119.3 |
C11—C2—C1 | 118.4 (3) | C19—C18—H18 | 119.3 |
C3—C2—C1 | 121.2 (3) | C20—C19—C18 | 121.6 (3) |
C8—C3—C4 | 118.3 (3) | C20—C19—C14 | 119.7 (3) |
C8—C3—C2 | 118.1 (3) | C18—C19—C14 | 118.7 (3) |
C4—C3—C2 | 123.6 (3) | C21—C20—C19 | 121.3 (3) |
C5—C4—C3 | 120.2 (3) | C21—C20—H20 | 119.4 |
C5—C4—H4 | 119.9 | C19—C20—H20 | 119.4 |
C3—C4—H4 | 119.9 | C20—C21—C22 | 119.8 (3) |
C4—C5—C6 | 121.4 (3) | C20—C21—H21 | 120.1 |
C4—C5—H5 | 119.3 | C22—C21—H21 | 120.1 |
C6—C5—H5 | 119.3 | C13—C22—C21 | 121.5 (3) |
C7—C6—C5 | 120.1 (3) | C13—C22—H22 | 119.2 |
C7—C6—H6 | 120.0 | C21—C22—H22 | 119.2 |
C5—C6—H6 | 120.0 | | |
| | | |
O2W—Mg1—O1—C1 | 98.8 (2) | C3—C8—C9—C10 | −0.1 (4) |
O3—Mg1—O1—C1 | −80.6 (2) | C7—C8—C9—C10 | 179.7 (3) |
O1Wi—Mg1—O1—C1 | −171.1 (2) | C8—C9—C10—C11 | 0.9 (4) |
O1W—Mg1—O1—C1 | 6.6 (2) | C3—C2—C11—C10 | 1.4 (4) |
O3W—Mg1—O1W—Mg1ii | 47.12 (12) | C1—C2—C11—C10 | −176.4 (3) |
O2W—Mg1—O1W—Mg1ii | 137.89 (12) | C9—C10—C11—C2 | −1.5 (4) |
O3—Mg1—O1W—Mg1ii | −44.71 (11) | Mg1—O3—C12—O4 | −28.0 (4) |
O1—Mg1—O1W—Mg1ii | −132.21 (12) | Mg1—O3—C12—C13 | 149.89 (19) |
O3W—Mg1—O3—C12 | 118.8 (2) | O4—C12—C13—C22 | 132.9 (3) |
O1—Mg1—O3—C12 | −61.8 (2) | O3—C12—C13—C22 | −45.1 (4) |
O1Wi—Mg1—O3—C12 | 25.4 (2) | O4—C12—C13—C14 | −44.9 (4) |
O1W—Mg1—O3—C12 | −153.6 (2) | O3—C12—C13—C14 | 137.2 (3) |
Mg1—O1—C1—O2 | −5.7 (4) | C22—C13—C14—C15 | 178.5 (3) |
Mg1—O1—C1—C2 | 172.46 (18) | C12—C13—C14—C15 | −3.8 (4) |
O2—C1—C2—C11 | 128.3 (3) | C22—C13—C14—C19 | 0.9 (4) |
O1—C1—C2—C11 | −50.0 (4) | C12—C13—C14—C19 | 178.6 (2) |
O2—C1—C2—C3 | −49.5 (4) | C19—C14—C15—C16 | −0.6 (4) |
O1—C1—C2—C3 | 132.3 (3) | C13—C14—C15—C16 | −178.2 (3) |
C11—C2—C3—C8 | −0.6 (4) | C14—C15—C16—C17 | 0.1 (4) |
C1—C2—C3—C8 | 177.1 (2) | C15—C16—C17—C18 | 0.2 (5) |
C11—C2—C3—C4 | 177.9 (3) | C16—C17—C18—C19 | 0.0 (5) |
C1—C2—C3—C4 | −4.4 (4) | C17—C18—C19—C20 | 179.2 (3) |
C8—C3—C4—C5 | −1.4 (4) | C17—C18—C19—C14 | −0.5 (4) |
C2—C3—C4—C5 | −179.9 (3) | C15—C14—C19—C20 | −178.9 (3) |
C3—C4—C5—C6 | 0.6 (5) | C13—C14—C19—C20 | −1.2 (4) |
C4—C5—C6—C7 | −0.1 (5) | C15—C14—C19—C18 | 0.8 (4) |
C5—C6—C7—C8 | 0.3 (5) | C13—C14—C19—C18 | 178.5 (3) |
C4—C3—C8—C9 | −178.6 (3) | C18—C19—C20—C21 | −179.4 (3) |
C2—C3—C8—C9 | 0.0 (4) | C14—C19—C20—C21 | 0.3 (4) |
C4—C3—C8—C7 | 1.6 (4) | C19—C20—C21—C22 | 1.0 (4) |
C2—C3—C8—C7 | −179.8 (3) | C14—C13—C22—C21 | 0.3 (4) |
C6—C7—C8—C3 | −1.1 (5) | C12—C13—C22—C21 | −177.5 (3) |
C6—C7—C8—C9 | 179.1 (3) | C20—C21—C22—C13 | −1.3 (4) |
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 |
O1W—H1W···O2 | 0.88 (1) | 1.76 (1) | 2.621 (3) | 164 (3) |
O1W—H2W···O4ii | 0.87 (1) | 1.79 (1) | 2.637 (3) | 165 (3) |
O2W—H3W···O4Wii | 0.87 (1) | 1.88 (1) | 2.713 (3) | 159 (3) |
O2W—H4W···O3i | 0.87 (1) | 1.84 (1) | 2.704 (3) | 171 (3) |
O3W—H5W···O1ii | 0.87 (1) | 1.83 (1) | 2.693 (3) | 167 (3) |
O3W—H6W···O5Wi | 0.87 (1) | 1.86 (1) | 2.701 (3) | 161 (3) |
O4W—H7W···O4 | 0.88 (1) | 1.90 (2) | 2.691 (3) | 149 (3) |
O5W—H9W···O2 | 0.90 (1) | 1.85 (2) | 2.692 (3) | 155 (3) |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2. |
(CaNPH)
catena-poly[[diaquacalcium(II)]-bis(µ-1-naphthoato)-
κ3O,
O':
O;
κ3O:
O,
O']
top
Crystal data top
[Ca(C11H7O2)2(H2O)2] | F(000) = 872 |
Mr = 418.44 | Dx = 1.496 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2196 reflections |
a = 21.079 (1) Å | θ = 1–27.5° |
b = 11.4410 (6) Å | µ = 0.38 mm−1 |
c = 7.7200 (3) Å | T = 123 K |
β = 93.994 (3)° | Cut needle, colourless |
V = 1857.27 (15) Å3 | 0.28 × 0.12 × 0.06 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1641 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans | h = −27→27 |
4047 measured reflections | k = −14→14 |
2108 independent reflections | l = −10→9 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0258P)2 + 1.991P] where P = (Fo2 + 2Fc2)/3 |
2108 reflections | (Δ/σ)max < 0.001 |
138 parameters | Δρmax = 0.29 e Å−3 |
3 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
[Ca(C11H7O2)2(H2O)2] | V = 1857.27 (15) Å3 |
Mr = 418.44 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.079 (1) Å | µ = 0.38 mm−1 |
b = 11.4410 (6) Å | T = 123 K |
c = 7.7200 (3) Å | 0.28 × 0.12 × 0.06 mm |
β = 93.994 (3)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1641 reflections with I > 2σ(I) |
4047 measured reflections | Rint = 0.031 |
2108 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 3 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.29 e Å−3 |
2108 reflections | Δρmin = −0.30 e Å−3 |
138 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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ca1 | 0.0000 | 0.03980 (4) | 1.2500 | 0.01390 (13) | |
O1 | 0.04711 (5) | 0.09489 (10) | 0.99365 (14) | 0.0170 (3) | |
O2 | 0.07864 (5) | 0.11825 (10) | 0.72994 (14) | 0.0192 (3) | |
O1W | −0.07630 (6) | 0.17367 (12) | 1.11200 (15) | 0.0240 (3) | |
H1W | −0.0827 (9) | 0.1706 (18) | 1.0004 (12) | 0.036* | |
H2W | −0.0996 (9) | 0.2304 (14) | 1.143 (2) | 0.036* | |
C1 | 0.07467 (7) | 0.15460 (15) | 0.8834 (2) | 0.0152 (4) | |
C2 | 0.10026 (8) | 0.27320 (15) | 0.9348 (2) | 0.0159 (4) | |
C3 | 0.06320 (8) | 0.34445 (15) | 1.0302 (2) | 0.0184 (4) | |
H3 | 0.0238 | 0.3161 | 1.0656 | 0.022* | |
C4 | 0.08283 (8) | 0.45869 (16) | 1.0764 (2) | 0.0215 (4) | |
H4 | 0.0560 | 0.5075 | 1.1391 | 0.026* | |
C5 | 0.14031 (8) | 0.49945 (16) | 1.0311 (2) | 0.0197 (4) | |
H5 | 0.1532 | 0.5765 | 1.0628 | 0.024* | |
C6 | 0.18086 (8) | 0.42798 (15) | 0.9373 (2) | 0.0162 (4) | |
C7 | 0.24163 (8) | 0.46787 (16) | 0.8961 (2) | 0.0187 (4) | |
H7 | 0.2553 | 0.5438 | 0.9316 | 0.022* | |
C8 | 0.28081 (8) | 0.39944 (16) | 0.8064 (2) | 0.0206 (4) | |
H8 | 0.3213 | 0.4277 | 0.7794 | 0.025* | |
C9 | 0.26091 (8) | 0.28643 (16) | 0.7541 (2) | 0.0203 (4) | |
H9 | 0.2883 | 0.2389 | 0.6915 | 0.024* | |
C10 | 0.20274 (8) | 0.24413 (15) | 0.7919 (2) | 0.0174 (4) | |
H10 | 0.1903 | 0.1677 | 0.7555 | 0.021* | |
C11 | 0.16068 (7) | 0.31362 (15) | 0.8851 (2) | 0.0148 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ca1 | 0.0149 (2) | 0.0161 (3) | 0.0108 (2) | 0.000 | 0.00190 (17) | 0.000 |
O1 | 0.0183 (6) | 0.0187 (7) | 0.0143 (6) | −0.0020 (5) | 0.0031 (4) | 0.0022 (5) |
O2 | 0.0228 (6) | 0.0236 (7) | 0.0115 (6) | −0.0064 (5) | 0.0029 (5) | −0.0024 (5) |
O1W | 0.0272 (7) | 0.0293 (8) | 0.0154 (6) | 0.0116 (6) | 0.0017 (5) | −0.0017 (6) |
C1 | 0.0116 (8) | 0.0196 (9) | 0.0142 (8) | 0.0015 (6) | −0.0002 (6) | 0.0007 (7) |
C2 | 0.0197 (8) | 0.0177 (9) | 0.0101 (8) | −0.0007 (7) | −0.0005 (6) | 0.0016 (7) |
C3 | 0.0180 (8) | 0.0220 (10) | 0.0154 (8) | −0.0019 (7) | 0.0026 (6) | 0.0012 (7) |
C4 | 0.0270 (9) | 0.0205 (10) | 0.0174 (8) | 0.0043 (8) | 0.0040 (7) | −0.0041 (8) |
C5 | 0.0271 (9) | 0.0162 (9) | 0.0155 (8) | −0.0009 (7) | −0.0014 (7) | −0.0017 (7) |
C6 | 0.0199 (8) | 0.0167 (9) | 0.0116 (8) | −0.0017 (7) | −0.0019 (6) | 0.0015 (7) |
C7 | 0.0224 (9) | 0.0168 (9) | 0.0163 (8) | −0.0056 (7) | −0.0024 (7) | 0.0022 (7) |
C8 | 0.0167 (8) | 0.0251 (10) | 0.0201 (9) | −0.0043 (7) | 0.0009 (7) | 0.0034 (8) |
C9 | 0.0189 (9) | 0.0224 (10) | 0.0198 (9) | 0.0015 (7) | 0.0026 (7) | 0.0020 (7) |
C10 | 0.0188 (9) | 0.0161 (9) | 0.0171 (8) | −0.0012 (7) | 0.0006 (7) | 0.0005 (7) |
C11 | 0.0163 (8) | 0.0176 (9) | 0.0103 (8) | −0.0002 (7) | −0.0010 (6) | 0.0028 (7) |
Geometric parameters (Å, º) top
Ca1—O1 | 2.3608 (11) | C2—C3 | 1.378 (2) |
Ca1—O1i | 2.3608 (10) | C2—C11 | 1.432 (2) |
Ca1—O1Wi | 2.4143 (12) | C3—C4 | 1.409 (2) |
Ca1—O1W | 2.4143 (12) | C3—H3 | 0.9500 |
Ca1—O2ii | 2.4652 (12) | C4—C5 | 1.366 (2) |
Ca1—O2iii | 2.4652 (12) | C4—H4 | 0.9500 |
Ca1—O1ii | 2.5765 (12) | C5—C6 | 1.417 (2) |
Ca1—O1iii | 2.5765 (11) | C5—H5 | 0.9500 |
Ca1—C1ii | 2.8738 (17) | C6—C7 | 1.417 (2) |
Ca1—C1iii | 2.8738 (17) | C6—C11 | 1.425 (2) |
O1—C1 | 1.2638 (19) | C7—C8 | 1.361 (2) |
O1—Ca1ii | 2.5765 (12) | C7—H7 | 0.9500 |
O2—C1 | 1.2640 (19) | C8—C9 | 1.410 (3) |
O2—Ca1ii | 2.4652 (12) | C8—H8 | 0.9500 |
O1W—H1W | 0.863 (9) | C9—C10 | 1.368 (2) |
O1W—H2W | 0.856 (9) | C9—H9 | 0.9500 |
C1—C2 | 1.503 (2) | C10—C11 | 1.423 (2) |
C1—Ca1ii | 2.8738 (17) | C10—H10 | 0.9500 |
| | | |
O1—Ca1—O1i | 149.04 (6) | O1—Ca1—Ca1iv | 154.92 (3) |
O1—Ca1—O1Wi | 83.94 (4) | O1i—Ca1—Ca1iv | 38.46 (3) |
O1i—Ca1—O1Wi | 76.52 (4) | O1Wi—Ca1—Ca1iv | 76.19 (3) |
O1—Ca1—O1W | 76.52 (4) | O1W—Ca1—Ca1iv | 122.00 (3) |
O1i—Ca1—O1W | 83.94 (4) | O2ii—Ca1—Ca1iv | 74.03 (3) |
O1Wi—Ca1—O1W | 101.25 (7) | O2iii—Ca1—Ca1iv | 86.46 (3) |
O1—Ca1—O2ii | 124.92 (4) | O1ii—Ca1—Ca1iv | 123.17 (3) |
O1i—Ca1—O2ii | 79.59 (4) | O1iii—Ca1—Ca1iv | 34.74 (2) |
O1Wi—Ca1—O2ii | 150.20 (4) | C1ii—Ca1—Ca1iv | 97.70 (3) |
O1W—Ca1—O2ii | 93.60 (4) | C1iii—Ca1—Ca1iv | 60.70 (3) |
O1—Ca1—O2iii | 79.59 (4) | Ca1ii—Ca1—Ca1iv | 153.45 (3) |
O1i—Ca1—O2iii | 124.92 (4) | C1—O1—Ca1 | 161.56 (11) |
O1Wi—Ca1—O2iii | 93.60 (4) | C1—O1—Ca1ii | 90.20 (9) |
O1W—Ca1—O2iii | 150.20 (4) | Ca1—O1—Ca1ii | 106.81 (4) |
O2ii—Ca1—O2iii | 85.64 (6) | C1—O2—Ca1ii | 95.38 (9) |
O1—Ca1—O1ii | 73.19 (4) | Ca1—O1W—H1W | 117.9 (13) |
O1i—Ca1—O1ii | 127.48 (4) | Ca1—O1W—H2W | 137.4 (13) |
O1Wi—Ca1—O1ii | 155.86 (4) | H1W—O1W—H2W | 104.6 (15) |
O1W—Ca1—O1ii | 81.15 (4) | O1—C1—O2 | 121.12 (15) |
O2ii—Ca1—O1ii | 51.72 (4) | O1—C1—C2 | 118.93 (14) |
O2iii—Ca1—O1ii | 75.05 (4) | O2—C1—C2 | 119.88 (14) |
O1—Ca1—O1iii | 127.48 (4) | O1—C1—Ca1ii | 63.71 (8) |
O1i—Ca1—O1iii | 73.19 (4) | O2—C1—Ca1ii | 58.65 (8) |
O1Wi—Ca1—O1iii | 81.15 (4) | C2—C1—Ca1ii | 166.08 (11) |
O1W—Ca1—O1iii | 155.86 (4) | C3—C2—C11 | 120.01 (15) |
O2ii—Ca1—O1iii | 75.05 (4) | C3—C2—C1 | 117.95 (14) |
O2iii—Ca1—O1iii | 51.72 (3) | C11—C2—C1 | 122.04 (14) |
O1ii—Ca1—O1iii | 106.53 (5) | C2—C3—C4 | 121.10 (15) |
O1—Ca1—C1ii | 99.09 (4) | C2—C3—H3 | 119.5 |
O1i—Ca1—C1ii | 104.79 (4) | C4—C3—H3 | 119.5 |
O1Wi—Ca1—C1ii | 168.66 (5) | C5—C4—C3 | 120.13 (16) |
O1W—Ca1—C1ii | 90.08 (4) | C5—C4—H4 | 119.9 |
O2ii—Ca1—C1ii | 25.97 (4) | C3—C4—H4 | 119.9 |
O2iii—Ca1—C1ii | 76.33 (4) | C4—C5—C6 | 120.72 (16) |
O1ii—Ca1—C1ii | 26.09 (4) | C4—C5—H5 | 119.6 |
O1iii—Ca1—C1ii | 88.42 (4) | C6—C5—H5 | 119.6 |
O1—Ca1—C1iii | 104.79 (4) | C7—C6—C5 | 121.05 (16) |
O1i—Ca1—C1iii | 99.09 (4) | C7—C6—C11 | 119.25 (15) |
O1Wi—Ca1—C1iii | 90.08 (4) | C5—C6—C11 | 119.69 (15) |
O1W—Ca1—C1iii | 168.66 (5) | C8—C7—C6 | 121.26 (16) |
O2ii—Ca1—C1iii | 76.33 (4) | C8—C7—H7 | 119.4 |
O2iii—Ca1—C1iii | 25.97 (4) | C6—C7—H7 | 119.4 |
O1ii—Ca1—C1iii | 88.42 (4) | C7—C8—C9 | 119.63 (16) |
O1iii—Ca1—C1iii | 26.09 (4) | C7—C8—H8 | 120.2 |
C1ii—Ca1—C1iii | 78.59 (6) | C9—C8—H8 | 120.2 |
O1—Ca1—Ca1ii | 38.46 (3) | C10—C9—C8 | 121.08 (16) |
O1i—Ca1—Ca1ii | 154.92 (3) | C10—C9—H9 | 119.5 |
O1Wi—Ca1—Ca1ii | 122.00 (3) | C8—C9—H9 | 119.5 |
O1W—Ca1—Ca1ii | 76.19 (3) | C9—C10—C11 | 120.62 (16) |
O2ii—Ca1—Ca1ii | 86.46 (3) | C9—C10—H10 | 119.7 |
O2iii—Ca1—Ca1ii | 74.03 (3) | C11—C10—H10 | 119.7 |
O1ii—Ca1—Ca1ii | 34.74 (2) | C10—C11—C6 | 118.16 (14) |
O1iii—Ca1—Ca1ii | 123.17 (3) | C10—C11—C2 | 123.50 (15) |
C1ii—Ca1—Ca1ii | 60.70 (3) | C6—C11—C2 | 118.30 (15) |
C1iii—Ca1—Ca1ii | 97.70 (3) | | |
| | | |
O1i—Ca1—O1—C1 | 19.5 (3) | O1—C1—C2—C3 | −42.3 (2) |
O1Wi—Ca1—O1—C1 | −31.2 (3) | O2—C1—C2—C3 | 134.80 (16) |
O1W—Ca1—O1—C1 | 71.9 (3) | Ca1ii—C1—C2—C3 | 54.9 (5) |
O2ii—Ca1—O1—C1 | 156.8 (3) | O1—C1—C2—C11 | 138.69 (15) |
O2iii—Ca1—O1—C1 | −126.0 (3) | O2—C1—C2—C11 | −44.2 (2) |
O1ii—Ca1—O1—C1 | 156.6 (3) | Ca1ii—C1—C2—C11 | −124.0 (4) |
O1iii—Ca1—O1—C1 | −105.2 (3) | C11—C2—C3—C4 | 1.9 (2) |
C1ii—Ca1—O1—C1 | 159.8 (3) | C1—C2—C3—C4 | −177.15 (15) |
C1iii—Ca1—O1—C1 | −119.7 (3) | C2—C3—C4—C5 | −2.0 (3) |
Ca1ii—Ca1—O1—C1 | 156.6 (3) | C3—C4—C5—C6 | 0.1 (3) |
Ca1iv—Ca1—O1—C1 | −68.8 (3) | C4—C5—C6—C7 | −177.39 (16) |
O1i—Ca1—O1—Ca1ii | −137.05 (4) | C4—C5—C6—C11 | 1.9 (2) |
O1Wi—Ca1—O1—Ca1ii | 172.19 (5) | C5—C6—C7—C8 | 179.83 (16) |
O1W—Ca1—O1—Ca1ii | −84.68 (5) | C11—C6—C7—C8 | 0.5 (2) |
O2ii—Ca1—O1—Ca1ii | 0.25 (6) | C6—C7—C8—C9 | −0.3 (3) |
O2iii—Ca1—O1—Ca1ii | 77.38 (5) | C7—C8—C9—C10 | 0.0 (3) |
O1ii—Ca1—O1—Ca1ii | 0.0 | C8—C9—C10—C11 | 0.1 (2) |
O1iii—Ca1—O1—Ca1ii | 98.23 (7) | C9—C10—C11—C6 | 0.1 (2) |
C1ii—Ca1—O1—Ca1ii | 3.21 (5) | C9—C10—C11—C2 | −177.50 (15) |
C1iii—Ca1—O1—Ca1ii | 83.71 (5) | C7—C6—C11—C10 | −0.4 (2) |
Ca1iv—Ca1—O1—Ca1ii | 134.65 (7) | C5—C6—C11—C10 | −179.72 (14) |
Ca1—O1—C1—O2 | −170.2 (2) | C7—C6—C11—C2 | 177.31 (14) |
Ca1ii—O1—C1—O2 | −12.53 (15) | C5—C6—C11—C2 | −2.0 (2) |
Ca1—O1—C1—C2 | 6.9 (4) | C3—C2—C11—C10 | 177.74 (15) |
Ca1ii—O1—C1—C2 | 164.57 (13) | C1—C2—C11—C10 | −3.3 (2) |
Ca1—O1—C1—Ca1ii | −157.6 (3) | C3—C2—C11—C6 | 0.1 (2) |
Ca1ii—O2—C1—O1 | 13.16 (16) | C1—C2—C11—C6 | 179.11 (14) |
Ca1ii—O2—C1—C2 | −163.91 (12) | | |
Symmetry codes: (i) −x, y, −z+5/2; (ii) −x, −y, −z+2; (iii) x, −y, z+1/2; (iv) −x, −y, −z+3. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2v | 0.86 (1) | 1.88 (1) | 2.7120 (16) | 160 (2) |
Symmetry code: (v) −x, y, −z+3/2. |
(SrNPH)
catena-poly[[diaquastrontium(II)]-bis(µ-1-naphthoato)-
κ3O,
O':
O;
κ3O:
O,
O']
top
Crystal data top
[Sr(C11H7O2)2(H2O)2] | F(000) = 944 |
Mr = 465.98 | Dx = 1.616 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 13743 reflections |
a = 21.2740 (19) Å | θ = 1.0–30.0° |
b = 11.3397 (10) Å | µ = 2.85 mm−1 |
c = 7.9619 (5) Å | T = 123 K |
β = 94.520 (4)° | Cut fragment, colourless |
V = 1914.8 (3) Å3 | 0.20 × 0.20 × 0.10 mm |
Z = 4 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2312 independent reflections |
Radiation source: fine-focus sealed tube | 1853 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
ϕ and ω scans | θmax = 28.0°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −27→28 |
Tmin = 0.922, Tmax = 1.000 | k = −14→14 |
4336 measured reflections | l = −10→10 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0437P)2 + 1.1387P] where P = (Fo2 + 2Fc2)/3 |
2312 reflections | (Δ/σ)max < 0.001 |
138 parameters | Δρmax = 0.62 e Å−3 |
3 restraints | Δρmin = −0.45 e Å−3 |
Crystal data top
[Sr(C11H7O2)2(H2O)2] | V = 1914.8 (3) Å3 |
Mr = 465.98 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.2740 (19) Å | µ = 2.85 mm−1 |
b = 11.3397 (10) Å | T = 123 K |
c = 7.9619 (5) Å | 0.20 × 0.20 × 0.10 mm |
β = 94.520 (4)° | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2312 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1853 reflections with I > 2σ(I) |
Tmin = 0.922, Tmax = 1.000 | Rint = 0.059 |
4336 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 3 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.62 e Å−3 |
2312 reflections | Δρmin = −0.45 e Å−3 |
138 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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Sr1 | 0.0000 | 0.54911 (4) | 0.7500 | 0.01586 (14) | |
O1 | 0.08138 (10) | 0.3771 (2) | 0.7297 (3) | 0.0220 (5) | |
O2 | 0.04972 (10) | 0.4005 (2) | 0.9857 (2) | 0.0203 (5) | |
O1W | −0.07903 (12) | 0.6931 (2) | 0.5967 (3) | 0.0268 (6) | |
H1W | −0.0826 (18) | 0.688 (3) | 0.4875 (13) | 0.040* | |
H2W | −0.0992 (17) | 0.757 (2) | 0.616 (4) | 0.040* | |
C1 | 0.07734 (14) | 0.3404 (3) | 0.8781 (4) | 0.0173 (7) | |
C2 | 0.10307 (14) | 0.2211 (3) | 0.9292 (4) | 0.0171 (7) | |
C3 | 0.06709 (15) | 0.1487 (3) | 1.0219 (4) | 0.0201 (7) | |
H3 | 0.0275 | 0.1759 | 1.0538 | 0.024* | |
C4 | 0.08798 (16) | 0.0349 (3) | 1.0702 (4) | 0.0234 (8) | |
H4 | 0.0620 | −0.0146 | 1.1317 | 0.028* | |
C5 | 0.14525 (16) | −0.0041 (3) | 1.0292 (4) | 0.0231 (7) | |
H5 | 0.1588 | −0.0809 | 1.0629 | 0.028* | |
C6 | 0.18528 (15) | 0.0676 (3) | 0.9368 (4) | 0.0182 (7) | |
C7 | 0.24615 (15) | 0.0299 (3) | 0.8987 (4) | 0.0207 (7) | |
H7 | 0.2607 | −0.0459 | 0.9343 | 0.025* | |
C8 | 0.28399 (15) | 0.1004 (3) | 0.8122 (4) | 0.0234 (8) | |
H8 | 0.3244 | 0.0733 | 0.7870 | 0.028* | |
C9 | 0.26332 (15) | 0.2138 (3) | 0.7598 (4) | 0.0223 (8) | |
H9 | 0.2902 | 0.2626 | 0.6999 | 0.027* | |
C10 | 0.20490 (14) | 0.2543 (3) | 0.7942 (4) | 0.0186 (7) | |
H10 | 0.1918 | 0.3309 | 0.7579 | 0.022* | |
C11 | 0.16387 (15) | 0.1830 (3) | 0.8835 (4) | 0.0172 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sr1 | 0.0168 (2) | 0.0199 (2) | 0.0109 (2) | 0.000 | 0.00093 (14) | 0.000 |
O1 | 0.0257 (12) | 0.0265 (14) | 0.0140 (11) | 0.0098 (11) | 0.0022 (9) | 0.0021 (10) |
O2 | 0.0215 (12) | 0.0247 (13) | 0.0148 (11) | 0.0022 (10) | 0.0018 (9) | −0.0023 (10) |
O1W | 0.0322 (14) | 0.0322 (15) | 0.0159 (12) | 0.0128 (12) | 0.0010 (10) | 0.0011 (11) |
C1 | 0.0128 (14) | 0.0244 (19) | 0.0146 (15) | 0.0003 (13) | 0.0002 (12) | −0.0001 (13) |
C2 | 0.0190 (15) | 0.0201 (18) | 0.0116 (14) | 0.0008 (14) | −0.0023 (12) | −0.0012 (13) |
C3 | 0.0199 (16) | 0.0240 (19) | 0.0167 (16) | 0.0037 (14) | 0.0031 (13) | −0.0003 (14) |
C4 | 0.0247 (17) | 0.028 (2) | 0.0182 (16) | −0.0041 (16) | 0.0044 (13) | 0.0043 (14) |
C5 | 0.0286 (18) | 0.0221 (17) | 0.0181 (16) | 0.0034 (16) | −0.0011 (14) | −0.0011 (15) |
C6 | 0.0208 (15) | 0.0221 (19) | 0.0109 (14) | 0.0029 (14) | −0.0035 (12) | −0.0054 (13) |
C7 | 0.0222 (16) | 0.021 (2) | 0.0182 (15) | 0.0047 (14) | −0.0030 (12) | −0.0026 (13) |
C8 | 0.0195 (16) | 0.029 (2) | 0.0211 (17) | 0.0054 (15) | −0.0016 (13) | −0.0065 (15) |
C9 | 0.0218 (18) | 0.026 (2) | 0.0197 (16) | −0.0027 (15) | 0.0026 (14) | −0.0006 (14) |
C10 | 0.0172 (15) | 0.0222 (18) | 0.0157 (15) | 0.0012 (14) | −0.0028 (12) | −0.0013 (13) |
C11 | 0.0219 (16) | 0.0184 (18) | 0.0107 (15) | 0.0003 (14) | −0.0022 (12) | −0.0050 (12) |
Geometric parameters (Å, º) top
Sr1—O2i | 2.495 (2) | C2—C11 | 1.438 (4) |
Sr1—O2ii | 2.495 (2) | C3—C4 | 1.408 (5) |
Sr1—O1Wiii | 2.581 (2) | C3—H3 | 0.9500 |
Sr1—O1W | 2.581 (2) | C4—C5 | 1.360 (5) |
Sr1—O1 | 2.621 (2) | C4—H4 | 0.9500 |
Sr1—O1iii | 2.621 (2) | C5—C6 | 1.423 (5) |
Sr1—O2iii | 2.678 (2) | C5—H5 | 0.9500 |
Sr1—O2 | 2.678 (2) | C6—C7 | 1.419 (4) |
Sr1—C1iii | 3.014 (3) | C6—C11 | 1.439 (4) |
Sr1—C1 | 3.014 (3) | C7—C8 | 1.360 (5) |
O1—C1 | 1.262 (4) | C7—H7 | 0.9500 |
O2—C1 | 1.274 (4) | C8—C9 | 1.411 (5) |
O2—Sr1i | 2.495 (2) | C8—H8 | 0.9500 |
O1W—H1W | 0.868 (10) | C9—C10 | 1.373 (4) |
O1W—H2W | 0.865 (10) | C9—H9 | 0.9500 |
C1—C2 | 1.503 (4) | C10—C11 | 1.421 (4) |
C2—C3 | 1.376 (4) | C10—H10 | 0.9500 |
| | | |
O2i—Sr1—O2ii | 153.50 (11) | O2i—Sr1—Sr1i | 38.50 (5) |
O2i—Sr1—O1Wiii | 76.10 (7) | O2ii—Sr1—Sr1i | 154.98 (5) |
O2ii—Sr1—O1Wiii | 87.14 (7) | O1Wiii—Sr1—Sr1i | 76.38 (5) |
O2i—Sr1—O1W | 87.14 (7) | O1W—Sr1—Sr1i | 125.21 (5) |
O2ii—Sr1—O1W | 76.10 (7) | O1—Sr1—Sr1i | 84.78 (5) |
O1Wiii—Sr1—O1W | 101.48 (12) | O1iii—Sr1—Sr1i | 71.95 (5) |
O2i—Sr1—O1 | 123.26 (7) | O2iii—Sr1—Sr1i | 118.39 (5) |
O2ii—Sr1—O1 | 78.03 (7) | O2—Sr1—Sr1i | 35.45 (5) |
O1Wiii—Sr1—O1 | 95.23 (8) | C1iii—Sr1—Sr1i | 94.18 (6) |
O1W—Sr1—O1 | 148.27 (7) | C1—Sr1—Sr1i | 60.26 (6) |
O2i—Sr1—O1iii | 78.03 (7) | Sr1iv—Sr1—Sr1i | 148.74 (2) |
O2ii—Sr1—O1iii | 123.26 (7) | C1—O1—Sr1 | 95.39 (18) |
O1Wiii—Sr1—O1iii | 148.27 (7) | C1—O2—Sr1i | 159.8 (2) |
O1W—Sr1—O1iii | 95.23 (8) | C1—O2—Sr1 | 92.46 (18) |
O1—Sr1—O1iii | 83.85 (11) | Sr1i—O2—Sr1 | 106.05 (8) |
O2i—Sr1—O2iii | 124.41 (8) | Sr1—O1W—H1W | 116 (2) |
O2ii—Sr1—O2iii | 73.95 (8) | Sr1—O1W—H2W | 140 (2) |
O1Wiii—Sr1—O2iii | 159.48 (7) | H1W—O1W—H2W | 103 (2) |
O1W—Sr1—O2iii | 81.97 (8) | O1—C1—O2 | 121.5 (3) |
O1—Sr1—O2iii | 73.43 (7) | O1—C1—C2 | 120.0 (3) |
O1iii—Sr1—O2iii | 49.34 (6) | O2—C1—C2 | 118.5 (3) |
O2i—Sr1—O2 | 73.95 (8) | O1—C1—Sr1 | 59.97 (16) |
O2ii—Sr1—O2 | 124.41 (8) | O2—C1—Sr1 | 62.56 (16) |
O1Wiii—Sr1—O2 | 81.97 (8) | C2—C1—Sr1 | 167.3 (2) |
O1W—Sr1—O2 | 159.48 (7) | C3—C2—C11 | 120.4 (3) |
O1—Sr1—O2 | 49.34 (6) | C3—C2—C1 | 118.4 (3) |
O1iii—Sr1—O2 | 73.43 (7) | C11—C2—C1 | 121.2 (3) |
O2iii—Sr1—O2 | 101.97 (10) | C2—C3—C4 | 121.1 (3) |
O2i—Sr1—C1iii | 102.06 (8) | C2—C3—H3 | 119.5 |
O2ii—Sr1—C1iii | 98.69 (8) | C4—C3—H3 | 119.5 |
O1Wiii—Sr1—C1iii | 167.13 (8) | C5—C4—C3 | 120.1 (3) |
O1W—Sr1—C1iii | 91.09 (8) | C5—C4—H4 | 119.9 |
O1—Sr1—C1iii | 74.95 (8) | C3—C4—H4 | 119.9 |
O1iii—Sr1—C1iii | 24.64 (7) | C4—C5—C6 | 121.5 (3) |
O2iii—Sr1—C1iii | 24.98 (7) | C4—C5—H5 | 119.2 |
O2—Sr1—C1iii | 85.28 (8) | C6—C5—H5 | 119.2 |
O2i—Sr1—C1 | 98.69 (8) | C7—C6—C5 | 122.2 (3) |
O2ii—Sr1—C1 | 102.06 (8) | C7—C6—C11 | 118.9 (3) |
O1Wiii—Sr1—C1 | 91.09 (8) | C5—C6—C11 | 118.9 (3) |
O1W—Sr1—C1 | 167.13 (9) | C8—C7—C6 | 121.2 (3) |
O1—Sr1—C1 | 24.64 (7) | C8—C7—H7 | 119.4 |
O1iii—Sr1—C1 | 74.95 (8) | C6—C7—H7 | 119.4 |
O2iii—Sr1—C1 | 85.28 (8) | C7—C8—C9 | 120.2 (3) |
O2—Sr1—C1 | 24.98 (7) | C7—C8—H8 | 119.9 |
C1iii—Sr1—C1 | 76.50 (12) | C9—C8—H8 | 119.9 |
O2i—Sr1—Sr1iv | 154.98 (5) | C10—C9—C8 | 120.8 (3) |
O2ii—Sr1—Sr1iv | 38.50 (5) | C10—C9—H9 | 119.6 |
O1Wiii—Sr1—Sr1iv | 125.21 (5) | C8—C9—H9 | 119.6 |
O1W—Sr1—Sr1iv | 76.38 (5) | C9—C10—C11 | 120.7 (3) |
O1—Sr1—Sr1iv | 71.95 (5) | C9—C10—H10 | 119.6 |
O1iii—Sr1—Sr1iv | 84.78 (5) | C11—C10—H10 | 119.6 |
O2iii—Sr1—Sr1iv | 35.45 (5) | C10—C11—C2 | 123.8 (3) |
O2—Sr1—Sr1iv | 118.39 (5) | C10—C11—C6 | 118.2 (3) |
C1iii—Sr1—Sr1iv | 60.26 (6) | C2—C11—C6 | 118.0 (3) |
C1—Sr1—Sr1iv | 94.18 (6) | | |
| | | |
O2i—Sr1—O1—C1 | 4.4 (2) | O2ii—Sr1—C1—O2 | 155.47 (18) |
O2ii—Sr1—O1—C1 | 167.11 (19) | O1Wiii—Sr1—C1—O2 | 68.16 (18) |
O1Wiii—Sr1—O1—C1 | 81.16 (19) | O1W—Sr1—C1—O2 | −124.2 (3) |
O1W—Sr1—O1—C1 | −156.97 (19) | O1—Sr1—C1—O2 | 168.4 (3) |
O1iii—Sr1—O1—C1 | −66.96 (18) | O1iii—Sr1—C1—O2 | −82.97 (18) |
O2iii—Sr1—O1—C1 | −116.30 (19) | O2iii—Sr1—C1—O2 | −132.07 (17) |
O2—Sr1—O1—C1 | 6.44 (17) | C1iii—Sr1—C1—O2 | −108.4 (2) |
C1iii—Sr1—O1—C1 | −90.4 (2) | Sr1iv—Sr1—C1—O2 | −166.42 (17) |
Sr1iv—Sr1—O1—C1 | −153.45 (19) | Sr1i—Sr1—C1—O2 | −5.45 (15) |
Sr1i—Sr1—O1—C1 | 5.39 (18) | O2i—Sr1—C1—C2 | 90.0 (9) |
O2i—Sr1—O2—C1 | 171.8 (2) | O2ii—Sr1—C1—C2 | −106.6 (9) |
O2ii—Sr1—O2—C1 | −29.5 (2) | O1Wiii—Sr1—C1—C2 | 166.1 (9) |
O1Wiii—Sr1—O2—C1 | −110.40 (19) | O1W—Sr1—C1—C2 | −26.2 (12) |
O1W—Sr1—O2—C1 | 148.3 (2) | O1—Sr1—C1—C2 | −93.7 (10) |
O1—Sr1—O2—C1 | −6.36 (17) | O1iii—Sr1—C1—C2 | 15.0 (9) |
O1iii—Sr1—O2—C1 | 89.85 (18) | O2iii—Sr1—C1—C2 | −34.1 (9) |
O2iii—Sr1—O2—C1 | 49.14 (17) | O2—Sr1—C1—C2 | 98.0 (10) |
C1iii—Sr1—O2—C1 | 67.8 (2) | C1iii—Sr1—C1—C2 | −10.4 (9) |
Sr1iv—Sr1—O2—C1 | 15.44 (19) | Sr1iv—Sr1—C1—C2 | −68.4 (9) |
Sr1i—Sr1—O2—C1 | 171.8 (2) | Sr1i—Sr1—C1—C2 | 92.5 (9) |
O2i—Sr1—O2—Sr1i | 0.0 | O1—C1—C2—C3 | −135.5 (3) |
O2ii—Sr1—O2—Sr1i | 158.69 (8) | O2—C1—C2—C3 | 42.1 (4) |
O1Wiii—Sr1—O2—Sr1i | 77.77 (9) | Sr1—C1—C2—C3 | −49.2 (11) |
O1W—Sr1—O2—Sr1i | −23.5 (3) | O1—C1—C2—C11 | 44.8 (4) |
O1—Sr1—O2—Sr1i | −178.19 (13) | O2—C1—C2—C11 | −137.7 (3) |
O1iii—Sr1—O2—Sr1i | −81.98 (8) | Sr1—C1—C2—C11 | 131.1 (9) |
O2iii—Sr1—O2—Sr1i | −122.69 (9) | C11—C2—C3—C4 | −1.7 (5) |
C1iii—Sr1—O2—Sr1i | −104.00 (9) | C1—C2—C3—C4 | 178.5 (3) |
C1—Sr1—O2—Sr1i | −171.8 (2) | C2—C3—C4—C5 | 1.7 (5) |
Sr1iv—Sr1—O2—Sr1i | −156.39 (5) | C3—C4—C5—C6 | −0.2 (5) |
Sr1—O1—C1—O2 | −12.1 (3) | C4—C5—C6—C7 | 177.5 (3) |
Sr1—O1—C1—C2 | 165.4 (2) | C4—C5—C6—C11 | −1.1 (5) |
Sr1i—O2—C1—O1 | 168.5 (4) | C5—C6—C7—C8 | −179.1 (3) |
Sr1—O2—C1—O1 | 11.8 (3) | C11—C6—C7—C8 | −0.5 (5) |
Sr1i—O2—C1—C2 | −9.0 (8) | C6—C7—C8—C9 | 0.6 (5) |
Sr1—O2—C1—C2 | −165.7 (2) | C7—C8—C9—C10 | −0.3 (5) |
Sr1i—O2—C1—Sr1 | 156.7 (6) | C8—C9—C10—C11 | 0.0 (5) |
O2i—Sr1—C1—O1 | −176.31 (18) | C9—C10—C11—C2 | 177.7 (3) |
O2ii—Sr1—C1—O1 | −12.90 (19) | C9—C10—C11—C6 | 0.1 (4) |
O1Wiii—Sr1—C1—O1 | −100.21 (19) | C3—C2—C11—C10 | −177.3 (3) |
O1W—Sr1—C1—O1 | 67.5 (4) | C1—C2—C11—C10 | 2.5 (5) |
O1iii—Sr1—C1—O1 | 108.66 (19) | C3—C2—C11—C6 | 0.3 (4) |
O2iii—Sr1—C1—O1 | 59.56 (18) | C1—C2—C11—C6 | −179.9 (3) |
O2—Sr1—C1—O1 | −168.4 (3) | C7—C6—C11—C10 | 0.2 (4) |
C1iii—Sr1—C1—O1 | 83.28 (19) | C5—C6—C11—C10 | 178.8 (3) |
Sr1iv—Sr1—C1—O1 | 25.22 (18) | C7—C6—C11—C2 | −177.6 (3) |
Sr1i—Sr1—C1—O1 | −173.8 (2) | C5—C6—C11—C2 | 1.0 (4) |
O2i—Sr1—C1—O2 | −7.9 (2) | | |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, −y+1, z−1/2; (iii) −x, y, −z+3/2; (iv) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O1iv | 0.87 (1) | 1.89 (1) | 2.715 (3) | 160 (3) |
Symmetry code: (iv) −x, −y+1, −z+1. |
(BaNPH)
catena-poly[[diaquabarium(II)]-bis(µ-1-naphthoato)-
κ3O,
O':
O;
κ3O:
O,
O']
top
Crystal data top
[Ba(C11H7O2)2(H2O)2] | F(000) = 1016 |
Mr = 515.70 | Dx = 1.689 Mg m−3 |
Orthorhombic, Pbcn | Synchrotron radiation, λ = 0.82520 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 8174 reflections |
a = 20.464 (3) Å | θ = 3.7–32.9° |
b = 11.9699 (15) Å | µ = 1.99 mm−1 |
c = 8.2812 (10) Å | T = 150 K |
V = 2028.5 (4) Å3 | Plate, colourless |
Z = 4 | 0.10 × 0.10 × 0.01 mm |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 2355 independent reflections |
Radiation source: Daresbury SRS station 9.8 | 2196 reflections with I > 2σ(I) |
Silicon 111 monochromator | Rint = 0.172 |
fine slice ω scans | θmax = 33.0°, θmin = 3.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −26→26 |
Tmin = 0.673, Tmax = 1.000 | k = −15→15 |
14467 measured reflections | l = −10→10 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.126 | w = 1/[σ2(Fo2) + (0.0549P)2 + 1.7007P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max = 0.003 |
2355 reflections | Δρmax = 1.44 e Å−3 |
139 parameters | Δρmin = −1.46 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0135 (10) |
Crystal data top
[Ba(C11H7O2)2(H2O)2] | V = 2028.5 (4) Å3 |
Mr = 515.70 | Z = 4 |
Orthorhombic, Pbcn | Synchrotron radiation, λ = 0.82520 Å |
a = 20.464 (3) Å | µ = 1.99 mm−1 |
b = 11.9699 (15) Å | T = 150 K |
c = 8.2812 (10) Å | 0.10 × 0.10 × 0.01 mm |
Data collection top
Bruker SMART APEXII CCD area-detector diffractometer | 2355 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2196 reflections with I > 2σ(I) |
Tmin = 0.673, Tmax = 1.000 | Rint = 0.172 |
14467 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 3 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 1.44 e Å−3 |
2355 reflections | Δρmin = −1.46 e Å−3 |
139 parameters | |
Special details top
Experimental. SADABS `absorbtion correction' also includes a correction for synchrotron
beam decay. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ba1 | 0.5000 | 1.058363 (17) | 0.2500 | 0.01293 (18) | |
O1 | 0.55542 (9) | 0.89902 (15) | 0.0331 (2) | 0.0202 (4) | |
O2 | 0.58514 (11) | 0.87800 (18) | 0.2876 (3) | 0.0227 (5) | |
O1W | 0.58616 (10) | 1.20076 (18) | 0.0948 (2) | 0.0259 (5) | |
H1W | 0.5914 (16) | 1.186 (3) | −0.0081 (16) | 0.039* | |
H2W | 0.6251 (9) | 1.225 (3) | 0.120 (4) | 0.039* | |
C1 | 0.60220 (12) | 0.7246 (2) | 0.1049 (3) | 0.0150 (5) | |
C2 | 0.56422 (13) | 0.6626 (2) | 0.0018 (3) | 0.0205 (6) | |
H2 | 0.5252 | 0.6939 | −0.0404 | 0.025* | |
C3 | 0.58220 (15) | 0.5532 (2) | −0.0425 (4) | 0.0253 (6) | |
H3 | 0.5547 | 0.5107 | −0.1117 | 0.030* | |
C4 | 0.63869 (19) | 0.5084 (2) | 0.0137 (3) | 0.0235 (7) | |
H4 | 0.6506 | 0.4347 | −0.0173 | 0.028* | |
C5 | 0.68027 (13) | 0.5699 (2) | 0.1178 (3) | 0.0182 (6) | |
C6 | 0.66177 (12) | 0.67921 (19) | 0.1673 (3) | 0.0143 (5) | |
C7 | 0.70534 (16) | 0.7392 (3) | 0.2701 (3) | 0.0176 (6) | |
H7 | 0.6941 | 0.8123 | 0.3054 | 0.021* | |
C8 | 0.76338 (14) | 0.6921 (2) | 0.3186 (4) | 0.0237 (6) | |
H8 | 0.7920 | 0.7336 | 0.3863 | 0.028* | |
C9 | 0.7814 (2) | 0.5833 (4) | 0.2697 (4) | 0.0252 (7) | |
H9 | 0.8214 | 0.5514 | 0.3051 | 0.030* | |
C10 | 0.74053 (14) | 0.5246 (2) | 0.1709 (3) | 0.0236 (6) | |
H10 | 0.7527 | 0.4517 | 0.1370 | 0.028* | |
C11 | 0.57986 (12) | 0.8419 (2) | 0.1458 (3) | 0.0159 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ba1 | 0.0188 (2) | 0.0109 (2) | 0.0090 (3) | 0.000 | −0.00099 (6) | 0.000 |
O1 | 0.0285 (10) | 0.0176 (9) | 0.0144 (9) | 0.0065 (7) | −0.0021 (7) | 0.0025 (7) |
O2 | 0.0319 (11) | 0.0228 (10) | 0.0133 (9) | 0.0106 (9) | −0.0041 (9) | −0.0014 (9) |
O1W | 0.0254 (10) | 0.0344 (11) | 0.0178 (10) | −0.0105 (9) | −0.0011 (8) | −0.0002 (8) |
C1 | 0.0181 (12) | 0.0165 (11) | 0.0103 (11) | 0.0019 (9) | 0.0013 (9) | 0.0011 (9) |
C2 | 0.0196 (13) | 0.0215 (12) | 0.0204 (14) | 0.0020 (10) | −0.0042 (10) | −0.0014 (10) |
C3 | 0.0312 (16) | 0.0218 (14) | 0.0228 (16) | −0.0038 (11) | −0.0026 (13) | −0.0073 (10) |
C4 | 0.0316 (18) | 0.0184 (13) | 0.0206 (16) | 0.0019 (10) | 0.0032 (10) | −0.0049 (12) |
C5 | 0.0222 (13) | 0.0179 (12) | 0.0145 (14) | 0.0024 (9) | 0.0037 (10) | 0.0016 (9) |
C6 | 0.0185 (12) | 0.0148 (11) | 0.0097 (11) | 0.0001 (9) | 0.0030 (9) | 0.0038 (8) |
C7 | 0.0178 (15) | 0.0219 (15) | 0.0132 (12) | −0.0032 (12) | 0.0021 (10) | 0.0028 (10) |
C8 | 0.0211 (13) | 0.0313 (15) | 0.0187 (16) | −0.0024 (11) | −0.0034 (11) | 0.0021 (11) |
C9 | 0.0177 (18) | 0.0361 (17) | 0.0219 (16) | 0.0075 (17) | 0.0008 (11) | 0.0067 (13) |
C10 | 0.0263 (14) | 0.0255 (13) | 0.0190 (14) | 0.0105 (11) | 0.0021 (11) | 0.0008 (11) |
C11 | 0.0171 (11) | 0.0183 (12) | 0.0124 (13) | 0.0013 (9) | −0.0001 (10) | 0.0017 (9) |
Geometric parameters (Å, º) top
Ba1—O1i | 2.6536 (19) | C1—C11 | 1.515 (3) |
Ba1—O1ii | 2.6536 (19) | C2—C3 | 1.409 (3) |
Ba1—O1W | 2.769 (2) | C2—H2 | 0.9500 |
Ba1—O1Wiii | 2.769 (2) | C3—C4 | 1.356 (5) |
Ba1—O2iii | 2.792 (2) | C3—H3 | 0.9500 |
Ba1—O2 | 2.792 (2) | C4—C5 | 1.418 (4) |
Ba1—O1 | 2.8551 (18) | C4—H4 | 0.9500 |
Ba1—O1iii | 2.8551 (18) | C5—C10 | 1.417 (4) |
Ba1—C11iii | 3.183 (3) | C5—C6 | 1.422 (3) |
Ba1—C11 | 3.183 (3) | C6—C7 | 1.427 (4) |
O1—C11 | 1.260 (3) | C7—C8 | 1.375 (4) |
O1—Ba1i | 2.6536 (19) | C7—H7 | 0.9500 |
O2—C11 | 1.256 (3) | C8—C9 | 1.413 (5) |
O1W—H1W | 0.878 (10) | C8—H8 | 0.9500 |
O1W—H2W | 0.872 (10) | C9—C10 | 1.365 (5) |
C1—C2 | 1.373 (4) | C9—H9 | 0.9500 |
C1—C6 | 1.431 (3) | C10—H10 | 0.9500 |
| | | |
O1i—Ba1—O1ii | 157.84 (8) | O1i—Ba1—Ba1iv | 153.96 (4) |
O1i—Ba1—O1W | 75.15 (6) | O1ii—Ba1—Ba1iv | 39.15 (4) |
O1ii—Ba1—O1W | 91.13 (6) | O1W—Ba1—Ba1iv | 129.55 (4) |
O1i—Ba1—O1Wiii | 91.13 (6) | O1Wiii—Ba1—Ba1iv | 75.93 (4) |
O1ii—Ba1—O1Wiii | 75.15 (6) | O2iii—Ba1—Ba1iv | 81.86 (5) |
O1W—Ba1—O1Wiii | 104.01 (9) | O2—Ba1—Ba1iv | 69.33 (5) |
O1i—Ba1—O2iii | 77.49 (6) | O1—Ba1—Ba1iv | 112.50 (4) |
O1ii—Ba1—O2iii | 120.93 (6) | O1iii—Ba1—Ba1iv | 35.93 (4) |
O1W—Ba1—O2iii | 145.25 (7) | C11iii—Ba1—Ba1iv | 58.85 (5) |
O1Wiii—Ba1—O2iii | 97.49 (7) | C11—Ba1—Ba1iv | 89.81 (5) |
O1i—Ba1—O2 | 120.93 (6) | Ba1i—Ba1—Ba1iv | 142.707 (12) |
O1ii—Ba1—O2 | 77.49 (6) | C11—O1—Ba1i | 158.12 (17) |
O1W—Ba1—O2 | 97.49 (7) | C11—O1—Ba1 | 93.10 (16) |
O1Wiii—Ba1—O2 | 145.25 (7) | Ba1i—O1—Ba1 | 104.93 (6) |
O2iii—Ba1—O2 | 78.69 (10) | C11—O2—Ba1 | 96.20 (16) |
O1i—Ba1—O1 | 75.07 (6) | Ba1—O1W—H1W | 114 (2) |
O1ii—Ba1—O1 | 120.96 (6) | Ba1—O1W—H2W | 133 (2) |
O1W—Ba1—O1 | 82.30 (6) | H1W—O1W—H2W | 101 (2) |
O1Wiii—Ba1—O1 | 163.01 (6) | C2—C1—C6 | 120.1 (2) |
O2iii—Ba1—O1 | 70.19 (6) | C2—C1—C11 | 118.0 (2) |
O2—Ba1—O1 | 46.03 (6) | C6—C1—C11 | 121.9 (2) |
O1i—Ba1—O1iii | 120.96 (6) | C1—C2—C3 | 121.1 (2) |
O1ii—Ba1—O1iii | 75.07 (6) | C1—C2—H2 | 119.4 |
O1W—Ba1—O1iii | 163.01 (6) | C3—C2—H2 | 119.4 |
O1Wiii—Ba1—O1iii | 82.30 (6) | C4—C3—C2 | 120.0 (3) |
O2iii—Ba1—O1iii | 46.03 (6) | C4—C3—H3 | 120.0 |
O2—Ba1—O1iii | 70.19 (6) | C2—C3—H3 | 120.0 |
O1—Ba1—O1iii | 96.17 (8) | C3—C4—C5 | 121.0 (2) |
O1i—Ba1—C11iii | 100.17 (6) | C3—C4—H4 | 119.5 |
O1ii—Ba1—C11iii | 97.84 (6) | C5—C4—H4 | 119.5 |
O1W—Ba1—C11iii | 162.56 (7) | C10—C5—C4 | 120.8 (3) |
O1Wiii—Ba1—C11iii | 92.77 (6) | C10—C5—C6 | 119.6 (3) |
O2iii—Ba1—C11iii | 23.10 (6) | C4—C5—C6 | 119.5 (3) |
O2—Ba1—C11iii | 70.16 (7) | C5—C6—C7 | 117.9 (2) |
O1—Ba1—C11iii | 80.26 (6) | C5—C6—C1 | 118.2 (2) |
O1iii—Ba1—C11iii | 23.29 (6) | C7—C6—C1 | 123.8 (2) |
O1i—Ba1—C11 | 97.84 (6) | C8—C7—C6 | 120.5 (3) |
O1ii—Ba1—C11 | 100.17 (6) | C8—C7—H7 | 119.7 |
O1W—Ba1—C11 | 92.77 (6) | C6—C7—H7 | 119.7 |
O1Wiii—Ba1—C11 | 162.56 (7) | C7—C8—C9 | 121.3 (3) |
O2iii—Ba1—C11 | 70.16 (7) | C7—C8—H8 | 119.3 |
O2—Ba1—C11 | 23.10 (6) | C9—C8—H8 | 119.3 |
O1—Ba1—C11 | 23.29 (6) | C10—C9—C8 | 119.1 (3) |
O1iii—Ba1—C11 | 80.26 (6) | C10—C9—H9 | 120.5 |
C11iii—Ba1—C11 | 71.00 (9) | C8—C9—H9 | 120.5 |
O1i—Ba1—Ba1i | 39.15 (4) | C9—C10—C5 | 121.5 (3) |
O1ii—Ba1—Ba1i | 153.96 (4) | C9—C10—H10 | 119.3 |
O1W—Ba1—Ba1i | 75.93 (4) | C5—C10—H10 | 119.3 |
O1Wiii—Ba1—Ba1i | 129.55 (4) | O2—C11—O1 | 122.7 (2) |
O2iii—Ba1—Ba1i | 69.33 (5) | O2—C11—C1 | 120.1 (2) |
O2—Ba1—Ba1i | 81.86 (5) | O1—C11—C1 | 117.2 (2) |
O1—Ba1—Ba1i | 35.93 (4) | O2—C11—Ba1 | 60.70 (14) |
O1iii—Ba1—Ba1i | 112.50 (4) | O1—C11—Ba1 | 63.61 (14) |
C11iii—Ba1—Ba1i | 89.81 (5) | C1—C11—Ba1 | 165.96 (16) |
C11—Ba1—Ba1i | 58.85 (5) | | |
| | | |
O1i—Ba1—O1—C11 | −167.48 (18) | C8—C9—C10—C5 | −0.6 (5) |
O1ii—Ba1—O1—C11 | 29.24 (17) | C4—C5—C10—C9 | 179.2 (3) |
O1W—Ba1—O1—C11 | 115.91 (15) | C6—C5—C10—C9 | 0.4 (4) |
O1Wiii—Ba1—O1—C11 | −130.9 (2) | Ba1—O2—C11—O1 | 15.1 (3) |
O2iii—Ba1—O1—C11 | −85.66 (16) | Ba1—O2—C11—C1 | −163.85 (19) |
O2—Ba1—O1—C11 | 7.66 (14) | Ba1i—O1—C11—O2 | −160.5 (3) |
O1iii—Ba1—O1—C11 | −47.04 (14) | Ba1—O1—C11—O2 | −14.7 (3) |
C11iii—Ba1—O1—C11 | −64.11 (17) | Ba1i—O1—C11—C1 | 18.5 (6) |
Ba1i—Ba1—O1—C11 | −167.48 (18) | Ba1—O1—C11—C1 | 164.29 (19) |
Ba1iv—Ba1—O1—C11 | −13.84 (16) | Ba1i—O1—C11—Ba1 | −145.8 (5) |
O1i—Ba1—O1—Ba1i | 0.0 | C2—C1—C11—O2 | 139.5 (3) |
O1ii—Ba1—O1—Ba1i | −163.28 (5) | C6—C1—C11—O2 | −42.0 (4) |
O1W—Ba1—O1—Ba1i | −76.61 (7) | C2—C1—C11—O1 | −39.5 (3) |
O1Wiii—Ba1—O1—Ba1i | 36.6 (2) | C6—C1—C11—O1 | 139.0 (2) |
O2iii—Ba1—O1—Ba1i | 81.82 (7) | C2—C1—C11—Ba1 | 50.2 (8) |
O2—Ba1—O1—Ba1i | 175.14 (11) | C6—C1—C11—Ba1 | −131.3 (6) |
O1iii—Ba1—O1—Ba1i | 120.44 (8) | O1i—Ba1—C11—O2 | 178.06 (16) |
C11iii—Ba1—O1—Ba1i | 103.37 (7) | O1ii—Ba1—C11—O2 | 11.03 (17) |
C11—Ba1—O1—Ba1i | 167.48 (18) | O1W—Ba1—C11—O2 | 102.68 (17) |
Ba1iv—Ba1—O1—Ba1i | 153.64 (4) | O1Wiii—Ba1—C11—O2 | −61.6 (3) |
O1i—Ba1—O2—C11 | −2.24 (19) | O2iii—Ba1—C11—O2 | −108.33 (17) |
O1ii—Ba1—O2—C11 | −168.87 (17) | O1—Ba1—C11—O2 | 165.9 (3) |
O1W—Ba1—O2—C11 | −79.38 (17) | O1iii—Ba1—C11—O2 | −61.73 (17) |
O1Wiii—Ba1—O2—C11 | 152.44 (16) | C11iii—Ba1—C11—O2 | −83.83 (17) |
O2iii—Ba1—O2—C11 | 65.59 (15) | Ba1i—Ba1—C11—O2 | 174.40 (18) |
O1—Ba1—O2—C11 | −7.72 (15) | Ba1iv—Ba1—C11—O2 | −26.92 (16) |
O1iii—Ba1—O2—C11 | 112.70 (17) | O1i—Ba1—C11—O1 | 12.21 (18) |
C11iii—Ba1—O2—C11 | 87.91 (17) | O1ii—Ba1—C11—O1 | −154.82 (15) |
Ba1i—Ba1—O2—C11 | −4.84 (16) | O1W—Ba1—C11—O1 | −63.18 (15) |
Ba1iv—Ba1—O2—C11 | 151.06 (17) | O1Wiii—Ba1—C11—O1 | 132.5 (2) |
C6—C1—C2—C3 | 1.1 (4) | O2iii—Ba1—C11—O1 | 85.82 (16) |
C11—C1—C2—C3 | 179.6 (2) | O2—Ba1—C11—O1 | −165.9 (3) |
C1—C2—C3—C4 | −1.7 (4) | O1iii—Ba1—C11—O1 | 132.42 (14) |
C2—C3—C4—C5 | 0.4 (5) | C11iii—Ba1—C11—O1 | 110.32 (17) |
C3—C4—C5—C10 | −177.4 (3) | Ba1i—Ba1—C11—O1 | 8.55 (13) |
C3—C4—C5—C6 | 1.5 (4) | Ba1iv—Ba1—C11—O1 | 167.23 (14) |
C10—C5—C6—C7 | −0.2 (4) | O1i—Ba1—C11—C1 | −84.6 (7) |
C4—C5—C6—C7 | −179.1 (2) | O1ii—Ba1—C11—C1 | 108.4 (7) |
C10—C5—C6—C1 | 176.9 (2) | O1W—Ba1—C11—C1 | −160.0 (7) |
C4—C5—C6—C1 | −2.0 (4) | O1Wiii—Ba1—C11—C1 | 35.7 (8) |
C2—C1—C6—C5 | 0.7 (4) | O2iii—Ba1—C11—C1 | −11.0 (7) |
C11—C1—C6—C5 | −177.7 (2) | O2—Ba1—C11—C1 | 97.3 (7) |
C2—C1—C6—C7 | 177.6 (3) | O1—Ba1—C11—C1 | −96.8 (7) |
C11—C1—C6—C7 | −0.8 (4) | O1iii—Ba1—C11—C1 | 35.6 (7) |
C5—C6—C7—C8 | 0.3 (4) | C11iii—Ba1—C11—C1 | 13.5 (7) |
C1—C6—C7—C8 | −176.6 (3) | Ba1i—Ba1—C11—C1 | −88.3 (7) |
C6—C7—C8—C9 | −0.6 (5) | Ba1iv—Ba1—C11—C1 | 70.4 (7) |
C7—C8—C9—C10 | 0.8 (5) | | |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, −y+2, z+1/2; (iii) −x+1, y, −z+1/2; (iv) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2v | 0.88 (1) | 1.86 (1) | 2.713 (3) | 163 (3) |
Symmetry code: (v) x, −y+2, z−1/2. |
Experimental details
| (MgNPH) | (CaNPH) | (SrNPH) | (BaNPH) |
Crystal data |
Chemical formula | [Mg(C11H7O2)2(H2O)3]·2H2O | [Ca(C11H7O2)2(H2O)2] | [Sr(C11H7O2)2(H2O)2] | [Ba(C11H7O2)2(H2O)2] |
Mr | 456.72 | 418.44 | 465.98 | 515.70 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/c | Monoclinic, C2/c | Orthorhombic, Pbcn |
Temperature (K) | 123 | 123 | 123 | 150 |
a, b, c (Å) | 12.8896 (4), 8.0048 (2), 24.5300 (5) | 21.079 (1), 11.4410 (6), 7.7200 (3) | 21.2740 (19), 11.3397 (10), 7.9619 (5) | 20.464 (3), 11.9699 (15), 8.2812 (10) |
α, β, γ (°) | 90, 121.190 (1), 90 | 90, 93.994 (3), 90 | 90, 94.520 (4), 90 | 90, 90, 90 |
V (Å3) | 2165.13 (10) | 1857.27 (15) | 1914.8 (3) | 2028.5 (4) |
Z | 4 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Synchrotron, λ = 0.82520 Å |
µ (mm−1) | 0.13 | 0.38 | 2.85 | 1.99 |
Crystal size (mm) | 0.15 × 0.13 × 0.03 | 0.28 × 0.12 × 0.06 | 0.20 × 0.20 × 0.10 | 0.10 × 0.10 × 0.01 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | – | – | Multi-scan (SADABS; Bruker, 2001) | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | – | – | 0.922, 1.000 | 0.673, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8977, 4968, 2744 | 4047, 2108, 1641 | 4336, 2312, 1853 | 14467, 2355, 2196 |
Rint | 0.078 | 0.031 | 0.059 | 0.172 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 | 0.661 | 0.660 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.150, 1.02 | 0.036, 0.077, 1.07 | 0.045, 0.100, 1.06 | 0.041, 0.126, 1.14 |
No. of reflections | 4968 | 2108 | 2312 | 2355 |
No. of parameters | 319 | 138 | 138 | 139 |
No. of restraints | 15 | 3 | 3 | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.43 | 0.29, −0.30 | 0.62, −0.45 | 1.44, −1.46 |
Selected bond lengths (Å) for (MgNPH) topMg1—O3W | 2.016 (2) | Mg1—O1 | 2.069 (2) |
Mg1—O2W | 2.028 (2) | Mg1—O1Wi | 2.195 (2) |
Mg1—O3 | 2.058 (2) | Mg1—O1W | 2.200 (2) |
Symmetry code: (i) −x, y−1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (MgNPH) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2 | 0.88 (1) | 1.763 (12) | 2.621 (3) | 164 (3) |
O1W—H2W···O4ii | 0.87 (1) | 1.785 (12) | 2.637 (3) | 165 (3) |
O2W—H3W···O4Wii | 0.87 (1) | 1.883 (13) | 2.713 (3) | 159 (3) |
O2W—H4W···O3i | 0.87 (1) | 1.840 (11) | 2.704 (3) | 171 (3) |
O3W—H5W···O1ii | 0.87 (1) | 1.833 (11) | 2.693 (3) | 167 (3) |
O3W—H6W···O5Wi | 0.87 (1) | 1.859 (12) | 2.701 (3) | 161 (3) |
O4W—H7W···O4 | 0.88 (1) | 1.901 (17) | 2.691 (3) | 149 (3) |
O5W—H9W···O2 | 0.90 (1) | 1.854 (16) | 2.692 (3) | 155 (3) |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2. |
Selected bond lengths (Å) for (CaNPH) topCa1—O1 | 2.3608 (11) | Ca1—O2ii | 2.4652 (12) |
Ca1—O1i | 2.3608 (10) | Ca1—O2iii | 2.4652 (12) |
Ca1—O1Wi | 2.4143 (12) | Ca1—O1ii | 2.5765 (12) |
Ca1—O1W | 2.4143 (12) | Ca1—O1iii | 2.5765 (11) |
Symmetry codes: (i) −x, y, −z+5/2; (ii) −x, −y, −z+2; (iii) x, −y, z+1/2. |
Hydrogen-bond geometry (Å, º) for (CaNPH) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2iv | 0.863 (9) | 1.884 (10) | 2.7120 (16) | 160.1 (18) |
Symmetry code: (iv) −x, y, −z+3/2. |
Selected bond lengths (Å) for (SrNPH) topSr1—O2i | 2.495 (2) | Sr1—O1 | 2.621 (2) |
Sr1—O2ii | 2.495 (2) | Sr1—O1iii | 2.621 (2) |
Sr1—O1Wiii | 2.581 (2) | Sr1—O2iii | 2.678 (2) |
Sr1—O1W | 2.581 (2) | Sr1—O2 | 2.678 (2) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, −y+1, z−1/2; (iii) −x, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (SrNPH) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O1iv | 0.868 (10) | 1.885 (14) | 2.715 (3) | 160 (3) |
Symmetry code: (iv) −x, −y+1, −z+1. |
Selected bond lengths (Å) for (BaNPH) topBa1—O1i | 2.6536 (19) | Ba1—O2iii | 2.792 (2) |
Ba1—O1ii | 2.6536 (19) | Ba1—O2 | 2.792 (2) |
Ba1—O1W | 2.769 (2) | Ba1—O1 | 2.8551 (18) |
Ba1—O1Wiii | 2.769 (2) | Ba1—O1iii | 2.8551 (18) |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, −y+2, z+1/2; (iii) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (BaNPH) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2iv | 0.878 (10) | 1.860 (13) | 2.713 (3) | 163 (3) |
Symmetry code: (iv) x, −y+2, z−1/2. |
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Salt forms of active pharmaceutical ingregients (APIs) are commonly investigated as a simple route to altering the physicochemical properties of the API (Stahl & Wermuth, 2002) whilst, it is hoped, not changing its fundamental underlying biological activity [see Zhao et al. (2010) for an example of possible unforeseen consequences resulting from salt choice]. Many of the performance-critical properties of an API (such as solubility, melting point and hygroscopicity) are dependant upon its solid-state structure, and thus a true understanding of structure–property relationships should allow the most appropriate counterion to be chosen for any given desired property. However, structure–property relationships of this type are poorly understood, and thus salt selection of API forms is currently undertaken using time-consuming trial-and-error methods (Stahl & Wermuth, 2002). One reason for our lack of understanding is a general dearth of large groups of systematically related crystal structures of salt forms with associated phase-specific physicochemical data. Some such studies do exist (for example, Collier et al., 2006; Black et al., 2007; Kennedy et al., 2011) but they are relatively uncommon. As a contribution to this field, Arlin et al. (2011) showed that Mg, Ca and Sr (but not Ba) salt forms of a set of simple benzoate-derived anions could be systematically structurally classified, and that these structural features helped to rationalize comparative aqueous solubility data. This work was later extended to phenylacetic acid (Arlin et al., 2012). A major aim of this earlier work was to use the lessons learned from simple model compounds to predict behaviour in larger commercial APIs with similar functionality. Many APIs have carboxylate groups and six-membered aryl rings (e.g. profens, aspirin), as do the reported model benzoate structures. However, several important drug classes (e.g. naproxens, fluoroquinolones) have larger fused aromatic groups and this structural feature was not included in the model data set. To help fill this gap, the Mg, Ca, Sr and Ba complexes of 1-naphthoate (NPH) have now been investigated in order to investigate what effects the extra bulk of the aromatic region has on crystal stucture, and the results are presented here (Mg-, Ca-, Sr and BaNPH). Naphthalene derivatives with multiple carboxylate groups have been structurally examined (see, for example, Fitzgerald & Gerkin, 1994; Senkovska, 2006), but the only such simple Group 2 metal salt with a monocarboxylate naphthoate to have been structurally characterized to date is the Mg salt of 1-hydroxy-2-naphthoic acid (Huang & Song, 2008).
MgNPH is found to be [Mg(NPH)2(H2O)3].2H2O (Fig. 1), which has an approximately octahedral metal centre. The NPH ligands are mutually cis [O3—Mg—O1 = 87.58 (8)°] and each bonds to Mg through only one of its carboxylate O atoms, with the other O atom taking part only in hydrogen-bonding interactions. The C—O distances involving the non-metal-bound O atoms are approximately 0.02 Å shorter than those of the metal-bound O atoms (Table 1). Such large variations in C—O bond lengths are not found for the Ca, Sr or Ba salts (see below), which all have η2 rather than η1-COO bonding modes. Two of the water ligands are also terminal but the third, O1W, acts as a bridge between metal centres. Table 1 shows that the bridging Mg—O bonds are approximately 0.17 Å longer than the terminal bonds. The bridging water ligands are trans to one another [O1—Mg—O1Wi = 177.47 (5)°; symmetry code: (i) -x, y - 1/2, -z + 1/2] and this results in a one-dimensional coordination chain based on Mg—OH2—Mg units which propagates along the crystallographic b direction (Fig. 2). In contrast, the Mg salt of 1-hydroxy-2-naphthoic acid reported by Huang & Song (2008) is a discrete [Mg(L)2(H2O)4] complex.
Previous work has shown that a common motif for magnesium salts of carboxylate ions with no good hydrogen-bonding substituents (e.g. benzoate, halobenzoates and phenylacetate) is a one-dimensional coordination polymer that packs to give alternating inorganic layers and organic bilayers (Arlin et al., 2011, 2012). Although also a one-dimensional polymer, the structure of MgNPH differs from those of these smaller anions in significant ways. Firstly, for the benzene-based species the carboxylate group is found to be the bridging ligand, not water as in MgNPH. Indeed, a search of the Cambridge Structural Database (Version?; Allen, 2002) found no other structure of an Mg salt of an aryl carboxylate anion that bridges through water and not through the carboxylate group. Secondly, as shown in Fig. 3, the structure of MgNPH does not contain an inorganic layer. Instead, the one-dimensional chains are isolated from each other by the organic groups. With smaller anions, the inorganic layers tend to be formed by hydrogen bonding between the inorganic chains. Here, the larger naphthalene group seems to have a fundamental effect on the packing structure by separating out these chains. The presence of large nonpolar groups may also explain why two of the H atoms of the water molecules do not act as traditional hydrogen-bond donors (Table 2).
The structures of CaNPH and SrNPH were found to be essentially isostructural, with the composition [M(NPH)2(H2O)2] (Figs. 4 and 5). This reflects the structures of the benzoate and phenylacetate derivatives, where the Ca and Sr structures were found to have similar structural types and even (for salicylate, 4-aminosalicylate, 4-aminobenzoate and phenylacetate) to form isostructural pairs. In both CaNPH and SrNPH, the metal centre lies on a twofold axis and is formally eight-coordinate though, as Cotton & Bergman (1964) classically showed, if each chelated group is assigned to one coordination site rather than two, then the structures can be described as distorted octahedral (Tables 3 and 5). The water ligands are terminal and are trans to the chelated carboxylate groups [O1W—M···C1 = 168.66 (5) and 167.13 (8)° for CaNPH and SrNPH, respectively]. The NPH anions use both their O atoms to chelate to one metal centre, and one O atom of each ligand then bridges to a further metal centre. Thus, it is this coordination mode of the carboxylate (and not water as in MgNPH) that leads to propagation of a one-dimensional coordination polymer based on perfectly planar MOMO rings along the c-glide plane (Fig. 6). The aromatic rings form dihedral angles of 46.68 (5) and 44.59 (10)° with the CaOCaO and SrOSrO rings, respectively.
As with MgNPH above, the one-dimensional polymers in the Ca and Sr salts do not interact to form the two-dimensional sheets seen for the equivalent benzoate and phenylacetate structures (Senkovska & Thewalt, 2005; Arlin et al., 2011, 2012). However, both the geometry of the coordination polymer and the packing motif with inorganic channels shown in Fig. 7 are the same as those found in a second class of Ca and Sr salt structures of benzoate derivatives, but oddly this class of structure was observed previously only with benzoates containing hydrogen-bonding substituents, especially salicylate and 2-nitrobenzoate (Debuyst et al., 1979; Arlin et al., 2011).
Crystals of BaNPH formed as very thin plates (approximately 0.005 mm) which required the use of synchrotron radiation to characterize them. It was found to have the same [M(NPH)2(H2O)2] composition, and indeed the same coordination geometry (Table 7), the same polymeric one-dimensional coordination arrangement and the same packing mode featuring inorganic channels, as the Ca and Sr salts, though it is not isostructural with them. The dihedral angle between the MOMO plane and the aromatic plane [39.48 (9) °] is slightly less than in the Ca or Sr salts. The Ba ions again lie on a twofold rotation axis and the coordination polymer propagates along the crystallographic c direction. The similarity of the structure of BaNPH to the structures of CaNPH and SrNPH is somewhat unusual as, of the nine families of Group 2 metal salts of benzoate anions described by Arlin et al., (2011), only the Ba salt of 4-chlorobenzoate had a structure that was somewhat similar to its lighter analogues. All other Ba salts were found to be structurally varied and distinct. Finally, it is noted that each water molecule in the Ca, Sr and Ba salt structures uses only one H atom as a hydrogen-bond donor (Tables 4, 6 and 8).
In summary, whereas phenylacetate, with its additional Csp3 atom between the aryl and –COO groups, was found to have Mg, Ca and Sr salt structures that were closely related to those found for analogous benzoate and halobenzoate salts (Arlin et al., 2011, 2012), adding a larger aromatic fragment in the shape of naphthalene was found to give different structural types. The structure of MgNPH has an unusual motif based on Mg—OH2—Mg bridging and a change to the packing structure that can be understood in terms of the large nonpolar parts of the naphthoate anions preventing the polar/inorganic chains from hydrogen bonding to each other. The Ca, Sr and Ba salts of naphthoate all have similar one-dimensional polymeric coordination structures and similar packing modes. Again, the large size of the naphthoate fragments appears to prevent the one-dimensional inorganic chains from aggregating, but intruigingly the resulting structues are now of a type previously seen for Ca and Sr salts of salicylate and other benzoate derivatives with extra (rather than fewer) polar or hydrogen-bond-forming substituents.