Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104018207/de1248sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104018207/de1248Isup2.hkl |
CCDC reference: 251336
Crystals of the adduct were obtained from a 1:1 aqueous solution of 1-methylpiperazine and 4-nitrophthalic acid by slow concentration over a period of 2 d.
The value of the absolute structure parameter (Flack, 1983) of the title adduct is meaningless because Mo radiation was used and no atoms heavier than O are present. Therefore, in the absence of anomalous dispersion effects, 1574 Friedel pairs were merged before the final refinement. H atoms of the water molecule were found in difference Fourier maps. However, during refinement, their positions were fixed at O–H distances of 0.85 Å and their Uiso(H) values were set at 1.2Ueq(O). The O—H distances of the carboxy group were fixed at 0.82 Å and their Uiso(H) values were set at 1.2Ueq(O). H atoms of NH and CH groups were treated as riding, with N—H = 0.90–0.91 Å and C—H = 0.93–0.97 Å. For H atoms attached to atom C21, the Uiso(H) value is 1.5Ueq(C21); otherwise, Uiso(H) is 1.2Ueq(N,C).
Data collection: SMART (Bruker 1997); cell refinement: SMART; data reduction: SAINT (Bruker 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C5H14N22+·C8H3NO62−·C8H5NO6·H2O | F(000) = 564 |
Mr = 540.44 | Dx = 1.519 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 997 reflections |
a = 7.882 (2) Å | θ = 3.3–25.6° |
b = 12.050 (3) Å | µ = 0.13 mm−1 |
c = 12.602 (4) Å | T = 293 K |
β = 99.273 (5)° | Plate, colorless |
V = 1181.3 (6) Å3 | 0.18 × 0.16 × 0.10 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2514 independent reflections |
Radiation source: fine-focus sealed tube | 2127 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.975, Tmax = 0.990 | k = −11→15 |
6800 measured reflections | l = −13→15 |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0403P)2 + 0.3064P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2514 reflections | Δρmax = 0.21 e Å−3 |
346 parameters | Δρmin = −0.16 e Å−3 |
1 restraint | Absolute structure: Flack H D (1983) |
Primary atom site location: structure-invariant direct methods |
C5H14N22+·C8H3NO62−·C8H5NO6·H2O | V = 1181.3 (6) Å3 |
Mr = 540.44 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.882 (2) Å | µ = 0.13 mm−1 |
b = 12.050 (3) Å | T = 293 K |
c = 12.602 (4) Å | 0.18 × 0.16 × 0.10 mm |
β = 99.273 (5)° |
Bruker SMART CCD area-detector diffractometer | 2514 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2127 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.990 | Rint = 0.028 |
6800 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 1 restraint |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.21 e Å−3 |
2514 reflections | Δρmin = −0.16 e Å−3 |
346 parameters | Absolute structure: Flack H D (1983) |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.1233 (4) | 0.3547 (3) | 0.6614 (2) | 0.0541 (8) | |
N2 | 0.4103 (4) | 0.8937 (3) | 0.6566 (2) | 0.0504 (8) | |
N3 | 0.4062 (3) | 0.1911 (2) | 1.00073 (19) | 0.0349 (6) | |
H3 | 0.3862 | 0.1433 | 1.0533 | 0.042* | |
N4 | 0.7599 (3) | 0.1399 (2) | 0.9869 (2) | 0.0378 (6) | |
H4A | 0.8574 | 0.1015 | 1.0080 | 0.045* | |
H4B | 0.7788 | 0.1878 | 0.9352 | 0.045* | |
O1 | 0.0471 (3) | 0.57654 (18) | 0.18987 (18) | 0.0443 (6) | |
H1 | 0.1176 | 0.6008 | 0.2395 | 0.053* | |
O2 | −0.1122 (4) | 0.4293 (2) | 0.1566 (2) | 0.0618 (8) | |
O3 | 0.2337 (4) | 0.3215 (2) | 0.2087 (2) | 0.0724 (9) | |
O4 | 0.1703 (4) | 0.1751 (2) | 0.3001 (2) | 0.0630 (8) | |
H4 | 0.2220 | 0.1420 | 0.2583 | 0.076* | |
O5 | 0.2059 (5) | 0.2688 (3) | 0.6838 (2) | 0.0758 (10) | |
O6 | 0.0658 (4) | 0.4114 (3) | 0.7267 (2) | 0.0805 (10) | |
O7 | 0.3406 (3) | 1.0687 (2) | 0.17533 (19) | 0.0480 (6) | |
O8 | 0.5550 (3) | 0.9524 (2) | 0.1699 (2) | 0.0553 (7) | |
O9 | 0.2537 (3) | 0.80318 (18) | 0.18081 (16) | 0.0431 (6) | |
O10 | 0.2350 (4) | 0.6908 (2) | 0.3174 (2) | 0.0603 (8) | |
O11 | 0.3649 (4) | 0.8008 (3) | 0.6795 (2) | 0.0687 (8) | |
O12 | 0.4435 (4) | 0.9692 (3) | 0.7214 (2) | 0.0789 (10) | |
C1 | 0.0305 (4) | 0.4521 (2) | 0.3351 (2) | 0.0324 (6) | |
C2 | 0.1091 (4) | 0.3508 (3) | 0.3643 (2) | 0.0338 (7) | |
C3 | 0.1412 (4) | 0.3195 (3) | 0.4720 (3) | 0.0388 (7) | |
H3A | 0.1946 | 0.2522 | 0.4923 | 0.047* | |
C4 | 0.0928 (4) | 0.3893 (3) | 0.5477 (3) | 0.0391 (7) | |
C5 | 0.0143 (4) | 0.4900 (3) | 0.5215 (3) | 0.0432 (8) | |
H5 | −0.0171 | 0.5359 | 0.5744 | 0.052* | |
C6 | −0.0165 (4) | 0.5210 (3) | 0.4143 (3) | 0.0407 (8) | |
H6 | −0.0692 | 0.5887 | 0.3950 | 0.049* | |
C7 | −0.0143 (4) | 0.4868 (3) | 0.2182 (2) | 0.0346 (7) | |
C8 | 0.1757 (4) | 0.2811 (3) | 0.2822 (2) | 0.0374 (7) | |
C9 | 0.4357 (4) | 0.9616 (2) | 0.3301 (2) | 0.0291 (6) | |
C10 | 0.3607 (4) | 0.8639 (2) | 0.3583 (2) | 0.0269 (6) | |
C11 | 0.3568 (4) | 0.8416 (3) | 0.4664 (2) | 0.0322 (6) | |
H11 | 0.3086 | 0.7759 | 0.4864 | 0.039* | |
C12 | 0.4248 (4) | 0.9172 (3) | 0.5433 (2) | 0.0376 (7) | |
C13 | 0.5005 (5) | 1.0138 (3) | 0.5180 (3) | 0.0450 (8) | |
H13 | 0.5467 | 1.0635 | 0.5714 | 0.054* | |
C14 | 0.5065 (4) | 1.0354 (3) | 0.4108 (3) | 0.0427 (8) | |
H14 | 0.5586 | 1.1002 | 0.3921 | 0.051* | |
C15 | 0.4460 (4) | 0.9935 (2) | 0.2150 (2) | 0.0319 (7) | |
C16 | 0.2780 (4) | 0.7821 (2) | 0.2760 (2) | 0.0303 (6) | |
C17 | 0.4536 (4) | 0.1247 (3) | 0.9105 (2) | 0.0396 (8) | |
H17A | 0.4653 | 0.1738 | 0.8511 | 0.048* | |
H17B | 0.3621 | 0.0724 | 0.8858 | 0.048* | |
C18 | 0.6193 (4) | 0.0622 (3) | 0.9432 (3) | 0.0410 (8) | |
H18A | 0.6044 | 0.0074 | 0.9973 | 0.049* | |
H18B | 0.6496 | 0.0236 | 0.8814 | 0.049* | |
C19 | 0.7140 (4) | 0.2025 (3) | 1.0797 (3) | 0.0399 (8) | |
H19A | 0.8059 | 0.2537 | 1.1067 | 0.048* | |
H19B | 0.6999 | 0.1514 | 1.1371 | 0.048* | |
C20 | 0.5507 (4) | 0.2656 (3) | 1.0464 (2) | 0.0372 (7) | |
H20A | 0.5206 | 0.3043 | 1.1083 | 0.045* | |
H20B | 0.5682 | 0.3207 | 0.9931 | 0.045* | |
C21 | 0.2446 (5) | 0.2550 (3) | 0.9642 (3) | 0.0461 (8) | |
H21A | 0.2122 | 0.2944 | 1.0241 | 0.069* | |
H21B | 0.1543 | 0.2047 | 0.9355 | 0.069* | |
H21C | 0.2636 | 0.3070 | 0.9096 | 0.069* | |
O13 | 0.0129 (4) | 0.9875 (3) | 0.0404 (2) | 0.0713 (9) | |
H13A | 0.0731 | 0.9610 | 0.0967 | 0.107* | |
H13B | 0.0479 | 0.9632 | −0.0156 | 0.107* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0573 (19) | 0.072 (2) | 0.0319 (16) | −0.0199 (18) | 0.0049 (14) | 0.0022 (16) |
N2 | 0.062 (2) | 0.064 (2) | 0.0242 (15) | 0.0119 (16) | 0.0029 (13) | −0.0059 (14) |
N3 | 0.0456 (15) | 0.0340 (14) | 0.0263 (13) | −0.0066 (12) | 0.0092 (11) | 0.0029 (11) |
N4 | 0.0427 (15) | 0.0389 (14) | 0.0325 (14) | −0.0049 (12) | 0.0083 (11) | 0.0029 (12) |
O1 | 0.0667 (16) | 0.0338 (12) | 0.0290 (12) | −0.0162 (11) | −0.0024 (11) | −0.0004 (10) |
O2 | 0.0852 (19) | 0.0509 (15) | 0.0430 (14) | −0.0340 (15) | −0.0088 (13) | 0.0005 (12) |
O3 | 0.118 (3) | 0.0521 (16) | 0.0605 (18) | 0.0059 (17) | 0.0555 (18) | 0.0024 (14) |
O4 | 0.101 (2) | 0.0396 (15) | 0.0595 (18) | 0.0210 (14) | 0.0450 (16) | 0.0083 (13) |
O5 | 0.114 (3) | 0.063 (2) | 0.0439 (16) | −0.011 (2) | −0.0054 (16) | 0.0122 (14) |
O6 | 0.076 (2) | 0.136 (3) | 0.0330 (14) | 0.001 (2) | 0.0183 (14) | −0.0100 (18) |
O7 | 0.0705 (17) | 0.0411 (13) | 0.0359 (13) | 0.0198 (12) | 0.0188 (11) | 0.0110 (10) |
O8 | 0.0611 (15) | 0.0567 (16) | 0.0557 (16) | 0.0181 (13) | 0.0326 (12) | 0.0125 (13) |
O9 | 0.0697 (16) | 0.0386 (13) | 0.0213 (10) | −0.0088 (11) | 0.0080 (10) | −0.0044 (9) |
O10 | 0.095 (2) | 0.0411 (14) | 0.0369 (14) | −0.0322 (14) | −0.0131 (13) | 0.0118 (11) |
O11 | 0.107 (2) | 0.066 (2) | 0.0347 (14) | 0.0015 (18) | 0.0163 (14) | 0.0061 (14) |
O12 | 0.113 (3) | 0.088 (2) | 0.0326 (15) | −0.004 (2) | 0.0030 (14) | −0.0261 (15) |
C1 | 0.0332 (15) | 0.0317 (15) | 0.0333 (16) | −0.0092 (13) | 0.0081 (12) | 0.0003 (13) |
C2 | 0.0327 (15) | 0.0359 (17) | 0.0338 (15) | −0.0034 (13) | 0.0081 (12) | 0.0024 (13) |
C3 | 0.0383 (17) | 0.0414 (18) | 0.0376 (17) | −0.0041 (14) | 0.0088 (13) | 0.0096 (14) |
C4 | 0.0412 (18) | 0.0485 (19) | 0.0286 (16) | −0.0150 (15) | 0.0086 (13) | 0.0016 (14) |
C5 | 0.052 (2) | 0.0451 (19) | 0.0357 (18) | −0.0098 (17) | 0.0172 (15) | −0.0120 (15) |
C6 | 0.049 (2) | 0.0336 (17) | 0.0423 (18) | −0.0033 (15) | 0.0156 (15) | −0.0043 (15) |
C7 | 0.0424 (17) | 0.0275 (16) | 0.0334 (16) | −0.0048 (14) | 0.0051 (13) | −0.0011 (13) |
C8 | 0.0440 (18) | 0.0393 (18) | 0.0299 (15) | 0.0034 (14) | 0.0091 (13) | 0.0037 (14) |
C9 | 0.0294 (14) | 0.0281 (15) | 0.0303 (15) | 0.0042 (12) | 0.0060 (11) | −0.0006 (12) |
C10 | 0.0319 (14) | 0.0254 (14) | 0.0231 (13) | 0.0035 (12) | 0.0039 (11) | −0.0002 (11) |
C11 | 0.0368 (16) | 0.0340 (16) | 0.0258 (14) | 0.0023 (13) | 0.0046 (11) | 0.0009 (13) |
C12 | 0.0408 (18) | 0.0447 (18) | 0.0257 (15) | 0.0097 (15) | 0.0001 (13) | −0.0048 (14) |
C13 | 0.053 (2) | 0.0406 (19) | 0.0369 (19) | 0.0001 (16) | −0.0066 (15) | −0.0145 (15) |
C14 | 0.049 (2) | 0.0325 (16) | 0.045 (2) | −0.0090 (15) | 0.0034 (15) | −0.0052 (15) |
C15 | 0.0406 (17) | 0.0231 (14) | 0.0339 (16) | −0.0023 (13) | 0.0117 (13) | 0.0015 (12) |
C16 | 0.0349 (16) | 0.0275 (15) | 0.0284 (15) | −0.0007 (13) | 0.0052 (12) | 0.0007 (12) |
C17 | 0.0491 (19) | 0.0432 (18) | 0.0269 (16) | −0.0124 (15) | 0.0070 (13) | −0.0091 (14) |
C18 | 0.0513 (19) | 0.0370 (18) | 0.0356 (18) | −0.0079 (15) | 0.0096 (15) | −0.0079 (14) |
C19 | 0.053 (2) | 0.0366 (18) | 0.0290 (16) | −0.0085 (16) | 0.0018 (13) | −0.0034 (14) |
C20 | 0.055 (2) | 0.0296 (16) | 0.0274 (15) | −0.0075 (15) | 0.0089 (13) | −0.0049 (13) |
C21 | 0.051 (2) | 0.051 (2) | 0.0370 (18) | 0.0034 (16) | 0.0099 (15) | 0.0036 (16) |
O13 | 0.079 (2) | 0.090 (2) | 0.0412 (15) | 0.0265 (18) | −0.0003 (14) | 0.0092 (15) |
N1—O6 | 1.213 (5) | C4—C5 | 1.378 (5) |
N1—O5 | 1.231 (5) | C5—C6 | 1.384 (5) |
N1—C4 | 1.473 (4) | C5—H5 | 0.9300 |
N2—O12 | 1.223 (4) | C6—H6 | 0.9300 |
N2—O11 | 1.225 (4) | C9—C10 | 1.389 (4) |
N2—C12 | 1.477 (4) | C9—C14 | 1.398 (4) |
N3—C17 | 1.486 (4) | C9—C15 | 1.515 (4) |
N3—C20 | 1.491 (4) | C10—C11 | 1.393 (4) |
N3—C21 | 1.497 (4) | C10—C16 | 1.502 (4) |
N3—H3 | 0.9100 | C11—C12 | 1.375 (4) |
N4—C19 | 1.484 (4) | C11—H11 | 0.9300 |
N4—C18 | 1.488 (4) | C12—C13 | 1.368 (5) |
N4—H4A | 0.9000 | C13—C14 | 1.385 (5) |
N4—H4B | 0.9000 | C13—H13 | 0.9300 |
O1—C7 | 1.259 (4) | C14—H14 | 0.9300 |
O1—H1 | 0.8200 | C17—C18 | 1.507 (5) |
O2—C7 | 1.219 (4) | C17—H17A | 0.9700 |
O3—C8 | 1.200 (4) | C17—H17B | 0.9700 |
O4—C8 | 1.299 (4) | C18—H18A | 0.9700 |
O4—H4 | 0.8200 | C18—H18B | 0.9700 |
O7—C15 | 1.276 (4) | C19—C20 | 1.496 (5) |
O8—C15 | 1.210 (4) | C19—H19A | 0.9700 |
O9—C16 | 1.211 (3) | C19—H19B | 0.9700 |
O10—C16 | 1.286 (4) | C20—H20A | 0.9700 |
C1—C2 | 1.391 (4) | C20—H20B | 0.9700 |
C1—C6 | 1.393 (4) | C21—H21A | 0.9600 |
C1—C7 | 1.517 (4) | C21—H21B | 0.9600 |
C2—C3 | 1.393 (4) | C21—H21C | 0.9600 |
C2—C8 | 1.492 (4) | O13—H13A | 0.8499 |
C3—C4 | 1.371 (5) | O13—H13B | 0.8500 |
C3—H3A | 0.9300 | ||
O6—N1—O5 | 124.1 (3) | C12—C11—C10 | 119.6 (3) |
O6—N1—C4 | 118.7 (4) | C12—C11—H11 | 120.2 |
O5—N1—C4 | 117.2 (3) | C10—C11—H11 | 120.2 |
O12—N2—O11 | 124.2 (3) | C13—C12—C11 | 122.3 (3) |
O12—N2—C12 | 117.5 (3) | C13—C12—N2 | 119.5 (3) |
O11—N2—C12 | 118.3 (3) | C11—C12—N2 | 118.2 (3) |
C17—N3—C20 | 110.5 (2) | C12—C13—C14 | 118.2 (3) |
C17—N3—C21 | 110.3 (2) | C12—C13—H13 | 120.9 |
C20—N3—C21 | 111.6 (3) | C14—C13—H13 | 120.9 |
C17—N3—H3 | 108.1 | C13—C14—C9 | 121.1 (3) |
C20—N3—H3 | 108.1 | C13—C14—H14 | 119.4 |
C21—N3—H3 | 108.1 | C9—C14—H14 | 119.4 |
C19—N4—C18 | 110.5 (2) | O8—C15—O7 | 125.0 (3) |
C19—N4—H4A | 109.6 | O8—C15—C9 | 119.8 (3) |
C18—N4—H4A | 109.6 | O7—C15—C9 | 115.0 (3) |
C19—N4—H4B | 109.6 | O9—C16—O10 | 124.9 (3) |
C18—N4—H4B | 109.6 | O9—C16—C10 | 121.9 (3) |
H4A—N4—H4B | 108.1 | O10—C16—C10 | 113.2 (2) |
C7—O1—H1 | 109.5 | N3—C17—C18 | 111.9 (3) |
C8—O4—H4 | 109.5 | N3—C17—H17A | 109.2 |
C2—C1—C6 | 119.5 (3) | C18—C17—H17A | 109.2 |
C2—C1—C7 | 121.5 (3) | N3—C17—H17B | 109.2 |
C6—C1—C7 | 119.0 (3) | C18—C17—H17B | 109.2 |
C1—C2—C3 | 119.9 (3) | H17A—C17—H17B | 107.9 |
C1—C2—C8 | 120.1 (3) | N4—C18—C17 | 110.4 (3) |
C3—C2—C8 | 119.6 (3) | N4—C18—H18A | 109.6 |
C4—C3—C2 | 119.0 (3) | C17—C18—H18A | 109.6 |
C4—C3—H3A | 120.5 | N4—C18—H18B | 109.6 |
C2—C3—H3A | 120.5 | C17—C18—H18B | 109.6 |
C3—C4—C5 | 122.5 (3) | H18A—C18—H18B | 108.1 |
C3—C4—N1 | 118.9 (3) | N4—C19—C20 | 110.2 (3) |
C5—C4—N1 | 118.6 (3) | N4—C19—H19A | 109.6 |
C4—C5—C6 | 118.2 (3) | C20—C19—H19A | 109.6 |
C4—C5—H5 | 120.9 | N4—C19—H19B | 109.6 |
C6—C5—H5 | 120.9 | C20—C19—H19B | 109.6 |
C5—C6—C1 | 120.9 (3) | H19A—C19—H19B | 108.1 |
C5—C6—H6 | 119.6 | N3—C20—C19 | 111.8 (3) |
C1—C6—H6 | 119.6 | N3—C20—H20A | 109.3 |
O2—C7—O1 | 122.7 (3) | C19—C20—H20A | 109.3 |
O2—C7—C1 | 119.1 (3) | N3—C20—H20B | 109.3 |
O1—C7—C1 | 118.2 (3) | C19—C20—H20B | 109.3 |
O3—C8—O4 | 124.0 (3) | H20A—C20—H20B | 107.9 |
O3—C8—C2 | 121.8 (3) | N3—C21—H21A | 109.5 |
O4—C8—C2 | 114.1 (3) | N3—C21—H21B | 109.5 |
C10—C9—C14 | 119.3 (3) | H21A—C21—H21B | 109.5 |
C10—C9—C15 | 123.4 (3) | N3—C21—H21C | 109.5 |
C14—C9—C15 | 117.3 (3) | H21A—C21—H21C | 109.5 |
C9—C10—C11 | 119.4 (3) | H21B—C21—H21C | 109.5 |
C9—C10—C16 | 122.3 (2) | H13A—O13—H13B | 110.6 |
C11—C10—C16 | 118.2 (3) | ||
C6—C1—C2—C3 | −0.5 (4) | C9—C10—C11—C12 | 1.0 (4) |
C7—C1—C2—C3 | −177.1 (3) | C16—C10—C11—C12 | −177.2 (3) |
C6—C1—C2—C8 | −174.0 (3) | C10—C11—C12—C13 | −1.5 (5) |
C7—C1—C2—C8 | 9.4 (4) | C10—C11—C12—N2 | 176.8 (3) |
C1—C2—C3—C4 | 0.6 (4) | O12—N2—C12—C13 | 10.8 (5) |
C8—C2—C3—C4 | 174.2 (3) | O11—N2—C12—C13 | −169.8 (3) |
C2—C3—C4—C5 | −0.4 (5) | O12—N2—C12—C11 | −167.6 (3) |
C2—C3—C4—N1 | 178.6 (3) | O11—N2—C12—C11 | 11.8 (5) |
O6—N1—C4—C3 | −173.0 (3) | C11—C12—C13—C14 | 0.7 (5) |
O5—N1—C4—C3 | 6.6 (5) | N2—C12—C13—C14 | −177.7 (3) |
O6—N1—C4—C5 | 6.1 (5) | C12—C13—C14—C9 | 0.7 (5) |
O5—N1—C4—C5 | −174.3 (3) | C10—C9—C14—C13 | −1.2 (5) |
C3—C4—C5—C6 | 0.1 (5) | C15—C9—C14—C13 | 179.0 (3) |
N1—C4—C5—C6 | −178.9 (3) | C10—C9—C15—O8 | −79.1 (4) |
C4—C5—C6—C1 | 0.0 (5) | C14—C9—C15—O8 | 100.7 (4) |
C2—C1—C6—C5 | 0.1 (5) | C10—C9—C15—O7 | 104.7 (3) |
C7—C1—C6—C5 | 176.8 (3) | C14—C9—C15—O7 | −75.5 (4) |
C2—C1—C7—O2 | 59.7 (4) | C9—C10—C16—O9 | −9.2 (4) |
C6—C1—C7—O2 | −116.9 (4) | C11—C10—C16—O9 | 168.9 (3) |
C2—C1—C7—O1 | −122.7 (3) | C9—C10—C16—O10 | 171.8 (3) |
C6—C1—C7—O1 | 60.7 (4) | C11—C10—C16—O10 | −10.0 (4) |
C1—C2—C8—O3 | 33.1 (5) | C20—N3—C17—C18 | 54.1 (3) |
C3—C2—C8—O3 | −140.5 (4) | C21—N3—C17—C18 | 178.0 (3) |
C1—C2—C8—O4 | −149.2 (3) | C19—N4—C18—C17 | 57.6 (3) |
C3—C2—C8—O4 | 37.2 (4) | N3—C17—C18—N4 | −55.9 (3) |
C14—C9—C10—C11 | 0.3 (4) | C18—N4—C19—C20 | −58.4 (3) |
C15—C9—C10—C11 | −179.9 (3) | C17—N3—C20—C19 | −55.0 (3) |
C14—C9—C10—C16 | 178.4 (3) | C21—N3—C20—C19 | −178.1 (3) |
C15—C9—C10—C16 | −1.8 (4) | N4—C19—C20—N3 | 57.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O7i | 0.91 | 1.87 | 2.766 (3) | 170 |
N4—H4A···O13ii | 0.90 | 1.84 | 2.715 (4) | 163 |
N4—H4B···O9iii | 0.90 | 2.00 | 2.877 (3) | 163 |
O1—H1···O10 | 0.82 | 1.65 | 2.430 (3) | 160 |
O4—H4···O7iv | 0.82 | 1.75 | 2.569 (3) | 177 |
O13—H13A···O9 | 0.85 | 2.51 | 3.253 (4) | 147 |
O13—H13A···O7 | 0.85 | 2.54 | 3.017 (4) | 117 |
O13—H13B···O2v | 0.85 | 1.97 | 2.810 (4) | 171 |
O13—H13B···O1v | 0.85 | 2.59 | 3.058 (4) | 116 |
C6—H6···O5vi | 0.93 | 2.55 | 3.476 (5) | 172 |
C11—H11···O10 | 0.93 | 2.35 | 2.677 (4) | 100 |
C13—H13···O10vii | 0.93 | 2.55 | 3.436 (4) | 159 |
C17—H17B···O12iv | 0.97 | 2.58 | 3.022 (4) | 108 |
C18—H18A···O8i | 0.97 | 2.37 | 3.262 (4) | 153 |
C18—H18B···O12iv | 0.97 | 2.46 | 3.121 (4) | 125 |
C19—H19A···O2viii | 0.97 | 2.27 | 3.140 (4) | 148 |
C21—H21A···O3ix | 0.96 | 2.33 | 3.198 (5) | 150 |
C21—H21B···O1x | 0.96 | 2.57 | 3.499 (5) | 164 |
C21—H21C···O8iii | 0.96 | 2.57 | 3.445 (4) | 153 |
Symmetry codes: (i) x, y−1, z+1; (ii) x+1, y−1, z+1; (iii) −x+1, y−1/2, −z+1; (iv) x, y−1, z; (v) −x, y+1/2, −z; (vi) −x, y+1/2, −z+1; (vii) −x+1, y+1/2, −z+1; (viii) x+1, y, z+1; (ix) x, y, z+1; (x) −x, y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C5H14N22+·C8H3NO62−·C8H5NO6·H2O |
Mr | 540.44 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 7.882 (2), 12.050 (3), 12.602 (4) |
β (°) | 99.273 (5) |
V (Å3) | 1181.3 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.18 × 0.16 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.975, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6800, 2514, 2127 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.090, 1.05 |
No. of reflections | 2514 |
No. of parameters | 346 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.16 |
Absolute structure | Flack H D (1983) |
Computer programs: SMART (Bruker 1997), SMART, SAINT (Bruker 1997), SHELXTL (Sheldrick, 2001), SHELXTL.
N1—O6 | 1.213 (5) | O3—C8 | 1.200 (4) |
N1—O5 | 1.231 (5) | O4—C8 | 1.299 (4) |
N2—O12 | 1.223 (4) | O7—C15 | 1.276 (4) |
N2—O11 | 1.225 (4) | O8—C15 | 1.210 (4) |
O1—C7 | 1.259 (4) | O9—C16 | 1.211 (3) |
O2—C7 | 1.219 (4) | O10—C16 | 1.286 (4) |
O6—N1—O5 | 124.1 (3) | O3—C8—O4 | 124.0 (3) |
O12—N2—O11 | 124.2 (3) | O8—C15—O7 | 125.0 (3) |
O2—C7—O1 | 122.7 (3) | O9—C16—O10 | 124.9 (3) |
C7—C1—C2—C8 | 9.4 (4) | C15—C9—C10—C16 | −1.8 (4) |
C2—C1—C7—O2 | 59.7 (4) | C10—C9—C15—O8 | −79.1 (4) |
C2—C1—C7—O1 | −122.7 (3) | C10—C9—C15—O7 | 104.7 (3) |
C1—C2—C8—O3 | 33.1 (5) | C9—C10—C16—O9 | −9.2 (4) |
C1—C2—C8—O4 | −149.2 (3) | C9—C10—C16—O10 | 171.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O7i | 0.91 | 1.87 | 2.766 (3) | 170 |
N4—H4A···O13ii | 0.90 | 1.84 | 2.715 (4) | 163 |
N4—H4B···O9iii | 0.90 | 2.00 | 2.877 (3) | 163 |
O1—H1···O10 | 0.82 | 1.65 | 2.430 (3) | 160 |
O4—H4···O7iv | 0.82 | 1.75 | 2.569 (3) | 177 |
O13—H13A···O9 | 0.85 | 2.51 | 3.253 (4) | 147 |
O13—H13A···O7 | 0.85 | 2.54 | 3.017 (4) | 117 |
O13—H13B···O2v | 0.85 | 1.97 | 2.810 (4) | 171 |
O13—H13B···O1v | 0.85 | 2.59 | 3.058 (4) | 116 |
C6—H6···O5vi | 0.93 | 2.55 | 3.476 (5) | 172 |
C11—H11···O10 | 0.93 | 2.35 | 2.677 (4) | 100 |
C13—H13···O10vii | 0.93 | 2.55 | 3.436 (4) | 159 |
C17—H17B···O12iv | 0.97 | 2.58 | 3.022 (4) | 108 |
C18—H18A···O8i | 0.97 | 2.37 | 3.262 (4) | 153 |
C18—H18B···O12iv | 0.97 | 2.46 | 3.121 (4) | 125 |
C19—H19A···O2viii | 0.97 | 2.27 | 3.140 (4) | 148 |
C21—H21A···O3ix | 0.96 | 2.33 | 3.198 (5) | 150 |
C21—H21B···O1x | 0.96 | 2.57 | 3.499 (5) | 164 |
C21—H21C···O8iii | 0.96 | 2.57 | 3.445 (4) | 153 |
Symmetry codes: (i) x, y−1, z+1; (ii) x+1, y−1, z+1; (iii) −x+1, y−1/2, −z+1; (iv) x, y−1, z; (v) −x, y+1/2, −z; (vi) −x, y+1/2, −z+1; (vii) −x+1, y+1/2, −z+1; (viii) x+1, y, z+1; (ix) x, y, z+1; (x) −x, y−1/2, −z+1. |
The design of new piperazine derivatives for application in medicinal chemistry and materials science has recently engrossed the author. Piperazine derivatives, which are efficient host–guest systems, have been studied extensively in the context of hydrogen-bond patterns and non-linear optical materials (Jin et al., 2003; Loehlin et al., 1994). The author's interest in piperazine derivatives stems from their use as canalization of drug discovery and host–guest systems. The author has recently reported the crystal structure of N-[4-(4-methylpiperazin-1-ylsulfonyl)phenyl]acetamide monohydrate (Guo, 2004c), 4-ammonio-1-methylpiperazin-1-ium oxalate dihydrate (Guo, 2004b), 2-(4-methylpiperazin-4-ium-1-ylcarbonyl)benzoate monohydrate (Guo, 2004 d) and N-(4-methyl-1-piperazinyl)phthalimide (Guo, 2004a). The structure of the adduct 1-methylpiperazinium-1-ium 4-nitrophthalate 4-nitrophthalic acid monohydrate, (I), is reported here.
The hydrogen bonding of the adduct of (I) and the atom-numbering scheme are illustrated in Fig. 1. Interestingly, the crystal structure has the unexpected result of co-crystallization of one neutral molecule of the anions in addition to an ionic pair.
The bond distances and angles in the cation, anion, neutral molecule and water molecule are normal, within experimental error. Selected geometric parameters are shown Table 1.
The crystal packing of (I) is illustrated in Fig. 2, for the piperazine dications and water molecules. The piperazine dication adopts a normal chair conformation, as reported previously (Kuppayee et al., 1999). The piperazine dication participates in hydrogen bonds between the N3/H3 group and atom O7i of a 4-nitrophthalate anion, the N4/H4B group and atom O9iii of an anion, and the N4/H4A group and atom O13ii of a water molecule. In addition, there also exist some C–H···acceptor weak interactions (Steiner, 1996), namely C19—H19A···O2viii, C18—H18A···O8i, C18—H18B···O12iv, C21—H21A···O3ix, C21—H21B···O1x and C21—H21C···O8iii. The water molecules, which play an important role, link the 4-nitrophthalic acid moiety, the 4-nitrophthalate anion and the piperazine dication together via intermolecular O13—H13A···O9, O13—H13A···O7i, O13—H13B···O1v and O13—H13B···O2v hydrogen bonds. On the other hand, the 4-nitrophthalic acid moiety and the 4-nitrophthalate anion are linked together via O1—H1···O10 and O4—H4···O7iv hydrogen bonds and C—H···acceptor weak interactions (C13—H13···O10vii and C6—H6···O5vi). In the crystal structure, these hydrogen bonds form different size rings and build up a three-dimensional molecular network (Fig.3 and Table 2).
This study was initiated as an exploration of the salt 1-methylpiperazinium-1-ium 4-nitrophthalate via hydrogen bonding. However, the crystalline product from the mixture system of a 1:1 molar ratio aqueous solution of 1-methylpiperazine and 4-nitrophthalic acid is the title adduct rather than 1-methylpiperazinium-1-ium 4-nitrophthalate. The title adduct is thus more stable and easily obtained in the crystalline form. This adduct crystallizes in the monoclinic space group P21. It is expected that (I) can be used in canalization of optical material.