In the title compound, C18H22N6O42+·2Br2-·4H2O, the centrosymmetric organic cation interacts with the bromide ions and water molecules by way of an extensive hydrogen-bonding network.
Supporting information
CCDC reference: 643008
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.005 Å
- R factor = 0.042
- wR factor = 0.113
- Data-to-parameter ratio = 16.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.95
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ... 615.70 Ang-3
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.17
Alert level G
ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be
replaced by the scaled T values. Since the ratio of scaled T's
is identical to the ratio of reported T values, the scaling
does not imply a change to the absorption corrections used in
the study.
Ratio of Tmax expected/reported 0.949
Tmax scaled 0.585 Tmin scaled 0.411
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
4,4'-Bis[(2-acetylhydrazino)carbonyl]-1,1'-ethylenedipyridinium dibromide
tetrahydrate
top
Crystal data top
C18H22N6O42+·2Br−·4H2O | Z = 1 |
Mr = 618.30 | F(000) = 314 |
Triclinic, P1 | Dx = 1.667 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9315 (13) Å | Cell parameters from 2077 reflections |
b = 9.374 (2) Å | θ = 3.4–26.4° |
c = 11.721 (3) Å | µ = 3.35 mm−1 |
α = 107.570 (3)° | T = 294 K |
β = 92.101 (4)° | Block, colorless |
γ = 96.389 (3)° | 0.30 × 0.20 × 0.16 mm |
V = 615.7 (2) Å3 | |
Data collection top
Bruker SMART 1000 CCD diffractometer | 2493 independent reflections |
Radiation source: fine-focus sealed tube | 2196 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ω scans | θmax = 26.4°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→6 |
Tmin = 0.433, Tmax = 0.617 | k = −11→11 |
3546 measured reflections | l = −10→14 |
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)] = 0.042 | Hydrogen site location: difmap and geom |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0623P)2 + 0.5546P] where P = (Fo2 + 2Fc2)/3 |
2493 reflections | (Δ/σ)max = 0.001 |
155 parameters | Δρmax = 0.85 e Å−3 |
6 restraints | Δρmin = −0.94 e Å−3 |
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 | |
Br1 | 0.05892 (6) | 0.20313 (4) | 0.39239 (3) | 0.03798 (16) | |
O1 | 1.3817 (5) | 0.5801 (4) | −0.0779 (3) | 0.0500 (8) | |
O2 | 0.7872 (4) | 0.8790 (3) | −0.0664 (2) | 0.0373 (6) | |
N1 | 1.1310 (5) | 0.7225 (3) | −0.1210 (3) | 0.0324 (6) | |
H1 | 1.0814 | 0.7650 | −0.1708 | 0.039* | |
N2 | 1.0330 (5) | 0.7405 (3) | −0.0125 (3) | 0.0295 (6) | |
H2 | 1.0815 | 0.7010 | 0.0396 | 0.035* | |
N3 | 0.5490 (5) | 0.8993 (3) | 0.3392 (2) | 0.0266 (6) | |
C1 | 1.3949 (7) | 0.6270 (5) | −0.2684 (4) | 0.0421 (9) | |
H1A | 1.5450 | 0.6817 | −0.2568 | 0.063* | |
H1B | 1.2971 | 0.6688 | −0.3134 | 0.063* | |
H1C | 1.4012 | 0.5228 | −0.3116 | 0.063* | |
C2 | 1.3034 (6) | 0.6388 (4) | −0.1487 (3) | 0.0317 (7) | |
C3 | 0.8592 (5) | 0.8225 (4) | 0.0071 (3) | 0.0263 (6) | |
C4 | 0.7557 (5) | 0.8449 (3) | 0.1263 (3) | 0.0247 (6) | |
C5 | 0.5789 (6) | 0.9334 (4) | 0.1491 (3) | 0.0322 (7) | |
H5 | 0.5293 | 0.9756 | 0.0918 | 0.039* | |
C6 | 0.4780 (6) | 0.9587 (4) | 0.2551 (3) | 0.0322 (7) | |
H6 | 0.3594 | 1.0173 | 0.2693 | 0.039* | |
C7 | 0.7192 (6) | 0.8125 (4) | 0.3201 (3) | 0.0343 (8) | |
H7 | 0.7658 | 0.7715 | 0.3787 | 0.041* | |
C8 | 0.8248 (6) | 0.7844 (4) | 0.2135 (3) | 0.0339 (8) | |
H8 | 0.9423 | 0.7247 | 0.2007 | 0.041* | |
C9 | 0.4389 (6) | 0.9276 (4) | 0.4552 (3) | 0.0309 (7) | |
H9A | 0.4480 | 0.8433 | 0.4863 | 0.037* | |
H9B | 0.2797 | 0.9377 | 0.4426 | 0.037* | |
O3 | 0.1787 (7) | 0.5681 (4) | 0.3847 (3) | 0.0728 (11) | |
H3A | 0.0918 | 0.6207 | 0.4324 | 0.087* | |
H3B | 0.1721 | 0.4761 | 0.3833 | 0.087* | |
O4 | 0.2477 (5) | 0.6047 (3) | 0.1579 (3) | 0.0477 (7) | |
H4A | 0.2096 | 0.5674 | 0.2133 | 0.057* | |
H4B | 0.3431 | 0.5596 | 0.1116 | 0.057* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0402 (2) | 0.0450 (2) | 0.0359 (2) | 0.02108 (16) | 0.00758 (15) | 0.01703 (17) |
O1 | 0.0564 (17) | 0.069 (2) | 0.0409 (16) | 0.0405 (15) | 0.0144 (13) | 0.0283 (15) |
O2 | 0.0388 (13) | 0.0522 (16) | 0.0306 (13) | 0.0230 (12) | 0.0056 (11) | 0.0207 (12) |
N1 | 0.0332 (14) | 0.0426 (17) | 0.0298 (15) | 0.0188 (12) | 0.0105 (12) | 0.0178 (13) |
N2 | 0.0319 (14) | 0.0360 (15) | 0.0255 (14) | 0.0169 (12) | 0.0070 (11) | 0.0119 (12) |
N3 | 0.0290 (13) | 0.0272 (13) | 0.0229 (13) | 0.0068 (11) | 0.0053 (11) | 0.0053 (11) |
C1 | 0.040 (2) | 0.056 (2) | 0.038 (2) | 0.0222 (17) | 0.0092 (16) | 0.0192 (18) |
C2 | 0.0314 (17) | 0.0344 (18) | 0.0327 (18) | 0.0149 (14) | 0.0059 (14) | 0.0113 (15) |
C3 | 0.0270 (15) | 0.0285 (16) | 0.0249 (16) | 0.0091 (12) | 0.0030 (12) | 0.0086 (13) |
C4 | 0.0246 (15) | 0.0267 (15) | 0.0238 (15) | 0.0085 (12) | 0.0024 (12) | 0.0072 (13) |
C5 | 0.0349 (17) | 0.0361 (18) | 0.0314 (18) | 0.0175 (14) | 0.0041 (14) | 0.0144 (15) |
C6 | 0.0310 (16) | 0.0349 (18) | 0.0349 (19) | 0.0180 (14) | 0.0074 (14) | 0.0115 (15) |
C7 | 0.0383 (18) | 0.044 (2) | 0.0286 (17) | 0.0191 (15) | 0.0047 (14) | 0.0175 (15) |
C8 | 0.0334 (17) | 0.0413 (19) | 0.0317 (18) | 0.0222 (15) | 0.0052 (14) | 0.0118 (15) |
C9 | 0.0319 (16) | 0.0338 (18) | 0.0275 (17) | 0.0056 (14) | 0.0103 (14) | 0.0090 (14) |
O3 | 0.111 (3) | 0.0495 (19) | 0.069 (2) | 0.0279 (19) | 0.049 (2) | 0.0231 (17) |
O4 | 0.0453 (15) | 0.0594 (18) | 0.0515 (17) | 0.0310 (13) | 0.0166 (13) | 0.0266 (14) |
Geometric parameters (Å, º) top
O1—C2 | 1.229 (4) | C4—C8 | 1.380 (5) |
O2—C3 | 1.225 (4) | C4—C5 | 1.393 (4) |
N1—C2 | 1.347 (4) | C5—C6 | 1.367 (5) |
N1—N2 | 1.390 (4) | C5—H5 | 0.9300 |
N1—H1 | 0.8600 | C6—H6 | 0.9300 |
N2—C3 | 1.339 (4) | C7—C8 | 1.385 (5) |
N2—H2 | 0.8600 | C7—H7 | 0.9300 |
N3—C6 | 1.346 (4) | C8—H8 | 0.9300 |
N3—C7 | 1.349 (4) | C9—C9i | 1.529 (7) |
N3—C9 | 1.494 (4) | C9—H9A | 0.9700 |
C1—C2 | 1.501 (5) | C9—H9B | 0.9700 |
C1—H1A | 0.9600 | O3—H3A | 0.8558 |
C1—H1B | 0.9600 | O3—H3B | 0.8537 |
C1—H1C | 0.9600 | O4—H4A | 0.8521 |
C3—C4 | 1.513 (4) | O4—H4B | 0.8547 |
| | | |
C2—N1—N2 | 120.4 (3) | C8—C4—C3 | 124.6 (3) |
C2—N1—H1 | 119.8 | C5—C4—C3 | 117.2 (3) |
N2—N1—H1 | 119.8 | C6—C5—C4 | 120.3 (3) |
C3—N2—N1 | 116.7 (3) | C6—C5—H5 | 119.8 |
C3—N2—H2 | 121.7 | C4—C5—H5 | 119.8 |
N1—N2—H2 | 121.7 | N3—C6—C5 | 120.5 (3) |
C6—N3—C7 | 120.8 (3) | N3—C6—H6 | 119.8 |
C6—N3—C9 | 120.3 (3) | C5—C6—H6 | 119.8 |
C7—N3—C9 | 118.8 (3) | N3—C7—C8 | 120.2 (3) |
C2—C1—H1A | 109.5 | N3—C7—H7 | 119.9 |
C2—C1—H1B | 109.5 | C8—C7—H7 | 119.9 |
H1A—C1—H1B | 109.5 | C4—C8—C7 | 120.0 (3) |
C2—C1—H1C | 109.5 | C4—C8—H8 | 120.0 |
H1A—C1—H1C | 109.5 | C7—C8—H8 | 120.0 |
H1B—C1—H1C | 109.5 | N3—C9—C9i | 108.9 (3) |
O1—C2—N1 | 121.2 (3) | N3—C9—H9A | 109.9 |
O1—C2—C1 | 123.2 (3) | C9i—C9—H9A | 109.9 |
N1—C2—C1 | 115.6 (3) | N3—C9—H9B | 109.9 |
O2—C3—N2 | 122.5 (3) | C9i—C9—H9B | 109.9 |
O2—C3—C4 | 120.8 (3) | H9A—C9—H9B | 108.3 |
N2—C3—C4 | 116.7 (3) | H3A—O3—H3B | 115.4 |
C8—C4—C5 | 118.1 (3) | H4A—O4—H4B | 115.5 |
| | | |
C2—N1—N2—C3 | −178.5 (3) | C7—N3—C6—C5 | −0.7 (5) |
N2—N1—C2—O1 | −2.0 (5) | C9—N3—C6—C5 | 179.8 (3) |
N2—N1—C2—C1 | 179.8 (3) | C4—C5—C6—N3 | 0.5 (5) |
N1—N2—C3—O2 | 0.4 (5) | C6—N3—C7—C8 | 0.5 (5) |
N1—N2—C3—C4 | −178.8 (3) | C9—N3—C7—C8 | −179.9 (3) |
O2—C3—C4—C8 | 179.4 (3) | C5—C4—C8—C7 | −0.1 (5) |
N2—C3—C4—C8 | −1.4 (5) | C3—C4—C8—C7 | 179.6 (3) |
O2—C3—C4—C5 | −0.9 (5) | N3—C7—C8—C4 | −0.2 (6) |
N2—C3—C4—C5 | 178.3 (3) | C6—N3—C9—C9i | −88.6 (4) |
C8—C4—C5—C6 | −0.1 (5) | C7—N3—C9—C9i | 91.9 (4) |
C3—C4—C5—C6 | −179.8 (3) | | |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1ii | 0.86 | 2.81 | 3.623 (3) | 158 |
N2—H2···O4iii | 0.86 | 2.14 | 2.990 (4) | 172 |
O3—H3A···Br1iv | 0.86 | 2.48 | 3.312 (3) | 164 |
O3—H3B···Br1 | 0.85 | 2.61 | 3.445 (3) | 167 |
O4—H4A···O3 | 0.85 | 2.02 | 2.820 (5) | 156 |
O4—H4B···O1v | 0.85 | 2.30 | 2.853 (4) | 122 |
O4—H4B···O1vi | 0.85 | 2.18 | 2.955 (4) | 151 |
Symmetry codes: (ii) −x+1, −y+1, −z; (iii) x+1, y, z; (iv) −x, −y+1, −z+1; (v) x−1, y, z; (vi) −x+2, −y+1, −z. |