The crystal structure of the title compound, (C
6H
5CH
2NH
3)
4[Cu(NO
3)
4](NO
3)
2, consists of alternating organic and inorganic layers. The aromatic groups constitute the organic layer, while the nitrate ions, ammonium groups and [Cu(NO
3)
4]
2− anions form the inorganic layer; the complex anions lie on twofold rotation axes. Strong classical N—H
O hydrogen bonds in the inorganic layer result in a complex two-dimensional hydrogen-bonding network.
Supporting information
CCDC reference: 298470
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.004 Å
- R factor = 0.043
- wR factor = 0.127
- Data-to-parameter ratio = 23.0
checkCIF/PLATON results
No syntax errors found
Alert level A
DIFF019_ALERT_1_A _diffrn_standards_number is missing
Number of standards used in measurement.
DIFF020_ALERT_1_A _diffrn_standards_interval_count and
_diffrn_standards_interval_time are missing. Number of measurements
between standards or time (min) between standards.
Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O4 .. 6.72 su
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O5
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N5
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1B .. N5 .. 2.66 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1C .. N5 .. 2.65 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2C .. O3 .. 2.65 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2
C7 H10 N
2 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
9 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
5 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003) and WinGX (Farrugia, 1999).
Tetrakis(benzylammonium) tetranitratocuprate(II) dinitrate
top
Crystal data top
(C7H10N)4[Cu(NO4)3](NO3)2 | F(000) = 1804 |
Mr = 868.24 | Dx = 1.545 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 476 reflections |
a = 30.79 (3) Å | θ = 2–31° |
b = 5.749 (9) Å | µ = 0.68 mm−1 |
c = 21.293 (14) Å | T = 295 K |
β = 97.93 (7)° | Block, blue |
V = 3733 (7) Å3 | 0.50 × 0.50 × 0.50 mm |
Z = 4 | |
Data collection top
Oxford Excalibur2 diffractometer | 5929 independent reflections |
Radiation source: fine-focus sealed tube | 4603 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω/2θ scans | θmax = 32.0°, θmin = 4.4° |
Absorption correction: multi-scan (Blessing, 1995) | h = −44→45 |
Tmin = 0.714, Tmax = 0.714 | k = −8→5 |
17698 measured reflections | l = −30→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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.071P)2 + 0.4182P] where P = (Fo2 + 2Fc2)/3 |
5929 reflections | (Δ/σ)max = 0.001 |
258 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.74 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 | |
O1 | −0.00078 (4) | 0.51036 (19) | 0.84279 (5) | 0.0355 (3) | |
O4 | −0.06425 (4) | 0.4501 (2) | 0.73340 (6) | 0.0375 (3) | |
C7 | 0.22386 (7) | 0.0182 (3) | 0.69590 (10) | 0.0456 (4) | |
H7 | 0.2195 | −0.1129 | 0.7198 | 0.055* | |
N4 | −0.08162 (5) | 0.6563 (3) | 0.73080 (6) | 0.0351 (3) | |
O6 | −0.12115 (4) | 0.6739 (3) | 0.71617 (7) | 0.0534 (4) | |
O5 | −0.05672 (5) | 0.8235 (2) | 0.74217 (7) | 0.0485 (3) | |
C6 | 0.26161 (7) | 0.0378 (4) | 0.66773 (11) | 0.0548 (5) | |
H6 | 0.2825 | −0.0802 | 0.6729 | 0.066* | |
C9 | −0.11423 (5) | −0.0697 (3) | 0.55755 (8) | 0.0365 (3) | |
N1 | 0.11133 (5) | 0.1578 (3) | 0.68094 (8) | 0.0439 (3) | |
H1A | 0.0894 | 0.1502 | 0.7040 | 0.066* | |
H1B | 0.1117 | 0.0291 | 0.6578 | 0.066* | |
H1C | 0.1076 | 0.2810 | 0.6554 | 0.066* | |
C2 | 0.19256 (5) | 0.1928 (3) | 0.68870 (8) | 0.0361 (3) | |
C3 | 0.19970 (6) | 0.3858 (3) | 0.65233 (10) | 0.0463 (4) | |
H3 | 0.1789 | 0.5042 | 0.6469 | 0.056* | |
C14 | −0.11807 (6) | 0.1150 (4) | 0.59834 (9) | 0.0425 (4) | |
H14 | −0.0981 | 0.1304 | 0.6351 | 0.051* | |
C13 | −0.15124 (7) | 0.2761 (4) | 0.58474 (11) | 0.0515 (5) | |
H13 | −0.1536 | 0.3993 | 0.6124 | 0.062* | |
C1 | 0.15359 (6) | 0.1795 (4) | 0.72360 (9) | 0.0462 (4) | |
H1D | 0.1570 | 0.0467 | 0.7520 | 0.055* | |
H1E | 0.1527 | 0.3183 | 0.7493 | 0.055* | |
C4 | 0.23723 (7) | 0.4035 (4) | 0.62421 (11) | 0.0542 (5) | |
H4 | 0.2415 | 0.5331 | 0.5997 | 0.065* | |
N2 | −0.04000 (4) | −0.1950 (3) | 0.53864 (7) | 0.0360 (3) | |
H2A | −0.0192 | −0.3009 | 0.5495 | 0.054* | |
H2B | −0.0294 | −0.0540 | 0.5488 | 0.054* | |
H2C | −0.0487 | −0.2020 | 0.4970 | 0.054* | |
C8 | −0.07757 (6) | −0.2415 (4) | 0.57272 (10) | 0.0489 (5) | |
H8A | −0.0676 | −0.2381 | 0.6180 | 0.059* | |
H8B | −0.0886 | −0.3965 | 0.5620 | 0.059* | |
C5 | 0.26852 (7) | 0.2301 (4) | 0.63217 (11) | 0.0547 (5) | |
H5 | 0.2940 | 0.2433 | 0.6136 | 0.066* | |
O3 | 0.01356 (4) | 0.2967 (2) | 0.92662 (6) | 0.0437 (3) | |
N3 | 0.00426 (4) | 0.3077 (2) | 0.86831 (6) | 0.0314 (3) | |
O2 | 0.00023 (5) | 0.1350 (2) | 0.83423 (7) | 0.0555 (4) | |
C10 | −0.14412 (7) | −0.0906 (4) | 0.50340 (10) | 0.0503 (5) | |
H10 | −0.1421 | −0.2148 | 0.4760 | 0.060* | |
C12 | −0.18063 (7) | 0.2548 (4) | 0.53067 (12) | 0.0587 (5) | |
H12 | −0.2030 | 0.3635 | 0.5216 | 0.070* | |
C11 | −0.17716 (7) | 0.0723 (5) | 0.48965 (11) | 0.0628 (6) | |
H11 | −0.1970 | 0.0587 | 0.4527 | 0.075* | |
O7 | 0.10816 (5) | 0.6966 (3) | 0.63794 (7) | 0.0547 (4) | |
N5 | 0.08195 (5) | 0.6599 (3) | 0.58950 (7) | 0.0379 (3) | |
O8 | 0.05945 (5) | 0.8189 (3) | 0.56389 (8) | 0.0698 (5) | |
O9 | 0.07946 (7) | 0.4542 (3) | 0.57094 (10) | 0.0735 (5) | |
Cu1 | 0.0000 | 0.48583 (5) | 0.7500 | 0.03026 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0433 (6) | 0.0361 (6) | 0.0272 (5) | 0.0026 (5) | 0.0054 (4) | 0.0024 (4) |
O4 | 0.0309 (6) | 0.0406 (6) | 0.0409 (6) | −0.0003 (5) | 0.0050 (5) | −0.0015 (5) |
C7 | 0.0494 (10) | 0.0420 (10) | 0.0444 (10) | 0.0084 (8) | 0.0034 (8) | 0.0041 (7) |
N4 | 0.0327 (6) | 0.0432 (8) | 0.0294 (6) | 0.0018 (6) | 0.0049 (5) | 0.0023 (5) |
O6 | 0.0312 (6) | 0.0639 (9) | 0.0634 (9) | 0.0088 (6) | 0.0002 (6) | 0.0047 (7) |
O5 | 0.0476 (7) | 0.0444 (7) | 0.0540 (8) | −0.0098 (6) | 0.0089 (6) | 0.0001 (6) |
C6 | 0.0444 (10) | 0.0609 (12) | 0.0582 (12) | 0.0221 (9) | 0.0043 (9) | 0.0006 (10) |
C9 | 0.0320 (7) | 0.0415 (8) | 0.0374 (8) | 0.0034 (7) | 0.0100 (6) | 0.0067 (7) |
N1 | 0.0336 (7) | 0.0491 (9) | 0.0498 (9) | −0.0013 (6) | 0.0091 (6) | −0.0082 (7) |
C2 | 0.0328 (8) | 0.0366 (8) | 0.0376 (8) | −0.0001 (6) | −0.0001 (6) | −0.0054 (6) |
C3 | 0.0373 (9) | 0.0365 (9) | 0.0652 (12) | 0.0074 (7) | 0.0073 (8) | 0.0056 (8) |
C14 | 0.0357 (8) | 0.0550 (11) | 0.0373 (9) | −0.0023 (8) | 0.0066 (6) | −0.0052 (8) |
C13 | 0.0469 (10) | 0.0485 (11) | 0.0625 (13) | 0.0004 (9) | 0.0196 (9) | −0.0119 (9) |
C1 | 0.0402 (9) | 0.0573 (11) | 0.0414 (9) | −0.0031 (8) | 0.0061 (7) | −0.0079 (8) |
C4 | 0.0483 (11) | 0.0510 (11) | 0.0648 (13) | −0.0024 (9) | 0.0135 (9) | 0.0113 (10) |
N2 | 0.0326 (7) | 0.0380 (7) | 0.0378 (7) | 0.0039 (5) | 0.0057 (5) | 0.0002 (6) |
C8 | 0.0434 (9) | 0.0536 (11) | 0.0533 (11) | 0.0120 (8) | 0.0197 (8) | 0.0215 (9) |
C5 | 0.0384 (9) | 0.0713 (14) | 0.0557 (12) | 0.0047 (9) | 0.0115 (8) | −0.0014 (10) |
O3 | 0.0514 (7) | 0.0517 (7) | 0.0266 (6) | −0.0010 (6) | 0.0005 (5) | 0.0058 (5) |
N3 | 0.0271 (6) | 0.0369 (7) | 0.0298 (6) | −0.0019 (5) | 0.0033 (5) | 0.0006 (5) |
O2 | 0.0792 (10) | 0.0375 (7) | 0.0477 (8) | −0.0040 (7) | 0.0016 (7) | −0.0110 (6) |
C10 | 0.0479 (10) | 0.0572 (11) | 0.0445 (10) | 0.0062 (9) | 0.0012 (8) | −0.0116 (9) |
C12 | 0.0422 (10) | 0.0636 (13) | 0.0709 (14) | 0.0184 (10) | 0.0101 (9) | 0.0058 (11) |
C11 | 0.0461 (11) | 0.0876 (16) | 0.0505 (12) | 0.0155 (12) | −0.0082 (9) | −0.0040 (12) |
O7 | 0.0492 (8) | 0.0581 (8) | 0.0510 (8) | 0.0108 (6) | −0.0132 (6) | −0.0128 (7) |
N5 | 0.0321 (7) | 0.0490 (8) | 0.0329 (7) | −0.0028 (6) | 0.0051 (5) | −0.0028 (6) |
O8 | 0.0501 (9) | 0.0942 (13) | 0.0633 (10) | 0.0146 (8) | 0.0017 (7) | 0.0354 (9) |
O9 | 0.0771 (12) | 0.0688 (10) | 0.0764 (12) | −0.0181 (9) | 0.0165 (9) | −0.0363 (9) |
Cu1 | 0.02681 (14) | 0.03910 (17) | 0.02504 (14) | 0.000 | 0.00415 (9) | 0.000 |
Geometric parameters (Å, º) top
O1—N3 | 1.286 (2) | C13—H13 | 0.9300 |
O1—Cu1 | 1.9841 (18) | C1—H1D | 0.9700 |
O4—N4 | 1.299 (2) | C1—H1E | 0.9700 |
O4—Cu1 | 1.972 (2) | C4—C5 | 1.380 (3) |
C7—C6 | 1.384 (3) | C4—H4 | 0.9300 |
C7—C2 | 1.385 (3) | N2—C8 | 1.472 (2) |
C7—H7 | 0.9300 | N2—H2A | 0.8900 |
N4—O6 | 1.218 (2) | N2—H2B | 0.8900 |
N4—O5 | 1.233 (2) | N2—H2C | 0.8900 |
C6—C5 | 1.373 (4) | C8—H8A | 0.9700 |
C6—H6 | 0.9300 | C8—H8B | 0.9700 |
C9—C10 | 1.378 (3) | C5—H5 | 0.9300 |
C9—C14 | 1.387 (3) | O3—N3 | 1.2366 (19) |
C9—C8 | 1.501 (3) | N3—O2 | 1.226 (2) |
N1—C1 | 1.486 (3) | C10—C11 | 1.384 (3) |
N1—H1A | 0.8900 | C10—H10 | 0.9300 |
N1—H1B | 0.8900 | C12—C11 | 1.378 (4) |
N1—H1C | 0.8900 | C12—H12 | 0.9300 |
C2—C3 | 1.388 (3) | C11—H11 | 0.9300 |
C2—C1 | 1.498 (3) | O7—N5 | 1.237 (2) |
C3—C4 | 1.377 (3) | N5—O8 | 1.228 (2) |
C3—H3 | 0.9300 | N5—O9 | 1.246 (3) |
C14—C13 | 1.379 (3) | Cu1—O4i | 1.972 (2) |
C14—H14 | 0.9300 | Cu1—O1i | 1.9842 (17) |
C13—C12 | 1.368 (3) | | |
| | | |
N3—O1—Cu1 | 109.82 (10) | C3—C4—H4 | 119.8 |
N4—O4—Cu1 | 108.04 (11) | C5—C4—H4 | 119.8 |
C6—C7—C2 | 120.41 (19) | C8—N2—H2A | 109.5 |
C6—C7—H7 | 119.8 | C8—N2—H2B | 109.5 |
C2—C7—H7 | 119.8 | H2A—N2—H2B | 109.5 |
O6—N4—O5 | 123.92 (17) | C8—N2—H2C | 109.5 |
O6—N4—O4 | 118.53 (15) | H2A—N2—H2C | 109.5 |
O5—N4—O4 | 117.53 (16) | H2B—N2—H2C | 109.5 |
C5—C6—C7 | 120.49 (18) | N2—C8—C9 | 113.14 (15) |
C5—C6—H6 | 119.8 | N2—C8—H8A | 109.0 |
C7—C6—H6 | 119.8 | C9—C8—H8A | 109.0 |
C10—C9—C14 | 119.09 (17) | N2—C8—H8B | 109.0 |
C10—C9—C8 | 121.21 (19) | C9—C8—H8B | 109.0 |
C14—C9—C8 | 119.70 (18) | H8A—C8—H8B | 107.8 |
C1—N1—H1A | 109.5 | C6—C5—C4 | 119.4 (2) |
C1—N1—H1B | 109.5 | C6—C5—H5 | 120.3 |
H1A—N1—H1B | 109.5 | C4—C5—H5 | 120.3 |
C1—N1—H1C | 109.5 | O2—N3—O3 | 122.94 (15) |
H1A—N1—H1C | 109.5 | O2—N3—O1 | 119.15 (15) |
H1B—N1—H1C | 109.5 | O3—N3—O1 | 117.91 (14) |
C7—C2—C3 | 118.66 (19) | C9—C10—C11 | 120.3 (2) |
C7—C2—C1 | 120.05 (18) | C9—C10—H10 | 119.9 |
C3—C2—C1 | 121.14 (17) | C11—C10—H10 | 119.9 |
C4—C3—C2 | 120.58 (18) | C13—C12—C11 | 120.1 (2) |
C4—C3—H3 | 119.7 | C13—C12—H12 | 120.0 |
C2—C3—H3 | 119.7 | C11—C12—H12 | 120.0 |
C13—C14—C9 | 120.46 (19) | C12—C11—C10 | 120.0 (2) |
C13—C14—H14 | 119.8 | C12—C11—H11 | 120.0 |
C9—C14—H14 | 119.8 | C10—C11—H11 | 120.0 |
C12—C13—C14 | 120.1 (2) | O8—N5—O7 | 120.45 (18) |
C12—C13—H13 | 120.0 | O8—N5—O9 | 124.0 (2) |
C14—C13—H13 | 120.0 | O7—N5—O9 | 115.50 (17) |
N1—C1—C2 | 113.24 (16) | O4—Cu1—O4i | 168.04 (8) |
N1—C1—H1D | 108.9 | O4—Cu1—O1 | 92.07 (8) |
C2—C1—H1D | 108.9 | O4i—Cu1—O1 | 88.77 (8) |
N1—C1—H1E | 108.9 | O4—Cu1—O1i | 88.77 (8) |
C2—C1—H1E | 108.9 | O4i—Cu1—O1i | 92.07 (8) |
H1D—C1—H1E | 107.7 | O1—Cu1—O1i | 171.85 (7) |
C3—C4—C5 | 120.4 (2) | | |
| | | |
Cu1—O4—N4—O6 | 174.55 (12) | C7—C6—C5—C4 | −0.6 (4) |
Cu1—O4—N4—O5 | −4.01 (16) | C3—C4—C5—C6 | 0.9 (4) |
C2—C7—C6—C5 | −0.1 (3) | Cu1—O1—N3—O2 | −13.76 (18) |
C6—C7—C2—C3 | 0.5 (3) | Cu1—O1—N3—O3 | 165.38 (11) |
C6—C7—C2—C1 | −175.03 (19) | C14—C9—C10—C11 | 0.8 (3) |
C7—C2—C3—C4 | −0.2 (3) | C8—C9—C10—C11 | −178.7 (2) |
C1—C2—C3—C4 | 175.28 (19) | C14—C13—C12—C11 | 0.0 (3) |
C10—C9—C14—C13 | −0.3 (3) | C13—C12—C11—C10 | 0.5 (4) |
C8—C9—C14—C13 | 179.22 (17) | C9—C10—C11—C12 | −0.9 (4) |
C9—C14—C13—C12 | −0.1 (3) | N4—O4—Cu1—O4i | 178.14 (10) |
C7—C2—C1—N1 | −115.8 (2) | N4—O4—Cu1—O1 | 84.25 (10) |
C3—C2—C1—N1 | 68.7 (2) | N4—O4—Cu1—O1i | −87.64 (10) |
C2—C3—C4—C5 | −0.5 (3) | N3—O1—Cu1—O4 | 91.75 (10) |
C10—C9—C8—N2 | 81.2 (3) | N3—O1—Cu1—O4i | −76.32 (10) |
C14—C9—C8—N2 | −98.3 (2) | | |
Symmetry code: (i) −x, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.89 | 2.37 | 2.997 (3) | 127 |
N1—H1A···O5ii | 0.89 | 2.48 | 3.156 (3) | 133 |
N1—H1B···O7iii | 0.89 | 1.96 | 2.803 (4) | 158 |
N1—H1B···N5iii | 0.89 | 2.66 | 3.509 (4) | 159 |
N1—H1C···O9 | 0.89 | 2.13 | 2.953 (4) | 153 |
N1—H1C···O7 | 0.89 | 2.42 | 3.228 (5) | 151 |
N1—H1C···N5 | 0.89 | 2.65 | 3.530 (4) | 169 |
N2—H2A···O3ii | 0.89 | 2.37 | 3.096 (5) | 139 |
N2—H2A···O8iii | 0.89 | 2.50 | 3.036 (4) | 120 |
N2—H2A···O1ii | 0.89 | 2.54 | 3.154 (3) | 127 |
N2—H2B···O3i | 0.89 | 2.12 | 3.006 (4) | 172 |
N2—H2C···O9iv | 0.89 | 2.17 | 2.891 (3) | 138 |
N2—H2C···O8v | 0.89 | 2.55 | 3.072 (3) | 118 |
N2—H2C···O3vi | 0.89 | 2.65 | 3.136 (3) | 116 |
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x, y−1, −z+3/2; (iii) x, y−1, z; (iv) −x, −y, −z+1; (v) −x, −y+1, −z+1; (vi) x, −y, z−1/2. |