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The accuracy that can be achieved in single-pulse pump-probe Laue experiments is discussed. It is shown that with careful tuning of the experimental conditions a reproducibility of the intensity ratios of equivalent intensities obtained in different measurements of 3-4% can be achieved. The single-pulse experiments maximize the time resolution that can be achieved and, unlike stroboscopic techniques in which the pump-probe cycle is rapidly repeated, minimize the temperature increase due to the laser exposure of the sample.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0909049510019710/kv5081sup1.cif
Contains datablocks global, Cu4I4pip4

CCDC reference: 767793

Experimental top

Crystals of title compound were obtained according to the literature (see for example Ford et al., 1999).

Refinement top

C—H hydrogen atoms were initially located in a difference Fourier map and were refined with a riding model. These atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.95 − 1.00 Å. Uiso values were fixed such that they were 1.2Ueq of their parent atom Ueq for CH's and 1.5Ueq of their parent atom Ueq in case of methyl groups. The N—H hydrogen atoms was freely refined (Sheldrick, 2008).

Computing details top

Data collection: Data collection monitored with APEX2 APEX2 (ver. v2009.11-0), Bruker AXS (2009); cell refinement: Cell determination and refinement perfomed with APEX2 APEX2 (ver. v200911-0), Bruker AXS (2009); data reduction: Integration performed with SAINT SAINT (ver. V7.68A), Bruker AXS (2009); program(s) used to solve structure: Solved with SHELXS97 Sheldrick, G. M.: (2008) Acta Cryst. A64, 112-122; program(s) used to refine structure: Refined with SHELXL97 Sheldrick, G. M.: (2008) Acta Cryst. A64, 112-122.

tetrakis((µ3-iodo)-piperidine copper(I)) top
Crystal data top
C20H44Cu4I4N4Dx = 2.274 Mg m3
Mr = 1102.39Melting point: not measured K
Tetragonal, P42/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 4bcCell parameters from 7987 reflections
a = 14.6049 (12) Åθ = 2.8–30.3°
c = 7.5464 (12) ŵ = 6.46 mm1
V = 1609.7 (3) Å3T = 90 K
Z = 2Block, yellow
F(000) = 10400.10 × 0.02 × 0.02 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
2460 independent reflections
Radiation source: Rigaku rotating anode2056 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.077
ω scansθmax = 30.5°, θmin = 3.3°
Absorption correction: multi-scan
Absorption correction done by SORTAV Blessing, R. H.: (1995) Acta Cryst. A51, 33-38
h = 2020
Tmin = 0.589, Tmax = 1.155k = 2020
33915 measured reflectionsl = 1010
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.0105P)2 + 1.0213P]
where P = (Fo2 + 2Fc2)/3
2460 reflections(Δ/σ)max = 0.002
77 parametersΔρmax = 0.60 e Å3
0 restraintsΔρmin = 1.51 e Å3
Crystal data top
C20H44Cu4I4N4Z = 2
Mr = 1102.39Mo Kα radiation
Tetragonal, P42/nµ = 6.46 mm1
a = 14.6049 (12) ÅT = 90 K
c = 7.5464 (12) Å0.10 × 0.02 × 0.02 mm
V = 1609.7 (3) Å3
Data collection top
Bruker SMART APEXII CCD
diffractometer
2460 independent reflections
Absorption correction: multi-scan
Absorption correction done by SORTAV Blessing, R. H.: (1995) Acta Cryst. A51, 33-38
2056 reflections with I > 2σ(I)
Tmin = 0.589, Tmax = 1.155Rint = 0.077
33915 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.060H atoms treated by a mixture of independent and constrained refinement
S = 1.11Δρmax = 0.60 e Å3
2460 reflectionsΔρmin = 1.51 e Å3
77 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
xyzUiso*/Ueq
I10.773669 (11)0.594696 (11)0.04554 (2)0.01247 (6)
Cu10.66225 (2)0.73564 (2)0.12409 (4)0.01304 (8)
N10.55194 (15)0.72116 (15)0.0420 (3)0.0117 (4)
C10.48374 (19)0.79537 (19)0.0195 (4)0.0174 (5)
H1A0.51460.85510.03560.021*
H1B0.45950.79330.10300.021*
C30.35720 (18)0.69503 (19)0.1373 (4)0.0183 (5)
H3A0.31040.68970.23150.022*
H3B0.32610.68900.02130.022*
C20.40415 (18)0.78870 (19)0.1492 (4)0.0177 (5)
H2A0.42700.79830.27130.021*
H2B0.35910.83740.12280.021*
C50.50760 (18)0.62964 (19)0.0283 (4)0.0164 (5)
H5A0.48460.62090.09390.020*
H5B0.55390.58160.05180.020*
C40.42821 (18)0.61837 (19)0.1582 (4)0.0177 (5)
H4A0.39830.55850.13780.021*
H4B0.45220.61890.28090.021*
H10.576 (2)0.7281 (19)0.165 (4)0.005 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01390 (9)0.01253 (9)0.01096 (9)0.00020 (5)0.00093 (5)0.00333 (5)
Cu10.01093 (14)0.01635 (16)0.01184 (15)0.00100 (11)0.00207 (11)0.00041 (11)
N10.0102 (10)0.0137 (10)0.0112 (10)0.0001 (7)0.0004 (7)0.0003 (8)
C10.0131 (12)0.0163 (12)0.0227 (13)0.0028 (9)0.0012 (10)0.0040 (10)
C30.0108 (11)0.0230 (14)0.0209 (13)0.0013 (10)0.0014 (10)0.0002 (11)
C20.0121 (11)0.0210 (13)0.0201 (13)0.0016 (9)0.0030 (10)0.0002 (11)
C50.0140 (12)0.0157 (12)0.0194 (13)0.0023 (9)0.0025 (10)0.0014 (10)
C40.0139 (12)0.0171 (12)0.0220 (13)0.0039 (9)0.0048 (10)0.0003 (10)
Geometric parameters (Å, º) top
I1—Cu12.6901 (4)C3—H3A0.9900
Cu1—N12.052 (2)C3—H3B0.9900
N1—C11.482 (3)C2—H2A0.9900
N1—C51.489 (3)C2—H2B0.9900
N1—H11.00 (3)C5—C41.527 (4)
C1—C21.523 (4)C5—H5A0.9900
C1—H1A0.9900C5—H5B0.9900
C1—H1B0.9900C4—H4A0.9900
C3—C21.533 (4)C4—H4B0.9900
C3—C41.534 (4)
Cu1i—I1—Cu158.905 (12)N1—C1—C2113.1 (2)
Cu1i—I1—Cu1ii58.609 (12)N1—C1—H1A109.0
Cu1—I1—Cu1ii57.444 (12)C2—C1—H1A109.0
N1—Cu1—Cu1ii142.33 (6)N1—C1—H1B109.0
N1—Cu1—Cu1i147.18 (6)C2—C1—H1B109.0
Cu1ii—Cu1—Cu1i60.566 (8)H1A—C1—H1B107.8
N1—Cu1—Cu1iii144.66 (6)C2—C3—C4110.1 (2)
Cu1ii—Cu1—Cu1iii60.567 (8)C2—C3—H3A109.7
Cu1i—Cu1—Cu1iii58.864 (15)C4—C3—H3A109.7
N1—Cu1—I1iii105.86 (6)C2—C3—H3B109.7
Cu1ii—Cu1—I1iii111.767 (8)C4—C3—H3B109.7
Cu1i—Cu1—I1iii61.256 (16)H3A—C3—H3B108.2
Cu1iii—Cu1—I1iii60.649 (16)C1—C2—C3111.1 (2)
N1—Cu1—I1105.16 (6)C1—C2—H2A109.4
Cu1ii—Cu1—I161.748 (12)C3—C2—H2A109.4
Cu1i—Cu1—I160.446 (13)C1—C2—H2B109.4
Cu1iii—Cu1—I1110.178 (11)C3—C2—H2B109.4
I1iii—Cu1—I1112.842 (12)H2A—C2—H2B108.0
N1—Cu1—I1ii103.38 (6)N1—C5—C4112.5 (2)
Cu1ii—Cu1—I1ii60.808 (12)N1—C5—H5A109.1
Cu1i—Cu1—I1ii109.432 (11)C4—C5—H5A109.1
Cu1iii—Cu1—I1ii60.133 (13)N1—C5—H5B109.1
I1iii—Cu1—I1ii112.068 (12)C4—C5—H5B109.1
I1—Cu1—I1ii116.224 (12)H5A—C5—H5B107.8
C1—N1—C5110.9 (2)C5—C4—C3111.6 (2)
C1—N1—Cu1112.49 (16)C5—C4—H4A109.3
C5—N1—Cu1113.07 (16)C3—C4—H4A109.3
C1—N1—H1105.9 (16)C5—C4—H4B109.3
C5—N1—H1108.1 (16)C3—C4—H4B109.3
Cu1—N1—H1106.0 (17)H4A—C4—H4B108.0
Cu1i—I1—Cu1—N1147.92 (7)I1ii—Cu1—N1—C156.24 (18)
Cu1ii—I1—Cu1—N1141.75 (6)Cu1ii—Cu1—N1—C5118.01 (16)
Cu1i—I1—Cu1—Cu1ii70.329 (9)Cu1i—Cu1—N1—C53.6 (2)
Cu1ii—I1—Cu1—Cu1i70.329 (9)Cu1iii—Cu1—N1—C5126.12 (16)
Cu1i—I1—Cu1—Cu1iii32.684 (16)I1iii—Cu1—N1—C564.82 (17)
Cu1ii—I1—Cu1—Cu1iii37.645 (18)I1—Cu1—N1—C554.85 (18)
Cu1i—I1—Cu1—I1iii32.994 (14)I1ii—Cu1—N1—C5177.20 (16)
Cu1ii—I1—Cu1—I1iii103.324 (11)C5—N1—C1—C255.6 (3)
Cu1i—I1—Cu1—I1ii98.454 (14)Cu1—N1—C1—C2176.64 (18)
Cu1ii—I1—Cu1—I1ii28.125 (16)N1—C1—C2—C355.4 (3)
Cu1ii—Cu1—N1—C1115.43 (17)C4—C3—C2—C153.1 (3)
Cu1i—Cu1—N1—C1122.93 (16)C1—N1—C5—C455.1 (3)
Cu1iii—Cu1—N1—C10.4 (2)Cu1—N1—C5—C4177.54 (18)
I1iii—Cu1—N1—C161.74 (18)N1—C5—C4—C354.8 (3)
I1—Cu1—N1—C1178.58 (16)C2—C3—C4—C553.1 (3)
Symmetry codes: (i) y+3/2, x, z+1/2; (ii) x+3/2, y+3/2, z; (iii) y, x+3/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC20H44Cu4I4N4
Mr1102.39
Crystal system, space groupTetragonal, P42/n
Temperature (K)90
a, c (Å)14.6049 (12), 7.5464 (12)
V3)1609.7 (3)
Z2
Radiation typeMo Kα
µ (mm1)6.46
Crystal size (mm)0.10 × 0.02 × 0.02
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionMulti-scan
Absorption correction done by SORTAV Blessing, R. H.: (1995) Acta Cryst. A51, 33-38
Tmin, Tmax0.589, 1.155
No. of measured, independent and
observed [I > 2σ(I)] reflections
33915, 2460, 2056
Rint0.077
(sin θ/λ)max1)0.715
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.060, 1.11
No. of reflections2460
No. of parameters77
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.60, 1.51

Computer programs: Data collection monitored with APEX2 APEX2 (ver. v2009.11-0), Bruker AXS (2009), Cell determination and refinement perfomed with APEX2 APEX2 (ver. v200911-0), Bruker AXS (2009), Integration performed with SAINT SAINT (ver. V7.68A), Bruker AXS (2009), Solved with SHELXS97 Sheldrick, G. M.: (2008) Acta Cryst. A64, 112-122, Refined with SHELXL97 Sheldrick, G. M.: (2008) Acta Cryst. A64, 112-122.

 

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