Poly[di­ethyl­ammonium [tetra-μ₂-cyanido-κ⁸C:N-tricuprate(I)]], a two-dimensional network solid

The title compound, (C₄H₁₂N)[Cu₃(CN)₄]_n, crystallizes as a CuCN network solid, with di­ethyl­ammonium cations sandwiched between planar CuCN sheets comprised of trigonal planar and digonally coordinated Cu^I atoms bridged by linear CN groups to form 24-membered rings. The digonally coordinated Cu^I atoms and the di­ethyl­ammonium cations lie on separate crystallographic twofold rotation axes. One of the two independent CN groups has a 50:50 disordered orientation, while the other has one orientation favored due to a N—H...NC hydrogen bond between the di­ethyl­ammonium cation and the anionic CuCN framework. These hydrogen bonds link the sheets together into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 302 K
• Mean [sigma](C-C) = 0.012 Å
• Disorder in main residue
• R factor = 0.031
• wR factor = 0.069
• Data-to-parameter ratio = 18.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C High   'MainMol' Ueq as Compared to Neighbors of        Cu1 Check
PLAT242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of        C31 Check
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............      0.012 Ang.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          4 Report
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          2 Note
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          2 Info
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          4 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT300_ALERT_4_G Atom Site Occupancy of N1         Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of N1A        Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of C1         Constrained at        0.5 Check
PLAT300_ALERT_4_G Atom Site Occupancy of C1A        Constrained at        0.5 Check
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        71% Note
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          ! Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  14 ALERT level G = General information/check it is not something unexpected

   1 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
   6 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor,1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Poly[diethylammonium [tetra-µ₂-cyanido-κ⁸C:N-tricuprate(I)]]

Crystal data

(C4H12N)[Cu3(CN)4]	F(000) = 364
Mr = 368.85	Dx = 1.861 Mg m^−3 Dm = 1.84 (1) Mg m^−3 Dm measured by flotation in CCl4/dibromoethane mixtures
Monoclinic, C2	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: C 2y	Cell parameters from 791 reflections
a = 12.6825 (8) Å	θ = 3.3–27.4°
b = 8.3355 (5) Å	µ = 4.78 mm^−1
c = 7.2205 (5) Å	T = 302 K
β = 120.444 (3)°	Irregular block, pale green
V = 658.07 (8) Å^3	0.15 × 0.13 × 0.08 mm
Z = 2

Data collection

Enraf–Nonius KappaCCD diffractometer	1487 independent reflections
Radiation source: fine-focus sealed tube	1191 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 9 pixels mm^-1	θmax = 27.4°, θmin = 3.3°
combination of ω and φ scans	h = −16→16
Absorption correction: multi-scan (Otwinowski & Minor,1997)	k = −10→10
Tmin = 0.51, Tmax = 0.68	l = −9→9
2500 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.021P)^2 + 0.730P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.069	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.22 e Å^−3
1487 reflections	Δρmin = −0.29 e Å^−3
82 parameters	Extinction correction: SHELXL-2017/1 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.015 (3)
Primary atom site location: heavy-atom method	Absolute structure: Twinning involves reflection, so the Flack parameter of 0.13 (5) implies the presence of a small amount of the inverted form
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.13 (5)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Hydrogen atoms on the C atoms were constrained, with C—H distances of 0.97 Å for the methylene group and 0.96 Å for the methyl group. The N—H atom was refined, with a restraint on the N—H bond length but not on the temperature factor.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.000000	0.0002 (2)	0.000000	0.0860 (6)
Cu2	0.18717 (6)	−0.02348 (14)	0.78258 (9)	0.0636 (3)
C1	0.1211 (4)	−0.0060 (10)	0.4775 (7)	0.0605 (12)	0.5
N1A	0.1211 (4)	−0.0060 (10)	0.4775 (7)	0.0605 (12)	0.5
N1	0.0777 (4)	−0.0015 (11)	0.2956 (8)	0.0683 (16)	0.5
C1A	0.0777 (4)	−0.0015 (11)	0.2956 (8)	0.0683 (16)	0.5
C2A	0.2142 (6)	0.1819 (7)	0.9323 (10)	0.066 (2)	0.22 (8)
N2	0.2142 (6)	0.1819 (7)	0.9323 (10)	0.066 (2)	0.78 (8)
N2A	0.2525 (7)	0.2919 (8)	1.0428 (11)	0.064 (2)	0.22 (8)
C2	0.2525 (7)	0.2919 (8)	1.0428 (11)	0.064 (2)	0.78 (8)
N3	0.000000	0.3473 (8)	0.500000	0.0606 (17)
H3	0.033 (6)	0.277 (6)	0.606 (8)	0.09 (2)*
C31	0.0968 (5)	0.4390 (8)	0.4846 (11)	0.071 (2)
H31A	0.140222	0.506523	0.610650	0.106*
H31B	0.155145	0.363683	0.484731	0.106*
C32	0.0488 (8)	0.5391 (14)	0.2931 (14)	0.118 (4)
H32A	0.115278	0.590203	0.288774	0.177*
H32B	−0.004388	0.619311	0.297044	0.177*
H32C	0.003720	0.473602	0.167536	0.177*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0970 (8)	0.0960 (16)	0.0395 (5)	0.000	0.0158 (5)	0.000
Cu2	0.0685 (4)	0.0588 (4)	0.0457 (3)	0.0009 (4)	0.0157 (3)	0.0021 (4)
C1	0.057 (2)	0.068 (3)	0.047 (2)	0.007 (3)	0.0188 (19)	0.003 (3)
N1A	0.057 (2)	0.068 (3)	0.047 (2)	0.007 (3)	0.0188 (19)	0.003 (3)
N1	0.065 (3)	0.081 (5)	0.045 (2)	0.008 (3)	0.017 (2)	−0.001 (3)
C1A	0.065 (3)	0.081 (5)	0.045 (2)	0.008 (3)	0.017 (2)	−0.001 (3)
C2A	0.079 (4)	0.051 (4)	0.050 (3)	0.000 (3)	0.020 (3)	0.002 (3)
N2	0.079 (4)	0.051 (4)	0.050 (3)	0.000 (3)	0.020 (3)	0.002 (3)
N2A	0.074 (4)	0.053 (4)	0.047 (4)	0.004 (3)	0.016 (3)	0.007 (3)
C2	0.074 (4)	0.053 (4)	0.047 (4)	0.004 (3)	0.016 (3)	0.007 (3)
N3	0.056 (4)	0.056 (4)	0.062 (4)	0.000	0.023 (3)	0.000
C31	0.054 (3)	0.067 (6)	0.077 (4)	0.001 (3)	0.023 (3)	0.006 (3)
C32	0.089 (5)	0.158 (12)	0.097 (6)	0.007 (6)	0.040 (5)	0.049 (6)

Geometric parameters (Å, º)

Cu1—N1^i	1.842 (5)	N3—C31^iii	1.497 (7)
Cu1—N1	1.842 (5)	N3—H3	0.885 (14)
Cu2—N2A^ii	1.889 (7)	C31—C32	1.457 (10)
Cu2—C1	1.925 (4)	C31—H31A	0.9700
Cu2—N2	1.960 (7)	C31—H31B	0.9700
C1—N1	1.139 (6)	C32—H32A	0.9600
N2—C2	1.149 (7)	C32—H32B	0.9600
N3—C31	1.497 (7)	C32—H32C	0.9600
N1^i—Cu1—N1	179.1 (6)	C32—C31—H31A	108.9
N2A^ii—Cu2—C1	128.3 (3)	N3—C31—H31A	108.9
N2A^ii—Cu2—N2	116.4 (2)	C32—C31—H31B	108.9
C1—Cu2—N2	114.7 (3)	N3—C31—H31B	108.9
N1—C1—Cu2	176.5 (6)	H31A—C31—H31B	107.7
C1—N1—Cu1	176.8 (6)	C31—C32—H32A	109.5
C2—N2—Cu2	167.0 (6)	C31—C32—H32B	109.5
N2—C2—Cu2^iv	178.3 (5)	H32A—C32—H32B	109.5
C31—N3—C31^iii	118.6 (7)	C31—C32—H32C	109.5
C31—N3—H3	111 (5)	H32A—C32—H32C	109.5
C31^iii—N3—H3	109 (5)	H32B—C32—H32C	109.5
C32—C31—N3	113.5 (5)

Symmetry codes: (i) −x, y, −z; (ii) −x+1/2, y−1/2, −z+2; (iii) −x, y, −z+1; (iv) −x+1/2, y+1/2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N2	0.89 (1)	2.44 (4)	3.230 (6)	149 (6)