A C-centered monoclinic modification of bis­(di-2-pyridyl­methanediol-κ³N,O,N′)copper(II) di­acetate tetrahydrate

Di-2-pyridyl ketone undergoes hydro­lysis when reacted with copper(II) acetate to form the title compound, [Cu(C₁₁H₁₀N₂O₂)₂](C₂H₃O₂)₂·4H₂O. The crystal structure consists of octahedral cations that are linked to the anions and to the uncoordinated water molecules, giving rise to a three-dimensional network structure. This C-centered monoclinic modification is less compact than the primitive monoclinic modification reported by Reinoso et al. [(2003). Acta Cryst. E59, m548–m550]. The Cu atom is located at a center of inversion.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.037
• wR factor = 0.119
• Data-to-parameter ratio = 18.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT420_ALERT_2_B D-H Without Acceptor       O1W    -   H1W2   ...          ?
PLAT420_ALERT_2_B D-H Without Acceptor       O2W    -   H2W2   ...          ?

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT199_ALERT_1_C Check the Reported cell_measurement_temperature         293
PLAT200_ALERT_1_C Check the Reported cell_ambient_temperature ....        293
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O1      ..       7.39 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C12
PLAT415_ALERT_2_C Short Inter D-H..H-X       H1O    ..  H4      ..       2.11 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

bis(di-2-pyridylmethanediol-κ³N,O,N')copper(II) diacetate tetrahydrate

Crystal data

[Cu(C11H10N2O2)2](C2H3O2)2·4H2O	F(000) = 1372
Mr = 658.11	Dx = 1.366 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9126 reflections
a = 23.557 (2) Å	θ = 2.5–27.0°
b = 8.5744 (6) Å	µ = 0.75 mm^−1
c = 15.848 (1) Å	T = 293 K
β = 91.983 (1)°	Prism, purple
V = 3199.2 (4) Å^3	0.36 × 0.34 × 0.28 mm
Z = 4

Data collection

Rigaku Mercury CCD diffractometer	3587 independent reflections
Radiation source: rotating-anode generator	3064 reflections with I > 2s(I)
Graphite Monochromator monochromator	Rint = 0.017
w scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	h = −30→29
Tmin = 0.772, Tmax = 0.811	k = −10→7
9295 measured reflections	l = −19→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0725P)^2 + 1.3743P] where P = (Fo^2 + 2Fc^2)/3
3587 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cu1	0.2500	0.7500	0.5000	0.0350 (1)
O1	0.3031 (1)	0.7385 (1)	0.3740 (1)	0.0401 (3)
O2	0.3104 (1)	0.5265 (2)	0.2831 (1)	0.0509 (4)
O3	0.4117 (1)	0.7548 (2)	0.3886 (2)	0.0714 (6)
O4	0.4208 (1)	0.5351 (2)	0.3183 (1)	0.0731 (5)
O1w	0.4533 (1)	1.0333 (2)	0.4485 (1)	0.0828 (6)
O2w	0.4696 (1)	1.2386 (2)	0.3210 (1)	0.0912 (8)
N1	0.1975 (1)	0.6555 (2)	0.4103 (1)	0.0399 (4)
N2	0.2900 (1)	0.5442 (2)	0.5072 (1)	0.0378 (3)
C1	0.1405 (1)	0.6602 (3)	0.4097 (1)	0.0510 (5)
C2	0.1080 (1)	0.5935 (3)	0.3456 (2)	0.0627 (6)
C3	0.1343 (1)	0.5209 (3)	0.2806 (2)	0.0617 (6)
C4	0.1929 (1)	0.5140 (3)	0.2810 (1)	0.0496 (5)
C5	0.2231 (1)	0.5829 (2)	0.3467 (1)	0.0387 (4)
C6	0.2875 (1)	0.5824 (2)	0.3561 (1)	0.0379 (4)
C7	0.3040 (1)	0.4816 (2)	0.4331 (1)	0.0369 (4)
C8	0.3307 (1)	0.3385 (2)	0.4295 (2)	0.0515 (5)
C9	0.3439 (1)	0.2610 (3)	0.5041 (2)	0.0656 (7)
C10	0.3295 (1)	0.3262 (3)	0.5792 (2)	0.0658 (7)
C11	0.3025 (1)	0.4677 (3)	0.5790 (1)	0.0504 (5)
C12	0.4408 (1)	0.6456 (3)	0.3601 (2)	0.0647 (6)
C13	0.5040 (1)	0.6478 (5)	0.3797 (3)	0.122 (2)
H1o	0.3230	0.8018	0.3501	0.048*
H2o	0.3451	0.5261	0.2884	0.061*
H1w1	0.4387	0.9503	0.4353	0.099*
H1w2	0.4460	1.0592	0.4964	0.099*
H2w1	0.4480	1.3097	0.3055	0.109*
H2w2	0.4964	1.2805	0.3466	0.109*
H1	0.1226	0.7096	0.4537	0.061*
H2	0.0686	0.5976	0.3464	0.075*
H3	0.1128	0.4766	0.2365	0.074*
H4	0.2115	0.4639	0.2378	0.060*
H8	0.3396	0.2950	0.3779	0.062*
H9	0.3625	0.1653	0.5033	0.079*
H10	0.3379	0.2750	0.6298	0.079*
H11	0.2927	0.5117	0.6301	0.061*
H13a	0.5204	0.5508	0.3625	0.183*
H13b	0.5108	0.6619	0.4393	0.183*
H13c	0.5211	0.7321	0.3497	0.183*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0398 (2)	0.0393 (2)	0.0258 (2)	0.0078 (1)	−0.0004 (1)	−0.0038 (1)
O1	0.0468 (8)	0.0398 (7)	0.0337 (7)	−0.0021 (5)	0.0028 (6)	0.0048 (5)
O2	0.0502 (8)	0.0726 (10)	0.0303 (7)	0.0053 (7)	0.0070 (6)	−0.0119 (6)
O3	0.0493 (10)	0.0669 (12)	0.0980 (16)	−0.0015 (7)	0.0024 (10)	−0.0202 (9)
O4	0.0517 (9)	0.0812 (13)	0.0872 (13)	0.0029 (8)	0.0117 (9)	−0.0212 (10)
O1w	0.0945 (14)	0.0654 (12)	0.0882 (14)	0.0032 (10)	−0.0007 (11)	−0.0099 (10)
O2w	0.0921 (18)	0.0816 (17)	0.101 (2)	0.0132 (10)	0.0156 (15)	0.0048 (11)
N1	0.0398 (8)	0.0463 (9)	0.0335 (8)	0.0062 (6)	−0.0009 (6)	−0.0043 (6)
N2	0.0424 (8)	0.0410 (8)	0.0299 (7)	0.0066 (6)	0.0021 (6)	0.0016 (6)
C1	0.0423 (10)	0.0614 (13)	0.0490 (12)	0.0101 (9)	0.0000 (8)	−0.0061 (10)
C2	0.0412 (11)	0.0831 (17)	0.0630 (14)	0.0045 (11)	−0.0093 (10)	−0.0070 (13)
C3	0.0569 (13)	0.0753 (16)	0.0515 (13)	−0.0014 (11)	−0.0172 (10)	−0.0130 (11)
C4	0.0551 (12)	0.0583 (13)	0.0352 (10)	0.0018 (9)	−0.0038 (8)	−0.0091 (9)
C5	0.0421 (9)	0.0440 (10)	0.0298 (8)	0.0043 (8)	−0.0004 (7)	−0.0007 (7)
C6	0.0417 (9)	0.0452 (10)	0.0269 (8)	0.0042 (7)	0.0035 (7)	−0.0044 (7)
C7	0.0371 (9)	0.0385 (9)	0.0350 (9)	0.0017 (7)	0.0033 (7)	−0.0020 (7)
C8	0.0551 (12)	0.0434 (11)	0.0564 (13)	0.0107 (9)	0.0098 (10)	−0.0040 (9)
C9	0.0699 (17)	0.0475 (13)	0.080 (2)	0.0200 (11)	0.0061 (14)	0.0119 (11)
C10	0.0732 (16)	0.0640 (16)	0.0601 (15)	0.0182 (12)	0.0022 (12)	0.0261 (12)
C11	0.0571 (12)	0.0580 (13)	0.0364 (10)	0.0080 (10)	0.0037 (8)	0.0100 (9)
C12	0.0468 (12)	0.0762 (17)	0.0717 (16)	−0.0011 (12)	0.0095 (11)	−0.0063 (13)
C13	0.0510 (16)	0.137 (4)	0.177 (4)	0.0064 (19)	−0.002 (2)	−0.062 (3)

Geometric parameters (Å, º)

Cu1—O1	2.394 (1)	C8—C9	1.383 (4)
Cu1—O1^i	2.394 (1)	C9—C10	1.368 (4)
Cu1—N1	2.021 (2)	C10—C11	1.369 (3)
Cu1—N1^i	2.021 (2)	C12—C13	1.512 (4)
Cu1—N2	2.002 (2)	O1—H1o	0.82
Cu1—N2^i	2.002 (2)	O2—H2o	0.82
O1—C6	1.414 (2)	O1w—H1w1	0.82
O2—C6	1.379 (2)	O1w—H1w2	0.82
O3—C12	1.254 (3)	O2w—H2w1	0.83
O4—C12	1.240 (3)	O2w—H2w2	0.82
N1—C1	1.343 (2)	C1—H1	0.93
N1—C5	1.344 (2)	C2—H2	0.93
N2—C11	1.338 (2)	C3—H3	0.93
N2—C7	1.343 (2)	C4—H4	0.93
C1—C2	1.376 (3)	C8—H8	0.93
C2—C3	1.370 (3)	C9—H9	0.93
C3—C4	1.382 (3)	C10—H10	0.93
C4—C5	1.375 (3)	C11—H11	0.93
C5—C6	1.518 (3)	C13—H13a	0.96
C6—C7	1.535 (3)	C13—H13b	0.96
C7—C8	1.380 (3)	C13—H13c	0.96
O1—Cu1—O1^i	180	N2—C7—C6	114.0 (2)
O1—Cu1—N1	73.81 (5)	C8—C7—C6	124.9 (2)
O1—Cu1—N1^i	106.19 (6)	C7—C8—C9	118.8 (2)
O1—Cu1—N2	75.68 (5)	C10—C9—C8	119.4 (2)
O1—Cu1—N2^i	104.32 (5)	C9—C10—C11	119.3 (2)
O1^i—Cu1—N1	106.19 (6)	N2—C11—C10	121.7 (2)
O1^i—Cu1—N1^i	73.81 (5)	O4—C12—O3	124.1 (2)
O1^i—Cu1—N2	104.32 (5)	O4—C12—C13	118.2 (3)
O1^i—Cu1—N2^i	75.68 (5)	O3—C12—C13	117.7 (3)
N1—Cu1—N1^i	180.0	C6—O1—H1o	133.1
N1—Cu1—N2	87.84 (6)	Cu1—O1—H1o	133.1
N1—Cu1—N2^i	92.16 (6)	C6—O2—H2o	109.5
N1^i—Cu1—N2	92.16 (6)	H1w1—O1w—H1w2	112.2
N1^i—Cu1—N2^i	87.84 (6)	H2w1—O2w—H2w2	106.2
N2—Cu1—N2^i	180	N1—C1—H1	119.2
C6—O1—Cu1	93.9 (1)	C2—C1—H1	119.2
C1—N1—C5	118.9 (2)	C3—C2—H2	120.4
C1—N1—Cu1	125.4 (1)	C1—C2—H2	120.4
C5—N1—Cu1	115.7 (1)	C2—C3—H3	120.2
C11—N2—C7	119.6 (2)	C4—C3—H3	120.2
C11—N2—Cu1	124.8 (1)	C5—C4—H4	120.8
C7—N2—Cu1	115.6 (1)	C3—C4—H4	120.8
N1—C1—C2	121.6 (2)	C7—C8—H8	120.6
C3—C2—C1	119.3 (2)	C9—C8—H8	120.6
C2—C3—C4	119.6 (2)	C10—C9—H9	120.3
C5—C4—C3	118.4 (2)	C8—C9—H9	120.3
N1—C5—C4	122.2 (2)	C9—C10—H10	120.3
N1—C5—C6	113.6 (2)	C11—C10—H10	120.3
C4—C5—C6	124.2 (2)	N2—C11—H11	119.2
O2—C6—O1	113.0 (2)	C10—C11—H11	119.2
O2—C6—C5	109.7 (2)	C12—C13—H13a	109.5
O1—C6—C5	105.6 (2)	C12—C13—H13b	109.5
O2—C6—C7	112.0 (2)	H13a—C13—H13b	109.5
O1—C6—C7	108.4 (1)	C12—C13—H13c	109.5
C5—C6—C7	107.7 (2)	H13a—C13—H13c	109.5
N2—C7—C8	121.1 (2)	H13b—C13—H13c	109.5
N2—Cu1—O1—C6	44.7 (1)	C3—C4—C5—N1	0.3 (3)
N2^i—Cu1—O1—C6	−135.3 (1)	C3—C4—C5—C6	179.1 (2)
N1—Cu1—O1—C6	−47.2 (1)	Cu1—O1—C6—O2	179.6 (1)
N1^i—Cu1—O1—C6	132.8 (1)	Cu1—O1—C6—C5	59.7 (1)
N2—Cu1—N1—C1	129.4 (2)	Cu1—O1—C6—C7	−55.6 (1)
N2^i—Cu1—N1—C1	−50.6 (2)	N1—C5—C6—O2	−171.3 (2)
O1—Cu1—N1—C1	−154.9 (2)	C4—C5—C6—O2	9.8 (3)
O1^i—Cu1—N1—C1	25.1 (2)	N1—C5—C6—O1	−49.2 (2)
N2—Cu1—N1—C5	−50.6 (1)	C4—C5—C6—O1	131.9 (2)
N2^i—Cu1—N1—C5	129.4 (1)	N1—C5—C6—C7	66.5 (2)
O1—Cu1—N1—C5	25.1 (1)	C4—C5—C6—C7	−112.4 (2)
O1^i—Cu1—N1—C5	−154.9 (1)	C11—N2—C7—C8	0.7 (3)
N1—Cu1—N2—C11	−130.7 (2)	Cu1—N2—C7—C8	−178.6 (2)
N1^i—Cu1—N2—C11	49.3 (2)	C11—N2—C7—C6	−179.6 (2)
O1—Cu1—N2—C11	155.5 (2)	Cu1—N2—C7—C6	1.1 (2)
O1^i—Cu1—N2—C11	−24.5 (2)	O2—C6—C7—N2	170.4 (2)
N1—Cu1—N2—C7	48.6 (1)	O1—C6—C7—N2	45.0 (2)
N1^i—Cu1—N2—C7	−131.4 (1)	C5—C6—C7—N2	−68.8 (2)
O1—Cu1—N2—C7	−25.3 (1)	O2—C6—C7—C8	−9.9 (3)
O1^i—Cu1—N2—C7	154.7 (1)	O1—C6—C7—C8	−135.3 (2)
C5—N1—C1—C2	−0.4 (3)	C5—C6—C7—C8	110.9 (2)
Cu1—N1—C1—C2	179.6 (2)	N2—C7—C8—C9	−1.2 (3)
N1—C1—C2—C3	−0.2 (4)	C6—C7—C8—C9	179.1 (2)
C1—C2—C3—C4	0.9 (4)	C7—C8—C9—C10	1.1 (4)
C2—C3—C4—C5	−0.9 (4)	C8—C9—C10—C11	−0.5 (4)
C1—N1—C5—C4	0.3 (3)	C7—N2—C11—C10	0.1 (3)
Cu1—N1—C5—C4	−179.6 (2)	Cu1—N2—C11—C10	179.3 (2)
C1—N1—C5—C6	−178.5 (2)	C9—C10—C11—N2	−0.1 (4)
Cu1—N1—C5—C6	1.5 (2)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···O3	0.82	2.19	2.564 (2)	108
O2—H2o···O4	0.82	1.83	2.643 (2)	171
O1w—H1w1···O3	0.82	1.93	2.738 (3)	171
O2w—H2w1···O4^ii	0.83	2.05	2.790 (3)	149

Symmetry code: (ii) x, y+1, z.