(Acetyl­acetonato)(dicyanamido)(1,10-phenanthroline)copper(II) dihydrate

In the title compound, [Cu(C₅H₇O₂)(C₂N₃)(C₁₂H₈N₂)]·2H₂O, the Cu^II atom is five-coordinated in a square-pyramidal geometry with two acetyl­acetonate O and two phenanthroline N atoms forming the base. The apical position is occupied by the central N atom of the dicyanamide ligand. The dicyanamide N atoms are each involved in hydrogen bonds to water mol­ecules. There are also hydrogen bonds between both the water mol­ecules and their centrosymmetric pairs, creating a hydrogen-bonded chain along the b-axis direction.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.034
• wR factor = 0.082
• Data-to-parameter ratio = 22.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N3     --  C18     ..       7.70 su

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3     --  C19     ..       6.67 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    --  N1      ..       6.60 su
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....         10
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              H2 O
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        702

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

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

   0 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
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Metal dicyanamide (dca) compounds are of great interest due to the variety of observed topologies, this being related to the versatility of dca as a ligand, and its potential application in functional materials. In the present work, we describe the synthesis and crystal structure of a new Cu^II complex using the diimine ligand (phen), a bidentate ligand with two oxygen donor atoms (acac) and the anionic co-ligand dicyanamide (dca) (Fig. 1). To date, a number of higher - dimensional coordination networks of different transition metals have been reported with dca as a bridging ligand, but there are few compounds with dca acting as a monodentate ligand through the amide nitrogen. To the best of our knowledge, this complex is one of the few cases where dca is acting as a terminal ligand through the amide nitrogen. The molecule of the title compound is shown in Fig. 1 with selected bond lengths and angles listed in Table 1. In this molecule the coordination is square pyramidal with the two acac O and two phen N atoms forming the base. The apical position is occupied by the N of the dicyanamido ligand with the Cu—N3 distance (Cu1—N3 2.3920 (15) Å) being much greater than those in the basal plane Cu1—O1, 1.906 (1), 1.907 (1) Å and Cu1—N1, 2.010 (1), 2.014 (1) Å. The dicyanamide N atoms, N4, N5 are each involved in hydrogen bonds to water molecules. There are also hydrogen bonds between both the water molecules and their centrosymmetric pairs creating a one dimensional hydrogen bonded polymer in the b direction (see Fig. 2). Geometrical details are listed in Table 2.

Related literature

Dicyanamide (dca) has been shown to be a versatile ligand and may coordinate to metal ions as a terminal ligand through a nitrile or amide nitrogen. It also acts as a bridging ligand. Until now, as many as eight structurally characterized coordination modes of dicyanamide had been reported in the literature, see: Chattopadhyay et al. (2008); Liu et al. (2005); Miller & Manson (2001); Xu et al. (2003).

S2. Experimental

Acetylacetone (0.103 ml, 1 mmol) was added to a 20 ml methanolic solution of CuCl₂.2H₂O (170 mg, 1 mmol). After 30 min of stirring, a solution of phen (198 mg, 1 mmol) in 10 ml methanol was added dropwise to this solution. A solution of 1 mmol of sodium dicyanamide (89 mg) dissolved in 5 ml water was then added slowly with stirring. After 10 h of stirring at room temperature, the resulting solution was filtered to remove any undissolved materials. A dark blue crystalline product separated after 2 weeks.

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.95–0.98 Å and with U_iso(H) = 1.2 times U_eq(C) for CH and U_iso(H) = 1.5 times U_eq(C) for those on terminal C atoms. Anisotropic displacement parameters were employed throughout for the non-hydrogen atoms. Hydrogen atoms on water molecules were located in the difference Fourier map and refined with O-H bond lengths restrained to ideal values.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The Molecular structure projected oblique the basal coordination plane. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level. H atoms are drawn as spheres with arbitrary radii.
	Fig. 2. The hydrogen-bonded polymer.

(Acetylacetonato)(dicyanamido)(1,10-phenanthroline)copper(II) dihydrate

Crystal data

[Cu(C5H7O2)(C2N3)(C12H8N2)]·2H2O	Z = 2
Mr = 444.93	F(000) = 458
Triclinic, P1	Dx = 1.549 Mg m^−3
Hall symbol: -p 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2825 (8) Å	Cell parameters from 5220 reflections
b = 9.9853 (7) Å	θ = 3.5–32.5°
c = 12.1109 (7) Å	µ = 1.18 mm^−1
α = 76.388 (5)°	T = 100 K
β = 79.236 (7)°	Slab, blue
γ = 83.554 (7)°	0.44 × 0.38 × 0.15 mm
V = 953.90 (13) Å^3

Data collection

Oxford Diffraction Gemini diffractometer	6254 independent reflections
Graphite monochromator	4672 reflections with I > 2σ(I)
Detector resolution: 10.4738 pixels mm^-1	Rint = 0.028
ω scans	θmax = 32.6°, θmin = 3.5°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2009)	h = −12→10
Tmin = 0.667, Tmax = 0.847	k = −15→14
10664 measured reflections	l = −17→17

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0386P)^2] where P = (Fo^2 + 2Fc^2)/3
6254 reflections	(Δ/σ)max = 0.002
280 parameters	Δρmax = 0.52 e Å^−3
6 restraints	Δρmin = −0.42 e Å^−3

Special details

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

The water molecule hydrogen geometries were restrained to ideal values.

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

	x	y	z	Uiso*/Ueq
Cu1	0.44471 (3)	0.77615 (2)	0.641559 (16)	0.01300 (6)
O1	0.30198 (14)	0.93968 (11)	0.64219 (9)	0.0147 (2)
O2	0.46649 (15)	0.78689 (11)	0.48019 (9)	0.0151 (2)
N1	0.61346 (17)	0.61447 (13)	0.65445 (11)	0.0131 (3)
N2	0.47043 (17)	0.76076 (13)	0.80625 (11)	0.0136 (3)
N3	0.20994 (18)	0.64152 (14)	0.69007 (12)	0.0195 (3)
N4	0.24313 (19)	0.38636 (15)	0.73851 (12)	0.0207 (3)
N5	−0.04970 (19)	0.77968 (15)	0.73930 (13)	0.0232 (3)
C1	0.6620 (2)	0.57862 (16)	0.75956 (13)	0.0128 (3)
C2	0.7799 (2)	0.47088 (16)	0.78859 (13)	0.0146 (3)
C3	0.8485 (2)	0.39566 (17)	0.70360 (14)	0.0166 (3)
H3	0.928	0.3205	0.7195	0.02*
C4	0.7992 (2)	0.43239 (17)	0.59769 (14)	0.0182 (3)
H4	0.845	0.383	0.5397	0.022*
C5	0.6813 (2)	0.54268 (16)	0.57561 (14)	0.0158 (3)
H5	0.6486	0.5672	0.5019	0.019*
C6	0.8253 (2)	0.44452 (17)	0.90081 (14)	0.0171 (3)
H6	0.905	0.3712	0.9219	0.021*
C7	0.5862 (2)	0.65973 (16)	0.84136 (13)	0.0128 (3)
C8	0.6326 (2)	0.63354 (16)	0.94977 (13)	0.0151 (3)
C9	0.5529 (2)	0.71780 (17)	1.02540 (14)	0.0174 (3)
H9	0.5812	0.705	1.0999	0.021*
C10	0.4343 (2)	0.81839 (17)	0.99064 (14)	0.0180 (3)
H10	0.3791	0.875	1.0412	0.022*
C11	0.3953 (2)	0.83697 (16)	0.87987 (13)	0.0157 (3)
H11	0.3125	0.9063	0.8567	0.019*
C12	0.7560 (2)	0.52296 (17)	0.97732 (14)	0.0180 (3)
H12	0.7895	0.5045	1.0506	0.022*
C13	0.1266 (2)	1.13270 (17)	0.57670 (14)	0.0190 (3)
H13A	0.0297	1.0988	0.632	0.028*
H13B	0.0922	1.1839	0.5043	0.028*
H13C	0.1812	1.1938	0.6083	0.028*
C14	0.2445 (2)	1.01218 (16)	0.55433 (13)	0.0140 (3)
C15	0.2838 (2)	0.98785 (16)	0.44328 (13)	0.0152 (3)
H15	0.2332	1.0492	0.3847	0.018*
C16	0.3917 (2)	0.88016 (16)	0.41157 (13)	0.0134 (3)
C17	0.4305 (2)	0.86863 (17)	0.28774 (13)	0.0171 (3)
H17A	0.5449	0.89	0.2564	0.026*
H17B	0.3564	0.934	0.2433	0.026*
H17C	0.4154	0.7744	0.2828	0.026*
C18	0.2200 (2)	0.50592 (17)	0.71782 (13)	0.0152 (3)
C19	0.0677 (2)	0.70993 (16)	0.71876 (14)	0.0163 (3)
O1W	0.1223 (2)	0.12775 (15)	0.88013 (13)	0.0353 (4)
O2W	−0.13527 (19)	0.96983 (16)	0.89006 (12)	0.0292 (3)
H1A	0.165 (3)	0.195 (2)	0.8385 (17)	0.054 (8)*
H1B	0.137 (3)	0.117 (2)	0.9432 (13)	0.034 (7)*
H2A	−0.059 (3)	1.016 (2)	0.877 (2)	0.044 (8)*
H2B	−0.116 (3)	0.9122 (19)	0.8518 (18)	0.041 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01465 (11)	0.01279 (10)	0.01157 (10)	0.00093 (7)	−0.00271 (7)	−0.00316 (7)
O1	0.0164 (6)	0.0138 (5)	0.0137 (5)	−0.0002 (5)	−0.0029 (4)	−0.0026 (4)
O2	0.0184 (6)	0.0135 (5)	0.0135 (5)	0.0005 (5)	−0.0035 (4)	−0.0033 (4)
N1	0.0146 (7)	0.0136 (6)	0.0112 (6)	−0.0029 (5)	−0.0013 (5)	−0.0026 (5)
N2	0.0155 (7)	0.0118 (6)	0.0129 (6)	−0.0011 (5)	−0.0010 (5)	−0.0026 (5)
N3	0.0163 (7)	0.0138 (7)	0.0267 (8)	−0.0019 (6)	0.0011 (6)	−0.0042 (6)
N4	0.0201 (8)	0.0182 (7)	0.0235 (7)	0.0007 (6)	−0.0052 (6)	−0.0037 (6)
N5	0.0179 (8)	0.0182 (7)	0.0317 (8)	−0.0021 (6)	−0.0017 (6)	−0.0033 (6)
C1	0.0118 (7)	0.0128 (7)	0.0141 (7)	−0.0028 (6)	−0.0015 (6)	−0.0031 (6)
C2	0.0130 (8)	0.0139 (7)	0.0167 (7)	−0.0023 (6)	−0.0028 (6)	−0.0021 (6)
C3	0.0142 (8)	0.0145 (8)	0.0216 (8)	0.0001 (6)	−0.0033 (6)	−0.0049 (6)
C4	0.0189 (9)	0.0173 (8)	0.0196 (8)	−0.0002 (7)	−0.0013 (6)	−0.0085 (6)
C5	0.0174 (8)	0.0167 (8)	0.0147 (7)	−0.0014 (6)	−0.0028 (6)	−0.0061 (6)
C6	0.0150 (8)	0.0179 (8)	0.0181 (8)	−0.0004 (6)	−0.0053 (6)	−0.0016 (6)
C7	0.0133 (8)	0.0130 (7)	0.0120 (7)	−0.0018 (6)	−0.0020 (6)	−0.0022 (6)
C8	0.0155 (8)	0.0165 (8)	0.0141 (7)	−0.0037 (6)	−0.0025 (6)	−0.0035 (6)
C9	0.0196 (9)	0.0214 (8)	0.0128 (7)	−0.0048 (7)	−0.0020 (6)	−0.0056 (6)
C10	0.0216 (9)	0.0189 (8)	0.0145 (7)	−0.0020 (7)	−0.0006 (6)	−0.0072 (6)
C11	0.0177 (8)	0.0137 (7)	0.0154 (7)	−0.0016 (6)	−0.0011 (6)	−0.0040 (6)
C12	0.0176 (9)	0.0212 (8)	0.0158 (8)	−0.0014 (7)	−0.0061 (6)	−0.0025 (6)
C13	0.0186 (9)	0.0177 (8)	0.0201 (8)	0.0034 (7)	−0.0031 (6)	−0.0054 (6)
C14	0.0119 (8)	0.0126 (7)	0.0175 (8)	−0.0029 (6)	−0.0017 (6)	−0.0026 (6)
C15	0.0159 (8)	0.0153 (7)	0.0143 (7)	0.0001 (6)	−0.0053 (6)	−0.0014 (6)
C16	0.0121 (8)	0.0151 (7)	0.0139 (7)	−0.0048 (6)	−0.0030 (6)	−0.0024 (6)
C17	0.0211 (9)	0.0178 (8)	0.0133 (7)	−0.0005 (7)	−0.0041 (6)	−0.0044 (6)
C18	0.0127 (8)	0.0223 (8)	0.0118 (7)	−0.0021 (6)	−0.0020 (6)	−0.0057 (6)
C19	0.0181 (8)	0.0142 (7)	0.0168 (8)	−0.0072 (6)	−0.0035 (6)	−0.0008 (6)
O1W	0.0484 (10)	0.0288 (8)	0.0272 (8)	−0.0153 (7)	−0.0032 (7)	0.0003 (7)
O2W	0.0272 (8)	0.0325 (8)	0.0322 (8)	0.0022 (7)	−0.0080 (6)	−0.0150 (6)

Geometric parameters (Å, º)

Cu1—O1	1.9061 (11)	C6—H6	0.95
Cu1—O2	1.9072 (11)	C7—C8	1.394 (2)
Cu1—N1	2.0100 (14)	C8—C9	1.412 (2)
Cu1—N2	2.0136 (13)	C8—C12	1.440 (2)
Cu1—N3	2.3920 (15)	C9—C10	1.373 (2)
O1—C14	1.2775 (19)	C9—H9	0.95
O2—C16	1.2805 (19)	C10—C11	1.404 (2)
N1—C5	1.332 (2)	C10—H10	0.95
N1—C1	1.362 (2)	C11—H11	0.95
N2—C11	1.329 (2)	C12—H12	0.95
N2—C7	1.361 (2)	C13—C14	1.505 (2)
N3—C18	1.313 (2)	C13—H13A	0.98
N3—C19	1.324 (2)	C13—H13B	0.98
N4—C18	1.162 (2)	C13—H13C	0.98
N5—C19	1.154 (2)	C14—C15	1.395 (2)
C1—C2	1.396 (2)	C15—C16	1.398 (2)
C1—C7	1.436 (2)	C15—H15	0.95
C2—C3	1.413 (2)	C16—C17	1.503 (2)
C2—C6	1.435 (2)	C17—H17A	0.98
C3—C4	1.374 (2)	C17—H17B	0.98
C3—H3	0.95	C17—H17C	0.98
C4—C5	1.398 (2)	O1W—H1A	0.812 (15)
C4—H4	0.95	O1W—H1B	0.778 (15)
C5—H5	0.95	O2W—H2A	0.795 (15)
C6—C12	1.358 (2)	O2W—H2B	0.806 (15)
O1—Cu1—O2	95.58 (5)	C8—C7—C1	120.19 (14)
O1—Cu1—N1	171.80 (5)	C7—C8—C9	116.93 (15)
O2—Cu1—N1	90.01 (5)	C7—C8—C12	118.38 (15)
O1—Cu1—N2	91.52 (5)	C9—C8—C12	124.68 (15)
O2—Cu1—N2	168.73 (5)	C10—C9—C8	119.60 (15)
N1—Cu1—N2	82.08 (5)	C10—C9—H9	120.2
O1—Cu1—N3	89.74 (5)	C8—C9—H9	120.2
O2—Cu1—N3	94.16 (5)	C9—C10—C11	119.45 (15)
N1—Cu1—N3	95.85 (5)	C9—C10—H10	120.3
N2—Cu1—N3	94.62 (5)	C11—C10—H10	120.3
C14—O1—Cu1	124.52 (11)	N2—C11—C10	122.19 (15)
C16—O2—Cu1	124.19 (11)	N2—C11—H11	118.9
C5—N1—C1	118.31 (14)	C10—C11—H11	118.9
C5—N1—Cu1	128.97 (11)	C6—C12—C8	121.43 (15)
C1—N1—Cu1	112.72 (10)	C6—C12—H12	119.3
C11—N2—C7	118.32 (13)	C8—C12—H12	119.3
C11—N2—Cu1	129.06 (11)	C14—C13—H13A	109.5
C7—N2—Cu1	112.58 (10)	C14—C13—H13B	109.5
C18—N3—C19	119.10 (15)	H13A—C13—H13B	109.5
C18—N3—Cu1	123.48 (12)	C14—C13—H13C	109.5
C19—N3—Cu1	114.92 (11)	H13A—C13—H13C	109.5
N1—C1—C2	123.32 (15)	H13B—C13—H13C	109.5
N1—C1—C7	116.23 (14)	O1—C14—C15	125.18 (15)
C2—C1—C7	120.45 (14)	O1—C14—C13	115.20 (14)
C1—C2—C3	117.10 (15)	C15—C14—C13	119.63 (14)
C1—C2—C6	118.67 (15)	C14—C15—C16	125.02 (14)
C3—C2—C6	124.22 (15)	C14—C15—H15	117.5
C4—C3—C2	119.32 (15)	C16—C15—H15	117.5
C4—C3—H3	120.3	O2—C16—C15	125.37 (14)
C2—C3—H3	120.3	O2—C16—C17	114.54 (14)
C3—C4—C5	119.77 (15)	C15—C16—C17	120.08 (14)
C3—C4—H4	120.1	C16—C17—H17A	109.5
C5—C4—H4	120.1	C16—C17—H17B	109.5
N1—C5—C4	122.17 (15)	H17A—C17—H17B	109.5
N1—C5—H5	118.9	C16—C17—H17C	109.5
C4—C5—H5	118.9	H17A—C17—H17C	109.5
C12—C6—C2	120.86 (15)	H17B—C17—H17C	109.5
C12—C6—H6	119.6	N4—C18—N3	174.12 (19)
C2—C6—H6	119.6	N5—C19—N3	174.19 (18)
N2—C7—C8	123.49 (14)	H1A—O1W—H1B	112 (2)
N2—C7—C1	116.31 (13)	H2A—O2W—H2B	109.1 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2B···N5	0.81 (2)	2.08 (2)	2.879 (2)	173 (2)
O2W—H2A···O1W^i	0.80 (2)	1.98 (2)	2.761 (2)	167 (2)
O1W—H1A···N4	0.81 (2)	2.10 (2)	2.910 (2)	172 (3)
O1W—H1B···O2W^ii	0.78 (2)	2.00 (2)	2.742 (2)	160 (2)

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