catena-Poly[[[{1-[(E)-phenyl(pyridin-2-yl-κN)methylidene]semicarbazidato-κ²N¹,O}copper(II)]-μ-dicyanamido-κ²N¹:N⁵] monohydrate]

The Cu^II atoms in the title coordination polymer, {[Cu(C₁₃H₁₁N₄O)(C₂N₃)]·H₂O}_n, are N,N′,O-chelated by the deprotonated Schiff base ligands, and adjacent metal atoms are bridged by the dicyanamide ions, generating a polymeric chain that propagates along the b axis. The two independent metal atoms show a square-pyramidal N₄O coordination. The two independent water mol­ecules are disordered over two positions; each water mol­ecule is a hydrogen-bond donor to a carbonyl O atom. Weak N—H...N hydrogen bonding is also observed.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in solvent or counterion
• R factor = 0.050
• wR factor = 0.166
• Data-to-parameter ratio = 17.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        N13

Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N9
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        N10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C27
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C28
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C29
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C30
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0066 Ang
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H41    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N8     -   H81    ...          ?
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -1.856
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          8

Alert level G
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained Atom Sites ....          2
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          8
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       9.82
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ...................        100 Perc.
PLAT311_ALERT_2_G Isolated Disordered Oxygen Atom (No H's ?) .....       O1W'
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          6
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1     (II)          2.42
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu2     (II)          2.41
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         12
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          4

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  12 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   5 ALERT type 5 Informative message, check

---

S1. Comment

2-Benzoylpyridine semicarbazone (de Lima et al., 2008) is a Schiff base that is capable of N,N',O-chelation to transition metal ions. This feature has been documented a copper(II) dichloride adduct; in this, the Schiff base exists as a neutral molecule (Peŕez-Rebolledo et al., 2006). However, the Cu^II atom in the coordination polymer, [Cu(C₂N₃)(C₁₃H₁₁N₄O)^.H₂O]_n (I), is N,N',O-chelated instead by the deprotonated Schiff base (Fig. 1). Adjacent metal atoms are bridged by the dicyanamide ion to generate a chain that propagates along the b axis of the orthorhombic unit cell (Fig. 2). The two independent metal atoms show square pyramidal coordination. The two independent water molecules are disordered over two positions; each water molecule is a hydrogen-bond donor to a carbonyl O atom.

Related literature

For the synthesis of the Schiff base ligand, see: de Lima et al. (2008). For a related copper(II) derivative, see: Peŕez-Rebolledo et al. (2006).

S2. Experimental

A methanol solution (20 ml) of 2-benzoylpyridine semicarbazone (0.240 g,1 mmol) (de Lima et al., 2008), copper acetate monohydrate (0.199 g, 1 mmol) and sodium dicyanamide (0.089 g, 1 mmol) was heated for 5 h. The dark green solid was collected and recrystallized from methanol.

S3. Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The amino H-atoms were similarly treated (N–H 0.88 Å) and their temperature factors tied by a factor of 1.2 times.

Omitted owing interference from the beam stop were (2 1 0), (0 0 2), (1 1 2), (1 1 4) and (1 2 1).

The presence of water was indicated by an infrared spectral measurement. The two independent water molecules are both disordered over two positions; the occupancy could not be refined, and was assumed as a 1:1 type of disorder. For one molecule, the disorder is such that two components are separated by about 2 Å, so that one hydrogen atom should be midway between two oxygen atoms. For the other, the two are separated by about 1 Å, so that one hydrogen atom should be occupying the site of the other oxygen atom. For both, hydrogen atoms were positioned on only one component oxygen atom so that each water molecule forms only one hydrogen bond. Furthermore, the hydrogen atoms were given full occupancy, i.e., hydrogen atoms were not placed on those atoms that do not engage in hydrogen bonding. The temperature factors of the primed atoms were set to those of the unprimed ones, and the anisotropic temperature factors were tightly restrained to be nearly isotropic.

Computing details

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of a portion of the chain structure of [Cu(C2N3)(C13H11N4O)^.H2O]n at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in the water molecules is not shown.
	Fig. 2. Dicyanamide-bridged chain structure. Water molecules are not shown.

catena-Poly[[[{1-[(E)-phenyl(pyridin-2-yl-κN)methylidene]semicarbazidato-κ²N¹,O}copper(II)]-µ-dicyanamido-κ²N¹:N⁵] monohydrate]

Crystal data

[Cu(C13H11N4O)(C2N3)]·H2O	F(000) = 3152
Mr = 386.86	Dx = 1.477 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9967 reflections
a = 12.3996 (2) Å	θ = 2.7–26.5°
b = 21.0115 (4) Å	µ = 1.28 mm^−1
c = 26.7059 (5) Å	T = 293 K
V = 6957.8 (2) Å^3	Prim, green
Z = 16	0.40 × 0.30 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer	7982 independent reflections
Radiation source: fine-focus sealed tube	5027 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→14
Tmin = 0.629, Tmax = 0.784	k = −27→27
110924 measured reflections	l = −34→34

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.166	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0668P)^2 + 9.8211P] where P = (Fo^2 + 2Fc^2)/3
7982 reflections	(Δ/σ)max = 0.001
457 parameters	Δρmax = 0.80 e Å^−3
12 restraints	Δρmin = −0.46 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.74889 (4)	0.32160 (2)	0.591725 (16)	0.03950 (15)
Cu2	0.51236 (4)	0.06952 (2)	0.406562 (15)	0.03717 (15)
O1	0.6417 (2)	0.38125 (13)	0.61888 (10)	0.0541 (8)
O2	0.6166 (2)	0.13248 (12)	0.38040 (10)	0.0489 (7)
O1W	0.4729 (16)	0.4332 (10)	0.5571 (8)	0.269 (7)	0.50
H1W1	0.5266	0.4228	0.5745	0.404*
H1W2	0.4808	0.4710	0.5475	0.404*
O2W	0.8427 (16)	0.1463 (9)	0.4332 (7)	0.234 (6)	0.50
H2W1	0.7879	0.1336	0.4177	0.280*
H2W2	0.8367	0.1858	0.4373	0.280*
O1W'	0.4691 (17)	0.5292 (11)	0.5296 (8)	0.269 (7)	0.50
O2W'	0.7929 (19)	0.1888 (10)	0.4402 (8)	0.234 (6)	0.50
N1	0.8834 (3)	0.26882 (16)	0.58984 (12)	0.0469 (8)
N2	0.7736 (3)	0.31179 (14)	0.66329 (11)	0.0362 (7)
N3	0.7020 (3)	0.33965 (15)	0.69487 (11)	0.0419 (7)
N4	0.5629 (3)	0.41008 (19)	0.69133 (14)	0.0644 (11)
H41	0.5184	0.4351	0.6749	0.077*
H42	0.5586	0.4073	0.7241	0.077*
N5	0.3807 (3)	0.01320 (15)	0.40768 (10)	0.0396 (7)
N6	0.4882 (2)	0.06112 (14)	0.33509 (11)	0.0358 (7)
N7	0.5555 (3)	0.09307 (15)	0.30382 (11)	0.0394 (7)
N8	0.6909 (3)	0.16608 (17)	0.30793 (13)	0.0555 (9)
H81	0.7353	0.1909	0.3246	0.067*
H82	0.6936	0.1649	0.2750	0.067*
N9	0.6399 (4)	0.2399 (2)	0.58076 (14)	0.0683 (12)
N10	0.5250 (4)	0.1525 (2)	0.55530 (14)	0.0735 (13)
N11	0.5158 (3)	0.09809 (17)	0.47568 (12)	0.0497 (8)
N12	0.7496 (3)	0.35269 (18)	0.52272 (13)	0.0509 (9)
N13	0.7622 (4)	0.3993 (2)	0.43995 (14)	0.0799 (15)
N14	0.8717 (3)	0.48903 (18)	0.41363 (13)	0.0539 (9)
C1	0.9380 (4)	0.2496 (2)	0.54957 (17)	0.0673 (14)
H1	0.9131	0.2611	0.5180	0.081*
C2	1.0297 (5)	0.2132 (3)	0.5532 (2)	0.0814 (18)
H2	1.0658	0.1998	0.5246	0.098*
C3	1.0669 (5)	0.1972 (2)	0.6000 (2)	0.0747 (16)
H3	1.1305	0.1741	0.6035	0.090*
C4	1.0095 (4)	0.2154 (2)	0.64189 (17)	0.0546 (11)
H4	1.0326	0.2039	0.6737	0.066*
C5	0.9172 (3)	0.25110 (17)	0.63568 (14)	0.0419 (9)
C6	0.8486 (3)	0.27313 (16)	0.67749 (13)	0.0360 (8)
C7	0.8605 (3)	0.24717 (17)	0.72905 (13)	0.0384 (8)
C8	0.7886 (4)	0.2016 (2)	0.74534 (17)	0.0546 (11)
H8	0.7321	0.1890	0.7247	0.066*
C9	0.8002 (5)	0.1745 (2)	0.7924 (2)	0.0696 (14)
H9	0.7519	0.1436	0.8032	0.084*
C10	0.8835 (5)	0.1935 (3)	0.82286 (19)	0.0758 (16)
H10	0.8909	0.1758	0.8546	0.091*
C11	0.9552 (5)	0.2379 (3)	0.80682 (19)	0.0831 (17)
H11	1.0119	0.2504	0.8275	0.100*
C12	0.9440 (4)	0.2645 (2)	0.76020 (17)	0.0653 (13)
H12	0.9937	0.2947	0.7494	0.078*
C13	0.6370 (3)	0.37643 (18)	0.66655 (14)	0.0427 (9)
C14	0.3281 (4)	−0.0096 (2)	0.44722 (15)	0.0527 (11)
H14	0.3484	0.0040	0.4790	0.063*
C15	0.2455 (4)	−0.0522 (3)	0.44297 (19)	0.0741 (16)
H15	0.2098	−0.0671	0.4713	0.089*
C16	0.2161 (5)	−0.0725 (3)	0.3959 (2)	0.0832 (18)
H16	0.1602	−0.1016	0.3920	0.100*
C17	0.2703 (4)	−0.0494 (2)	0.35449 (17)	0.0626 (13)
H17	0.2513	−0.0627	0.3225	0.075*
C18	0.3520 (3)	−0.00673 (18)	0.36126 (13)	0.0403 (8)
C19	0.4168 (3)	0.02092 (17)	0.32052 (13)	0.0368 (8)
C20	0.4045 (3)	−0.00038 (17)	0.26745 (13)	0.0369 (8)
C21	0.3209 (4)	0.0214 (2)	0.23788 (15)	0.0562 (11)
H21	0.2697	0.0492	0.2508	0.067*
C22	0.3144 (4)	0.0011 (3)	0.18867 (17)	0.0664 (13)
H22	0.2580	0.0154	0.1687	0.080*
C23	0.3888 (4)	−0.0392 (2)	0.16898 (16)	0.0644 (14)
H23	0.3844	−0.0514	0.1356	0.077*
C24	0.4709 (4)	−0.0618 (2)	0.19901 (19)	0.0647 (14)
H24	0.5207	−0.0906	0.1862	0.078*
C25	0.4789 (4)	−0.0417 (2)	0.24776 (17)	0.0521 (10)
H25	0.5354	−0.0562	0.2676	0.062*
C26	0.6197 (3)	0.13029 (17)	0.33247 (14)	0.0409 (9)
C27	0.5897 (4)	0.1987 (2)	0.56680 (14)	0.0471 (10)
C28	0.5253 (3)	0.12554 (19)	0.51235 (14)	0.0447 (9)
C29	0.7585 (3)	0.3768 (2)	0.48527 (16)	0.0483 (10)
C30	0.8225 (3)	0.4478 (2)	0.42797 (13)	0.0455 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0501 (3)	0.0411 (3)	0.0272 (2)	−0.00041 (19)	0.00001 (19)	−0.00053 (18)
Cu2	0.0476 (3)	0.0394 (3)	0.0245 (2)	−0.0023 (2)	−0.00390 (18)	−0.00204 (17)
O1	0.070 (2)	0.0597 (18)	0.0327 (14)	0.0195 (15)	−0.0050 (13)	0.0012 (12)
O2	0.0662 (19)	0.0471 (16)	0.0334 (14)	−0.0157 (14)	−0.0080 (13)	−0.0001 (11)
O1W	0.220 (9)	0.323 (11)	0.266 (10)	0.038 (8)	−0.025 (8)	−0.002 (8)
O2W	0.247 (10)	0.253 (11)	0.201 (8)	0.037 (8)	−0.069 (8)	−0.052 (8)
O1W'	0.220 (9)	0.323 (11)	0.266 (10)	0.038 (8)	−0.025 (8)	−0.002 (8)
O2W'	0.247 (10)	0.253 (11)	0.201 (8)	0.037 (8)	−0.069 (8)	−0.052 (8)
N1	0.059 (2)	0.0457 (18)	0.0354 (17)	0.0038 (16)	0.0107 (15)	0.0022 (14)
N2	0.0452 (18)	0.0354 (16)	0.0281 (14)	0.0019 (14)	−0.0007 (13)	−0.0020 (12)
N3	0.046 (2)	0.0472 (18)	0.0323 (16)	0.0081 (15)	−0.0028 (14)	−0.0045 (14)
N4	0.075 (3)	0.078 (3)	0.0401 (19)	0.036 (2)	0.0021 (18)	0.0022 (18)
N5	0.0458 (19)	0.0448 (17)	0.0282 (15)	−0.0011 (14)	0.0010 (13)	0.0004 (13)
N6	0.0418 (18)	0.0395 (17)	0.0261 (14)	−0.0010 (13)	−0.0031 (12)	−0.0002 (12)
N7	0.0487 (19)	0.0429 (17)	0.0266 (14)	−0.0060 (15)	−0.0046 (13)	0.0028 (13)
N8	0.070 (3)	0.054 (2)	0.0427 (19)	−0.0245 (19)	−0.0014 (17)	0.0026 (16)
N9	0.090 (3)	0.063 (2)	0.052 (2)	−0.027 (2)	0.001 (2)	−0.0150 (19)
N10	0.097 (3)	0.082 (3)	0.041 (2)	−0.045 (3)	0.021 (2)	−0.029 (2)
N11	0.062 (2)	0.055 (2)	0.0321 (17)	−0.0067 (17)	−0.0025 (15)	−0.0054 (15)
N12	0.058 (2)	0.056 (2)	0.0389 (19)	−0.0099 (17)	0.0001 (16)	0.0063 (16)
N13	0.100 (3)	0.096 (3)	0.043 (2)	−0.056 (3)	−0.028 (2)	0.030 (2)
N14	0.061 (2)	0.058 (2)	0.0425 (19)	−0.0145 (19)	−0.0045 (17)	0.0155 (16)
C1	0.089 (4)	0.068 (3)	0.044 (2)	0.022 (3)	0.027 (2)	0.007 (2)
C2	0.101 (4)	0.084 (4)	0.060 (3)	0.041 (3)	0.036 (3)	0.007 (3)
C3	0.079 (4)	0.069 (3)	0.076 (4)	0.035 (3)	0.031 (3)	0.011 (3)
C4	0.062 (3)	0.051 (2)	0.051 (3)	0.012 (2)	0.007 (2)	0.009 (2)
C5	0.050 (2)	0.0348 (19)	0.041 (2)	0.0007 (17)	0.0088 (17)	0.0028 (15)
C6	0.043 (2)	0.0308 (17)	0.0345 (18)	−0.0025 (16)	0.0010 (15)	0.0002 (14)
C7	0.043 (2)	0.0394 (19)	0.0326 (18)	0.0044 (16)	0.0035 (16)	0.0042 (15)
C8	0.062 (3)	0.047 (2)	0.056 (3)	−0.007 (2)	0.004 (2)	0.005 (2)
C9	0.079 (4)	0.056 (3)	0.074 (3)	−0.002 (3)	0.023 (3)	0.020 (3)
C10	0.088 (4)	0.089 (4)	0.051 (3)	0.012 (3)	0.002 (3)	0.034 (3)
C11	0.081 (4)	0.121 (5)	0.048 (3)	−0.013 (4)	−0.019 (3)	0.025 (3)
C12	0.064 (3)	0.085 (3)	0.047 (2)	−0.025 (3)	−0.011 (2)	0.016 (2)
C13	0.051 (2)	0.042 (2)	0.035 (2)	0.0092 (18)	−0.0012 (17)	−0.0034 (16)
C14	0.059 (3)	0.065 (3)	0.033 (2)	−0.002 (2)	0.0065 (19)	0.0007 (18)
C15	0.066 (3)	0.106 (4)	0.051 (3)	−0.023 (3)	0.011 (2)	0.014 (3)
C16	0.071 (4)	0.118 (5)	0.061 (3)	−0.043 (3)	−0.003 (3)	0.013 (3)
C17	0.064 (3)	0.082 (3)	0.042 (2)	−0.032 (3)	−0.006 (2)	0.003 (2)
C18	0.042 (2)	0.048 (2)	0.0305 (18)	−0.0046 (17)	−0.0027 (15)	−0.0003 (15)
C19	0.042 (2)	0.0369 (19)	0.0314 (18)	−0.0001 (16)	−0.0041 (15)	0.0008 (14)
C20	0.042 (2)	0.0375 (19)	0.0307 (18)	−0.0070 (16)	−0.0029 (15)	−0.0030 (14)
C21	0.059 (3)	0.071 (3)	0.038 (2)	0.011 (2)	−0.011 (2)	−0.008 (2)
C22	0.076 (3)	0.084 (3)	0.039 (2)	−0.002 (3)	−0.023 (2)	−0.008 (2)
C23	0.086 (4)	0.074 (3)	0.034 (2)	−0.028 (3)	0.004 (2)	−0.019 (2)
C24	0.071 (3)	0.055 (3)	0.069 (3)	−0.007 (2)	0.020 (3)	−0.032 (2)
C25	0.053 (3)	0.054 (3)	0.049 (2)	−0.001 (2)	−0.003 (2)	−0.007 (2)
C26	0.050 (2)	0.037 (2)	0.0356 (19)	0.0002 (17)	−0.0006 (17)	0.0036 (16)
C27	0.060 (3)	0.053 (2)	0.0280 (18)	−0.007 (2)	0.0055 (18)	−0.0048 (17)
C28	0.052 (2)	0.049 (2)	0.033 (2)	−0.0117 (19)	0.0037 (17)	−0.0062 (17)
C29	0.047 (2)	0.054 (2)	0.043 (2)	−0.0148 (19)	−0.0113 (18)	0.0046 (19)
C30	0.050 (2)	0.062 (3)	0.0252 (18)	−0.008 (2)	−0.0133 (17)	0.0066 (17)

Geometric parameters (Å, º)

Cu1—N2	1.946 (3)	C1—H1	0.9300
Cu1—N12	1.955 (3)	C2—C3	1.376 (7)
Cu1—O1	1.966 (3)	C2—H2	0.9300
Cu1—N1	2.004 (4)	C3—C4	1.380 (6)
Cu1—N9	2.205 (4)	C3—H3	0.9300
Cu2—N6	1.940 (3)	C4—C5	1.377 (6)
Cu2—N11	1.941 (3)	C4—H4	0.9300
Cu2—O2	1.977 (3)	C5—C6	1.479 (5)
Cu2—N5	2.016 (3)	C6—C7	1.488 (5)
Cu2—N14^i	2.228 (4)	C7—C8	1.378 (6)
O1—C13	1.278 (4)	C7—C12	1.378 (6)
O2—C26	1.281 (4)	C8—C9	1.387 (7)
O1W—H1W1	0.8401	C8—H8	0.9300
O1W—H1W2	0.8401	C9—C10	1.375 (8)
O2W—H2W1	0.8400	C9—H9	0.9300
O2W—H2W2	0.8400	C10—C11	1.359 (8)
N1—C1	1.333 (5)	C10—H10	0.9300
N1—C5	1.346 (5)	C11—C12	1.371 (6)
N2—C6	1.292 (5)	C11—H11	0.9300
N2—N3	1.358 (4)	C12—H12	0.9300
N3—C13	1.349 (5)	C14—C15	1.364 (7)
N4—C13	1.334 (5)	C14—H14	0.9300
N4—H41	0.8800	C15—C16	1.377 (7)
N4—H42	0.8800	C15—H15	0.9300
N5—C14	1.331 (5)	C16—C17	1.383 (7)
N5—C18	1.356 (4)	C16—H16	0.9300
N6—C19	1.284 (5)	C17—C18	1.365 (6)
N6—N7	1.358 (4)	C17—H17	0.9300
N7—C26	1.353 (5)	C18—C19	1.472 (5)
N8—C26	1.332 (5)	C19—C20	1.494 (5)
N8—H81	0.8800	C20—C25	1.372 (6)
N8—H82	0.8800	C20—C21	1.381 (6)
N9—C27	1.129 (5)	C21—C22	1.384 (6)
N10—C28	1.280 (5)	C21—H21	0.9300
N10—C27	1.296 (6)	C22—C23	1.358 (7)
N11—C28	1.143 (5)	C22—H22	0.9300
N12—C29	1.127 (5)	C23—C24	1.381 (7)
N13—C29	1.300 (5)	C23—H23	0.9300
N13—C30	1.303 (6)	C24—C25	1.372 (6)
N14—C30	1.127 (5)	C24—H24	0.9300
N14—Cu2^ii	2.228 (4)	C25—H25	0.9300
C1—C2	1.372 (7)
N2—Cu1—N12	163.76 (14)	N2—C6—C7	125.0 (3)
N2—Cu1—O1	79.14 (12)	C5—C6—C7	121.8 (3)
N12—Cu1—O1	97.91 (14)	C8—C7—C12	118.6 (4)
N2—Cu1—N1	80.51 (13)	C8—C7—C6	118.8 (4)
N12—Cu1—N1	99.07 (14)	C12—C7—C6	122.4 (4)
O1—Cu1—N1	157.69 (13)	C7—C8—C9	120.3 (5)
N2—Cu1—N9	98.30 (14)	C7—C8—H8	119.9
N12—Cu1—N9	97.91 (15)	C9—C8—H8	119.9
O1—Cu1—N9	97.52 (15)	C10—C9—C8	119.6 (5)
N1—Cu1—N9	94.37 (16)	C10—C9—H9	120.2
N6—Cu2—N11	165.22 (14)	C8—C9—H9	120.2
N6—Cu2—O2	79.29 (12)	C11—C10—C9	120.3 (4)
N11—Cu2—O2	96.58 (13)	C11—C10—H10	119.8
N6—Cu2—N5	80.58 (12)	C9—C10—H10	119.8
N11—Cu2—N5	100.68 (13)	C10—C11—C12	120.0 (5)
O2—Cu2—N5	158.01 (11)	C10—C11—H11	120.0
N6—Cu2—N14^i	96.54 (13)	C12—C11—H11	120.0
N11—Cu2—N14^i	98.04 (14)	C11—C12—C7	121.1 (4)
O2—Cu2—N14^i	96.66 (13)	C11—C12—H12	119.5
N5—Cu2—N14^i	94.34 (14)	C7—C12—H12	119.5
C13—O1—Cu1	110.4 (2)	O1—C13—N4	118.9 (4)
C26—O2—Cu2	110.4 (2)	O1—C13—N3	125.2 (3)
H1W1—O1W—H1W2	108.7	N4—C13—N3	115.9 (3)
H2W1—O2W—H2W2	107.9	N5—C14—C15	122.6 (4)
C1—N1—C5	119.4 (4)	N5—C14—H14	118.7
C1—N1—Cu1	127.6 (3)	C15—C14—H14	118.7
C5—N1—Cu1	112.9 (3)	C14—C15—C16	118.6 (4)
C6—N2—N3	124.0 (3)	C14—C15—H15	120.7
C6—N2—Cu1	117.9 (2)	C16—C15—H15	120.7
N3—N2—Cu1	117.5 (2)	C15—C16—C17	119.5 (5)
C13—N3—N2	106.8 (3)	C15—C16—H16	120.3
C13—N4—H41	120.0	C17—C16—H16	120.3
C13—N4—H42	120.0	C18—C17—C16	119.1 (4)
H41—N4—H42	120.0	C18—C17—H17	120.5
C14—N5—C18	119.1 (4)	C16—C17—H17	120.5
C14—N5—Cu2	128.3 (3)	N5—C18—C17	121.2 (4)
C18—N5—Cu2	112.3 (2)	N5—C18—C19	114.2 (3)
C19—N6—N7	124.2 (3)	C17—C18—C19	124.5 (3)
C19—N6—Cu2	117.7 (2)	N6—C19—C18	114.3 (3)
N7—N6—Cu2	117.7 (2)	N6—C19—C20	123.7 (3)
C26—N7—N6	107.4 (3)	C18—C19—C20	121.8 (3)
C26—N8—H81	120.0	C25—C20—C21	119.7 (4)
C26—N8—H82	120.0	C25—C20—C19	119.0 (3)
H81—N8—H82	120.0	C21—C20—C19	121.4 (3)
C27—N9—Cu1	168.1 (4)	C20—C21—C22	119.0 (4)
C28—N10—C27	122.9 (4)	C20—C21—H21	120.5
C28—N11—Cu2	166.7 (3)	C22—C21—H21	120.5
C29—N12—Cu1	170.9 (4)	C23—C22—C21	121.4 (5)
C29—N13—C30	122.2 (4)	C23—C22—H22	119.3
C30—N14—Cu2^ii	164.2 (3)	C21—C22—H22	119.3
N1—C1—C2	122.2 (5)	C22—C23—C24	119.4 (4)
N1—C1—H1	118.9	C22—C23—H23	120.3
C2—C1—H1	118.9	C24—C23—H23	120.3
C1—C2—C3	118.5 (4)	C25—C24—C23	119.9 (4)
C1—C2—H2	120.7	C25—C24—H24	120.1
C3—C2—H2	120.7	C23—C24—H24	120.1
C2—C3—C4	119.7 (5)	C20—C25—C24	120.7 (4)
C2—C3—H3	120.1	C20—C25—H25	119.7
C4—C3—H3	120.1	C24—C25—H25	119.7
C5—C4—C3	118.8 (4)	O2—C26—N8	119.4 (4)
C5—C4—H4	120.6	O2—C26—N7	124.6 (3)
C3—C4—H4	120.6	N8—C26—N7	116.0 (3)
N1—C5—C4	121.2 (4)	N9—C27—N10	173.3 (5)
N1—C5—C6	114.9 (3)	N11—C28—N10	172.7 (5)
C4—C5—C6	123.9 (4)	N12—C29—N13	173.4 (5)
N2—C6—C5	112.9 (3)	N14—C30—N13	174.2 (4)
N2—Cu1—O1—C13	−7.3 (3)	C3—C4—C5—N1	−0.8 (7)
N12—Cu1—O1—C13	−171.1 (3)	C3—C4—C5—C6	179.6 (4)
N1—Cu1—O1—C13	−31.8 (5)	N3—N2—C6—C5	−178.4 (3)
N9—Cu1—O1—C13	89.8 (3)	Cu1—N2—C6—C5	10.5 (4)
N6—Cu2—O2—C26	−5.6 (3)	N3—N2—C6—C7	7.6 (6)
N11—Cu2—O2—C26	−171.2 (3)	Cu1—N2—C6—C7	−163.6 (3)
N5—Cu2—O2—C26	−29.6 (5)	N1—C5—C6—N2	−7.2 (5)
N14^i—Cu2—O2—C26	89.9 (3)	C4—C5—C6—N2	172.5 (4)
N2—Cu1—N1—C1	−178.0 (4)	N1—C5—C6—C7	167.1 (3)
N12—Cu1—N1—C1	−14.5 (4)	C4—C5—C6—C7	−13.2 (6)
O1—Cu1—N1—C1	−153.6 (4)	N2—C6—C7—C8	72.8 (5)
N9—Cu1—N1—C1	84.3 (4)	C5—C6—C7—C8	−100.8 (5)
N2—Cu1—N1—C5	3.5 (3)	N2—C6—C7—C12	−110.7 (5)
N12—Cu1—N1—C5	167.1 (3)	C5—C6—C7—C12	75.7 (5)
O1—Cu1—N1—C5	28.0 (5)	C12—C7—C8—C9	0.6 (7)
N9—Cu1—N1—C5	−94.2 (3)	C6—C7—C8—C9	177.3 (4)
N12—Cu1—N2—C6	−98.0 (5)	C7—C8—C9—C10	0.3 (7)
O1—Cu1—N2—C6	−178.9 (3)	C8—C9—C10—C11	−0.9 (9)
N1—Cu1—N2—C6	−8.1 (3)	C9—C10—C11—C12	0.6 (9)
N9—Cu1—N2—C6	84.9 (3)	C10—C11—C12—C7	0.4 (9)
N12—Cu1—N2—N3	90.3 (6)	C8—C7—C12—C11	−1.0 (8)
O1—Cu1—N2—N3	9.4 (3)	C6—C7—C12—C11	−177.5 (5)
N1—Cu1—N2—N3	−179.8 (3)	Cu1—O1—C13—N4	−175.2 (3)
N9—Cu1—N2—N3	−86.8 (3)	Cu1—O1—C13—N3	5.1 (5)
C6—N2—N3—C13	180.0 (3)	N2—N3—C13—O1	2.2 (5)
Cu1—N2—N3—C13	−8.9 (4)	N2—N3—C13—N4	−177.5 (4)
N6—Cu2—N5—C14	−179.3 (4)	C18—N5—C14—C15	−0.4 (7)
N11—Cu2—N5—C14	−14.2 (4)	Cu2—N5—C14—C15	−173.8 (4)
O2—Cu2—N5—C14	−155.3 (3)	N5—C14—C15—C16	0.4 (9)
N14^i—Cu2—N5—C14	84.8 (4)	C14—C15—C16—C17	−0.2 (10)
N6—Cu2—N5—C18	6.9 (3)	C15—C16—C17—C18	0.0 (9)
N11—Cu2—N5—C18	172.0 (3)	C14—N5—C18—C17	0.2 (6)
O2—Cu2—N5—C18	30.9 (5)	Cu2—N5—C18—C17	174.7 (4)
N14^i—Cu2—N5—C18	−89.0 (3)	C14—N5—C18—C19	−179.1 (4)
N11—Cu2—N6—C19	−104.8 (6)	Cu2—N5—C18—C19	−4.7 (4)
O2—Cu2—N6—C19	−179.8 (3)	C16—C17—C18—N5	0.0 (8)
N5—Cu2—N6—C19	−8.7 (3)	C16—C17—C18—C19	179.2 (5)
N14^i—Cu2—N6—C19	84.7 (3)	N7—N6—C19—C18	−178.9 (3)
N11—Cu2—N6—N7	82.0 (6)	Cu2—N6—C19—C18	8.4 (4)
O2—Cu2—N6—N7	7.0 (2)	N7—N6—C19—C20	5.5 (6)
N5—Cu2—N6—N7	178.1 (3)	Cu2—N6—C19—C20	−167.3 (3)
N14^i—Cu2—N6—N7	−88.5 (3)	N5—C18—C19—N6	−2.1 (5)
C19—N6—N7—C26	−179.3 (3)	C17—C18—C19—N6	178.6 (4)
Cu2—N6—N7—C26	−6.6 (4)	N5—C18—C19—C20	173.7 (3)
N2—Cu1—N9—C27	−157 (2)	C17—C18—C19—C20	−5.7 (6)
N12—Cu1—N9—C27	24 (2)	N6—C19—C20—C25	74.0 (5)
O1—Cu1—N9—C27	123 (2)	C18—C19—C20—C25	−101.3 (4)
N1—Cu1—N9—C27	−76 (2)	N6—C19—C20—C21	−105.0 (5)
N6—Cu2—N11—C28	−52.0 (19)	C18—C19—C20—C21	79.7 (5)
O2—Cu2—N11—C28	20.8 (16)	C25—C20—C21—C22	−0.3 (7)
N5—Cu2—N11—C28	−145.5 (16)	C19—C20—C21—C22	178.7 (4)
N14^i—Cu2—N11—C28	118.5 (16)	C20—C21—C22—C23	−0.5 (8)
C5—N1—C1—C2	−1.6 (8)	C21—C22—C23—C24	1.8 (8)
Cu1—N1—C1—C2	−179.9 (4)	C22—C23—C24—C25	−2.3 (7)
N1—C1—C2—C3	−1.0 (9)	C21—C20—C25—C24	−0.3 (6)
C1—C2—C3—C4	2.7 (9)	C19—C20—C25—C24	−179.3 (4)
C2—C3—C4—C5	−1.8 (8)	C23—C24—C25—C20	1.6 (7)
C1—N1—C5—C4	2.5 (6)	Cu2—O2—C26—N8	−175.3 (3)
Cu1—N1—C5—C4	−179.0 (3)	Cu2—O2—C26—N7	4.0 (5)
C1—N1—C5—C6	−177.8 (4)	N6—N7—C26—O2	1.5 (5)
Cu1—N1—C5—C6	0.7 (4)	N6—N7—C26—N8	−179.2 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H42···N7^iii	0.88	2.13	3.006 (5)	176
N8—H82···N3^iv	0.88	2.15	3.025 (5)	179
O1w—H1w1···O1	0.84	2.05	2.88 (2)	169
O2w—H2w1···O2	0.84	2.34	3.151 (19)	161

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